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Armao dos Bzios - Rio de Janeiro, Brazil



































J. M. (MIKE)




Unidos da







Technologies, Inc.










Unidos da
















LECO Corporation



Industrial de



University of





Artificial Maturation

Artificial Maturation

Division of


































Petrobras S.A.





















Research &

Artificial Maturation

Center of



J. M. (MIKE)



Unidos da



Technologies, Inc.





29 Quai des



Grsillons, 92622

























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Federal do Rio

Artificial Maturation

Grande do Sul







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Federal do Rio
Grande do Sul

Artificial Maturation








Artificial Maturation































Artificial Maturation




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Uni. of Oklahoma










Unidos da


Gas and Surface



Gas and Surface







Gas and Surface

Gas and Surface






Research and

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Center (CENPES)












Surface Exploration




Chemistry of GeoOrganic Molecule




PDVSA Intevep




Stanford University

Facultad de

Organic Molecule

Ciencias Instituto


Unidos da

Chemistry of Geo-

Chemistry of Geo-





de Ciencias de la
Tierra, Universidad

Surface Exploration

Oil Geochemistry

Central de

Organic Molecule





Catlica do Rio de







PDVSA Intevep

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Oil Geochemistry



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and Geophysics,






















State University




Darcy Ribeiro



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Ecopetrol S.A.

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de Qumica,


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Centre Potsdam,
GFZ German
Research Centre
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14473 Potsdam,
Germany ; Institute
for Geology and
Geochemistry of
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Coal, EMR Group;
RWTH Aachen
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Aachen University,



and Organic

Geology and

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Institute for

Janeiro, Brazil



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Source Rock



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Oil Geochemistry






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Petroleum Systems


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Geology and

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Source Rock

Unit, IfG,



and Organic




and Coal, EMR

Petroleum Systems

Aachen University,



of Petroleum

Group, RWTH

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Estado do Rio de





Universidade do

& Production

and Organic

Janeiro, RJ, Brazil


Total, Exploration









7193 ISTeP ?



Petroleum Systems

- Exploration

Source Rock




Source Rock


06 et CNRS, UMR





UPMC Univ. Paris

and Organic

Source Rock









Source Rock

de janeiro, RJ,








Unidos da

Stanford University


Petroleum Systems


Universit de



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Instituto de




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Ecopetrol S.A.,
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School of Geology




and Geophysics,


University of

Petroleum Systems





The use of Rock-Eval can now be extended to assess

unconventional fossil resource prospects, assuming an adequate
choice of the heating program. Currently Rock-Eval pyrolysis can


be applied to assess the potential of oil shale, to characterize heavy

Best Practice for Rock-Eval pyrolysis with

emphasis on unconventional prospects
Violaine Lamoureux-Vara*, Alain-Yves Hucb, Valrie Beaumonta,
Maria-Fernanda Romero-Sarmientoa,
Daniel Pillota, Gremie Letorta, Bernard Carpentiera, Khomsi
Trabelsia, Bruno Garciaa
a IFP Energies nouvelles, 1 et 4 avenue de Bois-Prau, 92852
Rueil-Malmaison, France
b Associate Professor UPMC - Universit Pierre et Marie Curie Institut des Sciences de la Terre Paris (UMR 7193 UPMC-CNRS) /
Institute of Earth Sciences in Paris

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee
following review of information contained in an abstract submitted by the author(s).

The Rock-Eval is a versatile, high-tech instrument which imposed
itself as a standard technics of geochemical characterization and
which has evolved over the last decades in terms of hardware,
software and interpretation capabilities. Primarily built as a
screening tool assessing basic organic attributes of source rocks
such as petroleum potential and thermal maturity, it progressively
enlarged its scope providing information on organic content and
kinetic parameters of source rocks. More recently it allowed
scrutinizing content and nature of mineral carbon of rock samples.
Moreover by adjusting the heating program it proved its applicability
to get an insight into the occurrence and nature of accumulated
hydrocarbons within reservoir sections. In this respect, four builtin methods are readily available: Basic/Bulk-Rock, Reservoir,
Pure Organic Matter and Kinetics.
As far as technology is concerned, the Rock-Eval instrument
displays unique features, which implications have to be emphasized.
Particularly, its twin oven design (pyrolysis and oxidation) is well fitted
to allow the formation of a permanent carbonaceous coating of the
inner pyrolysis furnace surface. This coating, which is oxidized in
single oven machines, prevents further adsorption and subsequent
loss of hydrocarbons interfering with S1 and S2 values. This design
also prevents unwanted oxidation of hydrocarbons condensed on
the splitter outlet directed towards the CO/CO2 line.

oil sections and oil sands and to pinpoint tar mats in a reservoir.
This paper reviews the two main operational Rock-Eval methods
Basic/Bulk-Rock and Reservoir and introduces a new method
devoted to shale plays assessment, the Shale Plays method.

Basic / Bulk-Rock Method

The choice of a specific analytical method is mandatory and
depends on the objectives and type of rock considered. In the
case of source rocks, the Basic/Bulk-Rock method allows a
rapid quantification of total organic carbon (TOC), mineral carbon
content (MinC), estimation of thermal maturity (Tmax), residual
petroleum potential (S2), hydrogen index (HI) and oxygen index (OI)
(Espitali et al., 1977; Espitali and Bordenave, 1993; Lafargue et
al., 1998; Behar et al., 2001). Recently, a specific methodology
for the quantification of different types of carbonates, such as
calcite, dolomite and siderite was developed (Pillot et al., 2013).
The Basic/Bulk-Rock method is usually employed as a rapid
screening tool for core samples or cuttings, which mainly focuses
on characterization of source rocks in a conventional way. It is
not dedicated to an accurate quantification of free hydrocarbons
(S1), for two reasons: (i) it often relies on samples for which quality,
storage conditions and potential contamination by mud fluids do
not guarantee the reliability of S1 peak; (ii) during the analysis, the
initial heating/recording temperature is set at 300C for the sake of
rapidity, and consequently a part of the light hydrocarbons is lost
and not recorded. The Basic/Bulk-Rock method is well adapted
as a proxy of the Fisher assay providing the retorting potential of an
oil shale (Madec and Espitali, 1984).

Reservoir Method
For studying reservoir rocks, the Reservoir method allows the oil
content to be quantified specifically through a heating/recording
program starting at 180C. It also allows checking at a glance if the
oil is conventional or heavy. Moreover the API gravity can be rapidly
estimated (Trabelsi et al., 1994). In the presence of tar mats, a RockEval screening allows identifying their occurrence and location
within a reservoir section penetrated by a well (Carpentier et al.,
1995) or helps in steering directional drilling to keep away from the
tar layers (Halpern et al., 1998). Regarding oil sands prospects,
bitumen contents and traces of carbonates can be quantified by
the means of the Reservoir method. Forecast of CO2 production
from carbonates during steam injection for enhanced oil recovery
is a valuable operational application of this approach (Uzcategui et
al., 2011).

Shale Plays - Method


As far as tight, fractured or hybrid shale plays are concerned,

We are grateful to the Norwegian Petroleum Directorate (NPD) and

hydrocarbons present as fluids and the thermal maturity of rocks

we specifically thank Dag Bering for his kindness and efficiency for

are the focuses of geochemical studies. In this respect assessing

providing rock samples.

properly the amount and nature of the free hydrocarbons is

on the sedimentary environment, maturity, migration and age of

bedrock in some cases.1However, the separation and identification

GCGC as a tool to determine maturation and

biodegradation chemical markers in crude oils

of biomarkers becomes a difficult task because of the variety of

compounds, chemical classes, volatilities and polarities that can
also be found in low concentrations. In this sense, two-dimensional

a*Noroska G. S. Mogolln, aPaloma S. Prata, Fabio Augustoa.

gas chromatography plays an important role in the identification,

characterization and separation of biomarkers through increased

instrumental. Accordingly, and following our previous discussion,


the use of the Basic/Bulk-Rock method which biases the S1

Behar, F., Beaumont, V. I., De B. Penteado, H. L., 2001. Rock-Eval 6

1UniversidadeEstadual de Campinas, Instituto de

sensitivity and detectability.3An additional advantage isthat this

peak should be banned. In the first instance, the source rock

Technology: Performances and Developments. Oil & Gas Science and

Qumica13083-970, So Paulo, SP, Brazil.

technique may avoid the fractionating of petroleum because of the

system being addressed as a reservoir rock, the Reservoir

Technology, 56, 111-134.

method should be preferred. Using the Reservoir method

Carpentier, B., Huc, A.Y., Hamou, P., Wilhems, A., 1995. Detection,

the vaporizable hydrocarbon content of the shale play can be

distribution and origin of thin tar mats in the Miller field (North Sea, UK).

Copyright 2014, ALAGO.

of the parameters needed in two-dimensional gas chromatography

quantified and easily discriminated from the kerogen response on

Org. Geochem. 17th Int. Meet. on Org. Geochem., San Sebastian, 1995,

This paper was selected for presentation by an ALAGO Scientific Committee

GCGC for separation and identification of biomarkers in crude oil

the pyrogram (Fig.1A, 1B and 2). In order to refine the Rock-Eval


following review of information contained in an abstract submitted by the author(s).

and its comparison with the conventional method by GC-MS.

characterization of the shale plays, a specific modified reservoir

Espitali, J., Laporte, J.L., Madec, M ., Marquis, F., et al., 1977. Mthode

method has been developed: the Shale Plays method (Romero-

rapide de caractrisation des roches mres,de leur potentiel ptrolier et de



Sarmiento et al., 2014, this conference). This method provides

leur degr dvolution. Revue de lInstitut Franais du Ptrole (Oil Gas Sci.

The separation of compounds in crude samples is one of the

One Brazilian crude oil samples was selected. For sample

improved parameters to quantify the content of hydrocarbons and

Technol.) 32, 23-43.

most challenging tasks withinchemical analysis. This difficulty

processing and analysis chromatographic grade n-hexane and

their nature (Fig.1C and 2). Through this temperature program

Espitali, J., Bordenave, M.L., 1993. Screening techniques for source rocks

is based uponthe large number of compounds being present in

n-pentane from TediaBrazil (So Paulo, Brazil) was used. For the

devoted to the distillation and pyrolysis steps, the areas of interest

evaluation; tools for source rocks routine analysis; Rock-Eval pyrolysis.

each sample type. For example, in middle distillates it is estimated

satured biomarker analysis approximately 0.1 g of each crude

for the production of shale plays can be tentatively anticipated.

App. Petrol. Geol., 273-261.

that one million compounds of interest are considered.1 Due to

oil were deposited in the top of glass column and eluted with

Halpern, H.I., Jones, P.J., Tobey, M.H., Al-Dubaisi, J.M., et al., 1998.

the complexity of the sample a pre-treatment is required in order

60 mL of n-hexane. Moreover, for analysis by GCGC-FID and

Development and application of a technique to predict oil API gravity from

to facilitate the study of its specific class of compounds that can

GCGC-qMSit the fractioning of the sample was not necessary,

reservoir core samples. Saudi Aramco Journal of Technology, 1998, 33-40.

provide certain desired information. This pre-treatment meansthe

approximately 0.1 g of each crude oil were also weighed and then

Lafargue, E., Marquis, F., Pillot, D., 1998. Rock-Eval 6 applications in

separation of the petroleum in its various fractions which are called

desasphatated with n-pentane.

hydrocarbon exploration, production, and soil contamination studies. Revue

Saturates, Aromatics, Resins and Asphaltenes (SARA).2This

de lInstitut Franais du Ptrole (Oil Gas Sci. Technol.),53, 4, 421-437.

separation is accomplished by a prior asphaltene precipitation with

The lab-made GCGC-FID prototype was based on HP-6890

Madec, M., Espitali, J., 1984. Application of pyrolysis to the characterization

n-pentane, the remaining fractions are separated through a column

Series II GC-FID (Agilent, Santa Clara CA, USA). The column

and the upgrading of the Toarcian oil shales from the Paris basin. Fuel, 63,

of conventional glass, silica or alumina as the stationary phase,

set used consisted on a 30 m 0.25 mm 0.25 m HP-5


and three solvent mixtures as mobile phase which will increase

(5% phenylmethysiloxane) column (Agilent) connected through

Pillot, D., Deville, E., Prinzhofer, A., 2013., Identification and Quantification

progressively in polarity.The elution of saturated compoundsis

a capillary of 1 m 0.20 mm to a middle polar Rxi-17 (50%

of Carbonate Species Using Rock-Eval Pyrolysis. Oil & Gas Science and

performed with n-heptane, the aromatics with a 2:1 mixture of

phenylmethysiloxane) column (Restek)1.0 m 0.15 mm 0.15

C. Shale Plays Method

Technology, 1-9.

n-heptane/toluene and finally the resin fraction is eluted with

m. The modulation period was set to 8.0 s and data acquisition

Figure 1. Pyrograms for the reference shale Jet Rock-1 (courtesy

Romero-Sarmiento, M., Letort, G., Pillot, D., Lamoureux-Var, V., Beaumont,

1:1:1 methylene chloride/toluene/methanol. Then each fraction

was performed at 100 Hz. The oven temperature was programmed

of the Norwegian Petroleum Directorate-NPD),

V., Huc, A.-Y., Garcia, B., 2014. New Rock-Eval method for characterization

is analyzed by the conventional method,a one-dimensional gas

from 100C for 0.89 min to 330C at 2.5C min-1; the injector and

TOC=11.9%, measured with the different Rock-Eval methods: A.

of shale plays. This congress.

chromatography. Such a pre-treatment resultsin an increase of

detector temperatures were set at 280C and 300C, respectively.

Basic/Bulk-Rock; B. Reservoir; C. Shale Plays.

Trabelsi, K., Espitali, J., Huc, A.-Y., 1994. Characterization of Extra Heavy

the analytical errors during the characterization of the sample.

Hydrogen at 0.6 mL min-1was used as carrier gas.

Oils and Tar Deposits by modified Pyrolysis Methods. In Proceedings of

However, the analysis of its fractions is necessary due to the

the Heavy Oil Technologies in a Wider Europe Thermie EC Symposium,

amount of compounds present in crude oil,which is so high that a

The GCGC-qMS system consisted in a modified QP2010+

Berlin 1994, 30-40.

sample of crude quickly exceeds the peak of capacity available on

(Shimadzu, Kyoto - Japan) GC-qMS. The column set and other

Uzcategui, D., Lamoureux-Var, V. and Berger, E. 2011. H2S and CO2

conventional chromatography.Since 1990 the introduction of the

chromatographic conditions were the same as above. The MS ion

generation mechanisms on a steam injection project on Petrocedeo Field,

two-dimensional gas chromatography has shown great potential

source temperature was set to 280C, and the photomultiplier was

Orinoco Belt. Paper WHOC11-112, World Heavy Oil Congress, Edm

for the analysis of complex samples, providing high resolution,

operated at 0.7 kV. The mass scan range was set from m/z 100

sensitivity, detectability and higher peak of capacity, enabling the

to 600, resulting an acquisition rate of 12.5 spectra per second.

discovery of new compounds in complex matrices.GCGC has

Identification of peaks were performed by comparison with

generally been applied to the analysis of hydrocarbons in order

literature mass spectra, retention time and elution order.

Figure 2. Oil content of the reference shale Jet Rock-1 (courtesy of

to identify as many compounds being present in the sampleas

The GC-qMS system was anAgilent GC 7890A/5975C VL MSD.

the NPD) measured with the different Rock-Eval methods, at IFPEN

possible, including biomarkers which are used in geochemistry

The column used was on a 30 m 0.25 mm 0.25 m HP-5

and NPD.

since they exhibit fingerprintsthat provideimportant information

(5% phenylmethysiloxane) column (J&W). The MS ion source

HC content

A. Basic/Bulk-Rock Method


B. Reservoir Method



Sh0 Sh1




increment in the peak of capacity, which also reduces errors during

the analysis. Thus, the main objective of this work is the optimization


temperature was 280C, the temperature of the transfer line was

mentneitherfractionationofthesamples, in thesamewayduetothe

300C and the mass scan range was set from m/z 50 to 600.




and Type III from Mamu Formation, Benin Flank Basin (Nigeria)
was object of this study. For type I kerogen the hydrous pyrolysis


iliesofcompoundssuch as 8,14 secohopanos, diahopanosand

Results and Discussion

3-methylhopanes, whichwerecoelutedonconventionalchromato-

The chromatograms from GC-qMS for the first petroleum fraction

graphic. Besides, theseresultswereusedto determine thegeochem-

composed of saturated hydrocarbons for the biodegraded oil is


shown below.

mationbyconventionaltechniquessuch as GC-MS and GC-MS / MS.

Effect of artificial maturation at different types

of potential source rocks: Focusing on polar
compounds evaluation by FT-ICR-MS technique

experiments were performed at different Temperatures (T = 300,

310, 320, 340, 350, 355 e 360)C and fixed time (t = 72 h) giving
up a total of seven samples of expelled oil (Binotto et all 2010).
Eight samples of expelled oil from Type III kerogen was obtained

whichprovidedfurthergeologicalinforRosana C. L. Pereiraa*, Rosane A. Fontesa,Regina

fixing the T(340C) and varying the hydrous pyrolysis time t (1, 2.5,

Binottoa,Manoel J. R. Guimares Netoa, BoniekG. Vazb

5, 10,20,50,100 e 200)h. The expelled oil samples (~ 1 mg) were

dissolved in 10 mL of toluene, and 0.5 mL of the resulting solution

The authors thank CNPq (Brazilian Research Council) for its fellow-

a PETROBRAS/CENPES, Rio de Janeiro, RJ, Brazil

were transferred to a 1 mL vial and diluted with 0.5 mL of methanol

ship; ANP (Brazilian Petroleum Agency),Petrobras S/A andFUN-

b Instituto de Qumica Universidade Federal de Gois, Goinia, GO, Brazil

containing 0.2% ammonium hydroxide. The general ESI conditions

CAMP UNICAMP for their financial support.


were as follows: capillary voltage of 3.10 kV, tube lens -100 V and
ow rate of 3 L min-1. Ultrahigh resolution MS was performed

Figure 1. Chromatogram obtained in GC-qMS for the saturatedfractionfor the


Copyright 2014, ALAGO.

using a Thermo Scientific 7.2 Tesla Fourier transform ion cyclotron

biodegraded oil

1Peters K.E, Moldowan J.M, 1993, The Biomarkers Guide. Interpreting

This paper was selected for presentation by an ALAGO Scientific Committee

resonance mass spectrometer (LTQ FT Ultra, ThermoScientic,

Molecular Fossils in Petroleum and Ancient Sediments, Prentice Hall, New

following review of information contained in an abstract submitted by the author(s).

Bremen, Germany). A scan range of m/z 2001000 was used, and

It can be observedhow the complexity of the chromatogram

one scan of 100 microscans was collected in each run.


increases with biodegradation of oil, in comparison to the non-


biodegraded oil,whichalso contains a higher coelution, whereby

2Grice, K., Alexander, R., Kagi, R.I., 2000.Diamondoid hydrocarbon

Generation and expulsion of oil from organic sedimentary rocks

Results and Discussion

an ion monitoring is necessary to obtain higher detectability of

ratios as indicators of biodegradation in Australian crude oils. Organic

have been achieved in the laboratory by a technique known as

The ESI (-) FT-ICR mass spectraand the class profile (Figure 1)


Geochemistry 31, 6773

hydrous pyrolysis. This technique maintains a liquid water phase

of original extracts of Type I and III kerogen show significant

in contact with organic sedimentary rocks during their heating at

compositional differences. The Type III kerogen presents a

3Reddy, C.M., Nelson, R.K., Sylva, S.P., Xu, L., Peacock, E.A.,

subcritical water temperatures. The expelled oil accumulates on

distribution of low molecular weight compounds that not checked

Raghuraman, B., Mullins, O.C., 2007. Identication and quantication

the water surface and contains measurable hydrocarbons. The

for Type I, which have high mass molecular profile Similar results

of alkene-based drilling uids in crude oils by comprehensive two-

pyrolysate expelled by this technique is more closely analogous

were reported by Salmon et al (2011) in the studies of molecular

dimensional gas chromatography with ame ionization detection. Journal

to crude oil expelled in the natural system than that techniques

characterization by ESI FT-ICR (-) MS of sample of kerogen Type I

of Chromatography A 1148, 100107.

that employer carrier gases, cryogenic traps, or solvent extraction

from Green River formation.The extract of Type III is characterized


In hydrous pyrolysis systems, it was observed that

by a greater diversity of classes of heteroatom-containing

thepyrolysis products from kerogen or lignite degradation are

compounds, while kerogen Type I show basically oxygen and

dominatedby heteroatomic compounds, called NSOs, of very

nitrogen-containing compounds.

On the other hand, the chromatogram of crude oil by GCGCis

shown in Figure 2

highmolecular weight (Lewan 2002).

Figure 2. Chromatograms obtained in GCGCfor biodegraded oil.
A clearadvantageisobserved in thechromatogramobtainedby GCGC ofcrudeoil,

To achieve a better understanding of the polar components

whereanincrease in separation, detectionandsensitivityprovides a structuredan-

composition at expelled oil,samples from kerogen Type I and Type

dresolvedchromatogram, whichgivesan overview ofthesample. Thisisanaddi-

III were selected and their hydrous pyrolysis products at different

tional tool for theanalystatthe time ofidentification, sincehomologous series

temperatures were analyzed by negative-ion electrospray Fourier

are groupedintoclearlydefinedregionsof a GCGC plot. Weidentifiedthe se-

transform ion cyclotron resonance mass spectrometry (ESI(-) FT-

ries of 8,14 secohopanesanddiahopanesrelatedwithbiodegradation, along-

ICR MS). FT-ICR MS provides significant mass resolving power, m/



m50%> 200,000 (m50% is the mass spectral full peak width

hardlydetectedandresolvedby GC. The geochemicalparametersweredeter-

at half-height), from 225 <m/z< 1000, enabling the differentiation

minedfromsamples, whichrevealthatthedevelopmentoforganicmatterwas in

of compounds with the same nominal mass but differing exact

lacustrineenvironment, with a biodegradationthatmoderatelyincreaseswith-

masses with an accuracy within < 0.3 ppm. ESI is the most

proximitytothesurfaceoforganicmatterbesidesof a medianthermalevolution.

commonly used ionization technique for liquid samples, and it

Likewise, thesecohopanes, diahopanesandmethylhopanessupportedthein-

selectively ionizes nonvolatile acidic and basic compounds in

Figure1.ESI (-) FT-ICR mass spectra and acidic NSO classes profile of


crude oils and their related derivatives without the interference of

extracts of two different kerogen type

fromthe data usingconventionaltecniques as GC-MS

nonpolar compounds, such as hydrocarbons.


The changes observed on NSO profile and in the distribution of the



series (DBE- double bond equivalent) within a specific class during

It waspossibletoconducttheanalysisofcrudeoils, without pre-treat-

A Type I kerogen from Trememb Formation, Taubat Basin, Brazil

hydrous pyrolysis in different conditions are illustrated inFigure 2.





isotope analysis generally convert analytes to simple molecules

Lewan, M. D.; Ruble, T. E. 2002. Comparison of petroleum generation








The Isotopic Structures of Organic Compounds

(e.g., combustion of organics to CO2); this procedure provides only

an overall inventory of 13C or D, averaged across all possible sites

pyrolysisOrg. Geochem.33, 1457-1475.

Binotto, R.; Rondn, N. D. F.; Lewan, M. D.; Santos Neto, E. V.; Mendona

established analytical techniques: Conventional methods of stable

John M. Eiler1, Daniel A. Stolper1, Alexandre A. Ferreira2, Eugnio

and numbers of substitutions but destroys any information that

V. Santos Neto2, Alex L. Sessions1

might have been recorded by differences in proportions of individual

isotopologues. Established methods of clumped isotope analysis

Filho, J. G.; Spigolon, A. L. D. 2010. Insights onbiomarker parameters

of the Trememb Formation (Type I kerogen), Brazil, based on hydrous

1 - Division of Geological and Planetary Sciences, California Institute of

use low-resolution gas source mass spectrometers that can

pyrolysis experiments, 27th

Technology, MC 100-23, Pasadena, CA 91125, USA.

only provide useful measurements of simple compounds having

Annual Meeting of The Society for Organic Petrology (TSOP), Denver,

2 - Division of Geochemistry, PETROBRAS Research and Development

straightforward mass spectra (e.g., CO2 or O2). SNIF-NMR and

Colorado, USA.

Center (CENPES), PETROBRAS, Rua Horcio Macedo, 950, Ilha do

the various methods based on chemical or pyrolitic degradation

Fundo, Rio de Janeiro, RJ 21941-915, Brazil.

of organics generally only can observe single substitutions (usually

only of 13C), and so miss most of the isotopic diversity that is

Salmon, E.; Behar, F.; Hatcher, P. G. 2011. Molecular characterization

of Type I kerogen from the Green River Formation using advanced NMR

found in the deuterated and clumped isotopic species. These

methods also generally require large amounts of analyte and/or

techniques in combination with electrospray ionization/ultrahigh resolution

Copyright 2014, ALAGO.

labor intensive procedures and so have been slow to develop into

Figure 2.Acidic NSO class relative abundanceforoils expelled

This paper was selected for presentation by an ALAGO Scientific Committee

useful applied geochemical tools.

during hydrous pyrolysis experiments at different temperatures and

following review of information contained in an abstract submitted by the author(s).

mass spectrometryOrg. Geochem.42, 301-3015.

time of 72 h and O Class DBE distribution for oilsgenerated at 320

We will present the results of a recent effort to develop and

and 360C.

Most natural organic compounds are mixtures of a large number

apply methods of high-resolution gas source mass spectrometry

of isotopologues that differ in the molecular site(s) and/or number

that enable the precise analysis of proportions of dozens of

Theheteroatom class distribution for the oils obtained from Type I

of their rare isotope substitutions. Most alkanes, fatty and amino

isotopologues of common organic compounds, including site-

kerogen at different temperatures and hydrous pyrolysis time (t)

acids, sugars and similar-sized compounds posses dozens to

specific substitutions and clumped isotope abundances. These

of 72 h and the comparison of O Class DBE distribution from oils

hundreds of singly and doubly substituted species (generally

methods make use of a pair of gas source mass spectrometers:

generated during Exp1 in two extreme temperatures (T = 320 and

present in ppm or greater abundances), and a great many more

the Thermo IRMS 253 Ultra a prototype having a double

360 C) are presented. It is showed that the relative abundance

rarer species containing three or more rare isotopes.

focusing analyzer that reaches mass resolutions of ~25,000 and

ofO2 classincreases while O3 and O4 decreasewith temperature

a moveable array of multiple collectors and the Thermo DFS-

increasing. The changes observed for O-containing compoundsare

Measurements of the proportions of individual isotopologues of

a reverse geometry double focusing instrument that achieves

related to a sequence of dehydration and/or decarboxylation

organic compounds could potentially advance our understanding of

mass resolutions up to 80-100,000, has a single collector, and is

reactions.Thechanges observed in DBE distribution of O class show

a variety of geochemical, biochemical, and environmental problems.

adapted for our purposes by connection to a duel inlet sample

an increase on the relative intensity of series with higher DBE values

For example, it is recognized that a population of molecules that

introduction system (i.e., to enable sample-standard comparison).

for the oil generated at higher temperature. These series, DBE 7 to

achieves equilibrium with respect to its isotopic distribution will

Used together, these instruments are capable of mass resolution

17, correspond to compounds with a larger number of aromatic and

form excesses of multiply substituted species (isotopic clumps),

13C from D-bearing isotopologues of molecular and fragment ion

naphthenic cores. These results confirm the well-known occurrence

in abundances that are inversely proportional to temperature.

species up to ~100-150 amu, and routinely achieve precisions of

of aromatization reactions, justifying theobserved shift to higher DBE

This phenomenon is the basis of clumped isotope thermometry

~0.1-1.0 for most species of interest.


of CO2, carbonate and O2, and could potentially be applied to

other compounds including many organics. Similarly, SNIF-NMR

The first well-established tool developed using these instruments


measurements of the carbon isotope structures of sugars and

is a clumped isotope thermometer for methane, which examines

The NSO composition of two kerogen (Type I and III) revealed by

long-chain alkanes demonstrate the existence of distinctive site-

the temperature dependent formation of 13CH3D (with trace

ESI(-) FT-ICR MS shows significant differences. Also, compositional

specific variations in 13C abundances of many compounds, some

contributions from 12CH2D2). This analysis can be made using

changes were easily observed on oils generated duringhydrous

of which can be interpreted as a record of biosynthetic pathways.

only the Ultra, and has been applied to diverse natural and synthetic

pyrolysis experiments in different temperature and time conditions.

Similar observations of site-specific isotope effects have been

materials, including conventional and unconventional gas deposits,

These results strongly encourage the application of FT-ICR MS

made by mass spectrometry of N2O, and by selective chemical or

various biogenic and hydrothermal methanes, and methane

as an analytical tool for kinetic studies monitoring during artificial

pyrolytic degradations of organic compounds.

formed by laboratory cracking reactions and microbial cultures.

maturation experiments.

Results to-date indicate that natural methane normally forms in

However, until recently direct observations of proportions of

internal isotopic equilibrium and that this formation temperature is


specific isotopologues have been made for only a few compounds,

generally preserved through later gas migration or geological uplift

The authors thank Petrobras S/A for financial support.

and have generally considered only a handful of the many possible

of host rocks. We will present case studies in which this tool is used

isotopic substitutions. This largely reflects the limitations of

to discriminate low temperature biogenic from high temperature




thermogenic gas in mixed deposits, and to recognize the products

of secondary cracking in very mature parts of petroleum deposits,

A Review of advanced Geochemical

Technologies for source determination and
quantification of Oil Mixtures

even when they are mixed into lower maturity constituents. Finally,
we will show data from laboratory cultures and natural samples
that reveal kinetic isotope effects producing non-equilibrium

biomarkers such as steranes (CSIA-Bs), hopanes (CSIA-Bh) and

conventional oil, condensate, seepage oil, heavy oil and source rock

isoprenoids (CSIA-Bi).

extracts. Diamondoids, especially the larger ones, are virtually inert

4. Analysis of asphalteneand kerogenpyrolysates from biodegraded

to both thermal and biological degradation. They can be applied to

heavy oil and immature source rocks.

any correlation effort.

Quantitative diamondoid analysis (QDA)

abundances of the clumped species in some biogenic gases.

J. M. (Mike)

This phenomenon appears to be common in biological systems


having rapid growth rates and high partial pressures of H2, but







Multiple applications of QDA have evolved since this method was

introduced by Dahl et al. (1999). Initially it was found that diamondoid
concentrations in oil respond to the level of conversion of liquid oil

has not been observed to-date in natural sub-surface biogenic

gas, perhaps due to slower growth rates and lower pH2. We will

a Biomarker Technologies, Inc. (BTI), 638 Martin Avenue, Rohnert

to gas and pyrobitumen (oil cracking).Diamondoid levels begin to

present complementary data on proportions of 13C2H6, 13CH3

Park, CA 94928, USA;

increase simultaneously with the depletion of certain biomarkers.

12CH212CH3 and 12CH313CH212CH3 in natural gases,

b Stanford Institute for Materials and Energy Science (SIMES),

It was found that the C29-20R-sterane goes to a very low

which appear to record the mechanisms and progress of cracking

Stanford University, Stanford, CA 94305, USA;

concentration at the same point as oil begins to crack, and the level


c GB Scientific, Inc., 1090 Industrial Avenue, Suite B, So. Lake

of conversion of liquid to gas and pyrobitumen can be calculated.

Tahoe, CA 96150 USA

Isotopically labeled diamondoids of the same carbon structures

are added as internal standards to insure accuratemeasurements.

Integration of data from the DFS with the Ultra enables analysis
of a great many additional measurements that are challenging or

Increased diamondoid concentrations often occur in black oil with

impossible using either instrument alone. Examples we will present


significant C29-20R-sterane concentrations. Such cases reveal

oil that was co-sourced from both a deep and shallow sources.

include: (1) measurement of 12CH2D2 in methane, which can be

used to distinguish high-temperature equilibrated methane from

Copyright 2014, ALAGO.

biogenic methane having a kinetic isotope fractionation, and/or

This paper was selected for presentation by an ALAGO Scientific Committee

Additionally it was found that the ratios of certain diamondoids can

to deconvolve mixtures of methane sources, and (2) 13C and D

following review of information contained in an abstract submitted by the author(s).

be used as source parameters (Schultz et al., 2001). However,

isotopic structures of hexane, which includes several isotopologues

fingerprints of the light diamondoids are prone to being augmented

Figure 1. Diamondoid correlation parameters are tested in their role to

that may constrain its biological sources, natural of its cracking

by secondary effects.Higher-diamondoid distributions are an

unravel oil mixtures. (a) Cretaceous and Oligocene end-member oil samples

extension of this method that is less prone to secondaryfractionation

from Eastern Venezuela are mixed in the ratios specified by the key. Non-

effects and offers more options for source-related fingerprinting

mixed end-member oils show different QEDA fingerprints and the mixtures

(see QEDA, below).

can be quantified by assessing their intermediate profiles. (b) the same end-


reactions, and temperatures of its formation and/or storage.

Classical biomarker analysis, gas chromatography

and bulk

isotope analysis have played a role in defining the worlds petroleum

member oil-sample mixtures, including an additional sample of Oligocene

systems. But those methods have reached their limitations in

Because diamondoids are volatile and biodegradation resistant,

condensate, are evaluated by CSIA-D to show how such mixtures can be

many cases. After many repetitive studies the same conclusions

yet less volatile than gas, QDA is used to determine the location of

quantitatively unraveled.

can be reached and the same components can always be missed

marine oil and gas seeps through piston core surveys.More recently

when only the same technology is being applied. Often a missed

QDAapplicationshave been successfully extended to land-based

Diamondoid isotopic analysis (CSIA-D)

source component can even account for the major charge in a

studies for hydrocarbon seepages onto soil (Dahl et al., 2014).QDA

Correlation by CSIA-D issimilar to QEDA (Moldowan et al., 2011),

basin. Computer-generated basin models cannot compensate

is now beingapplied to determinethe level of oil-cracking in tight

except it relies on source-related isotopic differences in the

for missed hydrocarbon sources, which means that application

shale as an aid to production and prospecting for unconventional

diamondoids, rather than fingerprint histograms of their relative

of new advanced geochemical technologies (AGTs) is a must for

oil and gas (Dahl et al., 2011).

concentrations.CSIA-D is complimentary to QEDA as isotope

basin modelers who want to propose new drilling targets that lead
to discoveries.In this presentation we review several key AGTs that

Quantitative extended diamondoid analysis (QEDA)

in the cages of diamondoid molecules. This is not the case for

have opened new vistas in petroleum system models where ever

Using the knowledge from QDA that ratios of diamondoids of different

biomarkers and most other molecules in oil. Like QEDA, CSIA-D

they have been applied.

structures are source dependent we developed a method to measure

measurements are applicable to all liquid-petroleum sample types.

extended diamondoids including triamantane, three tetramantane

We have also found that oil generated in the laboratory from

isomers, four pentamantane isomers and cyclohexamantane

either kerogen or isolated asphaltenes contains source related

(Zinniker et al, 2011). Because these molecures are present in

diamondoid assemblages that can be used for correlation.

Technologies Reviewed


ratios are to biomarker parameters, except there is a great stability

1. Quantitative diamondoid analysis (QDA) as an indicator of

extremely low concentrations it was necessary to standardize the

source, maturity and mixing.

analysis with synthetically-produced isotopically labeled (deuterium-

Biomarker isotope analysis (CSIA-B)

2. Quantitative extended diamondoid analysis (QEDA) fingerprinting

labeled) diamondoids of the same carbon structures. The value of

CSIA measurements (Figure 2) can also be taken on alkanes

diamondoids exceeding three molecular cages.

application of QEDA to source correlation, along with CSIA-D (Figure

and sterane, hopane and isoprenoid biomarkers that can be

3. Compound specific isotope analysis (CSIA), which includes

1) cannot be overstated as the universal correlation method. This is

sequestered for the analysis. The special requirement for accurate

applications to alkanes (CSIA-Ac), diamondoids (CSIA-D), and

because diamondoids are universally present in all petroleum liquids:

and precise CSIA measurements of any compound is to prepare a


petroleum fraction that displays the GC-FID peak of interest without


a significant co-elution from other compounds. Fractionations to

obtain the unencumbered peaks are often dependent on specific

the two methods are compared, and suggest that IRIS-based

measurements of formation water are possible.

2H/1H Ratios of Formation Waters from the

Potiguar Basin, Brazil: a Comparison Between
Isotope Ratio Infrared Spetroscopy (IRIS) and
Isotope Ratio Mass Spectrometry (IRMS)

zeolites that are selected based on the molecular cross-sections of

the compoundsto be segregatedcompared to the molecular crosssection of the specific zeolite channels. Electronic interactions

Samples were drawn from the easternmost Brazilian equatorial
basin, the Potiguar Basin, deposited during the rifting of Gondwana
in the Early Cretaceous (Santos Neto & Hayes, 1999). A total

between the zeolite and the hydrocarbon might also play a role.
Alexandre A. Ferreira1, 4, Eugnio V. Santos Neto1, Alex L.

of 11 formation waters were collected from production wells

Sessions2, Arndt Schimmelmann3, Peter E. Sauer3, Cleverson J.

(onshore) not subject to water injection or any other Enhanced Oil

a Mean 2H (1) from replicate injections. SD are standard

F. Oliveira1, Francisco R. Aquino Neto4

Recovery method, meaning that the original isotopic signatures

deviations, identified for each method.

of the formation waters should be preserved. 2H values were

1 Division of Geochemistry, PETROBRAS Research and
Development Center (CENPES), PETROBRAS, Rua Horcio
Macedo, 950, Ilha do Fundo, Rio de Janeiro, RJ 21941-915,
2 Division of Geological and Planetary Sciences, California
Institute of Technology, MC 100-23, Pasadena, CA 91125, USA.
3 Department of Geological Sciences, Indiana University, 1001
Figure 2. Four oil-source types from West Africa (Angola and Gabon) are

East Tenth Street, Bloomington, IN 47405-1405, USA.

distinguished by hopane and sterane isotope analysis. The four types in

4 Universidade Federal do Rio de Janeiro, Instituto de Qumica,

order of increasingly heavy hopanes include: rift-derived lacustrine (lightest),

LAGOA-LADETEC, Ilha do Fundo, 21941-909, Rio de Janeiro,

Tertiary predominantly terrestrial, unspecified marine and open marine

RJ, Brazil.

(heaviest), respectively.

Schultz, L.K.; Wilhelms, A.; Rein, E.; Steen, A.S. (2001) Application of

Copyright 2014, ALAGO.

diamondoids to distinguish source rock facies. Organic Geochemistry 32,

This paper was selected for presentation by an ALAGO Scientific Committee


following review of information contained in an abstract submitted by the author(s).

Dahl, J.E.; Moldowan, J.M.; Peters, K.E.; Claypool, G.E.; Rooney, M.A.;

determined according to the following methods: (a)IRMS1

conversion to H2 gas at 500 oC in contact with Indiana Zinc, with
dual-inlet analysis on a Thermo-Finnigan DeltaPlusXP isotoperatio mass spectrometer. Samples were analyzed in duplicate or
triplicate, and results were normalized to the VSMOW and SLAP
standards; (b)IRMS2 chromium reduction at 750 oC using
Thermo H-device and the same spectrometer as in (a). Samples
were analyzed in triplicate; (c)IRIS1 off-axis integrated cavity
output spectroscopy (OA-ICOS) using the Liquid Water Isotope
Analyzer (Los Gatos Research) coupled to a CTC-LC-PAL.

Figure 1.Average 2H values (, VSMOW) of formation waters

Samples were analyzed in six replicates, with the first three results

plotted for visual comparison of the applied methods. Error bars

being discarded. Standards were spaced between samples within

correspond to the measured standard deviations.

each run. A previous clean-up step included the use of activated

charcoal and solid phase extraction; (d)IRIS2 wavelength-

In order to evaluate the differences among all methods, they were

scanned cavity ring-down spectroscopy (WS-CRDS) using the

compared, two at a time, using Students t-test and Snedecors

isotopic water analyzer L1102-i (Picarro, Inc.). In this case, each

F distribution from STATISTICA. The comparisons were made

sample was analyzed eight times and the first four 2H values

through the average 2H values (of all samples) calculated for each

were discarded.A proprietary method from Picarro, including the

method. It was assumed that these values were normally distributed

clean-up procedure, was applied in this case.

and that the samples were homogeneous and independent. All the

Michael, G.E.; Mello, M.R.; Kohnen, M.L. (1999) Diamondoid hydrocarbons


as indicators of natural oil cracking. Nature 399, 54-57.

Over the last few decades, studies of the origin and evolution of

Moldowan, J.; Zinniker, D.; Liu, Z.; Rovenskaya-Nemchenko, A.; Dahl, J.;

formation waters in sedimentary basins have indeed improved our

Results and Discussion

that, in all cases, no statistically significant difference was found for

Nemchenko, T. (2011) Geochemical parameters for unravelling mixtures.

understanding of the subsurface flow of fluids (Monjerezi et al.,

The measured 2H values are listed in Table 1 and plotted in

a level of confidence of 95%.

25th IMOG, September 18-23, Interlaken, Abs P-291, p. 424.

2011). The isotopic characterization of these waters usually plays

Zinniker, D.; Moldowan, J.M.; Dahl, J.; Denisevich, P. (2011) New techniques

a key role in this context. 2H/1H and 18O/16O ratios of formation

for understanding and mapping high-maturity

waters have been used as proxies for evaporation, isotope

petroleum systems. Examples from the San Joaquin Basin, San Juan

exchange with rock minerals under high-temperature conditions,

Basin, and US Gulf Coast. 25th IMOG, September 18-23, Interlaken,

and mixing with seawater or sedimentary brines (Varsnyi &

AbsP-031, P. 179.

.Kvacs, 2009). In this study, we present a comparison of the

Dahl, J.; Moldowan, S.; Moldowan, J.M. (2011) Designing tight-shale

2H values of formation waters measured by IRMS methods and

production strategies using diamondoid nanotechnology. 25th IMOG,

IRIS (Isotope Ratio Infrared Spectroscopy) methods. The latter has

September 18-23, Interlaken, Abs O-73, p. 134.

been recognized as a rapid, cost-effective and field-deployable

Dahl, J.; Moldowan, J.M.; Nali, M.; Galimberti, R. (2014) Diamondoids

technology, with similar results to the traditional methods for clean

in Surface Sediments for Identification of Petroleum Seeps. Abstract

water samples (West et al., 2010), but is susceptible to interference

accepted for oral presentation at the AAPG International Meeting, Istanbul,

from organic molecules, particularly alcohols. Clean-up procedures

Turkey. September 14-17, 2014. To be presented.

were thus tested and applied before the IRIS methods in order
to eliminate the presence of organic contaminants that could
influence the isotopic measurements due to interferences on
the water absorption spectrum (Schmidt et al., 2012). Data from

calculated t and F values were lower than the listed ones, meaning

Figure 1 for each sample. Standard deviations (SD) were higher

for IRMS1, which could be interpreted as a result of the multiple


transfer steps (H2O and H2) during the procedure using Indiana

2H/1H ratios of 11 formation water samples were determined

zinc. Besides, SD values were more variable due to random errors

using two IRMS conventional methods and two IRIS laser-based

present in this process. The lowest SD values, on the other hand,

methods. The dispersion of values was higher for IRMS1 and

were observed for IRMS2 and IRIS2. Deviations in 2H values

the most precise methods were IRMS2 and IRIS2. Although

for sample MA2 could be associated with the higher organic

no statistically significant differences among all methods were

content of this sample. Sample NA1, on its turn, is the one with the

observed and the spectroscopic analyses seem to be a natural

higher salinity, and could have especifically impacted the optical

alternative over the mass spectrometers, we suggest a careful

measurements, causing the higher observed discrepancies. There

pre-treatment of formation water samples to remove dissolved

were no known reasons for the depletion in 2H for sample PA7

organic compounds as well as salts. In both cases, measurements

(IRMS2) or the enrichment in 2H for sample PA2 (IRMS1).

based on IRIS methods can be directly affected either by spectral

interference or changes on the injected water volume, respectively

Table 1. Average 2H values(, VSMOW)a of formation waters

(at least with the hardware applied in this work).

obtained by IRMS (light gray) and IRIS methods (dark gray). All the
values were represented with one decimal place for comparison.




Two crude oil samples and four condensate samples were drawn

The authors thank PETROBRAS for permission to publish the

results of this investigation and Mark Davis and Gregor Hsiao for

Compound Specific Carbon Isotope Analysis

of Light Hydrocarbons (C1 - C10): Application
on the Geochemical Characterization of Marine
Oils from Northeastern Brazil

the water analyses at Picarro.


from a northeastern Brazilian basin. Compound specific carbon

isotope analysis of the correspondent light fractions (C3-C10) were
performed on an Agilent 7890 gas chromatograph coupled to a
Delta V Plus mass spectrometer via a Conflo III interface (Thermo
Scientific). The chromatograph was equipped with a split-splitless
injector (280 C), and the samples were introduced (0.1 L) in

Monjerezi, M.; Vogt, R.D.; Aagaard, P.; Gebru, A.G.; Saka, J.D.K., 2011.
Using 87Sr/86Sr and 2H isotopes along with major chemical composition

Alexandre A. Ferreira*1, Clarisse L. Torres2, Juliana A. Iemini1,

to assess groundwater salinization in lower Shire valley, Malawi. Applied

Jarbas V.P. Guzzo1, Ygor S. Rocha1

Geochemistry, 26 (12), 2201-2214.

1 Division of Geochemistry, PETROBRAS Research and

split mode (20:1), without dilution. GC oven temperature was

programmed from 35 C (hold 10 min) to 96 C with a heating

The proposal for the existence of two petroleum systems - A and

B - in the study area was based on the following observations: (a)
similarities in the isotopic profile, absolute 13C values and isotopic
amplitudes regarding distinct classes of compounds within the
same group, condensates (A) or oils (B) (Fig. 1); (b) different ranges
of isotopic variation for C1-C4 (Fig. 2). In this case, the observed
parallelism could be attributed to differences in thermal maturation.
However, the 2H profile clearly distinguishes the same two
groups, reflecting the existence of two source rocks; (c) finally, the
average C1 content for gases from system A was higher than 85%,
whereas, for system B, was about 60%.

rate of 1.1 C/min. Then a heating rate of 30 C/min was applied

until 320 C and held for 5 min. Helium was the carrier gas, with
a constant flow rate of 1.3 mL/min. For the isotopic calibration,

Santos Neto, E.V.; Hayes, J.M., 1999 Use of hydrogen and carbon stable

Development Center (CENPES), PETROBRAS, Rua Horcio

isotopes characterizing oils from the Potiguar Basin (onshore), northeastern

Macedo, 950, Ilha do Fundo, Rio de Janeiro, RJ 21941-915, Brazil.

from different classes (n-heptane, toluene, 4-methyl-heptane,

Brazil. American Association of Petroleum Geologists Bulletin, 83 (3), 496-518.

2 Fundao Gorceix, Rua Carlos Walter Marinho Campos, 57,

n-octane, ethyl-cyclohexane, m-xylene and n-decane), diluted in

Vila Itacolomy, Ouro Preto, MG 35400-000, Brazil.

n-hexane - was used (Torres & Ferreira, 2014). Compounds were

a secondary standard - a mixture of seven pure compounds

separated using an HP-PONA (50 m x 0,20 mm x 0,50 m).

Schimdt, M.; Maseyk, K.; Lett, C.; Biron, P.; Richard, P.; Bariac, T.; Seibt,


U., 2012. Reducing and correcting for contamination of ecosystem water

Carbon isotope analyses of the gases (C1-C4) were performed

stable isotopes measured by isotope ratio infrared spectroscopy. Rapid

Communications in Mass Spectrometry, 26 (2), 141-153.

Copyright 2014, ALAGO.

on an Agilent 6890 gas chromatograph coupled to a Delta V

This paper was selected for presentation by an ALAGO Scientific Committee

Advantage mass spectrometer via a GC Combustion III interface

following review of information contained in an abstract submitted by the author(s).

Varsnyi, I.; .Kovcs, L., 2009 Origin, chemical and isotopic evolution of
formation water in geopressured zones in the Pannonian Basin, Hungary.


Chemical Geology, 264 (1-4), 187-196.

The geochemical characterization of crude oils has been widely

used in the petroleum industry to improve our understanding of

(Thermo Scientific). The samples were manually injected (10

L) in a split/splitless inlet (split ratio 54:1; T=200 C). The oven
temperature was programmed from 40C (hold 1.5 min) to 200 C
with a heating rate of 30 C/min (hold 3.2 min). Helium was used as
the carrier gas (constant flow, 1.7 mL/min).

West, A.G., Goldsmith, G.R., Brooks, P.D., Dawson, T.E., 2010

the distribution of hydrocarbons in the subsurface. Information

Discrepancies between isotope ratio infrared spectroscopy and isotope

For the isotopic calibration, a secondary standard (natural gas

regarding reservoir continuity, filling history or biodegradation, for

sample) was employed. GC separation was provided by a Poraplot

ratio mass spectrometry for the stable isotope analysis of plant and soil

example, has been provided for the optimization of exploration

Q column (25 m x 32 mm i.d.). In both cases, the criteria for the

waters. Rapid Communications in Mass Spectrometry, 24 (14), 1948-1954.

strategies or the prediction of oil quality.

acceptance of the isotopic values included complete baseline

separation and signal intensities (m/z 44) above ~ 500 mV, and the

Most of the geochemical interpretation for oils is based on the

assumed error was 0.5 .


biomarkers characterization and carbon and hydrogen isotope

ratios of n-alkanes (~C15-C30) (Guzzo et al., 2011). We have recently
established and optimized an additional tool for the geochemical
characterization of light oils and condensates: the carbon isotopic
determination (13C) of light hydrocarbons, ranging from 3 to 10

Figure 2. a - 13CVPDB and b - DVSMOW values of C1-C4, present in

the associated gas phase of each correspondent well.

Results and Discussion

13C values of the C3-C10 and C1-C4 hydrocarbons are plotted in
Figure 1 and Figure 2, respectively.

carbon atoms (Torres et al., 2011; Torres & Ferreira, 2014).

We suggest the existence of two petroleum systems based on the

carbon isotope analysis of light hydrocarbons (C1 - C10) present in
gases, condensates and oils of a northeastern Brazilian basin. This
tool was particularly useful in this case, where biomarkers data and
isotopic profiles of the n-alkanes (~C15-C30) could not be used to
suggest the presence of such systems.

This analytical technique is especially recommended for that kind

Curiale, J., Morelos, J., Lambiase, J., Mueller, W., 2000. Brunei Darussalam
characteristics of selected petroleums and source rocks. Organic
Geochemistry 31, 14751493.

of sample, as light oils and condensates which can incorporate

biomarkers from less mature rocks during migration or by reservoir
contamination (Curiale et al., 2000), which in turn may mislead the

Guzzo, J.V.P.; Santos Neto, E.V.; Ferreira, A.A., 2011. Improved genetic
characterization of Brazilian oils using combined molecular (biomarkers)
and isotope geochemistry. International Meeting on Organic Geochemistry,
25. Interlaken, Switzerland.

geochemical interpretation based on these compounds.

In this particular work, 13C values of light compounds. (C3C10) were measured for a set of oils and condensates in order

Torres, C. L.; Ferreira, A. A., 2014. Compound specific carbon isotope

analysis of light hydrocarbons (C10- fraction): an improved method for
condensate characterization. South American Symposium on Isotope
Geology, 9. So Paulo, Brazil.

to investigate the existence of two petroleum systems in the

correspondent study area. Biomarkers characterization and
13C values of n-alkanes were not clear enough to confirm this
hypothesis. We complement the results with carbon isotopic data
of C1 to C4 for each studied well.

Figure 1.13CVPDB values of the 20 light compounds monitored in the

range of C3-C10 for oils and condensates.


Torres, C. L.; Ferreira, A. A.; Silva, J. T.; Conde, S. A., 2011. Compound
Specific Carbon Isotope Analysis of Gasoline Range Hydrocarbons in Light
Crude Oils. Brazilian Congress on Geochemistry, 13. Gramado, Rio Grande
do Sul, Brazil.

protected from biodegradation, but they are rarely used because


biodegraded whole oil, Faja-Z, shows a tight correlation with the non-

Figure 2 HT-SimDis provides quantitative profiles of the entire n-C10 to

biodegraded Cretaceous oil sample from Eastern Venezuela; whereas

n-C100boiling point/molecular weight range ofan oil.(A) High-Temperature

by hydrous pyrolysis can be used to determine sources of

the non-biodegraded Oligocene oil does not correlate.

The severely

Gas Chromatograms (HTGC) of related conventional (36 API) and heavy

severely biodegraded oil. Isotopic analysis of the biomarkers and

biodegraded Faja-Q oil does not match any of the others and probably

(13 API) oils from the same Californian basin. (B) HT-SimDis profiles

diamondoids and the fingerprints of diamondoids can delineate

derives from a different source or source facies. (b) Comparisons of

generated from the HTGC data reveal the heavy biodegraded oil contains a

the oil sources over the charging history of heavy oil reservoirs.

asphaltene pyrolysates from the same oil samples lead to the same

much smaller C10 to C100fraction than the relatedconventional oil.

Knowledge of all the heavy oil sources opens a window for basin

correlation conclusions as (a), although the fingerprint graphs show

of the more tedious protocols for their analysis. We found that

alkanes, biomarkers and diamondoids released from asphaltenes

Novel geochemical technologies reveal

everything you wanted to know about Heavy Oil
J. M. (Mike) Moldowana, Robert M. K. Carlsonb, Peter
Denisevicha, Jeremy Dahlb, Shaun Moldowana*

modelers to identify deeper prospects and the less biodegraded

reserves of lighter oil.

a Biomarker Technologies, Inc. (BTI), 638 Martin Avenue, Rohnert

different patterns.Differences seen in chart-(a) are confirmed by those


registered in chart-(b).

Several novel geochemical technologies are used to characterize

even the most severely biodegraded oils.CSIAand QEDA

Park, CA 94928, USA; Stanford Institute for Materials and Energy

Alkanes and biomarkers that can remain in biodegraded oil might

Science (SIMES), Stanford University, Stanford, CA 94305, USA

be there due to mixing of multiple pulses of charge to the reservoir,

High temperature simulated distillation (HT-SimDis, Figure 2) is


and they could relate primarily to later charges that have not had a

a powerful method for estimating the overall compositionsand

asphaltenes by hydrous pyrolysis and CSIA and QEDA ofthe

long duration in place. Typically the last charge to a reservoir will

valuesof oil reserves and comparingthem in some detail to other

biodegradation-inertdiamondoids in the maltenes are used

experience the least severity of biodegradation.

reserves in the area or elsewhere (Altgeltand Boduszynski,1994).

for source correlation. Combining thosewith biomarker acids

It provides profiles of the distillable compositionofoils (out to

analysis and high temperature simulated distillation(HT-SimDis)

n-C100,i.e., 1328 F atmospheric equivalent boiling point, AEBP,

measurementsprovides unprecedented insight intothe origins,

or ~1400 MW) and so complements geochemical analyses that

transformations, and movements of petroleum resources within

We correlated heavy oil from the two heavy-oil fields, Z and Q, in







Copyright 2014, ALAGO.

the Faja (Orinoco heavy oil belt) of Venezuela with non-biodegraded

This paper was selected for presentation by an ALAGO Scientific Committee

Cretaceous and Oligocene oil samples from the Eastern Venezuela

following review of information contained in an abstract submitted by the author(s).

Basin on order to evaluate these methods and possibly shed some

measure molecular markers present at ppm concentrations.

prospective provinces. Geologic knowledge can be provided

light on the origins of the Orinoco Belt heavy oil. QEDA, CSIA-D and

Thepercentagesofdistillable fractions account for the large share of

where previously only guesswork was possible.

CSIA of biomarkers (CSIA-B) of the oils, CSIA-B, CSIA of alkanes

oil mass and value,andafford a record of geologic transformations.

(CSIA-A), and QEDA were run on the HyPy oils. Heavy oil Z did not

ComparisonsofHT-SimDis profiles of heavy biodegraded oil samples


to those of related non-degraded oil samples yield a quantitative

Altgelt, K.H. and Boduszynski, M.M., 1994.Composition and Analysis of

measure of which fractions have been diminished and increased

Heavy Petroleum Fractions. Marcel Dekker, Inc., New York, 1994.

during the course of biodegradation.Figure2demonstrates how HT-

Carlson, R.M.K.; Pena, M.M.; Boduszynski, M.M.; Rechsteiner, C.E.;

Methods that have recently been put into application to evaluate

SimDis analyses of two related California oils are used to determine

Shafizadeh, A.S.G.; Henshaw, P.C.,7th UNITAR International Conference,

the reservoir history and composition of the oil include biomarker

a 28 mass % difference due to biodegradation in the cumulative

Beijing, Paper No.1998.203, 1998.

acids analysis (BAA) and high temperature simulated distillation

composition up to n-C20. HT-SimDis analyses can also provide

Henshaw, P.C., Carlson, R.M.K., Pena, M.M., Boduszynski, M.M.,


data valuable in mappingviscosity distributions in heavy oil fields

Rechsteiner, C.E., Shafizadeh, A.S., SPE 46205, (1998).

Novel technologies have been developed to determine reservoir

match perfectly with heavy oil Q, but there is an excellent match

charging history, quantify biodegradation history, correlate severely

between Cretaceous oil and Heavy oil Z. Thus, heavy oil Q might be

biodegraded oil and determine multiple co-sources. All of these

a mixture or derive from a different source or facies than Z.

factors are important to design correct petroleum system models.

Here we describe new technologies to see past the effects of
biodegradation to the pristine oil from which it came and to evaluate
the composition of the oil in place. The latter has implications for
better estimation of oil losses and determining its compositional
changes during biodegradation.

Single-rank biodegradation scales usually provide only the

biodegradation level of the freshest charge to the reservoir;

Although correlation of heavy oil can sometimes be accomplished

whereas, biomarker acids analysis provides a history of multiple

by standard biomarker fingerprinting methods, at other times the

charging events along with their subsequent biodegradation to

(Henshaw et al., 1998)and estimating various heavy oil properties

(Carlson et al., 1998) using samples only a fraction of a gram in size.

different levels and their relative importance to the composition of

biodegradation alters those fingerprints and the left-overs are difficult

the entire oil sample. Biomarker acids were analyzed in a selection

to interpret. Furthermore, in many cases heavy oil accumulations

of oil samples to calibrate their appearance and disappearance at

have arisen from multiple sources making correlation more difficult.

various levels of biodegradation severity.

We have applied several methods to difficult heavy-oil correlation

This technique allows

the quantitative estimation of the fraction of an oil sample that has

problems to demonstrate their efficacy in different situations.

reached each of five levels of biodegradation. The combined totality

of those fractions comprises the biodegradation profile of the oil.

Results and Discussion

Correlation based on compound specific isotope analysis of
diamondoids (CSIA-D) and quantitative extended diamondoid
analysis (QEDA, Figure 1) are the most universally applicable methods
for heavy oil correlation since most diamondoid compounds are
either very recalcitrant or inert to biodegradation. Full suites of
diamondoids remain in even the most severely biodegraded oil and
diamondoid correlation measures apply conveniently without any
special consideration about biodegradation effects.

Figure 1.QEDA can be run for any liquid sample or extract, regardless
of severe biodegradation. (a) QEDA fingerprint data from the severely

Asphaltenes are a storehouse of molecules that have been



The NanoSIMS: organic geochemistry at subm lateral resolution

older than previously describedmicrofossils fromPalaeoarchaean

are no C, CN or S enrichments within these. The yellow arrows on the

NanoSIMS micro-analysis of Carbon isotopic composition of organic matter.

siliciclastic environments. The NanoSIMS permitted to map the

27Al+ map show less distinct microporous structures, resulting from higher

The carbon isotopic fields for most of the solvent-extracted hydrocarbons

distribution of carbon, nitrogen and sulfur with sub-micron lateral

degrees of decay and/or compaction of the microbial remains, these are

(white) and bulk organic matter (white) from the Roy Hill Shale Member

resolution, unachievable by X-ray analysis.

also apparent in the 56Fe+ map.

have been included for comparison. The precision of individual data points
is indicated by vertical lines (1s).

NanoSIMS carbon (a) and nitrogen (b) images, with optical image (c).

Daniel Andradea, Philippe Saliotb, Franois Horrardb*

NanoSIMS and TEM images and analyses are very complementary

for identification of organic roles at small scale: TEM has the highest
lateral resolution but lacks of light element sensitivity and is limited

a CAMECA Business Unit Ametek do Brasil Ltda., CEP 13337-

to small field of view. The NanoSIMS can bring sensitivity especially

300 Indaiatuba SP, Brazil.

on light elements, image larger fields in their context and allows

b CAMECA, 29 Quai des Grsillons, 92622 Gennevilliers, France.

isotopic mapping.

After a presentation of the technology, this poster presents and illustrates
through some examples the new capabilities in organic geochemistry for
in-situ analysis and mapping of trace elements and isotopes at sub-micron
scale offered by the NanoSIMS.

Isotopic in-situ microanalysis


The localized isotopic analysis capability is illustrated in a


Copyright 2014, ALAGO.

The NanoSIMS permits to detect and map electronegative elements

third article [3] where the NanoSIMS was used to measure

[1] Microfossils of sulphur-metabolizing cells in 3.4-billion-year-old rocks

This paper was selected for presentation by an ALAGO Scientific Committee

(carbon, oxygen, nitrogen, sulfur) as well as electropositive

13C/12C isotopic ratio in-situ, from small areas of 5 x 5m on

of Western Australia. David Wacey, et al . NATURE GEOSCIENCE, 21

following review of information contained in an abstract submitted by the author(s).

elements such as metals. In this second article [2], TEM-EDS

sections of metamorphosed shales with isotopic reproducibility


and NanoSIMS were combined to study endolithic microfossils

and precision sufficient to reassess the first appearance of

[2] A combined TEM and NanoSIMS study of endolithic microfossils in


in altered seafloor basalt. Rounded to elongated pores 0.52 m

eukaryotes and cyanobacteria on earth. The study eliminated the

altered sea!oor basalt. N. McLoughlin et al, Chemical Geology 289 (2011)

The NanoSIMS 50L is an original secondary ion mass spectrometer

across were found embedded in compact palagonite that have

evidencefor oxygenic photosynthesis 2.7 Gyr ago and excluded

[3] Reassessing the first appearance of eukariotes ans cyanobacteria.

(SIMS), also called Ion Microprobe, optimized to measure and map

sizes and shapes comparable to microbial cells. In-situ elemental

previousbiomarker evidence for a long delay (300 million years)

Birger Rasmussen et al, NATURE, vol. 455, 23 Oct 2008.

isotopic ratios or elemental composition from sub-m areas with

mapping revealed that the micropore rims are comparable in

very high sensitivity. The NanoSIMS 50L is based on a parallel

composition to the bulk palagonite and that some are enriched in

Mattauch-Herzog magnetic sector mass analyzer allowing the

manganese. Elevated concentrations of carbon and nitrogen were

detection of seven masses (elements or isotopes) in parallel, with

also found in some of the micropores. Hence these structures

high mass resolution resolving the numerous mass interferences of

were interpreted as fossilised bacteriomorphs of endolithic

natural samples.

microorganisms that inhabited fractures in the basaltic glass. The

betweenthe appearance of oxygen-producing cyanobacteria and

the rise inatmospheric oxygen 2.452.32Gyr ago.

preferential accumulation of Mn in some of the cell encrustations

The NS50L uses one single immersion lens placed only 300m

suggests the mineralisation of Mn-oxidising bacteria. These data

from the sample in order to focus the primary ion beam of Cs+

provide further evidence for the involvement of microorganisms in

or O- into a spot size (= lateral resolution) of 50 nanometers, and

the colonisation and chemical alteration of recent sea!oor volcanic

to extract and refocus the sputtered secondary ions toward the

glass and identify micro-scale Mn enrichments associated with


micropores as a promising biosignature in such rocks.

After a description of the instrumentation principle we will illustrate

a few of the various fields of organic geochemistry that have
beneficiated from this unique combination of high lateral resolution,

Reflected light photomicrographs of kerogen. a, Two bands containing

high sensitivity and high mass resolution.

abundant kerogen laminae (ker). b, Close-up of the kerogen-rich layer

(top) in a, located between pyrite-rich (white) and kerogen-poor (dark

Elemental in-situ microanalysis






grey) matrix. c, d, Close-up of two areas in kerogen-rich band in b (two




insets) showing areas of analysis (white box) and their 13C values. e,

thatmicrobes with metabolisms based on sulfur existed almost3.5

Isolated streak of kerogen with three analytical areas (white squares) and

billion years ago, leading to suggestions that the earliestmicrobial

Above: NanoSIMS ion images from a palagonite filled fracture in recent

ecosystems were sulfur-based. However, morphologicalevidence

seafloor lavas from the arctic Mohns Ridge. The 48x48m 28Si map

for these sulfur-metabolizing bacteriahas been elusive. The

shows a central planar crack with dense banded compact palagonite (CP)

presence of microstructuresfrom the 3.4-billion-year-old Strelley

and an outer zone of microporous palagonite (MP) surrounded by epoxy

Pool Formation inWestern Australia that are associated with

resin; all the other maps show the boxed area. Irregular shaped areas are

micrometre-sizedpyrite crystals was reported [1] based on

visible in the C, CN and S maps and these contain no metals (lower row of

measurements using different microscopies and isotopic and

images). Sub-spherical micropores ~2m across (white arrows) are visible

elemental analysis. These microfossilsare about 200 million years

in the Al, Mn, Fe, and Ti maps with especially pronounced Mn rims; there

corresponding13C values.



One important feature arises from the full spectrum that this scale

Dzou, L. I.; Holba, A. G.; Ramn, J. C.; Moldowan, J. M.; Zinniker, D.,

A set of 14 crude oil samples from the Llanos Orientales Basin,

presents, whereby any pattern of oil mixture can be traced and

1999. Application of new diterpane biomarkers to source, biodegradation

Colombia, were analyzed in a Solarix 9.4 T (Bruker Daltonics,

compared to others. Oils with high SA Index values show some

and mixing effects on Central Llanos Basin oils, Colombia. Organic

Germany) apparatus using an electrospray ion source operated

level of dispersion that demands more experiments. Nonetheless,

Geochemistry 30, 515-534.

in the negative ion mode. Mass spectra (m/z 200-1000) were

these results ultimately suggest that the scale is ready for further

Renzo C. Silvaab*, Eustquio V. R. de Castrob, Henrique L. B.

obtained from 200 scans, achieving a resolving power of 530,000

testing in other petroleum systems.

Penteadoc, Dbora A. Azevedoa.

at m/z 400. Data were processed using the Composer software

practical biodegradation scale for use in reservoir geochemical studies of

(Sierra Analytics, USA). GC-MS and GC-FID were also used to

biodegraded oils. Organic Geochemistry 45, 66-76.

Increasing the resolution of biodegradation
scales with non-GC experiments

Larter, S.; Huang, H.; Adams, J.; Bennett, B.; Snowdon, L. R., 2012. A

a Lagoa/Ladetec, Universidade Federal do Rio de Janeiro - Brazil;

evaluate typical biodegradation parameters.

b LabPetro, Universidade Federal do Esprito Santo Brazil;

Results and Discussion

Vaz, B. G.; Silva, R. C.; Klitzke, C. F.; Simas, R. C.; Lopes Nascimento,

c E&P-EXP, Petrobras Brazil;

Whole oil chromatogram, demethylated terpane series (m/z 177)

H. D.; Pereira, R. C. L.; Garcia, D. F.; Eberlin, M. N.; Azevedo, D A.,

and 25NH/H30 information, when analyzed altogether, show very

2013. Assessing biodegradation in the Llanos Orientales crude oils by

erratic biodegradation patterns among the samples. Many Llanos

electrospray ionization ultrahigh resolution and accuracy Fourier transform

Orientales crude oils are composed of variable mixtures of early-

mass spectrometry and chemometric analysis. Energy and Fuels 27, 1277-

Copyright 2014, ALAGO.

charged biodegraded oils from Late Cretaceous source rocks and


This paper was selected for presentation by an ALAGO Scientific Committee

later charges of oils derived from Tertiary sections (Dzou et al.,

Figure 2. Scheme representing reservoir processes (relative biodegradation

following review of information contained in an abstract submitted by the author(s).

1999). Therefore, traditional GC parameters are not sufficient to

and recharge rates) effects to the sample position in the scale.


evaluate differences of biodegradation extent and mixture in these



The use of this scale in petroleum system studies can also be

approached. Estimated impacts of both biodegradation and

The evolution of organic geochemistry as an autonomous discipline

owes acknowledgements to the advances in analytical technology

Previous studies used differences between double bond equivalent

recharge rates are shown in Figure 2. In case of mixtures, less

that supported its keys achievements, e.g. gas chromatography

(DBE) profiles of class O2 compounds as the basis for two

biodegraded oils have a lower impact on the resulting oil because

(GC) and mass spectrometry. Nowadays, novel analytical

continuous biodegradation parameters, SA Index (DBE 1-6) and

of their lower acid content. Recharges of pristine oils would affect

techniques with unmatched resolution allow a quasi-molecule-

modified A/C Index (DBE 1 / DBE 2-6), all obtained from FT-

more the A/C than the SA Index since DBE 1 O2 species are slightly

to-molecule analysis of petroleum fluids (petroleomics), which

ICR MS experiments (Vaz et al., 2013). Briefly, the main effect of

more abundant in them. Experimental efforts to check these and

can also offer nice tools for organic geochemistry assessments.

biodegradation on DBE profiles is the increase of relative intensities

other assumptions are ongoing.

One notorious example is the Fourier transform ion cyclotron

of mono- to pentacyclic saturated acids. In this study, a new

resonance mass spectrometry (FT-ICR MS), whose analytical

sample set of highly biodegraded oils was very suitable to expand


features immensely improved the understanding of petroleum

the scope of this biodegradation scale (up to 25NH/H30 ratio =

The use of high resolution mass spectrometry techniques to probe

compositional complexity, especially in the polar fraction.

5.36 in m/z 191) (Figure 1).

acid species offers new dimensions to solve common problems

of biodegradation scales based on gas chromatography. In this
study, the biodegradation scale based on class O2 compounds

Geochemistry assessments based on traditional oil biodegradation

proposed previously is expanded with a heavily biodegraded crude

scales have the point of view of removed or modified substances

oils sample set and has its features and impacts explored. The next

(typically hydrocarbons) during the biodegradation process. One of

steps toward a full acceptance would be proofs of its usefulness

their major drawbacks comes from their inability to classify mixtures

to petroleum system studies as well as correlations with physical

(Bennett and Larter, 2008). New scales (i.e. Manco scale, Larter et

properties, both of which are ongoing efforts.

al., 2012) were developed to address these concerns by increasing

the scale resolution, although still relying on results coming from


traditional gas chromatography mass spectrometry experiments.

The authors thank Ecopetrol SA for providing the samples.

Nowadays, FT-ICR MS experiments offer the chance to analyze acid

CNPq (Brazilian research council) for fellowships; ANP (Brazilian

components produced by biodegradation processes. Therefore,

Petroleum Agency), Petrobras S/A and for financial support. The

new biodegradation metrics can be approached. The present

help on FT-ICR MS experiments from W. Romo and G. Vanini is

study takes the next step towards a biodegradation scale based


on class O2 compounds as analyzed by ultrahigh resolution and

accuracy mass spectrometry, which was previously proposed by
Vaz et al. (2013). It shows results for heavily biodegraded samples,

Figure 1. Biodegradation map comprising all 30 samples used (14 new


explores petroleum system implications and shows indications of

ones). Proposed biodegradation metrics (x- and y-axis) for the new scale

Bennett, B.; Larter, S. R., 2008. Biodegradation scales: Applications and

further developments needed.

are obtained from ESI(-) FT-ICR MS measurements.

limitations. Organic Geochemistry 39, 1222-1228.



Isolation and analysis of polycyclic aromatic
hydrocarbons (PAHs) in crude oil using
molecularly imprinted solid-phase extraction
(MISPE) coupled with gas chromatographymass spectrometry (GC/MS)

The application of these synthetic polymers as sorbents allows

Dimethyl- phenanthrene




cleanup process. Besides larger PAH molecules, the procedure

not only pre-concentration and cleaning of the sample but also





was expanded to extract also smaller PAH molecules (2-3 rings).

selective extraction of the target analyte, which is important,





particularly when the sample is complex and impurities can interfere






with quantification. The use of MIPs as SPE sorbents has led this





The authors thank Petrobras S/A for the financial support.

practice becoming known as molecularly imprinted solid-phase

*n.d. = not detected; **coelution with internal standard.


extraction, MISPE (Hu et al., 2013).

Firstly, the blank sample of the oil aromatic fraction was analyzed

Hu, Y., Pan, J., Zhang, K., Lian, H., Li, G. 2013. Novel applications


for the presence of background contamination. Figure 2(a) shows

of molecularly imprinted polymers in sample preparation. Trends in

The MISPE used was SupeIMIPTM SPE PAHs from Supelco.

the full scan chromatogram of the oil aromatic fraction sample. The

Analytical Chemistry 43, 37-52.


Initially, a standard mix of PAHs compounds was used to method

method was applied to the spiked fraction and the recovery values

Development Center (CENPES), PETROBRAS, Rua Horcio

validation. The standard mix was prepared in cyclohexane and

were corrected for the background levels found in the blank fraction

Tarley, C. R. T.; Sotomayor, M. D. P. T.; Kubota, L. T., 2005.

Macedo, 950, Ilha do Fundo, Rio de janeiro, RJ 21941-915, Brazil



sample. The results are shown in Table 1. The manufacturer advice

Polmeros biomimticos em qumica analtica. Parte 1: preparao

naphthalene, fluorene, dibenzothiophene, phenanthrene, methyl-

the use of SupeIMIPTM SPE PAHs to large PAH molecules. In

e aplicaes de MIP (molecularly imprinted polymers) em tcnicas


fact, the recovery was higher for the larger PAH compounds (more

de extrao e separao. Qumica Nova 28, 1076-1086.

Cristiane Rossi de Oliveira*,a, Cleverson Jos F. de Oliveiraa













than 4 rings). Moreover, the isolation of smaller PAH compounds

benzo(a)pyrene and perylene.

(2-3 rings) were also able following this method protocol in lower

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following

Briefly, the MISPE was conditioned with 1 mL of cyclohexane.

review of information contained in an abstract submitted by the author(s).

1.0 mL of standard mix solution at the level of 10 g/mL was


loaded into the MISPE. The MISPE was washed again with 1.0 mL

Analyzing the full scan chromatogram of the oil aromatic fraction


cyclohexane to remove the compounds that did not get inside the

after the method procedure (Figure 2(b)) it was possible to see that

A fast and simple solid-phase extraction (SPE) method using

sorbent. The analyte elution was done with 3 x 1 mL of solvent.

the PAH isolation and concentration were achieved with success.

molecularly imprinted polymer (MIPs) as selective material

Acetone and toluene were tested as elution solvent. The analyte

Furthermore, besides the spiked compounds, the MISPE was also

followed by gas chromatography-mass spectrometry (GC/MS)

elution was dried under N2 steam. 5-Cholane, Fluorene-d12 and

able to isolate other PAHs present in the oil aromatic fraction as:

was developed for isolation and analysis of polycyclic aromatic

pyrene-d12 were spiked as the internal standard (IS) at the level of

methyl-fluorene (C1-fluorene), tetramethyl-naphthalene (C4-naph),

hydrocarbons (PAHs) in crude oil sample.

30 g/mL and the eluate was analyzed by GC/MS.

trimethyl-phenanthrene (C3-phen) and chrysene.

MIPs are tailor-made materials with high selectivity for a target

A crude oil aromatic fraction sample was obtained from medium

molecule. This selectivity arises from the synthetic procedure

pressure liquid chromatography (MPLC) on silica column. The

followed to prepare the MIP, in which a template molecule is linked,

aromatic fraction was spiked with the standard mix of PAHs in

by covalent bonds or non-covalent forces, to suitable monomer(s)

duplicate at the level of 20 g/mL and 0.5 g of the spiked fraction

containing functional groups (Figure 1). This link is responsible for

sample was extracted by the procedure described above.

the subsequent specific binding sites imparted to the MIP (Tarley

Results and Discussion

et al., 2005).

The PAHs recovery was evaluated using acetone and toluene as

analyte elution solvent and is shown in Table 1. Although the values
for acetone showed a significant error, it was chosen as analyte
elution solvent due to the best chromatographic profile.
Table 1. PAHs recoveries from MISPE

Recovery (%)
Acetone Toluene

Spiked Oil
(with Acetone)





Figure 2. Full scan chromatogram obtained by GC/MS from (a) crude oil





aromatic fraction; and (b) isolated PAHs.





Figure 1. Schematic representation of the Molecular Imprinting Process:






(a) self-organizing, (b) polymerization, (c) desorption/extraction; and (d)





The isolation and concentration of PAHs from a crude oil sample






using MISPE and analysis by GC/MS were described. The isolation





method is simple and includes only a few MPLC and MISPE



Comparative bitumen extraction from an
immature petroleum source rock using

mg of organic matter already generated by kerogens cracking per

Compared to the original rock, it was observed that the aliquots of


gram of rock (S1).

rock extracted by ASE and SFE had not suffered any changing in

Given the high closeness of the results for saturated and aromatic

its non-extractable organic portion measured (S2). The S2values

biomarkers, total carbon isotopes and Rock-Eval pyrolysis

The extraction in ASE was performed by an ASE system (Dionex,

found for original rock and extracted rocks by ASE and SFE were

obtained post SFE and ASE extractions, we concluded that SFE is

ASE 350), where 10 g of rock were extracted in triplicate by the

foundapproximatelythe same, inside the normal variation range for

a promising application in extractive processes of bitumen of rocks

injection of 100 ml of dichloromethane divided equally into five

Rock-Eval analysis (10%).

when the purpose is performing geochemical analyzes over this

Rodrigo C. Silva1*, Beatriz X. C. Rocha1,Cleverson J. F.

static cycles, at 75 C and 1500-1700 psi (103-117 bar), totaling

Oliveira1,Gilberto P. Silva1, Rafael S. Mello1, Thiago A. D. Silva1

45 minutes of extraction.

soluble organic fraction.

Concerning to total carbon isotopic analysis over the bitumen
extracted by ASE and SFE, the results showed little variation

The authors thank Petrobras S.A. for all support provided.

1Petrobras S.A., Centro de Pesquisas e Desenvolvimento

The extraction in SFE was conducted in a SFE system (Jasco Inc.,

between the extracts 13C values. The 13Cstandard deviations

(CENPES), 21941-915, Rio de Janeiro, RJ, Brazil

2000 Plus Series) by submitting triplicates of 9 g of rock to 10% of

calculated among the triplicates of each type of extraction, and

dichloromethane in CO2, under a flow rate of 15 ml / min, at 65 C

also between the different extractions performed, were found lower


and 3190 psi (220 bar), during 15 minutes.

than 0.5 .

McNally, M.E.P.,1995.Advances in Environmental SFE.AnalyticalChemis-


try67, 308-315A.
Copyright 2014, ALAGO.

The extracts obtained using both techniques, as well as the residue

The Figure 2 shows the results of the percentage of saturated,

This paper was selected for presentation by an ALAGO Scientific Committee following

of extracted rock, were reserved for subsequent geochemical

aromatic and NSO compounds, resulting from the submission

Silva, R.D.V., Aguiar, P.F., Oliveira, C.J., Silva, R.C.,Capilla, R.,2010.

review of information contained in an abstract submitted by the author(s).

analysis.Those extracts were analyzed using anEA-IRMSsystem

of the bitumen extracted via ASE and SFE to chromatographic

Otimizao de metodologia de extrao de rochas geradoras para

(Thermo Scientific, Flash EA 1112 Series) and posteriorly had

separation by MPLC.These results indicate a greater presence

posterior anlise de CL, CG-DIC e CG-EM. Abstract. Simpsio Brasileiro


their fractions of saturated, aromatic and polar (NSO) compounds

of polar compounds in the bitumen extracts derived from ASE

de Cromatografia e Tcnicas Afins, Campos do Jordo, p. 256.

In Organic Geochemistry, the extraction of sedimentary rocks

isolated by MPLC system (Margot KhnemWillsch, MKWMPLC).

extraction.In parallel, it was perceived a relative increase of

for bitumen isolation is very well known. Amongthe extraction

The saturated and aromatic biomarkers profiles were determined

saturated and aromatic portions isolated from the extracts obtained

techniques the commonly applied are Accelerated Solvent

by GC-MS (Agilent Technologies, GC 6890 and MSD 5973).In

by SFE, compared to those acquired via ASE.Moreover, even

Extraction (ASE) and Supercritical Fluid Extraction (SFE).

addition, the residues of extracted rock were also analyzed in a

throughFigure 2, we observed high similarity of chromatographic

Total Organic Carbon Content (TOC) analyser(Leco, SC-144)and

profiles pertinent to GC-MS analysis of biomarkers as terpanes,

Rock-Evalpyrolysis system (Vince Technologies,Rock-Eval 6).

steranes,monoaromatics and triaromatics present into saturated

Concerning petroleum source rocks application, the ASE technique

and aromatic hydrocarbon fractions isolated from bitumencoming

integrates the use of organic solvents under high temperatures and

high pressures in order to reach a greater solvation for the soluble

Results and Discussion

organic matter content. Compared to conventional processes,

By the following Figure 1, it can be noted that the removal of

such as Sohxlet extraction, ASE requires a short period of time and

soluble organic matter in both extraction process was 1% of the

a reduced amount of solvent to achieve almost complete extraction

organic matter originally present into the rock sample.Compared to

of the bitumen intothe rock pores (Silvaet al., 2010).

the potential of extraction in ASE for removing S1, SFE extraction

from ASE and SFE extractions.

reached 10% less of this potential.These values were calculated

The SFE is an environmentally friendly technique because it often

from the equation: 1 - (S1Original Rock - S1SFE)/(S1Original Rock -

uses an inert fluid in the process such as carbon dioxide (CO2).

S1ASE). However, based on the results of bitumen concentration

In general, the CO2 under a supercritical state is applied to rock

on the aliquots of rock extracted by ASE and SFE was found

samples due to its high potential of extraction.The high density,

that the extraction technique performed by SFE showed a lower

similarly to liquid, gives to the fluid a dipole moment rearrangement

potential of extraction, 19% inferior than that obtained via ASE.

for the constituent molecules, ensuring a higher solvating power.

Resembling what happens in a gas performance, low viscosity and
high diffusivity promote an easy and fast penetration into the matrix
pores.The process is triggered in order to raise the solute mass
transfer rates from the matrix to the supercritical fluid (Mcnally, 1995).
This work shows comparison results of ASE and SFE techniques in
its application over bitumen extraction from source rock.
Figure 1.Results of analysis for the aliquots extracted by ASE and SFE


regarding to TOC, pyrolysis in Rock-Eval, bitumen concentrationand total

Figure 2.Biomarkers profiles obtained from the saturated and aromatic

To fulfill the extraction tests we selected animmature petroleum

carbon isotopes. All values refer to averages calculated from the analyzed

hydrocarbon fractions isolated from the bitumen extracted by ASE and SFE.

source rock pulverized to 60 mesh, containing 18% of TOCand 7.8

triplicates of rock and extract (bitumen).




(Molecular Composition of Inclusion) protocols developed by CSIRO

Oil-bearing Fluid Inclusion Biomarkers from

the Pre-Salt Succession, Offshore Brazil

detailed description of which can be forward at George et al.

Carlos E. S. Coelhoa*, Andr L. S. Pestilhoa, Juliana A. Ieminia,

analysis of the tiny amounts of oil trapped in FI is the complete


(Commonwealth Scientific and Industrial Reseah Organisation;

Flash pyrolysis coupled to GCGCTOF

MS and GCHigh Resolution TOF MS
for chararcterization of crude oil and
petroleum fractions

(1998, 2007). The results permit the direct geochemical correlation

between inclusion and crude oils. A pre-requisite for the successful

Katia Wagnera, Ygor dos S. Rochaa, Sandra B. Jorgeb

removal of oil and any other contaminants from the outside of the

a Division of Geochemistry,

inclusion oil (off-line method). The oils were analyzed by GC-MS

Figure 1.Two oil-bearing fluid inclusions under UV light hosted in quartz

using a DFS system, and quantification was carried out using

from Pre-Salt carbonatic reservoir.

grains prior to crushing of the rock under solvent to recover the

PETROBRAS Research and

Development Center (CENPES),Rua Horcio Macedo, 950, Ilha do

single ion monitoring (SIM).

Fundo, Rio de Janeiro, RJ 21941-915, Brazil

Table 1. Biomarkers data for fluid inclusions and reservoired oil in an

b FUNDAO GORCEIX,Rua Carlos Walter Marinho Campos, 57,

Ouro Preto Minas Gerais, MG 35.400-000, Brazil

Oil-Bearing Fluid Inclusions Characterization


primary fluid inclusions hosted in quartz and calcitic cements from

offshore well.

Clcio F. Klitzkea*, Joe Binkleya, Jeffrey Patricka

a LECO Corporation, 3000 Lakeview Avenue, 48085 Saint Joseph,
MI, United States

Oil-bearing fluid inclusions are brown to light-brown two-phase


reservoir secondary porosity features. These FIs generally have blue

Copyright 2014, ALAGO.

(Figure 1) to white fluorescence colors, with major calcitic hosted FI

This paper was selected for presentation by an ALAGO Scientific Committee following

having oblate shapes while quartz hosted FI display oblate to more

review of information contained in an abstract submitted by the author(s).

angular shapes.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee
following review of information contained in an abstract submitted by the

Molecular Composition of Inclusions


Two suitable core samples and one free oil sample from the same

Oil-bearing fluid inclusions (FI) are natural cavities in minerals


well were selected for analysis. Data from the FI oils and free oil

filled with hydrocarbons that commonly occur within petroleum

Petroleum is the most complex matrix in nature, constituted by many

were interpreted with respect to its palaeo-depositional conditions

reservoirs and along migration pathways. They are tiny droplets


thousands of compounds,and presents an analytical challenge. For

The authors would like to thank Petrobras S/A, and all Petrobras/

comprehensive analysis we need a chromatographicseparation

Biomarker distributions show similar correlation between inclusion

CENPES staff whose contribution was of a paramount importance

to establish our discussions and conclusions.

with high peak capacity and for mass spectrometry analysis we

oils and free oil for both terpanes and steranes (Table 1). Biomarkers

of the same source rock, and thermal maturation.

(usually <10 m) of oil encapsulated in defects in mineral grains

and diagenetic cements. Therefore, they preserve oil in a closed
system and consequently it is protected from secondary alteration
processes such as biodegradation, water-washing or other

ratios suggest correlation with lacustrine source rocks. For

processes that may affect free oil after emplacement (e.g., George

example, C24 tetracyclic terpane/C26 tricyclic terpane ratios are


in relative low abundance, which is consistent with a low input of

George S.C., Lisk M., Eadington P.J., Quezada R.A. 1998.

terrestrial organic matter. C26/C25 tricyclic terpane ratios are high,

Geochemistry of a palaeo-oil column: Octavius 2, Vulcan Sub-

consistent with a lacustrine depositional environment (Sofer, 1993;

basin, in The Sedimentary Basins of Western Australia 2. In: Purcell

charge history from Pre-Salt carbonatic reservoir.

Schiefelbein et al., 1999). The C23/C21 tricyclic terpane ratios are

P.G. & Purcell R.R. (eds) Petroleum Exploration Society of Australia

similar to lacustrine oils (Sofer, 1993). The gammacerane/C30

Symposium, Perth, WA, p. 195-210.

Analytical Procedures and Samples

hopane ratios are low, certainly corroborating a lacustrine source.

et al., 2007). Since fluid inclusion oils are trapped during low oilwater saturation they can be interpreted as representative of first
reservoir oil charges. This study aimed the application of oil-bearing
fluid inclusions molecular composition to the constraining of oil

In order to perform this study, analytical procedures were as follows:

(i) Sample selection from drill cores; (ii) Fluid inclusion petrography;
(iii) Analysis of Molecular Composition of Inclusion. Sample selection

need high resolvingpower and high mass accuracy.

As the worlds remaining deposits of petroleum become heavierits
important to understand the chemical nature of heavy crude oil
and its fractions. The analysisof high boiling point constituents of
crude oils adds a new dimension for the completecharacterization
of crude oil. In this study we evaluated the use of a pyrolysis
probe (Py) coupledto gas chromatography (GC and GCGC)

Furthermore, the relative abundance of Tetracyclic Polyprenoids

George S.C., Volk H., Ahmed M. 2007. Geochemical analysis

time-of-flight (TOF) and GC high resolution time-of-flight(HRTOF)

(TPP/TPP+DIA - tetracyclics polyprenoids/C27diasterane) strongly

techniques and geological applications of oil-bearing fluid

mass spectrometry (MS) for the characterization of crude oils and

confirms lacustrine-source for the three oils analyzed (Table 1).

inclusions, with some Australian case studies. Journal of Petroleum


Science and Engineering , 57. 119-138.

was carried out in oil-prone reservoir zone aiming carbonate facies

Maturity-dependent ratios show small variation for inclusion oils in

that displayed better porosities. Selected samples were used to


comparison with free oil for Tri/Hop, NORNEO/C29 hopane, DIAH/

Roedder, E.1984. Fluid Inclusions. Mineralogical Society of

C30 hopane and TS/(TS+TM) ratios, with relatively lower maturity

America, Reviews in Mineralogy, Virgnia, EUA: Mineralogical

as displayed by inclusion oils (Table 1).

Society of America, v. 12, 644 p.

Conclusions: Oil Charge History Constraints

Sofer Z. 1993. Distribution of genetic oil families in West Africa

The geochemical data suggest that the oil trapped in fluid inclusions

based on biomarker ratios. In: Latin American Congress on

in Well A is from the same source rock, generated at a relative

Organic Geochemistry, 3rd, Manaus, Brazil, Extended abstracts,

lower maturity than the average of the oil now produced from the

p. 134-137.

Interface, valve oven and transfer line were at 300 oC. Helium was

quartz and calcite happened soon after initial charge and stopped

Schiefelbein C.F., Zumberge J.E., Cameron N.R., Brown S.W.


to be trapped due to an inhibition of diagenetic cementation as a

1999. Petroleum systems in the South Atlantic margins. In:

chromatograms obtained.

result of an emplacement of progressively higher maturity oil. Those

Cameron N.R., Brooks JM., Bernard B.B., Zumberge J.E., Brown

For PyGCHRTOF MS analysis a Pegasus GCHRT (LECO

conditions and the relatively small variation between inclusion oils

S. (eds.) The oil and gas habitats of the South Atlantic. Geological

Corporation, St. Joseph, MI, USA) was used in high resolution

The oil trapped within FI in the quartz-calcite cements of core

and free oil suggest that reservoir charges occurred soon after the

Society, London, Special Publications., v.153, p.169-179.

mode (25,000). Electron energy of 70 eV was applied. The mass

doubly-polished thin section manufacture and a replicated sample

for each depth was saved for FI molecular analysis.
Fluid inclusions petrography was performed on a standard
petrographic microscope coupled to an ultra-violet source,
because oil-bearing fluid inclusions can be readily detected by
fluorescence microscopy due to its fluorescence color emission.
FIuid petrography was performed on samples screening, identifying

reservoir. The relatively high proportion of inclusion oil trapped in

the richest ones through distinct fluid inclusion assemblages

(Roedder, 1984). The richest FI content samples showed the
best inclusions, such fact enhanced the interpretations of the FI

first oil incursions.

samples was extracted and analyzed accordingly to the MCI


Crude oil and asphaltene samples obtained from several countries

were analyzed by PyGCGCTOF MSandPyGCHRTOF MS.
The samples were placed into a quartz tube of a Pyroprobe Model
5200 (CDS Analytical Inc., Oxford, PA, USA) interfaced to an Agilent
7890A GC (Palo Alto, CA, USA). Analyses were performed at 350
oC and 500 oC for thermal desorption, and 800 oC for pyrolysis.
used as carrier gas from the pyroprobe to the GC at a flow rate of

range was 35-510 m/z and the acquisition rate was 6 spectra/s.

Separation by GC was achieved with a Restek (Bellefonte, PA, USA)

With only one dimension chromatography these same compounds


Rxi-5MS 30 m column in the condition of 1mL.min -1 of Helium at

can be identified using high resolution mass spectrometry. High

Chiaberge, S.; Fiorani, T.; Cesti, P., 2011. Methyldibenzothiophene isomer

constant flow. The oven has a initial temperature of 50 oC held

resolution and high mass accuracy increase the signal to noise

ratio in crude oils: gas chromatography tandem mass spectrometry

for 1 minute, raised to 320 oC at 5 oC.min-1and held at the final

ratio discriminating interferences with the same nominal mass.

analysis. Fuel Processing Technology. 92, 2196-2201.

temperature for 10 min. The temperature of the inlet, transfer line

Even co-eluted species can be easily identified and quantified

and ion source were respectively 280, 320 and 250 oC.

using the exact mass.

A Pegasus 4D (LECO Corporation, St. Joseph, MI, USA) was

used for PyGCGCTOF MS analysis with the experimental

Analyses of bicyclic and tricyclic acids

biomarkers in Potiguar Basin Brazil Oils

Sarmah, M.K.; Borthakur, A.; Dutta, A., 2010. Pyrolysis of petroleum

asphaltenes from different geological origins and use of methylnaphthalenes

Lucinaldo S. Silvaa, Marcio S. Rochaa, Sidney G. Limaa*, Jos A. D.

and methylphenanthrenes as maturity indicators for asphalenes. Bulletin of

Lopesa, Antnia Maria G. L. Cita, Antnia L. da S. Santosa, Igor

Materials Science33, 509-515.

conditions of 70 eV in the ion source, and acquisition rate of 200


V. A. F. Souzab

spectra/s in the mass range of 40 to 700 m/z. The separationin the

a Universidade Federal do Piau UFPI , Laboratrio de Geoqumica

first dimension used a 30 m Restek (Bellefonte, PA, USA) column

Orgnica - LAGO, 64049-550, Teresina, PI, Brazil.

Rxi-5MS. In the second dimension separation was done using a

b Petrobras - Research and Development Center

1.25 m Restek Rxi-17MS column. The oven program has a initial

temperature of 60 oC for 1 minute, raised to 320 oC at 4 oC.min-


1and held at the final temperature for 10 min. The temperature of

the inlet, transfer line and ion source were respectively 280, 320

Copyright 2014, ALAGO.

and 250 oC.Secondary oven temperature offset was 5 oC. The

This paper was selected for presentation by an ALAGO Scientific Committee following

quad-jet dual stage modulator had a temperature offset of 15 oC,

review of information contained in an abstract submitted by the author(s).

modulation period of 4 s, with 0.6 seconds long hot pulse.

Results and Discussion
Typically crude oil samples are analyzed in two steps of isothermal
desorption (350 oCand 500 oC). After that the remaining residue

Figure 2.Comparison of the analytical ion chromatogram (A), extracted ion

Naphthenic acids comprise a complex mixture of alkyl-substituted

chromatogram (198 m/z) (B), and the extracted ion chromatogram for the

acyclic and cycloaliphatic carboxylic acids. They are found in

exact mass of the MDBTisomers (198.04977) (Cand D).

is pyrolyzed at 800 oC. Isomeric ratios of polycyclic aromatic

petroleum because either the deposit has not undergonesufficient

catagenesis or it has been biodegraded by bacteria (Peter et al.,

hydrocarbons (PAHs) and polycyclic aromatic sulfur hydrocarbons

Figure 2 shows the comparison of the total ion chromatogram (A),

(PASHs) were evaluated, and may reflect thediversity of organic

extracted ion chromatogram for the nominal mass of 198 (B), and

source input, thermal maturity, biodegradation level, and

depositionalenvironments (Chiaberge et al, 2011; Sarmah et

the extracted ion chromatogram for the exact mass of the MDBT

al., 2010). An analytical difficulty normally observed using one

isomers (C&D).

dimension GC is the co-elution of some PAHs and PASHs with the

2005). Working with marine evaporitic oils from Fazenda Belem,

Potiguar Basin, Lopes et al. (2005) found a good correlation
between acidic and neutral biomarkers. However the acidic
fraction requires laborious techniques of separation, purification
and derivatization which considerably delay the analysis of these
these compounds.

Pyrolysis of crude oil and asphaltene samplesshow distinct

same nominal mass.

composition in terms of light and heavy PAHs, PASHs, and isomers,

This study compared ESI and APCI methods in determining the

To increase the chromatographic separation for better identification

related to sample characteristics. Preliminary results show that

molecular distribution of naphthenic acids (n-alkanes, byciclic and

of co-eluted compounds analysis using GCGC was implemented.

the pyrolysis products of asphaltene samples havecompositional

tryciclic) in crude oil and in acidicfraction,resulting from theliquid-

Figure 1 shows the contour plot region of methyldibenzothiophene

similaritywith the pyrolysis of the crude oil residue indicating that the

liquid extraction.

(MDBT) isomers in a PyGCGCTOF MS analysis of a crude

residue obtained after thermal desorption at500 oC is constituted

oil sample.The signals with lower retention time in the second

dimension are alkyl naphthalenes (isobars that co-elute with MDBT
in the first dimension).

mainly by asphaltene. The composition of products obtained by


asphaltene pyrolysis is very similar to the composition of the relative

Studied oils: Oil samples used in this study were obtained from

crude oil.

The pyrolysis of asphaltenes from discretecrude oil samples
shows distinct composition in terms of light and heavy aromatic
hydrocarbons and alkyldibenzo-thiophenes.The use of Py
GCGCTOF MSis crucial for the determination of isomeric

Fazenda Belm field, in northwestern part of Potiguar Basin. More

detailed geological information on this Basin was presented by
Lopes et al. (1999).
Liquid-liquid Extraction: About 500mgof oil samplewas dissolved
indichloromethaneand extracted with 5% sodiumbicarbonate

composition, and PyGCHRTOF MS with high resolution and

ESI and APCI MS TOF Analysis: The acidic fractions and crude

high mass accuracy complements the identification by unequivocal

oil were analyzed in a high resolution micrOTOF-Q II (BRUKER),

chemical formula assignments.The study of the relationships of the

small amount of sample was dissolved in 500 L toluene:methanol

crude oil and asphaltene composition are in progress.

(1:1) and then, 20 L of concentrated NH4OH was added. Electrospray ionization (ESI) source was optimized as follows: negative

Figure 1.Contour plot of methyldibenzothiophene isomers.




ionization mode, capillary voltage 3.0 kV, nitrogen was used as

x 5 cm) and washed with dichloromethane:methanol (9:1, 250-350

mL). The extract was evaporated to dryness. Extract fractionation

nebulizing gas with a flow rate of 5 L/min and a temperature of

200 oC at 0.3 bar. The atmospheric pressure chemical ionization
(APCI) source was optimized as follows: negative ionization mode,
capillary voltage 4.0 kV, nitrogen was used as nebulizing gas with
a flow rate of 4 L/min, temperature of dry gas of 200 oC and
temperature of vaporizer of 450 oC at 2.0 bar.

Matrix solid-phase dispersion for

hydrocarbon isolation from bituminous rock

into hydrocarbon families followed the D-6560 and D2007 ASTM

Elena E. Stashenko*, Jairo Ren Martnez, Julin Castrilln

The spectrometric and chromatographic data were obtained with


a gas chromatograph GC 7890 (Agilent Technologies, AT, Palo

GC/MS Analysis: The analyses were performed using a Thermo

Scientific TSQ Quantum XLS Ultra Triple Quadrupole GC-MS

Universidad Industrial de Santander, Center for Chromatographyand

Alto, CA, U.S.A.) equipped with a triple quadrupolemass selective

Mass Spectrometry, CROM-MASS, 680002, Bucaramanga,Colombia

detector AT 7000 [Electron impact ionization (EI), 70 eV; AT, Palo

Alto, CA, U.S.A.], split/splitless injector (1:30 split ratio) and Mass-

instrument. Capillary chromatographic column (Equity TM-1, 30 m,

0.25 mm ID). Initial temperature of 70 C (4 min hold), followed by

Hunter data processing software. A fused-silica capillary columns

DB-5MS ((J&W Scientific, Folsom, CA, U.S.A.) of 60 m x 0.25 mm

a ramp of 2 C/min up to a final temperature of 300 C (20 min

hold). The carrier gas was helium at a constant flow rate of 1.0 mL/
Figure 2. Expansion of highlighted region from previous Fig. 1.

min. Transfer line temperature was 310 C. The quadrupole mass

spectrometer was operated in full scan mode over the mass range

Soft ionization methods (APCI- and ESI-TOF) produce one major

50650 Da (EI mode at 70 eV).

ion from each compound, with little further fragmentation, and it

avoidsextraction,purification andderivatization steps, required for

Results and Discussion

Copyright 2014, ALAGO.

i.d., coated with 5%-phenyl polydimethylsiloxane (0.25 m film

This paper was selected for presentation by an ALAGO Scientific Committee

thickness)) was used. The GC oven temperature was programmed

following review of information contained in an abstract submitted by the

from 120 C (1 min) to 220 C (3 min) at 6 C min-1, then to 275 C (15


min) at 5 C min-1. Helium (99.995%, Linde, Bucaramanga, Colombia)

was used as carrier gas, with 155 kPa column head pressure and
26.4 cm s-1 linear velocity (1 mL min-1, at constant flow).

the analysis ofnaphthenic acids. Atmospheric pressure chemical


ionization is a supplementary technique to electrospray. It is a soft

For the analysis of organic matter contained in rocks, the isolation

ionization technique but notas soft as ESI. Because charged ions

of sufficient amount of the organic matter originally present in

Results and Discussion

are not generated in APCI and it operates at high temperatures

the sample is a fundamental prerequisite. The Soxhletextraction

Although the MSPD lasted 1/6 the time required for Soxhlet or

this technique is used to analyze smaller, thermally stable polar

technique is the method traditionally used. Ultrasound-assisted

ultrasound-assisted solvent extraction, its extraction yields were

solvent extraction has been the alternative method. There has

generally higher for the various rock types processed. MSPD

been recent interest in matrix solid-phase dispersion, MSPD, a

has the additional advantage that the sample amount could be

new technique which provides extraction yields similar to those

increased by a factor of 4 (from 50 to 200 g) without changing the

Analyses by both methods showed that It was possible to evaluate

obtained with the Soxhlet technique in shorter experimental time

glassware size or the procedure employed.

Naphthenic acids were also evaluated in crude oil by both ESI

the distribution of n-alkane, bicyclic and tricyclic acidic biomarkers

and with lower environmental impact (Laganet al., 2010). In this

and APCI MS techniques to simplify the analytical procedures,

without laborious processes of purification and derivatization of oil

work, MSPD, Soxhlet and ultrasound-assisted extraction were

One of the goals of implementing the MSPD technique was to

preserving the relative composition of compounds in the oils

sample, for high to moderate level of biodegradation.

employed to isolate hydrocarbons from sedimentary rocks from

extract the largest amount of organic matter without discrimination

the Simit, La Luna, Umir, and La Paz formations, collected in the

of any type of organic component in the sample. The OH groups

municipality of Girn, Santander, Colombia. Extraction yields and

in silica gel could lead to increased retention of polar hydrocarbons

characterization of molecular fossil in crude oil. In general

the distribution of hydrocarbons among the saturated, aromatic,

(asphaltenes, for example). However when alumina or sand were

naphthenic acids are known to be difficult to analyze; some respond

resins, and asphaltene families were compared. The highly specific

used as dispersing agents instead of silica gel, the hydrocarbon

well in ESI, and others respond better in APCI mode. ESI and APCI

multiple reaction monitoring GC-QQQ-MS technique was used to

distribution of the extracts obtained was the same, as well as the

- MS methods were evaluated for naphthenic acids analyses.

monitor the changes resultant from passing through zeolites the

extraction yields.

Based on analyses of n-alkanoics, mono and sesquiterpenoids

saturated hydrocarbon fraction, in order to improve the detection

Hydrocarbons were detected by GC/MS, and carboxylic acids

were obtained by liquid-liquid extraction and then detected by
ESI-TOF MS and APCI-TOF MS. The GC-MS analyses showed
low hopane/sterane ratios, high gammacerane (>60) and
bisnorhopane (>10). Ts/Tm, C35/C34 indices of the oils allowed

and non-polar compounds. Signal suppression due to unknown

their classification as marine evaporitic type. Biodegradation was

matrix interferences is a common problem in quantitative analysis,

confirmed by the presence of 25-norhopane and the total loss of

especially in ESI, so this is a limitation.

n-alkanes and isoprenoids.

samples and detecting higher homologues. The acidic oil fractions


were analyzed in a high resolution ESI- and APCI-TOF MS by direct

LC-MS (ESI and APCI) is an analytical method for the sensitive

infusion (Figure 1). Working with negative Electrospray IonizationESI, we detected a series of bicyclic (C15-C20) and tricyclic acids

carboxylic acids, ESI in the negative ion mode was found to be

superior, howeverboth techniqueshavetheir specificity.


of petroleum biomarkers.

asphaltenes, resins, and aromatic fractions were observed in


Lopes, J. A. D.; Santos Neto, E. V.; Koike, L.; Marsaioli, A. J., 1999. 3-Alkyl
and 3-carboxyalkyl steranes in marine evaporitic oils of the Potiguar Basin,
Brazil. Chemical Geology158, 12.

Peters, K. E.; Walters, C. C.; Moldowan, J. M., 2005. The biomarkers

Figure 1.Comparison of ESI vs APCI results (Full scan negative ion mode,

Guide, Cambridge University Press.

scan range 100 1000 m/z).

extracts from the same rock obtained with the three techniques
under study. This indicates that MSPD is not selective towards a

The authors thank CNPq (Brazilian research council) for fellowships;

ANP (Brazilian Petroleum Agency), Petrobras S/A.

No significant differences in relative amounts of saturated,

Soxhlet extraction of powdered rock (50 g) employed a

particular compound family and can be used to isolate organic

dichloromethane-methanol (9:1 v/v, 150 mL) for 24 h. The extract

matter from sedimentary rocks with higher yields and in shorter

was rotoevaporated to dryness. The same solvent mixture (200

time than the Soxhlet and ultrasound-assisted solvent extraction

mL) was used in ultrasound-assisted extraction, performed under

techniques. Another advantage of MSPD is its lower environmental

reflux for 24 h. The extract was filtered over paper (red strip),

impact due to the smaller amounts of solvent (1/5) that it requires,

washed 3 times with the solvent mixture (30 mL) and evaporated

in comparison with the other two techniques.

to dryness. For MSPD, the ground rock sample (50 200 g) was
mechanically mixed (1:1 v/v) with a dispersing agent (silica gel,
alumina or sand). The mixture was placed into a glass column (40




(hold for 2 min) at 8C min-1, under a hydrogen pressure of 15

sterane and hopane distributions. As shown in Figure 2 HyPy of

MPa. A hydrogen sweep gas flow of 5 l min-1, ensured that the

the asphaltenes generated pristine, n-alkane, and sterane profiles,


products were quickly removed from the reactor, with the products

allowing for source and maturity characterisation of the seeps to

trapped on dry ice cooled silica.

be undertaken.

Recent developments in hydropyrolysis

(HyPy) for petroleum geochemistry
Will Mereditha*, Colin E. Snapea
Figure 1.

a Faculty of Engineering, University of Nottingham, Innovation

Comparison of fragmentogramsof specific biomarkers isolated from

Park, Energy Technologies Building, Jubilee Campus, Nottingham,

sedimentary rock with and without previous treatment with zeolite ZSM5.

NG7 2TU, UK.

Profiles obtained with the multiple reaction monitoring experiment to select

metastable transitions characteristic of hopanes or triterpanes.


Figure 1 shows that the treatment of the saturated hydrocarbon

fraction with ZSM5 zeolites removes chemical noise (mostly
paraffines) and permits reaching higher sensitivity in the

Copyright 2014, ALAGO.

determination of petroleum biomarkers. The detection of

This paper was selected for presentation by an ALAGO Scientific Committee following

hopanesortriterpanesin these samples is used as an example of the

review of information contained in an abstract submitted by the author(s).

Results and discussion

One aspect where standard techniques that concentrate on
the free, solvent extractable phase cannot be applied is for the
characterisation of heavily biodegraded oils and bitumens.
Hydrocarbon classes such as the n-alkanes and small alkylsubstituted aromatic compounds are very susceptible to
biodegradation, while more resistant compounds such as the
steranes and hopanes, which are widely applied in source, maturity
and correlation studies, are vulnerable to alteration at higher levels.

Figure 2.TIC and m/z 217 mass chromatograms of the aliphatic hydrocarbons

Once these compound classes have been irrevocably altered, the

in the maltene fractions (free phase) and asphaltenes hydropyrolysates

biomarkers, covalently-bound into the macromolecular matrix of

(bound phase) from the Ilubinrin tar sand bitumen (numbers refer to carbon

the asphaltene faction, which are not bioavailable to the degrading

chain lengths of n-alkanes) (from Sonibare et al., 2009).

microbes, are thought to represent a remnant of the original oil.

Molecular indices of thermal maturity are typically calculated from

signal enhancement observed when zeolite-treated and untreated

samples are compared with GC-QQQ-MS using the highly specific

the biomarkers isolated from the free, solvent extractable phase of


multiple reaction monitoring experiment.

oils or kerogens. For kerogens, this free phase is representative of

Continuous-flow pyrolysis conducted with a suitable catalyst at high


hydrogen gas pressures (15 MPa), termed catalytic hydropyrolysis

The use of matrix solid-phase dispersion for the extraction of

or HyPy, was first utilised as a means to produce high yields of liquid

organic matter from sedimentary rock is a viable alternative to

only a small proportion of the total organic matter (typically <5%).

Thus it does not follow that the distributions of the free biomarkers
are necessarily representative of those covalently-bound to the

products from solid fossil fuels. It was later found that HyPy could

solvent extraction techniques. MSPD is particularly convenient

macromolecular structure (Love et al., 1995). A study by Murray

be harnessed as an analytical technique for applications involving

to laboratories with no sophisticated or expensive sample

preparation equipment. Extraction yields are similar or superior

the fragmentation of geomacromolecules and release of diagnostic

to those obtained with other techniques, solvent consumption is

lipid biomarker structures. HyPy possesses the unique ability to

lower, and the experimental time is shorter. The zeolite treatment of

produce high yields of hydrocarbon biomarkers from source rock

the saturated hydrocarbon fraction of the extracts obtained does

et al. (1998) observed a systematic change in epimer ratios with

increasing maturity for hopanes and steranes covalently-bound
in kerogens. While less mature in terms of isomerisation at both
ring system and side-chain chiral centres, these biomarkers were

kerogens, sediments and petroleum asphaltenes, whilst minimising

increase the sensitivity and the selectivity of biomarker analysis.

observed to undergo the same epimerisation reaction pathways

structural alteration by isomerisation and cracking (Love et al.,


1995). The technique can be used in petroleum geochemistry for

The authors thank financial support from the National Hydrocarbon

applications where conventional biomarkers fail; e.g. characterising

Agency (grant RC-747-2009) and from the Colciencias supervised

heavily biodegraded oils, samples contaminated by oil-based

donations program, grant 110254832637.

as their free counter-parts in the bitumen. Therefore, the range of

ratios such as the moretane/hopane index for the HyPy products
was found to be much larger than that for the bitumens (ca. 5
times), indicating a much greater sensitivity to relatively small

drilling mud, oil field solids such as tar mats/pyrobitumens,

changes in maturity (Murray et al., 1998).

and for deciphering basin filling history of migrated petroleum


fluids.HyPy has also gained prominence in geobiology studies

ASTM D6560. 2012. Standard Test Method for Determination of

informing the evolution of lifeon Earth. It has also been utilised

Asphaltenes (Heptane Insolubles) in Crude Petroleum and Petroleum

for the characterisation of the insoluble macromolecular material in

Products. American Society for Testing and Materials.http://www.astm.

meteorites, andfor the isolation and quantification of black carbon


in soils.
ASTM D2007-11.2011.Standard Test Method for Characteristic Groups in
Rubber Extender and Processing Oils and Other Petroleum-Derived Oils


by the Clay-Gel Absorption Chromatographic Method, ASTM.http://www.

HyPy wasundertaken using the apparatus described by Love et al.

(1995). Briefly, the asphaltenes (50 mg) were pyrolysed on a bed

Lagan, A.;Cavaliere, C.; Giansanti, P.; Gubbiotti, R.; Samperi, R;Capriotti,

of sulphided molybdenum catalyst (250 mg), with resistive heating

A., 2010. Recent developments in matrix solid-phase dispersion extraction.

from 50C to 250C at 300C min-1, and then 250C to 520C

Journal of Chromatography A, 1217, 2521-2532.


Figure 1.Schematic of HyPy apparatus

The ability of HyPy to provide meaningful information from samples

at elevated, post oil window maturity, where free phase biomarkers

HyPy is able to access these biomarkers in high yields, with

appear in much lower concentration, and have often long since

asystematic study of the free and bound biomarkers obtained

reached equilibrium was demonstrated by Lockhart et al. (2008).

from heavily biodegraded petroleum undertaken by Sonibare et al.

For a suite of Type II kerogen Kimmeridge Clay source rocks from

(2009), who, following characterisation of the free, maltene fraction,

the UK North Sea, with hydrogen index (HI) values as low as ca.

subjected the asphaltenes isolated from three oil seeps from SW

50 mg HC/g TOC, it was found that the isomerisation reactions of

Nigeria to HyPy. These seeps had been subjected to such severe

the kerogen-bound biomarkers were retarded with respect to the

biodegradation that the maltene fraction contained no n-alkanes,

free phase until a hydrogen index (HI) value of ca. 300. Beyond

few identifiable aromatic hydrocarbons, and significantly altered

this point ring system isomerisation within the kerogen-bound

phase is still retarded (until an HI of ca. 200), whilst the side chain


isomerisation for both hopanes and steranes is similar in the free

and bound phases.

Compositional Description ofBrazilian

Type-I Kerogen Using
Hydrous Pyrolysis Products

Catalytic hydropyrolysis (HyPy) has been demonstrated to be a

Sampling and Methods

C56+,the latter called PK10 to PK60 after di Primio & Horsfield

Hydrous pyrolysis (HP) was applied to assess the products of

(2006).Gas and liquid phase components vary systematically

petroleum generation in samples from the Trememb Formation,

with increasing TR, and do not present any evidence of oil to gas

outcropping in So Paulo State (Brazil), in Taubat Basin. The


Oligocene lacustrine sedimentswere deposited in a tertiary onshore

rift in southeastern Brazil and can be considered a representative

highly versatile technique with a range of different applications

across petroleum geochemistry. Despite the obviously attractive

Joelma P. LOPESa*, Regina BINOTTOa, Luciene S. JESUINOb,

of a Type-I kerogen (TOC=10,1weight %; S2=74 mg/grock;

capabilities of HyPy for analysing covalently-bound and highly

Henrique L.B. PENTEADOc, Andr L.D. SPIGOLONa, Luiz F.C.

HI=730mg/g TOC and Ro= 0,32%).

functionalised lipid biomarkers, the technique has taken time

Each maturationexperiments consistedin 275gof crushed source-

to become more widely used due to the specialist nature of the

equipment required to perform this high pressure treatment safely

a - Division of Geochemistry, PETROBRAS Research and Develop-

rock chips ranging in size from 0.5to 2 cm, heated isothermally in 1

and routinely. Recently though, a commercially available system has

ment Center (CENPES), PETROBRAS, Rua Horcio Macedo, 950,

L reaction vesselsat temperatures between 280 and 360C for 36

been developed, with 9 systems are currently installed worldwide

Ilha do Fundo, Rio de Janeiro, RJ 21941-915, Brazil

to 144hr in the presence of liquid water, based on the methodology

in both academic and commercial institutions. The efficacy of

b - FUNDAO GORCEIX, Rua Carlos Walter Marinho Campos,

presented by Lewan (1997).

HyPy is founded upon optimised reactor design and analytical

57, Ouro Preto Minas Gerais, MG 35.4000-000, Brazil

run conditions that allow for excellent reproducibility of molecular

c - E&P Exploration Division, Avenida Repblica do Chile, 330,

Total organic carbon (TOC) contents in source-rock aliquots, before

Figure 1.

profiles and retention of the major structural and stereochemical

Centro, Rio de Janeiro, RJ 20031-170, Brazil

and after the HP experiments, were determined by combustion in

Quantitative Cumulative generation curves of compound classes produced

a Leco carbon analyzer and the organic parameters were obtained

by hydrous pyrolysis of a type I source rock (Trememb Fm., Brazil). Gas

by Rock-Eval pyrolysis.

and liquid phase components increase as with

features of biomarker hydrocarbon products. The key empirical

biomarker lipid systematics, as demonstrated for recent and


transformation ratios

(yiYelds are reported as mg/g TOCoriginal).

ancient kerogens, show that the kerogen-bound hopane and

sterane biomarkers released by HyPy exhibit a slightly less mature

Copyright 2014, ALAGO.

Generatedgases and oils were collected and quantified.Molecular

isomeric distribution than the corresponding free (extractable)

This paper was selected for presentation by an ALAGO Scientific Committee following

compositions of the gases were obtained by gas chromatography

biomarker hydrocarbons.

review of information contained in an abstract submitted by the author(s).

(GC) with a Flame Ionization Detector (FID) for hydrocarbons,and

The kerogen-bound biomarker pool

a Thermal Conductivity Detector (TCD) for non-hydrocarbons (O2,

is immobile and protected against alteration of structural and

stereochemical features during thermal maturation reactions since


N2, CO, CO2, H2S, NO, etc.). Quantitative GC analyses were carried

this pool is sequestered by binding within a high molecular weight

Oil and gas formation and accumulation result from theevolution

out on the expelled oil samples. API gravities were measured only

macromolecular matrix.

of petroleum systems during geological time.Basin modellinguse

in some samples because low-maturity experimental conditions

kinetics of description of primary and secondary cracking reactions,

did not yield enough oil for further analyses.


obtained by artificial maturation of source rock samples,to

Lockhart, R.S., Meredith, W., Love, G.D., Snape, C.E., 2008. Release of bound

reproduce, besides the migration paths and accumulations, the

Results and Discussion

aliphatic biomarkers via hydropyrolysis from Type II kerogen at high maturity.

compositional aspects of oil trapped.

Total organic carbon (TOC) contents,in the samples aliquots, varied

from 10.1 (non-heated sample) to 4.28%(most mature residual

Figure 2.

The possibility of modeling petroleum composition during

sample) as the transformation ratio (TR) increased from zero to 90

API gravity (a) and gas-to-oil ratio (GOR, b) of expelled petroleum obtained

Love, G.D., Snape, C.E., Carr, A.D., Houghton, R.C., 1995. Release of covalently-

generation, aswell as, the PVT behavior of the fluids during

(%).The artificial maturation trend was corroborated by an increase

by hydrous pyrolysis as a function of transformation ratio of a source rock

bound alkane biomarkers in high yields from kerogen via catalytic hydropyrolysis.

migration has only become availablerecently in modern basin

in vitrinite reflectance, which varied from an original value of 0.32%

containing type I kerogen (Trememb Fm., Brazil).

Organic Geochemistry 23, 981-986.

modelling software packages.

to a maximum value of 1.14%.

Organic Geochemistry 39, 1119-1124.

API gravity values are almost constant (around 30) with TR (Figure
Murray, I.P., Love, G.D., Snape, C.E., Bailey, N.J.L., 1998. Comparison of

It is noticeable the great similarity between the hydrous pyrolysis

The mass-balance of productsindicates recovery factor over 90%.

2a), a featurethat correlates very well with API values of unaltered

covalently-bound aliphatic biomarkers released via hydropyrolysis with their

products and the natural petroleum fluids, even into the physical

Non-hydrocarbon gases such as N2, H2S and CO2 are part of

natural fluids from type I kerogen found at Campos and Santos

solvent-extractable counterparts for a suite of Kimmeridge clays. Organic

and chemical properties.

the compositional description of the gases,although they were not

basins. On the other hand, GOR first decreases and then slightly

taken into account in GOR calculations.

increases with TR. Modifications in the compositions of organic

Geochemistry 29, 1487-1505.

phases occur because of complex physiochemical transformations

The aim of this work is to get new insights into petroleum

Sonibare, O.O., Snape, C.E., Meredith, W., Uguna, Love, G.D., 2009.

composition phases and PVT parameters, such as gas-to-oil ratio

Cumulative generation curves are presented in Figure 1. The fluid

during artificial maturation. In the early maturation stages (TR <

Geochemical characterisation of heavily biodegraded oil sand bitumens by

(GOR) and API gravities, along an artificial maturation trend of a

description consists of individual compounds as C1, C2 and C3,

30%), there are no conditions for efficient oil generation and

catalytic hydropyrolysis. Journal of Analytical and Applied Pyrolysis 86, 135-140.

type I source rock submitted to hydrous pyrolysis experiments.

and composite classes of compounds grouped by carbon number:

expulsion, and GOR presents the highest values, because the

C4, C5, C6-C15, C16-C25, C26-C35, C36-C45, C46-C55 and

early gas is gradually being dissolved in the expelled liquid. A slight




increase in GOR (up to 80 m3/m3) was observed only at TR >

and the signature of the converted petroleum generation potential

(S2) acquired directly from open-system Rock-Evalpyrolysis.

60%, when gas production appears to overcome oil generation

(Figure 2b).

New approach for comparing kinetic models

of petroleum generation based on RockEval and hydrous pyrolysis experiments

A compositional model for hydrocarbon generation and maturation

The kinetic parameters were obtained by non-linear regression

using GeokinTM software (Lorant, 2001). The bulk kinetic models

Sampling and Methods

presented in this study describe reactions based on a discrete

Three rock samples were selected for this work containing each

distribution of activation energies between 40 to 80kcal/mol witha

type of kerogen. Type-I is represented by an immature source

step width of1kcal/mol and constant frequency factors (s-1).

Results and Discussion

of a type-I kerogen was developed based on cumulative data from

Regina Binottoa*, Andr L. D. Spigolona, Luiz F. C. Coutinhoa,Rosane

rock from Trememb Formation, Oligocene of Brazil (TOC=10.1%,

hydrous pyrolysis experiments.

A. Fontesa, Jefferson D. Baltara, Carlos G. C. Reetza, Luciene S.

S2=74 mg/g rock, HI=730 mg HC/g TOC, 0.32%Ro). Type-II is


an early mature source rock from Itaja-Au Formation, Turonian

The activation energies distribution, frequency factors (A)

of Brazil (TOC=3.4%, S2=16 mg/g rock, HI=480 mg HC/g TOC,

andgeological extrapolations (1oC/Ma) for each type of kerogen

0.50%Ro). Type IIIis a lignitefrom Hambach mine, Miocene of

are shown in figure 2.

Gas and liquid phases increase systematically with transformation

ratio (TR), and do not present evidence of oil to gas cracking up to

a Division of Geochemistry, Research& Development Center of

a TR of 90%.

b Fundao Gorceix

Germany (TOC=51.2%, S2=90mg/g rock, HI=175 mg HC/g TOC,


API gravity values are almost constant (around 30) with TR, a
feature that replicates the distribution of API gravities of natural


non-biodegraded petroleums derived from type-I kerogens, in

Nonisothermal open-system anhydrous pyrolysis experiments

were carried out in the Rock-Eval 6 Turbo apparatus (Behar et

Campos and Santos basins.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following

GOR presents the highest valuesat low TRs because of the

review of information contained in an abstract submitted by the author(s).

al., 2001) at different heating rates (5, 10, 15 and 25oC/min). The
experimental data used in the numerical inversion correspond to
the petroleum generation rates (S2 curves).

contribution of early gas, then decreases during the main oilgenerating phase, and increases again at TR > 60%.

One of the most important aspects to evaluate petroleum systems

The compositional description presented in this work gives reliable

is theextend and timing of petroleum generation that could be

knowledge about the modification of the petroleum classes as

predicted bybasin modelling in which the calibrated thermal

a function of increasing thermal stress. These data will be used

histories are coupled with appropriate kinetic parameters of organic

to develop a compositional kinetic model to be applied in basin

matter transformation.

modeling software to predict natural petroleum composition and

phase behavior.

Kinetic parameters have been usually acquired by mathematical

inversion of thermogravimetric data obtained by artificial maturation


Isothermal closed-system pyrolysis experiments were performed

in the presence of water (Lewan and Ruble, 2002).The hydrous
pyrolysis experiments were conducted in the same isothermal
conditions for Type-I and -II samples and in a different condition
for Type-III (Fig 1). The original and pyrolyzed rocksof each
experiment were analyzed by Rock-Eval pyrolysis to S2 (mgHC/g
rock) determination.The decomposition of reactant was monitoring

Figure 2.Comparison of bulk kinetic models derived by open and closed-

by the decrease of the remaining petroleum potential (S2residual)

systems and geological extrapolations (1oC/Ma) for each type of kerogen.

during the increase of thermal maturation.

(A) Type-I, (B) Type II and (C) Type-III.

of source rocks and coals. Laboratory essays are carried out by

The authors would like to thank Petrobras to allow publishing this

The results of bulk kinetic models represent the best numerical

heating immature samples at higher temperatures and shorter


inversion of the input data associated with lower error function

times than those involved in the natural process.The derived

and reasonable geological extrapolation. Comparing open versus

kinetic parameters depend not only on the pyrolysis experimental


closed-system bulk kinetic models,similar geological extrapolations

conditions (open or closed, hydrous or anhydrous, isothermal or

were obtained for the Type-I kerogen, despite of some differences

non-isothermal) but also on the inversion method used.

in the frequency factors and activation energies distribution.

Lewan M. D.(1997) Experiments on the role of water in petroleum formation.

Geochimica et Cosmochimica Acta 61 (17), 3691-3723.

However, open-system kinetic behaves slightly more reactive

Despite of large number of work dealing with these pyrolysis

techniques, few studies have established a full comparison between

Figure 1.Time-temperatureconditions employed in the hydrous pyrolysis

than the closed-systemuntil 55% of conversion (Fig. 2A). Kinetic

DiPrimio R. and Horsfield B. (2006)From petroleum-typeorganofacies to

the kinetic models with respect to the reaction mechanisms,


model for the Type-II kerogen showed the largest differences in

hydrocarbonphase prediction. AAPG Bull., 90, No. 7, 10311058.

generated products and geological extrapolations (e.g. Lewan and

Ruble, 2002).

The propose of this study is present a new approach to compare

bulk kinetic parameters using two types of experimental data:
the signature of the remaining petroleum potential (S2 residual)
monitored through residues of closed-system pyrolysis experiments

terms of frequency factor, activation energies distribution and

Hydrous pyrolysis experimental data used in the numerical inversion

geological extrapolations. Closed-system kinetic model for Type-

correspond to the conversion into petroleum or transformation

II kerogen shows fast conversions than open-system until 25%.

ratios (TR) that were calculated for each experiment following the

After that,open system kinetic model shows earlier generation (Fig.

equation:(S2 original S2 residual / S2original)*100. This approach

2B). Similar behavior was also observed for the Type-III kerogen.

is the same applied by Tissot and Welt (1984) to describe the

Moreover, activation energy distribution for the Type-III kerogen is

organic matter conversion into petroleum inthe natural series.

broader than the others (Fig. 2C).



Intervals of non-reaction are characteristic of the closed-system

n-heptane. The occluded biomarkers into the asphaltene structure

were released according to the method described by Liao and

kinetic models, in opposite way of the open-system, which shows

Effect of hydrous pyrolysis in biomarker

distribution of occluded compounds inthe
asphaltene structures

a continuous activation energy spectrum (Fig. 2).

There are differences between kinetic parameters derived by the
open and closed-systems pyrolysis.

Geng(2002). Free and occluded biomarkers were characterized

methods were performed on the unheated sample.

NoeliaFrancoa, Tais F. Silvaa, Milton C. Silvaa, Luiz Guilherme C.

Results and Discussion


Liquid products yields and geochemical characterization (Table

Regina Binottob,J.G. Mendona


by gas chromatography/mass spectrometry (GC/MS). The same

1) of the pyrolyzated samples evidenced that hydrous pyrolysis

In general, kinetic models of the open-system Rock-Eval pyrolysis

a Universidade Federal do Rio de Janeiro, Laboratrio de

conditions increased the thermal evolution of the Irati oil shale

Palinofcies e Facies Orgnica, IGEO Ilha do Fundo 21941-909,

obtaining expelled oil as a result. However, the TOC content

Rio de Janeiro, RJ, Brazil.

and hydrogen index (HI) indicate that the recovered sample at

minor for the Type-I kerogen. The decrease of reactant (S2residual)

b Geochemistry Sector, Petrobras Research & Development

340C/72h still preserve generation potential.At this condition the

when compared with original S2is also an alternative to predict


sample is in the early oil window (Tmax, Table 1).These results are

showed a more reactive behavior if compared to closed-system

hydrous pyrolysis for all kerogen types, although the differences are

the timing of petroleum generation with reasonable geological

Figure 1.Mass chromatograms (m/z 85)of bitumen extracted from unheated

sample (a), occluded biomarker into asphaltene structures of this bitumen
(b), expelled oil at 320C/72h (c) andoccluded biomarkers into asphaltene
structures of this expelled oil (d).

in agreement with lacking variations in biomarker ratios such as:Ts/


(Ts+Tm), 22S/(22S+22R), 20S/(20S+20R).Generated bitumens

In theterpanes distributions was observed that tricyclic terpanes

and oils do not show differences between biomarker ratios.

were more abundant than pentacyclicterpanesin all the m/z


Copyright 2014, ALAGO.

The free n-alkanes distribution in bitumen extracted from unheated

191mass chromatograms of occluded biomarkers in both

To PETROBRAS for the authorization to publish this research, as well as, to

This paper was selected for presentation by an ALAGO Scientific Committee following

sample (Fig. 1a) was compared with the occluded n-alkane

generated bitumen and expelled oil.No remarkable differences

USGS and UFRGS by the use of laboratory facilities.

review of information contained in an abstract submitted by the author(s).

distribution into its asphaltene (Fig. 1b). The same comparison was

were observed in the sterane distribution.

made for the expelled oil at 320C/72h (Fig. 1c and 1d). The main



differences among these n-alkane distributions are the presence

Hydrous pyrolysis is a technique to simulating oil generationduring

of n-alkenes and the low concentration of low-molecular-weight

basin subsidence. Lewan 1993 has shown that the heating

n-alkanes in the occludedbiomarkers. The low concentration of

ofwhole rocks in the presence of water generate oil-likesubstances

these n-alkanes may be attributed to the loss of these compounds

whose chemical properties closely mimicthose of crude oils.The

during the cleaning process of asphaltenes with n-heptane. On the

effects of thermal evolution on the main geochemical parameters

other hand, the presence of n-alkenes into the asphaltene structures

used in thecharacterization ofpetroleum source rocks and oils can

suggests that during heating these n-alkenes are released from the

kinetics by isothermal hydrous and nonisothermal open-system pyrolysis.

also be studied from the products generated by hydrous pyrolysis.

kerogen and when occluded insideof these asphaltene structures

Organic Geochemistry 33, 1457-1475.


Changesin biomarkerdistributions, such as thoseof steranes and

they are protected of the effect of temperature.

The authors are gratefulto PETROBRAS-Brazil for the financial

Behar, F., Beaumont, V., Penteado, H.L.B., 2001. Rock-Eval 6 Technology:
Performances and Developments. Oil & Gas Science and Technology
Rev. IFP 56 (2), 111-134.

Lewan, M.D.and Ruble, T.E., 2002. Comparison of petroleum generation

Despite of hydrous pyrolysis in Irati oil shale expelled oilsin all

experiments, the thermal evolution was not enough to change
the biomarkers distributions. Furthermore, the analyses of the
occluded biomarkersintoasphaltenes suggest that occlusion could
protect these compounds from thermal alteration at least until early
oil window.

hopanes, during the hydrous pyrolysis of kerogensand whole rock

supportthroughtheprojectentitled Estudo Geoqumico de Resinas

Lorant, F., 2001. Acquisition of Kinetic Data with GeokinTM Classic

samples are well documented(Abbott et al., 1990, Pan 2010).

e Asfaltenos: Relao com a Composio do Querognio e a

Practical Aspects, Institut Franais du Ptrole.

However, the characterization of occluded compounds into the

Evoluo Trmica.

asphaltene structurehas not been reported until now. Based

Tissot, B.P., Welte, D.H., 1984. Petroleum formation and occurrence,

on the usefulness of this technique, the main goal of this study


second ed. Springer-Verlag, Berlin.

was characterize and compare the occluded compoundsinto

Abbott, G.D., Wang, G.Y., Eglinton, T.I., Home, A.K., Petch,

G.S., 1990. The kinetics of sterane biological marker release and

the asphaltene structures of bitumens and oils generated during

degradation processes during the hydrous pyrolysis of vitrinite

hydrous pyrolysis experiments with their respective free biomarkers.

kerogen. GeochimicaetCosmochimicaActa54, 2451-2461.


Lewan, M.D., 1993. Laboratory simulation of petroleum formation:

Hydrous pyrolysis experiments wereperformedon a sample of Irati

Hydrous Pyrolysis. In.: Engel, M.H. & Macko, S.A. (Eds.). Organic

oil shale (Paran Basin, Brazil), at temperatures range from 280C

Geochemistry. Plenum Press, New York, 419-442.

to 340C for 72h, using a Stainless Steel reactor (300 mL). The


expelled oil was collected from the water surface with a Pasteur

Table1.Yieldsof liquid hydrocarbons products, biomarker ratios of original

pipette. The bitumen generated during the experiment was

and generated bitumen, TOC and Rock-Eval parameters for unheated

extracted from the residual source rock with Soxhlet using CH2Cl2

sample and pyrolyzed samples of Irati oil shale, Paran Basin, Brazil. All

as solvent. Total Organic Carbon (TOC) contents and Rock-Eval

experiments were performed for 72h.

Liao, Z., Geng, A., 2002. Characterization of n-C7-soluble fractions

of theproducts from mild oxidation of asphaltenes. Organic
Geochemistry33, 1477-1486.
Pan, C., Geng, A.,Zhong, N., Liu, J., 2010. Kerogen pyrolysis in

analyses were conducted in unheated and pyrolyzated samples.

the presence and absence of water and minerals: steranes and

The asphaltenes of these products were precipitated using

triterpenoids. Fuel 89, 336-345.



For the analyses of bitumen the samples were extracted in a soxhlet

extractor and were then analysed for n-alkanes and isoprenoids
by chromatographic and GC-MS techniques. GC-MS techniques
were also applied to determine the hydrocarbon characteristis of
the expelled oils. (bitumen and oil).

Artificial Maturation Applying Hydrous

Pyrolysis Experiments on Organic- Rich
Shales From The Ipubi Mbr., Santana Fm.,
Araripe Basin, Brazil

The hydrous pyrolysis experiments were conducted in a closed

system (350C at 0, 20, 50 h), which allowed calculations of the

Tnia Valria de O.


Marleny B.


Table 2: Yield of bitumen and expelled oil generated by

hydrous pyrolysis at 350 C for oh, 20 and 50 h.
Time (h)
Expelled oil (g)
Bitumen (g)
0 h

20 h

50 h



quantitative distributions of various organic fractions with increasing

Barrionuevo1, Joo Adauto de Souza Neto2, Wolfgang Kalkreuth1

thermal maturity. The sample was crushed and homogenized to

chips (1-2 cm) and was not pre-extracted prior to the experiments.

1 Universidade Federal do Rio Grande do Sul, Laboratrio de

An average bulk density was determined for the rock chips and used

Anlise de Carvo e Rochas Geradoras de Petrleo, Porto Alegre-

to calculate the amount of water needed to maintain liquid water

in contact with the rock before, during, and after the experiments


in 250 ml reactors composed of stainless steel. For each of the

2Center for Technology and Earth Sciences, Federal University of

hydrous pyrolysis runs 45 g of rock and 86 ml of distilled water

Pernambuco, Recife-PE

were used. After loading and sealing the reactor, the remaining
headspace was evacuated and filled with 30 psi of helium.


At or prior to these apparent maximum yields, the bitumen

decomposes to oil that is expelled from the bitumen-impregnated
rock as was observed by the distinct compositional differences
between the polarrich bitumen and the expelled oil rich in saturate
and aromatic fractions and characterized by less polar fractions
(Table 3).
Table 3:Relative chemical distribution of total hydrocarbon
fraction under the selected T/t conditions.O.R.: original shale
sample,H.R.: pyrolyzed shale sample, Bitumen (B), expelled
oil (E.O.). F1% = saturated HC; F2% = aromatic HC; F3% =

Changes in oil properties with the advance
of thermal maturation induced by hydrous
pyrolysis for a Brazilian source rock
containing a Type-I kerogen
Andr L. D. Spigolona,d*, Michael D. Lewanb, Henrique L. B.
Penteadoc, Luiz F. C. Coutinhoa, Joo G. Mendona Filhod
a Division of Geochemistry, PETROBRAS Research and Development
Center (CENPES), 21941-915, Rio de Janeiro, RJ, Brazil
b United States of Geological Survey (USGS-Denver)
c Basin and Petroleum System Modeling of PETROBRAS
d Universidade Federal do Rio de Janeiro, Instituto de Geocincias,
21.949-900, Rio de Janeiro, RJ, Brazil
Copyright 2014, ALAGO.


Products (pyrolyzed rock, expelled oil, bitumen) were recovered,

This paper was selected for presentation by an ALAGO Scientific Committee following

The Araripe Basin is located in the interior of the northeasten

region of Brazil. The basin covers the most southern part of Cear,
and parts of Pernambucoand Piau states, and geologically is
characterized by a predominantly Mesozoic succession. The
development of the basin is directly linked to the opening of
the South Atlantic, with deposition during the postrift fase of a
sequence of organic-rich shales associated with evaporitic rocks
of the Aptian Ipubi Formation, Group Santana.

quantified and characterized from each experiment, allowing

review of information contained in an abstract submitted by the author(s).

to determine the thermal evolution of the pyrolyzed rock, and to

determine the fractional composition and geochemical properties
of the generated expelled oils and retained bitumen.

Results and Discussion

The results of the organic petrological and geochemical examination
of the original sample showed the following characteristics: TOC
content of 25.7 wt.%, S1 yield of 15.2 mg HC/g rock, remaining

The objectives of this study were to evaluate a) the thermal

evolution of the organic-rich rocks; b) their hydrocarbon generating
potential via hydrous pyrolysis experiments The experiments were
carried out using the same maximum temperature (350 C) with
time increments of 0h, 20h and 50h. Specific aspects of this
study (Delgado, 2012) include a quantitative assessment of the
generative potential of the organic-rich rocks, the determination
of the composition of liquid hydrocarbons generated from the
shale at various time, and the determination of geochemical and
petrographical changes of the organic matter in the residual rocks
after the hydrous pyrolysis experiments. Preliminary results of this
study were published by

HC generative potential (S2) of 126.0 mg HC/g rock, Hydrogen

F1% F2% F3%

O.R. 5,9


0h (B) 2.4 7.3 90.2
20h (B) 9

50h (B)
12.7 24.1 63.3

0h (E.O)
28.4 28.4 44.6

20h (E.O)
30.8 25.6 43.6

50h (E.O)
14.3 48.8 36.9

Index (HI) of 489 mg HC/g TOC and Tmax of 408 C.

The maturation effects caused by the hydrous pyrolysis experiments
were firstly observed by significantly reduced source rock potential
in the pyrolized shale, with S2 values ranging from 126.0 mg HC/g
rock in the original sample to 12 HC/g rock, after 50 hr at 350C.
A similar trend was observed in the Hydrogen Index that showed
a maximum of reduction at 350C at 50 h experiment time, where
the HI was lowered to 124 mg HC/g TOC (Table 1).
Table 1: Rock-Eval/TOC data of selected Ipubi Formation

The experiments were performedunder specific conditions such

as sample mass, reactor volume, mass ofwater added, andthe
reaction temperatureto ensure theliquid phaseduring heating
(Lewan, 1993; 1997).

shale rock sample:O.R.: original shale sample,H.R.: pyrolyzed

shale sample. S1= mg HC/g rock; S2 = mg HC/g rock; S3 = mg

The results from the hydrous pyrolysis experiments showed that

by increasing experiment time the rate of transformation from
kerogen into hydrocarbons increased, as indicated by the increase
in hydrocarbon yields (bitumen and expelled oil). At the same time
hydrogen indices (HI) and hydrocarbon generation potential (S2)
of the pyrolyzed rock were significantly reduced with increasing
experiment time.
The results on chemical composition of the expelled oils indicated
enrichment in the saturated fraction, whereas the bitumen retained
in the rock was characterized by enrichment of the heavier fraction

CO2/g rock; HI = mg HC/g TOC

TOC (wt.%)

Sampling and Sample Preparation




Tmax (C) HI

O.R 25,7 15.2 126 1.87 408 489

The shale samples were collected by the Center for Technology and
Earth Sciences, Federal University of Pernambuco. The samples
were crushed, homogenized and and representative sub-samples
were prepared for the various hydrous pyrolyses experiments.
The original samples were also analysed by TOC and Rock Eval
Pyrolysis parameter (Weatherford Laboratories, Texas).


0h 8,89 1.06 61.9 1.11 415 696

20h 8.95 0.8 19.5 2.16 437 218
50h 10 1.01 12 2.06 444 120
Table 2 show the product yields of bitumen and expelled oil for
the hydrous pyrolysis runs (0, 20, 50 h at 350 C). The maximum
bitumen yield occurs at 0 h. Yields of expelled oil have a maximum
of 4.7 mg HC/g at 350 C and 50 h experiment time.

The original samples were also prepared and analyzed by

petrographic incident light analyses (vitrinite reflectance and maceral
analysis); and petrographic transmitted light analyses (spore color
index and qualitative analysis of organic matter by fluorescence).

Delgado T.V.O. 2012. Trabalho de Conluso: Maturao Artificial

de Rochas Geradoras de Petrleo-Caracterizao Geoqumica e
Petrografia de Folhelhos do Membro Ipubi da Formao Santana,
Bacia do Araripe, PE/CE, 90p.
Lewan, M.D. 1997. Experiments on the role of water in petroleum
formation: Geochimica et Cosmochimica Acta, v. 61: 3691 3723.
Lewan, M.D. 1993. Assessing natural expulsion from source rock
by laboratory pyrolysis; p 201-210. In: Magoon B.L., Dow G.W.
The petroleum system-from source to trap. Tulsa Oklahoma. 1994.

Introduction and goal

To understand the thermochemical transformation of kerogen
with increasing maturation and the compositional variation of the
generated products, the petroleum industry has used laboratory
pyrolysis experiments to artificially mature source rocks at relatively
high temperatures and short times under an inert atmosphere.
Because of the use of several pyrolysis conditions, such as
open or closed system, hydrous or anhydrous and isothermal or
nonisothermal pyrolysis, significant differences are observed in
the generated petroleum products. However, the composition of
oils generated and expelled in hydrous pyrolysis are the closest to
that of natural oils (Lewan, 1997; Ruble et al,. 2001; Lewan et al.,
2006), and therefore, provide the best method to evaluate changes
in oil properties with thermal maturity.
This research investigates changes in expelled oil generated
by hydrous pyrolysis from an immature organic-rich lacustrine
source rock (TOC=28.8%; HI=892 mg HC/g TOC; 0.3%Ro) of
Aptian age from the Araripe Basin (NE-Brazil). The tested sample
is representative of a Type-I kerogen and can be considered a
reasonable analog for Brazilian lacustrine source rocks of Lower
Cretaceous age, which are responsible for most of the oil generated
in the Brazilian continental margin.

Analytical Methods
The hydrous pyrolysis experiments were conducted under
isothermal conditions at twelve different temperatures for 72 hours
(280, 300, 310, 320, 325, 330, 340, 345, 350, 355, 360, 365C)
and at 310, 325, 340, and 355C for different times (e.g., 12,
24, 30, 36, 48, 72, 96, 104, 120, 132 hours) to simulate the full
range of petroleum generation from early bitumen generation to
maximum oil generation.
Generated gases were characterized by molecular composition
including C1-C6 saturated and unsaturated hydrocarbons, H2S,
CO2, O2, N2, He and Ar. The expelled oils were characterized
by their bulk properties (sulfur content, API gravity, stable carbon

isotopes and SARA fractions) and molecular properties (alkane

distribution and biomarker signatures). Product yields in mg/g
TOC and gas/oil ratios (GOR m3/m3) were calculated for each
experiment. Based on the maximum expelled oil yield at 360C
for 72h, the transformation ratios (TR) for generation of expelled
oil were determined for all the experiments. Physico-chemical
properties of expelled oils were evaluated in a function of TR (Fig. 1).

show a 12C depletion with increasing transformation ratio from

-30.65for the low temperature (280oC) to -28.48 for the high
temperature (365oC) for 72 hours.
Although the results show pristane/n-C17 and phytane/n-C18
ratios decrease with increasing transformation ratios, the pristane/
phytane ratio remains nearly constant (Fig. 1B). During oil
generation, the concentration of Stigmastane in the expelled oils
decreases with increase transformation ratio and is associated
with low concentrations of 3-4 Methyldiamantanes. At maximum
oil generation (360C/72h), the concentration of Stigmastane is
zero, and the concentration of diamandoids is still very low, which
indicates no oil cracking to gas according to Dahl et al. (1999).
Final Remarks

Results and Discussion

The petroleum yields (oil + hydrocarbon gases) increase linearly
with the advance of transformation ratio at a maximum of 728.23
mg/g TOC. The hydrocarbon gases (C1-C5) generated at the oil
peak represent 9% of total (Fig. 1A). The beginning of oil generation
stage corresponds to 0.2TR, when the bitumen is effectively
decomposed (320-325oC).

In the case of Type I kerogen-bearing source rock, bulk properties

(API gravity, 13C, sulfur content, SARA fractions) of expelled oils
from the hydrous pyrolysis experiments show some systematic
changes during the oil generation stage. Among molecular ratios,
pristane/n-C17 and Phytane/n-C18 are strongly controlled by
the thermal maturation and show a consistent behavior with the
advance of transformation ratios during the oil generation stage.
As indicated by gas/oil ratios, biomarkers, and diamandoids, no oil
cracking to gas was observed under the experimental conditions

In general, the geochemical results indicate that there are some

changes in bulk parameters of the expelled oils, mainly related to
API gravity, SARA fractions, and whole-oil stable carbon isotopic
composition (13C). The molecular properties like the distribution
of n-paraffins and isoprenoids also change systematically with
increasing thermal maturation (Fig. 1B).
However, relatively small variations are observed in gas/oil ratios.
GOR initially decreased from 500 to 80 m3/m3 and then remained
essentially constant until the oil peak. The high GOR values occur
during early bitumen generation at the onset of oil generation (Fig.
1C). Similar trends were obtained by Lewan and Henry (2001)
for different types of kerogens (Type-I, -II and -IIS) during the oil
generation by hydrous pyrolysis.

The authors are grateful to PETROBRAS and USGS for financial and
analytical support of this research within the PhD of the first author.

Dahl, J.E., Moldowan, J.M., Peters, K., Claypool, G., Rooney, M., Michael,
G., Mellos, M., Kohnen, M., 1999. Diamondoid hydrocarbons as indicators
of oil cracking. Nature 399, 5456.

Hydrous pyrolysis experiments on a
Permian coal sample from the
Leo-Buti Coalfield, Paran Basin
Leandro S. Putti, Marleny B. Gonzlez, Simone Barrionuevo,
Wolfgang Kalkreuth, Thaysa L.C. de Morais
Instituto de Geocincias, UFRGS, Rua: Bento Gonalves 9500,
CEP: 91501-970, Porto Alegre, Rio Grande do Sul, Brasil.

In Brazil, the most important coal bearing sedimentary succession
occurs in the Permian Rio Bonito Formation, Paran Basin, located
in the states of Rio Grande do Sul(RS) and Santa Catarina (SC).
The objectives of this study were the determination of a) the physicchemical variability between the coal seams that constitute the So
Vicente Norte Mine, Leo-Buti Coalfield; b) to determine changes
in chemical composition and petrographic parameters caused by
artificial maturation of the organic matter contained in seam S2/
S3 using hydrous pyrolysis experiments at 350 C with experiment
times ranging from 0 50 hours; c) to evaluate the hydrocarbon
potential of this Permian coal.
The Hydrous pyrolysis experiments refer to the thermal
decomposition which takes place when organic matter is heated
to high temperatures in the presence of water (Lewan, 1993, 1997;
Ruble et al., 2001; Franco et al., 2010). Pyrolysed coal, bitumen
and expelled oil were recovered, quantified and characterized
from each hydrous pyrolysis run, allowing determining the thermal
evolution of the coal sample and to study the effect on the amounts
and distribution of hydrocarbons generated during the experiments.

Lewan, M.D., 1997. Experiments on the role of water in petroleum

formation. Geochimica et Cosmochimica Acta 61 (17), 36913723.
Lewan, M.D. and Henry, A.A., 2001. Gas:Oil Ratios for Source Rocks
Containing Type-I, -II, -IIs, and III Kerogens as Determined by Hydrous
Pyrolysis. In: Dyman, T.S. and Kuuskraa, V.A. (Ed.). Geologic Studies of
Deep Natural Gas Resources. USGS Digital Data Series DDS-67, version
Lewan, M.D., Kotarba, M.J., Curtis, J.B., Wieclaw, D., Kosakowski,

Sampling and Sample Preparation

Coal samples were collected from the So Vicente Norte Mine,
Leo-Buti coalfield (Putti, 2012).From the base to the top of
the coal-bearing sequence, the coal seams are named: camada
Inferior 2 (I2), camada Inferior (CI), Leito 4 (L4), camada Superior 3
(S3), Leito 3 (L3), camada Superior 2 (S2), Leito 2 (L2), Leito 1 (L1),
and camada Superior 1 (S1).

Cosmochimica Acta 70, 33513368.

The coal samples were prepared for petrographical and chemical

analyses according to standardized procedures (Bustin et al,
1989), and the sample from the S2/S3 interval was prepared for
hydrous pyrolysis experiments

Figure 1. Relationship between the geochemical parameters of expelled

Ruble, T.E., Lewan, M.D., Philp, R.P., 2001. New insights on the Green River


oils generated by hydrous pyrolysis with their transformation ratios. Yields

petroleum system in the Uinta basin from hydrous pyrolysis experiments.

of expelled oil and hydrocarbon gas are given in mg/g of original TOC (A),

American Association of Petroleum Geologists Bulletin 85, 13331371.

This coal used in the hydrous pyrolysis runs was subjected to organic
petrologic and geochemical studies prior to the experiments that
included vitrinite reflectance measurement to determine the rank of
the coal; determination of maceral composition; Chemical analysis;
TOC; Rock-Eval pyrolysis.

P., 2006. Oil-generation kinetics for organic facies with Type-II and -IIS
kerogen in the Menilite Shales of the Polish Carpathians. Geochimica et

molecular ratios (B), and gas/oil ratios in m3/m3 (C).

Spigolon, A.L.D., Lewan, M.D., Mendona Filho, J.G., Penteado, L.H.B.,

Variations in the API gravity ranging 22 to 32 show a complex

relationship with transformation ratios. As expected, increasing
API gravities correlate with increasing saturates and decreasing
asphaltenes (Spigolon et al., 2013).Sulfur contents ranging of
0.82 to 1.55 wt% and systematically decrease with the advance
of TR. Stable carbon isotope composition (13C) of whole oils

Coutinho, L.F.C., 2013. New insights on changes in the oil quality during

chips (1-2 cm) and was not pre-extracted prior to the experiments.
An average bulk density was determined for the rock chips
and used to calculate the amount of water needed to maintain
liquid water in contact with the rock before, during, and after the
experiments in 250 ml reactors composed of stainless steel. For
each of the hydrous pyrolysis runs 45 g of rock and 86 g of distilled
wate were used. After loading and sealing the reactor, the remaining
headspace was evacuated and filled with 7 Mpa of helium.
Products (pyrolyzed coal, expelled oil, bitumen) were recovered
quantified and characterized in each experiment, allowing
determining the thermal evolution of remaining coal, fractional
composition, geochemical properties of the generated and
expelled oils and retained bitumen.

Results and Discussion

The results 0f the organic petrological and geochemical studies
of the original sample (S2/S3 seam) showed the following
characteristics: TOC content of 44.19 wt.%, S1 yield of 1.08 mg
HC/g rock, remaining HC generative potential (S2) of 75.68 mg
HC/g rock, Hydrogen Index (HI) of 171 mg HC/g TOC, Oxygen
Index of 5 mg HC/g TOC, Tmax of 418 C, vitrinite reflectance of
0.45% Rr.
The maturation effects caused by the hydrous pyrolysis experiments
were firstly observed by significantly reduced source rock potential
in the pyrolized coal, with S2 values ranging from 75.68 mg HC/g
rock in the original sample to 18.60mg HC/g rock, after 50 hr at
350C. A similar trend was observed in the hydrogen Index that
showed a maximum of reduction at 350C at 50 h duration where
the HI was lowered to 54 mg HC/g TOC.
Tmax values ranged from 418 (original sample) to a maximum of
469, whereas vitrinite values ranged from 0.45 (original sample) to
a maximum of 1.14 %Rrandom;
Both rank parameter indicate immature stage for the original
sample, whereas the pyrolysed coal are well within the oil window
based on the level of vitrinite reflectance and at the transition to the
overmature stage based on Tmax values.
Figure 1 shows the product yields of bitumen and expelled oil for
the hydrous pyrolysis runs (0, 20, 50 h at 350 C). The maximum
bitumen yield occurs at 20 h. Yields of expelled oil have a maximum
of 0.700 mg HC/g at 350 C and 50 h experiment time (Fig. 1)
At or prior to these apparent maximum yields, the bitumen
decomposes to oil that is expelled from the bitumen-impregnated
rock as was observed by the distinct compositional differences
between the polarrich bitumen and the expelled oil rich in saturate
and aromatic fractions and characterized by less polar fractions.

petroleum formation by hydrous pyrolysis on a Brazilian source rock

containing Type-I kerogen.

Abstracts. 26th International Meeting on

Organic Geochemistry 1, Costa Adeje, Tenerife, Spain, p. 417-418.


The hydrous pyrolysis experiments were conducted in a closed

system (350C at 0, 20,50 h);, which allows calculations of the
quantitative distributions of various organic fractions with increasing
thermal maturity. The sample was crushed and homogenized to



Figure 1. Changes in hydrous pyrolysis products generated at 350 C for 0,

20 and 50h experimental time for the S2/S3 sample, Leo-Buti coalfield.

The authors thank to Petrobras for sponsorship of this study as

well as authorization for its publication.

Fluorescence Behavior of Alginites in

Artificial Maturation Experiments

The results on chemical composition of all expelled oils indicated

enrichment in the saturated fraction, whereas the bitumen retained
in the coal was characterized by enrichment of the heavier fraction
(heterocomponents), an effect of the mineral matrix, retaining
preferentially molecules of larger size in the bitumen fraction,
whereas the lighter hydrocarbons are being expelled).

Araujo, C.V., Vieth-Redemann, A., Pradier, B., Kalkreuth, W.,
Gomez Borrego, A., Gurba, L., Hagemann, H., Hufnagel,W., Koch,
M., Kuili, J., Laggoun-Defarge, F., Lo, H., Newman, J., Spanic, D.,
Suarez-Ruiz, I., Thompson-Rizer, C., 1998. Interlaboratory exercise
on the application of microspectral fluorescence measurements as
maturity parameters. Revista Latino Americana de Geoqumica
Orgnica 4, 41-49.

Carla Viviane Araujoa*, Renata Brenand Alvarenga das Chagasb,

Jaques Soares Schmidta, ,
Igor Viegas A. F. de Souza.a



The results from the hydrous pyrolysis experiments showed that

by increasing experiment time the rate of transformation from
coal into hydrocarbons increased, as indicated by the increase in
hydrocarbon yields (bitumen and expelled oil). At the same time
hydrogen indices (HI) and hydrocarbon generation potential (S2) of
the pyrolyzed coals were significantly reduced.


Araujo, C.V, Borrego, A., Brenand, R., Cardott, B. Flores, D.,

Gonalves, P. , Hackley, P., Hower, J., Kern, M., Kus, J., Mastalerz,
M., Mendona Filho, J.G. Mendona, J., Menezes, T., Newman,
J. Suarez-Ruiz, I., Sobrinho, F & Viegas, I., 2014. Petrographic
thermal indices of a Devonian shale maturation series, Appalachian
Basin, USA. ICCP Thermal Indices Working Group interlaboratory
exercise. Manuscript under review.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).


Maturity parameter such as vitrinite reflectance and Tmax oC

indicate immaturity for the original sample prior to the experiments,
whereas at 50 h experiment time at 350 oC the pyrolyzed sample is
well within the oil window as indicated by vitrinite reflectance and/
or at the transition mature/overmature as indicated by the Tmax
oC value.

The objective of this study is to investigate fluorescence properties

of alginites, as maturity parameters, in artificial maturation
experiments, as well as compare these properties with those
derived from natural maturation series.
Fluorescence microscopy has become an important tool in
maturation assessment of source rocks since spectral fluorescence
methods were presented in pioneering studies by Jacob (1965),
van Gijzel (1967, 1975, 1981), Teichmuller and Ottenjann (1977)
among others. Quantitative methods such as spectral fluorescence
and its derivative parameters (max, red-green Quotient) are very
useful when vitrinite is rare absent or ambiguous (Wolf & Corra da
Silva, 1984 and Stasiuk, 1994). The evaluation of max has shown
great applicability as a maturation parameter in natural series
(Araujo et al., 1998 and Araujo et al., 2014). Nevertheless, when
studies on fluorescence parameters are carried out on artificial
maturation series derived from hydrous pyrolysis experiments no
consistent results are obtained.

The quantitative hydrous pyrolysis data from this study provide a

useful means to evaluate compositional variations in bitumen and
expelled oils generated from coal with increasing thermal maturity.
The data also offer insights into the physiochemical processes that
take place during hydrous pyrolysis

The authors acknowledge and appreciate the analytical support
provided by the Laboratory for Coal and Source Rocks, UFRGS.

Franco, N., Kalkreuth, W.; Peralba, M. C., 2010. Geochemical
Characterization of Solid Residues, Bitumen and Expelled Oil
Based on Steam Pyrolysis Experiments from Irati Oil Shale, Brazil:
A preliminary study. Fuel 89: 1863 1871.

Figure 1 Fluorescence microspectrophotometry of prasinophyte alginites

from the 350C isotherm experiments at 1 and 20 h. Raw data presented
in red and adjusted data by the correction function in blue.

Visual observation reveals that alginites are gradually less abundant

with increasing duration of experiments. Furthermore, they tend to
present a halo between the alginite body and the matrix suggesting
a shrinkage process due to possible condensation reactions.
Alginites are present in experiments up to 20 h (fig.2). No alginites
were observed in experiments from 50 up to 200 h.
Spectral fluorescence measurements carried out on immature
organic-rich rock of the Oligocene-Miocene Trememb Formation
in the Taubat Basin (Brazil) revealed a similar behavior with no
significant change in max with increasing experimental temperature
and time run. Furthermore a disappearance of alginites in the more
severe experiments was noticed (Souza et al., (2011).

50 m

Spectral fluorescence measurements were carried out on
prasinophyte alginites from two isothermal series of hydrous
pyrolysis experiments. For this purpose a Devonian sample from
Ponta Grossa Formation of Parana Basin was selected. Sixteen
experiments of 1 up to 200 h at 350 and 360C were performed.
Polished blocks from samples derived from these assays were
analyzed in fluorescence mode, as well as the original rock sample.
Fluorescence intensities from 400 to 750 nm were obtained and
corrected with a correction function (Baranger et al., 1991 and
Araujo et al., 1998).

Lewan, M.D. 1997. Experiments on the role of water in petroleum

formation: Geochimica et Cosmochimica Acta, v. 61: 3691 3723.
Lewan, M.D. 1993. Assessing natural expulsion from source rock
by laboratory pyrolysis; p 201-210. In: Magoon B.L., Dow G.W.
The petroleum system-from source to trap. Tulsa Oklahoma. 1994.
Putti L. C. 2012. Caracterizao petrolgica, geoqumica e
maturao artificial de carvo da mina So Vicente Norte, jazida
Leo-Buti, Formao Rio Bonito, Bacia do Paran, RS. Trabalho
de Concluso de Geologia, Instituto de Geocincias, Universidade
Federal do Rio Grande do Sul, Porto Alegre, p.103.

Results and Discussion

The max derived from spectral fluorescence measurements
carried out on prasinophyte alginites of original sample is at 590 nm
and Ro% is 0.57%. However, unlike the behavior observed in the
study of the natural series the gradual advancement of the max
of the green to red region is not observed as would be expected
with increasing maturation. The max remains predominantly
unchanged in experiments of 1 to 20 h (fig. 1), as well as the redgreen quotient. Nevertheless, vitrinite reflectance reaches up to

Ruble T.E., Lewan M. D., Philip R.P. 2001. New Insights on the
Green River Petroleum System in the Uinta Basin from Hydrous
Pyrolysis Experiments. AAPG Bulletin, v.85 (8): 1333 1371.


Baranger, R., Martinez, L., Pittion, J-l., Pouleau, J., 1991. A

new calibration procedure for fluorescence measurements of
sedimentary organic matter. Organic Geochemistry 17, 467-475.
Jacob, H., 1965. Neue erkenntnisse auf dem gebiet der
lumineszenzmikroskopie fossiler brennstoffe. Fortschr. Geol.
Rheinld. u. Westf.12, 569-588
Souza, I.V.A.F.; Araujo, C.V.; Menezes, T.R.; Coutinho, L.F.C.;
Santos Neto, E.V.; Binotto, R.; Spigolon, A.L.D.; Cioccari, G.;
Lewan, M.D.; Rondon, N.; Mendona Filho, J.G., 2011. Hydrous
pyrolysis experiments: new insights about generation, saturation
and petroleum expulsion through organic petrographic evidences.
IMOG Meeting. Interlaken, Switzerland, Abstract.
Stasiuk, L.D., 1994. Fluorescence properties of Paleozoic oilprone alginite in relation to hydrocarbon generation, Williston basin,
Saskatchewan, Canada. Marine and Petroleum Geology 11(2),
Teichmller, M., and Ottenjann, K., 1977. Liptinite und lipoid Stoffe
in einem Erdlmutterdestein . Erdl und Kohle, 30, 387-398.

2.5 h

10 h

20 h


50 h

van Gijzel, P., 1967. Autofluorescence of fossil pollen and spores

with special reference to age determinationand coalification. Leids
geol. Meded. V.40 p.263-317.
microphotometry of fresh and fossil plant substances, with special
reference to the location and identification of dispersed organic
material in rocks. In: Alpern, B., (ed.), Ptrographie de la matiere
organique des sediments. Relations avec la paleotemperature et le
potential ptrolier, CNRS, Paris, 67-91.

Figure 2 - Photomicrographs of prasinophyte alginites in fluorescence mode.

Presenting the original sample (i) and the 350C isotherm experiments of
1 to 50h.

The observation of phenomena such as no change of max and
red-green quotient suggests that the severity of hydrous pyrolysis
experiments does not allow the evaluation of maturation increase
by fluorescence properties that show a severe degradation in
experiments of long duration and high temperatures in contrast to
that observed in the natural series.

van Gijzel, P., 1981. Applications of the geomicrophotometry

of kerogen, solid hydrocarbons and crude oils to petroleum
exploration. In: Brooks, J. ed., Organic Maturation Studies and
Fossil Fuel Exploration, Academic Press, London, 351-377.
Wolf, M., Corra da Silva Z.C., 1974. Petrographic description
and fcies analysis of some samples from the oil shale of the Irati
Formation (Permian). In: Congresso Brasileiro de Geologia, 28,
Porto Alegre. Anais, Sociedade Brasileira de Geologia 1, 159-170.


Geochemical characterization
of the Hydrous Pyrolysis Products
from a recent Microbial Mat

palynofacies according Mendona Filho et al. (2011), cyanobacterial


content analyses was conducted using optical microscopy, the taxa

Anagnostidis, K.; Komrek, J., 1988. Modern approach to the classification

were identied as described by Anagnostidis and Komrek (1988)

system of cyanophytes 3 Oscillatoriales. Archiv Hydrobiologie Algological

and geochemical characterization was performed by total organic

Studies, Supplement, 80 (1-4): 327-472.

carbon (TOC) and gas chromatographic-mass spectrometric (GCMS) methods.

DasSarma, S.; Arora, P., 2001. Halophiles. In: Nature Publishing Group / of life sciences.1-9.

Mendona Filho, J.G.a*, Franco, N.a, Silva, T.F.a, Stojanovi, K.b,

Carvalhal-Gomes, S.B.Va, Silva, F.S.a, Fontana, L.F.a, Furukawa,

Hydrous pyrolysis experiments were performed at temperatures


of 280C and 330C for 20h, using a Stainless Steel reactor (300

Grimalt, J.O.; Wit, R.; Teixidor, P.; Albaiges, J., 1992. Lipid biogeochemistry

mL). TOC content was determined in pyrolyzated samples. Liquid

of Phormidium and Microcoleus mats. Organic Geochemistry 19, 509-530.

a Universidade Federal do Rio de Janeiro, Laboratrio de

hydrocarbons products, expelled oil and extractable organic matter

Mendona Filho, J.G.; Chagas, R.B.A.; Menezes, T.R.; Mendona, J.O.;

Palinofcies e Facies Orgnica, IGEO, Ilha do Fundo 21941-909,

(EOM), were analyzed by GC-MS.

da Silva, F.S.; Sabadini-Santos, E., 2010. Organic facies of the Oligocene

Rio de Janeiro, RJ, Brazil.

lacustrine system in the Cenozoic Taubat basin, Southern Brazil.

b University of Belgrade, Faculty of Chemistry, Studentski trg 12-

International Coal Geology 84, 166-178.

16, 11000 Belgrade, Serbia.

Mendona Filho, J.G.; Menezes, T.R.; Mendona, J.O.; Oliveira, A.D.;
Carvalho, M.A.; Santana, A.J., 2011. Kerogen: Composition and
Figure 2. Mass chromatograms (m/z 85, 191, 217) of (a) the extractable

classification. In: Flores, D.; Marques (Eds.), M. ICCP Training Course on

Copyright 2014, ALAGO.

organic matter (EOM) from original unheated sample and (b) the expelled oil

Dispersed Organic Matter. Plenimagem, 17-23.

This paper was selected for presentation by an ALAGO Scientific Committee following

at 330C/20h. *Isomeric phytenes.

review of information contained in an abstract submitted by the author(s).

Experimental conditions used in hydrous pyrolysis experiments


were enough to obtain expelled oil (591.12 mgHC/gTOCo at

Microbial mats are multi-layered microbial communities spatially

330C/20h) from the studied sample. The effect of temperature

organized as a result of physicochemical gradients. They typically

on geochemical parameters determined on the pyrolyzated

have steep gradients of oxygen and sulfide, and characteristically

samples was evidenced by the decrease of TOC content in the

are dominated by only a few functional groups of microbes:

original unheated sample from 3.88 wt% to 2.20 at 330C for

cyanobacteria, colorless sulfur bacteria, purple sulfur bacteria,

Figure 1. Microbial mat sample collected from Lagoa Vermelha, Rio de

20h. Biomarkers of liquid products also confirm the increase of

and sulfate-reducing bacteria. The organic matter of the

Janeiro, Brazil.

thermal evolution of the organic matter content in the sample. The

biomarker profile shown in Figure 2b strongly suggests the release

hypersaline microbial mats, including the lipid content, must also

be distributed according to this fine stratification which patterns

Results and Discussion

of compounds from the organic matter and the transformation to

may be complicated by strong seasonal salinity fluctuations in the

The cyanobacterial content characterization of microbial mat sample

the most stable structure at experimental conditions (e.g. Hop-

overlying water column. These variations may even involve shifts

identified fourteen species of cyanobacterias being the Microcoleus

17(21)-ene in the original unheated sample to -Hopane, -

of the predominant cyanobacterial species (e.g. from Microcoleus

chtonoplastes the predominant specie. This specie is known to be

Hopane and -Hopane in the expelled oil at 330C/20h).

to Aphanothece and vice versa) which represents a considerable

a halophilic species able to bear high concentrations of salinity (Das

increase in complexity when studying the biogeochemical

Sarma & Arora, 2001). Its predominance in the fabric of this type of


processes of these fluctuating environments (Grimalt et al., 1992).

microbial mat is justified by the fact that it develops predominantly

The occurrence of expelled oils and their biomarkers profile

Consequently, study of these mats may provide reference data for

in the supralittoral zone and withstands long periods of subaerial

during hydrous pyrolysis experiments, using a microbial mat

the understanding of the depositional processes occurring in the

exposure with increasing salinity and temperature conditions.

sample, evidenced the efficiency of this technique to simulate the

mats formed under seasonally fluctuating conditions. Therefore,

Results of palynofacies analyses showed that bacterial amorphous

transformation of organic matter content into liquid hydrocarbons

the main goal of this work is simulate the transformation processes

organic matter (AOM) is the most abundant group with 97.1%,

as well as, the potential of this type of organic material to generate

of organic matter in microbial mats from Lagoa Vermelha, Rio de

following by 1.7% of palynomorphs and 1.2% of phytoclasts.

hydrocarbons. These results will allow a possible correlation with

Janeiro, Brazil.

Two different AOM were observed in this sample pelicular (84.3%)

ancient microbial carbonates in Brazilian and foreign sedimentary

and in plates (19.1%), according Mendona Filho et al (2010).

basins for understanding their processes of formation and


Geochemical characterization of microbial mat shows that total

sedimentary diagenesis.

A sample of microbial mat (Fig. 1) was collected from Lagoa

organic carbon content in the sample is 3.88 wt%. This value

Vermelha, a small shallow hypersaline lagoon located on the coast

can be attributed to the fact that this microbial mat is composed


east of Rio de Janeiro, Brazil.

by alternating carbonate, and non-lithified organic layers (Fig. 1).

The authors are grateful to PETROBRAS-Brazil, FAPERJ and CNPq

Hydrocarbon fraction of the EOM shows the expected profile for

for the financial support. We would like to thank Dr. Rosane Nora

The sample was freeze-dried to geochemical characterization and

this type of sample,n-C17 was the most abundant n-alkane. The

from UFRRJ for her help in the protocol development for biomarker

xed in a 4% formaldehyde solution for microscopical analyses. The

occurrence of terpenes and sterenes and biological configurations


organic content characterization of the sample was performed by

was also observed (Fig. 2).











with chemometric treatment may become an innovative and

The authors thank CAPES (Brazilian research council) for

advantageous tool in the search for assessment of biodegradation

fellowships,Petrobras S/A andCPG UNICAMP for financial

of crude oils.The application of these tools involving the fingerprint


of environment samples were developed. With the application of

New Strategies Chemometric for Evaluation

of Biodegradation of Crude Oils By Gcxgc

these tools regions of the chromatogram or peaks with higher


importance in the description of biodegradation are estimates.

1 Abbas, O.; Rebufa, C.; Dupuy, N.; Permanyer, A.; Kister, j., 2008.


Paloma S. Prata, Noroska G. S. Mogolln, Fbio Augusto.

Figure 1. Profile of a non-biodegraded oil.

Assessing petroleum oils biodegradation by chemometric analysis of

spectroscopic data. Talanta75, 857-871.

Four Brazilian crude oil samples were selected because of their

a Universidade Estadual de Capinas, Instituto de Qumica, 13083970, So Paulo-SP, Brazil.

difference in biodegradation (A,B, C and D Sample). For sample

2 Sierra-Garca, I. N.; Alvarez, J. C.; Vasconcellos, S. P.; Souza, A. P.; Neto,

processing and analysis chromatographic grade n-hexane

E. V. S.; Oliveira, V. M., 2014. New Hidrocarbon Degradation Pathways

and n-pentane from TediaBrazil (So Paulo, Brazil) was used.

in the Microbial Metagenome form Braziliam Petroleum Reservoirs. PLOS

Approximately 100mg of each crude oil were weighed and

ONE9(2), 1-13.

desasphatated with 10 mL of n-pentane (4x). The concentration of

15 mg/mL was maintained for all samples.

Copyright 2014, ALAGO.

3 Peters, K. E.; Walters, C. C.; Moldowan, J. M., 2005, The Biomarker

guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments,

This paper was selected for presentation by an ALAGO Scientific Committee following

The lab-made GCGC-FID prototype was based on HP-6890

review of information contained in an abstract submitted by the author(s).

Series II GC-FID (Agilent, Santa Clara CA, USA). The column

set used consisted on a 30 m 0.25 mm 0.25 m SLB-5 ms


(5% phenylmethysiloxane) column (Supelco) connected through

Biodegradation of oil is a physicochemical process, which alters

a capillary of 1 m 0.20 mm to a middle polar Rxi-17 (50%

the composition and quality of the oil, increasing the concentration

phenylmethysiloxane) column (Restek) 1.0 m 0.15 mm 0.15

of asphaltenes and resins, reducing the amount of saturated and

m. The modulation period was set to 8.0 s and data acquisition

aromatic hydrocarbons1.Bacteria and microorganisms responsible

was performed at 100 Hz. The oven temperature was programmed

for biodegradation of oil in their tanks in the distance of millions of

from 70C for 330C at 2.5C min-1 with split 1:1; the injector and

years. The degradation of compounds by processes of microbial

detector temperatures were set at 300C and 350C, respectively.

activities and factors that enhance biodegradation are studied today

Hydrogen at 0.6 mL min-1 was used as carrier gas. The modulator

because of the degree of difficulty encountered in microbiological

used was the Loop with two turns using nitrogen gas, and

sampling of some species, and access to the oil reservoir2.

pressures in the cold jet valve 4 psi and 100 psi hot jet valve.
The chromatograms generated by GGxGC-FID of crude oils

Oil composition as measured by gas chromatography is dependent

were used to build the multivariate calibration model based on

upon the biodegradationOil composition carried out by gas

chemometric tool NPLs-DA, and were aligned routine developed

chromatography is dependent on the level biodegradation, and

at the Laboratory of Chemometrics in Analytical Chemistry,

the higher this level, the greater the unresolved complex mixture

UNICAMP. For the data processing Matlab version 2011and PLS-

(UCM)3. Because of the great number of individual components

toolbox software.

contained in the UCM, is particularly difficult to correlate oils using

gas chromatography. Because of the great number of individual

Results and Discussion

components contained in the UCM, is particularly difficult to

The figures below show the chromatographic profiles of the

correlate oils using gas chromatography3. By using comprehensive

samples. It is possible to observe the disappearance of lighter

two-dimensional chromatography, these problems could be

compounds, as well as reducing color that demonstrates the low

solved4. Comprehensive two-dimensional gas chromatography

concentration of these compounds.

withflame ionization detection (GCxGC/FID) applied to oil samples

Figure 2. Profile of a biodegraded iol.

The model had as objective the discrimination of oils for

biodegradability, separated into two distinct groups (biodegradable
and non-biodegradable). The validation was carried out by applying
samples with different levels of biodegradability. As expected,
samples from the calibration set were correctly predicted. It was

second ed., New Jersey.

4 Oliveira, C. R.; Oliveira, C. J. F.; Ferreira, A. A.; Azevedo, D. A.; Aquino

Neto, F. R., 2012. Characterization of aromatic steroids and hopanoids
in marine and lacustrinecrude oils using comprehensive two dimensional
gas chromatography coupledto time-of-ight mass spectrometry (GCxGCTOFMS). Org. Geochem.53, 131-136.

found that all chromatograms employed in the model building held

a high range of information and were extremely diversified among
themselves. Moreover, it was possible to identify compounds which
have been degraded and compounds that appear with increased
biodegradability. Based on this model, the regression coefficients
thus facilitating the visualization of the variables of greatest
relevance in the model building NPLs-DA, which were correlated
with the compounds responsible for the biodegradation, using the
calculated retention index was obtained.

The application of chemometric tools was essential in the

evaluation of data of a complex nature. Its application enabled
the simplification of data, highlighting the relevant information and
reducing noise.

The chemometric tool NPLs-DA was essential to correlate the
level of biodegradability with the information obtained from the

surpasses typical GC, and so have been applied for more accurate

two-dimensional chromatograms, due to its greater increase in

determination of the level of biodegradation.

detectability, offered by the compression of the chromatographic

band modulator. So this worked presented a potential tool for

Given the wealth of information obtained from the data acquisition

predicting the level of biodegradation in large sample sets.



Tarball Characterization by Esi(-) Ltq Xl

tarball sample deposited at Taipus de Fora beach, located in the


southeastern state of Bahia, Brazil. The region is located near

We conclude that the tarball sample has higher abundance of

active offshore oil production and shipping routes.

oxygen classes, but the oxygen species are not useful as conserved
internal polar markers to identify origin of tarballs. We also estimate


that the time after the oil spill that originates the tarball sample is

Laercio L. Martinsa, Hilda L. A. Bastosa, Clio F. F. Angolineb, Anita

The tarball sample collected at Taipus de Fora beach was

more than 511 days. Other tarball samples from Taipus de Fora

J. Marsaiolib, Eliane S. de Souzaa, Georgiana F. da Cruza*

crushed and pulverized before oil extraction with dichloromethane

beach will be analyzed in a higher resolution and higher mass

solvent using Soxhlet system. The oil obtained was fractionated

Figure 1. Distribution of heteroatom classes determined by ESI(-) LTQ XL

accuracy analytical techniques to confirm the results obtained in

a Laboratory of Engineering and Petroleum Exploration, Darcy

in asphaltene and maltene fractions using n-pentane, and

Orbitrap mass spectra to asphaltene fraction of tarball sample.

this study, and also to assess potential species (i.e. NS class) as

Ribeiro North Fluminense State University LENEP/UENF, Maca,

the asphaltene was purified in Soxhlet system3. The tarball

a conserved internal polar markers to indentify the origin of these

RJ, Brazil;

asphaltene and maltene fractions were dissolved at 0.5 mg mL-1


b Chemistry Institute, University of Campinas - UNICAMP, POB

in toluene:methanol (1:1 v/v) with 0.5% of NH4OH prior to LTQ XL

6154, 13084-971 Campinas, SP, Brazil.

Orbitrap analysis.

The authors thank PRH20-ANP, LENEP/UENF and IQ/UNICAMP,


Results and Discussion

and Petrobras/Rede de Geoqumica for providing the necessary

The relative abundance of heteroatom classes in the asphaltene

infrastructure to conduct research.

Copyright 2014, ALAGO.

and maltene fractions of the tarball sample is presented in Figure 1

This paper was selected for presentation by an ALAGO Scientific Committee following

and Figure 2, respectively. The compound classes indentified are

Figure 2. Distribution of heteroatom classes determined by ESI(-) LTQ XL


review of information contained in an abstract submitted by the author(s).

characterized by the type and the number of heteroatoms. Only

Orbitrap mass spectra to maltene fraction of tarball sample.

1 Wang, Z., Fingas, M., Yang, C., Hollebone, B., 2004. Biomarker

the detected heteroatom classes of >1% of the total summed

Fingerprinting: Application and Limitation for Correlation and


relative abundances are presented (O2, O3, O4, N, NO, NO2,

In a study with weathered samples collected as oil residues from

Source Identification of Oils and Petroleum Products. Prepr. Pap.-

Due to the wide variety of geological conditions and ages under

NO4, N2O4 classes). The relative abundance for the N and N2 are

the motor vessel (M/V) Cosco Busan oil spilled4, it was found that

Am. Chem. Soc., Div. Fuel Chemistry 49 (1), 331.

which oil has formed, every crude oil exhibit an essentially unique

also showed, although these classes have low relative abundance

compounds which contain one nitrogen (N1) generally decrease

biomarker fingerprint. Therefore, chemical analysis of source-

(<1%), since these are important for the distinction of potential spill

in relative abundance with increased exposure, whereas classes

2 Stout, S. A., Uhler, A. D., McCarthy, K. J., Emsbo-Mattingly, S.,

characteristic and environmentally-persistent biomarkers generates

sources according to a previous work4.

containing oxygen increase in relative abundance with increased

in: Introduction to Environmental Forensics (B. L. Murphy and R. D.

length of exposure. In this work, we also observed higher abundance

Morrison, eds.), Academic Press, London, 2002, Chapter 6.

information of great importance in determining the source of spilled

oil, differentiating oils, monitoring the degradation process and

The O2 and O4 classes represent acidic compounds, presumably

of oxygen compounds (like O2, O4, NO classes abundances

weathering state of oils under a wide variety of conditions1,2.

carboxylic and dicarboxylic acids, and it is expected that these

showed in Figure 1 and Figure 2) which is in agreement with the

3 Azevedo, D. A., Silva, T. F., Silva, D. B., 2009. Avaliao

The spilled oil generally form tarballs, which are soft clumps of

classes present higher relative abundance in the tarball sample

fact that this kind of compounds are products of biodegradation

geoqumica de biomarcadores ocludos em estruturas asfaltnicas.

weathered oil, mingled with sand, and other beach material,

and the N and N2 classes present least relative abundance, since

and photo-oxidation, which are processes that weathered samples

Qumica Nova, 32 (7), 1770-1776.

ranging from the size of a pinhead to larger chunks.

this sample is severely biodegraded. Among the OO classes,

like tarballs have undergone. Thereby, oxygen species in oils spilled

the O1 class showed the lowest abundance. Alcohols, mainly

not remain consistent into marine environment after the oil release

4 Corilo, Y. E., Podgorski, D. C., McKenna, A. M., Lemkau, K. L.,

Normally, the identification of spilled oil source is performed using

phenols, which are considered as intermediates in a number of

and this kind of compounds are not useful as a conserved internal

Reddy, C. M., Marshall, A. G., Rodgers, R. P., 2013. Oil Spill Source

biomarker diagnostic parameters obtained by GC analysis1.

biodegradation pathways of petroleum components, dominate this

polar marker to identify oil spill source of tarballs.

Identification by Principal Component Analysis of Electrospray

However, GC-based analytical techniques are restricted to light

class5. These intermediates compounds may be almost completely

petroleum components and have limited application for polar

consumed during further biodegradation. The relative abundance

According to the cited study about M/V Cosco Busan oil spilled4,

compounds analysis such as the N, NO, NS, O2 heteroatom

of N1OO classes is high to this sample, which is in agreement

the relative abundance of N species remains consistent up until

species. Thus, biomarker diagnostic parameters fail to identify

with the fact that the compounds in these classes appears to be

day 511 and after 617 days, the relative abundance of nitrogen-

5 Liao Y., Shi Q., Hsu, C. S., Pan, Y., Zhang, Y., 2012. Distribution

weathered products generated after the spill, such as oxidized

biodegradation products of N-containing compounds, it being

containing classes (NS, NO and N1) decrease concomitantly and

of acids and nitrogen-containing compounds in biodegraded

species. Thus, electrospray ionization (ESI) high-resolution mass

formed, for example to the N1O2 class, from ring opening of

coincide with an increased abundance of O2 species (naphthenic

oils of the Liaohe Basin by negative ion ESI FT-ICR MS. Organic

spectrometry such as LTQ Orbitrap can be used for characterize oil

hydroxyl dibenzocarbazoles with additional of a carboxyl group5.

acids). The higher concentration of oxygen species in the sample

Geochemistry 47, 51-65.

Ionization Fourier Transform Ion Cyclotron Resonance Mass

spilled (tarball) and can be useful to monitor compositional changes

effectively suppresses the ionization efficiency for less acidic

in polar fractions in order to estimate the time after oil spills.

species, such NS, N and N2 heteroatom class compounds. This

Spectra. Analytical Chemistry, 85, 90649069.

effect can be observed in the Figure 1 and Figure 2, which show

The main goal of this study is polar fraction characterization to

lower relative abundance to the N and N2 classes. Based on this,

examine the time after the oil spill, and the possible origin of one

it can be estimate that the time after the oil spill that originated this
tarball sample is more than 511 days.



widened the range of analyzed compounds. Here we selected four


different oil samples sharing the same source rock and of similar

CNPq; ANP (Brazilian Petroleum Agency),FAPESP


maturity level, of different biodegradation levels(Figure 1)

Using O-containing acidic polar compounds

of biodegraded petroleum as biomarker of

Microbial degradation of phenanthrene and

methylphenanthrenes in
laboratory conditions

Cruz, G.F.; Angolini, C.F.F.; Dellagnezze, B.M.; Garcia, I.N.S.; Oliveira, W.M.;
Santos Neto, E.V.; Marsaioli, A.J. 2011,Could petroleum biodegradation be

Clio Fernando Figueiredo Angolinia, Ramss Capillab, Anita

a joint achievement of aerobic and anaerobic microrganisms in deep sea

Gabriel Sousaa, Laercio L. Martinsa, Georgiana F. da Cruzaa*,

Jocelyne Marsaioliaa*

reservoirs? AMB Express 1, 47.

Bruna M. Dellagnezzeb, Valria M. de Oliveirab

a State University of Campinas, Chemistry institute, P.O. Box

Head, I.M., Jones, D.M., Larter, S.R., 2003. Biological activity in the deep

a Laboratory of Engineering and Petroleum Exploration, Darcy

6154, CEP 13083-970, Campinas-SP. B) Organic Geochemistry /

subsurface and the origin of heavy oil. Nature 426, 344352.

Ribeiro North Fluminense State University LENEP/UENF, POB

Figure 1. The O2 class abundance increased with biodegradation.

CENPES Petrobrs

119562, 27910-970 Maca, RJ, Brazil;

Kim, S.; Stanford, L. A.; Rodgers, R. P.; Marshall, A. G.; Walters, C. C.;

b Microbial Resources Division, Research Center for Chemistry,

Qian, K.; Wenger, L.M.; Mankiewicz, P. 2005,Microbial alteration of the

Biology and Agriculture (CPQBA), University of Campinas

In non-biodegraded samples there is a predominance of linear

acidic and neutral polar NSO compounds revealed by Fourier transform ion

UNICAMP, CEP 13148-218, Paulinia, Brazil.

Copyright 2014, ALAGO.

carboxylic acids (DBE 1), but in our samples of biodegradation

cyclotron resonance mass spectrometry. Organic Geochemistry 36, 1117-

This paper was selected for presentation by an ALAGO Scientific Committee following

level equal 2, the aliphatic carboxylic acids were not so abundant.



review of information contained in an abstract submitted by the author(s).

Additionally we observed that their depletion increased at higher

biodegradation levels as these compounds are in turn biodegraded

Larter, S., Wilhelms, A., Head, I., Koopmans, M., Aplin, A., Di Primio, R.,

Copyright 2014, ALAGO.


after the hydrocarbons In general, each DBE class abundance

Zwach, C., Erdmann, M., Telnaes, N., 2003. The controls on the composition

This paper was selected for presentation by an ALAGO Scientific Committee following

Microorganisms degrade petroleum following different biological

increase at the beginning of the biodegradation process followed

of biodegraded oils in the deep subsurface-part 1: biodegradation rates in

review of information contained in an abstract submitted by the author(s).

pathways (Widdel and Rabus, 2001; Prince et al., 2002) at rates

by an abundance decrease at higher biodegradation levels (Figure

petroleum reservoirs. Organic Geochemistry 34, 601613.

that strongly depend on the availability of inorganic and organic

2). Those oscillations synchronize with those observed in the

electron acceptors (Head et al., 2003; Larter et al., 2003).. These

analyses of the corresponding hydrocarbon

Prince, R.C., 2002. Petroleum and other hydrocarbons, biodegradation

Many compounds present in petroleum, like polycyclic aromatic

biological transformations lead to the systematic alteration of the

of. In: Britton, G. (Ed.), Encyclopedia of Environmental Microbiology. John

hydrocarbons (PAHs), are recalcitrant and may long persist in

crude oil chemical and physical properties e.g., degraded oils

Wiley, New York, pp. 24022416.

the environment. The PHAs, including phenanthrene (P) and

have higher specific gravity, viscosity and heteroatom-containing

methylphenanthrenes (MP), are generated in large quantities and

compounds are more abundant (Kim et al., 2005), which are are

Vasconcellos, S. P; Crespim, E.; da Cruz, G.F.; Senatore, D.B.; Simioni,

introduced in the environment mainly due to the use of oil-related

more resistant to microbial catabolism than pure hydrocarbons.

K.C.M.; dos Santos Neto, E. V.; Marsaioli, J.M.; Oliveira, V.M.; 2009.

activities and derivatives. These compounds are less susceptible

In particular, the carboxylic acids which are produced during the

Isolation, biodegradation ability and molecular detection of hydrocarbon

to biodegradation than other hydrocarbons due to the complexity

biodegradation have a correlation with this process, prompting us

degrading bacteria in petroleum samples from a Brazilian offshore basin.

of their chemical structure and low water solubility1. Currently, the

to use them as marker of biodegradation extension in petroleum

Organic Geochemistry, 40, 574-588.

bioremediation is the most applied strategy for the removal of such


compounds from the environment. This technique employs living

Figure 2.

In this work we used four oil samples obtained in July 2005 from a
Pampo Sul Oilfield production platform in the Campos Basin.These

Widdel, F., Rabus, R., 2001. Anaerobic biodegradation of saturated and

organisms aiming at the mineralization of pollutants, resulting in the

aromatic hydrocarbons. Current Opinion in Biotechnology 12, 259276.

removal or attenuation of the pollutant compounds to less harmful

products in the contaminated area2. In this context, the aim of
this study was to investigate the PHAs degradation ability of four

samples showed distinct biodegradation levels (Figure 1), and were


previously studied by Vasconcellos et al. (2009) and Cruz et al.

Similar to the biodegradation ofthe hydrocarbons we understand

(2011).The acidic fractions all oil samples were extractedwith silica

that biodegradation of O-containing compounds occurs in a

/ KOH (25g KOH for 200g of silica) in a soxhlet apparatus.

sequential way, with biodegradation of less complex structure

(lower DBE) over more complex structure (higher DBE). Also

Results and Discussion

the O-containing classes are more recalcitrant than their

The relationship between the carboxylic acids and biodegradation

corresponding hydrocarbons, but they are quickly biodegraded

has been a topic of research in our lab for the last 15 years, and the

when their precursors are depleted. These classes were pointed

access to fast analyses like petroleomics (Rodger et al., 2005) has

out biodegradation biomarkers.


bacterial strains, four metagenomic clones and clone consortium.

The evaluation was performed in artificial seawater microcosms
by comparison between the composition of samples which were
exposed to the microorganisms and the control samples using
crude oil as carbon and energy source.

The metagenomic clones (2B, 1A, 9E and 10A), bacterial
strains (Dietzia maris, Micrococcus sp, Bacillus subtilis and

Achromobacter alcanovirax) and the consortium (clone pool) were

revealing great potential for further biotechnological applications.

microbial catabolism under varying conditions6. The metagenomic

derived from Brazilian petroleum reservoirs (Campos Basin, RJ and

Furthermore a considerably high biodegradation potential was

clones (individually or in consortium), in general, showed the

Potiguar Basin, RN). The assays were performed in triplicate and

confirmed for phenanthrene and methylphenanthrenes mainly

following order of susceptibility of biodegradation of the MPs:

incubated in rotational shaker, 120 rpm, at 37 C for the clones

by clones 2B and 10A and the bacterial strains D. maris and

3-MP>2-MP> 1-MP~9-MP. No preferred order of degradation for

and at 28 C for the bacterial strains. The microcosms were

Micrococcus sp. (Figure 2).

the bacterial strains was observed.

monitored for 21 days, being evaluated for petroleum degradation


each seven days. Triplicate erlenmeyer flasks were sacrificed

Orinoco Oil Belt Crudes Produced by
Differential Biodegradation

Results showed that under the conditions used in this experiment,

at each time point (0, 7, 14 and 21 days) and oil extraction was
carried out following the methodology previously described by
da Cruz et al. (2008)3. The extracted oil was then separated into

clones 2B and 10A, bacterial strains Micrococcus sp. and Dietzia

Copyright 2014, ALAGO.

maris (CBMAI 705) and clone pool exhibited a considerably high

This paper was selected for presentation by an ALAGO Scientific Committee following

bioremediation potential in the biodegradation of phenanthrene

SARA components: saturated, aromatic and polar fractions using

and methylphenanthrenes.

silica gel column chromatography. Phenanthrene (m/z 178) and

methylphenanthrenes (3-MP, 2-MP, 9-MP and 1-MP, m/z 192)


were analyzed by CG-MS using SIM mode.

The authors thank CNPq for fellowships, PRH20-ANP, LENEP/

UENF for financial support and Petrobras/Rede de Geoqumica

Results and Discussion

for providing the necessary infrastructure to conduct research.

Severely biodegraded oils are generally enriched in polar

B.M.D. was supported by grants from FAPESP (process number

compounds and depleted in saturated hydrocarbons. Results


obtained from SARA analysis allowed to evaluate the proportion of

these compounds and estimate qualitatively which microorganisms

Figure 2. Biodegradation rate of the phenanthrene and MPs from the


are potentially degraders. This analysis showed a predominance

extracts of the control sample and all microcosms evaluated during the

1 Alexander, M., Biodegradation and Bioremediation, Academic Press,

of polar components in all samples after 21 days, revealing that

biodegradation experiment.

New York, 1994.

During the biodegradation experiment, the most distinct change in

2 Fernandez-Luqueno et al., 2011. Microbial communities to mitigate

abundance of phenanthrene was observed for the metagenomic

contamination of PAHs in soil-possibilities and challenges: a review.

clones 2B and 10A, that consumed more than 90% of this

Environmental Science and Pollution Research 18, 12-30.

all microorganisms are potentially degraders, especially clones 2B

and 10A and the bacteria D. maris and Micrococcus sp. (Figure 1).

compound after 21 days. Among the bacterial strains, Micrococcus

sp. was the most efficient in biodegrading phenanthrene with rates

3 Da Cruz, G. F., Santos Neto, E. V., Marsaioli, A. J., 2008. Petroleum

> 99% compared to the control sample.

degradation by aerobic microbiota from the Pampo Sul Oil Field, Campos
Basin, Brazil. Organic Geochemistry 39, 1204-1209.

The degree of alkylation is a critical factor controlling the rate of

PHAs biodegradation. Normally, the rate decreases with increasing

4 Huang, H., et al., 2004. The effect of biodegradation on polycyclic

number of alkyl substituents4. However, in this study, when using

aromatic hydrocarbon in reservoired oils from the Liaohe basin. NE China.

D. maris and A. alcanovirax, MPs concentrations decreased faster

Organic Geochemistry 35, 1619-1634.

than that of phenanthrene. MPs abundance also underwent a

5 Budzinski, H., et al., 1998. Aerobic biodegradation of alkylated aromatic

significant decrease during this experiment. The clones 2B and

hydrocarbons by a bacterial community. Organic Geochemistry 28, 337-

10A also were more efficient in this case, but not as prominent


as that of phenanthrene, since after 21 days they biodegraded 70

and 64%, respectively, compared to the control sample. On the

6 Peters, K. E., Walters, C. C., Moldowan, J. M., 2005. The Biomarker

other hand, D. maris was the most efficient in the degradation of

Guide. Biomarkers and Isotopes in Petroleum Systems and Earth History,

MPs compared to the phenanthrene, consuming more than 99%

vols. 1 and 2, Cambridge University Press, USA, p. 1155.

review of information contained in an abstract submitted by the author(s).

During the process of quantification and certification of reserves
of the Orinoco Oil Belt (FPO), a set of samples of crude oil
(100), core and wall (262), were collected. Also, geochemical
characterization was performed. With the precedent data, it was
established the presence of oil groups having different degrees
of altering compounds highlighting two trends of homohopanes
biodegradation. The first trend involves the formation of 25 norhopanes, while the second one implies the absence of 25 norhopanes, as it has previously been reported by Peters et al., 1996,
for other basins.S ASdditional samples were identified where the
order of alterSed compounds, commonly employed in determining
the level of biodegradation of crude oil, appears to differ from that
proposed by the traditional scales.
The aim of this study isS(sin coma), Sto define the implications of
biodegradation in the generation of different groups of crudeSs in
the Orinoco Oil Belt.

API gravity and concentration of S, V, and Ni were determined in
crude samples. Extracts were obtained from wall-core samples with
dichloromethane. Both, the extract and Scrudes were separated
into fractions of saturates, aromatics, resins and asphaltenes
(SARA) using the HPLC technique. The saturated fraction was
analyzed Swith a gas chromatograph with a FID detector and GCMS, while the aromatics, were analyzed by GC-MS.

Results and Discussion

In this study, only samples that are thought to have a common
origin and that show no evidence of crude mixtures were analyzed.
This has been done for the purpose of determining the sole effect
of biodegradation on the generation of different oil types.
Based on the different stages of biodegradation, the oils were
classified into four groups according to the characteristics observed
in the gas chromatograms C15 +, analysis of fragmentograms m/z:
191, 177, 217, 218, and 412 of the saturated fraction and m/z:
192, 198, 178, and 184 of the aromatic fraction. This allowed S to
group the oils as follows:

after 21 days. The clone pool biodegraded more than 80% of

Figure 1. Ternary diagram of SARA analysis.

phenanthrene and about 60% of MPs after 21 days.

Group 1, presents steranes unchanged, 25-norhopanes and

demethylated terpanes. (Fig 1 A)

Studies of crude oil biodegradation in reservoir and in laboratory

Group 2 shows presence of 25-norhopanos and no steranes.

(Fig 1 B)

conditions5 indicate that the 9-MP is less susceptible to

The investigated microorganisms also showed high percentages

biodegradation than other MPs isomers, as observed in this study,

of biodegradation of n-alkanes and isoprenoids (data not shown),

Group 3, shows partly-altered hopanes, unaltered steranes and

the first members of the 25-norhopanes (C31 - C33).

except for the D. maris, reflecting differences in the rate of the



demethylated terpanes in the m/z 177. B - Steranes removed in the m/z

Group 4, presents 25-norhopanSes, steranes and hopanes

completely removed and demethylated tricyclic terpanes.

217 and presence of 25-norhopanSeos in the m/z 177.

Four oil groups were found to be generated by different processes
of biodegradation.

An important feature is that in group 2, the quality parameters such

as API gravity, viscosity and %S and SARA are similar. However,
the samples of group 3, having similar values of API gravity, and
SARA composition have viscosities at 40 C ranging from 14149
to 318232 mm2/s; this could indicate that, although they seem
to have the same degree of biodegradation, according to the
parameters studied, a number of compounds that are preferentially
biodegraded in various crudes. This biodegradation seems to
depend on the areal and vertical location of the samples. This
in turn, could be caused by specific bacterial communities and
reservoir conditions, as pointed Peters et al., (2005).

The process that generates the most significant changes in the

oils of the FPO, seems to be the differential biodegradation of
This work revealed at least three distinct stages of biodegradation
for the same level of biodegradation of the Peters and Moldowan
The correlation between quality parameters and oil groups
generated by biodegradation could be useful for exploitation

Similarly to homohopanes, alteration of tricyclic terpanes appears

to follow two trends. The first one involves an alteration which
starts during the homohopanes demethylation or before and
continuing even when these compounds have been completely
removed; in this case demethylated tricyclic terpanes are present.
The second trend involves the degradation of steranes, prior to the
homohopanes and no apparent signs of degradation of tricyclic
terpanes in demethylated; in this case tricyclic terpanes are not
observed. Although some authors such as Connan (1984) and Lin
et al. (1984), indicate that tricyclic terpanes are altered at a similar
level of biodegradation as diasteranes (> 8 pm), we found in this
area biodegradation that is consistent with the proposal by Alberdi
et al., (2001), who concluded that demethylation of terpanes
occurs during the destruction of steranes and demethylation of
hopanes, although at a lower rate.

Evaluation of crude (COL) as a standard in
compound-specific isotope analysis of C15+
in saturated fraction of crude oils
Delfn E. Rivas, Miriam M. Daz, Felipe R. Quintero
Petrleos de Venezuela PDVSA-Intevep, Gerencia General de
Exploracin, Gerencia Departamental de Investigacin Estratgica
(EYIE), Caracas 1070-A, Republica Bolivariana de Venezuela

The sample path started in the injection port at 250 C where it is

volatilized and introduced into the capillary column (OV-1, 60m x
0.32 mm ID, 0.25 m film thickness) with a gas flow drag of 1.5 ml /
min at an initial temperature of 30 C for 3 min. Subsequently, three
heating ramps were used starting at 10 C / min to 100 C for 1
min then with 4 C / min to 220 C for 1 min and finally 10 C / min
until 300 C for 10min. After separation of sample components,
the products are directed towards the oxidation reactor at 980 C
according to their retention time, where they are oxidized producing
CO2, NOx and H2O. Successively, these gases are passed to a
reduction reactor at 650 C where NOx are transformed into N2
and excess of O2 is eliminates before that, the products pass
through a water trap comprising a tubular Nafion membrane which
is responsible for removing H2O.Finally, the sample is introduced to
the IRMS through a open Split system where carbon isotope ratios
in the form of CO2 were analyzed for each separate compound.

Results and Discussion

Figure 1 shows gas chromatogram of C15+ saturated fraction


Copyright 2014, ALAGO.

of COL-5X obtained with the GC-C-IRMS. good separation of

The authors would like to thank PDVSA - Intevep / CVP for allowing
the publication of the data and the conduct of this study.

This paper was selected for presentation by an ALAGO Scientific Committee following

n-alkanes from n-C15 to n-C32 including isoprenoids as pristane

review of information contained in an abstract submitted by the author(s).

(Pr ) and phytane (Ph) was observed. Furthermore, the absence of

Alberdi M., Moldowan J.M., Peters K.E. and Dahl J.E. (2001). Stereoselective
biodegradation of tricyclic terpanes in heavy oils from the Bolivar Coastal
Fields, Venezuela. Organic Geochemistry, 32, pp. 181191
Connan, J. (1984) Biodegradation of crude oils in reservoirs. In: Advances
in Petroleum Geochemistry, Vol. 1 (J. Brooks and D. H. Welte, eds.),
Academic Press, London, pp. 299-335.
Hudges W.B. (1984). Use of thiophenic organosulphur compounds in
characterizing of oils derived from carbonate versus siliciclastic sources.
In: Palacas G., ed., Petroleum Geochemistry and Source Rock Potential of
Carbonate Rocks: AAPG Studies in Geology, No. 18, 181-196.
Lin, L. E., Michael, G. H., Kovachev, G., et al. (1989) Biodegradation of tarsands bitumens from the Ardmore and Anadarko basins, Carter County,
Oklahoma. Organic Geochemistry, 14, 511-23.
Peters K., Moldowan M., McCaffrey M. and Fago F. (1996). Selective
biodegradation of extended hopanes to 25-norhopanes in petroleum
reservoirs. Insights from molecular mechanics. Organic Geochemistry. Vol.
24, No. 8/9, pp. 765 - 78.
Peters, K., Clifford, W. y Moldowan, J. (2005). The biomarker guide (V. II),
2 Ed. Cambridge: Press Syndicate of the University of Cambridge. 1155 p.

Compounds-specific isotope analysis (CSIA) consists essentially
on the separation of complex mixtures with help of gas
chromatography (GC), followed by the combustion (C) or pyrolysis
(P) of each of the separated compounds. Finally, the isotope ratios
of these compounds are analyzed individually in the isotope ratios
mass spectrometer (IRMS).

This paper shows the first steps of PDVSA-Intevep in the

development of methods for Compounds-specific isotopic
analysis for different mixtures of geochemical interest. The purpose
of this work is the evaluation of crude COL-5X as a standard in
compound-specific isotope analysis of C15+ in saturated fraction
of crude oils using GC-IRMS for isotope measurement.

Sample pretreatment involves weighing the C15+ saturated fraction

of COL-5X and dilution in hexane (HPLC reagent grade, Honeywell)
to a final volume of 1ml for subsequently injecting 5 l in the GCC-IRMS where the gas chromatograph (GC) used was Trace GC
Ultra with the GC combustion (C) III as interface coupled to (IRMS)
model Delta V plus, all these equipment manufactured by Thermo.

suffered apparently biodegradation process. This is an excellent

finding because the COL-5X can be proposed as a potential internal
standard for the PDVSA Intevep CSIA stable isotope laboratory.

CSIA has been widely used in the characterization of crude oils

which provide important indication of the origin and represents
a possibility to correlate crude-crude and crude-source rock.
In addition, it provides the opportunity to identify processes of
maturation, migration and biodegradation because of individual
isotopic composition changes in these events. Furthermore, it has
been demonstrated that 13C individual values, of n-alkanes and
isoprenoid saturated oil fraction, show a variation with maturation
(Bjory et al 1992, 1994a, b). For this reason, the study of this
fraction of crude oil is very important while cyclic and aromatic
hydrocarbons isotopic values are not affected in the maturation
process. Biodegradation studies have shown heavy isotopic values
of n-alkane because biodegradation processes are preferential for
removing the lighter isotopes(Clayton, 1991).


Fig.1. A - Steranes unchanged in the m/z 217, 25-norhopanSeos and

Unresolved Complex Mixture (UCM) suggest that COL-5X has not

Figure 1.Gas chromatogram of C15+ saturated fraction of COL-5X obtained


After optimizing the chromatographic conditions for the separation

of C15+ saturated fraction of COL-5X, the reproducibility of 13C
measurements were evaluated for each separate n-alkanes
including isoprenoid. For that, 30 measurements were made
obtaining a standard deviation of 0.5 which is characteristic
for this type of analysis.Furthermore, Figure 2 shows that 13C
measurements for different n-alkanes and isoprenoids were similar
to each other with an average and standard deviation for all values
of -29.4 0,4 .



The potential of CSIA for determining source is shown in Figures 1 and

2. Can be seen in Figure 1, the gas chromatogram shows that the
n-alkane distribution is characteristic of a crude oil of marine source.
This observation is consistent with Figure 2 which shows a linear trend
typical of the crude oil of marine source (Guthrie et al., 1996).

Acetate in formation waters at the

southeast of the Maracaibobasin
Beatriz Anguloa*, Frank Cabreraa, Jos Centenoa, Ramn
Monterob, Eyleen Riveroc
a PDVSA INTEVEP, Gerencia de Investigacin Estratgica en
Exploracin y Yacimientos; Los Teques, Venezuela,
b Instituto de Ciencias de la Tierra, Universidad Central de
Venezuela, Caracas, Venezuela
c PDVSA INTEVEP, Gerencia de Qumica Analtica, Los Teques,

Figure 2. 13C values of C15+ saturated fraction of COL-5X .

chloride, bromide, sulfate, carbonate, bicarbonate, acetate and

components of analyzed waters in this study. Since acetate and

formiatewere determined. For cation analysis was prepared 20

bicarbonate are different chemical species, it is expected that

mL aliquot of each sample. Prior to analysis these samples were

the chemical behavior of water to be different, depending on the

filtered using 0.20 m poreTeflon membranes, in order to exclude

proportion of these anions. If each of these species are quantified

colloidal species.

independently, is obtained that for M2 and M3, the major anion is

the chloride and acetate M1.

Ca, Mg, Na and K were analyzed using inductively coupled

plasma optical emission spectroscopy (ICP-OES) technique with a

A direct consequence of discriminating alkalinity components is

Teledyne Prodigy equipment.

to know the actual concentration of bicarbonate in the samples,

allowing a more accurate way to estimate rates of carbonate

Analyses of carbonate and bicarbonate were performed according

to titrationtechnique, during the first 72 hours. Titrations were
carried out with sulfuric acid (Hach standardized 0.16 N) and
phenolphthalein and bromocresol green indicators (Hach).

Chloride, bromide, sulfate, acetate and formiate anions were

The results obtained shows that the COL-5X can be used as a
standard in Compounds-specific isotopic analysis.
Carbon isotopic analysis of individual hydrocarbon compounds is
an useful tool used to determine the source of an oil


The authors thank to Strategic Research Department in Exploration
(EYIE) and the Stable Isotope Laboratory of PDVSA-Intevep for
providing full support to this work.

These models allow us to estimate the possibility of formation

chromatography using a DIONEX equipment ICS-3000 with a 4

information that facilitates decision-making in the field of

This paper was selected for presentation by an ALAGO Scientific Committee following

x 250mm IonPac AS18 column and KOH as mobile phase with

environmental management and studies of secondary oil recovery.

review of information contained in an abstract submitted by the author(s).

gradient concentration. The amperage was modified of 120mA to

Furthermore, these anions of carboxylic acids associated with oil

15mA specifically for the detection of formiate and acetate.

reservoirs can play an important role in processes of diagenesis to

concentrations in oilfields, constituting 99% of the alkalinity

Bjory,M.,Hall,P.B.,Hustad,E.,Williams,J.A.,1992. Variation in stable carbon

reported in some formation waters(Kharaka y Harnor, 2003).

isotope ratios of individual hydrocarbons as a function of artificial maturity.

Their presence is not detected since generally the most abundant

of single components in the C4C20 fraction of oils and condensates.

of all carboxylic anions, acetate anion has an equivalent point

Organic Geochemistry 21,761776.

similar to bicarbonate anion. This is why it is wrongly assumed that

act as ligands which facilitate formation of complexes of elements

Results and Discussions

such as aluminum, iron, lead and zinc(Kharaka y Harnor, 2003).

The five waters are considered Na-HCO3 type as is shown in Figure

1 (a). This however, would be different when discriminating the
contribution to alkalinity by carboxylic acid anions, see Figure 1 (b),
given that the determination of bicarbonate anion using the titration
technique is indirect and does not allow distinguish between the
equivalence point of bicarbonate and acetate.

Carboxylic acid anions acetate and formiate contribute between 48
and 70% of total alkalinity for the 5 wells tested.
The determination of the anions of organic acids in petroleum
reservoirs at temperatures between 80 C and 160 C is important

the alkalinity is provided exclusively by carbonate and bicarbonate

because its estimate allows a better understanding of processes as

anions when is determined by titration method.

n-alkanes in Central Graben oils. Organic Geochemistry 22,355381

areas of the oil industry.

Copyright 2014, ALAGO.


Bjory,M., Hall,P.B.,Moe,R.P., 1994b. Stable carbon isotope variation of

models of carbonates saturation indexes more accurate in various

of carbonate precipitates around wells and pipes. Also generate

Anions of carboxylic acids (AAC) can be present in high

Bjory,M.,Hall,P.B.,Moe,R.P.,1994a. Variation in the isotope composition

Determining concentrations of acetate is useful for generating

filtered using 0.45 m poreTeflon membrane and analyzed by liquid


Organic Geochemistry 19,89105.

analyzed from an aliquot of 20 mL of each sample, previously

mineral saturation.

mineral dissolution and precipitation, affecting models of porosity

Clayton,C.J., 1991. Effect of maturity on carbon isotope ratios of oils and

An over-estimation of bicarbonate values in water alters the results

condensates. Organic Geochemistry 17,887899.

of geochemical modeling of water for prediction of formation

and permeability of the reservoir.

damage by clogging or carbonate scales, estimating support for

Guthrie,J. M., Trindade, L. A. F., Eckardt, C. B. and Takaki, T. 1996.

This leads to better predictive models of the behavior of the water,

water injection secondary recovery processes and estimation of

Molecular and carbon isotopic analysis of specific biological markers:

evidence for distinguishing between marine and lacustrine depositional

fouling behavior of produced waters intended for reuse (Zhang y

environments in sedimentary Brazil. Presented at the Annual Meeting of the

Dawe, 1995; Kharaka y Harnor, 2003; Cantucci et al. 2009).

which in turn allow better management of reservoir productivity and

produced water management.

American Association of Petroleum Geologists.


Additionally, the action of organic acids as ligands has important

Authors want to thanks PDVSA Occidente for its support during

implications in the reactive metal transport (Fein, 1991).

sample collection.



Five producers oil wells were selected in a depth range from4734mto

Cantucci, B.; Montegrossi, G.; Vaselli, O.; Tassi, F.; Quatrocchi, F.

5444mand temperatures between 96oC and 120oC with water

y Perkins, E.,2009. Geochemical modeling of CO2 storage in deep

cut higher to 30% depending on their potential to present organic

anions dissolved in water.
Cationssodium, potassium, calcium and magnesium and anions

Figure 1.AAC contribution in the composition of waters

reservoirs: The Weyburn Project (Canada) case study, Chemical

Geology,265, N 12, 181-197.

As shown in Figure 1, acetate is one of the major anionic


Fein, J., 1991. Experimental study of aluminum-, calcium-,


In this work, compounds (3b), (4b), (5b), (6b) and (8b) were

(8a) in the oil sample, even though the less abundant.Furthermore,

synthesized and co-injected with an oil sample derivatized to

compound (4b) was observed, so identifying acid (4a), which was

Synthesis of 3-n-propylergostane biomarkers.

Structural proof of 3-n-propylergostanoic
acids identified in Campos basin oils.

hydrocarbons to confirm the structures proposed by Lima et

not previously reported.

and magnesium-acetate complexing at 80C, Geochimica et

Cosmochimica Acta, 55, N 4, 955-964.
Kharaka, Y. y Harnor, J., 2003. Deep fluids in the continents: I.

compounds, we tried to evaluate alternative structures that do not

Felipe R.Sampaioa, Eugnio V. Santos Netob, Francisco de A. M.

Once three-dimensional structure of biomarkers is crucial,

possess clear differences in fragmentations. In order to test the


stigmasterol was chosen as starting material. The synthetic route

presence of 5, 14, 17 and 20S epimers, co-injection was made

consisted in a series of stereo and regioselective reactions leading

with racemic mixture (20R + S) of compound (8b), but it was not

a Universidade Estadual de Campinas, Instituto de Qumica,

to formation of compounds with different side chains attached to

identified. Analyzing mass spectra of HHA, we may conclude that

13083-970, Campinas, SP, Brasil.

C-17. First of all, synthesis was based on obtaining a hydroxy-

stereochemistry of compounds is 5(H) (m/z 191 ion) and 17(H)

aldehyde, which was the key intermediate. In a second step, this

(m/z 259 ion). For C-17, mass spectra show a signal more intense

intermediate was used in a set of Wittig reactions with different

for m/z 301 than for m/z 299, suggesting a 17(H) configuration.
Another possibility is the existence of regioisomers at A ring. Lima
et al. (2010) fixed the propyl group at C-3 by analogy to a whole
series of alkyl-steranes with substitution at that position. These
alternatives can only be confirmed by the synthesis of those
compounds and co-injecting with oil sample.

Zhang, Y. y Dawe, R.,1996. Effect of organic acids on the

determination of carbonate species in solutions, Analytica Chimica
Acta,318, 2, 239-249.

As co-injection did not confirm the structures of majority


Sedimentary Basins, Treatise on Geochemistry. 5, 5.16. Elseiver,


al.(2010) for the new biomarkers.

b Petrobras/Cenpes/PDGEO, Av. Horcio Macedo 950, Cidade

Universitria-Ilha do Fundo, 21941-915, Rio de Janeiro, RJ, Brazil
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

alkyl groups, followed by dehydration and catalytic hydrogenation.

Analysis by 13C NMR and mass spectrometry confirmed the
stereochemistry 3-propyl, 5(H), 14(H), 17(H) and 20R.

review of information contained in an abstract submitted by the author(s).

The oil sample was fractioned, obtaining the acidic fraction which


was submitted to a derivatization processaccording to Lima et al.

Working with saline lacustrine oils from Campos basin, Lima

(2010) and references cited therein.

et al. (2010) identified a family of biomarkers composed of3-npropylergostanoic acids. 14 compounds were first detected by

Co-injections were realized in an Agilent GC7890A/7000 MS Triple

GC-MS and GC-MS/MS of the respective hydrocarbons. For

Quad. The oven temperature programming was: 60 C (10 min);

compounds (3a), (6a) and (8a)each methyl ester were analyzed by

10 C/min to 190 C; 1 C/min to 250 C; 2 C/min to 300 C (30


min). Nitrogen was used at collision chamber, at 10 eV. The MMI-

These results are important not only because they are originals, but
also they may indicate a biodegradation process taking place in the
reservoirs. It was found that the compounds relative composition
varied according to biodegradation level (Lima et al., 2010). In
the biodegradation process, microorganisms attack carbon
chains in the sequence: linear hydrocarbons, isoprenoids, cyclic

type automatic injector was at 300 C with a split rate of 10:1.

Auxiliary temperature was configured to 300 C. Separation was
carried out with CPSIL-8CB column (60 m x 0,25 mm x 0,25 m).
He was used as carrier gas at 1,0 mL/min. MRM method was used
in co-injection.

hydrocarbons, etc (Peters et al., 2005).In Campos basins oils,

Results and Discussion

a homologous series of steranoic acids derived from ergostane

Identification of 3-n-propylergostanoic acids was made by Lima et

(Figure 1) was found, in which the side chain at C-17 goes through

al. (2010) based on fragmentation in mass spectrum of the methyl

progressive biodegradation, as evidenced,for the first time, by

esters, hydrocarbons (HHA) and deuterated hydrocarbons (HDA)

Lima et al. (2010).

derived from acids. In this identifications, the n-propyl group was

fixed at C-3 position and the stereochemistry of 5(H), 14(H) and
17(H) centers was established, but the configurations at C-20 (R

In this work, 5 standards nor-ergostanes were synthesized with
good yields and purity. These compounds are a homologous
series of ergostanes having different side chains attached to
C-17 and 5(H) configuration. These standards are the respective
hydrocarbons of 3-n-propylergostanoic acids found in oils from
Camposbasin and their structures were proposed by Lima et
al. (2010). These acids, besides being unpublished, might be
connected to a biodegradation process, in which is the C-17 side
chain that suffers microbial attack.
The co-injections confirmed the presence of (3a), (5a), (6a) and
(8a). Compounds of greater relative concentration reported by
Lima et al. (2010) did not co-elute with standards, despite having
close retention times and the same fragmentation, suggesting the
presence of isomers. Furthermore, it could identify a new biomarker (4a).

The authors thank CNPq (Brazilian research council) for fellowships;
Petrobras S/A andInstitute of Chemistry - UNICAMP for financial

Lima, S. G.; Steffen, R. A.; Reis, F. A. M.; Koike, L.; Neto, E. V. S.;
Cerqueira, J. R.; Lopes, J. A. D.; 2010. Propyl ergostanoic acids: Possible
new indicator for oil biodegradation. Organic Geochemistry 41, 325-339.

or S) and C-24 (R or S) could not be determined. Carboxyl group

was settled at side chain based on fragmentation of deuterated
hydrocarbons derivatives. Nevertheless, authors did not accurately

Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide,
second ed. Cambridge University Press, Cambridge, UK.

determine its position. Therefore, diastereoisomerically pure

synthesis of standards was made to confirm the structures.
Co-injections showed that the most intense peaks do not
correspond to synthesized compounds. However, the presence
of adjacent peaks, of lesser abundance, with the same retention
times and precursor ion product ion transitions of synthesized
Figure 1: Structure of 3-n-propylergostanoic acids and their derivative

standards confirmed the presence of the acids (3a), (5a), (6a) and



Characterization of PAHsinputs to a
tropical urban estuary (Guanabara Bay)
considering end-member composition
and a statistical approach (PCA/MLR)

MangueChannel (CM). The samples were filtered using 142 mm

PAHs, with predominance of alkylated over parental compounds

diameter and 0.7m porosity glass-fiber filters After filtration, the

suggesting degraded oil presence (C0<C1<C2<C3<C4).Factor 3

samples were freeze-dried and weighed to obtain the SPM mass.

represents 7.4% of the variance explaining the contamination by

Analyses of PAHs followed EPA3540C and EPA8270methods and

crude oil or recent oil inputwith a bell-shaped distribution of the

gas chromatography/mass spectrometry (GC/MS) (Finnigan Trace/

alkylated and parental compounds. Factors 4 and 5, account

FinniganPolaris Q).

for 7.3% of the variance with any distinguishing profile that could


propose a possible origin for PAH.


A total of 42 compounds, including parental and alkylated






from 30ng.L-1to 12,468 ng.L-1, with an average of 613ng.L11,459ng.L-1. In general, rivers in the eastern bay region (CB,

Cristiane R. Mauada*, Letcia Lazzaria,Mayara da S. Anicetoa,

GM and SU) were less contaminated than the rivers in the western

Carlos G. Massonea,Renato S. Carreiraa, Cssia de O. Fariasb,


Angela de L. R. Wagenera

The MLR model realized from the factor scores showed welladjusted (R2 = 0.99; F > 0.05). Figure 2ashowsthe first three
factorscontributions to the average concentration of each station
The highest average concentrations of PAHs, according MLR
model, were found in the IR (1,143 ng L-1), followed by IG and
(843 ng.L-1) and CC(556 ng.L-1).

Figure 2. Contributions of each factor on the predicted concentrations (a)

and the contributions of each factor in the cumulative variance of the first

Pontifcia Universidade Catlica do Rio de Janeiro,LABMAM/

GM station showed predominance of recent oil contamination (142

Departamento de Qumica,20453-900, Rio de Janeiro, RJ, Brazil.

three factors (b)

ng.L-1) representing 52.7% of PAHs contributions (figure 2b). For

Universidade do Estado do Rio de Janeiro,LAGON/Departamento

de Oceanografia, 20550-013, Rio de Janeiro, RJ, Brazil


CM, IG and SJM, the contribution of recent oil accounted only 0.9%,


3.9% and 1,5%, respectively.The highest average concentrations


of degraded oil were found in IG (744 ng L-1 / 72.5%) and IR (518

Aperfeioamento de Pessoal de Nvel Superior) for funding the

ng L-1 / 37.2%), being less representative in GM station (30.4 ng









L-1 / 11.3%).

Copyright 2014, ALAGO.


This paper was selected for presentation by an ALAGO Scientific Committee following

Combustion processes were clearly evidenced in IR, CC and CM

review of information contained in an abstract submitted by the author(s).

stations, being the main source of PAHs to the last two stations.


This can be seen as a result of high vehicular traffic near these

The understanding of the sources and fate of contaminants, like

Figure 1. Sampling stations surrounding Guanabara Bay.

polycyclic aromatic hydrocarbons (PAHs) to estuaries in large

urban settlements is of fundamental relevance to the management

The PCA/MLR approach (Sofowote, et. al., 2008) was used

of these aquatic systems. Whereas in temperate systems such

knowledge is relatively high, less information is available for tropical

to identify the main sources of PAHs in the river end-members

systems. In part, the difficulty derives from the limited application

contributingwith an average of 70% of continental water discharge

of diagnostic ratios among selected compounds for source

to GB.

assignment of PAHs in warmer climates (Wagener et. al. 2012).

Here, we used the composition of PAHs insuspended particulate

The factor analysis showed distribution of variables in five

matter (SPM) of river end-members and a multivariate statistical

factors(eigenvalues>1), contributing to a total of 89.5% of data

approach (principal component analysis with multiple linear

variance. However, only factors 1, 2 and 3 were responsible for

regression PCA/MLR) to characterize the input of PAHs from the

proposing possible sources of PAHs in the SPM. Those accounted

drainage basin to Guanabara Bay (GB), Rio de Janeiro.

for 82.2% of the total variance, which 50.6% was explained by

stations, with main roads such Avenida Brasil and Joo Goulard
highway (Linha Vermelha), nearIR and CC stations, and the high
traffic flow in the downtownand Novo Rio intercity bus terminal
(near CM station).

Sofowote, U.M., McCarry, B.E., Marvin, C.H., 2008. Source

Apportionment of PAH in Hamilton Harbour Suspended Sediments:
Comparison of Two Factor Analysis Methods. Environmental
Science & Technology 42, 6007-6014.

Wagener, A.L.R., Meniconi, M.F.G., Hamacher, C., Farias, C.O.,

da Silva, G.C., Gabardo, I.T., Scofield, A.L., 2012. Hydrocarbons
in sediments of a chronically contaminated bay: The challenge of
source assignment. Marine Pollution Bulletin 64, 284-294.

Although combustion processes have been observed in all

stations, the introduction of petrogenic PAHs from the SPM to GB
is well representative, distinct previous studies which indicate the
combustion events as the most relevant contribution of PAH. This
interpretation confirms the intense degradation processes of the
more labile petrogenic compounds in GB.

factor 1. This factor showed a positive correlation with PAHs of


higher molecular weight and parental preference with lower

The samples were collected in eight water bodies surrounding

abundanceof the alkylated compounds (with C0>C1>C2>C3>C4

the GB(Figure 1) once a month for eleven monthsCaceribu River

sequence), representing the pyrolytic processes.Factor 2 explained

(CB), Guapimirim River (GM), Suru River (SU),IguauRiver (IG), So

24.9% ofdata variance showing positive correlation to petrogenic

Joo de MeritiRiver (SJM), IrajRiver (IR), Cunha Channel (CC)and



methylene chloride: methanol (9:1) each time. Before the extraction,

Environmental Protection Agency (USEPA): anthracene (An),


a standards solution was added with n- tetracosane-d50. The

phenanthrene (Phe), fluoranthene (Fl), pyrene (Py), chrysene (Chr),

USEPA U.S. Environmental Protection Agency. 1984. Summary

extracts were subjected to liquid chromatography using silica

benzo[b]fluoranthene [Bz(b)] and benzo[k]fluoranthene [Bz(k)].

of the Issues with Regard to the Carcinogenicity, Mutagenicity, and

gel. The aliphatic and aromatic hydrocarbon fractions and polar

The PAH concentrations found in the samples are well below

Exposure of Polycyclic Organic Matter (Pom). Washington, D.C.,

compounds were eluted with hexane, hexane:methylene chloride

those established by the legislation, indicating an uncontaminated

EPA/600/8-88/076 (NTIS PB88220371).

Marcela M. Berga, Celeste Y.S. Siqueirab, Luiz Landaua, Francisco

and methylene chloride:methanol, respectively, and later analyzed


R. Aquino Netob

for GC/FID and GC/MS.

Aromatic Hydrocarbons in
Sediments of the Amazon Region

The Fe/An ratios from all of the samples had values less than 10,
a Universidade Federal do Rio de Janeiro, LAMCE/COPPE, 21941-

Results and Discussion

and the An/ (An +Phe) ratio was greater than 0.1 for all of the points.

909, Rio de Janeiro, RJ, Brazil.

In the ten analyzed samples, 31 aromatic compounds were

These results indicate the contribution of pyrogenic sources in the

b Universidade Federal do Rio de Janeiro, Instituto de Qumica,

identified. The total concentration of aromatic hydrocarbons in the

sediments. The pyrogenic origin of the PAHs was also indicted by

21941-909, Rio de Janeiro, RJ, Brazil.

samples varied from 46.33 ng/g to 1253.66 ng/g of dry sediment.

the Fl/Py ratio: the values of this ratio for all of the samples were

The majority of the aromatic compounds identified were of biogenic

greater than 1. Moreover, the Fl/(Fl+ Py) ratio indicates that the


combustion was derived from the burning of coal (Figure 1).

Copyright 2014, ALAGO.

The points sampled in the Solimes River showed a large

This paper was selected for presentation by an ALAGO Scientific Committee following

perylene concentration, varying from 173.34 ng/g to 219.70 ng/g

review of information contained in an abstract submitted by the author(s).

of sediment; however, the points from Coari Lake did not exhibit
the same behavior: their concentrations varied between 0.82 and


10.31 ng/g of sediment. In the Solimes River, the points sampled

The Amazon region has great global importance due to its biodiversity

are surrounded by plants on both riverbanks, which may explain

and freshwater reserves. The increase in industrial activities and

the greater contribution of perylene to the sediments. The lowest

the discovery of the Urucu oil province made prevention measures

perylene concentration among these three points is located exactly

and monitoring of this area necessary to avoid possible damage to

in front of TESOL, where the contribution from plants is the least.

the environment. The geochemical analysis of biomarkers allows

distinctions to be made between the contributions of biogenic and

Polycyclic aromatic hydrocarbons (PAHs) of biogenic origin, such

anthropogenic sources to the organic matter.

as retene, cadalene and monoaromatic lupane, were also identified.

Retene (1-methyl-7-isopropyl-phenanthrene) derives from abietic

Polycyclic aromatic hydrocarbons (PAH) are hydrophobic organic

acid, a natural diterpenoid constituent of the resin of plants. In

Figure 1: Plot of the ratios (a) Phe/An, (b) An/(An + Phe), (c) Fl/Py, and (d)

compounds consisting of two or more fused aromatic rings. They

addition to its natural occurrence, retene can also be a marker

Fl/(Fl + Py)

emerge from incomplete combustion of organic material and are

of wood combustion. Retene was not found in large quantities

thus ubiquitous in the environment. The main emissions of PAH

compared to the perylene concentration in the samples in the


are from anthropogenic sources like fossil fuel combustion and

study, having a maximum concentration of 8.84 ng/g. Cadalene

Several compounds were detected such as n -alkanes, Polycyclic

petrochemical production, refineries, power plants, asphalt, and

is the final product of the diagenetic degradation of compounds of

Aromatic Hydrocarbons (PAHs) but PAH concentrations found in

tire wear debris. Due to the toxicity and partial carcinogenicity of

cadinene-type compounds and, as a consequence, is the most

the samples are well below those established by the legislation,

these compounds, the United States Environmental Protection

common sesquiterpene reported in sediments. The cadalene

indicating an uncontaminated environment.

Agency listed 16 of them as pollutants of high priority (EPA

concentration varied from 0.19 8.79 ng/g, with the exception

PAH),that are thus monitored very frequently. This study focuses

of the sampling three sites, where cadalene was not detected.


on the identication of aromatic organic compounds, especially

Monoaromatic lupane is a pentacyclic triterpenoid derived from

The authors thank ANP (Brazilian Petroleum Agency), Petrobras

Polycyclic Aromatic Hydrocarbons (PAH) in the sediments of Coari

lupeol and is formed through the diagenesis of plant precursors

S/A, PEC/COPPE/UFRJ and IQ/UFRJ for technical andfinancial

Lake and Solimes River in the Amazon region, Brazil.

and natural products.



Among the aromatic compounds found in the samples, seven are

Samples were extracted using ultrasonic agitation with 50mL of

included on the list of priority pollutants from the United States



Occurrence of Polycyclic Aromatic
Hydrocarbons in Recent Sediments and
Benthic Organisms of an Amazon Estuary

for extraction of PAHs and their analysis. Samples extraction

fluoranthene (13%). The %Rec obtained in the organisms samples


processes followed the 3550C method described by USEPA

was >>100% indicating a matrix effect, but it just reduce the

GREGRIO, A.M.S.; MENDES, A.C. 2009. Batimetria E Sedimentologia

(2007) and the clean up process, the 3630C method described by

quantitative accuracy of results not affecting the qualitative result.

Da Baa Do Guajar, Belm, Estado Do Par, Brasil. Amaznia: Cincia e

USEPA (1996).

The sediments HPAs seems to influence the benthic organisms

Desenvolvimento 5, 53-72.

HPAs in both qualitative and quantitative ways (Table 1).

GCMS equipment Shimadzu QP2010 was used under the following


Camila C. Santosa*, Jos Augusto M. Correaa, Flaviana C.

operating conditions: helium (He) as the carrier gas; capillary

Mtodos CLAE e CG/EM na Determinao de Hidrocarbonetos Policclicos


column NST-05 (30 m 0.25 mm 0.25 m) from J & W Scientific;

Aromticos em Sedimentos Estuarinos Amaznicos. Anais de Artigos do

flow rate of 0.8 ml min-1; detector operated with zero relative

II Simpsio de Estudos e Pesquisas em Cincias Ambientais na Amaznia

a Universidade Federal do Par, Laboratrio de Cromatografia,

energy (1.5 kV); modes of operation SIM and splitless; and manual

2, 223 - 231.

Belm, PA, Brazil.

injection of 1L. The temperature ramp used was as follows: the

b Universidade Federal de Sergipe, Lab. de Anlises de Compostos

initial temperature was 40C oven for 2 min, increasing at a rate of

SOARES, L.C.T.; SANTOS-NETO, A.J. 2012. Protetores de Analitos e

Orgnicos Poluentes, Aracaj, SE, Brazil.

25C min-1 to 100C, then increased again to 5C min-1 to 230C,

Efeito de Matriz em CG. Scientia Chromatographica 4,139-152.

and finally increased to a rate of 2C min-1 up to 260C keeping

this temperature for 5 min. The total time of the chromatographic

USEPA. U.S. Environmental Protection Agency Method 3630C: Silica Gel

run was 50 min.

Clean Up. 1996. Available in: Accessed on: June 19th, 2013.

This paper was selected for presentation by an ALAGO Scientific Committee following

Results and Discussion

USEPA. U.S. Environmental Protection Agency Method 3550C: Ultrasonic

review of information contained in an abstract submitted by the author(s)

The fine sediments (%Fines) dominated in both sampling periods

Extraction. 2007. Available in: Accessed on: June 19th,

and it has a direct relation to the organic matter concentration



Copyright 2014, ALAGO.


(%OM). From the 16 PAHs studied, 10 of them were detected in

The Guajar bay, located at the mouth of Amazon River, near

sediments samples during the wet season and 8 during the dried

Belm city the capital of Par state. In this area occurs an intense

season. Even with a low diversity of aromatic compounds, dried

boat traffic, as well as transportation and sale of fuels in floating

season sediments presented greater HPAs total concentration

docks and activities related to the storage and transportation of

(HPAs), 1351.43 ng g-1. In wet season the total concentration of

petroleum products in a harbor named Miramar Petrochemical

PAHs was 263.99 ng g-1, which can be related to the increased

Table 1. Occurrence of polycyclic aromatic hydrocarbons in

Terminal (TEMIR).

hydrodynamic in the estuary this last period.

sediments and benthic organisms of the Guajar bay sediments

during two differents seasons.

Small spills and discharges of oil in water are sources of punctual

Correlation analysis indicated that PAHs were not influenced by

pollution by polycyclic aromatic hydrocarbons (PAHs). PAHs are

%Fine and %Organic Matter (OM). Benzo(a)pyrene corresponded


organic compounds generated by the incomplete combustion

to 87% of HPAs during the wet season, whereas the others

There is a predominance of higher molecular weight PAHs, which is

of organic matter (OM) and are one of the contaminants of most

PAHs had 3%. During the other period stood out: pyrene (18%

due to a lower volatility and higher stability of these compounds in

interest in environmental studies due to their mutagenic and

of HPAs) fluoranthene (16%), the chrysene, benzo(b)fluoranthene

the environment. The origin of PAHs in both arrays is predominantly

carcinogenic potential.

(15%) and benzo(a)pyrene (11%). Based on geochemical ratio

pyrogenic, and can be directly related to anthropogenic activity.

it was possible to confirm the predominance of aromatics from

pyrolytic origin.

This study aimed to evaluate the occurrence of the 16 PAHs

Anthropogenic activities that originated the PAHs levels observed

in sediments and benthic organisms are the discharge of untreated

considered as priority by the Environmental Protection Agency of the

United States in sediments and benthic organisms (Namalicastys

The PAHs seems to influence the density of polychaetes in

domestic sewage and emissions of particulates from cars and

abiuma Grube, 1872) of TEMIR harbor.

sediments. Reduction of about 50% in the number of organisms

small/medium boats.

was observed during the dry season, when there was the greater


amount of HPAs in their body structure. Eleven PAHs were


Field expeditions in the studied area were carried out in December

detected in the polychaetes during the dry season (HPAs =

The authors thank the Post-Graduate Program in Geology and

2012, March, May and June 2013 representing the dried, wet (two

848.71 ng g-1) and 10 of them in the wet season (HPAs = 141.85

Geochemistry of UFPA, the National Council for Scientific and

samples) and dried seasons, successively.

ng g-1). PAHs stood out during the dried season: indene(1,2,3-

Technological Development (CNPq) and the Laboratory of Organic

c,d)pyrene (47%) and pyrene (23%). During the wet season the

Compounds Pollutants Analysis of UFS.

major were: pyrene (23%), chrysene (17%), fluorene (17%) and

There were used 0.5 g of benthic organisms and 4 g of sediment



Isotopic evidence for sulfurization of humic
acid in sediments of the tropical upwelling
system of Cabo Frio (RJ).

(station 4) and BCCF1009 (station 9) were sampled at 120 m and

relative to dissolved sulfate. The sulfur isotopic composition of the

an ideal system for the re-oxidation of the sulfur species, and

117 m water depths and the last core (BCCF1015) was retrieved

humic acids in the Cabo Frio sediments suggests the incorporation

generate the sulfur intermediates species which react with the

from the inner-shelf area (station 15) at 80 m water depth(Figure 1).

of the diagenetic sulfur in the OM, thought reactions of the organic

OM to complete the sulfurization process. The presence of the

The sediment samples were processed within an O2-free glove bag

matrix with reduced species of sulfur produced by dissimilatory

benzothiophene in the humic acids also indicate the sulfurization

and were sliced in high resolution (1 cm). The extraction of the humic

sulfate reduction.

of the OM, but further analysis and interpretation must be done to

understand the absence of sulfur compounds with low molecular

substances was made using the basic extraction with NaOH 0.1M
Rut A. Daz1, Manuel Moreira1, Ursula Mendoza1, Wilson

and the precipitation of the humic acids using HCl 6M. The isotope

The incorporation of sulfur into OM appears to be most favorable

weight compounds.

Machado1, Michael E. Bttcher2, Christelle Anquetil3, Sylvie

compositions were measured by means of combustion isotope-

under conditions where partially oxidized aqueous species of

Derenne3, Ramses Capilla4, Ana L. Albuquerque1

ratio-monitoring gas mass spectrometry (Thermo Finnigan MAT

sulfur such may be present. The sediments off Cabo Frio were


253) coupled to a Thermo Flash elemental analyzer via a Confl o IV

deposited under highly dynamic redox conditions in the surface

This work was funded by the Geochemistry Networkof

1 Departamento de Geoqumica, Universidade Federal Fluminense,

split interface. For the analysis with Py-GC-MS, the humic acid was

layers beneath oxic bottom waters, and this condition maintains a

PETROBRAS/CENPES and the Brazilian NationalPetroleum and

Niteri, RJ 24020-150;

extracted with dichloromethane (DCM) and ethanol (MeOH) using a

constant process of re-oxidation of the sulfur species, which favor

the Biofuels Agency (ANP).

2 Marine Geologie, Institut fr Ostseeforschung Warnemnde,

proportion of 2:1 (v/v).

the sulfurization of the OM.


Rostock, Germany;
3 BIOEMCO, Universit Pierre et Marie Curie, France;4Petrobras/

BRCHERT, V., 1998. Early diagenesis of sulfur in estuarine sediments: The

Cenpes/Geoqumica, Ilha do Fundo, RJ

role of sedimentary humic and fulvic acids. Geochimica et Cosmochimica

Acta 62, 1567-1586.

Daz, R., Moreira, M., Mendoza, U., Machado, W., Bttcher, M.E., Santos,
H., Belm, A., Capilla, R., Escher, P., Albuquerque, A.L., 2012. Early

Copyright 2014, ALAGO.

diagenesis of sulfur in a tropical upwelling system: Cabo Frio, southeastern

This paper was selected for presentation by an ALAGO Scientific Committee following

Brazil.Geology 40, 879.882.

review of information contained in an abstract submitted by the author(s).


Zhu, M., Chen, L., Yang, G., Huang, X., Ma, C., 2014. Humic sulfur in

Among a variety of sulfur forms in marine sediments, organic sulfur

eutrophic bay sediments: Characterization by sulfur stable isotopes and

is quantitatively the second most important sulfur pool (only behind

K-edge XANES spectroscopy. Estuarine, Coastal and Shelf SciencE 138,

pyrite), frequently accounting for 35% of the total sedimentary sulfur


in marine environments. The sulfurization of the organic matter (OM)

Figure 1: Locations of study area and core sampling stations.

results from the incorporation of reduced inorganic sulfur species

Figure 2. Downcore Profiles: 34S of Chromium Reducible Sulfur (CRS),

pore water sulfur (SO42-) and Humic Acid (HA).

into sedimentary OM. This process is an important mechanism

for the preservation of functional organic compounds during

Results and Discussion

early diagenesis. In the course of the diagenesis, the sulfurization

The atomic ratio (S/C) in the humic acids ranges between 0.035

In the molecular characterization of the humic acids by Py-GS-

of the OM generates a gradual increase in the molecular weight

and 0.23, according to reported atomic ratios for several marine

MS were identified compounds like linear n-alkanes and alkenes,

of the compounds produced within the sedimentary OM, which

sediments and sedimentary rocks (0.0060.38). The fact that

branched-alkanes, alcohols, aromatic compounds and some

inhibits the degradation of the OM by bacteria and contributes to

S/C ratio in the humic acids is larger than the algal ratio in marine

compounds with oxygen and nitrogen.The sulfur compound

the preservation of organic compounds in a geologic time scale.

plankton (0.004-0.010) suggests the uptake of sulfur into the

identified was a micro-peak of benzothiophene with the principal

The present work aims to characterize the OM focusing on the

organic matter.

ion m/z 134. This compound is a sulfur compound with high

molecular weight, and generally indicates an advance maturity in

sulfurization of the OM during the early diagenesis,using the sulfur

isotopic composition (34S) of the humic acids and the molecular

The sulfur isotope composition of the humic acids cover a range

the sediments with a high aromatization process, what contrast with

characterization by Curie-Point Pyrolysis-Gas Chromatography-

between -8 and +5 , being significantly enriched in the lighter

the local sediments type. The presence of this sulfur compounds

Mass Spectrometry (Py-GC-MS).

isotope compared to pore water sulfate (about +21), but

may indicates the sulfurization of the OM.

depleted with respect to co-existing pyrite (CRS) (between -27


and -42) (Figure 2). The 34S of sulfur that is biosynthesized by


In the upwelling system of Cabo Frio, Southeast Brazil, four box-cores

marine organisms is close to seawater sulfurfrom which it is formed

The S/C ratio and the sulfur isotopic composition of the humic

were collected across the continental shelf. The shelf-edge core

and the diagenetic sulfur produced by the dissimilatory sulfate

acids (34S) indicate the OM sulfurization in the sediments from

BCCF1001 (station 1) was collected at 142 m, cores BCCF1004

reduction has an isotopic composition highly depleted in 34S

the upwelling system of Cabo Frio. These sediments represent




on a Agilent 6890N GC equipped with a Agilent 7683B Split/

Figure 1GC-MS Chromatograms at m/z 191 and 217 of oilyresidue

Uhler, A.D., Stout, S.A., Douglas, G.S. Chemical heterogeneity in

spliteless injector and interfaced to a Agilent 5975B quadrupole

collected from a turtle specimen (Chelonia mydas).

modernmarine residual fuel oils. In: Wang, Z., Stout, S.A. (Eds.), Oil Spill

mass selective detector (electron voltage 70 eV and quadrupole

Oil Spill Characterization Using

Organic Geochemistry Case Studies

temperature 150C). The samples were analyzed in selected ion

Incident 2

monitoring mode (SIM).




Press, Boston (2007).






magellanicus) was submitted to oil hydrocarbon fingerprint

Wang, Z.; Yang, C.; et al., Petroleum Biomarker for Oil Spill Characterization

Separation was performed on a DB-5MS fused silica capillary

analysis. The chromatogram showed a nearly normal distribution

and Source Identificartion, in Wang, Z.; Stout, S.; Eds: Oil Spill Environmental

column. The GC oven was temperature programmed from

of n-alkanes in a carbon range of C19 to C28 on a prominent UCM.

Forensics, Academic Press: Oxford (2007).

Petrobras method.Helium was used as carrier gas.

Diagnostic ratios of target biomarker compounds HOP/EST, H29/

Wagner L. BASTOS, Carlos A. CARBONEZI,Jarbas V. P. GUZZO,

Fabiano G. LEAL, Laura B. B. RIGO, Michelle S. GAMA, Patricia L.

EnvironmentalForensics: Fingerprinting and Source Identification. Academic

H30, TET/26Tri, H35/H34, prevalence of %27R&S, in addition

Division of Geochemistry, PETROBRAS Research and Development

Center (CENPES), PETROBRAS, Rua Horcio Macedo, 950, Ilha
do Fundo, Rio de Janeiro, RJ 21941-915, Brazil

Compounds were identified on the basis of mass chromatographic

with n-alkane GC profile indicated a heavy fuel, maybe obtained

responses and relative retention times by comparison with a

from Cuba oil (figure 2).

standard sample.
Copyright 2014, ALAGO.

Results and Discussion

This paper was selected for presentation by an ALAGO Scientific Committee following

In this work, two different samples, collected in different days,

review of information contained in an abstract submitted by the author(s).

were obtained from aGreen Sea Turtle (Chelonia mydas) and

MagellanicPenguin feathers (Spheniscus magellanicus). Samples
wereanalyzed from geochemical point of view.

Biological markers or biomarkers are molecular fossils, meaning

Incident 1

that these compounds are derived from formerly living organisms

An oily residue collected from a green sea turtle specimen (Chelonia

(Peters et al., 1993). Biomarkers are complex organic compounds

mydas) was submitted to GC fingerprint analysis. Thechromato-

composed of carbon, hydrogen, and other elements (Peters et

gram profileobtained from residue showed a distribution of n-al-

al., 1993). They are found in rocks and sediments and show no

kanes with maxima around C-20 on a UCM (unresolved complex

change in structure from their parent organic molecules in living

mixture). Diagnostic ratios of target biomarker compounds HOP/

organisms (Peters et al., 1993). Furthermore, due to the wide

variety of geological conditions and ages under which oil has
formed, every crude oil may exhibit an essentially unique biomarker

EST (Hopanes/Steranes), H29/H30 (C2917(H),21(H)-30-nor-

Figure 2: GC-MS Chromatograms at m/z 191 and 217 of oilyresidue

hopane/C3017(H),21(H)-hopane), TET/26Tri (C24 tetracyclic

collected from penguin feathers (Spheniscus magellanicus).

terpane/C26 tricyclic terpanes S+R), H35/H34 (C35 pentakisho-

fingerprint (Wang et al., 2007). This allows characterize and identify

the several petroleum systems in the sedimentary basin, and
consequently, the oils spills occurred in all nationwide, becoming
the biomarkers a powerful tool.

Based on these characteristics, two cases studies were carried out

in Brazilian territory showing it is possible to use biomarkers and

mohopaneS+R/C34 tetrakishomohopaneS+R), prevalence of


%27R&S(% of C27 14,17-cholestane S+R/C27+C28+C29

In both cases was possibleto conclude that the origin of

cholestanes S+R), absence of methyl-steranes, in addition with a

contamination refer to heavy fuels produced from foreigner crude

presence of 2-methylanthracene in the aromatic fraction indicated

oils. These facts occur frequently due to several ocean currents

a heavy fuel (Uhleret al., 2007), probably obtained from Middle East

which these marine animals are subjected and intense navigation

oil (figure 1).

in the Brasilian Coasts.


geological information to identify the origin of theseevents.

The authors thank Petrobras S/A for financial support.

Oil samples were fractionated using a semiautomated medium


pressure liquid chromatography technique to provide saturated

Peters, K. E.; Moldowan, J. M., The Biomarker Guide: Interpreting

and aromatic hydrocarbons fractions.

Molecular Fossils in Petroleum and Ancient Sediments, Prentice Hall, New

York (1993).

Gas chromatography coupled to mass spectrometry (GC-MS)

analyses of saturated hydrocarbon fractions were performed



residents and operators and is another issue that clearly needs to

be resolved.

Energy and the environment-relating releases

to sources with environmental forensics

Finally another aspect of hydrofracking is related to disposal wells

necessary to dispose of co-produced formation waters. Much
of this water is pumped back into the subsurface. However in
Oklahoma in particular with the dramatic increase in the amount
of drilling that has occurred over the past 5 years, there is a lot
more water being reinjected into the subsurface. At the same time
there has been a significant increase in the number of earthquakes
in the same areas. Now at this point no direct relationship has
been established between the earthquakes and the disposal wells.
However the circumstantial evidence is very strong.

R. Paul Philp
School of Geology and Geophysics, Uni. of Oklahoma, Norman,
OK. 73019.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

The second part of the talk will be devoted towards oil spills and
releases of refined hydrocarbon products. There are many parallels
between the increased drilling activity and environmental incidents
involving transportation of hydrocarbon products resulting from this
increased activity. One area in particular is related to transportation
of these products via trains vs. pipelines. In the past two years in N.
America there have been a number of significant incidents involving
crude oils being transported by rail. The unfortunate problem here
is that in many cases it is not simply the release of the oil following
the spill but the fact many of these spills are also accompanied by
explosions and fires.

review of information contained in an abstract submitted by the author(s).

With the ever increasing demand for all forms of energy both in
this country and would wide, it is inevitable that there will be more
and more releases of energy related products into the environment.
These releases may be oil or gas-even coal-or products related
to exploration and production activities. In terms of exploration
there are many issues associated with hydraulic fracturing which
will be discussed elsewhere at this meeting. This will inevitably
lead to increasing levels of litigation requiring more and more
sophisticated techniques to relate releases to their point of origin.
These releases may be accidental and unintentional or in some
cases even deliberate. Further complicating the issue is the fact
that in many areas releases may occur in the same area as natural
seeps or areas with significant tanker traffic that also contribute
to the overall contamination background. Every release will have
its own specific set of characteristics. These will depend on such
features as the nature of the product and environmental conditions
where the release occurred.


Origin of H2S in Franquera, Moporo and La
Ceiba oilfields: Evidence from sulfur isotopes
and chemical analysis of fluids
Cabrera Franka*, Vsquez Jhaissonb, Rivas Delfna, Angulo Beatriza,
Duno Laurysb, Guerrero Blancab

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

In the first part of this presentation the primary focus will be on

issues related to unconventional oil and gas exploration, in other
words hydrofracking. Hydrofracking and related activities can
have many potential impacts on the environment. First I think it
is important to emphasize that despite the large numbers of wells
that have been drilled in the US in the past decade, there are
relatively few examples of groundwater contamination following to
the hydrofracking. The two issues here are first the presence of the
chemicals that comprise a very small percentage of the drilling fluid.
One big issue here is the wide variety of chemicals that are used
and the fact that the oil companies are very reluctant to publish
lists of these compounds. The second issue whether any of these
chemicals or any oil or gas released from the shales actually enters
the groundwater. I think it is important to remember that is in the
best interests of the oil companies not to fracture the ground water
aquifers. By doing so they will end up producing large amounts
of water, which of course is not in their best interest and certainly
means loss of profits for them.

Reservoir souring is a common problem during waterflooding

operations into sweet reservoirs. In this case, the mechanism
that produces the hydrogen sulfide (H2S) is related to sulphatereducing bacteria (SRB). Similarly, the steam injection into heavy
and extra-heavy oil reservoirs (with high sulfur content) can produce
significant amounts of H2S due to acuathermolysis reactions.
On the other hand, the production of H2S can also be linked to
geologic past, a phenomenon named geologic souring. These
indigenous mechanisms are associated with some elements
of petroleum system. At the present day, the Upper Eocene B
reservoir has concentrations of 20-80 ppm H2S and 4-12%
CO2, suggesting the same source due to their close geographic
association for Franquera, Moporo and La Ceiba (FRAMOLAC)
oilfields. The Franquera, Moporo and La Ceiba (FRAMOLAC)
oilfields situated onshore and assigned to Sur Lago Trujillo Division
are located between Trujillo and Zulia States of Venezuela. The
isotopic composition of sulfur in H2S(g), SO42- from formation
water and crude oil allows to generate a map with the values of
34S in the interest area in order to study the main processes
controlling biogeochemical cycle of sulfur in the reservoir and
understand the predominant mechanism for generation of H2S in
oil reservoir.

Several samples of crude oil, formation water and H2S were

collected in head well and analyzed for sulfur isotopic relations
(34S/32S or 34S). Crude oil and formation water samples were
taken in plastic recipients. Separated water samples were filtered
through 0.45 m Millipore membrane and sulfate (SO42-) was
precipitated with BaCl2 solution. The gas samples were collected in
well head using a biphasic separator. The gas stream was passed

(g), SO42- (ac) and R-S (organic sulfur) did not identify uniquely
a single process for H2S source in the study area, probably due
to the potential that had Maracaibo Basin, in particular Upper
Eocene B reservoir, for fluid mixing and their subsequent effects
of rock-water interaction during the geological history. Particularly,
it believed that H2S generation was marked initially by organic
matter thermal cracking of marine origin (La Luna Formation).
Later, reservoir conditions could favor the microbiological activity
of sulphate-reducing bacteria (SRB). Evidences of these proposed
mechanisms, as well as ruling out other processes are described



Another aspect of the hydrofracking is the need for very large

amounts of freshwater for the fracking operation. This is an issue
that has to be addressed since many of these fracking operations
are underway in areas where there is a severe shortage of
freshwater. This in turn frequently results in friction between local

Several mechanisms were initially considered for Franquera,



Results and Discussion

Results and Discussion

Moporo and La Ceiba oilfields. Sulfur isotopic compositions of H2S

a Venezuelan Technological Institute of Petroleum (PDVSA Intevep),

Department of Strategic Research, 76343, Caracas 1070-A,
b Oil Company of Venezuela (PDVSA Occidente), Department of
Reservoir Integrated Studies, Maracaibo, Venezuela

review of information contained in an abstract submitted by the author(s).

In summary this talk will discuss two major environmental areas

related to the oil industry. The first is related to hydrofracking
issues now that is been used extensively in the industry. The
impacts of this approach are wide-ranging from ground water
contamination to earthquakes. The second issue to be discussed
will be environmental issues related to transportation of crude
oils and refined products. This has become an important area of
discussion in recent years with issues related to new pipelines vs.
transportation by train. Several major environmental issues related
to transportation by rail led to this discussion.

through a saturated solution AgC2H3CO2. This was allowed to

bubble the gas phase until the formation of solids of Ag2S (black
color). This solid was filtered using a 0.45 m Millipore membrane.
Finally, the samples were analyzed using Isotopic Relation Mass
Spectrometry (IRMS) of Thermo Scientific, Delta V plus model,
coupled to Elemental Analyzer (EA) of Thermo Scientific, Flash EA
1112 model. The standards used were PSO_1 y PSR_1 which
are referenced with international standard NBS-127. Results are
presented as 34S relative to Vienna Canyon Diablo Troilite (VCDT)
standard. The reproducibility for 34S measurements is 0.3.
The sulfur isotopic relations were analyzed like SO2 in IRMS.

Absence of evaporite sequences: Thermochemical Sulphate

Reduction (TSR) from anhydrite layers (CaSO4) is not a possible
source for H2S since evaporitic sequences were not deposited in
this area and H2S concentrations recorded at wellhead are very
low for this type geological mechanism in which the decomposition
of anhydrite systematically introduce large amounts of H2S.
Type of organic matter: The generation of H2S due to presence of
sulfur-rich organic matter in the source rock (La Luna Formation)
may be a possibility. The kerogen in the source rock has marine
characteristics associated with a reducing depositional environment
with significant sulfur content to generate H2S.
Biodegradation of crude: The studied crude oils are partially
biodegraded, suggesting that sulphate-reducing bacteria (SRB)
possibly contribute to H2S formation in the geological past.
Reservoir temperature: The average temperature in FRAMOLAC
is 273 F (133 C) for Unit B-1 and 287 F (141 C) for Unit B-4.
Therefore, these values deny the possibility that H2S is currently
caused by sulphate-reducing bacteria (SRB) since these bacteria
only survive at temperatures <170 F (77 C) (Machel, 1995), which
is less than the vast majority of values reported in the study area.
Correlation 34S (SO42-) and 34S (H2S). Figure 1 shows that
sulfur isotopes are slightly fractionated during the reduction process
(if the cause is due SRB). Therefore, sulfur isotopic composition of
H2S produced is different to precursor inorganic-sulfur species. All
values fall below the ranges reported for crude oil and sulfate.


The Innovative Applications Of Stable
Isotopes In Petroleum Geochemistry
YongchunTanga,*, Li Gaoa, Sheng Wua, PanqingHea, Andrei Deeva
a GeoIsoChem Corporation, Covina, CA, USA
Copyright 2014, ALAGO.

Figure 1. Sulfur isotopic values for crude oil, SO42- of formation water and H2S

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Isotopic fingerprint of H2S is more depleted in 34S than SO42in formation waters, within a relatively small range. A maximum
isotopic fractionation of 3.5 suggests that bacterial activity inside
a close system could be involved in the redox process at some
time of basin evolution. Larger values of isotopic fractionation can
be achieved when the bacterial activity is carried out inside an
open system (Cavallaro et al., 2006), which is not the case of

Carbon and hydrogen isotopes have been widely used in petroleum
geochemistry. Carbon isotopes of hydrocarbon gases provide
valuable information of gas origin, maturity, formation temperature,
reservoir compartment and many other major aspects of petroleum
systems. Hydrogen isotopes provide key constraints on gas
maturity and gas origin. Use of the C and H isotope ratios has thus
been a routine in exploration and production.

Correlation 34S (crude oil) and 34S (H2S). The values of

34S relatively similar for H2S and crude oil samples (figure 1);
suggest that hydrogen sulfide was produced in part during the
transformation of kerogen to hydrocarbons. Later, H2S along
hydrocarbons should migrate from source rock to reservoir rock.

isotope ratios.

Results and Discussion

(1) Production Decline Prediction Model
In the past, production decline trend has been mainly predicted
by Arps equation (Arps, 1944).However, the b value is poorly
constrained and the uncertainty can be significantly large. Our
method provides a new dimension to constrain the production
decline trends. The Barnett Shale Gas well shows large carbon
isotope variation (up to 2 per mil) during the study period of time
(up to 1 year). The application of our model to this well leads to an
estimate of the production rate change curve in the next several
decades (Figure 1).
(2) On-site Isotope Logging for C1,C2 and C3 gases
The evolutionary instrument GC-IR2 (Figure 2a) is now scheduled
for the first field trial in a Utica Field. The data can be presented
in the mud log for direct comparison with other geological data
(Figure 2b).

The origin of H2S in Eocene B Superior reservoir suggests a mixture

of processes that occurred in geologic past, each independent of
the other. The presence of sulfur relatively high in crude oil (1.51.9%), the quantity of H2S measured (15-80 ppm), the sulfur
isotopic compositions similar between crude oil and H2S and
other evidences, allow conclude that: i. H2S was initially formed
by thermal cracking of organic matter (carbonate source rock) and
ii. Bacterial sulfate reduction (BSR) occurred when the system
conditions favored the growth of bacteria.

Thank to PDVSA INTEVEP (Venezuelan Technological Institute of
Petroleum) and PDVSA OCCIDENTE (Petroleum of Venezuela).

We presented a series of novel methods and instruments for the

application of hydrocarbon gas isotopes in petroleum exploration
and production. Based on advanced isotope modeling and realtime isotope logging, we have better constrained production decline
prediction; we have made it true for real-time onsite isotope logging
for the C1, C2 and C3 gas isotope analysisby constructing the
first field-deployable isotope analyzer; We have also fully calibrated
the method of intra-molecular isotope analysis, which may provide
new power for hydrocarbon source delineation and origin.

Figure 1.Production decline prediction by Arps (blue line) and exponential
equations (orange line) for the study well, where t1 is the end time of
measuring production rates, and t2 is the predicted time when Arps

Cavallaro A. N., Cerroni M., Alberdi M. I., Ostera H. H2S Associated With
Heavy Oils in Reservoirs Under Primary Production: Cases of Grimbeek and
El Alba Fields in Gulf of San Jorge Basin, Argentina. SPE 103920, 2006
Machel H. G., Krouse H. R., Sassen R. Products and distinguishing criteria
of bacterial and thermochemical sulfate reduction. Applied Geochemistry
10, p. 373 389, 1995

(3) Intra-Molecular Isotope analysis

We established the analytical procedures for intra-molecular
isotope analysis (position-specific instead of compound-specific)
for propane. We first purify propane from natural gas (up to 99%),
and use a special enzyme to convert propane to propanol. We
then use a series of well-controlled chemical methods to convert
propanol to acetic acids. The position-specific carbon isotopes
can thus be calculated based on bulk propane and acetic acid

The funds for this work include DOE, GeoIsoChem Joint

Industrial Consortium, PetroChina fund (13HT10500000038) and
International Science &Technology Cooperation Program of China
(ISTCP) (2010DFB64070).

equation wont fit. Q1, Q2 and Q3 are the total production amounts in


different time windows.

Xia, X.; Tang Y., 2012. Isotope fractionation of methane during natural
gas flow with coupled diffusion and adsorption/desorption. Geochim.
Cosmochim. Acta77,489-503. doi:10.1016/j.gca.2011.10.014.

(2) On-site Isotope Loggingfor C1,C2 and C3 gases

We constructed the first of its kind field-deployable compoundspecific isotope analyzer, the gas chromatography-InfraRed
Isotope Ratio (GC-IR2) analyzer. In this novel instrument, we use
the transformative mid-Infrared sensing technology (i.e., the Hollow
Waveguide) and the latest semiconductor IR lasers to achieve
microliter sample injection volume and high accuracy (better than
0.5 per mil without the standard gas calibration).


isotopes (procedures in the box are vigorously calibrated with NMR


(1) Production Decline Prediction Model
We established our model based on our published work in carbon
isotope fractionation during diffusion and desorption (Xia and Tang,
2012). The inputs for our model are carbon isotopes of methane
and the production rate record from a production well. The study
site was a Barnett shale gas well. The 13C values of C1 were
measured by our field-deployable gas isotope analyzer (NGIA). The
production rates were recorded by our field geologists.

Figure 3.The protocol scheme of analysis of propane intra-molecular


In addition to the classic use, we have developed a series of

innovative methods/techniques based on extensive and proprietary
research in our group. Well present three of them: (1) The innovative
interpretation tool for production decline prediction using real-time
isotope analysis, (2) the worlds 1st real-time, onsite InfraRed
isotope analyzer for C1, C2 and C3 gases and (3) Intra-Molecular
isotope method - a new tool for gas isotope geochemistry.


comparison between our method and the NMR method from

University of Nantes, France. Our results show high consistency
for the two methods analyzing propanol (e.g., -28.9 vs. -29.3+/-0.9
per mil for the side carbon of a known standard, Figure 3). However,
the NMR method cannot be readily used for the propane-converted
propanol from natural gas, due to the low purity. For each chemical
reaction, we closely monitor the isotope values of reactants and
products. This method has been applied to our laboratory natural
gas and synchronized gas standards from different sources.

Arps, J.J., 1944. Analysis of decline curves. Trans. AIME. 160, 228-247.



Figure 2.The GC-IR2 instrument and the isotope logging data on surface log.

(3) Intra-Molecular Isotope analysis

Compared with previous efforts, our protocol is well-constrained
and complete. For example, we conduct an inter-laboratory


presence in the subsurface of substance of economic interest as

hydrocarbon or metal deposits. As a matter of fact, it has been
used extensively in both mineralization search and oil and gas
prospection. In the Solimes basin, around 10,000 points of soil
sampling have been studiedfor the amounts and proportions of
hydrocarbon gas (Mello et al, 1996). The two main parameters
which need to be assessed are the quantification of the superficial
bacterial background, hiding the possible presence of deeper
thermogenic gases, and the understanding of the thermogenic gas
composition, associated to the usual processes of a petroleum
system (source, maturity, Prinzhofer et al., 2000).Also, the process
of fractionating evaporation of the gas compounds in the soils must
be modeled. The removal of the main bacterial contribution in the
sampled gases is done through a statistical filtering of the data
(Figure 2a). From the remaining gas samples considered to contain
a significant proportion of thermogenic fluids, a model of retention/
evaporation in the soils has allowed to characterize the most active
microseeps (Figure 1). An estimate of the hydrocarbon maturity
of these active microseeps gives a map of repartition of maturity
through the whole basin (Figure 2b).

Oil Versus Gas Charge in the Solimes Basin

Prinzhofer A., Rostirolla S. Magnier C., And Takaki T.
Hrt-O&G, Ipex
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The Solimes Basin is located in the remote Brazilian Amazonia
sedimentary basin. Itcombinesimpressive geological complexities
and difficult logistics which may be comparable in many ways to
deep offshore exploration (Murakami et al., 1993). In order to find
adequate exploration guidelines in such a vast, protected and
inhabited land (450,000 km2), first hand geochemical field data
may be considered as paramount to begin to sort out the working
petroleum systems and to assess the best possible locations for
oil or gas accumulations. For a good hydrocarbon exploration
campaign, there are two main routes for petroleum geochemistry.
One, the careful study ofexisting drilled wells and compiled
geochemical data of collected fluids in reservoirs together with
source rocks, cuttings and cores studies. The second main input
comes from surface geochemistry. Quite often, as will be presented
in this study,the latter confirms the information in wells and outlines
new and valuable zones of exploration where no wells can serve as
proxies (Mello et al. 1996).

indicate the location of thermogenic gases (above) and the maturity of the
hydrocarbons (below), with a gas charge in the West and an oil charge in
the center of the area.

The authors thank HRT-P and Rosneft for the authorization of
presenting these data.

Eiras J.F. and Lima C.C.A. (2008): Petroleum exploration in the Solimes
basin. PetroGeo, May 2008, Manaus, Brazil, 5p.
Mello M.R., Gonalves F.T., Babinski N.A. and Miranda F.P. (1996):
Hydrocarbon prospecting in the Amazon Rain Forest: Application of
surface geochemical, microbiological and remote sensing methods. In D.
Schumacher and M.A. Abrams, eds., Hydrocarbon migration and its nearsurface expression: AAPG Memoir 66, p. 401-411.
Murakami, C.Y., Gonalves, F.T.T., Eiras, J.F., Becker, C.R., Lima, M.P.,
Daniel, L.M.F. (1993) Habitat of petroleum in the Solimes Basin, Brazil. 3rd
Latin-American Congress on Organic Geochemistry, Extended Abstracts,

In the area of the HRT blocks, the large majority of the wells have
been drilled in the Northern part. The southern half of the area
presents hardly one or two old wells. As the new HRT wells have
been also drilled in the already known area, the direct information
about the stratigraphy of the basin is only available in this area,
the southern part being only known by geophysics and through
surface geochemistry.

Mello, M.R. and Trindade, L.A.F. (eds.), p. 113-115.

Figure 1: Position of gas wells and thermogenic superficial gases in a C2-

Prinzhofer, A. and A.Y. Huc, 1995, Genetic and post-genetic molecular and

C3-nC4 triangle. A leakage model allows distinguishing the soil gases

isotopic fractionations in natural gases: Chemical Geology, v. 126, no. 3-4,

linked with the more active microseeps

p. 281-290.
Prinzhofer A., Mello M.R., da Silva Freitas L.C. &Takaki T. (2000): New
geochemical characterization of natural gas and its use in oil and gas

Two Devonian main siliciclastic marine source rocks (Frasnian and

Famennian) predominate in the Solimes Basin. The Frasnian aged
sediments have been characterized as more oil-prone as compared
to Famennian shales. The later extension and richness of these two
source-rocks throughout the basin imply a high gas potential in
the western part of the studied area. This trend is enhanced by a
severe secondary cracking occurring in the Northwest, due to a
local proximity of a magmatic sill with the petroleum system (Eiras
and Lima 2008).

evaluation, in M.R. Mello and B.J. Katz, eds., Petroleum systems of South
Atlantic margins : AAPG Memoir 73, p. 107-119.

The extreme thermal stress associated with this part of the basin,
associated with the presence of destabilized ferrous minerals,
increases the gas charge by a factor two, and induces unusual
geochemical pattern for the gas, as rollover and carbon isotope
inversion (Prinzhofer & Huc, 1995).
Figure 2: Statistical treatment of surface gas data (projection of gas

Gas surface geochemistry

compositions on the two first Eigen Vectors of a PCA). These parameters

Surface geochemistry is the only direct way to assess the


The origin of H2S in

Brazilian Presalt reservoirs

Surface geochemistry confirms the presence of thermogenic
gases in the northwestern part of the basin, as already known
through numerous wells. However, the main gas seeps are located
in the west of the Urucu fields, and in non-drilled areas, South and
Southeast of Urucu, where no real knowledge of source rocks and
maturity may be assessed directly, because of the lack of wells.
The hydrocarbon maturity calculated from surface geochemistry
confirms the extremely high maturity observed in the western part
of the basin, with only gas charge. On the contrary, going to the
center of the basin, around the Urucu field and in the more southern
areas, the assessed maturity decreases and is associated with oil
or condensate charges.


Well results summary


Erica Tavares de Moraisa* / Eugenio Vaz dos Santos Netoa /

Alexandre de Andrade Ferreiraa
a Petrobras R&D Center
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

H2S is a highly corrosive and toxic gas that can cause serious
damage to health and metals even in tiny concentrations. During
E&P activities in the southeastern offshore Brazilian basins, H2S was
found in some petroleum accumulations within presalt reservoirs.
Each possible concern on geological conditions must be taken
into account because it would govern fluid composition and can
bring impact in development costs of accumulations. This is even
more strategic when petroleum exploration is targeting increasingly
deeper carbonate reservoirs, more and more distant from
coastline in presalt reservoirs. Therefore, representative samples
were collected, H2S precipitated and analyzed for measurement
of 34S. Results were conclusive and made possible to identify
the process (TSR) that generated H2S as well as its respective
S-source (sulfate evaporites).
The main objective of this work was to identify the origin of H2S and
the respective sulfur source using 34S of representative samples.

Natural gas with hydrogen sulfide was bubbled in a solution of zinc
acetate (2 %) during approximately 30 minutes. Silver sulfide was
precipitated as a black solid residue, after the addition of silver
nitrate to the solution; it was filtered and dried in an oven (100 C
during 1 hour).
Aliquots of 0.5 mg of silver sulfide were weighted in tin capsules
with 0.5 mg of vanadium pentoxide. These samples were
analyzed in a Flash EA 1112 (Thermo Fisher Scientific) elemental
analyzer coupled to a MAT 253 (Thermo Fisher Scientific) mass
spectrometer for measuring d34S. Sulfur dioxide was used as the
reference gas.
The silver sulfides IAEA-S-1 (d34SV-CDT = 0.30 ), IAEA-S-2
(d34SV-CDT = +22.6 ) and IAEA-S-3 (d34SV-CDT = 32.30
) and zinc sulfide NBS-123 (d34SV-CDT = +17.09 ) were
used as primary standards for daily correction of the d34SSO2 in
order to obtain the d34S values for the samples. A standardized
cadmium sulfide (d34SV-CDT = +21.9 ) was used for calibration
of the analytical system. Results of d34S are reported in parts per
thousand () against the international standard Canyon Diablo
Troilite (V-CDT). The precision of d34S values is 0.2 .

Results and Discussion



The values of d34S measured for H2S recovered in presalt

reservoirs gas samples have shown d34S values between +10
to +21 that are considered isotopically enriched in 34S
and also typical of thermochemical sulfate reduction (Herbert et
al., 1985). These results overlap the values obtained for anhydrite
samples collected from the Aptian evaporite sequence, +17
< d34S < +22 (Figure 1). In nature there is no significant
isotopic fractionation between H2S and the sulfur source (Worden
et al., 2012). Thus, similar values of 34S suggest that evaporites
(anhydrite) are the most likely sulfur source for TSR.

The methodology precipitating Ag2S from H2S makes easier the

storage, transportation and sample handling. Also it preserves the
original isotopic signature of the sulfur.
d34S values indicated that the H2S recovered from the studied
presalt reservoirs was generated by thermochemical sulfate
reduction (TSR).
The correlation between H2S ( +10 < d34SH2S < + 21)
and CaSO4 ( +17 < d34SCaSO4 < +22 ) suggests that the
anhydrites from the Aptian evaporites were the source for the H2S.

The reservoirs that gas samples were collected have temperatures

lower than 100 C indicating that they were not places suitable for
H2S generation via TSR. This scenario indicates that the generation
of H2S occurred in deeper parts of the basin and that such gas
migrated up dip towards shallower reservoirs in the southeastern
offshore Brazilian basins.

The relatively low temperatures of the reservoirs where gas samples

were collected indicate that TSR reactions took place in other areas
with higher temperatures. Consequently, H2S may have migrated
from deeper beds to traps over significant distances.


Additionally, reactions of petroleum fluid and H2S are other possible

processes that can scrub the H2S from reservoirs as already
observed in Central Tarim Basin, China. The compelling evidence
for this type of reactions is the positive correlation between sulfur
content in petroleum and whole oil d34S (Cai et al., 2001). Such
feature has not been observed yet in the studied basins. Therefore,
this information seems to corroborate that the relatively low
concentrations of H2S in petroleum accumulations in the presalt
reservoirs found in the southeastern offshore Brazilian basins are
originally low.

We acknowledge PETROBRAS for the permission to publish

this paper, to the colleagues of the Geochemistry and Recovery
Technology Laboratories for the analyses and PVT gas sample
collection, and to Clarisse Lacerda Torres for the critical review of
the manuscript and d34S laboratory analyses.

Preliminary Results of a Surface
Geochemistry Studyusing Multiple Methods in
the Cinzento Diapir Seep, Recncavo Basin,
State of Bahia, Brazil
Carlos S. Bandeira de Melloa*, Antnio Fernando M.Freireb, Dennis
J. Millera, Ronaldo C. S. Gonalvesa, Ana Cristina S.Serrac.
a PETROBRAS Research and Development Center (CENPES),
Rua Horcio Macedo, 950, Ilha do Fundo, Rio de Janeiro, RJ
21941-915, Brazil.
b PETROBRAS, Exploration&Prodution, Avenida Chile, 330,
Centro, Rio de Janeiro, RJ 20031-170, Brazil.
c fundao GORCEIX
Rua Carlos Walter Marinho Campos, 57, Ouro Preto Minas Gerais,
MG35.400-000, Brazil.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following


review of information contained in an abstract submitted by the author(s).

Cai, C.; Hu, W.; Worden, R.H., 2001.Thermochemical sulphate reduction

in Cambro-Ordovician carbonates in Central Tarim, 2001, Marine and


Petroleum Geology 18, 729-741.

The CinzentoDiapiris located in the Recncavo Basin, state

ofBahia, Brazil. The diapir consists of shalesbelonging to the
IlhasGroup, whichintruded sandstones and conglomerates of
the So Sebastio Formation, both Lower Cretaceous in age.
Conspicuous oil seeps occur primarily at the outcropping contact
between shales of the Ilhas Group and conglomerates of the So
Sebastio Formation(Fig. 1).The purpose of this study was to test
different surface geochemistry methods at a well exposed onshore
oil seep.

Herbert, B.N.; Gilber, P.D.; Stockdsle, H.; Watkinson, R.J., 1985. Factors
controlling the activity of sulfat-reducing bacteria in reservoirs during water
injection, Society of Petroleum Engineers, SPE 13978.
Worden, R.H.; Smalley, P.C.; Fallick, A.E., 2012. Sulfur cycle in buried
evaporites, Geology 25 (7), 643-646

Thediapir area was studied employing the following methods:

traditional soil headspace sampling, direct gas readings from
probe samples, adsorbed gases (acid extraction), iodine
concentration, geomicrobiology, molecular biology, extraction for
higher molecular weight compounds (C15+), fluorescence, soilEh/
pH, elements concentration,passive adsorbent modules and
aC5-C17 hydrocarbons extraction method.Soil grain size was also
determined to better understand the distribution and dispersion of
geochemical results.

Sampling procedures
Sampling was performed in 97 stations located throughout the
diapir and its surroundings (Fig 2).Soil samples for headspace
analysis were collected in plastic containers with metal lids (Isojars)
adding water and a bactericide solution.A soil probe was used to
penetrate the soil in order to collect gases for direct measurements.
For microbiological analyses soil samples were collected with
propersterilized equipment to warrant asepsis.All samples
were frozen, including a selected number of samples for DNA

Figure 1. Sulfur isotopic composition of H2S from presalt reservoirs and of

anhydrite (Aptian evaporites). Notice the overlap between the d34S of both
groups of samples suggesting that anhydrite is the most likely source of
sulfur for TSR. Non overlapped part of the d34S of precipitated from H2S
can be, probably, derived from evaporite facies not yet sampled.

Soil samples for adsorbed gases, C15+ extraction and fluorescence

were placed in zip-lock plastic bags and frozen to minimize possible

microbial activity. Iodine, soilEh/pH, elements concentration and
C5-C17 hydrocarbons extraction samples were collected in the
same manner and left unfrozen.
Passive hydrophobic adsorbent modules were buried and exposed
for approximately seven days, after which they were retrieved and
sent to the laboratory for analysis.

Preliminary Results and Discussion

Results obtained so far refer to chemical elements, direct gas
measurements,soilEh/pH, microbiology and extraction methods.
Analyses pertaining to the remaining methods are in progress.
Geochemical concentrations were analyzed statistically using the
Statistica program. The normal and log-normal populationbehaviors
wereobtained. The latter, common to the most of the studied
variables, were convertedto logarithms and transformed to Z-score
values to facilitate comparison between different concentration
measurements. The variables were then analyzed through Principal
Component Analysis (PCA). The Surfer program was employed to
producenearly 180 maps of geochemical contours, in Z-scores, to
determine which variables relate direct or indirectly to the oil seep
at the Cinzentodiapir.
The geochemical contour maps were divided in two main groups,
i.e. apical and haloanomalies. The best apical anomalies were
indicated by Z-score sum of Sc, Ce, Rb and K. Beyond these
variables, F (Figure 2), U, Cu, Pb, Zn, Cd, Ni, Eh and pH also
showapical anomalies. The halo anomalies were pointed out by
2,4-Dimethyl Pentane, 1-Heptene and 1-Nonane. Ba, Be, Ca, Ce,
Co, K, La, Li, Lu,Mg, Mn, Na, Rb, Sr, Tb, Y and Ybanomalies correlate
with the outcropping diapir, which corresponds to an area of finer
grain size (silt-clay).Ratios of U, Th and K also show correlation with
the hydrocarbon seep at the diapir, U/Th normalization indicated
an apical anomaly and the K/Th normalization pointed out a halo
Direct gas measurements in soil indicated anomalous values
for total gases and CO2 within and surrounding the diapir. The
microbiology method did notproducesignificant anomalies in the

This preliminary study sheds light on the possibility of detecting
geochemical anomalies using methods other than the traditional
surface geochemistry methods such as headspace, through which
light gases (methane, ethane, propane, butane and pentane) are
measured for oil and gas exploration. It was possible to increase
the robustness of the geochemical results employing multiple
methodswhich correlate directly or indirectly with the oil seep.

The authors thank PetroleoBrasileiro SA Petrobras and the
Brazilian Petroleum Agency - ANP for permission to publish.
We also thankFernando Pellon de Miranda for suggestions and

Bandeira de Mello, C.S., Gonalves, R. C. S., Miller, D. J., Freire, A. F. M.,
Suaznabar, B. R. 2014.Levantamento Geoqumico de Superfcie na regio




do Dipiro do Cinzento na Bacia do Recncavo, BA. Relatrio Tcnico Final

para a ANP.

Geochemical monitoring: baselines for the

surface (soils) and for reservoir fluids of the
Zapatos-Mata R field, Area Mayor Anaco,
Eastern basin, Venezuela.

Silliman, A. H. & Anderson, H. S., 2014. Geochemical Survey of an Onshore

MacroseepDiapirodoCinzento, Reconcavo Basin, Brasil, Technical Report
for Petrobras.

Bruno Garciaa, Virgile Rouchona, Victor Alcobiab, Mercedes

a IFP nergies nouvelles (IFPEN), Direction Gosciences, 1 et 4
avenue de Bois-Prau, 92852 Rueil-Malmaison Cedex France
b Beicip-Franlab, 232, Avenue Napolon Bonaparte, 92502 RueilMalmaison Cedex - France
c PDVSA GAS. Nueva Esparta Avenue, PDSVA GAS Building, South
Hill Sector, 6001 (zip code) Barcelona, Anzotegui, Venezuela
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).


Figure 2. Plot of 84Kr/4He vs CO2 content (%) for the different analysed

Results and Discussion

reservoirs (reservoir baseline, circles), the different analysed soil samples

Concerning in situ measurements on soil points, the average CO2

flux obtained was equal to 0.060.04 during the M1
survey campaign and equal to 0.0560.053 during
the M2 survey campaign. The carbon isotopic composition of CO2,
13CCO2, of the 10 soil samples analysed during both the M1 and
M2 survey campaigns are comprised between -11.90.3 and
-22.30.3. The air/soil mixing model process (for the calculation
of the 13CCO2 values of soil samples) gives a range of 13CCO2
from -18 to -26 (figure 1).

(soil baseline, triangles) and the future injected CO2 (hypothesis, crosses)

The compositions of the different reservoirs sampled during the

M1 and M2 survey campaigns (from well-heads) follow the same
trend: CH4 is the major gas component 70%vol, followed by
C2 10%vol, CO2 and C3 in the same order of concentration
8%vol, and finally C4 and C5 represent 1-2%vol. The carbonisotopic composition of these reservoirs provide information on
gas sources. The carbon isotopic composition of CH4, 13CCH4
displays a value of -45 (M1 and M2 survey campaign for all field
samples) suggesting a thermogenic source. For CO2, 13CCO2
values are range from -2 to -15. These values can result
from a mixed thermogenic/inorganic source. For the other HC
compounds, 13C values ranging from -32 to -26 are not

PDVSA is launching an industrial project of Enhancing Oil Recovery

by CO2 injection (EOR-CO2). In a second phase, this project
will probably gear up as a candidate for a pilot study involving
carbon capture and storage (CCS) if prerequisites are met. In a
context of safety and public acceptance for EOR process and
underground CO2 storage, a surface background of natural CO2
content and surface fluxes prior to the EOR-CO2 and/or CCS
need to be performed. Complementary to the surface monitoring,
an integrated geochemical study of subsurface elements, including
fluid reservoirs, was performed. It compiles data and sets up a
reference geochemical baseline, an absolute prerequisite step in
the preparation of any EOR-CO2 project.

Figure 1. Geologic map and planned sample stations of the shale diapir area.

From two survey campaigns (M1 and M2) accomplished in 2012,

the gas composition of soils, the control of the variability of this
natural composition through time as well as the geochemical
composition of different reservoir fluids have been performed. A
complete baseline has be obtained and will serve as reference to
characterize potential CO2 leakage during future injection and then
assess the safety of the storage processes.

in the cases of 1) an oxycombustion capture process and 2) an amine

capture process.

In the event of a leak, the appropriate monitoring strategy includes
a good knowledge of the reservoir geology and particularly of the
structural aspects. Structural drains (where leaks can probably
occur) must be identified and typified together with associated
geo-fluids. 4 different geo-fluids are identified as end members
and must be typified for an efficient monitoring survey (reservoir,
aquifer, injected CO2 and soil). Depending on structural features
of reservoir and specific natural compositions of the fluids, different
strategy can be applied that will have to be determined during
baseline determinations.
In our case, the gas compositions obtained at the surface and
subsurface, together with the natural CO2 fluxes and contents
from soils can be used as a basis of methodological guidelines:
Leak detection at surface level: i) low natural CO2 fluxes and contents
are well suited to surface leak detection. ii) isotopic composition
of carbon (13CCO2) for soil samples has been identified as the
most discriminatory geochemical signature to detect an eventual
CO2 leakage. Finally, iii) the methane isotopic composition of the
reservoir, much lower than atmospheric methane composition is
well suited to leak detections at the surface.
Leak detection at both reservoir and aquifer levels: i) the CO2
isotopic composition of the reservoir, much heavier than biological
CO2 composition is well suited to track injected CO2 occurrence in
soils. ii) high He abundances in reservoirs (compared to atmosphere)
will trace efficiently leaks at both the surface level and aquifers.
Noble gas composition of reservoirs is the most discriminatory
geochemical signature to detect an eventual CO2 leakage at any
reservoir level or aquifer (figure 2).

Figure 1. 13CCO2 (per mil) in function of 1/ (CO2%vol) in a log scale, for


soil samples.

Garcia, B., Hy Billiot, J., Rouchon, V., Mouronval, G., Lescanne,

M., Lachet, V., Aimard, N. A Geochemical Approach for Monitoring
a CO2 Pilot Site: Rousse, France. A Major gases, CO2-carbon
isotopes and Noble Gases Combined Approach (2012). Oil Gas
Science and Technology, vol. 67; pp. 341-353.

The noble gas compositions of the fluids from reservoir and soil
points display specific signatures and provide information in term
of early identification of gas breakthrough (figure 2).

The IFPEN methodology for geochemical monitoring: Description
This methodology developed these last years is a major-gases,
CO2-carbon-isotopes and noble gases combined approach
(Garcia et al., 2012).

Figure 2.Z-score contour of the fluorineanomaly. The orange area correlates

roughly with the outcropping diapir.

In this project, - in situ measurements of i) HCs and CO2 contents

and ii) CO2 fluxes for the surface (soils) were realized. Moreover,
samplings of gas were performed for i) CO2-carbon isotope and
ii) noble gas analyses at laboratory. For each M1 and M2 survey
campaign, a total of 50 soil points were measured in situ and, 10
soil points together with 10 wells (reservoir fluids) were sampled for
complementary laboratory analyses.





Recognition of Onshore Surface Seeps

and Microseeps by Determination of Soil
Diamondoid Concentrations

Hydrocarbon Generation Potential in The
Talara Basin, Peru

Jeremy Dahl1, J.M. Moldowan2, Micaela Nali3, and Roberto


Liliana Lpez,Sandra Casado, Johnatan Soto and Salvador Lo


Stanford University
Biomarker Technology International

Instituto de Ciencias de la Tierra. Facultad de Ciencias. Universidad

Central de Venezuela

Recognition of onshore and offshore hydrocarbon seeps and

microseeps has been a fundamental aspect of petroleum
exploration since the inception of the industry. Thousands of
years ago, oil was collected for use where it leaked out of the
ground. Later many of these same sights were targeted for drilling
and became some of the first oil fields. Success onshore was
duplicated offshore, with the recognition of subsea seeps generally
through the analysis of piston cores.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

of X-ray diffraction (Siemens XD-8 Advance) and sulfur content,

vanadium and nickel concentrations by inductively coupled plasma
atomic emission spectroscopy (ICP-AES). Bitumen was extracted
with dichloromethane in a Soxhlet extractor, and then quantified.
In the bitumen extract, after asphaltenes precipitation, the maltene
fraction was separated into its saturated, aromatic and resin
fractions by means of adsorption chromatography, using alumina
as the stationary phase. The saturated hydrocarbon fractions were
eluted with n-hexane, the aromatic hydrocarbon fractions with
toluene, and the resin fractions with a toluene:methanol mixture.
Detailed analyses of the saturated and aromatic biomarkers were
performed by gas chromatography-mass spectrometry (GC-MS)
coupling a network gas chromatograph (Model 6890N, Agilent
Technologies) to a mass spectrometer (Model 5975, Agilent
Technologies). In this case, the GC system was equipped with a
type DB-1 or a type DB-5 fused silica capillary column (60m x 0.25
mm x 0.25 m) to analyze the saturated and aromatic fractions
respectively. The monitored ions were: m/z = 113, 191, 177, 217,
218 for n-alkanes and acyclic isoprenoids (pristane and phytane)
terpanes, steranes and diasteranes; m/z = 178, 192, 184, and 198
for phenanthrene, methylphenanthrenes, dibenzothiophene and
methyldibenzothiophenes, respectively.

The Talara Basin is located in the NW coast of Peru and includes
sedimentary sequences containing rocks from the Paleozoic to the
Tertiary ages. The Muerto (COT = 1.0-4.5%) and Redondo (COT <
1.0%) formations from the Cretaceous age, which contain kerogen
type II and II-III, have been considered as possible source rocks
(Martnez et al., 2005). Moreover, the Heath Formation from the
Tertiary (Oligocene) age, which is characterized by the presence
of high input of terrigenous organic matter, was also proposed
as a possible source rock (Fildani et al., 2005). Although these
studies indicated the high potential for hydrocarbon generation
in the Talara Basin, it is necessary to further identify the possible
source rocks through a detailed evaluation of oil-oil and oil-source
rock correlations of different stratigraphic sequences, in addition
to establishing the petroleum systems. Here, we present the
study of drilling cuttings samples extracted at different depths
from four wells in the Talara basin for source rock evaluation and
determination of the depth intervals with potential for hydrocarbon
generation. The potential of the samples as source rocks was
determined through the evaluation of lithology, organic matter
type, depositional redox environment, thermal maturity level,
and hydrocarbon-generating potential, using a combined suite
of rock analyses: (1) mineralogical composition, (2) total organic
carbon content, (3) bitumen concentration, (4) SARA (saturated,
aromatic, resins and asphaltenes) composition in bitumen extracts,
(5) biomarkers in saturated hydrocarbon fractions, (6) aromatic
markers in aromatic hydrocarbon fractions, (7) rock-eval pyrolysis,
and (8) trace elements (e.g., V and Ni).

With most of the major onshore seeps already mapped, it became

necessary to recognize and map microseeps. A variety of
methods have been employed for this end including subjecting soil
samples to hydrocarbon gas and liquid extraction and analysis
and microbial studies including DNA analyses.
Recently, we showed that the measurement of diamondoid
concentrations in piston core samples could be a valuable tool for
recognizing offshore oil and gas seeps. In many areas, even though
other methods fail to detect gas seeps, diamondoid concentrations
can rise an order of magnitude above the background. As such,
measuring diamondoid concentrations in piston core extracts
can be a highly valuable method of mapping offshore seeps and
As a result of this success, we were curious as to whether we
might be able to map out onshore surface seeps of oil and gas
using diamondoid concentrations in soil. To test this method we
mapped diamondoid concentrations over a known oil accumulation
and compared the values to surrounding areas. We showed that
diamondoid concentration over the oilfield are generally higher than
in the surrounding area, in some cases by an order of magnitude.
We believe this method could become a powerful tool for the
recognition of onshore microseeps. Furthermore, we believe this
will be the best method for mapping seeps of high-maturity fluids
like gas and condensates, which contain high concentration of
diamondoids, especially since many of the other methods have
limitations for recognizing these types of fluids.

Forty two drilling cuttings samplesin fourwells(LA,CO, OLandZA)
from the TalaraBasin(Peru) were analyzed. The total carbon
(TC) contents were determined using a carbon analyzer (LECO,
C-144). The inorganic carbon or carbonatic carbon contents
were measured using the Bernard calcimeter method and total
organic matter (TOC) was determined by difference. Kerogen type
and maturity level were determined on a standard Rock-Eval-6
following basic methods for whole rock analysis. For ten selected
samples, mineralogical composition was determined by means

Results and Discussion

All the samples presented TOC contents in the range 0.9-2.9%,
reaching TOC contents > 5% only in a few cases. Lateral and
vertical variations in the TOC contents were observed, where the LA
and OL wells presented TOC contents in the order of 6% whereas
the TOC contents in the CO and ZA wells reached maximum
values of 2%. This result indicates the wide variability of the organic
matter input of the basin. Samples with TOC content 1% can
be considered good source rocks, and those with TOC content
> 4% are considered excellent source rocks. The TOC content
values obtained suggest that the samples are potentially good
source rocks. On the other hand, the samples are characterized
by the presence of kerogen type II and II-III, with Tmax value in the
range of 443-440Cindicating that these samples are early mature
to onset of oil window maturity. The bitumen concentrations in
the samples are distributed within a wide range from 300 to 4000
ppm. The hydrocarbon/resin ratios as determined from the SARA
compositions are close to 1. Figure 1 shows a typical example of
a mass chromatogram for n-alkanes and acyclic isoprenoids (Pr =
pristane and Ph = phytane), terpanes and steranes. All analyzed the
samples presented Pr/Ph in the range from 1.0 to 1.9, the high
pristane/phytane ratio and plot pristane/n-C17 vs phytane/n-C18
indicate that these source rock contain mixed terrigenous and
marine type II-III and terrigenous type III organic matter deposited
under suboxic to oxic conditions (Figure 2). Additionally, in
homohopanes distribution (C35< C34), is, typical of suboxic to oxic
conditions during source rock deposition. The correlation between
dibenzothiophene/phenanthrene and Pr/Ph ratios suggests that the
samples come from marine shale. On the other hand, the regular
steranes distributions and the abundance of C27 steranes relative
to C29 steranes, as well as the presence of for tricyclic terpanes,
suggest a contribution of marine organic matter input. In addition,
the presence of 18(H)-oleanane in some intervals, indicates the
presence angiosperm plants during the sedimentation of source
rocks from the Cretaceous to the Tertiary ages. The relationship
between steranes and C27-diasteranes [C27-diasteranes/(C27diasteranes+steranes)] suggests the presence of siliclastic lithology

in the samples, where the main mineralogical phases are calcite,

quartz, kaolinite, illite, montmorillonite, plagioclase, and traces of
pyrite minerals. Both montmorillonite and illite could be responsible
for catalyzing the conversion of sterenes to diasterenes (with
a rearranged structure), which are then reduced to diasteranes.
Thus, in agreement with our findings, oils from clastic source rocks
tend to be rich in diasteranes. The concentrations of V (187-3840
ppm) are higher than those of Ni (40-246 ppm), and the values of
the V/(V + Ni) ratio are in the range of 0.7-0.9. Sulfur contents are in
the range of 0.7 to 1.5%. These results are typical of sedimentation
under suboxic conditions with low availability of S.

The core rock samples were identified as possible source rocks
with the following overall characteristics: (a) siliclastic lithology,
(b) mixed marine-terrigenous organic matter (type II-III kerogen),
(c) marine shale depositional environments with suboxic to oxic
conditions, (d) early mature to onset of oil window maturity, and (e)
regular to very good generating potential.

This work was funded by the Consejo de Desarrollo Cientfico y
Humanstico, Universidad Central de Venezuela, under the research
grant N PG-03-8204-2011 and Fondo Nacional para la Ciencia y
Tecnologa, under the research grant N 2012002299. We thank
the Laboratory ChemiConsult of Venezuela for donating the drilling
cuttings samples from the Talara Basin. References
Fildani, A., Hanson, D.H., Zhengzheng, C., Moldowan, J.M.,
Graham, S.A., Arriola, P.R., 2005. Geochemical characteristics of
oil and source rocks and implications for petroleum system, Talara
Basin, northwest Peru. American Association of Petroleum Bulletin
89, 1519-1545.
Martnez, E., Fernndez, J., Caldern Y., Hermoza, W., Galdos,
C., 2005. Tumbes and Talara Basins Hydrocarbon Evaluation.



Figure 1. Mass chromatograms of the n-alkanes and acyclic isoprenoids

(m/z = 113, top) terpanes (m/z = 191, middle) and steranes (m/z = 218,

New gas-condensates reservoir on Golfo de

Venezuela Basin, Offshore, Venezuela. Source
rock and fluids geochemical characterization

bottom) in the saturated hydrocarbon fractions isolated from the bitumen

of sample from OL.

Pirela, M.a; Berrios, Ia

a E&P General Management, PDVSA Intevep, S.A. Los Teques,
P.O. Box 76343 1070-A, Venezuela

following method was applied: API gravity and elements (V, Ni and
S) determination, GC of C15- fraction, SARA composition, 13C
determination of whole oil, saturated and aromatic fractions, and
specific compounds determination (diamondoids).
On the other hand, rocks samples (cuttings and core) were collected
from 12 wells located offshore and onshore on Golfo de Venezuela
Basin. These wells grouped samples from Tertiary and Cretaceous
intervals. Samples were characterized based on results coming
from Rock Eval Pyrolysis, organic petrography, and biomarkers
according to organic matters content, type and thermal maturity.
Results and Discussion

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Gas samples results (Well-2, -3 and -4) reflect values below 95

% in CH4 (wet gas) along with a value greater than 4% for C2H6
(ethane) and more than 7% of compounds C2+, also indicates
the source of generation is associated with hydrocarbon type

hydrocarbons thermal evolution must be located in a maturity

range of 0.9% Ro 1.3 - 1.6 (Pirela et al., 2013).
Regarding hydrocarbons origin, assessed by steranes, seems to
be associated with type III/II kerogen with terrestrial predominant
organic matter input. However, isotopic correlations between
saturates and aromatic hydrocarbons suggest a marine origin.
Steranes also indicates that lithology associated is siliciclastic,
and isotopic data (total 13Coil -23 0.3 ) suggests a Miocene
source rock (Peters et al., 2005).
Previous results correlate with rocks geochemical characterization
which suggests Miocene (TOC>2%; type II kerogen; immature) and
Oligocene (TOC 0.5 -1%; type II/III kerogen; immature) intervals
as potential source rocks on offshore wells located on (Well-1,2,-3,-4 and -5). However, Cretaceous intervals (TOC 3%; type II/
III kerogen; mature to overmature) were main potential source rock
on onshore wells (Well-9,-10,-11,-12).

Offshore exploration studies are currently one of the main objectives
of the Venezuelan oil industry; these have been extended in several
areas: East, Nor-east, Center and Western (Golfo de Venezuela
Basin) regions of country.

Figure 2.Pristane/n-C17 versus phytane/n-C18 showing the type II-III and

type III kerogen in samples from Talara basin.

In 2009 was drilled the first wells on northeast of Golfo de Venezuela

Basin (Cardon IV Field; Figure 1) and confirms the existence of gas
and light oil on Tertiary carbonate facies. Due to this discovery, has
been of great interest since it is estimated that more than 10 TFC
remain on the area, generating an intense exploration activity that
including drilling new wells in order to understand the petroleum
system on the area and to assess the genesis of hydrocarbons
discovered (Pirela et al., 2013).

On the same way, C2-C5 alkanes (including iso-butane) 13C

isotope suggests that gas were originated from type III-II kerogen
thermal cracking (thermogenic gas). Difference between ethane and
propane also indicate that gas in reservoir has been generated by
organic matters primary cracking, and it is maturity is equivalent to
1.1 % Ro and required a temperature above 180C for generation.
On same reservoir, liquid petroleum (condensates, type crude
oil paraffin) displayed API gravity values equal to 49 correlating
with SARA composition: saturated hydrocarbons (70 wt%) and
aromatics (30 wt%), with no concentration for asphaltenes and
resins fractions. In fact, distribution pattern suggests a greater
prevalence of lower molecular weight compounds <C15, typical
of light crude and also associated with a high maturity. Moreover
GC saturated fraction analysis (corresponding to C15+ fraction)
presents unimodal distribution pattern with predominance between
n-C14 and n-C16 paraffins, and odd paraffins, typical of oil
associated to marine organic matter (Figure 2). However, Pristane
/ Phytane ratio (3.367) indicates a contribution of terrestrial organic
matter deposited under oxic conditions.

Figure 1. Golfo de Venezuela basins relative location

Width range in maturity levels may be reflecting a possible mixture of

hydrocarbons with different thermal maturity; however this aspect,
from the point of view of organic matter there are not variations,
so if this hypothesis is true, mixture corresponds to hydrocarbons
associated with same source rock.


In this sense, this work presents rocks and fluid geochemical

characterizations with main objective to establish oil-oil, and some
cases oil-rocks correlations to determine if there are more than one
oil family or source rocks on the area.

The authors thank PDVSA Intevep for permission to publish this






Cretaceous sequences absence on North East region along with

presence of same age sequences (potential source rocks) in
South Eastern region suggest existence of at least two petroleum
systems in Golfo de Venezuela basin. First one Tertiary-Tertiary
(totally different and new) and second one made up of CretaceousTertiary (traditional petroleum system found onshore).

Gas and condensates samples were collected from Wells 2,3 and
4 to characterize fluids present in Cardn IV field. Interval evaluated
corresponds to a sequence calcareous from early Miocene
(Cuauderalito Member) with a thickness of approximately 750 ft,
located (by electric logs) between 9000 - 9700 ft to depth.
Gas samples were analyzed by chemical and molecular
composition based on the procedure described in analytical norm
COVENIN 2569-89 and 13CH4 was determined using isotope
ratio GC (GC-C-IRMS). Furthermore, for oil characterization

All geochemical results are consistent with Golfo de Venezuela

basin geological literature (e.g. Contreras, 2011; VIPA, 2000)
about existence of two regions (North Eastern and South Western)
separate by a tectonic feature known as Urumaco Through (Figure
1) and Lagarto system fault. On first region, absence of Cretaceous
intervals suggests that tectonic events (possibly movement of the
Caribbean plate during Paleocene-Eocene; Escalona and Mann,
2011) associated with Urumaco Through and Golfo de Venezuela
basin formation have caused erosion of older Oligocene sequences.
This is supported by high maturity degree reached by Cretaceous
sequences in South Western region and correlates with maturity
degree between Miocene sequences in both regions.

Pirela, M.; Prez, A.; Berrios, I., 2013. Geochemical characterization

of discovery new gas-condensates reservoir on Golfo de Venezuela
Basin, Offshore, Venezuela. On: 26th International Meeting on Organic
Figure 2. Well-2, -3 and -4 total oil crude chromatogram

Geochemistry (IMOG), Tenerife, Espaa, September 2013.

On the other hand, various geochemical parameters related to

oil maturity (diamondoids, isoprenoids relations and n-paraffins,
n-heptane and iso-heptane indexes) show no clear definition as
to this aspect is concerned. Considering all maturity parameters,

Peter, K., Walters, C.; Moldowan, M., 2005. Biomarkers and Isotopes in
Petroleum Exploration and Earth History, Cambridge University Press.



Escalona, P.; Mann, P., 1995. Tectonics, basin subsidence mechanisms,

and paleogeography of the Caribbean-South American plate boundary
zone, Marine and Petroleum Geology. 28, 8-39.

Origin of oil in western Shaim region,

West Siberian Basin, Russia

Contreras, D.R., 2011. Defining the Northeastern boundary of the

supergiant Maracaibo foreland basin, Venezuela. Geos 41:94-95. Master
Dissertation. University of Texas.

Makarova A.a, Jos R. Carballob*

Visin Integrada del Potencial Petrolfero de Venezuela, 2000. PDVSA.

a Repsol-Russia
b Repsol Sinopec Brasil

Internal Report.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

West Siberian Basin (WSB) is a quite mature basin and new
discoveries are rare. However, some areas, particularly in the
western and eastern borders, remains basically unexplored
as they have been classified as low potential.Recent drilling
results in the westernmost area WSB show that Jurassic and
Cretaceous petroleum plays extend further to the west from the
known hydrocarbon accumulations. Existing geochemical models
(Kontorovich, et al.) indicate that Jurassic organic reach facies,
which represent the major sources of hydrocarbon in the basin,
significantly degrade toward the borders of the basin showing poor
TOC content and generally being immature to barely mature for
hydrocarbon generation. A detailed geochemical study based on
GC-MS, biomarker and stable 13C isotope analysis of oil samples
has been performed in order to establish genetic relationships
with the known hydrocarbon source rocks and oils in the western
border of the basin.

Three samples of crude oils, including 2 tested oils from the first
exploration well and one heavy oil from Yeremenskoye field have
been analyzed by standard GC on Agilent Technologies 7890A GS
System. GC-MS analyses of crude oils and rock bitumens were
performed using CLARUS 500 (PerkinElmer) gas-chromatographmass spectrometer after separations into saturated and aromatic
hydrocarbons. Calculation of relative content of each compound
was done by method of simple peak area normalization.
Also geochemical analyses results of 23 oil samples from wells in
Shaim region (from Neftex research company) and published data
of 32 oil samples (Peters, Kontorovich et al., 1994) of the entire
WSB widely distributed by geographic locations and reservoir age
were selected andintegrated in the study for correlations.

Results and Discussion

Analyzed oils from Vikulovo and Leushinskaya fm show
geochemical characteristics that indicate deposition under marine
conditions. GC of saturated fraction of oil from Leushinskaya fm
has an unimodal n-alkanes distribution maximizing at n-C17-C18,
abundance of which gives the evidence of algal contribution to
source rock and relatively high thermal maturity. Oils from Vikulovo
and Leushinskaya fm have Pr/Ph ratio in the range 1.15-1.2,
which as well very typical for low-wax oils from marine source
rock. Analysis of Pr/nC17 versus Ph/nC18 for crude oils, saturated

fractions and bitumen extractions supported version of marine

(type II) or mixed (type II/III) source rock (Peters et al., 2004).
Normally oils from Bazhenov source rock have generally higher
sulfur content (>1.0 wt.%) and result from sulfate-reducing bacteria
activity, primarily in anoxic marine sediments and low Pr/Ph ratio
(<1.1 or even lower). Whilst typical oils from Tyumen fm show lower
sulfur content (0.01 wt.%) and higher Pr/Ph = 4 (Peters et al.,
1994). Oils from both intervals show medium sulfur content = 0.4
wt. %, and from Yereminskoye field = 0.9 wt.%.
The regular stair-step progression of C31-C35 homohopanes in
combination with value of ratio C31 22R/C30 hopane ranging
from 0.38 to 0.41 are consistent with suboxic bottom water during
deposition under marine shelf condition. Relative depletion of
28,30-Bisnorhopane compared to typical high-sulfur Bazhenovsourced oils also indicates oxic-suboxic environment.
A ternary diagram of 20R epimers of 5(H),14(H),17(H) forms of
C27-C28-C29 steranes (regular steranes) was used to distinguish
groups of crude oils from different source rocks. Oils from Tyumen
source rock are more abundant in C29 regular steranes due to
high contribution of terrestrial organic matter to the sediments.
As distinct from them oils from Bazhenov source rock are rich in
C27-C28 streranes. All oils from Shaim region, including oils from
Karabashskaya area have C27-C28-C29 steranes in nearly equal
concentration. Also ternary diagram of C27-C28-C29 diasteranes
(rearranged steranes) was used to support oil-oil correlation.
During burial and maturation R configuration at C-20 steranes are
gradually converted to a mixture of R and S configuration, causing
an increase in / (+), until equilibrium is reached (Peters et
al., 2004). On the same basis isomerization at C-22 in C31-C35
homohopane takes place, resulting in increasing of 22S/ (22S+22R)
ratio. In order to evaluate oil maturity two plots were used: 20S/
(20S+20R) vs %C29/(+) for the C29 sterane; %C3222S/
(22S+22R) vs %C2920S/(20S+20R). In comparison with oil related
to Tyumen source rock and majority of oils related to Bazhenov
source rock, oils from Vikulovo and Leushinskaya reservoirs are
less mature and correspond to early-middle oil window. The ratio
of C30 17,21 (H)-moretane to their corresponding 17,21 (H)hopane decreases with thermal maturity from 0.8 to 0.15 (and
even less), these values for Vikulovo = 0.13, Leushinskaya= 0.13
and Vikulovo (Yereminskoye field) = 0.07 are coincide with values
typical for mature oils.
GC of three related oils show different degree of biodegradation.
Compared with the non-biodegraded oil of Leushinskaya fm, the
oil of Vikulovo fm is slightly biodegraded as indicated by the loss of
n-alkanes. While the moderately biodegraded oil from Yereminskoye
field (Vikulovo fm) shows a more severe biodegradation evidenced
by the loss of both n-alkanes and acyclic isoprenoind.API gravity
decreases with increasing biodegradation among oils: 33 API in
Leushinskaya, 28 - Vikulovo, 19 - Vikulovo (Yereminskoye field).
Comparison of GC of oils from Vikulovo reservoir from different
depth show excellent vertical biodegradation gradients, with
degree of biodegradation increasing toward the OWC, because of
presence of water. Shallow depth of the reservoir as well favors
biodegradation, because of low temperature and sufficient porosity
to allow the diffusion of nutrients and bacteria activity.
As indicated by similar distribution of n- and i-alcanes, steranes and
diasteranes, triterpanes, monoaromatic and triaromatic steroids,
oils from Vikulovo y Leushinskaya reservoirs are genetically related
to oils from Shaim region. Therefore, HC from Karabashskiy area
most likely were generated from Jurassic organic facies analog to

bituminous shale of Bazhenov formation. The differences could be

explained by regional variations in source rock properties toward the
borders of the basin, where Bazhenov was deposited in shallower
depositional environments. Absence of strong arguments in
biomarkers characteristics in favor of significant input of terrestrial
organic matter from the Ural Mountains can be explained by their
relatively low relief and predominance of chemical weathering.

Results of geochemical analyses provide evidence that
hydrocarbons from Lower Cretaceous Vikulovo and Leushinskaya
reservoirs are genetically related to oils from Shaim region and
were generated from Upper Jurassic - Lower Cretaceous organic
facies analog to bituminous shale of Bazhenov formation. These
accumulations of oil rims with gas caps in Karabashskiy area result
from the process of separation-migration of originally single-phase
fluid deposits, containing oil and trapped in Jurassic reservoir.
Strike-slip faulting in Pre-Jurassic basement in Oligocene time
caused pressure release followed by phase separation, fluid
migration into shallower position and retrograde condensation.
Shallow depth favored microbial activity in Vikulovo reservoir
resulting in nonhomogeneous biodegradation of oil within the
It has to be pointed out that the results presented in this study
are not conclusive and on-coming drilling campaign should help
in solving problems such as reservoir continuity, oil and gas
composition changing, level of biodegradation, which can impact
greatly the economic value and producibility of petroleum.

Haworth, J., M. Sellens, and A. Whittaker, 1985, Interpretation of
hydrocarbon shows using light (C1-C5) hydrocarbon gases from mud-log
data: AAPG Bulletin, v. 69, p.1305-1310.
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Platform: Insights from 3D seismic imagery, C. R. Geoscience 344 (2012)
A. Kontorovich et al. Main oil source formations of the West Siberian
Basin, Petroleum Geoscience, Vol. 3 1997, pp. 343-358
A. Milkov Methanogenic biodegradation of petroleum in the West Siberian
Basin (Russia): Significance for formation of giant Cenomanian gas pool,
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1,2, 2004
K.E. Peters, A.Eh. Kontorovich, B.J. Huizinga, J.M. Moldowan, and C.Y.Lee
Multiple oil families in the West Siberian Basin, AAPG Bulletin, V.78, No.6
(June 1994), p.893-909
V.A. Savenko, Paleogeography and paleomorphology of Upper Jurassic
Neocomian sediments in Shaim oil and gas bearing region and adjoining
areas of West Siberia, Lithosphere, 2011
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A.Timurziev Strike-slip neotectonic in sedimentary basins: tectonophysics
and fluid dynamics, ScD theses, 2009
A.V. Vyssotski, V.N. Vyssotski, A.A. Nezhdanov Evolution of the West
Siberian Basin, Marine and Petroleum Geology, 23 , 2006



temperature was 310 C. The quadrupole mass spectrometer


was operated in full scan mode over the mass range 50650 Da
(EI mode at 70 eV). Collision Energy 10 eV. Collision Gas Ar. For

Identification of aryl isoprenoids in oils from

SergipeAlagoas Basin, northeastern Brazil
using Triple Quadrupole GC-MS/MS

Geochemical evaluation of oil migration in

Stromatolites Samples: influence of water
formation salinity

data acquisition by selected reaction monitoring (SRM) the masses

according to Figure 2(a) were used for the two compound groups
under investigation. The identification of biomarkers was done by
comparison of elution order, retention times and mass spectra with

Antnia L. da S. Santosa, Edymilas da S. Sousaa, Gustavo R.

Santos Jniorab, Marcio dos S. Rochaa,
Jos A. D. Lopesa, Antnia M. G. L. Cita, Francisco de A. M.
Reisb, Igor V. A. F. de Souzac, Sidney G. de Limaa*.

Rafael C. Pachecoa*/ Eliane S. DeSouzaa/ LeonamBragaa

literature data (Summons and Powel, 1987; Peter et al., 2005;

Zhang et al., 2011; Santos Jnior et al., 2013)



Results and Discussion

Figure 1 showed the distribution of aromatic hydrocarbon and aryl

a Universidade Federal do Piau UFPI , Laboratrio de Geoqumica

Orgnica - LAGO, 64049-550, Teresina, PI, Brazil.
b Universidade Estadual de Campinas UNICAMP, Instituto de
Qumica, 13083-970, Campinas, SP, Brazil.
c Petrobras - Research and Development Center, Brazil.

isoprenoids, TIC typical of the saturate fraction; RIC of m/z 134 and

Figure 2. SRM Transitions for TSQ Quantum XLS (a) and structures and

120, pointing out the aryl isoprenoids and remaining diagenetic

likely relationships between m/z 134 and 120 series (b).

isorenieratane products.
The chromatographic profiles (TIC, Figure 1) and geochemical


parameters from the saturated fractions in this study indicate that

they are not biodegraded and achieved similar thermal maturity

Copyright 2014, ALAGO.

levels (early to middle oil window) and that their source rocks were

This paper was selected for presentation by an ALAGO Scientific Committee following

deposited in a reducing depositional environment, under different

review of information contained in an abstract submitted by the author(s).

levels of salinity.


Figure 1 shows the chromatographic profile of the saturated and

Biomarker hydrocarbons in oils and sediments have considerable

This paper was selected for presentation by an ALAGO Scientific Committee following

The presence of diagenetic and/or catagenetic products of

isorenieratane in source rocks and crude oils suggests photic zone
anoxia during the deposition of organic-rich sediments. Additional
confirmation of the origin of aryl isoprenoids from Chrobiaceae
in this oils can be obtained if these compounds are isotopically
heavier than their carotane counterparts of algal origin. However,
the presence of these compounds have been often related to
anoxic depositional setting, and their structures are strongly
correlated to biological precursors derived from Chlorobiaceae and

aromatic fraction (m/z 120 and 134). m/z 134 mass chromatogram

potential for assessing the nature of biological processes in the

past, but only a few can be uniquely related to particular organisms.
In analysis of Sergipe-Alagoas basin, related to the lacustrine and

showing distribution of trimethyl aryl isoprenoids, and m/z 120


mass chromatogram showing the novel series of dimethyl aryl

We complemented previous studies (Sousa Jnior et al, 2013)

and identified a new series of dimethyl arylisoprenoids in oils of
the Sergipe-Alagoas Basin - Northeast of Brazil, saline lacustrine,
by GC-MS-MS (EI and CI). The co-occurrence of the dimethyl aryl
(m/z 120) and structurally related trimethyl aryl (m/z 134) series
may indicate that the former likely derive from the latter by way of a
demethylation process, as suggested by (Zhang et al., 2011), but
this this specificity needs to be further investigated.

isoprenoids. To m/z 120 series can be generated from the m/z 134

marine evaporitic source rocks, we identified a large range of

counterparts through loss of a methyl from the aromatic ring at C-6

diagenetic and catagenetic products of the aromatic carotenoid

or C-3 or C-4 (Zhang et al., 2011).

isorenieratene, including C40, C33, and C32 diaryl isoprenoids and

aryl isoprenoid derivatives (Sousa Jnior et al., 2013).
In this paper we re-evaluate the serie of trimethyl aryl and dimethyl
aryl isoprenoids by GC-MS and GC-MS-MS (EI, CI). In addition we


identified the co-occurrence of the dimethyl aryl, structurally related

The authors thank CNPq (Brazilian research council) for fellowships;

ANP (Brazilian Petroleum Agency), Petrobras S/A.

trimethyl aryl series may indicate that the former likely derive from
the latter by way of a demethylation process.


Sousa Jnior, G. R.; Santos, A. L. S.; De Lima, S. G.; Lopes, J. A. D.; Reis,
F. A. M.; Santos Neto, E. V.; Hung K. Chang., 2013. Evidence for euphotic
zone anoxia during the deposition of Aptian source rocks based on aryl
isoprenoids in petroleum, SergipeAlagoas Basin, northeastern Brazil.
Organic Geochemistry 63 94104.

Sample preparation:
About 80 mg of oil were subjected to PTLC on silica gel impregnated
with 5% AgNO3 and then the silica was developed using 98:1 (v:v)
n-hexane:ethyl acetate. The plates were then selectively scraped
and the silica was treated using dichloromethane:methanol 95:5

Peters, K. E.; Walters, C. C.; Moldowan, J. M., 2005, The biomarkers

Guide, Cambridge University Press.

(v:v) for desorption of the constituents The fractions thus obtained

(P1 saturated and P2 aromatic) were concentrated in a rotary

Figure 1. TIC typical of the saturate fraction;RIC of m/z 134 and 120,

evaporator and analyzed by GCMS and GC-MS-MS.

showing the aryl isoprenoids and remaining diagenetic isorenieratane


Acquisition Method for TSQ Quantum XLS:

The compounds (Figure 2) were identified by their respective

molecular ions, base peaks at m/z 134 (McLafferty rearrangement)
or m/z 133. In addition, m/z 119,120, 105, 91 and 77 were used
because they are typical of a poly substituted aromatic structure.
For data acquisition by selected reaction monitoring (SRM) the
masses according to Figure 2 were used for the two compound
groups under investigation.

The analyses were performed using a Thermo Scientific TSQ

Quantum XLS Ultra Triple Quadrupole GC-MS instrument. Capillary
chromatographic column (Equity TM-1, 30 m, 0.25 mm ID). Initial
temperature of 70 oC (4 min hold), followed by a ramp of 2 oC/
min up to a final temperature of 300 oC (20 min hold). The carrier
gas was helium at a constant flow rate of 1.0 ml/min. Transfer line

Copyright 2014, ALAGO.

Sumons, R. E.; Powel, T. G., 1987. Identification of aryl isoprenoids in

source rocks and crude oils: Biological markers for the green sulphur
bacteria. Geochimical et cosmochimica 51, 577-566.
Zhang, C.; Zhang, Y.; Cai, C., 2011. Aromatic isoprenoids from the 2565
Ma saline lacustrine formations in the western Qaidam Basin, NW China.
Organica Geochemistry, 42, 851855.

review of information contained in an abstract submitted by the author(s).

The compositional fractionation of petroleum accompanying
the migration process can be potentially used to infer distances
petroleum may have travelled and the ratio of oil in the reservoir to
that lost in the carrier beds1. Several researches have examined
the interaction oil components, mineral surfaces in reservoir rocks2
and the salinity of formation water that can have influence on
wettability and oil recovery3. Therefore, the purpose of this study
was to investigate the distribution of petroleum compounds during
the migration in recent analogues of Albian carbonate rocks of the
Brazilian pre- salt stromatolites, and to highlight theeffect of the
salinity level of synthetic formation waterduring the compositional

Initially, it was realized a mineralogical characterizationofstromatolites
samplesthrough X-ray diffraction. They were saturated with
syntheticformationwatersof different salinities: W1- 143 g/L
and W2- 286 g/L (postand pre-salt Brazilian water formation,
respectively). The migration process was performed by gravitational
ascension,in duplicates. It was used API gravity of 26o oil andfour
rocks samplessaturated withdifferent types of formationwater,
W1 and W2. After 60 days of migration in carbonate rock
samples, at room condition, the four stromatolitessampleswere
divided into 3 parts (Bottom, Middle and Top), and the oils were
removed by a Soxhlet extractor. Each extracted sample (free Oil)
was fractionated by liquid chromatography to obtain saturated
and aromatic hydrocarbons. The fractions were analyzed by
Gas chromatography/ mass spectrometry, to investigate the oil
compositional fractionationthroughn-alkanes (m/z 85),polycyclic
terpanes (m/z 191), steranes (m/z 217) and methyl-phenanthrenes
(m/z 192), as result of salinity level influence.

Results and Discussion

The result of stromatolite mineral characterization was Magnesian
Calcite, Quartz and Aragonite, respectively, 95.9%, 3.0% and
2.6% in the Top; 86.0%, 8.9% and 5.1%in the Middle; and 70.3%,
20.1% and 9.6% in the Bottom.
It was observed the compositional fractionation ofthe n-alkanes,
whenit content decreased from Bottom to the Top. Moreover, the
n-alkanes content inthe free oil of the subunits (Bottom, Middle

and Top) saturated with synthetic formation water W1 was higher

than obtained from stromatolites subunits saturated with synthetic
formation water W2 (Figure 1).

phenanthrene; DIA: diasteranes.

According PAN et al. (2005), the selective adsorption oil
components on clay minerals in sandstones reservoir could also
induce the variations of the (C23TTR+C30H)/C23-TTR. However,
in the results obtained in this present research in carbonates rocks
didnt show variations in this ratio during simulated migration
independently of the salinity level of formation water(Table 1).


During the simulated migration, the effect of salinity of the

formationwater could be observed through the ration-C17 / 2-MP
(Table 1). This ratio showed lower variations along the carrier bed
saturated with synthetic formation water W2when compared with
subunits stromatolites saturated with synthetic formation water
W1.Thus,it might have occurred thepreferentialmigration of 2-MP
when compared ton-C17 and the decreasing the interactionsof
2-MPwithmineralsurface andsyntheticformationwater (W2, of more
salinity), principally.

Henrry Rivera D., Roman E. Gonzlez, Wilman F. Beltrn

The study of geochemical tracersto migration monitoring showed
a slight compositional fractionation of the oil during the simulated
migration as was observed inthe behavior of n-alkanes andratios:
phytane/n-C18, C21S/ (C21 +C29) Sand n-C17/ 2-MP.

Figure 1: Compositional fractionation of n-alkanes through simulated
migration in stromatolites samples.

It was detected changes in the values of phytane/n-C18along

the carrier bed, as consequence of the preferential migration of
phytane with respect to n-C18. Moreover, the ratio C21S/ (C21
+C29)Sincreased, about 50%, along carrier bed independently
of formation water salinity level (Table1).

The ratios C27DIA /C27S, / ( + ) S and (C23TTR+C30H)/

C23-TTR couldnt be recognized as sensitive indicators for oil
migration in this present research. Moreover, these ratios werent
affectedbythe salinity level of formation water.
The salinity offormationwater can have proportionated
different waterfilms (W1 and W2) on the rock.This can have
causeddifferentinteractions with oil compounds,influencingmainlythe
migration of 2- methyl phenanthrene.

The steranesratios, C27DIA/C27S and /(+),have been

recognized as sensitive indicators for oil migration, based on eld
observation for PAN et al. (2005) and SEIFERT&MOLDOWAN(1981).
However, in this present research in carbonates rock these ratios
did notdemonstratethe compositionalfractionationof oil during
simulated migration (Table 1).

The authors thank Petroleum Engineering and Exploration
DE GEOQUMICAandAgncia Nacional do Petrleo (ANP)for the
fellowships and financial support.

Table 1:Saturated and Aromatic hydrocarbonsratios.

B;BENNETT, B; YARDLEY, G; CARRUTHERS, D. 2000. An experimental
investigation of geochromatography during secondary migration of
petroleum performed under subsurface conditions with a real rock.
Geochemical Transactions 9.
[2] PAN, C; FENG, J; TIAN, Y; YU, L; LUO, X; SHENG, G; FU J. 2005.
Interaction of oil components and clay minerals in reservoir sandstones.
Organic Geochemistry 36, 6336547.
[3]TANG, G, Q; FIROOZABADI, A. 2002. Relative Permeability Modification
in Gas/Liquid Systems through Wettability to Intermediate Gas Wetting.
Society Petroleum Engineer (SPE). Reservoir Evaluation & Engineering 5
(6): 427-436.
[4] SEIFERT W. K. AND MOLDOWAN J. M. 1981. Paleoreconstruction by
biological markers. Geochimica et Cosmochimica Acta 45, 783-794.

*TTR:tricyclic terpanes;H: Hopanes; S: steranes; MP: methyl


Distribution of hydrocarbon
families in the central area of the
Neiva Sub-basin, Colombia. Processes for
migration and charge

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Since Neiva Sub-basin is recognized by its high petroleum
potential, reported low thermal maturity and its complex structural
setting challenges an explanation for the migration processes that
charged considerable oil volume in its restricted area.
The main source rocks in the Neiva sub-basin are the Cretaceous
Tetuan and La Luna Formations shales, siltstones and limestones,
which represent the lower and upper part of the Villeta Group. These
rocks have favorable geochemical properties for oil generation and
expulsion in the central Neiva Sub-basin.
The main reservoir rocks are the sandstones of the Cretaceous
Caballos and Monserrate Formations, and Miocene Honda Group.
Although two oil families have been identified in these reservoirs
(Sarmiento and Rangel, 2004), theirgeographical distribution and
the hydrocarbon migration and charge processes are not clear until

Several geochemical studies over the last two decades show
good source rock potential for the Cretaceous sequence in the
Neiva sub-basin. These analyses include: TOC, pyrolysis, organic
petrography, bitumen extractions, crude analyses, liquid and
gaseous chromatography, biomarkers and oil-rock correlations
(Ecopetrol, 2001).
This study uses previous analyses as input to identify spatial
distribution of oil families for each reservoir taking into account
their API gravity, sulfur content and biomarkers. The resulting
distributions along with burial history models and structural
maps were used to propose the kitchen areas and hydrocarbon
migration pathways. Despite this model accounting for oil families
distribution, there are inconsistences with Ro maturity in the area.
Results and Discussion
According to the API gravities and sulfur content trends, two main
oil families are interpreted to be present; the first one with light oil
and low sulfur content is related to the Honda Group in a shallow
position (located east of Tenay fault) and Caballos Fm. reservoirs.
The second one with medium to heavy oil and high sulfur content,
related to the Honda Group (located west of Tenay fault) and
Monserrate Fm. reservoirs.

Figure 1.API gravity map in the Neiva area.

The biomarkers interpretation for organic matter type suggests that

the first oil family has siliciclastic inputassociated to Tetuan Fm.,
which has more terrigenous facies in the area.The second oil family
has more carbonate affinity than the first one,and correlateswithLa
Luna Fm. source rock.
Taking into account the oil families distribution and the source rock
interpretations, there are four petroleum systems present in the
study area: 1) Tetuan-Caballos (!), 2) Tetuan-Honda (.), 3) La LunaMonserrate (!) and 4) La Luna-Honda (.).

Figure 2. Structural cross section in the Neiva area showing petroleum

systems and migration pathways (Ecopetrol, 2012).

Figure 2 shows that oil families distribution is controlled by structural

features. This is supported by a regional 3D hydrocarbon migration
analysis, suggesting kitchen areas that could explain the existing oil
fields and defined petroleum systems.
According to basin modelling analysis,the maturity of these
kitchen areas should be in the early oil window.However, there is
an inconsistence if the measured %Ro values are extrapolated in
these areas, where is expected thermal immaturity of the source
rocks. This discrepancy is supported by 1D geochemical models
sugesting that the hydrocarbon generation/expulsion event in
the Neiva syncline started in late Miocene timesand continues to
Present,with a maximum temperature at present day; nevertheless
the measured %Ro vs. Depth trend indicates that the oil window
only is reached at about 14.000 (where is expected a temperature
of 120C).
On other hand, there are other maturity parameters that are
incompatible with measured %Ro values, such asTmax, which
shows a range between 430C and 445C that correlates with %Ro
values higher than 0.5; and equivalent %Ro values from AFTA,that
also predicts higher maturity levels. Although this study does not


pretend to evaluate the analytical methods, it is considered the

presence of a vitrinite suppression effect (proposed originally by
Garcia & Carvajal 2006) that fits valid hydrocarbon migration routes
that could explain the oil distribution in the area.

Results and Discussion

Biomarker and n-alkanes isotope

profile study in oil samples from
Recncavo basin, Miranga field, Brazil.


Two Miranga oil samples, 7MG and 9MG,pooled in sandstone

reservoirs, bothof lacustrine origin and different biodegradation
levels were selected forour studycasesto explain 7MG oil
resistanceto the biodegradation process, notwithstanding its

There are four petroleum systems in the Central area of Neiva

Subbasin: Tetuan-Caballos (!), Tetuan-Honda (.), La LunaMonserrate (!) and La Luna-Honda (.).

Michel R. de B. Chavesa*, Celio F. F.

Anita J.





favorable conditions to microorganisms development. The analysis

of the bulk data of the saturated fractions of the samplesrevealed
high wax content, n-alkane distributions with abundant high

Oil accumulations in the Honda Group reservoir show that there is

a geographic variation in oil characteristics. East of Tenay fault the
Tetuan-Honda(.) petroleum system is present, while to the west of
that fault the Honda/La Luna petroleum system is found.

a Instituto de Qumica, Universidade Estadual de Campinas, PO

molecular weight components and odd predominance, pristane

BOX 6154, 13084-971 Campinas, SP, Brazil.

dominant over phytane (values 1.3- 1.6). TheC26tricyclic

b Organic Geochemistry Division, CENPES, Petrobrs, Ilha do

Fundo, Rio de Janeiro, Brazil.

Distribution of oil families is controlled by structural features, which

also determines the kitchen areas that could explain the existing oil

Copyright 2014, ALAGO.

Vitrinite reflectance in potential kitchens areas seems to be

suppressed, as it is compared to present day thermal gradient and
other maturity parameters.

terpanes over C25tricyclic terpaneswere relatively similar for

both samples(C26TT/C25TT) (Table 1), confirming the Lacustrine
depositional environment.
Table 1.Geochemical parameters obtained by GC-MS in SIM and SCAN mode.

from Recncavo basin, Miranga field.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Using saturated biomarkers parameters obtained by GC-MS



combined with the isotopic distribution profile of the n-alkanes in a

The Recncavo basin, has11500km2, is located at the

The present study is part of an Ecopetrol internal project on the

Upper Magdalena Valley Basin Petroleum Potential. We thank
Ecopetrol S.A. for authorizing the publication of this information.

GC-C-IRMS, we could characterize two oil samples from Miranga

northeastern part of Bahia state and is considered one of the most

oil field. These results are preliminary however depict different

petroliferous basins in Brazil. Miranga is among the seven biggest

fields in this basin,andunderstandinghow biodegradation works in


The oils samples showed different P/F ratios suggesting in few

Miranga oil field is of economicinterest. The investigation required a

ECOPETROL, 2001. Proyecto evaluacin regional de la cuenca valle superior

changes in the depositional environment. Both samples were

previous geochemical characterization of the oil samples focusing

thermally mature (Ts/(Ts+Tm)however 7MG was more, confirmed

del magdalena implicaciones en los sistemas petrolferos. Internalreport.

the isotopic composition. The oil samples will be evaluated using

the isotopic profile (13C) of the n-alkanes before and after

ECOPETROL, 2012. Definicin de los estilos estructurales presentes en la

Cuenca del Valle Superior del Magdalena, Gerencia de Exploracin Centro

biodegradation assays (future work).Knowing this, two oil samples

Sur. InternalReport.

from Miranga field in the Recncavo basin, were evaluated in order

to recognize their maturation level, depositional environment and

Figure 1. Isotopic composition distribution profile of n-alkanes in oil samples

by its CPIlevel.

biodegradation levels which will be used in future biodegradation

assays using polar fractions.

The authors thank PETROBRAS and FAPESP for the fellowship
and financial support.

Their biodegradation levels were also evaluated using the ratio






together with analyzing the presence of n-alkanes, confirming the

Gaglianone, P. C., Trindade, L. A. F., 1988, Caracterizao geoqumica dos

oil sample 9MG as the most biodegraded.

leos da bacia do Recncavo. Geochimica Brasiliensis, 2 (1), 15-39.

The oil samples were selected based on their biodegradation levelsand

The isotopic distribution of the n-alkanes wasobtained by GC-C-

Ortiz, J.E., Torres, T., Delgado, A., Julia, R., Lucini, M., Llamas, F.J.,Reyes, E.,

SARMIENTO, L.F. and RANGEL, A., 2004. Petroleum systems of the Upper

collected from reservoirsof different depths. Samplefractioning was

IRMS showing the presence of the n-alkanes ranging from C10 to

Soler, V., Valle, M. 2004. The palaeoenvironmental and palaeohydrological

Magdalena Valley, Colombia. Marine and Petroleum Geology 21 (pp. 373391).

performedusing a standard procedurewithdry silica gel column,

C34. The aquatic origin n-alkanes (nC15, nC17, nC19) showed

evolution of Padul Peat Bog (Granada, Spain) over one million years,

eluted with 15-20 mL of n-hexane to obtain the saturated fraction

values between -29,85 and -32,07 for sample 7MG and

which was analyzed byGC-MS usingSCAN and SIM mode

-30,58 and -36,979MG showing 13C contentfor the 9MG

GARCIA-GONZLEZ, M. and H. Carvajal; 2006. La supresin de la reflectancia

biodegradation levels.

de vitrinita en las Formaciones La Luna y Hondita y sus implicaciones en la

exploracin de hidrocarburos en las Cuencas del VSM Y VMM, Colombia. 9th


Simposio Bolivariano - Exploracin Petrolera en las Cuencas Subandinas.

from elemental, isotopic and molecular organic geochemical proxies.

Organic Geochemistry 35, 1243-1260.

oil. Then-alkanes representing superior vascularized plants (nC27,

n-alkane purification was achieved by crystallization of the aliphatic

nC29, nC31) showed values ranging from -37,58 to -40,52 for

fraction with a saturated solution of urea in methanol and analyzed

oil 7MG and from -30,47 to -35,04 for sample 9MG, showing

with a GC-C-IRMSThe isotopic values were measured in a Trace

GC Ultra with a Delta V Advantage mass spectrometer from Thermo
using splitless mode for analysis. The temperature programwas
starting at 80C (holding for 2 min.), increasing to 270C at 40C/
min., and then to 300C (holding for 25 min.) at 10C/min. using

different ratios of wax lipids from leaves of higher plants.Most of the

n-alkanes from C14 to C33in both oils showedhigher13C ratios in
n-alkanes ofodd carbon numbers, although the difference in 13C
values was greater in sample 9MG.

a DB-5 column (30m x 0,25 mm x 0,25m) . The 13C values

werecompared to the PDB standard and calibrated by CO2pulses.
The injector was kept at 300C, the interface at 350C and the
combustion oven at 850C.



wells B and C is sealant character to level unit B4.


Compartmentalization analysis
of three crudes from Lake Maracaibo Basin


Thank to PDVSA INTEVEP (Venezuelan Technological Institute of

Three wells were selected for analysis of compartmentalization (A,

Petroleum) and PDVSA OCCIDENTE (Petroleum of Venezuela)

B and C) located southeast of the Basin of Lake Maracaibo. In this

Department of Reservoir Integrated Studies, Maracaibo, Venezuela.

Jhaisson A. Vsqueza*, Frank C. Cabrerab, Beatriz C. Angulob,

sense, C15- samples were captured in amber bottles of 100 mL

Victor. Hernndez b, Ana K. Faracoa

and seal lips of 20 mm with gum septum and aluminum cap. For


this, it was necessary to have a high pressure hoses connected

Kaufman, R. L.; Ahmed, A. S.; Hempkins, W. B., 1987. A new technique for

a Petroleum of Venezuela (PDVSA Occidente), Department of

to biphasic pump, two leakage needles with coated copper of

the analysis of commingled oils and its application to production allocation

Reservoir Integrated Studies, Maracaibo, Venezuela

11/2 diameter one for injecting the fluid and the another to release

calculations. Jakarta: Indonesian Petroleum Association, pp. 247-268.

b Venezuelan Technological Institute of Petroleum (PDVSA Intevep),

pressure and gun sealing septum. The samples were transported

Department of Strategic Research, 76343, Caracas 1070-A,

to the laboratory for analysis by gas chromatography of total oil

Tocco, R; Alberdi, M., 1999. Geochemical study of Misoa Formation crude


(Whole Oil) in an equipment Agilent Technologies 6850 Series II.

oils, Centro Lago Field, Lake Maracaibo, Western Venezuelan Basin. Marine

From the results of the fingerprint were determined hundred eighty

and Petroleum Geology 16 (1999) 135-150.

seven relations of which were chosen twelve with higher standard

deviations for drawing diagrams stars. Therefore, a cluster analysis

Copyright 2014, ALAGO.

of three samples of crude oil was carried out from the composition

Dup: Duplicate

This paper was selected for presentation by an ALAGO Scientific Committee following

of the C15- fraction to establish the compartmentalization of the

Figure 1. Cluster analysis between wells A, B and C, unit B4.

review of information contained in an abstract submitted by the author(s).



Results and Discussion

The economic growth constant worldwide has led to a growing

C15- fraction corresponds to the light fraction of crude oil which

demand for oil that has reached 90 million barrels a day of liquid

is in the gasoline range and it is determined by the technique of

hydrocarbon. The current economy is mainly based on a high

gas chromatography of total oil (Whole Oil) which is widely used

consumption of oil and according to estimates by the International

for studies of oil-oil correlation, compartmentalization, maturity

Energy Agency the situation will not change much over the next

and establishes alteration processes within the reservoir as water

30 years. For this reason, it is vitally important geochemical

washing, biodegradation and evaporative fractionation. In general,

characterization of oil in order to optimize the exploitation plans. All

for studies of compartmentalization are applied the relations of

this has led to the geochemical analysis of oils from Basin of Lake

organic compounds obtained by gas chromatography of total

Maracaibo which is located western Venezuela and covers an areal

oil and then are generated the polar plots taking into account

surface 13210-13820 km2 representing one of the most important

the relations with higher standard deviations. According to the

reservoirs of oil.

shape of them if they are equal for all oils analyzed it is said that
the reservoir could be possibly connected and also come from

Organic geochemistry has played and important role in petroleum

the same origin or even have similar post-genetics processes.

exploration. Applications of organic geochemistry to reservoir studies

Otherwise, if the polar plots are different is due to the presence of

and production engineering have attracted a lot of attention in the

compartmentalized reservoirs with differences in origin of the oils.

petroleum wolrd (Kaufman et al., 1987; Tocco and Alberdi, 1999).

Based on the basic principle of the reservoir geochemistry within

In this sense, the results obtained by gas chromatography of total

the same reservoir where there are permeability barriers (structural

oil (Whole Oil) to the crudes A, B and C taking into account the

and stratigraphic seals) occurs a compositional homogenization of

twelve relations of organic compounds seem to indicate that the

oil, therefore, in any part of the reservoir the same composition or

oils are the same family due to the high grade of similitude of stars

figerprints be presented and to the extent that these differences

diagrams, although, these crudes have been subject to water

Figure 2. Structural section (TVD) and stars diagrams from wells B and C,

(subtle or noticeable) is observed in the crude might be attributed to

washing which explain the compositional similarities. However, the

unit B4.

effects of compartmentalization. This research aims to perform an

cluster analysis (figure 1) performed between the wells A, B and C

analysis of reservoir compartmentalization in the Eocene B (Misoa

using as criteria a cuttof five shows that the crudes A and C have


Formation) southeast of the Lake Maracaibo Basin, specifically in

a similar composition to except the oil B. This may suggests that

The compartmentalization analysis between wells A, B and C

the field belonging to La Ceiba Area, Trujillo state. For this, it was

the fault that separates the wells B and C is type sealant which

indicate that these crudes have been subject similar post-genetics

sampled the fraction C15- of three oils and it was conducted the

even cut the Cretacic. Therefore, the original oil water contact to

processes due to the similarities of stars diagrams. However,

analysis of fingerprint of hundred eighty seven relations where were

well B is higher deep than C supporting the compartmentalization

the cluster analysis suggests that wells A and C have a similar

selected the twelve with higher standard deviation. The cluster

of reservoirs (figure 2).

composition to except B. In this sense, the fault that separates

the wells B and C is sealant character from the point of view

analysis suggests that the oils A and C show a similar composition

geochemical and petrophysical.

to except the oil B. On the other hand, the fault that separate the


and source-rock lithology, such clay versus carbonate composition.

15, either the presence or absence of n-alkanes and isoprenoids


These source rock features represent key contributions to depict

compounds, as well as the relationship between the 25-Norhopane/

Our fully-integrated geochemical study clearly differentiates a

the source rock character, which usually includes kerogen typing

C30Hopane and the saturates content (%), indicate that mixing

multiple petroleum charge of Paleogene reservoir rocks in the

(e.g., type II versus type III or II/III), oil versus gas potential,

of pulses from different sources has taken place with a former oil

southwest of the Llanos Basin and based on novel technologies, it

depositional settings (e.g., deltaic versus marine; proximal versus

severely biodegraded whose physical properties has been then

poses the plausible age ranges for the various organic facies that

distal), and potential hydrocarbon characteristics (e.g., sulfur-rich

improved by a more recent refreshing process. The latter oil, where

have controlled the petroleum charge in the study area. Furthermore,

versus sulfur-poor; heavier versus lighter oil).

interpretations were possible, suggested source facies deposited

the level of understanding achieved on the biodegradation histories

within a proximal marine environment with a significant contribution

using biomarker acids analysis has implications for petroleum

Thermal maturity of the source sediments was also gleaned from

of terrestrial organic material under oxic conditions. Unequivocal

systems at regional scale in the Llanos, since its application has been

oil geochemistry and used as a proxy for the timing of oil generation

evidence of mixing revealed by the screening techniques employed

found useful in determining the overall composition of the oil and

within the petroleum system, since such an attribute has a

comes from the coexistence of prominent 25-Norhpane peaks, and

its migration and charging for any given reservoir. This multifaceted

a Instituto Colombiano del Petrleo-Ecopetrol S.A. Km7 va

fundamental effect on oil composition and its physical properties.

the complete hopanes series in the same m/z 191 fragmentogram,

research framework was complemented with a 2D petroleum

Piedecuesta. Colombia

Determination of the level of biodegradation and quantification of

where such compounds are expected to be depleted in the

system modelling which included the unprecedented utilization of

b Gerencia de Exploracin Regional Llanos. Vicepresidencia de

oil mixtures in the various oil samples as well as their implications

oil samples due to the intense palaeobiodegradation that has

yield curves obtained from high-temperature simulated distillation,

Exploracin-Ecopetrol S.A. Bogot. Colombia

on the petroleum system in terms of volume of petroleum charged

occurred in the reservoirs of the study area.

to compare between biodegraded oil and non-biodegraded oil of

c Biomarker Technologies, Inc (BTI). 638 Martin Avenue. Rohnert

within Tertiary reservoir rocks have also been addressed herein.

Source Facies diferenciation and Petroleum
Charge History In The Southwest Region
of The Llanos Basin using High-Resolution
Organic Geochemical Technologies















O. Villarreald

Park, CA 94928. USA

the same thermal maturity. This proxy for assessing the volumetrics,
More advanced techniques such as CSIA-B and QEDA reveal a

ultimately aided determining the proportion of oil that has been lost
as a consequence of the biodegradation processes.

d Schlumberger, Calle 100, Nmero 13-21 Piso 6-152. Bogot


remarkable divergence between compositional profiles for both the


The analytical program carried out on the oil samples consisted

oil samples and the asphaltenes isolated from the HyPy oils, which

of quantitative diamondoid analysis (QDA), saturate biomarkers by

implies that such an analysis delivers the most useful outcomes


GC-MS, aromatic biomarkers by GC-MS, saturate biomarkers by

for source differentiation. This is most likely due to the fact that the

The authors thank the Vice- Presidency of Exploration, Ecopetrol

GC-MS-MS, biomarker acids analysis (BAA), compound specific

extended diamondoids fingerprints do not appear to be affected

S.A. (VEX) and the Colombian Petroleum Institute for the

isotope analysis of alkanes-complete (CSIA-Ac),compound specific

by biodegradation or oil cracking and they are present in the

administrative and financial support to conduct the present study.

This paper was selected for presentation by an ALAGO Technical Committee following

isotope analysis of diamondoids (CSIA-D) and QEDA for both,

asphaltenes making them a universal source parameter. Figure 1

review of information contained in an abstract submitted by the author(s)

the whole oils and the asphaltenes isolated from the appropriate

shows the comparison between fingerprints of the whole-oil-QEDA


hydrous pyrolysate oils (HyPyoil).

and the asphaltene-QEDA for each sample.

Barbanti, S.M.; Moldowan, J.M.; Watt, D.S.; Kolaczkowska, E. (2011)

Although a significant contribution of the geochemical work as a

This comprehensive study includes biomarkers representing only

The QEDA fingerprint for each asphaltene pyrolysis sample is

part of the exploration process in the Llanos region has allowed

the shallow source units, and QDA, which provides information on

plotted together with that from the corresponding whole oil sample.

development of an improved understanding of the habitat of the

advanced maturity (extent of oil cracking), evaporative fractionation

The various concentrations of diamondoids relative to triamantane

Dahl, J.E.; Moldowan, J.M.; Peters, K.E.; Claypool, G.E.; Rooney, M.A.;

petroleum accumulations, a complete explanation on the origin of

(a phenomenon occurring during fluid migration) and the source

for each sample indicate significant differences between the oils

Michael, G.E.; Mello, M.R.; Kohnen, M.L. (1999) Diamondoid hydrocarbons

the various petroleum types, as well as on the regional distribution of

of the fluids, as well. We used CSIA-Ac as a method to correlate

and the asphaltene QEDA fingerprints, suggesting that the three

as indicators of natural oil cracking. Nature 399, 54-57.

their physical properties, remains ambiguous. Such a fact of course,

hydrocarbon sources ranging from the oil window into the wet gas

samples have multiple sources. Therefore, this research provides

has direct implications on both the mitigation of the exploration risk

window. Once the various HyPy oils were obtained, each sample

clear evidence of oil mixing in Tertiary reservoirs of the southwest

Zinniker, D.A. (2005) New insights into molecular fossils: the fate of terpenoids

and the reduction of exploitation costs within the study area. In

was subjected to various analyses in order to determine whether

Llanos with a distinctive proportion of the main pulses forming the

and the origin of gem-dialkylalkanes in the geological environment. Ph.D.

this work we aimed at producing and integrating conventional and

the asphaltenes are related entirely to the rest of the oil sample

oil sample 1 relative to samples 2 and 3 which appear to have a

thesis, Department of Geological & Environmental Sciences, Stanford

advanced high-resolution geochemical technologies in order to

or if it can be shown a mixing effect. Further to this, comparisons

common charge history and similar proportions of the mixture.

University, Stanford, CA, USA, UMI Number: 3162337.

better characterize the petroleum charge history in the petroleum

between CSIA-B data from maltenes (whole oils) and from HyPy

system under research. The ultimate target of this geochemical

oils were performed to

Copyright 2014, ALAGO.

New triaromatic steroids distinguish Paleozoic from Mesozoic oil. Organic


Geochemistry 42, 409-424.

approach is to incorporate not only the relevant outcomes, but also

the proposed work-flow into succeeding risk assessments for E&P

illustrate the existing relationships and to suggest where either

operations in the southwest portion of the Llanos.

mixed or singly sourced oils might occur.

For this geochemical approach, a set of well-head samples

Results and Discussion

were carefully selected and sampled in order to reach the best

Classic organic geochemical analyses were fundamental to

understanding of the source rocks and source rock facies through

evaluate the extent of biodegradation and its control on the

oil-oil and oil-source rock correlations. The products obtained from

various compound abundances that were used to perform further

the geochemical characterization encompass the following aspects:

interpretations on source and thermal maturity. Since the analyzed

estimation of possible source ages; depositional environment,

oils have experienced significant biodegradation the use of m/z

including palaeowater conditions; organic matter input, such

177 and m/z 85 fragmentograms provided insights on the actual

as the different types of organisms that have contributed to the

distribution of N-alkanes and demethylated series of hopanes and

Figure1. Quantitative extended diamondoid analysis (QEDA) of whole oils

assemblages of the petroleum lipids and their relative importance;

tricyclic terpanes respectively. Although API gravity varies from 8 to

and HYPyoils generated from asphaltenes




CS2. Then the sample is placed in the automatic injector of

There are slight compositional variations found by analyzing the

chromatograph HP-6890 model, for analysis.

fraction C15- oil Block V-VI Field, differentiate them into two groups,

Geochemical study of compartmentalization

in reservoirs of Block V-VI Lamar,
Maracaibo Basin, Venezuela.

Biomarkers in fractions saturated and aromatic hydrocarbons

structurally separated by a fault. However, The compositional

by GC-MS. saturated and aromatic hydrocarbons fractions are

variations due to the response in the geochemical parameters,

analyzed by gas chromatography coupled with mass spectrometry

could be associated with the formation waters washing the sample

Natasha Acostaa*, Jacqueline Grobasa, Alejandro Martneza, Jos

equipment. Laboratory PDVSA Intevep uses an equipment model

VLE-F well.

Durana, M. Lisandro Martneza, Carmen Rodrgueza

HP-6890 computer with a mass selective detector HP-5973


quadrupole MSD.

Thank to PDVSA-Intevep for letting me participate in this projectand


Chromatography of fraction C15-. Analysis of the light fraction of

thank to the Laboratory of Geochemistry of INTEVEP for supporting

oil was performed on a HP-6890 chromatograph equipped with

me in the analysis performed in this work

a capillary gas column type PNA of 1.05 m, with temperature

Copyright 2014, ALAGO.

programming, helium as carrier gas and FID detector (ionization

This paper was selected for presentation by an ALAGO Scientific Committee following

detector flame). The computer has software for the recognition of

review of information contained in an abstract submitted by the author(s).

the peaks corresponding to saturated and aromatic hydrocarbons

Figure 1.Polar diagram of oils studied

Agero, A. 1998. Caracterizacin geoqumica de crudos del yacimiento

VLE-305, Campo Bloque V-Lamar. Informe Tcnico. Intevep.

present in each sample (DHA system: Detailed Analysis

Alberdi, M. 1995. Geoqumica de yacimientos y delimitacin de



compartimientos en Bloque V-centro, Lago de Maracaibo. Informe Tcnico.

Geochemistry applied to the study of reservoirs can be used to

solve problems, such as, continuity in the reservoir, intervals

Results and Discussion

producer identification, identification of production problems,

The reservoirs studied show oils with API gravities between 23.5 to

and the presence of tarmats. (Kaufman, 1990). After the oil is

26.81 (medium oil), they have a higher proportion of the saturate

Berrios, I., y Toro, C. Informe Tcnico. Intevep. Estudio Geoqumico de

entrapment, it is subjected to secondary processes, both chemical

fraction and they are classified as paraffinic oils. According to the

Yacimientos del rea VLE-326 Bloque V, Campo Lamar Lago de Maracaibo.

and physical, which can alter the composition of the oil, therefore,

results suggest that biomarkers are oils mature, little altered from a


the fluid in each compartment will have characteristics which allow

source rock of marine origin.


Hernndez, V. 2009. Caracterizacin geoqumica de crudos y agua de

to differentiate it from the others. The study using light hydrocarbon

fractions (C15-) permit identify these compositional differences

Analyses in the C15- fraction corresponds to the visual method

formacin de los yacimientos Cretcicos, Lago de Maracaibo. Informe

acquired in each compartment and know the continuity of a

of polar diagrams, which are calculated using 10 ratios of

Tcnico. Intevep.


compounds, which presented the highest standard deviation,

which largely differentiates samples from the same population.

This paper shows the geochemical study of 7 oil samples from

(Hernndez, 2009). Figure 1 shows the polar diagram of crude oil

wells of Lamar Block V-VI, Maracaibo Basin; with the purpose of

studied, where we can see that the sample from the well VLE-F

verify the level of communication between reservoirs from level the

(blue line) is slightly different from other wells, this sample (VLE-F)

sand C2.

had in several analyzes differences compared to the other samples

showed less maturity, lower API gravity, and slight compositional


Figure 2.Dendrogram of samples studied

The dendrogram shows two families of oils, as suggested by

the diagram of stars; one family is represented by wells samples
VLE-A VLE-B, VLE-C, VLE-D,-E and VLE-G and other family is
represented by the well sample VLE-F.

The samples were taken from each wellhead, in hermetically

sealed vials to preserve lightweight compounds (C15-). For the

In the dendrogram (Figure 2) is located on one axis, 9 oil samples

evaluation of these samples, in order to determine whether or

that are compared with each other, while the other axis is placed

not communication between the reservoirs wells, the following

Euclidean distance between them. The difference between families

geochemical analyzes were carried out:

is given by a line (Cut off), which indicates the Euclidean distance

from crudes which are considered different. Cut off the analytical

Determination of composition saturates aromatics, resins and

location above is considered instrumental error of the method,

asphaltenes. A HPLC equipped with a Waters 600 controller,

which was calculated by performing the triplicate analysis of the

a rotatable 486 nm absorbance detector and 410 differential

sample (VLE-C). The second Cut off is considered above analytical

refractometer was used.

Cut off, and taking into consideration the average and standard
deviation of triplicate samples.

According the structural map at the top of the sand C2, the
sample from the well VLE-F is separated by faults of the other
wells, suggesting it is in different compartments. Recommended to
check more detail the structural and seismic maps to explain this
difference. Another explanation could be that the deposits are in
the same compartment, but the sample from the well VLE-F, has a
small alteration in its composition depth vertical variations.

The results of analysis of C15+ fraction and studied biomarkers

Gas chromatography, saturated fraction (C15+). For this analysis,

in crude Block V-VI Field, suggesting they were generated by a

a saturated hydrocarbon fraction is weighed and diluted with

source rock of marine origin, thermally mature.




microscope equipped with a range of objective lenses (including a

hydrocarbon migration. These HCFI contain oils characterized by

x100 objective lens) was used for fluid inclusion microthermometry.

API gravities between 40-50 and homogenization temperatures

Its calibration was made using synthetic fluid inclusion standards

between 92C and 113C. PVT modelling of coeval HCFI and

of pure CO2 and water. Precision is 0.2C at -56.5C and

aqueous fluid inclusions hosted within quartz overgrowths indicates

2C at 300C. The following fluid inclusion data was recorded: 1)

trapping temperatures and pressures of ~120C and ~250 bars (Figure

The homogenisation temperature (minimum trapping temperature

2). Isochores were constructed using VTFLINC programme. This

of the fluid: TH) followed by the temperature of last ice melting

software was developed to process microthermometric and volumetric

(indication of the salinity of trapped fluid: TLM) ; 2) The number

data from petroleum bearing fluid inclusions. The composition of the

1 ICP-ECOPETROL, Colombian Petroleum Institute, ECOPETROL-

of phases (liquid gas solid) present in each inclusion; 3)

generic volatile oil reported by Burruss, (2003) was used as an input.


Fluorescence colour of HCFI; 4) the volumetric proportion of liquid

The program then created the saturation pressures (bubble point and

2 Department of Earth and Ocean Sciences, National University of

relative to the total volume of the inclusion, at room temperature,

dew point curves) of this oil for a given homogenization temperature,

Ireland, Galway.

was determined using the Lucia software; 5) The salinity (calculated

using various equations of state. It also calculates the density of the oil

as equivalent wt% NaCl) was determined using the equation of

and uses this to create an isochore (line of equal density) in PT space.

Figure 3. Transgranular fluid inclusions with 40o 50o API gravity, from the

state of Bodnar (1993). In the case of two-phase (liquid + vapour)

This isochore intersects the homogenization temperature (minimum

Mirador Formation, Foothills 1 well, microphotograph under UV Light.

aqueous inclusions isochores were constructed using the FLUID

trapping temperature) of the coeval aqueous inclusions and is taken

Copyright 2014, ALAGO.

programme (Bakker, 2003). Isochores for two-phase (liquid +

as an estimate of the true trapping temperatures and pressures of

Microthermometric studies of the aqueous fluid inclusions hosted in

This paper was selected for presentation by an ALAGO Scientific Committee following

vapour) petroleum inclusions were constructed using VTFLINC

these fluids. Integration of trapping temperatures with the burial history

transgranular annealed fractures suggest at least two aqueous fluid

review of information contained in an abstract submitted by the author(s).


of Cusiana field suggests that these fluids were trapped approximately

migration events post-diagenesis. These fluids can be categorised

during the Miocene (~10Ma).

as follows: 1) A fluid with low to moderate salinity (2.0 12 eq. wt.

Hydrocarbon migration history in the

Llanos Foothills Basin, Colombia,
using fluid inclusions.
J. Naranjo1, M. Feely2, A. Mesa1



Results and Discussion

It should be noted here that fluorescence colours displayed by

% NaCl) and homogenization temperatures between 100C and

Fluid inclusions (commonly < 15 m in diameter) are samples of

Fluids present within quartz overgrowths

HCFI only provide at best a qualitative indication of the API gravity

137C; 2) An aqueous fluid with CH4 CO2 and homogenization

of oil trapped in the inclusions (Burruss, 1991; Goldstein and

temperatures that range from 102C to 127C

oil and aqueous fluids that circulated through a sedimentary basin

during its geological evolution. The presence of hydrocarbon

Microthermometric data from aqueous fluid inclusions found in

Reynolds, 1994; Parnell et al., 1998; OReilly et al., 1998; Feely

bearing fluid inclusions (HCFI) in authigenic cements and in annealed

authigenic quartz (Figure 1) indicates that quartz overgrowths

and Parnell,2003; Bodnar, 1990; Sellwood et al., 1993; Stasiuk

Fluids present within veins.

fractures in detrital quartz grains in basin sandstones may reflects

were precipitated by fluids with minimum trapping temperatures

and Snowdon, 1997), however this premise does not always hold

Fluid inclusion data from veins suggest a complex fluid migration

a history of petroleum migration and cementation during basin

between 92C and 130C. Last ice melting temperatures (TLM)

true (George et al., 1997; George et al., 2001).

history in the Llanos Foothills basin.

evolution (Burruss, 2003). Ultraviolet (UV) light microscopy is used

indicate that both aqueous fluids with low salinities (0.5 to 4.8 eq.

to determine the presence of HCFI in basin sandstones and veins.

wt% NaCl) and fluids with CH4 CO2 were present at the time of

In a vein hosted within the Guadalupe Formation (Foothills 6 Well)

This in turn identifies the stratigraphic levels where hydrocarbon

quartz overgrowth formation.

petroleum inclusions were found as both primary and secondary.

Primary hydrocarbon inclusions indicate that oil with an API gravity

migration has occurred. Petrographic studies of HCFI and aqueous

of 40-45 and homogenization temperatures between 80C and

fluid inclusions help develop a chronology of petroleum migration.

90C were present at the time of the vein formation. The presence

We report the results of fluid inclusion petrography (aqueous and

of secondary trails of petroleum inclusions may also indicate

HCFI), UV microscopy and microthermometric studies (HCFI) of the

later episodes of petroleum migration. Their homogenization

Llanos Foothills Basin, Colombia. Furthermore we demonstrate the

temperatures range from 40C to 82C. They have an API gravity

use of fluid inclusion studies in the development of an oil charge

of 45-50. However the similar characteristics in both fluorescence

history framework for the Llanos Foothills Basin.

Figure 2. Pressure-temperature diagram for the pretroleum fluid inclusions.

colours and microthermometry data of primary and secondary

inclusions may suggest a continuous hydrocarbon migration event.

Rluids present within annealed microfractures.

Nineteen fluid inclusion wafers from the following samples were

Fluid inclusion data from annealed microfractures suggest that

In the veins from the Lutitas de Macanal Formation (outcrop) a

microfractures were important fluid conduits for petroleum and

wide range of salinities and homogenization temperatures have

aqueous fluids. HCFI occur as subparallel trails in detrital quartz

been recorded. These fluids can be divided into three main groups

grains and in trails that transect both detrital and authigenic quartz

as follows: 1) A fluid with a high salinity (34 to 36 eq. wt.% NaCl)

Figure 1. Primary fluid inclusions trapped in quartz overgrowths, from

(Figure 3). This indicates that hydrocarbon migration occurred post

and homogenization temperatures between 240C and 290C.

A Nikon Diaphot microscope with an epifluorescence UV light

the Une Formation, Foothills 1 well. Photomicrograph in plane polarized

quartz overgrowth formation and that hydrocarbon bearing fluids

These fluids are found as primary inclusions; 2) A fluid with

source attachment (designed to transmit 365 nm wavelength light)

transmitted light.

migrated along fractures. The fluid inclusions display a range of

moderate salinity (10 to 17 eq. wt. % NaCl) and homogenization

fluorescence colours from yellow (25-30 API gravity) to blue-white

temperatures between 178C and 227C. They are hosted as

studied: 2 samples of outcrops, 9 samples of cuttings from the

Foothills 1 Well, 7 samples of core from the Foothills 3 Well, and
1 sample of core from the Foothills 6, (The names of the wells are
changed to comply with Ecopetrol-ICPS request for confidentiality).

was used both to examine the petrography of fluid inclusions and

to determine the presence of HCFI. A Linkam THMS 600 heating

HCFI in quartz overgrowths are uncommon. This may indicate that

(40-50 API gravity), suggesting at least two separate hydrocarbon

secondary inclusions, and 3) A fluid with moderate salinity (3.4-7.2

freezing stage mounted on a Nikon Labophot transmitted light

the main phase of quartz overgrowth formation preceded significant

migration events.

eq.wt. % NaCl and 6.812.2 eq. wt. % CaCl2) and homogenization



eq. wt. %NaCl and 6.812.2 eq. wt. %CaCl2) and homogenization

have been recorded from the fluid inclusions found within veins.

P.F., Eisenberg, L.I. et al., (1997) Geochemicalcomparison of oil-bearing

secondary inclusions.

temperatures of between 97C and 117C; y 4) A hydrocarbon fluid

These fluids can be divided into four main groups as follows: 1) A

fluid inclusions and produced oilfrom the Toro sandstone, Papua New


with API gravity of 40-45. Their homogenization temperatures

fluid with a high salinity (34 to 36 eq. wt. %NaCl) and homogenization

Guinea. Organ. Geochem, 26, 155-173.

Based on the results of this study, an attempt has been made to

range from 40C to 90C.

temperatures between 240C and 290C; 2) A fluid with moderate

temperatures between 97C and 117C.

They are found as

salinity (10 to 17 eq. wt. %NaCl) and homogenization temperatures

George S., Ruble T., Dutkiewicz A., Eadington P. (2001) Assessing the


between 178C and 227C; 3) A fluid with moderate salinity (3.4-7.2

maturity of oil trapped in fluid inclusions using molecular geochemistry data

The first fluid event identified is associated with the formation

1. Fluid inclusion studies from the Llanos Foothills Basin reveal

eq. wt. %NaCl and 6.812.2 eq. wt. % CaCl2) and homogenization

and visually-determined fluorescence colours. Applied Geochemistry. 16,

of quartz overgrowths. Microthermometric data indicates that

the presence of aqueous and hydrocarbon fluids hosted within

temperatures between 97C and 117C; and 4) A hydrocarbon

451 473

the fluids present in the formations at this time have minimum

quartz overgrowths and in annealed microfractures, indicating that

fluid with 40-50 API and homogenization temperatures between

temperatures between 92C and 130C. They have low salinities

these fluids were present during cementation and also during later

40C and 90C.

(0.5 to 4.8 eq. wt % NaCl) and some also CH4 CO2. The low

episodes of microfracturing.

build a fluid migration model for the Llanos Foothills Basin.

salinities indicate that they represent marine or meteoric waters

Goldstein, R. H. and Reynolds, T. J. (1994) Systematics of Fluid Inclusions

in Diagenetic Minerals. SEPM Short Course,31. U.S.A. Society for


Sedimentary Geology.

trapped within the pore spaces of these rocks. The presence of

2. Petroleum fluid inclusions within the overgrowths zone are rare

The authors wish to thank to the research group Flujo Regional de

Parnell, J., Carey, P., Duncan, W. (1998). History of hydrocarbon charge on

CH4 CO2 may be due to their liberation from rocks rich in organic

suggesting that the main phase of quartz overgrowth formation

Fluidos and ECOPETROL-ICP for suppling the samples, funding

the Atlantic margin: evidence from fluid inclusion studies, West of Shetland.

matter during the maturation process associated with the burial

preceded hydrocarbon migration. These oils are characterized by

and authorization for the publication of this study. JN would like to

Geology 26, 807-810.

and consequent increase in pressure and temperature of the rocks.

API gravities between 40-50 and homogenization temperatures

thank The Faculty of Science, National University of Ireland, Galway

Hydrocarbon inclusions were only occasionally found in quartz

between 92C and 113C. PVT modelling of coeval hydrocarbon

for a two-year postgraduate fellowship which funded this research.

Sellwood, B.W., Wilkes, M., James, B., (1993) Hydrocarbon inclusions in

overgrowths indicating that the main phase of quartz overgrowth

and aqueous inclusions hosted within quartz overgrowths indicates

JN would also like to thank The Geofluids Research Group,

late calcite cements: migration indicators in the Great Oolite Group, Weald

formation preceded hydrocarbon migration. Rare HCFI hosted

trapping temperatures and pressures of these fluids at ~120C and

Department of Earth and Ocean Science, NUI, Galway for a fruitful

Basin, S. England. Sediment. Geol. 84, 51 - 55.

within overgrowths have minimum trapping temperatures of 92C-

~250 bars. Integration of trapping temperatures with the burial

and pleasant working atmosphere. JN thanks to James Conliffe for

113C. They have a blue-white fluorescence colour (API gravity

history suggests that these fluids were trapped during the Miocene

the stimulating discussions about fluid inclusions.

= 40-50). From modelling of petroleum and aqueous inclusions


Stasiuk, L.D., Snowdon, L.R., (1997) Fluorescence micro-spectrometry of

synthetic and natural hydrocarbon fluid inclusions: crude oil chemistry, density


it is believed that these hydrocarbons were trapped during the

and application to petroleum migration. Appl. Geochem.12, 229 - 241.

3. The majority of hydrocarbon inclusions are commonly found

Bakker, R. J. (2003) Computer Programs (applied thermodynamic),

in annealed microfractures. They occur both as subparallel trails

University of Leoben, Austria. Online:

The second fluid event identified corresponds to fluid inclusions

in detrital quartz grains and as secondary inclusions in trails that


hosted within transgranular annealed microfractures in the

transect both detrital and authigenic quartz. This indicates that

sandstones. These fluid inclusions have been recorded cutting the

microfracturing was an important conduit for petroleum migration

Bodnar, R.J., (1990). Petroleum migration in the Miocene Monterey

quartz overgrowths. At least 2 aqueous and 2 hydrocarbon fluid

. two types of hydrocarbon were found within microfractures: 1)

Formation, California, USA: constraints from fluid inclusion studies. Mineral.

migrations events were recorded: 1) fluid with low to moderate

A hydrocarbon fluid with 40-50 API gravity and homogenization

Mag. 54, 295 - 304.

salinity (2.0 12 eq. wt. %NaCl) and homogenization temperatures

temperatures between 64C and 138C; 2)A hydrocarbon fluid with

between 100C and 137C; 2) An aqueous fluid with small volumes

25-30 API gravity.

Miocene (~10 Ma).

Bodnar, R.J., 1993. Revised equation and table for determining the freezing
point depression of H2ONaCl solutions. Geochimica et Cosmochimica

of either CH4 CO2. Their homogenization temperatures range

Acta 57, 683684.

from 102 to 127C; 3) Hydrocarbon fluid with 40 - 50 API gravity

4. Microthermometric data indicates that quartz overgrowths

and homogenization temperatures between 64C and 138C; and

were precipitated by fluids with minimum trapping temperatures

4) A Hydrocarbon fluid with 25-30 API gravity, these inclusions

between 92C and 130C. Last ice melting temperatures indicate

Burruss , R.C., (1991).

are typically < 3m. Because of their size they are difficult to resolve

that both aqueous fluid with low salinities (0.5 to 4.8 eq. wt% NaCl)

of petroleum fluid inclusions.

and no precise microthermometric data could be obtained from

and CH4 CO2 were present at the time of quartz overgrowth

Luminescence Microscopy: Qualitative and Quantitative Applications., In

these inclusions. The presence of inclusions within trails long


SEPM Short Course.25, 1-7.

5. Microthermometric studies from the aqueous fluid inclusions

Burruss, R.C. (2003) Petroleum Fluid Inclusions, an Introduction. In: Fluid

hosted in transgranular annealed fractures, suggest at least two

Inclusions Analysis and Interpretation. Samson I., Anderson A. and Marshall,

The third and final event identified corresponds to the fluid

aqueous migration events post-diagenesis. These fluids can be

D. Mineralogical Association of Canada. Short Course 32, 159-174.

inclusions found within the veins. At least three aqueous and one

divided as follows: 1) A fluid with low to moderate salinity (2.0

hydrocarbon fluid migration events were recorded: 1) Fluid with high

12 eq. wt.% NaCl) and homogenization temperatures between

Feely, M and Parnell J. (2003) Fluid inclusion studies of well samples from

homogenization temperatures (240C to 290C) and high salinities

100C and 137C; 2) An aqueous fluid containing CH4 CO2 and

the hydrocarbon prospective Porcupine Basin, offshore Ireland. Journal of

(34 to 36 eq. wt %NaCl); 2) A fluid with moderate salinity (10 to

homogenization temperatures that range from 102C to 127C.

Geochemical Exploration,7879, 55 59

6. A wide range of compositions and homogenization temperatures

George, S.C., Krieger, F.W., Eadington, P.J., Quezada, R.A., Greenwood,

Practical aspects of fluorescence microscopy

In Barker, C.E. and Kopp, O.


annealed fractures suggests that microfracturing was an important

conduit for both petroleum and aqueous migration.

17 eq. wt. %NaCl) and high homogenization temperatures (178C

to 227C); 3) A CaCl2 bearing fluid with moderate salinity (3.4-7.2




Crude oil and gas from the Campos

Basinof Brasil: a geochemical

Geochemical Study of Reservoir

Continuity in Cotoper-Oritupano Field
Jos A. Garca and Irenio Berrios

Rafael Tocco1*, Roger Baudino1 and Matthieu Pontet2

E&P General Management, PDVSA Intevep, S.A. Los Teques, P.O.
Box 76343 1070-A, Venezuela

1 Repsol Exploration, Direction of Geology, Mndez Alvaro 44,

28045, Madrid, Spain.
2 Repsol Sinopec Brasil, Praia de Botafogo 300, Rio de Janeiro,

gas). The B Well gases are also of thermogenic origin. The C Well
gases are of thermogenic origin (mixing of deep dry gases with
associated gases). Biodegradation process apparently did not
affect the sampled gases.
Geochemical analyses of post-salt hydrocarbons from Late
Cretraceous and Tertiary reservoirs, are compared with the previous
ones and allow revealing similities and differences.



The pre-salt oils are mixed oils with intermediate lacustrine-marine

organic matter input, or oils generated by a source rock with mixed
organic matter (marine-lacustrine). The oils are mature to highly
mature. Geochemical evaluation support oil-oil correlation between
A, B and C well oils. The analyzed gases are of thermogenic origin.

Figure 2. Structural map of the study area.

Copyright 2014, ALAGO.


From Fig. 2 and according to the standard of continuity evaluation

and the Px data, there are some differences between the GC
peak ratios of the wells A, B and D, and the continuity of the fluid
of the oil reservoir is good, while the wells D and E the continuity
of the fluid of the oil reservoir is regular, which reflects that the
continuity of the fluid is limited.


The authors thank Repsol Sinopec Brasil for approving the

presentation of this study.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The Cotoper-Orocual field is located in Northern Monagas (Fig
1). The reservoir is divided in five blocks by faults. The existence
of those faults needs to be reevaluated, because the fault sealing
and reservoir continuity of different fault blocks are very important
issues for the study of oil filling histories and production (Garca et
al., 2008; Hou et al., 2004).

The fluid continuity between Block 4 and Block 5 is limited.
Therefore, the impact on fluid of the fault B4/B5 should be taken
into consideration in future development of Cotoperi-Orocual field.

The authors would like to acknowledge PDVSA Intevep, S.A. for
permission to publish this paper and thank reviewers for their
useful comments.
Figure 1. Relative location of the fields in the North Monagas.

Garca J. A., Vargas A. and Canale G. Estudio Geoqumico de


Compartamentalizacin de Yacimientos en la Costa Oriental del Lago

Four dead oil samples were purchased in duplicate, taken at the

wellhead according to API RP 44. The samples were dried and
then removed the sediment according to ASTM D1796-97. C15fraction was analyzed in a gas chromatograph Agilent Technologies,
model 6850 Series II.

de Maracaibo. XI Latin-American Congress on Organic Geochemistry

November 2-6, 2008. Margarita Island, Venezuela.
Halpern H. I. (1995) Development and application of light-hydrocarbonbased star diagrams. AAPG Bull, 79(6): 801-815.

Results and Discussion

The Campos Basin is located in the Southeastern Brazilian Margin

and has a total area of about 300000 km2. It is part of a series
of basins formed along the Brazilian Atlantic margin during the
breakup of Gondwana in Early Cretaceous times. The Campos
basin is limited by the Vitria High, which separates it from the
Esprito Santo Basin to the north, and by the Cabo Frio High, that
separates it from the Santos Basin to the south. The Campos
Basin has for long accounted for the largest reserves of Brazil in
Late Cretaceous and Tertiary post-salt reservoirs and after the BMC-33 Repsol operated block, pre-salt discoveries also revealed to
be the place of large pre-salt accumulations.
Results and Discussion
The pre-salt oils are mixed oils with intermediate lacustrinemarine organic matter input, or oils generated by a source rock
with mixed organic matter (marine-lacustrine). These crude oils
were generated by a clay-rich source rock. Two oil groups (A and
B wells) show presence of moderate-high relative concentration
of gammacerane compound, being the major concentration in
the B Well oils. Gammacerane indicates that increased water
salinity during deposition of the source rock. The m/z 191 terpane
chromatograms for C Well oils show low signal-to-noise ratios.
Highly mature oils have low concentrations of biomarkers (very low
relative concentrations of branched saturate hydrocarbons). C Well
oils are more mature than A and B well oils.

Hou D., Zhang J., Long Z., Zhu J., Tang Y., Xu X. and Huang B. (2004)

Based on the basic principle that within a reservoir where there

are permeability barriers occur compositional homogenization of
oil therefore anywhere in the reservoir will be presented the same
composition or fingerprint (Kaufman et al., 1990) and, to the extent
that there are compositional differences, they may be attributed to
the effect of compartmentalization (Hunt, 1995). The GC peak ratios
of the oil samples were analyzed and studied. Fifteen representative
parameters (P1-P15) were selected (after Thompson, 1987) and
posted in a star plot (after Halpern, 1995; Fig. 2).

Study of fault sealing by geochemical techniques: Fault sealing evaluation in

petroleum migration and reservoir continuity. Proceedings of the 6th AAPG

Geochemical evaluation support oil-oil correlation between A, B

and C well oils.

International Conference. 201-208.

Hunt J. M. (1995) Petroleum Geochemistry and Geology. W. H. Freeman
and Company. New York, 743
Kaufman, R. L., A. S. Ahmed, and R. J. Elsinger, 1990, Gas Chromatography
as a development and production tool for fingerprinting oils from individual
reservoirs: applications in the Gulf of Mexico, in D. Schumaker, and B. F.
Perkins, eds., Proceedings of the 9th Annual Research Conference of the
Society of Economic Paleontologists and Mineralogists, October 1, 1990:
New Orleans, p. 263-282.
Thompson K.F.M. 1987 Fractionated aromatic petroleums and the
generation of gas-condensates. Org. Geochem., 11(6): 573-590

Some geochemical signals suggest that the oils are affected

by biodegradation. The only explanation for biodegradation
evidences could be that the oils have been affected by microbial
processes before the reservoir reached temperatures of 80C
(paleo-biodegradation). Generally oil accumulations which contain
a number of distinct charges or charge over time at different
rates, exhibit mixed geochemical signatures: mixing of fresh and
degraded oils . The biodegradation is not a significant feature that
affect the oil quality.
Gas samples from both Post- and Pre-Salt series were analyzed.
The A Well gases are of thermogenic origin (Post Salt gases: mainly
oil associated gas; Pre-Salt gases: mainly condensate associated


from the Colombian Institute of Petroleum (ICP) and recent studies

that were done within the context of this research.

Geochemical characterization
from the northern area of the Eastern
Llanos Basin, Colombia.

Quality control: A revision of the whole information was ran in order

to eliminate the data with error or lack of information such as depths
and pyrolysis data with total organic content (TOC) < 0,5%wt which
can cause problems at the moment of data interpretation.

Nelson Sanchez1,Felipe de la Parra1,Diego A. Martinez2*, Jenny P.

Ramirez2,Henry Suarez3

Biostratigraphic correlation: time intervals were identified from a

palinology research made by the biostratigraphy group of the ICP
and the available electrical registers for each well.

1Instituto Colombiano del Petrleo ICP-ECOPETROL, Piedecuesta,

2 Natfrac Corporation, Bucaramanga, Colombia
3 Empresa Colombiana del Petrleo ECOPETROL, Bogot,

Geochemical characterization: after the compilation of information

and identifying the time intervals in the correlation, the geochemical
characterization was made for each time interval from each well,
taking into account the standards from Peters & Cassa, 1994.
Integration of the information: after relating the geochemical
interpretation for each time interval and the correlation made on
step 2, the correlation for each time interval was made, which
allowed us to see the variations along the researched transect and
to identify the intervals with potential for hydrocarbons generation.

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Results and discussion


Organic material content: the Paleozoic interval showed poor to

regular organic material content with values that were between
0.2-0.9%wt. In the Late Cretaceous interval the TOC contents
increased from regular to good with values between 0.6-2.37%wt
towards Santa Mara-1 and La Heliera-1 wells, reaching very good
values in Chiguiro-1 well mainly in the interval known as Coniacian.
Finally within the Cenozoic interval are the best TOC values
between 0.5-5.6%wt which indicate regular to very good organic
material contents mainly towards Mid Miocene.

The main sources of hydrocarbons in the Eastern Llanos Basin

are cretaceous age rocks that belong to Gacheta Formation.
Nevertheless, due to the increase in the demand for hydrocarbons,
its necessary to explore for new sources that would improve
Within this context, its necessary the research and exploration of
new areas that werent taken into account before, which can have
new source rocks with conditions for hydrocarbons generation.
Among these new locations is the northern area of the Eastern
Llanos Basin.

Quality of the organic material and generator potential: The tools

to establish the kerogen type in the Paleozoic and Proterozoic
sections are the IH rates, which were associated to type III Kerogen
(gas generator). Organic petrography results (visual analyses of
Kerogen) indicate a predominance of liptinites and phytoclasts.
From this information was established that the Late Cretaceous
interval has type II Kerogen (gas and oil generator), related to
marine sediments where the mixture of organic material derived
from phytoplankton, zooplankton and bacteria took place; the
Cenozoic interval is characterized by a mixture of type I and II
kerogen (oil generator) associated to a mixture of lacustrine and
marine sediments.

This research is focused on Santa Maria-1, Joropo-1, Agualinda-1,

La Heliera-1, Chiguiro-1 and La Coral-1 wells, as shown in
figure 1, with the purpose of characterizing each time interval
from geochemical information, kerogen visual analyses and
biostratigraphy to identify the generator potential of these rocks in
this area of the Basin.

Maturity of organic material: the evaluation of the maturity for

Paleozoic and Proterozoic intervals was hard to discriminate
because vitrinite reflectance data (%Ro) was dismissed due to the
absence of flora within these intervals, hence there werent any
vitrinites to perform the analysis; the evaluation for this interval was
made taking into account the values of the color index for acritarchs
such us Leiosphere, Cymatiogaleaspp, Dictyotidiumspp among
others from the same age. These analysis suggest an immature
to early mature state for the area between Santa Maria-1 and
Joropo-1 wells with SCI values between 5.0-6.5 (Roeq 0.6-0.7%)
with and increase towards Agualinda-1, La Heliera-1, Chiguiro-1
and La Coral-1 wells, with states of Late Maturity getting out the
generation window with SCI values between 8.0-9.0 (Roeq 0.91.3%). On the other hand for the Mesozoic and Cenozoic sequence
we could count on Tmax, SCI, TAI and vitrinite reflectance data,

Figure 1. Location of the Wells used for this research, placed on the
northern area of the Eastern Llanos Basin.

The phases developed for this research were as follow:
\Compilation of bibliography: the main sources for this research
were the final reports that were made for each well, the database

where Tmax values are predominant below 435C, ICE 5.0-5.5,

IAT 2+ to 3+ and Ro values of 0.4-0.6% indicating an immature
thermal state of the organic material for this sequence.

Geochemical characterization of
oil seep and oil samples from wells of
adjacent areas, in order to determine the
origin, by oil-oil correlation, two study
cases, Monagas, Venezuela

S2 and S1 values are low in this area of the Basin, indicating low
generator potential.

In this area of the Basin, the Mesozoic and Cenozoic section, shows
an immature thermal state and through the Paleozoic section we
observed an increase of the thermal maturity of the rocks towards
SW-NE direction, which goes from Immature-early mature in
Santa Maria-1 and Joropo-1 wells to late mature in Agualinda-1,
La Heliera-1, Chiguiro-1 and La Coral-1 wells. Its observed that
the compiled thermal maturity data from different studies shows
variations, depending on the material that was taken to perform the
analysis or the techniques that were applied.

Y. J. Rincones1*, C. Rodrguez 1, J. Arenas 1

1 PDVSA, Intevep, Los Teques, 76343, Venezuela;
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The intervals with conditions for the best hydrocarbons generator

potential are placed to the NE between La Heliera-1, Chiguiro-1
and La Coral-1 wells in Coniacian age rocks, with good-very good
organic contents and good-very good generator potential with type
II kerogen mainly to the SW. In Santa Maria-1 well, two intervals with
good geochemical properties were identified; the first to the top of
Early Oligocene sequence with good organic contents, regular to
good generator potential mainly associated to type II kerogen and
the second to the middle part of Late Miocene interval, with good
to very good organic content, good generator potential, type I and
II kerogen.

The geochemical characterization is a specialty widely used in the
oil industry, with multiple applications that help to understand the
petroleum system in the area. Below are two study cases, in which
geochemical characterization was applied to determine the source
of oil seeps, in the area North of Monagas in Venezuela (figure 1).
The samples were analyzed by general and special geochemical
techniques, to determine the origin and maturity of these, as well as
any possible oil-oil correlation, to determine the source of the spill.

Brown; Ruth Laboratories, INC. Geochemical evaluation for
hydrocarbon source potential, Sun Chiguiro No.1_Colombia,
South America. Final report.
Dow, W. G.; Gonzalez, E., 1979. Geochemical evaluation of Rondon-1,
Corozal-1 and La Heliera-1, Wells, Llanos Basin, Colombia. Robertson
Research (US) Inc.
Dunn, M. E., 1986. Geochemical data for the well La Coral, Llanos Basin,
Colombia. Research Center.
Duddy, I. R.; GEOTRACK, 2013. Organic petrography analysis (vitrinite

Figure 1. Geographical Location

reflectance and visual kergeno analysis), in cutting samples from 3 wells.

Report prepared for ICP-ECOPETROL, Colombia.
ICP-ECOPETROL, 2013. Integracin de resultados geoqumicos y
litolgicos correspondiente a los pozos del proyecto palinoestratigrafa.
Reporte interno, 64p.

For the evaluation and characterization of the samples collected,
the following geochemical analyzes were carried out: SARA, GC on
saturates fraction and GC-MS of saturates and aromatic fraction
(figure 2).

Peters, K., 1986.Guidelinesforevaluatingpetroleumsource rock using

programmed pyrolysis. AAPG Bulletin 70, N 3, 318-329.
Peters, K.; Cassa, M., 1994.Applied source rock geochemistry the
petroleum system from source to trap. AAPG Memoir 60, 93-120.
Staff of E&P Operations, 1981. Final Well Report Santa Mara N1, Ariporo
rea, Colombia, 217p.
Garca, D. F.; Giraldo, B. N., 1999 Geoqumica del sector CapachosCuenca Llanos Orientales. Instituto Colombiano del Petrleo.


Figure 2. Methodological diagram of oil characterization


[1] Peters, K., Walters C., and Moldowan, M., 2005, The Biomarker Guide.

Results and discussions

Biomarkers and Isotopes in Petroleum Exploration and earth History. Vol. 2.

This paper presents two cases of oil leaks from old fields of NE
Venezuela. The first Case is about geochemical characteristics of
an oil sample A-1 from a spill in the area C, and an oil sample
B-1 from well B located in the area C. The results showed clear
differences between the samples, indicating a negative oil-oil
correlation between oil samples A and B, which indicates that
the oil sample A does not come from wells in the area, although
samples are associated with a carbonate rock deposited under
anoxic conditions and a marine origin, the differences were found
in the maturity and biodegradation.

Cambridge University Press.



[2] Rullktter, J. and Wendish, D., 1982, Microbial alteration of 17(H)hopano in Madagascar asphalts: Removal of C-10 methyl group and ring

Mogolln-Galvisa, Robert E. Marquez-Romeroa

[3] Seifert, W. K., and Moldowan, J. M., 1979, The effect of biodegradation


Acta, Vol. 43, p. 111-126.

were generated by several pulses of biodegradation.

The authors thank ECOPETROL and PEMEX for allowing to
present this work.

Mario A. Guzmn Vegaa, Diego F. Garca-Bautistaa, Leonardo

opening. Geochimica et Cosmochimica Acta, Vol. 46, p. 1534-1553.

on steranes and terpanes in crude oils. Geochemical et Cosmochemica

Gulf of Mexico province. In contrast the heavy oils from Colombia

Copyright 2014, ALAGO.

The second Case is about geochemical characteristics of oil

seepage samples E-1, E-2, E-3, E-4, E-5, E-6, detected in the field
D and an oil sample F-1, from well F, located in the field D, in order to
conduct an evaluation to determine if these oil samples correspond
to oil seepages or oil spills caused by abandoned wells in the area.
The results suggest that the oil seepage samples and the well oil
sample are positively correlated, indicating that the abandoned well
is leaking oil, in addition, the characterization determined that the
samples are associated with a carbonate rock deposited under
anoxic conditions, a marine origin and maturity is between early
and oil window. Besides the lack of paraffins and isoprenoids and
the presence of the compound 25-Norhopane established that the
samples show a high degree of alteration (grade 8) due to the effect
of biodegradation and/or oxidation of the compounds.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

64% of world reserves are related to heavy and extra heavy crudes
reservoirs. We analyzed here the formation of heavy oil in two
different tectonic environments: Extensional (case of Mexico) and a
compressive foreland (case of Colombia).

Results and Discussion

The Tithonian source rocks contain large amounts of organic sulfur
compounds and are considered the most important generative
subsystem in Mexico. Kerogens from Tithonian natural series and
related oils suggest that hydrocarbon generation in these rocks


begins and ends about 0.5% and 0.9% respectively, with peak

* In case 1, the results indicate that the oil samples A-1 and B-1

generation of about 0.8% Ro.

are associated to organic matter type II of marine origin, deposited

under reducing conditions, but the oil sample B-1 is more mature

In the central and southern portion of the Llanos Orientales

and less biodegraded than the oil sample A-1. In addition,

basin have been recognized at least 2 families of oils, a family

sample A-1 showed an abundance of branched and naphthenic

associated with Cretaceous marine source rocks and a second

compounds that are not in the sample B-1, which could indicate


a possible mixture of predominantly marine oil source with a lower

associated to source rocks of continental affinity. The

presence of unmethylated compounds is considered as a common

proportion of a biodegraded oil. These results indicate that the

characteristic of oils produced by marine rocks which is diagnostic

samples A-1 and B-1 do not have a positive correlation, therefore

of advanced biodegradation processes . Samples analyzed in

the oil sample A-1 does not come from wells in the area.

these compounds coexist with n -paraffins showing a complex

filling history. The distribution of heavy oils is not related to the

* In case 2, the results indicate that the oil seepage samples (E-1

depth and the current temperature of the reservoir. These fluids

to E-6) and the well oil sample (F-1), are associated to organic

were trapped in shallow and cold reservoirs (temperature <80

matter type II of marine origin, deposited under reducing conditions

C ) before the burial of the deposits to its current position These

and a maturity between medium to oil window, in addition, the

facts suggest the presence of a paleo - oil biodegradation affecting

characterization determined that the oil seepage samples and

pulses accumulated during early migration, being biodegraded to

the oil well sample are positively correlated, indicating that the oil

temperatures above 80 C.

seepages samples (E-1 to E-6) taken around the well (F-1) are the
result of a spill of this. Besides, the lack of paraffins and isoprenoids


and the presence of the compound 25-Norhopane established

The mineral matrix of the source rocks is an important factor that

that the samples show a high degree of alteration, this is because,

controls the quality of the crude. In rocks with clay matrix, iron is

the samples of oil seepages were taken at the surface, and the well

abundant and reacts with the sulfur in the sedimentary environment,

has been closed for a long time.

giving rise to pyrite and chalcopyrite, whereas in source rocks with

carbonate matrix, free sulfur reacts with organic matter giving rise


to sulfur rich kerogens which produce an early generation.

The authors thank to PDVSA Intevep all their support that made
possible to carry out this research.

This early generation process would be responsible for the heavy oil
deposits present in some of the Mexican reservoirs in the Mexican



i.d., 0.1 m df) was used as the second-dimension column (2D).

The selected samples were pre-fractionated to saturated
hydrocarbon and aromatic fractions. Due to the high content of
n-alkanes, some of the saturated fractions were treated with urea
to achieve the branched and cyclic hydrocarbon fraction (B/C). The
saturated hydrocarbon, B/C and aromatic fractions were dissolved
in dichloromethane before chromatographic analysis.

High-Resolution Molecular
Organic Geochemistry for the
Depositional Paleoenvironment
Classification of Brazilian Crude Oils

Results and Discussion

Alessandro Casilli1, Flix T. Gonalves1,Jaakko Laakia1, Maria

Regina B. Loureiro1,Dbora A. Azevedo1, Francisco R. Aquino

The use of a powerful analytical technique such as GCGC-TOFMS

accesses new opportunities forgeochemical data analysis, which
may be considered as a step towards a High Resolution Molecular
Organic Geochemistry. Recent results from our group have shown
how non-conventional compounds are important to differentiate
paleoenvironment depositional conditions. In fact, in a group of 20
oils from the same basin, minor differences in the GCGC-TOFMS
data analysis have been observed (Casilli et al., 2014). In another
example, Kiepper et al. (2014) differentiated samples with 3- and
2-methyl-hopane series (as suggested by Farrimond et al., 2004)
and onocerane isomers, present at trace level, as proxies of the
different depositional paleoenvironment.

1 Universidade Federal do Rio de Janeiro, Instituto de Qumica,

LAGOA-LADETEC, Ilha do Fundo, 21941-909, Rio de Janeiro,
RJ, Brazil.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

In this work, GCGC-TOFMS has been used as an important

tool in biomarker investigation, paving the path for a true HRMOG
approach. The oils investigated allowed the characterization of
different depositional paleoenvironment and their mixtures. The
biomarker ratios for H30/St (S+R), Tr26/Tr and % 3MH31/
H30 are, respectively: Oil A: 9, 1.74, 2; Oil B:12, 1.48, 2; Oil C:
8.99, 1.42, 1.93; Oil D: 7.53, 1.33, 1.87; Oil E: 9.3, 1.97, 1.73; Oil
F: 3.59, 1.3, 1.47; Oil G: 2.36, 1.21, 1.72; Oil H: 1.89, 0.9, 0.18;
Oil I: 0.79, 0.82, 0.66; Oil J: 1.01, 1.03, 0; Oil K: 1.57, 1.25, 0;
Oil L: 1.68, 1.41, 0.55. Plotting these values, the classification in
three depositional paleoenvironments was not clearly obtained by
conventional parameters (H30/St27 (S+R) vs Tr26/Tr25) (Figure
1a). On the other hand, the oils have been easily differentiated by
combining a non-conventional parameter (%3-MH31/H30) and a
conventional one (H30/St27 (S+R)) (Figure 1b).

The geochemical analysis of crude oils demands a lot of information
including vast characterization of its chemical constituents.
This task historically has involved different analytical techniques,
predominantly capillary gas chromatography (GC) in many cases
coupled to mass spectrometry (MS; MS/MS). Due to the lack of
information related to chromatographic coelutions and the limited
access to the spectral data of the SIM and MRM modes, in the last
years the investigation of complementary techniques have been
Comprehensive two-dimensional gas chromatography (GCGC)
hyphenated to time of flight mass spectrometry (TOFMS) provides
interesting results, mainly due to its higher separation capabilities,
the availability of the mass spectrum of each component and reliable
quantitative data. GCGC-TOFMS raises the analytical capability
beyond the presently known biomarkers, leading to the possibility
of refining the application of High-Resolution Molecular Organic
Geochemistry(HRMOG) to distinguish more subtle differences
in composition. This could lead to a better understanding of the
geochemical depositional paleoenvironment of complex petroleum

Another HRMOG example is related to the separation of C30

24-n-propylcholestanes - derived from 24-n-propylcholesterols,
which are biosynthesized by sea water Crysophyte algae (Peters
et al., 2005) -, from interferents like the C30 4-methyl-24ethylcholestanes.
The presence of these compounds in crude oil is an important tool
to identify marine organic material input in the source rock. Positive
identification of the 24-n-propylcholestanes by GC-MS/MS in
MRM mode (414>217) can be difficult due to low concentrations
and coelutions with C30 4-methyl steranes. On the contrary, as
reported in Figure 2, the GCGC-TOFMS permitted its separation
and reliable identification.

Vertical variability in crude oil composition:
Es-Soc Well, Socororo Field, Eastern
Venezuelan Basin
Salvador Lo mnaco and Liliana Lpez
Instituto de Ciencias de la Tierra. Facultad de Ciencias. Universidad
Central de Venezuela
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The determination of producing intervals and oil quality in a reservoir
requiresthe studyof different geochemical parameters. In particular,
oil quality reflects the compositional characteristics of hydrocarbons
that impact the economic viability of an exploration, development,
or production opportunity. In general, oil quality may affect the
direct economic value of the crude oil. Typical oil-quality properties
Figure 2.EIC m/z 414 showing the separation of 24-alkylcholestanes

include API gravity, viscosity, sulfur, asphaltene, and metals (e.g.,


vanadium, nickel) contents, and acidity. Biodegradation can







24-n-propylcholestane (b)

significantly impact essentially all oil-quality properties of crude oils

in producing zones. More specifically, oil biodegradation typically

GCGC-TOFMS allowed the separation and identification of nonconventional biomarkers, besides the usual ones. It is evident
the outstanding contribution of non-conventional compound
for the classification of Brazilian oils from different depositional

(a) decreases API gravity, (b) reduces the content of saturated and


becomes enriched in NSO compounds (resin and asphaltene

Petrobras SAP 4600349302, CNPq, FAPERJ.

fractions), sulfur and metals (Connan, 1984; Wenger et al., 2002;

oil viscosity, (d) increases oil acidity and (e) increases the sulfur
content and the concentration of certain metals (e.g., V and Ni).
As a consequence, the residual oil resulting from biodegradation

Larter et al., 2006). Knowledge of the lateral and vertical variations

Casilli, A., Silva, R.C., Laakia, J.,Cleverson, C.J.F., Ferreira, A.A., Loureiro,

aromatic hydrocarbons relative to polar compounds (c) increases

Azevedo, D.A., Aquino Neto, F.R., 2014. High Resolution

Molecular Organic Geochemistry Assessment of Brazilian Lacustrine Crude

in the oil-quality properties as a consequence of biodegradation

is an important key to the development and implementation of
enhanced oil recovery methods.

Oils. Organic Geochemistry, 68, 61-70.

In this study, a representative number of crude oils from different

Brazilian basins were selected and deeply investigated. GCGCTOFMS allowed the determination of minor molecular differences
resulting in their depositional paleoenvironment characterization.


Analyses were performed on a Pegasus 4D (Leco, St. Joseph, MI,
USA) GCGC-TOFMS, composed of an Agilent 6890 GC (Palo
Alto, CA, USA) equipped with a secondary oven, a non-moving
quad-jet dual-stage modulator and a Pegasus III (Leco, St.
Joseph, MI, USA) time of ight mass spectrometer. A DB-5 column
(Agilent Technologies, Palo Alto, CA, USA), 5%-phenyl95%methylsiloxane (30 m, 0.25 mm i.d., 0.25 m df) was used as the
rst-dimension column (1D). A BPX-50 column (SGE, Ringwood,
VIC, Australia), 50%-phenyl50%-methylsiloxane (1.5 m, 0.1 mm








Venezuela has one of the worlds largest reserves of heavy and

paleoenvironment of Brazilian crude oils from unusual biomarkers revealed

extra heavy biodegraded crude oils in the Eastern Venezuelan

using comprehensive twodimensional gas chromatography coupled to

Basin, which includes the widely studied Orinoco Oil Belt and the

time-of-flight massspectrometry.Organic Geochemistry, in press.

Socororo Major Area in the Maturin sub-basin. The Socororo field,

Farrimond, P., Talbot, H.M., Watson, D.F., Shulz, L.K., Wilhelms, A., 2014.
Methylhopanoids: Molecular indicators of ancient bacteria and a petroleum
correlation tool. GeochimicaetCosmochimicaActa, 68 (19), 3873-3882.

and in particular the ES-SOC oil well, in the Socororo Major Area
is the subject of this study. Here, we describe the vertical variability
in the extractable organic matter (EOM) of sidewall core samples
and oil composition. The latter was correlated to the characteristics

Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide,
Figure 1. Plot reporting the separation of 12 Brazilian oils formed in different

Biomarkers and Isotopes in Petroleum Exploration and Earth History, Vol 2.,

depositional paleoenvironments based on conventional parameters (a) and

p. 527. Cambridge University Press, Cambridge, UK.

adding a non-conventional one (b).


of the source rock (e.g., lithology, organic-matter input, redox

depositional conditions, and thermal maturity) in order to establish
oil quality as a consequence of biodegradation.



Alteration by biodegradation

The samples suites consisted of a freshly recovered crude oil

sample and sixteen sidewall core samples from the ES-SOC
well obtained from a relative depth interval of 878 m to 1373 m.
Organic carbon concentration (LECO, C-144), and sulfur content
(LECO SC-432) were determined. Extractable organic matter
(EOM, %m/m) was obtained using Soxhlet extraction technique
with dichloromethane. The oil samples were de-asphaltened to
obtain a maltene fraction, which was subsequently separated
into its saturated, aromatic and resin fractions by means of
adsorption chromatography, using packed columns with alumina
as the stationary phase. The saturated hydrocarbons were eluted
with n-hexane, the aromatic hydrocarbons with toluene, and the
polar compounds (resins) with a mixture of toluene and methanol.
Analyses of the saturated biomarkers were performed by gas
chromatography-mass spectrometry (GCMS) on a network gas
chromatograph (Model 6890N, Agilent Technologies) coupled to
a mass spectrometer (Model 5975, Agilent Technologies). The GC
system was equipped with DB-1 fused silica capillary column (60
m x 0.25 mm x 0.25 m). The monitored ions were m/z = 113 for
n-alkanes, pristane and phytane; m/z = 191, 177 for terpanes; and
m/z = 217, 218 for steranes and diasteranes.

The EOM concentrations in the core samples exhibited values lower

than 0.1% (0.02-0.89 %), except for a sample taken at the depth
interval of 1360 m were EOM reached a value of 2.4% (Figure 2).
The analyzed crude oil with 14 API and a sulfur content of 2.5%,
presented a SARA composition of 24% saturated hydrocarbons,
36% aromatic hydrocarbons and 40% polar compounds (resins +
asphaltenes). Figure 2 shows the n-alkanes and pristane phytane
distributions for the crude oil. The distributions are characterized
by a wide unresolved complex mixture (UCM) contribution under
a resolved peak envelope showing the presence of acyclic
isoprenoids (phytane and pristane) and variations in the relative
intensity of n-alkanes, indicative of alteration by biodegradation.
The abundance of C23 tricyclic terpanes, the slight alteration of
steranes, and the absence of 25-norhopanes (Figure 1) indicate
that the crude oil is biodegraded to at least a PM level 5 (Peters
and Moldowan, 1993). In contrast, crude oils from other wells in
the Socororo field showed the presence of isoprenoids pristane
and phytane, absence of n-alkanes and traces of 25-norhopanes,
indicating different loadings of oils to the reservoir, which were
subsequently biodegraded.

Results and Discussion

Crude oil type
Analysis of the C24/C23 and C26/C25 tricyclic terpanes ratios
and C27-C29regular steranes abundance indicates that the crude
oil originated from marine organic matter. The ratio C35/C34 1
suggests anoxic-suboxic conditions during source rock deposition
(Figure 1). Additionally, the calculated values for the C24/C23, C22/
C21 and C26/C25 tricyclic terpanes ratios and C31R/C30Hop
hopanes ratios suggest that the analyzed oil originated from either
a marine-carbonate or a marine-marl source rock. The calculated
values for the C29 sterane isomerization ratios C2920S = 54.5%
and C29 = 52.5% indicate that the endpoint has not been
reached (C2920S = 52-55% and C29 = 67-71% at endpoint;
Peters and Moldowan, 1993). These results suggest that the crude
oils were generated prior or at the beginning of the oil window.

Connan, J., 1984. Biodegradation of crude oils in reservoirs. In: Brooks,


J and Welte, D (Eds.)Advances in Petroleum Geochemistry. V. 1 Aademic

Carbon isotope analysis of

specific biomarkers in Brazilian oils:
novel patterns and limitations

Press, London, 299-335.

Larter, S., Huang, H., Adams, J., Bennett, B., Jokanola, O., Oldenburg,
T., Jones, M., Head, I., Riediger, C., Fowler, M., 2006. The controls on the
composition of biodegraded oil in the deep subsurface. Part II geological
controls on subsurface biodegradation fluxes and constraints on reservoirfluid property prediction. American Association of Petroleum Geologist
Bulletin 90, 921-938.
Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide. Interpreting
Molecular Fossils in Petroleum and Ancient Sediments, Prentice Hall,
Englewood Cliffs, New Jersey.
Wenger, L.M., Davis, C.L., Isaksen, G.H., 2002. Multiple controls on
petroleum biodegradation and impact on oil quality. SPE Reservoir
Evaluation & Engineering 5, 375-383.

Jarbas V. P.Guzzoa*, Mario D.Rangela, Eugenio V.Santos Netoa,

Ygor S. Rochaa, John M. Moldowanb*
a PETROBRAS Research & Development Center, Rio de Janeiro,
b Biomarker Technologies, Inc.,Rohnert Park, California, USA
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Compound specific isotope analyses of biomarkers (CSIA-B) were
carried out in a set of Brazilian oils with well constrained molecular
(biomarkers) and isotopic (CSIA-n-alkanes profiles) genetic based
classification. Factors that control carbon isotopic composition of
individual biomarkers are determined by paleobiologic origin and
paleoenvironmental conditions during deposition of the source
rocks (Hayes et al. 1990).
Carbon isotopic ratios of hopanes, tricyclic terpanes, steranes and
isoprenoids were investigated in representative oils of the three main
tectono-sedimentary stages of the Brazilian continental margin: a)
freshwater to saline lacustrine oils of the rift stage; b) evaporitic
oils of the Proto-Atlantic transitional/sag stage, and c) restricted
to open marine oils of the drift stage. This combined approach
provides advantages for the developing methodology (CSIA-B),
which is compared to a previous classification scheme. CSIA-B
adds new significant genetic and paleoenvironmental attributes to
a multivariate geochemical database.

Results and Discussion

Figure 2. Concentration (%m/m) of extractable organic matter (EOM) as a

function of well depth; SARA composition; and mass chromatogram for
n-alkanes and acyclic isoprenoids of the analyzed crude oil.

The crude oil extracted from the ES-SOC well, Socororo field,
was originated from either a marine-carbonate or a marine-marl
source rock with marine organic matter input deposited in anoxicsuboxic conditions and at an early oil window level of maturity. After
generation, the oil was biodegraded at a PM level 5.


and steranes (m/z = 217, bottom) in the saturated hydrocarbon fractions

This work was funded by the Consejo de Desarrollo Cientfico

y Humanstico, Universidad Central de Venezuela, under the
research grant N PG-03-8204-2011 and Fondo Nacional para la
Ciencia y Tecnologa, under the research grant N 2012002299.

isolated from ES-SOC oil samples.


Figure 1. Mass chromatograms of the terpanes (m/z = 191 and 177, top)


Great differences within hopane C-isotope ratios (generally > 10,

figure 1) occur between marine and lacustrine oils. Lacustrine
oils have characteristically 13C depleted hopanes (up to -39),
reflecting significant bacterial methane cycling (Summons et
al. 1994), restricted circulation and widespread water column
stratification during Brazilian Lower-Cretaceous episodes of
lacustrine source-rock deposition. Normal marine oils have 13C
enriched hopanes (up to -14) which is concordant with molecular
(biomarker) paleo-environmental inferences of non-stratified and
sub-oxic bottom waters during late drift phase. Pristane, phytane
and steranes generally show similar isotopic compositions (around
-27) between oil families, which is concordant with their presumed
phytoplanktonic origin. None of the oil families, except the normal
marine oils, present indications of important terrestrial organic
matter input. Thus, -27 can be considered as representative
of the isotopic composition of primary producers of the euphotic
zone (Schouten et al. 1998), for example, during Turonian times
in South Atlantic. Interestingly, the orphan biomarkers tricyclic
terpanes tend to follow the same range of values of isoprenoids
and steranes.


The carbon isotopic profiles of hopanes follow a pattern which

is indistinguishable among oils generated by freshwater/saline or
hypersaline source-rocks. These hopane isotopic profiles show a
recurrent feature represented by a large difference (characteristically
> 4) between the isotopic composition of C29 hopane (the most
13C depleted hopane) and C30 hopane. These two compounds
show quite similar isotopic compositions in the oils of marine origin.
The representative oils of Lower Cretaceous inland waterbodies
(generated by rift and sag source rocks) also have a remarkable
heavy sterane (C304-methylstigmastane), generally 4 heavier
than C27-C28-C29 regular co-occurring desmethyl steranes,
suggesting a distinct primary producer in continental waters
recording episodic algal blooms. The 4-methylsteranes are largely
derived from dinoflagellates, of which certain species can thrive in
evaporitic environments.

Origin and maturity of crude oils and oil seeps

from Falcn Basin, Western Venezuela
Leonardo Snchez-Carrasco a*
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).



We observed a general agreement between paleoenvironmental

scenarios provided by thetraditional geological and geochemical
approaches and those derived from the isotopic analysis of specific
biomarkers. CSIA of biomarkers is thekey tool to correlate isotopic
and molecular data directly to a particular paleobiologic source and/
or biosynthetic pathway. It has shown great potential to add new
and refined attributes to the paleoenvironmental reconstruction of
ancient ecosystems and for the investigation of mechanisms of
hydrocarbon generation.

Falcn Basin is a secondary oil and gas basin in Venezuela (Figure

1). Recent discoveries of excellent quality crude oil offshore Falcn,
have reactivated the exploration and the interest for the basin;
therefore a better understanding of the active petroleum systems
is necessary.

Hayes, J. M., Freeman, K. H., Popp, B. N., and Hoham, C. H., 1990.

Results and discussions

Falcn Basins crude oils are characterized for having an API gravity
between 25 and 55. The sulfur content is low (<0.5%). Oils can
be classified as paraffinic, and oil seeps are paraffinic-naphthenic
product of alteration by microorganisms.
Vanadium (V)/ Nickel (Ni) and Pristane (Pr)/ Phytane (Ph)
correlations allowed differentiating crude oils and oil seeps
according to the depositional conditions of the source rock.
Important differences were identified amongst the available
information. These dissimilarities suggest that, there is more than
one source rock in Falcn Basin. Figure 2 shows the relation Pr/Ph
vs. Dibenzothiophene (DBT)/ Phenantrene (PHEN) (Hughes et al.,
1995) where a group of crude oils originated from a fluvial/deltaic
source rock is observed followed by other group derived from a
siliciclastic marine source rock. Maracaibos Basin oils are located
in the zone of anoxic- euxinic conditions associated to marine
carbonate and lacustrine source rocks.
Figure 3 shows the spatial distribution of the redox conditions of
the sedimentary environment were source rock was deposited,
according to the crude oils and oil seeps studied. To the North of
the basin, crude oils are associated to a source rock deposited
in a disoxic sedimentary environment. Another group is related
to a source rock deposited in a suboxic-anoxic sedimentary
environment at the northeast and west of the basin. Finally a third
group was evidenced associated to a source rock deposited in
an anoxic environment in the Agua Salada Sub-Basin at the
Southeastern part of Falcn.

Compound-specific isotopic analyses: a novel tool reconstructionof ancient

biogeochemical processes. Organic Geochemistry16, 11151128.
Schouten S., Klein Breteler, W. C. M., Blokker P., Schogt N., Rijpstra W. I. C.,
Grice K., Baas M. and Sinninghe Damst, J. S., 1998. Biosynthetic effects

Figure 3. Spatial distribution of crude oils correlated according to

paleoenvironmental conditions of the sedimentary environment of the
source rock using Pr/Ph and V/Ni.

The maturity at the moment of generation and expulsion from

the source rock for the crude oils varies according to the relative
location on the basin. Maturity was estimated from biomarkers
in the saturated fraction (C29 Steranes, Ts/Tm, Moretane, C32
Homohopane) and aromatic fraction (MPI, %Rc, %Rm, TAs, MAs).
The maturity varies from early oil window (0.55%Ro) up to oil
generation peak (0.9%Ro). Maturity of crude oils and oil seeps in
Falcn Basin changes from East to West and from North to South
(Figure 4), suggesting different stages of maturation for the different
source rocks. These changes could help to identify different
events that could have taken place during the basin evolution like
differences in sedimentation rates and heat flow patterns, basin
tilting, and migration directions of crude oils. Integration of crude oil
characterization with geochemical rock data will allow establishing
the oil systems in the basin.

on the stable carbon isotopic compositions of algal lipids: implications

Six crude oil families were identified based on their origin and
maturity. A1 and A2 come from a type III fluvial-deltaic source rock
A1 generated at early oil window and A2 at oil peak. B1 and B2
from a type II-III marine siliciclastic source rock having the first a
minor maturity. C1 and C2 family are related to a marine anoxic
type II source rock with differences in the maturity level.

for deciphering the carbon isotopic biomarker record. Geochimica et

Cosmochimica Acta, 62, 13971406.
Summons, R. E., Jahnke, L. L., and Roksandic, Z., 1994. Carbon

Figure 1. Relative location of the Falcn Basin showing its main structural

isotopic fractionation in lipids from methanotrophic bacteria: relevance

characteristics, Western Venezuela (from Baquero et al., F. 2009).

for interpretation of the geochemical record of biomarkers. Geochimica et

Numerous studies have taken place in the basin with the main
goal of characterizing crude oils and oil seeps. However, many
of them have focused on analyzing individual samples or making
correlations with a limited amount of data. The differences of this
work from the others is that a regional scale study was applied in
order to show the family distribution of crude oils in the basin and
obtain the characteristics of the possible source rocks; therefore the
main goal of this work was to compile all the existing geochemical
information related to crude oils and oil seeps in the basin and carry
out an oil- oil correlation study. That way similarities and differences
among these oils could be established and their origin and level of
maturity determined.

Cosmochimica Acta, 58, 28532863

Figure 2. Pr/Ph vs. DBT/PHEN for crude oils from Falcn and Maracaibo Basin.

Another parameters used like n-alkane distribution, oleanane

index, steranes distribution and isotopes suggest that some crude
oils and oil seeps were generated from a type III kerogen, others
from a type II-III kerogen and southeast crude oils from a type II
kerogen. A similar distribution as Figure 3 was acquired for source
rock kerogen type.


Figure 1.Carbon Isotopic composition of specific biomarkers recorded in

Information from 24 crude oils and 63 oil seeps was collected.

The available analyses were API gravity (19), SARA composition
(78), %S (52), V/Ni (26), GC (25), GCMS (69) and isotopes (14).
This information was used for oil-oil correlation and compared
with information from Maracaibos Basin crude oils. Results were
represented in graphic, tables and classification maps according to
correlation parameters.

Brazilian oils of diverse origin. The data set includes lacustrine (freshwater
and saline) oils from Campos, Santos and Espirito Santo basins; evaporitic/
hypersaline (sag lakes) oils of Cear, Campos and Santos basins; and
restricted to normal marine oils from Campos, Santos, Espirito Santo and
Para-Maranho basins.

Figure 4. Spatial distribution of the maturity from crude oils and oil seeps,
Falcn and Maracaibo Basin.



Based on the available information the existence of more than one
source rock for Falcn Basins crude oils and oil seeps is evident.
Six crude oil families were identified. A1 and A2 generated by a
type III kerogen fluvial-deltaic source rock differentiating each other
in the maturity level. B1 and B2 families generated by a type II-III
marine siliciclastic source rock also with maturity level differences.
Finally C1 and C2 families originated by a type II marine anoxic
source rock with differences in the maturity level being the first
generated at early oil window and the second at the oil peak
(similar for the other families).

Advanced Geochemical Technologies

for Determining Multiple Sources, Facies
and Oil-Mixtures of Oil Produced in the
Santos Basin, Brazil
Silvana M. Barbantia,b, J. M. (Mike) Moldowanc, Jeremy E. Dahld,
Geoffrey Botte, Tikae Tikakia, Shaun M. Moldowanc
a Integrated Petroleum Expertise Company, IPEXco, Rio de
Janeiro, Brazil;
b current affiliation: Schlumberger, Reservoir Sampling and Analysis
Laboratories, Houston, USA.
c Biomarker Technologies Inc., 638 Martin Avenue, Rohnert Park,
CA 95472 USA;
d Stanford Institute for Materials and Energy Science (SIMES),
Stanford University, Stanford, CA 94305, USA;
e GB Scientific, Inc., 1090 Industrial Avenue, Suite B, So. Lake
Tahoe, CA 96150 USA

Baquero, M., Acosta, J., Kassabji, E., Zamora, J., Sousa, J., Rodrguez,
J., Grobas, J., Melo, L. Scheider, F. 2009. Polyphase development of the
Falcn Basin in northwestern Venezuela: implications for oil generation.
Geological Society, London, Special Publications 328, 587-612.
Hughes, W., Holba, W., Leona, D. 1995. The ratios of dibenzothiophene
to phenanthrene and pristane to phytane as indicators of depositional
environment and lithology of petroleum source rocks. Geochimica et
Cosmochimica Acta 59, 3581-359.
website: (corresponding author)
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

One of the principal sources in the Brazil Margin is in the synrift section, sometimes referred to as the pre-salt or the Lagoa
Feia Formation, which is deposited in a lacustrine depositional
environment. In Santos Basin the rift sources are lower Aptian
and Barremian. The other sources are broadly grouped as marine
sources for this discussion. They are younger in age, throughout
the rest of the lower (or middle) and upper Cretaceous. Biomarker
analysis can determine much about the source affinity of the oilwindow portion of the oil. However, many of the oils are cracked
and consist of contributions from both a deep and shallow source.
Oil mixtures, in general, and cracked-oil mixtures, in particular,
are difficult to unravel by using biomarker fingerprints alone. Here
we first examine biomarker parameters to determine the principal
shallow-source affinities and diamondoids to determine whether
deep sources are also represented in each individual oil sample. A
set of advanced geochemical technologies is applied to unravel the
oil mixtures in this sample suite.Oil samples in the study included
three from deep-water pre-salt production and nine from the
central Santos Basin from post-salt reservoirs.

Results and Discussion

1. Some key biomarker parameters
There is evidence for co-sourced oil in several cases by means
of age-related and paleo-environmentally controlled biomarkers.
These parameters refer only to the shallow (Oil Window)
sources. Possible deep sources are not considered in this initial
interpretation. The following biomarker indices are considered to
be the most important for source identification in this basin: C30steranes, C25-highly branched isoprenoid (C25-HBI, new method),

gammacerane, dinosterane, C27-C28-C29-sterane distribution,

and TPP.
C30-steranes (24-n-propylcholestanes) are only observed in
marine oils by using the m/z 414 217 in GC-MS-MS (Moldowan
et al., 1990), butinterferences can occur bycross-talk from
4-methylsteranes when lacustrine oil is present. This situation
occursfor end-member Lagoa Feia sourced oils and in mixtures
with a minor marine-source component.
C25-HBI along with oleanane provide an important source age
boundaries for Brazilian oil (Moldowan et al., 1994; Damst et al.,
2004, Barbanti et al., 2006). HBI derives fromrhizosolenid diatoms
that evolved and radiated in the Turonian and HBI is reported only
known to be in source rocks and oils of Turonian and younger
ages. Recent analytical advances allow HBI concentrations to be
measured down to a few ppm, previously only to about 100 ppm.
2. Advanced geochemical technologies to determine source
CSIA data distinguishes, with very strong isotopic differences,
the marine and lacustrine oil sources. These are a powerful
combination, together with diamondoid analyses used to determine
deep sources and mixtures.
Oil sourced from the Lagoa Feia Formation shows isotopically light
hopanes characteristic of a depositional environment featuring a
stratified water column with anoxic bottom waters. Occurrence of
chemoautotrophy and probably a carbon cycle of methanogenesismethanotrophy result in the isotopically light hopanes.

3. Recognizing and correlating the deep sources

Based on quantitative diamondoid analysis (QDA, Figure 2) it is
evident that the pre-salt oil samples have undergone little, if any,
cracking (Dahl et al., 1999). Among the remaining oils one appears
to be non-cracked, and its biomarkers give a Late Cretaceous
marine depositional environment signature.
In order to correlate the deep sources of this oil suite we applied the
quantitative extended diamondoid analysis (QEDA) which shows
three different patterns for these oil samples. The QEDA patterns
all together (Figure 2a) for comparison with break-out graphs
depict the purely lacustrine-sourced oils (Figure 2b) in contrast to
two distinct patterns for the marine sourced oils (Figure 2c). The
latter appears to indicate that two different marine sources within
the middle to upper Cretaceous sedimentary sequence have
effectively generated the marine-sourced oils, respectively.The presalt oil samples show a nearly perfect correlation of their QEDA
fingerprints. Because the pre-salt oils are not seen by QDA to be
cracked, they serve as the QEDA trace of the pre-salt lacustrine
source formation. Some highly cracked post-salt reservoired oil
samples show the same trend in QEDA establishing these mixedsource oils as having a lacustrine Lagoa Feia deep source. Some
thermally cracked oil samples that have an overall marine oil
biomarker signature show the QEDA signature of the pre-salt oils
implying they are mixed from a marine source in the oil-window and
a lacustrine source from deep.

Marine oil has isotopically heavy hopanes characteristic of a wellmixed water column without stable euxinic stratification or anoxic
bottom waters. The hopanes in this depositional system were
contributed by cyanobacterial phototrophs that incorporate CO2
from the atmosphere as a carbon source (Figure 1).

Figure 2. Diamondoid analyses show oil cracking and determine affinities

of deep sources. (a) QDA shows most Santos Basin oils are mixtures from
shallow and deep sources. The ans oils (pre-salt) andsample #39 show
low diamondoid concentrations typical oil generated only from a shallow
source. (b)Extended-diamondoid fingerprints show three patterns in the oil
set. (c) Pre-salt and related oils show one unique pattern. (d) Oils with
a marine source show two different patterns, which could be used to
Figure 1. Isotopic ratios of hopanes strongly differentiate the marine and

distinguish two different marine sources.

lacustrine sources in Brazil.Co-source contributions can be made for mixed

oils, such as Sample 14.


n-Alkane isotope ratios for lacustrine oils typically show a boat

pattern as determined for the three pre-salt oil samples in this study.
Facies differences are seen that distinguish the isotopic trace of
one pre-salt oil from those of the other two. Isotopic traces for the
alkanes isolated from the marine oils show a flat profile signaling
a similar algal input across the spectrum of carbon chain lengths.

Shallow sourcesin the Santos basin are defined by compound

specific isotope analysis of biomarkers (CSIA-B) coupled with
age-related and taxon-specific biomarkers. Shallow-sourced oil
mixtures are determined mostly by using CSIA-B and CSIA-A.
The occurrence of deep-sourced contributions and co-sourced
mixtures is common in the basin shown by QDA. The deep sources
are correlated by using QEDA and linked to source-rock families by


end-member non-cracked, non-mixed oils. Three deep-sourced oil

families, two marine and one lacustrine, have been indicated by
using the QEDA diamondoid fingerprinting method.

Geochemical composition of crude oils

and biodegraded seepage oils in Belize
and Guatemala: evidence for charging from
Cretaceous carbonate source rocks

Barbanti, S.M., Guzzo, J.V.P., Rangel, M.D.;et al.(2006) The C25 highly
branched isoprenoid as a specific tool for differentiating the African and
Brazilian oils from Lower to Late Cretaceous [abs.], in Proceedings of
10thALAGO, Salvador, Brazil, p. 133-134.

H.I. Petersena*, B. Hollandb, H.P. Nytoftc, A. Chod, J. de la Cruze,

J.H. Cornecf

Dahl, J.E.; Moldowan, J.M.; Peters, K.E.; et al. (1999) Diamondoid

hydrocarbons as indicators of natural oil cracking. Nature 399, 54-57.

a Maersk Oil, Esplanaden 50, DK-1263 Copenhagen K, Denmark

b Blue Creek Exploration Ltd., P.O. Box 30, Punta Gorda, Belize
c Geological Survey of Denmark and Greenland (GEUS), Oester
Voldgade 10, DK-1350 Copenhagen K, Denmark
d Geology and Petroleum Department, Ministry of Natural
Resources and the Environment, Market Square, Belmopan, Belize
e Perenco Guatemala Ltd., 5a. Av. 555 Zone 14, Europlaza Torre
4, Nivel 14, Guatemala City, Guatemala
f Consultant, 1867 South Marion Street, Denver, CO 80210, USA

Damst, J.S.; Muyzer, G.; Abbas, B.; et al. (2004) The Rise of the
Rhizosolenid Diatoms. Science, 304(5670), 584-587.
Moldowan, J.M.; Fago F.J.; Lee C.Y.; et al. (1990) Sedimentary
24-n-propylcholestanes, molecular fossils diagnostic of marine algae.
Science 247, 309-312.
Moldowan, J.M.; Dahl, J.; Huizinga, B.J.; et al. (1994) The molecular fossil
record of oleanane and its relation to angiosperms. Science 265, 768-771.

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

into saturated, aromatic, and polar fractions and analyzed by

GC, GC-MS and GC-MS-MS, mainly in Selected Ion Monitoring
(SIM) and Multiple Reaction Monitoring (MRM) modes. Because
of considerable biodegradation emphasis was put on biomarkers
resistant to alteration. The source rock samples were in addition
subjected to standard geochemical screening analyses and the
kerogen qualitatively investigated by reflected light microscopy.

Results and Discussion

The crude oils are non-biodegraded, whereas the seepage oils are
moderately to severely biodegraded. The oils were charged from
marine carbonate source rocks with comparable thermal maturity
and with some possible contribution from a lacustrine source in the
South Petn Basin. High C35 Homohopane Index values in most
samples but low Gammacerane Indices (Fig. 2) indicate source
rock deposition under reducing conditions in normal marine water.
Based on subtle variations in biomarker composition three main
groups of oils were defined: (i) Group 1 includes oils from the North
Petn Basin and the western Corozal Basin and are characterized
by high amounts of C28 steranes and very high tricyclic terpane
T22/T21 ratios, (ii) Group 2 contains oils from the South Petn
Basin; intermediate TPP ratios could suggest contribution from
lacustrine facies, (iii) Group 3, a heterogeneous assemblage of oils
from the southern part of the Corozal Basin with some oils possibly
derived from more marine shaly facies .

review of information contained in an abstract submitted by the author(s).

The petroleum geology of Guatemala and, in particular, of Belize
is poorly documented. The E-W trending La Libertad arch and
the Maya Mountains divide Guatemala into the North and South
Petn Basins and Belize into the northern Corozal Basin and the
southern Belize Basin. Together, these subbasins constitute the
greater Petn Basin. Oil production is mainly from the Xan Field in
North Petn Basin with lesser amounts produced by small fields in
both basins in Guatemala, (Bishop, 1980; Peterson, 1983; Dengo,
2007). The hydrocarbons are believed to have been charged
from Lower Cretaceous organic-rich carbonates of the Cobn
Formation. The petroleum system(s) is thus significantly different
than the nearby Reforma area and Campeche Shelf in the Gulf
of Mexico that are charged from Upper Jurassic marine shales.
Belize is significantly underexplored and has only two recently
discovered small fields in production, viz. the Spanish Lookout and
Never Delay fields, both in the Corozal Basin. However, numerous
onshore seeps have been known for a long time in Belize but until
recently the types, composition and sources of the seep and crude
oils were virtually unknown (Petersen et al., 2012).
The present study describes the geochemical composition of
crude and seepage oils, and a number of source rock samples
from onshore Belize and Guatemala. It documents the presence
of carbonate-sourced petroleum system(s) in the greater Petn
Basin, and suggests potential charge areas.

Figure 2.Gammacerane Indices (gammacerane/C30 hopane) are generally

low (<0.1) conforming to normal saline marine water during source rock
formation. Higher values are caused by biodegradation and preferential
removal of C30 hopane.

A yet unexplored and completely different petroleum system may

exist offshore Belize. Slicks and sea bed seeps are common,
and at Rocky Point on Ambergris Caye tar mats are found on the
reef. These have been claimed to contain angiosperm biomarkers
indicating an Upper Cretaceous or younger source. Further
analyses are required to resolve this and to exclude potential
contamination from oil spills from ships.

Crude and seepage oils in the greater Petn Basin can be divided
into three main groups, but they were all charged chiefly from
carbonate-rich source rocks, likely the Lower Cretaceous Cobn
Fm limestones. A possible lacustrine facies contribution is present
in the South Pten Basin. Seeps are spread over Belize and the
seepage oils are mostly severely biodegraded. However, they share
a common source with the crude oils in the area. The location of
kitchen areas in Guatemala is relatively well-known, whereas in
Belize these remain unresolved, although charging from the eastern
part of the North Petn Basin updip into the western Corozal Basin
seems likely. The location of the kitchen area for the seepage oils in
the Belize Basin is still speculative. A possible, younger petroleum
system may be present offshore Belize.

The study was carried out while the first author was employed at
the Geological Survey of Denmark and Greenland. The Ministry of
Natural Resources and the Environment (Belize) and the Ministerio
de Energia y Minas (Guatemala) are thanked for providing the oil
samples. We are grateful for logistical support provided by Blue
Creek Exploration Ltd.

Bishop, W.F., 1980. Petroleum geology of northern Central America.
Journal of Petroleum Geology 3, 359.
Figure 1. Bitumen (left) and oil in vug (right) in freshly broken Lower

Dengo, C.A., 2007. Chapter 30. Petroleum geology. In: Bundschuh, J.,

Cretaceous limestone, Belize Basin.

Alvarado, G.E. (Eds.), Central America: geology, resources and hazards.

The biodegraded seepage oils from the Corozal and Belize Basins
show geochemical features mainly related to Group 2, although
they constitute sub-groups.
Lower Cretaceous Cobn Fm source rocks have been drilled in
the North Petn Basin in Guatemala, but both source and kitchen
areas for the crude and seepage oils in Belize are unknown. Some
Cobn Fm limestone samples from the Belize Basin show good
quality oil-prone kerogen, but the TOC content is low.

Taylor & Francis Group, London, 895916.

Petersen, H.I., Holland, B., Nytoft, H.P., Cho, A., Piasecki, S., de la Cruz,
J., Cornec, J.H., 2012. Geochemistry of crude oils. Seepage oils and
source rocks from Belize and Guatemala: indications of carbonate-sourced
petroleum systems. Journal of Petroleum Geology 35, 127-164.
Peterson, J.A., 1983. Petroleum geology and resources of southeastern
Mexico, northern Guatemala, and Belize. U.S. Geological Survey, Geological
Survey Circular 760, 44 pp.

Nine Crude oils from Guatemala and Belize were acquired for
analysis together with 17 seepage oils collected during fieldwork
in Belize. The seep oils ranged from sticky bitumen to oil (Fig. 1). In
addition a number of source rock samples from the study area were
collected and analyzed. Asphaltene-free samples were separated



Samples excluded from the training set included: (1) heavily

biodegraded oils (rank 5 or more on the 110 scale of Peters
and Moldowan, 1993), and (2) highly mature condensates, where
biomarkers are low (e.g.,<10 ppm steranes). Source-related
biomarker and carbon isotope ratios for the remaining 112 non- or
mildly biodegraded oil samples were used to definethe training set.

Chemometric Recognition of
Genetically Distinct Oil Families
in the Los Angeles Basin, California
K.E. Petersa,b*, T.L. Wrightc, L. Scott Ramosd, J.E. Zumbergee

Chemometric (multivariate statistics) software (Pirouette and

InStep; Infometrix, Inc.) was used to create a multi-tiered decision
tree that identifiesgenetic oil families. We used geochemical
expertise and principal component loadings to select 24 sourcerelated parameters that differentiate the samples (details of the
method are described in Peters et al., 2005, 2007).

a Schlumberger Information Solutions, Mill Valley, CA 94941

b Department of Geological & Environmental Sciences,Stanford
University, Palo Alto, CA 94305
c Chevron Corporation (retired), San Anselmo, CA 94960
d Infometrix, Inc., Bothell, WA 98011eGeoMark Research, Houston,
TX 77095

Anoxic Upper Miocene (M.-U. Puente) marl source rock generated

tribe 3 west of NIFZ.
Anoxic Mohnian(?) marl generated tribe 4 west of NIFZ.
>12,000 ft
11, 12, 13
21, 22
31, 32, 33
41, 42

Anoxic M.-U. Miocene (L. Puente nodular shale) marl with

significant terrigenous plant input generated tribe 5 southwest of


Anoxic M.-U. Miocene (L. Modelo nodular shale) marl with

significant terrigenous plant input generated tribe 6 at low maturity
northwest of NIFZ.

Results and discussion

Figure 2. Map of the Los Angeles basin shows depth contours on base


Hierarchical cluster analysis and the decision tree identify six tribes
and 12 genetic oil families (Figure 1).

Mohnian (~14 Ma; Late Middle Miocene) >12,000 ft in pink. Oil tribes 1-2

Six genetically distinct Miocene petroleum systems (12 families)

occur in different parts of the Los Angeles basin. The NewportInglewood Fault Zone separates tribes 1-2 (families 11-12, 13,
21-22) to the east from tribes 3-6 (families 31-33, 41-42, 5, 6) to
the west.Chemometric analysis of biomarker and isotope ratios
anddistinct stratigraphic occurrence help identify the source rock
for each family. Oil familiesin the Los Angeles basin retain the
geochemical fingerprint of the vertical and lateral organofacies
variations in their source rocks.

are east of the Newport-Inglewood Fault Zone (NIFZ), while tribes 3-6 are
to the west. Base map is from Wright (1991).












Oil-like shale
not observed
(Philippi, 1965)




























~4 wt.% TOC, up
to 16 wt.%, Type I
and II kerogen
(Global Geochem.
Corp., unpub.)


Figure 1. Hierarchical cluster analysis dendrogram based on 24 source-



Cluster Distance







This paper uses source-related biomarker and isotope ratios to

evaluate genetic relationships among ~150 crude oil samples
from the basin. The extent of biodegradation for each sample was
assessed in order to identify a training set where the sourcerelated ratios are unaffected and can be used to identify genetic
oil families. The training set was used to create a chemometric
decision tree (multivariate statistics) that allows automated genetic
classification of additional oil or source-rock extracts that might
be collected, including samples where some of the source-related
ratios were altered by biodegradation.The chemometric analysis
also allows quantitative assessment of the degree of certainty
for each genetic assignment. Finally, the geochemical data and
stratigraphic occurrence of each oil family were used to infer their
source-rock organofacies.






West of NIFZ




Training Set



Oil Tribe

East of NIFZ

The prolific Los Angeles basin is a classic transform-margin

basin that may be the most petroliferous province on Earth per
volume of sedimentary fill. Since Brea-Olinda in 1880, 67 fields
were discovered, including three super-giants at Wilmington, Long
Beach, and Huntington Beach.Little exploration has occurred
since the early 1970s, although significant potential likely remains
in deep, especially offshore areas. Because most exploration in
the basin occurred prior to the advent of modern geochemical
methods, genetic relationships among the various petroleum
accumulations and their source rocks remain speculative.



We thank L.B. Magoon (USGS, retired) and Tess Menotti (Stanford
University) for useful discussions.

Blake, G.H., 1991. Review of the Neogene biostratigraphy and stratigraphy
of the Los Angeles basin and implications for basin evolution. AAPG

related biomarker and isotope ratios identifies six oil tribes.

Figure 3. Distinct stratigraphic occurrence of oil families supports their

The families within each tribe have different bulk properties (e.g.,
API gravity, sulfur, and metal content) that were previously explained
as mainly due to secondary processes, such as biodegradation or
thermal maturity (e.g., Jeffrey et al., 1991). However, the decisiontree classification is based on differences in genetic properties that
reflect distinct petroleum systems.

origins from different organofacies of Miocene Monterey source rock. Base

The oil families occur in different reservoirs from different parts of

the basin, consistent with origins from distinct pods of active source
rock (Figures 2-3). The source-rock depositional environment for
each oil family can be inferred using biomarker and isotope ratios
(e.g., Peters et al., 2005). Carbon isotope data for saturate and
aromatic hydrocarbons in the samples suggest Miocene marine
source rocks. Tribes 1-2 straddle the Central Trough, occur
mainly east of the Newport-Inglewood Fault Zone (NIFZ), and
show evidence of clay-rich source rock deposited under suboxic
conditions with elevated higher-plant and angiosperm input. Unlike
tribes 1-2, tribes 3-6 occur west of the NIFZ and show evidence
of more distal, clay-poor source rocks deposited under anoxic
conditions. Tribes 3-5 include the giant Wilmington, Long Beach,
and Huntington beach fields, which account for ~60% of the
conventional reserves in the basin.

Stratigraphic positions of the oils in each family help to identify

their source rocks. For example, family 13 (tribe 1) and tribe 6
occur in Lower Pliocene reservoirs in the northern portion of the
basin, suggesting that family 13 originated from Delmontian black
shale near the top of the organic-rich Miocene section. Tribe 6 oils
appear to originate from the Lower Modelo Formation (nodular
shale equivalent; Figure 3). The distributions of families 11 (tribe 1),
31 and 32 (tribe 3), and tribe 5 in the southern portion of the basin
suggest that family 11 originated from theUpper Puente Formation,
tribe 5 is from nodular shale in the basal Puente Formation, and
families 31 and 32 are from intermediate positions. These results
parallel those from the San Joaquin basin, where similar Miocene
oil families retain the geochemical fingerprint of vertical and lateral
organofacies variations in their source rocks (Peters et al., 2013).

Memoir 52, 135-184.

chart modified from Blake (1991). Unpublished data (Global Geochemistry

Jeffrey, A.W.A. et al., 1991. Geochemistry of Los Angeles basin oil and gas

Corporation) indicate that the Middle-Upper Miocene section contains

systems. AAPG Memoir 52, p. 197-219.

source rock due to high total organic carbon (~4 wt.%) and type I-II oilprone kerogen. The shallower Pliocene and Pleistocene units cannot be

Peters, K.E.;and Moldowan, J.M., 1993. The Biomarker Guide--Interpreting

source rock due to low thermal maturity (Philippi, 1965).

Molecular Fossils in Petroleum and Ancient Sediments. Prentice-Hall,

Englewood Cliffs, New Jersey, 363 p.

Procedures are similar to those in Peters et al. (2007). Asphaltenes
were removed from the oil samples using n-hexane. Saturate and
aromatic hydrocarbons were separated by column chromatography
using hexane and dichloromethane, respectively. Stable carbon
isotope ratios were determined using a Finnigan Delta E isotope
ratio mass spectrometer. C15+ saturated biomarkers were
analyzed on a Hewlett-Packard (HP) 5890 gas chromatograph
interfaced to a HP 5971 mass spectrometer. The HP-2 column (50
m x 0.2 mm id, 0.11-mm film thickness) was programmed from
150 to 325oC at 2oC/min. Mass spectrometry was in SIM mode
for m/z 177, 191, 205, 217, 218, 221, 231, and 259. Response
factors were determined by comparing m/z 221 for a deuterated
standard (d4-C29 20R sterane; Chiron Laboratories, Norway) with
terpane (m/z 191) and sterane (m/z 217) standards.

Peters, K.E.; Walters, C.C.;and Moldowan, J.M., 2005. The Biomarker

Guide. Cambridge University Press, Cambridge, U.K., 1155 p.
Peters, K.E. et al., 2007. Circum-Arctic petroleum systems identified using
decision-tree chemometrics. AAPG Bulletin 91, 877-913.
Peters, K.E. et al., 2013. Chemometric differentiation of crude oil families in
the San Joaquin Basin, California. AAPG Bulletin97, 103-143.
Philippi, G.T., 1965. On the depth, time and mechanism of petroleum
generation. Geochimica et Cosmochimica Acta 29, 1021-1049.
Wright, T.L., 1991. Structural geology and tectonic evolution of the Los
Angeles Basin, California. AAPG Memoir 52, 35-134.

In summary, geochemistry and stratigraphy of the oil families

suggest the following source rocks:
Suboxic Upper Miocene (Delmontian) shale with significant
angiosperm input generated tribes 1-2 in the Central Trough east
of NIFZ.



The software package Statistica 8 (Statsoft Inc.) was used in the

statistical calculations. A X(11x15) matrix for saturated and aromatic
biomarker ratios was created and a Principal component analysis
(PCA) was carried out based on the covariance matrix. All variables
were mean centered and scaled by the sample standard deviation.
Results and Discussion
The geochemical parameters were calculated for biomarkers in
B/C and in aromatic fractions. The main focus of this study was
the characterization of thermal maturity using biomarkers (Table
1). Since the origin and the degree of biodegration can affect
the abundance of most of the biomarkers used in the maturation
parameters, these aspects are briefly discussed for the analyzed

Application of Comprehensive TwoDimensional Gas Chromatography - Time

of Flight Mass Spectrometry to evaluate
maturation of Brazilian crude oils
Jaakko Laakia1, Alessandro Casilli1, Flix T. Gonalves1, Elaine
Marotta1, Cleverson J. F. Oliveira2, Alexandre A. Ferreira2, Maria
Regina B. Loureiro1,Dbora A. Azevedo1, Francisco R. Aquino
1 Universidade Federal do Rio de Janeiro, Instituto de Qumica,
LAGOA-LADETEC, Ilha do Fundo, 21941-909, Rio de Janeiro,
RJ, Brazil.
2 Division of Geochemistry, PETROBRAS Research and
Development Center (CENPES), PETROBRAS, Rua Horcio
Macedo, 950, Ilha do Fundo, Rio de Janeiro, RJ 21941-915,

Table 1. Selected biomarker ratios in B/C fractions of the crude oils

measured using GCGC-TOFMS.

considered less thermally evolved.

Figure 1. PCA score plot (A) and loadings (B) with (1, solid line) =
biodegradation saturated parameter, (2, dashed line) = maturation aromatic

Less routinely used saturated biomarker maturity ratios, however,

lead to somewhat conflicting results. According to the C29
trisnorhopane/C29 hopane (H29Ts/H29) ratio, which increases
with increasing maturation, S05, S07 and S09 should be the most
mature oil samples. On the other hand, according to the moretane/
hopane (M30/H30) ratio, which decreases with increasing
maturation, oils S05 and S07 are the most mature while the oils
S02 and S09 are the less mature. Finally, Ts/(Ts+Tm) ratios indicate
that S01, S02 and S09 oil samples has the lowest degree of thermal
maturity whereas S05 and S07 are the most mature samples.


GCGCTOFMS analysis was used to determine maturity ratios in
B/C and aromatic fractions for 11 Brazilian crude oil samples. PCA
allowed the integration of maturity parameters, pointing S05, S06
and S07 samples as the most mature oils and recognizing S02 as
the most biodegraded oil.

The authors thank CNPq, ANP, Petrobras, and FAPERJ.

Aromatic biomarker maturity ratios were also analized. Methyland dimethyl-dibenzothiophenes (MDBDT and DMBDT) ratios,
which can be used for highly mature oils, show the highest values
in the S06 and S07 oil samples. The percentage of mono- and
triaromatic steroid ratio of MA C21 / (MA C21 + C28)% and TA
C20/(TA C20 + C27)%, which increase with increasing maturation
show the highest values in the S05 oil sample.

Casilli, A., Silva, R.C., Laakia, J., Oliveira, C.J.F., Ferreira, A.A., Loureiro,
M.R.B., Azevedo, D.A., Aquino Neto, F.R., 2014. High resolution molecular
organic geochemistry assessment of Brazilian lacustrine crude oils. Organic
Geochemistry 68, 61-70.
Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide,
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Gas chromatography (GC) has been an essential technique for
the analysis of non-polar biomarkers, initially only connected to
flame ionization detectors (FID), later to also mass spectrometry
(MS) and nowadays, with a variety of manufacturers offering a
range of distinct setups. One of the setups that have proved to be
particularly powerful is the Comprehensive Two-Dimensional Gas
Chromatography - Time of Flight Mass Spectrometry (GCGC
In this study, 11 Brazilian crude oils from different origins and
depositional conditions (5 lacustrine, 5 marine and 1 mixture), with
variable biodegradation and maturity levels, were analyzed. The aim
was to evaluate the degree of maturation of the oil samples with
conventional and non-conventional biomarker ratios measured by
Analyses were performed on a Pegasus 4D (Leco, St. Joseph, MI,
USA) GCGC-TOFMS composed of an Agilent 6890 GC equipped
with a secondary oven, a non-moving quad-jet dual-stage
modulator and a Pegasus III time of ight mass spectrometer. A
DB-5 column (30 m, 0.25 mm i.d., 0.25 mm df) was used as the
rst-dimension column (1D). A BPX-50 (1.5 m, 0.1 mm i.d., 0.1
mm df) was used as the second-dimension column (2D). The 2D
column was connected to the TOFMS by means of a 0.5 m x 0.25
mm i.d. uncoated deactivated fused silica capillary.
The selected crude oils were pre-fractionated in saturated and
aromatic fractions. The saturated hydrocarbon fractions were
further processed to remove the n-alkanes via the formation of urea
adduct to obtain the branched and cyclic hydrocarbon fractions
(B/C). The B/C and aromatic fractions (total of 22 samples) were
dissolved in dichloromethane before chromatographic analyses
(Casilli et al., 2014).

Principle component analysis

Biomarkers and Isotopes in Petroleum Exploration and Earth History, Vol 2.

With the aim of integrating the results from the diverse parameters,
a PCA analysis was carried out with all ratios presented in Table 1.
The analysis allowed the separation of distinct groups of oils (Fig.
1A). PC1 analysis clearly separated oils S05, S06 and S07 from
the others, being the aromatic maturation parameters the principal
components (Fig. 1B). PC2 separated S02 and S09, being the
3-methylhopane index one driving force to this. In addition,
sample S02 is also influenced by biodegradation processes (25NH/
H30). Thus, maturation parameters separated samples S05, S06
and S07 as the most mature within this set of samples, and S02 as
the most biodegraded.

Cambridge University Press, Cambridge, UK.

Regarding the origin, some selected source-dependent parameters

(Table 1) St27-St29/H29-H33, Tr26/Tr25, 3-MH31/H30 %
indicates a lacustrine source for oils S01, S02, S08 and S09, a
marine source for oils S10, S04, S05, S6, S07 and S11, and a
mixture of sources for oil S03 (Peters et al., 2005).
The biodegradation process was monitored with the 25-norhopane
to C30 hopane (25NH/H30) ratio (Table 1). According to this
parameter, only samples S02 and S07 are significantly altered.
Biodegradation can affect other parameters. The hopanes, for
example, are preferentially removed compared to the tricyclic
terpanes. Tr19-Tr30 (S+R) /H28-H34 (S+R) ratio (Table 1),
corroborates that oils S02 and S07 are biodegraded. Interestingly,
the oil S09 although could be considered biodegraded according
to this ratio, but do not show nor-hopanes (25NH/H30 = 0.01).
Regarding maturity (Table 1), the routinely used steranes and
terpanes ratios indicate that most of the oils have reached a
moderate to high degree of maturity (between the beginning of
the oil window and the peak of oil generation). Practically all the
oils have reached the equilibrium for the 22S/(22S+22R) H32 ratio.
Oil samples S05 and S06 show the highest values for the [20S/
(20S+20R) St29] and[(S+R)/(S+R)+(S+R) St29] steranes
ratios, being considered the most mature, whereas oils S02, S03
and S09 show lower values for these ratios and therefore are




models of deformation in numerical simulations of petroleum

systems proved to be an effective tool to mitigate cases where
timing is a major risk.

and lithosphere flexure under differential loading (Garcia, 2012).

Thus, independent restorations were performed for different
sections looking for results with consistencybetween the
deformation and the sedimentary record described by the basin
stratigraphic chart.


The authors thank Petrobras forthe encouragement to publication
and the financial support.

Restored 1D geohistorieswere extracted from vertical projections of

the calibration wells on the geological sections.A local thermal field,
considering deformations of salt over time, was adequatelymodeled

Evaluating source-rock maturation changes

due to thermal contrast between salt and
other overlying sediments using an integrated
structural restoration approach


from these restored geohistories. The movement of salt responding

Arajo L.M.; Garcia S.F.M.; Queiroz C.L.; Cortez M.M.M.; Saito M., 2005. A

to sedimentation changed the thermal field through the overburden,

4-D Petroleum System Model in asouthern area in the Santos Basin, Brazil.

sometimes making it relatively hotter above a thick diapir,

sometimes less disturbing in areas withfault growing or minibasins

Svio F. M. Garciaa a* , Carlos Pinto Fracalossi a , Andr

Danderfer b, Dominique F. De Lamotte c

development (Mello et al., 1995).

Vitrinite reflectance and temperature data from a few wells in the

a Petrobras, E&P-EXP/GEO/MSP, 20000-000, Rio de Janeiro,

b Universidade Federal de Ouro Preto, Departamento de
Geologia, 34500-000, Ouro Preto, Brazil
c Universit de Cergy-Pontoise, LaboratoireGosciences et
EnvironnementCergy, 95031,Cergy-PontoiseCedex, France

studied area were used to calibrate a regional heat flow history

obtained fromthermal models of lithospheric stretching.
Thus, extrapolating the restored 1D thermal geohistoriestoa 2D
petroleum systems model, different thermal maturity levels were

In order to be used in a results comparison, another 2D


petroleum system modelling was performed without the restored

Structural restoration of halokinetic deformation in sedimentary

basins is often simplified or even neglected in numerical
simulations that evaluate the maturation of organic matter,
expulsion and migration of petroleum. Such procedure is usual
but unsophisticateddue to limitations of the software meshes,
in spite of the notoriously high contrast of thermal conductivities
between salt and other sedimentary lithologies,as wellaspossible
changesthat a salt diapirmay cause on the thermal maturity in its

backstripping or 2D restored sections, using only conventional 1D

and 2D approaches.

Results and Discussion

As expected, source rock maturity was differentially affected in all
directions close to salt structures (Garcia, 2008). This does not
mean that large differences occur between one structurally restored
model and an unrestored one. The comparison of simulation results
for both restored and unrestored models, albeit in a simplified

In order to measure effects of the structural deformation in a real

approach, showed the role of halokinesison sediments heating and

halokinesis case, the present paper workson a well-known area

on the thermal evolution of theunderlying source rock.

in the Santos Basin,previously studied by several authors,where

significant lateral movement along the Cabo Frio Fault could be

Although the thermal field becomes relatively warmer at positions

restored through time. This area has an entire record of the Santos

just above the salt bodies, organic matter remains immature for

Basin sedimentation coveringbothextensionaland compressional

petroleum generation due to the small burial magnitude in these

structural domains which also provides different timings of the

situations. Simulation results above the salt structures were almost

petroleum system activities.

the samebetweenrestored and unrestored models.However,where

ALAGO Workshop Basin Modeling, Buenos Aires (CDROM) 4, Abstracts, 3 p.

Figure 1.
Maturity levels calculated for restored (left) and unrestored (right) 2D models
showing maturation differences in the sediments underlying the salt layer in
the past, mainly because there was no overburden over the saltdiapir in the
unrestored model at that time.

Positions adjacent to salt bodies were more sensitive to the geometry

and size of the salt structures. The thermal effects on maturity in
some relatively narrow minibasins surrounded by largesalt bodies
were lower than those affecting broader depocenters, which
are less influencedby the higher salt thermal conductivity. These
situations did not show large differences betweenrestored and
non-restored models.

Garcia, S. F. M., 2008. Fenmenos trmicos associados aos evaporitos.

In: W.U. Mohriak, P. Szatmari, S. Anjos(Org.) Sal geologia e tectnica:
exemplos nas bacias brasileiras. Beca Edies Ltda., p.: 91-163.
Garcia, S. F. M., 2012.Restaurao estrutural da halotectnica na poro
central da Bacia de Santos e implicaes para os sistemas petrolferos.
PhD ThesisUniversidade Federal de Ouro Preto (Contribuies s Cincias
da Terra. Srie D) 235, 206pp.
Mello, U. T.; Karner, G. D.; Anderson, R. A., 1995.Role of salt in restraining
the maturation of subsalt source rocks. Marine and Petroleum Geology,
v.12, p 697-716.

Thermal simulations showed relatively less mature source

rocks underlying saltbodies of great volume and thickness.
Nevertheless,the effects on the maturity of sediments in the
restored structures were conditioned by the timingof those
sediments beingsubjected to higher temperatures. Another factor
affecting maturity of underlyingsediments was the lateral translation
(sliding) of salt structures, which changed the temperature flow.
Halokinetic deformations, as well as thermal evolution of
sediments,were strongly influenced by sedimentation rates and,
as consequence, by the sedimentary burial in different areas of
Santos Basin (Arajo et al., 2005). Thus, the timing of greatest
salt deformation was not necessarilysynchronous with the optimal
period for maturation of the underlying source rocksacross
the studied area. According to the simulation results, such
synchronicityoccurred only locally.These differences of maturity
scenarios can produce consequences for migration and timing for
petroleumentrapment processes.

the burial geometry was recomposed in the restoration model,


The goal is to use structural restoration and petroleum systems

local heat escape was hamperedby a relative insulation of the

modeling tools in an integrated and synergistic way in order to

less thermal conductive lithology, and the sediment maturation

assess the impact of salt tectonics on the maturity of underlying

source rocks.

differences weregreaterbetween both scenarios (Figure 1).

In the continental platform, closer to the shore, the earlier and

more expressive marine sedimentshastened the petroleum system
Along the region where the Cabo Frio Fault has causedmajor lateral
development, the salt restoration role is to determine the formation
of welds (salt windows) that would allow petroleum migration
pathways to the overlying post-salt section.

Geological sections were interpreted on seismic data in order
to characterize the geometry of salt bodies and the affected
sedimentary vicinity, as well as the rift sequence below salt
wherethe source rocks were deposited.

In the deepwater region, there is a lack of synchronism betweenthe

petroleum system constraints and the salt deformation which
fortunately minimizes errors of the simulations when these are
performedin unrestored sections.

Structural restoration of these sections provided incremental

shapes and relative positions of the layersduring salt deformation.
Furthermore, the structural restoration followed procedures to
include theeffects of compaction, isostasy, bathymetric changes

We can conclude by stating that the application of kinematic




source rock, due to the fact that this parameter is the most sensitive in
the Guo et al. (2011)and the Shuichang et al.(2013) equations.

An example of quantitative estimation of

overpressure caused by oil generation in
Campos Basin, Brazil.

In nature, the estimated values of pore saturation by residual oil

in source rocksgenerally are over 50% (Shuichang et al., 2013).
In tests made in Santos, Campos and Cear basins,these values
would need to be between64 and 80% to reach the measured
overpressure values in the order of 15 to 30MPa. According to
the calculations made in this study for a well in Campos Basin,
for a source with an average original TOC and HI of 4.2% and
700 mg HC/g TOC respectively, and a transformation ratio of 50%,
a residual oil saturation of 64%in the source rock is required for
overpressure to attain the value of 32 MPameasured in the well.
For a better prediction of the magnitude of overpressure,it is
important to obtain data whichwould allow estimating the residual
oil saturation in source rock, as well as porosity, permeability,
capillary pressure and residual TOC.

Carlos Pinto Fracalossia* . Hyalla Queiroz Valente da Silvaa . Laury

Medeiros de Araujoa , Henrique Luiz de Barros Penteadoa
a Petrobras, E&P-EXP/GEO/MSP, 20000-000, Rio de Janeiro, Brazil

In oil exploration, it has been quite usual to find abnormal high
pore pressures, which may be caused by one or more geological
processes. Repeatedly, mechanical problems during the drilling
phase have been reported wheninvestigating deep plays, especially
those that require drilling through source rocks.

A sensitivity analysis with parameters similar to those considered in

our simulation indicates that organic-leaner source rocks intervals
would require a higher transformation ratio and/or lighter petroleum
to achieve a residual oil saturation that leads to the same kind of
overpressure values. Conversely, richer source rock intervals
could achieve similar overpressures at lower transformation ratios,
because comparable residual oil saturation would be reached due
to the higher petroleum potential.

The conversion of solid kerogen into liquid oil and gas during the
process of petroleum generation results in fluid volume expansion
and pore pressure increase. This occurs due to the fact that the
original kerogen dispersed in the rock matrix is denser than the oil
and gas generated that moves into the pore space (Luo & Vasseur,
1996; Swarbrick et al., 1998; Xie et al., 2001; Guo et al., 2011;
Shuichang et al., 2013).

The authors thank Petrobras forthe authorization to publish this work.

In exploratory terms, pore pressure prediction is crucial in

engineering drilling projects, since the abnormal high pressure
zones require special equipment and some modifications in the well
casingwhich, if not previously diagnosed, can make the drilling of
a prospectimpracticable. With the increasing demand for reducing
the risks and costs of drilling, and to avoid ecological disasters,
the accuracy of this type of prediction has become a strategic
prerequisite for the planning of exploration activities.

Guo, X., He S., Liu, K., Zheng, L. 2011. Quantitative estimation of
overpressure caused by oil generation in petroliferous basins. Organic
Geochemistry 42, 1343-1350.
Luo, X., Vasseur, G. 1996. Geopressuring mechanism of organic matter
cracking: numerical modeling. AAPG, 80, p. 856-874.
Shuichang, Z., Bin, Z., Jin, S., Xiaomei, W. 2013. A conceptual model of oil

In petroleum systemmodeling, pore pressure has a criticalimportance

because it has a great influence in the porosity decay, in the thermal
field and in regional pressure regimes. The pore pressure field is
responsible for the petroleum migration pattern and for controlling
the capacity of hydrocarbon retention.

expulsion efficiency driven by hydrocarbon generation. 26th IMOG. Organic

Geochemistry: trends for the 21st Century. 2, 579-580.
Swarbrick, R.E., Osborne, M.J. 1998. Mechanisms that generate abnormal
pressures: an overview. AAPG memoir 70, p. 13-34.


Xie, X., Bethke, C.M., Li, S., Liu, X., Zheng, H. 2001. Overpressure and

This study was based on the equations proposed by Guo et al.

(2011) and Shuichang et al. (2013) which calculate overpressure
caused by petroleum generation as a function of hydrogen index
(HI), transformation ratio, kerogen mass, residual oil coefficient,
hydrostatic pressure, oil compressibility, water compressibility,
kerogen compressibility, pore water volume at hydrostatic pressure,
kerogen density and oil density.

petroleum generation and accumulation in the Dongying Depression of the

Bohaiwan Basin, China. Geofluids, p. 257-271.

Possible controls of Andes-associated
volcanic activity on Hydrocarbon generation
and leakage in the on/offshore northern Austral
Basin, southern Argentina, South America.

simulate the burial history of sediments including compaction,

pressure, temperature and maturation of organic matter, petroleum
generation, migration and accumulation through time. The model
was constructed using PetroMod software and covers the
continental Austral Basin, Austral Marina, the Rio Chico High and
the western Malvinas Basin.

Victoria F. Sachsea,c*, Zahie Ankaa, Rolando di Primioa, Ralf

Littkec, Jorge F. Rodriguezb, Marcelo Cagnolattib,
a Helmholtz Centre Potsdam, GFZ German Research Centre
for Geosciences, Section 4.3., Telegrafenberg, 14473 Potsdam,
b Petrobras Argentina S.A., Buenos Aires, Argentina
c Institute for Geology and Geochemistry of Petroleum and Coal,
EMR Group; RWTH Aachen University, Germany
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

Figure 1.Overview of the study area and provided seismic data (grey lines
within the red polygon). The outline of the 3D basin model is shown in red.

review of information contained in an abstract submitted by the author(s)

Results and Discussion

Numerous oil and gas fields have been developed on- and offshore
Austral Basin, southern Argentina.Whereas source rocks and
reservoirs are well known,the processes of hydrocarbon generation
and accumulation in time and space, including migration and
leakage dynamics remain not completely understood. In order to
better understand how the regional tectonic setting, i.e. the Andes
evolutionand associatedvolcanism may have influenced the HC
system history, we carry out an integrated basin analysis including
long-distance onshore-offshore correlations.Based on geophysical
and geochemical data3D modeling of basin subsidence as well
as hydrocarbon generation, migration and accumulation through
geologic time was performed.
The Austral and Malvinas Basins are part of the South American
plate and surrounded by the Nazca plate to the west, the Antarctic
plate to the southwest and south, the Scotian plate to the south
and the African plate to the east (Figure 1) and thus situated in
a zone of high tectonic activity.1D well backstripping across the
study area confirms three main tectonic stages (Diraison et al.,
2000), containing (1) the break-up phase forming basement graben
systems and the evolution of the ancient backarc Rocas Verdes
Basin (RVB), (2) the inversion of the RVB and the development of
the Austral Basin, and (3) the recent foreland Austral Basin.

In the model source rock qualities were assigned to the Lower

Cretaceous Springhill Formation (up to 6 %TOC), Lower Inoceramus
and Margas Verdes Formation (>2 %TOC). Reservoirs and seals
occur from Jurassic up to the Eocene, but the main reservoir is
present in the Early Cretaceous Springhill Formation. An initial
constant heat flow of 60mW/m was assigned, adjusted during the
calibration process for the model. A recent burial depth of up to 8
km in the southernmost northern Austral Basin shallowing up to
2.5 km on the western flank of the Rio Chico High were deduced
for the base of the Early Cretaceous. Modelled vitrinite reflectance
values indicate gas window or even over-mature ranges for organic
matter samples from the south-western basin where highest
thicknesses and deepest burial took place.A general decrease of
maturity is obvious to the north and east of the Austral Basin.Lower
vitrinite reflectance values were modelled for the eastern part,
where maturity ranges between immature and the oil window. This
maturation trend is depending on the geometry of the basin, with
shallower areas to the north and to the east. Of course, also the
decreasing sediment thickness of the potential source rocks will
play a role leading to the low petroleum generation rates observed
in the northernmost area.

In order to better understand the impact of tectonic events on basin
formation to its present-day structure we analyzed 2D seismic
reflection data covering about 95.000 km on- and 115.000
km offshore (Austral Marina and Malvinas Basin). A total of 10
seismic horizons, representing 9 syn- and post- rift sequences,
were mapped and tied to well data to analyze the evolution of
sedimentary supply and depocenter migration through time.In
additionto the seismo-stratigraphic analysis, 1D backstrippingwas
carried out in order to calculate the tectonic subsidence and
sediment accumulation rate.Based on the resulting maps of
the seismic interpretation, additional information about source
rocks (TOC, HI), potential reservoirs. and sealswere used for a
3D petroleum system/ basin model. This model was created to

The source rock parameters applied to calculate pore overpressure

caused by petroleum generation come from one analyzed well in
Campos Basin (Brazil), which has a residual total organic carbon
(TOC) of 2.7% and HI values around 390 mgHC/gTOC. An original HI
of 700 mgHC/gTOC, an original TOC of 4.2% and a transformation
ratio around 50%were estimated based on regional data.

Results and conclusions

The main challenge for the pore pressure prediction caused by
petroleumgeneration is to estimate the residual oil saturation inside the

Figure 2.3D BasinModel including the Austral Basin, the Rio Chico
High and the western Malvinas Basin.


Differences in maturity distribution can be explained by the
differential burial depth between the west and east. However, this
preliminary run of the petroleum system model does not comply
entirely with present-day accumulations known in the basin. Thus,
either the temperatures during burial were not high enough or the

The Link Between Stratigraphic and

Petroleum System Models:
Insights for Hydrocarbon Exploration

reservoir facies needs refinement. Increased past-temperatures can

be explained by volcanic activity during different times during the
Cenozoic. Identified seismic features which have been interpreted
as magmatic intrusions (sills and dikes) within the sediments, and
also at the surface, support this idea of increased heat flow field
in the past. However, they do not have a primary influence on the
hydrocarbon system. The 3D model indicates the occurrence of
two phases of major petroleum generation in the Austral Basin.
The primary generation phase is related to deep burial due to basin
subsidence in the Early and Late Cretaceous, as a consequence of
basin inversion and the sediment supply from the growing Andes in
the west. A second generation phase is also related to deep burial
in the Miocene, but it could be clearly shown, that the Miocene
volcanic episode plays a major role for the secondary petroleum
generation phase in the Austral Basin. Secondary cracking due to
volcanic activities cannot be excluded.

Luiz Felipe C. COUTINHOa*, Jos Eduardo FACCIONa, Jos

Alberto ARAUJOa, Pedro A. M. N. MIRANDAa, Marco Antnio S.
MORAESa, Stefane R. X. LOPESb, Alexandre Antnio O. LOPESc,
Wagner N. RIBEIROd


Copyright 2014, ALAGO.

The authors thank Petrobras Argentina S.A. for providing data

and for permission to publish this work. This project is part of the
German Research Foundation (DFG) - SAMPLE South Atlantic
Margin Processes and Links with onshore Evolution.

This paper was selected for presentation by an ALAGO Scientific Committee following

a - Petrobras Research and Development Center (CENPES), Rua

Horcio Macedo, 950, Ilha do Fundo, Rio de Janeiro, RJ 21941915, Brazil
b - Fundao Gorceix, Rua Carlos Walter Marinho Campos,57,
Vila Itacolomy, Ouro Preto, MG 35400-000, Brazil
c - Petrosoft, Rua Mrio Agostinelli, 55, Barra da Tijuca, Rio de
Janeiro, RJ 22775-046, Brazil
d INJ Tecnologia, Rua Sagrados Coraes, 95, Caiaras, Belo
Horizonte, MG 30770-220, Brazil

review of information contained in an abstract submitted by the author(s).

The three-dimensional numerical simulation of sedimentary
processes based on sequence stratigraphy concepts (i.e.
stratigraphic modeling) has been used in sedimentary basin
analysis to understand and represent the interplay between space
accommodation generation and filling, along with the action of
sedimentary processes that control facies distribution.

Diraison, M.; Cobbold, P.R.; Gapais, D.; Rossello, E.A.; Le Corre, C., 2000.
Cenozoic crustal thickening, wrenching and rifting in the foothills of the
southernmost Andes. Tectonophysics316, 91-119.

Two of the main products of stratigraphic modeling are (1) the

breaking of the basin-filling packages into stratigraphic sequences
of different orders and (2) the detailed representation of lithofacies
distribution within each sequence.
Petroleum systems modeling, on the other hand, allows the
geological history reproduction of sedimentary basins including the
processes of compaction, heat and fluid flow, along with generation,
migration and accumulation of petroleum. The technique involves
the dynamic calculation of essential parameters such as porosity,
pore pressure, temperature and maturation of source rocks. The
method is based on the mass conservation of components, and
solves numerically the governing equations for mass balance, and
also the equations for energy and momentum conservation.
Even though the petroleum systems models are highly sophisticated,
their representation of the stratigraphic framework and lithofacies
distribution is commonly poor. As a consequence, although the
independent application of these techniques by the oil industry
and the scientific community is quite widespread, their integration
remains not fully explored. This includes the assessing the
potential impact of incorporating detailed stratigraphic framework
and lithofacies distribution into the modeling of petroleum migration
and accumulation.

Objectives and Methodologies

The goal of this work is to establish a method to integrate
stratigraphic and petroleum systems modeling using PETROBRAS
proprietary softwares in order to apply such workflow to exploratory
frontier areas. Two synthetic petroleum systems models based on
common real situations were constructed with different stratigraphic
resolutions. The regional permeability structures based on lowand high-resolution sequences obtained by previous stratigraphic
simulations were compared in order to better understand the
formation of the carrier beds. The more detailed sequence and
lithological representation at the third-order scale allowed a better
definition of carrier beds and regional seals, which significantly
changed the patterns of petroleum secondary migration, favoring
the identification of plays not currently represented in lower
resolution models.

Results and Discussion

A) Stratigraphical Model
Three depositional sequences (sense of Vail et al., 1977 and
Posamentier et al., 1988) were simulated (Fig. 1). From the oldest
to the youngest, they can be described as follows: Sequence n
1 - a transgressive succession of three retrogradational 3rd order
depositional sequences corresponding to the beginning of basin fill
with a total time-span of 10 Ma; the main objective was to simulate
a classic source-rock depositional environment; Sequence
n 2 - a set of stratigraphic high-frequency of progradational
depositional sequences, typically representing the deposition
of potential reservoirs and seals; Sequence n 3 - a 3rd order
sequence integrated by a progradational basal unit followed by two
retrogradational episodes and a final progradational higher order
B) Basin Modeling Approach
In order to input the modeled facies into the petroleum systems
3D cells, it was necessary to define each Folks component as a
mixed lithotype (Fig. 2). The mixing rule used for each petrophysical
or thermal property is geometric, except for specific mass and
specific heat which is arithmetic.
A relative permeability evolution was applied with absolute
permeability, as a result of the porous space variation, based on
experimental and theoretical rules proposed by Okui et al. (1998).

Figure 2.Basin modeling migration results

The HC generation was modeled based on a kinetic model
presented in Behar et. al. (2008), considering a closed system and
type II kerogen, with a petroleum potential of 30 mg/g.
The models were simulated using an in-house software applying
the finite volume method to solve the governing equations (thermal
and migration) and tetrahedral meshes.
The high resolution model has 147186 tetrahedral elements and
the low resolution ones has 103896 elements, both models has
an approximate length of 36 km and a width of 34 km, with a total
thickness of 5 km.

Coupling stratigraphic and petroleum systems modeling leads to
a better representation of the lithological distribution and hence
of the spatial relationships among source rocks, carrier beds,
reservoirs and seals.
Concerning the studied case, the results obtained integrating such
technologies permitted:
1 a better understanding of the thermal evolution of the petroleum
system and, as a consequence, a best fit of source rock maturation
and hydrocarbon generation;
2 a more consistent representation of petroleum migration,
combining the vertical and lateral components, the latter specially
improved where the carrier beds are confined within the source
rocks (Fig. 2);
3 a significant improvement in the comprehension of petroleum
systems elements and processes, resulting in more realistic
predictions of generation, accumulation, losses, migration paths
and efficiency (Fig. 2).
The results obtained herein suggest that the improved
representation of lithological distribution is not just a matter of
resolution refinement. It comes from the construction of more
realistic geologic frameworks, where tools such as stratigraphic
forward modeling can be helpful.

Figure 1.Stratigraphic inverted model

Constant surface temperature (ST) and basal heat flow
(HF) values were applied to the whole model for each
time interval, ST = 15.5 C e HF = 50 mW/m2.

Okui, A., Siebert, R. M., Matsubayashi, H., 1998, Simulation of oil expulsion by
1-D and 2-D basin modelling saturation threshold and relative permeabilities
of source rocks. Geological Society of London Special Publications, 141, 45-72




Vail, P.R., R.M. Mitchum, Jr., and S. Thompson, III, 1977, Seismic stratigraphy
and global changes of sea level; Part 3, Relative changes of Relative changes
ofsea level from coastal onlap: AAPG Memoir 26, p. 63-81.


Possible Causes and Consequences

of Anomalous Geothermal Regimes in
Carbonate Platforms

Posamentier, H.W., Jervey, M.T., Vail, P.R., 1988, Eustatic controls on

clastic deposition. I. Conceptual framework. In: Wilgus, C.K., Hastings,
B.S., Kendall, C.G.St.C., Posamentier, H.W., Ross, C.A., Van Wagoner, J.C.



Khalid EL
and Antonio MARTIN
a Repsol Exploration, Direction of Geology, Mndez Alvaro 44,
28045, Madrid, Spain
b Repsol Exploration, Direction of Operations, Mndez Alvaro 44,
28045, Madrid, Spain
c Repsol Exploration, Exploration Africa, Mndez Alvaro 44, 28045,
Madrid, Spain

(Eds.), Sea Level ChangesAn Integrated Approach, vol. 42. SEPM Special
Publication, pp.110 124.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The geothermal regime is a key factor for the generation of

hydrocarbons and their preservation in sedimentary basins.
A correct estimation at both present and in the past is hence
mandatory to perform reliable predictive petroleum system models.
The latter are thermically based on the one hand on user defined
boundary conditions, surface temperature and basal heat influx
(through heat flow, temperature gradient or crustal architecture),
and on the other hand on thermal properties of the sedimentary
infill (including thermal conductivity and heat production). The
existence of calibration data allows tuning these parameters. But
they are not always available, and in such cases one have to rely
on general trends adapted to his regional geology knowledge (for
example the so called normal temperature gradient of 0.03C/m).
Unexpected temperature anomalies can however be encountered
when drilling, invalidating the predicted present day geothermal
regime. In addition, they arise a great uncertainty on any maturity
and generation/expulsion timing forecast since they could have
been affecting the prospected area during geological times.
Through several examples we will try to illustrate the occurrence of
geothermal regime anomalies in carbonate platforms.
One of the possible causes can be related to shallow phenomena,
such as fluid circulation, in intervals where the drilling program
rarely include sample and temperature data collection, as well
as their adequate correction and interpretation. The existence
of temperature anomalies has consequences on the reliability of
petroleum system model predictions, the maturity of source rocks
if it is long-lived, diagenetic processes and reservoir quality, and on
the preservation of hydrocarbon accumulations.
It is then clear that geothermal regime anomalies can greatly affect
the relative value of an exploration project or area, and they are
not always easy to detect. Their causes and consequences have
consequently to be considered in detail through an adequate data
collection and interpretation process.

The authors thank Repsol Exploration for allowing the presentation
of this work.

Basin Modeling: A Key Tool For Assessing

Unconventional Play
F. Schneidera, J.m. Laiglea, L. Kuhfuss Monvala, P. Lemouzya, P.
a Beicipfranlab, 232, Av. Napoleon Bonaparte, 92502 RueilMalmaison, France;
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Figure 1. Illustration of the different porosity that can store gas Retention



The objective is to demonstrate how a basin modeling study can

help 1) evaluating of the initial organic matter distribution, type and
quality inside a formation, and 2) assessing the present day total
organic content (TOC) and maturity level of the formation. These
parameters have a first order control on the volume of hydrocarbons
generated and still retained in the formation.

An important volume of hydrocarbons, mainly gas,is trapped,

through adsorption, inside the source rocks. The adsorption
capacity of the rock is modeled as a function of TOC, pressure and
temperature through Langmuir isotherms.

We present an improved expulsion model accounting for the

retention capacity as a function of maturity.

Hydrocarbons are generated from kerogen during the source rock
burial thanks to temperature elevation. It can be either of biogenic
origin, or of thermogenic origin.
Hydrocarbons composition and volumes generated and retained
depend on the initial organic matter properties and maturity.In
the past, expulsion modelswere designed in order to quantify the
expelled amounts. These models have to be revisited and improved
in order to better quantify the retained gas/oil.
The retention capacity is tightly linked to the TOC content, the
organic matter type and the maturity. Hydrocarbons can be stored
in source rocks by adsorption and as free hydrocarbons inside the
There are two types of porosity in mature source rockthat represent
a storage place for hydrocarbons:
1/ Effective porosity inside non-organic rock fraction. The evolution
of this porosity vs. depth is controlled by burial and possible
diagenetic phenomena
2/ Porosity inside the organic matter itself. This porosity is
created consequently to the loss of kerogen mass resulting of the
transformation of organic matter into hydrocarbons.

To assess the potential for shale gas/oil in a formation, it is
necessary to evaluate:
initial TOC, organic matter distribution, type and quality;
source rock present day maturity;
storage capacity in the non-organic porosity, organic porosity
and adsorption;
generated HC quantity and quality, in order to quantify how much
is retained in the source rock, in the porosity or by adsorption.
In order to achieve these tasks, numerical basin modelof the study
area is built and calibrated in temperature, maturity and pressure. It
is used to compute an evaluation of the shale gas potential of the
Initial TOC and kerogenHI are computed from present day values.
The present day TOC is deduced from logs using an improved
Carbolog methodology, which combines sonic and resistivity
logs. Forward stratigraphic model can also help in assessing
source rock extent, thickness and internal architecture.
The geochemical studyenables to define the kerogen type, quality
and relevant kinetic scheme. The calibrated basin modelallows
estimating the kerogentransformation ratio, used to calculate the
initial TOC.
Accurate compositional kinetic parameters for kerogen thermal
decomposition are key elements in this kind of study to predict the
hydrocarbons fluids quality and type as a function of maturity. IFP
kinetics schemes have proven to provide accurate and describe
reactions scheme, that able to predict early or late gas. A solution
for modeling biogenic gas has also been proposed.
The modeling of hydrocarbons generation allows estimating the
mass loss in the kerogen and the organic porosity consequently

created as a function of maturity.

identification. Large research effort is still required to understand

and to quantify the physical processes that occur in shaly organic

Gas adsorption potential on organic material is calculated using

a Langmuir model implemented within the simulator which takes
into account spatial distribution of pressure, temperature, and
remaining TOC.

matter (retention, adsorption, diffusion).

Behar, F.,Jarvie, D., 2011. Compositional modeling of gas generation from
two shale gas resource systems: Mississippian Barnett Shale (USA) and

The effective porosity in the shale matrix is estimated from log

analysis, using a methodology that allows correction from the effect
of organic matter.

Lower Jurassic Posidonia Shale (Germany), Hedberg Research Conference.

Bhar F., F. Lorant, and L. Mazeas, 2008, Elaboration of a new compositional

Modeling oil composition in reservoirs
submitted to biodegradation in offshore
oilfields in the Brazilian southeastern margin.
Gustavo Garciaa*, Svio F. M. Garciaa, Henrique L. B. Penteadoa,
Luciene S. Jesunob,Joelma P. Lopesb, Erica T. Moraisb, Rosane
A. Fontesb.

kinetic scheme for oil cracking: Organic Geochemistry, v. 39, p. 764-782.

Carpentier, B., A. Huc, and G. Bessereau, 1991, Wireline 550 logging and

The integration of these tasks allows estimating the retention the

formation, accounting for shale effective and organic porosity and
adsorption capacity (dependingmainlyon TOC distribution and
decreases with maturity.

source rocks.Estimation of organic carbon by the CARBOLOG method,

a Petrobras, Explorationteam, 20000-000, Rio de Janeiro, Brazil

b Petrobras, Research center, 21941-915, Rio de Janeiro, Brazil
Figure 1- Fractional distillation from pre-and post-salt oils with variable

The Log Analyst, 1991, p. 279297.


The Gas Initially in Place (GIIP) can then be directly deduced from
the basin modeling simulation results, as a function of this retention
capacity. The numerical model computes a GIIP value at play scale
and gives also access to spatial variations of gas distribution.

I. Moretti, and A.Y. Huc, 2012, Predicting TOC, Organic Porosity and
Gas Retention Distribution in a Shale-Gas System Using Petroleum Basin
Modeling: Search and Discovery Article #40973
Schneider, F. J. S., J. A. Noya, and C. Magnier, 2010, Model of low-maturity

Using experimental design and response surface-based

methodology, the calculated GIIP may be risked as a function of the
uncertainty associated to the values of some key input parameters.
GIIP percentiles are then computed (P10, P50 and P90).

generation of hydrocarbons applied to the Carupano Basin, Offshore

Venezuela, in K. Peters, D. Curry, and M. Kacewicz, eds., Basin and
Petroleum System

The methodology has been successfully applied in various
worldwide formations, in Algeria, Sudan, Argentina, or even United

Volumetric and compositional petroleum prediction constitutes a
crucial requirement to the exploratory process in areas subjected
to biodegradation. It is well known that biodegradation causes
a preferential loss of the light ends of oil, a relative enrichment
in resins and asphaltenes, a reduction in API gravity, and an
increase in acidity and viscosity. As a consequence, petroleum
biodegradation entails a substantial decrease of the volume of oil in
place, lower recovery factors, as well as a reduction in oil quality and
price. Therefore, there is a great need for modeling tools capable
of before-drilling prediction of the effects of biodegradation on
petroleum accumulations in order to avoid prospects with greater
risk of containing heavy oils.
This work was based on a detailed study of oil and gas samples
subjected to variable extents of biodegradation from offshore
oilfields in the Brazilian southeastern margin, and on numerical
simulations to quantify the alterations in geochemical and physical
properties in the petroleum accumulations due to biodegradation.
The main objectives of this study were: 1) to quantify compositional
changes in the oil and gas caused by progressive biodegradation;
and 2) to propose a set of parameters to simulate and reproduce
the volumes and compositions of petroleum affected by
Petroleum accumulations with non-biodegraded oil in the pre-salt
(Aptian) reservoirs were compared with oils subjected to various
intensities of biodegradation in Maastrichtian reservoirs. Among
the laboratory procedures, gas chromatography was utilized to
subdivide the oils in compositional classes (C6-C15, C15-C25, up
to C55+), PVT analyses to quantify the fluid properties (API gravity,
density, GOR, and others) and fractional distillation to estimate the
oil mass losses with the advancement of biodegradation.A method
was devised by Petrobras whereby cumulative distillation curves
are used. For a range of oils from the study area encompassing
non-biodegraded ones and others with variable extents of
biodegradation, mass losses can be calculated considering the
total cumulative yield and the residues at a high temperature. The
integration of these techniques allowed to estimate around 35% of
mass losses in a degraded oil with 18 API, which is the average
value found for biodegraded oils in the Maastrichtian level (Fig. 1).

Figure 2.Workflow used to assess shale gas potential

The methodology presented allows estimating the hydrocarbons
retention capacity of the formation and the composition of
hydrocarbons still retained. these properties can vary significantly
laterally and vertically, and that the shale gas potential of a formation
can then not be simply deduced from a local evaluation that would
be extrapolated throughout the basin. Shale development presents
huge opportunity and faces large geological uncertainty. Innovative
tools and methods are key to diminish the geological risk from
resource evaluation to optimal well development.
Basin modeling play a key role in the shale evaluation process
as it allows integrating all knowledge into a consistent and

extents of biodegradation from an oilfield in the Brazilian southeastern


Romero-Sarmiento M.F., M. Ducros, B. Carpentier, F. Lorant, S. Rohais,

Furthermore, petroleum systems modeling using PetroMod

(Schlumberger) was applied to simulate petroleum generation,
migration and accumulation, as well as the compositional
evolution of biodegraded oils. The quantitative approach to
biodegradationisbased on the assumption that different compound
classes in oil are biodegraded at different rates at the oil-water
contact, and that the rates are a function of compound susceptibility
to biodegradation and temperature (Krooss, B. M. and Di Primio,
R., 2007).
A biodegradation rate as a function of temperature and a
biodegradable fraction arethus assigned to each compound
class. The amount of methane generated by anaerobic degradation
of hydrocarbons was taken from the work of Zengler et al. (1999).
Reservoir temperature history and filling by petroleum were
calculated using the petroleum systems simulator.
As a first step in biodegradation modeling, the volumes and the
original properties of non-biodegraded accumulations in Aptian
pre-salt reservoirs were reproduced accurately by using a PVTbased compositional kinetic scheme.
Then, taking samples of non-biodegraded pre-salt oils as reference
for the original oils in biodegraded intervals and using mainly
the formation factor (Bo) and densities, volumes and masses of
biodegraded oil in Maastrichtian reservoirs were corrected for their
losses caused by biodegradation (equation 1).
Equation (1):
Surface oil Volume(biodegraded) = VOIP(biodeg.) / Bo(biodeg.), where
VOIP(biodeg.)= in place biodegraded oil volume;
Bo (biodeg.) = formation oil (biodegraded) factor.
Surface oil mass (biodegraded) = surface oil volume(biodeg) * oil
density on the surface (biodeg.)
Surface oil mass (non-biodegraded) = (surface oil mass (biodeg) *
100%) / percent of mass loss.
Surface oil volume (non-biodegraded) = surface oil mass (nonbiodeg.) / density (non-biodeg.).

comprehensive model, from early stages of exploration to pilot zone




VOIP (non-biodegraded)= surface oil volume (non-biodeg.) * Bo (nonbiodeg.)

Understanding geochemical properties by

compositional simulation of petroleum vertical
migration and evaporative fractionation

Biodegradation rates and degradable fractions were adjusted

for each compound class until a good match was achieved
between measured and calculated compositions. The simulated
biodegraded accumulations reproduced the mass losses, API
gravities and compositions of oils consistent with those assessedby
the integration of laboratory techniques (Fig. 2).

Lus Maurcio S.A. Corra, Henrique L. de B. Penteado, Laury M.

Arajo, Carlos P. Fracalossi & Hyalla Q.v. Da Silvaaa*
a Petrobras, Petroleum Systems Modeling Team,, carlos.,,
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Petroleum systems modeling allows the dynamic simulation of a
series of processes during the geological history of a basin. Among
these processes, physical and chemical changes in petroleum
associated with vertical migration are of utmost importance for
the assessment of petroleum volumes and composition in an
exploratory context.
Evaporative fractionation is one of the processes related
to petroleum migration which may cause alterations in the
composition of an accumulation. Thompson (1987, 2010) defined
evaporative fractionation as a product of either gas injection or
reservoir decompression in an oil accumulation, followed by phase
destabilization/separation and gas escape, which carries upwards
the light fractions derived from the oil in solution.

Figure 2 - Graph ofMaastrichtian reservoir filling history without petroleum

biodegradation, graphof APIgravity and temperature through time
and results table comparing properties of the reconstituted oil(without
biodegradation), oil in place and modeledbiodegraded oil.

These new achievements enable, using the set of biodegradation
parameters and reservoir filling history, to assess the biodegradation
risk, as well as the volume and oil composition in new prospects
located in areas subject to biodegradation.Further developments
in this model will be made as these parameters are tested and
validated in other geological areas.

Several studies have confirmed, by the analyses of reservoirs

fluid data and laboratory scale experiments, the occurrence of
evaporative fractionation in basins. In order to investigate the effects
of evaporative fractionation during petroleum vertical migration
using a basin simulator, tests were performed using a synthetic
geological model built in the PetroMod software (Schlumberger).
The method usedfor migration combines multiphase Darcy flow
and ray tracing, with petroleum composition based on a kinetic
scheme with eleven compound classes, which is representative of
the PVT properties of lacustrine oils from Brazil. PVT calculations
(phase separation, physical and chemical properties of each
phase) were undertaken for each accumulation during the whole
model history.

The authors thank Petrobras forthe authorization to publish this

Krooss, B. M. and Di Primio, R., 2007: Personal communication (apud

resulting in a single petroleum accumulation in the deepest

reservoir layer of the model. In scenarios 2, 4 and 6, all the seal
layers behave similarly, with capillary pressures equivalent to those
of a shale, thus allowing the simulation of a stack of petroleum
accumulations. The data on simulated petroleum accumulations
volumes, filling and leakage histories, as well as changes in
petroleum compositions have been analyzed through time and
space in all tested scenarios.
Regarding the kinetics of primary cracking assigned to the basal
source rock, the compositional scheme from Penteado& Araujo
(2009) was used. This scheme is characterized by ten classes of
compounds for primary cracking, including the gaseous (C1, C2
and C3-C5) and liquid (C6-C60+) fractions. The compositional
scheme also includes the kinetics of late C1 generation from
refractory kerogen, in addition to the parameters for secondary
cracking. Scenarios 1 and 2 were simulated using only the kinetics
for primary cracking. For scenarios 3 and 4, the kinetic scheme
for primary cracking was coupled with late methane generation.
Finally, scenarios 5 and 6 were simulated through the use of the
full kinetic scheme, including secondary cracking of compound
classes both within and outside the source rock.
Figure 1.Synthetic geological model showing the stacking of reservoir
(sandstone) and seal (shale) layers. At the base of the model, the source
rock layer in green.

Results and Conclusions

In scenario 1 (Fig. 2), the single oil accumulation in the deepest
reservoir remains a monophasic black oil with a constant
composition (27 API gravity and gas-to-oil ratio GOR of 100
m3/m3) throughout the model history because the mass fractions
of the compound classes are the same for all activation energies in
the kinetics for primary cracking.
In scenario 2 the lower capillary pressures in the seals favor
petroleum vertical migration (Fig. 2).

Synthetic Geological Model

T.; Hantschel, T.; Kauerauf. 2009, Fundamentals of Basin and Petroleum

To build the synthetic model for the flow simulation and numerical
tests, the PetroMod (v.2011) software was used. The model has
an area of 32 x32 km, a maximum depth of 7 km and a total of
23,808 grid cells. The model is characterized by stacked pairs
of a sandstone layer with petrophysical properties of a reservoir
rock overlain by a shale layer with properties of a seal rock (Fig. 1).
For the basal layer of the model, a shale source rock was defined.
The various layers comprise a domic structure with its apex at
the center of the model. Sedimentation, compaction, heat flow,
petroleum generation and migration were computed during a total
model history of 125 Ma.

Systems Modeling, Springer, 2009).

Lopes, J.P. e Penteado, H.L.B., 2009: Field-scale quantitative assessment
of petroleum mass losses due to biodegradation under reservoir conditions,
Proceedings of the24th International Meeting on Organic Geochemistry,
Bremen, Germany, pp. 480.
Penteado, H.L.B. e Lopes, J.P., 2007: Application of distillation data
for the estimation of mass losses in biodegraded oils: A new approach,
Proceedings of the 23rdInternational Meeting on Organic Geochemistry,
Torquay, England, pp. 847-848.

Simulated Scenarios
Six scenarios were performed to test variations in the capillary
pressure of the deepest seal layer and in the kinetics of petroleum
generation and cracking. In scenarios 1, 3 and 5, the capillary
pressure of a salt layer was assigned to the deepest seal layer,

Zengler, K.; Richnow, H.H.; Rossell-Mora, R.; Michaelis, W.and Widdel,

F. (1999). Methane formation from long-chain alkanes by anaerobic
microorganisms.Nature, 401:266-269.


Four other accumulations are formed farther above because of the

breach of the capillary barrier of the first seal layer, with slightly
greater API gravities and lower GOR values (between 35 and
100 m3/m3). As petroleum moves upwards, phase separation
takes place in some of these shallower reservoirs, and the gascondensate (API = 56 and GOR> 24000 m3/m3) cap is partly lost
to higher reservoirs and to the surface. Later, further burial andthe
associated increase in seal capillary pressure prevent further losses.
The model was thus able to simulate the occurrence of evaporative
fractionation by decompression, phase separation and loss of the
lighter fractions through the disrupted seal layers (self-depletion).
Scenario 3 differs from scenario 1 by the inclusion of late methane
generation, which causes an increase in GOR values until a phase
separation occurs in the lowermost reservoir layer (Fig. 2). In
scenario 4, accumulations are initially formed above the deepest

reservoir, with leakage of the gas cap through the seal. However, the
additional late C1 causes more dry gas to move upwards, leading
to phase separation in almost all the accumulations, gas washing
of the lighter oil fraction and enhanced vertical migration, with a
total of seven accumulations formed (Fig. 2). The injection of more
methane in the system increased the overall API gravity (between
27 and 55) and gas-to-oil ratios (between 130 and 2900 m3/m3)
of the upper accumulations. This suggests that late methane is
responsible for carrying the lighter fractions of petroleum towards
the top. Therefore, the results of scenario 4 demonstrate that the
process of evaporative fractionation by forced depletion can be
adequately modeled.

Scenarios 5 and 6 are the only ones that take into account
secondary cracking. In scenario 5, after all oil and gas generated
by primary cracking and late-gas cracking are accumulated in
the lowermost reservoir, GOR and API gravities increase in the
liquid phase until it is completely cracked (Fig. 2). In scenario 6, the
phases and compositions in all the accumulations are a result of
a complex interaction of evolving fluids with migration processes.
The end result of scenario 6 is a stratified pattern of accumulations:
the lowermost reservoirs contain essentially gas; intermediary
reservoirs are filled by volatile oils; and the shallower reservoirs
contain only gas condensates.
The results of the six modeled scenarios have shown that petroleum
vertical migration is a highly complex process as a function of: 1)
capillary seal breach induced by underlying accumulations; 2)
phase separations during vertical migration; 3) leakage of gas caps
through seals and losses to the surface; 4) gas washing caused
by upward migration of late methane sweeping light compounds
upwards, and 5) progressive cracking of heavier compound
classes as accumulations are buried deeper. Thus, the numerical
experiments have shown that evaporative fractionation both
by decompression (self-depletion) and by gas washing (forced
depletion) can be adequately reproduced in the scale of petroleum
systems modeling, and be used to assess its effects on fluid
composition in exploration prospects.
Figure 2.Petroleum accumulations resulting from the different modeling conditions
of scenarios 1 to 6.Liquid accumulations shown in green, and gas in red.

Penteado, H.B. & Araujo, L.M., 2009.Compositional kinetics with a PVT
description applied to the prediction of petroleum quality in Brazilian basins.
In: AAPG International Conference and Exhibition, Rio de Janeiro (abstract).
Thompson, K.F.M., 1987. Fractionated aromatic petroleums and the
generation of gas-condensates. Organic Geochemistry 11, 573-590.
Thompson, K.F.M., 2010. Aspects of petroleum basin evolution due to gas
advection and evaporative fractionation. Organic Geochemistry 41, 370-385.




In order to obtain an accurate kinetics estimate, sealed-gold tube

pyrolysis with well-controlled Temperature and Pressure conditions
is conducted (closed system) at two different heating rates, 20oC/
hr and 2oC/hr from T = 250 ~ 550oC; and all solid, liquid and
gaseous components were measured to derive their kinetics as
illustrated in Figure 1.

Geochemical Basin Models for

Unconventional Shale Plays
YongchunTanga,*, Li Gaoa, QishengMaa, James Chena

Prediction of Biogenic Gas Accumulations:

Application to the Eastern Mediterranean

a GeoIsoChem Corporation, Covina, CA, USA

Figure 3: Comparison of SARA distributions of the expelled oils from the

upper Bakken (left) with the field-observed SARA distribution in the middle

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following

review of information contained in an abstract submitted by the author(s).

Accurate assessment of the Original Oil-in-place (OOIP) or Original
Gas-in-place (OGIP) is one of the most essential tasks in petroleum
exploration and production. Geochemical basin models have a
focus on understanding effects of generation and compositions of
hydrocarbonson OOIP/OGIP predictions. Within the geochemical
framework, OOIP/OGIP is calculated from a product of the total
generated hydrocarbons (HC), the expulsion ratio R1 that is related
to hydrocarbons expelled from source rocks (primary migration),
and the migration/diffusion efficiency R2 for hydrocarbons travelling
from sources to the trap (secondary migration).
OOIP/OGIP = HC * R1 * R2

F. Schneider, M. Dubille, L. Montadert, P.Y. Chenet and R. Traby

Beicip-Franlab, 232 Avenue Napolon Bonaparte, 92500 RueilMalmaison, Frana

Figure 1: A comprehensive kinetic network for the hydrocarbon

generation and secondary cracking from kerogen sources. Each
dashed line represents a type of chemical reaction that follows the
Arrenhiuss Equation (2).
The mass balance and volumetric analyses wereusedto determine
the hydrocarbon expulsion from source rocks. At the early
generation stage, due to the volume expansion, the excessive
liquid compounds will be expelled according to their partitions
in solid/liquid phases, which can be calculated using the PengRobinson Equation of State (EoS).


In the unconventional shale plays, the majority of shale oil/gas

is stored locally inside the organic porous space or in the vicinal
natural fractures, and thus the primary migration (expulsion) is
the predominant effect on the shale oil/gas composition and
distributions. In this work, we present an integrated geochemical
basin model combiningthe hydrocarbon generation, expulsion
and secondary cracking processes.Theoretically predicted oil
properties, e.g., ratios of Saturates, Aromatics, Resin-NSO, and
Asphaltene (SARA) and the API gravity of shale oil are compared
and calibratedwith the geological field observation from the Bakken
Shale oil formation. Our models not only can provide important
shale oil properties, but also offer more accurate information of
gaseous components, especially the non-hydrocarbon gases such
as H2S and CO2 generations.

P = RT/(V-b) a(T)/(V2+2bV-b2)


Where P and V are the pressure and volume of system, and a(T)
and b are the EoS parameters. The retained oils will undergo
secondary cracking to give rise of more gaseous components.

Results and Discussion

The Bakken shale oil reserve consists of three layers, upper
Bakken, middle Bakken and lower Bakken. While the lower and
upper Bakken are primary shale sources, the middle dolomite
layer behaves as the oil bank to preserve shale oils for production.
Such a geological system offers excellent field data to calibrateour
geochemical basin models. For example, the shale oil composition
(SARA) in retained shale layers can be calculated and compared
with the field data (Figure 2). SARA distributions in expelled oils
from the upper/lower Bakken layers match the field-observed
SARA ratios in the middle Bakken layer (Figure 3).

Kinetics of hydrocarbon generations from kerogen and the
secondary cracking are determined through a series of parallel
chemical reactions, with each following the Arrenhius Equation:
k =A f exp (-E a /RT) (2)
whereAf is the frequency factor, Ea is the activation energy, R is the
thermal constant and T is the absolute temperature. Hydrocarbons
generated from kerogen decompositions can be grouped into:
o Heavy oils (C15+) that include Saturates (S), Aromatics (A), ResinNSO (N), and Asphaltene (Asph);

It is well recognized that the Bakken shale oil is very light, with an
oil API gravity above 40 degree. Our basin model also provides
the quantitative model to predict the oil viscosity. Because of the
distinguishable expulsion efficiencies for oil and SARA compounds,
the majority of viscous oil compounds such as asphaltene and
resins will be retained in source rocks as a deposit of solid contents.
Only the saturates/aromatics compounds that dissolved in the
liquid phase will be readily expelled and become easily producible.
H2S risk is another important issue in both conventional and
unconventional petroleum exploration and production. Our basin
model also provides a quantitative model to determine the amount
of H2S presented in the petroleum system. Our model also offers
the potential to distinguish the sources of H2S either fromkerogen
decomposition or from oil secondary cracking.

Geochemical basin models combining hydrocarbon generation and
expulsion processes can provide a systematic petroleum system
assessment for both conventional and unconventional reservoirs.
Our comprehensive kinetic network including individual generation/
expulsion/cracking of the oil SARA compounds is essential in order
to obtain a reliable geochemical model to better predict the oil/gas


Biogenic gas is becoming increasingly important as an exploration

target in the petroleum industry because it occurs in geologically
predictable circumstances and in large quantities at shallow depths
as free gas or gas hydrates. As accumulations of biogenic gas
result in a subtle synchronization between early generation and
early trapping, we integrated a macroscopic model of microbial
gas generation within a 3D basin and petroleum system forward
Based on microscopical considerations we developed the
macroscopical model of low maturity / biogenic gas generation
in which hydrocarbons are generated through first order kinetic
reactions at low maturity.

Microscopic model

This research was supported by the Joint Industrial Program

for the GeoIsoChem Corporation, Power Environmental Energy
Research Institute and industrial sponsors, PetroChina fund
(13HT10500000038) and International Science & Technology
Cooperation Program of China (ISTCP) (2010DFB64070).

Behar, F.; Vandenbroucke, M.; Tang, Y.; Marquis, F.; and Espitalie, J.; 1997.
Thermal Cracking of Kerogen in Open and Closed Systems: Determination
of Kinetic Parameters and Stoichiometric Coefficients for Oil and Gas
Generation. Org. Geochem. 26, 321-339.

Pepper, A. S.; and Corvi, P. J.; 1995. Simple Kinetic Models of Petroleum
Formation. Part 1: Oil and Gas Generation from Kerogen. Marine and
Petrol. Geo. 12, 291-319.
Figure 2: Comparison of SARA distributions of retained oils in the upper
Bakken shale oil formation, (left) theoretical prediction from the integrated
basin model and (right) observed field data.



Sandvik, E. I.; Young, W. A.; and Curry, D. J.; 1991. Expulsion from
Hydrocarbon Sources: the Role of Organic Absorption. Adv. in Org.
Geochem.19, 77-87.

Light oils (C6-C14) that include Saturates (S6) and

Aromatics (A6);
Condensates (C3-C5);
Ethane (C2);
Methane (C1);
Carbon Dioxide (CO2);
Hydrogen Sulfide (H2S); and
Nitrogen (N2).

review of information contained in an abstract submitted by the author(s).

Figure 1: Reaction scheme used in the 1D microscopic model

The microscopic model consists in a 1D sedimentary column that

accounts for sedimentation, compaction, Darcy flow and Diffusion
flow. The organic carbon is the only non-soluble element considered
in this version of the model. The dissolved elements are O2, SO4--,
CO2, H2, CH4COOH, and CH4. Methane is dissolved in water or
present as a free phase if its concentration exceeds its solubility at
given pressure and temperature. The reactions accounted for in
this version of the model are given in Figure 1.
The transformation of substrate into biomass is described through
a set of logistic equations coupled with the transport equations
(advection and diffusion).


The first results of the model (see Figure 2) are consistent with the
observations in terms of nutrients and microbes concentrations

methodology has been developed for identifying which layers could

develop a biogenic gas generation potential.
The computed HC composition indicated: (1) the gas, mostly
biogenic, completely dominates the shallow plays from the Pliocene
to the Oligocene; In particular, the Miocene play below the salt is
easily filled by biogenic gas (2) the oil/condensate content would
increase in the Eocene, and overall in the Cretaceous-Jurassic; (3)
then the gas (mostly thermogenic) content increases, up to 100%
in the Triassic play.
Recent works seem to demonstrate that the same deep biosphere
is responsible for early gas generation and biodegradation of
thermogenic hydrocarbons. Furthermore, the exploration for
unconventional gas demonstrated that late biogenic gas can
be generated from old source rocks. Further efforts will be done
toward a better modeling of the effects of the deep biosphere on
the petroleum systems.

Figure 2: Species and microbes concentrations calculated by the 1D model.


Macroscopic Model

Clayton, C., 1992, Source volumetrics of biogenic gas generation, in R.

Vially, ed., Bacterial Gas: Paris, Editions Technip, p. 191204.

Based on the previous microscopic considerations we developed

in TemisFlow a macroscopic model of low maturity / biogenic gas
generation in which hydrocarbons are generated through first order
kinetic reactions at low maturity.

Dubille M., L. Montadert, J.M. Laigle and F. Schneider, 2013, Offshore

Lebanon: biogenic and/or thermogenic plays? An answer from 3D
basin modeling, AAPG European Regional Conference: Exploring the
Mediterranean: New Concepts in an Ancient Seaway, 8-10 April, Barcelona,
Spain, abstract.

The sensitivity analysis carried out with the microscopic model

indicates that free methane generation is conditioned by the initial
TOC, the sedimentation rate and the thermal gradient. A modified
Clayton chart (Clayton, 1992) has then been derived in which the
lower boundary is now a function of the initial TOC. It should be
noticed that the upper boundary of the Clayton chart is not justified
by the microscopic model. Furthermore, methane generation
occurs at low temperature (< 80C) and low maturity (Ro < 0.6 %).
In order get a macroscopic model usable in a basin model, the
set of logistic reactions is up scaled into a set of first order kinetics
assuming that the biomass is a catalyst. It should be noticed that
the kinetic parameters calibrated from lab experiments are not able
to reproduce the nature of the fluids generated at low maturity.
Indeed, the kinetic parameters are mainly calibrated with kerogen
samples for which Ro is taken to be approximately 0.6%.

Schneider, F. J. S., J. A. Noya, and C. Magnier, 2012, Model of low-maturity

generation of hydrocarbons applied to the Carupano Basin, Offshore
Venezuela, in K. E. Peters, D. J. Curry, and M. Kacewicz, eds., Basin
Modeling: New Horizons in Research and Applications: AAPG Hedberg
Series, no. 4, p. 51 69.
Schneider F., Dubille M., and M. Ducros, 2013, Prediction of Low-Maturity
/ Biogenic Gas Accumulations: Application to the Offshore Lebanon. AAPG
Geosciences Technology Workshop: Challenges of New Frontier Off-Shore
Deep Water Hydrocarbon Basins, 27-29 May, Beirut, Lebanon, abstract.


Figure 1. Transformation ratio of carbonates in layer Lower Serdj(Late

Quantitative Prediction of CO2 and H2S in the

Gulf of Gabes, Offshore Tunisia
Aimee Browna, Michael D. Linesb, Jonathan McQuilkenb,C.
Ian Warburtonb,Taina Coutoc,e,Thomas Hantscheld, Armin I.
Kaueraufd, Adrian Kleinec,d,*, Peter Schlichtc,
a BG Brasil, Av.Republica do Chile, 330, 25 Andar, Torre Oeste, Rio
de Janeiro, 20031-170, Brazil
b BG Group, Thames Valley Park, Reading, RG6 1PT, UK
c Schlumberger Brazil Research and Geoengineering Center, Rua
Paulo Emdio Barbosa, 485, Quadra 7B, Parque Tecnolgico,
Cidade Universitria, Rio de Janeiro, Brazil
d Aachen Technology Center, Schlumberger, Ritterstr. 23, Aachen,
e SIS Brazil, Schlumberger,Rua Paulo Emdio Barbosa, 485,
Quadra 7B, Parque Tecnolgico, Cidade Universitria, Rio de
Janeiro, Brazil

Within the Gulf of Gabes, offshore Tunisia, the inert gases CO2
and H2S are an important exploration risk. A quantitative prediction
of occurrence of these gases at locations of interest is difficult.
We present new developments in basin and petroleum systems
modeling to improve the understanding on the behavior of such
inert gases. A number of CO2 and H2S specific processes have
newly been integrated in a coupled modeling approach, which
accounts for the interactions of those with geological processes.
Finally, this method was applied to an already existing modelof
the area (Grimmer et al., 2011)to better analyze and quantitatively
predict generation and migration amounts of inert gases.

The key mechanism for the generation of H2S in the basin is
Thermochemical Sulfate Reduction (TSR) which occurs mainly in
the carbonate reservoir intervals. A reaction scheme developed
by Tang (Tang et al., 2009) has been used for modeling of this
geological process (Kauerauf et al., 2012).
C_n H_m+SO_4^(2-)+H^+H_2 S+CO_2+H_2 O

In our simulations, most of the gas is generated at a very low

maturity: Ro less than 0.6 %. In this domain, it has been stated
that the thermal C-Cbound breakage is unlikely to be significant
without catalysis. Because microbial enzymes are the most efficient
low-temperature catalysts known, we could describe our kinetic
model as a microbial enhanced thermal model.

Helium isotope analysis indicates that generation of CO2 is mainly

from the thermal destruction of deeply buried carbonates (Grimmer
et al., 2011). The corresponding reaction
CaCO3CaO + CO2


Under subsurface conditions, both gases are highly soluble in

water and a mutual solubility model, based on work of Duan et al.,
2006 and Duan et al., 2007, has been implemented into petroleum
systems modeling. Excess inert gas amounts dissolve in liquid or
vapor phases of the petroleum.
Migration of the inert gases, which are dissolved in water, was
modeled with a diffusion equation based on Ficks law with diffusion
coefficients determined according to an Eyring type equation
Deff=D/, D=D0exp(-Ea RT)
with D0 the pure component diffusion coefficient, Deff the effective
diffusion coefficient, porosity, constrictivity, tortuosity, Ea
the activation energy, R the universal gas constant and T the
temperature. It has been observed, that, according to these
equations, high temperatures allow for a significant migration due
to diffusion inside the water phase. Especially, CO2 originating from
deeply buried carbonates might pass quite long distances.
The migration of CO2 and H2S dissolved in liquid or vapor
petroleum phases was performed with separate phase flow such
as Darcy flow or Invasion Percolation (Hantschel and Kauerauf
2009). Herein, the gases aredissolved within migrating petroleum
phases. The equilibrium between dissolution into water and the
petroleum phases was continuously updated in the entire model at
all locations and geological times.
Finally, a modeling method with a full coupling of all relevant
processes, namely generation of CO2 and petroleum, destruction
of petroleum with subsequent generation of H2S, mutual dissolution
of inert gases into water and petroleum phases, and migration via
diffusion and separate phase flow has been used.

Results and Discussion

Thismethod has been applied to a basin model inthe Gulf of
Gabes, offshore Tunisia (Grimmer et al., 2011). It already contained
an overall thermal analysis with generation and migration of
hydrocarbons, performed with established methods of petroleum
systems modeling. It has been found that large amounts of CO2
dissolve in the water, Table 1, and diffuse into reservoir layers which
are of interest for exploration.

is modelled by a kinetic equation based on Arrhenius law which

yields huge amounts of CO2, cmp. Fig. 1.

The previous model has been applied successfully on different
basins such as the Carupano Basin from the offshore Venezuela
(Schneider et al, 2012), Magdalena Delta (offshore Colombia) and
the offshore Vietnam where direct observations of low-maturity gas
were available. Furthermore, it has been applied in the offshore
Lebanon in order to check the viability of a biogenic gas system
(Dubille et al, 2013; Schneider et al., 2013).

Table 1.Mass Balance of CO2 and H2S.

An integrated interpretation of regional 2D seismic surveys

offshore Lebanon provided structural maps and an improvement
of the geological knowledge. These data allowed the building of a
geological model in 3 dimensions at the scale of the whole offshore
Lebanon. The thermogenic source rocks observed in surrounding
basins were implemented and tested in the model. An advanced





Due to a limited capacity of water to dissolve both inert gases,

dissolved CO2 inhibits dissolution of H2S.Significant amounts of
H2S are thus not dissolved into water and kept in the petroleum
phases. In total, measured concentrations of both inert gases
could be reproduced, see Table 2.

Petroleum Generation Kinetics: Single- vs.

Ramp Open-System Pyrolysis
K.E. Petersa,b* and A.K. Burnhamc
Table 2. CO2 and H2S concentrations at some specific locations.

aSchlumberger Information Solutions, Mill Valley, CA 94941;
bDepartment of Geological & Environmental Sciences, Stanford
University, Palo Alto, CA 94305
cAmerican Shale Oil Corporation, LLC, Livermore, CA 94550

Measured concentrations of both inert gases, H2S and CO2,
could be approximately reproduced by modeling. Mutual water
dissolution of inert gases and diffusion in deeply buried layers
are important processes, which are necessary for a quantitative
prediction of these gases. As such the overall workflow of basin
and petroleum systems modeling with incorporation of inert gas
processes has given a better understanding of the distribution of
H2S and CO2 in the Gulf of Gabes.

Copyright 2014, ALAGO
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in a abstract submitted by the authors.



The authors thank the BG Group for allowance to publish this study.

Some publications promote open-system pyrolysis using a single

heating ramp and fixed frequency factor (A) to determine the
petroleum generation kinetics of source rock because the method
is faster and less expensive than multiple-ramp experiments (e.g.,
Waples et al., 2002; Waples and Nowaczewski, 2014). According
to Waples, the key to single-ramp kinetics is to use a fixed A (1
or 2 x 1014 sec-1). Our paper compares the reliability of various
combinations of open-system pyrolysis heating rates to determine
the kinetics of petroleum generation. Three questions must be
addressed to evaluate the single-ramp method:

Duan, Z., Sun, R., Zhu, C., Chou, I-M., 2006. An improved model for the
calculation of CO2 solubility in aqueous solutions containing Na+, K+,
Ca2+, Mg2+, Cl-, and SO42-, Marine Chemistry 98, 131-139.
Duan, Z., Sun, R., Lui, R., Zhu, C., 2007. An accurate thermodynamic
model for the calculation of H2S solubility in pure water and brines, Energy
& Fuels 21, 2056-2065.
Grimmer, J., Brahim, A.B., Hamdi, A., Nadin, P., McQuilken, J., 2011
Tunisia: Gulf of Gabes - 3D Modelling of Hydrocarbon and CO2 Generation

Results and discussion

Sixteen single-ramp experiments on aliquots of the Bellagio Road
sample gave an average Ea of 53.54 0.28 kcal/mol. At a geological
heating rate of 3C/Ma, the predicted range in temperature at
10, 50, and 90% transformation ratio (TR) is 9.90 2.35, 2.69
2.03, and 7.63 2.85oC, respectively. This is the minimum error
for geological extrapolation of single-ramp experiments using our
Pyromat II. Replicate measurements by Burnham (1994) on a set
of samples where A was optimized give a standard deviation of ~1
kcal/mol with a compensating two-fold change in A, resulting in a
standard deviation of 3oC (1-2-3 rule) for geologic extrapolations,
similar to our results and also well within the range of geologic
Figure 1 shows deviation from average Ea for two samples from
the dataset versus the heating rate ratio. Open symbols are results
for combinations of two to six different heating rates where A was
optimized by Kinetics05. When only one heating rate is used (filled
symbols), the variability of Ea and the corresponding A is very
large. The variability of Ea becomes relatively small for heating rate
ratios >16. The dashed lines are the expected variation in Ea as
a function of heating rate ratio calculated from the Bellagio Road
standard deviation.

Activation Energy, kcal/mol


Are there real differences in A for different kerogens?

and Migration, AAPG Milano.

(all heating rates)




1 x 1012

1 x 1013

Are the differences large enough to have a significant impact on

extrapolation to geological time?

Systems Modeling, Springer.

Kauerauf, A.I., Hantschel, T., Tang, Y, Xia, D., Warburton, I., 2012.
Integration of Thermochemical Sulfate Reduction into Petroleum Systems
Modelling, AAPG Hedberg.

and Theoretical Determination of the Kinetics of Thermochemical Sulfate

Reduction, Goldschmidt Conf., Davos, Switzerland.


1 x 1015


What experimental conditions are required to answer questions 1 and 2?

Figure 1.


Kimmeridge Clay and Monterey Shale (type II and IIS kerogen, respectively).

To test precision of kinetic results, a source rock sample from

Bellagio Road containing type II kerogen was run 16 times by
Pyromat II micropyrolysis at 30C/min. Fifty-two well characterized
source rock samples (Peters et al., 2006) were analyzed to
compare results based on (1) one ramp (30oC/min) with a fixed
A (1 x 1014 sec-1), and (2) combinations of ramps (1, 3, 5, 10,
30, and 50oC/min) where A was optimized by the software. These
worldwide samples include kerogen types I, II, IIS, II/III, and III that
are immature to slightly mature with respect to oil generation. Rock
samples were ground to a fine powder (~150 mesh) in an agate
mortar and pestle. Two- to 10-mg aliquotsof the rock powder
were pyrolyzed using Pyromat II at one or more of the six heating
rates. Temperatures were measured by a calibrated thermocouple
in contact with the sample. Products were transferred to a flame
ionization detector by helium flow at 50 ml/min. Pyrolyzate peaks
were processed using Kinetics05 software (Burnham and Braun,
1999). We used discrete Ea distribution modeling with 1 kcal/mol
energy spacing for most samples. Some samples with very narrow
Ea distributions required nucleation-growth modeling.

Tang, Y., Ellis, G.S., Zhang, T., MA, Q., Armani, A., 2009. Experimental

1 x 1014

Frequency Factor,

Deviation from average activation energy (Ea) vs. heating

rate range (ratio of fastest to slowest heating rate) for samples from the

The kinetic parameters for these two samples are statistically

different (Figure 2). The points are for heating rateratios of 16 or
more. Using all heating rates yields parameters in the middle of the
range. The frequency factors differ by tenfold for the two samples.
The most precise temperature predictions are obtained using a
wide range ofheating rate ratios (Figure 1), but fast ramps such as
50oC/min should be used with caution.

Kimmeridge Clay
Monterey Shale

The 52 studied samples show a range of calculated A of about four

orders of magnitude (~1012 to1016 sec-1). These A values are
real because they are reproducible within experimental precision.
Furthermore, Burnham (1994) saw a similar range in A for his
samples. Based on his 1-2-3 rule, he calculated that using a fixed
A of 1 x 1014 sec-1 could result in error for geologic extrapolations
up to 20oC. Thus, our data show that one-ramp kinetic analysis
introduces the potential for significant error that can be avoided
by using high-quality kinetic measurements and multiple-ramp

Single-ramp pyrolysis using a fixed A to determine petroleum
generation kinetics is fast and inexpensive. However, our data
show that single-ramp experiments yield kinetic results that can
be inconsistent with multiple ramp experiments based on discrete
Ea distribution modeling. It is unwise to assume a universal value
for A. This work shows that for a worldwide 52-sample dataset, A
varies over four orders of magnitude (~1012 to1016 sec-1) and is
reproducible within experimental precision.
The data show that discrete Ea distribution modeling based on
three pyrolysis temperature ramps closely approximates the results
from additional ramps, provided that the ramps span an appropriate
range. We recommend three or more ramps that span at least a
twenty-fold variation of rates, such as 1, 5, and 25oC/min, or 1, 3,
9, 27oC/min. Caution is needed for ramps of 30 and 50oC/min,
which can cause temperature errors due to impaired heat transfer.
The product of heating rate and sample size should not exceed
~100 mgoC/min. Compound volatility may inhibit pyrolyzate yield
at the lowest heating rates depending on the effectiveness of the
gas sweep. For some kerogens having narrow activation energy
distributions, both single- and multiple-ramp discrete models are
insufficient and nucleation-growth models are necessary.

We thank Clifford C. Walters (ExxonMobil) for discussions, technical
assistance, and review of the draft.

Burnham, A.K., 1994. Comments on The effects of the mineral
matrix on the determination of kinetic parameters using modified
Rock-Eval pyrolysis by H. Dembicki Jr., and the resulting comment
by R. Pelet. Organic Geochemistry 21, 985-986.
Burnham, A.K.; and Braun, R.L., 1999. Global kinetic analysis of
complex materials. Energy & Fuels 13, 1-22.
Peters, K.E.; Walters, C.C.; Mankiewicz, P.J., 2006. Evaluation of
kinetic uncertainty innumerical models of petroleum generation.
AAPG Bulletin 90, 1-19.


Deviation from
Average Ea, kcal/mol

Hantschel, T., Kauerauf, A.I., 2009. Fundamentals of Basin and Petroleum

Kimmeridge Clay
Monterey Shale

(all heating rates)

Figure 2. Range of kinetic parameters derived for two samples using

multiple heating ramps shows that the differences in mean A and Ea are
real and not a measurement artifact.

Waples, D.W.; and Nowaczewski, V.S., 2014. Source-rock kinetics,

in Encyclopedia of Petroleum Geoscience, New York, Springer.


Waples, D.W.; Vera, A.; Pacheco, J., 2002. A new method for
kinetic analysis of source rocks: development and application as
a thermal and organic facies indicator in the Tithonian of the Gulf
of Campeche, Mexico: Abstracts, 8th Latin American Congress on
Organic Geochemistry, Cartagena, p. 296-298.








Heating Rate Ratio




depth of generation of biogenic gas generation is not the only issue

that needs to be understood. Migration and trap/seal mechanisms
of biogenic gas fields also need to be considered, especially as
conventional seals are not expected to have adequate sealing
properties at the shallow depths at which biogenic gas is assumed
to be generated. Both generation and seal quality evolution need to
be considered as closely coupled processes in these plays.

Controlling factors in mixed biogenic /
thermogenic petroleum systems a case
study from the Levantine Basin
Bjorn Wygrala1, Martin Neumaier1, Chris Clayton2, Thomas
Hantschel1, Adrian Kleine1, Abdulaziz Al-Balushi3, Alistair Fraser3

The Levantine Basin offers a particularly interesting laboratory

to test the variables that control the evolution of biogenic gas
fields. It is a sub-salt play with regionally extensive salt coverage
of Messinian age, however the gas is not trapped and sealed
directly below the salt but within Oligocene-Miocene silty/sandy
turbidite sequences which are assumed to be both the gas source
and reservoir. The most unusual feature is that the area was
subjected to a geologically extreme event during the Messinian
Salinity Crisis (MSC) between 5.96 and 5.33 Mabp when the sea
level in the entire Mediterranean Sea dropped by approximately
2000m followed by salt deposition of locally up to 2000m in a
very short time span of less than 50,000 years. This caused rapid
changes in the depositional environments and sediment surface
conditions, as well as in the pore pressures and temperatures in
the subsurface. As the timing and the conditions induced by the
event are reasonably well defined, it offers a unique opportunity to
test and possibly constrain some of the controlling factors in both
shallow and deep gas plays

1 Schlumberger SIS, Aachen, Germany;

2 Geochemistry Consultant, UK;
3 Dept. of Earth Science and Engineering,Imperial College,
London, UK
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The petroleum systems in the Levantine Basin in the Eastern
Mediterranean have an interesting combination of geological
features and processes, each of which are highly relevant to many
other exploration areas. These include biogenic gas generation,
successful entrapment of biogenic gas at shallow burial depths,
the potential for mixed biogenic and thermogenic systems, as well
as the effect of rapid changes in PT conditions on oil and gas in
petroleum systems. Petroleum systems modeling in the Levantine
therefore offers interesting opportunities to test hypotheses and
constraints concerning the relative importance of these factors and
the resulting exploration risks.

A 240 km long regional 2D type section which connects the three
major discoveries was interpreted and reconstructed (Fig.1), and
used for petroleum systems modeling to investigate the sequence
of events in the study area and their possible effects on the proven
biogenic and assumed thermogenic petroleum systems.

Occurrence, Distribution and Character of
Hydrocarbon Source Kitchens in the Southern
Foredeep of the Llanos Basin, Colombia
Y. Blancoa*, V. Blancob, N. Snchezb, E. Cardozoa, W. Espitiaa,
J. Lunab, M. Naranjob.
Figure 2. Conceptual model of the event sequence during the Messinian
Salinity Crisis, and the resulting effects on the boundary conditions and
subsurface pressure and temperatures in the Levantine Basin.

The regional type-section is used to show the data and

interpretations related to the construction and calibration of the
model, as well as the underlying assumptions that were used to
constrain the properties and boundary conditions of the model.
The properties andprocesses related to the formation of the
currently known biogenic system are then investigated within
these constraints. Only limited thermal calibration data is currently
publicly available, but uncertainties related to this will be shown
where applicable. Special emphasis will be placed on the topic of
biogenic gas generation, and various generation concepts will be
presented, from simple thermally controlled biogenic gas generation
to more complex approaches which, for example, enable deep
biogenic gas generation to be explained. This will then enable
an assessment of gas migration and accumulation timing and
additional controlling factors such as gas migration volumes and
rates, the impact of the pressure reduction on hydrocarbon volume
changes (density, gas exsolution from oil and water, desorption), as
well as seal quality evolution and potential entrapment processes
through geologic time.
In the final part, we then assess the assumed deeper thermogenic
petroleum systems which are at the moment speculative in the
study area, and show which range of conditions could lead to the
co-existence of biogenic and thermogenic petroleum occurrences
and the possible contributions from the different potential
thermogenic source units. Due to the extremely rapid changes in
the PT conditions in the subsurface during the Messinian Salinity
Crisis, there are considerable additional risks for the preservation of
oil and gas accumulations which were formed prior to and during
the event, and these are also investigated.

The Levantine has become an attractive area for oil and gas
exploration due to the discovery of a series of major gas fields
in the pre-salt sequences since 2009. More than 40 tcf of gas
have now been confirmed in several fields since the original
discovery was made. Information on whether the gas in these
new discoveries is of thermogenic or biogenic origin was at first
restricted, as the strategic implications are clear: if the discovered
gas is thermogenic, then the potential for deeper thermogenic oil
could be lower or even excluded. However, if the gas is biogenic,
an opportunity could exist for deeper thermogenic systems which
could include oil. It is now known that the gas is predominantly of
biogenic origin in Tamar, Leviathan and Aphrodite, with possible
minor thermogenic contributions. As a result, exploration for
deeper thermogenic systems and especially for oil is now planned
in the Levantine. This shows the importance of understanding the
processes which resulted in the formation of the newly discovered
gas fields.


Figure 1. Regional type section in the Levantine Basin with a) original

uninterpreted seismic data, b) interpreted seismic used for this study with
well control from Eratosthenes seamount and Levant margin, and c) 2D
seismic based petroleum systems model used for the study with lithology
overlay. Section length is 240 km.

Gas fields of biogenic origin have been producing from depths of

up to 4500m for more than 30 years in Northern Italy, and many
commercially important deeper biogenic gas discoveries have been
added in the last few years, in many cases opening completely new
plays. However, biogenic gas discoveries at very shallow depths
have also been made, such as the Peon field in Norway (at 160m
below the sediment surface!), and these show that the timing and

The petroleum systems modeling study proved to be an extremely

useful exercise to create awareness of which factors in the
geological history of the basin play a controlling role in the evolution
of the proven biogenic gas fields and the potential thermogenic oil
and gas prospects. Inspite of the limitations of the publicly available
data, the model already enables the interrelated processes,
constraints and risks to be assessed. Companies which are directly
involved in exploration in the area, and have access to additional
data which can be used to improve the calibration of the model,
will be able to further reduce the uncertainties and considerably
improve the predictive capabilities of the modeling and increase
their understanding of the potential risks.

a Gerencia de Exploracin Regional Llanos. Vicepresidencia de

Exploracin-Ecopetrol S.A. Bogot. Colombia
b Instituto Colombiano del Petrleo-Ecopetrol S.A. Km7 va
Piedecuesta. Colombia
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Technical Committee following
review of information contained in an abstract submitted by the author(s).

A foreland basin system like the Llanos Basin is an elongated
depozone formed as a consequence of geodynamic processes
linked to subduction and the adjacent fold-thrust belt which
according to DeCelles & Giles (1996), encompasses four distinctive
depocenters defined as wedge-top, foredeep, forebulge, and back
bulge. This work focuses on the evaluation of hydrocarbon source
kitchens within the southern foredeep depozone of the Llanos
foreland system and the relevant implications for exploration risk
assessments in the region. The configuration of the study area
is the unavoidable consequence of thrusting and as stated by
Hoffman, 1987, it contains a transitional stratigraphic record, in
time and space from shelf or cratonic conditions to orogeny.
The vertical stratigraphic successions present within the study area
reveal a lateral range of depositional conditions, which evolved
through geologic time to ultimately develop the various critical
features (e.g. quality, thickness and lateral continuity) for major
components of a given petroleum system such as: source, reservoirs,
and seals at a local scale. The Llanos foredeep depozone has been
filled throughout geological time with thick sediment packages,
which have been mainly sourced from the Eastern Cordillera as it
was uplifted and deposited within non-marine to shallow marine
environments. Furthermore, rapid sedimentation rates since the
Pliocene, coupled with the presence of multiple organic-rich beds
of Cretaceous and Paleogene age have complemented suitable
conditions for hydrocarbon generation from areas where such
source facies have achieved adequate thermal maturity.
On this basis, the present work aimed at establishing the spatiotemporal distribution of source rock properties such as: organic
matter content, hydrocarbon-generating potential, thermal maturity
and stratigraphic thicknesses, for Cretaceous and Paleogene
potential source-rocks which may have reached the hydrocarbon
window during the last 5 ma. The outcomes of a comprehensive
organic geochemical characterization enhanced with field
observations, well sample descriptions and biostratigraphic control
were integrated and then utilized to conduct a multi-1D petroleum
system modeling which allowed us to assess the timing of

generation, expulsion, migration and entrapment of hydrocarbons

within the reservoir rocks. A plausible scenario of the volumetrics
and petroleum charge has been estimated in order to build an
integrated approach with direct application on industry exploration
operations in the study area.

simulation of the petroleum system in the southern foredeep of

the Llanos was conducted using the PetroMod software, which
allowed illustrating the hydrocarbon potential on the bases of the
information gathered and the definition of thermal models.

Results and discussion

Methods and Materials

The present integrated approach reveals that, for both the

Cretaceous and Paleogene deposits, the key geochemical
properties required to develop hydrocarbon source kitchens
converge in specific locations. Lateral variations in both lithofacies
and organic facies are the main conditions controlling the
behavior of the petroleum potential in the sediments investigated.
With respect to the Paleogene source beds, the member of the
Carbonera Formation that has been addressed in this work,
exhibits a variable potential which ranges from fair to good (%TOC
ranging from 0.5 to 2.5 and HI from 17 to 341mg HC/g TOC),
with the most promising features for oil generation in the central
and north (nearby transect 4 in Figure1) parts of the study area.
Middle Eocene to Lower Eocene sediments corresponding to the
top of Mirador Formation show mainly gas prone facies (average
HI of 250) with a relative improvement in oil potential in the centre
of the basin, the area between transects 4 and 1. Good properties
appear to be maintained further to the north of the study area.
The Los Cuervos Formation (Paleocene) has its best features for
hydrocarbon generation toward the north (HI values between 50
and 598). Therefore, the petroleum potential of this unit is restricted
to the surrounding areas of transect 4. Regarding the Cretaceous
units, The Chipaque and Une Formations (Turonian to Santonian
and Aptian to Cenomanian respectively) display potential

Total organic carbon analysis (TOC) was the first step in order to
assess the source-rock generative potential of the various potential
source formations (i.e. Une, Chipaque, Los Cuervos, Carbonera
and Mirador). A total of 1250 well-cutting samples were analyzed in
a LECO C-230 carbon determinator. The majority of these samples
are from black-to-medium-grey mudstone beds in the selected
wells (Fig.1). Of the analyzed samples, 400 samples were discarded
for subsequent evaluation due to their negligible TOC values (i.e.
lower than 0.5%) and therefore poor petroleum potential. RockEval pyrolysis analyses were carried out on 850 samples by utilizing
a Rock-Eval 6 Turbo apparatus. In each case, a 60mg-aliquot of
powdered sample was initially heated at 300C for 3 minutes under
N2 atmosphere. Adsorbed and thermogenic hydrocarbons evolved
from kerogen were recorded as the S1 and S2 peaks respectively
and the temperature of maximum yield during the production of
S2 defined the Tmax parameter. S1 and S2 are expressed as mg
HC/g rock, while Tmax is expressed in oC. The S3 peak is defined
by the oxygen produced during the kerogen cracking phase (CO2),
which is measured in an infrared cell and then reported as (mg
CO2/g TOC). HI (S2 x100/TOC) and OI (S3 x100/TOC) represent
the amounts of hydrogen and oxygen in the kerogen respectively
and were useful to classify the various kerogen types.

for both liquid and gaseous hydrocarbons throughout the entire

area (HI values ranging from 50 to 551, and from 45 to 260
respectively) especially by the locations neighboring transect 4 and
the region between transects 1 and 2.

Vitrinite reflectance profiles and corresponding visual kerogen

analyses carried out for 13 wells were microscopically determined
utilizing a Leitz MPV SP system by means of 546nm reflected
light in both white and fluorescent light modes using oil immersion

The 1-D modelling study was useful to depict the maturity history
of the depozone, the gas and oil generation temperatures and the
burial history. From such outcomes we obtained the timing for
generation as well as the depth at which the various source facies
entered the hydrocarbon window. Finally, the vitrinite reflectance
model was superimposed onto the burial history to describe the
thermal maturation path of the evaluated source-rocks.

been provided regarding an enhanced petroleum potential of the

Cretaceous source formations compared to those of younger ages,
this geochemical characterization demands further investigation,
focusing on the Carbonera and Los Cuervos formations. The
preexisting information for these two formations is still limited and
critical characteristics to better understand their real petroleum
potential such as kinetics parameters and oil source-rock
correlations need to be addressed in detail.



Biological marker analysis of coal

samples from Chico Lom, Brazil

The authors thank the Vice- Presidency of Exploration, Ecopetrol

S.A. (VEX) and the Colombian Petroleum Institute for the technical,
administrative and financial support to conduct the present study.

Hoffman P. (1987). Early Proterozoic Foredeeps, Foredeep
Magmatism and Superior-Type Iron-Formations of the Canadian
Shield. American Geophysical Union.
DeCelles P., and Giles K. (1996). Foreland Basin Systems. Basin
Research., Vol8, Issue2, P. 105-123. DOI: 10.1046/j.13652117.1996.01491.x.

Janaina B. da Costaa*, Maria do Carmo R. Peralbaa, Tnia M.

Pizzolatoa, Wolfgang Kalkreuthb
a Universidade Federal do Rio Grande do Sul, Instituto de Qumica,
91501-970, Porto Alegre, RS, Brazil
b Universidade Federal do Rio Grande do Sul, Instituto de
Geocincias, 91501-970, Porto Alegre, RS, Brazil
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Coal is and will continue to be one of the world main energy sources.
This statement is justified not only by more than a thousand year
history of coal use but also by the scarcity of environmentally
friendly natural energy sources.
Biomarkers are molecular compounds which can be extracted
from crude oils, coals, and other of sedimentary rocks. They can
be detected by gas chromatography and mass spectrometry
techniques in the hydrocarbon fractions obtained from extracts of
recent and ancient sediments. These biomarkers allow recognizing
the main input of organic matter, estimating the paleodepositional
environment on which they were deposited determining the thermal
maturity of the sedimentary rocks.

Distributions of TOC (%), HI (mg Hc/g TOC) and thickness (ft) for
both Cretaceous and Paleogene source rocks varies from poor to
excellent, with the lowest concentrations attributed to significant
siliciclastic dilution taking place mostly toward the south, whereas,
these properties along with thermal maturity levels for hydrocarbon
generation indicated by Rock Eval Tmax (C) and vitrinite reflectance
(%) suggest the occurrence of local generation pods in the central
and north portions of the study area.

In the light of the new geochemical results, we have found that
the hydrocarbon generating potential of the various organicrich beds from different Cretaceous and Paleogene time-spans
reveal a generalized increase to the northwest and a rapid
depletion toward the east, where dilution of the organic material
by siliciclastic sediments played a major role in the preservation of
the source-rock properties laterally. Although, solid evidence has

Figure1. Location map of wells selected for sampling in the study area.

The new data set has been processed and incorporated into
a multidisciplinary framework (stratigraphy, sedimentology,
biostratigraphy, and geochemistry) to enable mapping of the
distribution of the various source-rocks properties in geological and
geographic terms within the study area. The multi 1-dimensional

Four coal samples collected from borehole

CBM 001-CL-RS located in Chico Lom, in the northeastern
state of Rio Grande do Sul, Brazil, were characterized by organic
geochemical methods. The coal samples were crushed (<
0.25 mm) and extracted with CH2Cl2 (93:7 v/v) using a Soxtec
system. Medium pressure liquid chromatography (MPLC) of the
maltene fraction enable isolation of saturate, aromatic and polar
compounds. The saturated hydrocarbons from all 4 samples were
analyzed by gas chromatography-mass spectrometry (GC-MSMS). Instrument: Agilent 6890 N gas chromatograph connected
to a Waters Quattro Micro GC tandem quadrupole mass
spectrometer. GC-column: Agilent HP-5, 30 m x 0.25 mm i.d.,
film thickness 0.10 m. Injection temperature: 70C (2 min hold.)
Temperature programme: 30C/min from 70 to 100C and 40C/
min from 100 to 308C (held 8 min). Method used: Selected Ion
Monitoring (SIM):m/z71.10 and 191.18 (n-alkanes and hopanes).

Results and Discussion

also present, and the value of the Ts/(Ts + Tm) ratio ranges between
0.03 and 0.42. All ratios obtained for hopanes, are consistent with
mature organic material.

The m/z 71 fragmentogram in the 12-045 sample coal from Chico

Lom revealed that saturated hydrocarbons in the coal extracts are
dominated by a series of n-alkanes ranging from C14 to C30with
a unimodal profile. Gas chromatographic analyses of saturated
hydrocarbons for the others samples show a similar n-alkane
distribution in all coal samples (Figure 1).

Biogeochemistry features of sediments
from Cabo Frio upwelling system
Mendona Filho, J.G.a, Carvalhal-Gomes, S.B.V.a, Silva, F.S.a,
Fontana, L.F.a, Innecco, B.R.a,Crapez, M.A.C.b, Laut, V.M.a,
Capilla, R.c

Figure 2.Mass fragmentogramof m/z191 (hopanes) from sample 12-023.

The results of organic geochemical investigationsuggest that the
coals from Chico Lom were formed in a sub-oxic deposition
Biomarker data from saturated fraction indicate that these coals
present characteristics of thermal maturity. The equilibrium value
of the C32 22S/22S + 22R homohopane epimerization is inside
0.570.62. The profile of hopanes showed the absence of hopane and the dominance of 17(H),21(H)-hopanes with the
22S epimer superior to 22R epimer;

Figure 1.Representative gas chromatogram of saturated fractions from

sample 12-045.

The carbon preference index (CPI) of n-alkanes in all samples

is ~1 (Table 1), indicating high rank of the coals. The pristane/
phytane ratio is a commonly applied geochemical parameter used
for assessment of depositional environment oxicity. It is based
upon a different type of reaction during phytoldefunctionalisation,
depending on the amount of oxygen available in the depositional
environment. In the studied coals, the Pr/Ph ratio varies between
2.72 and 8.30 (Table 1).Therefore, this parameter suggests suboxic
conditions for all studied samples.

The authors acknowledge the financial support of ConselhoNacional
de DesenvolvimentoCientfico e Tecnolgico (CNPq). Dr Hans
P. Nytoft and Dr Jorgen A. Bojesen-Koefoed from Geologycal
Survey of Denmark and Greenland (GEUS) are deeply thanked for
providing the facilities for the GC-MS-MS analyses.

Table 1- Geochemical parameters for Chico Lom coals.

Bielowicz, B., 2012. A new technological classification of low-rank coal on
the basis of Polish deposits. Fuel, 96, 497510.
Fabianska, M.J., Cmiel, S.R., Misz-Kennan, M., 2013. Biomarkers and
aromatic hydrocarbons in bituminous coals of Upper Silesian Coal Basin:
Example from 405 coal seam of the Zaleskie Beds (Poland). International
Journal of Coal Geology, 107, 96-111.
Killops, S.D., Killops, V.J., 2005.Introduction to Organic Geochemistry,
second ed. Blackwell Publishing, Oxford, UK. 393pp.

The coals from Chico Lom are characterized by the occurrence of

17(H),21(H)-hopanes (22S and 22R epimers) from C27 to C35.
One representative example of the m/z 191 mass fragmentogramof
the analyzed samples is show in Figure 2. The hopane parameters
for all analyzed samples are listed in Table 1.

Romero-Sarmiento, M-F., Riboulleau, A., Vercoli, M., Laggoun-Defarge,

F., Versteegh, G.J.M., 2011. Aliphatic and aromatic biomarkers from
Carboniferous coal deposits at Dunbar (East Lothian, Scotland):
Palaeobotanical and palaeoenvironmental significance. Palaeogeography,
Palaeoclimatogogy, Palaeoecology, 309, 309-326.

The dominant hopane in all samples is C3017(H),21(H)hopane. The extended hopanes decrease uniformly from 31
to 35 and the 22S/[22S+22R] ratio for all samples were 0.58,
a value situaded within the equilibrium range (0.57 to 0.62). The
C2717(H)-trisnorhopane (Tm) and 18(H)-trisnorhopane (Ts) are

a Universidade Federal do Rio de Janeiro, Laboratrio de

Palinofcies e Fcies Orgnica, IGEO, Ilha do Fundo, 21941-909,
Rio de Janeiro, RJ, Brazil.
b Universidade Federal Fluminense, Laboratrio de Microbiologia
Marinha, Departamento de Biologia Marinha, Cx Postal: 100.644,
24.001-970, Niteri, RJ, Brazil.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Coastal upwelling is a phenomenon characterized by uplift of
cold deep nutrient-rich waters into the ocean euphotic surface
layer in response of winds forces creating favorable conditions
for high primary productivity. The most important upwelling zones
are located off the west coast of South America, Africa and North
America. In Brazil, the coastal region of Cabo Frio is characterized
by the occurrence of unusual eastern upwelling system. The Cabo
Frio Upwelling System (CFUS) is located in an area where there is a
conspicuous change in the shoreline orientation, a predominance
of northeastern trade winds, mainly during austral summerspring,
and synergetic oceanographic mechanisms favors the upflit of
South Atlantic Central Water (SACW) resulting in different upwelling
areas on the shelf (Belem et al., 2013).The production of organic
matter in these systems is directly influenced by upwelling favoring
the production and accumulation of organic-rich sediments.
The main goal of this study is characterize the biochemistry and
geochemistry of organic matter associated with bacterial activity in
sediments cores (Box-cores and Kullenbergs cores).

Twelve Box Core (BC) samples and four Kullenbergs cores (CF1001C, CF10-04C, CF10-09C and CF10-15C) (Figure 1) were taken
from continental Cabo Frio. shelf. Total Organic Carbon (TOC)
and Sulfur (S) content analyses were performed on a LECO SC
144 device. The adopted methods were ASTM D 4239 (ASTM,
2008). Protein analyses were carried out according to Hartree
(1972) a Rice (1982). Carbohydrates content were obtained
according to Gerchacov and Hatcher (1972). Lipids were analyzed
according to Marsh and Wenstein (1966). Esterase enzyme
activity was performed according to Stubberfield and Shaw
(1990). Determination of the electron transport system was made
according to Trevors (1984) and Houri-Davignon (1989). Bacterial
respiratory activity was analyzed using methodology described by
Alef and Nannipieri (1995).Bacterial count was obtained according
to Kepner &Pratt (1994).

Figure 1.Map of the study area showing the box core and Kullenbergs core
sampling sites.

Results and Discussion

Box Cores samples showed contents of TOC ranging from 0.63 to
1.47wt% and sulfur (S) from 0.06 to 0.40%, and TOC:S ratio varied
from 4.6 to 12.12. The Bacterial respiratory activity predominantly
detected was aerobic, fermentation and denitrification. TOC:S
ratio associated with the bacterial metabolism showed a clear
preference of aerobic metabolism, which can classify the
environment as sub-oxic to oxic. The quantification of biopolymers
established averages of carbohydrates of 27.9 ( 8.86) mg.g-1,
proteins 9.9 ( 2.24) mg.g-1, and finally the lipid with an average
of 21.77 ( 3.61) mg.g-1 and showed the following relationship:
carbohydrate>lipid>protein. This relationship is considered normal
for marine environment. The biopolymers also showed different
distribution at the Cabo Frio shelf. High values of proteins and
lipids were found on the nearshore samples and on the middle
part of the shelf. On the other hand, high values of carbohydrates
were found predominantly on the offshore samples. The electron
transport system (ASTE) showed high concentrations and was
detectable on all sampling station, while the esterase enzymes
(EST) presented high values only offshore. Thebacterialpopulation
density observedwas high, but no majorchangesin their biomass
The samples of Kullenberg cores showed high mean values of TOC
and S at the CF10-04C and CF10-09C (middle part of shelf). In
contrast, low values were found at the CF10-01C and CF10-15C
cores. The amount of biopolymers showed a peculiar distribution
at the shelf with major values of carbohydrates for CF10-01C
core, lipids for CF10-15C and proteins for CF10-04C and CF1009C cores (Table 1). The relationship between biopolymers can
be expressed by carbohydrate>lipid>protein for CF10-01C and
CF10-15C cores and protein>carbohydrate>lipid for CF10-04C
and CF10-09C cores. The formation of particulate organic carbon
as a result of primary production plays a vital role in organic carbon
accumulation at different rates in specific deposits along continental
shelves (Sanders et al., 2014).The pattern of distribution of
biopolymers indicates different origins of organic matter on CFUS.


Marsh, J.B. & Wenstein D.B. 1966. A simple charring method for
determination of lipids. Journal of Lipid Research, 7:574576.
Rice D.L. 1982. The detritus nitrogen problem: new observations and
perspectives from organic geochemistry. Marine Ecology Progress Series
9: 153162.
Sanders C.J.; Caldeira, P.P.; Smoak, J.M.; Ketterer, M.E.; Belem, A.;
Table 1: Average values of geochemical and biochemical analyses on the

Mendoza, U.M.N.; Cordeiro, L.G.M.S., Silva-Filho E.V., Patchineelam, S.R.,

cores of CFUS.

Albuquerque, A.L.S. 2014. Recent organic carbon accumulation (100years)

along the Cabo Frio, Brazil upwelling region. Continental Shelf Research



Based on these results, TOC and S values determined on CFUS

samples are low when compared with other upwelling systems,
but it is in agreement with previous studies developed at the
same area. The presence of aerobic metabolism at the Box Cores
samples may be related to availability of O2 brought by upwelling.
It was also found that the bacteria present in sediments in the
region are metabolically active in the environment, with low energy
expenditure breakdown of organic matter (OM), showing that OM
is in abundance and ideal size for consumption (<600Da). The
peculiar distribution of TOC, S, biopolymers and relationships
among the biopolymers can indicate both different depositional
systems and organic matter sources.

Alkane Biomarker Stratigraphy
of Irati Formation in the southern
portion of Paran Basin
Darlly E. S. dos Reis*, Ren Rodrigues.
a Universidade do Estado do Rio de Janeiro, Faculdade de Geologia,
Rio de Janeiro. Departamento de Estratigrafia e PaleontologiaInstituto Nacional de leo e Gs (INOG) ANP/UERJ/PRH 17

Stubberfield, L.C.F. & Shaw, P.J.A. 1990. A comparison of tetrazolium

reduction and FDA hydrolysis with other measures of microbial activity. J of


Microbiology Methods, 12:151-162.

Copyright 2014, ALAGO.

Trevors, J. 1984. Effect of substrate concentration, inorganic nitrogen, O2

This paper was selected for presentation by an ALAGO Scientific Committee following

concentration, temperature and pH on dehydrogenase activity in soil. Water

review of information contained in an abstract submitted by the author(s).

Figure 1 - Chemostratigraphic units from Irati Formation (Units A to I).

The siliciclastic Taquaral Member (Units A, B and C) is characterized

by the predominance of normal alkanes in the GC trace, while the
limestones interbedded with shales, marls and two bituminous
shales of Assistncia Member (Units D and E) record the dominance
of iso alkanes, with the exception of its siliciclastic low TOC unit F,
where a higher proportion of normal alkanes was observed over iso
alkanes (Figure 2).

The black bituminous shale of Irati Formation is considered to be
the source rock of almost all oil shows of Paran Basin. For this
reason, it has been studied in different geochemical aspects, but still
remains as a gap in the organic geochemistry data of the southern
portion of the Paran Basin. The new data presented here provides
elements which may help understand the organic geochemical
variations due to a change in depositional environment conditions
during Early Permian time in the whole Paran Basin.

The authors are grateful to CNPq (National Council for Scientific
and Technological Development) and ANP (National Agency
of Petroleum Natural Gas and Biofuels) for scholarships; and to
PETROBRAS-Brazil for the financial support through the project
entitled Produtividade na ressurgncia costeira de Cabo Frio e
seu potencial de acmulo de matria orgnica: Interao Biosfera

The Irati Formation encompasses two Members: the shaly Lower

Taquaral Member deposited in a normal marine environmentand
the Upper Assistncia Member deposited in a more restricted
depositional environment, characterized by limestones interbedded
with shales and marls, and two bituminous shale intervals.

Alef, K.; Nannipieri, P. Enrichment, isolation and counting of soil
microorganisms. In: Methods in: applied soil microbiology and biochemistry


Figure 2 Mass-Chromatogram m/z 85, C, D, E and F chemostratigraphic Units.

Academic Press,123-186. 1995.

The Bulk geochemical analyses were carried out in 169 samplesof

an approximately 50m thick Irati Formation derived from the well
SC-20-RS drilled by CPRM in the less well known southern portion
of Paran Basin. Based on the bulk geochemical data, 29 samples
were chosen for organic extraction, liquid chromatography and
biomarker analysis.

The high proportion of high molecular weight n-alkanes, C27(Tm)

terpane and moretanes, observed in units A, C and F point to
the dominance of terrestrial organic matter input (Figure 3) (Henz
(1986); Henz et al., (1989); Arajo (1990) and Rodrigues (1995)).

American Society for Testing and Materials (ASTM), 2008. Standard test
methods for Sulfur in the analysis sample of coal and coke using hightemperature tube furnace combustion methods ASTM D 4239.
Belem, A.L.,Castelao,R.M.,Albuquerque,A.L. 2013.Controls of subsurface

All geochemical analyses were performed in the Chemical

Stratigraphy and Organic Geochemistry Laboratory of the State
University of Rio de Janeiro using the following equipment: LECO
SC 444 for TOC and S analysis, Rock-Eval 6 for pyrolysis analysis
and an Agilent system 6890 GC coupled to a 5977 Mass Detector
and 7000 GC-MS triple quad for biomarker analysis.

temperature variability in a western boundary upwelling system.Geophysics

Research Letters 40,13621366.
Gerchacov S.M. & Hatcher P.G. 1972. Improved technique for analysis of
carbohydrates in sediment. Limnology and Oceanography. 17: 938943.
Hartree E.F. 1972. Determination of proteins: a modification of the Lowry

Results and discussion

method that gives a linear photometric response. Analles of Biochemistry.

Based on TOC, sulfur and pyrolysis data it was possible to recognize

nine chemostratigraphic units named from A to I. From these units,
A to C belongs to the siliciclastic Lower Taquaral Member and D
to I are limestones, marls and interbedded shales from the Upper
Assistncia Member (Figure1).

48: 422427.
Houri-Davignon, C. & Relexans, J-C. 1989. Measurement of actual electron
transport system (ETS). Activity in marine sediments by incubation with INT.
Environmental Technology Letters, 10:91-100.
Kepner JR, R. & Pratt, J.R. 1994. Use of fluorchromes for direct
enumeration of total bacteria in environmental samples: past and present.
Microbiological Reviews, 58:603-615.

Figure 3 Mass-Chromatogram m/z 191.Moretanes= 17, 29M, 30M, and 31M.



On the other hand, the higher TOC content and hydrogen index
values, and the corresponding decreasing of the above mentioned
biomarkers in Unit B, record a maximum flooding interval, indicating
a better organic matter preservation and dominance of marine
organisms in the organic matter composition (Tissot & Welte, 1984).

geoqumica dos carves da jazida do FUERJ axinal, Municpio Arroio dos

Ratos, Rio Grande do Sul. Geochimica Brasiliensis, 1(2): 161-175.
REIS, D.E.S. 2012. A Geoqumica Orgnica Aplicada Formao IratiBacia do Paran, poo SC-20-RS, rea de Pinheiro Machado RS:
Identificao Ambiental, Origem da Matria Orgnica e Potencial Gerador.

The Assistncia Member was deposited in a more restricted

environment, where the interbedded limestones, marls and shale
intervals (units D and G) represent the maximum of salinity attained
for the depositional environment as also shown by its higher relative
proportion of gammacerane (Figure 3). The oil shale unit E, which
occurs just above the unit D, records a transgressive system tract
with salinity decreasing towards the top section, as also shown by
decreasing gammacerane (Figure 4).

Dissertao Mestrado. UERJ.

TISSOT, B.P.; WELTE, D.H. Petroleum Formation and occurrence. Berlin e
New York: Springer-Verlag, 1984.

Overview on Kwanza Basin
Potential Source Rocks
Cristina F. Rodriguesa,b, Jlia Carvalhob, Manuel J. Lemos de
a Universidade Fernando Pessoa,4249-004 Porto, Portugal
b Halliburton, Base Sonils, Luanda, Angola
c Academia das Cincias de Lisboa, Lisboa 1249-122, Portugal
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

review of information contained in an abstract submitted by the author(s).

Angola is currently developing oil and gas resource assessment
studies on the Kwanza Basin, in order to increase oil production,
eventually to reach the 2 million barrels/day, as well as, to build a
medium-long term sustainable oil sector.
Only recently, Kwanza Basin has been submitted to more accurate
petroleum system evaluations, since the well-known Congo Basin
has reached a mature production stage. Until now, Kwanza Basin
studies were mainly supported by seismic data and well reports
produced during the sixties. Additionally, the main contribution in
understanding the Kwanza Basin petroleum systems was provided
by geological analog studies with Congo Basin.

Figure 4 Change gammacerane proportion from the base to the top of

oil shale interval.

The low TOC siliciclastic Unit F presents similar GC trace and

biomarker distribution as the siliciclastic Taquaral Member (Units
A and C)

Geological Background
The Kwanza Basin, located in the central part of the Angolan
coast, belongs to the West-Central Coastal Province Geology of
the Sub-Saharan Africa region, and is about 300 km long (northsouth) and 170 km wide (east-west).Was formed during the Early
Cretaceous opening of the south Atlantic Ocean, when the Congo
Sao Francisco craton was rifted along the grain of the Proterozoic
west CongolianBraziliano orogen. In the GabonAngola region,
syn-rift strata were deposited in two margin-parallel troughs
separated by a chain of basement horsts.The Kwanza Basin, as
the others Angolan Coastal sedimentary basins, presents features
typical of the Atlantic-type marginal sag basins filled with MesoCenozoic deposits. The formation of these basins began during
the breakup of the Palaeozoic Gondwana supercontinent, in
the Late Jurassic to Early Cretaceous. The geological history of
Angolan coastal sedimentary basins can be divided into three main
stages: Pre-rift stage (Late Proterozoic to Late Jurassic); Synrift stage (Late Jurassic to Early Cretaceous), and Post-rift stage
(Late Cretaceous to Holocene).The Kwanza Basin is separated
into inner (onshore) and outer (offshore) basins and these in
turn are split into small-basins by basement structural highs,
produced by the major transform faults (Figure 1). The onshore
is an interior salt basin enclosed by the basement highs, and it is
dominated by salt movements and fold belts, formed by basement
shortening and uplift. The offshore is an open continental margin
basin that deformed by gravity spreading, resulting in updip
extension which is compensated by downdip shortening.The
independent development of both basins resulted in the deposition
of stratigraphically different but time-equivalent units, usually

Based on bulk geochemical parameters, mostly TOC, sulfur, RockEval pyrolysis and alkane biomarkers, it was possible to split the
Irati Formation into eight chemostratigraphic units, named from A
to C in the Taquaral Member and from D to I in the Assistncia
Member. Each of these units represents a distinct input of land
derived organic matter type and/or a response of the organisms
living in the water system to a change in salinity and anoxia during

The authors thank CNPq (Brazilian research council), FAPERJ (Rio
de Janeiro Research Foundation), INOG (National Institute of Oil
and Gas Institute), ANP/ UERJ/PRH 17/.

ARAUJO, C.V. 1990. Estudo petrogrfico e geoqumico de carves da
jazida de Santa Terezinha, Rio Grande do Sul, Brasil. Tese de Mestrado,
Univ. Fed. Rio Grande do Sul (UFRGS), Porto Alegre, 285 p.
HENZ, G.I. 1986. Organo-petrografia e organo-geoqumica dos carves
da jazida do Faxinal, Municpio de Arroio dos Ratos, Rio Grande do Sul,
Brasil. Tese de Mestrado, Univ. Fed. Rio Grande do Sul (UFRGS), 243 p.,
Porto Alegre.

described considering the basin development main stages. Pre-rift

deposits (Jurassic) of the onshore part of the Kwanza Basin contain
a terrigenous detrital sequence (basal red beds/red basal series)
which was deposited in continental-deltaic environments. Syn-rift
sequence (Neocomian to Barremian) of the onshore is represented
by lacustrine deposits and consists of tuffaceous rocks, shales,
organic-rich shales (Infra Cuvo and Maculungo formations), and
conglomerate, red sandstone and claystone, and interbedded
volcanic ash of continental origin (Lower Cuvo Formation). The
offshore is characterized of sandstone, siltstone, shale, organic-rich
shale, and minor limestone.Basal post-rift deposits (Lower Aptian)
in the onshore consist of sandstone, dolomite and limestone with
minor thin coals (Upper Cuvo Formation). The offshore includes
sandstone, siltstone, shale, and minor limestone of fluvial and
lacustrine origin. Syn-rift argillaceous sandstones of the Lower
Cuvo Formation are separated from the better-sorted sandstones
of the Upper Cuvo Formation by a breakup unconformity.The Aptian
to Albian evaporite units in the onshore basin were deposited as
a succession of evaporite cycles beginning with the Massive Salt,
and the offshore is represented by massive halite and interbedded


Figure 1. Structural Provinces in the Kwanza Basin(Hudec and Jackson


Two transitional carbonate-evaporite cycles (Quianga and

Binga formations) overlaid the salt, followed by the Tuenza
Formation, characterized by six depositional cycles. From Albian
to Maastrichtian widespread organic-rich marine mudstones
and marls (Quissonde to Teba formations) developed lateral to
and above the carbonate units (Catumbela/Tuenza formations).
A regional erosional event that began during the early Senonian
and continued into the Paleogene formed a general unconformity.
Cenozoic was dominated by progradational marine sedimentation.
The Paleocene and Eocene (Rio Dande to Cunga formations) are
represented by regressive sandstones and siltstones, turbidites,
and deep-marine shale units. The post-Miocene deposits consist


of poorly sorted marine rocks with localized channel-fill sandstones

and turbidites.

Investigating a Cambrian-Ordovician
source rock in the Parnaba Basin, Brazil

Overview on Kwanza Basin Source rocks

The Kwanza Basin is known by the occurrence of multiple and
hybrid petroleum systems based on at least six source formations
(Infra-Cuvo, Upper Cuvo, Binga, Teba, Cunga and Quifangindo)
of Neocomian to Eocene age. Other formations (Rio Dande,
Cabo Ledo and Quissonde) are also good to very good potential
sources but are not deep enough to have been submitted to
sufficient maturation. The Kwanza Basin is characterized by three
Petroleum Systems: Pre-salt Petroleum System, Post-salt Binga
Petroleum System and Post-salt Tertiary Petroleum System.The
Pre-salt Petroleum System is represented by two sub-systems:
the pre-salt/pre-salt and the pre-salt/post-salt sub-systems. The
first sub-system comprises pre-salt source rocks (Infra-Cuvo and
Cuvo formations) and oil/gas accumulations exist within pre-salt
reservoirs (sandstones from Cuvo Formation). The second subsystem is defined by pre-salt source rocks (Infra-Cuvo and Cuvo
formations) and post-salt reservoirs (Upper Cretaceous and Tertiary
sequences). The Post-salt Binga Petroleum System is represented
by Binga source rocks (Aptian and Albian) and several Cretaceous
reservoirs (Binga, Tuenza and Catumbela formations). The Post-salt
Tertiary Petroleum System comprises Tertiary source rocks (Cunga
and Quifangondo formations) and Tertiary reservoirs (Quifangondo
and Luanda sandstones).

Helio J. P. Severiano Ribeiro*, Eliane S. de Souza, Victor H.

Santos, Larcio L. Martins
a Laboratory of Engineering and Petroleum Exploration, Darcy
Ribeiro North Fluminense State University LENEP/UENF, POB
119562, 27910-970 Maca, RJ, Brazil;
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

Figure 1 Location of the Jaibaras Graben (Modified from Oliveira &

Mohriak, 2003)

Six collected outcrop samples from Pacuj Formation were all
crushed and pulverized. To geochemistry analysis, they were
submitted to extraction with a dichloromethane solvent using the
Soxhlet system. Then, the extracts from the rock samples were
fractioned into saturates, aromatics, and polar compounds by
successive elution with hexane, hexane/dichloromethane (8:2, v/v),
and dichloromethane/Methanol (9:1, v/v) on silica gel columns,
respectively. The saturate hydrocarbon fraction was analyzed by
Gas Chromatography/Mass Spectrometry (GC/MS). TOC analyses
were made in the Geochemistry Lab of the Stratigraphy and
Paleontology Department of UERJ. Equipment: LECO SC 444
Carbon Sulphur Analyzer.

review of information contained in an abstract submitted by the author(s).

The hydrocarbon generation in the Parnaba Basin, located at the
northeastern of Brazil, is well known as an atypical petroleum system,
which consists in the intrusion of basic igneous rocks inside the
rich organic matter shale of the Pimenteiras Formation (Devonian),
as like others Paleozoic sedimentary basins in Brazil, such as
Amazonas, Solimes and Paran basins. In the Parnaba Basin it is
so long recognized 1 the presence of the pre-Silurian sedimentary
packages, which are inside in several graben structures aligned
with the Transbrasilano Lineament (northeastern-southwestern).
Those pre-Silurian sediments were already described and cored
in several oil wells drilled by PETROBRAS in Parnaba Basin, they
were named as Riacho Formation (Cambrian to Ordovician)
and Mirador Formation (Late Proterozoic). In the basement at
northeastern portion of the Parnaba Basin outcrops several Early
Paleozoic grabens structures, being the most expressive the
Jaibaras Graben. As like as the grabens under the Parnaba Basin,
those outcropping grabens are either aligned with Transbrasilano
Lineament (Figure 1).

The Kwanza Basin was not one of the main targets in the last
decades; therefore, the first studies were developed by comparing
geochemically West African and Brazilian pre-salt and post-salt
deposits. This geochemical comparison has been pointed out
as an excellent way to identify the different petroleum systems
in the Kwanza Basin, due to stratigraphic and depositional
similarities between Campos and Kwanza basins. However, this
is particularly true for pre-salt source rocks deposited during the
Early Cretaceous (Neocomian/Barremian), a period of time when
the South American and African continents were close to each
other. Nevertheless, it is more difficult to establish a correlation
between post-salt source rocks deposited after the two continents
drifted apart, when the depositional regimes of both continental
coasts were submitted to a higher degree of organic diversity and
to different geodynamic regimes. In this context, it was already
defined six source rocks from Infra-Cuvo, Upper Cuvo, Binga,
Teba, Cunga and Quifangondo formations, which are organized
in three different petroleum systems: Pre-salt Petroleum System
(pre-salt/pre-salt sub-system and pre-salt/post-salt sub-system),
Post-salt Binga Petroleum System and Post-salt Tertiary Petroleum

For mineralogical analysis, the pulverized rock was reduced to

0,53 mm (280 Tyler series). Then, was made a tablet with 2,5g of
the sample and analyzed in a equipment D2 Phaser (Bruker) with
configuration 2Theta (Couple Two Theta/Theta) WI=1,54060.
Results and Discussion
The TOC values were very low, reaching the maximum value at
0,23%. This low value is attributed to the heat from basic igneous
intrusive rocks of the Parapu Suite inside Pacuj Formation or
from de Meruoca granite. In the GC/MS analysis were identified
n-Alkanes (C17 to C33), revealing there was a thermal maturation
for liquid hydrocarbon generation and suggesting a good quality
organic matter (Figure 2).

Gammacerane is present, which is an indicator of the depositional

paleo-environment salinity. The S/R ratio Homohopanes (C31 to
C35) shows a good level organic matter thermal maturity. The
relative abundance of the Tricyclic Terpanes over Pentacyclics
Terpanes characterizes algalic organic matter from CambrianOrdovician 5. In the mineralogical analysis was identified the
garronite, a mineral of the zeolite group, which suggest a very low
grade of metamorphism.

The samples of the Pacuj Formation collected around Santana
do Acara City are in a senile stage of maturity, because of the
very low grade of metamorphism caused by coeval igneous
rocks intrusions. But the good quality of the bitumen extract can
put some good expectative about the possibility to have a good
generation potential inside the grabens subjacent to the SilurianDevonian sedimentary package of the Parnaba Basin.
The authors thank FAPERJ (Rio de Janeiro State Research
Supporting Foundation) for financial support (APQ-1, Proc. n

1Ges, A.M.O., Souza, J.M.P. & Teixeira, L.B. 1990. Estgio exploratrio e
perspectivas petrolferas da Bacia do Parnaba. Boletim de Geocincias da
Petrobras, Rio de Janeiro, 4(1): 55-64
2 Oliveira, D.C. & Mohriak, W.U. 2003. Jaibaras Trough: na importante
element in the early tectonic evolution of the Parnaba interior sag basin,
Northern Brazil. Marine and Petroleum Geology, 20, 351-383.
3Galvo, C.C. 2002. Mapeamento Geolgico Estrutural da Regio
Nordeste de Santana do Acara-CE, com nfase na Deformao Frgil.
Undergraduate Final Repport, UFRN, 60p.
4 Torquato, J.R. & Nogueira Neto, J.A. 1996. Historia-grafia da regio de

Those grabens are interpreted as an Early Paleozoic rift stage2,

preceding the intracratonic sedimentary depositional phase of the
Parnaba Basin. In the Jaibaras Graben, the Cambrian-Ordovician
sedimentary package is named as Jaibaras Group, subdivided
in three formations: Massap, Pacuj and Aprazvel. There are
several citations in the bibliography about the occurrence of dark
shale in the Pacuj Formation 3 4. In such way, in this research
were collected some sample of the dark shale of Pacuj Formation
near Santana do Acara City (northwestern of the Cear State), to
evaluate its generation potential. These samples were submitted to
organic geochemistry and mineralogical analyzes.

dobramentos do Mdio Corea, Revista Brasileira de Geocincias, 26,

5 Peters, K., Walters, C. & Maldowan, M. 2007. The Biomarker Guide:
Biomarker and Isotopes in the Petroleum Exploration and Earth History.
2nd ed. Cambridge University Press, vol 2, 1155 p.

We gratefully acknowledge the support of various people from
Halliburton for their contribution to this paper.

Hudec, M. R.; Jackson. M. P. A., 2002. Regional restoration acrossthe
Kwanza Basin, Angola:Salt tectonics triggeredby repeated uplift of
ametastable passive margin. AAPG Bulletin, v. 8, no. 7, 971-990.
Figure 2 - Mass chromatograms (m/z 85 and 191) of saturated hydrocarbons
in a outcrop sample from Pacuj Formation. nC17 to nC33 =n-Alkanes; Tri23
= C23 Tricyclic terpanes; C31-C35 = Homohopanes; G = Gammacerane.




The TOC varied from 0.19 to 5.53% IH ranged from 278 to very
low values of 16 mg HC / g TOC, while the S2 peak ranged from
0.18 to 7.74 mg HC / g rock. The maximum temperature reached

The immature facies of Pimenteiras

Formation (Devonian) of the Parnaba
basin, state of Tocantins, Brazil:
palynofacies and organic geochemistry.

Organic geochemical
characterization of 30F-1X core samples
from Maracaibo Basin, Venezuela.

by Organic Matter (Tmax) was the maximum values of 433 C,

which allows us to infer that all samples are below the hydrocarbon
generation window are therefore immature.

Carlos Ramrez y Patricia Lugo*

By evaluating the Van Krevlen diagram expressing the function

Consuelo. L. N de Andrade*; Tereza R. M. Cardoso; Altair J.

Machado; Karina S. Garcia.

in the IO IH (Figure 1) can be classified in general the kerogen

Instituto de Ciencias de la Tierra. Facultad de Ciencias. Universidad

ofnsamples studied as primarily type II and III.

Universidade Federal da Bahia; Universidade do Estado do Rio

de Janeiro

In 90% of the of the samples the Amorphous Organic Matter


90% of the total components. The palynomorphs are second in

Central de Venezuela

(AOM) predominates getting to in some samples occupy above

the overall percentage, among which there is a predominance of

Copyright 2014, ALAGO.

Copyright 2014, ALAGO.

group achritarcs. The phytoclasts smallest percentage are in most

This paper was selected for presentation by an ALAGO Scientific Committee following

This paper was selected for presentation by an ALAGO Scientific Committee following


review of information contained in an abstract submitted by the author(s).

Figure 2 illustrates a ternary diagram containing the three basic


constituents of organic matter percentage in the samples. According

The Parnaba Basin is one of the largest Brazilian sedimentary

basins, has over 600.000Km2, however is one of the least known
of the geological point of view. Parnaba is characteristically
Palaeozoic but also contains Mesozoic and Cenozoic deposits bit

to palynofacies defined by Tyson (1995), also for percentage

values for the three principal groups of organic matter, most of
the samples is situated in in palynofacies VII and VIII, indicating
that deposition environments distal platform anoxic disoxic and

review of information contained in an abstract submitted by the author(s).

Figure 2: Ternary diagram with the percentages of the basic components

of the organic matter in samples studied in Pimenteiras Formation, state of
Tocantins, Brazil.

The AOM presented florescence in almost all samples, being less

intense in some (medium brown) and very intense in other (yellowgreen). The Palynomorphs showed intense fluorescence almost
always varied from green to yellow.

a distal platform disoxic-oxic, respectively. Only 4 samples would

The Pimenterias Formation is the main generator of the basin,

belongs to Devonian sequence (Group Canide) and is the largest
marine ingression known in the basin, as well as a significant
fossiliferous content. Are found in Pimenteiras Formation excellent
outcrops with radioactive shales rich in organic matter, including
on the western edge of the Basin (state of Tocantins) which was
rarely studied so far. Thus, the present study aims to characterize
palynofacies and dregree of thermal maturity of organic matter
found in outcrops on the west edge of Fm Pimenteiras, Parnaba

be classified as palinofcie V, corresponding to the platform oxic


environments, dominated by mud (distal platform) and 2 classified

Considering the geochemical results can infer the presence of a

predominantly Kerogen Type II, III and type IV a few samples. As
for the content of palynofacies can be said that overall the organic
matter is well preserved; very rich, including the presence of many
organisms with well preserved structures, and fluorescence. The
intense fluorescence of algae and Tmax indicates immaturity of the
organic matter.

as XIX (suboxic-anoxic distal basin).

The authors thank CAPES for the scholarship granted to the first
author; the UERJ, UENF, Universidad de Barcelona (Barcelona /
Spain) Universities and the Instituto Nacional del Carbn (Oviedo /
Spain) for their support and technical and scientific exchange.

Material and Methods

To achieve the proposed objective 30 samples were collected from
outcrops of Fm Pimenteiras located in the state of Tocantins. For
the analysis of the Palynofacies thin glass slides of the kerogen
were prepared, from the acid digestion of the inorganic fraction
with 32% hydrochloric acid and 40% hydrofluoric acid.
The slides were evaluated using optical microscopy with white light
and UV light. In each sample was carried out a quantitative and
qualitative analysis of palynofacies components, by counting 300
particles and identification of individual componetes organic matter
(phytoclasts, palynomorphs and amorphous organic matter) and
their relative proportions. The fluorescence of the kerogen was
used to characterize the level of preservation of the components.
The fluorescence of the kerogen was used to characterize the
levels of preservation of amorphous organic components and
palynomorphs and to assist in interpreting the maturity of the
maturity of organic matter. Hydrogen indices (HI) and Oxygen (IO),
the S2 and S3 peaks and Tmax were measured by Pyrolyzer RockEval and total organic carbon (TOC) was determined by Elemental

There are several studies on source rock characteristics from
Maracaibo Basin, Venezuela, which have helped in determining the
petroleum system in this basin. However, a little information has
been obtained by analyzing core samples 30F-1X located in west
of the basin.
In 1992, Gallango and Cassani studied extracts from the
Maracaibos Lake and only analyzed a sample of rock core 30F-1X.
For this reason, a larger number of samples in this study represent
a contribution to the petroleum system of Maracaibos Lake basin.

Five samples of ALPUF 30F-1X core from west Maracaibos Lake
basin were used. Total carbon concentration (Ct) was determinate
by LECO carbon analyzer C-144; carbonate-carbon (Cinorg) by
Bernard calcimeter method and total organic carbon (TOC) by
difference. Another analysis includes Tmax values obtained from
rock samples by Rock-Eval pyrolysis.


Bitumen was extracted from powdered rock by Soxhlet extraction

Tyson, R.V.,1995. Sedimentary Organic Matter. Londres: Chap. & Hall, 615 p.

with methylene chloride as solvent. Asphaltene was precipitated

from bitumen by n-heptane addition. Then, the maltene fraction
was separated by adsorption chromatography on alumina column
as stationary phase, using hexane to separate the saturate fraction,
toluene to aromatic fraction and toluene/methanol in a relation
The biomarkers were determined for m/z 113 in the aliphatic
fraction and m/z 178 and 192 in the aromatic fraction, with a mass
selective detector (MS)-(GC/MS), Agilent technologies, models
6890N (GC) coupled with 5975 mass spectrometer (MS).

Results and discussion

The ALPUF 30F-1X core samples contain organic carbon ranging
Figure 1: Diagram of Van Krevelen for classifying the type of kerogen found

Results and Discussion

in the samples studied in Pimenteiras Formation, state of Tocantins, Brazil.


from 4.2 to 8.9% and bitumen from 3196 to 15919 ppm. According
to these values, core rocks are considered excellent hydrocarbon
source rock (Hunt, 1995).

The Tmax values obtained from Rock-Eval pyrolysis range from

Killops, S., Killops, V., 2005. Introduction to organic geochemistry. Blackwell

431 to 438 C indicate a mature stage. The ratio C29 ( /( +

Publishing. Second edition, p. 393.

)) range from 0.51 to 0.53 and C29 (20S/(20S +20 R) range

from 0.43 to 0.48. This suggests that the samples have reached

Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide,

maturity stages to liquid generation hydrocarbons. The maturity

2nd. ed. Cambridge University Press, Cambridge, UK

parameter based on methyl phenanthrene index, MPI (Radke and

Welte, 1983), yields calculated vitrinite reflectances (Rc %) ranging

Radke, M., Welte, D.H., 1983. The methylphenanthrene index (MPI): a

from 0.7% to 0.8% corresponding to peak oil generation.

maturity parameter based on aromatic hydrocarbons. In: Bjoroy, M. (Ed.),

Advances in Organic Geochemistry 1981. Wiley, Chichester, pp. 504512.

The results of GC/FID show a unimodal distribution of lower

molecular mass n-alkanes which maximum in n-C16 and n-C18.

Organic facies distribution in the passive
margin of the Barinas Apure Basin: Coastal
limit movement application

a PDVSA Exploracin, Puerto La Cruz, Anzotegui, Venezuela


marine source (Killops and Killops, 2005, Peters et al., 2005),

Copyright 2014, ALAGO.

corresponding to sedimentary environment where the rock

This paper was selected for presentati on by an ALAGO Sci entific Committee

samples in this study was originated, La Luna Formation (Gonzlez

following review of information contained in an abstract submitted by the author(s).

Lateral and horizontal variations of a source rock in a petroleum
system can be established in a sedimentary basin by using organic
facies analysis. Through this type of analysis, fluid-rock correlations
are more accurate. Furthermore, if the potential of the source rock
is established, liquid and gas volumes of generation can be inferred.

The fragmentogram m/z=191 shows C23-3 in greater proportion

than C24-4, with a C23-3/(C24-4+C23-3) ratio shows values from
0.79 to 0.96 and C31 22R/C30 greater than 0.25 for all samples. The
fragmentogram m/z=217 shows a distribution C27>C28>C29. This is
characteristic of marine derived organic matter (Peters et al., 2005).

Specifically, for the Barinas-Apure Basin, this study allows

understanding the distribution and variation of the source rock
within the passive margin. Some inferences about the coastal line
movement were made; due to geochemical changes that occur
in this transition, with a positive correlation with paleo-bathymetric

The cross plot of dibenzothiophene/ phenanthrene versus pristane/

phytane (P/F vs MDTF/MF) indicates that all samples are derived
from marine environment with high sulfur concentration under
reducing conditions (Hughes et al., 1995).



The 30F-1X core was sedimented under, reducing conditions with

Organic facies (Haoet al., 1993) are determined by mapping initial

potential of a possible source rock in a delimited stratigraphic
sequence. Tectonostratigraphic chart of Barinas Apure Basin made
by Santiago et al., 2014 were used to establish petroleum potential
in depositional units and stratigraphic sequences. From this first
step, only two depositional units had some potential intervals of
source rock: UDII and UDIII. UDII is a passive margin and UDIII is
the beginning of the active margin. However, this study will focus
into the passive margin (UDII, Figure 1)

marine organic matter input as main contribution and the organic

matter is within the oil window.

The authors thank CDCH-UCV (Consejo de Desarrollo Cientfico y
Humanstico de la Universidad Central de Venezuela) for financial support
(Proyect PI-03.00.5889-2008).

Once organic facies maps were generated for each genetic

sequence of the passive margin; original HI from mature rocks
were determined by compositional model (Cooles et al., 1986) to
improve HI contours in organic facies lateral distribution maps.

Landann C. Escorciaa, Linda Montillaa y Nubia Santiago

This distribution show n-alkanes characteristic distribution from

et al., 1980; James, 2000).

made, and petrography evidence was found to correlate this type

of organic matter.

Gallango, O y Cassini, F., 1992.Biological marker maturity parameters of

Finally, organic facies vertical distribution was studied to establish

an interaction within the coastal border movement. Marine
and terrestrial organic facies limit could be different from the
transgression to the regression into the passive margin. Besides
that, coherence between this distribution and palobatymetric maps
were studied.

Results and Discussion

Three (3) organic facies were defined in Barinas-Apure Basin
where distribution is related to orogen position and sediment
direction during passive margin. Two organic facies present a
high marine influence and are located in the northern part of the
basin, deposited under neritic conditions: ABMI with the highest
HI, and ABMII with the lowest HI component. The other organic
facies has a terrestrial predominance; it is located in the southern
part and was deposited under transitional to continental paleobathymetries: ABTI. Principal characteristics and areal distribution
are described:
ABTI: 254 mgTOC/grock is the typical hydrogen index of this
organic facies. Petrographic studies, prove that it is composed
by amorphous (60 to 70%), herbaceous (5 to 10%), woody (10
to 20%), and coally (5 to 10%), with a predominance of woody
content and vitrinite. There are some samples of mycrite content in
terrestrial environment as an evidence of terrestrial organic input.
TOC distribution goes from poor to medium with a same pattern
from HI distribution.
ABMI: in this organic facies, hydrogen index is 634 mgTOC/
grock. Petrographic studies, it is composed by amorphous (70 to
90%), herbaceous (5 to 10%), woody (10 to 25%), and coally (5
to 10%), with a high level of amorphous content, possibly related
to initial marine organic matter. Moreover, there are evidences of
dinoflagellates. This organic facies is located in the northern part
of the basin.

marine crude oils and rock extracts from the Maracaibo Basin, Venezuela.

ABMII: hidrogen index from this organic facies is 399 mgTOC/

grock. Petrographic analysis show: amorphous (60 to 90%),
herbaceous (5 to 30%), woody (10 to 30%), and coally (0 to 10%).
Besides that, there are evidences of dinoflagellates and amorphous
fluoresce as well; located restrictively into the basal sequences of
the transgressive sequence in the south western.

Organic Geochemistry 18, 215-224.

Gonzlez De Juana, C., Piccard, X., Pimentel, N., 1980. Geologa de
Venezuela y de sus cuencas petrolferas. Ediciones Foninves, p.1001.
Hughes, W.B., Holba, A.G., Dzou, L.I.P., 1995. The ratios of
dibenzothiophene to phenanthrene and pristane to phytane as indicators

Figure 1. Tectonostratigraphic chart of Barinas-Apure Basin(Santiago et al.,

of depositional environment and lithology of petroleum source rocks.


Geochimica et Cosmochimica Acta 59, 35813598.

Lithostratigraphically the UDII is an Albian transgressive sequence

of aggrading sandy facies; then, that turned progressively into a
shaly facies until the maximum depth in Coniacian age at 88,8 m.a.
represented by MFS_4 surface (Figure 1).

Hunt, J.M., 1995. Petroleum Geochemistry and Geology, 2nd edition. W.H.
San Francisco, p. 743.

Based on stratigraphic sequences for the passive margin described

before, initial Hydrogen index (HI) values were mapped for each
M.F.S. in Figure 1. Then, relationships between the data were

James, K., 2000. The Venezuelan Hydrocarbon Habitat, Part 1: Tectonics, structure,
palaeogeography and source rocks. Journal of Petroleum Geology 23, 5-53.


Distributions of the organic facies developed during the passive

margin are shown in Figure 2 (ABTI, ABMI y ABMII). The movement
of coastal line in the passive margin can be observed in Figure 2
evolution of the distribution of the organic facies during passive
margin phase. There is a progressive advance of the marine line
during transgression and an advance of terrestrial line during
regression. More to the point that, ABMII organic facies is restricted
to basal sequences; its higher potential could be thought as paleodepocenter from the rifting phase in the basin and/or as a result of
a climate control.

Aromatic Steroids Biomarker applied to
high resolution Stratigraphy: Irati Formation,
Southern of Paran Basin, Brazil
Lina L. Osorio1/ Rene Rodrigues1*
1 Universidade do Estado do Rio De Janeiro, Departamento de
Estratigrafia e Paleontologia, DEPA UERJ, Rio de Janeiro, RJ
Figure 2. Organic facies distribution in genetic sequences from the passive


margin of Barinas-Apure Basin. From SG V to basal deposits (Figure 1).

Copyright 2014, ALAGO.


This paper was selected for presentation by the ALAGO Scientific Committee,

Organic facies methodology used in the Apure Barinas Basins

source rock intervals refined the potential of the basin to generate
hydrocarbons. Moreover, the study of marine and terrestrial
organic facies interaction into small stratigraphic levels, allowed
the evaluations of eustatics controls related with coastal limit
movement within the passive margin.

following review of information contained in an abstract submitted by the author(s).

Cooles, G.P., Mackanzie, A.S., Quigley, T.M., 1986, Calculation of petroleum
masses generated and expelled from source rocks, in: Leythaeuser, D.,
Rullktter, J. (eds.), Advances in Organic Geochemistry, 10, 235245.
Hao F, Chen J, Sun Y. y Liu Y.,1993, Application of organic facies studies
to sedimentary basin analysis: a case study from the Yitong Graben, China.
Organic Geochemistry20-1, Enero, 27-42.
Santiago, N., Bellizzi, L., Escorcia, L., Hernndez,M.,Hernndez, Z.,Lara,
J.,Marcano, J.,Moya, M.,Oliveros, R.,Oropeza, Y.,Parra, K., Pea, Y., Rivas,

The use of aromatic steroids in geochemical studies is almost absent
in Brazilian sedimentary basins. For this reason, it is intended to test
the application of these compounds in high-resolution stratigraphy
in the relatively well known Lower Permian Irati Formation. The
Irati Formation is around 40 meters thick, thermally immature,
and comprise two lithological distinct Members: siliciclastic
lowerTaquaral and calcareous member and the siliciclastic upper
Assistncia Member. Based on whole rock data, mostly TOC, sulfur,
Rock-Evalpyrolysis and alkanes biomarkers, was possible to split
the Irati Formation in eight chemostratigraphic units, named from
A to C in the TaquaralMember and from D to I in the Assistncia
Member. Each one of these units represents a distinct input of land
derived organic matter type and/or a response of the organisms
living in the water system to change in salinity and anoxia during

Y., 2014, Proyecto Evaluacin del Sistema Petrolfero Apure-Portuguesa.

Informe interno PDVSA.

Methods and samples

A total of 29 rock samples previously analyzed for bulk geochemical
parameters were selected from the well SC-20-RS drilled by
CPRM, located 6 Km southernfrom the Pinheiro Machado city, Rio
Grande do Sul State, Brazil.
The powdered rock samples were extracted using dichloromethane
and fractionated in alkanes and aromatic hydrocarbons. The
biomarker analyses were performed using a GC-MS (Agilent
Technologies 6890 GCcoupled to an Agilent 5977 Mass Detector)
and Mass SpectrometryAgilent 7000 GC-MS-MS System with a
triple quadripole analyzersystem.

Results and discussions

Distribution patterns of triaromatic steroids
The fingerprint of the demethylatedtriaromatic steroids, best
studied by the m/z 231 (Riolo et al., 1986), normally shows much
less variation than their methylated counterpart does. However,
compositional variations could be observed in the oil shale interval,
in which occurs a net increasing of C26 e C27 homologous
compared to the composition of others chemostratigraphic units.

Figure 1.Variation in distribution of methylated triaromatic steroid

hydrocarbons, as displayed by the m/z 245 fragmetogram of selected
samples from the well well SC-20-RS. TOC: Total organic carbon; IR:
Insoluble Residue (%);Cn= methylated triaromatic steroid.

On the other hand, the methylated triaromatic steroids has shown

the best possibilities to be applied as a source parameter in the
Irati Formation (Figure 1). The predominance of C29 homologous
in the low TOC siliciclastic intervals C and F; increasing of C27 and
C28 homologous in the interbeds of shales, marls and limestones
(interval D); and predominance of C28 homologous in the oil shale
interval E.
Distribution patterns of monoaromatic steroids
Variations in the relative amount of different homologous are
another geochemical parameter difficult to be considered because
of the co-elution of the different isomers and homologues.
Up to now, the best source rock parameter correspond to the
higher amounts of rearranged structures in the low TOC siliciclastic
intervals C and F, compared to the others intervals where practically
no rearranged structures were observed.

The authors thank CNPq (Brazilian research council)for
fellowships:INOG(National Oil and Gas Institute)and UERJ for
financial support.

MACKENZIE A. S.; HOTFMANN C. F.; MAXWELL J. R. 1981. Molecular
parameters of maturation in the Toarcianshales, Paris Basin, France. III.
Changes in aromatic steroid hydrocarbons. Geochim. Cosmochim. Acta
45, 1345-1355.
REIS, D. E. S.; RODRIGUES, R., 2013. Geoqumica orgnica
aplicada Formao Irati - Bacia do Paran, poo SC-20-RS, rea de
pinheiro machado RS. In: 7 CongressoPDpetro. Aracaju. Brasil.
RIOLO, J.; HUSSLER, G.; ALBRECHT, P.; CONNAN, J.; 1986. Distribution
ofaromatic steroids in geochemical samples: Their evaluation as
geochemicalparameters. Organic Geochemistry, v. 10. pp. 981-990.
TISSOT B.; OUDIN J. A. AND PELET R. 1972. Critresdorigineetdevolution
des ptroles. Application ltudegochimique des bassinssdimentaires. In
Advances in OrganicGeochemistry, pp. 113-134. Pergamon Press, Oxford.v




Rock analyses were performed on a Rock-Eval 6 device (IFPEN,

France), according to the Basic/Bulk Rock method described in
Behar, et al. (2001). The Rock-Eval measurements provide Total
Organic Carbon (TOC %wt) and Mineral Carbon (MinC %wt)
contents. Carbonate contents (CaCO3 %wt) are calculated from
MinC. Typology and maturity of the organic matter are determined
from hydrogen and oxygen indexes, (respectively, HI and OI) and
Tmax values.

Organic-Rich Sediments :
Quick Assessment Of Depositional
Environment Characterization.
Valrie Beaumonta*

The three-component sedimentation model of Ricken applied to
this basin enables to discriminate the different sedimentation styles
linked to the deposition of an exceptional source rock. This very
simple approach delivers information on redox conditions and
sedimentation controls, which can be readily obtained after RockEval data. Further application of the method will be developed
during the meeting.

Results and Discussion

acIFP Energies Nouvelles, 1 et 4 avenue de Bois Prau, 92852

Rueil-Malmaison, France

All OM samples display low thermal maturity indices (Tmax <

430C), well below the oil window, therefore excluding a significant
alteration due to burial or thermal diagenesis. In these conditions,
pristine TOC and CaCO3 contents were preserved. Hence,
coupled organic carbon-carbonates changes reflect changing
flux of carbonates, siliciclastic and organic matter components as
proposed by Ricken (1993).

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The depositional environment of organic-rich sediments is a matter

of interest in exploration and production of both conventional and
unconventional source rocks. Organic matter (OM) accumulation
results from enhance primary production and preservation.
Nutrients availability and reducing conditions promote the formation
of organic rich sediments, while increasing sedimentation rates
dilutes the OM content of a sediment. The distribution of OM in
the sediment is therefore controlled by three main factors: primary
productivity, redox conditions and sediments supply.

Comparison of beds 1 to 6 at Doniford bay and Saint Audries bay

suggests that despite lateral variation of facies, the same factors
control the dysaerobic event, recorded for both sections, and the
OM supply, which is constant and more or less diluted by the
carbonate input. It suggests that a global trigger precludes at this
dysaerobic event.

The extent of a source rock depends on the interplay of these

factors and notably on the local or global nature of the triggers
prevailing at the sediment depositional conditions. Determining
these conditions is paramount in understanding distribution of OM
at the basin scale.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).


Figure 2. TOC (%wt) vs CaCO3 (%wt) at Saint Audries bay (SA, lower
diagram) and Doniford bay (DN, upper diagram). Aerobic, dysaerobic and
anaerobic domains are displayed for sedimentation rates higher than 4m/
different redox conditions.

Thanks to Annachiara Bartolini (MNHN Paris) and Guillaume Paris
(Caltech) for sharing data.

Behar, F., Beaumont, V., De B. Penteado, H.L., 2001. Rock-Eval 6
Technology: Performances and Developments. OGST, 56, 111134.
Paris, G., Beaumont, V., Bartolini, A., Clmence, M.-E., Gardin, S., Page,
K., 2010. Nitrogen isotope record of a perturbated paleoecosystem in
theaftermath of the end-Triassic crisis, Doniford section, SW England. G3,

Geological setting and methods

Victoria F. Sachsea*, RalfLittkea


Ma. The diagrams illustrate two different sedimentation styles associated to

Sedimentological, geochemical and paleoecological data usually

provides key information in approaching the conditions of
depositional environment. Herein we propose a simple approach,
using basic geochemical data, i.e. total organic carbon and
carbonate contents together with Rock-Eval parameters. This
approach is based on a three-component sedimentation model
developed by Ricken (1993). For a given sedimentation rates,
it provides information on redox conditions and sedimentation
controls (carbonate, siliciclastic or organic matter driven). The
approach is exemplify on a serie of oil shales of Triassic/Jurassic

Late Cretaceous organic matter

rich sediments of onshore Morocco
(Tarfaya Basin) and their relation to
Oceanic Anoxic Events

a Institute of Geology and Geochemistry of Petroleum and Coal,

EMR Group, RWTH Aachen University

A general overview of TOC and CaCO3 contents for both sections

(Fig. 2) gives evidence that sedimentation is mainly controlled by
variations of carbonate deposition during Rhaetian and very Early
Hettangian. Then, three successive events of increasing rate of OM
deposition occur during Hettangian. These events are related to
dysaerobic to anaerobic conditions prevailing at the time of the
Blue Lias Formation deposition. During these events, deposition
of a high quality OM with HI higher than 700 mgHC/gTOC is
paramount, and led to the formation of a source rock with an
exceptional potential.



Oceanic anoxic events (OAEs) have been widely discussed in

literature and have been considered as key mechanism for organic
carbon burial for specific time intervals (i.e.Locklair et al., 2011;
Wagreich, 2012). The sediments are generally characterized by the
occurrence of organic matter-rich pelagic sediments, such as black
shales. Three factors were noted by Wagreich (2012) to qualify for
an OAE: (1) widespread organic- rich strata, (2) correlation in time
to qualify as a supra- regional single event and (3) accompanied
by a significant carbon isotope excursionIn contrast to the global
extents of the early Aptian OAE 1a and the Cenomanian-Turonian
OAE 2, Arthur and Schlanger (1979) describe the occurrence of
OAE 3 (Coniacian- Santonian) as regionally more restricted. The
TarfayaBasin in Morocco (Fig. 1) was highly affected by different
phases of OAE, as the influence of OAE 2 is clearly stated in previous
studies (i.e.Kuhnt et al., 2002,Sachse et al., 2012), but the possible
influence of OAE3 on type, quality and quantity of organic matter
is still poorly investigated. The main objective of the study was to
determine conditions of deposition and preservation of organic
matter based on a geochemical study on newly drilled cores.
Indicators describing the depositional environment are discussed
and a detailed overview on organic matter (OM) type, quantity, and
quality is presented to improve the overall geochemical information
available for the Tarfaya Basin. In addition, the relation to the OAE3
can help to improve the knowledge about the extent of this event,
its duration and quality with respect to source rock deposition
(Sachse et al., 2014).
In addition, these organic geochemical parameters give indication
for the petroleum potential of the investigated Late Cretaceous

11 (8).

The west Somerset coastline, (southern England) offers well

exposed marine strata of late Triassic to Early Jurassic age, where
a high-resolution sampling of Rhaetian to Hettangian samples was
performed for two outcrops located at Doniford bay and Saint
Audries bay. Outcrops are distant of few kilometers and lateral
facies variations are observed. Rhaetian environmental conditions
are essentially marine. A Maximum Flooding Surface is observed
during the deposition of the Westbury formation. The overlying
Lilstock formation marked by a sea level fall, corresponds, to an
inner-shelf tidal environment. Then a rapid sea level rise marked
the Early Hettangian and corresponding Blue Lias formation
correspond to an outer-shelf marine environment. An alternation of
laminated shales, marls and limestone constitutes the sedimentary
pile (Fig 1) (Paris, et al. 2010).

Ricken, W., 1993. Sedimentation as a Three-Component System, Springer,


Figure 1.Stratigraphic log of Doniford and Saint Audries bay sections.



Figure 1Location of the Tarfaya Basin in Morocco and the location of the

Figure 2Late Cretaceous ages plotted versus (A) Corgcontents for all

two wells (small red box bottom right).

available samples, (B) temperature evolution, and (C) the eustatic sea level
curve (Haq et al., 1987).

Organic geochemical and petrologicalanalyses have been carried
out for the whole Late Cretaceous (Cenomanian, Turonian,
Coniacian, Santonian and Early Campanian) sequence of the
Tarfaya Basin, southern Morocco. Core samples of two wells
(TarfayaSondage No. 1 and 2) and additional outcrop samples of
Cenomanian age were analyzed in order to obtain more information
about the depositional environment, the kind of organic matter and
the hydrocarbon generation potential.To estimate the quantity,
quality and maturity of organic matter, Corg measurements, RockEval pyrolysis and vitrinite reflectance measurements were carried
out. A modified van Krevelen diagram (HI/OI) and a cross-plot
between HI and Tmax were used for kerogenclassification.Thermal
maturity of sedimentary organic matter was evaluated by means of
pyrolysis parameters (Tmax, PI), microscopic color of liptinites in
fluorescence light (qualitatively) and vitrinite reflectance. In a next
step molecular organic geochemistry (GC, GC-MS) was performed
on selected samples to specify the depositional environment of the
organic matter. In addition sulphur content was measured giving
further insight into the depositional environment and intensity
of bacterial sulphate reduction. Corg vs TS ratios reflect the
importance of sulphide reduction in the decomposition of organic
matter, and thus give a qualitative indication of the redox status of
the environment of deposition.

A comparison of the investigated samples (outcrops, Sondage
No.1 and Sondage No. 2) shows clearly that not all OAEs record
similar depositional conditions as shown here for the temperature
dependence of preservation.More regional controls (continental
run off, salinity and water circulation) and models especially with
respect to organic matter productivity and preservationshould be
considered. In any case Late Cretaceous hothouse conditions
leading to low oxygen levels in deep water provided a situation
favorable for organic matter preservation.

We thank RWE Dea AG for financial support. ONHYM, W. Kuhnt,
and A. Holbourn (Christian-Albrecht University, Kiel) are gratefully
acknowledged for logistic support and sample supply.


Geochemical Characterization of Silurian

and Devonian Section, Southern Sector of
the Amazonas Basin, Brazil.
Igor V. A. F. de Souzaa*, Carla V. Araujoa, Ygor dos S. Rochaa,
Nilo S. Matsudab, Wilson R.Winterc.
a Division of Geochemistry, Research and Development Center
(CENPES), PETROBRAS, 21941-915, Rio de janeiro, RJ, Brazil.
b Division of Stratigraphy and Sedimentology, E&P-EXP,
PETROBRAS, Rio de janeiro, RJ, Brazil.
c Division of Stratigraphy and Sedimentology, UO-BC,
PETROBRAS, Maca, RJ, Brazil.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).


as causal factors in development of reef-reservoired giant oil fields. The

The Amazonas Basin, located in north part of Brazil, cover an area of

approximately 500,000 km is an intracratonic basin mainly filled by
Paleozoic rocks. This basin is considered an important exploratory
frontier as known worldwide Silurian and Devonian source rocks
sections respectively, Pitinga and Barreirinhas formations. Pitinga
Fm. belongs to Neo-Ordovician/Eo-Devoniano sequence and was
deposited during the Silurian maximum flooding surface (MFS).
Barreirinhas Fm. is mainly comprised by black shales and was
formed during the Frasnian/Famenian worldwide anoxic events. The
objective of this study is to carry out geochemical characterization
of these sequences and to integrate these data into a sequence
stratigraphy model in order to obtain information on source rock
potential, as well as prediction of organic facies variations.

Beckmann, B.;Flgel, S.; Hofmann, P., 2005.Linking Coniacian- Santonian

Results and Discussion

(OAE3) black- shale deposition to African climate variability: a reference

Highest Corg contents (Fig. 2A) can be correlated with times of or

close after temperature maxima as for the Cenomanian/Turonian
with a maximum at 93 Ma (Fig. 2B). Santonian and Campanian
(85- 75 Ma) also represent periods of high temperatures, though
somewhat lower than during the Cenomanian and Turonian
(Fig. 2B). The variations of Corg can therefore be explained by
a stronger degradation of the organic matter due to increased
oxygen availability and decreased temperatures. In addition, the
higher amount of organic matter and its better preservation in
samples except the Campanian ones, can be explained by the
relative rise of the sea level (Haq et al., 1987, Fig. 2C) coupled with
oxygen deficient conditions during the initial phase of deposition
as a result from restricted water circulation.Thus our data supports
the assumption of various authors (i.e. Wagreich, 2012) that
OAE3 is distributed over a long time span and not a short term
event as OAE2. The negative feedback of organic carbon burial
and preservation in contrast to Cenomanian/Turonian is thus
related to decrease of global hothouse conditions during the Late
Cretaceous and the better solubility of O2as relatively high sea
water temperatures occurred during the Late Cretaceous (Fig. 2B).
As a consequence, changes in continent/ocean configuration as
the opening of the Atlantic, climate, water circulation and sea level
fluctuation (i.e. Beckmann et al., 2005, Fig. 2C) ultimately control the
production and deposition of organic matter in the Atlantic Ocean.

section from eastern tropical Atlantic at orbital time scales (ODP site 959,
off Ivory Coast and Ghana). In: Harris, N.B. (Ed.) The deposition of organicCarbon Rich Sediments: Models, Mechanisms, and Consequences.
SEPM Special Publications82, 125-143.
Haq, B.U.; Hardenbol, J.; Vail, P.R., 1987. Chronology of fluctuating sea
levels since the Triassic. Science235,1156 -1167.
Locklair, R.E.;Sageman, B.B.;Lerman, A., 2011. Marine carbon burial flux

Material and Methods

and the carbon isotope record of Late Cretaceous (Coniacian- Santonian)

Thirteen samples were collected during the fieldtrip carried out in

Tapajos river area in the south border of Amazonas Basin. Samples
were obtained from Pitinga, Erer, Barreirinhas e Curiri formations.
Total organic carbon (TOC), Rock-Eval pyrolysis, palynofacies
and maturation analyses (spore coloration index and vitrinite
reflectance) were carried out. Geochemical characterization of
bitumen composition were based on extraction with accelerated
solvent extractor method (ASE), carbon isotopic composition
(13C), liquid chromatography (MPLC), gas chromatography
(GC) and gas chromatography coupled with mass spectrometry
(GC-MS) analyses. The GC-MS was used in order to investigate
the molecular composition (terpanes and steranes biomarkers)
of the bitumen. Biomarkers data were used to define the origin
and thermal evolution of organic matter (Peters et al., 2005). Data
were inserted within stratigraphy sequence framework proposed
by Winter (2010 apud Matsuda et al., 2013) based on definitions
summarized by Catuneanu et al. (2009).

Oceanic Anoxic Event III. Sedimentary Geology235, 38-49.

Wagreich, M., 2012.OAE 3- regional Atlantic organic carbon burial during
the Coniacian- Santonian. Climate Past 8, 1447- 1455.
Kuhnt, W.;Holbourn, A.; Gale, A.;Chellai, E.A.; Kennedy, J., 2009.
Cenomanian sequence stratigraphy and sea-level fluctuations in the Tarfaya
Basin (SW Morocco). Geological Society America Bulletin 121, 1695-1710.
Sachse, V.F.;Littke, R.;Jabour, H.; Schmann, T.; Kluth, O., 2012.Late
Cretaceous (Late Turonian, Coniacian and Santonian) petroleum source
rocks as part of an OAE, Tarfaya Basin, Morocco. Marine and Petroleum
Geology 29, 35-49.
Sachse, V.F.; Heim, S.;Jabour, H.;Kluth, O.;Schmann, T.; Aquit, M.;Littke,
R., 2014.Organic geochemical characterization of Santonian to Early
Campanian organic matter-rich marls (sondage No. 1 cores) as related to
OAE3 from the Tarfaya Basin, Morocco. Marine and Petroleum Geology,

considered the MFS of this sequence. Samples were taken from

transgressive systems tract (TST) and highstand systems tract
(HST). TOC contents are low, around 1%. The hydrocarbon
source rock potential (S2) is poor, lower than 5 mg HC/g rock.
Hydrogen and oxygen indices (HI and OI) point out type-II kerogen.
The palynofacies assemblage is mainly composed by acritarchs
and prasinophytes (marine algae). Tyson (1995) and Souza (2007)
interpreted this type of palynofacies as an indication of proximal oxic
shelf. The geochemical composition of bitumen from Pitinga Fm.
is characterized by light 13C (lighter than -31) high hopanes/
steranes ratio, TPP (Tetracyclic polyprenoid ratio) and TET24/26TRI
(C24 Tetracyclic/C26 Tricyclic ratio) and predominance of C29
steranes. This geochemical composition was interpreted to reflect
continental input in a marine environment. Rodrigues (1995) studied
the Devonian section of the Parnaiba basin. This author observed
a good correlation between the high values of Hopanes/Steranes
ratio with the increment of continental input in a marine setting.


Arthur, M. A.; Schlanger, S. O., 1979. Cretaceous oceanic anoxic events

American Association of Petroleum Geologists Bulletin 63, 870885.



Results and Discussions

Ordovician-Devonian Sequence: Two samples were collected in
pelitic section of this sequence. Outcrop presents by 2 meters
of siltstones and shales with one level of concretions which is

Devonian-Tournaisian Sequence: Two samples were collected from

Erer outcrop wich is mainly composed by heterolic facies interpreted
as a deltaic environment. TOC content is moderate, lower than 2%.
The S2 values are good, ranging from 5.15 to 7.24 mg HC/g rock.
HI and OI suggest type-II kerogen. Palynofacies is characterized
by predominance of palymorph group which is mainly composed
by acritarchs. It is worth to mention the relative raise of phytoclasts
and spores, pointing out an increment of fluvial input. Souza (2007)
observed a similar behavior in the palynofacies assemblage in HST
of the Pimenteiras Fm. Geochemical composition of bitumens from
Erer Fm. is characterized by heavier 13C, when compared to
Pitinga Fm. ( -29.7), low values of Hopanes/Steranes and TPP
ratios, as well as C29 steranes predominance.
Eight samples were collected from two outcrops of the Barreirinhas
Fm. Both outcrops are mainly composed by black and gray shales
deposited in a distal marine environment. Four samples were
taken from the outcrop A which represents the lower section
of Barreirinhas Fm. According to Winter (2010) this outcrop is
composed by TST and the base of HST. It is important to highlight
the presence of concretions with 1m height which marks the more
important MFS of the Amazonas Basin. This MFS is attributed to
Frasnian world wide anoxic event. The TOC content is high, varying
from 4.21% to 5.62%. S2 values are very good, reaching up to
24.73 mg HC/g rock. HI and OI suggest Type-II kerogen. The HI
reaches up to 460 mg HC/g TOC. The palynofacies is characterized
by predominance of amorphous organic matter (AOM), suggesting
an anoxic distal marine environment (Tyson, 1993; 1995). Samples
from lower part of Barreirinhas Fm. show low values of Hopanes/
Steranes, TPP and TET24/26TRI ratios associated to high values
of Tricyclic/Hopanes. Some authors correlate high amount of
tricyclic terpanes with prasinophytes (Greenwood et al, 2000). The
upper section of the Barreirinhas Fm. (Outcrop B) and Curiri Fm.
were deposited under HST influence. Samples from this sections
present moderate TOC content, varying from 1.64% to 2.12%. The
S2 valuesare good, reaching up to 6.15 mg HC/g rock. However,
these values are lower than values observed in the lower part of
Barreirinhas Fm. HI and OI indicate type II-kerogen. As well as S2
values, HI tends to be lower when compared to the lower section
of the Barreirinhas Fm. The 13C of bitumens from Barreirinhas
and Curiri formations are similar to the values observed in the
Erer Fm. Otherwise, biomarkers of the extracts from upper part
of Barreirinhas Fm. and Curiri Fm. show significant increment in
Hopanes/Steranes and TPP ratios that can be attributed to the rise



of continental contribution. Palynofacies assemblage from upper

section of the Barreirinhas Fm. and Curiri Fm. is characterized
by predominance of acritarchs. Sample from Curiri Fm. presents
the highest phytoclast abundance, suggesting the highly proximal

Making Movies of Oil Generation

Jeremy Dahl1, Marc Castagna2, Kimball Skinner2, Eric Goergen2
and Hermann Lemmens2

Maturation: The vitrinite reflectance is lower than 0.6% and is

associated to a spore coloration index around 4.5, pointing out a
low maturation stage, with the exception of the sample collected
from Curiri Fm which presents Ro of 0.69%. Nevertheless, these
results of the Curiri Fm. could be influenced by reworked vitrinites.
The maturation indicators obtained from biomarkers, such as Ts/
(Ts+Tm), /(+) and 20S/(20S+20R), suggest low stage
of thermal evolution and is in agreement with petrographic data
and Tmax results.

It was possible to observe the variation of the geochemical data
within the stratigraphic framework that allows a better sampling
as well as prediction of the source rock potential quality. TOC
and pyrolysis results of samples collected from outcrops in the
Tapajs River area in the south border of Amazon Basin point out
poor source rock potential for Pitinga Fm. Samples from Erer
and Curiri formations present moderate source rock potential. On
the other hand, samples from Barreirinhas Fm. show the highest
source rock potential. All studied section is immature for petroleum
generation. It is worth to mention that the studied area represents
the sedimentation near from southern paleoborder. The quality
of source rocks tends to become better into the basin center.
Better paleoenvironmental conditions for source rock formation is
associated to the MFS.

Stanford University
FEI Corporation

Gustavo R. de Sousa Jra, Renata L.L. Hidalgob, Bruno Q. Arajoa,

Afonso C.R. Nogueirab, Candido A.V. Mourab, Eugnio V. Santos
Netoc, Francisco de A. M. Reisa*

Scanning Electron Microscopy (SEM) of organic-rich shales is a

powerful tool for understanding the distribution of organic matter,
mineral content, porosity and permeability . Focused Ion Beam
Scanning Electron Microscopy (FIB-SEM) makes possible digitized
3-d shale reconstructions in which thin layers can be sequentially
stripped away or added on a computer-rendered 3- d image.
These types of movies show the interconnections of pore
networks. These important methodologies are routinely utilized to
better understand unconventional oil and gas plays.

a Universityof Campinas, InstituteofChemistry, 13083-970,

Campinas, SP, Brazil;
b Faculdade de Geologia, Instituto de Geocincias,
Universidade Federal do Par. Rua Augusto Corra 1,
Guam, 66075-110 Belm, PA, Brazil;
c Petrobrs/Cenpes/PDGEO, Av. Horcio Macedo 950,
Cidade Universitria-Ilha do Fundo, 21941-915, Rio de
Janeiro, RJ, Brazil

Here we report another breakthrough methodology, namely making

movies of oil generation, through the use of an Environmental
Scanning Electron Microscope (ESEM) with a heating stage. By
heating a thermally immature, organic-rich shale while continuously
recording the image beneath an ESEM, we were able to make a
movie showing the oil generation process. The heating program
used was the same as that used by Rock-Eval pyrolysis and water
vapor was pumped into the chamber to enhance the image making
the pyrolysis in effect a hydrous pyrolysis.
The movie can be found at:

Catuneanu, O., Abreu, V., Bhattacharya, J.P., Blum, M.D., Dalrymple, R.W.,
Eriksson, P.G., Fielding, C.R., Fisher, W.L., Galloway, W.E., Gibling, M.R.,

From this movie, it is possible to actually visualize many of the

processes that occur during oil generation. These include the
creation of porosity and permeability by the conversion of solid
kerogen to liquid and gas and the subsequent migration of those
hydrocarbons. In the case of this experiment, migration is into
the vacuum. In nature, migration is either within or out of the tight
shale. Furthermore, pressure associated with kerogen and oil
to gas cracking can be observed in the movie by the creation of
fractures parallel to bedding. At high maturities, as the amount of
oil and gas being generated decreases, the fracture can be seen to
begin to close. Fracturing parallel to bedding, as seen in the film,
would result in horizontal migration within the carrier bed.

Giles, K.A., Holbrook, J.M., Jordan, R., Kendall, C.G.St.C., Macurda,

B., Martinsen, O.J., Miall, A.D., Neal, J.E., Nummedal, D., Pomar, L.,
Posamentier, H.W., Pratt, B.R., Sarg, J.F., Shanley, K.W., Steel, R.J.,
Strasser, A., Tucker, M.E., Winker, C., 2009. Towards the standardization of
sequence stratigraphy. Earth Sci. Rev. 92, 133.
Greenwood, P.F.; Arouri, K.R.; George, S.C., 2000. Tricyclic terpenoid
composition of Tasmanites kerogen as determined by pyrolysis GC-MS.
Geochimica et Cosmochimica Acta, Vol. 64, No. 7, pp. 12491263.
Matsuda, N.S.; Zerfass, H.; Wanderley Filho, J.R.; Farias, L.C.N.; Monteiro,
E.F.B.; Winter, W.R., 2013. Roteiro Geolgico do Paleozico do Rio Tapajs
Borda Sul da Bacia do Amazonas, Par. Field trip guide. Reserved Material.

Analysis of Molecular Biomarkers

of cap carbonate from Amazonian Craton,
Neoproterozoic, Brazil

Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

The Neoproterozoic Era was characterized by global glaciations
events so extreme that ocean surface was completely frozen. This
theory is known as Snowball/slushball Earth (Hoffman et al., 1998).
These events of extreme climatic changes were responsible by
significant stress in the ocean life and triggered the deposition of
organic matter after glaciation, mostly in the Neoproterozoic cap
carbonate succession.

limestone of the basal Guia Formation (Figure 1).

The samples were submitted to acid treatment (HCl and HF). The
remainder was extracted to Soxhlet extractor by 72 h using CHCl3.
The organic extracts were fractioned using preparative TLC using
hexane/ethyl acetate (95:5 v/v) and fractions were submitted
to GC-MS e MRM GC-MS-MS analysis.The chromatographic
separations were achieved using HP-5MS capillary column and
Helium as gas carrier at 1.0 mL/min flow. For GC-MS analysis
a GC 7890A/5975C VL MSD Agilent instrument was used. The
temperature program was 70 C (1 min.) up to 300 C (20 min.) at
4 C/min. The injector was configured to split mode (1:1 split ratio)
at 280 C. For the full SCAN (50-600 Da) and SIM mode, the ions
source was adjusted to EI (70 eV) at 210 C. The transfer line was
maintainedat 310 C.For the MRM GC-MS analysis was used a
GC 7890A/7000 MS Triple Quad Agilent instrument with the same
conditions for GC-MS analysis. The MRM transitions were chosen
based on literature (Peters et al., 2005).

Results and Discussion

All samples exhibit a distribution ofn-alkanes from C14 to C36,
monomethylalkanes, from C15 to C22, alkylcyclohexane and
alkylcyclopentane from C15 to C30, and isoprenoides from C15 to
C25.The Pr/(Pr+Ph) ratios ranged between 0.36 and 0.54.
The m/z 191 mass chromatogram of the samples from Mirassol
dOeste locality is dominated for a distribution of tricyclic terpanes
from C19 to, at least, C39. The mass chromatogram shows yet
absence of the hopanoids compounds, including 17-22,29,30trisnorhopane (Tm), which prevents the use of the Ts/(Ts+Tm) ratio,
as a more accurate evaluation of the thermal evolution. The m/z
191 mass chromatogram of Tangar da Serra samples exhibited
not only tricyclic terpanes, but also a complete distribution of
hopane-type compounds and gammacerane (Figure 2).The low
values for Pr/(Pr+Ph) ratio and the presence of gammacerane, in
case of the Tangar da Serra samples, indicate anoxic conditions
associatedwitha saline paleoenvironment(Peters et al., 2005).
Both suite of samples (Mirassol dOeste and Tangar da Serra)
showed a strong predominance of C27pseudohomologues in
theirm/z217 and m/z 218 mass chromatograms and M+m/z
217 MRM chromatograms. The intensity of M+ 358m/z217
response reveals that the C26pseudohomologues are the second
most abundant.None of observed peaks in M+ 386 m/z 217
and M+ 400 m/z 217 MRM chromatograms correspond to
elution positions expected for C28 and C29 components.Ring
A-methylated and A-dimethylated steranes, respectively, were
observed in M+386m/z 231 and M+ 400 m/z 245 MRM
chromatogram, with stereoisomer distributions comparable to
those of the steranes.
Mirassol d'Oeste samples


Palynofacies. Chapman and Hall, London. 615 pp.






















Time (minutes)





Tyson, R.V., 1995. Sedimentary Organic Matter: Organic Facies and



Netherlands, pp. 153191.


AppliedMicropaleontology. Kluwer Academic Publishers, Dordrecht, The

Tangar da Serra samples


Tyson, R.V., 1993. Palynofacies analysis. In: Jenkins, D.G. (Ed.),



Petrleo. Master Dissertation, IGEO/UFRJ, Rio de Janeiro.



In Brazil, the record of post-glacial cap carbonate related to the last

event of Cryogenian was firstly reported by Nogueira et al. (2001,
2003, 2007)in outcrops nearby Mirassol dOeste city, State of Mato
Grosso, Center-western Brazil. Afterwards, Soares and Nogueira
(2008)described a new occurrence of cap carbonate in Tangar
da Serra city, 135 km to the NE of Mirassol dOeste (Figure 1). The
cap carbonate represent the basal portion of the Araras Group,
that include the dolostones of Mirassol dOeste Formation and the

Bacia do Parnaba (Formao Pimenteira): Implicaes para Gerao de

TT30 TT31


Souza, I.V.A.F., 2007. Faciologia Orgnica de Sees Devonianas da



TT25 TT26


Figure 1. Geological, location map and general stratigraphy of study area.


Thesis, IG/UFRGS, Porto Alegre.



Rodrigues R., 1995. A Geoqumica Orgnica na bacia do Parnaba. Ph.D


The making of ESEM movies of oil and gas generation from organicrich shales will lead to a better understanding of the process in
both conventional and unconventional plays.

2nd ed., 2v. Cambridge University Press, Cambridge.


Peters, K.E.; Walters, C.C.; Moldowan, J.M., 2005. The Biomarker Guide.






Figure 2. m/z 191 Mass chromatogram for selected samples.

Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide:

Since C28 and C29 steranes have not been detected, the coelution problems are eliminated, allowing to use C27 20S/(20S
+ 20R) and C27/( + ) as maturity parameter. All samples
exhibited C27 20S/(20S + 20R) ration between 0.47 and 0.50 and
C27/( + ) ratio between 0.59 and 0.64.

Biomarkers and Isotopes in the Petroleum Exploration and Earth History,


2nd ed. Cambridge University Press, Cambridge, UK.

Soares, J.L., Nogueira, A.C.R., 2008. Depsitos carbonticos de Tangar
da Serra (MT): uma nova ocorrncia de capa carbontica neoproterozica
no sul do Crton Amaznico. Revista Brasileira de Geocincias 38, 715-

Although cyanobacteria is the only microorganism known to

biosynthesize monomethylalkanes, several origins have been
suggested for these compounds, such as direct biological
contributions of branched alkanes, or as diagenetic products
of carboxylic acids. Furthermore, monomethylalkanes can be
generated by chemical process like equilibration of a limited range
of isomers, or produced by thermal cracking of alkenes (Summons
and Walter, 1990).Since the Amazonian Craton sedimentary rocks
studied here showed an early mature thermal evolution level,
catagenetic reactions as the origin for the monomethylalkanes is
less likely and a contribution of cyanobacteria to the OM is more

Summons, R.E., Walter, M.R., 1990. Molecular fossils and microfossils of
prokaryotes and protists from Proterorozoic sediments. American Journal
of Science 290-A, 212-244.

Oil exploration in the Mediterranean Basin: the

pre-Messinian source rocks
Albert Permanyer, Robert Jorge, Llus Gibert
Dept. de Geoqumica, Petrologia i Prospecci Geolgica, Universitat
de Barcelona. Mart i Franqus, s/n. 08028 Barcelona, Catalonia
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

Figure1. Fluorescence microscopy. Finely banded organo-mineral matrix,

amorphous, displaying intense greenish-yellow and red fluorescence.

review of information contained in an abstract submitted by the author(s).

The last hydrocarbon discoveries in the eastern Mediterranean
basin have generated a specific interest on organic rich sediments
that pre-date the extensive evaporitic deposits originated during
the Messinian Salinity Crisis (MSC). Southeastern Spain has a
large number of Late Neogene basins with substantial evaporitic
deposits that developed under an overall NNW-SSE compression
regime because of the African-European plate collision. These
basins are in the Alpine Betic range, and can be considered as
marginal Mediterranean basins that became gradually isolated
from the Mediterranean Sea due to tectonic uplift.

A full suite of n-alkanes C15-C36 in all samples indicatea
well preserved organic matter.Both sets of samples have
homologous series of alkylcyclopentanes, alkylcyclohexanes
and methylalkanes. All these compounds indicate a contribution
of cyanobacteria to sediment and are considered characteristic
biomarkers of Neoproterozoic organic matter.The RIC m/z 217
mass chromatogram exhibited the same sterane composition
with predominance of C27 normal steranes for both location,
but m/z 191 mass chromatogram revealed very low abundance
(or absence) of hopanes and a large prevalence of tricyclic in
Mirassol dOeste samples.Tangar da Serra samples showed
a more usual profile of m/z 191 mass chromatogram with the
presence of tricyclic,hopane biomarkers and gammacerane.The
observed geochemical differences were probably due to local
palioenvironmental variations that affected production and/or
preservation of the primary organic matter.

The Messinian evaporitic deposition was related first to a restriction

in the communication with the Atlantic Ocean during the period
~6-5.5 Ma followed by an isolation of the Mediterranean Sea
between ~5.5-5.3 Ma. Different evaporitic units accumulated in
these marginal basins before and during the restriction stage of
the MSC. Evaporitic conditions seems to follow periods of organic
matter accumulation.


Previous studies of the pre-evaporitic deposits from Lorca Basin

showed: a) high oil potential, b) marine origin of the organic matter
and c) low degree of maturity (Permanyer et al, 1994; 2013). In the
present work we show the results obtained from Late Tortonian
organic rich shales collected from boreholes, mines and outcrops
in the marine Lorca Basin and other less open or isolated Betic
basins: Minas de Helln, Cenajo and Socovos.

The authors thank CNPq (Brazilian research council) for fellowship,

Petrobras S/A andUnicamp for financial support.

Hoffman, P.F., Kaufman, A.J., Halverson, G.P., Schrag, D.P., 1998. A
Neoproterozoic Snowball Earth. Science 281, 1342-1346.
Nogueira, A.C.R., Riccomini, C., Kerkis, A., Fairchild, T.R., Hidalgo, R.L.,

Figure 2. Scanning electron microscopy. Laminated organic matter with

authigenic dolomite crystals (d), chert nodules (c), and diagenetic halite (h);
titanium crystals aggregate (Ti) and planktonic foraminifer (f).

The laminae denote an undisturbed sedimentary environment, in

which some authigenic calcite, dolomite and quartz crystals as well
as micro nodules of chert and diagenetic halite grew (Fig. 1). The
occurrence of benthic and planktonic foraminifera is noticeable,
suggesting a marine environment (Fig. 2).


2001. Hydrocarbons in carbonate rocks of the Neoproterozoic Alto

This work examines first the petrological features of the organic

matter using fluorescence and scanning electron microscopy,
and second the main geochemical features by using Rock Eval
pyrolysis, Gas Chromatography and Gas Chromatography-Mass

Paraguai basin, Mato Grosso, Brazil. Anais da Academia Brasileira de

Cincias pp. 464-464.
Nogueira, A.C.R., Riccomini, C., Sial, A.N., Moura, C.a.V., Fairchild, T.R.,
2003. Soft-sediment deformation at the base of the Neoproterozoic Puga
cap carbonate (southwestern Amazon craton, Brazil): Confirmation of rapid


icehouse to greenhouse transition in snowball Earth. Geology 31, 613-616.

Studied samples appear to be made up of thin laminae in which the

organic matter is optically amorphous, displaying intense greenishyellowish and red fluorescence with inverse fading.

Nogueira, A.C.R., Riccomini, C., Sial, A.N., Moura, C.a.V., Trindade, R.I.F.,
Fairchild, T.R., 2007. Carbon and strontium isotope fluctuations and
paleoceanographic changes in the late Neoproterozoic Araras carbonate
platform, southern Amazon craton, Brazil. Chemical Geology 237, 168-190.



Figure 3. HI vs OI diagram. HI between 700 and 850, oil potential up to 150


to 183, and high organic sulfur content (>8%), lead to classify this kerogen

Permanyer, A.; Baranger, R.; Lugardon, B., 1994. Oil shale characterization

as type I-S to II-S

in Messinian pre-evaporitic sediments from the Lorca basin (south-east

Spain). Bull.Centres Rech. Explor.-Prod. Elf Aquitaine, 18, 135-149.

The geochemistry results show an organic carbon content up to

20%; Hydrogen Index values between 400 and 900 mg HC/g
of TOC; and oil potential reaching 150 to 183 mg HC/g of rock.
Immaturity of organic matter is indicated by Tmax values varying
from 380 to 420C (Fig. 3).

Permanyer, A.; Marn, P.; Gibert, L., 2013. Pre-evaporitic Messinian

Sediments: a New Challenge for Oil Exploration in the Mediterranean
Basin. AAPG Search and Discovery Article #901612013 AAPG European

Geochemical evaluation of Outcrops
from Tapajs River Valley, Southern Edge
of The Amazonas Basin
Marcus F. Tenrioa,b, Silvana M. Barbantia, Luiz Landaub

Regional Conference, Barcelona, Spain, 8-10 April 2013.

a Integrated Petroleum Expertise Company, 22280-030, Rio de

Janeiro, RJ, Brazil
b Universidade Federal do Rio de Janeiro, COPPE, 21941-909,
Rio de Janeiro, RJ, Brazil

Figure 1.Totalorganic carbon content ofthe outcrop samples.

Copyright 2014, ALAGO.

The saturated hydrocarbon fractions show distribution of shortchain n-alkanes, indicatingmainly algalcontribution. n-Alkanes are
in the range of C12 to C36 with an odd-even predominance. These
features are associated with marine environments and indicate a
possible contribution of marine algae and phytoplankton to the
original sedimentary environment (Mello et al., 1988).

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Amazonas basin has been the target ofgeological investigationssince
the 1960s, aiming at thediscovery ofpetroleum systemsfor the
exploitation ofliquid and gaseous hydrocarbons. The generation
ofhydrocarbonswas initiallydetectedby analysis ofwell testsand
potential of hydrocarbon generation, unfortunately with subcommercial character. Aiming ata better understandingof the
Amazonas basin, outcrop samples from the BarreirinhaFormation,
which is considered the main source rock within the basin, were
collected and analyzed toassess the hydrocarbon generative
potential and to determine origin and thermal maturity by using
screening analyses, such as total organic carbon and pyrolysis, as
well as biomarker analysis.

Figure 4. Mass fragmentogram (ion 71) showing n-alkanes and isoprenoids.

Note the odd members predominance between n-C23 and n-C33.

Euxinic environment is supported by the presence of sulfur

compounds and low values of Pr/Ph ratio. The predominance of
odd n-alkanes between n-C23 and n-C33 could be related to a
bacterial origin of the organic matter, which is in agreement with
microscopical observations (Figs. 4 & 5).

Twenty outcrop samples from Amazonas basin were selected to
determine their generative potential, origin and thermal maturity. To
assess the generative potential total organic carbon and pyrolysis
analyses were performed. The samples were extracted using Soxhlet
apparatus and the organic extracts were fractionated by liquid
chromatography into saturate and aromatic hydrocarbons, and polar
compounds. The percentage of hydrocarbon fractions can assist in
the interpretation of the thermal evolution and the type of organic
material of rock samples (Tissot & Welte, 1984). Thesaturated
hydrocarbonfractionswere analyzed by gas chromatography
usingAgilent7890AGCequipmentwith a flame ionization detector,
FID. The branched and cyclichydrocarbonfractionswereanalyzed
bygas chromatography coupled tomass spectrometry(GC-MS)
using anAgilent Technologies7890Ninstrumentcoupled with amass
selective detectorAgilent5975C, and some of those fractions were
selected for a more detailed biomarker analysis by MRM-GC-MS
using a high resolution mass spectrometer, DFS-Thermo Scientific.

Figure 5. Mass fragmentograms (ions 184, 198 and 212) of aromatic

fraction showing abundance of sulfur compounds. (BT: dibenzothiophenes;
MDBT: methyl-dibenzothiophenes).

The Tortonian and Messinian deposits from the marginal
Mediterranean basins show high oil potential but did not reach
sufficient burial to produce oil. In an offshore situation, the presence
of similar deposits might be expected. There, these organic rich
shales might be covered by up to ~3,000-4,000 m of sediments,

Overall, low values for hopanes/steranes ratio (< 4) indicate

deposition of marine organic matter with higher contribution
of planktonic organisms, whereas high values (> 7) indicate
deposition of terrestrial and/or microbial reworked organic matter.
Therefore, the molecular parameters, such as hopanes/steranes,
ratio, relative abundance of steranes, and presence of C30steranes corroborate a marine origin for these samples (Moldowan
et al., 1990). The samples reveal a predominance of C29-steranes
and concentration of C30-steranes in the range of 90 to 300 ppm
(Figure 2).
The maturity parameters based on biomarkers, such as 20S/
(20S+20R) and /(+) C29-steranes, Ts/(Ts+Tm), 22S/
(22S+22R) C32-hopanes, and concentration of biomarkers,
indicate these samples are at immature stage of thermal evolution.

Figure 2.Concentration (ppm)of steranes by MRM-GC-MS.

formed by detrital deposits derived from the Messinian subaerial

exposure, Messinian evaporites and Pliocene sediments.

Results and Discussion


The possibility of finding source rock deposits below the sealing

Total organic carbon content is in the range of 3.7 to 6.6 % indicating

the samples are organic carbon rich and have therequiredcontent
of carbon for pyrolysis analysis (Figure 1). Based onpyrolysis
data (hydrogen index, Tmax andproduction rate) the samples are
considered thermallyimmature.

The study of outcrops is important because it allows direct

observation of the sediment section, enabling sampling for
geochemical analyzes and thus allowing its chemical and
geochemical characterization, in addition to dating and verifying
the fossil content.

Messinian Salt associated with conditions of high burial and

heat flow provides an exploration challenge in the Western
Mediterranean offshore.



The outcrop samples from Barreirinha Formation analyzed in this

study show high organic carbon content, with values ranging from
3.7 to 6.6 %. The organic matter was classified as type II reaching
hydrogen index (HI) with values between 326 to 444 mg HC/g
TOC that corresponds predominantly to the biomass of marine
origin. The pyrolysis data indicate the outcrop samples exhibited
excellent generative potential but are in the immature stage of
thermal evolution. These characteristics are associated with marine
environments with contribution of phytoplankton and seaweed.
The distribution of n-alkanes, hopanes/steranes ratio, relative
abundance of C27, C28, C29 and C30-steranes infer that the
organic matter present in Barreirinha Formation is predominantly



Copyright 2014, ALAGO.

The authors thank Integrated Petroleum Expertise Company,

IPEXco, and Universidade Federal do Rio de Janeiro, COPPE.

This paper was selected for presentation by an ALAGO Scientific Committee following



Tenrio, M.F., 2013.Avaliao do Potencial Gerador e Caracterizao de

The Amazon basin has been studied since the beginning of the
last century. The organic geochemical investigations carried out
since 1970 haves shown that oil and gas generation occurred
in the basin, but few papers have been published related to
biomarker characterization of the Upper Devonian section,
where the main source rock interval is included. The new data
presented here provide elements which may help understand the
organic geochemical variations due to a change in depositional
environment conditions during Upper Devonian time in the whole
Amazonas Basin.

Biomarker Characterization
Of Barreirinha And Curiri Formations,
Upper Devonian Of Amazonas Basin

GC and GC-MS trace characterized by a lower proportion of low

molecular weight n-alkanes (<20) and high hopanes/steranes ratio
(Table 01). Between the terpanes, a predominance of C19 and C20
tricyclic terpanes can be observed, as well as a series of C24, C25
and C26 des-e tetracyclic terpanes and high C27(Tm)/C30 hopane
ratio, all pointing to a terrestrial organic matter input (Fig.01).

The authors thank Capes, CNPq, FAPERJ; ANP/UERJ/PRH-17 for
financial support.

and SIMONEIT, B. R. T. (1989) Organic geochemistry of geographically

Pedro H. V. Garcia*, Ren Rodrigues

a Universidade do Estado do Rio de Janeiro, Rio de Janeiro, RJ,

As can be in the Table 01, the Urari Member of Barreirinha

Formation shows a better biomarker correlation to the Curiri
Formation, which suggests different lithostratigraphic position for it.

unrelated Tasmanites. 14th International Meeting on Organic Geochemistry,

Paris, September 18-22, 1989, Abstract No. 189
CUNHA, P. R. C., MELO, J. H. G., SILVA, O. B. 2007. Bacia do Amazonas,

As can be seen in Table 01, the Urari Member of Barreirinha

Formation shows a better biomarker correlation to the Curiri
Formation, which suggests a different lithostratigraphic position for it.

Boletim de Geocincias da Petrobrs. Rio de Janeiro, Brasil, v. 15, n.2, p.


review of information contained in an abstract submitted by the author(s).

Biomarcadores em Afloramentos Rochosos do Vale do Rio Tapajs, Borda

Sul da Bacia do Amazonas. Master thesis, Universidade Federal do Rio de
Janeiro, pp. 173.
Mello, M.R., 1988, Geochemical and Molecular Studies of the Depositional
Environments of Source Rocks and their Derived Oils from the Brazilian
Marginal Basins. Ph.D., University of Bristol, pp. 240.
Moldowan, J.M.; Fago F.J.; Lee C.Y.; et al. (1990) Sedimentary
24-n-propylcholestanes, molecular fossils diagnostic of marine algae.

Table 01: T: tricyclic terpanes; Te: tetracyclic terpanes; H: hopanes; Tm:

trisnorhopane; Hop/Est: hopane/sterane ratio; nC17/nC27: ratio of low

The Barreirinha Formation encompasses three shaly members

deposited in a normal marine environment: the radioactive shales
of Lower Abacaxis Member, the non-radioactive shales of the
Urubus Member and the non-radioactive and high resistivity
shales of the Upper Urari Member. On the other hand, the Curiri
Formation is mostly composed of diamectite with sandstone and
shales interbedded (Cunha et al. 2007).

Science 247, 309-312.

Tissot, B.P. & Welte, D.H., 1984. Petroleum formation and occurrence, 2nd
ed., Springer-Verlag, Berlin, pp. 699.

and higher molecular weight of n-alkanes.

The Bulk geochemical analyses were carried out in 64 samples
of an approximately 230m thick Barreirinha and Curiri Formations
derived from one well drilled by Petrobras. Based on the bulk
geochemical data, 7 samples were chosen for organic extraction,
liquid chromatography and biomarker analysis.
All geochemical analyses were performed in the Chemical
Stratigraphy and Organic Geochemistry
Laboratory of the State University of Rio de Janeiro using the
following equipment: LECO SC 632 for TOC and S analysis,
Rock-Eval 6 for pyrolysis analysis and an Agilent system 6890 GC
coupled to a 5977 Mass Detector and 7000 GC-MS triple quad for
biomarker analysis.

Results and Discussion

The radioactive shales of Barreirinha Formation record a GC and
GC-MS trace characterized by a higher relative proportion of low
molecular weight n-alkanes (<20), low hopanes/steranes ratio and
higher tricyclic/pentacyclic terpanes ratio suggesting a normal
marine environment and an algal input (probably Tasmanites,
Aquino Neto et al., 1989) to organic matter composition (Table 01).
On the other hand, the diamectites of Curiri Formation display a

Figure 01. Mass chromatogram of Curiri Formation at the depth of 1189,4

m, showing the series of tetracyclic terpanes from 24 to 26 of carbon


Evaluation of hydrocarbon generation
potential of the Cretaceous sequence in the
northern sector of the Middle Magdalena
Valley Basin, Colombia
Robert Mrquez1*, Maria A. Martnez2 and Tatiana Juliao1
1. Ecopetrol S.A., ICP, Piedecuesta Colombia
2. Ecopetrol S.A., VEX-GEE, Bogot Colombia


Mora, C., Cordoba F, Luna O., Sarmiento L.F., Rangel A., Giraldo B.N.,

The geochemical characterization of the samples was done by

Total Organic Carbon (TOC),Rock- Eval pyrolysis and organic
petrography analyses. Based on the results of these analyzes,
samples were selected for accelerated extraction using an ASE350 equipment. The recovered extracts were fractionated into
their saturated, aromatics, resins and asphaltenescomponents
by open liquid chromatography technique, using activated silica
packed column as the stationary phase, and organic solvents as
mobile phase. Solvent free extracts were analyzed by whole oil gas
chromatography. The saturated and aromatic fractions were then
analyzed by gas chromatography coupled to mass spectrometer
(GC-MS) with an electron impact ionizationsystem.

Bartels H., Reyes J.P. 1996, Petroleum Systems of the Middle Magdalena
Valley, Colombia: AAPG Boletn, v.80/8, Association Round Table, p.1316.

This paper was selected for presentation by an ALAGO Scientific

Committee following review of information contained in an abstract
submitted by the author(s)

The analysis of rock samples for organic geochemistry techniques
allows to describe the quantity, quality and thermal maturity
of the rocks, and thus establish whether they reached the right
conditions (temperature, pressure, amount of organic matter,
etc.) for the effective generation of hydrocarbons. Rock samples
(cuttings) from ten wells located in the northern sector of the Middle
Magdalena Valley Basin (MMVB) were selected in order to perform
a geochemical characterization of the Cretaceous sequence
hydrocarbon generating potential (Fig. 1).

molecular fossils in petroleum and ancient sediments. New Jersey, Prentice

Ramn, J.,Dzou, L, Giraldo, B., 1997. Geochemical evaluation of the Middle
Magdalena Basin, Colombia.CienciaTecnologa y Futuro 1 (3), 47-66.
Ramn, J., Dzou, L., 1999. Petroleum geochemistry of the Middle
Magdalena Valley, Colombia. Organic Geochemistry 30, 249-266.

Results and Discussion

Mora, C., Cordoba, F., Luna, O., Reyes, J.P., 1996, Oil potential of the

The highest organic contents are found in Tablazoand La

Lunaformations, with TOC values between 2 and 5%, and 4 to
8%, respectively. Umir Formationalso has a high organic content,
with TOC values between 6 and 50%, due to the presence of coal
seams. TOC values forTablazoFm.are overestimated in some cases
by the presence of solid bitumen. Rock Eval pyrolysis and organic
petrography data suggests the predominance of type II kerogen
(mainly in La Luna Fm.), with mixtures of type II and III kerogenin
several intervals of Simit, Tablazo, Paja and Rosablancaformations.

Cretacicmegasequence and associated oil families in the Middle Magdalena

The best hydrocarbons source rock (TOC,kerogen type, and
maturity) characteristics are found in La Luna (Galembo and
SaladaMembers) and Tablazoformations. Other potential source
rock intervals within the Cretaceous sequence would have limited
conditions to generate hydrocarbons.The presence of abundant
solid bitumen in TablazoFm. suggests that part of the hydrocarbon
generated could not be expelled and migrate, and subsequently
was transformed into gas and solid bitumen by thermal cracking.
Migrated and/or in situhydrocarbons are identified in rock samples
ofLa Luna, Rosablanca, andPaja formations. La Luna and Tablazo
formations are in the hydrocarbon generation windowin this part of
the basin, with varying levels of maturity.This explains the differences
in some physical properties (API, viscosity, etc.) of the hydrocarbons
produced in the basin. La Luna and Tablazoformations also
present good conditions as potential hydrocarbon reservoir rocks
in situ and/or migrated (shale oil and shale gas naturally fractured
or combinations thereof).
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

Tissot, B.P., Welte, D.H., 1984. Petroleum formation and occurrence. 2 ed.
New York, Springer.

review of information contained in an abstract submitted by the author(s).

During the Early Toarcian enhanced organic carbon accumulation
of trans-regional extent led to deposition of prolific hydrocarbon
source rocks on the NW-shelf of the Tetyhs Ocean during the socalled Toarcian Oceanic Anoxic Event (T-OAE). Comparable source
rocks have been deposited in other regions of the World, e.g. the
Gordondale Fm. of the Western Canada, the Los Molles Fm. of
the Neuquen Basin Argentina, or the Tyumen Fm. of Northwestern
On the NW-shelf of the Tethys Ocean the Toarcian source rocks
have been studied in substantial detail by sedimentology and
sequence stratigraphy, accompanied by bulk, isotope and
molecular geochemistry. Thus a framework of conditions governing
sedimentation of organic matter exists. We have extended existing
knowledge by investigating cyclicity in the depositional regime and
hence in the amount and composition of organic matter in a source
rock of the NW-Paris Basin.

Crdoba, F., Malagn, F., Valentn, D., 2001. Evaluacin del potencial


Agencia Nacional de Hidrocarburos (ANH), 2007. Colombian Sedimentary
Basins: Nomenclature, Boundaries and Petroleum Geology, a New

generador de hidrocarburos de las formaciones Rosablanca, Paja y

Tablazo, cuenca Valle Medio del Magdalena, Colombia. Informe interno
Ecopetrol, Bogot.
Mora, A.R., Naranjo, J.F., Moreno, N.R., Gmez, P.D., Sierra, J.M.
(2009). Correlaciones y Mapas de Paleo-Ambientes en el Valle Medio
del Magdalena. ECOPETROL- ICP. Unidad de Investigacin. Empresa

a Organic Geochemistry Unit, IfG, Christian-Albrechts-University,

Kiel, Germany
b Department of Geoscience, University of Calgary, Calgary,
c WA-OIGC, Curtin University, Perth, Australia

Proposal. Informe interno Ecopetrol, Bogot.

The authors thank Ecopetrol for support our participation in the XIV
Latin American Congress on Organic Geochemistry.

Basin (ANH, 2007).

Valley: V CongresoLatinoamericano de Geoqumica Orgnica, Cancn, 105 p.

Lorenz Schwark a,c Wolfgang Rbsama, Bernhard Mayerb

After establishing the cyclicity, the temporal constraints determining

cycle lengths and frequencies were calculated and environmental
factors driving the cyclicity identified. The sub-basin morphology and
the supra-regional paleogeography (the Viking Corridor connecting
the Tethys with the Boreal Ocean) were found to control the degree
of basin restriction, the exchange of polar, low salinity, nutrientenriched surface waters with equatorial, high salinity nutrientdeprived bottom waters. Water column salinity stratification was
extreme and thus stabilized bottom water anoxia/euxinia, hence
leading to excellent preservation of organic matter. Fluctuations
in redox conditions in dependence of orbitally controlled sealevel have been determined by a wide array of different isotopic,
elemental and molecular proxies.


Figure 1. Generalized stratigraphic colum of the Middle Magdalena Valley

Orbital Controls On Lower Jurassic

Source Rock Deposition

Peters, K.E., Moldowan, J.M., 1993. The biomarker guide: Interpreting

Rangel, A., Giraldo, B., Magoon, L., Sarmiento, L. F., Bartels, H.,



contratista UT EOS, DTH.

Our paleofacies reconstruction attempt requires a high-resolution

approach realized using continuous scanning techniques (spectral
XRF, colour and magnetic susceptibility) on a drill core with full core
recovery over the entire study interval of almost 40 m. Continuous
records were complemented by analysis of a large number (>600)
of discrete samples for determination of molecular, isotopic and
elemental proxies. The isotope proxies included 13C and 13O

on carbonates, 13C 15N on organic matter, 34S on sulfides

and 98Mo on sediment to determine water and organic matter
sources, microbial processes and organic matter diagenesis.
Organic matter quality and abundance was assessed by Rock
Eval, and biomarker studies (n= 150).

This indicates a drawdown of certain trace elements caused by

diminished connectivity to the open ocean, where commonly Mo is
not a biolimited trace element.

The deposition of source rocks, commonly assumed to reflect
monotonous sedimentary regimes and organic facies associations,
has been shown to be far more complex than anticipated.
Discovery of rhythmic variations in organic matter qualityrequires
ultra-high resolution (up to <1 cm sample spacing) analytical
approaches, previously not applied in source rock characterization.
Interpretation of cyclic variations in organic matter quality shed
light on the key factors controlling source rock quality: i) organic
productivity stimulated by nutrient supply via fresh surface waters
and ii) exceptional water column stratification stabilized by
hyposaline surface water enforcing the establishment of stable
bottom water anoxia/euxinia causing excellent organic matter
preservation. Orbitally-induced changes in organic matter quality
occurred in the 20, 40 and 100 ka year frequency band. Given a
total sedimentation time of the Toarcian black shale of app. 1.5 Ma,
up to 15 Obliquity cycles may occur.

Results and Discussion

This work investigates 30 m of Upper Pliensbachian and Lower
Toarcian organic rich strata (TOC up to 12 wt.%) from the Lorraine
Basin (NE-Paris Basin), covering the entire T-OAE. High-resolution
bulk geochemistry (>650 samples) reveals strong evidences
for a significant cyclicityin organic matter enrichment. Rock Eval
Pyrolysis confirms a primary marine origin for organic matter from
the serpentinum zone (Kerogen Type II), whereby organic matter
from the tenuicostatumzone and from the Domerian is of mixed
origin (Type II/III). Fluctuations in water masses led to massive
salinity changes in surface waters, expressed in carbonate 18Ovalues and in molecular salinity proxies based on distribution of
alkylated chromans. The triggering mechanism for southward
progradation of hyposaline cold surface waters is seen in landlocked and sea-ice melting in Polar Regions controlled by obliquity.

Review on the CBM potential of Permian Coals
from the Paran Basin, Brazil Based on Results
from exploration wells in Rio Grande do Sul
And Santa Catarina

P*., 1Levandowski, J., 1Oliveira, J., 1Simo, G.,

1Kalkreuth, W., 2Holz, M., 3Prissang, R., 4Krooss, 4Weniger, P.
1 Instituto de Geocincias, UFRGS, Porto Alegre, RS
2 Instituto de Geocincias, UFBA
3 Institut fuer Geologische Wissenschaften, FU Berlin, Germany
4 Institute of Geology and Geochemistry of Petroleum and Coal,
RWTH Aachen, Germany

Overall restriction of the Lorraine sub-basin is evidenced by

exceptionally low TOC/Mo-ratios, typical for the NW-Tethys shelf.

Copyright 2014, ALAGO.

This paper was selected for presentation by an ALAGO Scientific Committee following
review of information contained in an abstract submitted by the author(s).

Economically important coal deposits occur in the southern part
of the ParanBasin (Fig. 1) in the provinces of Rio Grande do Sul
(RS) and Santa Catarina (SC). Based on coal rank, coal distribution
and depth of the coal seams the Santa Terezinha and Chico-Lom
coalfields (RS) and the Southern Santa Catarina Coalfield (SC) have
been the target for CBM exploration since 2007 (Fig. 1).

a temperature-controlled box, a process taking another 5 to 10

The temperature in the box containing the canisters was
corresponding tothe estimated reservoir temperature at the depth,
where the coals and carbonaceousshales had been collected. This
temperature level was based on a geothermal gradientdetermined
from the bottom hole temperature of a nearby petroleum exploration
welland the average annual temperature of the area.
The measurement of desorbed gas volumes started immediately
after the canisterswere closed, following the procedure as outlined
by Mavor and Nelson (1997). Themeasurement of desorbed gas is
a simple technique, by which the canisters areperiodically opened
and the volume of gas liberated from the coal is determined via
aconnection to a water-filled burette, from which the volume (cm)
replacedby the gas is read off a scale. Each time a measurement
was taken, the ambientpressure and temperature were also
recorded and used for calculation of the final valueof the desorbed
gas volume.

Results and Discussion

The first CBM exploration well in Brazil was drilled in the Santa
Terezinha Coalfield in 2007, and encountered 12 coal seams
at a depth between 606.35 638.22 m, with a cumulative coal
thickness of 7.41 m (Table 1). Desorbed gas values were found
to range between 0.32 1.63 cm3/g. Results from geological 3D
modeling suggest a total of > 5 Billion m3 gas associated with the
coal seams of the Santa Terezinha coalfield (Kalkreuth et al, 2013).

Table 1. Well identification, number of seams encountered, cumulative coal

thickness, depth range, rank, vitrinite reflectance range and total desorbed
gas volumes for the wells drilled in the Santa Terezinha, Chico-Lom and
South Santa Catarina coalfields.
In the Chico-Lom Coalfield the CBM exploration well was drilled in 2013,
and encountered 9 coal seams at a depth between 386.95 - 429,27 m, with
a cumulative coal thickness of 11.46 m (Table 1). The coal-bearing sequence
has been altered severely by a 10 m thick volcanic intrusion transforming
coal seams near the contact zone into anthracite and semi-coke. Desorbed
gas values were found to range between nil 0.53 cm3/g. Results from
geological 3D modeling suggest a total of > 1.3 Billion m3 gas associated
Figure 1. Map showing the distribution of coal deposits in RS and SC and
the locations of the CBM wells drilled in the Santa Terezinha, Chico-Lom
and South Santa Catarina coalfields

Figure 1.Variation in Toarcian source rock quality as governed by surface water mixing and intensity of water column stratification [A*-values derived from
L*a*b-colour space, HHI= homohopene index]. Note high-frequency oscillations in all parameters determined. Short-lived oxygenation events, associated with
break-down of water column stratification are highlighted in grey. These water column mixing events are initiated by a decline in boreal hyposaline water supply
and sea level drop. Water mixing is enhanced, oxygen supply to deep waters increases to an extent where episodic bioturbationoccurs (e.g. by massive storm
events) and trace element (Fe/S; V/Cr) or biomarker (HHI) proxies indicate oxygenation events. TOC and HI values are significantly reduced in these intervals,
thus hydrocarbon generation potential of the entire source rock is significantly lowered by extent and frequency of these short-lived events.

The core samples of coal and carbonaceous shale were collected

in 2 or 3 mintervals using a wireline coring device. In this technique
the core samples are broughtrapidly to surface, minimizing the loss
of gas during retrieval.At surface the core was cut into intervals of
36 cm length, corresponding to the sizeof the canisters. The core
was then put into the canisters, which were closed and placedinto

with the coal seams of the Chico-Lom coalfield (Levandowski, 2013).

In the South Santa Catarina Coalfield three coal exploration wells

were accompanied to determine the gas contents associated
with the seams. The drilling was carried out from 2011 to 2013,
and encountered 3 to 7 coal seams at a depth between 166.14
339.83 m, with a cumulative coal thickness ranging from 5.38 to
6.35 m (Table 1). Desorbed gas values were found to be very low
ranging between nil 0.11 cm3/g. The low gas values associated
with the coal seams are most likely related to the fact that most
if not all of the generated gas has been lost due to the relatively
shallow depth of the coal seams (Lourenzi, 2011, 2013).


This study received financial support from ElPaso/Petrobras

and Pronex, CNPq/ Fapergs Project 10/0025-9. The authors
also like to thank Carbonfera Criciuma and Eng. Cludio Zilli
(SATC Associao Beneficiente da Indstria Carbonfera de
Santa Catarina) for logistical support to collect coal samples for
gas desorption measurements. P. Lourenzi and J. Levandowski
acknowledge financial support in form of student grants by CNPq
during their M.Sc and Ph.D. program, respectively.

Pozo D-129 Formation, new shale play? A
case study in an oil field on the fold belt of
GolfoSan Jorge Basin, Argentina
Martin E. Fasolaa*, Yanina A. Basilea
a YPF S.A., MacachaGuemes 515, CABA Argentina.CP 1106



Kalkreuth,W.; Holz, M.; Levandowski, J.; Kern, M.; Casagrande, J.; Weniger,
P and Krooss, B. 2013. The coalbed methane (CBM) potential and CO2

Copyright 2014, ALAGO.

storage capacity of the Santa Terezinha Coalfield, Paran Basin, Brazil 3D

This paper was selected for presentation by an ALAGO Scientific Committee following

modelling, and coal and carbonaceous shale characteristics and related

review of information contained in an abstract submitted by the author(s).

desorption and adsorption capacities in samples from exploration Borehole

Experimental and Workflows

In order to evaluate this source rock as a shale reservoir, 3400 rock
samples from 200 wells were analysed. Data gathered includeTotal
Organic Carbon (%TOC) by acidization and LECO, Programmed
Pyrolysis by Rock Eval and different organic petrography techniques
(vitrinite reflectance (%Ro), visual kerogen, thermal alteration index
and maceralanalysis).
In order to predict the fluid type to be produced from the shales,
mud gas from some conventional wells were interpreted and
samples extracted from cores and cutting were analysedthrough
GC thermal extract, High Resolution Gas Chromatography, MPLC
(for saturates, aromatic, resins and asphaltenes), Saturate and
Aromatic Biomarkers by GCMS and Stable Carbon Isotopes in
Saturate and Aromatics Fraction.

CBM001-ST-RS. Energy Exploration & Exploitation. Vol 31, number 4.



Hydrocarbons associated with unconventional reservoirs have a

continuous, regional-scale distribution and are independent from
trap type.Shales are one of the Earths most common sedimentary
rocks. It is a fine-grain rock composed mainly of clay flakes and
tiny fragments of other minerals, especially quartz and calcite.
Shale can be a gas/oil reservoir, but only formations with certain
characteristics (source rock, seal and reservoir) are viable for

Also, oil productionsamples were collected from conventional

wells(oil sands reservoirinterbeddedwithin the organic shales) and
studied following the same analytical program than the extracted
samples from rocks. Additionally, gas production and mud gas
samples were analysed by GC Compositional Analysis and Carbon
and Deuterium Isotope Analysis [13C/12C (13C) and 2H/1H
(D)]on the gas components.

According to the US Energy Information Administration, Argentina

holds the second largest recoverable shale gas reserves worldwide
and the fourth largest recoverable shale oil reserves worldwide
(Kuuskraa et al, 2013). In 2010, YPF started a complete evaluation
and data acquisition from the different sources rock in Argentina,
among them the shales of the Golfo San Jorge Basin.

Most of the analytical results were used to calibrate the basin

modelling in 1 & 3 dimensions and finally, different geochemical
maps were generated to determine sweet spots in shale (Figure 1).

Levandowski, J. 2013. Caractersticas Petrogrficas e Geoqumicas das

camadas de carvo do poo CBM 001-CL-RS, Jazida Chico-Lom, e sua
relao com coalbed methane associado. Tese de doutorado. Instituto de
Geocincias, Universidade Federal do Rio Grande do Sul.
Lourenzi, P. 2011. Avaliao do Potencial de coalbed methane (gs natural)
das camadas de carvo da Formao Rio Bonito, Maracaj-SC, Bacia
do Paran. Trabalho de concluso de curso. Instituto de Geocincias,
Universidade Federal do Rio Grande do Sul.
Lourenzi, P. 2013. O Potencial de gerao CBM (coalbed methane)
na Jazida Sul Catarinense da Bacia do Paran, Brasil: caractersticas
petrogrficas e qumicas das camadas Barro Branco, Irapu e Bonito.

This rift to sag basin is located in southern Argentina between

the Somoncuraand Deseadocratons in the north and south
respectively.It trends roughly east-west between 45-47 south
latitude (Fitzgerald et al, 1990). The study area is located in the
western part of the basin (Figure 1). The main source rock in the
basin is the Pozo D-129 Formation, responsible for most part of
the oil production in the basin which to date has produced more
than600 x 106 m3 (3800 x 106 barrels) of oil and 70.3 x 109 m3
(2.5tcf) of gas.It is a lower Cretaceous lacustrine unit with high
pyroclastic participation and the maximum thickness reaches up
to 1500 m in the central area of thebasin.Based on lithological and
geochemical variations, three main sections have been recognized,
where the upper section shows the highest TOC and HI values with
a type I kerogen (Basile y Utg, 2011).

Dissertao de Mestrado. Instituto de Geocincias, Universidade Federal

do Rio Grande do Sul.
Mavor M. and Nelson C.R., 1997. Coalbed reservoir gas-in-place analysis.
GRI-97/0263, Gas Research Institute, Chicago, Illinois, USA. pp. 183.

The present work aims to introduce a complete geochemical

characterization and analysis of the upper section of PozoD-129
Formation as a shale playin anoil field on the San Bernardo fold
beltof GolfoSan Jorge Basin.

Figure1.Location map, wells and maturity trend.


play cut off parameters(%TOC, thickness, depth, type of kerogen

and rock mineralogy). However, the maturity, as a key parameter,
did not reach the minimum value to be considered a shale reservoir.
Due to this interpretation and the excellent productionresults
obtained from conventional wells, Pozo D-129 formation was
classified as a hybrid shale oil play.
As a follow-up of this research, one well was stimulated in
unconventional way to evaluate thePozo D-129 formation as a
hybrid shale oil reservoirand the results showed a very good match
between the geochemical studies and the type of production fluids.

Results and Discussion

In the study area, the upper section of Pozo D-129 formation has
a variable thickness from 100 to 250 meters and an average depth
of 1800 meters.
The organic richness ranged from 0.5 to 5.5% of actual TOC with
averages close to 2.5-2.8%, representing a very good source
rock (Figure 2). The S1 peak from pyrolysis showed the presence
of free hydrocarbon(S1 values are higher than 1 mg HC/gr rock)
and the S2 peaks reach values of 20-25 mg HC/gr rock, showing
excellent petroleum potential.The S1/TOC parameter also shows
the presence of producible hydrocarbons.

Figure 2.Geochemical log and geochemical graphs from oil and extracted

The authors thank YPF S.Ato give permission to present this
abstract; Ricardo Clavijo, Ignacio Brisson, SilvanaUtg, Pedro
Kressand Virginia Martinez Cal for their valuable comments.

Basile y Utg, 2011. Caracterizacin de la Fm. Pozo D-129, sus
condiciones generadoras y su potencialidad como un reservorio no

Maturity fromvitrinite reflectance varies from top to base between

0.56% and 0.74%, the Tmaxvalues from pyrolysis did not show
changes in the entire analyzed interval and the hydrogen indexes
(HI) decrease from top to baseand the high values measured on the
topsamples (up to 800 mg HC/gr TOC) are related to the maturity
of the rock (immature to low mature).

convencional. Informe Interno YPF.

Fitzgerald, M., Mitchum, R., Uliana, M. and Biddle, K.,1990. Evolutionofthe
San Jorge Basin, Argentina. The American AssociationofPetroleumGeologist
Bulletin, V. 74, No. 6, p. 879-920.
Kuuskraa, V.L., Stevens, S.H., andMoodhe, K.: TechnicallyRecoverable-

No match could be observed between the compositional fractions

and maturity parameter obtained from the extracted samples
from rocks and production oil. Extracted samples correspond to
medium and early mature oils, whereas the production samples
show a very high saturated hydrocarbons phase and high maturity
oils.Gas production samples showed a very rich gas composition
and an equivalent maturity from isotopes around 1.2 %VRE for C1
and a 0.9% VRE for C2. These different isotope behaviors for C1
and C2 gases were associated to different sources rocks or the
same source rock with different maturity degrees.

ShaleOilandShaleGasResources: AnAssessmentof 137 ShaleFormations in

41Countries Outsidethe United States, U.S.A. Energy InformationAdministrationReport, 2013.

In conclusion, the Pozo D-129 Formationshowed adequate shale



OI) and biomarker identification, a specific workflow was built up

as follows:

Paleoenvironmental control on primary fluids

characteristics of lacustrine source rocks, the
example of the Autun Basin (France)

Hydrocarbon profiles of total extracts were first obtained by gaschromatography coupled to a mass spectrometer (GC-MS).

Sylvain Garela,b*,Franoise Beharb, Olivier Brouckeb, Matthieu

Buissona, Johann Schnydera ,Franois Baudina

Kerogens were isolated by specific treatment (Durand and Nicaise,

1980) and analyzed by Rock-Eval 6, their extracts by GC-MS, and
submitted to elemental analyses to obtain kerogens characteristics
and biomarker profiles

a UPMC Univ. Paris 06 et CNRS, UMR 7193 ISTeP, 4 place Jussieu,

75005 Paris, France.
b Total Exploration & Production Exploration division, 2 place
Jean Millier La Dfense 6, 92078 Paris La Dfense Cedex, France.

Then, kerogens were heated in gold tubes reactor at 325C during

72 h. This T/t conditions were selected to reach a significant
Transformation Ration (>50 %) with a limitation of secondary
cracking reactions. The mass-balances were performed on
pyrolysis products in order to determine the proportion of the light
fraction and the total hydrocarbon profile.

Copyright 2014, ALAGO.

changes, switching from the dominance of amorphous organic

matter of aquatic origin to the dominance of phytoclasts (i.e.
derived from higher plants).
These preliminary results tend to indicate that primary-fluid
characteristics are controlled by paleoenvironmental variations,
such as water table level changes, along with paleoclimatic
modifications during the Autunian. The same approach will be
applied to the Recncavo Basin.

The authors thank IFPen (French Petroleum Institute) for kerogen
preparation and Total for financial support.

Durand, B., Nicaise, G., 1980. Procedure for kerogen isolation. In Durand,

Finally, palynofacies observations along with GC-MS analyses were

systematically performed for paleoenvironmental reconstructions.

review of information contained in an abstract submitted by the author(s).

TassaR. MENEZESa*, Regina BINOTTOa, Juliana A. IEMINIa, Jorge

a Petrobras Research & Development Center, Division of
b Petrobras Argentina S.A.
Copyright 2014, ALAGO.
This paper was selected for presentation by an ALAGO Scientific Committee following

Lebedel, V., 2009. Etude sdimentologique des variations du potentiel


ptroligne des schistes bitumineux de lAutunien du bassin dAutun.

First experiences on unconventional shale-oils in USA focused

mainly on Type II organic matter (OM) such as in the Eagle Ford
Formation. Key parameters to define a sweet spot are volume in
place and quality: typically, it