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APPLIED PETROLEUM

GEOLOGY AND
GEOCHEMISTRY FOR
THERMOGENIC SHALE-
GAS EVALUATION
A Primer for Scientists and Engineers Focused on
Marcellus Exploration and Development in the
Appalachian Basin

Christopher D. Laughrey
Weatherford Laboratories, Golden, Colorado
V2. November 2009
Introductions, Acknowledgements,
and Orientation

Photo courtesy of Gary Lash


WORKSHOP TOPICS
Introductions and Objectives of shale-gas
orientation reservoir assessment
Natural gas: origins and Petrology and
characteristics geochemistry of shale
Conventional versus and shale-gas:
unconventional petroleum analytical programs and
reservoirs interpretations
Characteristics of The Marcellus Shale:
unconventional shale-gas Overview and examples
reservoirs Other Devonian,
Ordovician, and Mesozoic
thermogenic shale-gas
plays
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Total Organic Carbon Inorganic petrography:
(TOC): Optical mineralogy
Definitions
Measurement Scanning electron
Applications microscopy (SEM) and
energy dispersive
Organic petrography: spectroscopy (EDS)
Reflectance and
fluorescence microscopy X-ray diffraction
Kerogen types and Applications
evolution
Vitrinite reflectance (Ro)
Hydrocarbon types and
thermal maturation
Applications
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Rock-Eval Pyrolysis: Biomarkers
Definitions Natural gas isotope
Quantity of organic matter geochemistry:
Quality or type of organic Hydrocarbons
matter Non-hydrocarbons
Thermal maturation of
Noble gases
organic matter
Applications
Problems and limitations
Recent advances
Applications
NATURAL GAS: ORIGINS AND
CHARACTERISTICS
Schematic of Oil and Gas
Generation
Primary
Organic Matter Bitumen Cracking
Oil
(Kerogen) Secondary
Cracking

CO2 Wet
Gas
Sources of Gas Biodegradation
Dry Gas
1. Kerogen cracking
2. Oil Cracking
Dead Carbon
3. Microbial processes

Modified from Jarvie et al., 2007


Natural gas is the gaseous phase
of petroleum.
Typical reservoir gas: Typical reservoir gas:
Hydrocarbons: Variable percentages
70 to 100% methane of nonhydrocarbons:
(CH4) Nitrogen
1 to 10% ethane (C2 H6) Carbon Dioxide
Lower percentages of Hydrogen Sulfide
higher hydrocarbons Hydrogen
through the hexanes
Helium and other noble
Traces up through gases
nonanes (C9 H20)

- Hunt, 1996
Some important parameters:
Dry gas: < 0.1 gallons of Associated gas occurs with
condensable liquids per 1000 oil as free gas, gas dissolved
ft3 (<1.3 liters per m3). in oil, or liquefied gas.
Wet gas: > 0.3 gallons of Nonassociated gas occurs
condensable liquids per 1000 alone as free gas and as gas
ft3 (>4 liters per m3). dissolved in water.
Gas wetness = (C2 + C3 + C4 Natural gas is highly
C1 + C2 + C3 + C4) 100 compressible compared with
Sweet and sour gas: low oil or water.
and high, respectively, in H2 S At high temperatures (>200F
Reservoir gas may occur (93C)) and pressures (>4000
underground in the free psia) hydrocarbon gases and
gaseous state or as gas oil exist as a single phase
dissolved in oil or water. petroleum fluid with gas
dissolved in oil or vice versa).
-Hunt, 1996
-Miles, 1994
Some important parameters:
Natural gas is very mobile
in the subsurface:
More widely distributed
both vertically and laterally
than oil because it migrates
more easily.
Natural gas is generated
from source rocks that are
more widely distributed
than source rocks of oil.
Hunt, 1996
WORLD NATURAL GAS
RESERVOIRS

From Whiticar, 1993


THE MAJOR SOURCES OF
HYDROCARBON NATURAL GASES:
Methanogenic
bacteria
All types of kerogen
Coal
Oil in source and
reservoir rocks
Sources of natural gas:
The major nonhydrocarbon gases - CO2, H2S,
and N2 are formed by both organic and
inorganic processes. Associated He and Ar
originate in both the crust and mantle.
All known commercial hydrocarbon gas
accumulations are biogenic in origin:
Decomposition of organic matter in the earths crust
No known commercial abiogenic methane
accumulations exist based on stable isotope
measurements.
Natural Gas Types (Whiticar, 1993)
Primary: Secondary:
Diagenetic (< temperature) Mixed gases
Microbial: Altered or bacterial
CO2 reduction (marine) oxidized
Fermentation Weathered or water
(freshwater) washed
Thermogenic: Migration fractionation
Associated and Artificial (bit
nonassociated metamorphism)
Hydrogen-rich and
hydrogen poor source
rocks
Thermal maturity
Geothermal, hydrothermal
Crystalline
Abiogenic or juvenile
-Howell and
others, 1993
Generation of gases from organic
matter with increasing temperature:
Diagenesis:
microbial methane generation
up to ~ 50C
~ 20% methane in
conventional reservoirs
Important in some shale
reservoirs in the Michigan and
Illinois basins
Primary cracking:
thermal cracking of kerogen
and coal to generate methane
~25% to 40% of gases
Secondary cracking:
thermal cracking of oil
~40% to 55% of gases
Metagenesis?

- Hunt, 1996
Microbial Gas Generation
Biogenic vs. microbial or
bacterial gas
C1/(C2 + C3) >> 100
13C1 < 60 permil
DC1 < 150 permil
Covariance of D values of
formation water and CH4
Alkalinity of associated formation
water (> 10 meq/kg)
Positive 13C of DIC (> 10
permil)
Microbial fermentation
CO2 reduction
Microbial Gas Generation
Acetate fermentation:
CH3COOH CH4 +
CO2
CO2 reduction:
CO2 + 4H2 CH4 +
2H20
Thermogenic Gas Generation
C1/(C2 + C3) < 100
13C1 >> 50 permil
DC1 > 275 permil
Primary Cracking (Thermogenic)
From kerogen:
C5H5 (kerogen) CH4 (gas) + C4H (pyrobitumen)
From coal kerogen as above and:
C5H9 (oil) 2CH4 (gas) + C3H (pyrobitumen)
From oil:
C5H9 (oil) 2CH4 (gas) + C3H (pyrobitumen)
The Conversion of Oil to Gas in
Petroleum Reservoirs
Crude oils are considered to break
down via hydrogen transfer
reactions to yield gas and
pyrobitumen.
The conversion is assumed to
proceed via systems of first-order
constituent reactions.
Kinetic models of oil degradation
are commonly used, in addition to
petroleum generation models, to
help predict the occurrence of oil
versus gas in time and space.
The high temperatures required to
bring about the complete
conversion of oil to gas (in
experimental work) indicate that
oil to gas conversion in nature is
likely to occur deeper than the
depth range over which petroleum
is generated from kerogen.
Welte and others, 1997
The Conversion of Oil to Gas in
Petroleum Reservoirs
Petroleum generation from
kerogen ~ 90% complete for
temperatures in the range 170 -
190C and heating rates between
0.53 5.3C Ma-1
Oil generation and destruction are
separated from one another in
time and space rather than
gradually merging from one to the
next as the classical oil window
concept might infer.
Determining the onset, rather
than the peak, of oil to gas
cracking is very important
because, depending P-V-T
conditions, only a small
conversion may be required to
result in the formation of a
separate gas phase and the
displacement of the liquid
phase to shallower structures.
Welte and others, 1997
CONVENTIONAL VERSUS
UNCONVENTIONAL RESERVOIRS
APPALACHIAN BASIN
UNCONVENTIONAL RESERVOIRS

Low-permeability oil
Tight-gas sandstones (and
carbonates!)
Fractured reservoirs
Coal bed methane
Gas shales
2nd Bradford sandstone,
Laughrey, 2009

The Bradford Era


http://images.townnews.com/bradfordera.com/content/articles/2009/08/25/news/doc4a
91ee1090812778965848.jpg
Ovg.
Pyrite

Detrital quartz

Brachiopod
fragments

Calcite
Ovg. cement

Ovg. Bitumen
CHARACTERISTICS OF
UNCONVENTIONAL
RESERVOIRS
Unconventional
Natural Gas Reservoir Structural
Elements
Reservoir Spectrum
Tight
Sand Shale Coal

0 25 50 75 100
Organic Content, wt. %
kg<0.1 0.001 kg<0.05 ka >1
Absolute Permeability Controlling Production, md

Gas Filled Porosity


(Compression)
Gas Filled Micropores
Water Filled Porosity (Adsorption)

From Hartman, 2009


Shale Resource Systems
Shale Gas
Microbial (biogenic)
Recent
Ancient
Indigenous Thermogenic
Thick organic-rich lithofacies
Low thermal maturity
High thermal maturity
Very high thermal maturity
Thin organic-lean lithofacies
Migrated thermogenic
Mixed microbial-thermogenic
Combination (vertical wells)
Shale Oil (not oil shale!)
Tight, mixed lithofacies
Fractured, mixed lithofacies

Modified from Jarvie, 2008


SHALE-GAS PETROLEUM
SYSTEM

SOURCE

SEAL RESERVOIR

TRAP
Key Characteristics of
Productive Thermogenic
Shale-Gas Reservoirs
Original organic richness and generation
potential
Primary and secondary cracking of kerogen
and retained oil
Retention of oil for cracking to gas by
adsorption
Porosity resulting from organic matter
decomposition
Brittle mineralogical composition
Shale Gas Petroleum System
Adsorbed petroleum
also trapped by surface
chemistry
Shale diagenesis
Dissolution-
reprecipitation
processes may
diminish gas reservoir
properties by releasing
gas from the system at
high thermal maturities
OBJECTIVES OF SHALE-GAS
RESOURCE ASSESSMENT
What type of shale-gas system Depth and thickness of the
is the prospect? shale
Microbial Reservoir seals and barriers
Thermogenic (high or low Structural geology:
thermal maturity?)
Faults
Organic richness Fractures
Hydrocarbon potential Engineering how will the
Does thermal maturity match shale respond to stimulation?
the petroleum composition? Is there gas production in the
What is the gas content? region?
Gas wetness Infrastructure
Isotope geochemistry of the
gas

Ruble, 2008
Important Geological Parameters
for Shale-Gas Assessment
Basin analysis:
Stratigraphy and
sedimentary history
Structural geology and
tectonic history
Mineralogy
Porosity and
permeability
Shale Diagenesis
Photo courtesy of Gary Lash
Rock Properties
Important Geochemical Parameters
for Shale Gas Assessment
Organic richness
Kerogen type
Conversion or
organic matter to oil
and gas
Thermal maturity
Transformation ratio
Gas composition
and isotope
geochemistry
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Total Organic Carbon Inorganic petrography:
(TOC): Optical mineralogy
Definitions
Measurement Scanning electron
Applications microscopy (SEM) and
energy dispersive
Organic petrography: spectroscopy (EDS)
Reflectance and
fluorescence microscopy X-ray diffraction
Kerogen types and Applications
evolution
Vitrinite reflectance (Ro)
Hydrocarbon types and
thermal maturation
Applications
TOTAL ORGANIC CARBON (TOC)
Definition
Measurement
Applications
TOTAL ORGANIC CARBON (TOC)
A measure of the organic carbon in a rock,
expressed as weight percent, used as a
fundamental parameter in classifying source
rocks in conjunction with kerogen type and
maturation (Miles, 1994).
TOC in sediments is derived from organic debris
from living and dead organisms incorporated
into sediments during deposition.
Closely related to sediment particle size.
High TOC in sediments are due to the
preservation and transport of organic matter, not
organic productivity (Hunt, 1996)
TOTAL ORGANIC CARBON (TOC)
TOC includes both kerogen and bitumen:
Kerogen is the particulate fraction of organic
matter remaining after extraction of pulverized
sedimentary rock with organic solvents
Bitumen in rocks is that fraction of the
organic matter that is soluble in organic
solvents.

Peters and Casa, 1994


Kerogen
Described and
differentiated into 4 major
groups (Type I IV)
according to:
Bulk characteristics (H/C;
O/C)
S content
Microscopic examination:
Plant fragments
Woody tissue
Amorphous, unstructured
organic matter
Bitumen
Fraction of organic matter
soluble in organic
solvents
Organic matter which
may be thermally
extracted from rocks
May be a precursor to oil
May be the substance
that occurs naturally in
veins, pools, or dispersed
in reservoir or source
rocks
Solidified bitumen
Extractable Organic Matter
(EOM)
Carbon preference index
(CPI):
Relative abundance of odd
versus even carbon-
numbered n-alkanes
CPI values significantly
above or below 1.0 indicate
an extract is thermally
immature
Organic matter input
affects CPI
Bitumen filling fractures and
migrating along a stylolite in the
Woodford Shale, OK

From Hunt, 1996


EGSP PA# 3, Huron Shale, 623.6 ft.
TOTAL ORGANIC CARBON (TOC)
TOC includes both
kerogen and bitumen:
Kerogen is the particulate
fraction of organic matter
remaining after extraction
of pulverized sedimentary
rock with organic solvents
Bitumen in rocks is that
fraction of the organic
matter that is soluble in
organic solvents.
TOC is not a clear
indicator of petroleum
From Hunt, 1996, Plate 4B
potential.
The TOC Myth: If I have high TOC, I have
a good source rock. (Dembicki, 2009)
Although a good source
rock must have high
TOC, not all organic
matter is created equal.
The more hydrogen
associated with the
carbon, the more
hydrocarbon it can
generate.
We also need an
indicator for the amount
of hydrogen present in
the organic matter.
From, Dembicki, H. (2009), Three common source rock evaluation errors made by
geologists during prospect or play appraisals, AAPG Bulletin, v. 93, p. 341 - 356
TOC Measurement
Remove inorganic carbonates
by acid digestion
Heat samples in an O2 supply
Collect and weigh the CO2
Small sample requirements,
inexpensive, accurate
Beware inaccuracies due to
dolomite, S
Care must be taken to ensure
the sample is representative
Methods For Measuring TOC
Direct combustion
Modified (nonfiltering)
direct combustion
Indirect (by
difference)
Pyrolysis plus
combustion products
Recent Developments
Geophysical methods

Peters and Casa, 1994


Direct Combustion TOC
Most commonly used method for
TOC.
Weighed, pulverized rock (1 2 g)
is treated with HCl (6N HCl) in
Leco filtering crucibles
Spent acid and wash water are
removed by vacuum filtration
The dried residue (100C/30
minutes) is mixed with metal-
accelerator (elemental iron and
copper), combusted using a high-
frequency induction furnace
(1200C), and measured as CO2.
Watch for:
Samples containing immature
oil-prone organic matter may
lose from 10% to 44% TOC as
hydrolyzate with the acid filtrate
prior to combustion.

Peters and Casa, 1994


Modified (nonfiltering) Direct
Combustion
Pulverized rock is weighed into Leco nonfiltering
crucibles and treated drop wise with HCl until all
CO2 evolution ceases, followed by reaction
overnight.
Spent acid and washwater are decanted, the
residue is dried, mixed with accelerator, and
analyzed as described for direct combustion.
This method prohibits the loss of hydrolyzate.
Watch for:
Method is laborious
Difficulties removing all acid can result in corrosion of
the drying oven

Peters and Casa, 1994


Indirect (by difference) TOC
Two weighted aliquots of Indirect TOC is generally
a pulverized, more accurate for
homogeneous sample organic-poor (< 0.5 wt.%
are treated separately: TOC) carbonate-rich
One is mixed with samples than direct TOC.
accelerator and combusted Watch for:
to yield total carbon (TC =
Corganic + Ccarbonate) For samples with TOC >
0.5 wt.% cumulative errors
Another aliquot is treated resulting from
drop wise with HCl and the measurements for two
evolved CO2 is measured. aliquots make this
TOC = difference approach less satisfactory
between TC and Ccarbonate than others.

Peters and Casa, 1994


CARBON DATA SUMMARY
Indirect (by difference) TOC
Amoco Wilhour #1
DEPTH TOTAL ORGANIC INORGANIC CaCO3
CARBON* CARBON* CARBON* EQUIVALENT
10340 ft. 10.05 0.24 9.81 81.72
10440 ft. 9.63 0.13 9.50 79.13
10660 ft. 10.19 0.05 10.14 84.47
10700 ft. 10.12 0.03 10.09 84.05
10730 ft. 10.85 0.04 10.81 90.05
11690 ft. 11.21 0.04 11.17 93.05
11710 ft. 11.21 0.04 11.17 93.05
11740 ft. 11.22 0.3 11.19 93.21

*Weight percent
DEPTH (Feet) TOC (wt.%)

9850 10030 1.37

9970 10030 0.75

10030 10090 0.74

10090 10150 0.4

10150 10190 0.64

10440 10500 0.18

10500 10560 0.3

10560 10620 0.13

10620 - 10630 0.12


DEPTH (ft.) TOC (indirect) TOC (direct)

10,340 0.24 wt.% 0.64 wt.%


10,444 0.13 wt.% 0.18 wt.%
10660 0.05 wt.% 0.12 wt.%
10,700 0.03 wt.% 0.14 wt.%
10,730 0.04 wt.% 0.12 wt.%
11,690 0.04 wt.% 0.16 wt.%
11,710 0.04 wt.% 0.13 wt.%
11,740 0.3 wt.% 0.18 wt.%
Pyrolysis plus combustion products
TOC
Some pyrolysis systems allow
TOC measurements by
summing the carbon in the
pyrolyzate with that obtained
by oxidizing the residual
organic matter at 600C.
For small samples (~ 100 mg),
this method provides more
reliable data than conventional
combustion methods, which
require 1 2 g of ground rock.
Watch for:
Mature samples, with Ro > 1%
yield poor TOC data because
temperature is insufficient for
complete combustion.

Peters and Casa, 1994


Recent Developments
Source Rock Analyzer
(SRA)
Weatherford Instruments
Division
Source Rock
Characterization:
Organic carbon content
Oil content
Remaining hydrocarbon
generation potential
Thermal maturity
Rock-Eval 6
TOC up to 100% C
Geophysical Methods
Wireline identification
of source rocks:
Lower density
Lower sonic transit
time
Higher resistivity
Caveats:
Sufficient TOC
Thickness within the
resolution of the
sondes
Petrophysical properties of kerogen
Bulk density 1.1 1.4 g/cm3

Low Pe 0.24

Uranium 0.18 0.28

Neutron porosity 50 65 pu

Gamma ray activity 500 4000 gAPI

Sonic velocity 80 160 s, ft-1


(slowness)
From Hartman, 2008
Gamma Ray Logs
Organic-rich rocks may have a
higher gamma-ray reading 5550
(>150 gAPI) than ordinary
shales and carbonates.
Higher radioactivity levels in
marine shales correlate to the
presence of organic matter
(uranium enrichment). 5600
Organic-rich lacustrine shales
do not exhibit anomalously
high gamma ray readings due
to the scarcity of uranium ions
in fresh water.
Gamma ray values do not 5650
correlate directly to TOC
Density Logs
Low density reflects high
porosity and/or high TOC
Lower is better (< 2.53 g/cm3)
Formation bulk density
consists of the combined
matrix density and the fluid
density.
= ma b ma b
If source rocks is less than shale
then it must be a function of
the organic matter present in
the shale:
Volume % organic matter =
shale source rock shale OM
Density Logs
Schmoker, 1993:
TOC = (A/) B
A and B are constants for
a particular black shale
facies
is formation density in
grams per cubic
centimeter
For Devonian black shales
in the western Appalachian
basin,
TOC = 55.822 [(b/) 1]
Caveat: density increases with
increasing thermal maturity
Schmoker, 1993,
Figure 2, p. J4
Density Logs
TOC = 55.822 [(b/) 1] EGSP PA #3, Erie County, PA
b = 2.65 g/cm3
= 2.4 g/cm3
b/ = 1.1042
TOCcalculated = 5.82 wt.%
TOCmeasured = 5.16 wt.%
Sonic Logs
Sonic logs show the
difference in compaction
between organic-rich and
organic-lean source
rocks.
A relative decrease in
sonic transit time and an
increase in resistivity
indicate an organic-rich
layer in nonpermeable
sediments.
Resistivity Logs
Petroleum source rocks are
often laminated and therefore
electrically anisotropic.
This anisotropy increases the
resistivity measured by
spherically focused logs.
High resistivity is good (reflects
thermal maturation)
Sonic/resistivity and
density/resistivity cross plots
are helpful for source rock
identification.
Geochemical Log
Kerogen from multiple
inputs:
Density
Uranium
Gamma ray
Lithodensity (Pe)
Lithology
Core data calibrations
CL DC DEPTH R IL D N PRL PHI SW PH I ADSRBGAS GASADAC R
5 IN 15 FT 5 OH MM 500 20 PER C -10 1 de c. 0 1 dec. 0 0.2 d ec. 0 0 bcf/sq m 50 0 mcf/ac-f 5 00
GRGC BDH FL G R IL M D EN PYRITE SWOH _1 PH ISW TOTALGAS FRGASACR
0 GAPI 20 0 0 flg. 5 5 OH MM 500 2.4 G/C3 2.9 1 de c. 0 1 dec. 0 0.2 d ec. 0 0 bcf/sq m 50 0 mcf/ac-f 5 00
TOC PD PE KEROG PH IE_ 1 ADSGASC TGASACR
0 wt. % 10 BD0HFLG 0 B/E 10 1 de c. 0 0.2 d ec. 0 50 0 scf/t 0 0 mcf/ac-f 5 00
BIT D COR LIMESTON PH ISW OH _ TOTGASC C RACKED
5 IN 15 0.95 G/C3 -0.05 1 0 0.2 d ec. 0 50 0 scf/t 0 0 mcf/a-ft 4 000
SILT
1 de c. 0 PHI PHISW 0 AD SRBGAS 0 GASAD ACR
CL AY
1 de c. 0 PHISW 0 ADSR BGAS TOTAL GAS FRGASACR GASAD ACR
SHAL E_1
1 de c. 0 PHIE_1
PHISW_1 TOTGASC AD SGASC GASADAC R TGASACR

78 00


PETROPHYSICAL LOG OUTPUT MARCELLUS SHALE
CLDC DEP TH RILD NP RL PHI SW PHI A DS RB GAS GA SA DA CR
5 IN 15 FT 5 OHMM 500 20 P ERC -10 1 dec. 0 1 dec. 0 0.2 dec. 0 0 bcf/sqm 50 0 m cf /ac-f 500
GRGC B DHFLG RILM DE N PY RI TE S WOH_1 PHI SW TOTA LGAS F RGA SACR
0 GAP I 200 0 f lg. 5 5 OHMM 500 2. 4 G/ C3 2. 9 1 dec. 0 1 dec. 0 0.2 dec. 0 0 bcf/sqm 50 0 m cf /ac-f 500
TOC P DPE KE ROG PHI E_1 A DS GASC T GASA CR
0 wt . % 10B DHFLG
0 0 B /E 10 1 dec. 0 0.2 dec. 0 500 scf /t 0 0 m cf /ac-f 500
BI T DCOR LIME STON PHI SWOH_ TOTGA SC CRACKE D

5 IN 15 0. 95 G/ C3 -0.05 1 0 0.2 dec. 0 500 scf /t 0 0 m cf /a-ft 4000
SI LT
Marcellus Shale 1 dec.
CLA Y
0 PHI P HISW 0 ADSRB GAS 0 GAS ADACR

Houser Unit #1 1 dec.


SHALE_1
0 PHIS W 0 A DSRBGAS TOTA LG AS FRGAS ACR GAS ADACR

1 dec. 0 PHIE _1
P HISW _1 T OTGAS C ADSGA SC GAS ADACR TGA SACR

Kerogen
Total Gas

7800

Cracked Gas


TOC MEASURED VS. LOG DERIVED
Measured TOC Log Derived TOC

Marcellus Shale Marcellus Shale


Houser Unit #1 Houser Unit #1

Average TOC = 2.4% Average TOC = 2.5%


Total Organic Carbon
Measure of the organic carbon in wt. %
Increased Maturation

Hydrocarbon Total Organic Carbon (wt. %)


Oil Potential
Poor 0 0.5
Fair 0.5 1.0
Gas Good 1.0 2.0
Very Good 2.0 4.0
Excellent > 4.0
Dead Carbon
Avg all shales 0.9 %
Avg all source rocks 1.8%
Avg source shales
2.2%
2.2
*Why is TOC Important?
LO G 1: O RG ANIC RICH NESS

TOC provides the carbon 55 4 0


Org ani c

for hydrocarbons Rich

55 6 0

TOC provides increased


porosity with increasing 55 8 0

thermal maturation 56 0 0

TOC provides adsorptive


sites for hydrocarbons
56 2 0

DEPTH(f eet)
To retain oil for cracking to 56 4 0

gas
Storage of adsorbed gas
56 6 0

Shale gas EURs are 56 8 0

directly proportional to 57 0 0

TOC and thickness


57 2 0

*Jarvie, 2007; Ruble, 2008 57 4 0


0 .0 5 .0 1 0 .0
TO C ( wt.%)
Applications
Applications of TOC Data
Gas-in place (GIP)
Estimated ultimate
recovery (EUR)
EUR assumes 10%
recovery, 400 ft.-thick
shale, and 1.6% Ro
Shale gas EURs are
directly proportional to Tim Ruble, Weatherford
TOC and thickness Laboratories
Adsorbed Gas Storage Capacity vs.
TOC in Shale Reservoirs
The organic material is the primary sorbent within the shale matrix
80
Measured Data
95% Confidence Interval
70
Linear (Measured Data)
Methane Storage Capacity, scf/ton

60

50 y = 6.1936x + 7.3965
2
R = 0.9914
40

30

20

10

0
0 2 4 6 8 10
Total Organic Content, weight %
Applications of TOC Data
Adsorption:
Retention of bitumen
for cracking to gas

Tim Ruble, Weatherford


Laboratories
Applications of TOC Data

Tim Ruble, Weatherford Laboratories


Applications of TOC Data
Porosity increase
due to the
decomposition of
organic carbon.

From Jarvie and others, 2007


Courtesy of Tim Ruble, Omni Laboratories
Marcellus Shale: TOC (PA)
Measured TOC (present
day) ranges from 0.89 to
11.16 weight percent.*
TOC (original) ranged
from 1.11 to 14 weight
percent
These values are based
on screening samples Marcellus Average TOC

collected from well


cuttings and cores. Actual
values were likely higher.

*TOC values from the Pennsylvania Geological Survey database:


http://www.dcnr.state.pa.us/topogeo/oilandgas/sourcerock_index.aspx
Marcellus Shale: TOC (PA)
Highest values in the
PGS database are Gamma ray log

observed in the A. W.
Bennett # well core,
Sullivan County, PA
A. W. Bennett # 1 Well (8260 8379 ft.)

12
TOCpd (wt. %) in the Marcellus Shale

10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Sample Number
Isopach map of
organic-rich
Utica and
equivalent rocks
in the
Appalachian
basin
>1% TOC
Minimum Threshold for
Hydrocarbon
Generation/Expulsion

95
4% TOC
Excellent Quality
Source Rock
e.g. Barnett Shale

96
15% TOC
High Grade
Oil Shale
e.g. Bakken Shale

97
>50% TOC
Carbonaceous Shale
Coal
50%
Fat

98
Total Organic Carbon
Guidelines
Present day organic richness of source rock

Quality TOC (wt%)


Poor <0.5
Fair 0.5 to 1 Threshold Shale Oil (?)

Good 1 to 2 Threshold Shale Gas

Very good 2 to 4
Excellent >4
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Total Organic Carbon Inorganic petrography:
(TOC): Optical mineralogy
Definitions
Measurement Scanning electron
Applications microscopy (SEM) and
energy dispersive
Organic petrography: spectroscopy (EDS)
Reflectance and
fluorescence microscopy X-ray diffraction
Kerogen types and Applications
evolution
Vitrinite reflectance (Ro)
Hydrocarbon types and
thermal maturation
Applications
Organic Petrography
Relevance
Reflectance and
fluorescence microscopy
Kerogen types and
thermal evolution
Vitrinite reflectance (Ro)
Thermal Alteration Index
(TAI)
Conodont Alteration
Index (CAI)
Applications

Plate 1 from Obermajer and others, 1997, p.234


Organic Geochemistry, v. 26, p. 229 - 246
Kerogen
Described and
differentiated into 4 major
groups (Type I IV)
according to:
Bulk characteristics (H/C;
O/C)
S content
Microscopic examination:
Plant fragments
Woody tissue
Amorphous, unstructured
organic matter
Reflectance and Fluorescence
Microscopy

40

35 Unknown Formation
11910 Core Chips
30 Mixed Kerogen
Frequency

25

20 Average %Ro =4.07


Caved/Suppres?Vit Std. Dev. = 0.18
15 Recycled Vitrinite
No. Pts. = 24
Inertinite
10

0
0.0
0.24
0.6
1.8
1.0
1.24
1.6
2.80
2.2
2.4
2.68
3.0
3.2
3.46
4.8
4.0
4.24
4.6
5.80
5.2
5.4
5.6
6.80
0.

0.

1.

2.

3.

3.

4.

5.

07-4447-177911
%Ro
Microscopic examination of
kerogen: macerals
Defined by shape and
character in transmitted
light and under
fluorescence:
Vitrinite (woody)
Inertinite (inert)
Liptinite (lipid-rich)
Amorphous
More specific names reflect
the source:
Resinite
Cutinite
http://www.uky.edu/KGS/coal/coalcomp.htm
Sporinite
Alginite
Amorphous Kerogen

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm
Maceral Macerals Organic Kerogen
Group precursors type
Liptinite Alginite I Fresh water I
algae
Liptinite Alginite II Marine algae II

Liptinite Exinite spores., pollen II

Liptinite Cutinite Leaf cuticle II

Liptinite Resinite Resin, tree sap II

Vitrinite Vitrinite Woody tissue III


(pseudovitrinite)

Inertinite Semifusinite Reworked IV


Fusinite and/or oxidized
Sclerotonite material,
charcoal
Etc.
Alginite

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm
Cyanobacterium

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm
Cutinite

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kero
gen1.htm
Cutinite

Photomicrographs by Richard Tyson: http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm


Resinite

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm
Structured phytoclasts (woody
vitrinite precursors)

Photomicrographs by Richard Tyson:


http://www.ceg.ncl.ac.uk/facilities/kerogengallery/kerogen1.htm
Sporinite and Vitrinite
Inertinite
Molecular Structure of Kerogen

Complex and difficult to


determine
Models of kerogen
structures based on
presence and relative
abundance of various
functionalities:
Carboxylic acid 500 nm
Carbonyl
Hydroxy groups
Alkene unsaturation
Aromaticity

Kempe and others, 2002


An example of the change in kerogen
structure (with loss of H) in the oil window
From chemical models of
Behar and Vendenbrouke
(1987):
Elemental analysis
Electron microscopy
13C NMR
Thermogravimetry
analyses
Pyrolysis
Structures evolve from
high to low H/C with
increasing thermal
maturation
Chemical model of thermally
immature Type I kerogen
Green River Shale, Uinta
basin, Utah
Paraffins are white
CnH2n+2 (normal straight chains
and branched alkanes)

Naphthenes are red


CnH2n (rings)

Aromatics are yellow


CnH2n-6 (contain one or more
benzene rings)
From Hunt, 1996, Plate 3A and
H/C = 1.64; O/C = 0.06 Behar and Vendenbroucke, 1987
Chemical model of an early mature
Type II kerogen
Toarcian Shale, Paris
basin
H/C = 1.25; O/C =
0.089
H/C = 1.64 H/C = 1.25

Shift in the dominance of paraffins (white) to a


dominance of naphthenes plus aromatics
Chemical model of thermally late
mature Type I kerogen
Green River Shale, Uinta
basin, Utah
H/C = 0.83; O/C = 0.013
Most paraffins and
naphthenes have been
converted to oil, leaving
condensed aromatic rings
connected by a few
paraffin chains
The aromatic rings form
From Hunt, 1996, Plate 3A and
parallel plates Behar and Vendenbroucke, 1987
comparable to graphite
H/C = 1.64

H/C = 1.25

In
cr
e as
in
g
th
er
m
al
m
at
ur
ity

H/C = 0.83
Kerogen Formation
Degradation/recondensation
Selective preservation
Natural sulphurization
Encapsulation of proteins
Protection by clay minerals
Oxidative reticulation
Degradation/recondensation
pathway
Classical pathway
(random
condensation
reactions)
Organic matter does
not retain any of the
morphological
features of the source
organisms

http://www.enscp.fr/labos/SOSPN/LARGEAU/
meca.html
Selective preservation pathway
A major portion of
kerogen is inherited
directly from cell walls
(and other biopolymeric
components) of
organisms
The living organisms
(especially microalgae)
produce insoluble
biomacromolecules http://www.enscp.fr/labos/SOSPN/LA
RGEAU/meca.html
highly resistant to
chemical and microbial
degradation
Natural sulphurization pathway
H2S produced by sulfate-
reducing bacteria under anoxic
conditions is incorporated into
potentially labile organic
compounds (some lipids and
sugars)
Resulting changes in structure
especially the cross-linking
of alkyl chains by sulfur http://www.enscp.fr/labos/SOSP
bridges lead to the formation N/LARGEAU/meca.html
of complex macromolecules
that are resistant to microbial
degradation
These kerogens appear as
homogeneous, gel-like
amorphous material
Protection by clay minerals
Mineral matrix can play a
role in organic matter
preservation
Labile organic
compounds are adsorbed
onto minerals as
molecular monolayers
and/or physically
protected as alternating
organic and clay
nanolayers:
Prevent diagenetic
degradation
Promote condensation into
kerogen
Encapsulation of proteins
Physical protection of
proteinaceous
materials via
encapsulation in
resistant aliphatic
organic matter
Oxidative reticulation pathway
Documented in Kashpir oil shales (Russian platform)
Relatively low TOC (~ 2%)
Intense bioturbation
Isolated kerogens are low in sulfur and high in oxygen
Kerogens have randomly located ether linkages between
alkyl chains that originated from oxidative polymerization
of unsaturated lipids that were incorporated into the
kerogen structures and protected from microbial
degradation
Formation of this kerogen was promoted by
diagenesis under relatively oxic conditions!
Modified from
Tegelarr and
others (1989) and
Brassell (1992)
Classical Pathway Revised Pathway
Fluorescence Microscopy
Cutinite
Sporinite
Blebs of resinite
Brown coal from
Nagoorin oil shale,
Queensland, Australia
Field width = 0.44 mm
From Hutton, 1991, Plate 1
Fluorescence Microscopy
Cutinite
Resinite
Lowmead oil shale,
Queensland, Australia
Field width = 0.44 mm

From Hutton, 1991, Plate 1


Fluorescence Microscopy
Telalginite

From Hutton, 1991, Plate 1


Fluorescence Microscopy
Telalginite from
tasmanitid alga
Antrim Shale
Field width = 0.56 mm

From Hutton, 1991, Plate 1


Fluorescence Microscopy
Lamalginite in oil Condor oil shale,
Australia
shale

Green River Formation,


Wyoming

From Hutton, 1991, Plate 1


Maceral/kerogen types - summary
Maceral composition is determined via
petrographic analysis of pellitized samples or
thin sections
Three primary maceral groups:
1. Liptinite (hydrogen-rich)
2. Vitrinite (oxygen-rich)
3. Inertinite (carbon-rich)
There are numerous macerals and sub-
macerals in each maceral group
Always characterize kerogen types through
optical mineralogy AND Rock-Eval pyrolysis
Maceral Macerals Organic Kerogen
Group precursors type
Liptinite Alginite I Fresh water I
algae
Liptinite Alginite II Marine algae II

Liptinite Exinite spores., pollen II

Liptinite Cutinite Leaf cuticle II

Liptinite Resinite Resin, tree sap II

Vitrinite Vitrinite Woody tissue III


(pseudovitrinite)
Inertinite Semifusinite Reworked IV
Fusinite and/or
Sclerotonite oxidized
material,
Etc. charcoal
Kerogen types in early mature Marcellus
Shale, southwestern Ontario
*Obermajer and
others (1997):
Hydrogen-rich Type II
Marine OM
Algal-dominated:
Unstructured bituminite
Unicelluar alginite

Plate 1 from Obermajer and


*Organic Geochemistry, v. 26, p. 229 - 246 others, 1997, p.234
The Marcellus Shale is an excellent
petroleum source rock.
High amounts of oil-
prone marine organic
matter:
Variably degraded
bituminite and varying
proportions of
unicelluar alginite.
Total organic carbon
(TOC) ranges from
2.0 to over 10 weight
percent
Marcellus Shale Organic Petrology
Two major
populations of
bituminite:
Low-reflecting, non-
fluorescing bituminite
Medium-reflecting,
weakly brown-
fluorescing bituminite
Well-preserved
Leiosphaeridia and
Tasmanites alginite
Vitrinite Reflectance (Ro)
Ro is the most widely
40
used parameter to 35 Unknown Formation
9149 Core Chips
indicate the thermal 30 Mixed Kerogen

Frequency
25

maturity of a source 20

15
Caved/Suppres? Vit
Recycled Vitrinite
Average %Ro =3.91
Std. Dev. = 0.16
No. Pts. = 8
rock. 10
Inertinite

5
Routinely measured 0

Relatively abundant

0
0. 2
4
6
8
0
1. 2
4
6
2. 8
2. 0
2
2. 4
2. 6
8
0
2
3. 4
3. 6
8
4. 0
4. 2
4
6
5. 8
0
2
4
6
6. 8
0
0.
0.

0.
0.
1.
1.

1.
1.

2.

3.
3.
3.

4.

4.
4.

5.
5.
5.
5.
07-4447 -17 7901
% Ro
Primary calibration
parameter for
modeling the
temperature history
Vitrinite Reflectance (Ro)
Ro should be measured with
primary telocollinite or another
primary submaceral of the 40

high-gray vitrinite-1 group. 35 Unknown Formation


11910 Core Chips
Ideally, measurements should 30 Mixed Kerogen

Frequency
be made on vitrinite in coals, 25
20 Average %Ro =4.07
coaly shales,, and siltstones; 15
Caved/Suppres? Vit
Recycled Vitrinite
Std. Dev. = 0.18
No. Pts. = 24
organic-rich marine shales with 10
Inertinite

type II kerogen generally 5

contain suppressed > 0

hydrogen vitrinite

0. 0
0. 2
4
0. 6

1. 8
0
1. 2
1. 4
1. 6
8
2. 0
2. 2
2. 4
6
2. 8

3. 0
2
3. 4
3. 6
4. 8
0
4. 2

4. 4
4. 6
8
5. 0

5. 2
4
5. 6
6. 8
0
0.

0.

1.

2.

3.

3.

4.

5.

5.
(anomalously < reflectance) % Ro 07-4447-17 791 1

A linear increase in
temperature causes an
exponential increase in
reflectance (straight line on a
semilog graph) - Hunt, 1996
Chemical Changes In Vitrinite With
Increasing Thermal Maturation
Successive release of:
H20
CO2
Higher hydrocarbons
CH4
Decrease in these
components results in a
reduction of the H/C ratio
in vitrinite correlates
with the increase in
reflectance
Vitrinite Reflectance (Ro)
Ro increases during
thermal maturation
due to complex,
irreversible
aromatization
reactions.
Values have been
assigned for
beginning, middle,
and end of oil
generation.
Vitrinite Reflectance (Ro)
Kerogen is isolated from Vitrinite becomes
sedimentary rocks and anisotropic at high levels
embedded in epoxy on a of thermal maturation (>
slide and polished to a Ro ~ 1.0) resulting in the
flat shiny surface. terms Rmin and Rmax for
Measurements are made respective values
of the percentage of measured upon rotation
incident light reflected of each particle; most
from vitrinite particles kerogen studies report
under oil immersion. random mean Ro
because rotation of the
microscope stage is not
necessary.
Vitrinite Reflectance (Ro) Caveats
ALL optical techniques are
subjective compared with
chemical techniques both
must be used to verify
conclusions
Two basic problems:
1. Analyst should limit the
reflectance readings to the
low-hydrogen vitrinite-1
group:
Telocollinite and telenite
2. Ideally, the analyst could
limit readings to coals and
coaly particles to avoid
hydrogen-suppressed
vitrinite
Problems obtaining true Ro
maturities (from Hunt, 1996, p. 515)
Properly identified Factors affecting accurate
vitrinite: Ro measurements:
Primary Rough-textures vitrinite:
Recycled Weathered
Cavings Partially dissolved
Mud additives Fractured
Subtypes with varying Ro Oxidized vitrinite
Inclusions (pyrite, bitumen,
Material that may look other macerals)
like vitrinite: Oily vitrinite
Solid bitumen Natural coking
Pseudovitrinite TOO FEW READINGS
semifusinite
Vitrinite Reflectance 5595(ft)

Readings
3

0
0.95 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70
Vitrinite Reflectance ( %)

Vitrinite Reflectance 5652(ft)

4
Readings

0
1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90
Vitrinite Reflectance ( %)

Vitrinite Reflec ta nce 5725(ft)

7
6

5
Readings

2
1

0
1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00
Vit rinite Ref lect ance ( %)
Thermal Maturity Guidelines

Immature <0.6% Ro
Oil window 0.6-1.1% Ro
Wet gas window 1.1-1.4% Ro
Dry gas window 1.4-~3.2% Ro
Gas destruction >~3.2% Ro (?)

151
<435Tmax <0.6% Ro

Bitumen
Immature 152
~450Tmax ~0.9% Ro

Peak Oil Oil

Window 153
~470Tmax ~1.2% Ro

Condensate
Wet Gas
Window 154
>470Tmax* >1.4% Ro

Pyrobitumen
Dry Gas
Window 155
Thermal Alteration Index (TAI)
Numerical scale based on
thermally induced color
changes in spores and pollen.
Advantages:
Greatest color change in the
oil window
Low cost; quick turn around
Scale calibrated to Ro
Visual kerogen types
Disadvantages:
Imprecise (color description is
subjective)
Barren samples
Palynomorph thickness and
type affect results
Conodont Alteration Index (CAI)
Burial and Thermal History
Modeling
All models are
wrong, but some are
useful.
Dr. Bruce Wienke,
Director,
Computational Nuclear
Physics Laboratory,
LANL
The Marcellus Shale is thermally
mature to post mature throughout
much of the Appalachian basin.

From Rowan, 2006


USGS Open-File Report 2006-1019
Eol
i
T ra an
nsp
ort
Fl
uv
ia
lS
ys
te
m
Bedrock Ages
(Ma)
Appalachian-derived
zircons in the Navajo
Sandstone (L. Jurassic),
Utah

Our finding requires the


existence of a transcontinental
sediment-dispersal system
capable of moving a large
volume of detritus westward
(modern coordinates) through-
out the late Paleozoic and
early Mesozoic. (Rahl et al.
(2003)
Rahl et al. (2003)

Rahl, J.M., et al., 2003, Combined single-grain (U-Th)/He and U/Pb dating of detrital zircons from the Navajo
Sandstone, Utah: Geology, 31, 761-764.
Dickinson, W.R., & Gehrels, G.E., 2003, U-Pb ages of detrital zircons from Permian and Jurassic eolian
sandstones of the Colorado Plateau, USA; paleogeographic implications: Sedimentary Geol.,163, 29-66.
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Total Organic Carbon Inorganic petrography:
(TOC): Optical mineralogy
Definitions
Measurement Scanning electron
Applications microscopy (SEM) and
energy dispersive
Organic petrography: spectroscopy (EDS)
Reflectance and
fluorescence microscopy X-ray diffraction
Kerogen types and Applications
evolution
Vitrinite reflectance (Ro)
Hydrocarbon types
and thermal
maturation
Applications
INORGANIC PETROGRAPHY
Relevance
Optical mineralogy
Scanning electron
microscopy (SEM)
and energy dispersive
spectroscopy (EDS)
X-ray diffraction
Geophysics
Applications
Why is inorganic petrography
important?
Mineralogy is an
important factor in gas
production from tight
shale-gas systems that
require well stimulation
(Jarvie and others, 2007).
Brittleness and fracture
gradients
Clay, quartz, pyrite, and
carbonate contents
Reservoir bulk properties
and gas deliverability
Inorganic Petrography Relevance
Stratigraphic and
sedimentological
interpretations
Formation damage
assessment:
Mechanical damage (fines
migration; solids invasion)
Fluid sensitive zones
(filtrate-rock interactions)
Porosity/permeability
Thermal maturation
Optical Mineralogy
Standard and polished
thin sections.
Preparation of good thin
sections challenging due to
the softness of shales and
mudrocks.
Special epoxy resins,
multiple epoxy
impregnation, diamond
laps
Sedimentary and
microfabric features,
mineralogy, diagenesis,
and fossil content
Polished thin sections are ideal.
Useful for a variety of
microscopic analyses:
Transmitted and
reflected light
microscopy
Fluorescence
microscopy
Cathodoluminescence
microscopy
SEM (SE and BE)
In conjunction with EDS
and XRF

www.geo.utexas.edu/sscd/MonthImageGallery.htm
Thin section analysis of shales:
Mineralogy
Texture
Microfossils
Cements
Pore space
Microlamination
Interpretation:
Classification
Provenance
Diagenesis
Paleoecology
Correlation
Depositional environments
Courtesy Tim Ruble
Thin section analysis of shales
caveats:
Thin sections must be prepared to proper
30m thickness
Utilize fluorescent-spiked epoxy for
impregnation for epifluorescence
examination (microporosity distribution)
Mineral staining options
Experienced petrographer!
Rine, 2008
Scanning Electron Microscopy (SEM) and
Energy Dispersive Spectroscopy (EDS)
SEM Analysis:
Secondary electrons
(SE)
Backscattered
electrons (BE)
Energy Dispersive
Spectroscopy (EDS)
EDS or EDX
Electron Source
Electron beam comes from a
filament (a loop of tungsten or
other suitable material which
functions as the cathode).
Voltage is applied to the loop
causing it to heat up.
The anode (+ with respect to
the filament) forms powerful
attractive forces for electrons.
Electrons accelerate toward
the anode. Some accelerate
right by the anode and on
down the column to the sample
SEM Ray Diagrams
Ray traces for two
probe-forming lens
focusing conditions:
Small working
distance (left)
Large working
distance (right)
Both conditions have
the same condenser
lens strength and
aperture size.
Secondary electron image Backscattered electron image
KEROGEN
Porosity in shales
Porosity increase
due to the
decomposition of
organic carbon.

From Jarvie and others, 2007


Early Oil Window: Ro = 0.7 %
Late Mature: Ro = 1.35%
Postmature: CAI = 5.0
KEROGEN MESOPORES,
WHAT ABOUT PYROBITUMEN?
Green dots are
10 nm diameter

Tim Ruble, Weatherford


Laboratories
Argon Ion Milling

Arg on ion Shield plate


gun

Arg on io ns

Sh ield plate
Specime n

Sp ecimen

Cross-sectio na l
site

Tim Ruble, Weatherford Laboratories


Argon Ion Milling

Argon ion milling produces a debris-free surface on shale


samples for SEM analysis. The small black holes represent
micropores associated with organic material.

Tim Ruble, Weatherford Laboratories


Triple Porosity Gas Storage
Micro- (<2 nm) and Meso-Porosity (< 50 nm)
Gas Storage by Adsorption
Mass Transfer by Diffusion
Macro-Porosity
Gas Storage by Solution and Compression
Mass Transfer by Diffusion and Darcy Flow
Natural or Induced Fractures
Gas Storage by Solution and Compression
Mass Transfer by Darcy Flow
Gas Storage Components
Adsorbed gas contained within organic material
Requires organic content estimates
Generally correlates to lithology
Logs: natural gamma ray
spectral gamma ray
neutron-density porosity difference
Free gas contained within gas-filled porosity
Correlates to density
Logs: bulk density & resistivity
Wellbore
Induced
Fracture

Shale Fracture Porosity

Macro-Porosity
Flow Micro-Porosity

Schematic

Very Low
Very Low
Perm
Perm Darcy
Darcy Pipe
Diffusion
Diffusion
Sorption Diffusion Darcy Flow
Flow
Flow Flow

Tim Ruble, Weatherford Laboratories


Shale Gas Transport Insights
Measured matrix gas permeabilities appear
to be erroneous compared to permeabilities
required in reservoir simulations to match
field production rates.
New research indicates Darcy flow is an
incomplete model of gas flow through shale
matrices
Nano pore matrix and kerogen/pyrobitumen
coated grains facilitate unique transport
phenomena
Grain Pore System in Shale
Reservoirs

or Pyrobitumen

Tim Ruble, Weatherford Laboratories


IMPORTANCE OF PYROBITUMEN
Direct evidence for thermal
cracking of residual oil to gas
Pyrobitumen film
Provides residual organic
matrix for gas sorption
Mesopores in pyrobitumen
may provide porosity for free
gas storage
Brittle nature of pyrobitumens Tim Ruble, Weatherford Laboratories
may provide fracture network
for gas recovery
X-Ray Diffraction
Bulk mineral composition
Relative abundance of clay minerals
Percentage of smectite interlayers in mixed-
layer illite-smectite (% expandability!)
Potential clay-fluid sensitivity problems
Problematic minerals that affect grain density
(Fe-rich: chlorite, pyrite, ferroan dolomite)
Must be supplemented with thin section/SEM
analysis
X-ray diffraction
Comparison of thermogenic shale-
gas lithologies
Marcellus Barnett Haynesville Fayetteville

Argillaceous Siliceous Argillaceous Siliceous


mudstone mudstone calcareous mudstone
mudstone

TOCavg: 6% TOCavg: 5% TOCavg: 4% TOCavg: 4%


avg: 6% avg: 7% avg: 10% avg: 6.5%

- Lyle, 2009
Average Marcellus Shale
Mineralogy
Clay minerals (50%):
Illite: 70%
Chlorite: 15%
Illite-smectite: 15%
Illite-chlorite: trace
Kaolinite: trace*
Allogenic minerals (20%):
Quartz: 20%
K-feldspar*
Plagioclase*
Authigenic minerals (30%):
Carbonate: 25%
Pyrite: 5%
Other*
Hosterman and Whitlow,
1981;1983
*PGS recent laboratory work
Mineral composition and rock
properties
The brittleness of
thermogenic-gas shales
affects their response to
hydraulic fracture
stimulation and proppant
embedment.
Induced fractures provide
linkage between well bore
and microporosity
Silica content versus clay
content
Pyrobitumen can impart
brittleness to a shale!
Sedimentology
From Sageman and others, 2003
Relative roles of organic matter production,
decomposition, and dilution in the
accumulation of organic-rich strata
Few organic-rich Devonian shales were deposited under
pervasive anoxic-sulfidic water columns.
Establishment and breakdown of seasonal thermoclines,
on annual or longer timescales, were the predominant
mode of stratification.
Remineralization of bio-limiting nutrients may have
played a key role in organic matter burial by creating a
eutrophication pump.
The master variable for organic matter accumulation
was relative sea level change.

Sageman and others, 2003


Geochemical proxies for
dilution/condensation
Relative to TOC:
Ti/Al
Si/Al
CaCO3
Note interpreted eolian
silt content associated
with TOC enrichment
suggests that TOC
enrichment correlates
with maximum sediment
starvation.

Sageman and others, 2003


Dilution was a major control on
organic carbon burial flux
Deposition of each black
mudstone was associated
with shoreline
transgression.
Progressive basinward
progradation resulting
from filling of the foreland:
Gradual eustatic fall
Decreasing subsidence of
the foreland basin

Sageman and others, 2003


Redox conditions and dominant
microbial processes
Relative to TOC:
Mn
V + Cr
Mo
DOP
34Spyrite
Preservation of
organic matter was
enhanced by high
burial flux
Sageman and others, 2003
Production and nutrient cycling
Relative to TOC:
13Corg
Corg/Ntot
Corg/Ptot
Macerals are dominated
by amorphous organic
matter
Algal matter
predominance over
terrestrial input in the
preserved organic matter

Sageman and others, 2003


Sedimentology - summary
Marcellus is condensed relative to
the gray shales of the Hamilton
Group:
Maximum flooding surface of sea
level rise event Ie (Johnson and
Sandberg, 1988)
Decrease in bulk sedimentation
played a significant role in TOC
enrichment.
C/N/P elemental data suggest
decompositional release of
nutrients from organic matter, but
there is no isotopic evidence for
enhanced OM production._
Anoxic conditions dominated
during deposition.
PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Rock-Eval Pyrolysis: Biomarkers
Definitions Natural gas isotope
Quantity of organic geochemistry:
matter Hydrocarbons
Quality or type of organic Non-hydrocarbons
matter
Noble gases
Thermal maturation of
organic matter Applications
Problems and limitations
Recent advances
Applications
Rock-Eval Pyrolysis
Definitions
Quantity of organic matter
Quality of organic matter
Thermal maturation of
organic matter
Problems and limitations
Recent advances
Applications
Rock-Eval Pyrolysis - Definitions
Pyrolysis is the heating of
organic matter in the
absence of oxygen to
yield organic compounds
(Peters, 1986).
Rock-Eval Pyrolysis:
Pulverized samples are
gradually heated under an
inert atmosphere
Heating distills the free
organic compounds Instrumentation
(bitumen), then cracks
pyrolytic products from the Operation:
insoluble organic matter Samples of ground whole rock
(kerogen) (up to ~ 100 g) are pyrolyzed at
300C for 3-4 minutes, followed by
programmed pyrolysis at
25C/minute to 550C (or higher)
Rock-Eval 2
Delsi, Inc.
~ 100 mg crushed rock is weighed
accurately into a small metal crucible and
placed into the instrument
Sample is transferred to a furnace and is
first heated to 300C for 3 minutes in an
inert (He) atmosphere
Free hydrocarbons thermally desorbed
from the sample
Abundance of free hydrocarbons
measured using a FID and recorded as S1
Sample is then pyrolyzed by increasing
the temperature of the furnace from 300
to >550C at 25C/minute
Hydrocarbons generated during this
phase measured using FID and reported
as S2
Temperature at which the maximum rate of
pyrolysate generation occurs = T max
measured in C
Pyrolysate generated over the range of
300to 390C is split:
One proportion is passed through a TCD
to measure CO2 as the S3 peak (O2 content
of the organic matter)
Rock-Eval 6
Vinci Technologies
Improves Rock-Eval 2
technology
CO and CO2 evolution is
monitored throughout the
pyrolysis by an IR detector
Completely automated, with
two micro-ovens which can
be heated up to 850C
controlled by a
thermocouple located in
contact with the sample
TOC analysis up to 100% C
Source Rock Analyzer (SRA)
Weatherford
Advanced FID
Requires no acid
preparation of samples
for TOC analyses
Improved low end
sensitivity for S2 and
S3
Improved high end
linearity for S2
Measured parameters:
S1 (first peak) milligrams of
hydrocarbon that can be thermally
distilled from one gram of the rock.
S2 (second peak) milligrams of
hydrocarbon generated by
pyrolytic degradation of the
kerogen in one gram of rock.
S3 (third peak) milligrams of
CO2 generated from a gram of
rock during temperature
programming up to 390C
(analyzed by thermal conductivity
detection)
During pyrolysis, temperature is
monitored by a thermocouple.
Tm ax: temperature at which the
maximum amount of S2
hydrocarbons is generated.

Peters, 1986
Rock-Eval Pyrolysis: Measured
Parameters
S1 = the amount of free
hydrocarbons (gas and
oil) in the sample (mg
HC/gram of rock)
If S1 > 1 mg/g, it may be
indicative of an oil show
S1 normally increases with
depth
Contamination of samples
by drilling fluids and mud
can yield an abnormally
high value for S1.
Rock-Eval Pyrolysis: Measured
Parameters
S2 = the amount of
hydrocarbons generated
through thermal cracking
of nonvolatile organic
matter
S2 is an indicator of the
quantity of hydrocarbons
that the rock has the
potential of producing
should burial and thermal
maturation continue
S2 normally decreases with
burial depths > 1 km
Rock-Eval Pyrolysis: Measured
Parameters
S3 = the amount of CO2
(in mg CO2/gram of rock)
produced during pyrolysis
of kerogen
S3 is an indicator of the
amount of oxygen in a
sample and is used to
calculate the oxygen index
(discussed below)
Suspect contamination of
the sample if S3 is
abnormally high; >
concentrations of
carbonate that break down
at T< 390C also cause
>S3 than expected.
Rock-Eval Pyrolysis: Measured
Parameters
T max = the temperature (C) at
which the maximum release of
hydrocarbons from cracking of
kerogen occurs during
pyrolysis (top of the S2 peak)
Tmax is an indication of the
stage of thermal maturation of
the organic matter in the
sample.
Tmax should not be confused
with geologic temperatures.
Tmax is partly determined by
the type of organic matter in
the sample.
Tmax oC

reliable data

Erie Tmaxavg = 440.4 oC

Mercer Tmaxavg = 433.8 oC


Rock-Eval Pyrolysis: Measured
Parameters
The Rock-Eval II and Rock-Eval 6 apparatus can also be
used to determine the TOC of the sample:
TOC from Rock-Eval II: Oxidize the residual organic carbon
(as CO2, S4) in an oxidative oven kept at 600C. TOC is
determined by adding this residual organic carbon to the
pyrolyzed organic carbon, which in turn is measured from the
hydrocarbon compounds issuing from pyrolysis (remember-
mature samples (Ro > 1%) yield poor TOC data because
temperature is insufficient for complete combustion).
TOC from Rock-Eval 6: oxidize the residual organic carbon at
850C, a temperature which approaches that of the Leco TOC
analyzer overcoming the problem of incomplete combustion.
S1 ROCK-EVAL
S2 MEARUREMENTS

S2 -- Poor
Petroleum Rock Eval Pyrolysis
Potential S1 S2
S1 -- Poor Poor 0 0.5 0 2.5
Fair 0.5 1.0 2.5 5.0
Good 1.0 2.0 5.0 10.0
Very Good 2.0 4.0 10.0 20.0
Excellent > 4.0 > 20.0
Rock-Eval Pyrolysis: Calculated
Parameters
Production Index
(PI)
Hydrogen Index (HI)
Oxygen Index (OI)
Production Index (PI)
A thermal maturity parameter derived from pyrolysis. It is
the ratio of hydrocarbons already generated in the
sample to potential hydrocarbons that could still be
generated in the sample:
PI = S1 (S1 + S2)
In fine-grained rocks, PI gradually increases with depth as thermally
labile components in the kerogen (S2) are converted to free
hydrocarbons (S1)
Immature samples have a ratio of 0.1 or less
Mature samples have a ratio of 0.1 to 0.4
When expulsion occurs, the S1 no longer increases
The presence of migrated oil affects the ratio
Reservoir rocks show anomalously high PI values compared to
adjacent fine-grained rocks
For Tmax values < 435C, PI values > 0.2 are anomalous
For Tmax values ~ 435C to 445C, PI values > 0.3 are anomalous
Production Index
Devonian Shales
Late Mature
(oil)

Peak
Mature
Early Mature
Immature
Hydrogen Index (HI)
HI = (S2 TOC) x 100, mg HC/g TOC
HI has a direct relationship with elemental H/C; it is
proportional to the amount of hydrogen in the kerogen
and thus indicates the potential of the rock to generate
oil.
For immature kerogen:
HI = 600 950 indicates Type I kerogen
HI = 400 600 indicates Type II kerogen
HI = 0 300 indicates Types III and IV (or IIIB) kerogen
Kerogen types become indistinguishable at high levels of
thermal maturity because their chemical compositions
are similar.
If the kerogen type is known, then the HI can be used to indicate
the maturity of the kerogen
Peters and Casa, 1994
Miles, 1994
Type IV
None
< 50 mg/g

Type III
Gas
50 - 200 mg/g
Type I
Oil
Type II/III
> 600 mg/g
Mixed Oil & Gas
200 - 300 mg/g

Type II
Oil
300 600 mg/g
Hydrogen Index (HI)
The average
hydrogen index in a
rock interval is best
determined from the
slope of a regression
line on a graph of S2
versus TOC Ibrahimbas and Riediger, 2004

(Langford and Blanc-


Valleron, 1990)
Kerogen Type

Oil Prone
Oil Prone Type II
Type I
Mixed oil/gas
Prone

Gas Prone
Kerogen Quality
Kerogen types become
indistinguishable at high levels
of thermal maturity because
their chemical compositions
are similar.
If the kerogen type is known,
then the HI can be used to
indicate the maturity of the
kerogen
Hydrocarbon yield
determination:
Use visual kerogen data to From Ruble, 2009
calculate the original HIo
Calculate the original TOCo
Use HIo and TOCo to calculate
the original potential, S2o
Kerogen Quality
Hydrocarbon yield
determination:
Use visual kerogen data to
calculate the original HIo
Calculate the original TOCo
Use HIo and TOCo to
calculate the original
potential, S2o
Calculate hydrocarbon
yields: From Ruble, 2009
Generated Hydrocarbons =
Original (S2o) Remaining
(S2)
Oxygen Index (OI)
OI = (S3/TOC) x 100, mg CO2/g TOC
A measure of the amount of oxygen in the
kerogen:
Not as reliable as the other Rock-Eval
parameters (interference of carbonate
minerals; kerogen oxidation during sample
preparation)
Direct relationship with elemental O/C
ratios
Oxygen Index (OI) versus
Hydrogen Index (HI)
Type I Modified van Krevelen plot
Oil prone Erie and Mercer Counties, PA

Type II
Hydrogen Index, mg HC/g TOC

Oil/gas prone Erie oil prone to oil/gas prone


Tmax = 439 - 442C
PI (x) = 0.13
Early mature (oil)

Mercer oil/gas prone to gas


prone
Type III Tmax = 437 - 441C
Gas prone PI (x) = 0.2
Early mature (oil & gas)

Oxygen Index, mg CO2/g TOC


Modified van Krevelen plot

Gas prone
Tmax values are unreliable
PI (x) = 0.0.5 0.76
Ro = 2.2 2.8 %
Post mature (gas only)
Recent Rock-Eval Pyrolysis
bibliography:
http://www.tsop.org/refs/rockeval.htm
SUMMARY OF PRINCIPAL ORGANIC
GEOCHEMICAL MEASUREMENTS

From Peters and Casa, 1994


SUMMARY OF PRINCIPAL ORGANIC
GEOCHEMICAL MEASUREMENTS

From Peters and Casa, 1994


SUMMARY OF PRINCIPAL ORGANIC
GEOCHEMICAL MEASUREMENTS

From Peters and Casa, 1994


PETROLOGY AND GEOCHEMISTRY OF SHALE
AND SHALE-GAS: ANALYTICAL PROGRAMS
AND INTERPRETATIONS
Rock-Eval Pyrolysis: Biomarkers
Definitions Natural gas isotope
Quantity of organic matter geochemistry:
Quality or type of organic Hydrocarbons
matter Non-hydrocarbons
Thermal maturation of
Noble gases
organic matter
Applications
Problems and limitations
Recent advances
Applications
Biomarkers (molecular maturity
parameters)
Individual organic
constituents of
sediments, sedimentary
rocks, and petroleum
which are derived from
biological precursors.
Undergo systematic
and sequential
transformations during
diagenesis; changes in
composition used as
measures of thermal
history
Distinguishing characteristics of
a biomarker
The compound shows a
structure indicating that it
was, or could have been, a
component in a living
organism
The parent compound is in
high concentration in the
organisms, which show
widespread distribution
The principal identifying
structural characteristics of
the compound are
chemically stable during
sedimentation and early
burial
Example:

Thermal conversion of a C29-monoaromatic to C28 triaromatic


steroid:
Aromatization of the A and B rings loss of a methyl group
and 7 hydrogen atoms attached to these rings.
The ratio increases from 0 to 100% during maturation.
Adapted from Peters and
Moldowan, 1993 and Hunt, 1996
Biomarkers (molecular maturity
parameters)
Critical factors:
Sensitive to maturity change
Useful in a relevant range of sediment maturity
T max limit for biomarkers ~ 450to 460C (peak late oil
window)
Based on widely occurring compounds
Easily measured in GC-MS analyses
The most useful parameters are measured from a single
mass chromatogram and span both the oil generation
threshold and the oil window:
20S/20R C29 steranes
Proportion of monoaromatic to triaromatic steroidal
hydrocarbons
Biomarkers in the Huron Shale
Huron Shale,
605.4 ft.
EGSP PA# 3 well:
CPI = 1.10, a value
consistent with an
early oil window
maturation level
Relatively high
hydrocarbon yields
and high proportion of
hydrocarbons 623.6 ft.
(HC/EOM = 0.74)
Relatively low
concentration of
isoprenoids relative to
n-alkanes
Steranes
m/z 217 Huron Sh.
Mature sterane 605.4 ft.
distribution
Isomerization of C29
steranes (20S)/(20R +
20S) approaching
equilibrium values
(early stage of oil m/z 217 Huron Sh.

generation) 605.4 ft.


Terpanes
Relatively high values m/z 191 605 ft.

for C31 (22S)/(22S +


22R) - 59.0 to 61.5
indicate early oil
window

m/z 191
623.6 ft.
Adapted from Peters and
Moldowan, 1993 and Hunt, 1996
Huron Shale Biomarker
Summary
Biomarker 605.4 ft. 623.6 ft. Thermal
Maturation
C29 sterane 20S/(20S + 47.1 47.5 Oil window
20R) C29

/( + ) 55.9 54.4 Oil window


C29

520S/520R 0.89 0.91 Oil window


C29

Hopanes Ts/Ts + Tm 64.9 63.2 Oil window

%C31 61.5 59.0 Oil window


(22S)/(22S +
22R)
Natural Gas Geochemistry
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural Reservoir
gases compartmentalization
Thermal maturity of Discriminate between
natural gases: free and adsorbed gas
Maturity of source material components in
Onset of low-maturity and thermogenic shale gas
high-maturity thermogenic and coal bed gases
gas generation
Origin of problematic non-
Recognition of gas leakage
and gas destruction hydrocarbon gases:
(preservation basement) N2
Correlation of natural H2S
gases with their sources CO2
Stable Hydrocarbon Isotopes
Isotope Mass Protons Neutrons Natural
Abundance
12C 12 6 6 98.89%
13C 13 6 7 1.11%
1H 1 1 1 99.98%
2H (D) 2 1 2 0.0156%

13C = (Rsample Rreference) Rreference; R = 13C/12C


Rstandard = 0.01124 permil
Atmospheric CO2 ~ -8 permil
Plants, kerogen, coal ~ -8 to -55 permil
Oil ~ -22 to -55 permil
Natural gas ~ < - 25 to > - 55 permil

D = (Rsample Rreference) Rreference; R = 2H/1H


Stable Natural Gas Isotopes
Isotope Fractionation
Fractionation is coupled to various geological processes
(tracers):
Gas generation (and alteration/destruction)
Adsorption and desorption
Migration and diffusion
Fractionation is a result of different kinetics for 13C, 12C,

D, 1H:
Kinetically easier to break chemical 12C and 1H bonds
Preferred rupture of these bonds during thermal maturation
Results in 12C enriched (lighter) products (methane) and 13C
enriched (heavier) residue (C2+, kerogen, coal)
Stable Carbon Isotopes
Secondary Effects
Migration and diffusion:
Preferential migration of and diffusion of 12C
over 13C
Migrated and diffused gas becomes enriched
in 12C
Compositional fractionation:
Enrichment of CH4 over higher hydrocarbons
Migrated gas becomes drier
Organic Reaction Facies
From Whiticar, 1994
Schoell, 1983
Interpretive Graphs

Schoell, 1983
Schoell, 1983
Schoell, 1983
Schoell, 1983
Whiticar, 1994
Bernard and others, 1978
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of Reservoir
natural gases compartmentalization
Thermal maturity of Discriminate between
natural gases: free and adsorbed gas
Maturity of source material components in
Onset of low-maturity and thermogenic shale gas
high-maturity thermogenic and coal bed gases
gas generation
Origin of problematic non-
Recognition of gas leakage
and gas destruction hydrocarbon gases:
(preservation basement) N2
Correlation of natural H2S
gases with their sources CO2
Triassic
Basin,
southeastern
PA
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural Reservoir
gases compartmentalization
Thermal maturity of Discriminate between
natural gases: free and adsorbed gas
Maturity of source components in
material thermogenic shale gas
Onset of low-maturity and coal bed gases
and high-maturity
thermogenic gas Origin of problematic non-
generation hydrocarbon gases:
Recognition of gas leakage N2
and gas destruction H2S
(preservation basement) CO2
Correlation of natural
gases with their sources
From Schoell, 1995
Huron Shale Gas Isotopes
13C1: -53 to -55.74 permil
DCH4: -301.2 to -307.6 permil
C2: 3.33 to 6.1 percent
13C2 = -41.79 permil
C3: 1.8 to 2.9 percent
13C3 = -36.27 permil

Wet thermogenic
natural gases generated
in the early oil window
Possible mixing with
bacterial methane


-25
0C 100C

Microbial gas mixing


200C
-30

13C2 (permil)
-35

-40

-45
-50 -40
13C1 (permil)
?
-25
0C 100C

Microbial gas mixing


200C
-30

13C2 (permil)
-35

-40

-45
-50 -40
13C1 (permil)
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural Reservoir
gases compartmentalization
Thermal maturity of Discriminate between
natural gases: free and adsorbed gas
Maturity of source material components in
Onset of low-maturity and thermogenic shale gas
high-maturity thermogenic and coal bed gases
gas generation
Origin of problematic non-
Recognition of gas
leakage and gas hydrocarbon gases:
destruction N2
(preservation H2S
basement) CO2
Correlation of natural
gases with their sources
Marcellus gas isotopes, southwestern Pennsylvania

13C of Devonian organic


matter (Maynard, 1981)
0

-10

-20
13
Cn
-30

-40
Hexane precursor

300 K
-50 400 K
500 K
600 K
-60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
1/Cn
-20

Gases generated from two types -25

of organic matter in Middle Range of


-30
Ordovician age source rocks, possible
source rock
increasing
depth

_13C ()
Utica/Antes, Appalachian basin -35
13
C

-40
o
127 C
o
227 C
-45
13C organic matter range: possible
endmember
-34 to -24 -50
butane propane ethane methane

-55
0 0.2 0.4 0.6 0.8 1
Figure 5a 1/C n

-25
Range of
possible
source
increasing
depth
-35
_ C
13

-45
possible
endmember
227 oC

127 oC
-55

butane propane ethane methane


-65
0 0.2 0.4 0.6 0.8 1
Figure 5b
1/C n
-25
Sil. NAG
-32 Ord. NAG NY
Ord. NAG 40% remaining
Ord. NAG PA
Sil. OAG 30% remaining
-30 alpha = 1.015
Ord. OAG
alpha =1.021

13C -35
ethane 13
C
-37
-40

-45

-42 -50
0 0.5 1 1.5 2 2.5 3 -1.5 -1 -0.5 0 0.5 1
1/mol % ethane ln mol % ethane

Mixing between oil associated gas Raleigh fractionation on


and Silurian non-associated gases Ordovician non-associated gases
-25

Raleigh fractionation
-30

Mixing

-35

13 C
ethan Sil. NAG
Ord. NAG
-40
Sil. OAG
Ord. OAG
-15 per mil
-22 per mil
-45
Mixing

Possible end-member

-50
0.0 2.0 4.0 6.0 8.0 10.0 12.0
Figure 10 mol % ethane
-20
Possible range of D
for formation water
-40
Lee Cty, VA
Swan Creek Magnitude of
-60 fractionation at
Rome Trough, KY
o
about 200 to 250 C
Silurian, OH, PA
-80 Kukersite
L&B, Cambrian, OH
-100 TBR
D
methan
-120

-140

-160

-180

-200

-220
-60 -55 -50 -45 -40 -35 -30 -25 -20
13C methane
Devonian Shale Chung Plot
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural gases Reservoir
compartmentalization
Thermal maturity of natural
gases: Discriminate between free and
adsorbed gas components in
Maturity of source material thermogenic shale gas and
Onset of low-maturity and coal bed gases
high-maturity thermogenic gas Origin of problematic non-
generation hydrocarbon gases:
Recognition of gas leakage N2
and gas destruction H2S
(preservation basement) CO2
Correlation of natural gases
with their sources
UD ss
Oriskany
Marcellus
Utica
Trenton
Tuscarora
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural Reservoir
compartmentalization
gases Discriminate between free and
Thermal maturity of adsorbed gas components in
natural gases: thermogenic shale gas and
coal bed gases
Maturity of source material Origin of problematic non-
Onset of low-maturity and hydrocarbon gases:
high-maturity thermogenic N2
gas generation H2S
Recognition of gas leakage CO2
and gas destruction
(preservation basement)
Correlation of natural
gases with their sources
Geochemical
Flow Units Flow Unit
Definition
Courtesy of Martin Schoell
From Hartman, 2008
-50

-45

-40

-35
13C-methane,

-30

-25

-20

-15

-10

-5

0
0 2 4 6 8
Elapsed Time, days
Utility of Isotope Geochemistry in
Unconventional Gas Exploration and
Development
Genetic origin of natural Reservoir
compartmentalization
gases Discriminate between free and
Thermal maturity of adsorbed gas components in
natural gases: thermogenic shale gas and
coal bed gases
Maturity of source material Origin of problematic non-
Onset of low-maturity and hydrocarbon gases:
high-maturity thermogenic N2
gas generation H2S
Recognition of gas leakage CO2
and gas destruction
(preservation basement)
Correlation of natural
gases with their sources
Hydrogen Sulfide and Nitrogen in
Trenton/Black River Reservoir, PA
Wolpert #1 well,
Bradford County, PA
0.51 mole percent
H2S
14.14 mole percent
N2
Limits to deeper
Ordovician gas? ?
H
2 S,
N
2?
What is the Source of the H2S?
34S = 14.7 permil
Stable isotope
composition suggests a
sulfate source for the
H2S:
Dissolved sulfate in brine
Anhydrite
H2S formed in the
reservoir at high
temperatures (> 140C)
through thermochemical
sulfate reduction (TSR)
Evidence for TSR
Sulfur isotope composition of the Petrographic evidence:
H2S (34S = 14.7 permil) Formation of late solid
Incorporation of sulfur in solid bitumen and pyrobitumen
bitumen > temperature replacement of
Carbon isotopic composition of solid sulfates by calcite
light hydrocarbon gases and Reprecipitation of dolomite
carbon dioxide (hydrocarbon and calcite cements with Ca
gases became more enriched in from dissolved CaSO4;
13C during TSR while CO became
2 poikilotopic anhydrite
more depleted) inclusions
Anhydrite concentrated along
stylolite surfaces
Metal sulfides
Accumulation of non-hydrocarbon
gases:
N2
H2S
CO2
What is the Source of the
Nitrogen?
15N2 = 0.4 permil
Deep crust or mantle
source
Further constrained by
noble gas data:
No fractionation due to
diffusion
Highly mature organic
matter source; possibly
metamorphic
Workshop Summary
Emphasis on:
Petrology and
geochemistry of shale
and shale-gas:
TOC
Organic petrography
Inorganic petrography
Rock-Eval pyrolysis
Biomarkers
Natural gas isotope
Photo courtesy of Gary Lash
geochemistry
So What?
What are the key
characteristics of
productive thermogenic
shale-gas reservoirs?
What are the objectives
of shale-gas resource
assessment?
How much gas is really
there?
How much can I really
recover?
Key Characteristics of
Productive Thermogenic
Shale-Gas Reservoirs
Original organic richness and generation
potential
Primary and secondary cracking of kerogen
and retained oil
Retention of oil for cracking to gas by
adsorption
Porosity resulting from organic matter
decomposition
Brittle mineralogical composition
OBJECTIVES OF SHALE-GAS
RESOURCE ASSESSMENT
What type of shale-gas system Depth and thickness of the
is the prospect? shale
Microbial Reservoir seals and barriers
Thermogenic (high or low Structural geology:
thermal maturity?)
Faults
Organic richness Fractures
Hydrocarbon potential Engineering how will the
Does thermal maturity match shale respond to stimulation?
the petroleum composition? Is there gas production in the
What is the gas content? region?
Gas wetness Infrastructure
Isotope geochemistry of the
gas

Ruble, 2008
Shale Gas & Shale Oil Risk Assessment Diagram

TOC (0 - 5)

TR (0 - 100) Ro (0.2 - 2.2)

Minimum Threshold Gas


Minimum Threshold Oil
Shale Oil Well No. 1
Shale Gas Well No. 2

Tmax (400 - 500) Dryness (0 - 100)

LOW RISK
Courtesy Tim Ruble, Weatherford Laboratories
Important Geological Parameters
for Shale-Gas Assessment
Basin analysis:
Stratigraphy and
sedimentary history
Structural geology and
tectonic history
Mineralogy
Porosity and
permeability
Shale Diagenesis
Rock Properties
How Much Gas Is Really There?
Volumetric calculation of hydrocarbons
generated in a source rock:
Source rock is identified and its boundaries
are defined
The mass of organic carbon in the source
rock is identified
The mass of hydrocarbons generated per unit
mass of organic carbon is estimated
The total mass of hydrocarbons generated is
determined by multiplication of these data
Schmoker, 1994
Source rock is identified and its
boundaries are defined
Organic richness
TOC
Subdivide, if
necessary, into units
of roughly
homogeneous
physical and
geochemical
properties
The mass of organic carbon in the
source rock is identified
Mass of organic
carbon: M (g TOC)
M (g TOC) = [TOC (wt.
%)/100] x (g/cm3) x
V (cm3)
(g/cm3) = average
formation density
V (cm3) determined
from thickness and
aerial extent
The mass of hydrocarbons generated
per unit mass of organic carbon (R) is
estimated
R (mg HC/g TOC) = HIo 18
Type I Oil Prone TYPE II Oil Prone

REMAINING HYDROCARBON POTENTIAL (mg HC/g Rock)


(mg HC/g TOC) HIp (mg 16
usu. lacustrine (usu. marine)

HC/g TOC) 14

12
This equation equates the Mixed Type II / III
Oil / Gas Prone
10
decline in generation
8
potential to hydrocarbons Organic
Lean
6
actually generated.
4
original HIo: Type III
Gas Prone
2

visual kerogen data 0


Dry
Gas Prone

Pyrolysis analysis of 0 0.5 1 1.5 2 2.5 3


TOTAL ORGANIC CARBON (TOC, wt.%)
3.5 4 4.5 5

thermally immature
samples
Van Krevelen diagram
trends
Compute the total mass of
hydrocarbons generated in the source
rock (HCG (kg HC)
HCG = R x M x 10-6 (kg/mg):
Minimum estimate of hydrocarbons derived
from the source rocks of a petroleum system
Does not account for hydrocarbons already
present in thermally immature shales
This method underestimates M and R (because
some organic carbon is lost by expulsion of
generated hydrocarbons)
Several approaches attempt to compensate for
these shortcomings
Parting thoughts
Unconventional Shale Gas
Petroleum System
Petroleum systems and
thermogenic gas shales
Source rock elements
remain the organic-rich
shale facies
Reservoir and seal vastly
different than those in
conventional systems:
Reservoir
low porosity, low
permeability shale
Organic-rich shale,
organic-lean shale,
siltstone, and carbonate
Shale Gas Petroleum System
Reservoir and seal
vastly different than
those in conventional
systems:
Seal
low porosity, low
permeability shale
Prevent the complete
escape of petroleum
from the shale to
conventional
siliciclastic and
carbonate reservoirs
Shale Gas Petroleum System
Reservoir and seal vastly
different than those in
conventional systems:
Adsorbed petroleum also
trapped by surface
chemistry
Shale diagenesis
Dissolution-reprecipitation
processes may diminish
gas reservoir properties by
releasing gas from the
system at high thermal
maturities
Key Characteristics of Productive
Thermogenic Shale-Gas Reservoirs
Original organic richness and generation
potential
Primary and secondary cracking of
kerogen and retained oil
Retention of oil for cracking to gas by
adsorption
Porosity resulting from organic matter
decomposition
Brittle mineralogical composition
Shale gas resources are
defined by:
Bulk rock properties
GIP volume
Gas composition
Organic richness
Kerogen type
Thermal maturity
Deliverability of shale gas
resource is defined by:
Permeability
Mineralogy
Mechanical rock
properties
Adjacent porous
lithologies
Evaluation Techniques
Geology
Geophysics
Organic petrology and
geochemistry
Resource Estimates
Milici and Swezey (2006):
259 Tcf gas-in-place
(GIP)
1,925 Bcf recoverable
Industry and academia
estimates of 50 to 500 Tcf
recoverable!
Wow!
Rational optimism: 100
200 Tcf recoverable
(1,600 Tcf in place)
depending on gas
prices (Stevens and
Kuuskraa, 2009)
Production and economics
GIP ~ 70 to 150 Bcf/mi2
Vertical wells:
150 Mcf/day 5MMcf/day
RF: 8 15%
Horizontal wells:
<400 Mcf/day 24.5
MMcf/day
RF: 20 40%
Chesapeake is reporting 6 Bcf
wells!

Personal communication, W. A. Zagorski and G. R.


Wrightstone
Drilled Marcellus
well

Permitted Marcellus
well

2456 permitted Marcellus


locations

1508 drilled/completed
Marcellus wells

Courtesy G. Wrightstone, 2009, Texas


Keystone Oil and Gas
Courtesy G. Wrightstone
Risks and Challenges
Topography
Completion effectiveness
Pipeline capacity and
transportation bottlenecks
Permitting and other
regulatory issues
Water use and disposal
issues
Fragmented land
ownership
Gas leakage and
groundwater
contamination
Water use and disposal issues
3 to 5 million gallons of
water per hydro-fracturing
job
Flowback is 1/2 to 1/3 of
this volume in a short
time!
Brine
Hydrocarbons
Metals
radioactive
Requires off-site
treatment
Concluding Remarks