Applications of Geochemistry To Source Rock Appraisals

Applications of Geochemistry to Source Rock Appraisals
The Applications of Organic Geochemistry to Source Rock Appraisal and Hydrocarbon Characteristics
By
Supaporn Pisutha-Arnond
9-Apr-04
GGG, PTT Exploration and Production Co. Ltd. Supaporn Pisutha-Arnond, Cambodia, 2004

(DRY) WELL 2
WEST
(SUCCESS) A B WELL 1 C
EAST
SHALE SOURCE
Hypothetical section across an area in the early stages of development (Barker, 1975)
9-Apr-04
Source Rock Appraisal

-Identification of source rock layers -Assessment of their maturity stages -To identify kitchen area -To determine the time of hydrocarbon generation -To trace migration path and entrapment process
9-Apr-04
Example of rift related environment (offshore SE, well A penetrated the post-rift Miocene and to Basement, well B drilled the post-rift and the upper part of the syn-rift sequence) (Bordenave, M.L., 1993, Applied Petroleum Geochemistry)
9-Apr-04
Source Rock Appraisal - Screening analysis 1. 2. 3. 4. Does the rock have sufficient organic matter? Is the organic matter of the right type? Has this organic matter generated petroleum? Has the generated petroleum migrated out?
9-Apr-04
KEROGEN
9-Apr-04

Green River Shales
Lower Toarcian Sediments
Van Krevelen Diagram atomic O/C ratio VS H/C ratio
Miocene Sed, Mahakam Delta
Reference: M.L. Bordenave, 1993, Applied Petroleum Geochemistry

9-Apr-04
KEROGEN
Type I : Lacustrine planktonic debris intensively reworked by bacteria Type II : Marine plankton debris sedimented under anoxic conditions Type III : Land-plant debris sedimented in terrestrial environment
Reference: M.L. Bordenave, 1993, Applied Petroleum Geochemistry

9-Apr-04
9-Apr-04

Trapping CO2
5500
Temperature
S3
3900 1000 3000
Rock-Eval Pyrolysis
Analysis Cycle
Pyrolysis Of kerogen
Volatilization Of existing HC
Cooling
Time
Cycle of analysis and example of record obtained by the pyrolysis method of Espitalie et al. 1977. (Ref: Milner, D. 1996)
S1
S2
Tmax
Example of record
S1
S2
S3
Increasing temp. of trapped CO2
Increasing temp. Of pyrolysis
Time
Oil or gas shows

S1 (g/ton of rock)
Oil or gas shows

Total Genetic potential S1+S2 (kg/ton of rock)
Oil or gas shows

S2/org.C Hydrocarbon Index S3/org.C Oxygen Index
Oil or gas shows

Transformation ratio S1/S1+S2 Peak temperature Tmax(*C)
Application to Petroleum exploration
9-Apr-04

Company Well/Area Sample Type File No. : : : : GOOD OIL Success 1 Unwashed Cuttings (Hubco Bags) GSI-01169 Extracted 5 hours (DCM 80% + MeOH 20%) Extracted 48 hours (DCM 90% + MeOH 10%)
TABLE ROCK-EVAL PYROLYSIS AND TOC CONTENT* Sample Depth (meters) 1440.00 1460.00 1740.00 1760.00 1780.00 1800.00 1820.00 TOC (wt.%) 0.96 0.71 0.66 0.62 0.51 0.50 0.56 mg/gm rock S1 0.07 0.04 0.02 0.05 S2 1.39 0.78 0.63 0.76 S3 0.95 0.59 0.26 0.28 Oil Potential Hydrogen Oxygen Tmax Production Yield Index Index (C) (S1+S2) Index 436.00 429.00 433.00 434.00 0.05 0.05 0.03 0.06 1.46 0.82 0.65 0.81 144.79 109.86 95.45 122.58 98.96 83.10 39.39 45.16
Lithology med gy Sh med gy Sh med gy Sh med gy Sh med gy Sh med gy Sh med gy Sh
S1 = Free Hydrocarbons S2 = Pyrolysable Hydrocarbons Oil Production Index = Transformation Ratio = S1/(S1+S2) Tmax = Temperature of Maximum S2 * Pyrolysis by Rock Eval II; TOC content by Leco Analyzer Hydrogen Index = (S2/TOC) x 100
S3 = Organic CO2 Oxygen Index = (S3/TOC) x 100

9-Apr-04

Company Well : PTTEP : Arthit 14-1X File No. : GSI-01167 Sample Type : Unwashed Cuttings (Hubco Bags) & SWC
FIGURE 2 Hydrogen Index v's Oxygen Index

(modified van Krevelen Diagram)
Classification of the 3 main Types of kerogen in a HI vs OI diagram
1000
Highly Oil Prone - Legend -
800
Interval Interval Interval Interval Interval Interval Interval
1149.0 - 1354.6 mTMD 1354.6 - 1695.6 mTMD 1695.6 - 1923.3 mTMD 1923.3 - 2093.2 mTMD 2093.2 - 2296.1 mTMD 2296.1 - 2997.7 mTMD 2997.7 - 3326.6 mTMD
600
II
Oil Prone
400
H drogen Inde (HI)
200
III
0
0.0 100.0
Gas Prone
200.0
300.0
400.0
Oxygen Index (OI)
9-Apr-04

Company : PTTEP Well : Arthit 14-1X Sample Type : Unwashed Cuttings (Hubco Bags) & SWC File No. : GSI-01167
FIGURE 1 Organic Matter Type and Thermal Maturity (Hydrogen Index/Tmax Diagram)
900
Type I Type II
750
0.5 % Ro
Kerogen type and thermal maturity In a Tmax vs HI diagram
- Legend Interval 1149.0 - 1354.6 mTMD Interval 1354.6 - 1695.6 mTMD Interval 1695.6 - 1923.3 mTMD Interval 1923.3 - 2093.2 mTMD Interval 2093.2 - 2296.1 mTMD Interval 2296.1 - 2997.7 mTMD Interval 2997.7 - 3326.6 mTMD
600
450
Hydrogen Index (mgHC/g TOC)
300
1.2 % Ro
150
Type III
0 400 420 440 460 480 500 520
Tmax (C)
IMMATURE OIL ZONE GAS ZONE
9-Apr-04

DUAL PETROLEUM SYSTEMS (Pattani)
110 0
KEROGEN TYPING IN THAILAND TERTIARY BASINS

MAE MOH
HYDROGEN INDEX (mg HC/g Or g. C)
Post rift: Coals and Coaly Shales (Fluvio-Deltaic), Type III Kerogen, Gas Condensate-Prone, Dominant System Early Syn-Rift: Lacustrine Algal Shales, Type I Kerogen, Oil-Prone, Supplemental System Oil: >500 MMBO Gas: 15 TCF Condensate: 500 MMBO
100 0
NONG YA PLONG
TYPE I (Oil-Prone)
LI MAE SOT PATTANI
900
800
700
600
TYPE II
500
400
300
200
100
TYPE III (Gas-Prone)

0 20 40 60 80 100 120 140 OX YGEN INDEX (mc CO 2/g O rg. C) 160 180
(Rui Lin, 2002)

9-Apr-04

VISUAL KEROGEN
Optical Method to identify organic richness
Developed from Coal Petrology, the description Of organic matter uses the maceral classification.
These techniques are still in their infacy and should be Considered as aids to research rather than commonly Used tools. (Bordenave, M.L. 1993, Applied Petroleum Geochemistry)
9-Apr-04

Company W ell Name Area/Block Sample Type
File no.
: : : :
:
GOOD OIL Success 1 Ditch Cuttings GSI-01169
KEROGEN DATA SUMMARY

Sample Depth (m) 1440 1560 1620 1660 1740 2790 2820 Amorphinite Exinite (Type I-II/III) (Type I/II) NF.A. % 30 30 50 40 61 20 25 F.A. % 10 5 A C S R SB % % % % % 7 5 3 2 tr 1 2 2 2 2 2 2 2 tr 1 2 2 3 3 3 2 3 tr 2 1 1 L % 2 5 7 10 7 7 5 22 21 15 18 12 16 9 OPK % Vitrinite Semifusinite Type III % Type IV % 43 47 33 37 20 57 56 5 2 2 5 5 5 5 Inertinite Type IV % tr tr tr tr 2 2 5 Preserv. Rec. of Organic Matter G G G G G G G Mean Ro % 0.35 0.44 0.45 0.46 0.51 0.49 0.46 TAS Fluorescence Colour F.A. 3/4 4 4 4-4/5 4-4/5 4/5 4/5 do do Herb o-do o-do o o o o o M M M M G M M SA-SR SA-SR SA-SR SA-SR SA-SR SA-SR SA-SR Srt Ang
M-G M-G P-M M-G P-M P-M P-M
NF.A F.A A C S R SB L NA NDP
: : : : : : : : : :
Non Fluorescent Amorphous Fluorescing Amorphous Alginite Cutinite Sporinite Resinite Suberinite Liptodetrinite No Analysis No Determination Possible.
OPK TAS Herb Tr Srt Ang
: : : : : :
Oil Prone Kerogen Thermal Alteration Scale Herbaceous Trace Sorting Angularity
g: y: o: do : br : dkbr :
green yellow orange dull orange brown dark brown
Fr : Pr : Bn : P: M:
Fair Poor Barren Poor Moderate
G A SA SR R
: : : : :
Good Angular Sub-Angular Sub-Rounded Rounded
9-Apr-04

100 Non Flour Amorph 90 80 70 60 50 40 30 20 10 0 Well 1 Well 2 Well 3 Well 4 Well 5 Well 6 Well 7 Oil Prone Kerogen Vitrinite Semi Fusinite Inertinite
9-Apr-04

Visual Kerogen Type from Rift Section
80 70 60 50 40 30 20 10 0
Well X 3110
Non Flour Amorph
14-1X
Well Y 3770
Oil Prone Kerogen Vitrinite
14-5(ST)
Well Z 3280
*Inertinite
14-6X
9-Apr-04
MATURITY
9-Apr-04

Recognition of Maturity Stages
1. Optical Methods 2. Chemical Methods
Optical Methods: Vitrinite Reflectance
Immature up to 0.5 %Ro Mature 0.5 to 2.0 %Ro Overmature 2.0 to 16.0 %Ro
9-Apr-04

Company : GOOD OIL : Success 1 Well Sample Type : Ditch cuttings : GSI-01169 File No.
TABLE VITRINITE REFLECTANCE RESULTS

Sample Depth (metres) 1 2 3 4 5 6 7 1440.0 1560.0 1620.0 1660.0 1740.0 2790.0 2820.0 Plug Type WR WR WR WR WR WR WR Mean Ro (%) 0.35 0.44 0.45 0.46 0.51 0.49 0.46 No. of Readings 18 18 15 18 44 21 19 Minimum Reflectance (%) 0.31 0.31 0.40 0.35 0.40 0.41 0.40 Maximum Reflectance (%) 0.42 0.60 0.51 0.54 0.77 0.67 0.58 SD 0.027 0.082 0.037 0.054 0.088 0.065 0.049
9-Apr-04

Company Well : PTTEP : Arthit 14-1X File No. : GSI-01167 Sample Type : Ditch Cuttings and SWC
FIGURE 5
Maturity Profile
DEPTH
(metres)
0
Vitrinite Reflectance VR (Ro)

0.8 1.0
Post-mature
%Ro Scale
0.3
Immature
0.4
0.5
0.6
Ma tu r e
-Plot against depth (Log scale)
250
500
750
'best fit' VR gradient

1000
1250
1500
1750
Top 'Oil Window'

c. 1800 m
2000
2250
2500
2750
3000
3250
9-Apr-04
Mean Vitrinite Reflectance (Indigenous) Mean Vitrinite Reflectance (Reworked/oxidised population) Mean Vitrinite Reflectance (Caving)

Maturity and VR Depth Plot
Depth vs Vitrinite Reflectance
0 0 1 1 2

0 0 -500 -1000 1 1 2
-500
-1000
-1500
Depth(m)
Depth(m)
-1500
Calculation Observed
-2000 -2500 -3000
-2000
-2500
-3500
-3000
-4000
-3500
-4500
Vitrinite Reflectance(%)
9-Apr-04

Maturity and VR Depth Plot
0 0 1 1 2
-500
-1000
Depth(m)
-1500
-2000
-2500
-3000
-3500
9-Apr-04

Maturity (%Ro)
1 0 10
Fm
Early Mature (oil) 0.5 0.7 (%Ro) Mid Mature (oil) 0.7 1.0 (%Ro) Late Mature (oil) 1.0 1.3 (%Ro) Main Gas Generation 1.3 2.6 (%Ro)
Fm3
Depth Subsurface (m)
1000
Fm2E Fm2D Fm2C

2000
Fm2B Fm2A
Fm1
3000 0 50 100 150 200 250
t=0
Maturity Temperature Early Mature (oil) 0.5 to 0.7 (%Ro) Mid Mature (oil) 0.7 to 1 (%Ro) Late Mature (oil) 1 to 1.3 (%Ro) Main Gas Generation 1.3 to 2.6 (%Ro) %Ro BHT
Temperature (C)
9-Apr-04
Hydrocarbon Volume Calculation
9-Apr-04

Volume of Hydrocarbon Generated
Reference from: Volumetric Calculation of Hydrocarbons Generated, page 323, AAPG Mem60
(M) Mass of Organic Carbon (g)

Gross Volume of Rock = 1.97 x 1014 cm3 Density of Rock (shale) = 2.5 g/cm3 TOC = 10 %
(R) HI mg HC/g
HI(present) = 200 mgHC/g HI (origin) = 500 mgHC/g hydrocarbon generated = 500-200 = 300 mgHC/g
9-Apr-04
Applications of Geochemistry to Source Rock Appraisals EXERCISE

Given: 1. Gross Volume of Rock of 1.55 x 109 x 3600 ft3 2. TOC = 10% 3. Density of shale = 2.5 gm/cm3 4. HI 200 mgHC/g
Reference: Volumetric Calculation of Hydrocarbons Generated, page323, AAPG Mem60
9-Apr-04

MASS HYDROCARBON GENERATION
TOC 1% Kerogen Type II F(oil) 60% F(gas) 40%
Characteristic
2300m
Bulk Rock Volume 1,800,000 MMm3
9-Apr-04

@ 2300m Bulk Rock Volume 1,800,000 MMm3
TOC 1% Type II F(oil) 60% F(gas)40%
MASS Hydrocarbon Generated OIL 43,000 MMBBL GAS 970 BCF

Expulsion efficiency for oil 65% for gas 80% Migration efficiency for oil 8% for gas 80%
Mass HC generated (Oil) subjected to traps 2,300 MMBBL Mass HC generated (Gas) subjected to traps 620 BCF
9-Apr-04

From 2300m
Expulsion Efficiency (OIL) 65% (GAS) 80% Migration Efficiency (OIL) 8% (GAS) 80%
Oil 43,000 MMBBL Gas 970 BCF
In source beds
To carrier beds
Ready for accumulation

9-Apr-04

GAS FIELD SIZE DISTRIBUTION
9-Apr-04

Oil Field Size Distribution
9-Apr-04

MIGRATION
9-Apr-04
GAS
9-Apr-04

Differential entrapment by Gussow (1954)
GAS
9-Apr-04

Differential entrapment by Gussow (1954)
GAS
9-Apr-04
HYDROCARBON FLUIDS GAS

OIL/CONDENSATE
9-Apr-04
CO2
9-Apr-04

W ell / Area Sample Type File No. : W ELL SP1 : Gas : GSI-01207
TABLE 10 GAS STABLE ISOTOPE COMPOSITION DATA

Sample ID (Cyl. No.) 13 C methane Depth (C 1 ) (mM D/mTM D-RT)* ( ) 1221.0 - 1238.0 1495.5 1598.0 1683.0 2000.0 - 2012.0 2335.5 - 2353.5 -37.11 -33.80 -33.29 -33.24 -32.88 -36.20 13 C ethane (C 2 ) ( ) -29.93 -28.62 -28.40 -26.94 -27.57 -28.18 13 C propane (C 3 ) ( ) -28.29 -28.33 -26.52 -27.33 -23.92 -24.89 13 C 13 C butanes (iC 4 ) (nC 4 ) ( ) ( ) -30.15 -29.00 -27.59 -28.81 -22.35 -24.75 -28.13 -29.35 -27.01 -27.18 -24.01 -23.56 13 C D carbon dioxide methane Gas (CO 2 ) (C 1 ) W etness ( ) ( ) (% ) -10.49 -3.22 -7.18 -5.39 -7.64 -10.35 -221 -195 -195 -197 -197 -199 25.62 8.63 8.06 9.72 9.57 27.08
TST-3 (TS-)8412 RFT-4 (PTK-003) RFT-3 (PTK-001) RFT-4 (PT-120) TST-2 (TS-)5815 TST-1 (TS-)3006
* TST sample depth unit: mMD RFT sample depth unit: mTMD-RT
9-Apr-04

Arthit-15-1X
WELL C Arthit-15-4X
WELL A
WELLB Arthit-15-6X
-1,000 -1,100 -1,200 -1,300 -1,400 -1,500 -1,600 -1,700 -1,800 -1,900 -2,000 -2,100 -2,200 -2,300 -2,400 -2,500 -2,600 -2,700 -2,800 -2,900 -3,000 -3,100 0 20
-1,000
-1,000
WELL A
-1,100 -1,200 -1,300 -1,400 -1,500 -1,600 -1,700 -1,800 -1,900 -2,000 -2,100 -2,200 -2,300 -2,400 -2,500 -2,600 -2,700 -2,800
WELL B
FM3 2E
-1,100 -1,200 -1,300 -1,400 -1,500 -1,600 -1,700 -1,800 -1,900 -2,000 -2,100 -2,200
WELL C
2D
2C 2B 2A
-2,300 -2,400 -2,500 -2,600 -2,700 -2,800 -2,900 -3,000 -3,100 0 20 40 60 80 100
CO2 Distribution
40 60 80 100
-2,900 -3,000 -3,100 0 20 40 60 80 100
FM1
Basement
Inorganic CO2 migration relates Directly to distance from the basement ????
9-Apr-04

A crossplot between CO2 content and stable carbon isotope Pattani and North Malay Basins (Rui Lin, 2001)
-4.00 -6.00 INORGANIC -8.00 Nearby Area I 13 C CO2 -10.00 MIXING -12.00 -14.00 -16.00 -18.00 0
9-Apr-04
Nearby Area II Nearby Area III
ORGANIC
10
20
30
40
50 CO2 (mole%)
60
70
Exploration and Production Co. Ltd. 80 GGG, PTT 90 100 Supaporn Pisutha-Arnond, Cambodia, 2004

13CPDB (%o)
-100 Solid Phase Marine Carbonate Dissolved Marine Bicarbonate Atmospheric CO2 Metamorphic CO2 Kerogen Petroleum
Increasing Maturity
-80
-60
-40
-20
Thermogenic CH4 Biogenic CH4 TST#3, WELL SP2
Carbon isotope compositions of major carbon reservoirs in sedimentary basin (modified from Emery & Robinson, 1993)
9-Apr-04

WELL SP1Models Three Possible CO2
Arthit SP1 1515- 3 X WELL
Seq3E Seq3D Seq3C
Seq 4
13C=-21 II
11% 22%
11.7 11.7
23.4
Seq3B Seq3A
23.4 23.3 23.3 21.6 21.6 25.4 25.4 75. 75.2
Seq 2 Seq 1
11% 22% 85% 48% 36%

Sample analysed 13C
85% 48% 36%

0
8 85.8
Seq2
48.4 48.4 46.5 46.5
36.2 36.2
13C=-7 Group I
Seq1
100 Content (%)
9-Apr-04

Sapropelic Source
20
Humic Source
68
Diagenesis
50 122
Rift-source generated very low CO2

100 CO2 C2H6+ CO2 212
Temperature (oF)
Temperature (oC)
Catagenesis
C2H6+
150
CH4
CH4
302
200
392
Metagenesis
Relative yield of gas from organic matter in fine-grained sediments
The generation of gases from organic matter with temperature

(modified from Hunt, 1996) 9-Apr-04
HYDROCARBON FLUIDS
GAS
OIL/CONDENSATE
9-Apr-04

CUTTINGS OIL/CONDENSATE
Extractable Organic Matter
Liquid Chromatography SAT % ARO % RES % ASP %
Gas Chromatography (GC) Gas Chromatography Mass Spectrometry (GC-MS) Stable Isotope
9-Apr-04

Company Well / Area Sample Type File No. TABLE 2 GAS CHROMATOGRAPHY DATA (C5+ WHOLE OIL ANALYSIS: NORMALISED PERCENT) TST-1 TST-2 TST-3 Cyl# TS-3006 Cyl# TS-5815 Cyl# TS-8412 : : : : Success Oil WELL SP1 Oils GSI-01207
Component
nC5 nC6 nC7 nC8 nC9 nC10 nC11 nC12 nC13 nC14
2.80 3.29 4.11 5.31 6.41 7.20 7.65 7.75 7.82 7.81
1.06 1.49 2.30 3.34 4.53 6.06 7.98 9.60 10.81 11.18
9.41 9.21 11.00 12.05 11.22 9.92 9.78 9.08 7.27 4.39
nC37 nC38 Total
0.00 0.00 100.00
0.00 0.00 100.00
0.00 0.00 100.00
Pris/Phy Pris/nC17 Phy/nC18 nC31/nC19 CPI
5.95 0.53 0.11 0.00 1.39
5.35 0.60 0.17 0.00 1.53
3.53 0.72 0.35 0.00 2.90
9-Apr-04

30000
nC10
Arthit-15-1X WELL SP1 Depth (m ) : 2,338 Condensate , TST #1 Test #4
25000
20000
nC15
Pr
nC20
15000
10
15
20
25
30
35
Arbitrary Y / Arbitrary X File # 5 = TST4
Gas Chromatogram of an Condensate
Paged Y-Zoom CURSOR Res=None
(note the high pr/ph ratio and declining n-paraffin envelope to n-C30) GGG, PTT Exploration and Production Co. Ltd. Supaporn Pisutha-Arnond, Cambodia, 2004
9-Apr-04
nC30 40
Ph
nC25
10000

Company Well / Area Sample Type File No. : Success Oil : WELL SP1 :
Oil
TABLE 8 CARBON ISOTOPE DATA *
: GSI-01207
13
Sample ID (Cyl. No.) TST-1 (TS-3006) TST-2 (TS-5815) TST-3 (TS-8412) Depth (mTMD-RT) 2335.5-2353.5 2000.0-2012.0 1221.0-1238.0
13
C
Cv -1.31 -2.80 -2.45
Saturates -27.98 -27.56 -27.76
Aromatics -27.23 -27.42 -27.49
9-Apr-04

Methane vs. Carbon Isotope vs. Gas Wetness Methane Carbon Isotope Gas Wetness in N. Malay Basin in the North Malay Basin (Arthit and Nearby Area) 100000 CO2-REDUCTION 10000 Shallow Gas C1/(C2+C3) 1000 BIOGENIC 100 Biogenic mixing
FM0&1
MEETHYL FERMENTATION "Deep" Petroleum System (FM 0) THERMOGENIC
10 "Shallow" Petroleum System (FM 2 coals) -90.00 -80.00 -70.00 -60.00 13C (o/oo) Arthit Area I
9-Apr-04
2D
Maturation
2A-2C
1 -100.00
-50.00
-40.00
-30.00
-20.00
Nearby Area Area II

Condensate Source Typing in the Arthit Field Condensate Source Typing in North Malay North Malay Basin 16 14 Pristane/Phytane 12 10
OBM
Basin
Coaly Condensates
8 6 4 2 0 -34.00 -32.00 -30.00 -28.00

13
Lacustrine Algal Oils -26.00 -24.00 -22.00 -20.00 -18.00
Coil (o/oo)
9-Apr-04

Stable Carbon Isotope Composition of Saturate HC vs Pr/Ph
16
13Cs and Pr/Ph ratio
Coal and coaly shale Northwest Java

12
Northwestern Java South Sumatra
Pr/Ph
Lacustrine Northwest Java
0 -32.00 -30.00 -28.00 -26.00 -24.00 -22.00 -20.00
13Cs
9-Apr-04
Geochemical Correlation
Exploration no guessing
9-Apr-04
Oil to Oil Correlation Source Rock Crude Oil Correlation Surface Seep Oil Correlation Correlation of Gasses
9-Apr-04

Applications of Geochemistry To Source Rock Appraisals

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