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Geoconvention 2019 13 May 2019
Jarvie Presentation on Geochemistry 1
Tight Oil Geochemistry:an introduction ©
Daniel M JarvieWildcat Technologies
TCU Energy Institute
© 2019 Copyright Daniel M Jarvie. All rights reserved.
IntroductionBackground
SamplingGeochemical Analyses
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 2
Goals of Presentation
• Introduce you to a few principles of organic geochemistry
• Food for thought related to producibility from tight oil and gas systems
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 3
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Geoconvention 2019 13 May 2019
Jarvie Presentation on Geochemistry 2
Exploration and ProductionGeochemical Input
• Exploration– Source potential
– Source maturity
– Kerogen type
– Depositional facies
– Product type
– Oil shows
– Product quality
– Hybrid nature, if any
– Leaky or tight seals
– Risk assessment
– Conventional opportunities
• Production
– Commerciality• OOIP
• Product (oil, NGLs, dry gas)
– Producibility• Baffles/barriers
• API gravity, viscosity
• Present of HM waxes
• Gas exsolution
• GOR
– Connectivity• Compartmentalization
• Allocation
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 4
PRODUCIBILITYOIL QUALITY
andPHASE
TOMTOH
OIL CONTENT(So, Sw)
BRITTLENESSand
Fracture Network
FRAC BARRIERS
or BAFFLES
SYSTEMTYPE
POR/PERM
PRESSURE
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 5
Unconventional Resource Systems
SourceRock
PetroleumSystem
{source, trap, seal}
A bit more complicated…
Variable source rock, interbeds, barriers / baffles, expulsion, expulsion/migration fractionation
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 6
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Jarvie Presentation on Geochemistry 3
Scaling
EOG Resources, 2010 Investor Presentation
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 7
Polarity: chemical attraction
+ - + ------
+ -+-
The presence of Sulfur and Nitrogen results in polarity in resins and asphaltenes,i.e., they are attracted to various surfaces including oil wet or water wet
The resin and asphaltene molecules also happen to be LARGE and VISCOUS.
Surface tension, Interfacial Tension
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 8
Background
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Jarvie Presentation on Geochemistry 4
Important Definitions Remainmissing in many scientific presentations
The nomenclature and scientific classification of petroleum are in a state of uncertainty and confusion. Geologists, chemists, lawyers, refiners, and engineers have all made attempts to define the naturally occurring forms, but for one reason or another, few of their definitions have gained widespread acceptance.
Levorsen, 1954Geology of Petroleum
Chapter 1, 2nd paragraph
Oil, hydrocarbons, petroleum, bitumen, pyrobitumen, primary and secondary cracking
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 10
Question Everything but note,often evidence and its interpretation are elusive
This does not just apply to the internet, Facebook and the like.It also applies to scientific journals (AAPG Bull.), presentations, news
articles and includes this author and presenter.
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 11
Sampling
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Jarvie Presentation on Geochemistry 5
Mud or Production Gasand cuttings sampling
Excellent data for both tight oil and gas plays (as well as conventional plays)
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 13
Rock Sample Sizefor routine geochem analyses
1 teaspoon of cuttings or core chips = 10 grams
1 tablespoon of cuttings or core chips = 30 grams
Sufficient forall geochemical
work
Sufficient forall work
includingmineralogy,
fluid inclusion,etc.
14Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 14
Know or specify samplepreparation!
Sieving:4 mesh on top (removes cavings)60 mesh in middle (portion to be analyzed)Pan on bottom (catches fines) There are organic detergents that aid in
the removal of surface contamination including OBM.*** Chips are recommended for best S1 yields
4 mesh
60 mesh
PowderedRock
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 15
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Jarvie Presentation on Geochemistry 6
Center-cut Core Plugs(avoid OBM contamination)
for geochem
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Optimum quantity of Oil needed for geochem analysis
Volume is from 1 – 7 millilitersOnly a drop of oil is needed for GC fingerprinting
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 17
Basic Geochemical Analyses:
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Jarvie Presentation on Geochemistry 7
Depiction of TOC and Pyrolysis Data
TOC (wt.%)
Generative Organic Carbon (wt.%)
Non-Generative Organic Carbon (wt.%)
Jarvie, 1991; 2015
S2 (pyrolysis yield),Tmax
S4 (yield of organic carbon in hydrogen-poor TOC)
S1 (oil
yield)
S3 (kerogen CO2 yield)
Note: TOC can be oil/bitumen-free or with oil/bitumen
Organic carbon in oil as measured by S1 is only 0.085% carbon
S2 is only measuring the GOC portion of kerogen
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 19
Thermal Extraction-Pyrolysis
ThermalExtraction
S1 Oil
PyrolysisReactiveKerogen
(S2)
Non-ReactiveKerogen
(S4)
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 20
Which is the better Source Rock?
TOCo = 3.00 wt.% TOCo = 5.00 wt.%
Total Petroleum Generation Potential:
HIo = 500 mg/gT HIo = 200 mg/gT
S2o = TOCo x HIo / 100 = 15 mg/gRTR = 1.00boe/acre-ft = 23 x 15 = 345 boe/afThickness (ft) = 100boe/section/100 ft = 345 x 640 x 100
= 22.1 mmboe/section/100 ft
S2o = TOCo x HIo / 100 = 10 mg/gRTR = 1.00boe/acre-ft = 23 x 10 = 230 boe/afThickness (ft) = 100boe/section/100 ft = 230 x 640 x 100
= 14.7 mmboe/section/100 ft
23 is a conversion factor derived by assuming a petroleum density of 0.85 g/cc and rock density of 2.7 g/cc
Original hydrogen content is equally important as original TOC content
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Jarvie Presentation on Geochemistry 8
Change from Original to Present-dayis amount of petroleum generated
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Determining Oil Content
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 23
Factors Affecting Measured Oil Content (S1 oil)
• Type of sample (cuttings, SWC, core)
• Organic richness (sorption)
• Type of oil in rock (black oil vs condensate)
• Type of lithofacies (shale, carbonate, sandstone)
• Permeability
• Sample storage, handling and processing
• Oil-based mud (OBM) or organic additives to drilling fluids
• Instrument and program used for analysis
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 24
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Jarvie Presentation on Geochemistry 9
S1 Oil Measurement
S1(oil)
S1’ (oil in S2)
Evap. Lossof oil
S2 (kerogen)
Total Oil = (S1 WR - S1 extracted rock) + (S2 whole rock – S2 extracted rock) + E.L.
S2 extracted rock
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 25
Comparison of Composition of Oil in measured S1 vs extracted S1
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Duvernay (EOG Cygnet well):Change in S1 after extraction
Data provided by and from Dong et al., 2019
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Jarvie Presentation on Geochemistry 10
Routine vs HAWK-PAM S1 Analysis
Classical Pyrolysis “S2 shoulder” is
resolved on HAWK-PAM
Maende, 2015
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Evaporative Loss
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 29
Evaporative Loss from Reservoir Rockvs produced oil and source rock
U. Bakken Shale
Middle Member Bakken Formation
Produced OilMiddle Member
Organic-rich,siliceous shale
S1m = 7.52 mg/g
Organic-lean,dolomite
S1m = 1.12 mg/g
42oAPIproduced oil
Jarvie et al., 2011
Evaporative lossWilliston Basin,Parshall Field
Bakken FormationMiddle Member
Production
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GC Fingerprinting:basically a histogram of resolvable compounds
0
50
100
150
200
250
300
350
400
450
n-C4 n-C5 n-C6 n-C7 n-C8 n-C9 n-C10 n-C11 n-C12 n-C13 n-C14 n-C15 n-C16 n-C17 n-C18 n-C19 n-C20 n-C21 n-C22 n-C23 n-C24 n-C25 n-C26 n-C27 n-C28 n-C29 n-C30 n-C31 n-C32 n-C33 n-C34 n-C35 n-C36 n-C37 n-C38 n-C39 n-C40 n-C41 n-C42
YIE
LD
Compound Name
YIELD
DISTRIBUTION (n-alkanes by increasing molecular weight)
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 31
Petroleum Correlation, Alteration, Organofacies
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Thompson, 1988; Dow, 1994
GC for Correlation and Alteration(also for connectivity and allocation assessments)
Correlated Oils
AlteredOils
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Pimienta Extract GC Histogram of Molar Yields of normal Alkanes (slide overlays)
Evaporative Loss
0
50
100
150
200
250
300
350
400
450
500
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39
Mo
lar
Yiel
d
n-Alkane Carbon Number
Exponential Restoration of C1 through C40
Predicted in situ Gas to Oil Index: 63%
GC Profile Analysis and Restoration
Restoration is only applicable to unaltered volatile oils and condensates
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 34
This allows restoring the lost petroleum(oil and gas) in S1 for volatile oils and condensates
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Prediction of GORfrom restored GC data
(also ethane and propane gas isotopes)
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Prediction of Gas to Oil Indexfrom restored GC
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Permian Wolfcamp FormationDelaware (Permian) Basin
Jarvie, 2017
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Oil Crossover Effect
S1 oil content normalized by TOC(oil saturation index (OSI))
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Jarvie Presentation on Geochemistry 14
Oil Crossover Effect
S1/TOC > 1or when
Oil Saturation Index
(S1/TOCx100) > 100 mg oil/g
TOC
Data from Lopatin et al., 2003; Jarvie, 2012 AAPG Memoir 97
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 40
EOG Cygnet Duvernay: S1 Oil vs TOC
Data from Dong et al., 2019Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 41
Prediction of Apparent Water Saturation (Sw) from pyrolysis data
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Jarvie Presentation on Geochemistry 15
Sorption(adsorption and absorption)
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Relationship between Sorptionof Petroleum and TOC
Modified from Longjiang and Barker, 1989 in Hunt, 1995; with adsorption from Sandvik et al., 1992
This shows that all oil cannot be expelled and that this retained oil is
ultimately cracked to gas
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Sorption bykerogen and petroleum (bitumen)
This is also related to
organoporosity
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Jarvie Presentation on Geochemistry 16
Geochemical Logsshowing adsorption and producible oil index
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 46
Difference in SARA yields between Production and Reservoir Rock
Produced PetroleumSARA Analysis
Extracted Petroleumfrom reservoir rock
SARA Analysis
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 47
Thermal Maturity
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Jarvie Presentation on Geochemistry 17
Assume we could track a source rock from deposition to present-day
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 49
Maturation Profile through Time
700 350
200
50
Oil
Oil- Gas
Gas
Dry Gas
Oil
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Barnett Shale Maturation Results
S2
Jarvie and Lundell, 1991
Pyrogram Maturity Tmax %Roe TOC S2 HI
Red Immature 432 0.62 5.21 19.80 380
Blue Early oil 435 0.67 4.53 13.45 297
Green Peak oil 437 0.71 4.11 10.27 250
Cyan Late oil 443 0.81 3.77 5.88 156
Orange Early gas 455 1.03 3.41 1.81 53
White Late wet gas 470 1.30 3.32 1.36 41
Black Dry gas 480 1.48 3.23 0.25 8
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Jarvie Presentation on Geochemistry 18
Change in vitrinite reflectivity
histograms with related chemical structural change
Sample selection is critical to provide the petrologist the
best opportunity to find vitrinite particles(Type III kerogen)
After Oberlin, 1980; Bordenave, 1993
Histogram of Vitrinite Reflectance Readings
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Correlation of Aromatic Ratios to Vitrinite Reflectance
Data from Don Rocher, Geomark Research
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 53
Optimum window for tight oil
Optimum window for open-fracture shale
Optimum window for high yield shale gas
Lean-to-dry gas
Factors:MaturitySystem typePermeabilityAlteration
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Jarvie Presentation on Geochemistry 19
Duvernay data set
Graphic from Dong et al., 2019
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 55
Sigmoidal Fit provides indication of original HI
2D Graph 2f = a/(1+exp(-(x-x0)/b))
X Data
400 420 440 460 480 500 520 540 560
Y D
ata
-200
0
200
400
600
800
x column 1 vs y column 1 Col 1 vs Col 2 95% Confidence Band 95% Prediction Band
Tmax (oC)
Hyd
roge
n I
nd
ex (
mg
/g)
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 56
TOCo = (TOCpd - (S1*.085) - (TOCpd * HIpd * 0.00085))/(1 - HIo * 0.00085)
TR1 = (HIo - HIpd) / HIo
TR2 = (1200 x (HIo - HIpd)) / (HIo x (1200 - HIpd))
Computed Total Petroleum Generationat given level of conversion (TR)
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Jarvie Presentation on Geochemistry 20
Range of Original HIfor Type II Kerogens
Distribution HIo GOCo (%) NGOCo (%)
P90 340 29% 71%
P50 475 40% 60%
P10 645 55% 45%
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Modeled Source Rock Conversionfrom source rock database
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 59
Kinetic Models:Hydrous Isothermal vs Anhydrous Non-Isothermal
Only one technique models Monterey data maturation
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Ref: Lewan and Ruble, 2002, Organic Geochemistry Journal
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Jarvie Presentation on Geochemistry 21
Kerogen Type:
Visual and Chemical
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Visual Kerogen Macerals
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 62
Hexane (C6 H14)
H/C: 2.35Cyclohexane (C6 H12)
H/C: 2.02Benzene (C6 H6)
H/C: 1.01
Six Carbon Atom Hydrocarbons:All with different relative hydrogen contents
Linear alkanes Cycloalkanes Aromatics
H
H
H
H
H
HH
H
H
H
H
H
HH
H
H
H
H
H
H
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Jarvie Presentation on Geochemistry 22
Kerogen Type for Immature OMbased on HI vs OI
Type I
Type II
Type III
Derived from Espitalie et al, 1977
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Visual and Chemical Characteristicsof oil, mixed, or gas prone OM
Sources: Jones, 1984; Hunt, 1995
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Bulk Petroleum Composition
SARASaturatesAromatics
ResinsAsphaltenes
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Jarvie Presentation on Geochemistry 23
When is Petroleum Fractionated?any time it moves…
Source Rock
Conventional Trap
ProducedPetroleum
2o Conventional Trap
Gas
Exs
olu
tion
Gas sampleOil sample
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 67
SATURATES AROMATICS RESINS ASPHALTENES
EOM
MINERAL MATTER MINERAL MATTER
Extractable Organic Matter (EOM)
KEROGEN
LIPTINITE AMORPHOUS VITRINITE INERTINITEEXINITE
POLLEN SPORES
DINO-FLAGELLATES
andACRITARCHS
ALGAE CHITINOZOA SCOLECODONTS
PARTIALLY STRUCTURED
(CUTICLES, CELLULAR DEBRIS)
MICROFOSSIBLE ASSEMBLAGES
WOODY PLANT DEBRIS
CARBONACEOUS
CHAR
???
OIL PRONEGAS
PRONENO
POTENTIAL
UNKNOWN OIL/GASJarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 68
Composition and Structure of Polar Compoundsaffects chemical properties(polars include resins and asphaltenes)
Polar Compounds Alkyl branches on polycondensed aromatics
• Carbon• Hydrogen• Oxygen• Sulfur• Nitrogen
sulfurnitrogen
oxygen Polarity allows interaction of oil
with water
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Jarvie Presentation on Geochemistry 24
Duvernay Oil - Severe Fractionationbetween reservoir rock and produced oil
This suggests that while produced oil is 43oAPI, reservoir rock is ca. 33oAPI
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Kerogen and PetroleumCracking
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 71
Cracking of Kerogen and Petroleum
Temperatures modified from Hunt, 1995
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Petroleum (Bitumen)
Sats Aros Resins
Asphaltenes
Asphaltenes
Asp
hs
ResinsArosSats Prechar
Sats
Aro
sResinsG
as
Gas
Gas
Res
ins
ArosSatsGas
Gas Sats Aros
Prechar-Pyrobitumen
Prechar-Pyrobitumen
Aro
sSa
tsGas Pyrobitumen
Bio
mar
kers
Bio
mar
kers
Bio
mar
kers
H2OCO2
H2S
H2
OCO2
H2S
H2S
Black Oil Phase
Bitumen Phase
Volatile Oil Phase
Condensate Phase
Dry Gas Phase
NGL Phase
SecondaryCracking
Bio
mar
ker
s
H2OCO2
H2S
Jarvie, 2015 (AAPG)Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 73
Cracking of Resinsresults in increase in saturates and API gravity
Data from Han et al. 2014
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Structural Rearrangementsleading to more refractory (pore
throat blocking) organics??
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Risking Maturity
DGR LGR Oil Vitrinite Interpreted
(C1/C1..C4)) C6+/(C1..C6)) Yield Mole % Reflectance Tmax Maturity
(%) (%) (bbls/mmcf) C7+ (%Roe) (oC) PI Window
< 0.55 <427 < 0.10 Immature
< 50 > 50 0 - 1999 > 500 > 20.0 <0.75 <440 Black
50 - 74 19.9 - 49.9 2000 - 3499 300 - 499 12.5 - 20.0 0.75 - 0.99 440 - 454 Volatile Oil
75 - 84 5.0 - 19.9 3500 - 49999 20 - 299 < 12.5 1.00 - 1.19 455 - 464 Condensate-Wet Gas
80 - 90 1.0 - 4.9 50,000 - 99,999 10 - 19 < 12.5 1.20 - 1.39 465 - 475 Wet Gas
> 90 < 1 < 10 >1.40 > 475 Dry Gas
Gas-to Oil
Ratio (GOR)
(scf/bbl)
>100,000
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Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 77
Thermal Disassociation of Carbonates to CO2modeled using an arbitrary 3.3oC/my constant heating rate
Jarvie and Jarvie, 2007, IMOG
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 78
Do Organic Acids affect carbonate rocks???including carbonic acid formed from CO2 and water from kerogen decomposition
Acid etching noted in various plays:
• Eagle Ford• Bakken• Smackover/Brown Dense
Jarvie, 2012b
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Biomarkersand
Diamondoids
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Applications
• Correlations
– Oil to oil
– Oil to rock
• Organofacies Assessment
• Thermal Maturity
Correlation and Organofacies Assessment
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Using Biomarker Datato correlate oils
Dembicki, 2017
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Low Maturity Oilswith high diamondoids: secondary charge
Zumberge et al., 2017
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Gas Compositionand
Isotopes
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Gas CompositionC1/(C1..C4) vs BTU
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 500 1000 1500 2000 2500 3000
Gas Calorific Content (btu)
Dry
Gas R
ati
o
Jarvie et al., 2003a,b; Jarvie et al., 2005
Early Oil Window
Peak Oil Window
Condensate-Wet Gas Window
Wet Gas WindowDry Gas Window
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Predictive Gas Composition Ratios
Dembicki, 2017
Oil zone
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Discrimination of Barnett Shalematurity windows by isotopic values
Illich et al., 2013
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Rollover alters Isotopic Maturity Plots
Data from Zumberge et al., 2012
Expected maturity trendbut reversed when rollover
occurs, ca. 1.5%Ro
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 88
Targeting Using Various Geochemicaland Rock Properties
EOG Resources, Investor Presentation, Nov 2016Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 89
Thank You !
danjarvie@wwgeochem.com
Presentation with additional slides available at: www.wildcattechnologies.com
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Appendices
• Meaning of acronyms
• Further definition of acronyms
• Conversions
• Flow charts
• GC peak identifications
• Biomarker peak identifications
• Visual kerogen examples and petroleum type
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QUICK START GEOCHEMISTRY(various esoteric abbreviations)
Organic richnessRelative oil contentConvertible kerogen contentRelative oxygenates yieldThermal maturity indicatorRelative hydrogen contentRelative oxygenates contentRatio of oil to oil+ S2 kerogenRatio of oil (S1) to TOCExtent of kerogen conversion
• TOC: total organic carbon
• S1: signal 1 in pyrolysis
• S2: signal 2 in pyrolysis
• S3: signal 3 in pyrolysis
• Tmax
• HI: hydrogen index
• OI: oxygen index
• PI: production index
• OSI: oil saturation index
• TR: transformation ratio
QUICK START GEOCHEMISTRY(various esoteric abbreviations)
• Vitrinite reflectance (%Ro):
• Visual kerogen (Vk):
• Gas chromatography (GC):
• Pyrolysis GC (PyGC):
• SARA (saturates, aromatics, resins, asphtenes):
• S-A carbon isotopes:
• Biomarkers (GCMS):
• Quantitative Aromatics, diamondoids (GCMSMS):
• Kinetics:
Visual thermal maturityKerogen type, color indexOil and extracted oil typeProducts generatedConstituents of petroleumCorrelation; typeCorrelation; organofacies
Chemical thermal maturityRate of OM decomposition
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Screening Data Parameters
• CC carbonate carbon (wt.%)• TOC Total organic carbon (wt.%)• S1 free oil that volatilizes at 300oC• S2 organic matter that pyrolyzes (cracks)
between 300-600oC• S3 “organic” carbon dioxide from kerogen• Tmax the temperature at maximum evolution of S2 peak• S4 not reported, but the oxidation of residual carbon when Rock-Eval
TOC is utilized• %Ro Reflectivity of vitrinite in oil immersion (VR often used)• %Roe conversion of Tmax to an approximate vitrinite reflectivity value• Vk visual kerogen – description of macerals in kerogen• GC gas chromatography• GCMS gas chromatography mass spectrometry• SARA saturates, aromatics, resins, and asphaltenes
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 97
Ratios from Rock-Eval and combined TOC data
• Hydrogen Index (Espitalie et al., 1977)– S2 / TOC x 100 (mg HC/g TOC)– relative hydrogen abundance
• Oxygen Index (Espitalie et al., 1977)– S3 / TOC x 100 (mg CO2 / – sometimes affected by weathering
• S2/S3 (Daly et al., 1979)– ratio of hydrogen to oxygen; sometimes useful at high thermal maturity for kerogen type
• Production Index (Espitalie et al., 1977)– S1/(S1+S2) (unitless) 0-1– an indication of free oil to total oil and kerogen, i.e., kerogen conversion– will be lower where expulsion has occurred; will be higher when migration into a
sediment (e.g., reservoir rocks)
• Normalized oil content (Jarvie and Baker, 1984)– free oil (S1) divided by TOC x 100 (mg HC/g TOC)– an indication of thermal maturity, but also reservoir intervals
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 98
Conversions
• TOC to hydrocarbons– divide TOC by 0.085 (some literature uses 0.083)– Why? (ca. 85% carbon in hydrocarbons and TOC is in
wt.percent whereas S2 (or S1) is parts per thousand (mg HC/g rock)
– TOCroc=10.00 (reactive organic carbon), S2 = 117.65
• Hydrocarbons to TOC– multiply hydrocarbons (S1 or S2) by 0.085 (or 0.083)– S2 = 10.00 mg HC/g rock, thereby contains 0.85 %TOC
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Conversions
• Rock-Eval hydrocarbon units to useful units
– Rock-Eval S1 or S2 = mg HC/g rock• To obtain results in ppm
– Multiple S1 or S2 by 1000• To obtain the oil content or remaining generation potential in bo/af
– Multiple S1 by 21.89 to 25.00 (heavier to lighter oil)– Multiple S2 by 21.89 to 25.00
– Conversion to total gas is more complicated:• Must know how much oil vs gas is formed in primary cracking of
kerogen• Must know how much gas and oil is expelled/retained• Must know how much oil can be cracked to gas
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 100
Some Terms…
• Kerogen– Organic matter that is insoluble
in organic solvents and acids
• Petroleum– Gas and Oil
• Gas– C1 = dry gas– C2-C4,5 = wet gas
• Oil– Black oil– Volatile oil– Condensate
– Hydrocarbons• Saturates• Aromatics
– Non-hydrocarbons• Resins• Asphaltenes
• Bitumen = Petroleum (Momper, 1975)– Earliest formed petroleum that
contains a high percentage of non-hydrocarbons
• Pyrobitumen– Any residue formed from kerogen or
petroleum cracking
• Sorption– Adsorption– Absorption
• SARA– Saturates– Aromatics– Resins– Asphaltene
Jarvie Unconventional Producibility Geoconvention 2019, Calgary , Albert, Canada, 13-17 May 2019 101
Consideration of the term ‘bitumen’
Bitumen: “a smelly but useful material of interest”
Bitumen: “any of various natural substances, as asphalt, maltha, or gilsonitethat consist mainly of hydrocarbons
Bitumen: soluble in carbon disulfide (pyrobitumen is not soluble) (Hunt, 1995)
“Solid bitumens are allochthonous, non-disseminated organic matter.Definition by solubility, fusibility, and H/C ratios are neither source-distinctive nor indicative of genesis” (Curiale, 1986)… Solid bitumens associated with source rocks classified as:
pre-oil: immature, early generation products of source rockspost-oil: alteration of once liquid oil which
is also a product of source rocksmigrated from a mature source rockFollowing generation and expulsion, both are subject to modification processes
However, the use of the term ‘bitumen’ is a catch-all and generally a visual description.Jarvie, 2015
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Jarvie Presentation on Geochemistry 35
Definitions
• Kerogen Cracking
• This is primary cracking•Yields
• gas and oil (petroleum)• carbonaceous residue
• Petroleum (bitumen or full SARA) cracking
• This is secondary cracking•Yields
•Gas and oil•carbonaceous residue
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Shale Resource System
A continuous system having an organic-rich source rock with or without
juxtaposed organic lean lithofacies
requiring hydraulic stimulation to flow commercial amounts of petroleum.
Jarvie, 2007
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Petroleum SystemComponents and Processes
• Components
– Source rock
– Migration pathway
– Trap
– Seal
– Overburden
• Processes
– Generation
– Expulsion
– Migration
– Accumulation
– Preservation
– Alteration espfractionation
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Source Rocks
• Proven (effective)
• Hypothetical
• Speculative
Correlation between source rock and reservoired petroleum has been achieved
Limited evidence of source rock (e.g., TOC)
Possible geological formation
Magoon and Dow, 1995
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Processes that AlterPetroleum Composition
• Thermal maturity
• Biodegradation
• Gas washing
• Gas exsolution
• Bacterial sulfate reduction (BSR)
• Thermochemical Sulfate Reduction (TSR)
• Primary Expulsion– Within source rock
• Secondary Expulsion– Out of source rock
• Fractionation• Wettability
• Production – From reservoir to surface
• Composition at surface• API• GOR
• Production operations– Choke dimensions– Separator conditions
Jarvie, 2015
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Dan Jarvie, Worldwide Geochemistry WTGS Applied Geochemistry for Exploration and Production 21 March 2019 108
Analytical Chart with Objective
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1 i-C4 21 11-DMCP 41 n-C9 60 n-C21
2 n-C4 22 3-MH 42 n-C10 61 n-C22
3 i-C5 23 c-13-DMCP 43 n-C11 62 n-C23
4 n-C5 24 t-13-DCMCP 44 n-C12 63 n-C24
5 22-DMB 25 3-EP 45 i-C13 64 n-C25
6 CP 26 t-12-DMCP 46 i-C14 65 n-C26
7 23-DMB 27 c-12-DMCP (cal) 47 n-C13 66 n-C27
8 2-MP 28 n-C7 48 i-C15 67 n-C28
9 3-MP 29 MCH 49 n-C14 68 n-C29
10 I-Std 30 ECP 50 i-C16 69 n-C30
11 n-C6 31 Tol 51 n-C15 70 n-C31
12 22-DMP 32 2-Methylheptane 52 n-C16 71 n-C32
13 MCP 33 4-Methylheptane 53 i-C18 72 n-C33
14 24-DMP 34 3-Methylheptane 54 n-C17 73 n-C34
15 223-TMB 35 n-C8 55 Pr 74 n-C35
16 Bz 36 E-Bz 56 n-C18 75 n-C36
17 33-DMP 37 m-xylene 57 Phy 76 n-C37
18 CH 38 p-xylene 58 n-C19 77 n-C38
19 2-MH 39 o-xylene 59 n-C20 78 n-C39
20 23-DMP 40 79 n-C40
GC Peaks
Peak Abbreviations
Oil GC Ratios by Area Thompson Ratios
Pristane / Phytane 1.07 Bz / n C6 0.05Pristane / n C17 0.37 Tol / n C7 0.24Phytane / n C18 0.42 (n C6 + n C7) / (CH + MCH) 2.76n C18 / (n C18 + n C19) 0.53 Isoheptane Value 2.21n C17 / (n C17 + n C27) 0.80 n C7 / MCH 2.05
Carbon Preference Index 0.99 CH / MCP 0.75BTEX (wt.%) 2.85 n C7 / 2-MH 4.26
n C6 / 2,2-DMB 475.36
Oil GC Ratios by Height Heptane Value 38.90
n-C6 / MCP 3.33Pristane / Phytane 1.16Pristane / n C17 0.29Phytane / n C18 0.29n C18 / (n C18 + n C19) 0.53
n C17 / (n C17 + n C27) 0.79Carbon Preference Index 0.97
Halpern Ratios Mango Ratios
Total C7 (17 compounds) 6.88Alteration-1 9.42 P1 34.71Alteration-2 39.69 P2 20.35
Alteration-3 13.95 P3 6.65Alteration-4 9.33 5N1 7.49Alteration-5 23.27 6N1 25.18Alteration-6 0.80 N2 5.62Alteration-7 5.12 K1 0.94Alteration-8 3.06 K2 0.26
Correlation-1 0.03 5N1 / 6N1 0.30Correlation-2 0.63 P3 / N2 1.18Correlation-3 0.14 2MH + 23DMP 0.85Correlation-4 0.02 3MH + 24DMP 0.90Correlation-5 0.18 P2 + N2 25.97
Invariant Ratio 1 0.94Invariant Ratio 2 0.26
CTemp (oC) 116GOR (calculated scf/bo) 622
Various GC
Ratios
GC Peak Identifications
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min2 4 6 8 10 12 14 16 18
Norm .
0
100
200
300
400
500
FID1 A, Front Signal (RREN-161203\RREN-161203A 2016-12-19 16-58-22\1203-001A.D)
i-C
4 n
-C4
i-C
5
n-C
5
22
-DM
B CP
23
-DM
B 2
-MP
3-M
P I
-Std
n-C
6
22
-DM
P M
CP
24
-DM
P
Bz
33
-DM
P C
H 2-M
H 2
3-D
MP
11
-DM
CP
3-M
H
c-1
3-D
MC
P t
-13
-DC
MC
P 3
-EP
t-1
2-D
MC
P
n-C
7
MC
H
EC
P
To
l
2-M
eth
ylh
ep
tan
e 4
-Me
thyl
he
pta
ne
3-M
eth
ylh
ep
tan
e
Peters et al., 2005
Comparison of Various Chemical Properties of Marine, Fluvial/Deltaic (Terrigenous), and Lacustrine source rocks
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Comparison of Various Physicochemical and Chemical Properties of Shales and Carbonates
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Jarvie Presentation on Geochemistry 39
Code Biomarker ID m/z
C19T C19H34 tricyclic diterpane 191
C20T C20H36 tricyclic diterpane 191
C21T C21H38 tricyclic diterpane 191
C22T C22H40 tricyclic terpane 191
C23T C23H42 tricyclic terpane 191
C24T C24H44 tricyclic terpane 191
C25S C25H46 tricyclic terpane 191
C25R C25H46 tricyclic terpane 191
TET C24H42 teteracyclic terpane 191
C26S C26H48 tricyclic terpane 191
C26R C26H48 tricyclic terpane 191
Ts 18a, 21b-22,29,30-trisnorhopane 191
C27T 17a,18a,21b-25,28,30-trisnorhopane 177
Tm 17a, 21b-22,29,30-trisnorhopane 191
C28DM C28 demethylated hopane 177
C28H 17a, 18a, 21b-28,30-bisnorhopane 191
C29DM C29 demethylated hopane 177
C29H Tm 17a, 21b-30-norhopane 191
C29D Ts 18a-30-norneohopane 191
C30X 17a, 15a-methyl-27-norhopane (diahopane) 191
OL oleanane 191
C30H 17a, 21b-hopane 191
C30M 17b, 21a-moretane 191
C31S 17a, 21b-30-homohopane (22S) 191
C31R 17a, 21b-30-homohopane (22S) 191
GA gammacerane 191
C32S 17a, 21b-bishomohopane (22S) 191
C32R 17a, 21b-bishomohopane (22R) 191
C33S 17a, 21b-trishomohopane (22S) 191
C33R 17a, 21b-trishomohopane (22R) 191
C34S 17a, 21b-extended hopane (22S) 191
C34R 17a, 21b-extended hopane (22R) 191
C35S 17a, 21b-extended hopane (22S) 191
C35R 17a, 21b-extended hopane (22R) 191
S1 13b, 17a-diacholestane (20S) 217
C35R 17a, 21b-extended hopane (22R) 191
S1 13b, 17a-diacholestane (20S) 217
S2 13b, 17a-diacholestane (20R) 217
S3 5a-cholestane (20S) + 5b-cholestane (20R) 217
S4 5a, 14b, 17b-cholestane (20R) +13b, 17a-diastigmastane (20S) 217
S4B same as S4 (m/z=218) 218
S5 5a, 14b, 17b-cholestane (20S) 217
S5B same as S5 (m/z=218) 218
S6 5a-cholestane (20R) 217
S7 diastigmastane 217
S8 5a-ergostane (20S) 217
S9 5a, 14b, 17b-ergostane (20R) + 5b-ergostane (20R) 217
S9B same as S9 (m/z=218) 218
S10 5a, 14b, 17b-ergostane (20S) 217
S10B same as S10 (m/z=218) 218
S11 5a-ergostane (20R) 217
S12 5a-stigmastane (20S) 217
S13 5a, 14b, 17b-stigmastane (20R) 217
S13B same as S13 (m/z=218) 218
S14 5a, 14b, 17b-stigmastane (20S) + 5b-stigmastane (20R) 217
S14B same as S14 (m/z=218) 218
ISTD d4-5a-stigmastane (20R) m/z=221 221
S15 5a-stigmastane (20R) 217
Common Biomarker Names and Diagnostic Ions
28 32 36 40 44 48
60 70 80
Tricyclic Terpanesm/z = 191
Pentacyclic Terpanesm/z = 191
C28S,R C29S,R C30S,R
C19T
C20T
C21T
C22T
C23T
C24T
C25S C25R
TET
C26S C26R
TsTm
C28H
C29H(Tm)
C29D(Ts)
C30XOL
C30H
C30M
C31S
C31R
GA
C32S
C32RC33S
C33RC34R
C34SC35S C35R
28 32 36 40 44 48
60 70 80
Tricyclic Terpanesm/z = 191
Pentacyclic Terpanesm/z = 191
C28S,R C29S,R C30S,R
C19T
C20T
C21T
C22T
C23T
C24T
C25S C25R
TET
C26S C26R
TsTm
C28H
C29H(Tm)
C29D(Ts)
C30XOL
C30H
C30M
C31S
C31R
GA
C32S
C32RC33S
C33RC34R
C34SC35S C35R
Steranesm/z = 217
Steranesm/z = 218
48 52 56 60 64 68 72
48 52 56 60 64 68 72
S1
S2 S3
S4
S5
S6
S7 S8
S9
S10
S11S12
S13
S14
S15
S14BS13B
S10B
S9BS5B
S4B
Steranesm/z = 217
Steranesm/z = 218
48 52 56 60 64 68 72
48 52 56 60 64 68 72
S1
S2 S3
S4
S5
S6
S7 S8
S9
S10
S11S12
S13
S14
S15
S14BS13B
S10B
S9BS5B
S4B
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Ratio PeaksC19/C23 Tricyclic Terpane C19/C23, peak heights from 191m/zC22/C21 Tricyclic Terpane C22/C21, peak heights from 191m/z
C24/C23 Tricyclic Terpane C24/C23, peak heights from 191m/zC26/C25 Tricyclic Terpane C26/C25, peak heights from 191m/z
Tet/C23 Tetracyclic C24 to Tricyclic Terpane C23 ratio, peak heights from 191m/zC27T/C27 25,28,30-trisnorhopane (177m/z)/191m/z(Ts+Tm)
C28/H Bisnorhopane/HopaneC29/H Norhopane/Hopane
X/H C30 diahopane/HopaneOL/H Oleanane/Hopane
C31R/H Homohopane (22R)/Hopane
GA/31R Gammacerane/HomohopaneC35S/C34S C35 Extended Hopane/C34 Extended Hopane (22S)
S/H S/H = (SS1-S15)/(Ts+Tm+C28H+C29D+C29H+C30H +SC31-C35SR)%C27 Relative % S5B
%C28 Relative % S10B%C29 Relative % S14B
S1/S6 C27 Rearranged/Regular SteranesC27Ts/Tm Trisnorhopane
C29Ts/Tm aka C29D/29HDM/H C29 demethylated hopane (177m/z)/Hopane 191m/z
Select Biomarker Ratios
Deposition of Source Rockand Hybrid Systems
Bishop et al., 2014
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TOC Values
Ronov, 1958 – Russian Platform from Kiev to Ufa – Upper Devonian shales
– Petroliferous areas:
• 1.37% mean for shales
• 0.50% mean for carbonates– Nonpetroliferous areas:
• 0.40% mean for shales
• 0.16% mean for carbonates
Text Books often state these ranges for minimum TOC:Shales: 1.00 wt.%Carbonates: 0.50 wt.%
Need more information to answer: (1) are these mature TOC values? (2) what is original HI? (3) what type of sample?
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Sample Issues
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Archived Cuttings Samplesmay yield lower values for TOC, S1, S2
17.60
3.04
1.05
7.45
0.38
6.24
5.43 5.75
20.68
0.27
0
5
10
15
20
25
CC TOC S1 S2 S3
Val
ue
(w
t.%
, m
g o
il/g
rock
, or
mg
CO
2/g
ro
ck)
Measurement
Old cuttings
Fresh RSWC
d 35%
d 178%d 547%
d 278%
d 71%
Jarvie, 2012
Comparison of offset well to a
well drilled in late 1970s;
cuttings were stored in Midland,
TX for 30 years
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Cracking of Organic Matter:Kerogen and SARA
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Cracking of Organic Matter:much SARA cracking occurs in oil window
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Restored Petroleum Potential
10
100
1000
0.1 2
OR
IGIN
AL
HYD
RO
GEN
IN
DEX
(m
g/g
)
ORIGINAL TOC (wt.%)
EXCELLENT OIL SOURCE(390-4600 boe/af)
GOOD OIL SOURCE(115-950 boe/af)
TRANSITIONAL OIL-GAS SOURCE (30-920 boe/af)
GAS SOURCE(10-250 boe/af)
POOR GAS SOURCE(1-70 boe/af) GOOD GAS SOURCE
(50-920 boe/af)FAIR GAS SOURCE(20-184 boe/af)
POOR DRY GAS ONLY SOURCE(1-230 boe/af)
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Prediction of in situ Oil Qualityfrom rock chips
Maende, 2015
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Maturation results in Polycondensation of Aromatics
Taylor et al. (1998)
Devolatilization (cracking) polycondensation
(Hydrogen-rich hydrogen-poor
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Restoring Measured Values (present-day) to Original Values
Ways to approximate original hydrogen index
1. Immature samples
2. Visual kerogen percentages: oil vs gas prone macerals x kerogen type HI values
3. Maturation series
4. P10, P50, and P90 values
5. Maturation equation to compute kerogen transformation ratio (not shown)
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Producibility less Sorption
Adsorption index is directly proportional to TOC
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Gas Composition Ratios
Haworth et al., 1985 (AAPG Bulletin)
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References
Dan Jarvie, Worldwide Geochemistry WTGS Applied Geochemistry for Exploration and Production 21 March 2019 132
Akulinitseva, V. and R. Boros, 2017, Wolfcamp Delaware: An assessment of recent activity with a GIS approach, in Oil & Gas Financial Jour., October 2017, p. 14-17. (shows GOR map of Delaware basin)Alpern, B., B. Durand, J. Espitalie, B. Tissot, 1972, Localisation, caractérisation et classification pétrographique des substances
organiques sédimentaires fossiles, in Adv. Org. Geochem., 1971, von Gaertner, H.R., and H. Werner, eds., Oxford-Braunschweig, Pergamon Press, 1972, pp. 1-28.
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