HAWK Wildcat Technologies Measurement Interpretation Applications

TOC, Rock-Eval, and Thermal
Maturity Data Assessment and

Applications
Dan Jarvie, Wildcat Technologies

Brian Jarvie, Geomark Research Rock Lab
David Weldon, Wildcat Technologies
Albert Maende, Wildcat Technologies
Jared Stewart, Wildcat Technologies
2011. Dan Jarvie. All rights reserved.
Wildcat Technologies, LLC

HAWK WorkStation www.wildcattechnologies.com
Total Organic Carbon
(TOC)

Understanding TOC
TOC is
A measure of present-day organic carbon content
as received in the laboratory
It is reported in weight percent but can be
converted to volume percent
It can be restored to original values with
knowledge of original kerogen composition
It, as most measurements, will be affected by the
presence of organic additives

Diagrammatic Illustration of TOC
for a given kerogen type, e.g., Type II
TOC (wt.%)
Generative Organic Non-Generative

Carbon (wt.%) Organic Carbon (wt.%)
Responsible for generation Does not generate any

of hydrocarbons appreciable amount of petroleum
Accounts for development of Does account for storage
organic porosity by adsorption

What happens with thermal maturation and expulsion to,
e.g., 50% transformation ratio (50% conversion of GOC)?
TOC (wt.%)
Generative Organic Non-Generative

Carbon (wt.%) Organic Carbon (wt.%)
Generative
Non-Generative Organic Carbon
Organic
(wt.%)
Carbon (wt.%)
Carbon in
expelled TOC (wt.%)
petroleum
(wt.%)
TOCpresent-day is now reduced from TOCoriginal
as a result of generation and expulsion
TOCPD (wt.%)
Generative
Organic Carbon
(GOCPD ) (NGOCPD) (wt.%)
Notes:
with 50% TR, TOC is not reduced 50%; only GOC is

reduced 50%
NGOC increases slightly due to hydrogen shortage in

kerogen and bitumen

At 100% conversion of organic matter,
the TOC cannot be reduced further; this is TOCmin
TOCPD (wt.%)
Generative
Organic Carbon
(GOCPD )
(NGOCPD) (wt.%)

(NGOCPD) (wt.%)
TOCPD (wt.%)

The distribution of TOC will vary by kerogen type
TOC (wt.%)
Type I
10% TOC Non-Generative
Generative Organic Carbon (wt.%) Organic Carbon
(wt.%)
TOC (wt.%)
Type II
10% TOC Generative Organic Carbon Non-Generative Organic
(wt.%) Carbon (wt.%)
Type III TOC (wt.%)

10% TOC Generative
Organic Non-Generative Organic Carbon (wt.%)
Carbon (wt.%)

At maximum conversion, the TOC will be lowest
on the highest petroleum generating kerogen
TOC
Type I (wt.%)
2% TOC Non-Generative
Organic Carbon
(wt.%)
TOC (wt.%)
Type II
5% TOC Non-Generative Organic
Carbon (wt.%)
TOC (wt.%)
Type III
8% TOC Non-Generative Organic Carbon (wt.%)

Factors Affecting TOC
Sample Type: Cuttings vs. Core Chips
6
y = 2.3611x - 0.3906
2
5 R = 0.7307
SWC TOC (wt.%)
1 Typical correction factor

for cuttings to core is 1.5x
0
0 1 2 3 4 5 6
Cuttings TOC (wt.%)

Main Question ref. TOC:
How much TOC is enough?
There are multiple parts to this question including:
What TOC are we talking about:
TOC present-day or TOC original?
TOC on cuttings vs SWC vs Core
TOC on cuttings is often 1-2.5x lower than SWC, core chips
What is the kerogen type
What is the original hydrogen content (~ hydrogen index)?
How much oil vs gas will be generated?
What is the thickness of the prospective source rock?
What type of system: tight mudstone or hybrid?
How deep to shale?
Where located?
Infrastructure?
Many other issues to assess how much TOC is enough

Consider a 1.00% TOCoriginal Type II Kerogen
assuming a 475 HIoriginal
TOCo = 1.00 wt.%
475 HIo / 1177 HImax= 40% GOC
GOCo = 0.40
NGOCO = 0.60 wt.%
wt.%

From a 1.00%TOCo with a 475HIo
there is 0.40 wt.% convertibility of
organic matter to petroleum and char
Total EUR
Shale Generation at 10% recovery
Thickness Potential 8 wells/section
GOCo C in TOC S2 (mg/g) S2 Conversion boe/a-f (feet) (boe/section) (boe/section)
0.40 0.085 4.71 21.89 103 100 6,592,753 82,409
Note: This is total generation potential not retained vs expelled in boe equivalent.
With an HIo of 475mg/gT, it is estimated that approx. 60% of generated products are
expelled and 40% is retained in the source rock.
As these are easy units to work with, you can multiple any organic richness with a HIo
of 475 mg/gT by a given TOC and thickness to estimate total generation, expelled,
and retained.

Thickness will certainly increase the
total generation potential
In this case the source rock thickness is increased to 1000 ft. but remains 1.00% TOC:
Total EUR
0.40 0.085 4.71 21.89 103 1000 65,927,529 824,094
The problem in this case is that the petroleum is dispersed over 1000 ft. of shale
and percent recovery will drop dramatically in this case to 1%.
Total EUR
0.40 0.085 4.71 21.89 103 1000 65,927,529 82,409
Of course if a hybrid system is present, i.e., with organic-lean rocks with matrix porosity,
there is increased likelihood of a commercial play. And certainly a different development
approach would enhance recovery, costs permitting.

TOC minimum
Typically it will be required to have a minimum of

1.00% GOCoriginal to have commercial
hydrocarbons with a reasonably thick source rock
(100+ ft.)
For a Type II kerogen (HIo = 475 mg/gT), this

means about 2.50% TOCoriginal
This also impacts the development of a

reasonable amount of organic porosity as
illustrated later in these guidelines

Rock-Eval
or
Wildcat Technologies HAWK Data

Pyrolysis Pyrogram Peaks
S2
S3
Yield
S1
Tmax
Time

Pyrogram (HAWK)
S1oil yield - the amount of thermally freed hydrocarbons (mg/g).
S1free oil

Pyrogram (HAWK)
S2kerogen yield - the amount of hydrocarbons generated through pyrolysis of
kerogen (mg/g).
S2kerogen yield

Pyrogram (HAWK)
Tmax - the temperature at which the maximum generation of hydrocarbons from
pyrolysis cracking of the kerogen occurs (C).
Tmax

Pyrogram (HAWK)
S3 - the amount of CO2 produced during pyrolysis (300 to 400 C) of kerogen
(mg/g).
S3

Rock-Eval and Hawk Parameters
S1: (Signal 1) free oil in sample as received in the laboratory
think of this as Soil yield
S2: (Signal 2) remaining convertible organic matter (GOC) in

sample
think of this as S kerogen yield
S3: organic carbon dioxide released from kerogen prior to

earliest inorganic carbon dioxide release
Tmax: temperature during pyrolysis of maximum release of S2

hydrocarbons
S4: non-generative organic carbon (NGOC) constituent of TOC

Ratios from Rock-Eval or HAWK 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); Oil Saturation Index (Jarvie, 2011)
free oil (S1) divided by TOC x 100 (mg HC/g TOC)
an indication of thermal maturity, but also reservoir intervals

Rock-Eval and HAWK Data
Conversions
To convert S1 or S2 to barrels of oil equivalent
per acre-foot, multiply by 21.89
To convert S1 or S2 to ppm, multiple by 1000
To determine carbon content in S1 or S2,

multiple by 0.085

Rock-Eval or HAWK Parameters
in TOC Model context
TOC (wt.%)
Generative
Organic
Carbon (GOC) (NGOC) (wt.%)
S
S2 S4
1

How much sample is needed for
geochemical testing?
1 teaspoon of cuttings or core chips = 10 grams Sufficient for

all geochemical
work
Sufficient for
all work
including
mineralogy,
fluid inclusion,
etc.
1 tablespoon of cuttings or core chips = 30 grams
HAWK WorkStation 26 Wildcat Technologies, LLC

www.wildcattechnologies.com
Rock-Eval or HAWK Analysis:
Sample Size
About the volume of the exposed

part of the eraser is all the sample
needed for 1 Rock-Eval or HAWK analysis
HAWK WorkStation 27 Wildcat Technologies, LLC

Formulation of TOC
from Rock-Eval or HAWK data
TOC = carbon in S1 and S2 plus carbon in S4
Assuming 85% carbon in petroleum, the following formula explains TOC:
TOC (wt.%) = (0.085 x (S1 + S2)) + (0.10 x S4)

Notes:
(1) S1 and S2 are in parts per thousand (mg/g) and therefore must be
converted to parts per hundred (wt.%)
(2) S4 is carbon in carbon dioxide also in parts per thousand but does
not require any other assumption

S1 Peak
(Signal 1 Yield)
(Soil yield)

Factors Affecting S1
Type of sample (cuttings, SWC, core)

Type of lithofacies (shale, carbonate, sandstone)
Sample handling and processing (esp. heating)
Oil-based mud (OBM) or organic additives to
drilling fluids

U. Bakken Shale
Factors Affecting S1:
lithofacies
Middle Member
Bakken Formation
Stored for exactly the
same amount of time
and conditions, the
shale member retains
far more hydrocarbons
Produced Oil
than the Middle Middle Member
Member

Factors Affecting S1: Oil-Based Mud
(also affects S2, Tmax, HI, S3)
Whole rock samples contaminated with OBM
14
Whole rock cuttings
12.53 Extract rock cuttings
12
10
Yield (mg/gR)
6.21
6
4 3.57
2
0.58
0
S1 S2

Cleaning OBM Samples
Many organic solvents are used to clean samples drilled with OBM
The best solvent system is a binary azeotrope of chloroform-

methanol (89:11, vol:vol) to remove all indigenous and organic
additives
The technique used is not as important as the solvent:

Soxhlet~SoxTec~Cold Soak
This will mean the loss of the S1 yield
Some S2 is usually lost and will give an accurate assessment of the

present-day HI

How is the total oil content measured?
Generally S1 yield, but often carry over into S2
Overlap in S1 and S2
S1 S2
Overlap of free oil and oil carried over into S2
This is a function of oil type and isolated organic

pores

Measuring the total oil less
evaporative losses in a rock sample
1. Run whole rock sample note any low temperature peaks or
shoulders in S2 pyrogram
2. If noted, then sample should be extracted in organic solvent and re-analyzed as an
extracted rock
The total oil without evaporative losses is:
Total Oil = (S1whole rock S1extracted rock) + (S2whole rock S2extracted

rock) + EL
(EL is evaporative losses)

S2 Peak
(Signal 2 Yield)
(Skerogen yield)

Factors Affecting S2
Oil carry over into S2 peak

OBM or other organic additives
Salt ionization

Conversion of S2 (kerogen potential)
with increasing thermal maturity
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
TOC decreases by amount of S2 conversion

Barnett Shale TOC and S2 Loss
with maturation
60
Type I Oil Prone
TYPE II Oil Prone
REMAINING HYDROCARBON POTENTIAL (mg HC/g Rock)
usu. lacustrine
(usu. marine)
50
40
Mixed Type II / III
Oil / Gas Prone
30
20 Barnett Shale
Maturation Type III
Trend Gas Prone
Organic
Lean
10 Difference is the
amount of
Dry
petroleum Gas Prone
0 generated
0 2 4 6 8 10 12 14 16
TOTAL ORGANIC CARBON (TOC, wt.%)
Jarvie and Lundell, 1991

Comparison of Whole vs Extracted Rock Bakken Tmax
values: oil in S2 lowers Tmax value until extracted
Extracted rock values run

2-5oC higher the
difference between
immature vs early oil
window

Mineral Salt Ionization
Is strictly an artifact and

does not indicate any
petroleum generation
potential Mineral salt
ionization at
In can sometimes high
dramatically inflate S2 and temperature
thereby HI, giving a high HI in S2 peak
value with high Tmax
Often occurs when mud is

allowed to dry onto
cuttings
Can often be removed by

treating the rock sample
with hot methanol

Kerogen Transformation Ratio (TR):
a measure of kerogen conversion,
aka, thermal maturity
TR in % = {(1177 (HIO HIPD)) / ((HIO x (1177-HIPD))} x 100
e.g., assume from example HIO=380, HIPD=8
TR% = {(1177 x (380-8)) / (380 x (1177-8))} x 100
TR = 98.6%

Production Index
0
2000
4000
S1 / (S1+S2)
Depth (feet)
6000
with increasing burial Soil increases 8000
Skerogen decreases
10000
Affected by expulsion 12000

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Production Index (PI or S1 / (S1 + S2))
Not as reliable as S1/TOC for A well profile of PI with no expulsion events

predicting reservoir intervals
A useful tool for estimating the

level of kerogen conversion
especially in immature to early
mature window
A well profile of PI with high relative oil content

S2 / S3 Ratio
An indication of kerogen type; not widely used
due to better techniques (HI, visual kerogen)
Useful for high maturity shales to understand

what original kerogen type may have been
Interpretation (with extreme caution):

S2/S3 < 5 gas prone kerogen
S2/S3 > 5 oil prone kerogen

Role of TOC
in
Organic Porosity
Development

Interest of TOCoriginal ?
Provides an indication of the total generative
capacity of the rock
Can compute the total hydrocarbon yield
Can estimate adsorption capacity
Can use to model expulsion and adsorption thresholds
Can compare rocks when GIPs are not yet available
Provides an indication of organic porosity
development

Computation of GOC
from HIoriginal and Organic Porosity (max)
Determination of HIO is 434 mg HC/g TOC
GOCO in % of TOCO = 434 / 1177 = 36.9% of TOCO
IF TOCO is 7.00%, then GOCO is 2.58%
Max organic porosity creation is about 2.58 x 2 = 5.16% porosity

TOC loss is directly related to S2 loss,
i.e., S2 = GOC

HIo Dependent TOC Reductions
(and recalculation of TOCoriginal)
For example,
TOCpd = 10.00
HIo = 400
TOCo = 16.00
Jarvie, 2011, AAPG Memoir 97

Barnett Shale TOC Original Determination

Conversion of TOC in wt.% to vol.%
which is about
TOC is 7 weight percent 14 volume percent

Formation of Organic Porosity
from Generative Organic Carbon
Assumptions:
7.00 wt.% TOCo
14.00 vol.% TOCo
TOCo is 37% GOC
Kerogen density is
1.2g/cc

Present-day (high maturity) TOC

Organic Porosity Development
from GOC conversion
Loucks et al., 2009

TOC and Porosity:
Tight Mudstone vs Hybrid System
Doig TOC correlates to porosity (organic porosity);
Montney shows inverse correlation (matrix porosity

Calculation of original TOC

Thermal Maturity Basics

Oil and Gas Windows
(depends on kerogen type !)
In general for Type II

marine kerogen
<0.55%Roe: Immature
0.55 0.99%Roe: Oil Window
1.00 1.40%Roe: Condensate-Wet Gas Window
>1.40%Roe: Dry Gas Window
>3.00%Roe: High risk for gas preservation

Assessing Thermal Maturity
from various parameters
Tmax values
Transformation ratios
Gas dryness
Measured vitrinite reflectance
Carbon isotopes of methane, ethane, propane
Gas chromatographic fingerprint of residual oil

Tmax: a chemical indicator
of thermal maturity
Tmax < 430oC: usually immature

Tmax 430-455oC: Oil Window
Tmax 456-475oC: Condensate/Wet Gas Window
Tmax > 475oC: Dry Gas Window

Tmax-equivalent
Vitrinite Reflectance
%Roe from Tmax = 0.018 x Tmax 7.16
(Jarvie et al., 2001)
Measured Tmax-Equivalent
%VRo %VRo
0.20 409
0.40 420
0.55 428
0.85 445
1.00 455
1.10 460
1.20 465
1.40 475
2.00 510

Change in Bakken Shale Tmax values
before and after extraction
444
442 1:1 Line
440
Extracted Rock Tmax (oC)
438
436
434
432
430
428
426
426 428 430 432 434 436 438 440 442 444
Whole Rock Tmax (oC)

Barnett Shale Maturation Profile:
Decrease in Hydrogen Index and Increase in Tmax
Remember: Only immature HI values are indicative of kerogen type as HI
decreases with increasing thermal maturity
1000
Hydrogen Index (mg HC/g TOC)
900
800
700
600
500
400
300
200 y = 3E+76x-28.03
R = 0.9434 Maturation
100 Trend
0
380 400 420 440 460 480 500
Tmax (oC)

Factors that can affect Tmax values:
Rock-Eval II Pyrogram Examples
Normal pyrogram: return to Pyrogram with low S2: small S1
baseline between S1 and S2, peak, but no distinguishable S2
good peak shape on S2 peak poor Tmax; may be organic
lean or highly mature.

Noisy S2 peak results in erratic Low temperature peak on S2 peak
Tmax values; often seen in usually indicative of oil carryover
coals or from fines into S2 peak. High S3 suggests
potential contamination as cause of
low temperature peak.

Low temperature peak is higher High temperature S2 peak is
than kerogen peak probably usually an artifact from mineral salt
due to oil in sample; Tmax will ionization. This will inflate S2 value,
be on low temperature peak increase HI artificially, and give a
very high Tmax value (500+)

Conversion of Organic Matter by Type
(unique samples, not universal for all Type I, II, or III kerogens)
%VRo Tmax (oC)
Type II Type II-OS Type III Type I
0.40 420
0.60 430
0.75 440
0.95 450
1.10 460
1.30 470
1.50 480

Monterey Shale Rock-Eval Yields and Tmax shift
with increasing maturity, a Type II-S kerogen
396
403
Note Tmax values

For a Type II-ONS kerogen !
426
396oC: Immature
403oC: 20% TR
426oC: 50% TR
449oC: 75% TR
517oC: 95% TR
449
517
300 400 500 600 700
Tmax (oC)

Relationship between Transformation Ratio and
Vitrinite Reflectance
It is evident that there is no universal %Ro-TR correlation

that is appropriate for all kerogen types.
(Waples and Marzi, 1998)
BTU to Dry Gas Ratio:
Estimated Dry Gas Contents based on BTU
and equivalent vitrinite reflectance values
100%
Dry Gas Window
%Roe >1.40% Wet Gas Window
90%
%Roe >1.00 1.40% Condensate-Wet Gas Window
80%
%Roe >0.80 1.00% Peak Oil Window
Dry Gas Ratio
70%
60% %Roe <0.80% Early Oil Window
50%
40%
30%
20%
10%
0%
0 500 1000 1500 2000 2500 3000
Gas Calorific Content (btu)
Jarvie et al., 2003

Case 1: Thermal Maturity Assessment
%Roe from gas composition
%Roe from TR
%Roe from Tmax
%Ro
Immature Oil Zone Wet Gas Dry Gas
0.2 0.7 1.2 1.7 2.2

Vitrinite Reflectance (%Ro)

Maturation Profile
0
Depth = -8981 Log(Ro) + -3613, R = 0.91
-500
Case 1: -1000
-1500
maturation
-2000
Depth (feet)
-2500
profile -3000
(all data -3500
Barnett Shale
points -4000
measured %Ro in
oil window
-4500
regressed) -5000
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 2.0
Ro (%)
Immature Oil Zone Wet Gas Zone Dry Gas Zone
Humble Geochemical Services Division

Case 1: Maturation Profile
0
Depth = -8981 Log(Ro) + -3613, R = 0.91
-500
maturation
-1000
profile
-1500
(only samples
-2000
above Barnett
Depth (feet)
-2500
Shale regressed)
-3000
showing gas
-3500
window maturity Barnett Shale

projected %Ro in
-4000
matching Tmax gas window

-4500
and TR
-5000
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 2.0
Ro (%)
Immature Oil Zone Wet Gas Zone Dry Gas Zone
Humble Geochemical Services Division

Well 2: Comparison of Maturity Parameters
%Roe from TR
%Roe from Tmax
%Ro
0.2 0.7 1.2 1.7 2.2


Well 2: after solvent extraction
%Roe from TR
%Roe from Tmax
%Ro
0.2 0.7 1.2 1.7 2.2


Assessing Kerogen Type

Kerogen Type
Is it oil prone, mixed oil/gas, gas prone ?
Kerogen type depends on

chemistry of original biomass
e.g., woody, herbaceous, bacterial, algae
percentages of each given biomass
preservation of deposits
diagenetic alteration
Kerogen type is evaluated by:

its chemical composition
visual examination of particulate matter in kerogen

Chemical Definition of Kerogen Type:
Hydrogen Index
only for immature kerogen
Type I: >700 mg/gT
Type II: 350 700 mg/gT
Type III: 50 200 mg/gT
Type IV: <50 mg/gT

Jones, 1984

Modified Espitalie Kerogen Type
and Thermal Maturity Plot
Modified from Espitalie et al., 1984

Modified van Krevelen
Kerogen Typing Plot
1000
Eagle Ford Shale,
900 Comstock roadcuts
Immature
Hydrogen Index (mg kerogen/g TOC)
Type I
800 700-1200
700
600
Immature Maturation Decarboxylation
Type II Pathway
500
300-700
400
Immature
300 Mixed II - III
200-350
200
Immature Type III - III 50 - 200
100
Immature Type IV 0-50
0
0 20 40 60 80 100 120 140 160 180 200
Oxygen Index (OI)
van Krevelen, 1961: Espitalie et al., 1977

Kerogen Type Plot (when immature);
Shale Gas Window for High Maturity, Type II Kerogens

Assessment
of HI original
Worldwide
Collection of
Marine Shale
Source Rocks
(n=157)
HIo: 250-850
mg/g

Average Hydrogen Index
529 mg HC/g TOC

Overall Distribution
of hydrogen indices
40
35
30
25
Count
20
15
10
0
200-299 300-399 400-499 500-599 600-699 700-799
Original Hydrogen Index (mg HC/g TOC)

Cumulative Distribution of
Worldwide Marine Source Rocks
Percentage of Source Rocks Exceeding HIo Values 1.2
0.8
0.6
0.4
0.2
0
>200 >300 >400 >500 >600 >700
HIo Values

P10, 50, 90 Distribution Values
for original HI
Distribution HI original
P90 340
P50 475
P10 645
i.e., 90% of the marine shale source rocks studied would have an HIo > 340;
only 10% would have a HIo value > 645

Percentage of TOCo
represented by GOC and NGOC
Distribution HI %GOC %NGOC

P90= 375 32% 68%
P50= 450 38% 62%
P10= 720 61% 39%
i.e., a source rock with a HIo of 375, would have 32% of its TOCo as generative organic carbon
e.g., a 10% TOCo would mean 3.20 wt.% OC is convertible to hydrocarbons

Visual Kerogen Assessment
of Kerogen Type
AOM + Exinite
Excellent 10 90 Strongly Oil Prone
20 80
Good 30 70 Oil Prone
40 60
Fair 50 50 Mixed Oil-Gas
60 40
Poor 70 30 Gas Prone
80 20
Very Poor 90 10 Dry Gas Prone
Inertinite 10 20 30 40 50 60 70 80 90 Vitrinite

Visual and Chemical Kerogen
Descriptions and Classifications
Organic Matter Classification
at low thermal maturity
Organic Kerogen
Matter Kerogen Coal Maceral Type Depositional Internal Principal
Classification Description Petrography Description Assignment H/C O/C HI OI Environment Structures Products
Sapropelic Algal Alginite Type I, II > 1.4 ~0.1 >700 10-40 Anoxic (saline); Finely Laminated Oil
Amorphous usu. lacustrine;
rare marine
Sapropelic Amorphous Liptinite (Exinite) Amorphous Types I, II 1.2 - 1.4 ~0.1 350-700 20-60 anoxic Laminated; Oil, gas
Algal usu. marine well bedded
Sapropelic Hebaceous Sporinite Type II 1.0 - 1.2 ~0.2 200-350 40-80 Variable; Poorly bedded Gas, oil
Cutinite often deltaic Gas, oil
Resinite Oil, gas
Humic Woody Vitrinite Teleinite Type III 0.7 - 1.0 ~0.4 50-200 50-150 Midly Oxic; Poorly bedded; Gas
Collinite Shelf/Slope; bioturbated
Coals
Humic Coaly Inertinite Fusinite Type III, IV 0.4 - 0.7 ~0.3 <50 20-200 Highly Oxic Massive; Dry Gas
Micronite bioturbated
Sclerotinite
Sources: Jones, 1984; Hunt, 1995

Adsorption by Kerogen Type
100
SORPTION CAPACITY (mg HC/g TOC)
90
80
70
60
50
40
30
20
10
0
I II III
KEROGEN TYPE
Ref: Noble et al., 1997

Relative Adsorption of Bitumen by
varying amounts of TOC
800
BITUMEN ADSORPTION (A.U.)
700
600
500
400
300
200
100
0
0 5 10 15
T.O.C. (wt.%)
Longjiang and Barker 1989 adapted from Hunt, 1995

Finding Producible Oil

Oil Effect: Oil Crossover
a simple measure is derived from empirical evidence
linking Rock-Eval oil values to potential production:
when oil crosses TOC in absolute value,

producible oil or gas may be found
this suggests that around 100 mg HC/ g TOC is the

saturation threshold for oil (depending on system)

Laboratory Analysis of Oil in Rocks
Oil content is always lower than in the reservoir

Loss dependent on
Oil type
Lithofacies
Handling
Oil content can be described functionally as:
Moveable oil
Immobile oil (or less mobile oil)
Total oil

Oil Crossover:
when S1 crossovers TOC, potential hydrocarbon reservoir
When oil crossover occurs, indicative of high oil saturation

Intermittant source rock is generating/expelling
Broad interval hydrocarbon reservoir (or contamination!)
Unconventional:
e.g., Monterey, Bakken, Barnett, Eagle Ford, Niobrara
Conventional:
e.g. Sisquoc, Madison, Red River, sands GOM
When oil crossover does not occur, variable results but usually
negative
Thus, risk is lower when crossover occurs

Illustration
Case 1 Clean 60% TOC coal with 5 mg oil
5 mg oil / 60% TOC, no crossover = 8 mg/g TOC
- Non-reservoir, in fact, cannot get back most of the oil
that was mixed with the coal why? Adsorption
Case 2 Clean 0.60% TOC carbonate with 5 mg oil

5 mg oil / 0.60% TOC, cross over = 833 mg/g TOC
- Potential reservoir
- Oil saturation is very high, adsorption factor very low

Key to Producible Shale Oil Resource System?
Presence of producible oil
Utilizing the
Oil Crossover
Effect:
S1/TOC > 1
or when
Oil Saturation
Index
(S1/TOCx100)
> 100 mg oil/g
TOC
Data extracted from Lopatin et al., 2003; Jarvie, 2011, AAPG Memoir 97

In what other basins does
oil crossover effect occur with related production from the
same unconventional zone?
Bakken Shale, Middle Member, and Three Forks,
Williston Basin
Niobrara Formation, B carbonate, Denver Basin
Antelope Shale, San Joaquin Basin
Eagle Ford Shale, Gulf Coast Basin
Barnett Shale, Fort Worth Basin
Mowry Shale, Powder River Basin
Toarcian Shale, Paris Basin
Bazhenov Shale, West Siberian Basin

A high free oil content (S1) does not necessarily
indicate producible oil

Impact of Evaporation on S1/TOC Ratio
Suppose a rock sample has a TOC of 0.50% with a total oil content of 1 mg/g rock:
Description of oil preservation S1 (mg/gR) original Loss Adj S1 (mg/gR) TOC (%) (S1/TOC)x100 Units
At no loss (100% of oil remains): 1.00 0% 1.00 0.50 200 mg oil/g TOC
Assume 50% oil loss: 1.00 50% 0.50 0.46 109 mg oil/g TOC
where oil is assumed to be 85% carbon
Thus, at 50% evaporative loss S1/TOC will still exceed 100 mg/gT.
Organic-rich, tight shales will not have as much evaporative loss as

organic-lean lithofacies whether the latter is tight or not.
Heating at 100oC will cause near 90% loss of indigenous petroleum.

Obtaining the Total Free Oil
from Rock-Eval data
Run whole rock
obtain S1wr
obtain S2wr
Run solvent extracted rock
obtain S1xr
obtain S2xr
Total free oil = (S1wr - S1xr) + (S2wr S2xr)
i.e., the light, free oil plus the heavy, free oil
Jarvie et al., 2011, RMAG Special Pub

How is oil stored in shale?
Open fractures (existing production)
Matrix porosity (water + oil)
Organic porosity (oil + gas only)
Organic porosity is pore space created by organic matter

decomposition and is the most difficult oil to produce due to
1. Its isolation in the shale
2. Its adsorptive capacity for oil
Adsorption increases by oil composition:
Saturates<Aromatics<<Resins<<<Asphaltenes

Generation, Retention, and Expulsion
Sandvik et al., 1992

More Producible Oil
from high carbonate carbon rocks
Eagle Ford Shale

Adsorption and Lithofacies:
shale-oil systems
Adsorption
Organic-rich shales
High adsorptive capacity depending upon
Organic richness
Thermal maturity
Maceral type
Quartz: low organic adsorptive capacity
Carbonate: low organic adsorptive capacity
Brittleness versus adsorption
High quartz content an important element in ability to stimulate, i.e.,
brittleness, but
High quartz content is also closely associated with high organic content, therefore
brittleness is good, but pore throats easily occluded
High carbonate content is generally not associated with high organic contents (not
always!) and is often in thin to thick intervals

Assessing Geochemical Data for
Potential Oil Production
1. Run TOC, carbonate carbon, Rock-Eval or HAWK,
extracted rock Rock-Eval, GC of extract
2. Assess if oil crossover occurs: S1 > TOC or
S1x100/TOC > 100 mg/gT
3. Check pyrogram for any S2 shoulders or peaks; if
present, extract, compute Total Oil
4. Run special GC fingerprint to evaluate evaporative
losses
5. Compute adsorption retention
6. Compute producible oil content

Geochemical Log Presentation of
TOC and Rock-Eval Data
Jarvie et al., 2011, RMAG Bakken CD

Thank you !


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TOC, Rock-Eval, and Thermal

Maturity Data Assessment and

Dan Jarvie, Wildcat Technologies

2011. Dan Jarvie. All rights reserved.

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Generative Organic Non-Generative

Responsible for generation Does not generate any

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Generative Organic Non-Generative

with 50% TR, TOC is not reduced 50%; only GOC is

NGOC increases slightly due to hydrogen shortage in

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Non-Generative Organic Carbon

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Type III TOC (wt.%)

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1 Typical correction factor

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TOCo = 1.00 wt.%

475 HIo / 1177 HImax= 40% GOC

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Typically it will be required to have a minimum of

For a Type II kerogen (HIo = 475 mg/gT), this

This also impacts the development of a

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S2: (Signal 2) remaining convertible organic matter (GOC) in

S3: organic carbon dioxide released from kerogen prior to

Tmax: temperature during pyrolysis of maximum release of S2

S4: non-generative organic carbon (NGOC) constituent of TOC

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Oxygen Index (Espitalie et al., 1977)

S2/S3 (Daly et al., 1979)

Production Index (Espitalie et al., 1977)

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To convert S1 or S2 to ppm, multiple by 1000

To determine carbon content in S1 or S2,

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1 teaspoon of cuttings or core chips = 10 grams Sufficient for

1 tablespoon of cuttings or core chips = 30 grams

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About the volume of the exposed

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TOC = carbon in S1 and S2 plus carbon in S4

Assuming 85% carbon in petroleum, the following formula explains TOC:

TOC (wt.%) = (0.085 x (S1 + S2)) + (0.10 x S4)

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Type of sample (cuttings, SWC, core)

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Factors Affecting S1:

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