Tracing the Origins of Crude Oil San Joaquin Geological Society

Bakersfield, October 11, 2010

 Ken Peters

Ken is Scientific Advisor (Geochemistry) for Schlumberger.

He uses geochemistry and PetroMod® modeling to study
petroleum systems and has >30 years of experience with
Chevron, Mobil, ExxonMobil, USGS, and Schlumberger.
He taught geochemistry and basin modeling at Chevron,
Mobil, ExxonMobil, Oil & Gas Consultants International,
UC Berkeley, and Stanford. Ken is principal author of The
Biomarker Guide (2005) and Consulting Professor at
Stanford, where he co-founded the Basin & Petroleum
System Modeling Industrial Affiliates Program. He is Chair of the AAPG
Research Committee (2007-2010), AAPG Distinguished Lecturer (2009 and
2010), Associate Editor for AAPG Bulletin and Organic Geochemistry, and
Editor for the 2009 AAPG CD “Getting Started in Basin & Petroleum System
Modeling”. In 2009, Ken received the Schlumberger Henri Doll Prize for
Innovation and the Alfred E. Treibs Medal presented by the Geochemical
Society to scientists having a major impact on the field of organic
geochemistry. He has B.S. and M.S. degrees in geology from UCSB and a
Ph.D. in geochemistry from UCLA.
Tracing the Origins of Crude Oil
Ken Peters
Objectives of This Talk

• What is petroleum and how does it form?

• What is a biomarker?
• Direct and indirect oil-oil and oil-source
rock correlation
• Chemometrics as a tool to evaluate
petroleum systems, e.g., San Joaquin
basin and coastal California
Petroleum Originates From Organic-Rich Source Rocks

Products
Aquatic Plants
0
METAGENESIS CATAGENESIS DIAGENESIS

Oxic
Biogenic Land Plants Anoxic
IMMATURE

Gas Seal
1
Biomarkers Potential Trap
Crude Source Rock
Burial and Heat Oil and Gas
Oil
Depth (km)

2 Migration
OIL

Effective
3 Source Rock
WET
GAS

Heat
DRY GAS

4
Thermogenic
Gas Biomarker Guide, p. 9
Biomarkers: Micro–Microfossils Establish Petroleum Systems

Method of Study Fossil Size

Visual
Tenths of
a Centimeter
Microscopy

Thousandths
of a Centimeter

Gas Chromatography-
Mass Spectrometry (GCMS)

Billionths
of a Centimeter
Cholestane
Cholesterol is a Widespread and Abundant Sterol Biomarker

• All organisms except certain bacteria

contain sterols
• Organisms generally contain 0.01% to
0.1 wt.% sterols

HO
Cholesterol Cholestane
Sterols are Components in Eukaryotic Cell Membranes

Nuclear
Membrane
Cell
Membrane

Sterol

~20 Å

Phospholipid
Biomarker Guide, p. 46
Selected Ion Monitoring GCMS: Characteristic Fragments

Compound Transfer Mass Ion

Separation Ionization Analysis Detection Data Processing

m/z 217 x
Magnetic
Syringe
Tape Drive

Printer/Plotter
Oven

Computer
Column

Transfer Ion Mass Analyzer Electron

Line Source (Quadrupoles) Multiplier
Terminal
Display Screen(s)

Gas Mass
Chromatograph Spectrometer
Biomarker Guide, p. 209
Selected Ion Monitoring GCMS: Characteristic Fragments

Steranes
Terpanes
m/z 217 x
m/z 191

x
Mass Chromatograms Show Peaks Not Visible on GC

nC17 GCMS
Pristane
Terpanes
(m/z 191)
GCFID

nC27

Time Steranes
(m/z 217)

GCMS

Biomarker Guide, p. 211

Mass Chromatograms Show Peaks Not Visible on GC

nC17 GCMS
Pristane
Terpanes
(m/z 191)
GCFID

nC27

Time Steranes
(m/z 217)

GCMS

Biomarker Guide, p. 211

Steranes Help Establish Petroleum Systems in West Siberia

X
%C28
Bazhenov source rock
Bazhenov-related oil
Probable Tyumen-
related oil
X = H, CH3, C2H5

Bazhenov-Neocomian(!)

Peters et al. (1994)

%C27 %C29
e.g., %C27 = %C27/(C27+C28+C29)
Biodegradation Can Interfere With Correlation

Light n-Alkanes

Isoprenoids
1
2

Steranes
Biodegradation Rank

Hopanes
Moderate

C26-C29 Aromatics
4

Diasteranes
5
Heavy
6

Peters and Moldowan (1993)

(6)
7
Very Heavy
8
9
Severe
10

Extent of Destruction of Compound Class

Diasteranes Support Conclusions Based on Steranes

X
%C28
Bazhenov source rock
Bazhenov-related oil
Probable Tyumen-
related oil

X = H, CH3, C2H5

Biomarker Guide, p. 536

%C27 %C29
Oil from Tertiary Source Rock Has Oleanane Ratios >20%

%Oleanane/(Ol+Hop)

• Number of Families
120

80
100
Nerium oleander
60 80

60
40 Oleanane
40
20
20

0 0
Early Late Paleogene Neogene
Jurassic
Cretaceous Tertiary
MESOZOIC CENOZOIC

180 140 95 65 25 <5

Time (Ma) Biomarker Guide, p. 573

C26 Steranes in Oils Help to Assess Age of Source Rock

0.8
24-Nordiacholestane Ratio
0.7 Diatomaceous
Marine Shale
Marine Marl Source Rocks
0.6 Marine Carbonate
Deltaic Diatoms
>0.55 – Oligocene
Lacustrine Shale Proliferate
0.5 and younger

0.4
First Diatom
0.3 Morphology
>0.25 Cretaceous
0.2 and younger

0.1

0
500 400 300 200 100
Cambrian Sil. Carbonif. Trias. Cretaceous
Ordovician Devon. Perm. Jurassic Tertiary

Geologic Age (Ma) Biomarker Guide, p. 541

Age-Related Biomarkers Help to Define Petroleum Systems

%Oleanane/(Ol + Hopane)
Lubna-18,
20 Dolni Lomna-1
Zdanice-7,
Damborice-16
Tynec-34
15
Sedlec-1 Oil from Paleogene

Rocks
Karlin-1 source rock
Nemcicky-1
10

5
Oil from Jurassic
source rock

0
0 20 40 60 80

%C26 24/(24 + 27) Nordiacholestanes

Biomarker Guide, p. 541
Picha and Peters (1998)
Biomarkers Allow Direct and Indirect Oil-Source Correlation

• Many homolog ratios allow direct oil-oil and oil-

source rock correlation
• Biomarkers allow indirect correlation by
indicating source-rock depositional setting,
redox, lithology, organic matter input, and age
• Biodegradation and thermal maturity can alter
correlation parameters; discard unsuitable
samples from training sets
• Confirm in situ origin of source-rock bitumen
Stable Isotopes of Carbon Differ by One Neutron

Proton

Neutron

Electron
Carbon-12 (12C) = Carbon-13 (13C) =
98.89% of carbon 1.11% of carbon

Biomarker Guide, p. 137

PDB Standard: Cretaceous Peedee Formation, S. Carolina

 Sofer Plot Differentiates Miocene and Eocene Oil, California

-22 San Joaquin Basin

Eocene Kreyenhagen/Tumey
-23
Miocene Monterey
-24
d13Caromatics, ‰

-25
-20
-26 -21
Terrigenous Miocene

d13C Aromatics, ‰
-22

-27 -23
-24
-25 Eocene
-28 -26
-27
-29 Marine -28 Lillis and Magoon (2003)
-29 Peters et al. (1994)

-30 -32 -31 -30 -29 -28 -27 -26 -25 -24 -23 -22
d13C Saturates, ‰
-31
-31 -30 -29 -28 -27 -26 -25 -24 -23

d13Csaturates,‰ Peters et al. (2010, unpublished)

Multiple Eocene and Miocene Oil Families: San Joaquin Basin

Purpose
• Correlate 180 produced oil samples into
genetic families (oil-oil correlation)
• Infer source rock for each oil sample
(oil-source rock correlation)
• Build a predictive chemometric model to
classify new samples
• Map distributions of oil families to better
understand origins

Photo courtesy of Don Arnot,

West Kern Oil Museum
Chemometrics for 180 Oils Used 17 Biomarker/Isotope Ratios

Carbon Isotopes Terpanes Steranes

d13Csat , ‰

d13Caro, ‰

C27T/C27

Dia/Ster
Sample

C19/C23

C22/C21

C24/C23

C26/C25

BNH/H
Tet/C23

31R/H
C29/H

%C27

%C28

%C29
Ol/H

S/H
KND359E -30.51 -29.08 0.03 0.36 0.77 1.03 0.20 0.01 0.02 0.49 0.04 0.20 1.04 31.0 41.2 27.9 1.60

EH11UM -24.15 -22.78 0.03 0.24 0.77 1.03 0.14 1.49 0.31 0.47 0.15 0.25 1.08 32.9 39.7 27.3 0.22
TN398M -24.14 -23.01 0.34 0.25 0.76 1.14 0.12 0.49 0.15 0.41 0.38 0.20 1.63 30.3 41.3 28.4 0.51
Chemometrics Extracts Information from Multivariate Data

Visual
• Hierarchical Cluster Analysis (HCA)

Modeling
• Principal Component Analysis (PCA)
• K-Nearest Neighbor (KNN)
• PCA Modeling of Class (SIMCA*)

*Soft Independent Modeling of Class Analogy

How Similar Are Samples? Calculated in 2 or n-Dimensions

dab = [(x2 – x1)2 + (y2- y1)2]1/2

b (x2,y2)
Y (e.g., d13Csat)

dab = [(ai – bi)2]1/2  HCA

a (x1,y1)

X (e.g., Oleanane/Hopane)
Calculate the Distance Between Points

A simple example with

2 measurements on 7
samples.
Measurement 2

Measurement 1
Calculate the Distance Between Points

1
Measurement 2

Measurement 1
Calculate the Distance Between Points

1
Measurement 2

Measurement 1
Calculate the Distance Between Points

1
Measurement 2

Measurement 1
Calculate the Distance Between Points

1
4
Measurement 2

Measurement 1
Calculate the Distance Between Points

1
4 5
Measurement 2

Measurement 1
HCA Dendrograms Are Based on Cluster Distance in n-Space

HCA Dendrogram

1
5
4 5 2

2
Measurement 2

3 4
5

1
4

2 1
6

Measurement 1 Cluster Distance

Hierarchical Cluster Analysis: Distance-Based Classification
Tribe 1

Eocene

180 Oil
Samples
Tribe 2

Similarity Line

Miocene
Tribe 3

Cluster Distance
Chemometric Decision Tree Classifies New Samples

Sample

Miocene Monterey Miocene Monterey

Eocene North (Buttonwillow) South (Tejon)

11 12 13 14 21 22 23 31 32

Upper Monterey
Lower Monterey
SIMCA*
231 232 233

*Soft independent modeling of class analogy

“Decision-tree chemometrics” (Peters et al., 2007)
2331 2332 2333 2334
Eocene Oil Families Originated from One Depocenter

Eocene Tumey and Kreyenhagen Miocene Monterey

Buttonwillow

3D Petroleum
System Model
Bakersfield
Arch

Tejon

Peters et al. (2008)

Family 11 is Localized, While Family 13 is Widely Scattered

Kreyenhagen Tumey
Source Rock Source Rock
Stratigraphy of Tribe 1 Oils Indicates Their Source Rocks

Family 11: Kreyenhagen Family 13: Tumey Source

Source Rock and Good Seal Rock and „Leaky‟ Plumbing

Tumey Source Rock

Kreyenhagen Seal (Non-Source)

Kreyenhagen Source Rock 4 Miocene (Zilch, Burbank)

3 Oligocene (Temblor)
2 Eocene (Kreyenhagen)

2 Miocene (Freeman-Jewett, Temblor) Stratigraphic column

8 Eocene (Lodo, Kreyenhagen, Gatchell) from Peters et al. (2008)
1 Lower Cretaceous (Moreno)
Bakersfield Arch Controls Distribution of Miocene Families
Tribe 2
Tribe 3
South of Arch: Distinct Upper and Lower Monterey Families

Upper Monterey Lower Monterey

(South) Source Rock (South) Source Rock
South of Arch: Distinct Upper and Lower Monterey Families

Family 31: Miocene Family 32: No Access

Stevens Sand Pools to Stevens Sand

Upper Monterey
(South) Source Rock
Lower Monterey
(South) Source Rock
8 Upper Miocene (Chanac,
Reef Ridge, Stevens)
1 Pliocene (Etchegoin)
1 Miocene (Monterey)
4 Miocene (Monterey)
5 Miocene (Temblor)
3 Eocene (Tejon)
North of Arch: Distinct Upper and Lower Monterey Families

Upper Monterey Lower Monterey

(North) Source Rock (North) Source Rock
North of Arch: Distinct Upper and Lower Monterey Families

Family 21: Mostly Family 22: Pre-

U. Miocene Pools Monterey Pools

Upper Monterey
(North) Source Rock
Lower Monterey
(North) Source Rock

Oligocene Pools
Lower Miocene-
1 Pliocene (Etchegoin)
19 Upper Miocene (Reef Ridge,
Monterey)
1 Middle Miocene (Temblor)

1 Lower Miocene (Temblor)

5 Lower Miocene (Freeman-Jewitt)
5 Oligocene (Vedder, Temblor)
Source Imprint is Retained With Little Cross-Stratal Migration

Source Rock Oil Family

U. Monterey* 21, 232, 2331-2334
U. Monterey† 31
L. Monterey* 22, 231
L. Monterey† 32

Bakersfield Arch
*North (Buttonwillow)
†South (Tejon)

Tumey 13

Kreyenhagen 11, (12), 14

Internal Stratigraphic Seals Explain Isolation of Oil Families

Miocene Antelope Shale, Chico Martinez Creek

Courtesy of R. Behl, CSULB

Conclusions for the San Joaquin Study

• Fourteen families of San Joaquin Basin oils retain the geochemical

imprint of vertical and lateral organofacies variations in their
source rocks:

1.) Eocene Tumey and Kreyenhagen (4 families)

2.) Miocene Monterey (North depocenter, 8 families)
3.) Miocene Monterey (South depocenter, 2 families)

• Eocene oil families originated in one depocenter from basal

Kreyenhagen and overlying Tumey source-rock organofacies.
• Miocene families originated from Upper and Lower Monterey
source-rock organofacies in two depocenters.
• Both Eocene and Miocene families show little cross-stratigraphic
migration due to internal seals within the source rocks as
previously observed in the Elk Hills field by Zumberge et al. (2005).
• These results show the value of chemometrics applied to large
petroleum databases where all samples are analyzed using the
same procedures and instrumentation.
Floating Tar Whip,
Point Conception
Families of Miocene Oils, Seeps, Tarballs: Coastal California

Purpose
• Correlate produced oil, seep oil, and tarball
samples into genetic families (oil-oil
correlation)
• Infer source rock for each oil sample (oil-source
rock correlation)
• Build a predictive chemometric model to classify
new samples
• Map distributions of oil families to better
understand origin and transport
Oil Samples Range from Point Reyes to Los Angeles

CA
Point
Reyes

Monterey
Bay
Tribe 3

Point
Tribes 1 and 2

Conception

N Channel Los
Islands Angeles
19 Variables Characterize 388 Training Set Samples

d13C Terpanes and Steranes Aromatics

Sample

DDBT/DP
29Ts/29H

TDBT/TP
26Tri/Tet
20/23 Tri
22/21 Tri
24/23 Tri
26/25 Tri
28/29 Tri

35S/34S
PDB, ‰

PAH-RI
C28/C29
BNH/H
Ts/Tm

31S/H
29/H

OI/H
G/H
6
Sulfur < 0.5%
Pristane/Phytane

1 -23.3
Paleozoic-Mesozoic Sulfur > 0.5%
Deltaic Oils
Marine Shale and
4 Paleozoic Carbonate
100 -24.0 Miocene

Chung et al. (1992)

Oils
Oils
200 -23.2
2

388 -23.3
Mesozoic Carbonate Oils
-32 -30 -28 -26 -24 -22 -20
Carbon Isotopic Ratio of Oil (‰)
Hierarchical Cluster Analysis (HCA): Three Oil Tribes

South
1

Similarity
Line 388-Sample
Training Set
Oil Tribe
2

South
3

North

Cluster Distance
„Decision Tree‟ Fine Tunes Classification of New Samples

New Sample
388-Sample
Training Set
KNN model
Tribe

1 2 3
SIMCA KNN SIMCA
Family

11 12 13 14 31 32 33 34 35

21 22
SIMCA
SIMCA KNN (Nearest Neighbor)
SIMCA (Fit)

211 212 213

Locations of Tribes 1-2 (South) Differ from Tribe 3 (North)

Point Stinson
San Francisco
Reyes Bay

S. La Honda

Sargent

Monterey
Monterey
Canyon Bay

Big Sur San Ardo

Tribe 3

Morro Bay
Arroyo
Shell Grande

Lions Head
Boathouse
Irene
‘Discontinuity’
Hidalgo
Tribes 1 and 2

Harvest Naples Hondo Holly

Hermosa Dos
Heritage,
Harmony Cuadras
Amberjack Los
High Angeles

Santa Cruz
Island
N Point
Conception
Catalina
Island
Block Rotation Explains Discontinuity and Oil Distribution

Early Miocene Present-Day

Tribe 3

Lompoc
Lions Head Naples Beach
Discontinuity Discontinuity
Tribes 1-2

Los Angeles
Ventura
Los Angeles
Point
San Conception
Diego
Ventura

Naples Beach N San

Lompoc Diego

Modified from Crouch and Suppe (1993)

Biomarkers in Oil Samples Characterize Their Source Rocks

Worldwide Dataset
C24/C23 Tricyclic Terpanes

1.2
Source Rock
„Shale‟
1.0
„Marl‟
„Carbonate‟
0.8

Peters et al. (2005) courtesy

0.6
of GeoMark Research, Inc.

0.4

0.2
0.2 0.4 0.6 0.8 1.0 1.2 1.4

C22/C21 Tricyclic Terpanes

Coastal Samples are from Different Source-Rock Lithofacies

Coastal California Dataset

C24/C23 Tricyclic Terpanes

1.0

Oil Tribe
1 „Shale‟
0.8
2 „Marl‟
3 „Carbonate‟
0.6

0.4

0 0.2 0.4 0.6 0.8 1.0 1.2

C22/C21 Tricyclic Terpanes
Oils from the Carbonate Lithofacies Have Little Oleanane

Flowering
Plants
Oil Tribe
0.3
1 „Shale‟
2 „Marl‟
Oleanane/Hopane

3 „Carbonate‟
0.2

0.1

No flowering 0.5 1.0

plants
Less clay Ts/Tm More clay
Biomarkers Identify Source Organofacies for the Oil Tribes

Higher
Clay Carbonate Oxicity Plants
Tribe
Ts/Tm 20/23TT 22/21TT 29/H 35/34S BNH/H OI/H

0.56 0.25 0.27 0.60 0.95 0.39 0.10

1 0.17 0.07 0.08 0.09 0.28 0.26 0.04

0.28 0.18 0.47 0.69 1.69 1.30 0.04

2 0.08 0.05 0.09 0.07 0.26 0.54 0.02

0.21 0.10 0.91 0.76 2.03 0.92 0.03

3 0.03 0.01 0.15 0.09 0.31 0.43 0.01
„Prograding Margin Model‟ Suggests Origins for Oil Tribes

Seaward Landward

Miocene Monterey Mixed Terrigenous-

Marine Organic Matter
Formation
Marine
Organic Clayey-Siliceous
Matter Member
Carbonaceous
Marl Member 1
Lower Calcareous- 2 4.5/216
Siliceous Member (6 samples)
9.9/360
3 5.0/406 (13 samples)
(13 samples)

Total Organic Carbon (%) Modified from

Katz and Royle (2001)
Hydrogen Index (mg HC/g TOC) Isaacs et al. (1996)
Samples Near Point Conception Are Dominantly Family 22

Jalama
Beach Family
22
212
32

Point
Conception

Tar Government Point

mounds

Tar whip
Ten Tarballs Were Analyzed by Decision-Tree Chemometrics
Decision Tree Indicates Natural Origin for Tarball Samples

Location Sample Family Source Rock SIMCA Fit

1 22 Marl Excellent
Moss
5 212 Marl Excellent
Landing
7 34 Carbonate Excellent
8 33 Carbonate Excellent
Asilomar 9 32 Carbonate Good
12 33 Carbonate Excellent
14 33 Carbonate Excellent
Half 15 33 Carbonate Excellent
Moon
Bay 16 33 Carbonate Excellent
18 22 Marl Excellent
Tarballs Originated from Seeps During 2007 Storm

Moss Landing (2/24/07) Asilomar Beach (2/14/07)

Sample 7; Family 34 Sample 8; Family 33
Coal Oil Point Seeps (UCSB) Are More Active After Storms

Trilogy
Seep

January, 2005
Conclusions: Coastal California Oil Families

• >600 coastal California tarball, seep, and produced

oil samples correlate into 3 tribes and 13 families:
Peters et al. (2008) AAPG Bulletin 92: 1131-1152.
• Geochemistry indicates source-rock organofacies,
depositional environment, lithology, age
• „Decision-tree chemometrics‟ classifies new
samples based on 388-sample training set and
addresses uncertainty
• Tribes 1 and 2 are S and Tribe 3 is N of Point
Conception; distribution controlled by stratigraphy
and burial depth of inferred Miocene source rock
Summary: Oil-Oil and Oil-Source Rock Correlation

• Biomarker and isotope ratios are useful for direct

correlation of oils and source rocks
• Biodegradation can alter correlation parameters;
rank samples before study
• Confirm in situ origin of source-rock bitumen
• Biomarkers allow indirect correlation: age of
source rock, depositional setting, lithology,
organic matter input, redox conditions
• Decision-tree chemometrics: correlation using
multivariate source parameters that assigns the
level of certainty to the correlation
Some Useful References

• Peters, K.E. et al., 2008, Families of Miocene crude oil, seep, and
tarball samples, coastal California: AAPG Bulletin 92, 1131-1152.
• Peters, K.E. et al., 2008, A four-dimensional petroleum systems
model for the San Joaquin Basin, California, in A. Hosford
Scheirer, ed., 2007, Petroleum systems and geologic assessment
of oil and gas in the San Joaquin Basin province, California: USGS
Prof. Paper 1713, Chapter 12, 35 p.
• Peters, K.E. et al., 2007, Circum-Arctic petroleum systems
identified using decision-tree chemometrics: AAPG Bulletin 91,
877-913.
• Peters K.E. et al., 2008, De-convoluting mixed crude oil in Prudhoe
Bay field, North Slope, Alaska: Organic Geochemistry 39, 623-645.
• Peters, K.E. et al., 1994, Identification of petroleum systems
adjacent to the San Andreas Fault, California, USA, in L.B. Magoon
and W.G. Dow, eds., The Petroleum System-From Source to Trap:
AAPG Memoir 60, 423-436.
• Zumberge, J.E. et al., 2005, Charging of Elk Hills reservoirs as
determined by oil geochemistry. AAPG Bulletin 89: 1347-1371.