KenPeters_TracingOil

8/7/2019 KenPeters_TracingOil

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Tracing the Origins of Crude Oil San Joaquin Geological SocietyBakersfield, October 11, 2010


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Ken Peters

Ken is Scientific Advisor (Geochemistry) for Schlumberger.He uses geochemistry and PetroModmodeling to study

petroleum systems and has >30 years of experience withChevron, 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 atStanford, where he co-founded the Basin & PetroleumSystem Modeling Industrial Affiliates Program. He is Chair of the AAPGResearch Committee (2007-2010), AAPG Distinguished Lecturer (2009 and2010), Associate Editor for AAPG Bulletinand Organic Geochemistry, andEditor for the 2009 AAPG CD Getting Started in Basin & Petroleum System

Modeling. In 2009, Ken received the SchlumbergerHenri Doll Prize forInnovation and the Alfred E. Treibs Medal presented by the GeochemicalSociety to scientists having a major impact on the field of organicgeochemistry. He has B.S. and M.S. degrees in geology from UCSB and aPh.D. in geochemistry from UCLA.


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Tracing the Origins of Crude OilKen Peters


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What is petroleum and how does it form? What is a biomarker? Directand indirectoil-oil and oil-source

rock correlation Chemometrics as a tool to evaluatepetroleum systems, e.g., San Joaquinbasin and coastal California

Objectives of This Talk


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Petroleum Originates From Organic-Rich Source Rocks

Biomarker Guide, p. 9

Products

Biomarkers

CrudeOil

ThermogenicGasDR

YGAS

OIL

IMMATURE

4

3

2

1

0

Depth(km)

METAGENESISCATAGENESIS

DIAGENESIS

Trap

Land PlantsAquatic PlantsOxic

Anoxic

PotentialSource Rock

Burial and Heat

EffectiveSource Rock

Heat

Oil and GasMigration

BiogenicGas

WET

GAS

Seal


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Biomarkers: MicroMicrofossils Establish Petroleum Systems

Method of Study

Visual

Fossil Size

Microscopy

Tenths ofa Centimeter

Gas Chromatography-

Mass Spectrometry (GCMS)

Thousandthsof a Centimeter

Billionthsof a Centimeter

Cholestane


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All organisms except certain bacteriacontain sterols

Organisms generally contain 0.01% to

0.1 wt.% sterols

Cholesterol

Cholesterol is a Widespread and Abundant Sterol Biomarker

CholestaneHO


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NuclearMembrane

CellMembrane


Sterol

Phospholipid

~20

Sterols are Components in Eukaryotic Cell Membranes


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GasChromatograph

MassSpectrometer

CompoundSeparation TransferIonization MassAnalysis IonDetection Data Processing

Syringe

TransferLine

IonSource

Mass Analyzer(Quadrupoles)

ElectronMultiplier

MagneticTape Drive

Computer

Terminal

Display Screen(s)

Printer/Plotter


Column

Oven

Selected Ion Monitoring GCMS: Characteristic Fragments

m/z 217 x


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m/z 217 x

Steranes

m/z 191

x

Terpanes

Selected Ion Monitoring GCMS: Characteristic Fragments


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GCFID

nC17Pristane

nC27

Terpanes(m/z 191)

Time

GCMS

Steranes(m/z 217)

GCMS


Mass Chromatograms Show Peaks Not Visible on GC


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Mass Chromatograms Show Peaks Not Visible on GC

GCFID

nC17Pristane

nC27

Terpanes(m/z 191)

Time

GCMS

Steranes(m/z 217)

GCMS



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Steranes Help Establish Petroleum Systems in West Siberia

%C29

%C28 Bazhenov source rockBazhenov-related oil

Probable Tyumen-related oil

X = H, CH3, C2H5

X

Peters et al. (1994)

Bazhenov-Neocomian(!)

%C27e.g., %C27= %C27/(C27+C28+C29)


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Light

123

Moderate45

Heavy6

(6)

7Very Heavy

89

Severe10

Diasteranes

Steranes

Isoprenoids

H

opanes

C26-C29Arom

atics

n-Alkanes

Biodegradation Can Interfere With Correlation

Biodegrada

tionRank

Petersan

dMoldowan(1993)

Extent of Destruction of Compound Class


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Diasteranes Support Conclusions Based on Steranes

%C27 %C29

%C28

X = H, CH3, C2H5

Bazhenov source rockBazhenov-related oilProbable Tyumen-related oil

X



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Oil from Tertiary Source Rock Has Oleanane Ratios >20%

Oleanane

80

60

40

20

0%Oleanane

/(Ol+Hop)

JurassicCretaceous Tertiary

Early Late Paleogene Neogene

MESOZOIC CENOZOIC

180 140 95 65 25


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C26 Steranes in Oils Help to Assess Age of Source Rock

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

24

-Nordiacho

lestaneRa

tio

500 400 100200300

TertiaryJurassicPerm.Devon.Ordovician

CretaceousTrias.Carbonif.Sil.Cambrian

DiatomsProliferate

First DiatomMorphology

Marine ShaleMarine MarlMarine CarbonateDeltaicLacustrine Shale

>0.55 Oligoceneand younger

>0.25 Cretaceousand younger

DiatomaceousSource Rocks

Biomarker Guide, p. 541Geologic Age (Ma)


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Age-Related Biomarkers Help to Define Petroleum Systems

0

5

10

15

20

0 20 40 60 80

%C26 24/(24 + 27) Nordiacholestanes%

Oleanane/(Ol+Hopane) Lubna-18,

Dolni Lomna-1Zdanice-7,Damborice-16Tynec-34Sedlec-1Karlin-1Nemcicky-1 R

ocks Oil from Paleogene

source rock

Oil from Jurassicsource rock

Biomarker Guide, p. 541Picha and Peters (1998)


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Many homolog ratios allow directoil-oil and oil-source rock correlation

Biomarkers allow indirectcorrelation byindicating source-rock depositional setting,redox, lithology, organic matter input, and age

Biodegradation and thermal maturity can altercorrelation parameters; discard unsuitablesamples from training sets

Confirm in situorigin of source-rock bitumen

Biomarkers Allow Directand IndirectOil-Source Correlation


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Stable Isotopes of Carbon Differ by One Neutron

Carbon-12 (12C) =98.89% of carbon

Carbon-13 (13C) =1.11% of carbon

Proton

Neutron

Electron


PDB Standard: Cretaceous Peedee Formation, S. Carolina


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-31

-30

-29

-28

-27

-26

-25

-24

-23

-22

-31 -30 -29 -28 -27 -26 -25 -24 -23

d13Caromat

ics,

d13Csaturates,

San Joaquin Basin

Eocene Kreyenhagen/TumeyMiocene Monterey

d13C Saturates,

d13CAromatics,

-29

-28

-27

-26

-25

-24

-23

-22

-21

-20

-32 -31 -30 -29 -28 -27 -26 -25 -24 -23 -22

Miocene

Eocene

Lillis and Magoon (2003)Peters et al. (1994)

Terrigenous

Marine

Sofer Plot Differentiates Miocene and Eocene Oil, California

Peters et al. (2010, unpublished)


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Photo courtesy of Don Arnot,West Kern Oil Museum

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 chemometricmodel toclassify new samples Map distributions of oil families to better

understand origins


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Sample

d13Csat,

d13Caro,

C19/C23

C22/C21

C24/C23

C26/C25

Tet/C23

C27T/C27

BNH/H

C29/H

Ol/H

31R/H

S/H

%C27

%C28

%C29

Dia/Ster

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 1.60EH11UM -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

Carbon Isotopes Terpanes Steranes

Chemometrics for 180 Oils Used 17 Biomarker/Isotope Ratios


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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

Chemometrics Extracts Information from Multivariate Data


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

a (x1,y1)

b (x2,y2)dab = [(x2 x1)2 + (y2- y1)2]1/2

dab = [(ai bi)2]1/2 HCA

Y(e.g.,d13Csat)

X (e.g., Oleanane/Hopane)


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A simple example with2 measurements on 7samples.

Calculate the Distance Between Points

Measureme

nt2

Measurement 1

C l l h Di B P i


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1

Measureme

nt2

Measurement 1


C l l h Di B P i


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1

2

Measureme

nt2

Measurement 1


C l l t th Di t B t P i t


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1

2

3

Measureme

nt2

Measurement 1




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1

2

4

3

Measureme

nt2

Measurement 1




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1

2

4

3

5

Measureme

nt2

Measurement 1


HCA D d A B d Cl t Di t i S


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1

2

4

3

5

6

1

2

1

2

4

3

4

5

5

6

6

Measurement2

HCA Dendrogram

Measurement 1 Cluster Distance

HCA Dendrograms Are Based on Cluster Distance in n-Space

Hierarchical Cluster Analysis Distance Based Classification


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Hierarchical Cluster Analysis: Distance-Based Classification

Similarity Line

Tribe1

Tribe3

Tribe

2

Cluster Distance

Eocene

Miocene

180 OilSamples

Chemometric Decision Tree Classifies New Samples


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2322

232231

21 3231

233

2331 2332 2334 2333

11 12 1413

Sample

MioceneMontereySouth (Tejon)

MioceneMontereyNorth (Buttonwillow)Eocene

SIMCA*

Chemometric Decision Tree Classifies NewSamples

*Soft independent modeling of class analogyDecision-tree chemometrics (Peters et al., 2007)

Upper MontereyLower Monterey

Eocene Oil Families Originated from One Depocenter


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3D PetroleumSystem Model

Buttonwillow

Tejon

BakersfieldArch

Eocene Oil Families Originated from One Depocenter

Eocene Tumey and Kreyenhagen Miocene Monterey

Peters et al. (2008)

Family 11 is Localized While Family 13 is Widely Scattered


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KreyenhagenSource Rock

TumeySource Rock

Family 11 is Localized, While Family 13 is Widely Scattered

Stratigraphy of Tribe 1 Oils Indicates Their Source Rocks


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Family 11: KreyenhagenSource Rock and Good Seal

2 Miocene(Freeman-Jewett, Temblor)8 Eocene(Lodo, Kreyenhagen, Gatchell)1 Lower Cretaceous(Moreno)

Family 13: Tumey SourceRock and Leaky Plumbing

4 Miocene(Zilch, Burbank)3 Oligocene(Temblor)2 Eocene(Kreyenhagen)

Kreyenhagen Source Rock

Tumey Source Rock

Kreyenhagen Seal (Non-Source)

Stratigraphic columnfrom Peters et al. (2008)

Stratigraphy of Tribe 1 Oils Indicates Their Source Rocks

Bakersfield Arch Controls Distribution of Miocene Families


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Tribe2

Tribe3

Bakersfield Arch Controls Distribution of Miocene Families

South of Arch: Distinct Upper and Lower Monterey Families


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Upper Monterey(South) Source Rock

Lower Monterey(South) Source Rock

Southof Arch: Distinct Upper and Lower Monterey Families

South of Arch: Distinct Upper and Lower Monterey Families


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8 Upper Miocene(Chanac,Reef Ridge, Stevens)1 Miocene(Monterey)

Family 31: MioceneStevens Sand Pools

1 Pliocene(Etchegoin)4 Miocene(Monterey)5 Miocene(Temblor)3 Eocene(Tejon)

Family 32: No Accessto Stevens Sand

Upper Monterey(South) Source Rock

Lower Monterey(South) Source Rock

Southof Arch: Distinct Upper and Lower Monterey Families

North of Arch: Distinct Upper and Lower Monterey Families


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Upper Monterey(North) Source Rock

Lower Monterey(North) Source Rock

Northof Arch: Distinct Upper and Lower Monterey Families

North of Arch: Distinct Upper and Lower Monterey Families


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1 Pliocene(Etchegoin)19 Upper Miocene(Reef Ridge,

Monterey)1 Middle Miocene(Temblor)

Family 21: MostlyU. MiocenePools

1 Lower Miocene(Temblor)5 Lower Miocene(Freeman-Jewitt)5 Oligocene(Vedder, Temblor)

Family 22: Pre-Monterey Pools

Upper Monterey(North) Source Rock

Lower Monterey(North) Source Rock

LowerMiocene-

OligoceneP

ools

Northof Arch: Distinct Upper and Lower Monterey Families


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Internal Stratigraphic Seals Explain Isolation of Oil Families


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Courtesy of R. Behl, CSULB

MioceneAntelope Shale, Chico Martinez Creek

Internal Stratigraphic Seals Explain Isolation of Oil Families

Conclusions for the San Joaquin Study


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Fourteen families of San Joaquin Basin oils retain the geochemicalimprint of vertical and lateral organofacies variations in theirsource 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 basalKreyenhagen 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 thesame procedures and instrumentation.

Conclusions for the San Joaquin Study


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Floating Tar Whip,Point Conception

Families of Miocene Oils, Seeps, Tarballs: Coastal California


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Purpose

Correlate produced oil, seep oil, and tarballsamples into genetic families (oil-oilcorrelation)

Infer source rock for each oil sample (oil-source

rock correlation) Build a predictive chemometricmodel to classify

new samples Map distributions of oil families to better

understand origin and transport

Families of Miocene Oils, Seeps, Tarballs: Coastal California

Oil Samples Range from Point Reyes to Los Angeles


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Oil Samples Range from Point Reyes to Los Angeles

Point

Conception

LosAngeles

ChannelIslands

N

MontereyBay

Tribes1and2

Tribe3

Point

Reyes

CA

19 Variables Characterize 388 Training Set Samples


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Sample

d13C Terpanes and Steranes AromaticsPDB,

Ts/Tm

26Tri/Tet

20/23Tri

22/21Tri

24/23Tri

26/25Tri

28/29Tri

29/H

31S/H

35S/34S

BNH/H

OI/H

G/H

29Ts/29H

C28/C29

PAH-RI

DDBT/DP

TDBT/TP

1 -23.3

100 -24.0

200 -23.2

388 -23.3

-32 -30 -28 -26 -24 -22 -20

Paleozoic-MesozoicMarine Shale and

Paleozoic CarbonateOils

2

4

6

Deltaic Oils

MioceneOils

Mesozoic Carbonate Oils

Pristane/Phytan

e

Chun

getal.(1992)

Sulfur < 0.5%

Sulfur > 0.5%

19 Variables Characterize 388 Training Set Samples

Carbon Isotopic Ratio of Oil ()

Hierarchical Cluster Analysis (HCA): Three Oil Tribes


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2

1

3

388-SampleTraining Set

North

South

South

SimilarityLine

OilTri

be

Cluster Distance

Hierarchical Cluster Analysis (HCA): Three Oil Tribes

Decision Tree Fine Tunes Classification of New Samples


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New Sample

Tribe

Family

KNN model

2

21 22

KNN

1

11 12 13 14SIMCA

KNN (Nearest Neighbor)SIMCA (Fit)

3

31 32 33 34 35SIMCA

SIMCA

211 212 213

388-Sample

Training Set

SIMCA

Decision Tree Fine Tunes Classification of New Samples


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Block Rotation Explains Discontinuity and Oil Distribution


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Modified from Crouch and Suppe (1993)

Tribe3

Tribes1-2

Lions HeadLompoc

Naples Beach

SanDiego

Ventura

Los Angeles

Discontinuity

PointConception

Present-Day

N

SanDiego

Los Angeles

Ventura

Naples BeachLompoc

Early Miocene

Discontinuity

p y

Biomarkers in Oil Samples Characterize Their Source Rocks


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C24

/C23Tricycl

icTerpanes

0.2

0.4

0.6

0.8

1.0

1.2

0.2 0.4 0.6 0.8 1.0 1.2 1.4

Peters et al. (2005) courtesyof GeoMark Research, Inc.

C22/C21 Tricyclic Terpanes

Worldwide DatasetSource RockShale

Marl

Carbonate

p


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Oils from the Carbonate Lithofacies Have Little Oleanane


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Ts/Tm

Oleanane/Hopane

0.1

0.5

0.2

1.0

0

0.3

Oil Tribe

1 Shale2 Marl

3 Carbonate

More clayLess clay

FloweringPlants

No floweringplants

Biomarkers Identify Source Organofacies for the Oil Tribes


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Tribe Clay Carbonate Oxicity

Higher

Plants

Ts/Tm 20/23TT 22/21TT 29/H 35/34S BNH/H OI/H

1

0.56

0.17

0.25

0.07

0.27

0.08

0.60

0.09

0.95

0.28

0.39

0.26

0.10

0.04

20.280.08

0.180.05

0.470.09

0.690.07

1.690.26

1.300.54

0.040.02

3 0.210.03 0.100.01 0.910.15 0.760.09 2.030.31 0.920.43 0.030.01

y g

Prograding Margin Model Suggests Origins for Oil Tribes


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Lower Calcareous-Siliceous Member

CarbonaceousMarl Member

Clayey-Siliceous

Member

MarineOrganicMatter

Mixed Terrigenous-Marine Organic Matter

Total Organic Carbon (%)Hydrogen Index (mg HC/g TOC)

Seaward Landward

Miocene MontereyFormation

4.5/216(6 samples)

5.0/406(13 samples)

9.9/360(13 samples)

Modified fromIsaacs et al. (1996)

3

2

1

Katz and Royle (2001)

g g g gg g

Samples Near Point Conception Are Dominantly Family 22


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N

JalamaBeach

Government PointTar

mounds

Tar whip

PointConception

Family22212

32

y y

Ten Tarballs Were Analyzed by Decision-Tree Chemometrics


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Decision Tree Indicates Natural Origin for Tarball Samples


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Location Sample Family Source Rock SIMCA Fit

MossLanding

1 22 Marl Excellent5 212 Marl Excellent

7 34 Carbonate Excellent

Asilomar


9 32 Carbonate Good


Half

MoonBay




18 22 Marl Excellent

Tarballs Originated from Seeps During 2007 Storm


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Moss Landing (2/24/07)Sample 7; Family 34 Asilomar Beach (2/14/07)Sample 8; Family 33

Coal Oil Point Seeps (UCSB) Are More Active After Storms


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January, 2005

TrilogySeep

Conclusions: Coastal California Oil Families


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>600 coastal California tarball, seep, and producedoil samples correlate into 3 tribes and 13 families:Peters et al. (2008) AAPG Bulletin92: 1131-1152.

Geochemistry indicates source-rock organofacies,depositional environment, lithology, age

Decision-tree chemometrics classifies newsamples based on 388-sample training set andaddresses uncertainty

Tribes 1 and 2 are S and Tribe 3 is N of Point

Conception; distribution controlled by stratigraphyand burial depth of inferred Miocene source rock

Summary: Oil-Oil and Oil-Source Rock Correlation


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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 situorigin of source-rock bitumen

Biomarkers allow indirectcorrelation: age ofsource rock, depositional setting, lithology,organic matter input, redox conditions

Decision-tree chemometrics: correlation using

multivariate source parameters that assigns thelevel of certainty to the correlation

Some Useful References


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Peters, K.E. et al., 2008, Families of Miocene crude oil, seep, andtarball samples, coastal California: AAPG Bulletin 92, 1131-1152.

Peters, K.E. et al., 2008, A four-dimensional petroleum systemsmodel for the San Joaquin Basin, California, inA. HosfordScheirer, ed., 2007, Petroleum systems and geologic assessmentof oil and gas in the San Joaquin Basin province, California: USGSProf. 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 PrudhoeBay 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, inL.B. Magoonand 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 asdetermined by oil geochemistry. AAPG Bulletin 89: 1347-1371.

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