Chemometric Recognition of Genetically Distinct Oil Families in the Los Angeles Basin*

K. E. Peters1,2, L. Scott Ramos3, and J. E. Zumberge4 Search and Discovery Article #41149 (2013)**
Posted July 22, 2013 *Adapted from oral presentation given at 2013 Pacific Section AAPG, SEG and SEPM Joint Technical Conference, Monterey, California, April 19-25, 2013 **AAPG2013 Serial rights given by author. For all other rights contact author directly.
1 2

Schlumberger Information Solutions, Mill Valley, CA 94941 (kpeters2@slb.com) Stanford University , Stanford, CA 94305 3 Infometrix, Inc., Bothell, WA 98011 4 GeoMark Research, Houston, TX 77095

Abstract Multivariate statistical analysis (chemometrics) of selected source-related biomarker and stable carbon isotope ratios for 112 nonbiodegraded or mildly biodegraded crude oil samples from the prolific Los Angeles basin identifies five tribes and a total of 12 genetically distinct oil families. These families occur in different parts of the basin and exhibit different bulk properties, such as API gravity, sulfur, and metal content that are principally controlled by source rock organofacies rather than secondary processes, such as thermal maturity or biodegradation. Stable carbon isotope data for saturate and aromatic fractions of the samples suggest Neogene source rock, although not necessarily all from the basal Mohnian nodular shale unit of the Modelo Formation. Biomarker ratios allow indirect assessment of the character to the source rock for each family. For example, tribes 1 and 2 straddle the Central Trough to the east of the Newport-Inglewood Fault Zone and show evidence of elevated clastic and higher-plant input (e.g., elevated C24/C23 tricyclic terpanes and oleanane, respectively). Some families clearly originated from source rock in different depocenters on opposite sides of the Newport-Inglewood Fault Zone and from different stratigraphic intervals. For example, unlike tribes 1 and 2, tribe 5 occurs west of the Newport-Inglewood Fault Zone and shows evidence of a more distal, clay-poor source rock (e.g., lower C24/C23 tricyclic terpanes and oleanane, elevated steranes/hopanes and bisnorhopane). As another example, tribe 5 oils occur in deeper intervals (9007-10,480 ft) than tribe 3 oils (3531-6842 ft) in the Wilmington field. The 112 crude oil samples were used as a training set to build a chemometric decision tree, which allowed classification of nearly 50 additional samples that were affected to varying degrees by severe thermal maturation or biodegradation. Selected References Blake, G.H., 1991, Review of the Neogene biostratigraphy and stratigraphy of the Los Angeles basin and implications for basin evolution: AAPG Memoir 52, p. 135-184. Jeffrey, A.W.A., H.M. Alimi, and P.D. Jenden, 1991, Geochemistry of Los Angeles basin oil and gas systems: AAPG Memoir 52, p. 197-219.

McCulloh, T.H., D.W. Kirkland, A.J. Koch, W.L. Orr, and H.M. Chung, 1994, How oil composition relates to kerogen facies in the worlds most petroliferous basin: AAPG Search and Discovery Article #90986 (1994), AAPG Annual Convention, Denver, CO, June 12-15, 1994. (http://www.searchanddiscovery.com/abstracts/html/1994/annual/abstracts/0210b.htm?q=%2BtextStrip%3Amcculloh+%2BtextStrip%3A9098 6). Peters, K.E., and J.M. Moldowan, 1993, The biomarker guide; interpreting molecular fossils in petroleum and ancient sediments: Englewood Cliffs, Prentice Hall, 363 p. Philippi, G.T., 1965, On the depth, time and mechanism of petroleum generation: Geochim. Cosmochim. Acta, v. 29, p. 1021-1049. Wright, T.L., 1991, Structural geology and tectonic evolution of the Los Angeles Basin, California: AAPG Memoir 52, p. 35-134.

Chemometric Recognition of Genetically Distinct Oil Families in the Los Angeles Basin
K.E. Peters1,2, L.S. Ramos3, J.E. Zumberge4
1
2 Dept.

Schlumberger Information Solutions, Mill Valley, CA 94941; kpeters2@slb.com Geology & Environmental Sciences, Stanford University, Stanford, CA 94305 3 Infometrix, Inc., Bothell, WA 98011 4 GeoMark Research, Houston, TX 77095 Acknowledgements

Tess Menotti (maps of sample locations) Tom Wright (discussions of LA basin stratigraphy) Les Magoon (general discussions)

April 21-25, 2013 Monterey, CA

Sedimentology and Biogeochemistry of the Monterey Formation and Modern Upwelling Sediments: a Session Dedicated to Bob Garrison

Significant Characteristics of the Los Angeles Basin

Richest basin in the world based on amount of petroleum
relative to volume of sedimentary fill. Classic model of transform-margin basin. Since Brea-Olinda in 1880, 67 fields were discovered; three supergiants include Wilmington, Long Beach, and Huntington Beach. Little exploration since the early 1970s. Significant potential likely remains in deep, especially offshore areas.

Purpose of the Los Angeles Basin Study

Measure biomarker and isotope ratios for ~150 crude oil
samples from the basin to evaluate genetic relationships.

Assess the extent of biodegradation for each sample to

identify a training set where source-related biomarker or isotope ratios are unaffected.

Identify oil families; create a chemometric (multivariate

statistics) decision tree to classify new samples.

Map the distribution of oil families; use biomarker and

isotope ratios to infer their source rock organofacies.

Map Shows Families and Base Mohnian (~14 Ma) >12,000 Ft.
A

A
Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

>12,000 ft

PALOS VERDES HILLS

F
Modified from Wright (1991)

Oil Families: 24 Source-Related Biomarker & Isotope Ratios

Oil Sample
Biodegradation*

Terpanes
C35S/C34S C27Ts/Tm C27T/C27 Ga/31R Tet/C23 C19/C23 C22/C21 C24/C23

Steranes
C29Ts/Tm S/H %C27 C31R/H S1/S6

Isotopes

C26/C25

d13Caro
-23.68 -22.94 -23.16 -23.67 -23.64 -23.73 -23.05 -22.96 -22.91

d13Csat
-25.02 -23.88 -23.87 -25.06 -24.95 -25.04 -23.68 -23.66 -23.59

C26/Ts

C28/H

C29/H

Ol/H

%C28

%C29

X/H

ElS5S LB6M BvH7S BvH26S CvH27S SwN28S Wht42S

0 4 3 0 0 1 4

0.0350

0.2470

0.7517

0.7903

1.8274

0.1190

0.0378

0.3835

0.5460

0.0192

0.1162

0.2847

0.1006

0.9857

0.4668

0.2008 1.7745 31.1369 41.6277 27.2354

0.1793

0.0332

0.1781

0.6544

1.1647

2.6412

0.1335

0.0590

0.4458

0.5961

0.0167

0.1319

0.2269

0.6705

0.8730

0.3510

0.1628 1.8849 29.7768 44.5270 25.6962

0.1514

0.0263

0.2458

0.9474

0.8300

2.6974

0.1033

0.0329

0.2743

0.5091

0.0256

0.1405

0.2452

0.2843

0.9021

0.5314

0.2110 1.6759 30.0511 43.9406 26.0083

0.2100

0.0202

0.2926

0.7979

0.8203

2.0286

0.1268

0.0560

0.3661

0.5678

0.0151

0.1439

0.2741

0.2774

0.9107

0.4159

0.1811 1.3432 31.9467 39.9842 28.0690

0.0125

0.0237

0.2735

0.8494

0.9053

2.0887

0.1302

0.0499

0.1838

0.5275

0.0216

0.1478

0.2242

0.4121

0.6551

0.5258

0.1826 1.2655 30.6225 39.4825 29.8950

0.1942

0.0202

0.2647

0.7878

0.8106

2.0852

0.1262

0.0559

0.3621

0.5702

0.0139

0.1472

0.2723

0.4088

0.9618

0.3826

0.1758 1.5505 30.6532 40.9345 28.4122

0.1608

0.0555

0.2478

0.8727

1.0259

2.8864

0.0908

0.0815

0.2331

0.4251

0.0319

0.2837

0.1736

0.6051

0.6676

0.7019

0.2142 1.3942 32.0455 40.8963 27.0582

0.2966

Wil78S
Wil79S

5
4

0.0169

0.2394

0.7959

0.7684

3.8077

0.0926

0.0514

0.4284

0.7302

0.0286

0.1976

0.3393

0.5113

0.9033

0.3726

0.1649 0.7196 32.7066 41.3216 25.9717

1.1362

0.0166

0.2464

0.8045

0.7615

3.6745

0.0908

0.0573

0.3370

0.6352

0.0256

0.1622

0.2890

0.5523

0.9238

0.4197

0.1587 1.0619 33.0806 40.7143 26.2051

0.4414

*0-10 biodegradation scale of Peters and Moldowan (1993)

CV
-0.92 -2.16 -2.67 -0.80 -1.01 -0.98 -2.91 -2.76 -2.83

Training Set: No Biodegradation of Steranes or Terpanes

1 2 3 Moderate 4 5 Heavy 6 (6)
7 Very Heavy 8 9 Severe 10
Isoprenoids

Light

n-Alkanes

Biodegradation Ranik

Steranes

Terpanes

C26-C29 Aromatics

Diasteranes

Extent of Destruction of Compound Class

Peters and Moldowan (1993)

Rejected

Oil Having Biodegradation Rank 5 or More was Rejected

CvH27S
Cheviot Hills
nC15 Pristane Phytane
Nonbiodegraded PM* Rank = 0 1.90 wt.% S

SwN28S
Sawtelle North

nC15

Pristane Phytane

Mildly Biodegraded PM* Rank = 1 3.00 wt.% S

Wil78S
Wilmington

Moderately Biodegraded PM* Rank = 5 8.02 wt.% S

*PM = 0-10 biodegradation scale of Peters and Moldowan (1993)

UCM

Biomarker Region

6 Tribes: East/West of Newport-Inglewood Fault Zone (NIFZ)

East of NIFZ Oil Tribe 1 112-Sample Training Set

2
Similarity line

West of NIFZ

4
5 6
Repeatability line

Cluster Distance

All Samples Have a Miocene Isotopic Signature (13C-Rich)

-21.5

112-Sample Training Set

13C d13d C , aromatics aromatics

-22.0

-22.5

East West
-25.0 -24.5 -24.0 -23.5

1 2 3 4 5 6

-23.0

-23.5

-24.0 -25.5

-23.0

13C 13 dd Csaturates saturates ,

Tribes 1 and 2 are Enriched in Higher-Plant Biomarkers

0.80

East West
0.03 0.04 0.05 0.06 0.07 0.08 0.60

1 2 3 4 5 6

Oleanane/Hopane

Nerium oleander

0.40

0.20

0.00 0.00

0.01

0.02

C19/C23 Tricylic Terpanes

Chemometric Decision-Tree Classifies New Oil Samples

112-Sample Training Set Six Tribes; 12 Families
New Sample SIMCA*

SIMCA*

21 22
11 12 13 31 32 33

41 42

*Soft independent modeling of class analogy

Families East/West of Newport-Inglewood Fault Zone (NIFZ)

Beverly Hills Sawtelle Cheviot Hills Venice Beach Playa del Rey Rosecrans El Segundo Alondra San Vicente Union Station Las LA Cienegas Downtown Inglewood Bandini East LA

Potrero
Whittier

Central Trough

Santa Fe Springs West Coyote Richfield

>12,000 ft
(base Mohnian)
Torrance

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

Long Beach Seal Beach

PALOS VERDES HILLS Wilmington

Belmont

Huntington Beach

Families in Tribe 1 Originated from Source Rock East of NIFZ

Union Station Sawtelle

12

LA Downtown Inglewood Bandini

Potrero
Rosecrans

13
Whittier Springs West Coyote

Central 12Santa Fe

Trough

11
Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6
Long Beach PALOS VERDES HILLS Seal Beach

Richfield

Belmont

Families in Tribe 1 Originated from Source Rock East of NIFZ

Family 11
Union Station Sawtelle

28.2o API 1.00 wt.% S

12
Inglewood
0.25

LA Downtown Bandini

TAS3(CR)

0.20 0.15 0.10 0.05 0.00 0.8

13 11 12

Potrero
Rosecrans

13
Whittier Springs West Coyote

MPI = 1.08

Central 12Santa Fe

Trough
1.0 1.2 1.4

Richfield

MPI

11
Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6
Long Beach PALOS VERDES HILLS Seal Beach

Family 12 31.6o API 1.26 wt.% S MPI = 1.12

Belmont

Family 13 30.2o API 1.18 wt.% S MPI = 1.13

Families in Tribe 2 Originated from Source Rock East of NIFZ

Las Cienegas LA Downtown

21
Bandini Rosecrans

Central Trough

22
Santa Fe Springs

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

PALOS VERDES HILLS

Families in Tribe 2 Originated from Source Rock East of NIFZ

Las Cienegas LA Downtown

Family 21 35.3o API 1.41 wt.% S MPI = 1.49

21
0.25

TAS3(CR)

22 21
Rosecrans

Bandini

0.20 0.15 0.10 0.05 0.00 0.8 1.0 1.2 1.4

Central Trough

22
Santa Fe Springs

MPI

Family 22

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

32.6o API
PALOS VERDES HILLS

0.23 wt.% S MPI = 1.39

Tribe 3 Families Originated from Source Rock West of NIFZ

33
Torrance

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

Long Beach Seal Beach

PALOS VERDES HILLS

32

Wilmington

31

Huntington Beach

Wilmington and adjacent fields 58% of total resource, 10% of area (Wright, 1991)

Tribe 3 Families Originated from Source Rock West of NIFZ

Family 31 24.7o API 1.42 wt.% S
0.25

TAS3(CR)

22

21

MPI = 0.99

0.20 0.15 0.10 0.05 0.00 0.8 1.0

31
6

32

33
1.2 1.4

MPI

33
Torrance

Family 32
Long Beach Seal Beach

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

-- o API 1.57 wt.% S MPI = 1.04

PALOS VERDES HILLS

32

Wilmington

31

Huntington Beach

Family 33
-- o API 1.58 wt.% S MPI = 1.14

Wilmington and adjacent fields 58% of total resource, 10% of area (Wright, 1991)

Tribe 4 Families Originated from Source Rock West of NIFZ

Sawtelle

Venice Beach Playa del Rey

42

El Segundo

Torrance

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

PALOS VERDES HILLS

41
Wilmington

Tribe 4 Families Originated from Source Rock West of NIFZ

Family 41 17.8o API
Sawtelle Venice Beach
2.5 2.0

-- wt.% S MPI = 1.07

42
Playa del Rey

V/Ni

1.5 1.0 0.5 0.0 0 1 2 3 4 5

42

41
El Segundo

Sulfur, wt.%

Family 42
Torrance

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

25.9o API
PALOS VERDES HILLS

41
Wilmington

4.27 wt.% S MPI = 1.04

Tribes 5 and 6 Originated from Source Rocks West of NIFZ

Beverly Hills Sawtelle Cheviot Hills San Vicente

6
Playa del Rey

Inglewood

El Segundo

5
Torrance

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

PALOS VERDES HILLS Wilmington

Huntington Beach

Tribes 5 and 6 Originated from Source Rocks West of NIFZ

Beverly Hills Sawtelle Cheviot Hills
2.5 2.0

San Vicente

Family 5 29.4o API 1.24 wt.% S

6
Playa del Rey

Inglewood

MPI = 1.02

V/Ni

1.5 1.0 0.5 0.0 0 1 2 3 4 5

6
El Segundo

Sulfur, wt.%

5
Torrance

Family 6 25.5o API

Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

PALOS VERDES HILLS Wilmington

2.50 wt.% S
MPI = 0.86

Huntington Beach

Cross Sections Reveal Stratigraphy of Some Oil Families

A
San Vicente

Inglewood Playa del Rey

A
Family 11, 12, 13 21, 22 31, 32, 33 41, 42 5 6

West Coyote

PALOS VERDES HILLS

Seal Beach Wilmington

A-A Section Reveals Stratigraphy of Tribe 6 and Family 13

SW

A Depth, x1000 ft

Santa Monica Bay

Playa del Rey

Inglewood

East Beverly San Hills Vicente

A Depth, km

P ? Catalina Schist ? Mo ?

Q P P

Q Mo Tt

R
R D

R
Mo Tt Tt Bc ? D Mo

10

Catalina Schist

20

Family 13 6

Section modified from Wright (1991)

F-F Section Reveals Stratigraphy of Families 5, 11, 31, 32

WilmingtonBelmont

San Pedro Bay

Seal Beach

NE

West Coyote

Sansinena
M Q P R D Mo Tt D u R m l D Pg-K AN P u m l P R Tt Bc Tt Tt

F
Mo P P R Mo D Mo L Tm-Tt Catalina Schist R D M

Depth, x1000 ft

10

Mo

D Mo

3
Tt

Tvs

Tvs

NIFZ

Bc

Mo
Tt

20

Family 11 31, 32 5

Section modified from Wright (1991)

Depth, km

Stratigraphy Suggests Source Rocks for Oil Families

EPOCH
LATE PLEIST

NIFZ

BENTHIC SANTA FORAM MONICA STAGE MOUNTAINS

HALLIAN WHEEL. FERNANDO
(NOT EXPOSED)

PALOS VERDES HILLS

TIMMS PT. SLT.

LOS ANGELES BASIN WEST EAST

SAN PEDRO LA HABRA UPPER UPPER MIDDLE LOWER

PICO

PICO

LOMITA MARL

MIDDLE LOWER

LATE

PLIOCENE

VENT.
REPETT.

13

REPETTO
MALAGA MUDSTONE

REPETTO
UPPER

11

REPETTO
UPPER

11

Oil-like shale hydrocarbons not observed (Philippi, 1965)

MODELO

DELMONT. LATE

32 31
PUENTE

MONTEREY

MIOCENE

MOHNIAN MIDDLE

VALMONTE DIATOMITE ALTAMIRA UPPER MIDDLE

PUENTE

UPPER

MIDDLE

MIDDLE LOWER TOPANGA GROUP

LOWER

6
TOPANGA GP. LUISIAN RELIZIAN
CALABASAS CONEJO VOLC. TOPG. CYN

LOWER NODULAR SHALE

~4 wt.% TOC, up to 16 wt.%, Type I and II kerogen (Global Geochem. Corp., unpub.)

LOWER

EARLY

TOPANGA GP. SCHIST CONG.

A-A

NIFZ

VOLC. SD.

F-F

Modified from Blake (1991)

Source Rock Can be Inferred from Stratigraphy-Biomarkers

Suboxic Upper Miocene (Delmontian) shale with significant

angiosperm input generated Tribes 1-2 at moderate-high maturity in the Central Trough east of NIFZ. Anoxic Upper Miocene (M.-U. Puente) marl source rock generated Tribe 3 west of NIFZ. Anoxic Mohnian(?) marl generated Tribe 4 west of NIFZ. Anoxic M.-U. Miocene (L. Puente nodular shale) marl with significant terrigenous plant input generated Tribe 5 southwest of NIFZ. Anoxic M.-U. Miocene (L. Modelo nodular shale) marl with significant terrigenous plant input generated Tribe 6 at low maturity northwest of NIFZ.

Conclusions: Los Angeles Basin Geochemistry

At least six genetically distinct Miocene petroleum systems
(12 families) occur in different parts of the basin.

The Newport-Inglewood fault separates tribes 1-2 (families

11, 12, 13, 21, 22) to the east from tribes 3-6 (families 31-33, 41-42, 5, 6) to the west.

Biomarker and isotope ratios as well as distinct stratigraphic

occurrence help to identify likely source rock for each family.

Thermally mature source rock samples for direct oil-source

rock correlation and 3D petroleum system modeling with partner(s) would useful to delineate pods of active source rock, migration paths, and undiscovered accumulations.

Thanks for Your Attention!

References
Blake, G.H., 1991, Review of the Neogene biostratigraphy and
stratigraphy of the Los Angeles basin and implications for basin evolution: AAPG Memoir 52, 135-184. Jeffrey, A.W.A. et al., 1991, Geochemistry of Los Angeles basin oil and gas systems: AAPG Memoir 52, 197-219. McCulloh, T.H. et al., 1994, How oil composition relates to kerogen facies in the worlds most petroliferous basin: AAPG Search and Discovery Article #90986, AAPG Annual Convention, Denver, CO, June 12-15, 1994. Wright, T.L., 1991, Structural geology and tectonic evolution of the Los Angeles Basin, California: AAPG Memoir 52, 35134.