chemometric recognition of genetically distinct oil families in the los angeles basin
DESCRIPTION
Chemostratigraphy, Oil, CaliforniaTRANSCRIPT
Chemometric Recognition of Genetically Distinct Oil Families in the Los Angeles Basin*
K. E. Peters1,2
, L. Scott Ramos3, and J. E. Zumberge
4
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
**AAPG©2013 Serial rights given by author. For all other rights contact author directly.
1Schlumberger Information Solutions, Mill Valley, CA 94941 ([email protected]) 2Stanford University , Stanford, CA 94305 3Infometrix, Inc., Bothell, WA 98011 4GeoMark 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 world’s
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.
K.E. Peters1,2, L.S. Ramos3, J.E. Zumberge4
1 Schlumberger Information Solutions, Mill Valley, CA 94941; [email protected] 2 Dept. Geology & Environmental Sciences, Stanford University, Stanford, CA 94305 3 Infometrix, Inc., Bothell, WA 98011 4 GeoMark Research, Houston, TX 77095
Chemometric Recognition of Genetically Distinct Oil Families in the Los Angeles Basin A
pr
il 2
1-2
5, 2
01
3
Mo
nt
er
ey
, C
A
Sedimentology and Biogeochemistry of the Monterey Formation and
Modern Upwelling Sediments: a Session Dedicated to Bob Garrison
Acknowledgements •Tess Menotti (maps of sample locations)
•Tom Wright (discussions of LA basin stratigraphy)
•Les Magoon (general discussions)
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 1970’s.
• 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.
F’
F
>12,000 ft
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
Modified from Wright (1991)
A
A’
PALOS VERDES
HILLS
Oil
Sam
ple
Bio
de
grad
atio
n*
Terpanes Steranes Isotopes
C1
9/C
23
C2
2/C
21
C2
4/C
23
C2
6/C
25
C2
6/T
s
Tet/
C2
3
C2
7T/
C2
7
C2
8/H
C2
9/H
X/H
Ol/
H
C3
1R
/H
Ga/
31
R
C3
5S/
C3
4S
C2
7Ts
/Tm
C2
9Ts
/Tm
S/H
%C
27
%C
28
%C
29
S1/S
6
d1
3C
sat
d1
3C
aro
CV
ElS5S 0 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 -25.02 -23.68 -0.92
LB6M 4 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 -23.88 -22.94 -2.16
BvH7S 3 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 -23.87 -23.16 -2.67
BvH26S 0 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 -25.06 -23.67 -0.80
CvH27S 0 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 -24.95 -23.64 -1.01
SwN28S 1 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 -25.04 -23.73 -0.98
Wht42S 4 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 -23.68 -23.05 -2.91
Wil78S 5 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 -23.66 -22.96 -2.76
Wil79S 4 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 -23.59 -22.91 -2.83
Oil Families: 24 Source-Related Biomarker & Isotope Ratios
*0-10 biodegradation scale of Peters and Moldowan (1993)
Light
1
2
3 Moderate
4
5 Heavy
6
(6)
7 Very Heavy
8
9 Severe
10
Dia
ste
ran
es
Ste
ran
es
Iso
pre
no
ids
Te
rpa
ne
s
C2
6-C
29 A
rom
ati
cs
n-Alkanes
Extent of Destruction of Compound Class
Bio
deg
rad
ati
on
Ran
ik
Training Set: No Biodegradation of Steranes or Terpanes
Peters and Moldowan (1993)
Reje
cte
d
Oil Having Biodegradation Rank 5 or More was Rejected
Pristane
Phytane
Wil78S Wilmington
CvH27S Cheviot Hills
SwN28S Sawtelle North
Nonbiodegraded
PM* Rank = 0
1.90 wt.% S
Mildly Biodegraded
PM* Rank = 1
3.00 wt.% S
Moderately Biodegraded
PM* Rank = 5
8.02 wt.% S
nC15
Pristane
Phytane nC15
*PM = 0-10 biodegradation scale
of Peters and Moldowan (1993)
UCM Biomarker
Region
6
5
4
3
2
1
Cluster Distance
We
st
of
NIF
Z
Ea
st
of
NIF
Z
Similarity
line
112-Sample
Training Set
6 Tribes: East/West of Newport-Inglewood Fault Zone (NIFZ)
Oil Tribe
Repeatability
line
-24.0
-23.5
-23.0
-22.5
-22.0
-21.5
-25.5 -25.0 -24.5 -24.0 -23.5 -23.0
d1
3C
aro
mati
cs
d13Csaturates
112-Sample
Training Set
All Samples Have a Miocene Isotopic Signature (13C-Rich)
1
2
3
4
5
6
East
West
d13Csaturates, ‰
d1
3C
aro
mati
cs,
‰
1
2
3
4
5
6
East
West
0.00
0.20
0.40
0.60
0.80
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Ole
an
an
e/H
op
an
e
C19/C23 Tricylic Terpanes
Tribes 1 and 2 are Enriched in Higher-Plant Biomarkers
Nerium oleander
21
5
SIMCA*
SIMCA*
New Sample
11
Chemometric Decision-Tree Classifies New Oil Samples
112-Sample Training Set
Six Tribes; 12 Families
*Soft independent modeling of class analogy
22
12 13 31 33 32
41 42
6
Families East/West of Newport-Inglewood Fault Zone (NIFZ)
>12,000 ft (base Mohnian)
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
Huntington
Beach
Beverly
Hills
Torrance
Wilmington
Seal
Beach
Santa Fe
Springs West
Coyote
Whittier
Las
Cienegas
El Segundo Alondra
Playa del Rey
Venice
Beach
Cheviot
Hills
Sawtelle
San Vicente
Bandini
Union
Station
Rosecrans
East LA
Potrero
Richfield
Long
Beach
Central
Trough
Inglewood
LA
Downtown
Belmont
PALOS VERDES
HILLS
Families in Tribe 1 Originated from Source Rock East of NIFZ
12
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
12
13
Central
Trough
Seal
Beach
Santa Fe
Springs West
Coyote
Whittier
Bandini
Union
Station
Rosecrans
Potrero
Richfield
Inglewood
LA
Downtown
11 Long
Beach
Belmont
Sawtelle
PALOS VERDES
HILLS
Families in Tribe 1 Originated from Source Rock East of NIFZ
11
12
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
13
Central
Trough
Family 11
28.2o API
1.00 wt.% S
MPI = 1.08
Family 12
31.6o API
1.26 wt.% S
MPI = 1.12
Family 13
30.2o API
1.18 wt.% S
MPI = 1.13
11 12
13
0.00
0.05
0.10
0.15
0.20
0.25
0.8 1.0 1.2 1.4
TA
S3
(CR
)
MPI
Seal
Beach
Santa Fe
Springs West
Coyote
Whittier
Bandini
Union
Station
Rosecrans
Potrero
Richfield
Inglewood
LA
Downtown
Long
Beach
Belmont
Sawtelle
PALOS VERDES
HILLS
12
Families in Tribe 2 Originated from Source Rock East of NIFZ
21
22
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
Santa Fe
Springs
Las
Cienegas
Bandini
Rosecrans
LA
Downtown
Central
Trough
PALOS VERDES
HILLS
Families in Tribe 2 Originated from Source Rock East of NIFZ
21
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
Family 21
35.3o API
1.41 wt.% S
MPI = 1.49
Family 22
32.6o API
0.23 wt.% S
MPI = 1.39
21 22
0.00
0.05
0.10
0.15
0.20
0.25
0.8 1.0 1.2 1.4
TA
S3
(CR
)
MPI
22 Central
Trough Santa Fe
Springs
Las
Cienegas
Bandini
Rosecrans
LA
Downtown
PALOS VERDES
HILLS
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
31
33
Wilmington and adjacent fields – 58% of total resource, 10% of area (Wright, 1991)
Tribe 3 Families Originated from Source Rock West of NIFZ
Huntington
Beach
Wilmington
Torrance
Seal
Beach
Long
Beach
32
PALOS VERDES
HILLS
32
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
31
33
Tribe 3 Families Originated from Source Rock West of NIFZ
Family 31
24.7o API
1.42 wt.% S
MPI = 0.99
Family 32
-- o API
1.57 wt.% S
MPI = 1.04
Family 33
-- o API
1.58 wt.% S
MPI = 1.14
Huntington
Beach
Wilmington
Torrance
Seal
Beach
Long
Beach
6
21 22
31
32 33
0.00
0.05
0.10
0.15
0.20
0.25
0.8 1.0 1.2 1.4
TA
S3
(CR
)
MPI
PALOS VERDES
HILLS
Wilmington and adjacent fields – 58% of total resource, 10% of area (Wright, 1991)
Tribe 4 Families Originated from Source Rock West of NIFZ
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
42
41
Torrance
Wilmington
Playa del Rey
Venice
Beach
Sawtelle
El Segundo
PALOS VERDES
HILLS
Tribe 4 Families Originated from Source Rock West of NIFZ
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
42
41
Family 41
17.8o API
-- wt.% S
MPI = 1.07
Family 42
25.9o API
4.27 wt.% S
MPI = 1.04
41
42
0.0
0.5
1.0
1.5
2.0
2.5
0 1 2 3 4 5
V/N
i
Sulfur, wt.%
Torrance
Wilmington
Playa del Rey
Venice
Beach
Sawtelle
El Segundo
PALOS VERDES
HILLS
Tribes 5 and 6 Originated from Source Rocks West of NIFZ
5
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
6
5 Huntington
Beach
Torrance
Wilmington
Beverly
Hills
Cheviot
Hills
Sawtelle
San Vicente
Inglewood
El Segundo
Playa del Rey
PALOS VERDES
HILLS
Tribes 5 and 6 Originated from Source Rocks West of NIFZ
5
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
6
5
Family 5
29.4o API
1.24 wt.% S
MPI = 1.02
Family 6
25.5o API
2.50 wt.% S
MPI = 0.86
6 5
0.0
0.5
1.0
1.5
2.0
2.5
0 1 2 3 4 5
V/N
i
Sulfur, wt.%
Huntington
Beach
Torrance
Wilmington
Beverly
Hills
El Segundo
Playa del Rey
Cheviot
Hills
Sawtelle
San Vicente
Inglewood
PALOS VERDES
HILLS
Cross Sections Reveal Stratigraphy of Some Oil Families
F’
F
Family
11, 12, 13
21, 22
31, 32, 33
41, 42
5
6
Wilmington
Seal Beach
West
Coyote A
A’
Playa del Rey
San Vicente
Inglewood
PALOS VERDES
HILLS
10
20 6
Dep
th, km
Dep
th, x1000 f
t
A A’
Section modified from Wright (1991)
Santa Monica
Bay Inglewood Playa del Rey
San
Vicente
SW East Beverly
Hills
P Q
Tt
Catalina
Schist
Bc
Q
?
?
3
P
R
D
P
Tt
R
Mo
Mo
? ?
R Tt
?
D
Family
13
6
A-A’ Section Reveals Stratigraphy of Tribe 6 and Family 13
Catalina
Schist
Mo
Mo
Mo
Mo
Mo
Mo
D
D D
D
D
Mo
P
P
P
P P Q
R
R
R R
Mo
u
m
l
u
R m
l
M M
Tt Tt
Tt
Tt
Tt
Tm-Tt
Mo
L Tt D
10
20 6
3
Dep
th, k
m
Dep
th, x1000 f
t
San Pedro
Bay
Wil
min
gto
n-
Be
lmo
nt
West
Coyote
Seal
Beach
Sansinena
NIF
Z
Catalina
Schist Bc AN
Tvs Pg-K Tvs
Bc
F F’
NE
Family
11
31, 32
5
F-F’ Section Reveals Stratigraphy of Families 5, 11, 31, 32
Section modified from Wright (1991)
EPOCH
BENTHIC
FORAM
STAGE
LOS ANGELES BASIN
WEST EAST
SANTA
MONICA
MOUNTAINS
PALOS
VERDES
HILLS
Stratigraphy Suggests Source Rocks for Oil Families P
LE
IST
P
LIO
CE
NE
LA
TE
M I
O C
E N
E
DELMONT.
LUISIAN
LA
TE
E
AR
LY
MID
DL
E
LA
TE
E
E
REPETT.
MOHNIAN
RELIZIAN
HALLIAN
WHEEL.
VENT.
FERNANDO
LOWER
TO
PA
NG
A G
P.
(NOT EXPOSED)
M O
D E
L O
CONEJO VOLC.
UPPER
CALABASAS
TOPG. CYN
SAN PEDRO
LOWER
TOPANGA
GP.
LA HABRA
REPETTO
MALAGA
MUDSTONE
UPPER
M O
N T
E R
E Y
VALMONTE
DIATOMITE
MIDDLE
PU
EN
TE
ALT
AM
IRA
REPETTO REPETTO
LOWER
UPPER
MIDDLE
LOWER
UPPER
MIDDLE TOPANGA
GROUP SCHIST
CONG. VOLC. SD.
LOWER
UPPER
MIDDLE
TIMMS PT.
SLT.
PIC
O
LOMITA MARL
LOWER
“NODULAR’
SHALE
UPPER
MIDDLE
PU
EN
TE
P
ICO
Modified from Blake (1991)
Oil-like shale
hydrocarbons
not observed
(Philippi, 1965)
~4 wt.% TOC, up
to 16 wt.%, Type I
and II kerogen
(Global Geochem.
Corp., unpub.)
A-A’ F-F’
6
13
5
11
32
31
11
NIF
Z
NIF
Z
• 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.
Source Rock Can be Inferred from Stratigraphy-Biomarkers
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 world’s 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, 35-
134.