Thermal Maturity

of Woodford Fluids
Anadarko Basin, USA

J. B. Curtis, J. E. Zumberge and S.W. Brown

GeoMark Research, Ltd.

6 Sept 2018
 Conclusions

❑ Maturity-dependent terpane, sterane & other biomarker ratios

are used to estimate the C20+ (heavy-end) maturity of crude
oils
❑ Likely reflects the source rock maturity when this early fraction
of the oil was expelled (primary migration)
❑ Maturity-dependent alkyl naphthalene & phenanthrene ratios
are used to estimate the ~C10-C15 (mid-range) maturity of
crude oils
❑ Likely reflects the source rock maturity when this later, often
more mature fraction of the oil was expelled
❑ Calculated maturities of laterally co-produced oils and gases
from the Woodford Formation of the Anadarko Basin, OK
generally agree
❑ However, anomalous positive methane carbon isotopes and
high diamondoid concentrations were detected in some lower-
maturity black Woodford oils.

Maturity of Woodford Fluids

 Biomarkers

• Hydrocarbons whose structures can be recognized in

living organisms

• Occur in some reasonable abundance in nature

• Stable during diagenesis

• They are Molecular Fossils!!

Maturity of Woodford Fluids

Example Biomarker

Steranes (m/z 217)

Cholestane C27

Maturity of Woodford Fluids

 Biomarker ‘Tree of Life’
Animals
Eucarya
b-carotane Steranes
Plants Flagellates
Microsporidia
Fungi
Ciliates

Slime moulds
Diplomonads

•Carotenoids are yellow, orange or red colored pigments

•Prime function is for light harvesting & photoprotection
Bacteria
Terpanes/Hopanes
Green non-sulfur
bacteria
okenane Gram positive Sulfolobus
bacteria Desulfurococcus
12-24m Purple sulfur bacteria Thermotoga
Pyrodictium
Thermoproteus Archaea
Nitrospira Pyrobaculum Methanogenic
PZE Cyanobacteria
Pyrococcus M ethanobacterium
Green sulfur Thermoplasma
isorenieratane bacteria
Archaeoglobus
<100m
M ethanopyrus Halobacterium
M ethanococcus C20 and C25 acyclic isoprenoids
cyclic biphytanes
chlorobactane 15-100m Aquifex GDGTs
M ethanosarcina
rRNA tree modified after Woese

Maturity of Woodford Fluids

Carbon Isotopes – A Reminder!

Maturity of Woodford Fluids

 Changes in Carbon Isotope Ratios with
Thermal Maturation (after M. Schoell)

After M. Schoell
 Biomarkers & Isotopes

Oil Biomarkers and Carbon Isotopes of Oils and Gases

can provide insight into:

❖Source Rock Type

❖Depositional Environment
❖Geologic Age
❖Organic Matter Maturity
❖Migration Timing
❖Migration Distance & Direction (On a good day…)

Maturity of Woodford Fluids

 2.0
Oil Thermal Maturity (VRE via biomarker maturity ratios)
4.5
a) b)
1.8 4.0

1.6

C27 Diasterane/C27 Regular Sterane

3.5

1.4
3.0
Fam 2 EF Marls
1.2 Fam 3 EF Shales
C29 Ts/Tm

2.5 Fam7 EF Carbonates

1.0
2.0
0.8

Fam 2 EF Marls 1.5

0.6 Fam 3 EF Shales
Fam7 EF Carbonates
1.0
0.4

0.2 0.5

0.0 0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 0.00 0.05 0.10 0.15 0.20 0.25
C27 Ts/Tm C30 Diahopane/C30 Hopane

4.5 3.5
c) d)
MDR - methyldibenzothiophene ratio (4-MDBT/1-MDBT)

4.0
3.0
3.5

Fam 2 EF Marls
3.0 Fam 3 EF Shales 2.5
Fam7 EF Carbonates

2.5 nC18/Phytane
2.0
2.0

1.5 1.5
Fam 2 EF Marls
Fam 3 EF Shales
1.0 Fam7 EF Carbonates
1.0
0.5

0.0 0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
TAS3 - triaromatic steranes (C20+C21)/(SC20-C28) nC17/Pristane

Maturity of Woodford Fluids

 Oil Family/Maturity Map
Family 3 Oils
2 marl

3 shale Giddings Field

San Marcos Arch

0 16 32 mi.

10 20 30 40 50 km.
Family 7 Oils
7 carbonate

First Shot Field

Family 2 Oils
TX1828
Pearsall Field 7800’
TX1953 8519’

TX1952
maturity increase
9167’
TX1950
10406’
TX1951 Swenson #1-H
10771’
oil

wet gas

dry gas

Maturity of Woodford Fluids

 But Wait – There’s More!
Gas Chromatograph-Triple Quadrapole Mass Spectrometer (aka QQQ)

Only Only
GC 156+ 141+
Filter 1
time/volatility

Filter 2 Filter 3

% VREQ 0.92 1.10 1.22

ppm Diamondoids 51 68 382
ppm Naphthalenes 146 90 61 ~200 Target Compounds
ppm Phenanthrenes 37 21 7 Quantified – in One Run
ppm Dibenzothiophenes 30 12 1 ‘dilute & shoot’
ppm Methylchrysenes 4 4 1
ppm Steranes 31 9 0
ppm Tricyclic Terpanes 19 6 2 VRE = Vitrinite Reflectance Equivalent
ppm Pentacyclic Terpanes 14 1 0 Derived from the Triple-Quad
ppm Carotenoids 3 1 0
ppm Triaromatic Steroids 4 1 0
ppm Monoaromatic Steroids 5 1 0

Maturity of Woodford Fluids

 Woodford Oils & Gases
Anadarko Basin
124

symbol color approximates oil color

124

75 1.4

1.30%
135

1.28
1.3
1.25
Alkyl Aromatic Ratios

1.23
1.22 1.22 1.22
70 123 1.21 1.21
1.2 1.2 1.2
123 1.18
1.19

1.16
1.2
135 1.14

1.1
1.09 1.09
1.08 1.08 1.08 1235
1.07 1.07 1.1

% VREQ
1.06
65 1.05
1.04
1.02 124
0.99 0.99
0.98 0.98 0.98 0.981234
0.97 1
1235 135
0.94 0.94 0.94
0.93
0.92 0.92
1245
60 0.88
0.89 0.89
0.9
0.85
0.84

1234
0.79
1245 0.8

0.80%
55 123

C3 Benzenes: %135/(135+123) 0.7

1235

50 0.6
OK 58
OK 63
OK 02
OK 38
OK 73
OK 72
OK 99
OK 01
OK 00
OK 68
OK 59
OK 31
OK 58
OK 70
OK 60
OK 71
OK 56
OK 30
OK 67
OK 72
OK 71
OK 98
OK 76
OK 75
OK 65
OK 57
OK 69
OK 55
OK 58
OK 57
OK 36
OK 56
OK 64
OK 34
OK 35
OK 55
OK 62
OK 57
OK 33
OK 61
OK 59
OK 54
OK 60
OK 32
OK 74
66
03
04
05
04
04
03
04
05
05
04
02
04
04
04
02
03
02
04
04
04
04
04
04
04
04
03
04
04
02
02
04
04
04
04
04
02
04
04
04
04
04
02
04
04
04
04
OK

1245

Maturity of Woodford Fluids

1234
 Diamondoid Conc. ppm

50
100
150
200
250
300
350
400
450
500

0
OK0358
OK0463
OK0502
OK0438

OK0502
OK0473
OK0372
OK0499
OK0501
OK0500
OK0468
OK0259

OK0501
OK0431
OK0458
OK0470
OK0260
OK0371
OK0256
OK0430
OK0467
OK0472
OK0471
OK0498
OK0476
OK0475
OK0465
OK0357
OK0469
OK0455
OK0258
OK0257
OK0436
OK0456
Diamondoid concentration
symbol color approximates oil color

OK0464

Maturity of Woodford Fluids

OK0434
OK0435
OK0255
VREQ vs Diamondoids

OK0462
OK0457
OK0433
OK0461
OK0459
OK0254
OK0460
OK0432
OK0474
OK0466
0.60
0.70
0.80
0.90
1.00
1.10
1.20
1.30
1.40

% VREQ
Co-Produced Liquid vs Gas Maturity

Produced Lateral Woodford Fluids - Anadarko Basin

1.30
R2 = 0.85
1.25
R2 = 0.90
1.20

1.15

1.10
% VREQ oil

1.05

1.00

0.95
OK0501
0.90 C3 Propane
C2 Ethane
OK0502
0.85
C1 Methane

0.80
-55.0 -50.0 -45.0 -40.0 -35.0 -30.0 -25.0
d C gas
13

Maturity of Woodford Fluids

Diamondoid Enrichment: >1.1% VREQ
ppm C40 Carotenoids: Woodford ppm Diamondoids: Woodford

Diamondoid
A enrichment starts
at 1.1% VREQ

B
C

VREQ
ppm Diamondoids: Wolfcamp

Diamondoid

Also measured using starts“gone wild”

Diamondoids
enrichment
startsVREQ
at 1.1% at 1.3% VREQ

GC-Triple Quad MS
(aka QQQ)

Maturity of Woodford Fluids

Anadarko Woodford Source Rock Maturity

%VRE Measured
UD Woodford Fm. Tmax * %Ro %VREQ
Kingfisher Co. OK Core 1 Ave 0.98 0.97 1.02
9,393-9,432 ft Std Dev 0.02 0.06 0.01 n=6
Canadian Co. OK Core 2 Ave 1.07 1.05 1.09
10,326-10,426 ft Std Dev 0.03 0.07 0.02 n=7

*after solvent extraction

TOC: 3-11%
HI = 200
HI = 110

Maturity of Woodford Fluids

 Oils from ‘unconventional’ source rock reservoirs:
Anadarko & Midland basins
Data
Datapoint
pointcolor
colorapproximates
approximatesoil
oilcolor
color % VREQ
1.35

Wet Gas
APIg ~GOR
1.20 Gas 48° 5000
Condensate
S of 13 Ratios

1.10
45° 2500

‘Volatile’ Oil
1.00 43° 1500

0.90
40° 800
‘Black’ Oil
0.80 37° 400
Woodford-sourced Oils Wolfcamp-sourced Oils

Maturity of Woodford Fluids

 Oils from ‘conventional’ SS Cretaceous reservoirs:
Powder River Basin
Data point color approximates oil color
Data point color approximates oil color % VREQ
1.35

Wet Gas
APIg ~GOR
1.20 Gas 48° 5000
Condensate
S of 13 Ratios

1.10 45° 2500

‘Volatile’ Oil
1.00 43° 1500

0.90 40° 800

‘Black’ Oil
0.80 37° 400
Mowry-sourced Oils Niobrara-sourced Oils

Maturity of Woodford Fluids

 Conclusions

❑ Maturity-dependent terpane, sterane & other biomarker ratios

are used to estimate the C20+ (heavy-end) maturity of crude
oils
❑ Likely reflects the source rock maturity when this early fraction
of the oil was expelled (primary migration)
❑ Maturity-dependent alkyl naphthalene & phenanthrene ratios
are used to estimate the ~C10-C15 (mid-range) maturity of
crude oils
❑ Likely reflects the source rock maturity when this later, often
more mature fraction of the oil was expelled
❑ Calculated maturities of laterally co-produced oils and gases
from the Woodford Formation of the Anadarko Basin, OK
generally agree
❑ However, anomalous positive methane carbon isotopes and
high diamondoid concentrations were detected in some lower-
maturity black Woodford oils.

❑ Migration Happens!
Maturity of Woodford Fluids
Thank You For Your Attention

Maturity of Woodford Fluids