geoforensics for oil characterization wbpc2015
TRANSCRIPT
Making chemistry data meaningful
Geoforensic Chemical Analysis of Oil Samples from the Madison Group
What Can It Tell Us?
Phil Richards and Court Sandau
© 2015 Chemistry Matters Inc.
2 © 2015 Chemistry Matters Inc.
Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Origin of Madison oil?
7 samples of oil from 2 areas in Canadian WB: o Area A – 2 Midale o Area B – 2 Midale o Area B – 3 Frobisher
From: USGS 2010. Geological Assessment of Undiscovered Oil and Gas Resources in the Madison Group, Williston Basin, North Dakota and Montana
Origin of Madison oil?
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Madison Group (Lodgepole, Frobisher, Midale, Ratcliffe, Poplar) (Carbonate)
Bakken Formation (Shale)
From: Obermajer et al. 2000, Org. Geochem. 31, 959.
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
o Originally proposed that “Bakken shale” was the source of overlying oil reservoirs of the Madison Group.
o Later established that the “Madison carbonates” were the most probable source for the Madison Group.
o Variations within localized traps. o Potential for localized mixing-in of
Bakken oil.
Origin of Madison oil?
From: Obermajer et al. 2000, Org. Geochem. 31, 959.
5
GC-MS
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
nC8
nC9
nC10
nC12
nC11
nC13
nC14
nC15
nC16
nC17
nC18
nC19
nC20
nC21
nC22
nC
23
nC24
nC
25
nC26
nC
27
nC29
nC28
nC30
nC32
nC31
nC33
nC
34
nC35
nC36
nC37
nC38
o Alkanes o Isoprenoids o Alkylcyclohexanes o Sesquiterpanes o Adamantanes o Alkylbenzenes o PAHs o Alkyl-PAHs o Hetero-PAHs o Steranes and
Terpanes…
2DGC-TOFMS
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Alkanes
Bicyclic Alkanes
Naphthalenes BT DBT PAHs
Steranes
Hopanes
MAS
TAS
Biomarkers
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Originate from complex biological molecules Membrane structural chemicals o Terpanes – prokaryotes (archea and bacteria)
o Steranes – eukaryotes (plants and animals)
Relative concentrations of biomarkers can provide information of the origin and history of the oil.
Biomarkers
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Typical Bakken
Typical Lodgepole
Example of Madison oil product
Terpanes
1. Pattern of C21-C24 tricyclic terpanes 2. Ratio of Ts/Tm 3. Ratio of 17a21b-30-norhopane relative to 17a,21b-hopane 4. Enrichment of C35 homohopanes
1 2 3 1 2 3 1 2 3 4 4 4
From: Obermajer et al. 2000, Org. Geochem. 31, 959.
Biomarkers
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Typical Bakken
Typical Lodgepole
Example of Madison oil product
Steranes
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%& '()*!+,)* )- +.& " '*/+$01 2)314)!05-*6 78 9:;;;< =>=?=@A QZ3
C27
C28 C29
C27
C28
C29
Pattern of cholestanes (C27-C28-C29)
From: Obermajer et al. 2000, Org. Geochem. 31, 959.
Isoprenoids
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Pristane (Pr) and Phytane (Ph) originate from the decomposition of chlorophyll
oxidizing
reducing
0.0#
0.4#
0.8#
1.2#
1.6#
2.0#
Sample#1#
Sample#2#
Sample#3#
Sample#4#
Sample#5#
Sample#6#
Sample#7#
Pr#/#Ph#Ra
(o#
Isoprenoids
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Pristane / Phytane ratio <1, conditions generally in line with Lodgepole (carbonate) source. Some differences (Sample 3 and 4)
Bakken oils
Lodgepole oils
Pristane
Phytane 0.0#
1.0#
2.0#
3.0#
4.0#
5.0#
6.0#
7.0#
Midale#A1#
Midale#A2#
Midale#B3#
Midale#B4#
Frob#####B5#
Frob####B6#
Frob####B7#
DBT
$/$Phe
n$ra,o
$
0.0#
1.0#
2.0#
3.0#
4.0#
5.0#
6.0#
7.0#
Midale#A1#
Midale#A2#
Midale#B3#
Midale#B4#
Frob#####B5#
Frob####B6#
Frob####B7#
DBT$/$Ph
en$ra
,o$
Other indicators (PAHs)
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Bakken oils
Lodgepole oils
DBT
Phen
High sulfur content of Lodgepole carbonates.
0"
0.4"
0.8"
1.2"
1.6"
2"
Midale"A1"
Midale"A2"
Midale"B3"
Midale"B4"
Frob"""""B5"
Frob""""B6"
Frob""""B7"
Ts#/#Tm#ra
(o#
Other indicators (Terpanes)
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Ts
Tm
Bakken oils
Lodgepole oils
More detailed analysis
All 7 samples conform with general Lodgepole origin.
• Bakken Contributions • Maturity • In situ degradation
14 Geoforensic Chemical Analysis of Oil Samples from the Madison Group
What Can It Tell Us? © 2015
Chemistry Matters Inc.
0.3$0.4$0.5$0.6$0.7$0.8$0.9$1.0$1.1$1.2$
2.0$ 3.0$ 4.0$ 5.0$ 6.0$ 7.0$
Pr#/#Ph#
DBT#/#Phen#
Sample$1$Sample$2$Sample$3$Sample$4$Sample$5$Sample$6$Sample$7$
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Dibenzothiophene Phenanthrene
Pristane
Phytane
Potential For Bakken Contributions
Bakken
0.15%
0.2%
0.25%
0.3%
0.35%
0.4%
0.6% 1.1% 1.6% 2.1%
Ts#/#(T
s+Tm
)#
TAS#/#MAS#
Midale%A1%Midale%A2%Midale%B3%Midale%B4%Frob%B5%Frob%B6%Frob%B7%
M-B
0.15%
0.2%
0.25%
0.3%
0.35%
0.4%
0.6% 1.1% 1.6% 2.1%
Ts#/#(T
s+Tm
)#
TAS#/#MAS#
Midale%A1%Midale%A2%Midale%B3%Midale%B4%Frob%B5%Frob%B6%Frob%B7%
16
Maturity Indicators
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Triaromatic Steranes Monoaromatic Steranes
Ts
Tm
0.0#
0.5#
1.0#
1.5#
2.0#
2.5#
0.4# 0.6# 0.8# 1.0#
n12$/$i13$
Pr$/$Ph$
Sample#1#Sample#2#Sample#3#Sample#4#Sample#5#Sample#6#Sample#7#
Mixing and in-situ degradation
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
‘Wea
ther
ing’
M-A
M-B
F-B
Frobisher samples present ‘in situ’ weathering - loss of light end straight-chain hydrocarbons
Bakken
0.15%
0.2%
0.25%
0.3%
0.35%
0.4%
0.6% 1.1% 1.6% 2.1%
Ts#/#(T
s+Tm
)#
TAS#/#MAS#
Midale%A1%Midale%A2%Midale%B3%Midale%B4%Frob%B5%Frob%B6%Frob%B7%
In-situ degradation
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
Midale o Normal profile of hydrocarbons
Frobisher o Altered profile
• Biodegradation • Water / CO2 flood
Summary
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Geoforensic Chemical Analysis of Oil Samples from the Madison Group What Can It Tell Us?
• Standard geoforensic analysis Midale and Frobisher samples are of carbonate origin
• Detailed geoforensic analysis Midale samples demonstrate origin differences
o 2 samples may present minor Bakken contributions o 1 sample presents distinctly higher maturity
Frobisher samples present alteration o ‘in situ’ biodegradation / washing