Geoforensics for oil characterization WBPC2015

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




Madison Group (Lodgepole, Frobisher, Midale, Ratcliffe, Poplar) (Carbonate)

Bakken Formation (Shale)

From: Obermajer et al. 2000, Org. Geochem. 31, 959.



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.



5

GC-MS



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



Alkanes

Bicyclic Alkanes

Naphthalenes BT DBT PAHs

Steranes

Hopanes

MAS

TAS

Biomarkers



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



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


Biomarkers



Typical Bakken

Typical Lodgepole

Example of Madison oil product

Steranes

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

*K>&<*&(' #) 783P78GP78Q "'1>+*" .:'"*&'.2 RA%+' :A'!"#!#":%#& #) :A' 78G $'$K'" %. :A' +#?'.: *&< 1'&;'"*++, .%$%+*" %& *++ #%+ )*$%+%'.6 :A' !"#!#":%#& #) 783

*&< 78Q $'$K'". %. $#"' @*"%*K+'2 S& :A' )*$%+, - #%+.6:A' 78Q .:'"*&' #((>". %& .*$' (#&('&:"*:%#& *. 783

.:'"*&' /D*K+' 842 S& (#&:"*.:6 :A' "'+*:%@' *K>&<*&(' #)78Q .:'"*&' *"' %&("'*.%&1+, 1"'*:'" %& :A' "'$*%&%&1)*$%+%'.6 "'*(A%&1 $#"' :A*& TNU %& #%+ )*$%+%'. C *&<B /*@'"*1' #) TEU *&< TGU6 "'.!'(:%@'+,42 DA' !"#;!#":%#& #) 783P78GP78Q "'1>+*" .:'"*&'. %. (#&.%<'"'< :#K' * A%1A+, .!'(%V( (#""'+*:%#& %&<'I /W':'". *&< X#+;<#?*&6 EQQ96 !!2 EG8YEGZ46 :A'"')#"' !"#@%<%&1 )>":A'".>!!#": )#" (+*..%),%&1 .:><%'< #%+ .*$!+'. %&:# (#$!#;.%:%#&*+, <%.:%&(: #%+ (*:'1#"%'.2

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

J>%:' @*"%*K+' *&< %&(#&(+>.%@' ?%:A "'.!'(: :# <':'";$%&%&1 $*:>"%:, #) #%+.2 DA' 78Q !""M/!!!\!""4 "'1;>+*" .:'"*&' %.#$'"%H*:%#& "*:%# %. :A' A%1A'.: %& #%+)*$%+%'. - *&< 76 #):'& *!!"#*(A%&1 'J>%+%K"%>$ @*+>'.2S&:'"'.:%&1+,6 :A%. :"'&< %. &#: !*"*++'++'< K, :A' 78Q !!!5M/5\]4 %.#$'"%H*:%#& "*:%# ?A%(A %. :A' A%1A'.: %& #%+)*$%+%'. B *&< C2 DA'.' @*"%*K+' "*:%#. *"' &#: *+?*,.(#&.%.:'&: ?%:A $*:>"%:, <*:* <'"%@'< )"#$ :A' 1*.#+%&'"*&1' !*"*$':'". *&< :A' <%.:"%K>:%#& #) $;*+[*&'. *&<

0%12 G2 ]'!"'.'&:*:%@' !"# 8E3 $*.. )"*1$'&:#1"*$. #) :A' .*:>"*:' )"*(:%#& .A#?%&1 :A' <%.:"%K>:%#& #) .:'"*&'. %& :A' R%++%.:#&-*.%& #%+.2 78E; !"'1&*&'6 783<%*;E3!/F46 E9"/F46 E3!/F4 8N5; 783 <%*.:'"*&'6 78QY78Q "'1>+*" .:'"*&'2

%& '()*!+,)* )- +.& " '*/+$01 2)314)!05-*6 78 9:;;;< =>=?=@A QZ3

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

*K>&<*&(' #) 783P78GP78Q "'1>+*" .:'"*&'.2 RA%+' :A'!"#!#":%#& #) :A' 78G $'$K'" %. :A' +#?'.: *&< 1'&;'"*++, .%$%+*" %& *++ #%+ )*$%+%'.6 :A' !"#!#":%#& #) 783

*&< 78Q $'$K'". %. $#"' @*"%*K+'2 S& :A' )*$%+, - #%+.6:A' 78Q .:'"*&' #((>". %& .*$' (#&('&:"*:%#& *. 783

.:'"*&' /D*K+' 842 S& (#&:"*.:6 :A' "'+*:%@' *K>&<*&(' #)78Q .:'"*&' *"' %&("'*.%&1+, 1"'*:'" %& :A' "'$*%&%&1)*$%+%'.6 "'*(A%&1 $#"' :A*& TNU %& #%+ )*$%+%'. C *&<B /*@'"*1' #) TEU *&< TGU6 "'.!'(:%@'+,42 DA' !"#;!#":%#& #) 783P78GP78Q "'1>+*" .:'"*&'. %. (#&.%<'"'< :#K' * A%1A+, .!'(%V( (#""'+*:%#& %&<'I /W':'". *&< X#+;<#?*&6 EQQ96 !!2 EG8YEGZ46 :A'"')#"' !"#@%<%&1 )>":A'".>!!#": )#" (+*..%),%&1 .:><%'< #%+ .*$!+'. %&:# (#$!#;.%:%#&*+, <%.:%&(: #%+ (*:'1#"%'.2

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

J>%:' @*"%*K+' *&< %&(#&(+>.%@' ?%:A "'.!'(: :# <':'";$%&%&1 $*:>"%:, #) #%+.2 DA' 78Q !""M/!!!\!""4 "'1;>+*" .:'"*&' %.#$'"%H*:%#& "*:%# %. :A' A%1A'.: %& #%+)*$%+%'. - *&< 76 #):'& *!!"#*(A%&1 'J>%+%K"%>$ @*+>'.2S&:'"'.:%&1+,6 :A%. :"'&< %. &#: !*"*++'++'< K, :A' 78Q !!!5M/5\]4 %.#$'"%H*:%#& "*:%# ?A%(A %. :A' A%1A'.: %& #%+)*$%+%'. B *&< C2 DA'.' @*"%*K+' "*:%#. *"' &#: *+?*,.(#&.%.:'&: ?%:A $*:>"%:, <*:* <'"%@'< )"#$ :A' 1*.#+%&'"*&1' !*"*$':'". *&< :A' <%.:"%K>:%#& #) $;*+[*&'. *&<

0%12 G2 ]'!"'.'&:*:%@' !"# 8E3 $*.. )"*1$'&:#1"*$. #) :A' .*:>"*:' )"*(:%#& .A#?%&1 :A' <%.:"%K>:%#& #) .:'"*&'. %& :A' R%++%.:#&-*.%& #%+.2 78E; !"'1&*&'6 783<%*;E3!/F46 E9"/F46 E3!/F4 8N5; 783 <%*.:'"*&'6 78QY78Q "'1>+*" .:'"*&'2

%& '()*!+,)* )- +.& " '*/+$01 2)314)!05-*6 78 9:;;;< =>=?=@A QZ3

C27

C28 C29

C27

C28

C29

Pattern of cholestanes (C27-C28-C29)


Isoprenoids



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



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)



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)



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$7$



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#


16

Maturity Indicators



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



‘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#


In-situ degradation



Midale o  Normal profile of hydrocarbons

Frobisher o  Altered profile

•  Biodegradation •  Water / CO2 flood

Summary



•  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

Thank You

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Geoforensics for oil characterization WBPC2015