dreyfus on trace metals

7/31/2019 Dreyfus on Trace Metals

1/31

COQG, New Orleans, LA, 03/06/2008

Co208Pb/206Pb

V

206Pb/207Pb

208Pb/206

Pb

208 Pb/

206 Pb

187Os

/188Os

207Pb/204Pb

208Pb/206Pb

208Pb/2

06

Pb

208Pb/206

Pb

Ni

Fe

Mo

Cu

Sr

Hg

As Ba

Os

Re

Origin and Nature of Trace Metals in Crude Oils

Sebastien Dreyfus

COQG, New Orleans, LA

March 6, 2008


2/31


+ + + + + + + + + Granite + + + + + + + + + + +

+ + + + + + + + + + + + + + + + + + + + + + +

+ + + + + + + + + + + + + + + + + + + + + +

+ + + + + + + + + + + + + +

+ + + + + +

Gas + Oil migration

Mineral deposit

Hydrothermal fluids

Metals transfer

Sourc

eroc

k

Volcanics

Volcanics & granite debris

Origin of trace elements in crude oils

V Ni FeMoCo

OsRe

CaBa

Sr,etc..Fe

Drilling + completion fluids

Ca, Ba, Fe, Pb, Cu, etc

Hg

Pb

Cu

As


3/31


Origin of some trace elements in

crude oils

Porphyrins

Porphyrins are organic compounds containing four pyrrole rings, occurring

universally in protoplasm, and functioning as a metal-binding cofactor inhemoglobin, chlorophyll, and certain enzymes

These structures are present in plant and animal remains via thehemoglobin in animals and the chlorophyll in plants


4/31



crude oils

Metal Porphyrins

Porphyrin with a metal at its center is called a metalloporphyrin Common metals in metalloporphyrins: Vanadium (2+), Nickel (2+),..

From Yen, 1975. DPEP and Etioporphyrin


5/31



crude oils

Chlorophyll to Metalloporphyrin

a long way

From Yen, 1975

Pheophytinization: removal of Mg

PH2 + M2+ MP + 2H+

PH2 = Free base porphyrin M2+ = Metal ions MP = Metalloporphyrin

H = Hydrogen ions


6/31


Factor controlling the proportionality

of trace elements in source rocks andpetroleum

-0.75

-0.50

-0.25

0.00

0.25

0.50

0.75

Cu(s)

U

L

Cu+2

(aq) CuSO4(aq)

CuO2

-2

(aq)

Cu+(aq)

CuO(s)

Cu2O(s)

Cu(s)o

o

Cu2S(s)

CuS(s)

ms

ox

re

(a)U

L

Fe+2

(aq)

FeSO4

Fe(s)o

ms

ox

re

Fe+2(aq)

(aq)

(aq)-Fe(OH)3

Fe2O3(s)

Fe3O

4(s)

FeS2

(s)

FeS(s)

(b)

-0.75

-0.50

-0.25

0.00

0.25

0.50

0.75

0 2 4 6 8 10 12 14

pH

NiO(s)

Ni(OH)3

Ni3S

4(s)

ms

Ni3S

2(s)

ox

re

U

L

Ni(aq)

+2

Ni(aq)

+2

NiSO4

(aq)

Ni(s)o

NiS2

(s)

Ni3

S2

(s)

(aq)

-

( c )

0 2 4 6 8 10 12 14

pH

U

L

Co+2

(aq)

CoHS

HCoO2

-

(aq)

C o (s)o

m s

Co+2

(aq)

( a q )

+

Co(HS)2(aq)

ox

re

Co3S

4(s)

CoS2

(s)

(d)

From MD Lewan, 1984 and 2007

+Ni2+


7/31


Factor controlling the proportionality

of trace elements in petroleum

Oil-source rock correlation and oil quality

According to Lewan, 3 regimes can bedefined from the Eh-pH diagram

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

% Total Sulfur (wt. %)

V/Ni+V

Regime IIIRegime II

Regime I

Marine Clastic

Marine Carbonate

Lacustrine

Key to Source Facies

Marine Marly

Terrigenous Deltaic

Marine Clastic

Marine Carbonate

Lacustrine

Key to Source Facies

Marine Marly

Terrigenous Deltaic


8/31


Application of metals in biodegradation studies:

Biodegradation Lowers HC Quality

Lowers recoveryefficiency

Lowers oil value

Increases oil acidity (TAN:Total Acid Number)

Increases proneness foremulsion formation &

foaming

Significant risk fordeepwater, cool

reservoirs

Moderate Biodegradation

Unbiodegraded Incr

easingBiodegradationHeavy Biodegradation

21

27

36

47C

74C

93C

Temp API


9/31


Increasing Biodegradation

Application of Ni and V in biodegradation

studies

0 21 3 4 5-6

Relative biodegradation

scale

0

5

10

15

20

25

0 2 4 6 8 10 12 14Vanadium (ppm)

Nickel(ppm)

VANADIUM / NICKELVANADIUM / NICKEL

RATIO


10/31


Accumulat ion

PetroleumMigrat ion

Sea l

Reservoir

Leak age

PetroleumCharge

Sour c e Roc k

M igra t ion P a thways

D e t e r m i n eA g e o f

Oi ls

Coa lyS o u r c e M o d e l

........... .... ...

........ .......

.... .... ........... .......

.... .... ...........

........... .... ...

........

....

...............

.... .... ...........

....

.... ....

........... ........ ............

.... ........ ............

........

........

.... ................

G am ma D en s ity Resis t i v i t yH e a v y

O il

Li teO il

G a s

0 m y

Generation

Rate

Pred ic t O i l Qua l ity

1 0 0 m y

S o u r c e R o c k P r e d i c ti o n

S e q u e n c eStrat igraphy

Challenges

Use of inorganic information to

characterize petroleum systems :

Elemental and isotopic information?


11/31


Can we improve the detection limits in order toaccess to new potential inorganic tracers, and get

better precision on the data?

Can we measure with sufficient precisioninorganic isotopic ratios in crude oils?

Which analytical and sample introductionstrategies should we use?


12/31


Detector

Analytical strategies:

Direct organic analysis by ICP-MS

Skimmer cone

Lens and CCTQuadripole mass filter

Plasma torch

Mass Spectrometer Interface ICP

Sampler cone

Petroleum sample

diluted in xylene

Introduction system

Ar nebulizer (0.5 L/mn)

Nebulizer

Spray chamber

Chilled (-10C)

Platinum

Platinum

PFA-100

Microflow

nebulizer

+ O2 nebulizer (0.066

L/mn)

Drain


13/31


1

10

100

1000

10000

100000

Li /

7

B /

10

Na /

23

Mg /

24

Al /

27

Si /

28

P /

31

K /

39

Ca /

40

Ti /

48

V /

51

Cr /

52

Mn /

55

Fe /

56

Co /

59

Ni /

60

Cu /

63

Zn /

66

As /

75

Se /

78

Sr /

88

Mo /

95

Ag /

107

Cd /

111

Sn /

118

Ba /

137

Hg /

202

Pb /

208

C

onc.ng/g

ICP-MS with reaction cell.

ICP-MS

ICP-AES

Direct analysis of crude oil using a reaction cell.

Expending the range of trace elements measurable by ICP-MS


14/31


Before

1. Ni2. V Present 1. Ni

2. V

3. Cu

4. Fe5. Co

6. Mo

7. Ag

8. Cd

9. Sn10. Ba

11. Pb

12. As

13. Hg

14. Ca15. Cr

16. Na

17. etc..

Detection limits of atomic spectroscopy methods

0.001

0.01

0.1

1

10

100

1000

10000

XRF

ICP/AES

GFAASICP/MS

Detection

limits(ppb)

Evolution of detection limits and

unravelling of new geochemical

markers

14. Lead isotopic information00.2

0.4

0.6

0.8

1000 10000 100000 1000000

206Pb/counts.s-1

RSD(%)

RSD (%) observed

RSD (%) poisson0.6 ng.g-1

1.2 ng.g-1

4 ng.g-1

10 ng.g-1

RelativeStandarddeviation

(%)


15/31


Sample preparation for trace metal analysis

Crude oil

Separation:1 g of crude oil + 50 cc of n-Heptanein a PFA filter

Maltenes (> 90% of the oil)

(soluble in n-Heptane)

Asphaltenes (< 10% of the oil)

(precipitation on a PFA filter)

Sample preparation of crude oil is a critical step to remove any potential contamination of theHCs:

Oil centrifugation + water washing : to clean the oil from water and potential contamination fromdrilling and completion fluids

Oil fractionation

Samples preparation must be performed under clean room conditions


16/31


Application of Fe in crude after oil centrifugation for

oil-source rock correlation

0.1

1.0

10.0

100.0

2050

09

2028

23

2028

24

2080

92

2318

16

204797

2078

30

2337

52

2087

10

2336

29

2086

45

2086

47

C

onc(ppm

)

Fe

Ni

V

After centrifugation and water washing

of marine oils, Fe show a similar trend

than Ni

V/(V+Fe) vs. V/(V+Ni) can be used to

characterise the source of marine oils

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

V/(V+Ni)

V/(V+Fe)

Fe

0.0

10.0

20.0

30.0

40.0

50.0

60.0

Neat Centrifuged 1st wash 2nd wash

Co

nc.ppm


17/31


Calcium naphthenates are an emerging problem in offshore production

Calcium naphthenates on atube heat exchanger,deepwater West Africa.

About 400 tons of solids wereremoved from topsides unitsand tanks and the processtrains were shut down forcleanout every 28 to 30 daysresulting in ~2 million barrels oflost oil production.

O

OH

O

HO

O

HO

O

OH

C80H142O81231.070472

[C80H141O8]-

1230.062647

1" 17'

18'16'

10'

20

10"

18"

1"'

1'

18'

10'

6

119'

16'

20'

19

1718

1016

17'

Naphthenate Deposits from Biodegraded Oil Production

Salts of naphthenic acids frominteraction of acids from oilbiodegradation with formation water

Mutual solubility of calciumnaphthenate in oil & water promotes

tight emulsions

Deposition is pH-sensitive

Formed by a C80 tetra-acid (fromhyperthermophilic methanogens?)

Lutnaes et al., (2006)


18/31


Analysis of Ca in crude oil by ICP-MS

Isotope Ion Rsolution

Interfrant R=M/ M56Fe 40Ar16O 250075As 40Ar35Cl 780080Se 40Ar40Ar 970040Ca 40Ar 193000

Resolution needed (M/ M) to resolve certain

interferences

R (M/ M)

Q-ICP/MS 0.3- 1 uma (20- 800)ICP/MS TOF 1800ICP/MS Magnetic Sector 7500-20000

Maximum resolution (M/ M) of different

ICP-MS technique

Interference on Ca is now easely removed using H2 as a reaction gas.

Comparison with ICP-AES analysis shows similar concentration.

0.434

3 DL

ng/g

108000H240Ca

Conc.

ng/g

ORS

Mode

MassElement

From C. Pecheyran


19/31


Ca concentration in crude oils after centrifugation and water

washing

DST: Drill Stem Test, large volume sample forassay, usually clean of drilling mud

By centrifuging and water washing prior toanalysis, calcium content can be significantly

reduced

Analyses of separated water phase indicatedcontamination by CaCl2 completion fluid used in

the DST procedure

WFT (Wireline Formation Test) samples arerelatively uncontaminated

Real organic calcium concentration for thissample: 3 ppm

Ca (ppm)

DST

Assay

DST

centf.

WFT WFT

centf.

754 48 3 3

Individual Reservoir by Test

Type/Processing


20/31


Ni and V concentrations after centrifugation and water

washing

Both nickel and vanadiumcontents of all oils do not

vary with centrifuging orwater washing

Unlike calcium, V & Ni areentirely associated with the

organic phase and the

source of the oil

NickelConc.(ppm)

Oil A

11.2 12.0 12.4 13.5

05

10

1520

Uncentr.

Centr.

1st

wash

2nd

wash

Oil B

29.1 30.3 30.8 32.9

01020

3040

Uncentr.

Centr.

1st

wash

2nd

wash

Oil F

6.3 5.8 5.7 6.6

02468

10Uncent

r.

Centr.

1st

wash

2nd

wash

Oil D

4.6 4.4 4.4 5.6

02

6

10 U

ncentr.

Centr.

1st

wash

2nd

wash

Oil C

16.3 17.0 16.5 18.4

0

10

20

30 U

ncentr.

C

entr.

1st

w

ash

2nd

w

ash

Oil E

10.5 10.0 9.82 10.5

05

101520

Uncent

r.

Centr.

1st

wash

2nd

wash


21/31


Application of trace metals in the Potiguar Basin

1

1

1

234

6

Modified after L.A.F. Trindade et al., 1992

BASSIN DE POTIGUAR

N BRESIL

OCEAN

ATLANTIQUE

25 km

78

9

5

A

A

B

B

Hypersaline source

Freshwater source

Onshore Basin

Biodeg

radatio

nNon

biodeg

raded


22/31


1

10

100

1000

0 10 20 30 40 50 60 70 80 90 100

Distance from the source (km)

Concentration(ng.g-1)

Cu

Pb

1

10

100

1000

10000

100000

0 10 20 30 40 50 60 70 80 90 100

Distance from the source (km)

Concentration(ng.g-1)

V

Ni

Mo

Evolution of metals concentration in crude

oils vs distance of migration

V, Ni, and Mo are associated

with the origin of the oil

A A

A A


23/31


Evidence of oil maturity

R2

= 0.8029

0.3

0.35

0.4

0.45

0.5

0.55

0.6

0 1 2 3 4 5 6 7 8

98Mo/118Sn

C29Stera

nes

/(+

)

Increasingtherm

almaturity

Mo/Sn :

Positive correlation

with organic tracerof thermal maturity


24/31


R2

= 0.9945

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

0 2000 4000 6000 8000 10000 12000 14000

V maltenes (ng.g-1

)

Nimaltenes(ng.g

-1

)

0 21 3 4 5-6

Moldovan scale

Evidence of biodegradation in Potiguar, Ni-V in

maltenes

Source of oilSource of oil

0,36


25/31


Direct determination of Lead

isotope ratios in crude oils by

ICP-MS

PFA-100

Microflow

nebulizer

Dual inlet

torch

Interface ICP

Petroleum sample

diluted in xylene

Scott-type doublepass spray chamber

Chilled (-10C)

Ar nebulizer (0.5 l/mn)

+ O2nebulizer (0.066 l/mn)

Drain

12 rpmPlatinum

sampler and

skimmer

cones

Introduction

system140C2C

SRM 981

30 rpm

SRM 981

30 rpm

Ar nebulizer (0.6 l/mn)Ar nebulizer (0.6 l/mn)

PFA-100

Microflow

nebulizer

Dual inlet

torch

Interface ICP

Petroleum sample

diluted in xylene

Scott-type doublepass spray chamber

Chilled (-10C)

Ar nebulizer (0.5 l/mn)

+ O2nebulizer (0.066 l/mn)

Drain

12 rpmPlatinum

sampler and

skimmer

cones

Introduction

system140C2C

SRM 981

30 rpm

SRM 981

30 rpm

Ar nebulizer (0.6 l/mn)Ar nebulizer (0.6 l/mn)

204PbM/Z

207Pb

208Pb

206Pb

Dreyfus et al., JAAS, 2006


26/31


Precision and Accuracy of

Direct Lead Isotope Ratios

Determination in Crude Oils byICP-MS

0

0.2

0.4

0.6

0.8

1000 10000 100000 1000000

206Pb/counts.s-1

RSD(%)

RSD (%) observed

RSD (%) poisson0.6 ng.g-1

1.2 ng.g-1

4 ng.g-1

10 ng.g-1

2.15

2.155

2.16

2.165

2.17

1 ng.g-1

SRM 981

Reference

values*

208Pb/206Pb

2.3582.36

2.3622.3642.3662.3682.37

2.3722.3742.376

1 ng.g-1

SRM 981

Reference

values*

208Pb/207Pb

1.088

1.09

1.092

1.094

1.096

1.098

1.1

1 ng.g-1 SRM

981

Reference

values*

206Pb/207Pb

* Values from Hirata (1996) obtained with 2 g.g-1 of SRM 981 using multi-collector ICP-MS

Validation of the methodology: Comparison between direct analyse and aqueous analysis

after digestion of crude oils

2.07

2.08

2.09

2.1

2.11

2.12

2.13

2.14

Organic* Aqueous*

208Pb/206P

b

2.34

2.35

2.36

2.37

2.38

2.39

2.42.41

2.42

2.43

Organic* Aqueous*

208Pb/207P

b

1.1241.1261.1281.13

1.1321.1341.1361.1381.14

1.1421.144

Organic* Aqueous*

206Pb/207P

b

* Analysis of a crude oil containing 1000 ng.g-1 of lead. Sample is blank corrected. Isotope ratios are corrected

for mass discrimination using SRM 981.

From Dreyfus et al., JAAS, 2006


27/31


MORB

Mangaia

Tubuaii (Australes chain)

St Helena

Terceira (Azores)

Ascension

Canary

Easter

Fernando de Noronha

1.8

1.82

1.84

1.861.88

1.9

1.92

1.941.96

1.98

2

2.022.04

2.06

2.08

2.1

2.12

2.142.16

2.182.2

2.22

2.24

2.26

1 1.02 1.04 1.06 1.08 1.1 1.12 1.14 1.16 1.18 1.2 1.22 1.24 1.26 1.28 1.3 1.32 1.34 1.36 1.38 1.4

206Pb/

207Pb

2

08Pb/206Pb

Potiguar basin oil

12

3

4

5

6

7

8

9

Direct determination of Lead isotope ratios in

crude oils from Potiguar

Crustal or

Anthropic signature?

Mantle (hot spot)

signature


28/31


17,0 17,5 18,0 18,5 19,0 19,5 20,0 20,5 21,0

36,5

37,0

37,5

38,0

38,5

39,0

39,5

40,0

15,4

15,6

15,8

16,016,216,4

208Pb/204Pb

207Pb/204

Pb

206Pb/204Pb

Mantle End-Member

Crustal End-Member

Anthropic End-Member

2

3

1

6

7

8

9

5

4

17,0 17,5 18,0 18,5 19,0 19,5 20,0 20,5 21,0

36,5

37,0

37,5

38,0

38,5

39,0

39,5

40,0

15,4

15,6

15,8

16,016,216,4

208Pb/204Pb

207Pb/204

Pb

206Pb/204Pb

Mantle End-Member

Crustal End-Member

Anthropic End-Member

2

3

1

6

7

8

9

5

4

Lead isotopes in crude oils : geological tracer for the

reconstruction of petroleum systems history:Use of206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb ratios reveals 3 different isotopic signatures


29/31


Future of trace element analysis in petroleum: LA-ICP/MS

Micro scale exploration : trace element analysis in fluid inclusions


30/31


Application of this work in its

widest extent

Downstream

Control of crude oil, gasoline and diesel quality during refining process

Identification of foulants and deposits in refineries andprocess plants

Control and quantification of contaminants

Upstream

Application of inorganic isotopic information to better understand fluid

interactions in sedimentary basin

Application of trace metals to study of heavy oils

Characterization of solids and water associated with crude oil


31/31


Acknowledgements

Thank you very much for your attention

Olivier Donard

Christophe Pcheyran

Julien Malherbe

Alain Prinzhofer

Caroline Magnier

Charles-Phillip Lienemann

and all the LCABIE team

Co208Pb/206Pb

V

206Pb/207Pb

208Pb/206

Pb

208 Pb/

206 Pb

187

Os/188Os

207Pb/204Pb

208Pb/206Pb

208

Pb/2

06

Pb

208Pb/206

Pb

Ni

Fe

Mo

Cu

Sr

Hg

As

Ba

OsR

e

IFP

UPPA

dreyfus on trace metals

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