Origin and Nature of Trace Metals in Crude Oils

Sebastien Dreyfus
COQG, New Orleans, LA March 6, 2008

Co

Cu

208

/ 7 Os 18

88 O s 1

As
Mo
207 P

Pb/ 206 Pb

20 8

b/ 206 P
206 Pb 208 Pb/
COQG, New Orleans, LA, 03/06/2008

b 207 P

Ba
Pb

20 8

Pb

Pb / 206 Pb
/ 206 Pb

b/ 204

208Pb/206Pb

Re

Os

Fe

/ 206 Pb

Sr

Ni

Hg

20 8

Pb

Origin of trace elements in crude oils

Drilling + completion fluids Ca, Ba, Fe, Pb, Cu, etc

Metals transfer Mineral deposit Hydrothermal fluids Gas + Oil migration

Ca

Ba F e

Sr, etc..

Volcanics & granite debris

rc e ou S

k ro c

Mo

V
Hg
Cu

Ni Fe

Co Re

Os

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

+ + + + + + + + + + + + + + + + + + + + s ++++++++++++++++++++++ A Pb + + + + + + + + + Granite + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +

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 in hemoglobin, chlorophyll, and certain enzymes These structures are present in plant and animal remains via the hemoglobin in animals and the chlorophyll in plants
COQG, New Orleans, LA, 03/06/2008

Origin of some trace elements in crude oils Metal Porphyrins

From Yen, 1975. DPEP

and Etioporphyrin

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

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

Origin of some trace elements in crude oils

From Yen, 1975

Chlorophyll to Metalloporphyrin a long way

Pheophytinization: removal of Mg PH2

+ M2+ MP + 2H+

PH2 = Free base porphyrin M2+ = Metal ions MP = Metalloporphyrin H = Hydrogen ions
COQG, New Orleans, LA, 03/06/2008

From MD Lewan, 1984 and 2007

0.75
+2

Factor controlling the proportionality of trace elements in source rocks and petroleum
(a)
CuO(s) U CuO2
(aq) -2

0.50

Cu

ms

(aq)

CuSO4(aq) Cu
+ (aq)

Fe

+2

ms

(b)
U Fe 2O3(s)
ox re

(aq)

0.25

FeSO4
(aq)

0.00

CuS(s)

ox re

Cu2O(s) Cu(s)
o

L Fe (aq) Fe (s)
o
+2

-0.25

FeS2(s)

-0.50

Cu(s)
ms

Cu2S(s) NiO(s) U NiSO4(aq)

FeS(s)
s

Fe 3O4(s) Fe(OH)3 (aq)

-0.75 0.75
( c ) m

(d)
U

0.50

Ni

+2

(aq)

Co
(aq)

+2

0.25

0.00

L Ni
+2 (aq)

+ Ni2+

ox re

Ni(OH)3
(aq)

L Co
+2 (aq)

ox re

HCoO2
(aq)

-0.25

NiS2(s)
o

Ni S
3

CoS2(s) CoHS
( a q )

(s)
2

-0.50

Ni(s)
-0.75

Ni3S2(s)
4 6 8 10

Ni3S4(s)
C o

(s)

Co(HS) 6

(aq)2

Co3S4(s)
8 10 12 14

12

14 0

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

pH

Factor controlling the proportionality of trace elements in petroleum

1.0

Oil-source rock correlation and oil quality

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

0.9 0.8 0.7

Regime II
V / Ni + V
0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0
Key to Source Facies Marine Clastic Marine Marly Marine Carbonate Terrigenous Deltaic Lacustrine

Regime III

Regime I
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

% Total Sulfur (wt. %)

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

Application of metals in biodegradation studies: Biodegradation Lowers HC Quality

Temp API

47C

21 Heavy Biodegradation

Lowers recovery efficiency Lowers oil value Increases oil acidity (TAN: Total Acid Number) Increases proneness for emulsion formation & foaming Significant risk for deepwater, cool reservoirs

74C

Moderate Biodegradation

Increasing Biodegradation

27

Unbiodegraded 93C

36

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

Application of Ni and V in biodegradation Non biodegraded oil studies

V Ni Ni V Asphaltenes (heaviest fractions)
V-Ni concentrations in oils from Potiguar
Magnier et al.. 2002

25 20 Nickel (ppm) 15 10 5
Non biodegraded oils VANADIUM / NICKEL RATIO <1 Biodegraded oils

Saturates Aromatics Resins

Maltenes

Biodegradation process
V Ni Ni V

6 8 10 Vanadium (ppm)
Relative biodegradation scale

12

14

0 1 2 3

4 5-6

Increasing Biodegradation

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

Biodegraded oil

Challenges
Use of inorganic information to characterize petroleum systems : Elemental and isotopic information?

P r e d ic t O il Q u a lity
Generation Rate

G am m a

D e n s ity

R e s is tiv ity

D e te rm in e Age of O ils

H eavy O il

L ite O il

G as

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

C o a ly S o u rc e M o d e l
Leakage

100 m y

0 my

S o u rc e R o c k P r e d ic tio n

A c c u m u la tio n

S eal R e s e rv o ir P e tro le u m C h a rg e P e tro le u m M ig ra tio n

Sequence S tr a tig ra p h y

S o u rc e R o c k

M ig r a tio n P a th w a y s
COQG, New Orleans, LA, 03/06/2008

 Can we improve the detection limits in order to access to new potential inorganic tracers, and get better precision on the data? Can we measure with sufficient precision inorganic isotopic ratios in crude oils?

Which analytical and sample introduction strategies should we use?

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

Analytical strategies: Direct organic analysis by ICP-MS

Mass Spectrometer

Interface

ICP

Introduction system
Ar nebulizer (0.5 L/mn) + O2 nebulizer (0.066 L/mn) Nebulizer
PFA-100 Microflow nebulizer

Plasma torch Detector Quadripole mass filter Lens and CCT Spray chamber
Drain

Platinum Skimmer cone

Platinum Sampler cone

Chilled (-10C)

Petroleum sample diluted in xylene

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

Direct analysis of crude oil using a reaction cell.

Expending the range of trace elements measurable by ICP-MS

100000

ICP-MS with reaction cell. ICP-MS ICP-AES

10000

Conc. ng/g

1000

100

10

1
Li / 7 B/ 10 Na / Mg / Al / 23 24 27 Si / 28 P/ 31 K/ 39 Ca / Ti / 40 48 V/ 51 Cr / Mn / Fe / Co / Ni / Cu / Zn / As / Se / Sr / Mo / Ag / Cd / Sn / Ba / Hg / Pb / 52 55 56 59 60 63 66 75 78 88 95 107 111 118 137 202 208

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

Before

1. Ni 2. V
10000 1000

Evolution of detection limits and unravelling of new geochemical markers

1. Ni 2. V 3. Cu 4. Fe 5. Co 6. Mo 7. Ag 8. Cd 9. Sn 10. Ba 11. Pb ICP/MS 12. As 13. Hg 14. Ca 15. Cr 16. Na 17. etc.. 14. Lead isotopic information

Present

Detection limits of atomic spectroscopy methods

Detection limits (ppb)

100 10 1 0.1 0.01 0.001

Relative Standard deviation (%) RSD (%)

XRF ICP/AES GFAAS

0.8 0.6 0.4 0.2 0 1000

0.6 ng.g-1

RSD (%) observed RSD (%) poisson

1.2 ng.g-1

4 ng.g-1

10 ng.g-1

10000

100000
-1

1000000

206Pb/counts.s

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

Sample preparation for trace metal analysis

Sample preparation of crude oil is a critical step to remove any potential contamination of the HCs: Oil centrifugation + water washing : to clean the oil from water and potential contamination from drilling and completion fluids Oil fractionation Samples preparation must be performed under clean room conditions

Crude oil

Separation: 1 g of crude oil + 50 cc of n-Heptane in a PFA filter Asphaltenes (< 10% of the oil) (precipitation on a PFA filter)

Maltenes (> 90% of the oil) (soluble in n-Heptane)

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

Application of Fe in crude after oil centrifugation for oil-source rock correlation

Fe
60.0 50.0

100.0

C onc (ppm )

10.0

Fe Ni V

Conc. ppm

40.0 30.0 20.0 10.0 0.0 Neat Centrifuged 1st wash 2nd wash

1.0

0.1
23 24 92 16 97 30 52 10 09 29 28 28 80 45 20 86 18 47 78 37 87 50 36 86 20 47

20

20

20

20

23

20

20

23

20

0.8

V/(V+Fe)

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

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 V/(V+Ni)

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

23

Naphthenate Deposits from Biodegraded Oil Production

Calcium naphthenates are an emerging problem in offshore production Salts of naphthenic acids from interaction of acids from oil biodegradation with formation water Mutual solubility of calcium naphthenate in oil & water promotes tight emulsions Deposition is pH-sensitive Formed by a C80 tetra-acid (from hyperthermophilic methanogens?)
HO 1" O O HO 1'
18' 19' 20' 17' 17' 10' 18' 16' 20 10' 16' 16 10 19 18 6 1 17 10" 18" 1"'

Calcium naphthenates on a tube heat exchanger, deepwater West Africa. About 400 tons of solids were removed from topsides units and tanks and the process trains were shut down for cleanout every 28 to 30 days resulting in ~2 million barrels of lost oil production.

OH

O O OH

C80H142O8 1231.070472

Lutnaes et al., (2006)

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

[C80H141O8] 1230.062647

Analysis of Ca in crude oil by ICP-MS

Resolution needed (M/M) to resolve certain interferences Maximum resolution (M/M) of different ICP-MS technique Isotope Ion Rsolution Interfrant R=M/M R (M/M) 56Fe 40Ar16O 2500 75As 40Ar35Cl 7800 Q-ICP/MS 0.3- 1 uma (20- 800) 80Se 40Ar40Ar 9700 ICP/MS TOF 1800 40Ca 40Ar 193000 ICP/MS Magnetic Sector 7500-20000
From C. Pecheyran

Interference on Ca is now easely removed using H2 as a reaction gas. Comparison with ICP-AES analysis shows similar concentration.
Element Ca Mass 40 ORS Mode H2 Conc. ng/g 108000 3 DL ng/g 0.434

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

Ca concentration in crude oils after centrifugation and water washing

Individual Reservoir by Test Type/Processing DST: Drill Stem Test, large volume sample for assay, usually clean of drilling mud By centrifuging and water washing prior to analysis, calcium content can be significantly reduced
3 3

Ca (ppm)
754 48

Analyses of separated water phase indicated contamination by CaCl2 completion fluid used in the DST procedure WFT (Wireline Formation Test) samples are relatively uncontaminated Real organic calcium concentration for this sample: 3 ppm

DST Assay

DST WFT centf.

WFT centf.

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

Ni and V concentrations after centrifugation and water washing

Oil A
Uncentr. Centr. 1st wash 2nd wash

Oil B
Uncentr. Centr. 1st wash 2nd wash

20 15 10 5 0

11.2

12.0

12.4

13.5

40 30 20 10 0

29.1

30.3

30.8

32.9

Both nickel and vanadium contents of all oils do not vary with centrifuging or water washing

Oil C
Uncentr.

Oil D
Centr. 1st wash 1st wash 2nd wash 2nd wash

Nickel Conc. (ppm)

Uncentr.

Centr.

30 20 10 0

16.3

17.0

16.5

18.4

10 6 2 0

4.6

4.4

4.4

5.6

Unlike calcium, V & Ni are entirely associated with the organic phase and the source of the oil

Oil E
Uncentr. Uncentr. Centr. 1st wash 2nd wash

Oil F
Centr. 1st wash
5.7

20 15 10 5 0

10.5

10.0

9.82

10.5

10 8 6 4 2 0

6.3

5.8

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

2nd wash
6.6

Application of trace metals in the Potiguar Basin

BASSIN DE POTIGUAR

N
OCEAN ATLANTIQUE

BRESIL

Hypersaline source Freshwater source Onshore Basin

25 km

No

d bio n

d ade e gr
A
9

n tio ada 6 gr 87 de Bio

43

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

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

Evolution of metals concentration in crude oils vs distance of migration

100000

A
Concentration (ng.g-1)
10000

1000

V Ni Mo

V, Ni, and Mo are associated with the origin of the oil

100

10

1000
1

10

20

30

40

50

60

70

80

90 100

Concentration (ng.g-1)

Distance from the source (km)

A
100

A
Cu Pb

10

1 0 10 20 30 40 50 60 70 80 90 100

Distance from the source (km)

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

Evidence of oil maturity

0.6

= 0.8029

C29 Steranes /(+)

0.55

0.5

In cr ea

si

ng

0.45

th er m al

0.4

m at ur it y

Mo/Sn : Positive correlation with organic tracer of thermal maturity

0.35

0.3 0 1 2 3 4 5 6 7 8

98

Mo/

118 Sn

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

Nickel (ppm)

Evidence of biodegradation in Potiguar, Ni-V in maltenes 25

20 15 10 5 0
20000

Biodegraded oils VANADIUM / NICKEL RATIO <1

Increasing Biodegradation
Moldovan scale

Non biodegraded oils

0 1 2 3 4 5-6 14
Biodegraded oils

6 8 10 12 Vanadium (ppm)
R = 0.9945
2

18000 16000

Quantification of biodegradation: Loss of HC: up to 70%

Ni maltenes (ng.g )

-1

14000 12000 10000 8000 6000 4000

Source of oil 0,36<V / (Ni+V)<0,40

2000 non biodegraded oils 0 0 2000 4000 6000 8000

-1

10000

12000

14000

V maltenes (ng.g )

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

208Pb

206Pb 207Pb

Direct determination of Lead isotope ratios in crude oils by ICP-MS

M/Z

204Pb
Interface ICP
2C

Introduction system
140C Ar nebulizer (0.6 l/mn)

30 rpm

SRM 981

Ar nebulizer (0.5 l/mn) + O2 nebulizer (0.066 l/mn) PFA-100 Microflow nebulizer

Platinum sampler and skimmer cones

Dual inlet torch

Scott-type double pass spray chamber Drain Chilled (-10C)

12 rpm

Petroleum sample diluted in xylene

Dreyfus et al., JAAS, 2006

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

0.8 RSD (%) 0.6 0.4 0.2 0 1000

0.6 ng.g-1

RSD (%) observed RSD (%) poisson

1.2 ng.g-1

4 ng.g-1

10 ng.g-1

Precision and Accuracy of Direct Lead Isotope Ratios Determination in Crude Oils by ICP-MS
From Dreyfus et al., JAAS, 2006
2.376 2.374 2.372 2.37 2.368 2.366 2.364 2.362 2.36 2.358

10000

100000

1000000

206Pb/counts.s-1
1.1 2.17

206Pb/207Pb

1.098 1.096 1.094 1.092 1.09 1.088

208Pb/206Pb

2.165 2.16 2.155 2.15

1 ng.g-1 SRM 981

Reference values*

1 ng.g-1 SRM 981

Reference values*

208Pb/207Pb

1 ng.g-1 SRM 981

Reference values*

* 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
1.144 1.142 1.14 1.138 1.136 1.134 1.132 1.13 1.128 1.126 1.124 2.14

206Pb/207Pb

208Pb/206Pb

2.12 2.11 2.1 2.09 2.08 2.07

Organic*

Aqueous*

Organic*

Aqueous*

208Pb/207Pb

2.13

2.43 2.42 2.41 2.4 2.39 2.38 2.37 2.36 2.35 2.34

Organic*

Aqueous*

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

Direct determination of Lead isotope ratios in crude oils from Potiguar

2.26 2.24 2.22 2.2 2.18 2.16 2.14 2.12 2.1 2.08 2.06 2.04 2.02 2 1.98 1.96 1.94 1.92 1.9 1.88 1.86 1.84 1.82 1.8 1

Potiguar basin oil

Pb/206Pb

Crustal or 9 Anthropic signature?

2 1

74

MORB

8 5

Easter Fernando de Noronha

208

Canary

Terceira (Azores) Ascension

Mantle (hot spot) signature

St Helena Tubuaii (Australes chain) Mangaia

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 1.4 206

Pb/207Pb

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

Lead isotopes in crude oils : geological tracer for the reconstruction of petroleum systems history:
Use of 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb ratios reveals 3 different isotopic signatures

40,0 39,5 39,0 38,5 38,0

Crustal End-Member
7 4

Mantle End-Member

208Pb/204Pb

1 9 2

37,0

Anthropic End-Member

36,5 17,0 17,5 18,0 18,5 19,0 19,5 20,0 20,5 21,0 2

06Pb/204Pb

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

207Pb/204Pb

37,5

16,4 16,2 16,0 15,8 15,6 15,4

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

Micro scale exploration : trace element analysis in fluid inclusions

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

Application of this work in its widest extent

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 Downstream Control of crude oil, gasoline and diesel quality during refining process Identification of foulants and deposits in refineries and process plants Control and quantification of contaminants

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

Acknowledgements

Co
Olivier Donard Christophe Pcheyran Julien Malherbe Alain Prinzhofer Caroline Magnier Charles-Phillip Lienemann IFP
UPPA

/ 7 Os 18

88 O s 1
7

Cu

208

/20 b 206 P

As B a b o P
M
207 P

Pb/ 206 Pb 2 Pb / 06 Pb
20 8

20 8

Pb

/ 206 Pb

Fe

Thank you very much for your attention

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

20 8

Pb

and all the LCABIE team

Os

/ 206 Pb

Re

b/ 204Pb

208Pb/206Pb

Ni Sr

206 Pb 208 Pb/

Hg