Abiogenic hydrocarbons produced under upper mantle conditions

Alexander Goncharov
Geophysical Laboratory, Carnegie Institution of Washington, USA

Participants:
Anton Kolesnikov1,2

Raja S. Chellappa1
Maddury Somayazulu1 Subramanian Natarajan1 Russell J. Hemley1 Vladimir Kutcherov3

1 Geophysical

Laboratory, Carnegie Institution of Washington, USA 2 Lomonosov Moscow State Academy of Fine Chemical Technology, Russia 3 Royal Institute of Technology, Stockholm, Sweden

Deep abiotic organics

Russian-Ukrainian School
Oil Company View

Synthesis of hydrocarbons
nCaCO3 +(9n+3)FeO+(2n+1)H2 O nCa(OH)2 +(3n+1)FeO4 +Cn H2n+2 3
Kenney, Kutcherov et al. (2002), KONAK chamber 3-5 GPa, 1200-1500K

CaCO3 +12FeO+H2 O CaO+4Fe3 O4 +CH4

Scott et al. (2004), DAC, 5-11 GPa, 773-1773K
Is this viable for:

Realistic Earths minerals? Heavier hydrocarbons synthesis? Oxidizing conditions?

H H H H H H H

Methane polymerization
H

C
H H

C
H H

T, p

H C H

+ H

Laser heating in the diamond anvil cell

Probe (Raman spectroscopy & X-ray diffraction)

Sketch

Laser Heating

b
Ruby

Microphotograph

Diamond Anvils

Sample

Coupler

Gasket

Methane in Re gasket with Ir coupler

In situ measurements at high temperature Mapping of quenched samples

Sample preparations: minerals

Before:

Fayalite (Fe1.92Mn0.08SiO4): Rockport

Olivine (Mg1.8Fe0.2SiO4): San Carlos

Mineral Assemblages: Peridodite & Basalt

Carbonate in 1:8 molar ratio ground and mixed in diamonite mortar/pestle Ir coupler or compacted powder Loaded with H2O Adequate care with all aspects of cleaning

After:
Reaction Zone

Methanogenesis from minerals

Fayalite (Fe1.92Mn0.08SiO4): Rockport

Olivine (Mg1.8Fe0.2SiO4): San Carlos Mineral Assemblages: Peridodite & Basalt

Methane formation at relatively low temperatures; suggested pathway: 6 Fe2SiO4 + CaCO3 + 2 H2O = 4 Fe3O4 + CH4 + 6 SiO2+ CaO Hydrous phases were not observed 5-6 GPa, < 800 K
(Fe0.96Mn0.04)2SiO4:CaCO3 8:1 molar ratio
Fe3O4 CH4 Ice VII

after Laser Heating

n(SiO2)

< 800 K
X3

n(SiO4) starting sample

n(CO3)

Methanogenesis from minerals

Fayalite (Fe1.92Mn0.08SiO4): Rockport

Olivine (Mg1.8Fe0.2SiO4): San Carlos Mineral Assemblages: Peridodite & Basalt

Methane formation at T > 2000 K, 5-6 GPa Hydrous phase formation
(Mg0.90Fe0.10)2SiO4:CaCO3 8:1 molar ratio
CH4
X3

l = 0.3757

After leaser heat at 5.6 GPa

After Laser Heating

Fe3O4? n(SiO4)

Olivine + hydrous Mg2SiO4 phases

n(CO3)
starting sample

5.6 GPa

Ice VII

2q

Methanogenesis from minerals

Fayalite (Fe1.92Mn0.08SiO4): Rockport

Olivine (Mg1.8Fe0.2SiO4): San Carlos

No methane formation at T > 1500 K, 5-6 GPa Hydrous phase formation
Peridodite : CaCO3 10:1 weight ratio
Laser Heating n (OH)

Mineral Assemblages: Peridodite & Basalt

n(SiO4)
Resistive Heating

as-loaded sample

n(CO3)

Ice VII

Methanogenesis from minerals

Fayalite (Fe1.92Mn0.08SiO4): Rockport
Olivine (Mg1.8Fe0.2SiO4): San Carlos

Mineral Assemblages: Peridodite & Basalt

Conclusions
Carbonate reduction to CH4 observed even with Mg-rich mantle minerals Further XRD characterization of reaction products and thermochemical calculations are needed. Diamond reactivity (found in control experiments) need to be better addressed Explore polymerization to higher hydrocarbons.

Methane and ethane reactivity: in situ Raman diagnostics

Temperature:
Raman Intensity (arb. units)

(a)

C2H6 C3H8

C (graphite)

H2 1500 K

Methane: CH4
CH4

H2 CH4 CH4

C2-C4 alkanes +H2

C +H2

Positions: 3 2 1

900 K 300 K

500 50 m (b)

900

1400

1800 2800 Raman Shift (cm ) (c)

C4H10 H2
-1

3200 4000

4400

To check reaction reversibility

Ethane: 3C2H6 2C3H8+ H2 C2H6 + H2 2CH4

Position:
Diamond anvils

Gasket/Coupler:
C 2H 6 C2H6 C3H8 C 3H 8 CH -Ir-W 4 6.64 GPa CH4-Fe O -Re 3 4 2.19 GPa C2H6-Ir-Re C CH4

Raman Intensity (arb. units)

Position 1 Position 3 x10 C 2H 6 H2 Position 2

400 900

(CH4)n(H2)m H2

5.00 GPa CH -Ir-Re 4 3.83 GPa CH -Au-B 4 4.04 GPa

Gasket: Re, W, Au (liner) Coupler: Ir, B, Fe3O4

CH4 C (graphite) CH4 Position 3 H2

1000

2000 3000 4000 Raman Shift (cm-1)

500

1000 1500 Raman shift (cm-1)

Thermal insulation: Al2O3 (in selected exp.)

X-ray diffraction of the quenched products in oxidized conditions with Fe3O4 coupler
Laser heating products: magnetite in methane
Diffraction pattern Graphite Ice VII bcc Fe Diamond Alumina Methane

Single-crystal diffraction

Fe

Intensity (arb. units)

Methane

Diamond
Single crystal Fe3O4
8 10 12 14 16 18 20

TwoTheta (degree)

Fe3O4+2CH4 3Fe+2C+4H2O

P-T-fO2 conditions in the DAC experiments and in the upper mantle

a
-2 2000 0

b
65

Depth (km) 127 188

Temperature (K)

log fO2[FMQ]

1500

ic

ge ot

-4

he
1000

rm
-6 South Africa Yakutia Slave 2.19 GPa DAC with IM buffer

Hydrocarbon formation

ce an

-8 1000 1200 1400 Temperature (K) 1600

500 0

g eld hi

e oth

rm
CH 4 m elting
6

2 4 Pressure (GPa)

Conclusions
Methane above 2 GPa and 1000-1500 K partially reacts and forms saturated hydrocarbons (C2-C4 alkanes: ethane, propane, butane), molecular hydrogen and graphite.

The reaction does not require catalysts and proceed in oxidized conditions.
Formation of methane in similar experiments on ethane suggests reversibility of hydrocarbon formation. The experimental P-T-fO2 conditions of methane derived hydrocarbon synthesis are appropriate for the Earths mantle, creating the possibility of the abiogenic synthesis of petroleum components in of the Earths upper mantle.

Outlook: Chemical Reactivity of Deep Earths Carbon Bearing Phases using Optical spectroscopy at high P-T
Future scientific directions: shorter time-scale to study chemical kinetics & dynamics to make data comparable to molecular dynamic simulations
(c) 2
Radiative temperature 10,000 K

114 G P a
2 50 0 K

fluid

Pulsed laser heating in DAC

Intensity (arb. units)

fluid

1 8 40 K

Pulsed Raman probe

1 5 90 K

125 GPa silicate perovskite

'

1 0 50 K

30 0 K

2350

2 4 00

24 5 0
-1

2500

600 650 Wavelength (nm)

Ra m a n S hift (cm )

Future technical developments of the laser heated DAC: 1. Pulsed laser heating 2. CARS & broadband fs spectroscopy in the DAC 3. Pump-probe spectroscopy- fs time scale

Pump Time resolution (determined by the laser pulse width 10s fs) is comparable with bond break/creation time.
Lupke et al., 2003

Probe

Acknowledgements
Minerals: Shell Inc. CDAC Prof. Dimitri Sverjensky (JHU) Dr. Dionysis Foustoukos (GL) Dr. Anurag Sharma (GL) Smithsonian Institution
Methane: K. Litasov Y. Fei J. C. Crowhurst, M. Somayazulu, V. Struzhkin, R. Cohen, D. Foustoukos, J. Montoya, T. Strobel S. Sinogeikin

Support: A. K.: support of INTAS through YSF Ref. Nr. 06-1000014-6546. V. K.: support from INTAS Ref. Nr. 06-1000013-8750. A. G.: NSF-EAR, CDAC