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Licensed Unlicensed Requires Authentication Published by De Gruyter February 9, 2017

High-pressure high-temperature Raman spectroscopy of kerogen: Relevance to subducted organic carbon

Laurel B. Childress EMAIL logo and Steven D. Jacobsen
From the journal American Mineralogist

Abstract

The amount of insoluble macromolecular organic matter in the Earth’s crust, commonly referred to as kerogen, far exceeds the mass of living organic matter. The fraction of kerogen in sediments subducted into the mantle remains poorly constrained and will vary depending on the physical-chemical properties of kerogen along different slab geotherms. We studied the pressure-temperature evolution of carbon vibrational frequencies in isolated kerogen, previously not subjected to metamorphism, using Raman spectroscopy in a sapphire optical cell up to 3.2 GPa and 450 °C, correspondingto colder subduction geotherms. For blue-green laser excitation, we find optical irradiance exceeding ~3 kW/cm2 induces changes in spectral features of the primary graphitic (G-band) and two main disordered modes (D1 and D2) that might otherwise be mistaken for thermal maturation. Whereas previous in situ studies have investigated the changes in these molecular vibrations of kerogen at high temperature or high pressure, we collected Raman spectra of isolated kerogen at simultaneous high P-T conditions. Although instantaneous and irreversible changes in band ratios of isolated kerogen were observed above ~350°C at room-pressure, long-duration (2–8 h) heating experiments at 450 °C and 2.7–3.0 GPa reveal no permanent change in band structure. The reduction in vibrational frequencies of the disordered carbon modes with temperature (dv/dT) at pressures >1 GPa is slightly less than found at room pressure, further indicating that pressure effectively increases the thermal stability of kerogen. Our results suggest that kerogen reaching depths of 60 km where the temperature is below ~450 °C may subduct into the mantle, providing a potential source for the organic-rich component of carbon recently detected in certain lower-mantle diamonds.

Acknowledgments

This research was supported in part by NSF grant EAR-1452344, the David and Lucile Packard Foundation, and the Carnegie DOE Alliance Center to S.D.J. L.B.C. was supported in part by a Schlanger Scientific Ocean Drilling Fellowship and by NSF award OCE-1144483 to Neal Blair at Northwestern University. We thank M. Siqueira at Almax-easyLab for discussions about fabrication of custom sapphire-anvils and W.A. Bassett for help with construction of the high-temperature sapphire cell.

References cited

Ammar, M.R., Charon, E., Rouzaud, J.-N., Aleon, J., Guimbretière, G., and Simon, P. (2011) On a reliable structural characterization of polished carbons in meteorites by Raman microspectroscopy. Spectroscopy Letters, 44, 535–538.10.1080/00387010.2011.610417Search in Google Scholar

Beny-Bassez, C., and Rouzaud, J.-N. (1985) Characterization of carbonaceous materials by correlated electron and optical microscopy and raman microspectroscopy. Scanning Electron Microscopy, 1, 119–132.Search in Google Scholar

Beyssac, O., Rouzaud, J.-N., Goffè, B., Brunet, F., and Chopin, C. (2002a) Graphitization in a high-pressure, low-temperature metamorphic gradient: a Raman microspectroscopy and HRTEM study. Contributions to Mineralogy and Petrology, 143, 19–31.10.1007/s00410-001-0324-7Search in Google Scholar

Beyssac, O., Goffè, B., Chopin, C., and Rouzaud, J.-N. (2002b) Raman spectra of carbonaceous material in metasediments: A new geothermometer. Journal of Metamorphic Geology, 20, 859–871.10.1046/j.1525-1314.2002.00408.xSearch in Google Scholar

Beyssac, O., Brunet, F., Petitet J.-P., Goffè, B., and Rouzaud, J.-N. (2003a) Experimental study of the microtextural and structural transformations of carbonaceous materials under pressure and temperature. European Journal of Mineralogy, 15, 937–951.10.1127/0935-1221/2003/0015-0937Search in Google Scholar

Beyssac, O., Goffe, B., Petitet, J.-P., Froigneux, E., Moreau, M., and Rouzaud, J.-N. (2003b) On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy. Spectrochimica Acta—Part A: Molecular and Biomolecular Spectroscopy, 59, 2267–2276.10.1016/S1386-1425(03)00070-2Search in Google Scholar

Blair, N.E., and Aller, R.C. (2012) The fate of terrestrial organic carbon in the marine environment. Annual Review of Marine Science, 4, 401–423.10.1146/annurev-marine-120709-142717Search in Google Scholar

Blair, N.E., Leithold, E.L., Ford, S.T., Peeler, K.A., Holmes, J.C., and Perkey, D.W. (2003) The persistence of memory: The fate of ancient sedimentary organic carbon in a modern sedimentary system. Geochimica et Cosmochimica Acta, 67, 63–73.10.1016/S0016-7037(02)01043-8Search in Google Scholar

Blair, N.E., Leithold, E.L., and Aller, R.C. (2004) From bedrock to burial: The evolution ofparticulate organic carbon across coupled watershed-continental margin systems. Marine Chemistry, 92, 141–156.10.1016/j.marchem.2004.06.023Search in Google Scholar

Blair, N.E., Leithold, E.L., Brackley, H., Trustrum, N., Page, M., and Childress, L. (2010) Terrestrial sources and export of particulate organic carbon in the Waipaoa sedimentary system: Problems, progress and processes. Marine Geology, 270, 108–118.10.1016/j.margeo.2009.10.016Search in Google Scholar

Bonal, L., Quirico, E., Bourot-Denise, M., and Montagnac, G. (2006) Determination of the petrologic type of CV3 chondrites by Raman spectroscopy of included organic matter. Geochimica et Cosmochimica Acta, 70, 1849–1863.10.1016/j.gca.2005.12.004Search in Google Scholar

Bouchez, J., Beyssac, O., Galy, V., Gaillardet, J., France-Lanord, C., Maurice, L., and Moreira-Turcq, P. (2010) Oxidation of petrogenic organic carbon in the Amazon floodplain as a source of atmospheric CO2. Geology, 38, 255–258.10.1130/G30608.1Search in Google Scholar

Burdige, D.J. (2005) Burial of terrestrial organic matter in marine sediments: A reassessment. Global Biogeochemical Cycles, 19, 1–7.10.1029/2004GB002368Search in Google Scholar

Busemann, H., Alexander, C.M.O., and Nittler, L.R. (2007) Characterization of insoluble organic matter in primitive meteorites by microRaman spectroscopy. Meteoritics & Planetary Science, 1416, 1387–1416.10.1111/j.1945-5100.2007.tb00581.xSearch in Google Scholar

Courrèges-Lacoste, G.B., Ahlers, B., and Pérez, F.R. (2007) Combined Raman spectrometer/laser-induced breakdown spectrometer for the next ESA mission to Mars. Spectrochimica Acta-Part A: Molecular and Biomolecular Spectroscopy, 68, 1023–1028.10.1016/j.saa.2007.03.026Search in Google Scholar

Czaja, A.D., Kudryavtsev, A.B., Cody, G.D., and Schopf, J.W. (2009) Characterization of permineralized kerogen from an Eocene fossil fern. Organic Geochemistry, 40, 353–364.10.1016/j.orggeochem.2008.12.002Search in Google Scholar

Dartnell, L.R., Page, K., Jorge-Villar, S.E., Wright, G., Munshi, T., Scowen, I.J., Ward, J.M., and Edwards, H.G.M. (2012) Destruction of Raman biosignatures by ionising radiation and the implications for life detection on Mars. Analytical and Bioanalytical Chemistry, 403, 131–144.10.1007/s00216-012-5829-6Search in Google Scholar

Drenzek, N.J., Hughen, K.A., Montluçon, D.B., Southon, J.R., dos Santos, G.M., Druffel, E.R.M., Giosan, L., and Eglinton, T.I. (2009) A new look at old carbon in active margin sediments. Geology, 37, 239–242.10.1130/G25351A.1Search in Google Scholar

Dunn, D.S., Sridhar, N., Miller, M.A., Price, K.T., Pabalan, R., and Abrajano, T.A. (2007) Development of a surface-enhanced Raman technique for biomarker studies on mars. Applied Spectroscopy, 61, 25–31.10.1366/000370207779701424Search in Google Scholar

Durand, B. (1980) Sedimentary organic matter and kerogen. Definition and quantitative importance of kerogen. In B. Durand, Ed., Kerogen, Insoluble Organic Matter from Sedimentary Rocks, pp. 13–34. Editions Technip, Paris, France.Search in Google Scholar

Durand, B., and Nicaise, G. (1980) Procedures for kerogen isolation. In B. Durand, Ed., Kerogen, Insoluble Organic Matter from Sedimentary Rocks pp. 35–54. Editions Technip, Paris, France.Search in Google Scholar

Ellery, A., Wynn-Williams, D., Parnell, J., Edwards, H.G.M., and Dickensheets, D. (2004) The role of Raman spectroscopy as an astrobiological tool in the exploration of Mars. Journal of Raman Spectroscopy, 35, 441–457.10.1002/jrs.1189Search in Google Scholar

Everall, N., Lumsdon, J., and Christopher, D. (1991) The effect of laser-induced heating upon the vibrational Raman spectra of graphites and carbon fibres. Carbon, 29, 133–137.10.1016/0008-6223(91)90064-PSearch in Google Scholar

Ferralis, N., Liu, Y., Bake, K.D., Pomerantz, A.E., and Grossman, J.C. (2015) Direct correlation between aromatization of carbon-rich organic matter and its visible electronic absorption edge. Carbon, 88, 139–147.10.1016/j.carbon.2015.02.075Search in Google Scholar

Ferrari, A., and Robertson, J. (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Physical Review B, 61, 14095–14107.10.1103/PhysRevB.61.14095Search in Google Scholar

Galimov, E.M. (1980) C13/C12 in kerogen. In B. Durand, Ed., Kerogen, Insoluble Organic Matter from Sedimentary Rocks pp. 271–300. Editions Technip, Paris, France.Search in Google Scholar

Galy, V., France-Lanord, C., Beyssac, O., Faure, P., Kudrass, H., and Palhol, F. (2007) Efficient organic carbon burial in the Bengal Fan sustained by the Himalayan erosional system. Nature, 450, 407–410.10.1038/nature06273Search in Google Scholar

Galy, V., Beyssac, O., France-Lanord, C., and Eglinton, T. (2008) Recycling of graphite during Himalayan erosion: a geological stabilization of carbon in the crust. Science, 322, 943–945.10.1126/science.1161408Search in Google Scholar

Hayes, J.M., and Waldbauer, J.R. (2006) The carbon cycle and associated redox processes through time. Philosophical transactions of the Royal Society of London, 361, 931–950.10.1098/rstb.2006.1840Search in Google Scholar

Hilton, R.G., Galy, A., Hovius, N., Horng, M.J., and Chen, H. (2010) The isotopic composition of particulate organic carbon in mountain rivers of Taiwan. Geochimica et Cosmochimica Acta, 74, 3164–3181.10.1016/j.gca.2010.03.004Search in Google Scholar

Hochleitner, R., Tarcea, N., Simon, G., Kiefer, W., and Popp, J. (2004) Micro-Raman spectroscopy: A valuable tool for the investigation of extraterrestrial material. Journal of Raman Spectroscopy, 35, 515–518.10.1002/jrs.1190Search in Google Scholar

Huang, E.-PE., Huang, E.-PE., Yu, S.-C., Chen, Y.-H., Lee, J.-S., and Fang, J.-N. (2010) In situ Raman spectroscopy on kerogen at high temperatures and high pressures. Physics and Chemistry of Minerals, 37, 593–600.10.1007/s00269-010-0360-9Search in Google Scholar

Hutchinson, I.B., Parnell, J., Edwards, H.G.M., Jehlicka, J., Marshall, C.P., Harris, L.V., and Ingley, R. (2014) Potential for analysis of carbonaceous matter on Mars using Raman spectroscopy. Planetary and Space Science, 103, 184–190.10.1016/j.pss.2014.07.006Search in Google Scholar

Kagi, H., Tsuchida, I., Wakatsuki, M., Takahashi, K., Kamimura, N., Iuchi, K., and Wada, H. (1994) Proper understanding of down-shifted Raman spectra of natural graphite: Direct estimation of laser-induced rise in sample temperature. Geochimica et Cosmochimica Acta, 58, 3527–3530.10.1016/0016-7037(94)90104-XSearch in Google Scholar

Kelemen, S.R., and Fang, H.L. (2001) Maturity trends in Raman spectra from kerogen and coal. Energy and Fuels, 15, 653–658.10.1021/ef0002039Search in Google Scholar

Kennedy, C.S., and Kennedy, G.C. (1976) The equilibrium boundary between graphite and diamond. Journal of Geophysical Research, 81, 2467–2470.10.1029/JB081i014p02467Search in Google Scholar

Kremer, B., Bauer, M., Stark, R.W., Gast, N., Altermann, W., Gursky, H.-J., Heckl, W.M., and Kazmierczak, J. (2012) Laser-Raman and atomic force microscopy assessment of the chlorococcalean affinity of problematic microfossils. Journal of Raman Spectroscopy, 43, 32–39.10.1002/jrs.2985Search in Google Scholar

Lahfid, A., Beyssac, O., Deville, E., Negro, F., Chopin, C., and Goffé, B. (2010) Evolution of the Raman spectrum of carbonaceous material in low-grade metasediments of the Glarus Alps (Switzerland). Terra Nova, 22, 354–360.10.1111/j.1365-3121.2010.00956.xSearch in Google Scholar

Leithold, E.L., Blair, N.E., and Perkey, D.W. (2006) Geomorphologic controls on the age of particulate organic carbon from small mountainous and upland rivers. Global Biogeochemical Cycles, 20, 1–11.10.1029/2005GB002677Search in Google Scholar

Mackenzie, F.T., Lerman, A., and Andersson, A.J. (2004) Past and present of sediment and carbon biogeochemical cycling models. Biogeosciences Discussions, 1, 27–85.10.5194/bg-1-11-2004Search in Google Scholar

Marshall, A.O., Corsetti, F.A., Sessions, A.L., and Marshall, C.P. (2009) Raman spectroscopy and biomarker analysis reveal multiple carbon inputs to a Precambrian glacial sediment. Organic Geochemistry, 40, 1115–1123.10.1016/j.orggeochem.2009.08.006Search in Google Scholar

Matsuda, J., Morishita, K., Tsukamoto, H., Miyakawa, C., Nara, M., Amari, S., Uchiyama, T, and Takeda, S. (2010) An attempt to characterize phase Q: Noble gas, Raman spectroscopy and transmission electron microscopy in residues prepared from the Allende meteorite. Geochimica et Cosmochimica Acta, 74, 5398–5409.10.1016/j.gca.2010.06.009Search in Google Scholar

Morishita, K., Nara, M., Amari, S., and Matsuda, J. (2011) On the effect of laser-induced heating in a raman spectroscopic study of carbonaceous material in meteorite. Spectroscopy Letters, 44, 459–463.10.1080/00387010.2011.610400Search in Google Scholar

Pasteris, J.D., and Wopenka, B. (1991) Raman spectra of graphite as indicators of degree of metamorphism. Canadian Mineralogist, 29, 1–9.Search in Google Scholar

——(2002) Images of the Earth’s earliest fossils? Nature, 420, 476–467.10.1038/420476bSearch in Google Scholar PubMed

Quirico, E., Raynal, P-I., and Bourot-Denise, M. (2003) Metamorphic grade of organic matter in six unequilibrated ordinary chondrites. Meteoritics & Planetary Science, 38, 795–811.10.1111/j.1945-5100.2003.tb00043.xSearch in Google Scholar

Rahl, J.M., Anderson, K.M., Brandon, M.T., and Fassoulas, C. (2005) Raman spectroscopic carbonaceous material thermometry of low-grade metamorphic rocks: Calibration and application to tectonic exhumation in Crete, Greece. Earth and Planetary Science Letters, 240, 339–354.10.1016/j.epsl.2005.09.055Search in Google Scholar

Raravikar, N., Keblinski, P, Rao, A., Dresselhaus, M., Schadler, L., and Ajayan, P. (2002) Temperature dependence of radial breathing mode Raman frequency of single-walled carbon nanotubes. Physical Review B, 66, 1–9.10.1103/PhysRevB.66.235424Search in Google Scholar

Rouzaud, J.N., and Oberlin, A. (1989) Structure, microtexture, and optical properties of anthracene and saccharose-based carbons. Carbon, 27, 517–529.10.1016/0008-6223(89)90002-XSearch in Google Scholar

Rull, F., Maurice, S., Diaz, E., Lopez, G., Catala, A., and the RLS Team (2013) Raman Laser Spectrometer (RLS) for Exomars 2018 Rover Mission: Current status and science operation mode on powdered samples. Lunar and Planetary Science Conference, 1–2.Search in Google Scholar

Sadezky, A., Muckenhuber, H., Grothe, H., Niessner, R., and Pöschl, U. (2005) Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information. Carbon, 43, 1731–1742.10.1016/j.carbon.2005.02.018Search in Google Scholar

Sandford, S., Aleon, J., Alexander, C., Araki, T., Bajt, S., Baratta, G., Borg, J., Bradley, J., Brownlee, D., Brucato, J., and others. (2006) Organics Captured from Comet 81P/Wild 2 by the Stardust Spacecraft. Science, 314, 1720–1724.10.1126/science.1135841Search in Google Scholar PubMed

Schopf, J.W., and Kudryavtsev, A.B. (2005) Three-dimensional Raman imagery of precambrian microscopic organisms. Geobiology, 3, 1–12.10.1111/j.1472-4669.2005.00044.xSearch in Google Scholar

Schopf, J.W., Kudryavtsev, A.B., Agresti, D.G., Wdowiak, T.J., and Czaja, A.D. (2002) Laser-Raman imagery of Earth’s earliest fossils. Nature, 3, 73–76.10.1038/416073aSearch in Google Scholar PubMed

Steele, A., Mccubbin, F.M., Fries, M., Kater, L., Boctor, N.Z., Fogel, M.L., Conrad, PG., Glamoclija, M., Spencer, M., Morrow, A.L., and others (2012) A reduced organic carbon component in Martian basalts. Science, 337, 212–215.10.1126/science.1220715Search in Google Scholar PubMed

Syracuse, E.M., van Keken, P.E., and Abers, G.A. (2010) The global range of subduction zone thermal models. Physics of the Earth and Planetary Interiors, 183, 73–90.10.1016/j.pepi.2010.02.004Search in Google Scholar

Tissot, B., Durand, B., Espitalie, J., and Combaz, A. (1974) Influence of nature and diagenesis of organic matter in formation of petroleum. The American Association of Petroleum Geologists Bulletin, 58, 499–506.Search in Google Scholar

Trots, D.M., Kurnosov, A., Boffa Ballaran, T., Tkachev, S., Zhuravlev, K., Prakapenka, V., Berkowski, M., and Frost, D.J. (2013) The Sm:YAG primary fluorescence pressure scale. Journal of Geophysical Research: Solid Earth, 118, 5805–5813.10.1002/2013JB010519Search in Google Scholar

Tsu, R., Gonzalez, J.H., and Hernandez, I. (1978) Raman scattering in graphite. Bulletin of the American Physical Society, 23, 302–303.Search in Google Scholar

Vandenbroucke, M., and Largeau, C. (2007) Kerogen origin, evolution and structure. Organic Geochemistry, 38, 719–833.10.1016/j.orggeochem.2007.01.001Search in Google Scholar

Walter, M.J., Kohn, S.C., Araujo, D., Bulanova, G.P., Smith, C.B., Gaillou, E., Wang, J., Steele, A., and Shirey, S.B. (2011) Deep mantle cycling of oceanic crust: Evidence from diamonds and their mineral inclusions. Science, 334, 54–57.10.1126/science.1209300Search in Google Scholar

Wang, Y., Alsmeyer, D.C., and Mccreery, R.L. (1990) Raman spectroscopy of carbon materials: Structural basis of observed spectra. Chemistry of Materials, 2, 557–563.10.1021/cm00011a018Search in Google Scholar

Whiticar, M.J. (1996) Stable isotope geochemistry of coals, humic kerogens and related natural gases. International Journal of Coal Geology, 32, 191–215.10.1016/S0166-5162(96)00042-0Search in Google Scholar

Wopenka, B. (1988) Raman observations on individual interplanetary dust particles. Earth and Planetary Science Letters, 88, 221–231.10.1016/0012-821X(88)90079-9Search in Google Scholar

Wopenka, B., and Pasteris, J.D. (1993) Structural characterization of kerogens to granulite-facies graphite: applicability of Raman microprobe spectroscopy. American Mineralogist, 78, 533–557.Search in Google Scholar

Received: 2016-2-10
Accepted: 2016-9-12
Published Online: 2017-2-9
Published in Print: 2017-2-1

© 2017 by Walter de Gruyter Berlin/Boston

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