Abstract
The main obstacle to understanding of the geological role of reduced, CH4-bearing fluids is the absence of a reliable experimental technique applicable to solid-media high-pressure apparatuses, allowing their observation and direct characterisation under laboratory conditions. In this study, we describe the main pitfalls of earlier designs and technical aspects related to achievement of strongly reduced oxygen fugacity (fO2) conditions (i.e., Fe–FeO, IW) and maintenance of a constant fluid equilibrium during an experiment. We describe a new triple-capsule design made of an Au outer capsule with an Au-inner capsule containing a metal/metal oxide oxygen buffer and water, as well as an inner olivine container filled with a harzburgitic sample material and Ir powder that serves as a redox sensor. The bottom of the outer capsule is covered with a solid fluid source (e.g., stearic acid). The outer capsule is surrounded by a polycrystalline CaF2 pressure medium to minimise H2-loss from the assembly. Application of this design is limited to temperatures below the melting temperature of Au, which is pressure dependent. Metals other than Au can lead to fluid disequilibrium triggered by a dehydrogenation and carbonation of the methane. Test experiments were carried out at 5 GPa, temperatures < 1300 °C, at Mo–MoO2 and Fe–FeO buffer conditions. IrFe alloy sensors demonstrate successful achievement and maintenance of reduced fluid environment at ∆logfO2 ≈ IW + 0.5. The fluid phase was trapped in numerous inclusions within the olivine sample container. Raman spectra reveal that the fluid consists mainly of CH4, along with small amounts of higher hydrocarbons like C2H6. No water was detected, but H2 was found to be present in fluid and incorporated into the olivine structure. Our results are inconsistent with published fluid speciation models that predict significant H2O contents at these fO2 conditions. It is also apparent that fluids with significant CH4 contents are likely to be stable under the conditions recorded by some mantle samples.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Akella J, Kennedy GC (1971) Melting of gold, silver and copper—proposal for a new high-pressure calibration scale. J Geophys Res 76(20):4969. https://doi.org/10.1029/JB076i020p04969
Andersen DJ, Lindsley DH, Davidson PM (1993) QUILF: a pascal program to assess equilibria among Fe–Mg–Mn–Ti oxides, pyroxenes, olivine, and quartz. Comput Geosci 19(9):1333–1350
Arculus RJ (1985) Oxidation status of the mantle: past and present. Annu Rev Earth Planet Sci 13:75–95. https://doi.org/10.1146/annurev.ea.13.050185.000451
Ardia P, Hirschmann MM, Withers AC, Stanley BD (2013) Solubility of CH4 in a synthetic basaltic melt, with applications to atmosphere-magma ocean-core partitioning of volatiles and to the evolution of the Martian atmosphere. Geochimica Et Cosmochimica Acta 114:52–71. https://doi.org/10.1016/j.gca.2013.03.028
Ballhaus C, Berry RF, Green DH (1991) High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle. Contrib Mineral Petrol 107:27–40
Barr JA, Grove TL (2010) AuPdFe ternary solution model and applications to understanding the fO(2) of hydrous, high-pressure experiments. Contrib Mineral Petrol 160(5):631–643. https://doi.org/10.1007/s00410-010-0497-z
Belonoshko AB, Saxena SK (1992) A unified equation of state for fluids of C–H–O–N–S–Ar composition and their mixtures up to very high temperatures and pressures. Geochimica Et Cosmochimica Acta 56(10):3611–3626. https://doi.org/10.1016/0016-7037(92)90157-e
Blundy J, Cashman K (2008) Petrologic reconstruction of magmatic system variables and processes. Miner Incl Volcan Process 69:179–239. https://doi.org/10.2138/rmg.2008.69.6
Blundy J, Cashman KV, Rust A, Witham F (2010) A case for CO2-rich arc magmas. Earth Planet Sci Lett 290(3–4):289–301. https://doi.org/10.1016/j.epsl.2009.12.013
Boldyrev VV (2002a) Thermal decomposition of silver oxalate. Thermochim Acta 388(1–2):63–90. https://doi.org/10.1016/s0040-6031(02)00044-8
Boldyrev (2002b) Thermal decomposition of silver oxylate. Thermochim Acta 388:63–90. https://doi.org/10.1016/S0040-6031(02)00044-8
Borisov A, Palme H (2000) Solubilities of noble metals in Fe-containing silicate melts as derived from experiments in Fe-free systems. Am Mineral 85(11–12):1665–1673
Borisov A, Behrens H, Holtz F (2015) Effects of melt composition of Fe3+/Fe2+ in silicate melts: a step to model ferric/ferrous ratio in multicomponent systems. Contrib Mineral Petrol 169:24. https://doi.org/10.1007/s00410-015-1119-6
Brey GP, Weber R, Nickel KG (1990) Calibration of a belt apparatus to 1800 °C and 6 GPa. J Geophys Res Solid Earth Planets 95(B10):15603–15610. https://doi.org/10.1029/JB095iB10p15603
Cahn RW (1991) Binary alloy phase diagrams–second edition. T. B. Massalski, Editor‐in‐Chief; H. Okamoto, P. R. Subramanian, L. Kacprzak, Editors. ASM international, Materials Park, Ohio, USA. December 1990. xxii, 3589 pp., 3 vol., hard‐back. $995.00 the set. Adv Mater 3:628–629. https://doi.org/10.1002/adma.19910031512
Chou IM (1986) Permeability of precious metals to hydrogen at 2 kb total pressure and elevated temperatures. Am J Sci 286(8):638–658
Christensen KO, Chen D, Lodeng R, Holmen A (2006) Effect of supports and Ni crystal size on carbon formation and sintering during steam methane reforming. Appl Catal A 314 (2006):9–22. https://doi.org/10.1016/j.apcata.2006.07.028
Concha BE, Bartholomew GL, Bartholomew CH (1984) CO hydrogenation on supported molybdenum catalysts: effects of support on specific activities of reduced and sulfided catalysts. J Catal 89(2):536–541. https://doi.org/10.1016/0021-9517(84)90332-4
Eugster HP (1957) Heterogeneous reactions involving oxidation and reduction at high pressures and temperatures. J Chem Phys 26(6):1760–1761. https://doi.org/10.1063/1.1743626
Evans KA, Tomkins AG (2011) The relationship between subduction zone redox budget and arc magma fertility. Earth Planet Sci Lett 308(3–4):401–409. https://doi.org/10.1016/j.epsl.2011.06.009
Evans WJ, Lipp MJ, Yoo C-S, Cynn H, Herberg JL, Maxwell RS, Nicol MF (2006) Pressure-induced polymerization of carbon monoxide: disproportionation and synthesis of an energetic lactonic polymer. Chem Mater 18:2520–2531
Freda C, Baker DR, Ottolini L (2001) Reduction of water loss from gold-palladium capsules during piston-cylinder experiments by use of pyrophyllite powder. Am Mineral 86(3):234–237
French BM (1966) Some geological implications of equilibrium between graphite and a C–H–O gas phase at high temperatures and pressures. Rev Geophys 4(2):223. https://doi.org/10.1029/RG004i002p00223
Frost DJ, McCammon (2008) The redox state of Earth’s mantle. Annu Rev Earth Planet Sci 36:389–420
Hanley L, Xu Z, Yates JT (1991) Methane activation on Ni(111) at high pressures. Surf Sci Lett 248:L265–L273
Holloway JR, Burnham CW, Millhollen GL (1968) Generation of H2O–CO2 mixtures for use in hydrothermal experimentation. J Geophys Res 73:20
Huizenga JM (2005) COH, an Excel spreadsheet for composition calculations in the C–O–H fluid system. Comput Geosci 31(6):797–800. https://doi.org/10.1016/j.cageo.2005.03.003
Huizenga JM, Crossingham A, Vijoen F (2012) Diamond precipitation from ascending reduced fluids in the Kaapvaal lithosphere: thermodynamic constraints. CR Geosci 344:67–76
Jakobsson S (2012) Oxygen fugacity control in piston-cylinder experiments. Contrib Mineral Petrol 164(3) https://doi.org/10.1007/s00410-012-0743-7
Jakobsson S, Blundy J, Moore G (2014a) Oxygen fugacity control in piston-cylinder experiments: a re-evaluation. Contrib Mineral Petrol 167(6) https://doi.org/10.1007/s00410-014-1007-5
Jakobsson S, Blundy J, Moore G (2014b) Oxygen fugacity control in piston-cylinder experiments: a re-evaluation. Contrib Mineral Petrol 167(1007) https://doi.org/10.1007/s00410-014-1007-5
Jamieson HE, Roeder PL, Grant AH (1992) Olivine–pyroxene–Pt–FeL alloy as an oxygen geobarometer. J Geol 100(1):138–145
Kratzer P, Hammer B, Nørskov JK (1996) A theoretical study of CH4 dissociation on pure and gold-alloyed Ni(111) surfaces. J Chem Phys 105(13):5595–5604
Kress VC, Carmichael ISE (1991) The compressibility of silicate liquids containing Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states. Contrib Mineral Petrol 108:82–92
Lamadrid HM, Lamb WM, Santosh M, Bodnar RJ (2014) Raman spectroscopic characterization of H2O in CO2-rich fluid inclusions in granulite facies metamorphic rocks. Gondwana Res 26:301–310
Lazarov M, Woodland AB, Brey GP (2009) Thermal state and redox conditions of the Kaapvaal mantle: a study of xenolith from the Finsch mine, South Africa. Lithos 112S:913–923
Luth RW, Stachel T (2014) The buffering capacity of lithospheric mantle: imlications for diamond formation. Contrib Mineral Petrol 168:1083. https://doi.org/10.1007/s00410-014-1083-6
Massalski TB, Murray JL, Bennett LH, Baker H (1986) Binary alloy phase diagrams. American Society for Metals, Metals Park
Matjuschkin V, Brooker RA, Tattitch B, Blundy JD, Stamper CC (2015) Control and monitoring of oxygen fugacity in piston cylinder experiments. Contrib Mineral Petrol. https://doi.org/10.1007/s00410-015-1105-z
Matjuschkin V, Blundy JD, Brooker RA (2016) The effect of pressure on sulphur speciation in mid-to deep-crustal arc magmas and implications for the formation of porphyry copper deposits. Contrib Mineral Petrol. https://doi.org/10.1007/s00410-016-1274-4
Matveev S, Ballhaus C, Fricke K, Truckenbrodt J, Ziegenbein D (1997) Volatiles in the Earth’s mantle.1. Synthesis of CHO fluids at 1273 K and 2.4 GPa. Geochimica Et Cosmochimica Acta 61(15):3081–3088. https://doi.org/10.1016/s0016-7037(97)00142-7
Matzen AK, Baker MB, Beckett JR, Stolper EM (2011) Fe-Mg partitioning between olivine and high-magnesian melts and the nature of Hawaiian parental liquids. J Petrol 52(7–8):1243–1263. https://doi.org/10.1093/petrology/egq089
Melekhova E, Annen C, Blundy J (2013) Compositional gaps in igneous rock suites controlled by magma system heat and water content. Nat Geosci 6(5):385–390. https://doi.org/10.1038/ngeo1781
Moore G, Roggensack K, Klonowski S (2008) A low-pressure-high-temperature technique for the piston-cylinder. Am Mineral 93(1):48–52. https://doi.org/10.2138/am.2008.2618
Mosenfelder JL, Deligne NI, Asimow PD, Rossman GR (2006) Hydrogen incorporation in olivine from 2 to 12 GPa. Am Mineral 91(2–3):285–294. https://doi.org/10.2138/am.2006.1943
Mutch EJF, Blundy JD, Tattitch BC, Cooper FJ, Brooker RA (2016) An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer. Contrib Mineral Petrol 171(10) https://doi.org/10.1007/s00410-016-1298-9
O’Neill HStC (1986) Mo–MoO2 (MOM) oxygen buffer and the free energy of formation of MoO2. Am Mineral (71):1007–1010
Pownceby MI, O’Neill HSC (1994a) Thermodynamic data from redox reactions at high-temperatures. III. Activity-composition relations in Ni–Pd alloys from EMF-measurements at 850–1250 K, and calibration of the NiO–NiPd assemblage as a redox sensor. Contrib Mineral Petrol 116(3):327–339. https://doi.org/10.1007/bf00306501
Pownceby MI, O’Neill HSC (1994b) Thermodynamic data from redox reactions at high-temperatures. IV. Calibration of the Re–ReO2 oxygen buffer from Emf and NiO–Ni–Pd redox sensor measurements. Contrib Mineral Petrol 118(2):130–137. https://doi.org/10.1007/bf01052864
Pownceby MI, O’Neill HSC (1995) Thermodynamic data from redox reactions at high-temperatures. V. Thermodynamic properties of NiO-MnO solid solutions from EMF-measurements. Contrib Mineral Petrol 119(4):409–421
Pownceby MI, O’Neill HSC (2000) Thermodynamic data from redox reactions at high temperatures. VI. Thermodynamic properties of CoO–MnO solid solutions from emf measurements. Contrib Mineral Petrol 140(1):28–39. https://doi.org/10.1007/s004100000162
Ratajeski K, Sisson TW (1999) Loss of iron to gold capsules in rock-melting experiments. Am Miner 84(10):1521–1527
Rauch M, Keppler H (2002) Water solubility in orthopyroxene. Contrib Mineral Petrol 143:525–536
Rosenbaum JM, Slagel MM (1995) C–O–H Speciation in piston-cylinder experiments. Am Miner 80(1–2):109–114
Rostrup-Nielsen JR (1993) Production of synthesis gas. Catal Today 18(4):305–324. https://doi.org/10.1016/0920-5861(93)80059-a
Serra E, Bini AC, Cosoli G, Pilloni L (2005) Hydrogen permeation measurements on alumina. J Am Ceram Soc 88(1):15–18. https://doi.org/10.1111/j.1551-2916.2004.00003.x
Sisson TW, Ratajeski K, Hankins WB, Glazner AF (2005) Voluminous granitic magmas from common basaltic sources. Contrib Mineral Petrol 148(6):635–661. https://doi.org/10.1007/s00410-004-0632-9
Sokol AG, Palyanova GA, Palyanov YN, Tomilenko AA, Melenevsky VN (2009) Fluid regime and diamond formation in the reduced mantle: experimental constraints. Geochimica Et Cosmochimica Acta 73(19):5820–5834. https://doi.org/10.1016/j.gca.2009.06.010
Sokol AG, Tomilenko AA, Bul’bak TA, Palyanova GA, Sokol IA, Palyanov YN (2017) Carbon and nitrogen speciation in N-poor C–O–H–N fluids at 6.3 GPa and 1100–1400 degrees C. Sci Rep. https://doi.org/10.1038/s41598-017-00679-7
Solymosi F, Erdohelyi A (1980) Hydrogenation of CO2 to CH4 over alumina-supported noble metalsHydrogenation of CO2 to CH4 over alumina-supported noble metals. J Mol Catal 8(4):471–474. https://doi.org/10.1016/0304-5102(80)80086-1
Stamper CC, Melekhova E, Blundy JD, Arculus RJ, Humphreys MCS, Brooker RA (2014) Oxidised phase relations of a primitive basalt from Grenada, Lesser Antilles. Contrib Mineral Petrol 167(1):1–20
Taylor WR, Foley SF (1989) Improved oxygen-buffering techniques for C–O–H fluid-saturated experiments at high-pressure. J Geophys Res Solid Earth Planets 94(B4):4146–4158. https://doi.org/10.1029/JB094iB04p04146
Taylor WR, Green DH (1987) The petrogenetic role of methane: effect on liquidus phase relations and the solubility mechanism of reduced C–H volatiles. In: Mysen BO (ed) Magmatic processes: physicochemical principles. Geochemical Society, Pennsylavania State University, Philadelphia, pp 121–138
Taylor JR, Wall VJ, Pownceby MI (1992) The calibration and application of accurate redox sensors. Am Mineral 77(3–4):284–295
Tiraboschi C, Tumiati S, Recchia S, Miozzi F, Poli S (2016) Quantitative analysis of COH fluids synthesized at HP–HT conditions: an optimized methodology to measure volatiles in experimental capsules. Geofluids 16(5):841–855. https://doi.org/10.1111/gfl.12191
Truckenbrodt J, Johannes W (1999) H2O loss during piston-cylinder experiments. Am Miner 84(9):1333–1335
Truckenbrodt J, Ziegenbein D, Johannes W (1997) Redox conditions in piston-cylinder apparatus: the different behavior of boron nitride and unfired pyrophyllite assemblies. Am Mineral 82(3–4):337–344
Uenver-Thiele L, Woodland AB, Seitz HM, Downes H, Altherr R (2017) Metasomatic processes revealed by trace element and redox signatures of the lithospheric mantle beneath the Massif Central, France. J Petrol 58(3):395–422. https://doi.org/10.1093/petrology/egx020
Vannice MA (1977) Catalytic synthesis of hydrocarbons from H2-CO mixtures over group VIII metals. V. Catalytic behaviour of silica supported metals. J Catal 50(2):228–236. https://doi.org/10.1016/0021-9517(77)90031-8
Woermann E, Rosenhauer M (1985) Fluid phases and the redox state of the Earth’s mantle: explorations based on experimental, phase-theoretical and petrological data. Fortschr Mineral 63(2):263–349
Wood BJ (1990) An experimental test of the spinel peridotite oxygen barometer. J Geophys Res 95(B10):15845–15851
Woodland AB, Koch M (2003) Variation in oxygen fugacity with depth in the upper mantle beneath the Kaapvaal Craton, southern Africa. Earth Planet Sci Lett 214:295–310
Woodland AB, O’Neill HS (1997) Thermodynamic data for Fe-bearing phases obtained using noble metal alloys as redox sensors. Geochimica Et Cosmochimica Acta 61(20):4359–4366. https://doi.org/10.1016/s0016-7037(97)00247-0
Yang X, Keppler H, Li Y (2016) Molecular hydrogen in mantle mienerals. Geochem Perspect 2:160–168. https://doi.org/10.7185/geochemlet.1616
Zellmer GF, Edmonds M, Straub SM (2015) Volatiles in subduction zone magmatism. Role of volatiles in the genesis. Evol Erupt Arc Magmas 410:1–17. https://doi.org/10.1144/sp410.13
Zhang C, Duan Z (2009) A model for C-O-H fluid in the Earth’s mantle. Geochim Cosmochim Acta 73:2089–2102. https://doi.org/10.1016/j.gca.2009.01.021
Zhang C, Duan ZH (2010) GFluid: an Excel spreadsheet for investigating C–O–H fluid composition under high temperatures and pressures. Comput Geosci 36(4):569–572. https://doi.org/10.1016/j.cageo.2009.05.008
Acknowledgements
The Deutsche Forschungsgemeinschaft is gratefully acknowledged for funding the project WO652/26-1. This work has benefited from discussions with Daniel J. Frost and Sonja Aulbach.
Author information
Authors and Affiliations
Corresponding author
Additional information
Communicated by Jochen Hoefs.
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Matjuschkin, V., Woodland, A.B. & Yaxley, G.M. Methane-bearing fluids in the upper mantle: an experimental approach. Contrib Mineral Petrol 174, 1 (2019). https://doi.org/10.1007/s00410-018-1536-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00410-018-1536-4