Decarbonization of siderite in the water-rich upper mantle

Abstract

The aqueous fluids within subducted slabs have the potential to influence the form of carbonate presence and the carbon cycling process. Experiments were performed on resistive heating diamond anvil cell using siderite crystals and grains with water under conditions of pressure as high as 11.4 GPa and temperatures reaching up to 530 °C. These experiments aimed to simulate geological reactions that may occur within a depth range of 340 km in subducted slabs. Raman spectroscopy was employed to monitor the reactions and microscale phenomena within the sample chamber as pressure and temperature increase. The recovered products were analyzed using scanning electron microscopy and transmission electron microscopy. The results indicate that at 0.8 GPa and 108 °C, a Fischer-Tropsch Type (FTT) reaction occurred on the sample surface, resulting in the formation of organic compound formaldehyde, followed by the observation of formic acid. At higher pressure and temperature (3.5 GPa, 420 °C), the formation of γ-Fe₂O₃ and γ-FeOOH was observed on the sample surface, accompanied by the release of CO₂ and H₂. Transmission electron microscope analysis of the quenched product powders indicated that the generated iron oxides were consistent with the phases observed at high pressure and temperature conditions. High pressure and temperature dissolution experiments of siderite in water reveal that carbon may be released into the mantle wedge entirely in the form of CO₂ in warm subducted slabs and cold subducted slabs that subduct to depths of 75 km. The released CO₂ participates in the carbon cycle of the island arc volcanic systems in the upper mantle at depths of 70–120 km and accelerates the transfer of subducted carbon to the Earth’s surface.

Keywords

Siderite / Water / Dissolution / Decarbonization / Carbon dioxide / Carbon cycle

References

Y. Bang, H. Hwang, T. Kim, H. Cynn, Y. Park, H. Jung, C. Park, D. Popov, V.B. Prakapenka, L. Wang. The stability of subducted glaucophane with the Earth’s secular cooling. Nat. Commun., 12 (2021), p. 1496,

J. Binck, L. Bayarjargal, S.S. Lobanov, W. Morgenroth, R. Luchitskaia, C.J. Pickard, V. Milman, K. Refson, D.B. Jochym, P. Byrne. Phase stabilities of MgCO3 and MgCO3-II studied by Raman spectroscopy, X-ray diffraction, and density functional theory calculations. Phys. Rev. Mater., 4 (2020), Article 055001,

Y.-X. Chen, A. Demény, H.-P. Schertl, Y.-F. Zheng, F. Huang, K. Zhou, Q.-Z. Jin, X.-P. Xia. Tracing subduction zone fluids with distinct Mg isotope compositions: Insights from high-pressure metasomatic rocks (leucophyllites) from the Eastern Alps. Geochim. Cosmochim. Acta, 271 (2020), pp. 154-178,

C. ChengYe, W. QinXian, C. DuoF. Genesis of siderite in Miocene marine shale in Kuohsing area, Taiwan. Acta Sedimentol. Sinica, 40 (2022), 10.14027/j.issn.1000-0550.2021.047

P. Colomban, S. Cherifi, G. Despert. Raman identification of corrosion products on automotive galvanized steel sheets. J. Raman Spectrosc., 39 (2008), pp. 881-886,

F. Datchi, A. Dewaele, Y. Le Godec, P. Loubeyre. Equation of state of cubic boron nitride at high pressures and temperatures. Phys. Rev. B, 75 (2007), Article 214104,

F. Datchi, V.M. Giordano, P. Munsch, A.M. Saitta. Structure of carbon dioxide phase IV: Breakdown of the intermediate bonding state scenario. Phys. Rev. Lett., 103 (2009), Article 185701,

D.L. De Faria, S. Venâncio Silva, M.T. de Oliveira. Raman microspectroscopy of some iron oxides and oxyhydroxides. J. Raman Spectrosc., 28 (1997), pp. 873-878,

D.P. Dobson, P.G. Meredith, S.A. Boon. Simulation of subduction zone seismicity by dehydration of serpentine. Science, 298 (2002), pp. 1407-1410,

S. Farsang, M. Louvel, C. Zhao, M. Mezouar, A.D. Rosa, R.N. Widmer, X. Feng, J. Liu, S.A. Redfern. Deep carbon cycle constrained by carbonate solubility. Nat. Commun., 12 (2021), p. 4311,

Y. Fei, Mao, H.k., Hemley, R.J.,. Thermal expansivity, bulk modulus, and melting curve of H2O-ice VII to 20 GPa. J. Chem. Phys., 99 (1993), pp. 5369-5373,

Hacker, B.R., Abers, G.A., Peacock, S.M., 2003. Subduction factory 1. Theoretical mineralogy, densities, seismic wave speeds, and H2O contents. J. Geophys. Res., Solid Earth 108, 2029. DOI:

J.A. Hernandez, R. Caracas. Proton dynamics and the phase diagram of dense water ice. J. Chem. Phys., 148 (2018), Article 214501,

N.G. Holm, J.L. Charlou. Initial indications of abiotic formation of hydrocarbons in the Rainbow ultramafic hydrothermal system, Mid-Atlantic Ridge. Earth Planet. Sci. Lett., 191 (2001), pp. 1-8,

W.-P. Hsieh, Y.-H. Chien. High pressure Raman spectroscopy of H2O-CH3OH mixtures. Sci. Rep., 5 (2015), p. 8532,

H.L. James. Sedimentary facies of iron-formation. Econ. Geol., 49 (1954), pp. 235-293,

N. Kang, M.W. Schmidt, S. Poli, E. Franzolin, J.A. Connolly. Melting of siderite to 20 GPa and thermodynamic properties of FeCO3-melt. Chem. Geol., 400 (2015), pp. 34-43,

W. Kenan, W. Benshan, X. Wansheng, X. Shiping, L. Guangcai, Z. Huizi. Experimental study on hydrocarbon formation due to reactions between carbonates and water or water-bearing minerals in deep earth. Chinese J. Geochem., 18 (1999), pp. 115-120,

F. Klein, W. Bach, N. Jöns, T. McCollom, B. Moskowitz, T. Berquó. Iron partitioning and hydrogen generation during serpentinization of abyssal peridotites from 15°N on the Mid-Atlantic Ridge. Geochim. Cosmochim. Acta, 73 (2009), pp. 6868-6893,

A.P. Lee, J. Webb, D.J. Macey, W. van Bronswijk, A.R. Savarese, G.C. de Witt. In situ Raman spectroscopic studies of the teeth of the chiton Acanthopleura hirtosa. J. Biol. Inorg. Chem., 3 (1998), pp. 614-619,

X. Li, Z. Zhang, J.F. Lin, H. Ni, V.B. Prakapenka, Z. Mao. New high-pressure phase of CaCO3 at the topmost lower mantle: Implication for the deep-mantle carbon transportation. Geophys. Res. Lett., 45 (2018), pp. 1355-1360,

J. Liu, J.-F. Lin, V.B. Prakapenka. High-pressure orthorhombic ferromagnesite as a potential deep-mantle carbon carrier. Sci. Rep., 5 (2015), p. 7640,

Y. Luo, D. Zhu, J. Pan, X. Zhou. Thermal decomposition behaviour and kinetics of Xinjiang siderite ore. Min. Process. Extr. Metall., 125 (2016), pp. 17-25,

C.E. Manning, M.L. Frezzotti. Subduction-zone fluids. Elements, 16 (2020), pp. 395-400,

M. Marocchi, H. Bureau, G. Fiquet, F. Guyot. In-situ monitoring of the formation of carbon compounds during the dissolution of iron(II) carbonate (siderite). Chem. Geol., 290 (2011), pp. 145-155,

T.M. McCollom. Formation of meteorite hydrocarbons from thermal decomposition of siderite (FeCO3). Geochim. Cosmochim. Acta, 67 (2003), pp. 311-317,

T.M. McCollom, B.R. Simoneit. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate. Orig. Life Evol. Biosph., 29 (1999), pp. 167-186,

V. Milesi, F. Guyot, F. Brunet, L. Richard, N. Recham, M. Benedetti, J. Dairou, A. Prinzhofer. Formation of CO2, H2 and condensed carbon from siderite dissolution in the 200–300 ℃ range and at 50 MPa. Geochim. Cosmochim. Acta, 154 (2015), pp. 201-211,

D.R. Mitchell. DiffTools: Electron diffraction software tools for DigitalMicrograph™. Microsc. Res. Tech., 71 (2008), pp. 588-593,

P.S. Mozley. Relation between depositional environment and the elemental composition of early diagenetic siderite. Geology, 17 (1989), pp. 704-706,

M. Munoz, W.R. Premo, P. Courjault-Rade. Sm–Nd dating of fluorite from the worldclass Montroc fluorite deposit, southern Massif Central, France. Miner. Depos., 39 (2005), pp. 970-975,

M. Nieuwoudt, J. Comins, I. Cukrowski. The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro-spectroscopy and electrochemical polarisation. Part I: near-resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds. J. Raman Spectrosc., 42 (2011), pp. 1335-1339,

S.J. Oh, D. Cook, H. Townsend. Characterization of iron oxides commonly formed as corrosion products on steel. Hyperfine Interact., 112 (1998), pp. 59-66,

S.M. Peacock. Fluid processes in subduction zones. Science, 248 (1990), pp. 329-337,

C.J. Pickard, R.J. Needs. Structures and stability of calcium and magnesium carbonates at mantle pressures. Phys. Rev. B, 91 (2015), Article 104101,

T. Plank, C.E. Manning. Subducting carbon. Nature, 574 (2019), pp. 343-352,

V.B. Prakapenka, N. Holtgrewe, S.S. Lobanov, A.F. Goncharov. Structure and properties of two superionic ice phases. Nat. Phys., 17 (2021), pp. 1233-1238,

A.V. Romanenko, S.V. Rashchenko, A. Kurnosov, L. Dubrovinsky, S.V. Goryainov, A.Y. Likhacheva, K.D. Litasov. Single-standard method for simultaneous pressure and temperature estimation using Sm2+: SrB4O7 fluorescence. J. Appl. Phys., 124 (2018), Article 165902,

Z. Ronghua, H. Shumin, Z. Xuetong. Kinetics of hydrothermal reactions of minerals in near-critical and supercritical water. Acta Geol. Sin-Engl., 74 (2000), pp. 400-405,

L.B. Salviano, Cardoso, T.M.D.S., Silva, G.C., Dantas, M.S.S., Ferreira, A.D.M.. Microstructural assessment of magnetite nanoparticles (Fe3O4) obtained by chemical precipitation under different synthesis conditions. Mater. Res., 21 (2018), p. e20170764

N. Sleep, A. Meibom, T. Fridriksson, R. Coleman, D. Bird. H2-rich fluids from serpentinization: geochemical and biotic implications. Proc. Natl. Acad. Sci. USA, 101 (2004), pp. 12818-12823,

E.M. Syracuse, P.E. van Keken, G.A. Abers. The global range of subduction zone thermal models. Phys. Earth Planet. Inter., 183 (2010), pp. 73-90,

R. Tao, Y. Fei, L. Zhang. Experimental determination of siderite stability at high pressure. Am. Mineral., 98 (2013), pp. 1565-1572,

Taylor, L.A., Mao, H., Bell, P., 1973. “ Rust” in the Apollo 16 rocks, in: Proceedings of the Lunar Science Conference, 829-839.

R.J. Thibeau, C.W. Brown, R.H. Heidersbach. Raman spectra of possible corrosion products of iron. Appl. Spectrosc., 32 (1978), pp. 532-535,

V. Vadillo, J. Sánchez-Oneto, J.R. Portela, E.J. Martínez de la Ossa. Chapter 10 - Supercritical Water Oxidation. S.C. Ameta, R. Ameta (Eds.), Advanced Oxidation Processes for Waste Water Treatment, Academic Press (2018), pp. 333-358

S.J. Wang, S.G. Li. Magnesium isotope geochemistry of the carbonate-silicate system in subduction zones. Natl. Sci. Rev., 9, nwac036 (2022),

X. Wang, Z. Ouyang, S. Zhuo, M. Zhang, G. Zheng, Y. Wang. Serpentinization, abiogenic organic compounds, and deep life. Sci. China Earth Sci., 57 (2014), pp. 878-887,

Z. Zhang, Z. Mao, X. Liu, Y. Zhang, J. Brodholt. Stability and reactions of CaCO3 polymorphs in the Earth's deep mantle. J. Geophys. Res. Solid Earth, 123 (2018), pp. 6491-6500,