XANES spectroscopy of sulfides stable under reducing conditions
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Brendan A. Anzures
,
Stephen W. Parman
Abstract
X‑ray absorption near-edge structure (XANES) spectroscopy is a powerful technique to quan‑ titatively investigate sulfur speciation in geologically complex materials such as minerals, glasses, soils, organic compounds, industrial slags, and extraterrestrial materials. This technique allows non-destructive investigation of the coordination chemistry and oxidation state of sulfur species ranging from sulfide (2– oxidation state) to sulfate (6+ oxidation state). Each sulfur species has a unique spectral shape with a characteristic K-edge representing the s → p and d hybridization photoelectron transitions. As such, sulfur speciation is used to measure the oxidation state of samples by comparing the overall XANES spectra to that of reference compounds. Although many S XANES spectral standards exist for terrestrial applications under oxidized conditions, new sulfide standards are needed to investigate reduced (oxygen fugacity, fO2, below IW) silicate systems relevant for studies of extraterrestrial ma‑ terials and systems. Sulfides found in certain meteorites (e.g., enstatite chondrites and aubrites) and predicted to exist on Mercury, such as CaS (oldhamite), MgS (niningerite), and FeCr2S4 (daubréelite), are stable at fO2 below IW-3 but rapidly oxidize to sulfate and/or produce sulfurous gases under terrestrial surface conditions. XANES spectra of these compounds collected to date have been of variable quality, possibly due to the unstable nature of certain sulfides under typical (e.g., oxidizing) laboratory conditions. A new set of compounds was prepared for this study and their XANES spectra are analyzed for comparison with potential extraterrestrial analogs. S K-edge XANES spectra were collected at Argonne National Lab for FeS (troilite), MnS (alabandite), CaS (oldhamite), MgS (niningerite), Ni1–xS, NiS2, CaSO4 (anhydrite), MgSO4, FeSO4, Fe2(SO4)3, FeCr2S4 (daubréelite), Na2S, Al2S3, Ni7S6, and Ni3S2; the latter five were analyzed for the first time using XANES. These standards expand upon the existing S XANES end-member libraries at a higher spectral resolution (0.25 eV steps) near the S K-edge. Processed spectra, those that have been normalized and “flattened,” are compared to quantify uncertainties due to data processing methods. Future investigations that require well-characterized sulfide standards, such as the ones presented here, may have important implications for understanding sulfur speciation in reduced silicate glasses and minerals with applications for the early Earth, Moon, Mercury, and enstatite chondrites.
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Funding
We acknowledge the experimental and analytical facilities at Brown University and GeoSoilEnviroCars (Sector 13), Advanced Photon Source, Argonne National Laboratory. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We acknowledge the funding of NASA grant no. NNX15AH63G and NASA Earth and Space Sciences fellowship no. 80NSSC18K1245.
References cited
Bunker, G., and Stern, E.A. (1984) Experimental study of multiple scattering in X-ray-absorption near-edge structure. Physical Review Letters, 52, 13–16.10.1103/PhysRevLett.52.1990Suche in Google Scholar
Farrell, S.P., and Fleet, M.E. (2001) Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]. Physics and Chemistry of Minerals, 28, 17–27.10.1007/s002690000129Suche in Google Scholar
Farrell, S.P., Fleet, M.E., Stekhin, I.E., Kravtsova, A.N., Soldatov, A.V., and Liu, X. (2002a) Evolution of local electronic structure in alabandite and niningerite solid solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using sulfur K- and L-edge XANES spectroscopy. American Mineralogist, 87, 1321–1332.10.2138/am-2002-1007Suche in Google Scholar
Farrell, S.P., Stekhin, I., and Soldatov, A. (2002b) In situ analysis of the formation steps of the gold nanoparticles synthesis XANES spectroscopy: shape resonances and multiple scattering final states. American Mineralogist, 87, 1321–1332.10.2138/am-2002-1007Suche in Google Scholar
Fleet, M.E. (1972) The crystal structure of α-Ni7S6. Acta Crystallographica, B28, 1237–1241.10.1107/S0567740872004029Suche in Google Scholar
Fleet, M.E. (2005) XANES spectroscopy of sulfur in Earth materials. Canadian Mineralo‑ gist, 43, 1811–1838.10.2113/gscanmin.43.6.1811Suche in Google Scholar
Fogel, R.A. (2005) Aubrite basalt vitrophyres: The missing basaltic component and high-sulfur silicate melts. Geochimica et Cosmochimica Acta, 69, 1633–1648.10.1016/j.gca.2003.11.032Suche in Google Scholar
Head, E.M., Lanzirotti, A., Newville, M., and Sutton, S. (2018) Vanadium, sulfur, and iron valences in melt inclusions as a window into magmatic processes: A case study at Nyamuragira volcano, Africa. Geochimica et Cosmochimica Acta, 226, 149–173.10.1016/j.gca.2018.01.033Suche in Google Scholar
Holzheid, A., and Grove, T.L. (2002) Sulfur saturation limits in silicate melts and their implications for core formation scenarios for terrestrial planets. American Mineralogist, 87, 227–237.10.2138/am-2002-2-304Suche in Google Scholar
Kravtsova, A.N., Stekhin, I.E., Soldatov, A.V., Liu, X., and Fleet, M.E. (2004) Electronic structure of MS (M = Ca, Mg, Fe, Mn): X‑ray absorption analysis. Physical Review B, 69, 134109.10.1103/PhysRevB.69.134109Suche in Google Scholar
Langman, J.B., Blowes, D.W., Veeramani, H., Wilson, D., Smith, L., Sego, D.C., and Paktunc, D. (2015) The mineral and aqueous phase evolution of sulfur and nickel with weathering of pyrrhotite in a low sulfide, granitic waste rock. Chemical Geology, 401, 169–179.10.1016/j.chemgeo.2015.02.024Suche in Google Scholar
Li, D., Bancroft, G.M., Kasrai, M., Fleet, M.E., Feng, X.H., Yang, B.X., and Tan, K.H. (1994) S K- and L-edge XANES and electronic structure of some copper sulfide minerals. Physics and Chemistry of Minerals, 21, 317–324.10.1007/BF00202096Suche in Google Scholar
Li, D., Bancroft, G.M., Kasrai, M., and Fleet, M.E. (1995) S K- and L-edge X‑ray absorption spectroscopy of metal sulfides and sulfates: applications in mineralogy and geochemistry. Canadian Mineralogist, 33, 949–960.Suche in Google Scholar
Namur, O., Collinet, M., Charlier, B., Grove, T.L., Holtz, F., and McCammon, C. (2016a) Melting processes and mantle sources of lavas on Mercury. Earth and Planetary Science Letters, 439, 117–128.10.1016/j.epsl.2016.01.030Suche in Google Scholar
Namur, O., Charlier, B., Holtz, F., Cartier, C., and McCammon, C. (2016b) Sulfur solubility in reduced mafic silicate melts: Implications for the speciation and dis‑ tribution of sulfur on Mercury. Earth and Planetary Science Letters, 448, 102–114.10.1016/j.epsl.2016.05.024Suche in Google Scholar
Nash, W.M., Smythe, D.J., and Wood, B.J. (2019) Compositional and temperature effects on sulfur speciation and solubility in silicate melts. Earth and Planetary Science Letters, 507, 187–198.10.1016/j.epsl.2018.12.006Suche in Google Scholar
Nittler, L.R., Starr, R.D., Weider, S.Z., McCoy, T.J., Boynton, W. V., Ebel, D.S., Ernst, C.M., Evans, L.G., Goldsten, J.O., Hamara, D.K., and others (2011) The major-element composition of Mercury’s surface from MESSENGER X‑ray spectrometry. Science, 333, 1847–1850.10.1126/science.1211567Suche in Google Scholar PubMed
Osborne, M.D., and Fleet, M.E. (1984) Mossbauer Investigation of Niningerite Solid Solutions (Mg, Fe)S. Physics and Chemistry of Minerals, 10, 245–249.10.1007/BF00311948Suche in Google Scholar
Pauling, L. (1960) The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chemistry. Cornell University Press, Ithaca, New York.Suche in Google Scholar
Ravel, B., and Newville, M. (2005) Data analysis for XAS using IFEFFIT computer programs. Journal of Synchrotron Radiation, 12, 537–541.10.1107/S0909049505012719Suche in Google Scholar PubMed
Settle, J. (2006) On the effect of variable endmember spectra in the linear mixture model. IEEE Transactions on Geoscience and Remote Sensing, 44, 389–396.10.1109/TGRS.2005.860983Suche in Google Scholar
Soldatov, A.V., Kravtsova, A.N., Fleet, M.E., and Harmer, S.L. (2004) Electronic structure of MeS (Me = Ni, Co, Fe): X‑ray absorption analysis. Journal of Physics: Condensed Matter, 16, 7545–7556.10.1088/0953-8984/16/41/031Suche in Google Scholar
Somers, B., Asner, G.P., Tits, L., and Coppin, P. (2011) Endmember variability in Spectral Mixture Analysis: A review. Remote Sensing of Environment, 115, 1603–1616.10.1016/j.rse.2011.03.003Suche in Google Scholar
Stockstill-Cahill, K.R., McCoy, T.J., Nittler, L.R., Weider, S.Z., and Hauck, S.A. (2012) Magnesium-rich crustal compositions on mercury: Implications for magmatism from petrologic modeling. Journal of Geophysical Research E: Planets, 117.10.1029/2012JE004140Suche in Google Scholar
Tompkins, S., Mustard, J.F., Pieters, C.M., and Forsyth, D.W. (1997) Optimization of endmembers mixture analysis for spectral. Remote Sensing of Environment, 59, 472–489.10.1016/S0034-4257(96)00122-8Suche in Google Scholar
Webb, S.M. (2005) SIXPack a graphical user interface for XAS analysis using IFEFFIT. Physica Scripta, 2005, 1011.10.1238/Physica.Topical.115a01011Suche in Google Scholar
Weisberg, M.K., Prinz, M., and Nehru, C.E. (1988) Petrology of ALH85085: a chondrite with unique characteristics. Earth and Planetary Science Letters, 91, 19–32.10.1016/0012-821X(88)90148-3Suche in Google Scholar
Wilke, M., Klimm, K., and Kohn, S.C. (2011) Spectroscopic studies on sulfur speciation in synthetic and natural glasses. Reviews in Mineralogy and Geochemistry, 73, 41–78.10.1515/9781501508370-003Suche in Google Scholar
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Artikel in diesem Heft
- Heavy halogen geochemistry of martian shergottite meteorites and implications for the halogen composition of the depleted shergottite mantle source
- The distribution and abundance of halogens in eclogites: An in situ SIMS perspective of the Raspas Complex (Ecuador)
- Pressure dependence of Si diffusion in γ-Fe
- Seismic detectability of carbonates in the deep Earth: A nuclear inelastic scattering study
- Equations of state, phase relations, and oxygen fugacity of the Ru-RuO2 buffer at high pressures and temperatures
- Experimental determination of the phase relations of Pt and Pd antimonides and bismuthinides in the Fe-Ni-Cu sulfide systems between 1100 and 700 °C
- Layer stacking disorder in Mg-Fe chlorites based on powder X-ray diffraction data
- Elasticity of single-crystal Fe-enriched diopside at high-pressure conditions: Implications for the origin of upper mantle low-velocity zones
- XANES spectroscopy of sulfides stable under reducing conditions
- Zircon and apatite geochemical constraints on the formation of the Huojihe porphyry Mo deposit in the Lesser Xing’an Range, NE China
- Textural and compositional evolution of iron oxides at Mina Justa (Peru): Implications for mushketovite and formation of IOCG deposits
- Siwaqaite, Ca6Al2(CrO4)3(OH)12·26H2O, a new mineral of the ettringite group from the pyrometamorphic Daba-Siwaqa complex, Jordan
- Negevite, the pyrite-type NiP2, a new terrestrial phosphide
- Transjordanite, Ni2P, a new terrestrial and meteoritic phosphide, and natural solid solutions barringerite-transjordanite (hexagonal Fe2P–Ni2P)
