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The stability and composition of sulfate melts in arc magmas

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Abstract

The stability field and composition of immiscible sulfate melts in equilibrium with silicate magmas has been determined using experiments over a range of crustal pressures, allowing an assessment of their possible role in transporting sulfur into the sub-volcanic arc and porphyry copper deposit systems. Experimental starting materials were based on natural trachyandesite and trachydacite compositions, with 3.5–7 wt% H2O and 3.5–5.5 wt% sulfur added to produce large, analyzable amounts of sulfate phases. Conditions ranged over 800–1200 °C, 0.2-1GPa and ƒO2 > NNO + 2.5. Sulfate melts formed at temperatures above 1000 °C at 0.75 and 1 GPa and above 900 °C at 0.2 GPa, suggesting some pressure dependence on their stability. At temperatures below 1100 °C sulfate melts and anhydrite crystals commonly coexist. Sulfate melts quenched to an intergrowth that was difficult to prepare for analysis. However, the composition was approximated by EPMA and further constrained by mass balance calculations. Sulfate melts were dominated by CaO and SO3, but also contained, in order of decreasing abundance, Na2O, K2O, MgO, FeO, Cl and P2O5. Chlorine showed a particular preference for the sulfate melt relative to the coexisting silicate melt, and calculated partition coefficients for sulfate/silicate melts were 5–13 at 1200 °C, 0.75–1 GPa. Experimental data show that, in the absence of an exsolved, hydrous fluid phase, sulfate melts can form in natural arc magmas at near-liquidus temperatures ≥ 1000 °C, assuming that magmas are oxidized and contain sufficient sulfur (> 2000–3000 ppm S). These results suggest that sulfate melt could be an important component in transporting sulfur as well as chlorine to shallow levels in the crust for hydrous magmas under a specific range of conditions. Both the non-quenchable and water-soluble nature of sulfate melts (and anhydrite) make them difficult to identify, unless trapped as mineral inclusions similar to the “wormy anhydrite” trapped in high-temperature amphiboles from Yanacocha, Peru.

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the source of additional water is the hydration of sulfate powders used as starting materials

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References

  • Alt JC, Shanks WC III, Jackson MC (1993) Cycling of sulfur in subduction zones: the geochemistry of sulfur in the Mariana Island Arc and back-arc trough. Earth Planet Sci Lett 119:477–494

    Google Scholar 

  • Andres RJ, Rose WI, Kyle PR, DeSilva S, Francis P, Gardeweg M, Moreno Roa H (1991) Excessive sulfur dioxide emissions from Chilean volcanoes. J Volcanol Geotherm Res 46:323–329

    Google Scholar 

  • Arculus RJ, Johnson RW, Chappell BW, McKee CO, Sakai H (1983) Ophiolite-contaminated andesites, trachybasalts, and cognate inclusions of Mount Lamington, Papua New Guinea: anhydrite-amphibole-bearing lavas and the 1951 cumulodome. J Volcanol Geotherm Res 18:215–247

    Google Scholar 

  • Baker DR, Moretti R (2011) Modeling the solubility of sulfur in magmas: a 50-year old geochemical challenge. Rev Mineral Geochem 73:167–213

    Google Scholar 

  • Bernard A, Demaiffe D, Mattielli N, Punongbayan RS (1991) Anhydrite-bearing pumices from Mount Pinatubo: further evidence for the existence of sulphur-rich silicic magmas. Nature 354:139–140

    Google Scholar 

  • Blundy JD, Cashman K (2005) Rapid decompression-driven crystallization recorded by melt inclusions from Mount St Helens volcano. Geology 33:793–796

    Google Scholar 

  • Blundy JD, Mavrogenes J, Tattitch B, Sparks S, Gilmer A (2015) Generation of porphyry copper deposits by gas–brine reaction in volcanic arcs. Nat Geosci 8:235–240

    Google Scholar 

  • Botcharnikov RE, Linnen RL, Holtz F (2010) Solubility of Au in Cl- and S-bearing hydrous silicate melts. Geochim Cosmochim Acta 74:2396–2411

    Google Scholar 

  • Brooker R, Holloway JR, Hervig R (1998) Reduction in piston-cylinder experiments: the detection of carbon infiltration into platinum capsules. Am Mineral 83:985–994

    Google Scholar 

  • Brooker RA, Kjarsgaard BA (2011) Silicate–carbonate liquid immiscibility and phase relations in the system SiO2–Na2O–Al2O3–CaO–CO2 at 0·1–2·5 GPa with applications to carbonatite genesis. J Petrol 52:1281–1305

    Google Scholar 

  • Burnham CW (1979) The importance of volatile constituents. In: Yoder HS (ed) The evolution of the igneous rocks. Princeton University Press, Princeton, NJ, pp 439–482

    Google Scholar 

  • Carmichael ISE, Turner FJ, Verhoogen J (1974) Igneous Petrology. McGraw-Hill

  • Carroll MR, Rutherford MJ (1985) Sulfide and sulfate saturation in hydrous silicate melts. J Geophys Res 90:C601–C612

    Google Scholar 

  • Carroll MR, Rutherford MJ (1987) The stability of igneous anhydrite: experimental results and implications for sulfur behavior in the 1982 El Chichon Trachyandesite and Other Evolved Magmas. J Petrol 28:781–801

    Google Scholar 

  • Carroll MR, Rutherford MJ (1988) Sulfur speciation in hydrous experimental glasses of varying oxidation state–results from measured wavelength shifts of sulfur X-rays. Am Mineral 73:845–849

    Google Scholar 

  • Chambefort I, Dilles JH, Kent AJR (2008) Anhydrite-bearing andesite and dacite as a source for sulfur in magmatic-hydrothermal mineral deposits. Geology 36:719–722

    Google Scholar 

  • Chambefort I, Dilles JH, Longo AA (2013) Amphibole Geochemistry of the Yanacocha Volcanics, Peru: Evidence for Diverse Sources of Magmatic Volatiles Related to Gold Ores. J Petrology 54:1017–1046

    Google Scholar 

  • Clémente B, Scaillet B, Pichavant M (2004) The solubility of sulphur in hydrous rhyolitic melts. J Petrol 45:2171–2196

    Google Scholar 

  • Costa F, Scaillet B, Pichavant M (2004) Petrological and experimental constraints on the pre-eruption conditions of Holocene dacite from Volcán San Pedro (36 S, Chilean Andes) and the importance of sulphur in silicic subduction-related magmas. J Petrol 45:855–881

    Google Scholar 

  • Coursol P, Pelton AD, Chartrand P, Zamalloa M (2005) The CaSO4–Na2SO4–CaO phase diagram. Can Metall Q 44:537–546

    Google Scholar 

  • de Hoog JCM, Taylor BE, van Bergen MJ (2001) Sulfur isotope systematics of basaltic lavas from Indonesia: implications for the sulfur cycle in subduction zones. Earth Planet Sci Lett 189:237–252

    Google Scholar 

  • Devine JD, Gardner JE, Brack HP, Layne GD, Rutherford MJ (1995) Comparison of microanalytical methods for estimating H2O contents of silicic volcanic glasses. Am Mineral 80:319–328

    Google Scholar 

  • Dickson FW, Blount CW, Tunell G (1963) Use of hydrothermal solution equipment to determine the solubility of anhydrite in water from 100 °C to 275 °C and from 1 bar to 1000 bars pressure. Am J Sci 261:61–78

    Google Scholar 

  • Dilles JH (1987) Petrology of the Yerington Batholith, Nevada; evidence for evolution of porphyry copper ore fluids. Econ Geol 82:1750–1789

    Google Scholar 

  • Dirksen O, Humphreys MCS, Pletchov P, Melnik O, Demyanchuk Y, Sparks RSJ, Mahony S (2006) The 2001–2004 dome-forming eruption of Shiveluch volcano, Kamchatka: observation, petrological investigation and numerical modelling. J Volcanol Geotherm Res 155:201–226

    Google Scholar 

  • D’Souza RJ, Canil D (2018) Effect of alkalinity on sulfur concentration at sulfide saturation in hydrous basaltic andesite to shoshonite melts at 1270°C and 1 GPa. Am Mineral 103:1030–1043

    Google Scholar 

  • Du H (2000) Thermodynamic assessment of the K2SO4-Na2SO4–MgSO4–CaSO4 system. J Phase Equilibria 21:6

    Google Scholar 

  • Eugster HP (1957) Heterogeneous reactions involving oxidation and reduction at high pressures and temperatures. J Chem Phys 26:1760–1761

    Google Scholar 

  • Freestone IC, Hamilton DL (1980) The role of liquid immiscibility in the genesis of carbonatites—an experimental study. Contrib Mineral Petrol 73:105–117

    Google Scholar 

  • Ghiorso MS, Evans BW (2008) Thermodynamics of Rhombohedral Oxide Solid Solutions and a Revision of the Fe-Ti Two-Oxide Geothermometer and Oxygen-Barometer. Am J Sci 308:957–1039

    Google Scholar 

  • Ghiorso MS, Gualda GAR (2015) An H2O–CO2 mixed fluid saturation model compatible with rhyolite-MELTS. Contrib Mineral Petrol 169:53

    Google Scholar 

  • Grove TL, Elkins-Tanton LT, Parman SW, Chatterjee N, Müntener O, Gaetani GA (2003) Fractional crystallization and mantle-melting controls on calc-alkaline differentiation trends. Contrib Mineral Petrol 145:515–533

    Google Scholar 

  • Gustafson LB, Hunt JP (1975) The porphyry copper deposit at El Salvador, Chile. Econ Geol 70:857–912

    Google Scholar 

  • Hannington M, Herzig P, Stoffers P, Scholten J, Botz R, Garbe-Schönberg D, Jonasson IR, Roest W (2001) First observations of high-temperature submarine hydrothermal vents and massive anhydrite deposits off the north coast of Iceland. Mar Geol 177:199–220

    Google Scholar 

  • Huang R, Keppler H (2015) Anhydrite stability and the effect of Ca on the behavior of sulfur in felsic magmas. Am Mineral 100:257–266

    Google Scholar 

  • Humphris SE, Bach W (2005) On the Sr isotope and REE compositions of anhydrites from the TAG seafloor hydrothermal system. Geochim Cosmochim Acta 69:1511–1525

    Google Scholar 

  • Hutchinson MC, Dilles JH (2019) Evidence for magmatic anhydrite in porphyry copper intrusions. Econ Geol 114:143–152

    Google Scholar 

  • Jakobsson S, Blundy J, Moore G (2014) Oxygen fugacity control in piston-cylinder experiments: a re-evaluation. Contrib Mineral Petrol 167:1007

    Google Scholar 

  • Jugo PJ, Luth RW, Richards JP (2005a) Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts. Geochim Cosmochim Acta 69:497–503

    Google Scholar 

  • Jugo PJ, Luth RW, Richards JP (2005b) An experimental study of the sulfur content in basaltic melts saturated with immiscible sulfide or sulfate liquids at 1300°C and 1·0 GPa. J Petrol 46:783–798

    Google Scholar 

  • Klimm K, Kohn SC, Botcharnikov RE (2012) The dissolution mechanism of sulphur in hydrous silicate melts. II: Solubility and speciation of sulphur in hydrous silicate melts as a function of fO2. Chem Geol 322–323:250–267

    Google Scholar 

  • Krawczynski MJ, Grove TL, Behrens H (2012) Amphibole stability in primitive arc magmas: effects of temperature, H2O content, and oxygen fugacity. Contrib Mineral Petrol 164:317–339

    Google Scholar 

  • Kress VC, Carmichael IS (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

    Google Scholar 

  • Larsen JF, Nye CJ, Coombs ML, Tilman M, Izbekov P, Cameron C (2010) Petrology and geochemistry of the 2006 eruption of Augustine Volcano: Chapter 15 in The 2006 eruption of Augustine Volcano. Alaska, US Geological Survey

    Google Scholar 

  • Li C, Ripley EM (2009) Sulfur contents at sulfide-liquid or anhydrite saturation in silicate melts: empirical equations and example applications. Econ Geol 104:405–412

    Google Scholar 

  • Liu Y, Samaha N-T, Baker DR (2007) Sulfur concentration at sulfide saturation (SCSS) in magmatic silicate melts. Geochim Cosmochim Acta 71:1783–1799

    Google Scholar 

  • Le Voyer M, Rose-Koga EF, Shimizu N, Grove TL, Schiano P (2010) Two contrasting H2O-rich components in primary melt inclusions from Mount Shasta. J Petrol 51:1571–1595

    Google Scholar 

  • Luhr JF (1990) Experimental phase relations of water-and sulfur-saturated arc magmas and the 1982 eruptions of El Chichón volcano. J Petrol 31:1071–1114

    Google Scholar 

  • Luhr JF (2008) Primary igneous anhydrite: Progress since its recognition in the 1982 El Chichón trachyandesite. J Volcanol Geotherm Res 175:394–407

    Google Scholar 

  • Luhr JF, Carmichael ISE, Varekamp JC (1984) The 1982 eruptions of El Chichón Volcano, Chiapas, Mexico: Mineralogy and petrology of the anhydrite bearing pumices. J Volcanol Geotherm Res 23:69–108

    Google Scholar 

  • Luhr JF, Logan MAV (2002) Sulfur isotope systematics of the 1982 El Chichón trachyandesite: an ion microprobe study. Geochim Cosmochim Acta 66:3303–3316

    Google Scholar 

  • Maria AH, Luhr JF (2008) Lamprophyres, basanites, and basalts of the Western Mexican volcanic belt: volatile contents and a vein-wallrock melting relationship. J Petrol 49:2123–2156

    Google Scholar 

  • Masotta M, Keppler H (2015) Anhydrite solubility in differentiated arc magmas. Geochim Cosmochim Acta 158:79–102

    Google Scholar 

  • Masotta M, Keppler H, Chaudhari A (2016) Fluid-melt partitioning of sulfur in differentiated arc magmas and the sulfur yield of explosive volcanic eruptions. Geochim Cosmochim Acta 176:26–43

    Google Scholar 

  • 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 171:66

    Google Scholar 

  • Matjuschkin V, Brooker RA, Tattitch B, Blundy JD, Stamper CC (2015) Control and monitoring of oxygen fugacity in piston cylinder experiments. Contrib Mineral Petrol 169:9

    Google Scholar 

  • Matthews SJ, Gardeweg MC, Sparks RSJ (1997) The 1984 to 1996 cyclic activity of Lascar Volcano, northern Chile: cycles of dome growth, dome subsidence, degassing and explosive eruptions. Bull Volcanol 59:72–82

    Google Scholar 

  • Matthews SJ, Sparks RSJ, Gardeweg MC (1999) The Piedras Grandes-Soncor Eruptions, Lascar Volcano, Chile; Evolution of a Zoned Magma Chamber in the Central Andean Upper Crust. J Petrol 40:1891–1919

    Google Scholar 

  • McDade P, Wood BJ, Van Westrenen W, Brooker R, Gudmundsson G, Soulard H, Najorka J, Blundy J (2002) Pressure corrections for a selection of piston-cylinder cell assemblies. Mineral Mag 66:1021–1028

    Google Scholar 

  • Métrich N, Schiano P, Clocchiatti R, Maury RC (1999) Transfer of sulfur in subduction settings: an example from Batan Island (Luzon volcanic arc, Philippines). Earth Planet Sci Lett 167:1–14

    Google Scholar 

  • Narvaez DF, Rose-Koga EF, Samaniego P, Koga KT, Hidalgo S (2018) Constraining magma sources using primitive olivine-hosted melt inclusions from Puñalica and Sangay volcanoes (Ecuador). Contrib Mineral Petrol 173:80

    Google Scholar 

  • Pallister JS, Hoblitt RP, Reyes AG (1992) A basalt trigger for the 1991 eruptions of Pinatubo volcano? Nature 356:426–428

    Google Scholar 

  • Ridolfi F, Renzulli A (2012) Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130° C and 2.2 GPa. Contrib Mineral Petrol 163:877–895

    Google Scholar 

  • Robie RA, Hemingway BS (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 Pascal) pressure and at higher temperatures. US Geol Surv Bull 2131:462

  • Rowe JJ, Morey GW, Silber CC (1967) The ternary system K2SO4-MgSO4-CaSO4. J Inorg Nucl Chem 29:925–942

    Google Scholar 

  • Schilling F, Wunder B (2004) Temperature distribution in piston-cylinder assemblies: numerical simulations and laboratory experiments. Eur J Mineral 16:7–14

    Google Scholar 

  • 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 167:954

    Google Scholar 

  • Stormer JC (1983) The effects of recalculation on estimates of temperature and oxygen fugacity from analyses of multicomponent iron-titanium oxides. Am Mineral 68:586–594

    Google Scholar 

  • Ulmer P (1989) Partitioning of high field strength elements among olivine, pyroxenes, garnet and calc alkaline picro-basalt: Experimental results and an application. Annual Report of the Director Geophysical Laboratory Carnegie Institution of Washington 1988–1989:42–46

    Google Scholar 

  • Varekamp JC, Luhr JF, Prestegaard KL (1984) The 1982 eruptions of El Chichón Volcano (Chiapas, Mexico): character of the eruptions, ash-fall deposits, and gas phase. J Volcanol Geotherm Res 23:39–68

    Google Scholar 

  • Veksler IV, Dorfman AM, Dulski P, Kamenetsky VS, Danyushevsky LV, Jeffries T, Dingwell DB (2012) Partitioning of elements between silicate melt and immiscible fluoride, chloride, carbonate, phosphate and sulfate melts, with implications to the origin of natrocarbonatite. Geochim Cosmochim Acta 79:20–40

    Google Scholar 

  • Vigouroux N, Wallace PJ, Kent AJR (2008) Volatiles in High-K Magmas from the Western Trans-Mexican Volcanic Belt: Evidence for Fluid Fluxing and Extreme Enrichment of the Mantle Wedge by Subduction Processes. J Petrol 49:1589–1618

    Google Scholar 

  • Wallace PJ, Edmonds M (2011) The sulfur budget in magmas: evidence from melt inclusions, submarine glasses, and volcanic gas emissions. Rev Mineral Geochem 73:215–246

    Google Scholar 

  • Watson E, Wark D, Price J, Van Orman J (2002) Mapping the thermal structure of solid-media pressure assemblies. Contrib Mineral Petrol 142:640–652

    Google Scholar 

  • Webster JD, De Vivo B (2002) Experimental and modeled solubilities of chlorine in aluminosilicate melts, consequences of magma evolution, and implications for exsolution of hydrous chloride melt at Mt. Somma-Vesuvius Am Mineral 87:1046–1061

    Google Scholar 

  • Wendlandt RF (1982) Sulfide saturation of basalt and andesite melts at high pressures and temperatures. Am Mineral 67:877–885

    Google Scholar 

  • Woodhead JD, Harmon RS, Fraser DG (1987) O, S, Sr, and Pb isotope variations in volcanic rocks from the Northern Mariana Islands: implications for crustal recycling in intra-oceanic arcs. Earth Planet Sci Lett 83:39–52

    Google Scholar 

  • Wu C (2008) Bayan Obo Controversy: Carbonatites versus Iron Oxide-Cu-Au-(REE-U). Resour Geol 58:348–354

    Google Scholar 

  • Zajacz Z, Tsay A (2019) An accurate model to predict sulfur concentration at anhydrite saturation in silicate melts. Geochim Cosmochim Acta 261:288–304

    Google Scholar 

  • Zimmer MM, Plank T, Hauri EH, Yogodzinski GM, Stelling P, Larsen J, Singer B, Jicha B, Mandeville C, Nye CJ (2010) The role of water in generating the calc-alkaline trend: new volatile data for aleutian magmas and a new tholeiitic index. J Petrol 51:2411–2444

    Google Scholar 

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Acknowledgements

Support for this project came from National Science Foundation grant EAR-1624547. Ion probe time was supported by grant IMF608/1016. We would like to express our gratitude to Frank Tepley, Stuart Kearns and Ben Buse for assistance with microprobe analyses and to Richard Hinton and Cristina Talavera for help with SIMS analyses. This study benefited greatly from discussions with Brian Tattitch and from careful reviews by Zoltan Zajacz and Matteo Masotta.

Funding

This study was funded by the National Science Foundation (NSF grant EAR-1624547). Ion probe time at the Edinburgh Ion Microprobe Facility was supported on grant IMF608/1016.

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All authors contributed to the conception of the study, and to experimental design. Experimental work, sample preparation and analytical work was performed by Michael Hutchinson with assistance from Richard Brooker. All authors contributed to the interpretation of data. The first draft of the manuscript was written by Michael Hutchinson and all authors contributed to editing of the manuscript. All authors read and approved the final manuscript.

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Hutchinson, M.C., Brooker, R.A., Dilles, J.H. et al. The stability and composition of sulfate melts in arc magmas. Contrib Mineral Petrol 175, 92 (2020). https://doi.org/10.1007/s00410-020-01729-6

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