Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter July 2, 2018

Effect of alkalinity on sulfur concentration at sulfide saturation in hydrous basaltic andesite to shoshonite melts at 1270 °C and 1 GPa

  • Rameses J. D’Souza and Dante Canil EMAIL logo
From the journal American Mineralogist


We have measured the effect of alkalis on S concentration at sulfide saturation (SCSS) in an underexplored compositional space of natural hydrous arc melts (basaltic andesite to shoshonite) at 1270 °C and 1 GPa. At an oxygen fugacity approximately 2.5 log units below the fayalite-magnetite-quartz (FMQ) buffer, SCSS increases with Na2O (562 ppm S/wt% Na2O), K2O (98 ppm S/wt% K2O), and total alkalis (88 ppm S/wt% Na2O+K2O) over the compositional range we have studied (1.6–3.1 wt% Na2O; 0–6.5 wt% K2O; 1.9–6.3 wt% FeOtot). Experiments with ~1.3 wt% H2O show approximately half the increase in SCSS with alkalinity compared to those with ~3.0 wt% H2O. Our results show a possible limit to the increase in SCSS solely by increasing alkali concentration at ~7.5 wt% total alkali concentration. Using our results and published data, we retrained earlier SCSS models to provide a better fit to test data. We also developed a new empirical model using theoretical optical basicity as a compositional parameter that predicts SCSS in the overall data set with slightly better accuracy compared to previous models:


with temperature (T) in Kelvin, pressure (P) in GPa, the optical basicity (Λ) and mole fractions (X) of FeO (calculated from Kress and Carmichael 1991), and H2O in the melt. The discrepancies between observed and predicted SCSS for our experiments of varying alkalinity reflects the heavy bias toward anhydrous, alkali-poor basalt compositions in the underlying data sets on which most models are developed.

2 Kuhn, M. Contributions from J. Wing, S. Weston, A. Williams, C. Keefer, A.Engelhardt, T. Cooper, Z. Mayer, B. Kenkel, the R Core Team, M. Benesty, R. Lescarbeau, A. Ziem, L. Scrucca, Y. Tang, C. Candan, and T. Hunt. (2017) caret: Classification and Regression Training. R package version 6.0-77.


We thank M. Raudsepp (UBC), E. Czech (UBC), and A. Locock (UA) for assistance with EPMA, A. Brolo, A. Wlasenko, and S. Konorov for assistance with the Raman measurements, and L. Coogan for helpful discussions. We are also grateful to E. Cottrell for the use of her FTIR standard glasses in our Raman work. We acknowledge the reviews from P. Jugo and an anonymous reviewer and of J. Wykes on an earlier version of this manuscript. This work was supported by a National Sciences and Engineering Research Council of Canada Discovery Grant to D. Canil.

References cited

Akella, J., and Kennedy, G.C. (1971) Melting of gold, silver, and copper—proposal for a new high-pressure calibration scale. Journal of Geophysical Research, 76, 4969–4977.10.1029/JB076i020p04969Search in Google Scholar

Ariskin, A.A., Danyushevsky, L.V., Bychkov, K.A., McNeill, A.W., Barmina, G.S., and Nikolaev, G.S. (2013) Modeling solubility of Fe-Ni sulfides in basaltic magmas: The effect of nickel. Economic Geology, 108, 1983–2003.10.2113/econgeo.108.8.1983Search in Google Scholar

Baker, D.R., Barnes, S.J., Simon, G., and Bernier, F. (2001) Fluid transport of sulfur and metals between sulfide melt and basaltic melt. Canadian Mineralogist, 39, 537–546.10.2113/gscanmin.39.2.537Search in Google Scholar

Beermann, O., Botcharnikov, R.E., Holtz, F., Diedrich, O., and Nowak, M. (2011) Temperature dependence of sulfide and sulfate solubility in olivine-saturated basaltic magmas. Geochimica et Cosmochimica Acta, 75, 7612–7631.10.1016/j.gca.2011.09.024Search in Google Scholar

Behrens, H., Roux, J., Neuville, D.R., and Siemann, M. (2006) Quantification of dissolved H2O in silicate glasses using confocal microRaman spectroscopy. Chemical Geology, 229, 96–112.10.1016/j.chemgeo.2006.01.014Search in Google Scholar

Botcharnikov, R.E., Koepke, J., Holtz, F., McCammon, C., and Wilke, M. (2005) The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt. Geochimica et Cosmochimica Acta, 69, 5071–5085.10.1016/j.gca.2005.04.023Search in Google Scholar

Bradbury, J.W. (1983) Pyrrhotite solubility in hydrous albite melts. Ph.D. thesis, Pennsylvania State University.Search in Google Scholar

Brenan, J.M. (2008) Re–Os fractionation by sulfide melt–silicate melt partitioning: a new spin. Chemical Geology, 248, 140–165.10.1016/j.chemgeo.2007.09.003Search in Google Scholar

Buchanan, D.L., Nolan, J., Wilkinson, N., and de Villiers, J.R. (1983) An experimental investigation of sulphur solubility as a function of temperature in synthetic silicate melts. In Geological Society of South Africa Special Publication, 7, 383–391.Search in Google Scholar

Carroll, M.R., and Rutherford, M.J. (1985) Sulfide and sulfate saturation in hydrous silicate melts. Journal of Geophysical Research, 90, C601–C612.10.1029/JB090iS02p0C601Search in Google Scholar

Carroll, M.R., and Rutherford, M.J. (1987) The stability of igneous anhydrite: experimental results and implications for sulfur behaviour in the 1982 El Chicon trachyandesite and other evolved magmas. Journal of Petrology, 28, 781–801.10.1093/petrology/28.5.781Search in Google Scholar

Carroll, M.R., and Rutherford, M.J. (1988) Sulfur speciation in hydrous experimental glasses of varying oxidation state: results from measured wavelength shifts of sulfur X-rays. American Mineralogist, 73, 845–849.Search in Google Scholar

Cicconi, M.R., Giuli, G., Ertel-Ingrisch, W., Paris, E., and Dingwell, D.B. (2015) The effect of the [Na/(Na+K)] ratio on Fe speciation in phonolitic glasses. American Mineralogist, 100, 1610–1619.10.2138/am-2015-5155Search in Google Scholar

Clemente, B., Scaillet, B., and Pichavant, M. (2004) The solubility of sulphur in hydrous rhyolitic melts. Journal of Petrology, 45, 2171–2196.10.1093/petrology/egh052Search in Google Scholar

Danckwerth, P.A., Hess, P.C., and Rutherford, M.J. (1979) The solubility of sulfur in high-TiO2 mare basalt. In Proceedings of the 10th Lunar and Planetary Science Conference, 517–530.Search in Google Scholar

Day, D.E. (1976) Mixed alkali glasses-their properties and uses. Journal of Non-Crystalline Solids, 21, 343–372.10.1016/0022-3093(76)90026-0Search in Google Scholar

Dickinson, W.R. (1975) Potash-depth (K-h) relations in continental margin and intra-oceanic magmatic arcs. Geology, 3, 53–56.10.1130/0091-7613(1975)3<53:PKRICM>2.0.CO;2Search in Google Scholar

Ding, S., Dasgupta, R., and Tsuno, K. (2014) Sulfur concentration of martian basalts at sulfide saturation at high pressures and temperatures-Implications for deep sulfur cycle on Mars. Geochimica et Cosmochimica Acta, 131, 227–246.10.1016/j.gca.2014.02.003Search in Google Scholar

Ducea, M.N., Mclnnes, B.I.A., and Wyllie, P.J. (1994) Sulfur variations in glasses from volcanic rocks: effect of melt composition on sulfur solubility. International Geology Review, 36, 703–714.10.1080/00206819409465483Search in Google Scholar

Duffy, J.A. (1996) Optical basicity: A practical acid-base theory for oxides and oxyanions. Journal of Chemical Education, 73, 1138–1142.10.1021/ed073p1138Search in Google Scholar

Falcone, R., Ceola, S., Daneo, A., and Maurina, S. (2011) The role of sulfur compounds in colouring and melting kinetics of industrial glass. In H. Behrens and J.D. Webster, Eds., Sulfur in Magmas and Melts: its importance for natural and technical processes, 73, p. 113–139. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.10.1515/9781501508370-005Search in Google Scholar

Fincham, C.J.B., and Richardson, F.D. (1954) The behaviour of sulphur in silicate and aluminate melts. Proceedings of the Royal Society of London, 223A, 40–62.Search in Google Scholar

Fortin M.-A., Riddle, J., Desjardins-Langlais, Y., and Baker, D.R. (2015) The effect of water on the sulfur concentration at sulfide saturation (SCSS) in natural melts. Geochimica et Cosmochimica Acta, 160, 100–116.10.1016/j.gca.2015.03.022Search in Google Scholar

Gómez-Tuena, A., Mori, L., Goldstein, S.L., and Pérez-Arvizu, O. (2011) Magmatic diversity of western Mexico as a function of metamorphic transformations in the subducted oceanic plate. Geochimica et Cosmochimica Acta, 75, 213–241.10.1016/j.gca.2010.09.029Search in Google Scholar

Gupta, A.K. (2015) Origin of potassium-rich silica-deficient igneous rocks. Springer, India.10.1007/978-81-322-2083-1Search in Google Scholar

Gwinn, R., and Hess, P.C. (1989) Iron and titanium solution properties in peraluminous and peralkaline rhyolitic liquids. Contributions to Mineralogy and Petrology, 101, 326–338.10.1007/BF00375317Search in Google Scholar

Haughton, D.R., Roeder, P.L., and Skinner, B.J. (1974) Solubility of sulfur in mafic magmas. Economic Geology, 69, 451–467.10.2113/gsecongeo.69.4.451Search 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-2002-2-304Search in Google Scholar

Isard, J.O. (1969) The mixed alkali effect in glass. Journal of Non-Crystalline Solids, 1, 235–261.10.1016/0022-3093(69)90003-9Search in Google Scholar

Jenner, F.E., O’Neill, H.St.C., Arculus, R.J., and Mavrogenes, J.A. (2010) The magnetite crisis in the evolution of arc-related magmas and the initial concentration of Au, Ag and Cu. Journal of Petrology, 51, 2445–2464.10.1093/petrology/egq063Search in Google Scholar

Jugo, P.J. (2009) Sulfur content at sulfide saturation in oxidized magmas. Geology, 37, 415–418.10.1130/G25527A.1Search in Google Scholar

Jugo, P.J., Luth, R.W., and Richards, J.P. (2005a) An experimental study of the sulfur content in basaltic melts saturated with immiscible sulfide or sulfate liquids at 1300 °C and 1.0 GPa. Journal of Petrology, 46, 783–798.10.1093/petrology/egh097Search in Google Scholar

Jugo, P.J., Luth, R.W., and Richards, J.P. (2005b) Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts. Geochimica et Cosmochimica Act, 69, 497–503.10.1016/j.gca.2004.07.011Search in Google Scholar

Jugo, P.J., Wilke, M., and Botcharnikov, R.E. (2010) Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity. Geochimica et Cosmochimica Acta, 74(20), 5926–5938.10.1016/j.gca.2010.07.022Search in Google Scholar

Klimm, K., Kohn, S.C., O’Dell, L.A., Botcharnikov, R.E., and Smith, M.E. (2012) The dissolution mechanism of sulphur in hydrous silicate melts. I: Assessment of analytical techniques in determining the sulphur speciation in iron-free to iron-poor glasses. Chemical Geology, 322, 237–249.10.1016/j.chemgeo.2012.04.027Search in Google Scholar

Kress, V.C., and Carmichael, I.S.E. (1991) The compressibility of silicate liquids containing Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states. Contributions to Mineralogy and Petrology, 108, 82–92.10.1007/BF00307328Search in Google Scholar

Lang, J.R., Lueck, B., Mortensen, J.K., Russell, J.K., Stanley, C.R., and Thompson, J.F.H. (1995) Triassic-Jurassic silica-undersaturated and silica-saturated alkalic intrusions in the Cordillera of British Columbia: implications for arc magmatism. Geology, 23, 451–454.10.1130/0091-7613(1995)023<0451:TJSUAS>2.3.CO;2Search in Google Scholar

Le Losq, C., Neuville, D.R., Moretti, R., and Roux, J. (2012) Determination of water content in silicate glasses using Raman spectrometry: Implications for the study of explosive volcanism. American Mineralogist, 97, 779–790.10.2138/am.2012.3831Search in Google Scholar

LeBas, M.J., Lemaitre, R.W., Streckeisen, A., and Zanettin, B. (1986) A chemical classification of volcanic rocks based on the total alkali silica diagram. Journal of Petrology, 27, 745–750.10.1093/petrology/27.3.745Search in Google Scholar

LeMaitre, R., Ed. (2002) Igneous Rocks: IUGS Classification and Glossary. Cambridge University Press.10.1017/CBO9780511535581Search in Google Scholar

Li, C., and Ripley, E.M. (2005) Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita, 40, 218–230.10.1007/s00126-005-0478-8Search in Google Scholar

Li, C., and Ripley, E.M. (2009) Sulfur contents at sulfide-liquid or anhydrite saturation in silicate melts: empirical equations and example applications. Economic Geology, 104, 405–412.10.2113/gsecongeo.104.3.405Search in Google Scholar

Liu, Y., Samaha, N.-T., and Baker, D.R. (2007) Sulfur concentration at sulfide saturation (SCSS) in magmatic silicate melts. Geochimica et Cosmochimica Acta, 71, 1783–1799.10.1016/j.gca.2007.01.004Search in Google Scholar

Logan, J.M., and Mihalynuk, M.G. (2014) Tectonic controls on early mesozoic paired alkaline porphyry deposit belts (Cu-Au +/-Ag-Pt-Pd-Mo) within the Canadian Cordillera. Economic Geology, 109, 827–858.10.2113/econgeo.109.4.827Search in Google Scholar

Long, D.A. (1977) Raman Spectroscopy, 276 p. MacGraw-Hill, New YorkSearch in Google Scholar

Mandeville, C.W., Webster, J.D., Rutherford, M.J., Taylor, B.E., Timbal, A., and Faure, K. (2002) Determination of molar absorptivities for infrared absorption bands of H2O in andesitic glasses. American Mineralogist, 87, 813–821.10.2138/am-2002-0702Search in Google Scholar

Mavrogenes, J.A., and O’Neill, H.St.C. (1999) The relative effects of pressure, temperature and oxygen fugacity on the solubility of sulfide in mafic magmas. Geochimica et Cosmochimica Acta, 63, 1173–1180.10.1016/S0016-7037(98)00289-0Search in Google Scholar

McInnes, B.I.A., and Cameron, E.M. (1994) Carbonated, alkaline hybridizing melts from a sub-arc environment: mantle wedge samples from the Tabar-Lihir-Tanga-Feni arc, Papua New Guinea. Earth and Planetary Science Letters, 122, 125–141.10.1016/0012-821X(94)90055-8Search in Google Scholar

McLinden, C.A., Fioletov, V., Shephard, M.W., Krotkov, N., Li, C., Martin, R.V., Moran, M.D., and Joiner, J. (2016) Space-based detection of missing sulfur dioxide sources of global air pollution. Nature Geoscience, 9, 496–500.10.1038/ngeo2724Search in Google Scholar

Médard, E., McCammon, C.A., Barr, J.A., and Grove, T.L. (2008) Oxygen fugacity, temperature reproducibility, and H2O contents of nominally anhydrous piston-cylinder experiments using graphite capsules. American Mineralogist, 93, 1838–1844.10.2138/am.2008.2842Search in Google Scholar

Metrich, N., and Clocchiatti, R. (1996) Sulfur abundance and its speciation in oxidized alkaline melts. Geochimica et Cosmochimica Acta, 60, 4151–4160.10.1016/S0016-7037(96)00229-3Search in Google Scholar

Mills, K.C. (1993) The influence of structure on the physico-chemical properties of slags. ISIJ international, 33(1), 148–155.10.2355/isijinternational.33.148Search in Google Scholar

Morgan, G.B., and London, D. (1996) Optimizing the electron microprobe analysis of hydrous alkali aluminosilicate glasses. American Mineralogist, 81, 1176–1185.10.2138/am-1996-9-1016Search in Google Scholar

Morgan, G.B., and London, D. (2005) Effect of current density on the electron microprobe analysis of alkali aluminosilicate glasses. American Mineralogist, 90, 1131–1138.10.2138/am.2005.1769Search in Google Scholar

Moune, S., Holtz, F., and Botcharnikov, R.E. (2009) Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano. Contributions to Mineralogy and Petrology, 157, 691–707.10.1007/s00410-008-0359-0Search in Google Scholar

Müller, D., and Groves, D.I. (1993) Direct and indirect associations between potassic igneous rocks, shoshonites and gold-copper deposits. Ore Geology Reviews, 8, 383–406.10.1016/0169-1368(93)90035-WSearch in Google Scholar

Mysen, B.O., Virgo, D., and Seifert, F.A. (1985) Relationships between properties and structure of aluminosilicate melts. American Mineralogist, 70, 88–105.Search in Google Scholar

Naldrett, A.J. (1969) A portion of the system Fe-S-O between 900 and 1080°C and its application to sulfide ore magmas. Journal of Petrology, 10, 171–201.10.1093/petrology/10.2.171Search in Google Scholar

O’Neill, H.St.C., and Mavrogenes, J.A. (2002) The sulfide capacity and the sulfur content at sulfide saturation of silicate melts at 1400°C and 1 bar. Journal of Petrology, 43, 1049–1087.10.1093/petrology/43.6.1049Search in Google Scholar

Paul, A., and Douglas, R.W. (1965) Ferrous–ferric equilibrium in binary alkali silicate glasses. Physics and Chemistry of Glasses, 6, 207–211.Search in Google Scholar

Peach, C.L., and Mathez, E.A. (1993) Sulfide melt-silicate melt distribution coefficients for nickel and iron and implications for the distribution of other chalcophile elements. Geochimica et Cosmochimica Acta, 57, 3013–3021.10.1016/0016-7037(93)90290-DSearch in Google Scholar

Peach, C.L., Mathez, E.A., Keays, R.R., and Reeves, S.J. (1994) Experimentally determined sulfide melt-silicate melt partition coefficients for iridium and palladium. Chemical Geology, 117, 361–377.10.1016/0009-2541(94)90138-4Search in Google Scholar

Reagan, M.K., Hanan, B.B., Heizler, M.T., Hartman, B.S., and Hickey-Vargas, R. (2008) Petrogenesis of volcanic rocks from Saipan and Rota, Mariana Islands, and implications for the evolution of nascent island arcs. Journal of Petrology, 49, 441–464.10.1093/petrology/egm087Search in Google Scholar

Righter, K., Pando, K., and Danielson, L.R. (2009) Experimental evidence for sulfur-rich martian magmas: Implications for volcanism and surficial sulfur sources. Earth and Planetary Science Letters, 288, 235–243.10.1016/j.epsl.2009.09.027Search in Google Scholar

Ryerson, F.J., and Watson, E.B. (1987) Rutile saturation in magmas: implications for TiNbTa depletion in island-arc basalts. Earth and Planetary Science Letters, 86, 225–239.10.1016/0012-821X(87)90223-8Search in Google Scholar

Sarbas, B., and Nohl, U. (2008) The GEOROC database as part of a growing geoinformatics network. In S.R. Brady, A.K. Sinha, and L.C. Gundersen, Eds., Geoinformatics 2008—Data to Knowledge, p. 42–43. Proceedings of the U.S. Geological Survey Scientific Investigations Report 2008-5172.Search in Google Scholar

Sattari, P., Brenan, J.M., Horn, I., and McDonough, W.F. (2002) Experimental constraints on the sulfide-and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology, 97, 385–398.10.2113/gsecongeo.97.2.385Search in Google Scholar

Scaillet, B., and Macdonald, R. (2006) Experimental and thermodynamic constraints of the sulphur yield of peralkaline and metaluminous silicic flood eruptions. Journal of Petrology, 47, 1413–1437.10.1093/petrology/egl016Search in Google Scholar

Scaillet, B., and Pichavant, M. (2005) A model of sulphur solubility for hydrous mafic melts: application to the determination of magmatic fluid. Annals of Geophysics, 48, 671–698.Search in Google Scholar

Shima, H., and Naldrett, A.J. (1975) Solubility of sulfur in an ultramafic melt and the releveance of the system Fe-S-O. Economic Geology, 70, 960–967.10.2113/gsecongeo.70.5.960Search in Google Scholar

Sillitoe, R.H. (2010) Porphyry copper systems. Economic Geology, 105, 3–41.10.2113/gsecongeo.105.1.3Search in Google Scholar

Stolper, E., and Newman, S. (1994) The role of water in the petrogenesis of Mariana trough magmas. Earth and Planetary Science Letters, 121, 293–325.10.1016/0012-821X(94)90074-4Search in Google Scholar

Smythe, D.J., Wood, B.J., and Kiseeva, E.S. (2017) The S content of silicate melts at sulfide saturation: New experiemnts and a model incorporating the effects of sulfide composition. American Mineralogist, 102, 795–803.10.2138/am-2017-5800CCBYSearch in Google Scholar

Tsujimura, T., and Kitakaze, A. (2005) Experimental study of sulfur solubility in silicate melts coexisting with graphite as a function of silicate melt composition. Resource Geology, 55, 55–60.10.1111/j.1751-3928.2005.tb00228.xSearch in Google Scholar

Watson, E.B., and Harrison, T.M. (1983) Zircon saturation revisited: temperature and composition effects in a variety of crustal magma types. Earth and Planetary Science Letters, 64, 295–304.10.1016/0012-821X(83)90211-XSearch in Google Scholar

Watson, E.B., Wark, D.A., Price, J.D., and Van Orman, J.A. (2002) Mapping the thermal structure of solid-media pressure assemblies. Contributions to Mineralogy and Petrology, 142, 640–652.10.1007/s00410-001-0327-4Search in Google Scholar

Wendlandt, R.F. (1982) Sulfide saturation of basalt and andesite melts at high pressures and temperatures. American Mineralogist, 67, 877–885.Search in Google Scholar

Wykes, J.L., O’Neill, H.St.C., and Mavrogenes, J.A. (2015) The effect of FeO on the sulfur content at sulfide saturation (SCSS) and the selenium content and selenide saturation of silicate melts. Journal of Petrology, 56, 1407–1424.10.1093/petrology/egv041Search in Google Scholar

Zhu, B., Fang, B., and Li, X. (2010) Dehydration reactions and kinetic parameters of gibbsite. Ceramic International, 36, 2493–2498.10.1016/j.ceramint.2010.07.007Search in Google Scholar

Received: 2017-11-22
Accepted: 2018-03-28
Published Online: 2018-07-02
Published in Print: 2018-07-26

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 28.3.2023 from
Scroll Up Arrow