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Sulfur Degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) Volcanoes: Implications for Degassing Processes and Oxygen Fugacities of Basaltic Systems J

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Sulfur Degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) Volcanoes: Implications for Degassing Processes and Oxygen Fugacities of Basaltic Systems J University of Rhode Island DigitalCommons@URI Graduate School of Oceanography Faculty Graduate School of Oceanography Publications 2013 Sulfur degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) volcanoes: Implications for degassing processes and oxygen fugacities of basaltic systems J. M. de Moor T. P. Fischer See next page for additional authors Creative Commons License This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License. Follow this and additional works at: https://digitalcommons.uri.edu/gsofacpubs Citation/Publisher Attribution de Moor, J. M., et al. (2013), Sulfur degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) volcanoes: Implications for the degassing processes and oxygen fugacities of basaltic systems, Geochem. Geophys. Geosyst., 14, 4076–4108, doi:10.1002/ggge.20255 Available at: https://doi.org/10.1002/ggge.20255 This Article is brought to you for free and open access by the Graduate School of Oceanography at DigitalCommons@URI. It has been accepted for inclusion in Graduate School of Oceanography Faculty Publications by an authorized administrator of DigitalCommons@URI. For more information, please contact [email protected]. Authors J. M. de Moor, T. P. Fischer, Z. D. Sharp, P. L. King, M. Wilke, R. E. Botcharnikov, E. Cottrell, M. Zelenski, B. Marty, K. Klimm, C. Rivard, D. Ayalew, C. Ramirez, and Katherine A. Kelley This article is available at DigitalCommons@URI: https://digitalcommons.uri.edu/gsofacpubs/565 Article Volume 14, Number 10 2 October 2013 doi: 10.1002/ggge.20255 ISSN: 1525-2027 Sulfur degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) volcanoes: Implications for degassing processes and oxygen fugacities of basaltic systems J. M. de Moor Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, New Mexico, 87131, USA ([email protected]) Now at Observatorio Vulcanologico y Sismologico de Costa Rica, Universidad Nacional, Heredia, Costa Rica T. P. Fischer and Z. D. Sharp Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, New Mexico, USA P. L. King Institute of Meteoritics, University of New Mexico, Albuquerque, New Mexico, USA Now at Research School of Earth Sciences, Australian National University, Acton, Canberra ACT, Australia M. Wilke Deutsches GeoForschungsZentrum, Helmholtzzentrum Potsdam, Potsdam, Germany R. E. Botcharnikov Institut fur€ Mineralogie, Leibniz Universitat,€ Hannover, Germany E. Cottrell National Museum of Natural History, Smithsonian Institution, Washington, D.C., USA M. Zelenski Institute of Experimental Mineralogy, Russian Academy of Sciences, Moscow, Russia B. Marty Centre de Recherches Petrographiques et Geochimiques, CNRS, Ecole Nationale Superieure de Geologie, Vandoeuvre-les-Nancy,France K. Klimm Institut fur€ Geowissenschaften, Goethe Universitat€ Frankfurt, Frankfurt am Main, Germany C. Rivard European Synchrotron Radiation Facility, Grenoble, France D. Ayalew Department of Earth Sciences, School of Earth and Planetary Sciences, Addis Ababa University, Addis Ababa, Ethiopia The copyright line for this article was changed on 30 April 2015 after original online publication. © 2013. The Authors. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial- NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. 4076 DE MOOR ET AL.: SULFUR DEGASSING AT BASALTIC VOLCANOES 10.1002/ggge.20255 C. Ramirez Red Sismologica Nacional, University of Costa Rica, San Jose, Costa Rica K. A. Kelley Graduate School of Oceanography, University of Rhode Island, Narragansett Bay Campus, Narragansett, Rhode Island, USA [1] We investigate the relationship between sulfur andP oxygen fugacity at Erta Ale and Masaya volcanoes. Oxygen fugacity was assessed utilizing Fe3þ/ Fe and major element compositionsP measured in olivine-hosted melt inclusions and matrix glasses. Erta Ale melts have Fe3þ/ Fe of 0.15–0.16, reflecting fO2 of DQFM 0.0 6 0.3, which is indistinguishable from fO2 calculated from CO2/CO ratios in high-temperature gases. Masaya is more oxidized at DQFM þ1.7 6 0.4, typical of arc settings. Sulfur 34 34 isotope compositions of gases and scoria at Erta Ale ( Sgas À 0.5%; Sscoria þ 0.9%) and Masaya 34 34 ( Sgas þ 4.8%; Sscoria þ 7.4%) reflect distinct sulfur sources, as well as isotopic fractionation during degassing (equilibrium and kinetic fractionation effects).P Sulfur speciation in melts plays an important 6 role in isotope fractionation during degassing and S þ/ Sis<0.07 inP Erta Ale meltP inclusions compared to >0.67 in Masaya melt inclusions. No change is observed in Fe3þ/ Fe or S6þ/ S with extent of S degassing at Erta Ale, indicating negligible effect on fO2, and further suggesting that H2S is the dominant 2À gas species exsolved from the S -rich melt (i.e., no redistribution of electrons). High SO2/H2S observed in Erta Ale gas emissions is due to gas re-equilibration at low pressure and fixed fO2. Sulfur budget considerations indicate that the majority of S injected into the systems is emitted as gas, which is therefore representative of the magmatic S isotope composition. The composition of the Masaya gas plume (þ4.8%) cannot be explained by fractionation effects but rather reflects recycling of high 34S oxidized sulfur through the subduction zone. Components: 23,134 words, 11 figures, 6 tables. Keywords: basalts; sulfur; oxygen fugacity; sulfur isotopes; gas chemistry. Index Terms: 1043 Fluid and melt inclusion geochemistry: Geochemistry; 1041 Stable isotope geochemistry: Geochemis- try; 1036 Magma chamber processes: Geochemistry; 1031 Subduction zone processes: Geochemistry; 4870 Stable iso- topes: Oceanography: Biological and Chemical; 3613 Subduction zone processes: Mineralogy and Petrology; 3618 Magma chamber processes: Mineralogy and Petrology; 8413 Subduction zone processes: Volcanology. Received 9 May 2013; Revised 12 August 2013; Accepted 15 August 2013; Published 2 October 2013. de Moor, J. M., et al. (2013), Sulfur degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) volcanoes: Implications for the degass- ing processes and oxygen fugacities of basaltic systems, Geochem. Geophys. Geosyst., 14, 4076–4108, doi:10.1002/ggge.20255. 1. Introduction low and high-temperature environments. Sulfur is one of the most abundant constituents of volcanic 4þ [2] This study investigates sulfur (S) degassing gases, occurring predominantly as SO2 (S ) and 2À processes and S sources through the study of S iso- H2S(S ) and is an important volatile component tope compositions and speciation of magmatic gases of mafic magmas [Giggenbach, 1996]. Sulfur and basaltic scoria from Erta Ale (Ethiopia) and degassing has been proposed as a mechanism that Masaya (Nicaragua). The goal is to constrain condi- modifies the oxygen fugacity of magmas [Ander- tions of degassing such as oxygen fugacity, tempera- son and Wright, 1972; Burgisser and Scaillet, ture, and pressure in each system to ascertain 2007; Kelley and Cottrell, 2012] and subduction of oxidized sulfur (sulfate) may be partially re- primary magmatic S isotope compositions, assess S sponsible for oxidation of the subarc mantle isotope fractionation, and investigate the relationship [Evans, 2012; Kelley and Cottrell, 2009; Klimm between S degassing and oxygen fugacity. et al., 2012]. Fluxes of SO2 are routinely measured [3] The multiple valence states of S (2À to 6þ) in volcano monitoring because atmospheric con- result in complex geochemical behavior in both centrations of this species are easily detectable due 4077 DE MOOR ET AL.: SULFUR DEGASSING AT BASALTIC VOLCANOES 10.1002/ggge.20255 to its absorption of ultraviolet light [Galle et al., ing, and temperature (see Marini et al. [2011] for a 2002; Platt, 1994; Stoiber et al., 1983]. Sulfur review of fractionation processes). Hydrothermal dioxide is an important volcanic gas in terms of processes are associated with complex isotopic climate impact on earth due to the oxidation of fractionation due to multiple S valence states in 2À 2À 2À SO2 to sulfate aerosols in the atmosphere [Sigurds- vapors (H2S, SO2), fluids (SO4 ,S , SO3 , pol- À son, 1990]. Volcanic degassing of S has also been ythionates, S3 ), and solid phases (sulfates such as proposed as an important source of surface sulfur anhydrite, elemental sulfur, pyrite, sulfides, and on Mars [Banin et al., 1997; Settle, 1979] and vol- hauyne-nosean minerals), a wide range of tempera- canic SO2 has been proposed as an effective green- tures, and slow isotopic equilibration at hydrother- house gas in the martian climate [Gaillard and mal temperatures [e.g., Delmelle et al., 2000; Rye, Scaillet, 2009] that may have allowed liquid sur- 2005]. Gas interaction with hydrothermal fluids and face water to exist [Halevy et al., 2007; Johnson deposition or remobilization of hydrothermal min- et al., 2008]. On Earth, degassing of volcanic SO2 erals or sublimates can modify the isotope composi- during the Paleoproterozoic may have initiated the tion of fumarolic gases [Delmelle et al., 2000; modern biogeochemical sulfur cycle and atmos- Giggenbach,1987;Menyailov et al., 1986; Rowe, pheric oxygenation [Gaillard et al., 2011]. The 1994]. Whereas fumarolic gases are subject to mod- sulfur cycle is therefore important for chemical ification of S isotope signature from magmatic val- modification of Earth’s reservoirs, and is intri- ues by hydrothermal processes,
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