The oxidation state of sulfur in magmatic fluids

Sulfur compounds in volcanic gases are responsible for the global cooling after explosive eruptions and they probably controlled the early evolution of the Earth's atmosphere. We have therefore studied the oxidation state of sulfur in aqueous fluids under the pressure and temperature conditions and oxygen fugacities typical for magma chambers (0.5–3 kbar, 650–950 °C, Ni–NiO to Re–ReO₂ buffer conditions). Sulfur speciation was determined by Raman spectroscopy of quenched fluids trapped as inclusions in quartz. Our results show that sulfur in hydrothermal fluids and volcanic gases is much more oxidized than previously thought and in particular, some explosive eruptions may release a significant fraction of sulfur as SO₃ or its hydrated forms. In the pressure range from 500 to 2000 bar, the equilibrium constant K₁ of the reaction 2H₂S + 3O₂ = 2SO₂ + 2H₂O in aqueous fluids can be described by lnK₁ = ?(57.1 ± 7.1) + (173,480 ± 7592)T^? 1, where T is temperature in Kelvin. The equilibrium constant K₂ for the reaction SO₂ + ½O₂ = SO₃ in aqueous fluids, where SO₃ may include hydrated forms, such as H₂SO₄, was found to be strongly pressure dependent, with lnK₂ = ?(5.2 ± 5.7) + (19,243 ± 5993)T^? 1 at 1500 bar; lnK₂ = ?(11.1 ± 1.3) + (25,383 ± 1371)T^? 1 at 2000 bar and lnK₂ = ?(22.1 ± 2.2) + (37,082 ± 2248)T^? 1 at 2500 bar. Our data imply that volcanoes may directly inject hexavalent sulfur in the form of H₂SO₄ into the atmosphere, not only on Earth, but possibly also on Venus and on Mars, when it was still tectonically active. Remote measurements from satellites may have underestimated the sulfur yield of some recent eruptions. Moreover, the mechanisms of the interaction of volcanic gases with the stratosphere need to be reconsidered.