Sulfur degassing due to contact metamorphism during flood basalt eruptions

We present a study aimed at quantifying the potential for generating sulfur-rich gas emissions from the devolatilization of sediments accompanying sill emplacement during flood basalt eruptions. The potential contribution of sulfur-rich gases from sediments might augment substantially the magma-derived sulfur gases and hence impact regional and global climate. We demonstrate, from a detailed outcrop-scale study, that sulfur and total organic carbon have been devolatilized from shales immediately surrounding a 3-m thick dolerite sill on the Isle of Skye, Scotland. Localized partial melting occurred within a few centimetres of the contact in the shale, generating melt-filled cracks. Pyrite decomposed on heating within 80 cm of the contact, generating sulfur-rich gases (a mixture of H2S and SO2) and pyrrhotite. The pyrrhotite shows 32S enrichment, due to loss of 34S-enriched SO2. Further decomposition and oxidation of pyrrhotite resulted in hematite and/or magnetite within a few cm of the contact. Iron sulfates were produced during retrogressive cooling and oxidation within 20 cm of the contact. Decarbonation of the sediments due to heating is also observed, particularly along the upper contact of the sill, where increasing δ13C is consistent with loss of methane gas. The geochemical and mineralogical features observed in the shales are consistent with a short-lived intrusion, emplaced in <5 h. The dolerite magma contains pervasive pyrite and localized sulfur concentrations greater than the sulfur concentration at sulfide liquid saturation, consistent with addition of sulfur (perhaps from sediments) at a late stage. Our study provides evidence for desulfurization, as well as decarbonation, of shales adjacent to an igneous intrusion. The liberated fluids, rich in sulfur and carbon, are likely to be focused along regions of low pore fluid pressure along the margins of the sill. The sulfur gases liberated from the sediments would have augmented the sulfur dioxide (and hydrogen sulfide) yield of the eruption substantially, had they reached the surface. This enhancement of the magmatic sulfur budget has important implications for the climate impact of large flood basalt eruptions that erupt through thick, volatile-rich sedimentary sequences.