Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols

We present analyses of stable isotopic ratios 17O/16O, 18O/16O, 34S/32S, and 33S/32S, 36S/32S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ∼1 km3), Mt. Spurr (Alaska, 1953, <1 km3), Gjalp (Iceland, 1996, 1998, <1 km3), Pinatubo (Phillipines, 1991, 10 km3), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km3), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km3), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km3 and 2.04 Ma 2500 km3, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage.This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent (Δ17O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of‘ these isotopic ranges. Sulfate with Δ17O > 0.2‰ is present as 1–10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ17O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin.Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO2, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ34S range and exhibit fractionation relationships that do not follow the expected equilibrium slopes of 0.515 and 1.90 for 33S/32S vs. 34S/32S and 36S/32S vs. 34S/32S, respectively. The data presented here are consistent with modification of a chemical mass-dependent fractionation of sulfur isotopes in the volcanic plume by either a kinetic gas phase reaction of volcanic SO2 with OH and/or a Rayleigh processes involving a residual Rayleigh reactant—volcanic SO2 gas, rather than a Rayleigh product. These results may also imply at least two removal pathways for SO2 in volcanic plumes.Above-zero Δ17O values and their positive correlation with δ18O in sulfate can be explained by oxidation by high-δ18O and high-Δ17O compounds such as ozone and radicals such as OH that result from ozone break down. Large caldera-forming eruptions have the highest Δ17O values, and the largest range of δ18O, which can be explained by stratospheric reaction with ozone-derived OH radicals. These results suggest that massive eruptions are capable of causing a temporary depletion of the ozone layer. Such depletion may be many times that of the measured 3–8% depletion following 1991 Pinatubo eruption, if the amount of sulfur dioxide released scales with the amount of ozone depletion.