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We apply a recently developed measurement technique for methane (CH4) isotopologues* (isotopic variants of CH4—13CH4, 12CH3D, 13CH3D, and 12CH2D2) to identify contributions to the atmospheric burden from fossil fuel and microbial sources. The aim of this study is to constrain factors that ultimately control the concentration of this potent greenhouse gas on global, regional, and local levels. While predictions of atmospheric methane isotopologues have been modeled, we present direct measurements that point to a different atmospheric methane composition and to a microbial flux with less clumping (greater deficits relative to stochastic) in both 13CH3D and 12CH2D2 than had been previously assigned. These differences make atmospheric isotopologue data sufficiently sensitive to variations in microbial to fossil fuel fluxes to distinguish between emissions scenarios such as those generated by different versions of EDGAR (the Emissions Database for Global Atmospheric Research), even when existing constraints on the atmospheric CH4 concentration profile as well as traditional isotopes are kept constant. 

Abstract Basalts from the Samoan volcanoes sample contributions from all of the classical mantle endmembers, including extreme EM II and high³He/⁴He components, as well as dilute contributions from the HIMU, EM I, and DM components. Here, we present multiple sulfur isotope data on sulfide extracted from subaerial and submarine whole rocks (N = 16) associated with several Samoan volcanoes—Vailulu‘u, Malumalu, Malutut, Upolu, Savai‘i, and Tutuila—that sample the full range of geochemical heterogeneity at Samoa and upon exhaustive compilation of S‐isotope data for Samoan lavas, allow for an assessment of the S‐isotope compositions associated with the different mantle components sampled by the Samoan hotspot. We observe variable S concentrations (10–1,000 ppm) and δ³⁴S values (−0.29‰ ± 0.30 to +4.84‰ ± 0.30, 2σ). The observed variable S concentrations are likely due to sulfide segregation and degassing processes. The range in δ³⁴S reflects mixing between the mantle origin and recycled components, and isotope fractionations associated with degassing. The majority of samples reveal Δ³³S within uncertainty of Δ³³S = 0‰ ± 0.008. Important exceptions to this observation include: (a) a negative Δ³³S (−0.018‰ ± 0.008, 2σ) from a rejuvenated basalt on Upolu island (associated with a diluted EM I component) and (b) previously documented small (but resolvable) Δ³³S values (up to +0.027 ± 0.016) associated with the Vai Trend (associated with a diluted HIMU component). The variability we observed in Δ³³S is interpreted to reflect contributions of sulfur of different origins and likely multiple crustal protoliths. Δ³⁶S versus Δ³³S relationships suggest all recycled S is of post‐Archean origin.