Sulfuric acid weathering counteracts CO2 drawdown from silicate weathering in mountainous catchments from southwest China

Abstract

Sulfide oxidation, coupled with carbonate weathering is thought to be a source of CO2 over geological timescales to offset CO2 drawdown from silicate weathering. Its impact on the carbon budget of weathering at the catchment scale is generally constrained by utilizing riverine water chemistry and the isotope value (δ34S) of sulfate. However, the multiple origins of riverine sulfate and the high variability of sulfide-derived δ34S certainly limit the determination of sulfate sources and thus our understanding of the role of sulfuric acid-induced weathering in the carbon budget. In this study, to quantify the carbon budget between weathering by carbonic and sulfuric acids in mountainous catchments (the Yinjiang River, the Shiqian River, and the Yuqing River) in southwest China, a Monte Carlo inversion model is employed for major element concentrations and sulfate δ34S (δ34SSO4). This inversion quantitatively partitions the cations and sulfate between different sources, and further identifies the pyrite-derived δ34S and the flux ratios of alkalinity to dissolved inorganic carbon (ΔALK/ΔDIC). Inversion results reveal that the majority of major cations (>90 %) is derived from carbonate (calcite and dolomite) dissolution, and that riverine sulfate budget is predominately contributed by pyrite oxidation and precipitation. In the Yinjiang River, the average δ34SSO4 is 8.4 ‰ in the upper and middle reaches, but declines significantly to 0.4 ‰ in the lower reaches. In the Shiqian River and Yuqing River, δ34SSO4 mainly cluster around 3.6–5.7 ‰ and 5.5–8.5 ‰, respectively. Inversion results suggest that the primary controls on δ34SSO4 are the variability of lithology and the variation in the proportional contribution of pyrite oxidation to riverine sulfate. In the Yinjiang River, the fraction of H2SO4-driven weathering is highly variable, and higher in the lower reaches than in the upper reaches, attributing to distinct underlying lithology in the catchment (a widespread distribution of coal-bearing strata). The weathering fluxes with 1 < ΔALK/ΔDIC < 2 evidenced that the negative alkalinity flux from carbonate weathering driven by sulfuric acid from both pyrite oxidation and acid deposition counteracts much of the alkalinity flux from silicate weathering. This is implicated on the timescale between marine carbonate precipitation and sulfate reduction (>5–10 kyr and <10 Myr), indicating that weathering in these catchments acts as short-term sinks of atmospheric CO2 but long-term sources of it. Moreover, reanalysis of prior datasets of karst-dominated catchments in China also highlight the important role of pyrite oxidation and acid precipitation in the carbon budget.