Records of Carbon and Sulfur Cycling During the Silurian Ireviken Event in Gotland, Sweden

Abstract

Early Silurian (∼431 Ma) carbonate rocks record a ca. 4.5‰ positive excursion in the stable isotopic composition of carbonate carbon (δ^(13)C_(carb)). Associated with this isotopic shift is a macroevolutionary turnover pulse known as the 'Ireviken Event'. The onset of this carbon isotope excursion is commonly associated with a shallowing-upward facies transition that may have been accompanied by climatic change, as indicated by a parallel positive shift (∼0.6‰) in the stable isotopic composition of carbonate oxygen (δ^(18)O_(carb)). However, the relationships among carbon cycle perturbations, faunal turnover, and environmental changes remain enigmatic. Here we present a suite of new isotopic data across the Ireviken Event from multiple sections in Gotland, Sweden. These samples preserve no systematic change in δ^(18)O_(carb) but show positive excursions of equal magnitude in both carbonate (δ^(13)C_(carb)) and organic (δ^(13)C_(org)) carbon. In addition, the data reveal a synchronous perturbation in sulfur isotope ratios, manifest as a ca. 7‰ positive excursion in carbonate-associated sulfate (δ^(34)S_(CAS)) and a ca. 30‰ positive excursion in pyrite (δ^(34)S_(pyr)). The increase in δ^(34)S_(pyr) values is accompanied by a substantial, concomitant increase in stratigraphic variability of δ^(34)S_(pyr). The relatively constant offset between the δ^(13)C_(carb) and δ^(13)C_(org) excursions throughout the Ireviken Event could be attributed to increased organic carbon burial, or possibly a change in the isotopic composition of CO_2 sources from weathering. However, a positive correlation between carbonate abundance and δ^(13)C_(carb) suggests that local to regional changes in dissolved inorganic carbon (DIC) during the shallowing-upward sequence may have been at least partly responsible for the observed excursion. The positive excursion recorded in δ^(34)S_(CAS) suggests a perturbation of sufficient magnitude and duration to have impacted the marine sulfate reservoir. An inverse correlation between CAS abundance and δ^(34)S_(CAS) supports the notion of decreased sulfate concentrations, at least locally, consistent with a concomitant increase in pyrite burial. A decrease in the offset between δ^(34)S_(CAS) and δ^(34)S_(pyr) values during the Ireviken Event suggests a substantial reduction in the isotopic fractionations (ε_(pyr)) expressed during microbial sulfur cycling and pyrite precipitation through this interval. Decreased ε_(pyr) and the concomitant increase in stratigraphic variation in δ^(34)S_(pyr) are typical of isotope systematics observed in modern shallow-water environments, associated with increased closed-system behavior and/or oxidative sedimentary reworking during early sediment diagenesis. While the isotopic trends associated with the Ireviken Event have been observed in multiple locations around the globe, many sections display different magnitudes of isotopic change, and moreover, are typically associated with local facies changes. Due to the stratigraphic coherence of the carbon and sulfur isotopic and abundance records across the Ireviken Event, and their relationship to changes in local depositional environment, we surmise that these patterns more closely reflect biogeochemical processes related to deposition and lithification of sediment than global changes in carbon and sulfur burial fluxes.

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