Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes |
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| Institution: | 1. Faculty of Earth Sciences, University of Silesia, B?dzińska 60, 41-200 Sosnowiec, Poland;2. Institute of Geological Sciences, Polish Academy of Sciences, Research Centre in Kraków, ul. Senacka 1, 31-002 Kraków, Poland;3. Institute of Geophysics, Polish Academy of Science, Ks. Janusza 64, 01-452 Warszawa, Poland;4. School of Environment, Earth and Ecosystem Sciences, The Open University, Milton Keynes MK7 6AA, UK |
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| Abstract: | Subaerial exposure and oxidation of organic carbon (Corg)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial Corg oxidation are expected to shift new biomass δ13Corg composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ13Corg at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, Corg-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, Corg-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of Corg without producing a δ13C shift between acid rock drainage precipitates and shale. Moreover, 13C enrichment in inorganic carbon of precipitates does not support microbial Corg oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ34S = δ34Sshale ? δ34Sprecipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ15N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of Corg, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment. |
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| Keywords: | Ancient organic carbon Black shales Carbon Nitrogen and Sulfur isotopes Weathering Sulfide oxidation Organic matter oxidation |
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