| 1. |
- Chi Fru, Ernest, et al.
(author)
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Atmospheric weathering of Scandinavian alum shales and the fractionation of C, N and S isotopes
- 2016
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In: Applied Geochemistry. - : Elsevier BV. - 0883-2927 .- 1872-9134. ; 74, s. 94-108
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Journal article (peer-reviewed)abstract
- Subaerial exposure and oxidation of organic carbon (C-org)-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 C-org oxidation are expected to shift new biomass delta C-13(org) composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting delta C-13(org) at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C-org-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, C-org-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 C-org without producing a delta C-13 shift between acid rock drainage precipitates and shale. Moreover, C-13 enrichment in inorganic carbon of precipitates does not support microbial C-org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Delta S-34 = delta S-34(shale) - delta S-34(precipitates) approximate to 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 delta N-15 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 C-org, 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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| 2. |
- Fru, Ernest Chi, et al.
(author)
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Transient fertilization of a post-Sturtian Snowball ocean margin with dissolved phosphate by clay minerals
- 2023
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In: Nature Communications. - 2041-1723. ; 14:1
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Journal article (peer-reviewed)abstract
- Marine sedimentary rocks deposited across the Neoproterozoic Cryogenian Snowball interval, similar to 720-635 million years ago, suggest that post-Snowball fertilization of shallow continental margin seawater with phosphorus accelerated marine primary productivity, ocean-atmosphere oxygenation, and ultimately the rise of animals. However, the mechanisms that sourced and delivered bioavailable phosphate from land to the ocean are not fully understood. Here we demonstrate a causal relationship between clay mineral production by the melting Sturtian Snowball ice sheets and a short-lived increase in seawater phosphate bioavailability by at least 20-fold and oxygenation of an immediate post-Sturtian Snowball ocean margin. Bulk primary sediment inputs and inferred dissolved seawater phosphate dynamics point to a relatively low marine phosphate inventory that limited marine primary productivity and seawater oxygenation before the Sturtian glaciation, and again in the later stages of the succeeding interglacial greenhouse interval.
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