Atmospheric weathering of Scandinavian alum shales and the fractionation of C, N and S isotopes

Chi Fru, Ernest ORCID: https://orcid.org/0000-0003-2673-0565, Hemmingsson, Christoffer, Callac, Nolwenn, Perez, Nathalie, Panova, Elena G., Broman, Curt and El Albani, Abderrazzak 2016. Atmospheric weathering of Scandinavian alum shales and the fractionation of C, N and S isotopes. Applied Geochemistry 74 , pp. 94-108. 10.1016/j.apgeochem.2016.09.006

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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 d13Corg composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting d13Corg 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 d13C 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 D34S ¼ d34Sshale � d34Sprecipitates z 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 d15N 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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Earth and Environmental Sciences
Uncontrolled Keywords:	Ancient organic carbon; Black shales; Carbon, Nitrogen, and Sulfur isotopes; Weathering; Sulfide oxidation; Organic matter oxidation
Publisher:	Elsevier
ISSN:	0883-2927
Funders:	ERC
Date of First Compliant Deposit:	17 January 2017
Date of Acceptance:	15 September 2016
Last Modified:	02 Nov 2022 10:07
URI:	https://orca.cardiff.ac.uk/id/eprint/97501

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