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Biogeochemical cycling of sulphur in karst and transfer into speleothem archives at Grotta di Ernesto, Italy

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Abstract

Trace amounts of sulphur in speleothems suggest that stalagmites may act as archives of sulphur deposition, thereby recording aspects of atmospheric variability in sulphur content. Accurate interpretation of this novel sulphur archive depends upon understanding how biogeochemical cycling in the soil and epikarst above the cave may modify the precursor atmospheric values of sulphur concentration and isotopic composition prior to incorporation into the speleothem record. Dual isotope analysis of δ34S-SO4 and δ18O-SO4 is used to trace biogeochemical transformations of atmospheric sulphur through the cave system at Grotta di Ernesto in the Italian Alps and builds towards a framework for interpretation of speleothem sulphur archives which depends on overlying ecosystem dynamics and karst hydrological properties. A three component model of atmospheric sulphate signal modification is proposed to be driven by (1). vegetation and soil cycling, (2). the degree of groundwater mixing in the karst aquifer; and (3). redox status. The relative influence of each process is specific to individual drip flow sites and associated stalagmites, rendering each sulphur archive a unique signal of environmental conditions. Under conditions found in the soil and epikarst above Grotta di Ernesto, the dual isotope signatures of sulphate sulphur and oxygen incorporated into speleothem carbonate, closely reflect past conditions of industrial sulphur loading to the atmosphere and the extent of signal modification through biogeochemical cycling and aquifer mixing.

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Acknowledgments

The authors would like to thank the UK Natural Environment Research Council (NERC) for funding this work (Grant NE/C511805/1). Isotope analysis was undertaken at the University of Birmingham stable isotope facility. Thanks are also expressed to Michele Zandonati (Museo delle Scienze, Trento) for support in cave monitoring. Thanks are also expressed to Drs. K. Jarvis and K. Linge at the NERC ICP-MS facility, Kingston University for assistance with sulphur analysis in carbonate materials. We are also grateful to the two anonymous reviewers and Prof. Simon Bottrell whose suggestions helped to improve this manuscript.

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  1. Peter M. Wynn

    Present address: Lancaster Environment Centre, University of Lancaster, Lancaster, LA1 4YQ, UK

Authors and Affiliations

  1. The University of Newcastle, Callaghan, Newcastle, NSW, 2308, Australia

    Andrea Borsato & Silvia Frisia

  2. Museo Delle Scienze, Via Calepina 14, 38122, Trento, Italy

    Andrea Borsato & Renza Miorandi

  3. Connected Waters Initiative Research Centre, The University of New South Wales, 110 King Street, Manly Vale, Sydney, NSW, 2093, Australia

    Andy Baker

  4. School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, Edgbaston, B15 2TT, UK

    Ian J. Fairchild

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  1. Peter M. Wynn
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Correspondence to Peter M. Wynn.

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Wynn, P.M., Borsato, A., Baker, A. et al. Biogeochemical cycling of sulphur in karst and transfer into speleothem archives at Grotta di Ernesto, Italy. Biogeochemistry 114, 255–267 (2013). https://doi.org/10.1007/s10533-012-9807-z

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