Isotopic archives of sulphate in speleothems

The hemispheric impact of industrial emissions upon atmospheric sulphur loading is reflected in the sulphur depositional history recorded in cores from ice sheets. However, these do not reveal regional variations. Recently deposited speleothems are used here as archives of regional sulphur depositional history at two locations within the United Kingdom and Ireland. δ³⁴S-so₄ and δ¹⁸O-so₄ present within speleothem carbonate are measured for the first time as part of a dual isotope approach to decode the speleothem sulphur record. The largely refractory nature of δ³⁴S-so₄ under oxidising conditions enables source provenance of atmospheric SO₂, whereas the complex cycles of isotopic exchange and fractionation during incorporation of oxygen into sulphate molecules enable δ¹⁸O-so₄ signatures to yield insights into ambient environmental conditions and biogeochemical cycling in the ecosystem above the cave. δ³⁴S-so₄ values extracted from speleothem carbonate formed within Browns Folly Mine, UK, range from +3.5 to +5.5‰ and δ¹⁸O-so₄ +10.3 to +13.7‰. Both signatures lie within the range expected from sulphate deposition in industrial locations and reflect the transfer of sulphate into speleothem calcite with little fractionation. However, δ¹⁸O-so₄ signatures at Crag Cave, western Ireland, are isotopically heavier than expected and approach isotopic equilibrium with δ¹⁸O-h₂o under reducing conditions. Dual isotope analysis of δ³⁴S-so₄ and δ¹⁸O-so₄ optimises the correct identification of sulphur sources and biogeochemical cycling prior to incorporation into the speleothem record. At carefully selected cave sites where drip water flowpaths into the cave remain oxic, speleothems hold the potential to retain records of atmospheric sulphur loading at the local and regional scale.