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Durham University

Institute of Medieval and Early Modern Studies (IMEMS)

Staff and Governance

Core Staff

The day-to-day running of IMEMS is the responsibility of the Core Executive Committee, comprising the Director and Associate Directors and the Administrator. 

Publication details for Prof. James Baldini

Wynn, Peter M., Fairchild, Ian.J., Borsato, Andrea, Spötl, Christoph, Hartland, Adam, Baker, Andy, Frisia, Silvia & Baldini, James (2018). Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems. Geochimica et Cosmochimica Acta 226: 69-83.

Author(s) from Durham

Abstract

Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient DSO4 = (mSO4/mCO3)solid / (mSO4/mCO3)solution. High crystal growth rates (driven by either pH or saturation state) encouraged higher values of DSO4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, DSO4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of DSO4 were compared with DSO4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, DSO4 (x105) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14.9 (summer). These values approximate predicted DSO4 values based on our chamber experiments containing both low (2 ppm) and high (20 ppm) sulphate concentrations. Our experimental values of DSO4 obtained at crystal growth rates typical of stalagmites, closely match those observed in other cave sites from around the world. This validates the universality of the controls behind DSO4 and will enhance the use of speleothem CAS as a palaeoenvironmental proxy.


Full Executive Committee

Our Full Executive Committee is made up of the Core Executive Committee, listed above, plus a number of executive members including:


International Advisory Board

We are extremely fortunate to have be able to call on the help and guidance of colleagues from around the world who help to shape and guide our direction, strategy and international reach. Our current Advisory Board members are: