Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (delta O-18 and delta C-13), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH similar to 11) from Poole's Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal((aq)) complexes on the boundary between colloidal and dissolved (similar to 1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (K-d) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the 'free' fraction of total metal in aqueous solution (f(m)). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic K-d values and field measurements for metal partitioning into calcite occur where [free metal] << [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where f(m) approximate to 0, apparent inorganic K-d app values are also approximate to 0, but the true partition coefficient (K-d actual) is significantly higher. Importantly, the K-d of NOM-metal complexes [organic carbon-metal ratio) approaches 1 for the most stable aqueous complexes, as is shown here for Co, but has values of 24-150 for V, Ni and Cu. This implies that ternary surface complexation (metal-ligand co-adsorption) can occur (as for NOM-Co), but is the exception rather than the rule. We also demonstrate the potential for trace metals to record information on NOM composition as expressed through changing NOM-metal complexation patterns in dripwaters. Therefore, a suite of trace metals in stalagmites show variations clearly attributable to changes in organic ligand concentration and composition, and which potentially reflect the state of overlying surface ecosystems. (C) 2013 Elsevier Ltd. All rights reserved.