Trace elements in speleothems as recorders of environmental change

Speleothems are now established as important palaeoenvironmental archives and contain a number of suitable proxies, although trace elements have been much less widely used than oxygen and carbon isotopes. The complexity of the cave environment helps to explain this since the fluids from which speleothems form vary greatly in composition in space (even within a cave chamber), seasonally, and over longer periods. Understanding the forcing factors for this variability is the key to decoding the significance of the trace element records.A variety of techniques are available for trace element work and it is important to understand the strengths and limitations of each and also to seek an understanding, e.g. by micro-imaging techniques, of whether the elements are associated with inclusions in the CaCO₃, or are isolated within the crystal lattice. For some elements there is a more-or-less predictable relationship between element ratios to Ca in the water and in the calcite. Individual trace elements may be derived from atmospheric deposition, superficial deposits or bedrock and can be recycled in soil processes before being transferred to the cave. Some components show an instantaneous response to water infiltration, whereas others are only leached by slow-flowing seepage waters. Changing in the proportion of water from fracture-fed and seepage-flow aquifer compartments is an important factor in influencing trace element supply. High flows lead to higher fluxes of soil-derived colloidally transported elements. Conversely, under relatively dry conditions, degassing of CO₂ results in “prior calcite precipitation” upflow of the site of speleothem deposition and leads to higher ratios of Sr/Ca and Mg/Ca. Some trace element variations in speleothems over time are induced during crystal growth whereby faster growth leads to a greater departure from equilibrium element partitioning.Despite the demonstrated temperature-dependence of Mg partitioning into calcite, attempts at deriving palaeotemperature records from speleothems have been so far confounded by variations in solution Mg/Ca and/or crystallographic effects. A number of case studies have effectively used trace elements such as speleothem Mg as records of palaeo-aridity, using supporting arguments from modern monitoring or covariations with other parameters such as stable isotopes. Sr and U isotopes can also be indicators of palaeohydrology, although Sr isotope variations can also reflect varying aeolian input. Considerable progress has been made in decoding the meaning of annual trace element variations using criteria for understanding dripwater hydrology and pH. This should lead in the future to more specific interpretations of how seasonality evolves through time.