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Rosie Sandiford

Speleothems offer the opportunity to reconstruct historical environmental and climatic data through analysis of trace elements which are incorporated into the speleothem structure. Trace elements have only recently been readily studied as a reliable data proxy and there is still much research being done surrounding their presence in speleothems. Analysis of other data proxies such as stable isotopes is still more widely used. Trace elements come from a number of sources in the surrounding environment. There are a number of ways in which trace elements can be analysed and measured, some of which provide limitations in the outcome of precise data.

Speleothems are mineral deposits formed in caves, via the precipitation of calcium carbonate onto the cave floor from drip waters (Fairchild et al., 2007; Finch et al., 2001). Speleothems have been established as one of the most valuable resources for understanding Earth surface conditions in the past (Fairchild & Baker, 2012). Outside of drilling ice cores in the high polar latitudes, speleothems provide the opportunity to gather continuous terrestrial records with detailed chronologies (Fairchild & Treble, 2009). They have been studied as archives of past climate and environmental conditions, with the focus having been primarily on stable isotopes, mainly oxygen and carbon, however trace elements are also suitable data proxies and are being increasingly used for reconstructing past conditions (Fairchild et al., 2006). As a speleothem grows, trace elements, and other geochemical signals which are indicative of the surrounding physical environment, are incorporated into the structure (Finch et al., 2001; McMillan et al., 2005). Fairchild et al. (2006) established five types of influences on the geochemistry of speleothems, all of which apply to trace elements. These include atmospheric input, vegetation/soil, karstic aquifer, primary speleothem crystal growth, and secondary alteration (Fairchild et al., 2006). These five influences are therefore reflected in the species of trace elements present and their concentrations.

Although trace elements have been less widely used than stable isotopes, they provide the opportunity to reconstruct historical environmental and climatic conditions surrounding speleothems such as rainfall, temperature, soil conditions, and cave pCO2 (Fairchild & Treble, 2009). Speleothems have a wide range of growth rates which can influence composition of trace elements. Because caves cover a range of climatic, geomorphic and geologic environments, trace element composition can vary significantly between sites, including within the same cave chamber, and over time (Fairchild & Treble, 2009).

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Rosie Sandiford

Trace elements in carbonate speleothems formed by precipitation are controlled by the concentration of elements in drip waters, the physical conditions at the time of formation, and the nature of the crystallographic site (Finch et al, 2001). Finch et al. (2001) also indicate that the flow rate of drip waters and growth rate can affect the final composition. Analysis of trace elements in speleothems compares the ratios of elements to Ca as they substitute for it. It is suggested that calcite is able to incorporate any element in the periodic table into its structure, made possible by the positioning of the oxygen atoms to which cations bind (Fairchild & Baker, 2012). It has been proposed that temperature controls variation in speleothem trace elements however this has not been proven (Roberts, Smart & Baker, 1998). Mg/Ca ratios may vary annually as a result of seasonal temperature changes however Sr/Ca and Ba/Ca variations cannot be directly related to changes in temperature (Roberts et al., 1998). Roberts et al. (1998) suggest that variations may be indicative of differences in water residence time, resulting from changes in precipitation. Fairchild and Treble (2009) suggest that the main source of Mg and Sr is carbonate bedrock, and that P comes from the mineral apatite. Other sources of chemical species can be atmospheric deposition, sediment deposits, aeolian particles, inorganic soil constituents and elements recycled via soil biota (Fairchild & Treble, 2009).

There are a few methods used for analysing the trace element composition of speleothems. Commonly used instruments and techniques to analyse trace elements in speleothems are SIMS (Secondary Ionisation Mass Spectrometer), as well as laser-ablation ICP-MS (inductively-coupled plasma mass spectrometer). Many of the instruments used to analyse trace elements are very expensive and therefore not accessible to many researchers; the scanning proton microscope which is used to detect potassium and uranium, and the micro X-ray fluorescence spectrometer which can detect most elements, are some such instruments (Fairchild et al., 2006). ICP-MS is rapid and precise however the depth of excavation can limit spatial resolution (Fairchild et al., 2006). ICP-MS and ICPAES (inductively-coupled plasma atomic emission spectrometer) offer the greatest analytical accuracy but rely on precision from trained analysts to achieve reliable results (Fairchild & Treble, 2009). They both are solution based analyses which is impractical in the cave environment (Fairchild & Baker, 2012). Both laser ablation ICP-MS and SIMS require standards to be matrix-matched to samples to ensure removal of material and ionisation of species (Fairchild & Treble, 2009). Creating these standards is challenging and is a high priority if results are to be reliable. Comparison of visible growth laminae (small-scale layering) to the trace element ratios can show

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Rosie Sandiford

reproducible variability (Finch et al., 2001). In the case of Cold Air Cave in Southern Africa, an environmental signal control, likely rainfall, was revealed through matching the Sr/Ca and Br/Ca cycles to laminae (Finch et al., 2001). Finch et al. (2001) also uncovered contradictory data indicating trace element oscillations perpendicular to growth direction. It is stated that further investigation is required into the mechanisms of stalagmite growth before more can be understood. Therefore, time-series analysis on a large scale is required to detect regular trace element cyclicity (Finch et al., 2001).

Trace elements are a valuable data proxy in the analysis of speleothems in relation to paleoclimates. Although further research and studies are required to fully understand the significance of trace elements and their incorporation into speleothems, current evidence indicates how they may be representative of past climates and environments. There are limitations however which influence the outcome of accurate and reliable results. The accessibility to required instruments is an issue as many of them are costly. Another limitation is that of human error with most of these analyses requiring analysts to be precise and highly trained. Locating or creating matrix-matched standards can be challenging and mismatched standards can greatly affect results. With further research being conducted in this area, trace elements are becoming better understood in the context of speleothems and past climates. They have been widely examined in ice cores in the poles and are similarly being understood in speleothems.

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Rosie Sandiford

Fairchild, I.J., & Baker, A. (2012). Speleothem Science: From Process to Past Environments. Chichester, UK: Wiley-Blackwell. Fairchild, I.J., Frisia, S., Borsato, A., & Tooth, A.F. (2007). Speleothems. In D.J. Nash & S.J. McLaren (Eds.), Geochemical Sediments and Landscapes (p. 200-245). Chichester, UK: Wiley. Fairchild, I.J., Smith, C.L., Baker, A., Fuller, L., Sptl, C., Mattey, D., & McDermott, F. (2006). Modification and preservation of environmental signals in speleothems. Earth Science Reviews, 75, 105-153. doi: 10.1016/j.earscirev.2005.08.003 Fairchild, I.J., & Treble, P.C. (2009). Trace elements in speleothems as recorders of environmental change. Quaternary Science Reviews, 28, 449-468. doi: 10.1016/j.quascirev.2008.11.007 Finch, A.A., Shaw, P.A., Weedon, G.P., & Holmgren, K. (2001). Trace element variation in speleothems aragonite: potential for palaeoenvironmental reconstruction. Earth and Planetary Science Letters, 186, 255-167. McMillan, E.A., Fairchild, I.J., Frisia, S., Borsato, A., & McDermott, F. (2005). Annual trace element cycles in calcite-aragonite speleothems: evidence of drought in the western Mediterranean 1200-1100 yr BP. Journal of Quaternary Science, 20 (5), 423-233. doi: 10.1002/jqs.943 Roberts, M.S., Smart, P.L., & Baker, A. (1998). Annual trace element variations in a Holocene speleothem. Earth and Planetary Science Letters, 154, 237-246.