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Cave carbonate mineral deposits (speleothems) contain trace elements that are intensively investigated for their significance as palaeoclimate and environmental proxies. However, chlorine, which is abundant in marine and meteoric waters, has been overlooked as a potential palaeo-proxy, while cosmogenic 36Cl could, in principle, provide a solar irradiance proxy. Here, total Cl concentrations analysed from various speleothems were low (3–14 mg/kg), with variations linked to crystal fabrics. High-resolution synchrotron radiation micro X-ray fluorescence (μ-XRF) trace element mapping showed Cl often associated with Na, Si, and Al. We propose that speleothems incorporate Cl in two fractions: (1) water soluble (e.g., fluid inclusions) and (2) water insoluble and strongly bound (e.g., associated with detrital particulates). However, disparities indicated that alternate unidentified mechanisms for Cl incorporation were present, raising important questions regarding incorporation of many trace elements into speleothems. Our first measurements of 36Cl/Cl ratios in speleothems required large samples due to low Cl concentrations, limiting the potential of 36Cl as a solar irradiance proxy. Critically, our findings highlight a knowledge gap into how Cl and other trace elements are incorporated into speleothems, how the incorporation mechanisms and final elemental concentrations are related to speleothem fabrics, and the significance this may have for how trace elements in speleothems are interpreted as palaeoclimate proxies.
Pollen preserved in caves provides a little-appreciated opportunity to study past vegetation and climate changes in regions where conventional wetland sediments are either unavailable, contain little organic matter, and/or are difficult to date accurately. Most palynology in caves has focused on clastic infill sediments, but pollen preserved in growing speleothems provides important new opportunities to develop vegetation and climatic records that can be dated accurately with radiometric methods. However, when pollen is present in speleothems, concentrations can vary by orders of magnitude, highlighting how little we know about the processes that transport pollen into caves and onto speleothem surfaces, and that determine the pollen's preservation probability. To explore these aspects of speleothem pollen taphonomy, we investigated the distribution of pollen and microscopic charcoal within several stalagmites from southwest Australia. We examined spatial patterns in pollen and charcoal preservation in order to distinguish whether observed gradients result from preservation or are products of systematic transport processes working along stalagmite surfaces. We find that pollen grains and charcoal fragments are located preferentially on the flanks of most stalagmites. This suggests that pollen grain and charcoal deposition on speleothems is influenced by transport and accumulation of detrital debris on growing surfaces. These insights will assist in future sampling campaigns focusing on speleothem pollen and charcoal contents.
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