Fire-induced shifts in stalagmite organic matter mapped using synchrotron infrared microspectroscopy

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dc.contributor.authorMcDonough, LKen_AU
dc.contributor.authorCampbell, Men_AU
dc.contributor.authorTreble, PCen_AU
dc.contributor.authorMarjo, CEen_AU
dc.contributor.authorFrisia, Sen_AU
dc.contributor.authorVongsvivut, JPen_AU
dc.contributor.authorKlein, ARen_AU
dc.contributor.authorKovacs-Kis, Ven_AU
dc.contributor.authorBaker, AAen_AU
dc.date.accessioned2024-09-06T01:42:30Zen_AU
dc.date.available2024-09-06T01:42:30Zen_AU
dc.date.issued2024-09en_AU
dc.date.statistics2024-09en_AU
dc.description.abstractUnderstanding organic matter (OM) in cave mineral deposits (speleothems) is essential for interpreting land use and climatic changes, and the incorporation of trace elements associated with organic compounds. However, the sources and composition of OM in speleothems are poorly understood due to challenges associated with measuring OM at low concentrations and the destructive nature of most speleothem OM analysis techniques. Synchrotron Fourier-transform infrared (FTIR) microspectroscopy is a promising non-destructive technique that can be used to investigate stalagmite OM composition. We use FTIR to analyse vegetation, soil, calcium carbonate and ash end-members and demonstrate the use of Synchrotron infrared microspectroscopy (IRM) mapping to detect temporal changes in the OM composition of a stalagmite from a shallow cave in south-west Western Australia. Our analysis reveals predominant FTIR peaks in the stalagmite linked to amides and CH2 groups, suggesting potential microbial contributions, with smaller proportions of aromatic, CH3 and Cdouble bondO groups. High-resolution transmission electron microscopy revealed that this OM is likely hosted in sets of nanopores spaced hundreds of nanometers apart, aligned along calcite crystallographic orientations. Furthermore, we assess the impact of known wildfire events as discrete short term environmental changes on the stalagmite’s OM composition. The temporal variability in OM functional group composition after fires implies complex fire-soil-vegetation-microbial interactions. This research demonstrates the effectiveness of Synchrotron IRM mapping in providing insights into the short and long-term environmental influences on stalagmite OM composition. Expanding this research to other regions and climates could further enhance the interpretation of OM changes in speleothem-based palaeoclimate reconstructions. © Crown Copyright © 2024 Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).en_AU
dc.description.sponsorshipThe authors thank Peter Reece for helpful discussions on the differences in calcite crystal vs powder FTIR spectra. We also thank Mark Tobin for his assistance with Synchrotron IRM analyses. Thanks to Katie Coleborn and Anne Wood for the collection and preparation of vegetation samples from SW WA, Pauline Grierson for collection of ash samples, Calgardup Caves and Yanchep Caves for their assistance and to Henri Wong for supplying precipitated CaCO3 powder. SF is grateful to György Zoltán Radnóczi (CER) for obtaining the highest possible quality TEM lamellae and Béla Pécz for both granting access at the FIB and HREM and technical adviceen_AU
dc.identifier.articlenumber104842en_AU
dc.identifier.citationMcDonough, L. K., Campbell, M., Treble, P. C., Marjo, C., Frisia, S., Vongsvivut, J., Klein, A. R., Kovacs-Kis, V., & Baker, A. (2024). Fire-induced shifts in stalagmite organic matter mapped using synchrotron infrared microspectroscopy. Organic Geochemistry, 195, 104842. doi:10.1016/j.orggeochem.2024.104842en_AU
dc.identifier.issn0146-6380en_AU
dc.identifier.journaltitleOrganic Geochemistryen_AU
dc.identifier.urihttp://dx.doi.org/10.1016/j.orggeochem.2024.104842en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/15676en_AU
dc.identifier.volume195en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherElsevieren_AU
dc.subjectFiresen_AU
dc.subjectNatural disastersen_AU
dc.subjectSynchrotronsen_AU
dc.subjectCavesen_AU
dc.subjectAustraliaen_AU
dc.subjectWestern Australiaen_AU
dc.subjectSoilsen_AU
dc.subjectMineralsen_AU
dc.subjectAmidesen_AU
dc.subjectTracer techniquesen_AU
dc.titleFire-induced shifts in stalagmite organic matter mapped using synchrotron infrared microspectroscopyen_AU
dc.typeJournal Articleen_AU
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