Using Mg/Ca ratios from the limpet Patella depressa Pennant, 1777 measured by laser-induced breakdown spectroscopy (LIBS) to reconstruct paleoclimate

Measurement of the elemental composition of shells is increasingly emerging as an avenue for obtaining high-resolution insights into paleoclimate and past seasonality. Several studies have shown significant correlations between Mg/Ca ratios measured on shell carbonate and the sea surface temperature (SST) within which this carbonate was precipitated. However, other investigations have reported large variability in this relationship between species. Therefore, further studies, including taxa previously not considered are still required in order to validate these new species as suitable climate proxies. Here, we measured Mg/Ca ratios for limpet Patella depressa Pennant, 1777 samples live-collected in northern Spain for the first time. The elemental ratio was measured using laser-induced breakdown spectroscopy (LIBS), a technique that significantly decreases the time required for sample preparation and increases the number of shells that can be analyzed. In this study, calibration-free LIBS (CF-LIBS) methods were applied to estimate molar concentrations of chemical elements on biogenic calcium carbonate. The Mg/Ca ratio evolution along the shell growth axis was compared with stable oxygen isotope (δ18O) profiles obtained from these same limpets and the SST at the place where the mollusk grew to determine if the sequences obtained correctly reflected environmental conditions during the life-span of the mollusk. The results showed a significant correlation between Mg/Ca ratio series and both δ18O profiles and SST, highlighting the paleoenvironmental and archaeological potential of LIBS analyses on this mollusk species that is frequently found in archaeological contexts in the western Europe.This research was performed as part of the projects HAR2016-75605-R, HAR2017-86262-P and PID2019-107270RB-C21/AEI/10.13039/501100011033, funded by the Spanish Ministry of Economy and Competitiveness, MINECO. During the development of this research A.G.E was funded by the Basque Country Postdoctoral Program through a postdoctoral grant (POS_2020_2_0032). This study has also been supported by the Prehistoric Research Consolidated Group of the Basque Country University (IT-1223-19), funded by the Basque Country Government. P.R. is funded by the Max Planck Society