Comparison of Mg/Ca concentration series from Patella depressa limpet shells 
using CF-LIBS and LA-ICP-MS

Martínez-Minchero, Marina; Cobo, Adolfo; Méndez-Vicente, Ana; Pisonero, Jorge; Bordel, Nerea; Gutiérrez-Zugasti, Igor; Roberts, Patrick; Arrizabalaga, Álvaro; Valdiande, José; Mirapeix, Jesús; López-Higuera, José Miguel; García-Escárzaga, Asier

doi:10.1016/j.talanta.2022.123757

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Comparison of Mg/Ca concentration series from <i>Patella depressa</i> limpet shells using CF-LIBS and LA-ICP-MS

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Roberts, Patrick
Archaeology, Max Planck Institute for the Science of Human History, Max Planck Society;

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García-Escárzaga, Asier
Archaeology, Max Planck Institute for the Science of Human History, Max Planck Society;

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Citation

Martínez-Minchero, M., Cobo, A., Méndez-Vicente, A., Pisonero, J., Bordel, N., Gutiérrez-Zugasti, I., et al. (2023). Comparison of Mg/Ca concentration series from <i>Patella depressa</i> limpet shells using CF-LIBS and LA-ICP-MS. Talanta, 251: 123757. doi:10.1016/j.talanta.2022.123757.

Cite as: https://hdl.handle.net/21.11116/0000-000A-EB2B-E

Abstract

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R2 = 0.63–0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites.