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

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.

Human forager response to abrupt climate change at 8.2 ka on the Atlantic coast of Europe.

The cooling and drying associated with the so-called '8.2 ka event' have long been hypothesized as having sweeping implications for human societies in the Early Holocene, including some of the last Mesolithic hunter-gatherers in Atlantic Europe. Nevertheless, detailed 'on-site' records with which the impacts of broader climate changes on human-relevant environments can be explored have been lacking. Here, we reconstruct sea surface temperatures (SST) from δ18O values measured on subfossil topshells Phorcus lineatus exploited by the Mesolithic human groups that lived at El Mazo cave (N Spain) between 9 and 7.4 ka. Bayesian modelling of 65 radiocarbon dates, in combination with this δ18O data, provide a high-resolution seasonal record of SST, revealing that colder SST during the 8.2 ka event led to changes in the availability of different shellfish species. Intensification in the exploitation of molluscs by humans indicates demographic growth in these Atlantic coastal settings which acted as refugia during this cold event.

Automated Measurement of Magnesium/Calcium Ratios in Gastropod Shells Using Laser-Induced Breakdown Spectroscopy for Paleoclimatic Applications.

The chemical composition of mollusk shells offers information about environmental conditions present during the lifespan of the organism. Shells found in geological deposits and in many archeological sites can help to reconstruct past climatic conditions. For example, a correlation has been found between seawater temperature and the amount of some substituent elements (e.g., magnesium, strontium) in the biogenerated calcium carbonate matrix of the shell, although it is very species-specific. Here we propose the use laser-induced breakdown spectroscopy (LIBS) to estimate Mg/Ca ratios in modern specimens of the common limpet Patella vulgata. An automated setup was used to obtain a sequence of Mg/Ca ratios across a sampling path that could be compared with the seawater temperatures recorded during the organism's lifespan. Results using four shells collected in different months of the year showed a direct relationship between the Mg/Ca ratios and the seawater temperature, although the sequences also revealed small-scale (short-term) variability and an irregular growth rate. Nevertheless, it was possible to infer the season of capture and the minimum and maximum seawater temperatures from the LIBS sequences. This fact, along with the reduction in sampling and measurement time compared with other spectrometric techniques (such as inductively coupled plasma mass spectrometry [ICP-MS]), makes LIBS useful in paleoclimatic studies.