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.

海洋软体动物壳的元素组成可以提供有关软体动物在其生命周期中所经历的环境条件的宝贵信息。先前的研究表明，在软体动物壳的生物碳酸盐上测量的 Mg/Ca 浓度比与海面温度 (SST) 之间存在显着相关性。在这里，我们建议使用激光诱导击穿光谱 (LIBS) 和验证无校准 LIBS (CF-LIBS) 方法，以快速测量和估计髌骨内 Mg/Ca 摩尔浓度分布三角旗，1777 年的帽贝壳。为了实现这些目标，来自 CF-LIBS 方法的结果与从已建立的分析技术获得的结果进行比较，例如激光烧蚀电感耦合等离子体质谱 (LA-ICP-MS)。使用这两种方法获得的浓度系列显示了明确的时间模式，并反映了每个样本的捕获季节。结果证明 四个活采集的P. depressa中 CF-LIBS 和 LA-ICP-MS Mg/Ca 摩尔浓度曲线之间存在显着相关性 (R ^{2 = 0.63–0.81)}贝壳。在每个样本中，用 CF-LIBS 估计的摩尔浓度的平均误差低于 10%。通过本研究中使用的两种技术获得的结果之间的比较，我们首次证明了使用 CF-LIBS 技术准确推断出生物碳酸盐中测量的 Mg/Ca 摩尔浓度。CF-LIBS 方法验证代表了对这种在考古遗址中经常发现的软体动物物种进行快速和大规模古环境和考古分析的巨大潜力。