Mg/Ca profiles within archaeological mollusc (Patella vulgata) shells: Laser-Induced Breakdown Spectroscopy compared to Inductively Coupled Plasma-Optical Emission Spectrometry

© 2018 Elsevier B.V. Biogenic carbonate mollusc shells have the unique property of being a durable material found in many archaeological and geological sites, recording in their shell chemical composition the ambient environmental conditions during the mollusc's lifespan. In particular, mollusc shell Mg/Ca ratios have been suggested to be related to seawater temperature, although such a relationship is controversial and appears to be species- and even location-specific. This study investigates the use of Laser-Induced Breakdown Spectroscopy (LIBS) for the rapid measurement of Mg/Ca profiles within Patella vulgata shells, via comparison with one established analytical technique that is most often used for this purpose, ICP-OES. LIBS offers some advantages over other spectrometric techniques, including ICP-OES, the latter requiring initial micromilling of sample powders. LIBS offers faster measurement, reduced sample preparation, easier automation and less complex and lower cost instrumentation. A high correlation is evident between LIBS and ICP-OES Mg/Ca profiles within four archaeological P. vulgata shells, as well as strong similarities between LIBS measurements made in two different areas of each P. vulgata shell (i.e. the apex and a more conventional transect along the axis of shell growth). Validation of the LIBS technique for determination of Mg/Ca profiles within P. vulgata shells has implications for archaeological studies, because a greater number of shell specimens sampled from each archaeological site and chronological level can be measured, thereby improving the statistical robustness of data interpretation and conclusions. One example archaeological application that would benefit from application of the LIBS technique is identification of the season-of-capture of marine molluscs as a food resource for prehistoric societies

Shells and humans: molluscs and other coastal resources from the earliest human occupations at the Mesolithic shell midden of El Mazo (Asturias, Northern Spain)

Human populations exploited coastal areas with intensity during the Mesolithic in Atlantic Europe, resulting in the accumulation of large shell middens. Northern Spain is one of the most prolific regions, and especially the so-called Asturian area. Large accumulations of shellfish led some scholars to propose the existence of intensification in the exploitation of coastal resources in the region during the Mesolithic. In this paper, shell remains (molluscs, crustaceans and echinoderms) from stratigraphic units 114 and 115 (dated to the early Mesolithic c. 9 kys cal BP) at El Mazo cave (Asturias, northern Spain) were studied in order to establish resource exploitation patterns and environmental conditions. Species representation showed that limpets, top shells and sea urchins were preferentially exploited. One-millimetre mesh screens were crucial in establishing an accurate minimum number of individuals for sea urchins and to determine their importance in exploitation patterns. Environmental conditions deduced from shell assemblages indicated that temperate conditions prevailed at the time of the occupation and the morphology of the coastline was similar to today (rocky exposed shores). Information recovered relating to species representation, collection areas and shell biometry reflected some evidence of intensification (reduced shell size, collection in lower areas of exposed shores, no size selection in some units and species) in the exploitation of coastal resources through time. However, the results suggested the existence of changes in collection strategies and resource management, and periods of intense shell collection may have alternated with times of shell stock recovery throughout the Mesolithic.This research was performed as part of the project “The human response to the global climatic change in a littoral zone: the case of the transition to the Holocene in the Cantabrian coast (10,000–5000 cal BC) (HAR2010-22115-C02-01)” funded by the Spanish Ministry of Economy and Competitiveness. AGE was funded by the University of Cantabria through a predoctoral grant and IGZ was funded by the Spanish Ministry of Economy and Competitiveness through a Juan de la Cierva grant. We also would like to thank the University of Cantabria and the IIIPC for providing support, David Cuenca-Solana, Alejandro García Moreno and Lucia Agudo Pérez for their help. We also thank Jennifer Jones for correcting the English. Comments from two anonymous reviewers helped to improve the paper

Bayesian estimates of marine radiocarbon reservoir effect in northern Iberia during the Early and Middle Holocene

International audienceReconstructing the past variability of marine radiocarbon reservoir effects (MRE) is crucial for generating reliable chronologies for marine species and their consumers. We investigated the temporal MRE variability at the Early-to Mid-Holocene site of El Mazo (Asturias, northern Spain) by using a combination of new and previously published radiocarbon measurements on marine and terrestrial samples. The El Mazo site is characterized by overall well-defined archaeological layers of unknown occupation length with the predominant presence of two mollusc species (Patella vulgata Linnaeus, 1758 and topshell Phorcus lineatus [da Costa, 1778]) which were analysed for radiocarbon measurements. We employed the recently released IntCal20 calibration curve for the northern hemisphere and Bayesian modelling to reconstruct the site's chronology and temporal variability in MREs according to mollusc species. Obtained radiocarbon modelling results, although the estimate precision is not high, reveal a temporal variability in MREs that can be interpreted in view of known past climatic and environmental events such as the 8.2 ka event. The results also revealed differences in MREs according to mollusc species, which need to be taken into account in future chronological modelling. Overall, our results provide reference MRE values for the study of chronologies in northern Iberia during the Early-to Mid-Holocene. In this respect, a non-conservative ΔR reference for local marine samples dating earlier than c. 8.1 ka cal BP is −238 ± 28 14C years. © 2021 The Author

Comparison of light capturing approaches in Laser-Induced Breakdown Spectroscopy (LIBS) for multichannel spectrometers

LIBS technique requires the spectroscopic analysis of the light emitted by a laser-induced plasma plume. One challenge of the different approaches to capture the plasma light emission is the significant shot-to-shot variations of the plume inhomogeneities, position, and morphology. This is even more challenging when multichannel CCD spectrometers are used, because the light should be homogeneously divided among multiple capturing optical fibers (typically up to 8 fibers) with stable spectral efficiency for all channels. Otherwise, any further analysis of the atomic emission spectra involving multiple channels, such as line intensity ratios, Boltzmann plots, or calibration-free LIBS, could be compromised by the morphology-dependent spectral artifacts induced by the collection optics. In this work, we assess the performance of several collection optics in terms of overall capturing efficiency and channel-to-channel variations due to changes in plasma morphology. Results clearly show that this could be an issue even with the approaches with the best spatial homogenization, including optical fibers and Köhler optics.This work was supported by the R + D project PID2019-107270RBC21 (funded by MCIN/AEI10.13039/501100011033) and by Plan Nacional de I + D + and Instituto de Salud Carlos III (ISCIII), Subdirección General de Redes y Centros de Investigación Cooperativa, Ministerio de Ciencia, Innovación y Universidades, Spanish Network for Research in Infectious Diseases (REIPI RD16/0016/0007), CIBERINFEC (CB21/13/00068), CIBER-BBN (BBNGC1601), cofinanced by European Development Regional Fund “A way to achieve Europe”. A. O.-S was financially supported by the Miguel Servet II program (ISCIIICPII17–00011). AGE was supported by the Catalonia Government throughout a Beatriu de Pin´os fellowship (grant number 2020 BP 00240). We thanks Dr. A. Pic´on for providing the pure iron ingot and helpful suggestions to improve the experimental setup