BIVALVE SHELLS; SR/CA; HETEROGENEITY; PALEOCLIMATE; EDULIS; BA/CA; LIBS

Records of past environmental conditions in shell carbonate are usually derived from compositional analysis (i.e. trace elements, stable oxygen, carbon, and nitrogen isotopes) performed along the direction of the shell's growth and thus through time. However, compositional variations within isochronous parts of the shell can distort the environmental record and are difficult to assess without extensively mapping the whole shell. Here we apply Laser Induced BreakdownSpectroscopy (LIBS) to efficiently map the elemental change throughout the growth increments of three mollusc shells (Conomurex fasciatus, Ostrea edulis, Anomalocardia flexuosa). We employ an automated LIBS setup to map the Mg/Ca composition of whole shell sections with over 2000 data points per hour. By assessing the spatial variability of Mg/Ca intensity ratios this method has the potential to mitigate distorted results while increasing the resolution of derived palaeoenvironmental information.

Laser-induced breakdown spectroscopy; LIBS; laser spectroscopy; paleoclimate;MYTILUS-EDULIS; PECTEN-MAXIMUS; DA COSTA; ICP-MS; SCLEROCHRONOLOGY; TEMPERATURE; SEASONALITY; CHALLENGES; CHEMISTRY; BIVALVIA

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.