Metal localisation in gastropods shells: New insights from mass spectrometry techniques.

Gastropod shells are calcified structures made of several crystal layers. They grow throughout the lifecycle of mollusks by integrating some of the chemical elements present in their environment, including metals. This characteristic means mollusks can be useful bioindicators of metal exposure. The present study aimed to better understand the role of layer composition on metal accumulation. To that end, the gastropods Radix balthica were collected in a French river adjacent to a municipal wastewater treatment plant. Microchemical metal analyses in the different shell layers were performed by Femtosecond-Laser Ablation Inductively Coupled Plasma Mass Spectrometry (Fs-LA-ICP-MS) and analyses of the molecular environment of the metals were performed by Time-of-Flight secondary Ion Mass Spectrometry (TOF-SIMS). Strontium, Ba and Mn were well distributed within the whole shell and the high concentrations of these elements were found to be related to the aragonite structure of the shell. Copper, Ni, Pb and Zn were mostly present at the outer surfaces of the shell where the organic constituents were more concentrated. The analysis of metal distribution in shell layers could improve our understanding of the relationships between metal exposure and accumulation in mollusks, therefore providing evidences of their use as powerful integrated bioindicator of metal contamination.