A micro-scale method has been developed for analysis of trace-element concentration profiles in the calcium carbonate shell of the Great Scallop (Pecten maximus). UV laser ablation at 266-nm coupled with ICP-MS detection was used to analyse daily calcite striae of shell samples to obtain high temporal resolution of trace element incorporation. Analysis of scallop shells was carefully examined to determine the quality of calcium carbonate ablation and calibration. An accurate external calibration method based on matrix matching was developed. Twelve sodium-free enriched calcium carbonate standards containing up to twenty-four elements were prepared, by co-precipitation with aqueous ammonia and NH(4)HCO(3), and subsequently back-calibrated in the laboratory. These CaCO(3) standards were found to be homogenous and their use enabled sensitive quantitative analysis (detection limits of a few ng g(-1)) over a wide range of concentrations (0.1 to 500 microg g(-1)). Use of these CaCO(3) standards was also evaluated by analysis of three calcium-rich certified reference materials. Because calibration was consistent with the certified results, this analytical method is a sensitive tool for analysis of environmental calcium carbonate matrices. Repeated analysis of scallop shell samples collected simultaneously at the same location showed that the trace elements are homogeneously distributed along a stria. The reliability of such in-situ records of biogenic calcium carbonate (scallop shells) is apparent from the inter-individual and inter-annual reproducibility of the trace element profiles.

Barium : calcium and molybdenum : calcium ratios were investigated in shells of the tropical scallop Comptopallium radula. Three juvenile specimens were harvested alive in the southwest lagoon of New Caledonia after a 1-yr hydrological survey. Calcite samples representing a few hours of biomineralization were laser-ablated along the maximal growth axis and analyzed for Ba and Mo content with an inductively coupled plasma mass spectrometer. Absolute dates of shell precipitation assigned on the basis of periodic formation of shell growth patterns led to the accurate reconstruction of ontogenetic variations of elemental ratios with subweekly resolution. Interindividual variability of Ba : Ca and Mo : Ca time series was low, indicating an environmental control on the incorporation of these elements within shells. Both profiles were characterized by a background level punctuated by sharp peaks. The ingestion of diatoms enriched in Ba (adsorbed on iron oxyhydroxides associated with the frustules) is the most likely cause of the formation of Ba : Ca peaks. Some contribution of diatom-associated barite is also possible. In every instance, Ba : Ca would possibly be a proxy for the timing and magnitude of diatom blooms. Among all the theories that could be advanced to explain the occurrence of Mo : Ca peaks, the most plausible appears to be the ingestion of phytoplankton cells grown on NO { 3 , and therefore containing high levels of Mo required for the activity of nitrate reductase. If this is so, then Mo : Ca could be a new proxy for nitrate uptake by phytoplankton in coastal ecosystems, helping to reconstruct the balance between new and regenerated production in paleoenvironments.

During their growth, bivalves are recognized to archive minor and trace elements within their shells which may reflect environmental conditions at the sediment-water interface (SWI). Shells from juvenile Great Scallops (Pecten maximus (L.)), which develop a daily calcite growth layer, were collected in the Bay of Seine (France) and examined by matrix-matched LaserAblation ICP-MS analysis for Mn concentrations along their growth period, from April to October (year 2004). The backdated Mn concentration profiles were compared with environmental variables (e.g., temperature, salinity, chlorophyll a, oxygen, etc.) measured continuously at monitoring stations in riverine, estuarine, and coastal waters. The objective was first to perform microanalyses of Mn composition along the shell reflecting episodic enrichment or depletion in such environment, and second, to depict Mn cycling and inputs at the SWI according to the measured profiles. Basically, Mn concentration profiles mostly depend on established estuarine and coastal biogeochemical processes that lead to an increase of dissolved Mn concentration available for shell uptake. Potential particulate Mn fluxes from the Seine River, that control both particulate and dissolved Mn input to the bay, are strongly correlated with shell Mn concentrations from April to July (?r = 0.95, n = 8, p < 0.05). In late summer, riverine inputs can not only provide an explanation for the shell Mn enrichments which suggest additional sources of Mn. During this period, two other processes also contribute to the release of dissolved Mn in coastal waters and the increase of shell Mn content: (1) successive redox oscillations within the high turbidity zone of the macrotidal Seine estuary and (2) postbloom reductive conditions developed at the SWI of the Seine Bay under periodic seasonal eutrophication. This study demonstrates that incremental Mn concentrations profiles in scallop shells are a relevant natural archive to evaluate the processes governing Mn inputs into coastal environments at a daily scale.