High spatial resolution analysis of ferromanganese concretions by LA-ICP-MS†

A procedure was developed for the determination of element distributions in cross-sections of ferromanganese concretions using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The effects of carrier flow rates, rf forward power, ablation energy, ablation spot size, repetition rate and number of shots per point on analyte intensity were studied. It is shown that different carrier gas flow rates are required in order to obtain maximum sensitivities for different groups of elements, thus complicating the optimisation of ICP parameters. On the contrary, LA parameters have very similar effects on almost all elements studied, thus providing a common optimum parameter set for the entire mass range. However, for selected LA parameters, the use of compromise conditions was necessary in order to compensate for relatively slow data acquisition by ICP-MS and maintain high spatial resolution without sacrificing the multielemental capabilities of the technique. Possible variations in ablation efficiency were corrected for mathematically using the sum of Fe and Mn intensities. Quantification by external calibration against matrix-matched standards was successfully used for more than 50 elements. These standards, in the form of pressed pellets (no binder), were prepared in-house using ferromanganese concentrates from a deep-sea nodule reference material as well as from shallow-marine concretions varying in size and having different proportions of three major phases: aluminosilicates, Fe- and Mn-oxyhydroxides. Element concentrations in each standard were determined by means of conventional solution nebulisation ICP-MS following acid digestion. Examples of selected inter-element correlations in distribution patterns along the cross-section of a concretion are given

Archaeology and Sclerochronology of Marine Bivalves

International audienceIn a rapidly changing world, maintenance of the good health of the marine environment requires a detailed understanding of its mechanisms of change, and the ability to detect early signals of a shift away from the equilibrium state that we assume characterized it before there was any significant human impact. Given that instrumental measurements of the oceans go back no further than a few decades, the only way in which we can assess the long-term baseline variability that characterizes the pre-perturbation equilibrium state of the marine environment is by the use of proxy records contained in stratified or layered natural archives such as corals, fish otoliths and bivalve mollusc shells.In this chapter we will look at the ways in which the environmental signals recorded in the shells of bivalve molluscs can be used to shed light on marine variability both in the present and over past centuries and millennia, and specifically how they can be used to study marine climate, the marine environment and the economic and cultural history of the relationship between humans and the oceans.The chapter is divided into two parts: section one describes the morphological, geochemical and crystallographic techniques that are used to obtain information from the shells, while section two covers the use of bivalve shells in a wide range of applications, including ecosystem services, environmental monitoring, archaeology, climate reconstruction, and climate modeling