Testing fundamentals: The chemical state of geochemical tracers in biominerals.

Abstract:

The use of many carbonate-derived geochemical proxies is underpinned by the assumption that tracer elements are incorporated ‘ideally’ as impurities the mineral lattice, following relatively straightforward kinetic and thermodynamic drives. This allows comparison to inorganic precipitation experiments, and provides a systematic starting point from which to translate geochemical tracers to environmental records.

Biomineral carbonates are a prominent source of geochemical proxy material, and are far from an ideal inorganic system. They are structurally and compositionally heterogeneous mineral-organic composites, produced in tightly controlled biological environments, possibly via non-classical crystal growth mechanisms. Biominerals offer numerous opportunities for tracers to be incorporated in a ‘non-ideal’ state. For instance, tracers could be hosted within the organic component of the structure, in interstitial micro-domains of a separate mineral phase, or in localized high-impurity clusters. If a proxy element is hosted in a non-ideal state, our understanding of its incorporation and preservation is flawed, and the theoretical basis behind the proxies derived from it must be reevaluated. Thus far, the assumption of ideal tracer incorporation has remained largely untested, owing to the spatial resolution and sensitivity limits of available techniques.

Developments in high-resolution, high-sensitivity X-ray spectroscopy at Scanning Transmission X-Ray Microscopes (STXMs) have allowed us to measure trace element coordination in foraminiferal calcite, at length-scales relevant to biomineralisation processes and tracer incorporation. This instrument has allowed us to test the fundamental assumptions behind several geochemical proxy elements. We present a summary of four STXM studies, assessing the chemical state and distribution of Mg (Branson et al, 2014), B (Branson et al, 2015), S and Na (unpub.), and highlight the implications of these data for the use of these elements as geochemical tracers.

References: Branson et al (2013). doi:10.1016/j.epsl.2013.09.037, Branson et al (2015). doi:10.1016/j.epsl.2015.02.006