ALBERT

Description: In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0–134.8 μmol mol−1 for the Fe/Ca and 1.68(±0.41) μmol mol−1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1σ[Mn/Ca] = 0.35–2.07 μmol mol−1; 1σ[Fe/Ca] = 93.9–188.4 μmol mol−1). The Mn/Ca ratios in the calcite were generally relatively low (2.21–9.93 μmol mol−1) but in the same magnitude and proportional to the surrounding pore waters (1.37–6.67 μmol mol−1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0–101.0 μmol mol−1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Description: Confocal Raman microscopy (CRM) mapping was used to investigate the microstructural arrangement and organic matrix distribution within the skeleton of the coral Porites lutea. Relative changes in the crystallographic orientation of crystals within the fibrous fan-system could be mapped, without the need to prepare thin sections, as required if this information is obtained by polarized light microscopy. Simultaneously, incremental growth lines can be visualized without the necessity of etching and hence alteration of sample surface. Using these methods two types of growth lines could be identified: one corresponds to the well-known incremental growth layers, whereas the second type of growth lines resemble denticle finger-like structures (most likely traces of former spines or skeletal surfaces). We hypothesize that these lines represent the outer skeletal surface before another growth cycle of elongation, infilling and thickening of skeletal areas continues. We show that CRM mapping with high spatial resolution can significantly improve our understanding of the micro-structural arrangement and growth patterns in coral skeletons.

Description: Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusks) represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (~300 nm). Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystal lattice.