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It has been argued that skeletal Mg/Ca ratio in echinoderms is mostly governed by Mg 2+ and Ca 2+ concentrations in the ambient seawater. Accordingly, well-preserved fossil echinoderms were used to reconstruct Phanerozoic seawater Mg 2+ /Ca 2+ ratio. However, Mg/Ca ratio in echinoderm skeleton can be affected by a number of environmental and physiological factors, the effects of which are still poorly understood. Notably, experimental data supporting the applicability of echinoderms in paleoenvironmental reconstructions remain limited. Here, we investigated the effect of ambient Mg 2+ /Ca 2+ seawater ratio and diet on skeletal Mg/Ca ratio and growth rate in two echinoid species (Psammechinus miliaris and Prionocidaris baculosa). Sea urchins were tagged with manganese and then cultured in different Mg 2+ /Ca 2+ conditions to simulate fluctuations in the Mg 2+ /Ca 2+ seawater ratios in the Phanerozoic. Simultaneously, they were fed on a diet containing different amounts of magnesium. Our results show that the skeletal Mg/Ca ratio in both species varied not only between ossicle types but also between different types of stereom within a single ossicle. Importantly, the skeletal Mg/Ca ratio in both species decreased proportionally with decreasing seawater Mg 2+ /Ca 2+ ratio. However, sea urchins feeding on Mg-enriched diet produced a skeleton with a higher Mg/Ca ratio. We also found that although incubation in lower ambient Mg 2+ /Ca 2+ ratio did not affect echinoid respiration rates, it led to a decrease or inhibition of their growth. Overall, these results demonstrate that although skeletal Mg/Ca ratios in echinoderms can be largely determined by seawater chemistry, the type of diet may also influence skeletal geochemistry, which imposes constraints on the application of fossil echinoderms as a reliable proxy. The accuracy of paleoseawater Mg 2+ /Ca 2+ calculations is further limited by the fact that Mg partition coefficients vary significantly at different scales (between species, specimens feeding on different types of food, different ossicle types, and stereom types within a single ossicle)., (© 2020 John Wiley & Sons Ltd.)

Abstract: Using in situ (12h) pulse-labeling of scleractinian coral aragonitic skeleton with stable 86Sr isotope, the diel pattern of skeletal extension was investigated in the massive Porites lobata species, grown at 5m depth in the Gulf of Eilat. Several microstructural aspects of coral biomineralization were elucidated, among which the most significant is simultaneous extension of the two basic microstructural components Rapid Accretion Deposits (RAD; also called Centers of Calcification) and Thickening Deposits (TD; also called fibers), both at night and during daytime. Increased thickness of the 86Sr-labeled growth-front in the RADs compared to the adjacent TDs revealed that in this species RADs extend on average twice as fast as TDs. At the level of the individual corallite, skeletal extension is spatially highly heterogeneous, with sporadic slowing or cessation depending on growth directions and skeletal structure morphology. Daytime photosynthesis by symbiotic dinoflagellates is widely acknowledged to substantially increase calcification rates at the colony and the corallite level in reef-building corals. However, in our study, the average night-time extension rate (visualized in three successive 12h pulses) was similar to the average daytime extension (visualized in the initial 12h pulse), in all growth directions and skeletal structures. This research provides a platform for further investigations into the temporal calibration of coral skeletal extension via cyclic growth increment deposition, which is a hallmark of coral biomineralization. [Copyright &y& Elsevier]

A method to label marine biocarbonates is developed based on a concentration enrichment of a minor stable isotope of a trace element that is a natural component of seawater, resulting in the formation of biocarbonate with corresponding isotopic enrichments. This biocarbonate is subsequently imaged with a NanoSIMS ion microprobe to visualize the locations of the isotopic marker on sub-micrometric length scales, permitting resolution of all ultra-structural details. In this study, a scleractinian coral, Pocillopora damicornis, was labeled 3 times with Sr-enhanced seawater for a period of 48 h with 5 days under normal seawater conditions separating each labeling event. Two non-specific cellular stress biomarkers, glutathione-S-transferase activity and porphyrin concentration plus carbonic anhydrase, an enzymatic marker involved in the physiology of carbonate biomineralization, as well as unchanged levels of zooxanthellae photosynthesis efficiency indicate that coral physiological processes are not affected by the Sr-enhancement. NanoSIMS images of the Sr/Ca ratio in skeleton formed during the experiment allow for a determination of the average extension rate of the two major ultra-structural components of the coral skeleton: Rapid Accretion Deposits are found to form on average about 4.5 times faster than Thickening Deposits. The method opens up new horizons in the study of biocarbonate formation because it holds the potential to observe growth of calcareous structures such as skeletons, shells, tests, spines formed by a wide range of organisms under essentially unperturbed physiological conditions. [ABSTRACT FROM AUTHOR]

The structural phase transition from aragonite to calcite in biogenic samples extracted from the skeletons of selected scleractinian corals has been studied by synchrotron radiation diffraction. Biogenic aragonite samples were extracted en bloc without pulverization from two ecologically different scleractinian taxa: Desmophyllum (deep-water, solitary and azooxanthellate) and Favia (shallow-water, colonial, zooxanthellate). It was found that natural (not pulverized) samples contribute to narrow Bragg peaks with Δ d/ d values as low as 1 × 10−3, which allows the exploitation of the high resolution of synchrotron radiation diffraction. A precise determination of the lattice parameters of biogenic scleractinian coral aragonite shows the same type of changes of the a, b, c lattice parameter ratios as that reported for aragonite extracted from other invertebrates [Pokroy, Quintana, Caspi, Berner & Zolotoyabko (2004). Nat. Mater. 3, 900–902]. It is believed that the crystal structure of biogenic samples is influenced by interactions with organic molecules that are initially present in the biomineralization hydrogel. The calcite phase obtained by annealing the coral samples has a considerably different unit-cell volume and lattice parameter ratio c/ a as compared with reference geological calcite and annealed synthetic aragonite. The internal strain in the calcite structure obtained by thermal annealing of the biomineral samples is about two times larger than that found in the natural aragonite structure. This effect is observed despite slow heating and cooling of the sample. [ABSTRACT FROM AUTHOR]