Ca isotope fractionation upon synthesis of carbonated apatite

<p>Carbonated hydroxy-apatite (CHAP) was experimentally synthesized in batch-type set-ups by mixing of calcium (Ca)- and phosphate-bearing aqueous solutions and the transformation of calcite powder in aqueous solution between 11° and 65°C (Gussone et al., 2020). Compositional changes of the experimental solution and solid phase products were followed by elemental analysis, Raman spectroscopy, scanning-electron microscopy, and powder XRD. In the mixing experiments, crystallization of CHAP took place following the precipitation of metastable brushite as precursor that was then transformed into CHAP. In the transformation experiments using synthetic calcite as a precursor phase it was found that the reaction at pH values between 7.5 and 7.9 occurs via the direct replacement of calcium carbonate by CHAP.</p><p>Calcium isotope fractionation led to an enrichment of the light isotope in the solid CHAP compared to the aqueous solution by about -0.5 to -1.1 ‰, independent from the experimental approach, and the magnitude was essentially independent of temperature. The metastable brushite formed prior to transformation to CHAP showed a reduced fractionation compared to the CHAP. The observed Ca isotope fractionation into the CHAP lattice resembles that of natural phosphorites and lies within the range of the view existing theoretical and experimental studies.</p><p> </p><p>Reference: Gussone N., Böttcher M.E., Conrad A.C., Fiebig J., Pelz M., Grathoff G., Schmidt B.C. (2020) Calcium isotope fractionation upon experimental apatite formation. Chem. Geol., 551, 119737</p><p>The study was supported by German Science Foundation (DFG) to M.E.B and J.F. within the EXCALIBOR project (BO1548/8 and FI 948/7), and to N.G. (GU1035/10), and by Leibniz IOW.</p>

From particle attachment to space-filling coral skeletons

Reef-building corals and their aragonite (CaCO3) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.

Atom Probe Tomography (APT) Characterization of Organics Occluded in Single Calcite Crystals: Implications for Biomineralization Studies

Occlusion of organic components in synthetic calcite crystals has been recently used as a model to understand the role of intra-crystalline organics in biominerals. However, the characterization of the distribution of both types of organics inside these calcite crystals is very challenging. Here, we discuss the potential of using the technique of atom probe tomography (APT) for such characterization, focusing on the analysis of chitin incorporation in single crystals. Additionally, APT has at least the same spatial resolution as TEM tomography, yet with the advantage of obtaining quantitative chemical data. Results show that chitin, either after degradation with yatalase or in the form of nanofibers, forms discrete clusters (2 to 5 nm) in association to water and hydronium molecules, rather than forming a 3D network inside crystals. Overall findings indicate that APT can be an ideal technique to characterize intra-crystalline organic components in abiogenic and biogenic carbonates to further advance our understanding of biomineralization.

Rate of radiocarbon retention onto calcite by isotope exchange

Radiocarbon (14C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO3) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002–0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of 14C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

The Use of Mg/Ca as a Seawater Temperature Proxy

The underlying basis for Mg/Ca paleothermometry is that the amount of magnesium in calcite precipitated from seawater is dependent on temperature. Here we review the state of the art of the Mg/Ca seawater paleotemperature proxy, summarized by the following: 1) Calcite, whether formed abiotically or biologically as foraminifera and ostracode shells, incorporates variable amounts of magnesium into the crystal structure. 2) Uptake of Mg varies positively with temperature. 3) The relationship between temperature and the amount of Mg in calcite has been quantified by experiments on synthetic calcite growth and by culture, core top, and sediment trap experiments using living organisms. 4) The most careful calibrations of the Mg/Ca paleothermometer have been done for planktic foraminifera, then benthic foraminifera; there are species-specific variations in the amount of Mg incorporated into foraminifera shells. 5) The Mg/Ca ratio of calcite from planktic foraminifera in deep-sea cores has been widely used to interpret sea surface temperatures. 6) Measurement of both Mg/Ca and δ18O in planktic foraminifera have been used to calculate δ18O in seawater, and after correction for global ice volume, salinity could be inferred. 7) Mg/Ca from benthic foraminifera have been used to reconstruct deep-sea temperatures and cooling of ~12° over the last 50 million years. 8) One problem with the Mg/Ca seawater temperature proxy is partial dissolution of foraminifer shells, which lowers the Mg/Ca, and leads to an underestimation of ocean temperature. Benthic foraminifers appear to be more resistant to partial dissolution. 9) Past changes in the Mg/Ca ratio of seawater are an important factor in determining the amount of Mg in fossil skeletal calcite, and thus add another variable to the Mg/Ca temperature proxy. All Mg/Ca paleotemperature studies on fossil calcite older than Pleistocene should take into account the Mg/Ca of the seawater from which it precipitated.