MARINE BIOGENIC CARBONATES AND RADIOCARBON—A RETROSPECTIVE ON SHELLS AND CORALS WITH AN OUTLOOK ON CHALLENGES AND OPPORTUNITIES

ABSTRACT Many organisms living in the ocean create tests, shells, or related physical structures of calcium carbonate (CaCO3). As this is most often from dissolved inorganic carbon, using organisms that create calcium carbonate structures for climate research and dating purposes requires knowledge of the origin of carbon that is incorporated. Here, we give a short overview of research on marine carbonates over the last 60 years, especially that based on shell and coral samples. Both shells and corals exhibit annual growth patterns, like trees, and therefore offer possibilities for yearly resolution of past radiocarbon (14C) variations. We concentrate on their evolution in 14C dating including difficulties in determining reservoir ages as well as the possibilities they offer for archaeological dating, oceanography, calibration purposes as well as environmental research in general.

A 35-million-year record of seawater stable Sr isotopes reveals a fluctuating global carbon cycle

Changes in the concentration and isotopic composition of the major constituents in seawater reflect changes in their sources and sinks. Because many of the processes controlling these sources and sinks are tied to the cycling of carbon, such records can provide insights into what drives past changes in atmospheric carbon dioxide and climate. Here, we present a stable strontium (Sr) isotope record derived from pelagic marine barite. Our δ88/86Sr record exhibits a complex pattern, first declining between 35 and 15 million years ago (Ma), then increasing from 15 to 5 Ma, before declining again from ~5 Ma to the present. Numerical modeling reveals that the associated fluctuations in seawater Sr concentrations are about ±25% relative to present-day seawater. We interpret the δ88/86Sr data as reflecting changes in the mineralogy and burial location of biogenic carbonates.

No ion is an island: Multiple ions involved during boron incorporation into CaCO3

<p>Boron isotope ratios, as measured in marine calcium carbonate, are a proven tracer of past seawater and calcifying fluid pH and thus a powerful tool for the reconstruction of past atmospheric CO<sub>2</sub> and monitoring of coral physiology. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO<sub>3 </sub>polymorphs have often reported variable and even conflicting results, implying that we may not fully understand pathways of boron incorporation into calcium carbonate.  Here we address this topic with experimental data from calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that calcites display a higher degree of scatter, and diverge from the boron isotope composition of borate ion at low pH. We discuss these findings with reference to the simultaneous incorporation of other trace and minor elements, and highlight a number of mechanisms by which crystal growth mechanisms may influence the concentration and isotope composition of boron in CaCO<sub>3</sub>. In particular, we highlight the potential importance of surface electrostatics in driving variability in published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are likely to play a much more minor role during natural precipitation of biogenic carbonates.</p>

COMPARING DIRECT CARBONATE AND STANDARD GRAPHITE 14C DETERMINATIONS OF BIOGENIC CARBONATES

ABSTRACT The direct carbonate procedure for accelerator mass spectrometry radiocarbon (AMS 14C) dating of submilligram samples of biogenic carbonate without graphitization is becoming widely used in a variety of studies. We compare the results of 153 paired direct carbonate and standard graphite 14C determinations on single specimens of an assortment of biogenic carbonates. A reduced major axis regression shows a strong relationship between direct carbonate and graphite percent Modern Carbon (pMC) values (m = 0.996; 95% CI [0.991–1.001]). An analysis of differences and a 95% confidence interval on pMC values reveals that there is no significant difference between direct carbonate and graphite pMC values for 76% of analyzed specimens, although variation in direct carbonate pMC is underestimated. The difference between the two methods is typically within 2 pMC, with 61% of direct carbonate pMC measurements being higher than their paired graphite counterpart. Of the 36 specimens that did yield significant differences, all but three missed the 95% significance threshold by 1.2 pMC or less. These results show that direct carbonate 14C dating of biogenic carbonates is a cost-effective and efficient complement to standard graphite 14C dating.

RESULTS OF PETROGRAPHIC ANALYSIS OF MESHOKO CERAMICS

The article presents the results of petrographic analysis of the ceramics of the Chalcolithic settlement of Meshoko. A total of 42 fragments were examined (see appendix), 10 of which belong to the upper part of the monument's sediments (layers 1 and 2a; Fig. 1), 20 refer to the middle part of the sediments (layer 2b; Fig. 2), 12 – to the lower part (layer 3; Fig. 3). Based on the analysis, 5 groups of ceramics were identified (Fig. 4). Group 1 consists of fragments with an admixture of limestone, group 2 – with an admixture of diorite, group 3 – with an admixture of biogenic carbonates and sand, group 4 – with an admixture of calcite, group 5 – with an admixture of diorite and chamotte. Clays of smectite composition predominate in groups 1 and 2, while clays of smectite-carbonate composition predominate in groups 3 and 4. Comparison of these groups with stratigraphy revealed that most of the ceramics of groups 3 and 4 are confined to the lower layer, and groups 1 and 2 to the middle and upper layer (Table 1). In addition, the ceramics of these layers differ in the nature of the external surface treatment. Significant changes in the technology of making ceramics during the transition from the lower layer to the middle layer allow us to assume corresponding changes in the composition of the population.