Description: Brachiopods present a key fossil group for Phanerozoic palaeo-environmental and palaeo-oceanographical reconstructions, owing to their good preservation and abundance in the geological record. Yet to date, hardly any geochemical proxies have been calibrated in cultured brachiopods and only little is known on the mechanisms that control the incorporation of various key elements into brachiopod calcite. To evaluate the feasibility and robustness of multiple Element/Ca ratios as proxies in brachiopods, specifically Li/Ca, B/Ca, Na/Ca, Mg/Ca, Sr/Ca, Ba/Ca, as well as Li/Mg, we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years with closely monitored ambient conditions, carbonate system parameters and elemental composition of the culture medium. The experimental setup comprised of two control aquariums (pH0 = 8.0 and 8.15, T = 10 °C) and treatments where pCO2−pH (pH1 = 7.6 and pH2 = 7.35), temperature (T = 16 °C) and chemical composition of the culture medium were manipulated. Our results indicate that the incorporation of Li and Mg is strongly influenced by temperature, growth effects as well as carbonate chemistry, complicating the use of Li/Ca, Mg/Ca and Li/Mg ratios as straightforward reliable proxies. Boron partitioning varied greatly between the treatments, however without a clear link to carbonate system parameters or other environmental factors. The partitioning of both Ba and Na varied between individuals, but was not systematically affected by changes in the ambient conditions. We highlight Sr as a potential proxy for DIC, based on a positive trend between Sr partitioning and carbonate chemistry in the culture medium. To explain the observed dependency and provide a quantitative framework for exploring elemental variations, we devise the first biomineralisation model for brachiopods, which results in a close agreement between modelled and measured Sr distribution coefficients. We propose that in order to sustain shell growth under increased DIC, a decreased influx of Ca2+ to the calcifying fluid is necessary, driving the preferential substitution of Sr2+ for Ca2+ in the crystal lattice. Finally, we conducted micro-computed tomography analyses of the shells grown in the different experimental treatments. We present pore space – punctae – content quantification that indicates that shells built under increased environmental stress, and in particular elevated temperature, contain relatively more pore space than calcite, suggesting this parameter as a potential novel proxy for physiological stress and even environmental conditions.

Description: Lithium has proven a powerful tracer of weathering processes and chemical seawater evolution. Skeletal components of marine calcifying organisms, and in particular brachiopods, present promising archives of Li signatures. However, Li incorporation mechanisms and potential influence from biological processes or environmental conditions require a careful assessment. In order to constrain Li systematics in brachiopod shells, we present Li concentrations and isotope compositions for 11 calcitic brachiopod species collected from six different geographic regions, paralleled with data from culturing experiments where brachiopods were grown under varying environmental conditions and seawater chemistry (pH–pCO2, temperature, Mg/Ca ratio). The recent brachiopod specimens collected across different temperate and polar environments showed broadly consistent δ7Li values ranging from 25.2 to 28.1‰ (with mean δ7Li of 26.9 ± 1.5‰), irrespective of taxonomic rank, indicating that incorporation of Li isotopes into brachiopod shells is not strongly affected by vital effects related to differences among species. This results in Δ7Licalcite–seawater values (per mil difference in 7Li/6Li between brachiopod calcite shell and seawater) from −2.9‰ to −5.8‰ (with mean Δ7Licalcite–seawater value of −3.6‰), which is larger than the Δ7Licalcite–seawater values calculated based on data from planktonic foraminifera (~0‰ to ~−4‰). This range of values is further supported by results from brachiopods cultured experimentally. Under controlled culturing conditions simulating the natural marine environment, the Δ7Licalcite–seawater for Magellania venosa was −2.5‰ and not affected by an increase in temperature from 10 to 16 °C. In contrast, a decrease in Mg/Ca (or Li/Ca) ratio of seawater by addition of CaCl2 as well as elevated pCO2, and hence low-pH conditions, resulted in an increased Δ7Licalcite-seawater up to −4.6‰. Collectively, our results indicate that brachiopods represent valuable archives and provide an envelope for robust Li-based reconstruction of seawater evolution over the Phanerozoic.

Description: Highlights • δ13C and δ18O profiles increase from exterior to interior until reaching a plateau. • Primary Layer δ13C reflects the δ13C of the Dissolved Inorganic Carbon. • In high pCO2 experiments, δ13C and δ18O closer to equilibrium fields. • Brachiopods grow according to an incremental growth model. Abstract Brachiopod shells are ubiquitous since the Early Cambrian up to now. As they secrete a shell made of low-magnesium calcite, more resistant to diagenesis than biocarbonates richer in Mg, their geochemical signatures are generally considered a powerful tool for paleo-environmental and paleo-climatic reconstructions. However, gaps in knowledge still remain on the underlying controls of the shell chemistry, in particular at a high spatial resolution. In this study, in situ oxygen and carbon isotope measurements by SIMS (Secondary Ion Mass Spectrometry) were performed in brachiopod shells of the cold-temperate water species Magellania venosa, constituted of a primary and a secondary layer. The individual specimens studied here grew under controlled conditions mimicking the natural environment and in experiments under low-pH (high pCO2) and high-temperature conditions. Transversal carbon and oxygen profiles showed a “brachiopod pattern” typical of extant two-layered brachiopods, with the primary layer depleted in 18O and 13C relative to equilibrium and the secondary layer showing a gradual increasing trend until reaching a near-equilibrium plateau. Overall, shells cultured at low pH were found to have δ18O and δ13C values closer to equilibrium when compared to shells from the control experiment. These near-equilibrium values may reflect a decrease in shell precipitation rate, leading to less kinetic effects, and/or a more rapid kinetics for the equilibration between DIC species and water. By close pairing of seawater δ18O and δ13C to that of shell microstructure, our study enables us to derive layer-specific C and O enrichment factors, which show the extent of pH and temperature effects superimposed on the seawater δ18O and DIC δ13C signal inherited. Finally, we show that during brachiopod shell growth, newly precipitated calcite is added to the calcite already existing, thus empirically validating the conceptual accretionary growth model proposed by Ackerly (1989).