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Living organisms control the formation of mineral skeletons and other structures through biomineralization. Major phylogenetic groups usually consistently follow a single biomineralization pathway. Foraminifera, which are very efficient marine calcifiers, making a substantial contribution to global carbonate production and global carbon sequestration, are regarded as an exception. This phylum has been commonly thought to follow two contrasting models of either in situ ‘mineralization of extracellular matrix’ attributed to hyaline rotaliid shells, or ‘mineralization within intracellular vesicles’ attributed to porcelaneous miliolid shells. Our previous results on rotaliids along with those on miliolids in this paper question such a wide divergence of biomineralization pathways within the same phylum of Foraminifera. We have found under a high-resolution scanning electron microscopy (SEM) that precipitation of high-Mg calcitic mesocrystals in porcelaneous shells takes place in situ and form a dense, chaotic meshwork of needle-like crystallites. We have not observed calcified needles that already precipitated in the transported vesicles, what challenges the previous model of miliolid mineralization. Hence, Foraminifera probably utilize less divergent calcification pathways, following the recently discovered biomineralization principles. Mesocrystalline chamber walls in both models are therefore most likely created by intravesicular accumulation of pre-formed liquid amorphous mineral phase deposited and crystallized within the extracellular organic matrix enclosed in a biologically controlled privileged space by active pseudopodial structures. Both calcification pathways evolved independently in the Paleozoic and are well conserved in two clades that represent different chamber formation modes. [ABSTRACT FROM AUTHOR]

Most palaeo-deep-water reconstructions are based on geochemical information stored in the calcareous shells of Cibicidoides species but hardly anything is known about their life cycle, population dynamics or ecology. The number of specimens of a single Cibicidoides species can locally be very limited and species may be lacking completely during certain intervals in the geological past. As a consequence, geochemical analyses are often carried out on lumped Cibicidoides spp. assuming that they share the same epizoic to epifaunal habitat and precipitated their shell in comparable offsets to surrounding bottom water mass properties. However, there is a growing body of evidence that particularly Cibicidoides pachyderma and its morphotypes C. mundulus and C. kullenbergi , may not be reliable bottom water recorders. We have recently developed aquaria that allowed, for the first time, observations of Cibicidoides pachyderma var. C. mundulus under in situ pressure and temperature. Experiments were carried out with and without artificial sediments to simulate soft sediments and rocks, respectively. Seawater was set to pH 8 and pH 7.4 to simulate more or less particulate carbon export or more or less ventilation of bottom water. Our experiments demonstrate that C. mundulus may opt for an epifaunal or an infaunal habitat depending on elapsed time following physical disturbance, pH, current activity, the availability of sediments and growth. The specimen's initial response following transfer from atmospheric pressure into the high-pressure aquaria was to immerse into the sediment or to cover more or less parts of the test with aggregated sediments or algae. However, within 24 h a strong rheotaxis became apparent and most specimens moved to sites of increased current activity under normal pH conditions (pH 8). Only few specimens remained in algae cysts or in the sediment in the pH-8 experiment. On the contrary, all specimens under pH 7.4 agglutinated a firm sediment cyst around their test and remained infaunal throughout the experimental period of three months. Independent of pH, growth was only observed in specimens that lived within an agglutinated cyst or infaunal. A solid thick cyst covered the specimens of the pH 7.4 experiment throughout the experiment and possibly restricted water exchange between the in-cyst water and the surrounding artificial bottom water mass. We suggest that a more fragile and possibly more porous sedimentary envelope may, at least temporally, have covered the infaunal specimens under pH 8 but no evidence for this was found upon termination of the experiment. [ABSTRACT FROM AUTHOR]

Rationale: Boron isotopes are a powerful tool for pH reconstruction in marine carbonates and as a tracer for fluid–mineral interaction in geochemistry. Microanalytical approaches based on laser ablation multi‐collector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) often suffer from effects induced by the sample matrix. In this study, we investigate matrix‐independent analyses of B isotopic ratios and apply this technique to cold‐water corals. Methods: We employ a customized 193 nm femtosecond laser ablation system (Solstice, Spectra‐Physics) coupled to a MC‐ICP‐MS system (Nu Plasma II, Nu Instruments) equipped with electron multipliers for in situ measurements of B isotopic ratios (11B/10B) at the micrometric scale. We analyzed various reference materials of silicate and carbonate matrices using non‐matrix matched calibration without employing any correction. This approach was then applied to investigate defined increments in coral samples from a Chilean fjord. Results: We obtained accurate B isotopic ratios with a reproducibility of ±0.9‰ (2 SD) for various reference materials including silicate glasses (GOR132‐G, StHs6/80‐G, ATHO‐G and NIST SRM 612), clay (IAEA‐B‐8) and carbonate (JCp‐1) using the silicate glass NIST SRM 610 as calibration standard, which shows that neither laser‐induced nor ICP‐related matrix effects are detectable. The application to cold‐water corals (Desmophyllum dianthus) reveals minor intra‐skeleton variations in δ11B with average values between 23.01‰ and 25.86‰. Conclusions: Our instrumental set‐up provides accurate and precise B isotopic ratios independently of the sample matrix at the micrometric scale. This approach opens a wide field of application in geochemistry, including pH reconstruction in biogenic carbonates and deciphering processes related to fluid–mineral interaction. [ABSTRACT FROM AUTHOR]

The lithium (Li) isotopic composition of carbonates is considered to be a reliable archive of past seawater Li isotopic compositions, which are useful as a tracer of silicate weathering. However, δ7Li values have been shown to be dependent on either pH or DIC in two studies using similar species of large, benthic foraminifera from the genus Amphistegina. To resolve this issue, we conducted culture experiments on Amphistegina lessonii in decoupled pH–DIC conditions, under two different light treatments, and with normal or Li-enriched seawater. The δ7Li values and Li/Ca ratios in the foraminifera tests were analysed by ion microprobe and LA-ICP-MS, respectively. No links between either the pH or DIC and δ7Li or Li/Ca values were observed for any of the treatments, and growth rates also did not seem to influence the Li incorporation or isotopic fractionation, contrary to observations from inorganic carbonate-precipitation experiments. Overall, these findings appear to support the use of Li isotopes in large benthic foraminifera to reconstruct past seawater chemistry and to infer changes in chemical weathering during carbon-cycle perturbations. [ABSTRACT FROM AUTHOR]

A new matrix‐matched reference material has been developed – NFHS‐2‐NP (NIOZ Foraminifera House Standard‐2‐Nano‐Pellet) – with element mass fractions, and isotope ratios resembling that of natural foraminiferal calcium carbonate. A 180–355 µm size fraction of planktic foraminifera was milled to nano‐particles and pressed to pellets. We report reference and information values for mass fractions of forty‐six elements measured by six laboratories as well as for 87Sr/86Sr (three laboratories), δ13C, δ18O (five laboratories) and 206,207,208Pb/204Pb isotope ratios (one laboratory) determined by ICP‐MS, ICP‐OES, MC‐ICP‐MS, isotope ratio mass spectrometry, WD‐XRF and TIMS. Inter‐ and intra‐pellet elemental homogeneity was tested using multiple LA‐ICP‐MS analyses in two laboratories applying spot sizes of 60 and 70 µm. The LA‐ICP‐MS results for most of the elements relevant as proxies for palaeoclimate research show RSD values < 3%, demonstrating a satisfactory homogeneous composition. Homogeneity of 87Sr/86Sr ratios of the pellet was verified by repeated LA‐MC‐ICP‐MS by two laboratories. Information values are reported for Pb isotope ratios and δ13C, δ18O values. The homogeneity for these isotope systems remains to be tested by LA‐MC‐ICP‐MS and secondary‐ion mass spectrometry. Overall, our results confirm the suitability of NFHS‐2‐NP for calibration or monitoring the quality of in situ geochemical techniques. [ABSTRACT FROM AUTHOR]

Abstract: The hydrogen isotopic composition (δD) of long-chain alkenones derived from haptophyte algae has recently been applied as paleo sea surface salinity proxy, but this application has been complicated by reported differences in δD of individual C37 alkenones of up to 45‰. Here we show that this difference in D/H ratios is the result of the desaturation of the C37:2 alkenone to form the C37:3 alkenone and related to the relative abundance of the individual alkenones, and, therefore, the UK′ 37. For the purpose of reconstructing paleo sea surface salinities it is recommended to determine the δD of combined rather than individual C37 alkenones. [Copyright &y& Elsevier]

The article offers information on how thermal stress reduces pocilloporid coral resilience to ocean acidification by impairing control over calcifying fluid chemistry. It mentions that combination of thermal stress and ocean acidification (OA) that negatively affect coral calcification than an individual stressor.

Although the emergence of complex biomineralized forms has been investigated for over a century, still little is known on how single cells control morphology of skeletal structures, such as frustules, shells, spicules, or scales. We have run experiments on the shell formation in foraminifera, unicellular, mainly marine organisms that can build shells by successive additions of chambers. We used live imaging to discover that all stages of chamber/shell formation are controlled by dedicated actin-driven pseudopodial structures. Successive reorganization of an F-actin meshwork, associated with microtubular structures, is actively involved in formation of protective envelope, followed by dynamic scaffolding of chamber morphology. Then lamellar dynamic templates create a confined space and control mineralization separated from seawater. These observations exclude extracellular calcification assumed in selected foraminiferal clades, and instead suggest a semiintracellular biomineralization pattern known from other unicellular calcifying and silicifying organisms. These results give a challenging prospect to decipher the vital effect on geochemical proxies applied to paleoceanographic reconstructions. They have further implications for understanding multiscale complexity of biomineralization and show a prospect for material science applications. [ABSTRACT FROM AUTHOR]

It has long since been noted that minor element (Me) partitioning into biogenic carbonates is sometimes different from Me partitioning into inorganically precipitated carbonates. The prime example is the partitioning coefficient, which might be lower or even higher than the one of inorganically precipitated carbonate. Such a difference is usually termed “vital effect” and is seen as indicative of a biologically modified minor element partitioning. Over the last three decades interest in conceptual biomineralization models compatible with minor element and isotope fractionation has been steadily increasing. However, inferring features of a biomineralization mechanism from Me partitioning is complicated, because not all partitioning coefficients show vital effects in every calcium carbonate producing organism. Moreover, the partitioning coefficient is not the only aspect of Me partitioning. Other aspects include polymorph specificity and rate dependence. Patellogastropod limpets are ideally suited for analysing Me partitioning in terms of biomineralization models, because they feature both aragonitic and calcitic shell parts, so that polymorph specificity can be tested. In this study, polymorph-specific partitioning of the minor elements Mg, Li, B, Sr, and U into shells of the patellogastropod limpet Patella caerulea from within and outside a CO 2 vent site at Ischia (Italy) was investigated by means of LA-ICP-MS. The partitioning coefficients of U, B, Mg, and Sr (in aragonite) differed from the respective inorganic ones, while the partitioning coefficients of Li and Sr (in calcite) fell within the range of published values for inorganically precipitated carbonates. Polymorph specificity of Me partitioning was explicable in terms of inorganic precipitation in the case of Sr and Mg, but not Li and B. Seawater carbon chemistry did not have the effect on B partitioning that was expected on the basis of data on inorganic precipitates and foraminifera. Carbon chemistry did affect Mg (in aragonite) and Li, but only the effect on Mg was explicable in terms of calcification rate. On the one hand, these results show that Me partitioning in P. caerulea is incompatible with a direct precipitation of shell calcium carbonate from the extrapallial fluid. On the other hand, our results are compatible with precipitation from a microenvironment formed by the mantle. Such a microenvironment was proposed based on data other than Me partitioning. This is the first study which systematically employs a multi-element, multi-aspect approach to test the compatibility of Me partitioning with different conceptual biomineralization models. [ABSTRACT FROM AUTHOR]

The shallow water benthic foraminifera Ammonia aomoriensis and Amphistegina lessonii were grown at different seawater Sr/Ca and the test Sr/Ca ratio was determined by Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry. A. aomoriensis test Sr/Ca is positively correlated with seawater Sr/Ca. The linear regression has a slope of 0.17, representing the overall Sr partitioning coefficient K DSr . The slope remains unchanged, if seawater Ca concentration is changed in order to change the seawater Sr/Ca. In the case of A. lessonii , the slopes of the linear regressions representing K DSr differ from one another i.e., 0.16 if the Sr concentration is changed and 0.32 if the Ca level is changed. This difference in K DSr can be explained by the, relative to A. aomoriensis , high Mg content of A. lessonii (ca. 40 mmol/mol), distorting the calcite lattice and weakening the discrimination against Sr. The Mg content of A. aomoriensis is too low (ca. 4 mmol/mol) to observe the influence on Sr partitioning. All data are compatible with a recently developed model for minor element partitioning in foraminifera (Nehrke et al., 2013; Mewes et al., 2015a). On the whole, our data confirm the model (applicability of the model to Sr and dependence of the calcite Sr/Ca on seawater Sr/Ca, as opposed to seawater Sr concentration), and improve our understanding of the model (influence of calcite Mg/Ca on Sr partitioning). [ABSTRACT FROM AUTHOR]

Insight into past changes of upper ocean stratification, circulation, and nutrient signatures rely on our knowledge of the apparent calcification depth (ACD) and ecology of planktonic foraminifera, which serve as archives for paleoceanographic relevant geochemical signals. The ACD of different species varies strongly between ocean basins, but also regionally. We constrained foraminiferal ACDs in the Western Pacific Warm Pool (Manihiki Plateau) by comparing stable oxygen and carbon isotopes (δ 18 O calite , δ 13 C calcite ) as well as Mg/Ca ratios from living planktonic foraminifera to in-situ physical and chemical water mass properties (temperature, salinity, δ 18 O seawater , δ 13 C DIC ). Our analyses point to Globigerinoides ruber as the shallowest dweller, followed by Globigerinoides sacculifer , Neogloboquadrina dutertrei , Pulleniatina obliquiloculata and Globorotaloides hexagonus inhabiting increasing greater depths. These findings are consistent with other ocean basins; however, absolute ACDs differ from other studies. The uppermost mixed-layer species G. ruber and G. sacculifer denote mean calcification depths of ~ 95 m and ~ 120 m, respectively. These Western Pacific ACDs are much deeper than in most other studies and most likely relate to the thick surface mixed layer and the deep chlorophyll maximum in this region. Our results indicate that N. dutertrei appears to be influenced by mixing waters from the Pacific equatorial divergence, while P. obliquiloculata with an ACD of ~ 160 m is more suitable for thermocline reconstructions. ACDs of G. hexagonus reveal a deep calcification depth of ~ 450 m in oxygen-depleted, but nutrient-rich water masses, consistent to other studies. As the δ 13 C of G. hexagonus is in near-equilibrium with ambient seawater, we suggest this species is suitable for tracing nutrient conditions in equatorial water masses originating in extra-topical regions. [ABSTRACT FROM AUTHOR]

To deconvolve the effect of growth rate and temperature on the boron partitioning into calcite and its isotope fractionation, seeded calcite precipitation experiments were performed at a constant temperature and various growth rates and at a constant growth rate and various temperatures. We show that boron partitioning increases with increasing growth rate and decreases with increasing temperature. The B isotope fractionation between calcite and B(OH) 4 − increases with increasing growth rate favoring the lighter B isotope for incorporation into calcite whereas no effect of temperature was observed within the temperature range investigated (12 °C to 32 °C). At the lowest temperature and growth rate δ 11 B of the calcite almost equals that of B(OH) 4 − in solution. Applying the surface entrapment model (SEMO) of Watson and Liang (1995) to our data, we demonstrate that the observed effects of temperature and growth rate on B concentration can be explained by processes in the near surface layer of the calcite crystal. [ABSTRACT FROM AUTHOR]

Foraminiferal calcite Mg/Ca (Mg/Ca CC ) is used in paleoceanographic studies to reconstruct temperature. Furthermore, the Mg/Ca CC is influenced by different seawater Mg/Ca (Mg/Ca SW ). Foraminiferal calcite Sr/Ca (Sr/Ca CC ) can potentially be used to reconstruct Sr/Ca ratios of seawater (Sr/Ca SW ). As these elements are the most abundant of all elements incorporated into the calcium carbonate of the foraminiferal tests, they potentially might affect each other's incorporation. To investigate the effects of the Mg concentration in the test on Sr incorporation, we conducted a culture study with two species of benthic foraminifera producing carbonate tests with different Mg content. Foraminifers grew under controlled conditions in different Mg/Ca SW , whereas Sr/Ca SW was kept constant. By analyzing Sr/Ca CC of cultured specimens with laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS), we show that Sr/Ca CC increases with increasing Mg/Ca CC . We explain this observation by a stress in the crystal lattice, caused by elevated Mg/Ca CC , which may be compensated for by the additional incorporation of Sr. We discuss this finding in the context of biomineralization and evaluate the reliability of Sr/Ca CC as a possible Sr/Ca SW proxy. [ABSTRACT FROM AUTHOR]

In this study we introduce a new in situ technique which allows the determination of the boron isotopic composition and B/Ca ratios simultaneously at the nanogram level using a combination of optical emission spectroscopy and multiple ion counting MC ICP-MS with laser ablation. This technique offers a new application in the paleo-field of oceanography and climatology since small samples like e.g. single foraminiferal shells can be analyzed. The simultaneous determination of the boron isotopic composition and B/Ca ratios provides two independent proxies which allow the reconstruction of the full carbonate system. To test the new technique we performed measurements on the cultured, benthic foraminifer Amphistegina lessonii . Our results yielded an average boron isotopic composition δ 11 B = 18.0 ± 0.83‰ (SD) with an average internal precision of 0.52‰ (RSE). The boron concentration was 53 ± 7 μg/g (SD). These results agree with the range reported in the literature. The reconstructed mean pH value is in excellent agreement with the measured pH of the seawater in which the foraminifers grew. The analysis of a foraminifer consumed approximately 1200 ng calcium carbonate containing ca. 0.06 ng boron. Compared to bulk analytical methods, this new technique requires less material and reduces the time for sample preparation. [ABSTRACT FROM AUTHOR]

Magnesium, incorporated in foraminiferal calcite (Mg/Ca CC ), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/Ca CC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/Ca SW ). The physiological mechanisms responsible for these proxy relationships are still unknown. This culture study investigates the impact of different seawater [Mg 2 + ] on calcification in two benthic foraminiferal species precipitating contrasting Mg/Ca CC : Ammonia aomoriensis , producing low-Mg calcite and Amphistegina lessonii , producing intermediate-Mg calcite. Foraminiferal growth and test thickness were determined and, Mg/Ca was analyzed using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Results show that at present-day seawater Mg/Ca SW of ~ 5, both species have highest growth rates, reflecting their adaptation to modern seawater element concentrations. Test thickness is not significantly affected by different Mg/Ca SW . The relationship between Mg/Ca SW and Mg/Ca CC shows a distinct positive y-axis intercept, possibly reflecting at least two processes involved in foraminiferal biomineralization. The associated Mg partition (D Mg ) changes non-linearly with increasing Mg/Ca SW , hence suggesting that the D Mg is best described by an exponential function approaching an asymptote. [ABSTRACT FROM AUTHOR]

The calcium isotope ratios (δ44Ca = [(44Ca/40Ca)sample/(44Ca/40Ca)standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C−1, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C−1. The observation that δ44Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ18O) in calcium carbonate (CaCO3). These observations are explained by a model which considers that Ca2+-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for 40Ca and 44Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ44Ca isotope fractionation at liquid/solid transitions involves Ca2+-aquocomplexes (Ca[H2O]n2+ · mH2O) rather than pure Ca2+-ion diffusion. From our measurements we calculate that such a hypothesized Ca2+-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO3 in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca2+-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ44Ca as a temperature proxy will require careful study of species effects. [Copyright &y& Elsevier]

Calcium carbonate minerals produced by marine organisms play a central role in the global carbon cycle and carbonate sedimentation, which influence the climate by regulating atmospheric CO 2 levels. Foraminifera are important marine single-celled organisms that have produced calcite shells for over 300 million years. Here, we present new observations promoting our understanding for foraminiferal biocalcification by studying Amphistegina lessonii . We integrated in vivo confocal autofluorescence and dye fluorescence imaging with elemental analysis of the cell supporting the concept that the calcite shells of foraminifera are produced via deposition of intracellularly formed Mg-rich amorphous calcium carbonate (Mg-ACC) particles that transform into a stable mineral phase. This process is likely accompanied by the activity of endosymbiotic microalgae and seawater-derived endocytic vesicles that provide calcification substrates such as DIC, Ca 2+ , and Mg 2+ . The final transformation of semi-liquid amorphous nanoparticles into a crystalline shell was associated with Mg 2+ liberation., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Rationale: Boron isotopes are a powerful tool for pH reconstruction in marine carbonates and as a tracer for fluid-mineral interaction in geochemistry. Microanalytical approaches based on laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) often suffer from effects induced by the sample matrix. In this study, we investigate matrix-independent analyses of B isotopic ratios and apply this technique to cold-water corals., Methods: We employ a customized 193 nm femtosecond laser ablation system (Solstice, Spectra-Physics) coupled to a MC-ICP-MS system (Nu Plasma II, Nu Instruments) equipped with electron multipliers for in situ measurements of B isotopic ratios ( 11 B/ 10 B) at the micrometric scale. We analyzed various reference materials of silicate and carbonate matrices using non-matrix matched calibration without employing any correction. This approach was then applied to investigate defined increments in coral samples from a Chilean fjord., Results: We obtained accurate B isotopic ratios with a reproducibility of ±0.9‰ (2 SD) for various reference materials including silicate glasses (GOR132-G, StHs6/80-G, ATHO-G and NIST SRM 612), clay (IAEA-B-8) and carbonate (JCp-1) using the silicate glass NIST SRM 610 as calibration standard, which shows that neither laser-induced nor ICP-related matrix effects are detectable. The application to cold-water corals (Desmophyllum dianthus) reveals minor intra-skeleton variations in δ 11 B with average values between 23.01‰ and 25.86‰., Conclusions: Our instrumental set-up provides accurate and precise B isotopic ratios independently of the sample matrix at the micrometric scale. This approach opens a wide field of application in geochemistry, including pH reconstruction in biogenic carbonates and deciphering processes related to fluid-mineral interaction., (© 2023 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.)

The combination of thermal stress and ocean acidification (OA) can more negatively affect coral calcification than an individual stressors, but the mechanism behind this interaction is unknown. We used two independent methods (microelectrode and boron geochemistry) to measure calcifying fluid pH (pH cf ) and carbonate chemistry of the corals Pocillopora damicornis and Stylophora pistillata grown under various temperature and pCO 2 conditions. Although these approaches demonstrate that they record pH cf over different time scales, they reveal that both species can cope with OA under optimal temperatures (28°C) by elevating pH cf and aragonite saturation state (Ω cf ) in support of calcification. At 31°C, neither species elevated these parameters as they did at 28°C and, likewise, could not maintain substantially positive calcification rates under any pH treatment. These results reveal a previously uncharacterized influence of temperature on coral pH cf regulation-the apparent mechanism behind the negative interaction between thermal stress and OA on coral calcification., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Although the emergence of complex biomineralized forms has been investigated for over a century, still little is known on how single cells control morphology of skeletal structures, such as frustules, shells, spicules, or scales. We have run experiments on the shell formation in foraminifera, unicellular, mainly marine organisms that can build shells by successive additions of chambers. We used live imaging to discover that all stages of chamber/shell formation are controlled by dedicated actin-driven pseudopodial structures. Successive reorganization of an F-actin meshwork, associated with microtubular structures, is actively involved in formation of protective envelope, followed by dynamic scaffolding of chamber morphology. Then lamellar dynamic templates create a confined space and control mineralization separated from seawater. These observations exclude extracellular calcification assumed in selected foraminiferal clades, and instead suggest a semiintracellular biomineralization pattern known from other unicellular calcifying and silicifying organisms. These results give a challenging prospect to decipher the vital effect on geochemical proxies applied to paleoceanographic reconstructions. They have further implications for understanding multiscale complexity of biomineralization and show a prospect for material science applications., Competing Interests: The authors declare no conflict of interest., (Copyright © 2019 the Author(s). Published by PNAS.)

Anthropogenic carbon perturbation has caused decreases in seawater pH and increases in global temperatures since the start of the 20th century. The subsequent lowering of the saturation state of CaCO3 may make the secretion of skeletons more problematic for marine calcifiers. As organisms that precipitate thin aragonite shells, thecosome pteropods have been identified as being particularly vulnerable to climate change effects. Coupled with their global distribution, this makes them ideal for use as sentinel organisms. Recent studies have highlighted shell dissolution as a potential indicator of ocean acidification; however, this metric is not applicable for monitoring pH changes in supersaturated basins. In this study, the novel approach of high resolution computed tomography (CT) scanning was used to produce quantitative 3-dimensional renderings pteropod shells to assess the potential of using this method to monitor small changes in shell biometrics that may be driven by climate change drivers. An ontogenetic analysis of the shells of Cavolinia inflexa and Styliola subula collected from the Mediterranean was used to identify suitable monitoring metrics. Modern samples were then compared to historical samples of the same species, collected during the Mediterranean leg of the Thor (1910) and Dana (1921) cruises to assess whether any empirical differences could be detected. Shell densities were calculated and scanning electron microscopy was used to compare the aragonite crystal morphology. pH for the collection years was hind-cast using temperature and salinity time series with atmospheric CO2 concentrations from ice core data. Historical samples of S. subula were thicker than S. subula shells of the same size from 2012 and C. inflexa shells collected in 1910 were significantly denser than those from 2012. These results provide a baseline for future work to develop monitoring techniques for climate change in the oceans using the novel approach of high-resolution CT scanning., Competing Interests: The authors have declared that no competing interests exist.

Shelled pteropods play key roles in the global carbon cycle and food webs of various ecosystems. Their thin external shell is sensitive to small changes in pH, and shell dissolution has already been observed in areas where aragonite saturation state is ~1. A decline in pteropod abundance has the potential to disrupt trophic networks and directly impact commercial fisheries. Therefore, it is crucial to understand how pteropods will be affected by global environmental change, particularly ocean acidification. In this study, physiological and molecular approaches were used to investigate the response of the Mediterranean pteropod, Heliconoides inflatus, to pH values projected for 2100 under a moderate emissions trajectory (RCP6.0). Pteropods were subjected to pH T 7.9 for 3 days, and gene expression levels, calcification and respiration rates were measured relative to pH T 8.1 controls. Gross calcification decreased markedly under low pH conditions, while genes potentially involved in calcification were up-regulated, reflecting the inability of pteropods to maintain calcification rates. Gene expression data imply that under low pH conditions, both metabolic processes and protein synthesis may be compromised, while genes involved in acid-base regulation were up-regulated. A large number of genes related to nervous system structure and function were also up-regulated in the low pH treatment, including a GABA A receptor subunit. This observation is particularly interesting because GABA A receptor disturbances, leading to altered behavior, have been documented in several other marine animals after exposure to elevated CO 2 . The up-regulation of many genes involved in nervous system function suggests that exposure to low pH could have major effects on pteropod behavior. This study illustrates the power of combining physiological and molecular approaches. It also reveals the importance of behavioral analyses in studies aimed at understanding the impacts of low pH on marine animals., (© 2016 John Wiley & Sons Ltd.)

Magnesium, incorporated in foraminiferal calcite (Mg/Ca CC ), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/Ca CC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/Ca SW ). The physiological mechanisms responsible for these proxy relationships are still unknown. This culture study investigates the impact of different seawater [Mg 2 + ] on calcification in two benthic foraminiferal species precipitating contrasting Mg/Ca CC : Ammonia aomoriensis , producing low-Mg calcite and Amphistegina lessonii , producing intermediate-Mg calcite. Foraminiferal growth and test thickness were determined and, Mg/Ca was analyzed using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Results show that at present-day seawater Mg/Ca SW of ~ 5, both species have highest growth rates, reflecting their adaptation to modern seawater element concentrations. Test thickness is not significantly affected by different Mg/Ca SW . The relationship between Mg/Ca SW and Mg/Ca CC shows a distinct positive y-axis intercept, possibly reflecting at least two processes involved in foraminiferal biomineralization. The associated Mg partition (D Mg ) changes non-linearly with increasing Mg/Ca SW , hence suggesting that the D Mg is best described by an exponential function approaching an asymptote.

The ocean has been shielding the earth from the worst effects of rapid climate change by absorbing excess carbon dioxide from the atmosphere. This absorption of CO2 is driving the ocean along the pH gradient towards more acidic conditions. At the same time ocean warming is having pronounced impacts on the composition, structure and functions of marine ecosystems. Warming, freshening (in some areas) and associated stratification are driving a trend in ocean deoxygenation, which is being enhanced in parts of the coastal zone by upwelling of hypoxic deep water. The combined impact of warming, acidification and deoxygenation are already having a dramatic effect on the flora and fauna of the oceans with significant changes in distribution of populations, and decline of sensitive species. In many cases, the impacts of warming, acidification and deoxygenation are increased by the effects of other human impacts, such as pollution, eutrophication and overfishing. The interactive effects of this deadly trio mirrors similar events in the Earth's past, which were often coupled with extinctions of major species' groups. Here we review the observed impacts and, using past episodes in the Earth's history, set out what the future may hold if carbon emissions and climate change are not significantly reduced with more or less immediate effect., (Copyright © 2013. Published by Elsevier Ltd.)