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Anthropogenic activities increase the level of dissolved heavy metals in some tropical near‐shore environments threatening reef ecosystems. The skeleton of stony corals like Porites species potentially provides a high‐resolution geochemical archive for past heavy metal concentrations, with potentially century long records revealing baseline values before large‐scale human disturbance. However, few data exist for heavy metal partitioning into coral skeleton aragonite. To address this, culturing experiments exposing Porites lobata and Porites lichen to a mixture of dissolved Cr, Mn, Ni, Cu, Zn, Ag, Cd, Sn, Hg, and Pb over a wide concentration range have been performed. Water samples were taken frequently to monitor changes in the heavy metal concentration. Laser ablation ICP‐MS measurements of the coral aragonite revealed metal concentrations that were positively correlated with Cr, Mn, Ni, Zn, Ag, Cd, and Pb concentrations in seawater. The DTE values for most metals appear dependent on the seawater metal content, approximating a power law, and therefore stabilize at higher seawater metal/Ca ratios. The partitioning of Pb into the coral skeleton is a notable exception, with DPb being stable around 2 to 1 across a large range of “natural” to highly polluted seawater Pb concentrations. This and the general agreement with partition coefficients estimated by previous work suggests that the reconstruction of the heavy metal concentration in seawater for ecosystem monitoring is possible. However, the high variability within and between coral colonies requires further study and suggests that multiple records from multiple coral colonies should be combined to obtain robust reconstructions. Key Points Porites corals grow normally with increased exposure to multiple metals over >1 year Skeletal partitioning variable within and between colonies and with seawater metal content Good agreement with previous work, especially for Pb across a large range of metal content

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO₃). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO₂ increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC ⇒ anhydrous ACC ∼ biogenic anhydrous ACC ⇒ vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO₂ sequestration.

In situ carbon dioxide enrichment experiments show that ocean acidification poses a threat to coral reefs by reducing the saturation state of aragonite and the concentration of carbonate ions and that this impairs community calcification. Acid oceans threaten coral reefs Ocean acidification impairs coral calcification and poses a substantial threat to tropical coral reef ecosystems. Rebecca Albright and colleagues exposed a natural coral reef community in the southern Great Barrier Reef to levels of ocean acidification that are expected to occur later this century unless deep carbon emissions cuts are made, and monitored calcification. Net community calcification was reduced by 34% in the acidified reef. The findings suggest that acidification of the ocean will compromise coral reef function in the near future. Coral reefs feed millions of people worldwide, provide coastal protection and generate billions of dollars annually in tourism revenue 1 . The underlying architecture of a reef is a biogenic carbonate structure that accretes over many years of active biomineralization by calcifying organisms, including corals and algae 2 . Ocean acidification poses a chronic threat to coral reefs by reducing the saturation state of the aragonite mineral of which coral skeletons are primarily composed, and lowering the concentration of carbonate ions required to maintain the carbonate reef. Reduced calcification, coupled with increased bioerosion and dissolution 3 , may drive reefs into a state of net loss this century 4 . Our ability to predict changes in ecosystem function and associated services ultimately hinges on our understanding of community- and ecosystem-scale responses. Past research has primarily focused on the responses of individual species rather than evaluating more complex, community-level responses. Here we use an in situ carbon dioxide enrichment experiment to quantify the net calcification response of a coral reef flat to acidification. We present an estimate of community-scale calcification sensitivity to ocean acidification that is, to our knowledge, the first to be based on a controlled experiment in the natural environment. This estimate provides evidence that near-future reductions in the aragonite saturation state will compromise the ecosystem function of coral reefs.

The terminal Ediacaran Dengying Formation (c. 551.1-538.8 Ma) in South China is one of two successions where Ediacara-type macrofossils are preserved in carbonate facies along with skeletal fossils and bilaterian animal traces. Given the remarkable thickness of carbonate-bearing strata deposited in less than 12.3 million years, the Dengying Formation holds the potential for construction of a relatively continuous chemostratigraphic profile for the terminal Ediacaran Period. In this study, a detailed sedimentological and chemostratigraphic (δ13Ccarb, δ18Ocarb, δ13Corg, δ34Spyrite, and 87Sr/86Sr) investigation was conducted on the Dengying Formation at the Gaojiashan section, Ningqiang County of southern Shaanxi Province, South China. Sedimentological results reveal an overall shallow-marine depositional environment. Carbonate breccia, void-filling botryoidal precipitates and aragonite crystal fans are common in the Algal Dolomite Member of the Dengying Formation, suggesting that peritidal facies were repeatedly karstified. The timing of karstification was likely early, probably soon after the deposition of the dolomite sediments. The presence of authigenic aragonite cements suggests high alkalinity in the terminal Ediacaran ocean. Geochemical analysis of micro-drilled samples shows that distinct compositions are registered in different carbonate phases, which should be considered when constructing chemostratigraphic profiles representative of true temporal variations in seawater chemistry. Integrated chemostratigraphic data suggest enhanced burial of organic carbon and pyrite, and the occurrence of extensive marine anoxia (at least in the Gaojiashan Member). Rapid basinal subsidence and carbonate accumulation during a time of elevated seawater alkalinity and increased rates of pyrite burial may have facilitated the evolutionary innovation of early biomineralizing metazoans.

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days. Newly formed calcite nucleated at locations which were in contact with the fluid, at the shell surface, in the open pore system, and along growth lines. In the experiments with fluids simulating meteoric water, calcite crystals reached sizes up to 200 µm, while in the experiments with Mg-containing fluids the calcite crystals reached sizes up to 1 mm after 7 days of alteration. Aragonite is metastable at all applied conditions. Only a small bulk thermodynamic driving force exists for the transition to calcite. We attribute the sluggish replacement reaction to the inhibition of calcite nucleation in the temperature window from ca. 50 to ca. 170 °C or, additionally, to the presence of magnesium. Correspondingly, in Mg2+-bearing solutions the newly formed calcite crystals are larger than in Mg2+-free solutions. Overall, the aragonite–calcite transition occurs via an interface-coupled dissolution–reprecipitation mechanism, which preserves morphologies down to the sub-micrometre scale and induces porosity in the newly formed phase. The absence of aragonite replacement by calcite at temperatures lower than 175 °C contributes to explaining why aragonitic or bimineralic shells and skeletons have a good potential of preservation and a complete fossil record.

A soil improvement method based on a microbially induced carbonate precipitation (MICP) process has been developed in recent years. In this method, calcium carbonate is precipitated in-situ to act as a cementing agency. Calcium chloride is normally used as the calcium source for the MICP process. The use of calcium chloride causes two problems. The first is chloride is corrosive to concrete, and the second is the cost of calcium chloride is relatively high. An improvement to this method is to use other alternative calcium sources. A method to produce soluble calcium using calcium rich calcareous sand and use it as a calcium source for the MICP process to improve the properties of soil has been proposed in this paper. A comparative study between the effect of MICP treatment using soluble calcium produced from calcareous sand and that using calcium chloride with the same concentration of calcium was carried out. The results from both series of tests showed that with increasing amounts of cementation solutions, the strength and stiffness of the treated calcareous sand increased and the permeability decreased. The scanning electron microscopy (SEM) and X-ray diffraction analyses revealed that the aragonite crystals with an acicular mineral morphology were formed when the soluble calcium was used, whereas the calcite crystals with a rhombohedral mineral morphology were formed when calcium chloride was used. This study also shows that it is feasible to treat calcareous sand using a MICP method with soluble calcium produced from calcareous sand.

Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO ₂, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments.

Marine shells incorporate oxygen isotope signatures during growth, creating valuable records of seawater temperature and marine oxygen isotopic compositions. Secondary ion mass spectrometry (SIMS) measures these compositions in situ at finer length‐scales than traditional stable isotope analyses. However, determining oxygen isotope ratios in aragonite, the most common shell mineral, is hampered by a lack of ideal reference materials, limiting the accuracy of SIMS‐based seawater temperature reconstructions. Here, we tested the capability of SIMS to produce seawater temperature reconstructions despite the matrix calibration challenges associated with aragonite. We cultured Anadara trapezia bivalves at four controlled seawater temperatures (13–28°C) and used strontium labeling to mark the start of the temperature‐controlled shell increment, allowing for more spatially precise SIMS analysis. An improved matrix calibration was developed to ensure more accurate bio‐aragonite analyses that addressed matrix differences between the pure abiotic reference materials and the bio‐aragonite samples with intricate mineral‐organic architectures and distinct minor and trace element compositions. We regressed SIMS‐IRMS biases of abiotic and biogenic aragonites that account for their systematic differences in major, minor, and trace elements, allowing for more accurate SIMS analyses of the temperature‐controlled shell increment. The thorough matrix calibration allowed us to provide a SIMS‐based seawater‐corrected oxygen isotope thermometer of T(°C) = 23.05 ± 0.36 − 4.48 · (δ18Oaragonite [‰ VPDB] − δ18Oseawater [‰ VSMOW] ± 0.25) and 103lnαaragonite‐seawater = (17.78 ± 0.88) · 103/T (K) − (29.44 ± 2.40) that agrees with existing aragonitic IRMS‐based thermometer relationships and improves the applicability of SIMS‐based paleo‐environmental reconstructions of marine bio‐aragonites. Plain Language Summary In this study, we grew marine bivalves under tightly constrained aquaculture conditions at four different seawater temperatures and marked the start of the growth period in the shell structure using strontium labeling. The newly grown shell material between the strontium‐labeled increment and the shell edge was analyzed for its oxygen isotopic composition. The compositions were measured in situ using a high resolution ion microprobe and a newly developed analytical post‐processing strategy specifically designed for biomineral samples with mineral‐organic architectures. The strategy involved two reference materials and the major, minor, and trace element content in the shell and the reference materials. The new approach resulted in an accurate and robust model for determining past seawater temperatures from fossil or historic shells based on their oxygen isotope composition at over an order of magnitude finer length scales than traditional oxygen isotope analyses. Key Points Bivalve mollusks were cultured at different temperatures under tightly constrained seawater composition and environmental conditions SIMS δ18O accuracy was improved with a new paired proxy‐like matrix bias correction using major, minor, and trace element abundances The first high‐resolution SIMS‐based stable oxygen isotope calibration for determining modern and ancient seawater temperatures is derived

The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B∕Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B∕Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.