Aragonite Precipitation Research Articles

Formation of Calcium Carbonate Polymorphs Induced by Living Microalgae

Calcium carbonate (CaCO3) occurs in the three polymorphs calcite, aragonite and vaterite. The formation of these crystals in inorganic solutions is influenced by parameters like pH, temperature or impurities. Living freshwater microalgae can also induce the formation of CaCO3 when they live in a suitable environment containing saturated amounts of Ca2+. Through this biologically induced biomineralization only the formation of the polymorph calcite has been reported yet. We investigated the precipitates which have been formed in solutions containing the freshwater microalgae Scenedesmus obliquus and different zinc amounts (0, 3.27 and 6.53 mg Zn2+/l) by XRD and SEM. As references precipitates from the same solutions but without algae were investigated. We could show that the presence of living microalgae has a great influence on the precipitation of calcium carbonate crystals. In algae-containing media without or with a low zinc amount always calcite and aragonite are formed. In the corresponding medium with 6.53 mg Zn2+/l pure aragonite crystals were built. In contrast, in the inorganic, algae-free solutions without zinc, pure calcite is precipitated. Both inorganic solutions with zinc show major calcite precipitation and weak aragonite precipitation. Thus the algae cells advance significantly the formation of aragonite, which is enhanced by the presence of zinc cations in the media. Possible mechanisms are discussed.

Crystallization of CaCO3in Water–Alcohol Mixtures: Spherulitic Growth, Polymorph Stabilization, and Morphology Change

The presence of alcohol in binary alcohol–water mixtures can affect the precipitation pathways of anhydrous crystalline CaCO3 polymorphs and their morphology. We explored the formation pathways and the effects of several parameters on calcite, vaterite, and aragonite: concentration of simple alcohols, time, and shaking speed, and we derived a multiparameter model for predicting what phase is preferred. We found that shaking speed and alcohol concentration are the most important parameters for affecting the stability of vaterite and aragonite and for changing vaterite morphology, from cauliflower-shaped, spherical aggregates, to dendritic, flatter structures. In all our experiments, the precipitated aragonite was twinned, and both the vaterite and aragonite can be interpreted to form through spherulitic growth. Classical growth theory fully describes their formation; there is no need to invoke the popular hypothesis for nonclassical growth by self-assembly of nanocrystals. These studies, and future work with solutions of low water activity, are paving the way to a better understanding of how organisms select their preferred polymorph and engineer CaCO3 morphology during biomineralization.

Geochemistry of Ocean Floor and Fore-arc Serpentinites: Constraints on the Ultramafic Input to Subduction Zones

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg g−1 and 30 µg g−1, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg g−1 level), except Sr in carbonate-bearing serpentinites (thousands of µg g−1). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

The energetics of nanophase calcite

Calcium carbonate (CaCO 3) is an important component of the near-surface environment. Understanding the nature of its precipitation is important for a variety of environmental processes, as well as for the geologic sequestration of anthropogenic carbon dioxide. Calcite is the most thermodynamically stable bulk polymorph, but energy crossovers may exist that could favor the precipitation of vaterite or aragonite with decreasing particle size. The purpose of this study is to determine the surface energy of calcite, which is the first step towards understanding the effect of particle size on thermodynamic stability in the calcium carbonate system. The enthalpies of five well-characterized calcite samples (four nanophase and one bulk) were measured by acid solution isothermal and water adsorption calorimetric techniques. From the calorimetric data, the surface energies of calcite were determined to be 1.48 ± 0.21 and 1.87 ± 0.16 J/m 2 for hydrous and anhydrous surfaces. These values are similar to those measured for many oxides but larger than predicted from computational models for idealized calcite surfaces. The surfaces of synthetic CaCO 3 particles contain a range of planes and defect structures, which may give rise to the difference between the experimental and modeled values.

Geochemical evolution of hypersaline cave pools, Guadalupe Mountains, New Mexico

Several saline and hypersaline pools have been identified in caves of the Guadalupe Mountains in New Mexico, U.S.A. Among the many pools found scattered throughout 207 km of Lechuguilla Cave, the Briny Pool contains the highest TDS (6%) of any pool identified. In this first detailed investigation of Briny Pool chemistry, a conceptual model was developed to describe the geochemical evolution of the Briny Pool by using existing principles of brine evolution, which incorporates the concept of a chemical divide. The net effect of dolomite (CaMg(CO 3) 2) dissolution followed by the first chemical divide of calcite and/or aragonite (CaCO 3) precipitation produces a low-Ca water containing Mg in excess of alkalinity. With continued evaporative concentration, a second chemical divide is reached when the water becomes saturated with respect to hydromagnesite (Mg 5(CO 3) 4(OH) 2·4H 2O), and continues to evolve into a Mg–SO 4 dominated brine. The results of inverse and forward geochemical modeling calculations support the conceptual model. This study demonstrates a unique application of Hardie–Eugster principles, with modification to include Mg-bearing hydromagnesite (rather than sepiolite), to identify and quantify the geochemical origin and evolution of a hypersaline cave pool. The principles used to describe the evolution of the Briny Pool should be applicable in studies of other dolomite-hosted hypersaline cave pools in the Guadalupe Mountains and throughout the world.

Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein

Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature.

Reconstructing changes in seep activity by means of pore water and solid phase Sr/Ca and Mg/Ca ratios in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1–4), 93–109]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Biological and water chemistry controls on Sr/Ca, Ba/Ca, Mg/Ca and δ 18O profiles in freshwater pearl mussel Hyriopsis sp.

We investigated oxygen isotope and Sr/Ca, Ba/Ca and Mg/Ca ratios in shells of a commercially cultured freshwater pearl mussel ( Hyriopsis sp., Unionidae) and ambient water. The first-order fluctuations of oxygen isotope ratios of the outer shell layer along the maximum growth axis recorded the mussels' annual growth from 2002 to 2007. Clear annual Sr/Ca cycles suggest that Sr was incorporated into the shells at a high rate during warm seasons. All three examined shells showed a clear decrease in annual average Sr/Ca with age. Inter- and intra-annual trends suggest that Sr incorporation was higher during periods of faster growth. The Ba concentration and the Ba/Ca ratio of ambient water showed neither an annual periodicity nor a seasonal trend. In contrast to the findings of an inorganic aragonite precipitation experiment, Ba/Ca was positively correlated with ambient temperature. In addition, Ba/Ca and Sr/Ca ratios were positively correlated with each other. These results suggest that not thermodynamic equilibrium partitioning but the shell growth rate controls Ba incorporation into Hyriopsis shells. The Mg/Ca profiles of the three shells suggest that complex factors control the incorporation of Mg into shell aragonite. Water temperature and annual growth rates did not significantly influence Mg incorporation, and substantial interspecimen differences suggested that physicochemical factors do not exert any systematic control on Mg/Ca ratios in Hyriopsis. Instead, the Mg content of shell aragonite might reflect biological contamination with organic material or adsorption phenomena during crystal precipitation rather than regulated substitution into the aragonite crystal lattice. Our results suggest that trace element profiles in aragonitic bivalve shells could be interpreted as the result of strong biological controls over-riding environmental influences on trace element incorporation.

Trace element and stable isotope data from a flowstone in a natural cave of the mining district of SW Sardinia (Italy): evidence for Zn²⁺-induced aragonite precipitation in comparatively wet climatic conditions

Trace element and stable isotope data from a flowstone in a natural cave of the mining district of SW Sardinia (Italy): evidence for Zn²⁺-induced aragonite precipitation in comparatively wet climatic conditions

Aragonite Kinetics in Dilute Solutions

Aragonite was synthesized inorganically using a seeded-growth technique to characterize precipitation kinetics for the heterogeneous growth of solid from dilute solutions (ionic strength: 0.05–0.07 mol l−1). The concentration of all aqueous constituents, including Ca (~5–15 mmol l−1), Na (~10–35 mmol l−1), Cl (~30–35 mmol l−1), and carbon (as total alkalinity: ~10 to 17 meq l−1), was held constant by the addition of titrants that contained excess solute concentrations to balance the growth of solid phase during the precipitation reaction, and a CO2/N2 gas mixture (0.009–0.178) was bubbled through each solution to facilitate mass exchange between gaseous and aqueous carbon species. Forty-three experiments were conducted at 10° (n = 13), 25° (n = 21), and 40°C (n = 9), over a range of average saturation states with respect to aragonite from 8.3 to 28.5, 2.9 to 19.6 and 2.0 to 12.2, and average precipitation rates from 102.8 to 103.8, 102.3 to 104.0, and 102.5 to 104.1 micromol m−2 h−1, respectively. Reaction orders averaged 1.7 ± 0.10 at 10°, 1.7 ± 0.07 at 25° and 1.5 ± 0.06 at 40°, and they were independent of temperature while rate constants averaged 101.3 ± 0.12, 101.9 ± 0.06, and 102.6 ± 0.04 micromol m−2 h−1, respectively, increasing one-half order of magnitude for each 15°C rise in temperature. From these data, an Arrhenius activation energy of 71.2 kJ mol−1 is calculated for the heterogeneous precipitation of aragonite. This value is comparable to a sole independent measurement of 80.7 kJ mol−1 reported for the solid-solution recrystallization of monohydrocalcite to aragonite (Munemoto and Fukushi in J Mineral Petrol Sci 103: 345–349, 2008).

In situ δ7Li, Li/Ca, and Mg/Ca analyses of synthetic aragonites

In situ secondary ion mass spectrometry (SIMS) analyses of δ7Li, Li/Ca, and Mg/Ca were performed on five synthetic aragonite samples precipitated from seawater at 25°C at different rates. The compositions of δ7Li in bulk aragonites and experimental fluids were measured by multicollector inductively coupled plasma–mass spectrometry (MC‐ICP‐MS). Both techniques yielded similar δ7Li in aragonite when SIMS analyses were corrected to calcium carbonate reference materials. Fractionation factors α7Li/6Li range from 0.9895 to 0.9923, which translates to a fractionation between aragonite and fluid from −10.5‰ to −7.7‰. The within‐sample δ7Li range determined by SIMS is up to 27‰, exceeding the difference between bulk δ7Li analyses of different aragonite precipitates. Moreover, the centers of aragonite hemispherical bundles (spherulites) are enriched in Li/Ca and Mg/Ca relative to spherulite fibers by up to factors of 2 and 8, respectively. The Li/Ca and Mg/Ca ratios of spherulite fibers increase with aragonite precipitation rate. These results suggest that precipitation rate is a potentially important consideration when using Li isotopes and elemental ratios in natural carbonates as a proxy for seawater composition and temperature.

Morphological templating of metastable calcium carbonates by the amino acid leucine

The in vitro precipitation of the metastable CaCO3 phases aragonite and vaterite in the presence of leucine is investigated. Under normal conditions, the production of CaCO3 via the hydrolysis of urea method favours the formation of regular needle-like aragonite crystals, with very minor quantities of vaterite and calcite. However in the presence of leucine, aragonite forms highly branched structures and the vaterite yield is increased, forming flower-like clusters composed of nano-thin sheets. Both the degree of aragonite branching and the occurrence, regularity of shape and number of vaterite "petals" increases with leucine concentration. The two phases exhibit different variations in their crystallographic parameters with increasing concentration, while the molecular structure appears unaffected.

Microbial Processes Forming Daily Lamination in an Aragonite Travertine, Nagano-yu Hot Spring, Southwest Japan

An aragonite travertine at Nagano-yu hot spring, SW Japan, exhibits clear sub-millimeter-order lamination that resembles ancient ministromatolites. Thirty-three hours of continuous observation showed that the lamination is formed daily with no changes in physicochemical properties except light intensity. Phylotype analysis and fluorescence in situ hybridization indicate that Hydrogenophaga sp. is dominant and concentrated in diurnal layers containing abundant extracellular polymeric substances. Growth of Hydrogenophaga sp. is activated in the daytime, likely due to extracellular polymeric substance production by cyanobacterial photosynthesis. Daytime development of Hydrogenophaga-dominant biofilms, and the concurrent inhibiting effect on aragonite precipitation, explains the daily lamination observed.

Modern carbonate microbialites from an asbestos open pit pond, Yukon, Canada.

Microbialites were discovered in an open pit pond at an abandoned asbestos mine near Clinton Creek, Yukon, Canada. These microbialites are extremely young and presumably began forming soon after the mine closed in 1978. Detailed characterization of the periphyton and microbialites using light and scanning electron microscopy was coupled with mineralogical and isotopic analyses to investigate the mechanisms by which these microbialites formed. The microbialites are columnar in form (cm scale), have an internal spherulitic fabric (mm scale), and are mostly made of aragonite, which is supersaturated in the subsaline pond water. Initial precipitation is seen as acicular aragonite crystals nucleating onto microbial biomass and detrital particles. Continued precipitation entombs benthic diatoms (e.g. Brachysira vitrea), filamentous algae (e.g. Oedogonium sp.), dinoflagellates, and cyanobacteria. The presence of phototrophs at spherulite centers strongly suggests that these microbes play an important initial role in aragonite precipitation. Substantial growth of individual spherulites occurs abiotically through periodic precipitation of aragonite that forms concentric laminations around spherulite centers while pauses in spherulite growth allow for colonization by microbes. Aragonite associated with biomass (δ(13)C = -4.6‰ VPDB) showed a (13)C-enrichment of 0.8‰ relative to aragonite exhibiting no biomass (δ(13)C = -5.4‰ VPDB), which suggests a modest removal of isotopically light dissolved inorganic carbon by phototrophs. The combination of a low sedimentation rate, high calcification rate, and low microbial growth rate appears to result in the formation of these microbialites. The formation of microbialites at an historic mine site demonstrates that an anthropogenically constructed environment can foster microbial carbonate formation.

Environmental and biological controls on Mg and Li in deep-sea scleractinian corals

Deep-sea scleractinian corals precipitate aragonite skeletons that provide valuable archives of past ocean conditions. During calcification biological mediation causes variability in trace metal incorporation and isotopic ratios of the aragonite such that signals caused by environmental controls can be overwhelmed. This complicates the interpretation of geochemical proxies used for paleo-reconstructions. In this study we examine the environmental controls on the Mg/Li ratio of 34 individuals from seven genera of deep-sea scleractinian corals: Desmophyllum, Balanophyllia, Caryophyllia, Enallopsammia, Flabellum, Trochocyanthus, and Lophelia. In addition we examine the microscale distributions of Mg and Li in Desmophyllum and Balanophyllia using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Both Mg/Ca and Li/Ca ratios increased by more than a factor of two in the center of calcification regions compared to the outer, fibrous regions of the coral skeleton. As a result, replicate ~ 10 mg subsamples of coral show less variability in the Mg/Li ratio than Mg/Ca. Microscale Mg and Li results are consistent with Rayleigh-type incorporation of trace metals with additional processes dominating the composition within centers of calcification. Comparison of Mg/Li to seawater properties near the site of collection shows that the ratio is not controlled by either carbonate ion or salinity. It appears that temperature is the major control on the Mg/Li ratio. For all 34 samples the temperature correlation ( R 2 = 0.62) is significantly better than for Mg/Ca ( R 2 = 0.06). For corals of the family Caryophyllidae the R 2 value increases to 0.82 with the exclusion of one sample that was observed to have an altered, chalky texture . Despite this excellent correlation the scatter in the data suggests that the Mg/Li ratio of deep-sea corals cannot be used to reconstruct temperature to better than approximately ± 1.6 °C without better temperature control and additional calibration points on modern coral samples.

Calcium carbonate precipitation induced by the growth of the marine cyanobacteria Trichodesmium

In this laboratory study, we monitored the buildup of biomass and concomitant shift in seawater carbonate chemistry over the course of a Trichodesmium bloom under different phosphorus (P) availability. During exponential growth, dissolved inorganic carbon (DIC) decreased, while pH increased until maximum cell densities were reached. Once P became depleted, DIC decreased even further and total alkalinity (TA) dropped, accompanied by precipitation of aragonite. Under P‐replete conditions, DIC increased and TA remained constant in the postbloom phase. A diffusion‐reaction model was employed to estimate changes in carbonate chemistry of the diffusive boundary layer. This study demonstrates that Trichodesmium can induce precipitation of aragonite from seawater and further provides possible explanations about underlying mechanisms.

Preservation potential of microorganism morphologies in tufas, sinters, and travertines through geologic time

Microscopically, modern tufas, sinters, and travertines (TSTs) may contain filaments, spirilla, clotted micrite (peloids and/or grumeleuse), tubules, coccoids, or spheres that suggest a biological component to their constitution. However, examination of progressively older TST deposits reveals that the preservation of primary depositional features, including biological morphologies, is commonly obscured by diagenetic overprinting that may mask or obliterate original features. In the study reported here, we examined modern and ancient spring deposits to determine which biological morphologies remain identifiable through geologic time. The focus is on the preservation potential of fossil microorganisms, independent of the mineralogy or formation temperature of the original TST. Biologically induced biomineralization likely fossilizes microorganisms in situ within TST deposits. Biofilms, composed primarily of extracellular polymeric substances, bind calcium or silica ions, serve as nucleation sites, and change local microchemistries to favor precipitation of calcite, aragonite, or chert (less commonly, other minerals). The resultant precipitation entombs microbial material and may yield a fossilized remnant of the microbe’s former presence, albeit lacking details beyond general morphology. The preserved dimensions are almost always larger than those of the original microorganism. Recrystallization and the formation of cement, either calcite (or aragonite) or silica, are diagenetic processes that may occur early and rapidly, with resultant blurring of primary fabrics. Curiously, the commonly recognized spherule and coccoid forms from Holocene and Cenozoic deposits are rarely observable in Mesozoic and Paleozoic deposits, except as indistinct clots in thin section or as rounded mineralized forms. Filaments, however, retain much of their original dimensions, particularly their diameter, and if discovered stretching across a primary pore space may be considered one of the more reliable indicators of former microbial activity in ancient spring deposits.

Sr/Ca and Mg/Ca ratios of ontogenetically old, long-lived bivalve shells ( Arctica islandica) and their function as paleotemperature proxies

The Sr/Ca and Mg/Ca ratios of many biogenic skeletons provide useful paleotemperature estimates. As yet however, it has remained largely impossible to obtain such information from bivalve shells. In the present study, metal-to-calcium values in the hinge plate (aragonite, outer shell layer) of four ontogenetically old (85 to 374 year-old) specimens of the long-lived bivalve, Arctica islandica, were measured on a LA–ICP–MS. The shells were collected alive in 1868, 1986 and 2003 from three different localities around Iceland. With increasing ontogenetic age and decreasing growth rate, a distinct trend toward increasing Sr/Ca (max. 5.17 mmol/mol) and Mg/Ca values (max. 0.89 mmol/mol) and greater variance were observed. Three potential explanations for these trends include a reduced capacity for element selection due to cell ageing, changing metabolism and/or a relative increase in the number of organic-rich (= Mg-rich) and organic-poor (= Sr-rich) shell portions through ontogeny. Partition coefficients however, remained far below 1, indicating that physiology exerted a strong control over the element partitioning between the shells and the ambient water. After mathematical elimination of these vital effects, residuals exhibited a highly significant negative correlation (e.g., age-detrended Sr/Ca data: R = − 0.64, R 2 = 0.41, p < 0.0001, growth rate-detrended Mg/Ca data: R = − 0.52, R 2 = 0.27, p < 0.0001) with sea surface temperature. These results are in good agreement with results obtained from the precipitation of abiogenic aragonite. The results of the present study can help to develop new techniques to extract environmental signals from the metal-to-calcium ratios of bivalve shells.

Amorphous Ca-phosphate precursors for Ca-carbonate biominerals mediated by Chromohalobacter marismortui

Although diverse microbial metabolisms are known to induce the precipitation of carbonate minerals, the mechanisms involved in the bacterial mediation, in particular nucleation, are still debated. The study of aragonite precipitation by Chromohalobacter marismortui during the early stages (3-7 days) of culture experiments, and its relation to bacterial metabolic pathways, shows that: (1) carbonate nucleation occurs after precipitation of an amorphous Ca phosphate precursor phase on bacterial cell surfaces and/or embedded in bacterial films; (2) precipitation of this precursor phase results from local high concentrations of PO(4)(3-) and Ca(2+) binding around bacterial cell envelopes; and (3) crystalline nanoparticles, a few hundred nanometres in diametre, form after dissolution of precursor phosphate globules, and later aggregate, allowing the accretion of aragonite bioliths.

Enrichment of lanthanides in aragonite

Using the constant addition technique, the coprecipitation of lanthanum, gadolinium, and lutetium with aragonite in seawater was experimentally investigated at 25 °C. Their concentrations in aragonite overgrowths were determined by inductive coupled plasma mass spectrometer. All these lanthanides were strongly enriched in aragonite overgrowths. The amount of lanthanum, gadolinium, and lutetium incorporated into aragonite accounted for 57%–99%, 50%–89%, and 40%–91% of their initial total amount, respectively. With the increase of aragonite precipitation rate, more lanthanides were incorporated into aragonite while their relative fraction in aragonite overgrowths decreased consistently. It indicated that the coprecipitation of lanthanides with aragonite was controlled by the kinetics of aragonite precipitation.