Short-Term Coral Bleaching Is Not Recorded by Skeletal Boron Isotopes

Coral skeletal boron isotopes have been established as a proxy for seawater pH, yet it remains unclear if and how this proxy is affected by seawater temperature. Specifically, it has never been directly tested whether coral bleaching caused by high water temperatures influences coral boron isotopes. Here we report the results from a controlled bleaching experiment conducted on the Caribbean corals Porites divaricata, Porites astreoides, and Orbicella faveolata. Stable boron (δ¹¹B), carbon (δ¹³C), oxygen (δ¹⁸O) isotopes, Sr/Ca, Mg/Ca, U/Ca, and Ba/Ca ratios, as well as chlorophyll a concentrations and calcification rates were measured on coral skeletal material corresponding to the period during and immediately after the elevated temperature treatment and again after 6 weeks of recovery on the reef. We show that under these conditions, coral bleaching did not affect the boron isotopic signature in any coral species tested, despite significant changes in coral physiology. This contradicts published findings from coral cores, where significant decreases in boron isotopes were interpreted as corresponding to times of known mass bleaching events. In contrast, δ¹³C and δ¹⁸O exhibited major enrichment corresponding to decreases in calcification rates associated with bleaching. Sr/Ca of bleached corals did not consistently record the 1.2°C difference in seawater temperature during the bleaching treatment, or alternatively show a consistent increase due to impaired photosynthesis and calcification. Mg/Ca, U/Ca, and Ba/Ca were affected by coral bleaching in some of the coral species, but the observed patterns could not be satisfactorily explained by temperature dependence or changes in coral physiology. This demonstrates that coral boron isotopes do not record short-term bleaching events, and therefore cannot be used as a proxy for past bleaching events. The robustness of coral boron isotopes to changes in coral physiology, however, suggests that reconstruction of seawater pH using boron isotopes should be uncompromised by short-term bleaching events.     

Influence of seawater Sr content on coral Sr/Ca and Sr thermometry

The Ca content of a Porites coral from Xisha, South China Sea is quite uniform along its 18-year growth axis. A comparison with previously published data shows that the Ca content of corals from different sites varies by only 0.4%. This is much smaller than the variation of Ca in seawater (2.2%), indicating that Ca variations in seawater do not significantly affect the Ca compositions of coral skeletons. The variation in skeletal Ca contents results in only ±0.6°C of uncertainty in SST calculations, which is much smaller than the large disparities observed for previously established coral Sr/Ca thermometers. In contrast, Sr in tropical seawater varies spatially by as much as 2.4%, corresponding to ~4°C offset for coral Sr/Ca calibrations. The effect of seawater Sr variations on coral Sr/Ca thermometers is evaluated and we demonstrate that the content of seawater Sr is the major factor responsible for disparities in these coral Sr/Ca thermometers. The disparities can be significantly reduced when seawater Sr contents are included in the Sr/Ca thermometers.     

Chromium‐isotope signatures in scleractinian corals from the Rocas Atoll,Tropical South Atlantic

Chromium‐isotope compositions (expressed as δ⁵³Cr) of recent and ancient skeletal and non‐skeletal carbonates are currently explored as a (paleo‐) redox‐proxy for shallow seawater. The idea behind this approach is that biogenic and non‐biogenic carbonates could potentially be used as archives recording the Cr‐isotope composition of seawater in which they formed, and with this contribute to the reconstruction of past paleo‐environmental changes in the marine realm, and potentially to climate changes on land. However, investigations addressing the behavior and uptake mechanism of Cr, and the potential isotope fractionations between seawater and biogenic carbonates are scarce. Here, we present a study of Cr‐isotope variations in three species of corals and contemporary seawater from the Rocas Atoll, NE, Brazil. Cr‐isotope values of the studied coral species (Siderastrea stellata, Porites sp., and Montastrea cavernosa) vary from ?0.5 to +0.33‰ and point to significant isotopic disequilibrium with coexisting seawater characterized by a Cr‐isotope value of +0.92 ± 0.2‰. This isotopic offset requires reduction of hexavalent Cr(VI) in the sequestration process of all the studied coral species. Cr‐isotope values in a profile across an S. stellata colony returned homogeneous, slightly positively fractioned δ⁵³Cr values of +0.07 ± 0.08‰ (n = 8, 2σ), which we interpret to reflect a constant reductive uptake during the 20‐year growth period recorded in this coral. In contrast, samples across a 12‐year growth profile from Porites sp. display rather heterogeneous Cr‐isotope values with δ⁵³Cr varying from ?0.50 to +0.10‰, indicating Cr incorporation under changing redox processes during its growth intervals. We propose a mechanism whereby initial photoreduction of isotopically heavy Cr(VI) to isotopically lighter Cr(III) in the endodermal layer of corals must be followed by efficient and effective re‐oxidation of reduced Cr species to favor subsequent chromate () substitution during the calcifying processes ultimately leading to the formation of the coral skeleton.     

Effect of salinity and seawater calcite saturation state on Mg and Sr incorporation in cultured planktonic foraminifera

Trace elements incorporated in planktonic foraminiferal test carbonate are commonly used as paleoproxies. For instance, Mg/Ca ratios are frequently used for reconstructing sea surface temperature and, together with the foraminiferal stable oxygen isotope ratios, are also used as paleosalinity proxy. Foraminiferal Sr/Ca ratios constitute another example of the application of trace elements in paleostudies since they may reflect the Sr/Ca values of seawater. However, over the past few decades it has been proven that the incorporation of trace elements in foraminiferal calcite is controlled by more than one environmental parameter. To quantify the effect of salinity on Mg and Sr incorporation planktonic foraminifera Globigerinoides sacculifer (sensu stricto) were grown in the laboratory under different environmental conditions. Laboratory experiments allowed us to separate a direct salinity effect from a possible independent impact through differences in the calcite saturation state of the seawater (Ω). Although the temperature effect is more important than the salinity effect, a change of 4 salinity units is equivalent to a 1 °C bias on Mg/Ca-based temperatures. This effect of salinity on Mg incorporation is minor. However, when using Mg/Ca-based temperatures in combination with foraminiferal δ¹⁸O to calculate salinity, it cannot be neglected. The present study shows salinity as the overriding control on Mg incorporation within the range of Ω studied (Ω between 5.25 and 6.50; [CO₃²⁻] between 218 and 270 μmol/kg) at a constant temperature of 26 °C. In contrast, Ω appears to be the main control on foraminiferal Sr incorporation (0.10 mmol/mol per 100 µmol/kg rise in [CO₃²⁻]), whereas salinity has a non significant influence on Sr/Ca.     

Sponge erosion under acidification and warming scenarios: differential impacts on living and dead coral

Ocean acidification will disproportionately impact the growth of calcifying organisms in coral reef ecosystems. Simultaneously, sponge bioerosion rates have been shown to increase as seawater pH decreases. We conducted a 20‐week experiment that included a 4‐week acclimation period with a high number of replicate tanks and a fully orthogonal design with two levels of temperature (ambient and +1 °C), three levels of pH (8.1, 7.8, and 7.6), and two levels of boring sponge (Cliona varians, present and absent) to account for differences in sponge attachment and carbonate change for both living and dead coral substrate (Porites furcata). Net coral calcification, net dissolution/bioerosion, coral and sponge survival, sponge attachment, and sponge symbiont health were evaluated. Additionally, we used the empirical data from the experiment to develop a stochastic simulation of carbonate change for small coral clusters (i.e., simulated reefs). Our findings suggest differential impacts of temperature, pH and sponge presence for living and dead corals. Net coral calcification (mg CaCO₃ cm^?2 day^?1) was significantly reduced in treatments with increased temperature (+1 °C) and when sponges were present; acidification had no significant effect on coral calcification. Net dissolution of dead coral was primarily driven by pH, regardless of sponge presence or seawater temperature. A reevaluation of the current paradigm of coral carbonate change under future acidification and warming scenarios should include ecologically relevant timescales, species interactions, and community organization to more accurately predict ecosystem‐level response to future conditions.     

Effect of salinity on the skeletal chemistry of cultured scleractinian zooxanthellate corals: Cd/Ca ratio as a potential proxy for salinity reconstruction

The effect of salinity on the elemental and isotopic skeletal composition of modern zooxanthellate scleractinian corals (Acropora sp., Montipora verrucosa and Stylophora pistillata) was investigated in order to evaluate potential salinity proxies. Corals were cultured in the laboratory at three salinities (36, 38 and 40). The other environmental parameters were kept constant. For all species analyzed, Sr/Ca, Mg/Ca, U/Ca and Li/Ca ratios were not influenced by salinity changes. The Ba/Ca ratio also lacks a systematic relationship with salinity and exhibits high inter-generic variations, up to one order of magnitude. On the contrary, the Cd/Ca ratio decreases as a function of increasing salinity, and δ¹⁸O and δ¹³C also presented a significant response, but with opposite trends to salinity variations. Since Cd/Ca is usually considered as an upwelling proxy, its salinity dependence could compromise the upwelling signal, unless some corrections can be carried out. Regardless, if the dependence found in the present dataset proved to be widespread and systematic, the Cd/Ca ratio could represent a promising salinometer awaiting further investigation. This study also confirmed the reliability of the well-established temperature proxies Sr/Ca, Mg/Ca and U/Ca, as these ratios were insensitive to salinity variations. Moreover, our results showed that δ¹⁸O or δ¹³C can be considered as reliable temperature recorders as far as the salinity effect is removed from the parameter reconstructed (e.g., temperature). Investigating the influence of salinity on the skeletal chemistry of scleractinian corals grown under controlled environmental conditions confirmed previous results, validated isotopic corrections, and identified a promising proxy of salinity.     

Mg and Ca isotope fractionation during CaCO3 biomineralisation

The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered.     

Examining water temperature proxies in<Emphasis Type="Italic"> Porites</Emphasis> corals from the Great Barrier Reef: a cross-shelf comparison

Cores from colonies of the coral species Porites sp. were collected from inshore, mid-shelf, and outer reef localities (central Great Barrier Reef) to test the robustness of the major elemental sea surface temperature (SST) proxies (B/Ca, Mg/Ca, Sr/Ca, U/Ca) to the influence of inshore processes. Time series analyses of Sr/Ca, U/Ca, B/Ca, and Mg/Ca are compared to sea surface temperature (SST) in order to provide calibrations for these elements. This study shows that there are significant variations between the corals with respect to some of the proxies. In some cases, variations of ~6 °C are observed for a single U/Ca value. This magnitude of variation is also seen in the Mg/Ca proxy and, to a smaller extent, in the B/Ca–SST relationship. In two of the corals, both Mg/Ca and U/Ca do not follow a seasonal signal. The Mg/Ca and U/Ca ratios for two inshore corals are significantly different than the offshore corals (lower and higher, respectively). The other two proxies (B/Ca and Sr/Ca) do not display any inshore vs. offshore variations except for one inshore site that did not have a clear seasonal signal for either of these proxies. The Sr/Ca–SST relationship is the most robust, with a temperature variation of ~2 °C for a single Sr/Ca value, which is within error for this technique.     

Strontium:cakium concentration ratios in otoliths of herring larvae as indicators of environmental histories

Synopsis Elemental analyses, using wave-length dispersive electron microprobe techniques on otoliths from reared Atlantic herring larvae, Clupea harengus, showed trace quantities of strontium relative to that of calcium, and an inverse relationship between Sr/Ca concentration ratios and rearing temperature. These data are consistent with those for coral aragonite, in that there appears to be an inverse temperature effect on physiological incorporation of strontium in the otolith aragonite. Our determinations of Sr/Ca concentration ratios of lab-reared herring larvae showed that the deposition of strontium relative to calcium and the rearing temperature were related, where: T (° C) = −2.955 [Sr/Ca] × 1000 ± 19.172. This principle thus makes it possible to use Sr/Ca concentration ratios in fish otoliths to delineate past temperatures experienced by an individual. Further, combining electron microprobe analyses with scanning electron microscope (SEM) examinations of daily increments in the same otolith makes it possible to reconstruct the temperature history for an individual fish on a time scale of days. An example of the application of the technique to an approximately six-month-old field-caught herring larva is given, and the limitations of the technique are discussed.     

Coral acid rich protein selects vaterite polymorph in vitro

Corals and other biomineralizing organisms use proteins and other molecules to form different crystalline polymorphs and biomineral structures. In corals, it’s been suggested that proteins such as Coral Acid Rich Proteins (CARPs) play a major role in the polymorph selection of their calcium carbonate (CaCO₃) aragonite exoskeleton. To date, four CARPs (1–4) have been characterized: each with a different amino acid composition and different temporal and spatial expression patterns during coral developmental stages. Interestingly, CARP3 is able to alter crystallization pathways in vitro, yet its function in this process remains enigmatic. To better understand the CARP3 function, we performed two independent in vitro CaCO₃ polymorph selection experiments using purified recombinant CARP3 at different concentrations and at low or zero Mg²⁺ concentration. Our results show that, in the absence of Mg²⁺, CARP3 selects for the vaterite polymorph and inhibits calcite. However, in the presence of a low concentration of Mg²⁺ and CARP3 both Mg-calcite and vaterite are formed, with the relative amount of Mg-calcite increasing with CARP3 concentration. In all conditions, CARP3 did not select for the aragonite polymorph, which is the polymorph associated to CARP3 in vivo, even in the presence of Mg²⁺ (Mg:Ca molar ratio equal to 1). These results further emphasize the importance of Mg:Ca molar ratios similar to that in seawater (Mg:Ca equal to 5) and the activity of the biological system in a aragonite polymorph selection in coral skeleton formation.     

Asteriscus v. lapillus: comparing the chemistry of two otolith types and their ability to delineate riverine populations of common carp Cyprinus carpio

The chemical composition of common carp Cyprinus carpio asteriscus (vaterite) and lapillus (aragonite) otoliths from the same individual and reflecting the same growth period was measured to (1) determine whether there are differences in the uptake of trace metals (Mg:Ca, Mn:Ca, Sr:Ca and Ba:Ca ) and Sr isotope ratios (⁸⁷Sr:⁸⁶Sr) in co‐precipitating lapilli and asterisci and (2) compare the ability of multi‐element and isotopic signatures from lapilli, asterisci and both otolith types combined to discriminate C. carpio populations over a large spatial scale within a river basin. Depth profile analyses at the otolith edge using laser‐ablation inductively coupled plasma mass spectrometry showed that asterisci were enriched in Mg and Mn and depleted in Sr and Ba relative to lapilli, whilst ⁸⁷Sr:⁸⁶Sr values were nearly identical in both otolith types. Significant spatial differences among capture locations were found when all trace element and Sr isotope ratio data were aggregated into a multi‐element and isotopic signature, regardless of which otolith type was used or if they were used in combination. Discriminatory power was enhanced, however, when data for both otolith types were combined, suggesting that analysis of multiple otolith types may be useful for studies attempting to delineate C. carpio populations at finer spatial or temporal scales.     

An isotopic and geochemical study of carbonate-clay mineralization in basaltic caves: abiotic versus microbial processes

Stable isotope and geochemical data are used here to differentiate between contemporaneous abiotic and microbial processes leading to formation of modern carbonate‐ (calcite, aragonite and magnesite) and silicate‐rich (kerolite) mineralization in basaltic sea caves on the island of Kauai, Hawaii. Strontium isotope and Ca/Sr ratios in meteoric water and cave carbonates suggest that the majority of Sr and Ca are derived from rock–water interaction within the host basalts situated above the caves. Oxygen and hydrogen isotope ratios and chemical compositions of cave and surface waters indicate that evaporation does not control cave‐water composition. However, evaporation of drops and thin films of water in microenvironments can lead to precipitation of some phases. This behaviour is suggested by the covariance in δ¹⁸O and δ¹³C values of some carbonates, especially magnesite, which is considered to be a late‐stage evaporative precipitate. Modelling of water evolution suggests that evaporation can be a cause of supersaturation for magnesite, kerolite and some Ca carbonates. However, the highly elevated δ¹³C values (up to +8.2) of some Ca carbonates, compared to average dissolved inorganic carbon δ¹³C values (~?12), are best explained as the product of microbial photosynthesis, in particular by cyanobacteria, present in the upper layers of active microbial mats on cave surfaces. The preferential uptake of ¹²C by cyanobacteria is recorded in the low δ¹³C values (?29.1 to ?22.6) of organic matter in mats and mineralized microbialites. The resulting ¹³C‐enrichment of dissolved inorganic carbon is recorded in the elevated δ¹³C values of these Ca carbonates. A positive correlation exists between the δ¹³C values of the carbonates and coexisting organic matter. The large enrichment in ¹³C of carbonate minerals, relative to dissolved inorganic carbon, and its covariance with the δ¹³C values of coexisting organic matter are useful for identification of carbonate‐rich mineralization resulting from autotrophic microbial activity.     

Effects of Ca and Mg concentrations in seawater on the growth and energy budget of juvenile Paralichthys olivaceus (Temminck & Schlegel, 1846)

Effects of seawater calcium (Ca) and magnesium (Mg) concentrations on the growth and energy budget of juvenile Paralichthys olivaceus (Temminck & Schlegel, 1846) were investigated at 20°C and a salinity of 30 psu. The Ca/Mg ratio (Ca : Mg = 1 : 3) in the experimental water was kept constant. Five treatments were set: C1, C2, C3, C4, and C5, and the Ca and Mg concentrations were 700, 1100, 1600, 2200, and 2800 (mg L^?1), respectively. After a 60‐day feeding trial the P. olivaceus survival rates were not affected significantly by Ca or Mg concentrations in the range of 700–2800 mg L^?1. However, the specific growth rates (SGR) and weight gain (WG) of all treatments decreased with ascending Ca and Mg concentrations. The Ca and Mg concentrations had a strong influence on various energy parameters, namely, energy deposited for growth (G), energy lost for respiration (R), and energy lost in excretion (U), but had little influence on energy lost in feces (F). This indicated that the growth rate differences under different concentrations of Ca and Mg mainly resulted from differences of assimilation efficiency and energy channeled into respiration. The highest net growth efficiency was attained at the lowest concentration of Ca and Mg in seawater, and the higher concentrations of Ca and Mg increased the energy channeled to respiration and excretion, which led to significant reduction in growth. Therefore, the optimal growth of P. olivaceus could be obtained by regulating the concentration of Ca and Mg at 700 mg L^?1, where the average energy budget was: 100C (100% energy consumed in food) = 47.21 (±0.63) G + 32.89 (±0.42) R + 16.71 (±0.56) F + 3.19 (±0.05) U.     

Assessing between-colony oxygen isotope variability in the coral Porites lobata at Clipperton Atoll

The eastern Pacific warm tongue is a region of stable and elevated sea surface temperature (SST) located just north of the equator in the eastern Pacific. This warm water mass is thought to influence the position of the Intertropical Convergence Zone (ITCZ) in the eastern Pacific and to directly influence climate in Central America. To assess the use of corals in the development of paleoclimatic reconstructions in this region, we have developed oxygen isotope (δ¹⁸O) time-series from multiple specimens of the massive coral Porites lobata collected at Clipperton Atoll (10°18′N, 109°13′ W). Six near-monthly δ¹⁸O records from different sized (age) colonies where produced for the interval 1986–1994, and three of these were extended back to 1969. All corals sampled were found to contain numerous fish-grazing skeletal scars (～0.5?mm deep scallop shaped hiatuses). Samples collected at 1?mm intervals showed anomalous ¹⁸O/¹⁶O in the area of a bite scar, with 2 to 2.5?mm sampling intervals (10–12/year) minimizing these effects. Our results show that the average δ¹⁸O disequilibrium offset (vital effect) from equilibrium seawater composition for individual corals can vary by up to 0.4‰. However all δ¹⁸O results suggest that the vital effect offset is constant over time. Similar “offsets” are observed in the tops of old (age=～100?y) and young (age=～10?y) colonies, further suggesting that the biologically mediated vital effect offset does not change as a Porites colony ages. A 6-coral average composite δ¹⁸O record was constructed from 1985–1994 and a 3-coral average δ¹⁸O_anomaly record was constructed from 1969–1994. Regression analysis between monthly SST and the 6 coral average δ¹⁸O records yields an r ² correlation of 0.54 (individual r ²-values ranged from 0.27–0.55). The 3 coral δ¹⁸O_anomaly average record has an even lower correlation to SST, with an r ² of 0.40. Potential causes of the only moderate correlation to SST are explored and we find that inferred salinity effects, fish grazing scars, and slight chronology imperfections have all contributed to a reduced correlation to SST. Nevertheless, all El Niño events in this time period appear to be recorded by coral skeletal δ¹⁸O.     

Mg/Ca and δ18O in the brackish shallow-water benthic foraminifer Ammonia ‘beccarii’

Specimens of the benthic foraminifer Ammonia beccarii were cultured in the laboratory in order to determine the relation between temperature and Mg/Ca and oxygen isotope values in their tests. Asexual reproduction in this species provides a large number of juveniles that were allowed to grow into maturity at temperatures ranging from 10 to 27 °C and at salinities ranging from 18 to 33 PSU. The Mg/Ca in a calcite increase exponentially and δ¹⁸O decreases linearly with the temperature. Salinity has no significant impact on either Mg/Ca or δ¹⁸O. We show how the combination of these two parameters can be used to reconstruct seawater δ¹⁸O and temperature in shallow marine habitats.     

Trace and minor element ratios inHalimeda aragonite from the Great Barrier Reef

The calcareous green algaHalimeda can be a substantial contributor to aragonite sediment in reef ecosystems. In contrast to coral aragonite, little is known about the trace and minor element composition ofHalimeda aragonite, so it is difficult to test oceanographic hypotheses about factors controlling its past growth. We investigated adapting trace element cleaning protocols for modern and HoloceneHalimeda aragonite, modern and HoloceneHalimeda trace and minor element compositions, and the potential utility ofHalimeda aragonite for paleoceanographic investigations. We successfully adapted and applied sample treatment protocols developed for measuring trace elements in coral aragonite (generally less than 500 y old) toHalimeda aragonite (modern to approximately 5000 y old in this study). ModernHalimeda aragonite from John Brewer Reef in the Central GBR had mean Cd/Ca ratios of 5.19 ± 1.68 nmol/mol forHalimeda micronesica and 2.35 ± 0.38 nmol/mol for three closely related species important in bioherm accumulationHalimeda copiosa, Halimeda hederacea, andHalimeda opuntia. Mn/Ca ratios, with means from 89–239 nmol/mol for these four species, showed both intra-and inter-specific variability. Sr/Ca ratios (10.9 ± O.1 mmol/mol) and Mg/Ca ratios (1.35 ± 0.26 mmol/mol) were similar for all samples. HoloceneHalimeda aragonite samples from cores of two bioherms in the northern GBR seemed well preserved on the basis of mineralogy and Sr/Ca and Mg/Ca ratios similar to those in modernHalimeda aragonite. Cd/Ca ratios (overall mean 0.96 ± 0.15 nmol/mol) were lower than those measured in the modernHalimeda from the central GBR location. However, Mn/Ca ratios in both cores were substantially higher than in modernHalimeda aragonite. While it may be possible to extract paleoceanographic information fromHalimeda aragonite, substantial care is needed to evaluate and avoid the effects of post-depositional alteration.     

Stable isotope fractionation of strontium in coccolithophore calcite: Influence of temperature and carbonate chemistry

Marine calcifying eukaryotic phytoplankton (coccolithophores) is a major contributor to the pelagic production of CaCO₃ and plays an important role in the biogeochemical cycles of C, Ca and other divalent cations present in the crystal structure of calcite. The geochemical signature of coccolithophore calcite is used as palaeoproxy to reconstruct past environmental conditions and to understand the underlying physiological mechanisms (vital effects) and precipitation kinetics. Here, we present the stable Sr isotope fractionation between seawater and calcite (Δ^88/86Sr) of laboratory cultured coccolithophores in individual dependence of temperature and seawater carbonate chemistry. Coccolithophores were cultured within a temperature and a pCO₂ range from 10 to 25°C and from 175 to 1,240 μatm, respectively. Both environmental drivers induced a significant linear increase in coccolith stable Sr isotope fractionation. The temperature correlation at constant pCO₂ for Emiliania huxleyi and Coccolithus braarudii is expressed as Δ^88/86Sr = ?7.611 × 10^?3 T + 0.0061. The relation of Δ^88/86Sr to pCO₂ was tested in Emiliania huxleyi at 10 and 20°C and resulted in Δ^88/86Sr = ?5.394 × 10^?5 pCO₂ – 0.0920 and Δ^88/86Sr = ?5.742 × 10^?5 pCO₂ – 0.1351, respectively. No consistent relationship was found between coccolith Δ^88/86Sr and cellular physiology impeding a direct application of fossil coccolith Δ^88/86Sr as coccolithophore productivity proxy. An overall significant correlation was detected between the elemental distribution coefficient (D_Sr) and Δ^88/86Sr similar to inorganic calcite with a physiologically induced offset. Our observations indicate (i) that temperature and pCO₂ induce specific effects on coccolith Δ^88/86Sr values and (ii) that strontium elemental ratios and stable isotope fractionation are mainly controlled by precipitation kinetics when embedded into the crystal lattice and subject to vital effects during the transmembrane transport from seawater to the site of calcification. These results provide an important step to develop a coccolith Δ^88/86Sr palaeoproxy complementing the existing toolbox of palaeoceanography.     

Elemental chemistry of left and right sagittal otoliths in a marine fish Hippoglossus stenolepis displaying cranial asymmetry

The hypothesis was tested that the sagittae of age 2 year Pacific halibut Hippoglossus stenolepis are interchangeable, by analysing whole‐otolith preparations for element‐to‐calcium ratios of 10 trace metals (⁷Li, ²⁵Mg, ⁵⁵Mn, ⁵⁶Fe, ⁶⁰Ni, ⁶³Cu, ⁶⁶Zn, ⁸⁸Sr, ¹³⁸Ba and ²⁰⁸Pb) and carbon and oxygen stable isotope ratios (δ¹³C and δ¹⁸O). After detrending for significant (α= 0·05) relationships between elemental concentration and otolith mass, significant (paired t‐tests, P < 0·01) asymmetry was detected in δ¹³C and δ¹⁸O, and ⁸⁸Sr:⁴⁸Ca. Right (smaller) sagittae exhibited higher δ¹³C and δ¹⁸O, and lower ⁸⁸Sr:⁴⁸Ca, than left sagittae. Significant (α= 0·05) left–right differences were not detected in the remained trace metals. Given that sagittae are the same size at hatch and diverge as H. stenolepis age, the larger otolith is presumably biased towards later‐accreted carbonate. Estuarine‐reared flatfish probably exhibit more pronounced dissimilarities than observed here, given greater environmental variability in such habitats relative to coastal halibut nurseries, and the importance of salinity and temperature in regulating elemental uptake.     

Morphology,microstructure, crystallography,and chemistry of distinct CaCO3 deposits formed by early recruits of the scleractinian coral Pocillopora damicornis

Scleractinian corals begin their biomineralization process shortly after larval settlement with the formation of calcium carbonate (CaCO₃) structures at the interface between the larval tissues and the substrate. The newly settled larvae exert variable degrees of control over this skeleton formation, providing an opportunity to study a range of biocarbonate structures, some of which are transient and not observed in adult coral skeletons. Here we present a morphological, structural, crystallographic, and chemical comparison between two types of aragonite deposits observed during the skeletal development of 2‐days old recruits of Pocillopora damicornis: (1) Primary septum and (2) Abundant, dumbbell‐like structures, quasi‐randomly distributed between initial deposits of the basal plate and not present in adult corals—At the mesoscale level, initial septa structures are formed by superimposed fan‐shaped fasciculi consisting of bundles of fibers, as also observed in adult corals. This organization is not observed in the dumbbell‐like structures. However, at the ultrastructural level there is great similarity between septa and dumbbell components. Both are composed of <100 nm granular units arranged into larger single‐crystal domains.Chemically, a small difference is observed between the septae with an average Mg/Ca ratio around 11 mmol/mol and the dumbbell‐like structures with ca. 7 mmol/mol; Sr/Ca ratios are similar in the two structures at around 8 mmol/mol—Overall, the observed differences in distribution, morphology, and chemistry between septa, which are highly conserved structures fundamental to the architecture of the skeleton, and the transient, dumbbell‐like structures, suggest that the latter might be formed through less controlled biomineralization processes. Our observations emphasize the inherent difficulties involved in distinguishing different biomineralization pathways based on ultrastructural and crystallographical observations. J. Morphol. 276:1146–1156, 2015. © 2015 Wiley Periodicals, Inc.