Seawater Ca Research Articles

The effect of changing seawater Ca and Mg concentrations upon the distribution coefficients of Mg and Sr in the skeletons of the scleractinian coral Pocillopora damicornis

The skeletal composition of calcifying organisms, in particular Mg/Ca and Sr/Ca ratios, have been widely used to understand fluctuations in seawater chemistry throughout the Phanerozoic. While the success of applying these data to the geologic record depends on a knowledge of the distribution coefficients for these elements (DMg and DSr), there are scarcely any studies which have described how these values vary as a result of changing seawater Mg/Ca ratios. To address this, we have cultured the scleractinian coral, Pocillopora damicornis, in seawater with ranges of Mg and Ca concentrations. Here, we demonstrate that Mg/Ca and Sr/Ca ratios of coral skeletons correlate with total seawater Mg/Ca and Sr/Ca molar ratios, but that apparent DMg and DSr values do not remain constant across the range of experimental seawater treatments, with DMg values significantly increasing with seawater Mg/Ca ratios and DSr values significantly increasing with seawater Ca concentrations. These trends are not rate dependent and may be best explained by a Rayleigh distillation model, in which the calcifying space is semi-isolated from seawater during skeletogenesis (i.e. leaky). As there is a slight increase in DMg and decrease in DSr values between our “Jurassic” and “Modern” seawater treatments, the application of a constant distribution coefficient to estimate changes in ancient seawater chemistry may underestimate seawater Mg/Ca ratios and overestimate Sr/Ca throughout the Mesozoic and Cenozoic. We suggest that interpretations of seawater chemistry from fossil corals may be improved by using the relationships derived for skeletal and seawater Mg/Ca and Sr/Ca ratios established by our experiments, as they incorporate the effect of seawater Mg/Ca ratios on skeletal Mg/Ca and Sr/Ca ratios.

Controls over δ44/40Ca and Sr/Ca variations in coccoliths: New perspectives from laboratory cultures and cellular models

Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Demise of Ediacaran dolomitic seas marks widespread biomineralization on the Siberian Platform

Abstract The trigger for biomineralization of metazoans in the terminal Ediacaran, ca. 550 Ma, has been suggested to be the rise of oxygenation or an increase in seawater Ca concentration, but geochemical and fossil data have not been fully integrated to demonstrate cause and effect. Here we combine the record of macrofossils with early marine carbonate cement distribution within a relative depth framework for terminal Ediacaran to Cambrian successions on the eastern Siberian Platform, Russia, to interrogate the evolution of seawater chemistry and biotic response. Prior to ca. 545 Ma, the presence of early marine ferroan dolomite cement suggests dominantly ferruginous anoxic “aragonite-dolomite seas”, with a very shallow oxic chemocline that supported mainly soft-bodied macrobiota. After ca. 545 Ma, marine cements changed to aragonite and/or high-Mg calcite, and this coincides with the appearance of widespread aragonite and high-Mg calcite skeletal metazoans, suggesting a profound change in seawater chemistry to “aragonite seas” with a deeper chemocline. By early Cambrian Stage 3, the first marine low-Mg calcite cements appear, coincident with the first low-Mg calcite metazoan skeletons, suggesting a further shift to “calcite seas”. We suggest that this evolution of seawater chemistry was caused by enhanced continental denudation that increased the input of Ca into oceans so progressively lowering Mg/Ca, which, combined with more widespread oxic conditions, facilitated the rise of skeletal animals and in turn influenced the evolution of skeletal mineralogy.

Sr partitioning in the benthic foraminifera Ammonia aomoriensis and Amphistegina lessonii

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 KDSr. 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 KDSr 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 KDSr can be explained by the, relative to A. aomoriensis, high Mg content of A. lessonii (ca. 40mmol/mol), distorting the calcite lattice and weakening the discrimination against Sr. The Mg content of A. aomoriensis is too low (ca. 4mmol/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).

Calcium isotope constraints on the marine carbon cycle and CaCO3 deposition during the late Silurian (Ludfordian) positive δ13C excursion

This study investigates calcium isotope variations (δ44/40Ca) in late Silurian marine carbonates deposited in the Prague Basin (Czech Republic), which records one of the largest positive carbon isotope excursion (CIE) of the entire Phanerozoic, the mid-Ludfordian CIE, which is associated with major climatic changes (abrupt cooling) and global sea-level fluctuations. Our results show that during the onset of the CIE, when δ13C increases rapidly from ∼0‰ to ∼8.5‰, δ44/40Ca remains constant at about 0.3±0.1‰ (relative to NIST 915a), while 87Sr/86Sr in well-preserved carbonates are consistent with a typical Ludfordian seawater composition (ranging from ∼0.70865 to ∼0.70875). Such decoupling between δ13C and δ44/40Ca trends during the onset of the CIE is consistent with the expected order-of-magnitude difference in the residence times of Ca (∼106yr) and C (∼105yr) in the open ocean, suggesting that the mid-Ludfordian CIE was caused by processes where the biogeochemical pathways of C and Ca in seawater were mechanistically decoupled. These processes may include: (i) near shore methanogenesis and photosynthesis, (ii) changes in oceanic circulation and stratification, and/or (iii) increased production and burial of organic C in the global ocean. The latter, however, is unlikely due to the lack of geological evidence for enhanced organic C burial, and also because of unrealistic parameterization of the ocean C cycle needed to generate the observed CIE over the relatively short time interval. In contrast, higher up in the section where δ13C shifts back to pre-excursion baseline values, there is a correlated shift to higher δ44/40Ca values. Such coupling of the records of Ca and C isotope changes in this part of the study section is inconsistent with the abovementioned differences in oceanic Ca and C residence times, indicating that the record of δ44/40Ca changes does not faithfully reflect the evolution of the oceanic Ca reservoir, but rather some local processes in the Prague Basin. These can be related to restricted elemental/sediment cycling involving mixing of isotopically distinct Ca sources and carbonate polymorphs (calcite vs. aragonite), and/or possible kinetic Ca isotope effects due to changes in the rate of marine carbonate formation. Evidence supporting the ‘kinetic’ effect in the studied mid-Ludfordian carbonates is indicated by correlated δ44/40Ca and Sr-concentration data (rs=−0.76, p<0.001, n=41) yielding a slope of −0.00097, which is indistinguishable from the ‘kinetic’ slope of abiotic calcite precipitation. Kinetic processes are integral to the model of rapid carbonate precipitation recently proposed by Kozłowski (2015), to explain the origin of the mid-Ludfordian CIE, involving intense methanogenesis/photosynthesis in near shore settings coupled with rapid CaCO3 precipitation (i.e., massive whitings events) and eustatically-controlled carbonate hypersaturation of seawater. More Ca isotope studies are needed to shed light on the question of whether kinetics or mineralogy controls the coupled variations in carbonate δ44/40Ca and δ13C records observed in this study and other large positive CIEs in geological record.

Li partitioning in the benthic foraminifera Amphistegina lessonii

AbstractThe shallow water benthic foraminifer Amphistegina lessonii was grown in seawater of variable Li and Ca concentration and shell Li/Ca was determined by means of LA‐ICPMS. Shell Li/Ca is positively correlated to seawater Li/Ca only when the Li concentration of seawater is changed. If the seawater Ca concentration is changed, shell Li/Ca remains constant. This indicates that Li does not compete with Ca for incorporation in the shell of A. lessonii. A recently proposed calcification model can be applied to divalent cations (e.g., Mg and Sr), which compete for binding sites of ion transporters and positions in the calcite lattice. By contrast, the transport pathway of monovalent cations such as Li is probably diffusion based (e.g., ion‐channels), and monovalent cations do not compete with Ca for a position in the calcite lattice. Here we present a new model for Li partitioning into foraminiferal calcite which predicts our experimental results and should also be applicable to other alkali metals.

Phytoplankton calcification as an effective mechanism to alleviate cellular calcium poisoning

Abstract. Marine phytoplankton have developed the remarkable ability to tightly regulate the concentration of free calcium ions in the intracellular cytosol at a level of ~ 0.1 μmol L−1 in the presence of seawater Ca2+ concentrations of 10 mmol L−1. The low cytosolic calcium ion concentration is of utmost importance for proper cell signalling function. While the regulatory mechanisms responsible for the tight control of intracellular Ca2+ concentration are not completely understood, phytoplankton taxonomic groups appear to have evolved different strategies, which may affect their ability to cope with changes in seawater Ca2+ concentrations in their environment on geological timescales. For example, the Cretaceous (145 to 66 Ma), an era known for the high abundance of coccolithophores and the production of enormous calcium carbonate deposits, exhibited seawater calcium concentrations up to 4 times present-day levels. We show that calcifying coccolithophore species (Emiliania huxleyi, Gephyrocapsa oceanica and Coccolithus braarudii) are able to maintain their relative fitness (in terms of growth rate and photosynthesis) at simulated Cretaceous seawater calcium concentrations, whereas these rates are severely reduced under these conditions in some non-calcareous phytoplankton species (Chaetoceros sp., Ceratoneis closterium and Heterosigma akashiwo). Most notably, this also applies to a non-calcifying strain of E. huxleyi which displays a calcium sensitivity similar to the non-calcareous species. We hypothesize that the process of calcification in coccolithophores provides an efficient mechanism to alleviate cellular calcium poisoning and thereby offered a potential key evolutionary advantage, responsible for the proliferation of coccolithophores during times of high seawater calcium concentrations. The exact function of calcification and the reason behind the highly ornate physical structures of coccoliths remain elusive.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers related to test structure, mineralogy and environmental controls

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3–4°C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4‰ lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, δ44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal δ44/40Ca and Sr/Ca proxy signals.

Ca and Mg isotope constraints on the origin of Earth’s deepest [formula omitted]C excursion

Understanding the extreme carbon isotope excursions found in carbonate rocks of the Ediacaran Period (635–541Ma), where δ13C of marine carbonates (δ13Ccarb) reach their minimum (-12‰) for Earth history, is one of the most vexing problems in Precambrian geology. Known colloquially as the ‘Shuram’ excursion, the event has been interpreted by many as a product of a profoundly different Ediacaran carbon cycle. More recently, diagenetic processes have been invoked, with the very negative δ13C values of Ediacaran carbonates explained via meteoric alteration, late-stage burial diagenesis or growth of authigenic carbonates in the sediment column, thus challenging models which rely upon a dramatically changing redox state of the Ediacaran oceans. Here we present 257 δ44/40Ca and 131 δ26Mg measurements, along with [Mg], [Mn] and [Sr] data, from carbonates of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia to bring new isotope systems to bear on understanding the ‘Shuram’ excursion. Data from four measured sections spanning the basin reveal stratigraphically coherent trends, with variability of ∼1.5‰ in δ26Mg and ∼1.2‰ in δ44/40Ca. This Ca isotope variability dwarfs the 0.2–0.3‰ change seen coeval with the Permian–Triassic mass extinction, the largest recorded in the rock record, and is on par with putative changes in the δ44/40Ca value of seawater seen over the Phanerozoic Eon. Changes in both isotopic systems are too large to explain with changes in the isotopic composition of Ca and Mg in global seawater given modern budgets and residence times, and thus must be products of alternative processes. Relationships between δ44/40Ca and [Sr] and δ26Mg and [Mg] are consistent with mineralogical control (e.g., aragonite vs. calcite, limestone vs. dolostone) on calcium and magnesium isotope variability. The most pristine samples in the Wonoka dataset, preserving Sr concentrations (in the 1000s of ppm range) and δ44/40Ca values inherited from an originally aragonitic polymorph, have δ13Ccarb of -8‰ to -7‰, thereby providing strong geochemical evidence that extremely negative δ13Ccarb values are primary products of the Ediacaran surface environment.

Aragonite-calcite seas—Quantifying the gray area

Oscillations between the dominance of aragonite and calcite in abiotic marine CaCO3 precipitates throughout Earth history are closely coupled with the evolution of Earth’s seawater composition and represent the environmental context in which organisms evolved their ability to biomineralize. The most important factor controlling these Phanerozoic oscillations in CaCO3 polymorph composition is the ratio of Mg:Ca in seawater, which is thought to separate aragonite and calcite precipitation along a distinct temperature-controlled threshold. A sharp threshold, however, is contradicted by overlapping aragonite and calcite precipitation fields at a range of experimental conditions. Here we present experimental data that enable us to quantify the proportions of CaCO3 polymorphs as a function of Mg:Ca ratio and temperature. This allows us to convert published Mg:Ca ratio proxy data and models of the Phanerozoic Mg:Ca ratio into proportions of abiotic CaCO3 polymorphs at a given temperature, and thus provides a temperature-corrected view of aragonite-calcite sea conditions. In this revised view, abiotic calcite precipitation was inhibited during aragonite sea intervals at temperatures above 20 °C, whereas calcite sea intervals were characterized by the co-precipitation of aragonite and calcite in environments above 20 °C. This continuous prominence of aragonite precipitation in Phanerozoic warm-water environments explains the Phanerozoic increase of aragonite over calcite skeletal composition in calcifying organisms.

Effect of different seawater Mg2+ concentrations on calcification in two benthic foraminifers.

Magnesium, incorporated in foraminiferal calcite (Mg/CaCC), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/CaCC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/CaSW). The physiological mechanisms responsible for these proxy relationships are still unknown. This culture study investigates the impact of different seawater [Mg2 +] on calcification in two benthic foraminiferal species precipitating contrasting Mg/CaCC: 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/CaSW 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/CaSW. The relationship between Mg/CaSW and Mg/CaCC shows a distinct positive y-axis intercept, possibly reflecting at least two processes involved in foraminiferal biomineralization. The associated Mg partition (DMg) changes non-linearly with increasing Mg/CaSW, hence suggesting that the DMg is best described by an exponential function approaching an asymptote.

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

Summary 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.

Seawater chemistry driven by supercontinent assembly, breakup, and dispersal: COMMENT

[Muller et al. (2013)][1] present an interesting hypothesis that quantifies a relationship between temporal changes in the ratio of Mg and Ca in seawater and global hydrothermal flux through oceanic crust. The relationship is quantified through estimates of the area of oceanic crust <65 m.y. old

Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry

We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 μL aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 μL solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility.

How to think about the evolution of the ratio of Mg to Ca in seawater

Measurements on fluid inclusions (Timofeeff and others, 2006) indicate that over the last 110 million years, the Mg to Ca ratio in seawater has risen by at least a factor of four. Those by Zachos and others (2003) on planktic foraminifera suggest that about half of this rise occurred during the last 55 million years. Although Coggon and others9 (2010) measurements on ridge-flank basalts are consistent with a rise of this magnitude, they indicate that it occurred after 46 million years ago and perhaps even as recently as the last 15 million years. Based on the Mg to K trend in 36 million-year-old halite-hosted fluid inclusions, Brennan and others (2013) confirm Zimmerman9s (2000) conclusion that the Mg content of sea salt was about 35 percent lower than now at that time. Hence, if the Coggon and others9 (2010) results are to be believed, then the rise in Mg must have been accompanied by a drop in calcium. When account is taken that the CO2 content of the atmosphere 35 million years ago was about five times larger than it is today, then perhaps at that time, the dissolution rate of limestone was greater than today9s. If so, then the large increase in Mg to Ca ratio could be explained by a combination of a decrease in sea level which slowed the rate of dolomite formation and a drop in atmospheric CO2 content which slowed the delivery by rivers to the sea of Ca derived from limestone weathering. Unfortunately, as the deposition of gypsum prior to halite formation removed virtually all the calcium from the brine pools in which the halite subsequently formed, there is no record of Ca in Cenozoic-age fluid inclusions. Hence, in order to resolve the difference between the large Mg/Ca rise over the last 40 million years suggested by ridge-plank calcites and, the smaller one suggested by planktic foraminifera, an additional proxy for Ca is needed. As I suggested many years ago (Broecker, 1970), one such candidate is the uranium content of corals.

Identification and apical membrane localization of an electrogenic Na+/Ca2+exchanger NCX2a likely to be involved in renal Ca2+excretion by seawater fish

Seawater (SW) contains ∼10 mM Ca(2+), yet marine fish must drink seawater as their major water source. Thus marine teleosts fish need to excrete Ca(2+) to maintain whole body Ca(2+) homeostasis. In the intestine, seawater Ca(2+) interreacts with epithelial-secreted HCO(3)(-) by the intestinal epithelium, and the resulting CaCO(3) precipitates, which is rectally excreted. Recently the transporters involved in intestinal HCO(3)(-) secretion were identified. Ca(2+) is also excreted by the kidney, but the protein(s) involved in renal Ca(2+) excretion have not been identified. Here we identified a candidate transporter by using SW pufferfish torafugu (Takifugu rubripes) and its closely related euryhaline species mefugu (Takifugu obscurus), which are becoming useful animal models for studying molecular mechanisms of seawater adaptation. RT-PCR analyses of Na(+)/Ca(2+) exchanger (NCX) family members in various torafugu tissues demonstrated that only NCX2a is highly expressed in the kidney. Renal expression of NCX2a was markedly elevated when mefugu were transferred from freshwater to seawater. In situ hybridization and immunohistochemical analyses indicated that NCX2a is expressed in the proximal tubule at the apical membrane. NCX2a, expressed in Xenopus oocytes, conferred [Ca(2+)](out)- and Na(+)-dependent currents. These results suggest that NCX2a mediates renal Ca(2+) secretion at the apical membrane of renal proximal tubules and has an important role in whole body Ca(2+) homeostasis of marine teleosts.

Response of the coccolithophores Emiliania huxleyi and Coccolithus braarudii to changing seawater Mg 2+ and Ca 2+ concentrations: Mg/Ca, Sr/Ca ratios and δ 44/40Ca, δ 26/24Mg of coccolith calcite

Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ 44/40Ca and Δ 26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L −1, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2 σ) independent of species. Partition coefficient of Mg 2+ increased with increasing seawater Ca 2+ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2 σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr 2+ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ 26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ 26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.

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Temperature and salinity effects on elemental uptake in the shells of larval and juvenile softshell clams Mya arenaria

MEPS Marine Ecology Progress Series Contact the journal Facebook Twitter RSS Mailing List Subscribe to our mailing list via Mailchimp HomeLatest VolumeAbout the JournalEditorsTheme Sections MEPS 370:155-169 (2008) - DOI: https://doi.org/10.3354/meps07658 Temperature and salinity effects on elemental uptake in the shells of larval and juvenile softshell clams Mya arenaria Carly A. Strasser*, Lauren S. Mullineaux, Simon R. Thorrold Biology Department, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, USA *Email: cstrasser@whoi.edu ABSTRACT: The chemical composition of biogenic carbonate has great potential to serve as a natural tag in studies of marine population connectivity. Yet the degree to which carbonate chemistry reflects ambient water composition may be influenced by environmental parameters, physiology, and uptake kinetics. We explored the effects of temperature and salinity on the uptake of elements into shells of larval and juvenile softshell clams Mya arenaria. Clams were reared under controlled conditions using combinations of temperatures (15, 20, and 24°C) and salinities (22 and 30‰) commonly encountered in their natural habitat. We analyzed the ratios of a suite of elements (Mg, Mn, Sr, Ba and Pb) to Ca in seawater and shells using solution-based inductively coupled plasma-mass spectrometry (ICP-MS). Elemental ratios were translated into discrimination coefficients (Delement) to account for water chemistry variability among treatments. For larval shell, we found that DMn was lower in the low-temperature treatment than at higher temperatures, had mixed results for correlations with salinity, and exhibited an interactive effect between salinity and temperature. We also found that DBa of larval shell was higher in the 15°C treatment than at the other 2 temperatures. In juvenile shell, we found a temperature effect for DMn, however the exact relationship was unclear because DMn was higher in the mid-temperature treatment than either the low- or high-temperature treatments. DSr was negatively correlated with salinity in juveniles, with evidence of an interactive effect for temperature and salinity. DBa and DPb were both higher in juveniles in the low-temperature treatment than in the 2 higher temperatures. When discrimination coefficients significantly differed based on ANOVA, we used post hoc comparisons to further explore the effects of temperature and salinity. Correlation analyses showed that uptake differed significantly between larval and juvenile M. arenaria shell for all elements, with no predictable relationship in shell uptake between the 2 stages except for DBa. All of the elements examined in this study have the potential to be useful in tagging studies where geographic variability in temperature, salinity or elemental concentrations exists, although caution should be used to ensure any biological interactions with these variables are accounted for in data interpretation. KEY WORDS: Mya arenaria · Bivalve shell · Elemental uptake · Discrimination coefficients · Temperature · Salinity · Larva · Biogenic carbonate Full text in pdf format PreviousNextCite this article as: Strasser CA, Mullineaux LS, Thorrold SR (2008) Temperature and salinity effects on elemental uptake in the shells of larval and juvenile softshell clams Mya arenaria. Mar Ecol Prog Ser 370:155-169. https://doi.org/10.3354/meps07658 Export citation RSS - Facebook - Tweet - linkedIn Cited by Published in MEPS Vol. 370. Online publication date: October 28, 2008 Print ISSN: 0171-8630; Online ISSN: 1616-1599 Copyright © 2008 Inter-Research.

Reply to comment by D. Wang et al. on “Empirical partition coefficients for Sr and Ca in marine barite: Implications for reconstructing seawater Sr and Ca concentrations”

[1] Wang et al. [2007] argue that the empirical distribution coefficient for Sr in marine barite obtained from the Sr/Ba composition of Holocene core top marine barite could not be used to reconstruct past seawater Sr concentrations. The premise for this argument is that Sr substitution into barite is not primarily a function of ambient Sr concentrations at the time barite precipitated. Wang et al. [2007] base their argument on the relatively large range of Sr/Ba ratios measured by Averyt and Paytan [2003] in the core top barite. They suggest that variable spatial and temporal ocean temperatures are responsible for the variations and without knowledge of the seawater temperature at the time and location of barite precipitation, the empirical distribution coefficient may not be used. However, we believe that we arrived at the best possible partition coefficient for Sr in marine barite based on the data available in 2003 and that despite ignoring the temperature effects this coefficient is useful if applied correctly.