incorporation of ca isotopes in carapaxes of marine ostracods abstract we studied mg ca sr ca and ca isotope ratios of ostracod carapaxes from surface sediments retrieved during research cruises to the southern and equatorial eastern atlantic collected specimens originate from water depth between 30 and about 5000 mbsl and cover bottom water temperatures between 0 and 23 c analysed taxa include buntonia sp cytherella sp henryhowella sp krithe sp poseidonamicus sp and ruggieria sp calcium isotope ratios of the studied specimens are in the overall range of other marine calcifiers and show a variability of about 0 75 over a temperature range of 20 c there is no overall linear relation between temperature and ca isotope fractionation but some species show a maximum 44 40ca at intermediate temperatures mg ca and sr ca agree well with values of previously published carapaxes demonstrating large inter and intra species variability and different responses to bottom water temperatures magnesium is highly variably distributed within the carapax with mg enrichment in the inner part of the shell of most taxa this enrichment is independent from the incorporation of sr which shows less variability within the carapax the ca isotope vs sr ca systematic in the ostracods deviates from inorganic calcite and foraminifers the ostracod array is most likely controlled by either mixing of material originating from a precursor phase and newly grown calcite or rayleigh type fractionation during precipitation from a restricted fluid reservoir indicating varying degrees of ca and sr consumption during calcite precipitation the different slope of the ca isotope vs sr ca relation shown by the ostracods compared to those of inorganic calcite and foraminifers opens a new approach for the determination of ca isotope and sr ca ratios of past ocean water

clathrites archives of near seafloor pore fluid evolution δ44 40ca δ13c δ18o in gas hydrate environments aragonitic clathrites are methane derived precipitates that are found at sites of massive near seafloor gas hydrate clathrate accumulations at the summit of southern hydrate ridge cascadia margin these platy carbonate precipitates form inside or in proximity to gas hydrate which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation the clathrites record the preferential incorporation of 18o into the hydrate structure and hence the enrichment of 16o in the surrounding brine we measured 18o values as high as 2 27 relative to peedee belemnite that correspond to a fluid composition of 1 18 relative to standard mean ocean water the same trend can be observed in ca isotopes ongoing clathrite precipitation causes enrichment of the 44ca in the fluid and hence in the carbonates carbon isotopes confirm a methane source for the carbonates our triple stable isotope approach that uses the three main components of carbonates ca c o provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites this approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation thus recording the evolution of the geochemical environment of gas hydrate systems

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 degrees c gussone and filipsson 2010 calcium isotope ratios of the aragonitic species hoeglundina elegans on the other hand are about 0 4 parts per thousand 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 delta ca 44 40 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 delta ca 44 40 and sr ca proxy signals c 2015 elsevier ltd all rights reserved less

calcium isotope δ44 40ca variations of neogene planktonic foraminifera measurements of the calcium isotopic composition 44 40ca of planktonic foraminifera from the western equatorial pacific and the indian sector of the southern ocean show variations of about 0 6 over the past 24 myr the stacked 44 40ca record of globigerinoides trilobus and globigerina bulloides indicates a minimum in 44 40casw seawater calcium at 15 to 16 ma and a subsequent general increase toward the present interrupted by a second minimum at 3 to 5 ma applying a coupled calcium carbon cycle model we find two scenarios that can explain a large portion of the observed 44 40casw variations in both cases variations in the ca input flux to the ocean without proportional changes in the carbonate flux are invoked the first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux the second scenario generates an additional calcium flux from the exchange of ca by mg during dolomitization in both cases the calcium flux variations lead to drastic changes in the seawater ca concentrations on million year timescales our 44 40casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed

measurements of total carbon dioxide and alkalinity by potentiometric titration in the geosecs program abstract approximately 6000 determinations of the alkalinity and total carbon dioxide content of seawater have now been made in the atlantic pacific and indian oceans as part of the geosecs program by a computer controlled potentiometric titration technique the equations used to locate the equivalence points of the carbonic acid system on this titration curve were developed in 1971 but have not previously been published these functions may be represented by f 1 v 2 v v 0 n h k 1 c v 0 v v 0 h h s o 4 h f b o h 4 1 h k 1 c f 2 v 0 v v 0 h h s o 4 h f h c o 3 upon inspection these functions are analogous to the modified gran functions of hansson and jagner 25 with the omission of the contributions of oh and co 3 2 and with the contribution of b oh 4 being assessed at a chlorinity of 19 for all samples reprocessing the original titration e m f volume data with appropriate corrections and modified gran functions reveals an error of about 12 mol kg in the geosecs total carbon dioxide data in addition the protonation of dissolved phosphate species during the titration results in a contribution to measured total carbon dioxide equal to the total phosphate concentration differences in the application of the geosecs functions between the atlantic and the pacific indian oceans expeditions are also to be found so that the error deriving from this source for the atlantic expedition was only 5 mol kg the application of the correct functions increases precision enabling smaller differences such as those attributable to fossil fuel carbon dioxide potentially to be observed and increases accuracy so that the error in titrator total carbon dioxide previously diagnosed by takahashi 14 can be logically accounted for

calcium isotope fractionation in ikaite and vaterite abstract we investigated the isotopic composition of calcium in the metastable calcium carbonate polymorphs vaterite and ikaite the synthetic vaterite precipitates show a smaller degree of ca isotope fractionation than calcite or aragonite at comparable temperatures and revealed no significant temperature sensitivity between 10 and 50 c ikaite the water bearing ca carbonate modification caco 3 6h 2 o was precipitated at 2 c in controlled laboratory experiments and in addition recovered from marine sediments and sea ice synthetic and natural ikaites show similar values of ca isotope fractionation in general ikaite is less depleted in heavy isotopes compared to calcite or aragonite at low temperatures the observed offset of vaterite and ikaite to calcite or aragonite precipitated at similar temperatures is presumably mainly related to differences in precipitation rates and regimes which seem however to be typical for the growth of these carbonate minerals small differences in ca isotope ratios of naturally formed ikaites from different locations seem to be related to different geochemical conditions in the respective sediment settings

tropical atlantic sst history inferred from ca isotope thermometry over the last 140ka exploring the potentials of new methods in palaeothermometry is essential to improve our understanding of past climate change here we present a refinement of the published 44 40ca temperature calibration investigating modern specimens of planktonic foraminifera globigerinoides sacculifer and apply this to sea surface temperature sst reconstructions over the last two glacial interglacial cycles reproduced measurements of modern g sacculifer collected from surface waters describe a linear relationship for the investigated temperature range 19 0 28 5 c 44 40ca 0 22 0 05 sst c 4 88 thus a change of 44 40ca of 0 22 0 05 corresponds to a relative change of 1 c the refined 44 40camodern calibration allows the determination of both relative temperature changes and absolute temperatures in the past this 44 40camodern calibration for g sacculifer has been applied to the tropical east atlantic sediment core geob1112 for which other sst proxy data are available comparison of the different data sets gives no indication for significant secondary overprinting of the 44 40ca signal long term trends in reconstructed sst correlate strongly with temperature records derived from oxygen isotopes and mg ca ratios supporting the methods validity the observed change of sst of approximately 3 c at the holocene last glacial maximum transition reveals additional evidence for the important role of the tropical atlantic in triggering global climate change based on a new independent palaeothermometer

calcium isotope fractionation in modern scleractinian corals the 44ca 40ca ratios of cultured acropora sp and open ocean pavona clavus porites sp tropical reef corals are positively correlated with growth temperature the slope of the temperature fractionation relation is similar to inorganic aragonite precipitates however 44 40ca of the coral aragonite is offset from inorganic and sclerosponge aragonite by about 0 5 this offset can neither be explained by the very fast biologically controlled calcification of scleractinian corals nor as a consequence of calcification from a partly closed volume of fluid as corals actively transport calcium through several cell layers to the site of calcification the most likely explanation for the offset is a biologically induced fractionation our results indicate a limited use of ca isotopes in scleractinian corals as temperature proxy

calcium isotope ratios in calcitic tests of benthic foraminifers abstract we analysed ca isotope ratios of the infaunal foraminiferal species cassidulina laevigata elphidium spp gyroidinoides spp and uvigerina peregrina as well as the epifaunal cibicidoides wuellerstorfi over a depth temperature gradient the calcium isotope ratios of the benthic foraminifers tests show a distinct anomaly around 4 c this anomaly is observed in both epi and infaunal species but there are also characteristic differences between both the 44 40 ca characteristics of benthic foraminifers may be explained by the interference of temperature and carbonate chemistry of the fluid on ca isotope fractionation we suggest that ca isotope composition of benthic foraminifer tests is dominantly controlled by temperature at temperatures higher than 5 c while in the temperature range below 5 c calcite saturation cc becomes an increasingly important controlling factor due to the non linear shape of the cc 44 40 ca relation of actively transported calcium the potential applicability of ca isotope ratios in benthic foraminifers for reconstruction of either temperatures or 44 40 ca sw is limited by the complex fractionation pattern below 5 c however due to the minor temperature dependence in the temperature range above 5 c benthic foraminifers might provide a possible alternative archive for 44 ca sw avoiding some uncertainties associated with planktic records relocation habitat calcification depth short time climate variability as long as a defined bottom water temperature above 5 c can be secured

temperature dependence of δ 7 li δ 44 ca and li ca during growth of calcium carbonate abstract lithium and calcium isotope ratios together with the li ca element ratio have been measured in calcites precipitated inorganically at temperatures ranging from 5 to 30 c and on seasonal growth bands from a coral these measurements indicate the potential uses of these three environmental proxies carbonate li isotopes are lighter than the solution from which they grow probably due to equilibrium fractionation this fractionation is not significantly influenced by temperature and because li is not involved in any known biological process this suggests that carbonates will provide a recorder for the past li isotope composition of natural waters and hence for past weathering conditions as has been observed previously for inorganic aragonite the ca isotopes in inorganic calcite are lighter than the growth solution and are only weakly dependent on temperature this confirms that the temperature dependence observed in some species of foraminifera geochem geophys geosyst 1 2001 reflects additional isotope fractionation due to biological processes during mineralization ca isotopes may therefore provide a powerful tool with which to investigate the processes of biomineralization finally li ca ratios in inorganic and biogenic carbonates increase as temperatures decrease with a sensitivity of 4 per c this temperature dependence of li ca may prove useful to assess past temperatures in cold environments such as the deep ocean

significant increases in global weathering during oceanic anoxic events 1a and 2 indicated by calcium isotopes abstract calcium isotope ratios 44 42ca were measured in carbonate rich sedimentary sections deposited during oceanic anoxic events 1a early aptian and 2 cenomanian turonian in sections from resolution guyot mid pacific mountains coppitella italy and the english chalk at eastbourne and south ferriby uk a negative excursion in 44 42ca of 0 20 and 0 10 is observed for the two events these 44 42ca excursions occur at the same stratigraphic level as the carbon isotope excursions that define the events but do not correlate with evidence for carbonate dissolution or lithological changes diagenetic and temperature effects on the calcium isotope ratios can be discounted leaving changes in global seawater composition as the most probable explanation for 44 42ca changes in four different carbonate sections an oceanic box model with coupled strontium and calcium isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium isotope ratios the model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short lived to affect the oceanic calcium reservoir measurably a modelled increase in weathering flux on the order of three times the modern flux combined with increased hydrothermal activity due to formation of the ontong java plateau oae1a and caribbean plateau oae2 can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections this study presents the first major element record of a weathering response to oceanic anoxic events

calcium isotopic fractionation in microbially mediated gypsum precipitates abstract gypsum caso4 2h2o precipitation experiments were carried out at low ph in the presence of the sulfur oxidizing bacterium acidithiobacillus thiooxidans the observed ca isotopic fractionation expressed as 44 40cas f 44 40casolid 44 40cafluid at the end of each experimental time period 50 to 60 days was 1 41 to 1 09 in the biotic experiments 1 09 in the killed control and 1 01 to 0 88 in the abiotic controls as there were no strong differences in the solution chemistry and the rate at which gypsum precipitated in the biotic and abiotic controls we deduce a biological ca isotope effect on the order of 0 3 the isotope effect correlates with a difference in crystal aspect ratios between the biotic experiments 8 05 3 99 and abiotic controls 31 9 8 40 we hypothesize that soluble and or insoluble organic compounds selectively inhibit crystal growth at specific crystal faces and that the growth inhibition affects the fractionation factor associated with gypsum precipitation the experimental results help explain ca isotopic variability in gypsum sampled from a sulfidic cave system in which gypsum crystals exhibiting a diversity of morphologies microcrystalline to cm scale needles have a broad range of 44 40ca values 1 2 0 4 relative to the limestone wall 44 40ca 1 3 in light of the laboratory experiments the variation in ca isotope values in the caves can be interpreted as a consequence of gypsum precipitation in the presence of microbial organic matter and subsequent isotopic re equilibration with the ca source

ice stratigraphy at the pakitsoq ice margin west greenland derived from gas records horizontal ice core sites where ancient ice is exposed at the glacier surface offer unique opportunities for paleo studies of trace components requiring large sample volumes following previous work at the pakitsoq ice margin in west greenland we use a combination of geochemical parameters measured in the ice matrix d 18 oice and air occlusions d 18 oatm d 15 no f n 2 and methane concentration to date ice layers from specific climatic intervals the data presented here expand our understanding of the stratigraphy and three dimensional structure of ice layers outcropping at pakitsoq sections containing ice from every distinct climatic interval during termination i including last glacial maximum bolling allerod younger dryas and the early holocene are identified in the early holocene we find evidence for climatic fluctuations similar to signals found in deep ice cores from greenland a second glacial interglacial transition exposed at the extreme margin of the ice is identified as another outcrop of termination i rather than the onset of the eemian interglacial as postulated in earlier work consequently the main structural feature at pakitsoq is a large scale anticline with accordion type folding in both exposed sequences of the glacial holocene transition leading to multiple layer duplications and age reversals

controls on calcium isotope fractionation in sedimentary porewaters abstract the calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during ocean drilling program odp provides first insight into the different processes that control ca geochemistry in clastic marine organic rich sedimentary environments in 4 sites drilled during leg 204 at hydrate ridge cascadia margin offshore oregon usa sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section these reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate which is reflected in a pronounced decrease in calcium concentration although ca isotope fractionation is observed during carbonate precipitation ca concentration in the pore fluids from odp leg 204 is decoupled from ca isotopy which seems to be mainly controlled by the release of light ca isotopes that completely overprint the carbonate formation effect different processes such as the release of organically bound ca ion exchange and ion pair formation may be responsible for the released light ca deeper within the sedimentary section additional processes such as ash alteration influence the ca isotopic composition of the porewater two sites drilled into the deeper core of the accretionary prism reveal the nature of fluids which have reacted with the oceanic basement these deep fluids are characterized by relatively high ca concentrations and low 44 40ca ratios

seawater calcium isotope ratios across the eocene oligocene transition during the eocene oligocene transition eot ca 34 ma earth s climate cooled significantly from a greenhouse to an icehouse climate while the calcite caco3 compensation depth ccd in the pacific ocean increased rapidly fluctuations in the ccd could result from various processes that create an imbalance between calcium ca sources to and sinks from the ocean e g weathering and caco3 deposition with different effects on the isotopic composition of dissolved ca in the oceans due to differences in the ca isotopic composition of various inputs and outputs we used ca isotope ratios 44 40ca of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine ca cycle across the eot we show that the permanent deepening of the ccd was not accompanied by a pronounced change in seawater 44 40ca whereas time intervals in the neogene with smaller carbonate depositional changes are characterized by seawater 44 40ca shifts this suggests that the response of seawater 44 40ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater a minor and transient fluctuation in the ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with caco3 precipitation from seawater due to a combination of factors including changes in temperature and or in the assemblages of calcifying organisms

calcium isotope fractionation during coccolith formation in emiliania huxleyi independence of growth and calcification rate 1 recently calcium isotope fractionation in the coccolithophore emiliania huxleyi was shown to exhibit a significant temperature dependency an important subsequent question in this context is whether the observed fractionation patterns are caused by temperature itself or related growth rate changes in order to separate growth and calcification rate effects from direct temperature effects batch culture experiments with the coccolithophore e huxleyi were conducted under varying light intensities despite large changes in cellular growth and calcification rates calcium isotope fractionation remained constant independence of calcium isotope fractionation on growth and calcification was also obtained in two additional sets of experiments in which growth rates changed in response to varying calcium concentration and seawater salinity these experiments also showed no direct effects of calcium concentration and salinity on calcium isotope fractionation values for calcium isotope fractionation of e huxleyi coccoliths fell within a range of 1 0 to 1 6 1000 ln confirming earlier results this range is similar to that observed in several foraminiferal species and coccolith oozes suggesting a rather homogeneous calcium isotopic composition in marine biogenic calcite our data further show that the calcium isotope fractionation does not change with changing isotopic composition of seawater this is a basic requirement for reconstructing the calcium isotopic composition of the ocean over time

production and accumulation of calcium carbonate in the ocean budget of a nonsteady state present day production of caco3 in tne world ocean is calculated to be about 5 billion tons bt per year of which about 3 bt accumulate in sediments the other 40 is dissolved nearly half of the carbonate sediment accumulates on reefs banks and tropical shelves and consists largely of metastable aragonite and magnesian calcite deep sea carbonates predominantly calcitic coccoliths and planktonic foraminifera have orders of magnitude lower productivity and accumulation rates than shallow water carbonates but they cover orders of magnitude larger basin area twice as much calcium is removed from the oceans by present day carbonate accumulation as is estimated to be brought in by rivers and hydrothermal activity 1 6 bt suggesting that outputs have been overestimated or inputs underestimated that one or more other inputs have not been identified and or that the oceans are not presently in steady state one missing calcium source might be groundwater although its present day input is probably much smaller than that of rivers if as seems likely caco3 accumulation presently exceeds terrestial and hydrothermal input this imbalance presumably is offset by decreased accumulation and increased input during lowered sea level shallow water accumulation decreases by an order of magnitude with a 100 m drop in sea level while groundwater influx increases because of heightened piezometric head and the diagenesis of metastable aragonite and magnesian calcite from subaerially exposed shallow water carbonates

calcium isotope fractionation in coccoliths of cultured calcidiscus leptoporus helicosphaera carteri syracosphaera pulchra and umbilicosphaera foliosa four species of marine calcifying algae the coccolithophores calcidiscus leptoporus helicosphaera carteri syracosphaera pulchra and umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 c and one species c leptoporus under varying co32 ranging from 105 to 219 mol kg calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e g emiliania huxleyi coccolithophores and orbulina universa planktonic foraminifera as well as inorganically precipitated caco3 but also reveal small species specific differences in contrast to inorganically precipitated calcite but similar to e huxleyi and o universa the carbonate ion concentration of the medium has no statistically significant influence on the ca isotope fractionation of c leptoporus coccoliths however combined data of e huxleyi and c leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium since coccoliths constitute a significant portion of the global oceanic caco3 export production the ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the ca sink of the ocean one of the key parameters for modelling changes to the marine ca budget over time for the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic ca sink sed of about 1 3 but the observed inter and intra species differences point to possible changes in sed through earth history due to changing physico chemical conditions of the ocean and shifts in floral and faunal assemblages

evolution of the oceanic calcium cycle during the late mesozoic evidence from δ44 40ca of marine skeletal carbonates abstract the ca isotope compositions of 37 late mesozoic skeletal carbonates belemnites and brachiopods from the tethyan realm were analyzed by thermal tims and plasma mc icp ms ionization mass spectrometry a poor correlation between 44 40 ca and 18 o values of belemnites suggests only a weak temperature dependency for the ca isotope composition of belemnites likely less than 0 02 c the 44 40 ca record of belemnites was therefore used to reconstruct the ca isotope composition of paleo seawater 44 40 ca sw based on an experimentally determined fractionation factor between seawater ca and belemnite calcite cc sw of 0 9986 the inferred 44 40 ca sw record with an average stratigraphic resolution of 1 ma shows systematic temporal variation of 0 5 with the middle late jurassic 154 ma minimum of 1 4 and a subsequent general increase to the early cretaceous 124 ma maximum of 1 9 the global nature of the 44 40 ca sw record is supported by identical ca isotope compositions of coeval kimmeridgian belemnites collected from two distinct paleogeographic regions the southern new zealand and northern germany margin of the tethys ocean the observed late mesozoic 44 40 ca sw record was simulated using a simple ca isotope mass balance model and the results indicate that the variation in 44 40 ca sw record can be explained by changes in oceanic input fluxes of ca that were independent of the carbonate ion fluxes such as the hydrothermal ca flux or the release of ca to the oceans via dolomitization of marine carbonates

calcium isotopes in deep time potential and limitations abstract calcium is an essential element in the biogeochemical cycles that regulate the long term climate state of earth the removal of co2 from the ocean atmosphere system is controlled by the burial of carbonate sediments caco3 ultimately linking the global calcium and carbon cycles this fundamental link has driven the development of the stable calcium isotope proxy with application to both ancient skeletal and non skeletal bulk carbonate sediments calcium isotope ratios 44 40ca have been used to track long term changes in seawater chemistry e g aragonite vs calcite seas and to elucidate short term climatic perturbations associated with mass extinction events however developments in the calcium isotope proxy have shown that 44 40ca values in carbonate minerals also are sensitive to changes in precipitation rates mineralogy and diagenesis thereby complicating the application of the proxy to the reconstruction of global cycles first inorganic carbonate precipitation experiments have demonstrated that carbonate 44 40ca values are sensitive to precipitation rates with higher rates generally leading to larger fractionation second 44 40ca values are sensitive to carbonate mineralogy with inorganic aragonite and calcite being on average 1 5 and 0 9 depleted relative to contemporaneous seawater respectively the effects of both changes in carbonate mineralogy and precipitation rates affect primary and secondary minerals but are particularly pronounced during carbonate diagenesis where relatively slow rates of recrystallization and neomorphism can lead to significant changes in bulk sediment 44 40ca values third changes in faunal composition expressed in skeletal fossil archives can lead to large changes in carbonate 44 40ca values that are decoupled from changes in global cycles nevertheless when these factors are appropriately considered the application of calcium isotopes in ancient carbonate sediments becomes a powerful tool for understanding biogeochemical processes that operate over many scales from diagenetic changes within the sediment pore space to regional changes across ancient carbonate platforms and to global changes in seawater chemistry through time importantly the processes that contribute to variability in carbonate 44 40ca values are likely to impact other carbonate bound proxies highlighting the potential for calcium isotopes as a tool to better understand the variability of other isotope systems

cellular calcium pathways and isotope fractionation in emiliania huxleyi the marine calcifying algae emiliania huxleyi coccolithophores was grown in laboratory cultures under varying conditions with respect to the environmental parameters of temperature and carbonate ion concentration co32 concentration the ca isotope composition of e huxleyi s coccoliths reveals new insights into fractionation processes during biomineralization the temperature dependent ca isotope fractionation resembles previous calibrations of inorganic and biogenic calcite and aragonite unlike inorganically precipitated calcite the co32 concentration of the medium has no significant effect on the ca isotope composition of the coccoliths these results indicate a decoupling of the chemical properties of the bulk medium and the calcifying vesicle cellular ca pathways of e huxleyi indicate that fractionation cannot occur at the crystal surface as occurs during inorganic precipitation the dominant processes leading to the observed ca isotope fractionation pattern in e huxleyi are most likely the dehydration of the ca aquocomplex at the plasma membrane and the attachment of dissolved ca to proteins of ca channels the independence of ca isotope fractionation from co32 and the small temperature dependence of e huxleyi are also important for defining the isotopic signature of the oceanic ca sink since coccolithophores contribute to about half the global caco3 production a relatively uniform isotopic composition of the oceanic ca sink is further supported

calcium isotopes in the marine environment and the oceanic calcium cycle abstract a systematic investigation of 44 ca 40 ca ratios in the oceanic ca cycle indicates that the average ca isotopic composition of input and output are quite different suggesting that the present ocean is not in a steady state our data show that sea water has uniform 44 ca 40 ca as expected from the long residence time of ca in the oceans it also exhibits the heaviest isotopic composition among all samples measured consistent with recent results by skulan et al 1997 and must be maintained at this value by strong biogenic isotope fractionation during the precipitation of caco 3 our measurements show that the riverine input is variable the most radiogenic river waters we have measured lowest 44 ca 40 ca are from ganges tributaries which also have high 87 sr 86 sr although there does not appear to be a systematic correlation between ca and sr isotopic compositions based on available data there is also significant isotopic variability among samples of caco 3 precipitated from the present ocean with coccolith oozes showing the most highly fractionated isotopic values relative to seawater among foraminifera ca isotopes exhibit species dependent fractionation effects but also appear to display systematic temperature dependent fractionation within inidividual species

44ca 42ca and 143nd 144nd isotope variations in cretaceous eocene tethyan francolites and their bearing on phosphogenesis in the southern tethys measurements of 4 4 ca 4 2 ca and 1 4 3 nd 1 4 4 nd isotope ratios in carbonate fluorapatite cfa through the aptian eocene section of the negev israel together with quantified rates of p and ca accumulation and bulk sedimentation permit an examination of the relationships of these five factors to tethyan phosphogenesis the data provide an aptian eocene ca 70 ma record of the ca isotope composition of 35 cfa samples 24 of which were also analyzed for nd isotopes representing 11 time stratigraphic phosphate horizons within the sequence the 4 4 ca values are significantly lower in the aptian albian samples 4 4 ca 0 11 to 0 06 than in the campanian eocene samples 4 4 ca 0 22 to 0 42 whereas the e n d values increase from continental crust like in the aptian albian e n d t 10 9 to more radiogenic pacific like e n d t 6 6 to 6 1 in the campanian both peaks of 4 4 ca and e n d t in the campanian coincide with the peak of tethyan phosphogenesis in the negev which is marked by a sharp increase of p accumulation rates from 200 mol cm 2 k y 1 in pre campanian time to 1700 mol cm 2 k y 1 in the campanian and a decrease in rates of ca accumulation and bulk sedimentation the coincident increases of 4 4 ca and e n d t values and p accumulation rates in the negev area during the campanian suggest that they are related in this time interval and were induced by the global late cretaceous sea level rise and increasing circumequatorial tethyan flow

variations in the marine ca cycle over the past 20 million years a 20 million year marine ca isotope record is constructed based on measurements of 36 nannofossil ooze samples from dsdp site 590 the ca isotopic composition d 44 ca relative to our bbulk earthq average of carbonate ooze samples varies between 0 2 and 0 9 and the inferred d 44 ca of seawater calcium varies between 1 1 and 0 4 modern seawater value is 0 95 on our scale fluctuations in the seawater ca isotope ratio occur in 2 to 4 million year intervals and indicate that the supply and removal of ca from the oceans are seldom in balance the ca isotope record is used to reconstruct past weathering fluxes and marine calcium concentrations the inferred marine concentration of ca fluctuates by about f20 on 2 4 million year time scales and by about f50 over the 20 million year record these variations are presumably superimposed on the previously inferred 100 million year variations the seawater ca concentration was about 0 5 times present at 20 ma and generally increased until 6 ma 1 7 times present local maxima in seawater calcium concentrations occur at 6 4 and 4 ma preceding periods of enhanced marine productivity and high mass accumulation rates at site 590 while the calculated calcium concentrations are sensitive to the assumed d 44 ca value for the weathering flux the 2 4 million year features of the derived

minor element and ca isotope composition of calcareous dinoflagellate cysts of cultured thoracosphaera heimii abstract we investigated the influences of temperature salinity and ph on the calcium isotope as well as trace and minor element uranium strontium magnesium to ca ratios on calcium carbonate cysts of the calcareous dinoflagellate species thoracosphaera heimii grown in laboratory cultures the natural habitat of this species is the photic zone preferentially at the chlorophyll maximum depth of temperate to tropical oceans and it is abundant in deep sea sediments over the entire cenozoic in our experiments temperatures ranged from 12 to 30 c salinity from 36 5 to 38 8 and ph from 7 9 to 8 4 the 44 40ca of t heimii cysts resembles that of other marine calcifiers including coccolithophores foraminifers and corals however its temperature sensitivity is considerably smaller and statistically insignificant and t heimii might serve as a recorder of changes in seawater 44 40ca over geologic time the sr ca ratios of t heimii cysts show a pronounced temperature sensitivity 0 016 mmol mol c 1 and have the potential to serve as a palaeo sea surface temperature proxy no clear temperature and ph dependences were observed for mg ca u ca seems to be influenced by temperature and ph but the correlations change sign at 23 c and ph 8 2 respectively

strontium isotope fractionation of planktic foraminifera and inorganic calcite we have investigated the strontium isotope fractionation 88 86srcarb aq between inorganic calcite and aqueous sr2 ions by precipitation experiments at a constant temperature of 25 c and precipitation rates r ranging from 102 3 to 104 2 mol m2 h strontium isotope ratios were measured using the 87sr 84sr double spike technique it was found that strontium isotope fractionation in these calcites is strongly dependent on the precipitation rate view the mathml source the measured 88 86sr values are significantly correlated with previously measured 44 40ca and sr ca values of the same calcite samples 88 86srcarb aq 0 18 44 40cacarb aq 0 01 view the mathml source the slope of 88sr 86sr versus 44ca 40ca fractionation is 0 18 0 04 and compatible with a kinetic fractionation during dehydration of the strontium and calcium ions but not with isotope fractionation in a diffusive boundary layer using published equilibrium 44 40cacarb aq and view the mathml source values we estimate the equilibrium isotope fractionation of strontium to be very close to zero 88 86sreq carb aq 0 01 0 06 this estimate is confirmed by strontium isotope values of natural inorganic calcites that precipitated very slowly in basalts of the ocean crust the results from the inorganic calcites are used to explain strontium isotope fractionation of planktic foraminifera specimens of two warm water species globigerinoides ruber and globigerinoides sacculifer were picked from the holocene section of a caribbean sediment core we found no significant difference in 88 86sr between the two species in addition g ruber specimens from marine isotope stage 2 in the same core show 88 86sr values identical to the holocene specimens the strontium isotopes of both foraminifera species are strongly fractionated 88 86srcarb aq 0 248 0 005 when compared to published data of other major marine calcifiers applying the results from the inorganic precipitation experiments we find that the strong foraminiferal strontium isotope fractionation can be explained by calcification in a largely open system at high precipitation rates comparable in magnitude to rates known from scleractinian reef corals this interpretation is in good agreement with the kinetic calcification model for planktic foraminifera by kisakurek et al 2011 which was based on calcium isotopes and elemental sr ca ratios

the δ44ca temperature calibration on fossil and cultured globigerinoides sacculifer new tool for reconstruction of past sea surface temperatures we report direct 44ca temperature calibration on cultured and fossil calcite foraminifera showing that ca isotopes are potentially a new proxy for past sea surface temperatures sst samples have been analyzed using a 43ca 48ca double spike and thermal ionization mass spectrometry tims in order to avoid species dependent isotope fractionation we focused our investigations on a single foraminifera species globigerinoides sacculifer which is known to inhabit shallow euphotic waters in tropical and subtropical oceans ca isotope measurements were performed on cultured g sacculifer that grew in seawater kept at temperatures of 19 5 26 5 and 29 5 c a 44ca change of 0 24 0 02 per 1 c is defined by the weighted linear regression through reproduced 44ca data of the three temperatures 95 confidence level application of this new method to fossil g sacculifer of an equatorial east atlantic sediment core geob1112 5 46 7 s 10 45 0 w 3125 m indicates that the 44ca difference between marine isotope stage 1 mis 1 and mis 2 is 0 71 0 24 according to the current 44ca temperature calibration this value corresponds to a temperature difference between mis 1 and mis 2 of 3 0 1 0 c

variations of the 44ca 40ca ratio in seawater during the past 24 million years evidence from δ44ca and δ18o values of miocene phosphates abstract the ca isotope variation of 11 miocene and pleistocene authigenic marine phosphates is rather small compared to the corresponding variation in 18o values the 44ca values are not correlated with the 18o values and therefore they are not temperature controlled it is likely that the 44ca values of the phosphorites reflect the variation in the 44ca values of paleo seawater but in contrast to sr not the isotopic composition of seawater itself furthermore ca and sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with sr isotopic compositions changing to more radiogenic values while ca isotopic compositions remain rather stable all samples have 44ca values below present day seawater values suggesting that phosphate formation discriminates against heavy ca isotopes phosphorites and carbonaceous sediments have a similar ca isotopic variation during the miocene a systematic and more or less constant shift between marine carbonates and phosphates is observed the phosphate samples are slightly less enriched in 40ca compared to carbonates this shift has been related to a mineral dependent kinetic mass fractionation during precipitation from seawater the rather stable 44ca value for the 19 to 9 ma old phosphorites points to a constant 44ca fractionation of about 1 1 between seawater and phosphorites during the past and suggests steady state conditions for the mid miocene seawater sedimentation flux equals erosion flux

cretaceous calcareous dinoflagellate cysts as recorder of δ44 40caseawater and paleo temperature using sr ca thermometry abstract we evaluate the potential of calcareous dinoflagellates as archives for sr ca based paleo temperature reconstructions and 44 40caseawater fluctuations on sediments from ocean drilling program expedition 113 hole 690c weddell sea southern ocean between 73 and 68 ma sr ca ratios of two cretaceous dinoflagellate species pirumella krasheninnikovii and orthopithonella globosa show a pronounced decrease consistent with a significant drop in sea surface temperature as reflected by the 18o of planktic foraminifers the apparent temperature sensitivity of the dinoflagellate cysts sr ca is 0 06 and 0 08 mmol mol c 1 using 18o derived paleo sea surface temperatures which is significant and large enough to resolve paleoenvironmental temperature changes at current analytical precision as the chemical composition of the cyst calcite appears to have a good preservation the sr ca of calcareous dinoflagellates has a potential to serve as paleo temperature proxy although the chemical composition of the cretaceous seawater and potential impacts on the cyst geochemistry is pending further inspection the ca isotope composition of the two dinoflagellate species shows identical trends of increasing 44 40ca between 73 and 67 ma the planktic foraminifer archaeoglobigerina australis and the benthic foraminifer nuttallides truempyi reveal the same increase of about 0 4 but are offset relative to the dinoflagellates by about 0 5 presumably due to species specific ca isotope fractionation bulk carbonate sediment shows significant scatter likely caused by changes in faunal composition and does not reproduce the trend revealed by the dinoflagellate and foraminifer records these observations demonstrate the importance of taxon specific records and careful determination of fractionation factors of selected archives and highlight complications arising from utilizing less suitable archives such as bulk sediments for 44 40caseawater reconstructions our records indicate strong changes in the marine ca cycle associated with the global temperature decrease towards the end of the cretaceous

effects of ocean acidification on the marine calcium isotope record at the paleocene eocene thermal maximum highlights 44ca was measured in bulk carbonate and barite at two sites over the petm diagenetic effects on 44ca are observed associated with ocean acidification multiple sites and proxy archives necessary to reconstruct the past accurately abstract carbonates are used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales however these archives are susceptible to diagenetic alteration via dissolution recrystallization and secondary precipitation particularly during ocean acidification events when intense dissolution can occur despite the possible effects of diagenesis on proxy fidelity the impacts of diagenesis on the calcium isotopic composition 44ca of carbonates are unclear to shed light on this issue bulk carbonate 44ca was measured at high resolution in two pacific deep sea sediment cores odp sites 1212 and 1221 with considerably different dissolution histories over the paleocene eocene thermal maximum petm 55 ma 55 ma the 44ca of marine barite was also measured at the deeper site 1221 which experienced severe carbonate dissolution during the petm large variations 0 8 0 8 in bulk carbonate 44ca occur in the deeper of the two sites at depths corresponding to the peak carbon isotope excursion which correlate with a large drop in carbonate weight percent such an effect is not observed in either the 1221 barite record or the bulk carbonate record at the shallower site 1212 which is also less affected by dissolution we contend that ocean chemical changes associated with abrupt and massive carbon release into the ocean atmosphere system and subsequent ocean acidification at the petm affected the bulk carbonate 44ca record via diagenesis in the sedimentary column such effects are considerable and need to be taken into account when interpreting ca isotope data and potentially other geochemical proxies over extreme climatic events that drive sediment dissolution

negligible temperature dependence of calcium isotope fractionation in 12 species of planktonic foraminifera the influence of temperature on calcium ca isotope fractionation during biomineralization was investigated through the paired analyses of d44 42ca via mc icp ms and d18o on the calcite tests of 12 species of planktonic foraminifera from coretop sediments samples were collected from a suite of box cores from sites between 608n and 308s in the north atlantic and west indian oceans spanning a range in sea surface temperature of 9 27 8c the d44 42casrm915a of the samples ranged from 0 21x to 0 81x over a range in the d18ovpdb of the foraminiferal calcite of between 2 3x and 2 1x the bulk of the species investigated produced calcite with an average calcite seawater ca enrichment factor e of 0 65f0 08x n 45 the globorotaliid species and a single globigerina bulloides sample were confined to the upper 0 4x of the observed range in d44 42ca values with the globorotaliids displaying a lesser degree of fractionation of 0 56f0 23x n 15 possibly as a result of physiological or metabolic processes such as the production of calcite crusts at depth leading to the depletion of internal stores of ca no significant correlation between temperature and ca enrichment factor was observed in any of the 12 species of foraminifera investigated the influence of temperature on e was close to zero for the combined non globorotaliid species 0 07f0 10 k e versus 1000 k 0 0008f0 0012x 8c1 the results suggest that the theoretically expected relationship between the ca enrichment factor and temperature can be obscured by as yet unquantified metabolic and physiological processes in nature these processes are particularly relevant to the globorotaliid species and g bulloides in this core top study consequently their effects must be better understood before laboratory determined temperature calibrations can be applied to downcore material with confidence provided that the effects of metabolic and physiological processes on e remain constant through time orbulina universa globigerinoides sacculifer neogloboquadrina pachyderma and globigerinella aequilateralis are suitable for the investigation of temporal changes in the calcium isotopic composition of seawater

the major ion δ44 40ca δ44 42ca and δ26 24mg geochemistry of granite weathering at ph 1 and t 25 c power law processes and the relative reactivity of minerals abstract we dissolved boulder creek granodiorite in a plug flow reactor for 5794 h at ph 1 and t 25 c the primary purpose of the experiment was to identify controls on dissolved 44 40ca 44 42ca and 26 24mg values during granite weathering herein we also examine the origin of ca and mg isotopic variability among minerals composing the boulder creek granodiorite and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output nine ca bearing minerals display an 8 80 range of 44 40ca values and a 0 51 range of 44 42ca values three mg bearing minerals display a 1 53 range of 26 24mg values these ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks most of the 44 40ca variability reflects 40ca enrichment in k feldspar and to a lesser extent biotite due to the radioactive decay of 40k over the 1 7 ga age of the rock whereas the entire range of 44 42ca values reflects mass dependent isotope fractionation during igneous differentiation and crystallization the range of 26 24mg values may represent either fractionation during the chloritization of biotite or interaction of the boulder creek granodiorite with mg rich metamorphic fluids having low 26 24mg values the elemental and isotopic composition of the reactor output varied substantially during the experiment we synthesize the mineralogical and fluid data using coupled mass conservation equations solved at non steady state model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations while surface area normalized dissolution rate constants were time invariant specific surface area increased as a power law function of time through positive feedbacks between mechanical disaggregation chemical dissolution and mineral depletion variations in dissolved 44 40ca 44 42ca and 26 24mg values reflect conservative mixing rather than fractionation apatite and calcite initially control 44 40ca and 44 42ca values followed by biotite titanite epidote hornblende and plagioclase the release of radiogenic 40ca clearly defines the period where biotite dissolution dominates the brucite layer of chlorite initially controls 26 24mg values followed by biotite the tot layer of chlorite and hornblende through direct isotopic tracking these results demonstrate that trace minerals such as apatite and calcite in the case of ca and brucite in the case of mg dominate elemental release during the incipient stages of granite weathering the results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages the ca and mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies

controls over δ 44 40 ca 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 44 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

evaluating the ca isotope proxy the use of ca isotopes as a proxy for mass flux imbalances in the ca cycle is evaluated critically a compiled ca isotope record for the last 45 ma derived from bulk nannofossil ooze and with a temporal resolution of 0 5 ma and an interpretation of the record are presented in the context of the global ca cycle this analysis which assumes that nannofossil ooze records isotopic variations in seawater indicates a dynamic ca cycle in the cenozoic such dynamic behavior has serious implications for the c cycle and suggests feedbacks between the ca and c cycles to stabilize or buffer the oceanic carbon reservoir alternative applications of the ca isotope proxy are investigated using numerical models to determine the extent to which ca isotopes are sensitive to other aspects of the ca cycle the results of the simulations are applied to specific cases in the cenozoic the simulations illustrate how variations in the global fractionation factor between calcium carbonate and seawater can produce trends similar to those observed when comparing previously published ca isotopic compositions of marine barite to the nannofossil ooze record the large drop in the 44 ca value of bulk nannofossil ooze near the eocene oligocene boundary can be reconciled in two ways either as a substantial increase in weathering relative to sedimentation or as an indicator of changing depositional mode within the ocean though the preferred interpretation is not clear at present it is evident that ca isotopes stand to be a unique proxy for ca cycling once the isotope systematics are elucidated

stable isotope profiles ca o c through modern brachiopod shells of t septentrionalis and g vitreus implications for calcium isotope paleo ocean chemistry brachiopod shells are widely used as an archive to reconstruct elemental and isotopic composition of seawater studies focused on oxygen and carbon isotopes over the last decades are increasingly extending to the emerging calcium isotope system to date only little attention has been paid to test the reliability of fossil brachiopods on their modern counterparts in this context the present study investigates two modern brachiopods terebratulina septentrionalis eastern canada 5 30 m depth 7 1 c seasonal temperature variation two layer shell and gryphus vitreus northern mediterranean 200 m depth constant all year round temperature three layer shell both species were sampled along the ontogenetic growth direction and calcium oxygen and carbon isotopes as well as elemental concentration were measured calcium isotopes were analyzed on tims the elemental composition was analyzed by la icp ms and icp aes the results indicate an intra specimen 44 40ca variation ranging from 0 16 to 0 33 pointing to a fairly homogenous distribution of calcium isotopes in brachiopod shells however in the light of the suggested 0 7 increase in calcium isotopes over the phanerozoic such intra specimen variations constrain ocean reconstruction 44 40ca values of t septentrionalis do not seem to be affected by growth rate calcium isotopic values of g vitreus are heavy in the central part of the shell and trend towards lighter values in peripheral areas approaching the maximum isotopic composition of t septentrionalis the maximum inter species 44 40ca difference of 0 62 between t septentrionalis and g vitreus indicates that care should be taken when using different taxa species with different strontium content or brachiopods with specialized shell structure such as g vitreus for ocean water reconstruction in terms of ca isotopic composition t septentrionalis may record ca isotopic fractionation related to seasonal seawater temperature variations in its shell but this is difficult to resolve at the current analytical precision average 18o derived temperatures of the two investigated species are close to on site measured temperatures

calcium isotope fractionation in calcite and aragonite abstract calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite precipitation temperatures ranged from 0 to 28 c calcium isotope fractionation shows a temperature dependence in accordance with previous observations 1000 ln cc 1 4 0 021 t c for calcite and 1000 ln ar 1 9 0 017 t c for aragonite within uncertainty the temperature slopes are identical for the two polymorphs however at all temperatures calcium isotopes are more fractionated in aragonite than in calcite the offset in 44 40 ca is about 0 6 the underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals or to different ca reaction behavior at the solid liquid interface recently the observed temperature dependence of the ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting lemarchand et al 2004 we show that this mechanism can in principle also be applied to caco 3 precipitation in natural environments in normal marine settings following this model ca isotope fractionation in marine ca carbonates is primarily controlled by precipitation rates on the other hand the larger ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates the rate control model of ca isotope fractionation predicts a strong dependence of the ca isotopic composition of carbonates on ambient co 3 2 concentration while this model is in general accordance with our observations in marine carbonates cultured specimens of the planktic foraminifer orbulina universa show no dependence of ca isotope fractionation on the ambient co 3 2 concentration the latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water

reconstruction of caribbean sea surface temperature and salinity fluctuations in response to the pliocene closure of the central american gateway and radiative forcing using δ44 40ca δ18o and mg ca ratios the 18o values of planktonic foraminifera increased in the caribbean by about 0 5 relative to the equatorial east pacific values between 4 6 and 4 2 ma as a consequence of the closure of the central american gateway cag this increase in 18o can be interpreted either as an increase in caribbean sea surface mixed layer salinity sss or as a decrease in sea surface temperatures sst this problem represents an ideal situation to apply the recently developed paleotemperature proxy 44 40ca together with mg ca and 18o on the planktic foraminifer globigerinoides sacculifer from odp site 999 although differences in absolute temperature calibration of 44 40ca and mg ca exist the general pattern is similar indicating a sst decrease of about 2 3 c between 4 4 and 4 3 ma followed by an increase in the same order of magnitude between 4 3 and 4 0 ma correcting the 18o record for this temperature change and assuming that changes in global ice volume are negligible the salinity induced planktonic 18o signal decreased by about 0 4 between 4 4 and 4 3 ma and increased by about 0 9 between 4 3 and 4 0 ma in the caribbean the observed temperature and salinity trends are interpreted to reflect the restricted exchange of surface water between the caribbean and the pacific in response to the shoaling of the panamanian seaway possibly accompanied by a southward shift of the intertropical convergence zone itcz between 4 4 and 4 3 ma differences in mg ca and 44 40ca derived temperatures can be reconciled by corrections for secular variations of the marine mg casw and 44 40ca a salinity effect on the mg ca ratio and a constant temperature offset of 2 5 c between both sst proxy calibrations

biological control of calcium isotopic abundances in the global calcium cycle measurements of 44ca 40ca expressed as 44ca were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature the results document a span of 4 in 44ca measured with the double spike technique to a precision of 0 15 volcanic rocks including basalt and rhyolite show little variability and cluster near 44ca 0 0 2 systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes and that biological fractionation is the primary generator of calcium isotopic fractionation in nature preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains calcium carbonate shells of marine microorganisms and deep sea carbonate ooze have 44ca about 1 0 lower than seawater this fractionation causes seawater to be enriched in heavy calcium 44ca 0 9 relative to igneous rocks marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level the calcium isotopic composition of living and fossil organisms may record information on diet and environment

on the utility of quantitative modeling to the interpretation of ca isotopes abstract though the utility of calcium isotopes is broad examples of applications are still relatively sparse some of this paucity as with many metal isotope systems may derive from a perception that the analytical tool is difficult to access alternatively potential users may be deterred by a sense that calcium isotopes are ambiguous difficult to interpret and or complicated by too many interrelated processes here we provide an overview of the quantitative modeling approaches available to facilitate interpretation of calcium isotopes in earth systems in particular their ability to push interpretations beyond the qualitative while no method is perfect the variety of approaches described here offer an accessible toolset that is incredibly valuable we suggest that the calcium isotope community should be expanding the use of such techniques noting their limitations and striving to improve upon current methods over time

calcium isotopes in the global biogeochemical ca cycle implications for development of a ca isotope proxy abstract at the earth s surface calcium ca is a critical element at a variety of scales it is soluble in natural waters a biological nutrient and a major constituent of the dominant mineral sink for carbon in the ocean caco3 there is a 4 variation in the ca isotopic composition 44ca 40ca expressed as 44ca of various ca reservoirs on earth suggesting ca isotopes as a promising tracer of ca cycling in both the present and the past fifteen years of high precision ca isotope measurements has revealed much about the behavior of ca isotopes in the earth surface environment but there remain fundamental questions concerning how ca isotopes are used to elucidate the marine and terrestrial ca cycles the current work presents a data compilation of over 70 published ca isotope studies totaling over 2600 measurements presented on a common delta scale that includes data on rivers and groundwater dust soils and soil pore fluids vegetation rainwater silicate minerals rocks and authigenic marine minerals carbonates sulfates and phosphates both modern and ancient the data compilation suggests that 1 there is a significant difference between carbonate 0 60 and silicate 44ca 0 94 2 riverine 44ca 0 88 does not simply reflect the compiled carbonate 44ca and 3 terrestrial vegetation exhibits the largest range of ca isotopic compositions 3 5 in the terrestrial setting we discuss these observations in the context of the global ca cycle exploring the extent to which seawater 44ca variability is feasible and how we can achieve accurate reconstructions of seawater 44ca over geologic time scales the current study presents simple mass balance models that quantify the leverage of inputs to change the ca isotopic composition of the ocean as this directly impacts the manner in which ca isotopes are interpreted although ca fractionates isotopically in the modern system during continental cycling the 44ca range of riverine inputs to the ocean is considerably smaller than the variability observed in putative seawater proxies such as nannofossil ooze and marine barite in the terrestrial realm plants exhibit a wide 44ca range and there is evidence that ca fluxes via biomass degradation are significant at the catchment scale we therefore assess the ability of the continental biosphere to influence riverine and consequently seawater 44ca a steady state biosphere has little leverage to alter riverine 44ca except in cases where the 44ca of the recycling flux is isotopically distinct from the 44ca of the uptake flux a non steady state biosphere can substantially impact both soil and riverine 44ca driving exchangeable ca either heavier or lighter depending on the magnitude of the recycling flux relative to the uptake flux based on estimates of the size of the global biosphere 1 5 1015 mol ca we suggest a decaying biosphere has the potential to impact riverine 44ca by tenths of a permil over time scales in the marine realm we evaluate the effect of a variable fractionation factor accompanying global removal of ca from the ocean on seawater 44ca and suggest methods by which such a mechanism can be recognized in the rock record experimental data suggest that there is considerable leverage