mineralogy early marine diagenesis and the chemistry of shallow water carbonate sediments abstract shallow water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of earth s chemical and climatic history one of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post depositional diagenetic alteration in this study we use paired measurements of calcium 44ca 40ca or 44ca and magnesium 26mg 24mg or 26mg isotope ratios in sedimentary carbonates and associated pore fluids as a tool to understand the mineralogical and diagenetic history of neogene shallow water carbonate sediments from the bahamas and southwest australia we find that the ca and mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis the observed variability in bulk sediment ca isotopes is best explained by changes in the extent and style of early marine diagenesis from one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the fluid fluid buffered to one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the precursor sediment sediment buffered our results indicate that this process together with variations in carbonate mineralogy aragonite calcite and dolomite plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers 13c 18o major minor and trace elements in shallow water carbonate sediments in the geologic record our results also provide evidence that a large shallow water carbonate sink that is enriched in 44ca can explain the mismatch between the 44 40ca value of rivers and deep sea carbonate sediments and call into question the hypothesis that the 44 40ca value of seawater depends on the mineralogy of primary carbonate precipitations e g aragonite seas and calcite seas finally our results for sedimentary dolomites suggest that paired measurements of ca and mg isotopes may provide a unique geochemical fingerprint of mass transfer during dolomitization to better understand the paleo environmental information preserved in these enigmatic but widespread carbonate minerals

effect of dolomitization on isotopic records from neoproterozoic carbonates in southwestern mongolia abstract carbon isotope values from shallow marine carbonate rocks including those from many dolomitized successions are the primary lens through which we interpret the ancient carbon cycle carbon isotopes are typically regarded as being robust to alteration during dolomitization due to the high carbon content of the rock compared to the fluid however chemostratigraphic studies of the neoproterozoic tsagaan olom group in southwestern mongolia exhibit 3 12 differences in carbon isotopes between stratigraphically equivalent limestone and dolomitized successions to understand the origins of this geochemical variation we conducted detailed geological mapping petrographic isotopic 13c 18o 44 40ca and 26mg and fluid inclusion analyses of carbonates in the taishir ol and shuurgat formations of the tsagaan olom group stratigraphic and textural constraints distinguish fabric retentive early dolomitization dolomitization event 1 that occurred in the taishir and ol formations during and soon after deposition of the ca 635 ma marinoan cap dolomite of the ol formation and fabric destructive dolomitization that occurred after the deposition of the younger shuurgat formation dolomitization event 2 either prior to or during early cambrian foreland basin formation the dolomitizing fluids moved through porous stratigraphic units bound by impermeable shale of the khongor and zuun arts formations dolomitization homogenized the isotopic records of all neoproterozoic tsagaan olom group dolomites undolomitized successions show more extreme negative excursions from more positive background values the salinity and isotopic values of seawater the dolomitizing fluids and the original platform carbonate were estimated from fluid inclusion data and a numerical model of diagenetic dolomitization these results demonstrate that both early and late dolomitization can have a profound effect on carbon isotopic records of carbonates however with a multi isotope approach the original carbon isotopic composition of platform top carbonate can be distinguished from that of seawater and other dolomitizing fluids

riverine evidence for a fractionated reservoir of ca and mg on the continents implications for the oceanic ca cycle analysis of river water rock travertine and soil from the high altitude negligible vegetation setting of the southern tibetan plateau demonstrates that ca and mg isotope ratios are fractionated during weathering dissolved ca in the two rivers studied is derived primarily by limestone dissolution 44 42ca in the rivers averages 0 43 and is statistically distinct from limestone at 0 31 the range in 44 42ca in these small rivers is 0 43 equivalent to the entire range in 44 42ca recorded in marine carbonate over the last 80 ma precipitation of isotopically light travertine with a 44 42ca of 0 21 enriches solute ca in heavy isotopes the mg isotope composition of the rivers is intermediate between limestone and silicate rock averaging 1 5 silicate soil has a 26mg of 0 03 heavier than silicate rock by 0 5 these fractionations in the soil create a companion groundwater reservoir of heavy ca and light mg seasonal variations in ca and mg isotope ratios in the dissolved load are small but define an array which can be modelled as a mixture between a fractionated groundwater reservoir and surface runoff reflecting the isotopic composition of the lithology fractionation of ca during the weathering of the continents is of importance to the global cycle of ca the riverine input of ca to the oceans dominated by carbonate weathering is controlled not only by the composition of the primary continental crust but also by the size and composition of a fractionated reservoir on the continents the impact on the oceanic cycle of ca depends on the relative residence times of dissolved ca in the ocean and the storage time of fractionated ca

constraining the cause of the end guadalupian extinction with coupled records of carbon and calcium isotopes abstract a negative c 13 excursion in carbonate sediments near the guadalupian lopingian middle late permian boundary has been interpreted to have resulted from a large carbon cycle disturbance during the end guadalupian extinction event ca 260 ma however the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbation to the global carbon cycle calcium isotopes can be used to further constrain the cause of a carbon isotope excursion because the carbon and calcium cycles are coupled via caco3 burial in this study we present coupled carbon and calcium isotope records from three guadalupian lopingian g l sections in china penglaitan and chaotian and turkey koserelik tepe the c 13 and ca 44 40 records differ among our studied sections and do not co vary in the same manner no section shows c 13 and ca 44 40 changes consistent with massive rapid volcanic co2 emissions or methane clathrate destabilization additionally many sections with large 3 changes in c 13 exhibit o 18 evidence for diagenetic alteration only one section exhibits a large excursion in the ca 44 40 of limestone but the absence of a similar excursion in the ca 44 40 of conodont apatite suggests that the limestone excursion reflects a mineralogical control rather than a perturbation to the global calcium cycle hence we interpret the large isotopic changes observed in some sections to have resulted from local burial conditions or diagenetic effects rather than from a large carbon and calcium cycle disturbance perturbations to the global carbon and calcium cycles across the g l transition were much less intense than the disturbances that occurred across the subsequent permian triassic boundary this finding is consistent with the much smaller magnitude of the end guadalupian extinction relative to the end permian

calcium isotope evidence for suppression of carbonate dissolution in carbonate bearing organic rich sediments pore fluid calcium isotope calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep sea sediments containing abundant clay and organic material this type of study of deep sea sediment diagenesis provides unique information about the ultra slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo environmental information in carbonate fossils for this study calcium isotope ratios 44 40ca of pore fluid calcium from ocean drilling program odp sites 984 north atlantic and 1082 off the coast of west africa were measured to augment available pore fluid measurements of calcium and strontium concentration both study sites have high sedimentation rates and support quantitative sulfate reduction methanogenesis and anaerobic methane oxidation the pattern of change of 44 40ca of pore fluid calcium versus depth at sites 984 and 1082 differs markedly from that of previously studied deep sea sites like 590b and 807 which are composed of nearly pure carbonate sediment in the 984 and 1082 pore fluids 44 40ca remains elevated near seawater values deep in the sediments rather than shifting rapidly toward the 44 40ca of carbonate solids this observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate rich sites the data are fit using a numerical model as well as more approximate analytical models to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material our models give mutually consistent results and indicate that calcite dissolution rates at sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate rich sites and the rate correlates with the abundance of clay our calculated rates are conservative for these sites the actual rates could be significantly slower because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included the results provide direct geochemical evidence for the anecdotal observation that the best preserved carbonate fossils are often found in clay or organic rich sedimentary horizons the results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals slowing dissolution dramatically even in relation to the already slow rates typical of carbonate rich sediments

interpreting the ca isotope record of marine biogenic carbonates an 18 million year record of the ca isotopic composition 44 42ca of planktonic foraminiferans from odp site 925 in the atlantic on the ceara rise provides the opportunity for critical analysis of ca isotope based reconstructions of the ca cycle 44 42ca in this record averages 0 37 0 05 1 sd and ranges from 0 21 to 0 52 the record is a good match to previously published neogene ca isotope records based on foraminiferans but is not similar to the record based on bulk carbonates which has values that are as much as 0 25 lower bulk carbonate and planktonic foraminiferans from core tops differ slightly in their 44 42ca i e by 0 06 0 06 n 5 while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger leaving open the question of the cause of the difference modeling the global ca cycle from downcore variations in 44 42ca by assuming fixed values for the isotopic composition of weathering inputs 44 42caw and for isotope fractionation associated with the production of carbonate sediments sed results in unrealistically large variations in the total mass of ca2 in the oceans over the neogene alternatively variations of 0 05 in the ca isotope composition of weathering inputs or in the extent of fractionation of ca isotopes during calcareous sediment formation could entirely account for variations in the ca isotopic composition of marine carbonates ca isotope fractionation during continental weathering such as has been recently observed could easily result in variations in 44 42caw of a few tenths of permil likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean until better constraints on variations in 44 42caw and sed have been established modeling the ca2 content of seawater from ca isotope curves should be approached cautiously

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

ca and mg isotope constraints on the origin of earth s deepest δ13c excursion abstract understanding the extreme carbon isotope excursions found in carbonate rocks of the ediacaran period 635 541 ma where 13 c of marine carbonates 13 c carb 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 13 c 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 44 40 ca and 131 26 mg 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 26 mg and 1 2 in 44 40 ca 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 44 40 ca 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 44 40 ca and sr and 26 mg 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 44 40 ca values inherited from an originally aragonitic polymorph have 13 c carb of 8 to 7 thereby providing strong geochemical evidence that extremely negative 13 c carb values are primary products of the ediacaran surface environment

the calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance calcium isotope ratios relative to seawater were studied in natural waters in order to constrain the ca isotopic flux to the oceans and to discuss the oceanic ca budget this study includes the analysis of 1 ca isotopes in continental waters at the regional scale of the upper rhine valley and 2 the determination of the 44ca values of some major rivers and hydrothermal vents the data indicate that the global 44ca variability of the studied waters with a maximal range of 1 is limited and must be linked to mass fractionation processes at the scale of a small watershed aubure vosges france the 44ca river flux changes due to the variation of the proportion of waters resulting from chemical alteration of rocks and biologically fractionated soil solutions ca isotopes could therefore be an important tool to quantify the impact of the plants and the biosphere on the river water chemistry at the regional scale of the rhine valley as well as at the global scale of world rivers the 44ca variability of river samples ranges from 0 5 to 1 without any relationship with the lithology of the watershed or the climate similarly the 44ca value of hydrothermal vents is also uniform and close to the mean value of river waters consequently the 44ca flux to the ocean should remain rather constant through time with a mean of 1 1 0 2 this value confirms that the ca budget of the present day seawater is in steady state this was not necessarily the case in the past non steady state periods should have been due to intensity variations of incoming and outcoming ca fluxes rather than to the variations in their isotopic signatures

calcium isotopes in archaeological bones and their relationship to dairy consumption abstract the calcium isotope ratios 44 42 ca of bones from humans and fauna from three archaeological sites taforalt abu hureyra and danebury are evaluated in order to assess whether calcium isotope ratios of bones can be used to detect dairy consumption by adult humans at each site the fauna 44 42 ca is the same regardless of species while the humans have lower 44 42 ca than the local animals by 0 24 0 41 site means however we cannot ascribe this difference to dairy consumption given this human faunal difference also occurs in epipalaeolithic and mesolithic adult humans where dairy consumption is unlikely rather this difference appears to be a result of differences in metabolic processes or other aspects of diet between humans and fauna minimal isotopic change in sequential acid leaches of bone powders and consideration of the high calcium concentration in bone suggest that bone calcium isotope ratios are not substantially affected by diagenetic change

ca isotope study of ordovician dolomite limestone and anhydrite in the williston basin implications for subsurface dolomitization and local ca cycling abstract a difference of 0 61 is reported between dolomite 1 66 and its precursor limestone 1 05 in the yeoman formation red river equivalent of the williston basin southeastern saskatchewan the significance of the large difference found and the preference for light isotope enrichment in the dolomite is evaluated with assistance from 87 sr 86 sr ratios and dolomitization models previously proposed for the studied rocks in particular i explore the possibility that 44 ca values in dolomite reflect the 44 ca values of the dolomitizing fluids without any correction for mineral fluid fractionation this hypothesis is based on recent studies showing negligible isotopic fractionation between carbonates and ca 2 bearing waters at very low precipitation rates fantle and depaolo 2007 jacobson and holmden 2008 if correct calcium isotopes hold promise as a tool for discriminating among numerous hydrological models of dolomite formation as a case in point the 44 ca value of the yeoman dolomite 1 66 is too low to reflect ca derived from the following sources 1 the original limestone 1 05 2 overlying beds of anhydrite 1 28 or 3 evaporated seawater 0 25 paleozoic carbonates ranging as low as 1 7 appear to be the lightest source of ca in the basin succession suggesting that the mg containing dolomitizing fluid was a connate water with a previous history of water rock interactions with paleozoic carbonates possibly involving earlier episodes of dolomitization and light ca release into migrating basinal fluids the relatively high seawater 44 ca values inferred from measurements of yeoman limestone and lake alma anhydrite suggest that seawater in the williston basin 450 ma was 0 22 0 46 higher in 44 ca than the contemporaneous ocean based on globally distributed brachiopods farkas et al 2007 this finding suggests that 44 ca values preserved in the deposits of epeiric seas may bias the 44 ca reconstruction of the ocean secular record if local ca cycling effects are not taken into account equations describing the isotope balance of ca in an epeiric sea indicate that seawater 44 ca values may be higher lower or equal to the 44 ca value of the ocean depending on the sizes of local scale ca deposition and weathering fluxes in relation to seawater ca exchange fluxes

an early diagenetic deglacial origin for basal ediacaran cap dolostones abstract the beginning of the ediacaran period 635 ma is marked by conspicuous dolostone units that cap marinoan glacial deposits worldwide the extent and sedimentary characteristics of the cap dolostones indicate that anomalous carbonate over saturation coincided with deglacial sea level rise and ocean warming however the geochemical variability within cap dolostones both between continents across single continental margins and within individual stratigraphic sections has been difficult to reconcile with depositional models using a compilation of new calcium and magnesium isotope measurements in marinoan cap dolostone successions worldwide we show that the geochemical variability can be explained by early diagenetic dolomitization of aragonite along a spectrum of fluid and sediment buffered conditions dolostones from the outer platform formed under fluid buffered conditions whereas dolostones on the inner platform and foreslope environment formed under sediment buffered conditions this spatial pattern of dolomitizing conditions is consistent with buoyant recirculation of glacial seawater within carbonate platforms driven by the deglacial sea level rise and development of a meltwater surface ocean using a numerical diagenetic model to evaluate the geochemical differences between sediment and fluid buffered cap dolostone units we constrain the chemical and isotopic composition of both the dolomitizing fluid glacial seawater 13 c 0 2 the meltwater lens 13 c 11 and the primary aragonite sediment 13 c 6 to 3 these model end members do not imply that primary geochemical variability did not exist but demonstrates that it is not necessary to change the chemistry of seawater to explain the global stratigraphic variability in the geochemistry of basal ediacaran cap dolostones our results provide a novel framework for understanding the geochemical variability of cap dolostone units including large excursions in carbon isotopes and how this variability is the product of local diagenetic processes expressed globally in continental margin environments following the last snowball earth

coupled δ44 40ca δ88 86sr and 87sr 86sr geochemistry across the end permian mass extinction event abstract we report high resolution high precision 44 40ca 88 86sr and 87sr 86sr records spanning the permian triassic boundary ptb from the meishan and dajiang carbonate successions in south china the goal of the study was to understand the behavior of ca and sr isotopes during a time period in earth history characterized by severe biological and environmental perturbations including a major mass extinction flood basalt volcanism ocean acidification and sea level fluctuations dajiang displays negative 44 40ca and 88 86sr excursions and invariant 87sr 86sr ratios in the

the influence of seawater carbonate chemistry mineralogy and diagenesis on calcium isotope variations in lower middle triassic carbonate rocks abstract the geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks as a result calcium ca isotope ratios 44ca 40ca expressed as 44 40ca can help to constrain ancient carbon cycle dynamics if ca cycle behavior can be reconstructed however the 44 40ca of carbonate rocks is influenced not only by the 44 40ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation in this study we investigate the dominant controls on carbonate 44 40ca in upper permian to middle triassic limestones ca 253 to 244 ma from south china and turkey this time interval is ideal for assessing controls on ca isotope ratios in carbonate rocks because fluctuations in seawater 44 40ca may be expected based on several large carbon isotope 13c excursions ranging from 2 to 8 parallel negative 13c and 44 40ca excursions were previously identified across the end permian extinction horizon here we find a second negative excursion in 44 40ca of 0 2 within lower triassic strata in both south china and turkey however this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the 44 40ca of global seawater additionally 44 40ca values from turkey are consistently 0 3 lower than contemporaneous samples from south china providing further support for local or regional influences by measuring 44 40ca and sr concentrations sr in two stratigraphic sections located at opposite margins of the paleo tethys ocean we can determine whether the data represent global conditions e g secular variations in the 44 40ca of seawater versus local controls e g original mineralogy or diagenetic alteration the sr and 44 40ca data from this study are best described statistically by a log linear correlation that also exists in many previously published datasets of various geological ages using a model of early marine diagenetic water rock interaction we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate 44 40ca values the relationship between sr and 44 40ca holds potential for reconstructing first order secular changes in seawater 44 40ca composition

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 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

the abyssal and deep circulation of the northeast pacific basin abstract three dimensional abyssal and deep circulation of the region to the east and north of the emperor seamount chain hawaiian ridge is determined from a compilation of ctd and argo float data using a new overdetermined inverse technique for the geostrophic reference velocity and diapycnal lateral mixing coefficients the northeast pacific basin is primarily sourced from its northern boundary at a rate of 3 5 sv across 47 n below 3000 m bottom water in the western subarctic gyre recirculates cyclonically between the emperor seamount chain and 155 w bottom water east of 155 w takes a more direct path southward along the flank of a broad topographic slope in the deep water a ridge of potential vorticity lying along the mendocino fracture zone separates circulation systems north and south of 40 n the region has very weak diapycnal and lateral mixing and an aspect ratio for the overturning circulation that is correspondingly flat with bottom water parcels rising less than 1 km during their long transit from the aleutian trench to the latitude of hawaii

ca isotopes in carbonate sediment and pore fluid from odp site 807a the ca2 aq calcite equilibrium fractionation factor and calcite recrystallization rates in pleistocene sediments abstract the calcium isotopic compositions 44ca of 30 high purity nannofossil ooze and chalk and 7 pore fluid samples from odp site 807a ontong java plateau are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor s f between calcite and dissolved ca2 and the rates of post depositional recrystallization in deep sea carbonate ooze the value of s f at equilibrium in the marine sedimentary section is 1 0000 0 0001 which is significantly different from the value 0 9987 0 0002 found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean we hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for ca isotope fractionation during calcite precipitation we describe a steady state model that offers a unified framework for explaining ca isotope fractionation across the observed precipitation rate range of 14 orders of magnitude the model attributes ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface this model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation the ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly deposited carbonate ooze is 30 40 myr and decreases with age to about 2 myr in 2 3 million year old sediment the recrystallization rates determined from ca isotopes for pleistocene sediments are higher than those previously inferred from pore fluid sr concentration and are consistent with rates derived for late pleistocene siliciclastic sediments using uranium isotopes combining our results for the equilibrium fractionation factor and recrystallization rates we evaluate the effect of diagenesis on the ca isotopic composition of marine carbonates at site 807a since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation accordingly diagenesis produces a maximum shift in 44ca of 0 15 for site 807a sediments but will have a larger impact where sedimentation rates are low seawater circulates through the sediment pile or there are prolonged depositional hiatuses

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

ca cycling and isotopic fluxes in forested ecosystems in hawaii 1 biogeochemical processes fractionate ca isotopes in plants and soils along a 4 million year developmental sequence in the hawaiian islands we observed that plants preferentially take up 40ca relative to 44ca and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44ca in soil exchangeable pools our results imply moderate fluxes enriched in 44ca from strongly nutrient depleted old soils in contrast with high 40ca fluxes in young and little weathered environments in addition biological fractionation controls divergent geochemical pathways of ca and sr in the plant soil system while ca depletes progressively with increasing soil age sr ca ratios increase systematically sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial ca cycle ca isotopes in combination with sr ca ratios reveal more complex processes involved in the biogeochemistry of ca and sr

δ44ca evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite abstract to improve understanding of ca isotope transport during water rock interaction on the continents we measured dissolved 44 ca values along a 236 km flow path in the madison aquifer south dakota where fluids have chemically evolved according to dolomite and anhydrite dissolution calcite precipitation and ca for na ion exchange over a timescale spanning 15 kyr we used a reactive transport model employing rate data constrained from major ion mass balances to evaluate the extent to which calcite precipitation and ion exchange fractionate ca isotopes elevated 44 ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and ca for na ion exchange respectively however for the bulk of the flow path 44 ca values evolve by mixing between anhydrite and dolomite dissolution with no fractionation during calcite precipitation under saturated conditions we attribute the absence of ca isotope fractionation to the long timescale of water rock interaction and slow rate of calcite precipitation which have enabled fluids to chemically and isotopically equilibrate with calcite we therefore conclude that the equilibrium ca isotope fractionation factor between calcite and water cal w is very close to zero to the extent that the madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium this study suggests that groundwater contributions to 44 ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination

anhydrite and the sr isotope evolution of groundwater in a carbonate aquifer major element concentrations and 87 sr 86 sr ratios were measured in groundwaters and bedrock from the madison aquifer in western south dakota in this region the madison aquifer is primarily comprised of dolomite belonging to the madison limestone group the purpose of the study was to investigate controls on the downgradient evolution of dissolved sr 2 in a carbonate groundwater system that is recharged by waters with high 87 sr 86 sr ratios draining precambrian basement rocks and to establish the sources of sr 2 added to the waters by reaction with the aquifer lithology a mass balance model following previous workers was used to calculate amounts and effective rates of mineral dissolution and precipitation during groundwater transport along a 240 km flow path both the calculated reaction rates and data for the sr isotope geochemistry of the reacting phases were then used to develop a self consistent and quantitative description of the concentration and isotopic composition of dissolved sr 2 in the aquifer waters the major ion chemistry of madison aquifer groundwater is known to evolve according to dolomite dissolution anhydrite dissolution calcite precipitation and ion exchange with clay minerals dissolved 87 sr 86 sr ratios in the madison aquifer decrease downgradient input waters draining the igneous black hills have 87 sr 86 sr ratios of 0 723 while highly evolved waters in the aquifer have 87 sr 86 sr ratios of 0 708 dissolved sr 2 concentrations undergo a concurrent increase from 1200 to 66 000 nmol l model results indicate that dolomite dissolution exerts a critical control on the major ion chemistry but is not the primary source of nonradiogenic sr 2 as both the dissolution rate and sr concentration of dolomite are very low anhydrite is readily soluble in water has a low 87 sr 86 sr ratio 0 708 and a very high sr concentration 50 000 nmol g anhydrite is also greatly undersaturated in the groundwaters and the downgradient evolution of sr 2 accompanies an 80 fold increase in dissolved so 4 2 while anhydrite has a very low abundance in the aquifer rocks the flow model indicates that anhydrite dissolution provides 300 times more sr 2 per liter of water relative to dolomite dissolution these findings suggest that anhydrite dissolution governs the sr 2 geochemistry of madison aquifer groundwaters whereas dolomite dissolution and calcite precipitation control the bulk chemistry lastly it is shown that the calculation of net mineral masses transferred to solution requires very high relative proportions of anhydrite and clay to dolomite mineral masses obtained by this approach actually represent bulk contributions without consideration of the intrinsic reaction rates of the phases or their modal abundances in the aquifer rocks however consideration of these parameters in a transport equation for flow through porous media shows that the high apparent abundances are not a real requirement this latter approach is consistent with laboratory experiments and indicates that as little as 0 04 wt of very soluble anhydrite and 0 3 wt of exchangeable clay in the aquifer rock are sufficient to produce the observed groundwater chemistry in most of the flow path

geochemical modeling of the madison aquifer in parts of montana wyoming and south dakota stable isotope data for dissolved carbonate sulfate and sulfide are combined with water compo sition data to construct geochemical reaction models along eight flow paths in the madison aquifer in parts of wyoming montana and south dakota the sulfur isotope data are treated as an isotope dilution problem whereas the carbon isotope data are treated as rayleigh distillations all reaction models reproduce the observed chemical and carbon and sulfur isotopic composition of the final waters and are partially validated by predicting the observed carbon and sulfur isotopic compositions of dolomite and anhydrite from the madison limestone the geochemical reaction models indicate that the dominant groundwater reaction in the madison aquifer is dedolomitization calcite precipita tion and dolomite dissolution driven by anhydrite dissolution sulfate reduction ca mg2 ina cation exchange and halite dissolution are locally important particularly in central montana the groundwater system is treated as closed to c02 gas from external sources such as the soil zone or cross formational leakage but open to c02 from oxidation of organic matter coupled with sulfate reduction and other redox processes occurring within the aquifer the computed mineral mass transfers and modeled sulfur isotopic composition of madison anhydrites are mapped throughout the study area carbon 14 groundwater ages adjusted for the modeled carbon mass transfer range from modem to about 23 000 years b p and indicate flow velocities of 7 7 ftlyr 2 1 26 5 rnlyr most horizontal hydraulic conductivities calculated from darcy s law using the average 14 c flow velocities are within a factor of 5 of those based on digital simulation the calculated mineral mass transfer and adjusted 14 c groundwater ages permit determination of apparent rates of reaction in the aquifer the apparent rate of organic matter oxidation is typically 0 12 jlidol uyr sulfate and to a lesser extent ferric iron are the predominant electron acceptors the kinetic biochemical fractionation of 34 s between sulfate and hydrogen sulfide is approximately 44 o at 25 c with a temperature variation of

calcium isotope record of phanerozoic oceans implications for chemical evolution of seawater and its causative mechanisms a total of 280 brachiopods of ordovician to cretaceous age complemented by published data from belemnites and planktonic foraminifera are used to reconstruct the evolution of calcium isotope composition of seawater 44 40casw over the phanerozoic the compiled 44 40casw record shows a general increase from 1 3 nist srm 915a at the beginning of the ordovician to 2 at present superimposed on this trend is a major long term positive excursion from the early carboniferous to early permian as well as several short term mostly negative oscillations a numerical model of the global cycles of calcium carbon magnesium and strontium was used to estimate whether the recorded 44 40casw variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans the model uses the record of marine 87sr 86sr ratios as proxy for seafloor spreading rates a record of oceanic mg ca ratios to estimate rates of dolomite formation and reconstructed atmospheric co2 discharge and erosion rates to estimate continental weathering fluxes the model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed 44 40casw trends suggesting that the isotope signatures of these fluxes must also have changed as a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits i e the oscillating calcite aragonite seas the ultimate control of the calcium isotope budget of the phanerozoic oceans appears to have been tectonic processes specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic mg ca ratio which in turn controlled the dominant mineralogy of marine carbonates hence the 44 40casw as to the causes of the short term oscillations recorded in the secular 44 40casw trend we tentatively propose that these are related to variable rates of dolomite formation and or to changing chemical composition of the riverine flux in particular and ratios induced by variable proportions of silicate vs carbonate weathering rates on the continents

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

modeling novel stable isotope ratios in the weathering zone when rock is converted to weathering products the involved processes can be fingerprinted using the stable isotope ratios of metals for example li mg ca fe sr and metalloids b si here we construct a framework for interpreting these novel stable isotope ratios quantitatively in the compartments of the weathering zone in a geomorphic context the approach is applicable to any novel stable isotope system and is based on a simple steady state mass balance model that represents the weathering zone from the scale of a soil column to that of entire continents our model is based on the assumption that the two main processes associated with isotope fractionation are formation of secondary precipitates such as clays and uptake of nutrients by plants the model results show that the isotope composition of a given element in the weathering zone compartments depends on 1 the ratio between the release flux to water through primary mineral dissolution and the erosion flux of isotopically fractionated solid material consisting of secondary precipitates and organic matter 2 the isotope fractionation factors associated with secondary mineral precipitation and uptake by plants a relationship is established between isotope ratios isotope fractionation factors and indexes for chemical weathering such as chemical depletion fractions cdf and elemental mass transfer coefficients derived from simple elemental concentration measurements from this relationship isotope fractionation factors can be calibrated from chemical and isotope data measured on field material furthermore we show how the ratio of solid export to dissolved export of a given element from the weathering system can be estimated from the comparison of the isotope composition between bedrock water and sediment this calculation can be applied to samples from soils from rivers and from the sedimentary record and does not require knowing the isotope fractionation factors involved in the reactions finally we apply the model to the oceanic li isotope record reconstructed from marine carbonate sediments in order to discuss changes in global geomorphic regimes through the cenozoic

calcium isotope fractionation in selected modern and ancient marine carbonates the calcium isotope composition 44 42ca was analyzed in modern cretaceous and carboniferous marine skeletal carbonates as well as in bioclasts non skeletal components and diagenetic cements of cretaceous and carboniferous limestones in order to gain insight in ca2 aq caco3 isotope fractionation mechanisms in marine carbonates splits of samples were analyzed for sr mg fe and mn concentrations and for their oxygen and carbon isotopic composition biological carbonates generally have lower 44 42ca values than inorganic marine cements and there appears to be no fractionation between seawater and marine inorganic calcite a kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against 44ca in biological carbonates when compared to inorganic precipitates this is supported by a well defined correlation of the 44 42ca values with sr concentrations in cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration no significant temperature dependence of ca isotope fractionation was found in shells of cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from 18o values and mg concentrations the reconstruction of secular variations in the 44 42ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and cretaceous biological carbonates independent of chemical composition or mineralogy despite these variations that may be due to still unidentified biological fractionation mechanisms the 44 42ca values of cretaceous skeletal calcite suggest that the 44 42ca value of cretaceous seawater was 0 3 0 4 lower than that of the modern ocean

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

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

boron and calcium isotope composition in neoproterozoic carbonate rocks from namibia evidence for extreme environmental change the level and evolution of atmospheric carbon dioxide throughout earth s history are key issues for palaeoclimate reconstructions especially during times of extreme climate change such as those that marked the neoproterozoic the carbon isotope ratios of marine carbonates are crucial in the correlation and identification of neoproterozoic glacial deposits and they are also used as a record for biogeochemical cycling and potential proxy for atmospheric pco2 likewise the boron and calcium isotope compositions of marine carbonates are potential proxies for palaeo seawater ph and the ratio of calcium fluxes into and out of seawater respectively and together they may be used to estimate atmospheric carbon dioxide here we use b and ca isotopes to estimate palaeoenvironmental conditions in the aftermath of a major neoproterozoic glaciation in namibia the validity of the b and ca isotope variation in the ancient marine carbonates is evaluated using the oxygen isotope composition of the carbonates and its correlation to the carbon isotope variation a negative 2 7 to 6 2 11b excursion occurs in the postglacial carbonates and is interpreted to reflect a temporary decrease in seawater ph associated variations in 44ca values ranging between 0 35 and 1 14 are linearly coupled with the carbon isotope ratios and imply enhanced postglacial weathering rates the reconstructed seawater ph and weathering profiles indicates that high atmospheric co2 concentrations were likely during the melt back of neoproterozoic glaciations and precipitation of cap carbonates however the b isotope trend suggests that these concentrations rapidly ameliorated and they do not co vary with 13c thus models attempting to link long lived negative 13c excursions to elevated pco2 need to be reconsidered

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