87sr86sr in late proterozoic carbonates evidence for a mantle event at 900 ma ago abstract strontium isotopic measurements were made on late proterozoic carbonates from west african craton comparison of samples with acceptable trace element patterns with coeval data from southern africa and with the published australian results suggests that the 87 sr 86 sr ratio of the late proterozoic sea water evolved in the following manner about 0 7075 at 1000 50 ma 0 7056 to 0 7074 at 900 50 ma 0 7068 to 0 7091 0 7106 at 800 50 ma 0 7074 to 0 7077 at 700 50 ma and 0 7076 to 0 7089 0 7096 at 600 50 ma ago the variations are comparable in magnitude and frequency to those described previously for the phanerozoic strontium isotopic values in the radiogenic part of this range suggest that the continental river flux of sr into late proterozoic oceans was of comparable isotopic composition to its present day counterpart 0 711 consequently the non radiogenic 87 sr 86 sr value at 900 50 ma ago signifies a large flux of mantle strontium into the ocean at this time because the present time resolution is only about 75 25ma additional sampling as well as better stratigraphie resolution and more definite selection criteria are required for construction of a more detailed late proterozoic sea water curve

δ44 40ca variability in shallow water carbonates and the impact of submarine groundwater discharge on ca cycling in marine environments shallow water carbonates from florida bay the florida reef tract and a mexican caribbean fringing reef at punta maroma were studied to determine the range of ca isotope variation among a cohort of modern carbonate producers and to look for local scale ca cycling effects the total range of ca isotope fractionation is 0 4 at punta maroma yielding an allochem weighted average 44 40 ca value of 1 12 consistent with bulk sediment from the lagoon with a value of 1 09 these values are virtually identical to bulk carbonate sediments from the florida reef tract 1 11 and from one location in florida bay 1 09 near a tidal inlet in the florida keys no evidence was found for the 0 6 fractionation between calcite and aragonite which has been observed in laboratory precipitation experiments combining these results with carbonate production modes and 44 40 ca values for pelagic carbonates taken from the literature we calculate a weighted average value of 1 12 0 11 2 for the global scale ca output flux into carbonate sediments the 44 40 ca value of the input ca flux from rivers and hydrothermal fluids is 1 01 0 04 2 mean calculated from literature data that have been corrected for inter laboratory bias assuming that the ocean ca cycle is in steady state we calculate a 44 40 ca value of 1 23 0 23 2 for submarine groundwater discharge sgd on a global scale the sgd ca flux rivals river flows and mid ocean ridge hydrothermal vent inputs as a source of ca to the oceans it has the potential to differ significantly in its isotopic value from these traditional ca inputs in the geological past and to cause small changes in the 44 40 ca value of oceans through time in the innermost water circulation restricted region of northeastern florida bay sediments and waters exhibit a 0 7 gradient in 44 40 ca values decreasing towards the florida everglades this lowering of 44 40 ca is predominantly caused by local scale ca inputs from sgd which has a high ca concentration 450 mg l and low 44 40 ca value 0 96 mixing calculations show that ca inputs from sgd and surface water runoff from the florida everglades contribute between 8 and 60 of the dissolved ca to the studied waters with salinities between 30 and 14 respectively similar degrees of circulation restriction between epeiric seas and oceans in the geological past may have also led to overprinting of sedimentary carbonate 44 40 ca values in nearshore regions of epeiric seas due to local scale cycling of seawater through coastal carbonate aquifers local ca cycling effects may explain some of the scatter in 44 40 ca values present in the ca isotope evolution curve of phanerozoic oceans

microbial nucleation of mg rich dolomite in exopolymeric substances under anoxic modern seawater salinity new insight into an old enigma sulfate reducing bacteria are known to mediate dolomite formation under hypersaline conditions but details of the crystal nucleation process are still poorly constrained our laboratory study demonstrates for the first time that desulfobulbus mediterraneus a marine sulfate reducing bacterium mediates primary precipitation of mg rich dolomite under anoxic conditions in media replicating modern seawater chemistry at low temperature 21 c precipitation of crystals was associated with extracellular polymeric substances in a monospecific biofilm providing templates for nucleation by altering the molar mg ca ratio after initial nucleation of single nanospherulites 50 nm growth was mediated by aggregation resulting in spherulites of 2 3 m in diameter nucleation led to differences in mg ca ratios and 44 40ca values among the organic material i e biofilm including cells and extracellular polymeric substances 0 87 0 01 2 sd and 0 48 0 11 2 se respectively the crystals 1 02 0 11 2 sd and 0 08 0 24 2 se respectively and the liquid bulk medium after mineral precipitation 4 53 0 04 2 sd and 1 10 0 24 2 se respectively these data indicate a two step fractionation process involved in the sequestration of ca from the solution into the crystal lattice of the mineral precipitated our results demonstrate the capability of extracellular polymeric substances to overcome kinetic inhibition fostering the formation of kinetically less favorable mg rich dolomite and they also question the applicability of the ca isotopic system as a proxy for paleogeochemistry of seawater

effect of calcite precipitation on stable strontium isotopic compositions insights from riverine and pool waters in a karst cave abstract radiogenic and stable sr isotope ratios 87 sr 86 sr 88 86 sr serve as potential tracers for evaluation of weathering sources and associated physicochemical processes in terrestrial environments despite carbonate weathering sourcing two thirds of the total continental sr flux to the ocean however few attempts have been aimed at studying stable sr isotope fractionation in carbonate dominated aquifers here we present a monthly resolved monitoring dataset of major ion concentrations and sr isotope ratios for karst riverine and pool waters at the luofang cave in the central china to understand the potential controls responsible for water 88 86 sr compositions under various climatic conditions with the exception of some pool waters in the dry period significantly heavier 88 86 sr were detected in the riverine and pool waters 0 20 to 0 42 compared to bedrock 88 86 sr 0 24 to 0 28 which can t be interpreted solely by lithology a sequential leaching experiment of the local soils suggests limited stable sr isotope fractionation during incongruent silicate mineral dissolution local plant utilization and biological activity in the soil overlying the cave are possible processes for causing the observed heavier 88 86 sr in cave water however air partial pressure of co 2 in cave monitoring water ph and sr isotopic mass balance calculations suggest that plant utilization is unlikely to be the primary control on the heavier water 88 86 sr on the other hand significant stable sr isotope fractionation was found between the cave dripping waters and calcite precipitates and the 88 86 sr car aq was estimated to be 0 15 0 07 2sd precipitation of secondary calcites might be a potential process responsible for the heavier 88 86 sr in the waters the negative correlation between 88 86 sr and sr na ratios in the cave waters is consistent with a scenario of preferential incorporation of the light sr isotope by solid phase furthermore by combining the calcite saturation states and water ph our results suggest that calcite precipitation is the most likely process controlling 88 86 sr compositions in cave water we demonstrate that secondary calcite precipitation in carbonate dominated catchments could be important in controlling the riverine water 88 86 sr compositions

stable sr isotope sr ca mg ca li ca and mg li ratios in the scleractinian cold water coral lophelia pertusa the aragonitic skeletons of scleractinian cold water corals can serve as valuable archives in paleoceanographic studies the potential of 88 86sr sr ca mg ca li ca and mg li ratios of the cold water coral lophelia pertusa to record intermediate water mass properties has been investigated here we used samples from several locations along the european continental margin spanning a large temperature range from 6 to 14 c stable strontium isotope measurements were carried out with the recently developed double spike tims technique and our results differ from those obtained with less precise methods in contrast to the strong positive relationship with temperature of previous studies our results suggest that 88 86sr measured in scleractinian cold water corals is not controlled by seawater temperature but reflects the sr isotopic composition of seawater with an offset of 88 86sr 0 196 as found in previous studies the elemental ratios sr ca li ca and mg li measured in corals are significantly related to water temperature and do not correlate with salinity moreover sr ca ratios in l pertusa display the expected inverse correlation with temperature however the variance in the sr ca data severely limits the accuracy of paleotemperature estimates the li ca and mg ca ratios reveal other influences besides temperature such as ph and or growth or calcification rate however corresponding mg li ratios in l pertusa are more tightly related to temperature as they remove these secondary effects in particular the mg li ratio in l pertusa may serve as a new promising paleotemperature proxy for intermediate water masses our dataset represents the most extensive geochemical examination of l pertusa to date revealing a temperature sensitivity of 0 015 mol mmol c for mg li however using this temperature dependence and the precision of 5 3 2sd only temperature variations larger than 1 5 c can be resolved with 95 confidence

changing tectonic controls on the long term carbon cycle from mesozoic to present tectonic drivers of degassing and weathering processes are key long term controls on atmospheric co2 however there is considerable debate over the changing relative importance of different carbon sources and sinks existing geochemical models have tended to rely on indirect methods to derive tectonic drivers such as inversion of the seawater 87sr 86sr curve to estimate uplift or continental basalt area here we use improving geologic data to update the representation of tectonic drivers in the copse biogeochemical model the resulting model distinguishes co2 sinks from terrestrial granite weathering total basalt weathering and seafloor alteration it also distinguishes co2 sources from subduction zone metamorphism and from igneous intrusions we reconstruct terrestrial basaltic area from data on the extent of large igneous provinces and use their volume to estimate their contribution to degassing we adopt a recently published reconstruction of subduction related degassing and relate seafloor weathering to ocean crust creation rate revised degassing alone tends to produce unrealistically high co2 but this is counteracted by the inclusion of seafloor alteration and global basalt weathering producing a good overall fit to mesozoic cenozoic proxy co2 estimates and a good fit to 87sr 86sr data the model predicts that seafloor alteration and terrestrial weathering made similar contributions to co2 removal through the triassic and jurassic after which terrestrial weathering increased and seafloor weathering declined we predict that basalts made a greater contribution to silicate weathering than granites through the mesozoic before the contribution of basalt weathering declined over the cenozoic due to decreasing global basaltic area

geochemistry of modern brachiopods applications and implications for oceanography and paleoceanography abstract modern rhynchonellida terebratulida thecideida and a few inarticulated brachiopods were collected live or soon after death at 30 locations from depths of 2 3940 m from the equator to high latitudes covering the atlantic pacific indian caribbean and mediterranean oceans seas well preserved fibers of the secondary layer combined with sr 450 1928 mg kg mn 1 199 mg kg and fe 1 610 mg kg contents confirm with few exceptions the excellent preservation of the modern brachiopod material evaluation of the stable isotope compositions was conducted on 276 specimens and on 374 published samples for a total database of 650 samples from 80 locations it revealed that oxygen isotope incorporation into shell calcite secondary layer of modern articulated brachiopods in most cases occurs in equilibrium with the ambient water and as such reflects surrounding environmental conditions thecideida as a group shallow water and low latitude incorporate oxygen isotopes 3 04 to 0 35 into shell calcite in equilibrium with their ambient water a large majority of genera and species of the terebratulida shallow water and low mid latitude also incorporate oxygen 2 30 to 3 48 into shell calcite in isotopic equilibrium with their surrounding water in contrast equilibrium incorporation of oxygen isotopes into shell calcite by the rhynchonellida is uncertain but a vital effect probably applies to the craniida the question of equilibrium disequilibrium incorporation of carbon isotopes into shell calcite of modern brachiopods remains unresolved at this time isotope compositions range up to 4 5 5 6 and 1 5 for 13 c and up to 5 5 5 9 and 0 3 for 18 o for shallow water low mid and high latitude brachiopods respectively strontium isotopes of modern brachiopods as expected show no significant variation with location latitude water depth temperature salinity and general water conditions once local habitat and ecological influences of fossil brachiopods from similar latitudes are considered their isotopic elemental values should be valuable diagenetic indicators and important oceanographic chemostratigraphic proxies

chemical weathering mass loss and dust inputs across a climate by time matrix in the hawaiian islands we determined the total mass loss and rate of chemical weathering from three minimally eroded hawaiian lava flows that are 10 170 and 350 ka old using a backhoe we sampled the entire weathering zone at 28 sites and measured the depletion or enrichment of each major element in each soil horizon relative to parent material we were able to assess the influence of both climate and substrate age on chemical weathering because each flow crosses a precipitation gradient from 600 to 2500 mm yr 1 mass loss rates were highest for the 0 10 ka interval under the wettest climatic conditions 54 t km 2 yr 1 and decreased to near zero in the wet sites during the 10 170 and 170 350 ka intervals not surprisingly weathering rates were lower in drier sites 24 t km 2 yr 1 from 0 10 ka to b 2tk m 2 yr 1 thereafter however the effects of precipitation were non linear there was a precipitation threshold below which mass loss was relatively small and above which mass loss was substantial but insensitive to increased rainfall chemical weathering rates depend on tectonic uplift erosion climate rock type or some combination thereof by working on stable uneroded surfaces of a single rock type across a well constrained precipitation gradient we were able to identify another potential driver the rate of dust deposition although hawai i is one of the least dusty places in the northern hemisphere dust inputs reached 82 of the total mass loss from the weathering zone at some sites and averaged 30 on the 170 ka flow this highlights the potential importance of dust as a component of observed weathering fluxes from catchments worldwide

88 sr 86 sr fractionation and calcite accumulation rate in the sea of galilee abstract this study used the sea of galilee lake kinneret northern israel as a natural laboratory to investigate the fractionation of the stable sr isotope ratio 88 sr 86 sr during precipitation of inorganic primary calcite from the lake s water it was found that the absolute value of the 88 sr 86 sr fractionation factor 88 86 sr increases as a function of calcite accumulation rate 88 86 sr 0 05 to 0 042 log r mol m 2 d 1 where r is the accumulation rate furthermore the 87 sr 86 sr and 88 sr 86 sr ratios in the freshwater and brines that enter the lake were used to calculate the contributions of these sources to the lake sr budget the 87 sr 86 sr and 88 sr 86 sr ratios were measured in primary calcite aragonite shells of live melanopsis lake water and various water sources to the lake while the lake s 87 sr 86 sr ratios are determined by the mixture of freshwater of the jordan river and saline springs the 88 sr 86 sr ratios of the lake reflect a more complex mass balance that includes the effect of isotopic fractionation associated with the precipitation of primary calcite data analysis suggests that long term accumulation of inorganic calcite depleted in the heavy isotope 88 sr results in an increase of the 88 86 sr value of the lake water by 0 05 in contrast to the primary inorganic calcite biogenic aragonite of the melanopsis shells show a rather constant 88 sr 86 sr water caco 3 fractionation of 88 86 sr 0 21 similar 88 86 sr values were reported for the precipitation of coralline and inorganic aragonite from seawater and the precipitation of inorganic calcite from various continental waters the 88 86 sr value of inorganic calcite is modulated by the rate of carbonate precipitation as noted above and shown by precipitation experiments massive precipitation of primary calcite with a wide spread of accumulation rates occurs during the spring phytoplankton bloom in lake kinneret the bloom dictates the degree of calcite saturation in the lake and hence the stable sr isotopic composition of the precipitating calcite the correlation between 88 sr 86 sr and the calcite accumulation rate can be therefore used as a tool to reconstruct environmental and ecological variations in the historical lake by analyzing the 88 sr 86 sr ratio in the primary caco 3 recovered from the lake s sedimentary archives

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

the phanerozoic δ88 86sr record of seawater new constraints on past changes in oceanic carbonate fluxes the isotopic composition of phanerozoic marine sediments provides important information about changes in seawater chemistry in particular the radiogenic strontium isotope 87sr 86sr system is a powerful tool for constraining plate tectonic processes and their influence on atmospheric co2 concentrations however the 87sr 86sr isotope ratio of seawater is not sensitive to temporal changes in the marine strontium sr output flux which is primarily controlled by the burial of calcium carbonate caco3 at the ocean floor the sr budget of the phanerozoic ocean including the associated changes in the amount of caco3 burial is therefore only poorly constrained here we present the first stable isotope record of sr for phanerozoic skeletal carbonates and by inference for phanerozoic seawater 88 86srsw which we find to be sensitive to imbalances in the sr input and output fluxes this 88 86srsw record varies from 0 25 to 0 60 vs srm987 with a mean of 0 37 the fractionation factor between modern seawater and skeletal calcite 88 86srcc sw based on the analysis of 13 modern brachiopods mean 88 86sr of 0 176 0 016 2 standard deviations s d is 0 21 and was found to be independent of species water temperature and habitat location overall the phanerozoic 88 86srsw record is positively correlated with the ca isotope record 44 40casw but not with the radiogenic sr isotope record 87sr 86sr sw a new numerical modeling approach which considers both 88 86srsw and 87sr 86sr sw yields improved estimates for phanerozoic fluxes and concentrations for seawater sr the oceanic net carbonate flux of sr f sr carb varied between an output of 4 7x1010mol myr and an input of 2 3x1010mol myr with a mean of 1 6x1010mol myr on time scales in excess of 100myrs the f sr carb is proposed to have been controlled by the relative importance of calcium carbonate precipitates during the aragonite and calcite sea episodes on time scales less than 20myrs the f sr carb seems to be controlled by variable combinations of carbonate burial rate shelf carbonate weathering and recrystallization ocean acidification and ocean anoxia in particular the permian triassic transition is marked by a prominent positive 88 86srsw peak that reflects a significantly enhanced burial flux of sr and carbonate likely driven by bacterial sulfate reduction bsr and the related alkalinity production in deeper anoxic waters we also argue that the residence time of sr in the phanerozoic ocean ranged from 1myrs to 20myrs

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

strontium isotope stratigraphy potential resolution and event correlation abstract a new generation 87sr 86sr isotope curve for the phanerozoic seawater based on a compilation of 3635 stratigraphically well defined and well preserved skeletal components results in a substantially narrower band with some discrepancies if compared to the curve of burke et al 1982 which is based mostly on whole rock samples the results obtained from low mg calcite shells foraminifers belemnites brachiopods and oysters are mostly superior to those from phosphatic skeletal components such as conodonts even if the latter are exceptionally well preserved cai 1 5 at this stage the phanerozoic data set based on fossils is patchy for the cambrian upper ordovician lower devonian and upper carboniferous triassic intervals the major practical constraint that precludes delineation of an unequivocal sr isotope curve for the phanerozoic seawater is the uncertainty in the assignment of absolute ages to the samples as a result the curve is in reality a band this is a reflection of the limitations of biostratigraphy and geochronology that are inherited by any derivative correlation and dating technique including isotope stratigraphy it is therefore unlikely that in the near future the sr isotope stratigraphy will surpass the resolution capability of biostratigraphy as a global correlation tool on the other hand if complemented by lithostratigraphy it is potentially a valuable tool for correlation of sequences on intrabasinal and regional scales taking into account the above limitations careful consideration must be given to assignment of higher order isotope peaks to specific events within a biozone and to the use of such events as a global correlation tool

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

temperatures and oxygen isotopic composition of phanerozoic oceans abstract the temperature of ancient oceans is an important constraint for understanding the climate history of our planet the classical oxygen isotope paleothermometry on fossil shells while very proficient when applied to the younger cenozoic portion of the geologic record is believed to yield only unreliable results for the phanerozoic deep time either because the empirically well documented secular trend to more negative 18 o values with increasing age was generated by post depositional recrystallization processes or if primary implies ecologically unpalatable hot early oceans here we present a compilation of 18 o measurements for 58 532 low mg calcite marine shells that cover almost the entire phanerozoic eon argue that the secular decline of about 6 is primary propose that it reflects the changing oxygen isotopic composition of sea water and define a new baseline trend for 18 o of paleo sea water the latter providing a new template for calculation of ambient habitat temperatures of fossil specimens the resulting pattern for fossil taxa foraminifera brachiopods belemnites and bivalves mimics their modern counterparts in temperature ranges and modes this conceptual framework enables application of actualistic concepts to ambient habitat temperatures of fossils and provides us with a long overdue tool for interpretation of deep time geologic history

a new model for atmospheric oxygen over phanerozoic time a mathematical model has been constructed that enables calculation of the level of atmospheric o2 over the past 570 my from rates of burial and weathering of organic carbon c and pyrite sulfur s burial rates as a function of time are calculated from an assumed constant worldwide clastic sedimentation rate and the relative abundance and c and s contents of the three rock types marine sandstones and shales coal basin sediments and other non marine clastics red beds arkoses by our model values of o2 versus time using a constant total sedimentation rate agree with those for variable sedimentation derived from present day rock abundances and estimates of erosional losses since deposition this agreement is the result of our reliance on the idea that any increase in total worldwide sediment burial with consequently faster burial of c and s and greater o2 production must be accompanied by a corresponding increase in erosion and increased exposure of c and s on the continents to o2 consumption via weathering it is the redistribution of sediment between the three different rock types and not total sedimentation rate that is important in o2 control to add stability to the system negative feedback against excessive o2 fluctuation was provided in the modeling by the geologically reasonable assignment of higher weathering rates to younger rocks resulting in rapid recycling of c and s we did not use direct o2 negative feedback on either weathering of c and s or burial of c because weathering rates are assumed to be limited by uplift and erosion and the burial rate of c limited by the rate of sediment deposition the latter assumption is the result of modern sediment studies which show that marine organic matter burial occurs mainly in oxygenated shallow water and is limited by the rate of supply of nutrients to the oceans by rivers results of the modeling indicate that atmospheric o2 probably has varied appreciably over phanerozoic time during the late carboniferous and permian periods o2 was higher than previously because of the rise of vascular land plants and the widespread burial of organic matter in vast coal swamps a large decrease in o2 during the late permian was due probably to the drying up of the coal swamps and deposition of a large proportion of total sediment in c and s free continental red beds sensitivity study shows that major parameters affecting results are the mean c concentration in coal basins and the relative sizes of the reservoirs of young rapidly recycled versus old rocks less sensitivity was found for changes over time in total land area undergoing weathering and the use of direct o2 negative feedback on marine carbon burial good agreement for rates of c burial calculated via our model and via independent models which are based on the use of stable carbon isotopes indicates that the dominant factor that has brought about changes in atmospheric o2 level and the isotopic composition of dissolved inorganic carbon in seawater over phanerozoic time is sedimentation and not weathering or higher temperature phenomena such as basalt seawater reaction

effects of quaternary sea level cycles on strontium in seawater abstract the effects of quaternary sea level changes on the sr budget of the ocean are investigated using coupled numerical models of the seawater sr and ca budgets glacial interglacial sea level cycles influence the sr concentration of seawater directly through the periodic exposure and weathering of aragonite on continental shelves and indirectly by modulating the location and extent of carbonate deposition in the ocean as sea level recedes brief pulses of sr are added to the ocean from recrystallization of shelf aragonite this flux at its maximum is nearly ten times larger than the combined riverine and hydrothermal influx the large shelf recrystallization fluxes during glacial maxima produce rapid increases in the sr ca ratio of seawater despite the long residence time of sr in the ocean variations in the ratio of aragonitic vs calcitic sedimentation also influence on the sr content of seawater because the sr partitioning coefficient is higher in aragonite however this effect is minor compared to shelf aragonite recrystallization based on a variety of sensitivity tests the amplitude of sr ca variations ranges from 1 to 3 and is maximized by constant rates of total carbonate deposition extensive aragonite recrystallization and carbonate budgets which include dissolution of shelf carbonates such variation is sufficient to produce up to 1 5 c errors in paleotemperatures calculated from coral sr ca ratios since the last glacial maximum

origin of the sudbury complex by meteoritic impact neodymium isotopic evidence samarium neodymium isotopic data on whole rocks and minerals of the sudbury complex in canada gave an igneous crystallization age of 1840 21 x 10 6 years the initial epsilon neodymium values for 15 whole rocks are similar to those for average upper continental crust falling on the crustal trend of neodymium isotopic evolution as defined by shales the rare earth element concentration patterns of sudbury rocks are also similar to upper crustal averages these data suggest that the sudbury complex formed from melts generated in the upper crust and are consistent with a meteoritic impact

explaining the phanerozoic ca isotope history of seawater a new geochemical budget for the modern marine carbonate sink helps to explain the major features of the phanerozoic ca isotope record a large compilation of ca isotope ratios for modern carbonates incorporating more than 50 new measurements represents the quantitatively important components of the system with this data set distinct ca isotope ratios are identified for different types of marine carbonate the balance of which has changed over time with shifts between calcite and aragonite seas and with the development of pelagic calcification during the mesozoic it is suggested that large scale changes in the ca isotope ratio of seawater as exemplified by that in the carboniferous were no longer possible after jurassic time because of the generation of a deep sea calcite sink expressed by deposition of foraminiferal coccolith ooze across the world ocean this work demonstrates the close connection between isotopic cycling carbonate sedimentation seawater chemistry and evolutionary trends

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

strontium isotope stratigraphy of the middle devonian brachiopods and conodonts a set of 145 strontium isotope ratios based on skeletal components of emsian to frasnian age reveals a detailed structure of the seawater 87sr 86sr curve that can ultimately serve as a tool for high resolution isotope stratigraphy in the devonian brachiopod and conodont samples were collected in the eifel region of germany the area around the global stratotype for the middle devonian with an apparent average temporal resolution in the 105 y range preservation of the brachiopod shell material has been assessed by optical microscopy sem and cathodoluminescence and only the better preserved internal secondary layer of the shell has been utilized for strontium isotope measurements the 87sr 86sr curve shows a short decline from 0 7081 to 0 7078 through the late emsian followed by short term fluctuations with an amplitude of up to 10 4 around a mean of 0 7078 during the eifelian and givetian and a rise from late givetian into the late devonian the above high frequency oscillations and spikes are likely a reflection of condensed sedimentary records due to erosional and nondepositional events but a direct confirmation for such a scenario can be claimed only for the latest eifelian otomari event insufficient stratigraphic resolution precludes testing for the other events and isotopic spikes conodont skeletal elements even if well preserved at cai 2 5 yielded results that are mostly enriched in radiogenic 87sr if compared to coeval brachiopods although this enrichment is usually within the 10 5 range conodonts despite their superior stratigraphic resolution should be utilized only as a material of second choice in cases where brachiopods are rare or absent

diagenesis and sr isotopic evolution of seawater using data from dsdp 590b and 575 new sr isotopic and concentration analyses of bulk carbonate and porewaters from a carbonate rich miocene section sampled at dsdp site 575 are reported and used along with our earlier data from a section of similar age at dsdp site 590b in a numerical model to determine for each site the rate of sr exchange during diagenesis and the degree to which this amount of exchange has shifted the87sr86sr of the bulk carbonate from the ratio each increment of sediment had when first deposited despite the fact that the two sites have very different water depth 4536 m at 575 vs 1299 m at 590b different sedimentation rate 10 m my at 575 vs 40 m my at 590b and significantly different porewater sr2 gradients we find that the rate of sr exchange as a function of sediment age is almost indistinguishable between the two sites the rate of sr exchange determined at the two sites is such that the resulting shift in bulk carbonate87sr86sr due to diagenesis is small compared to the total range of87sr86sr values measured but large compared to the analytical uncertainty of the individual isotopic ratio measurements by taking this shift into account we reconstruct the original87sr86sr of each increment of carbonate sampled which when plotted as a function of age becomes our best estimate of the sr isotopic evolution of seawater because sr is very well mixed in the ocean at any given time there is a single worldwide value of seawater87sr86sr therefore if we are quantitatively accounting for the effect sr exchange we should find the same seawater evolution curve regardless of what dsdp site is used when we compare the observed bulk carbonate87sr86sr vs age at the two sites they are seen to differ by amounts that are sometimes large compared to the analytical uncertainties of the measurements however when these data are corrected for the post depositional sr isotopic shifts predicted by our diagenetic model we find almost perfect agreement this agreement suggests that we have made a realistic determination of the rate of sr exchange and its consequences in terms of shifting the87sr86sr of the bulk carbonate and more importantly that sr isotopes can be used to correlate marine sediments with an accuracy comparable to the very small analytical uncertainties of modern isotopic measurements

the timing and pattern of biotic recovery following the end permian mass extinction the aftermath of the great end permian period mass extinction 252 myr ago shows how life can recover from the loss of 90 species globally the crisis was triggered by a number of physical environmental shocks global warming acid rain ocean acidification and ocean anoxia and some of these were repeated over the next 5 6 myr ammonoids and some other groups diversified rapidly within 1 3 myr but extinctions continued through the early triassic period triassic ecosystems were rebuilt stepwise from low to high trophic levels through the early to middle triassic and a stable complex ecosystem did not re emerge until the beginning of the middle triassic 8 9 myr after the crisis a positive aspect of the recovery was the emergence of entirely new groups such as marine reptiles and decapod crustaceans as well as new tetrapods on land including eventually dinosaurs the stepwise recovery of life in the triassic could have been delayed either by biotic drivers complex multispecies interactions or physical perturbations or a combination of both this is an example of the wider debate about the relative roles of intrinsic and extrinsic drivers of large scale evolution from a much more devastated planet and biota than the others with only some 10 of species surviving the epme was much harsher than the other mass extinctions during which global species diversity reduced to only about 50 of the pre extinction total 1 2 24 26 this means that the triassic recovery has two profound implications first it may show qualitative as well as quantitative differences from the other post extinction recoveries and second it can act as an exemplar of what to expect at its most extreme when global biodiversity is pushed to the brink there are obvious implications for current concerns about biodiversity loss and recovery resulting from human impacts 27 28 in the past ten years attention has focused on the sedimentary successions in south china these are enormously laterally extensive with some formations extending more than 2 000 km from the zhejiang to yunnan provinces the huge exposures length of the sections and improving dating open up the opportunity to explore physical environmental and biotic changes through the extinction and recovery times in varied marine habitats and compare these with patterns elsewhere in the world fig 1 a fine scale forensic analysis of this extraordinary time in earth s history now becomes possible the end permian mass extinction the epme killed 80 96 of marine animal species and 70 of terrestrial vertebrate species

calcareous nannofossils and mesozoic oceanic anoxic events abstract twenty five years ago mesozoic oceanic anoxic events oaes were documented and formalised as intervals of widespread to global deposition of organic matter the toarcian early aptian oae1a and latest cenomanian oae2 oaes are truly global in nature commonly carbonate poor and typically represented by organic carbon rich black shales in some areas these oaes are also characterised by abundant radiolarian sands and silts they are associated with negative and positive excursions in the 87sr 86sr record in addition to large global carbon isotope anomalies in carbonate and or organic matter caused by a major perturbation of the global carbon budget increased rates of volcanism during the formation of the ontong java and manihiki and caribbean plates and the karoo ferrar traps are believed to have caused the geological responses associated with oae1a oae2 and the toarcian oae respectively excess volcanogenic co2 in the atmosphere most probably turned the climate into a greenhouse mode accelerating continental weathering and increasing nutrient content in oceanic surface waters via river run off higher fertility in the global ocean was also probably triggered directly by submarine igneous events that introduced enormous quantities of biolimiting metals within hydrothermal plumes because mesozoic oaes are often represented by carbonate poor sediments quantitative studies of calcareous nannofossils have been applied to explore a the causes and effects of igneous tectonic events and climate changes relative to nannofloral increases and crises as well as b dissolution events and c diagenetic modifications characterization of calcareous nannofloras in oae intervals can improve our understanding of the marine ecosystem and biological processes such as photosynthesis biological pump and biomineralisation carbonate pump that affect the organic and inorganic carbon cycle as well as adsorption of atmospheric co2 in the oceans types and rates of nannoplankton production and evolution are interpreted to trace the impact of major palaeoceanographic and palaeoclimatic events in selected sections it has been documented that calcareous nannofloras rapidly reacted to new conditions of fertility and higher pco2 by drastically reducing calcification as in the modern oceans during oaes the increase of nutrients and atmospheric co2 induced higher abundances of nannoplankton producing small placoliths and inhibited the deep photic zone nannoconids and schizosphaerellids similarly to the nannoconid crisis preceding deposition of the early aptian oae1a black shales a schizosphaerellid crisis is detected prior to the toarcian oae both oaes are further characterised by a rapid nannofloral speciation beginning approximately 1 5 myr before the oae but without extinctions global changes during the latest cenomanian oae 2 exerted different influences on calcareous nannoplankton that experienced a turnover due to most extreme environmental conditions this event in fact was a time of extinctions followed by originations within calcareous nannofossils precise timing of the events before during and after oae1a oae2 and the toarcian oae indicates that they were intervals of enhanced oceanic productivity and that anoxia dysoxia post dated biotic changes

radiogenic and stable sr isotope ratios 87 sr 86 sr δ 88 86 sr as tracers of riverine cation sources and biogeochemical cycling in the milford sound region of fiordland new zealand this study reports radiogenic sr isotope ratios 87sr 86sr stable sr isotope ratios 88 86sr and major ion concentrations for river rock sediment soil and plant samples collected from the cleddau and hollyford catchments in the milford sound region of fiordland new zealand the catchments primarily drain gabbro but some tributaries access limestone and volcanogenic sediments the goal of the study was to understand controls on riverine 88 86sr values in a landscape with multiple factors that may influence chemical weathering including dense vegetation high rainfall and abundant freshly eroded holocene fluvio glacial and landslide debris rivers draining gabbro have higher 88 86sr values than bedrock by as much as 0 14 and the 88 86sr values strongly correlate with molar ca sr ratios r2 0 69 leaching of rocks and sediment reveals no evidence for the preferential dissolution of minerals having high 88 86sr values and ca sr ratios in stream sr isotope fractionation seems unlikely because comparison against 87sr 86sr and ca sr ratios demonstrates that riverine 88 86sr values conservatively trace water mass mixing the riverine data are best explained by the input of soil water which is distinct from potential bedrock end members i e silicates and carbonates based on 88 86sr but indistinguishable in terms of ca sr and 87sr 86sr while strontium isotope fractionation during secondary mineral formation and pedogenesis is possible clay mineral formation is minor and most soils are poorly developed instead soil water 88 86sr values more likely reflect plant uptake plant samples yielded a wide range of 88 86sr values but on average they are lower than those for bedrock consistent with the expectation that plants preferentially incorporate lighter sr isotopes mass balance constraints together with 87sr 86sr ratios indicate that soil water 88 86sr values are 0 30 higher than bedrock 88 86sr values and mixing calculations show that the plant fractionated soil water pool contributes 27 of the riverine sr for tributaries accessing limestone and volcanogenic sediments ca sr and 87sr 86sr ratios appear consistent with two component mixing between silicate and carbonate weathering but 88 86sr values reveal a third contribution from soil water inputs similar to gabbro catchments the results of this study suggest that sr isotopes behave conservatively during water mass mixing and stream transport but non conservatively in soil where plant uptake can elevate soil water 88 86sr values relative to bedrock plant uptake or related biogeochemical processes such as ion exchange on organic matter surfaces also appear to modify soil water ca sr ratios many studies use 87sr 86sr and ca sr ratios to apportion riverine solutes between silicate and carbonate weathering but ca sr ratios may be non conservative in densely vegetated areas the stable sr isotope tracer shows promise for resolving riverine cation sources as well as effects from biological cycling

an oscillating trend in phanerozoic non skeletal carbonate mineralogy textural and compositional data on ancient ooids and cements suggest the existence of an oscillating phanerozoic temporal trend in non skeletal carbonate mineralogy the trend shows good correlation with eustatic climatic oscillations proposed by others the most likely mechanism appears to be plate tectonically influenced oscillations in pco2 the vapour pressure of co2 rather than change in oceanic mg ca ratio

evidence for stable sr isotope fractionation by silicate weathering in a small sedimentary watershed in southwestern taiwan abstract radiogenic sr isotopes 87 sr 86 sr are robust for provenance identification in hydrology affected mainly by the age of background lithologies and the degree of chemical weathering however there is limited knowledge concerning the fractionation mechanism of stable sr isotopes 88 sr 86 sr in rivers in this study river water was collected on a weekly to monthly basis throughout dry and wet seasons furthermore to study the variations of radiogenic and stable sr isotopes during intense weathering a major flooding event 2000 mm precipitation in three days typhoon morakot water was captured within a small drainage catchment system 161 km 2 along the hou ku river in southwestern taiwan for a better constraint on the end member compositions bedload sediments suspended particles and several host rocks were sampled for a systematic investigation the carbonate and silicate phases of these solids were chemically separated dissolved major elements indicate that the watersheds were predominated by silicate weathering stable sr isotopes show no significant variation 88 sr 0 24 0 31 temporally and spatially with an average of 0 28 additionally all solids showed lower 88 sr values than the river water while the host rocks had higher 88 sr values 88 sr 0 20 0 26 than the residual weathering products 88 sr 0 08 0 22 indicating preferential leaching of heavy sr into the hydrosphere and leaving light sr in the residual solids results of laboratory acid leaching experiments reveal that dissolution of high 88 sr value minerals occurred at an early stage of weathering the variation of weathering intensity does not alter stable sr isotopes in silicate weathering dominated river water which contains higher stable sr isotopes than the associated sediments the silicatic sedimentary rocks preferentially released higher stable sr isotopes into the hydrosphere during chemical weathering thus leaving lower stable sr isotopes in the residual solids

strontium isotopic variations in jurassic and cretaceous seawater a high resolution seawater strontium isotope curve has been generated through the analysis of well dated and well preserved belemnites and oysters from the middle and upper jurassic and the lower cretaceous of great britain analysis of fe and mn concentrations in these fossils has yielded criteria for eliminating samples that are diagenetically altered the strontium isotope curve remains relatively flat through the aalenian and early bajocian rapidly descends through the late bajocian and bathonian and reaches a minimum in the callovian and oxfordian it then begins a rapid increase in the kimmeridgian and portlandian that continues through much of the early cretaceous the curve levels off in the barremian suddenly dips downwards in the aptian and recovers gradually through the albian the strontium isotopic variations are sufficiently large and the data are presented with sufficient stratigraphic detail to allow precise correlation to the classic ammonite zones and lithologic sections of great britain using the techniques of strontium isotope stratigraphy model results indicate that much of the variation in seawater 87sr86sr between 120 and 40 ma can be explained by changing the intensity of mid ocean ridge hydrothermal fluxes proportionally to estimated mid ocean ridge crustal generation rates it is also possible that the variations during the rest of the mesozoic and the permian are primarily reflections of changing hydrothermal inputs the model results have several important implications first they provide an example in which the variations in the strontium isotope curve are not necessarily driven by changes in fluvial inputs second they suggest that from at least the aptian through the eocene variations in continental weathering were minimal this heightens the importance of the rapid rise in seawater 87sr86sr beginning 40 ma as a significant transition to an extended period of increasing fluvial 87sr fluxes continuing to the present finally the results suggest that several documented short term excursions towards lower 87sr86sr in the latest triassic pliensbachian toarcian callovian oxfordian aptian albian and cenomanian turonian are interpretable as pulses of seafloor hydrothermal activity if so the strontium isotope record offers a means of constraining the timing duration and magnitude of known or proposed hydrothermal events in the geological record

calcium isotope constraints on the end permian mass extinction the end permian mass extinction horizon is marked by an abrupt shift in style of carbonate sedimentation and a negative excursion in the carbon isotope 13c composition of carbonate minerals several extinction scenarios consistent with these observations have been put forward secular variation in the calcium isotope 44 40ca composition of marine sediments provides a tool for distinguishing among these possibilities and thereby constraining the causes of mass extinction here we report 44 40ca across the permian triassic boundary from marine limestone in south china the 44 40ca exhibits a transient negative excursion of 0 3 over a few hundred thousand years or less which we interpret to reflect a change in the global 44 40ca composition of seawater co2 driven ocean acidification best explains the coincidence of the 44 40ca excursion with negative excursions in the 13c of carbonates and organic matter and the preferential extinction of heavily calcified marine animals calcium isotope constraints on carbon cycle calculations suggest that the average 13c of co2 released was heavier than 28 and more likely near 15 these values indicate a source containing substantial amounts of mantle or carbonate derived carbon collectively the results point toward siberian trap volcanism as the trigger of mass extinction

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

recent calcium carbonate dissolution in the barents sea paleoceanographic applications abstract studies of benthic foraminifera in surface sediments of the arctic epicontinental barents sea show several indications of calcium carbonate dissolution low values of calcium carbonate correspond to low ratios of calcareous agglutinating foraminifera planktic benthic foraminifera high ratios of living dead foraminifera corroded calcareous foraminifera and high numbers of exposed organic linings of foraminifera dissolution increases eastwards and northwards in the study area we suggest that the dissolution is caused by the presence of dense cold saline and co 2 rich bottom water which is linked to sea ice production and the position of the oceanic polar front we also think calcium carbonate dissolution in this area indicates a sink for atmospheric co 2

conodont apatite δ88 86sr and δ44 40ca compositions and implications for the evolution of palaeozoic to early mesozoic seawater abstract we present high precision tims double spike stable isotope measurements of both 44 40 ca and 88 86 sr together with radiogenic 87 sr 86 sr ratios determined from conodont apatite these data represent five intervals ranging from the early ordovician to late triassic the conodont 44 40 ca values relative to nist 915a range from 0 47 to 0 15 with an apparent shift to more positive values between the early silurian and late devonian early carboniferous similar to the brachiopod based marine 44 40 ca record farkas et al 2007a we calculated a 44 40 ca seawater bio apatite fractionation factor of about 1 9 which allowed us to reconstruct a palaeo seawater 44 40 ca record from bio apatites despite a slightly positive offset of about 0 2 to 0 5 the 44 40 ca record obtained from bio apatites is consistent with the previously reported 44 40 ca seawater record inferred from carbonates we find that unlike the carbonate 44 40 ca records the 88 86 sr measurements from conodont apatite show unexpectedly large variations up to 1 with ratios ranging from 0 6 to 0 3 these reconnaissance data reveal a reasonable correlation between 88 86 sr and radiogenic 87 sr 86 sr r 2 0 60 n 13 p 0 002 suggesting that the controls from differential weathering regimes and or continental crustal compositions buffered ancient seawater compositions

stable isotope variations in modern articulate brachiopods abstract carbon and oxygen isotopic analyses were performed on several species of holocene articulate brachiopods from various locations in the caribbean sea and in the atlantic and pacific oceans from salinities ranging between 30 and 38 pmil and over a temperature range from 4 to 28 c 39 to 82 f the dgr18o of articulate brachiopods are systematically related to the dgr18o and temperatures of the ambient waters lowenstam in 1961 concluded that articulate brachiopods secrete calcium carbonate low magnesium calcite in isotopic equilibrium with the surrounding waters the data compiled in this study along with that of lowenstam closely approximate the equilibrium calcite water end page 500 line deviation from apparent equilibrium was most evident for samples from a few cold water sites intraspecific isotopic variations in several warmer water assemblages were up to 2 pmil and isotopic variation within individual specimens as high as 1 5 pmil were noted articulate brachiopods were not separable at any taxonomic level on the basis of ranges in isotopic values the two extant orders of brachiopods the terebratulida and the rhynchonellida as well as the suborder thecideidina had essentially equivalent isotopic ranges at any given locality thus there is no evidence for significant taxonomic control of oxygen isotope fractionation among articulate brachiopods no correlation appears to exist between dgr18o and dgr13c values our results suggest strongly that isotopic data from small populations or communities of well preserved articulate brachiopods can be used in paleogeographic and paleo oceanographic reconstructions end of article last page 501

radiogenic and stable strontium isotopes in provenance studies a review and first results on archaeological wood from shipwrecks abstract different approaches are used to study wood provenance but most of them are based on tracers in wood that are generally controlled by climatic factors the strontium isotopic ratio 87 sr 86 sr in trees and soils is related to the signature of the local bedrock despite being used in diverse archaeological studies sr isotopes have rarely been used to trace the provenance of archaeological wood and especially wood from shipwrecks in addition recent analytical advances have allowed the detection of mass dependent fractionation of sr isotopes during biogeochemical processes as reflected in the variation of 88 86 sr values between different environmental materials the 88 86 sr values could be used in conjunction with the 87 sr 86 sr isotope ratio to improve constraints on the sources of sr in the archaeological materials being studied this paper discusses the potential and limitations of using both of these sr isotope ratios to trace the provenance of wood from shipwrecks we review the 87 sr 86 sr and 88 86 sr variations in rocks waters soils plants and other living organisms and discuss how to determine the local sr isotopic signature of potential sites we also compile a list of known wood post mortem modifications in seawater possible implications in terms of the modification of the original sr isotope ratios of wood during storage in seawater are illustrated through preliminary observations this paper points out some limitations and perspectives for using sr isotopes in provenancing wood from shipwrecks and suggests future research to test and apply this approach for tracing the origin of archaeological wood

correlation and comparison of seawater δ34ssulfate records at the permian triassic transition abstract correlation of carbonate associated sulfate cas 34 s analysed permian triassic p tr sections via conodont biostratigraphy and sequence stratigraphy shows distinct phases in the oceanic 34 s sulfate evolution during the period 1 million years m y either side of the p tr boundary a 34 s sulfate rise in the changhsingian prior to the end permian mass extinction is followed by a period of about 350 000 years of erratic and substantial 34 s sulfate movements range 1 to 28 the mass extinction occurring in the middle of this period the sharp swings in this phase indicate severe changes in the oceanic sulfur geochemistry and perhaps stages of ocean inhomogeneity low 34 s sulfate values coincide with the mass extinction horizon suggesting the extinction is related to an input of relatively 32 s enriched sulfur into the oceanic sulfate reservoir the source of this sulfur most likely being h 2 s from euxinic waters after the erratic 34 s sulfate phase there is a stabilisation of 34 s sulfate values 17 until the later griesbachian however there is a possibility of discrepant panthalassan and tethyan data sets during the early to mid griesbachian but this requires further work for confirmation 34 s sulfate values are erratic in the late griesbachian to early dienerian suggesting further perturbation of the sulfur cycle the poorly age constrained smithian record shows a wide range of 34 s sulfate values probably indicating swings during that time also the 34 s sulfate movements from the changhsingian to smithian indicate the permian triassic transition is a time of intense changes in the sulfur fluxes to and from the oceans and perhaps stages of ocean inhomogeneity

isotopic evidence for an anomalously low oceanic sulfate concentration following end permian mass extinction abstract the cataclysmic end permian mass extinction was immediately followed by a global expansion of microbial ecosystems as demonstrated by widespread microbialite sequences disaster facies in shallow water settings here we present high resolution carbonate carbon 13 c carb and carbonate associated sulfate sulfur isotope 34 s cas records from the microbialite in the cili permian triassic p tr section in south china a stepwise decline in 13 c carb begins in the underlying skeletal limestone predating the main oceanic mass extinction and the first appearance of microbialite and reaches its nadir in the upper part of the microbialite layer the corresponding 34 s cas in the range of 17 4 to 27 4 is relatively stable in the underlying skeletal limestone and increases gradually from 2 m below the microbialite rising to a peak at the base of the microbialite two episodes of positive and negative shifts occurred within the microbialite layer and exhibit a remarkable co variance of sulfur and carbon isotope composition the large amplitude of the variation in 34 s cas as high as 7 per 100 kiloyears suggests a small oceanic sulfate reservoir size at this time furthermore the 13 c carb and 34 s cas records co vary without phase lag throughout the microbialite interval implying a marine driven c cycle in an anoxic ocean with anomalously low oceanic sulfate concentrations on the basis of a non steady state box model we argue that the oceanic sulfate concentration may have fallen to less than 15 perhaps as low as 3 of that in the modern oceans low oceanic sulfate concentration likely was the consequence of evaporite deposition and widespread anoxic sulfidic conditions prior to the main mass extinction by promoting methanogenesis and a build up of atmospheric ch 4 and co 2 low oceanic sulfate may have intensified global warming exacerbating the inimical environmental conditions of the latest permian

a chronology of paleozoic sea level changes sea levels have been determined for most of the paleozoic era 542 to 251 million years ago but an integrated history of sea levels has remained unrealized we reconstructed a history of sea level fluctuations for the entire paleozoic by using stratigraphic sections from pericratonic and cratonic basins evaluation of the timing and amplitude of individual sea level events reveals that the magnitude of change is the most problematic to estimate accurately the long term sea level shows a gradual rise through the cambrian reaching a zenith in the late ordovician then a short lived but prominent withdrawal in response to hirnantian glaciation subsequent but decreasingly substantial eustatic highs occurred in the mid silurian near the middle late devonian boundary and in the latest carboniferous eustatic lows are recorded in the early devonian near the mississippian pennsylvanian boundary and in the late permian one hundred and seventy two eustatic events are documented for the paleozoic varying in magnitude from a few tens of meters to 125 meters

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

oxygen and carbon isotopic composition of silurian brachiopods implications for coeval seawater and glaciations we collected 236 calcitic brachiopod shells covering the entire silurian period 30 m y at high temporal resolution from stratotype sections from anticosti island canada wales united kingdom the oslo region norway gotland sweden and podolia ukraine estonia latvia and lithuania data from petrography scanning electron microscopy cathodoluminescence isotopes and trace elements all confirmed that there was excellent preservation in most shells thus arguing for retention of primary isotope signals exceptions were samples from the oslo region the d18o and d13c values for the well preserved samples range from 2 to 6 5 and from 1 to 7 5 peedee belemnite respectively in terms of temporal trends oxygen and carbon isotopes vary in parallel with a slight decrease with declining age of 1 through silurian time with superimposed short term oscillations that are negatively correlated with sea level changes three successive positive d18o shifts in early aeronian latest aeronian and early wenlock time correlate with sea level lowstands and with glacial diamictite deposits in the amazon basin and in africa the high d18o and d13c values are attributed to cold episodes with low sea levels and low values to warm episodes with high sea levels during warm silurian episodes the d18o value of seawater is suggested to have been about 3 5 standard mean ocean water smow and the global tropical temperatures of about 20 30 c similar to the present day values in summer during glacial episodes seawater is proposed to have had a d18o value of 2 5 smow and temperature of about 14 23 c comparable to tropical temperatures proposed for the last glacial episode 14 to 28 c three positive d13c peaks in early and late wenlock and late ludlow time likely of regional to global significance appear to coincide with sea level lowstands but we are as yet unable to propose a convincing causative geologic scenario that would explain their origin

reconstructing first order changes in sea level during the phanerozoic and neoproterozoic using strontium isotopes the eustatic sea level curves published in the seventies and eighties have supported scientific advances in the earth sciences and the emergence of sequence stratigraphy as an important hydrocarbon exploration tool however validity of reconstructions of eustatic sea level based on sequence stratigraphic correlations has remained controversial proposed sea level curves differ because of site to site changes in local tectonics depositional rates and long wavelength dynamic topography resulting from mantle convection in particular the overall amplitude of global phanerozoic long term sea level is poorly constrained and has been estimated to vary between 400 m above present day sea level to 50 m below present day sea level to improve estimates of past sea level we explore an alternative methodology to estimate global sea level change we utilise the phanerozoic neoproterozoic 87sr 86sr record which at first order represents the mix of inputs from continental weathering and from mantle input by volcanism by compensating for weathering with estimates of runoff from a 3d climate model geoclimtec a corrected 87sr 86sr record can be obtained that solely reflects the contribution of strontium from mantle sources at first order the flux of strontium from the mantle through time is due to increases and decreases in the production of oceanic crust through time therefore the changing levels of mantle derived strontium can be used as a proxy for the production of oceanic lithosphere by applying linear oceanic plate age distributions we compute sea level and continental flooded area curves we find that our curves are generally within the range of previous curves built on classical approaches a phanerozoic first order cyclicity of 250 myr is observed that may extend into the neoproterozoic the low frequency i e on the order of 10 to 100 my sea level curve that we propose while open for improvement may be used as baseline for refined sequence stratigraphic studies at a global and basin scale

a simple model for the caco3 saturation state of the ocean the strangelove the neritan and the cretan ocean 1 a simple model of the caco3 saturation state of the ocean is presented it can be solved analytically and is intended to identify the fundamental controls on ocean carbonate ion concentration it should also attract researchers unfamiliar with complex biogeochemical models despite its limitations the model calculated caco3 saturation state of today s ocean agrees well with observations in general the model reveals three distinctly different modes of operation the strangelove ocean of high supersaturation which is dominated by inorganic caco3 precipitation 2 the neritan ocean of indefinite saturation dominated by biogenic shallow water caco3 precipitation and 3 the cretan ocean of low saturation dominated by biogenic pelagic caco3 precipitation in the latter mode the deep ocean co32 is remarkably stable provided that the biogenic production of caco3 exceeds the riverine flux of ca2 and co32 this explains the overall constancy of the saturation state of the ocean documented over the last 100 ma the model is then used to address diverse questions one important result is that the recovery of the oceanic carbonate chemistry from fossil fuel neutralization in the future will be accelerated due to expected reduced biogenic calcification

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

geobiology of microbial carbonates metazoan and seawater saturation state influences on secular trends during the phanerozoic abstract microbial carbonates are long ranging essentially bacterial aquatic sediments their calcification is dependent on ambient water chemistry and their growth is influenced by competition with other organisms such as metazoans in this paper these relationships are examined by comparing the geological record of microbial carbonates with metazoan history and secular variations in caco3 saturation state of seawater marine abundance data show that microbial carbonates episodically declined during the phanerozoic eon past 545 myr from a peak 500 myr ago this abundance trend is generally inverse to that of marine metazoan taxonomic diversity supporting the view that metazoan competition has progressively limited the formation of microbial carbonates lack of empirical values concerning variables such as seawater ionic composition atmospheric partial pressure of co2 and ph currently restricts calculation of caco3 saturation state for the phanerozoic as a whole to the use of modeled values these data together with palaeotemperature data from oxygen isotope analyses allow calculation of seawater caco3 saturation trends microbial carbonate abundance shows broad positive correspondence with calculated seawater saturation state for caco3 minerals during the interval 150 545 myr ago consistent with the likelihood that seawater chemistry has influenced the calcification and therefore accretion and preservation of microbial carbonates these comparisons suggest that both metazoan influence and seawater saturation state have combined to determine the broad pattern of marine microbial carbonate abundance throughout much of the phanerozoic in contrast for the major part of the precambrian it would seem reasonable to expect that seawater saturation state together with microbial evolution was the principal factor determining microbial carbonate development interrelationships such as these with feedbacks influencing organisms sediments and the environment are central to geobiology

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

sr isotope evolution of seawater the role of tectonics we use a high resolution seawater sr isotopic evolution curve for the last 100 m y in conjunction with modern riverine sr flux measurements and also geologic tectonic and geochronological data to make the case for a close relationship between seawater sr isotopic composition and the india asia continental collision using a simple seawater sr budget model we begin by showing that the sr flux associated with alteration of seafloor basalts is too small and does not have the right time evolution to account for much of the seawater sr isotopic curve of the last 100 m y the flux of dissolved sr carried by rivers originating in the himalaya tibet region on the other hand is presently a significant fraction of the global sr budget we calculate how this riverine flux would have had to change with time in order to match the observed seawater sr isotopic curve and find that the riverine flux remains relatively constant prior to the collision of india with asia but then increases very significantly after collision we note that the period of most rapid change in seawater sr isotopic ratio from 20 ma to 15 ma is also a period of exceptionally high erosion in parts of the himalayas and the tibetan plateau as further evidence that sr derived from the collision of india with asia plays a major role in the sr isotopic evolution of seawater we show that the total amount erosion of the himalaya tibetan plateau since collision which we calculate separately represents a total amount of sr that is very nearly the same as the cumulative amount required by the sr isotopic change of seawater since collision the relationship between erosion and riverine sr flux allows us to use the sr isotopic evolution of seawater to reconstruct a history of erosion since collision and we find that the erosion rate accelerates with time since collision with the present having the largest rate when we apply the sr budget model to the entire phanerozoic using a new compilation of deformed continental area versus time we find that we can account for the large scale structure of the seawater sr isotopic curve but fail to reproduce several local maxima and minima especially in the period 100 300 ma the present high s7sr s6sr of seawater and similar highs in the devonian and cambrian do correlate with extensive deformation on the continents

a sulfur isotope event at the end of the permian abstract a hypothesis of light sulfur injection to the ocean atmosphere system at the end of the permian was presented by kaiho et al kaiho k kajiwara y nakano t miura y kawahata h tazaki k ueshima m chen z q shi g r 2001 end permian catastrophe by a bolide impact evidence of a gigantic release of sulfur from the mantle geology 29 815 818 based on a negative shift of 34 s 32 s ratio of carbonate associated sulfate in south china this hypothesis was discussed in some papers with additional data in other areas however the cause and distribution of the negative shift has not been clarified here we show that a significant decrease in the 34 s 32 s ratio of carbonate associated sulfate occurred simultaneously in south china and hungary at the end of the permian coincident with the end permian mass extinction the cause of the abrupt negative shift of 34 s 32 s in these two distant sites is the injection of light sulfur to the surface ocean from the deep ocean rich in h 2 s or deposits rich in sulfide or the mantle this sulfur isotope event was likely caused by either an abrupt warming a bolide impact to the ocean mantle plume induced volcanism or a harmonizing of these possible direct causes are 1 massive release of h 2 s gas from the euxinic surface and intermediate waters due to abrupt warming by volcanic co 2 or impact shock wave in the ocean 2 a huge volcanism penetrated sediments or ore rich in sulfide 3 an extraterrestrial impact to sulfide rich sediments or ore deposit and 4 release of mantle origin sulfur by an impact of 70 km asteroid to the ocean these are four possible causes for a mass extinction there is also a possibility of a local oceanic event only in the tethys

end permian mass extinction in the oceans an ancient analog for the twenty first century the greatest loss of biodiversity in the history of animal life occurred at the end of the permian period 252 million years ago this biotic catastrophe coincided with an interval of widespread ocean anoxia and the eruption of one of earth s largest continental flood basalt provinces the siberian traps volatile release from basaltic magma and sedimentary strata during emplacement of the siberian traps can account for most end permian paleontological and geochemical observations climate change and perhaps destruction of the ozone layer can explain extinctions on land whereas changes in ocean oxygen levels co2 ph and temperature can account for extinction selectivity across marine animals these emerging insights from geology geochemistry and paleobiology suggest that the end permian extinction may serve as an important ancient analog for twenty first century oceans

compilation and time series analysis of a marine carbonate δ18o δ13c 87sr 86sr and δ34s database through earth history abstract the sr s o and c isotope database of marine carbonates contains over 55 000 published isotope values of low mg calcite from diagenetically little altered phanerozoic fossil shells as well as samples of whole rocks and calcite cements of ordovician to archean age carbon and oxygen isotope data for the shell material are divided into habitat subsets high mid low latitude and deep sea and whole rock data are separated by mineralogy into calcite dolomite subsets trend correlation wavelet and spectral analyses on gaussian filtered isotope records were applied to detect and quantify similarities and patterns in temporal records with the following results 1 oxygen isotope trends from the high latitude and deep sea habitats are almost indistinguishable through the last 115 ma consistent with the existence of the oceanic conveyor belt throughout this interval 2 all oxygen isotope habitat records show a strong coherent 30 45 ma 38 ma cyclicity throughout the cretaceous and the cenozoic 3 up to 70 of the multi million year variability in the 18o record of the last 115 ma can be simulated by the following equation 18 o 0 64 sin 2 t 120 ma 0 9 x sin 2 t 38 3 ma 1 1 with x ranging from 0 4 0 6 for the low high latitude and deep sea habitats to 0 8 for the mid latitude realm 1 a 120 20 ma cycle occurs in the paleozoic and neoproterozoic 18o record consistent with paleoclimate variability as interpreted from sedimentological and faunal records 2 the offset of 13c values between deep water and high latitude vs surficial habitats at lower latitudes is consistent with the operation of a biological pump in the oceans since at least the cretaceous 3 sr and s isotope records exhibit a 60 70 ma cyclicity throughout the phanerozoic

accuracy and precision of 88sr 86sr and 87sr 86sr measurements by mc icpms compromised by high barium concentrations barite baso4 is a widely distributed mineral that incorporates strontium sr during formation mass dependent fractionation of sr isotopes occurs during abiotic precipitation of barite and formation of barite associated with biological processes e g bacterial sulfide oxidation sr isotopes in barite can provide provenance information as well as potentially reconstruct sample formation conditions e g saturation state temperature biotic versus abiotic incomplete separation of ba from sr has complicated measurements of sr isotopes by mc icpms in this study we tested the effects of ba in sr sample solutions and modified extraction chromatography of sr using eichrom sr spec eichrom technologies llc usa resin to enable rapid accurate and precise measurements of 88sr 86sr and 87sr 86sr ratios from ba rich matrices sr isotope ratios of sample solutions doped with ba were statistically indistinguishable from ba free sample solutions below 1 ppm ba deviations in both 87sr 86sr and 88 86sr occurred above 1 ppm ba an updated extraction chromatography method tested with barite and ba doped seawater produces sr sample solutions containing 10 100 ppb levels of ba the practice of zr spiking for external mass discrimination correction of 88sr 86sr ratios was also evaluated and it was confirmed that variable zr levels do not have adverse effects on the accuracy and precision of 87sr 86sr ratios in the zr concentration range required to produce accurate 88 86sr values

δ13c and δ18o values of triassic brachiopods and carbonate rocks as proxies for coeval seawater and palaeotemperature abstract a dataset of 160 isotope 13c and 18o values from anisian ladinian carnian and rhaetian articulate brachiopod shells complemented by 158 carbon and oxygen isotope values from whole rock carbonates define the first continuous stable isotope baseline trends for the triassic seawater the carbon isotope data suggest the existence of several short term high amplitude excursions in the early triassic followed by a predominance of values around 0 5 1 during the middle triassic a rise to 3 5 during the carnian plateau at this level during the late carnian to early norian and a 1 5 decline in the middle norian to values around 2 during the late norian rhaetian interval the causation scenarios for these rapid oscillations are at present equivocal but may in part reflect a biological instability of the carbon cycle following the recovery from the end permian extinction event and or an input of mantle derived co2 from enhanced volcanic activity the 18o values from well preserved brachiopods from the tethyan realm range from 3 9 to 0 6 v pdb these values require open marine triassic seawater 18o values close to 0 v smow for the calculated temperatures to be within the range of tolerance of the coexisting reef building corals a 2 18o increase within the uppermost cordevolian and early julian suggests either a distinct temperature decline in the southern alps during that time interval an increase in seawater salinity or their combination oxygen isotope values for the muschelkalk brachiopods range between 6 2 and 2 0 and likely reflect a strong influx of meteoric waters into the germanic basin that shifted the oxygen isotopes to more negative values

enrichment of 88 sr in continental waters due to calcium carbonate precipitation abstract 88 86sr data published over the last few years suggest that continental waters are enriched with 88sr as compared to the rocks in their drainage basins in an attempt to understand this phenomenon this study established the fractionation in the 88sr 86sr ratio during precipitation of continental carbonates i e carbonates precipitated on land from surface pedogenic or ground waters and evaluated the contribution of this process to the 88sr enrichment in rivers for this stable and radiogenic sr isotopes 88sr 87sr and 86sr were measured in calcite samples and their precipitating waters collected in various continental environments such as soil cave streams and groundwater the results indicate that continental carbonates are 88sr depleted relative to their precipitating waters placing them as one of the most 88sr depleted reservoirs on earth the average difference in 88 86sr values between waters and solid caco3 tufas or speleothems that they precipitate is carb water 0 218 0 014 1sd an even larger fractionation e carb water 0 285 0 02 was measured in groundwater with particularly high carbonate alkalinity and high carbonate precipitation rate that depleted 65 of the sr in the groundwater resulting in substantial 88sr enrichment in the residual dissolved sr sr 88 86 0 656 results also suggest that pedogenic carbonate precipitation in soil profile removes 50 85 of the sr from the recharging soil water thereby increasing the 88 86sr value of the soil water from 0 18 to 0 3 0 6 similar 88sr enrichment was observed in drip water from a karst cave a maximum removal flux of sr into continental carbonates of about 20 gmol sr y 1 is required to yield the reported 88sr enrichment in global rivers sr 88 86 0 32 relative to their rock sources when using the fractionation factor derived in this study carb water 0 218 and the published 88 86sr composition of marine carbonates of 0 16 this surprisingly large flux requires that 40 of the originally weathered sr should co precipitate with continental carbonates this calculation may suggest that caco3 precipitation is a significant mechanism in the continental sr cycle it is possible however that other mechanisms such as sr uptake by plants or incongruent weathering of silicates could also contribute to the riverine 88sr enrichment alternatively the average 88 86sr value of marine carbonate rock sections undergoing weathering is higher than suggested in current literature it is concluded that additional 88 86sr data on marine carbonate rock sections should be collected to resolve the enigma of the high value of riverine 88 86sr

the evidence and implications of polar ice during the mesozoic abstract the mesozoic perhaps representing the longest period of warmth during phanerozoic earth history contains in general sparse and frequently equivocal evidence for polar ice although this time is undoubtedly punctuated by oscillations in climate whether sufficient to lead to polar cooling and the formation of polar ice an inviting mechanism to account for faunal and floral distribution patterns and large scale sea level change has been widely debated mesozoic evidence for glacial conditions includes abraded rock surfaces generally unsorted stone rich beds and the presence of dropstones rafted by ice within a finer grained host sediment faunal and floral evidence has also been utilised to determine the presence or absence of cold or sub freezing polar conditions together with more indirect evidence for glacial conditions derived from general circulation model gcm simulations of climate the analysis of clay mineral distributions glendonite abundance and palaeontological and sedimentological evidence for globally synchronous sea level change the extent of possible glacial environments during the mesozoic has been established by plotting published reports of glacial sediments on palaeogeographic reconstructions the general clustering of evidence at high palaeolatitudes suggests that the extent of polar ice during the mesozoic is likely to have been approximately one third the size of the present day based on such evidence a number of episodes of cold or sub freezing polar climates during the bajocian bathonian tithonian volgian valanginian and aptian are recognised evidence exists possibly also for a cold episode during the early jurassic pliensbachian although poorly constrained owing to limited biostratigraphical control the longevity of these events may be represented by a cold snap within a stage although undoubtedly the possible smearing of ages may have had the effect of lengthening and hence promoting the importance of these proposed events the climate regime of the earth during these times may be hypothesised to be characterised by a relatively steep pole to equator temperature gradient where low latitude regions are as warm or warmer than today the evidence to support such reasoning includes sharp increases in the areal distribution of both glendonites and deposits with affinities to glacial tillites and dropstones for these times coincidental falls of sea level arid events and an increased bipolarity of faunas at these times imparts further confidence that these events were of a magnitude to effect the earth as a whole

a glacial hangover the marine geochemical budget of some solutes does not add up a test case shows that at least part of the reason may lie in the timescale over which continental weathering recovers from glaciations

seawater sr isotope variations through time a procedure for constructing a reference curve to date and correlate marine sedimentary rocks a new curve of seawater 87 sr 86 sr variation through the past 450 m y enables dating and correlation of marine sedimentary rocks with quantifiable uncertainties we discuss the method by which this curve was constructed strictly standardized 87 sr 86 sr ratios and biostrat igraphic data for 1300 87 sr 86 sr analyses of marine minerals were input into a data base objective criteria were used to assign each data point a reliability score these scores were used as initial weights in a robust nonparametric regression lowess to obtain a curve of seawater 87 sr 86 sr variation with rigorous 95 confidence intervals for prediction of age uncertainty precise dating and stratigraphic correlation are feasible for much of the phanerozoic the main problem with future sr isotope stratigraphy is likely to be sample quality we discuss guidelines for sample selection

high temperature strontium stable isotope behaviour in the early solar system and planetary bodies abstract this study presents comprehensive strontium stable isotope 88sr 86sr data measured by multiple collector inductively coupled plasma mass spectrometry mc icp ms for a suite of carbonaceous chondrites differentiated meteorites lunar martian and terrestrial samples carbonaceous chondrites comprise a mixture of refractory inclusions and chondrules that have light 88sr values between 0 35 to 0 05 and matrix material that possesses a heavy 88sr composition of 0 65 confirming the results of earlier studies consequently bulk carbonaceous chondrites are relatively heterogeneous in composition ranging from 0 12 to 0 35 most likely reflecting clast matrix variability the light 88sr compositions of the refractory inclusions are consistent with mass dependent fractionation of other refractory elements ca and eu and are most likely produced by non equilibrium fractionation undercooling in the nebula gas during condensation of hibonite from the solar nebula simon and depaolo 2010 stable calcium isotopic composition of meteorites and rocky planets earth planet sci lett 289 457 466 carbonaceous chondrites angrites and martian meteorites have indistinguishable compositions at the level of analytical uncertainty of this study however statistical analysis indicates that melts derived from the earth s mantle have heavier 88sr values than bulk carbonaceous chondrites and martian meteorites but compositions indistinguishable from eucrites 88sr 0 26 0 12 moreover terrestrial basalts and andesites have restricted 88sr values 0 30 0 07 suggesting that mantle melting delivers rather homogenous melts to the earth s surface with respect to 88sr in contrast glasses from evolved terrestrial rocks and lunar basalts extend to very light 88sr values 0 20 the sr stable isotope composition covaries with europium anomaly eu eu as an index of plagioclase fractionation and 88sr can be successfully modelled by the heavy isotopes of sr being preferentially partitioned into plagioclase with a fractionation factor of 1 0007 for 88sr 86sr our results demonstrate that sr stable isotopes may be significantly fractionated at high temperatures and their measurement can provide insights into planetary evolution and magmatic processes

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

constraining the marine strontium budget with natural strontium isotope fractionations 87sr 86sr δ88 86sr of carbonates hydrothermal solutions and river waters we present strontium sr isotope ratios that unlike traditional 87sr 86sr data are not normalized to a fixed 88sr 86sr ratio of 8 375209 defined as 88 86sr 0 relative to nist srm 987 instead we correct for isotope fractionation during mass spectrometry with a 87sr 84sr double spike this technique yields two independent ratios for 87sr 86sr and 88sr 86sr that are reported as 87sr 86sr and 88 86sr respectively the difference between the traditional radiogenic 87sr 86sr normalized to 88sr 86sr 8 375209 and the new 87sr 86sr values reflect natural mass dependent isotope fractionation in order to constrain glacial interglacial changes in the marine sr budget we compare the isotope composition of modern seawater 87sr 86sr 88 86sr seawater and modern marine biogenic carbonates 87sr 86sr 88 86sr carbonates with the corresponding values of river waters 87sr 86sr 88 86sr river and hydrothermal solutions 87sr 86sr 88 86sr hydend in a triple isotope plot the measured 87sr 86sr 88 86sr river values of selected rivers that together account for not vert similar18 of the global sr discharge yield a sr flux weighted mean of 0 7114 8 0 315 8 the average 87sr 86sr 88 86sr hydend values for hydrothermal solutions from the atlantic ocean are 0 7045 5 0 27 3 in contrast the 87sr 86sr 88 86sr carbonates values representing the marine sr output are 0 70926 2 0 21 2 we estimate the modern sr isotope composition of the sources at 0 7106 8 0 310 8 the difference between the estimated 87sr 86sr 88 86sr input and 87sr 86sr 88 86sr output values reflects isotope disequilibrium with respect to sr inputs and outputs in contrast to the modern ocean isotope equilibrium between inputs and outputs during the last glacial maximum 10 30 ka before present can be explained by invoking three times higher sr inputs from a uniquely glacial source weathering of shelf carbonates exposed at low sea levels our data are also consistent with the weathering peak hypothesis that invokes enhanced sr inputs resulting from weathering of post glacial exposure of abundant fine grained material

low latitude ordovician to triassic brachiopod habitat temperatures bhts determined from δ18o brachiopod calcite a cold hard look at ice house tropical oceans abstract some researchers have suggested that phanerozoic land based ice sheets extended occasionally into the tropical realm if true the tropical ocean at those times must have been distinctly colder than at the last glacial maximum lgm when northern hemisphere ice sheets did not extend below 38 latitude low latitude ocean temperatures derived from oxygen isotopes of brachiopod shells test this hypothesis by comparing the temperature regime for paleozoic and early mesozoic low latitude settings to the tropical temperature regime of the modern interstadial ocean and to mean temperatures estimated for the tropical ocean at lgm a running mean of ph adjusted brachiopod habitat temperatures bhts shows that paleozoic low latitude oceans were on average cool to cold relative to the modern interstadial tropical ocean at times during pennsylvanian serpukhovian tournaisian and ordovician silurian glaciations these tropical seas were indeed significantly colder on average than at the lgm ice sheets within tropical latitudes can be reasonably predicted at those times abundant and diverse paleozoic brachiopod communities reflect these cool tropical oceans consistent with modern brachiopod ecological preference for colder waters amplified paleozoic temperature oscillations suggest recurring global warming events which episodically drove these cold tropical oceans to temperatures significantly higher than the warmest modern tropical ocean

lower triassic large sea floor carbonate cements their origin and a mechanism for the prolonged biotic recovery from the end permian mass extinction precipitation of inorganic calcium carbonate is a common occurrence in both modern and ancient marine environments however synsedimentary growth of large 5 10 cm crystalline carbonate cements directly onto the sea floor has been thought to be limited to the proterozoic when seawaters were highly oversaturated with calcium carbonate compared to average phanerozoic values outer shelf to slope deposits of the lower triassic union wash formation in east central california deposited in oxygen restricted settings contain crystalline calcium carbonate cements that appear to have grown directly on the sea floor paleoenvironmental analyses indicate that these large calcium carbonate cements grew under conditions that were similar to those proposed for the precipitation of inorganic calcite in the black sea sulfate reduction of organic matter led to an increase in the amount of bicarbonate ion in deep waters and a concomitant increase in co 2 and alkalinity mixing with surface waters led to co 2 degassing and precipitation of cements from waters supersaturated with calcium carbonate the presence of these cements and associated facies thus provides evidence of harsh environmental conditions in the early triassic at the regional level which may have acted in concert with biotic effects of the end permian mass extinction as well as similar deleterious conditions e g shelf anoxia in other regions to produce a prolonged as well as temporally and geographically variable biotic recovery from this mass extinction

relation between soil age and silicate weathering rates determined from the chemical evolution of a glacial chronosequence long term weathering rates rlt were determined from base cation depletion in soil profiles developed on six granitic glacial moraines varying in age from 0 4 to 297 ka in the wind river mountains wyoming weathering rates were found to decrease with soil age t according to the power law equation rlt 15 t 0 71 where rlt is in meq m 2 yr 1 and t is in ka comparable data from the literature are consistent with this function and it is similar to power law equations describing changes in laboratory weathering rates with time on the basis of our study we predict that for a catchment unaffected by anthropogenic inputs and in a steady state with respect to the organic and cation exchange pools rlt should be higher than present day weathering rates derived from stream fluxes rpd by a factor of about 3 4

impact of atmospheric co2 and galactic cosmic radiation on phanerozoic climate change and the marine δ18o record 1 a new model is developed and applied to simulate the phanerozoic evolution of seawater composition dissolved ca sr dissolved inorganic carbon alkalinity ph 18o marine carbonates sr ca 87sr 86sr 13c 18o atmospheric co2 and surface temperature the marine carbonate records sr ca 87sr 86sr 13c are used to reconstruct changes in volcanic tectonic activity and organic carbon burial over the phanerozoic seawater ph is calculated assuming saturation with respect to calcite and considering the changing concentration of dissolved ca documented by brine inclusion data the depth of calcite saturation is allowed to vary through time and the effects of changing temperature and pressure on the stability constants of the carbonate system are considered surface temperatures are calculated using the geocarb iii approach considering also the changing flux of galactic cosmic radiation gcr it is assumed that gcr cools the surface of the earth via enhanced cloud formation at low altitudes the 18o of marine carbonates is calculated considering the changing isotopic composition of seawater the prevailing surface temperatures and seawater ph repeated model runs showed that the trends observed in the marine 18o record can only be reproduced by the model if gcr is allowed to have a strong effect on surface temperature the climate evolution predicted by the model is consistent with the geological record warm periods cambrian devonian triassic cretaceous are characterized by low gcr levels cold periods during the late carboniferous to early permian and the late cenozoic are marked by high gcr fluxes and low pco2 values the major glaciations occurring during these periods are the result of carbon cycling processes causing a draw down of atmospheric co2 and a coevally prevailing dense cloud cover at low altitudes induced by strong gcr fluxes the two moderately cool periods during the ordovician silurian and jurassic early cretaceous are characterized by both high pco2 and gcr levels so that greenhouse warming compensated for the cooling effect of low altitude clouds the very high jurassic 18o values observed in the geological record are caused by low ph values in surface waters rather than cold surface conditions

the major ion composition of permian seawater abstract the major ion mg2 ca2 na k so42 and cl composition of permian seawater was determined from chemical analyses of fluid inclusions in marine halites new data from the upper permian san andres formation of texas 274 272 ma and salado formation of new mexico 251 ma analyzed by the environmental scanning electron microscopy esem x ray energy dispersive spectrometry eds method along with published chemical compositions of fluid inclusions in permian marine halites from north america two formations of different ages and the central and eastern european basins eight formations of four different ages show that permian seawater shares chemical characteristics with modern seawater including so42 ca2 at the point of gypsum precipitation evolution into mg2 na k so42 cl brines and mg2 k ratios 5 permian seawater however is slightly depleted in so42 and enriched in ca2 although modeling results do not rule out ca2 concentrations close to those in present day seawater na and mg2 in permian seawater are close to slightly below their concentrations in modern seawater permian and modern seawater are both classified as aragonite seas with mg2 ca2 ratios 2 conditions favorable for precipitation of aragonite and magnesian calcite as ooids and cements the chemistry of permian seawater was modeled using the chemical composition of brine inclusions for three periods lower permian asselian sakmarian 296 283 ma lower permian artinskian kungurian 283 274 ma and upper permian tatarian 258 251 ma parallel changes in the chemistry of brine inclusions from equivalent age evaporites in north america central europe and eastern europe show that seawater underwent secular variations in chemistry over the 50 million years of the permian modeled so42 concentrations are 20 mmol per kg h2o mmolal and 19 mmolal in the asselian sakmarian and artinskian kungurian with higher concentrations in the upper permian tatarian 23 mmolal modeled ca2 is at or above its concentration in modern seawater throughout the permian mg2 is close to slightly below its concentration in modern seawater 55 mmolal in the asselian sakmarian 52 mmolal and tatarian 52 mmolal but slightly higher than modern seawater in the artinskian kungurian 60 mmolal mg2 ca2 ratios are 3 5 total range 2 7 to 5 5 in the lower permian and rose slightly to 3 7 total range 3 1 to 5 8 in the upper permian primarily due to decreases in ca2 these results are consistent with models that predict oscillations in the major ion composition of phanerozoic seawater on the basis of changes in the midocean ridge river water flux ratio driven by changes in the rate of midocean ridge crust production the permian was characterized by low sea levels icehouse conditions and southern hemisphere glaciation such conditions analogous to the present ice age and the similarities between permian seawater and modern seawater all suggest that general phanerozoic supercycles driven by mantle convection and global volcanicity also control the major ion chemistry of seawater

determination of temperature dependent stable strontium isotope 88sr 86sr fractionation via bracketing standard mc icp ms stable strontium isotopes here 88sr 86sr are introduced as a new member of the nontraditional stable isotopes we have developed a bracketing standard method for the determination of 88 86sr using an axiom mc icp ms and normalizing to strontium srm nbs987 for individual measurements the external reproducibility is better than about 25 ppm 1 rsd for the iapso seawater standard a 88 86sr value of 0 381 0 010 2sem was determined for the first time a temperature dependent strontium isotope fractionation during calcium carbonate precipitation could be shown aragonite samples inorganically precipitated under temperature control between 10 and 50 c revealed a 88 86sr temperature dependency of 0 0054 5 c r2 0 987 in contrast for natural coral samples pavona clavus from a proxy calibration study 23 to 27 c we did determine 0 033 5 c r2 0 955 the processes causing this sixfold stronger temperature dependency for the natural coral samples have to be studied in more detail in future studies in a first approach the different slopes can be interpreted as effects of kinetic fractionation of strontium ions with or without a hydrate shell of 22 to 29 water molecules

permian triassic mass extinction pulses driven by major marine carbon cycle perturbations the permian triassic boundary approximately 251 9 million years ago marked the most severe environmental crisis identified in the geological record which dictated the onwards course for the evolution of life magmatism from siberian traps is thought to have played an important role but the causational trigger and its feedbacks are yet to be fully understood here we present a new boron isotope derived seawater ph record from fossil brachiopod shells deposited on the tethys shelf that demonstrates a substantial decline in seawater ph coeval with the onset of the mass extinction in the latest permian combined with carbon isotope data our results are integrated in a geochemical model that resolves the carbon cycle dynamics as well as the ocean redox conditions and nitrogen isotope turnover we find that the initial ocean acidification was intimately linked to a large pulse of carbon degassing from the siberian sill intrusions we unravel the consequences of the greenhouse effect on the marine environment and show how elevated sea surface temperatures export production and nutrient input driven by increased rates of chemical weathering gave rise to widespread deoxygenation and sporadic sulfide poisoning of the oceans in the earliest triassic our findings enable us to assemble a consistent biogeochemical reconstruction of the mechanisms that resulted in the largest phanerozoic mass extinction the end permian mass extinction was linked with ocean acidification due to carbon degassing associated with siberian trap emplacement according to boron isotopes from fossil shells and reconstruction of the carbon cycle

sr stable isotope composition of earth the moon mars vesta and meteorites abstract high precision stable sr isotopic variations 88 sr 86 sr are reported in a variety of terrestrial samples martian and lunar meteorites hed undifferentiated primitive meteorites chondrules and refractory inclusions almost all the whole rock samples are isotopically indistinguishable at a 50 parts per million ppm level the exceptions are cv and co chondrites which are isotopically light and for which we believe that their isotopic composition is controlled by the proportion of refractory material five separated chondrules and one refractory inclusion from allende are isotopically light with 88 86 sr fractionations up to 1 73 whereas the matrix is enriched in the heavy isotopes 88 86 sr 0 66 the depletion in heavy isotopes observed in chondrules and refractory inclusions could be attributed to the condensation of a material already depleted in sr however in that case more than 60 of the original material would be unaccounted we propose instead that isotopic fractionation by electromagnetic sorting of ionized heavy sr from neutral sr in the early solar system for the origin of the fractionation observed in refractory inclusions and redistribution of sr by aqueous alteration for the origin of the fractionation observed in chondrules and matrix we conclude that cv and co chondrites are not the primary building blocks for earth and mars

87sr 86sr record of permian seawater abstract a population of 169 permian articulate brachiopod shells was analysed for their 87 sr 86 sr ratios 51 of these characterised as well preserved and stratigraphically well defined are utilized for delineation of the permian seawater strontium isotope trend the 87 sr 86 sr curve shows values of about 0 7080 in the lowermost permian asselian followed by a gradual decline to 0 70685 in the capitanian and a minor rise in the dzhulfian and lower dorashamian to values of 0 70715 just below the permian triassic boundary the early permian decrease in the strontium isotope curve that commences in the early sakmarian is coincident with the advancing deglaciation of the gondwana and with the increased aridity in large parts of the pangaea these factors may have led to a reduced continental weathering of rb rich silicate rocks and thus to the decline in seawater 87 sr 86 sr starting with the artinskian the opening of the neotethys and the associated widespread basaltic volcanism supplied low radiogenic strontium to seawater from an enhanced hydrothermal flux in the capitanian basaltic volcanism in the entire palaeotethys ceased and this may have been the reason for a slightly more radiogenic seawater isotopic composition during the lopingian higher input of riverine sr due to expansion of humid areas may have been a contributory factor

influences of temperature and mg ca ratio on caco3 precipitates from seawater the mg ca ratio at which the calcium carbonate mineral that has pseudohomogeneously precipitated from seawater changes from calcite to aragonite was experimentally determined as a function of temperature results indicate a dramatic change in the critical mg ca ratio over a relatively small temperature range for example in normal seawater with a mg ca of 5 1 the critical temperature is 6 3 c at a temperature of 25 c however mg ca must be less than 1 4 0 1 for calcite to form these data indicate that paleoclimatic conditions at the time of carbonate deposition must be considered when attempting to make inferences about variation in other factors such as paleo p co 2 p pressure and paleo mg ca ratios that may control carbonate mineral formation by abiotic processes however the inverse relation between inferred global paleoclimatic conditions and the dominant type of caco 3 polymorph being abiotically deposited i e warm conditions and low mg calcite versus cool conditions and aragonite suggest that substantial changes must have taken place in ocean chemistry over phanerozoic time

an evaporite based high resolution sulfur isotope record of late permian and triassic seawater sulfate abstract variations in the sulfur isotope composition of dissolved marine sulfate through time reflect changes in the global sulfur cycle and are intimately related to changes in the carbon and oxygen cycles a large shift in the sulfur isotope composition of sulfate at the permian triassic boundary has been recognized for long time and a number of studies were carried out to understand the causes and significance of this shift however data for the middle and late triassic are very sparse and the stratigraphic evolution of the sulfur isotope composition of seawater is poorly constrained due to the small number of samples analyzed and or due to the limited stratigraphic intervals studied moreover in the last few years the triassic timescale has significantly changed due to a wealth of new radiometric and stratigraphic data in this study we show that for the late permian and the triassic it is possible to obtain a precise reconstruction of the evolution of the sulfur cycle for parts of it at sub million year resolution by analyzing exclusively gypsum and anhydrite deposits we base our reconstruction on new data from the middle and late triassic evaporites of northern switzerland and literature data from evaporites from germany austria italy and the middle east we propose a revised correlation between the well dated marine tethyan sections in northern italy and the evaporites from northern switzerland and from the germanic basin calibrated to the newest radiometric absolute age scale this new correlation allows for a precise dating of the evaporites and constructing a composite sulfur isotope evolution of seawater sulfate from the latest permian lopingian epoch to the norian we show that a rapid positive shift of approximately 24 at the permian triassic boundary can be used to constrain seawater sulfate concentrations in the range of 2 6 mm thus higher than previous estimates but with less rapid changes finally we discuss two possible evolution scenarios for the middle triassic negative shift to values of 15 that subsequently remain constant during the late triassic

isotope stratigraphy of the european carboniferous proxy signals for ocean chemistry climate and tectonics abstract carboniferous brachiopods from western europe and the former ussr have been utilized as carriers of isotopic proxy signals for paleoceanography and paleoclimatology during the assemblage of pangea this is of particular interest because this time interval coincides with the transition from greenhouse to icehouse conditions the 18 o values 3 ma running means show an overall 18 o increase from about 7 1 to 3 1 during the carboniferous the rise in the 18 o is stepwise with major shifts in the mid tournaisian and at the visean serpukhovian transition the comparable 13 c record shows a tournaisian peak at 5 a visean oscillation at about 2 5 1 a serpukhovian rise of more than 3 a plateau around 5 during the bashkirian and moscovian a 4 drop during the kasimovian and another rise of about 3 during the gzhelian the 87 sr 86 sr record shows an early carboniferous decline from 0 7083 to a mid visean minimum of 0 7077 followed by a rapid serpukhovian rise to a bashkirian and moscovian plateau at 0 7087 and a slight decline during the kasimovian and gzhelian the covariance of isotopic trends and the coincidence with geological phenomena indicates that the long term variations in ocean chemistry and climate may be coupled to the tectonic evolution of the earth system the namurian witnesses the onset of hercynian orogeny initiation of the main phase of carboniferous glaciation formation of the extensive coal deposits and the rise in 87 sr 86 sr 13 c and 18 o all this suggests that a tectonically controlled climate change resulting in cooling and increased carbon storage in the organic reservoir was the major triggering factor for all the above phenomena the late carboniferous glacial episode was interrupted by a warm interval in the stephanian the carbon and oxygen isotope data indicate that this episode may have been restricted to the early kasimovian a proposition at odds with the poorly dated record of glacial deposits that are interpreted as indicating a warm climate for the entire stephanian in addition the pattern of short lived peaks in 13 c and 18 o in the tournaisian and possibly visean may be interpreted as a reflection of short lived glacial episodes a proposition consistent with geologic records

strontium isotopes in early jurassic seawater abstract the analysis of well preserved well dated belemnites and oysters from the jurassic of great britain has resulted in a well constrained detailed seawater strontium isotope curve for the early jurassic the preservation of fossil low mg calcite was monitored using mn fe 13 c and 18 o iron was the most useful indicator with about 75 of the samples containing more than 150 ppm fe showing 87 sr 86 sr ratios elevated relative to adjacent points on the curve high mn concentrations less often correlated with elevated 87 sr 86 sr ratios however low mn concentrations 87 sr 86 sr 13 c and 18 o proved to be insensitive to diagenesis as it affects 87 sr 86 sr the principal features of the strontium isotope curve include a rise to about 0 70772 in the latest triassic and earliest jurassic hettangian from the hettangian the curve begins a roughly linear descent through the sinemurian and pliensbachian following a small levelling off and increase in the late pliensbachian the curve falls rapidly to its early jurassic minimum of 0 70706 it then gently increases through the toarcian until the falciferum zone where it shows an apparently abrupt increase to 0 70719 before continuing its slow increase to 0 70728 in the aalenian bajocian middle jurassic this reversal of the downwards trend established in the sinemurian and pliensbachian had not been previously identified the sinemurian and pliensbachian section of the curve potentially allows correlation and dating to within 1 or 2 ammonite subzones 0 5 to 1 ma

reassessing the stable δ88 86sr and radiogenic 87sr 86sr strontium isotopic composition of marine inputs the stable strontium isotope system 88 86sr has recently been suggested to be a suitable proxy for determining variations in the strength of the marine carbonate system the principal output flux of oceanic sr however in order to be able to interpret carbonate driven variations in 88 86srseawater a robust understanding of 88 86srinput is required surprisingly only a limited amount of 88 86sr data currently exists for rivers and hydrothermal fluids thus this study assesses the variability of 88 86sr and 87sr 86sr in global rivers hydrothermal fluids and porewaters as well as minor marine sr sources such as continental dust rainwater and glacial ice our analyses broadly confirm the findings of krabbenhoft et al 2010 and reveal flux weighted 88 86srriverine and 87sr 86srriverine compositions of 0 32 and 0 71299 respectively the hydrothermal fluids analysed in this study are consistent with an end member 88 86srhydrothermal composition that is the same as the oceanic crust at 0 24 although three samples that display 88 86sr compositions offset from the seawater hydrothermal mixing trend suggest that the precipitation of alteration phases such as anhydrite may drive 88 86srhydrothermal to higher values porewater fluids obtained from sediment cores in the atlantic and pacific oceans have 88 86sr compositions within error of seawater 0 39 implying that the diagenetic flux of sr may not significantly affect the 88 86sr composition of seawater continental loess samples have 88 86sr compositions that are consistently lighter than or equal to terrestrial silicates with their tendency to lower values thought to reflect the preferential removal of heavier sr isotopes into solution during weathering finally rainwater and glacial ice samples have 88 86sr compositions that are also isotopically lighter than their associated water sources a factor that may be attributed to interaction with isotopically light loess and additional sr contributions from the bedrock together the principal marine inputs define flux weighted oceanic 88 86srinput and 87sr 86srinput compositions of 0 32 and 0 71161 these values are consistent with an elevated supply of riverine sr to the oceans due to increased post glacial weathering but require the enhanced weathering of exposed carbonate shelves during glacial periods or significant changes in the rate of carbonate burial to match observed changes in the 87sr 86sr ratio of seawater our results confirm that providing a diagenetically robust proxy can be found the 88 86sr and 87sr 86sr isotope systems should provide a useful proxy for investigating changes in the marine carbonate system through time

rapid expansion of oceanic anoxia immediately before the end permian mass extinction tive of an expansion of oceanic anoxia and higher th u ratios from 0 06 to 0 42 indicative of drawdown of u concentrations in seawater using a mass balance model we estimate that this isotopic shift represents a sixfold increase in the flux of u to anoxic facies implying a corresponding increase in the extent of oceanic anoxia the intensification of oceanic anoxia coincided with or slightly preceded the eh and persisted for an interval of at least 40 000 to 50 000 y following the eh these findings challenge previous hypotheses of an extended period of whole ocean anoxia prior to the end permian extinction

revised middle upper jurassic strontium isotope stratigraphy abstract a study is conducted to supplement the uppermost lower jurassic lowermost cretaceous marine strontium isotope dataset and to present new statistical fits of the middle late jurassic seawater strontium isotope curve based on a numerical time scale and a detailed biostratigraphical zonal scheme the use of the stratigraphical scheme allows reduction of dating errors related to uncertainty of numerical age determinations the presented correlation charts enable direct calibration between strontium isotope stratigraphy and regional biostratigraphical frameworks new strontium isotope data have been obtained from well preserved lower bajocian uppermost callovian oxfordian kimmeridgian and upper volgian belemnite rostra the presented seawater 87 sr 86 sr curve is characterized by reliable 95 confidence limits mean width of 0 000007 which take into account precision of dating of particular data points a decrease of seawater 87 sr 86 sr ratio from ca 0 70730 to ca 0 70683 is observed throughout the middle aalenian early oxfordian 172 1 160 8 ma ago the steepest phanerozoic fall of the ratio with a rate of change of up to 0 00015 per 1 ma is recorded in the bajocian segment of the strontium isotope curve the phanerozoic minimum of the marine 87 sr 86 sr ratio occurred at the early middle oxfordian transition the 87 sr 86 sr ratio increased starting from the middle oxfordian till the end of the jurassic 160 8 145 7 ma reaching a value of ca 0 70720 at the jurassic cretaceous transition the middle earliest late jurassic decrease in seawater 87 sr 86 sr ratio is interpreted as a result of the increased hydrothermal activity of the seafloor during the breakup of gondwana and the formation of new atlantic tethyan oceanic basins the successive rise of the ratio is probably related to the decelerated hydrothermal venting of the oceanic crust although a partial increase in radiogenic strontium input from continental weathering cannot be excluded

evidence for end permian ocean acidification from calcium isotopes in biogenic apatite c record of carbonate rocks 13 c carb for the selective extinction of heavily calcifi ed marine animals and for the abrupt transition in carbonate facies across the extinction horizon an additional proxy is necessary to distinguish among these options calcium isotopes hold promise for differentiating between suggested scenarios for change in seawater carbonate chemistry linked with the end permian extinction the calcium cycle is linked to the carbon cycle through the weathering of limestone and the deposition of calcium carbonate sediments calcium isotopes fractionate by 0 6 and 1 3 in calcite and aragonite respectively during the precipitation of modern carbonate minerals meaning carbonate sediments are enriched in the lighter isotope relative to the seawater from which they precipitated skulan et al 1997 tang et al 2008 imbalances between calcium delivery and burial fl uxes and changes in the magnitude of fractionation during carbonate deposition will result in changes in the 44 40 ca of seawater and will be recorded in marine sediments depaolo 2004 farkao et al 2007 therefore variation in the

secular oscillations in the carbonate mineralogy of reef building and sediment producing organisms driven by tectonically forced shifts in seawater chemistry the primary mineralogy of oolites and early marine carbonate cements led sandberg nature 305 1983 19 22 to divide the phanerozoic eon into three intervals of aragonite seas and two intervals of calcite seas hardie geology 24 1996 279 283 has shown that these oscillations together with synchronous oscillations in the mineralogy of marine potash evaporites can be explained by secular shifts in the mg ca ratio of seawater driven by changes in spreading rates along mid ocean ridges the hardie model also predicts that high mg calcite should precipitate along with aragonite as it does in today s aragonite sea we have uncovered oscillations in the carbonate mineralogy of hypercalcifying organisms ones that have produced massive skeletons large reefs or voluminous bodies of sediment that correspond to sandberg s aragonite seas and calcite seas and that are predicted by the hardie model particular groups of corals sponges and algae appear to have been dominant reef builders only when favored by an appropriate mg ca ratio in seawater in early and middle paleozoic calcite seas calcite i reefs were dominated by calcitic tabulate heliolitid and rugose corals and calcitic stromatoporoids in contrast during the period of late paleozoic early mesozoic aragonite seas aragonite ii aragonitic groups of sponges scleractinian corals and phylloid algae as well as high mg calcitic red algae were principal reef builders during late cretaceous time at the acme of calcite ii massive rudists displaced aragonitic hermatypic corals in today s aragonite sea aragonite iii scleractinian corals are again dominant reef builders along with high mg calcitic coralline algae major sediment producing algae exhibit temporal patterns similar to those of reef builders calcitic receptaculitids flourished during calcite i whereas aragonitic dasycladaceans did not become dominant rock formers until aragonite ii during calcite ii calcitic nannoplankton formed massive coccolith chalks in warm shallow seas of the late cretaceous after the mg ca ratio of seawater had reached a very low value and calcium concentration a very high value as the mg ca ratio of seawater rose and calcium concentration fell during the cenozoic era individual coccoliths on average became less massive and encrusted cells less thickly by pliocene time during aragonite iii the prominent genus discoaster secreted only narrow rayed coccoliths that covered less than 25 of the cell surface also during aragonite iii the aragonitic green alga halimeda emerged as the dominant skeletal sediment producer in reef tracts the influence of seawater chemistry on skeletal secretion appears to have been especially strong for morphologically simple taxa that exert relatively weak control over their own calcification such groups include algae sponges corals and bryozoans morphological simplicity also permits these groups to adopt vegetative or colonial modes of growth that confer success in competition for space on reefs this linkage in addition to the basic chemical demands of hypercalcification has given the mg ca ratio of seawater strong control over the success of individual reef building taxa more generally this ratio appears to have strongly influenced evolutionary changes in the skeletal mineralogy of sponges and cheilostome bryozoans throughout their history we conclude that throughout phanerozoic time a chain of causation has extended from mid ocean ridge processes via seawater chemistry to the mineralogical and biological composition of reef communities and bioclastic carbonate deposits

evidence for mass dependent isotopic fractionation of strontium in a glaciated granitic watershed abstract the stable isotope composition of strontium expressed as 88 86sr may provide important constraints on the global exogenic strontium cycle here we present 88 86sr values and 87sr 86sr ratios for granitoid rocks a 150 yr soil chronosequence formed from these rocks surface waters and plants in a small glaciated watershed in the central swiss alps incipient chemical weathering in this young system whether of inorganic or biological origin has no resolvable effect on the 87sr 86sr ratios and 88 86sr values of bulk soils which remain indistinguishable from bedrock in terms of sr isotopic composition although due in part to the chemical heterogeneity of the forefield the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of sr a low degree of chemical weathering is also implied by bulk soil chemistry the isotopic composition of sr in streamwater is more radiogenic than median soil reflecting the preferential weathering of biotite in the catchment streamwater 88 86sr values however are indistinguishable from bulk soil 88 86sr values implying that no resolvable fractionation of sr isotopes takes place during release to the weathering flux in the damma forefield analyses of plant tissue reveal that plants rhododendron and vaccinium preferentially assimilate the lighter isotopes of sr such that their 88 86sr values are significantly lower than those of the soils in which they grow additionally 88 86sr values of foliar and floral tissues are lower than those of roots contrary to observations for ca for which sr is often used as an analogue in weathering studies we suggest that processes that discriminate against sr in favour of ca due to the different nutritional requirement of plants for these two elements are responsible for the observed contrast

permo triassic boundary superanoxia and stratified superocean records from lost deep sea pelagic cherts of japan and british columbia canada recorded a long term and worldwide deep sea anoxic oxygen depleted event across the permo triassic or paleozoic and mesozoic boundary 251 2 million years ago the symmetry in lithostratigraphy and redox condition of the boundary sections suggest that the superocean panthalassa became totally stratified for nearly 20 million years across the boundary the timing of onset climax and termination of the oceanic stratification correspond to global biotic events including the end guadalupian decline the end permian extinction and mid triassic recovery