a multiproxy approach to reconstructing sea surface conditions using coral skeleton geochemistry 1 we use elemental ratio mg ca sr ca u ca and ba ca and oxygen isotope data from a porites lutea coral head collected from offshore amedee island new caledonia 22 29 s 166 28 e to assess the degree to which changes in these geochemical variables reflect variations in sea surface conditions we have assessed the robustness of each geochemical proxy by comparing 25 years 1992 1968 of monthly geochemical variations with a local record of sea surface temperature sst and with the appropriate 1 by 1 grid box from a global gridded sst data set we conclude from our comparison that the most consistent proxies of monthly sst variations at this site are 18o r2 0 84 p 0001 and sr ca r2 0 84 p 0001 the fidelity of the coral based sr ca sst proxy was assessed via calibration verification exercises at new caledonia and rarotonga the paleoclimate accuracy of the coral sr ca sst technique is judged to be robust and the precision of the technique is estimated to be 0 3 0 5 2 based on the calibration verification exercise in contrast monthly variations in mg ca and u ca ratios are only moderately correlated with monthly sst variations r2 0 55 p 0001 for mg ca and r2 0 47 p 0001 the strength of the correlation between sst and mg ca and u ca varies as a function of time suggesting that variations in these ratios are not a simple function of sst variations this variability in goodness of fit between u ca sst and mg ca sst may ultimately limit the use of these ratios as coral paleothermometers averaging or stacking individual proxy sst records sr ca mg ca and u ca to generate a composite proxy sst record does not necessarily improve the proxy record if the signal to noise ratio in each proxy is highly variable for example stacking of sr ca mg ca u ca records at new caledonia produces a proxy sst time series that has greater standard error than the individual sr ca sst time series cf ordinary least squares standard error of 1 16 c versus 0 86 c ba ca variations have little correlation with sst sr ca mg ca or u ca variations at new caledonia in conclusion variations in oxygen isotopic composition of seawater calculated by removing the sr ca based temperature component of the 18o signal agree reasonably well with observed variations in sea surface salinity especially at the interannual timescale

confounding effects of coral growth and high sst variability on skeletal sr ca implications for coral paleothermometry massive corals offer continuous records of climate locked within their skeleton with the most commonly applied paleo thermometer being sr ca recently however problems with sr ca thermometry indicate that the intrinsic variance of single core sr ca time series differs between cores here we compare the sr ca records and growth parameters of two porites lutea colonies sampled from the same reef zone 0 72 km apart with two gridded sst datasets ersst and hadisst off ne madagascar specifically we address seasonal and interannual variability as well as trend differences between records over the same 43 year period the two gridded sst datasets showed strong seasonality and weak positive enso anomalies on a slow 43 year warming trend at significantly different rates both the coral sr ca records showed the same clear seasonality and similar amplitudes in sst however on interannual timescales they displayed diverging 43 year sr ca trends and opposite responses to weak enso anomalies moreover their growth response also differed as one coral showed increasing extension calcification rates and sr ca ratios cooling over the 43 years while the other coral showed decreasing extension calcification rates and sr ca ratios warming further during positive enso events the calcification rates of the two corals were negatively correlated while skeletal density anomalies were opposite possible explanations to why these corals are so different may be related to the corals growth response to sst changes the growth response of individual corals to increasing sst seems to be opposite which in turn are likely related to biological factors consequently coral growth responses explain much of the inter colony sr ca variability

tropical sea surface temperatures for the past four centuries reconstructed from coral archives most annually resolved climate reconstructions of the common era are based on terrestrial data making it a challenge to independently assess how recent climate changes have affected the oceans here as part of the past global changes ocean2k project we present four regionally calibrated and validated reconstructions of sea surface temperatures in the tropics based on 57 published and publicly archived marine paleoclimate data sets derived exclusively from tropical coral archives validation exercises suggest that our reconstructions are interpretable for much of the past 400 years depending on the availability of paleoclimate data within and the reconstruction validation statistics for each target region analysis of the trends in the data suggests that the indian western pacific and western atlantic ocean regions were cooling until modern warming began around the 1830s the early 1800s were an exceptionally cool period in the indo pacific region likely due to multiple large tropical volcanic eruptions occurring in the early nineteenth century decadal scale variability is a quasi persistent feature of all basins twentieth century warming associated with greenhouse gas emissions is apparent in the indian west pacific and western atlantic oceans but we find no evidence that either natural or anthropogenic forcings have altered el nino southern oscillation related variance in tropical sea surface temperatures our marine based regional paleoclimate reconstructions serve as benchmarks against which terrestrial reconstructions as well as climate model simulations can be compared and as a basis for studying the processes by which the tropical oceans mediate climate variability and change

an evaluation of enso asymmetry in the community climate system models a view from the subsurface abstract the asymmetry between el nino and la nina is a key aspect of enso that needs to be simulated well by models in order to fully capture the role of enso in the climate system here the asymmetry between the two phases of enso in five successive versions of the community climate system model ccsm1 ccsm2 ccsm3 at t42 resolution ccsm3 at t85 resolution and the latest ccsm3 nr with the neale and richter convection scheme is evaluated different from the previous studies not only is the surface signature of enso asymmetry examined but so too is its subsurface signature by comparing the differences among these models as well as the differences between the models and the observations an understanding of the causes of the enso asymmetry is sought an underestimate of the enso asymmetry is noted in all of the models but the latest version with the neale and richter scheme ccsm3 nr is getting closer to the observations than the earlier versions the net surface heat flux is found to damp th

surface ocean variability at galapagos from 1936 1982 calibration of geochemical tracers in corals a variety of geochemical tracers has been developed in reef corals as a means of reconstructing the natural variability of the tropical surface ocean over wide ranging time frames the purpose of this paper is to calibrate the performance of five of these tracers in a modern coral colony over an extended period a 47 year growth interval 1936 1982 in a colony of pavona clavus taken from san cristobal island galapagos islands was sectioned into 187 quarterly intervals and analyzed for 18o 13o ba ca cd ca and mn ca the resulting time series are compared with eastern pacific sea surface temperatures one of few instrumental data bases available for calibration over this time period linear least squares regressions of four of the tracers 18o 13o ba ca cd ca against peruvian sst show highly significant correlations p 0 0001 over the annual biennial and enso 3 8 years frequency bands cross spectral comparisons show even stronger coherency with sst frequently accounting for 70 80 of the variance in these tracers these results as well as the phase relationships determined from the spectral analyses suggest that the coupling between sst and 18o and the nutrientlike tracers ba and cd is controlled principally by seasonal upwelling cycles and interannual interruptions of these cycles brought about by el nino and anti el nino phenomena an inverse relationship between sst and 13c has its primary origins in the co occurrence of the warm sst phase with high light levels during the first half of the calendar year the association with sunlight derives from the photosynthetic response of algal symbionts which results in fractionation of light and heavy carbon isotopes between soft tissues and caco3 skeleton the fifth tracer the transition metal mn exhibits poorer correlations against both sst and the other tracers slight shifts in phasing of the historical mn ca annual cycle suggest that the general water column distribution of this tracer which is the reverse of a nutrient may not be stable the erratic behavior of mn illustrates how complex hydrography near galapagos may influence tracers with diverse source signatures

reply to comment by cahyarini et al on a snapshot of climate variability at tahiti at 9 5 ka using a fossil coral from iodp expedition 310

mg ca sr ca and u ca ratios of a porites coral from sanya bay hainan island south china sea and their relationships to sea surface temperature high resolution mg ca sr ca and u ca ratios are reported in the skeleton of porites sp collected from sanya bay on the south coast of the hainan island china using inductively coupled plasma mass spectrometry combined with isotope dilution technique icp ms id the coralline mg ca ratios covary with sea surface temperatures sst for the 10 year interval giving the relationship between mg ca and sst as t degrees c 14 13 0 31 8 846 0 068 x 10 3 mg ca with the mean square weighted deviation mswd of 9 7 using this equation we are able to reconstruct sst record with a precision better than 0 5 degrees c several sr ca and u ca ratios show poor linear relationships with the measured sst this study indicates that the growth rates of the coral do not significantly affect coralline mg ca sr ca and u ca ratios however the high meteoric precipitation in this area which may cause a heavy run off from the island may change seawater sr ca and u ca ratios and ruin the relationships between coralline sr ca or u ca ratios and sst this implies that in coastal areas like hainan coralline mg ca ratios are valid for reconstructing the sst records but sr ca and u ca ratios may be suspected c 2000 elsevier science b v all rights reserved

calcite and aragonite precipitation from seawater solutions of various salinities precipitation rates and overgrowth compositions abstract the reaction rate and composition of calcite and aragonite overgrowths precipitated from seawater solutions of various salinities i e s 5 15 25 35 44 were determined at 25 c and 10 2 5 atm co2 partial pressure using a constant disequilibrium seeded technique the rate data were fitted to an empirical rate law of the form log r n c or a 1 log k where n is the empirical reaction order and k is the rate constant calcite precipitation rates in seawater solutions do not vary appreciably as a result of salinity variations over the range investigated while those for aragonite show an increase in going from the higher i e s 35 44 to the lower i e s 5 15 25 salinity range this study also confirms previously published findings that above a given saturation state i e c 2 6 aragonite precipitates more rapidly than calcite at 25 c the incorporation of sr2 in aragonite and mg2 in calcite overgrowths are independent of the precipitation rate the partition coefficient of sr2 in aragonite is approximately equal to unity and is unaffected by salinity variations between 5 and 44 however the mg2 partition coefficient in calcite increases with decreasing salinity of the parent seawater solutions possibly as a result of variations in the sulfate content of the solutions and solids the experimental results were discussed in the context of a number of geological environments

empirical assessment of coral sr ca and mg ca ratios as climate proxies using colonies grown at different temperatures 1 coral strontium calcium sr ca and magnesium calcium mg ca ratios might be useful for reconstructing past sea surface temperature sst in tropical oceans where instrumental data are limited however the link between coral skeletal trace elements and sst is disputed and biological factors such as skeletal growth rate may also affect trace elements in a coral we studied the relationships between growth rate and sst and sr ca and mg ca ratios using corals porites spp cultured in thermostated tanks sr ca was controlled primarily by sst while mg ca mainly reflected the growth rate with negligible contribution from species on both the variations these relationships are consistent with modeled results of cation partitioning during aragonite crystal formation

geochemistry based coral palaeoclimate studies and the potential of non traditional non massive porites corals recent developments and future progression understanding the natural variability of the earth s climate system and accurately identifying potential anthropogenic influences requires long term geographically distributed records of key climate indicators such as temperature and precipitation that extend prior to the last 400 years of the holocene reef corals provide an excellent source of high resolution climate records and importantly represent the tropical marine environment where palaeoclimate data are urgently required recent decades have seen significant improvement in our understanding of coral biomineralisation the associated uptake of geochemical proxies and methods of identifying and understanding the effects of both early and late post depositional diagenetic alteration these processes all have significant implications for interpreting geochemical proxies relevant to palaeoclimatic reconstructions this paper reviews the current state of the art in terms of coral based palaeoclimate reconstructions and highlights a key remaining problem the majority of coral based palaeoclimate research has been derived from massive colonies of porites however massive porites are not globally abundant and may not provide material of a particular age of interest in those regions where they are present therefore there is great potential for alternate coral genera to act as complimentary climate archives while it remains critical to consider five key factors vital effects differential growth morphologies geochemical heterogeneity in the skeletal ultrastructure transfer equation selection and diagenetic screening of skeletal material in order to allow the highest level of accuracy in coral palaeoclimate reconstructions it is also important to develop alternate taxa for palaeoclimate studies in regions where porites colonies are absent or rare currently as many as nine genera other than porites have proven at least limited utility in palaeothermometry most of which are found in the atlantic caribbean region where massive porites do not exist even branching taxa such as acropora have significant potential to preserve environmental archives increasing this capability will greatly expand the number of potential geochemical archives available for longer term temporal records of palaeoclimate

a mid twentieth century reduction in tropical upwelling inferred from coralline trace element proxies abstract the cariaco basin is an important archive of past climate variability given its response to inter and extratropical climate forcing and the accumulation of annually laminated sediments within an anoxic water column this study presents high resolution surface coral trace element records montastrea annularis and siderastrea siderea from isla tortuga venezuela located within the upwelling center of this region a two fold reduction in cd ca ratios 3 5 1 7 nmol mol is observed from 1946 to 1952 with no concurrent shift in ba ca ratios this reduction agrees with the hydrographic distribution of dissolved cadmium and barium and their expected response to upwelling significant anthropogenic variability is also observed from pb ca analysis observing three lead maxima since 1920 kinetic control of trace element ratios is inferred from an interspecies comparison of cd ca and ba ca ratios consistent with the sr ca kinetic artifact but these artifacts are smaller than the environmental signal and do not explain the cd ca transition the trace element records agree with historical climate data and differ from sedimentary faunal abundance records suggesting a linear response to north atlantic extratropical forcing cannot account for the observed historical variability in this region

the solubility of calcite and aragonite in sulfate free seawater and the seeded growth kinetics and composition of the precipitates at 25 c the influence of dissolved sulfate ions on the precipitation kinetics and composition of calcite and aragonite overgrowths was investigated in artificial seawater solutions at 25 c using a constant disequilibrium technique the solubility of both minerals in sulfate free seawater was determined to allow the expression of the saturation state of precipitating solutions as the ratio of the caco3 ion concentration product to their stoichiometric solubility constant so2 4 ions inhibit both calcite and aragonite precipitation the inhibition in seawater is not selective and therefore whether in the presence or absence of 0 028 m so2 4 aragonite precipitates more rapidly on aragonite seeds than calcite does on calcite seeds from supersaturated solutions srco3 incorporation in aragonite is independent of the precipitation rate and unaffected by so2 4 ions in seawater the distribution coefficient of sr2 in aragonite overgrowths precipitated from seawater is 0 97 0 08 while a value of 1 05 0 09 is obtained in sulfate free seawater in contrast mgco3 incorporation in calcite overgrowths is influenced significantly by the presence or absence of so2 4 ions in seawater while the distribution coefficient of mg2 in calcite is also independent of the precipitation rate its value increases from 0 0172 0 0022 in seawater to 0 0230 0 0026 in sulfate free seawater corresponding respectively to the precipitation of 8 1 1 and 10 5 1 mole magnesian calcites

assessing coral sr ca sst calibration techniques using the species diploria strigosa the coral species diploria strigosa is a promising archive for paleoclimate reconstruction in the tropical atlantic but limited work has been accomplished thus far to quantify the relationship between strontium to calcium ratios and sea surface temperatures in this species in this study we collected three modern d strigosa coral colonies from anegada british virgin islands to refine the use of this species as a paleoclimate archive three regression techniques including ordinary least squares reduced major axis and weighted least squares were used to assess how assumptions implicit in these regression methods influence the calibration our analysis demonstrated that regression slopes were strongly impacted by the assumptions about data uncertainty we recommend using the unbiased weighted least squares regression technique for calibrating the sr ca paleothermometer especially when precise local sea surface temperature data are unavailable combining our sr ca data with previously published data from this species results in a multi site multi colony temperature sensitivity of 0 046 0 001 mmol mol c for mean centered monthly data 0 059 0 001 mmol mol c for monthly anomalies and 0 063 0 004 for annual anomalies we suggest these relationships are the best available characterization of the temperature dependence of sr ca in d strigosa and can be utilized in future paleoclimate reconstructions

refining temperature reconstructions with the atlantic coral siderastrea siderea abstract developing coral based temperature reconstructions for a particular coral species requires determining the optimal sampling path orientation and resolution for geochemical analysis to avoid sampling artifacts and to increase reproducibility furthermore a robust coral archive should have high intracolony and intercolony reproducibility for determining the common environmental signal here we assessed sampling path orientation and sampling resolution for siderastrea siderea colonies within the dry tortugas national park in the gulf of mexico 24 42 n 82 48 w to determine the optimal sampling protocol and to assess reproducibility of coral sr ca 18o and 13c we identified a sampling artifact due to extracting samples from the coral columella resulting in cold bias up to 5 2 c in coral sr ca we found no shift to higher coral sr ca values i e colder for years with a 50 reduction in average extension rate 2 1 mm year 1 or for sampling along paths up to 70 off the vertical axis of the colony our sampling resolution comparison 1900 1993 indicated that the resolution of 6 samples year 1 used in a previous study for coral sr ca and 18o may not capture seasonal extremes and thus produces muted seasonal cycles but that resolution is not biased towards one season reproducibility or average deviations assessed using absolute differences ad and root mean square rms among the monthly resolved coral sr ca records for intracolony to intercolony comparisons were within 2 of our analytical precisions average deviations were reduced by 19 to 61 when assessing interannual variability 36 month smoothed and mean annual suggesting that subannual dating uncertainties i e assigning a coral sr ca value to a particular month were the largest source of error in our monthly resolved coral sr ca reconstruction similarly coral 18o was reproducible within 2 of our analytical precision ad 0 10 and rms 0 07 however coral 13c and linear extension records were not reproducible our assessment of coral geochemical variations from multiple s siderea colonies suggests this species is suitable for paleoclimatic reconstructions including subfossil corals and microatoll colonies that grow laterally

are seawater sr ca variations preserved in quaternary foraminifera abstract high precision measurements of sr ca in planktonic foraminifera for the last 150 ka reveal sr ca variations of up to 12 on glacial interglacial time scales although records showing the largest variations appear to be strongly influenced by selective dissolution other records show sr ca variations of 3 5 that do not covary with indicators of dissolution intensity and that are reproduced in sites of contrasting quaternary dissolution histories these systematic variations are characterized by high sr ca ratios during glacial maxima followed by steep decreases during deglaciation and gradual increases through interstadial periods closely following 18 o curves foraminiferal sr ca variations may reflect changes in the sr ca ratio of seawater or they may be due to kinetically or biologically induced changes in sr partitioning coupled numerical models of the sr and ca budgets of the ocean reveal that sea level changes together with large changes in river fluxes and carbonate accumulation rates can produce seawater sr ca variations that approximate both the shape and amplitude of foraminiferal sr ca variations however such extreme changes in river and carbonate fluxes conflict with existing data on carbonate accumulation rates and sr isotopic constraints on the magnitude of variations in the river flux smaller variations 1 3 in the sr ca ratio of seawater likely characterize quaternary glacial cycles changes in sr partitioning due to glacial interglacial changes in the carbonate ion concentration and other environmental factors likely produce additional variation in the sr ca record of planktonic foraminifera

mid to late holocene changes in tropical atlantic temperature seasonality and interannual to multidecadal variability documented in southern caribbean corals proxy reconstructions of tropical atlantic sea surface temperature sst that extend beyond the period of instrumental observations have primarily focused on centennial to millennial variability rather than on seasonal to multidecadal variability here we present monthly resolved records of sr ca a proxy of sst from fossil annually banded diploria strigosa corals from bonaire southern caribbean sea the individual corals provide time windows of up to 68 years length and the total number of 295 years of record allows for assessing the natural range of seasonal to multidecadal sst variability in the western tropical atlantic during snapshots of the mid to late holocene comparable to modern climate the coral sr ca records reveal that mid to late holocene sst was characterised by clear seasonal cycles persistent quasi biennial and prominent interannual as well as inter to multidecadal scale variability however the magnitude of sst variations on these timescales has varied over the last 6 2 ka the coral records show increased seasonality during the mid holocene consistent with climatemodel simulations indicating that southern caribbean sst seasonality is induced by insolation changes on orbital timescales whereas internal dynamics of the climate system play an important role on shorter timescales interannual sst variability is linked to ocean atmosphere interactions of atlantic and pacific origin pronounced interannual variability in the western tropical atlantic is indicated by a 2 35 ka coral possibly related to a strengthening of the variability of the el nino southern oscillation throughout the holocene prominent inter to multidecadal sst variability is evident in the coral records and slightly more pronounced in the mid holocene we finally argue that our coral data provide a target for studying holocene climate variability on seasonal and interannual to multidecadal timescales when using further numerical models and high resolution proxy data

rapid 20th century warming in the caribbean and impact of remote forcing on climate in the northern tropical atlantic as recorded in a guadeloupe coral we have generated 104 year long 1895 1999 monthly 18o and sr ca time series from a fast growing diploria strigosa coral core drilled off guadeloupe island lesser antilles coral sr ca reliably records interannual to decadal surface air temperature sat variations in the region and shows a pronounced warming of approximately 1 5 c since 1950 with the strongest warming 1 2 c occurring since 1975 this warming is also evident in sat measured at guadeloupe which ends in 1951 thus our sr ca series extends the air temperature record by 56 years we find that the past few decades are the warmest years over the entire period of record the accelerated warming since 1950 is accompanied by a pronounced decrease in regional precipitation this dampens the warming signal indicated by coral 18o which is too low only 0 7 0 8 c since 1951 consistently 18osw estimated from the coral proxies also shows a strong decrease since 1950 our data suggest an inverse relationship between sat and precipitation i e warmer and drier for the latter half of the 20th century with the strongest trends since the mid 1970s this is consistent with recent observational and model data which report that while over the tropical oceans rainfall has increased due to an increase in sea surface temperatures precipitation over land regions is reduced a continuation of this warming and drying trend over caribbean land regions would have severe societal consequences especially in the context of anthropogenic warming the el nino southern oscillation enso and the north atlantic oscillation nao are the two major climate modes affecting large scale sst variability in the northern tropical atlantic both sr ca and 18o show a close relationship to enso and the nao a quantitative comparison between extremes in mean march may coral 18o and the nino3 and nao indices imply that climate variability in the northern tropical atlantic is mainly forced by tropical pacific and north atlantic variability spectral analysis suggests that the relative importance of enso and the nao is frequency dependent with enso dominating at interannual and the nao dominating at interdecadal time scales

trace elements and their isotopes in bones and teeth diet environments diagenesis and dating of archeological and paleontological samples fossil biogenic apatites display trace element te compositions that can record environmental and biological signals give insights into past water compositions or be used for dating paleontological and archeological bones and teeth processes of te incorporation into apatites of skeletal phosphatic tissues are described ranging from those active in living organisms to those active during diagenesis abiotic incorporation mechanisms have been modeled theoretically and experimentally and include crystallographic controls on te partitioning coefficients inorganic surface adsorption and adsorption mediated through chelation and diffusion adsorption processes each leading to specific fractionation patterns predictions from models and experiments have been tested against te concentration and isotopic composition data on remains of contemporary wild or raised animals and on fossils of various ages and environments in living organisms tes incorporated in apatite are separated in two categories non essential elements whose concentration is compared to that of an essential element with similar behavior e g sr ca to reconstruct trophic chains and essential elements whose isotopic ratios are used to trace metabolic activity diet etc in fossils elements are incorporated during diagenesis such as rare earth elements rees and trace diagenetic processes ranging from very early quantitative adsorption likely mediated by chelators protracted diagenesis through inorganic adsorption and fractionation through diffusion adsorption to low grade metamorphism associated with intense redistribution under crystal chemical control these different steps are also identified as steps of radionuclide incorporation only samples where the earliest steps can be deciphered are useful for determining stratigraphic and archeological ages other samples will date late diagenetic events that have obliterated the paleoenvironmental signals but may be of geological significance e g tectonic events

a model based test of accuracy of seawater oxygen isotope ratio record derived from a coral dual proxy method at southeastern luzon island the philippines 1 the oxygen isotope ratio in seawater 18osw is an important indicator of past hydroclimatic conditions in the tropics in this study we apply a dual proxy approach using 18o and sr ca in coral skeletons to estimate 18osw due to a lack of long term continuous observational data for 18osw a simplified one dimensional box model of the ocean surface associated with historical surface atmospheric data is used for comparison with coral derived 18osw record the atmospheric data consist of the precipitation and evaporation values together with their 18o compositions from the global isotope reanalysis data the model successfully reproduces a multidecadal time series for 18osw at southeastern luzon island the philippines for the period 1979 2001 r 0 57 p 0 01 the result suggests that the coral records are an accurate indicator of hydrological cycle changes at the site a discrepancy between the reproduction and the coral record in the wet season december february may be caused by seasonal variation in the depth of the mixed layer and upwelling since these factors are not accounted for in the model the reproduction is in good agreement with the coral records in the dry season april june implying that 18osw estimated using the coral dual proxy method is more robust at this time of year

influences of coral genotype and seawater pco2 on skeletal ba ca and mg ca in cultured massive porites spp corals abstract coral skeletal ba ca is a proxy for seawater ba ca used to infer oceanic upwelling and terrigenous runoff while mg2 is implicated in the control of coral biomineralisation we cultured large individuals 12 cm diameter of 3 genotypes of massive adult porites spp corals over a range of seawater pco2 to test how atmospheric co2 variations affect skeletal ba ca and mg ca we identified the skeleton deposited after a 5 month acclimation period and analysed the skeletal ba ca and mg ca by secondary ion mass spectrometry skeletal mg ca varies significantly between some duplicate colonies of the same coral genotype hampering identification of genotype and seawater pco2 effects coral aragonite seawater ba ca partition coefficients kd ba ca do not vary significantly between duplicate colonies of the same coral genotype we observe large variations in kd ba ca between different massive porites spp coral genotypes irrespective of seawater pco2 these variations do not correlate with coral calcification photosynthesis or respiration rates or with skeletal kd mg ca or kd sr ca seawater pco2 does not significantly affect kd ba ca in 2 genotypes but kd ba ca is significantly higher at 750 atm seawater pco2 than at 180 atm in 1 p lutea genotype genotype specific variations in kd ba ca between different porites spp could yield large errors 250 in reconstructions of seawater ba when comparing ba ca between corals analysis of fossil coral specimens deposited at low seawater pco2 may underestimate past seawater ba ca and ocean upwelling freshwater inputs when compared with modern specimens but the effect is small in comparison with the observed difference between coral genotypes

coccolith sr ca as a new indicator of coccolithophorid calcification and growth rate 1 polyspecific coccolith separates from core top sediments in the eastern equatorial pacific show variations of 15 in sr ca ratios across the equatorial upwelling zone with sr ca highest at the equator and decreasing off axis these variations cannot be due to changes in the sr ca of seawater which varies by less than 2 in the surface ocean variations in sr ca of coccolith sediments are similar to variations in primary productivity and alkenone estimated coccolithophorid growth rates in overlying surface waters and to caco3 rain rates measured in sediment traps because of these relationships and because calcification rate exerts a strong control on sr ca in abiogenic calcites we suggest that the observed sr ca variations in coccoliths may be strongly controlled by coccolithophorid growth and calcification rates although temperature may also influence coccolith sr ca to a lesser degree changes in dissolution intensity and coccolith assemblages appear to exert a minor influence if any on coccolith sr ca in these sediment core tops if further work confirms relationships between coccolith sr ca and coccolithophorid productivity sr ca records of past changes in coccolithophorid productivity may be useful in reconstructing past variations in the rain ratio of organic to carbonate carbon an important control on deep ocean ph and partitioning of co2 between the atmosphere and ocean in addition coccolith sr ca might provide an independent record of past changes in coccolithophorid growth rates which in combination with data on the carbon isotopic fractionation in coccolithophorid organic matter may permit more reliable calculations of past dissolved co2 in the surface ocean

a snapshot of climate variability at tahiti at 9 5 ka using a fossil coral from iodp expedition 310 1 the integrated ocean drilling program iodp expedition 310 recovered drill cores from the drowned reefs around the island of tahiti 17 40 s 149 30 w many of which contained samples of massive corals from the genus porites herein we report on one well preserved fossil coral sample a 13 6 cm long porites sp dated by uranium series techniques at 9523 33 years monthly 18o and sr ca determinations reveal nine clear and robust annual cycles coral 18o and sr ca determinations estimate a mean temperature of 24 3 c 3 2 c colder than modern for tahiti at 9 5 ka however this estimate is viewed with caution since potential sources of cold bias in coral geochemistry remain to be resolved the interannual variability in coral 18o is similar between the 9 5 ka coral record and a modern record from nearby moorea the seasonal cycle in coral sr ca is approximately the same or greater in the 9 5 ka coral record than in modern coral records from tahiti paired analysis of coral 18o and sr ca indicates cold wet warm dry interannual anomalies opposite from those observed in the modern instrumental record

annual cycles of u ca in coral skeletons and u ca thermometry abstract we have discovered annual variations in the 238 u 40 ca ratio of porites coral skeletons measurements were made using thermal ionization mass spectrometric techniques yielding precisions of 2 2 for 238 u 40 ca and l 2 for 88 sr 40 ca coralline aragonite subsamples weighed 2 mg enabling submillimeter sampling resolution corresponding to monthly temporal resolution the annual nature of the cycles was confirmed by comparison with annual banding observable in x radiographs for two modern and one fossil sample the amplitude of the u ca variation ranges from 6 to 23 well outside of analytical error as annual u ca cycles appear to be a general feature of primary coralline aragonite the preservation of such features will be important in identifying unaltered coral for u series dating studies u ca variations mimic and are in phase with annual variations in 88 sr 40 ca for a given fractional shift in sr ca the fractional shift in u ca is about 6 times larger for the two modern corals 238 u 40 ca is strongly anticorrelated with measured temperature suggesting that 238 u 40 ca has potential as a paleothermometer if temperature is the only significant control on coralline 238 u 40 ca we reach the following conclusions from analyses of fossil samples a vanuatu sample which grew halfway through the last deglaciation gives u ca temperatures 4 to 5 c below modern values u ca thermometry applied to published data for barbados corals indicates that 1 temperature generally correlates with sea level 2 glacial temperatures stages 2 and 4 were 4 to 6 c lower than interglacial temperatures stages 7a 5e and 1 and 3 temperatures rose from glacial to interglacial values early in the last deglaciation thermometry applied to papua new guinea corals indicates that 1 temperatures were 5 to 6 c lower than interglacial temperatures from 13 to 10 ky bp then rose to present values 9 ky bp 2 the temperature depression between 13 and 10 ky bp is consistent with low temperatures observed in vanuatu during the same time interval and 3 the papua new guinea deglacial temperature history differs from that of barbados the results generally support estimates of tropical temperatures obtained from sr ca thermometry and snow line elevation data but disagree with those based on foram transfer functions a thermodynamic model suggests that coralline 238 u 40 ca may also be sensitive to marine carbonate ion concentration raising the possibility that some of the observed glacial interglacial 238 u 40 ca variation may result from glacial interglacial carbonate ion changes however the key experiments that might establish a coralline 238 u 40 ca carbonate ion relationship have yet to be performed

the non tropical coral cladocora caespitosa as the new climate archive for the mediterranean high resolution weekly trace element systematics abstract high resolution weekly laser ablation icp ms trace element analyses b sr u mg ba are reported for the scleractinian coral cladocora caespitosa collected from the northern adriatic sea geochemical ratios sr ca b ca mg ca u ca ba ca were measured in a 38 mm long 10 years growth external coralline portion wall region and generally exhibit a close relationship with the in situ measured weekly fortnightly data on sea surface temperature sst available for the last 6 years in particular b ca ratios tuned to fine scale variations in sst show a high degree of correlation r 0 856 n 136 with sst and indicate that coral calcification only occurs above a minimum temperature threshold of 14 16 c in addition the ranges of trace element variability are larger than those typically recorded in tropical corals consistent with the large seasonal variations in sst of the adriatic this study thus demonstrates the feasibility of extracting and exploiting high resolution geochemical records from non tropical corals such as c caespitosa as a proxy for sst

the thermal oceanographic signal of el nino reconstructed from a kiritimati island coral central equatorial pacific sea surface temperature sst anomaly is a critical predictor of basin wide oceanographic and atmospheric effects of the el nino southern oscillation enso phenomenon we employ two geochemical thermometers measured on coralline aragonite to reconstruct an independent proxy based measure of central equatorial pacific sea surface temperature anomaly in addition we assess the observational error associated with extraction of large scale sst anomalies from 18o and sr ca measurements on the basis of paired data for the 1981 1987 period rms error for the estimation of sst from kiritimati coral 18o is about 0 4 c assuming no seawater 18o influence for sr ca the observational error is about 0 5 c singular spectrum analysis of the 18o time series suggests that 1 3 of the variance is explained by sst anomaly and that this variance may be separated from other signals in the frequency domain the interannual component of the 18o record shares 70 variance with the interannual component of local sst anomaly estimates 0 84 and correlates as highly with nino3 region 150 w 90 w 5 n 5 s sst anomaly estimates comparison of annual averages of the 18o data with analyzed sst for 55 years suggests that the error in deriving annually averaged sst anomalies at kiritimati is about 0 4 c a global sst correlation analysis suggests significant correlation with the rest of the pacific basin and the tropical indian and atlantic sectors the ocean wide level of correlation achieved using the coral data is indistinguishable from that achieved using the nino3 sst anomaly index and suggests that a few well located coral reconstructions with low observational error may be sufficient to reconstruct the global sst anomaly field associated with enso activity

improving coral base paleoclimate reconstructions by replicating 350years of coral sr ca variations abstract coral based climate reconstructions are typically based on a single record and this lack of replication leads to questions in regards to chronology accuracy and reliability of the inclusive geochemical variations to record climate viability here we present two multi century coral sr ca records recovered from a porites lutea colony offshore of amedee island new caledonia 22 28 8 s 166 27 9 e the chronology was developed by cross dating the coral sr ca time series and verifying the chronology with high precision absolute 230th dating we identify chronological discrepancies of 2 3 and 3 7 years century 1 for reconstructions based on a single core with uncertainty increasing after 250 years we assess the impact of porites skeletal architecture on coral geochemistry by characterizing centimeter scale architectural structures with respect to sampling optimal sampling paths are those on the slab surface parallel to the growth direction of individual corallites along the central axis of an actively extending corallite fan coral sr ca time series extracted from optimal skeletal structures are highly reproducible with a mean absolute difference of 0 021 mmol mol 1 or 0 39 c for monthly determinations suboptimal skeletal architecture is characterized by corallites extending through the slab surface and the coral sr ca determinations derived from suboptimal paths tend to produce a warm bias that varies between 0 04 and 2 30 c disorganized skeletal architecture is characterized by small terminating or unclear corallite fans that produce a cold bias of 0 11 to 2 45 c in coral sr ca determinations these problematic architecture types also produce biases in coral 18o determinations but to a lesser extent we assess the impact of sampling a coral colony along paths that vary from vertical to horizontal in large and small porites colonies with extension rates 6 mm year 1 and we determine there is no significant difference in the coral sr ca records

flow characterization through heat transfer evidence in a carbonate fractured medium first approach water temperature records at the outlet of a fractured carbonate system during an annual cycle show two types of variation slow variations over a small range resulting from the thermal equilibrium between water and rock in the aquifer and more rapid variations over a wider range transmitted more quickly due to the inflow of water through fractures or karstic pipes starting at the outlet we present first a model of thermal exchange for flow in a conduit then a model of thermal exchange in a porous medium between the surface and the reservoir the comparison with the data recorded at guichy nievre france allows us to establish the fact that on this site the vertical flow between the surface and the reservoir is rapid through a fracture network as is the case for the flow at the outlet

geochemical perspectives on coral mineralization corals open an exceptional window into many phenomena of geological geochemical climatic and paleontological interest from the paleozoic to the present corals provide some of the finest high resolution archives of marine conditions corals are likewise exceptional for chronometric purposes and even the terrestrial 14c timescale has now been calibrated against coral 230th 234u corals also represent a testing ground for basic ideas about mineralogy and geochemistry the shapes sizes and organization of skeletal crystals have been attributed to factors as diverse as mineral supersaturation levels and organic mediation of crystal growth the coupling between calcification and photosynthesis in symbiotic corals is likewise attributed to everything from photosynthetic alkalinization of the water to efforts by the coral to prevent photosynthetic alkalinization corals also leave a significant geochemical imprint on the oceans their aragonite skeletons accept about 10 times more strontium than does calcite hence the proportion of marine aragonite precipitation affects the oceanic chemical balance biological carbonates represent the biosphere s largest carbon reservoir hence calcareous organisms affect the ocean s ph co2 content and ultimately global temperatures through the greenhouse gas connection finally corals present some geochemical puzzles for ecology and conservation how do symbiotic corals obtain nutrients in some of the most nutrient deficient parts of the planet are global geochemical changes partially responsible for the widespread declines in coral reefs during recent decades we will address many of these issues but will concentrate on coral skeletal structure and calcification mechanism these topics bear most directly on the biomineralization process and generally affect the choice of skeletal materials and analytical techniques used in geochemical investigations the coral reef is probably the planet s most spectacular biomineralization product these grand and complex ecosystems build on the accumulated skeletal debris of countless generations of organisms especially calcareous algae and symbiotic

acropora interbranch skeleton sr ca ratios evaluation of a potential new high resolution paleothermometer the majority of coral geochemistry based paleoclimate reconstructions in the indo pacific are conducted on selectively cored colonies of massive porites this restriction to a single genus may make it difficult to amass the required paleoclimate data for studies that require deep reef coring techniques acropora however is a highly abundant coral genus in both modern and fossil reef systems and displays potential as a novel climate archive here we present a calibration study for sr ca ratios recovered from interbranch skeleton in corymbose acropora colonies from heron reef southern great barrier reef significant intercolony differences in absolute sr ca ratios were normalized by producing anomaly plots of both coral geochemistry and instrumental water temperature records weighted linear regression of these anomalies from the lagoon and fore reef slope provide a sensitivity of 0 05 mmol mol c 1 with a correlation coefficient r2 0 65 comparable to those of genera currently used in paleoclimate reconstructions reconstructions of lagoon and reef slope mean seasonality in water temperature accurately identify the greater seasonal amplitude observed in the lagoon of heron reef a longer calibration period is however required for reliable reconstructions of annual mean water temperatures

sea surface temperature and salinity reconstruction from coral geochemical tracers massive scleractinian corals secrete an aragonitic skeleton which incorporates a large array of chemical tracers corals present several advantages for palaeoclimate research they grow continuously and can live up to 1000 years they are easy to date and they can be sampled at high resolution weekly to monthly resolution both live and fossil corals can be collected in the field in the past two decades significant efforts have been made to identify robust tracers of sea surface temperature sst and salinity sss in corals to date sr ca and 18o are considered to be the most reliable sst tracers although changes in seawater 18o can significantly alter sst reconstructed from coralline 18o because these variations in seawater 18o can be linked to sss changes this initial problem can in fact be turned into an advantage and provide us with an sss tracer the sst component in the coral 18o signal can either be evaluated through sr ca measurements or in some case simply filtered out however there is still much uncertainty concerning the exact mode of incorporation of trace elements and stable isotopes into the coral skeleton the effects of growth rate light intensity feeding habits ph and water chemistry are still poorly documented a review of the strength and weaknesses of sr ca and 18o is presented together with some examples of sst and sss reconstructions other potential sst tracers are also reviewed it is expected that the ability to grow corals in aquarium under controlled conditions and that the development of sophisticated analytical techniques at the micrometric level should help us understand better the robustness of each tracers and the factors controlling their incorporation in coral aragonite

reef core insights into mid holocene water temperatures of the southern great barrier reef the tropical and subtropical oceans of the southern hemisphere are poorly represented in present day climate models necessitating an increased number of paleoclimate records from this key region to both understand the earth s climate system and help constrain model simulations here we present a site specific calibration of live collected massive porites sr ca records against concomitant in situ instrumental water temperature data from the fore reef slope of heron reef southern great barrier reef gbr the resultant calibration and a previously published acropora calibration from the same site was applied to subfossil coral material to investigate holocene water temperatures at heron reef u th dated samples of massive porites suggest cooler water temperatures with reduced seasonal amplitude at 5 2 ka 2 76 1 31i c cooler than present and 7 ka 1 26i c cooler than present at heron reef these results contrast the previous suggestion of a mid holocene thermal maximum in the central gbr around 5 35 ka and 4 48 ka yet may be explained by differences in temperature of the shallow ponded reef flat central gbr and the deeper reef slope waters this study and potential large reservoir correction errors associated with early radiocarbon dates combining coral based water temperature anomaly reconstructions from the tropical and subtropical western pacific indicates a coherent temperature response across the meridional gradient from indonesia and papua new guinea down to the southern gbr this similarity in reconstructed temperature anomalies suggests a high probability of an earlier expression of a mid holocene thermal maximum on the gbr between 6 8 and 6 0 ka

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

in situ measurements of oxygen isotopic composition in deep sea coral lophelia pertusa re examination of the current geochemical models of biomineralization abstract we present ion microprobe measurements of oxygen isotopic compositions in the deep sea coral lophelia pertusa compared to bulk skeletal aragonite fibres the emz early mineralization zone near the inside of the calyx was systematically depleted in 18 o rayleigh fractionation from a semi closed fluid reservoir does not explain this and other geochemical differences furthermore ph values estimated from skeletal 11 b data are inconsistent with the idea that emz or centres of calcification 18 o depletion reflects a more alkaline calcification environment our data combined with microstructural and geochemical observations indicate that the aragonitic fibres and emz are formed by a compartmentalized mineralization calicoblastic ectoderm which exerts strong biological control on the composition of the skeleton hence we propose a new model whereby amorphous calcium carbonates acc are precursors to the emz whereas the fibre precipitation is probably governed by kinetic processes

excess dissolved ca in the deep ocean a hydrothermal hypothesis abstract variations in seawater alkalinity and dissolved calcium provide information essential to establishing the integrated deep ocean calcium carbonate dissolution flux high precision ca measurements reported here confirm earlier suggestions that the deep ocean contains higher levels of dissolved ca than expected from calcium carbonate dissolution only i propose that the mid depth ca excess is a manifestation of the circulation of seawater through hydrothermal systems at mid ocean ridges qualitative agreement with 3 he distributions and evidence for deep water mg depletions support this hypothesis the magnitude of the mid depth ca excess implies a total hydrothermal flux larger than expected from the corresponding excess in 3 he and points to the relative importance of low temperature diffuse fluxes versus high temperature discrete fluxes for elements such as ca the implied total hydrothermal flux for ca is consistent with its oceanic mass balance requirements and resolves several long standing problems associated with our understanding of the chemical evolution of the ocean and in particular its low alkaline content

extracting a climate signal from the skeletal geochemistry of the caribbean coral siderastrea siderea 1 the first bimonthly time series of paired 18o and sr ca from the slow growing coral siderastrea siderea from the dry tortugas florida has been generated that documents that robust proxy climate records of the tropical atlantic and intraamerican seas can be produced from this massive coral the time series contain a 20 year long calibration window 1973 1992 for both 18o and sr ca and a 73 year long verification window 1900 1972 for sr ca these time series permit the quantification of the relationship between coral 18o sst and sr ca sst and the assessment of the stability of the proxy relationships over time both coral geochemical records are highly correlated with the augmented instrumental sst record through the calibration period and sr ca remains highly correlated through the verification period both at the bimonthly r 0 97 and annual average resolution r 0 72 coral 18o and sr ca are highly reproducible within the same core and sr ca exhibits no extension related vital effects this study sets the stage for generating multicentury scale climate records from the tropical atlantic ocean using the skeletal geochemistry of this massive but slow growing coral

the temperature relationship in coralline aragonite influence of variability in and skeletal growth parameters this paper provides an evaluation of two of the most likely pitfalls of sr ca thermometry i e the effect of biogenic cycling of sr vs ca in the surface ocean and the effect of variable extension rate on sr incorporation in coralline aragonite the authors also report calibration of the sr ca temperature relationship for three coral species porites lobata pocillopora eydouxi and pavona clavus collected for the hawaiian and galapagos islands analyses of seawater samples show significant spatial and depth variability in the sr ca ratio the uncertainty introduced by this effect is estimated to be 0 2 degrees c for corals located in tropical oligotrophic waters and potentially larger for corals located in upwelling areas sr ca along two different growth axes of a galapagos pavona clavus with annual extension rates of approximately 6 and 12 mm y respectively indicate an offset of 1 2 degrees c with higher sr ca values associated with slower extension rates the offset observed between the two growth axes may be the result of variations in extension and or calcification rate these results are important in determining past sea surface temperatures for reconstruction of paleoclimates

a high resolution sr ca and δ18o coral record from the great barrier reef australia and the 1982 1983 el nino abstract a high resolution near weekly sr ca and oxygen isotopic record is presented for a coral from the pandora reef in the great barrier reef gbr of australia during the period 1978 to 1984 the records are well correlated except for periods of high rainfall when river runoff has significantly modified the 18o value of seawater using the sr ca temperature calibration of de villiers et al 1994 the sr ca records exhibit seasonally controlled cyclical sst sea surface temperature variations of from 21 to 28 c during the very strong el nino of 1982 1983 the sr ca systematics indicate a sharp drop in the winter sst to 18 5 c this represents a temperature anomaly of 3 c which is approximately twice that given by the 18o variations suggesting an 2 amplification of the anomaly by the sr ca system possibly due to the increasing dominance of inorganically controlled aragoniteseawater fractionation the oxygen isotopic systematics show the combined effects of both temperature and changing seawater 18o values the latter reflecting the influx of 18o depleted runoff during periods of high rainfall due to the extremely low 10 3 sr and ca contents of river run off relative to seawater it is possible to use the sr ca thermometer to calculate temperatures independent of major floods and hence deconvolve the combined effects in the oxygen isotopic record of variable temperature and the 18o value of seawater using this approach it is possible to quantitatively reproduce the volume of runoff from the burdekin river during the periods of major flooding that occurred in early 1979 and 1981 the results of this study demonstrate that the combined use of high resolution sr ca and 18o systematics in scleractinian corals is a powerful tool for providing quantitative constraints on past climate

li sr mg and na in foraminiferal calcite shells from laboratory culture sediment traps and sediment cores abstract constant temperature laboratory culture experiments of the planktonic foraminiferal species globigerinoides sacculifer brady suggest that the ratios of li and sr to ca in the shells are a function of these ratios in the culture solutions mg ca and na ca in the shells did not vary with changes of these ratios in the culture solution these are the first direct determinations of the relationship between foraminiferal shell chemistry and solution composition the possibility of temperature dependence for the minor elemental composition of foraminiferal shells was also investigated in the laboratory and by analysis of several planktonic and one benthic foraminiferal species from sediment trap and sediment core samples the sr ca mg ca and na ca ratios in the natural samples roughly correlate with calcification temperature whereas differences in the li ca ratios are small and not systematically related to temperature however laboratory culture experiments at 20 c and 30 c showed no variation in the li ca sr ca mg ca and na ca ratios with calcification temperature for the planktonic foraminifera g sacculifer and orbulina universa therefore observed differences in the sr ca mg ca and na ca ratios for the sediment trap and core foraminiferal samples cannot be ascribed to direct effects of calcification temperature but may be due to some other environmental factor which is correlated with temperature

biogeochemical controls on palaeoceanographic environmental proxies a review scientific observations of our oceans and climate go back no more than a couple of hundred years most of our information about the evolution of earth s ocean climate system relies instead on proxies primarily measurements of sediment components that respond to changes in environmental parameters this paper provides an overview of some of the most important biological and geochemical proxies and outlines their contribution to our understanding of the ocean climate system we also discuss some of the challenges that need to be overcome to obtain accurate records these include better understanding of the controls on the mechanisms of biomineralization the impacts of post depositional dissolution and diagenesis on primary proxy relationships proxy validation and analytical considerations

mid holocene climate in new caledonia southwest pacific coral and pmip models monthly resolved results abstract the mid holocene climate is characterized by an insolation seasonality decrease in the southern hemisphere but measurements of its actual impact on monthly resolved sea surface temperature sst in the southwest pacific region are still insufficient a new caledonian 5 5 ka cal bp coral provides a 20 year long seasonally resolved record of ocean surface conditions as inferred from coral sr ca and ba ca results were compared to monthly series of paleoclimate modeling intercomparison project phase 2 pmip2 model simulations anomalous stable isotope and u ca values are observed in a restricted area of the skeleton related to dissolution features the mid holocene sst seasonal amplitude mean and variability are higher than presently in new caledonia the increased seasonal amplitude in the mid holocene being most probably due to the occurrence of colder winters other southwest pacific mid holocene coral data showed also such an increased seasonal amplitude this could mean that the south pacific convergence zone spcz was weaker or reached locations more northerly than at present which could fit with northward shifts of the inter tropical convergence zone itcz during south hemisphere winter inversely strong rainfalls during the summer deduced from the ba ca signal and reconstructed sea surface salinity sss were interpreted as reflecting pronounced southwestward shifts of the spcz in summer as those occurring today during la nina events none of the six pmip2 models used reproduce the proxy based mid holocene increase of sst seasonal amplitude model maps show a less intense spcz in winter that would be consistent with higher sst seasonal amplitude finally we stress the need for more seasonally resolved data to validate this enhanced mid holocene sst seasonal amplitude in the southwest pacific region and to better understand the underlying mechanisms

strontium heterogeneity and speciation in coral aragonite implications for the strontium paleothermometer sea surface temperatures ssts have been inferred previously from the sr ca ratios of coral aragonite however microanalytical studies have indicated that sr in some coral skeletons is more heterogeneously distributed than expected from sst data strontium may exist in two skeletal phases as sr substituted for ca in aragonite and as separate srco3 strontianite domains variations in the size quantity or both of these domains may account for small scale sr heterogeneity here we use synchrotron x ray fluorescence to map sr ca variations in a porites lobata skeleton at a 5 m scale variations are large and unrelated to changes in local seawater temperature or composition selected area extended x ray absorption fine structure exafs spectroscopy of low and high sr areas indicates that sr is present as a substitute ion in aragonite i e domains of sr carbonate strontianite are absent or in minor abundance variations in strontianite abundance are not responsible for the sr ca fluctuations observed in this sample the sr microdistribution is systematic and appears to correlate with the crystalline fabric of the coral skeleton suggesting sr heterogeneity may reflect nonequilibrium calcification processes nonequilibrium incorporation of sr complicates the interpretation of sr ca ratios in terms of sst particularly in attempts to extend the temporal resolution of the technique the micro exafs technique may prove to be valuable allowing the selection of coral microvolumes for sr ca measurement where strontium is incorporated in a known structural environment

beachrock formation via microbial dissolution and re precipitation of carbonate minerals cementation of beach sand in the intertidal zone produces beachrock such as that found on heron island heron reef great barrier reef australia although common to coastlines in many low latitude beach environments the cause of cementation is not fully understood in this investigation electron and x ray fluorescence microscopy were used to characterize previously undocumented features of beachrock two generations of beachrock were examined as a means of understanding the progression of cementation meniscus shaped attachments at point contacts appear to be the first cements to form in biofilms near the beachrock surface this is followed by isopachous fringe cements within the now enclosed beachrock composed of aragonite needles that are enriched in strontium and contain extracellular polymeric substances eps cement precipitation is driven by locally high concentrations of cations in solution undoubtedly generated via microbial dissolution of the detrital carbonate grains binding to negatively charged bacterial eps retains these cations within beachrock microenvironments the metabolism of cyanobacteria and associated heterotrophs induce the supersaturating conditions needed for cement precipitation deeper within beachrock mm to cm below the surface abundant microbialites are found on the edges of grains and contain trapped and bound detrital material these structures are laminated enriched in strontium in some layers and contain microfossils the results of this investigation clearly demonstrate a biological influence in the precipitation of aragonite cement involving internal recycling of cations through microbial dissolution and precipitation of carbonate minerals

coral barium calcium record of mid holocene upwelling activity in new caledonia south west pacific abstract a variety of inimical factors i e sea surface temperature nutrient input nature of substrates were invoked previously to explain the retardation in reef settlement in new caledonia during the holocene in order to clarify the respective role played by temperature and nutrient level in the growth of fringing reefs along the southwest coast of the island trace element ratios i e sr ca and ba ca were used respectively as a paleothermometer and as a tracer of nutrient load from modern and mid holocene about 6000 calendar years old massive porites coral colonies the results obtained from the modern coral record indicate that near the outer barrier reef upwelling activity is controlled by southeast winds blowing in summer by contrast along the southwest coastline the fringing reefs are subjected to barium input mainly derived from weathering of barite rich rocks cropping out in the adjacent mainland comparison between the fossil and modern coral sr ca and ba ca records shed light on three different aspects of the mid holocene climate and coral reef evolution in new caledonia 1 the variability of paleo sea surface temperature sst seems to have been similar to the modern one although the island probably experienced sst about 1 c higher than at present 2 upwelling activity appears to have been greater than at present barium being supplied from the open sea to coastal zones by strong wind generated upwelling currents in relation to cooling events 3 the onset of reef development in the southwest areas of new caledonia was delayed due to the stronger upwelling of nutrient enriched waters during the early middle holocene the flowing of upwelled waters over the southwest coastal areas began at 8200 calendar years bp and ceased at the time when the outer barrier reef crest reached present day sea level about 5500 to 5000 calendar years ago

seawater strontium and sr ca variability in the atlantic and pacific oceans abstract seawater sr and sr ca exhibit spatial gradients of 2 3 globally with the deep ocean more enriched relative to the surface in latitudinal transects the highest surface values are found at high latitudes and associated with areas of upwelling a pronounced upper ocean vertical sr gradient is attributable to the production of celestite skeletons by surface dwelling acantharia coupled to a shallow dissolution cycle the upper ocean residence time of sr with respect to celestite cycling is much shorter than its global oceanic residence time although the magnitude of seawater sr ca variability is relatively small it is significant with respect to high precision paleoceanographic applications sr ca gradients in the contemporary ocean also complicates evaluating quaternary changes in seawater sr ca that may have resulted from other processes such as aragonite recrystallization during sea level low stands

sr ca u ca and δ18o records in recent massive corals from bermuda relationships with sea surface temperature abstract high resolution records of sr ca u ca ratios and 18o have been obtained in two recent colonies of massive corals diploria labyrinthiformis from bermuda the three geochemical proxies display regular seasonal variations and are well correlated with each other however some important discrepancies are observed between the two colonies the average seasonal variations of the three geochemical proxies are lower by almost 50 in one of the profiles where the seasonal oscillation also displays a strong asymmetry with narrower summer maxima different calculations are discussed for calibrating sr ca and 18o with sea surface temperatures sst we show that the method using only temperature minima and maxima is slightly more accurate and is also more reliable our results from bermuda corals confirm that the temperature dependency of sr ca u ca and 18o is species dependent as previously shown by others and that vital effects are clearly involved in the geochemical incorporation of trace elements in the coral skeleton finally a simple model involving seasonal variation of the growth rate and a kinetic fractionation related to growth rate is presented to explain the differences between the two bermuda colonies it is shown that these factors may prevent corals from recording the complete temperature seasonality and could be the cause for the discrepancies observed between profiles resulting in significant biases of the sst reconstructions

bamboo coral ba ca calibration of a new deep ocean refractory nutrient proxy abstract it is poorly understood how intermediate water masses are affected by decadal scale climate via biogeochemical cycling export production and changes in circulation ventilation to this end a geochemical nutrient proxy from deep sea bamboo corals would provide decadal to centennial scale records of deep and intermediate water nutrient dynamics seawater barium basw has a nutrient like distribution in the water column similar to silicate so ba ca records in foraminifera shallow water surface corals and other deep sea corals have been used to trace refractory nutrients here we present the first calibration of a nutrient proxy from skeletal barium preserved in the calcitic internodes of deep sea bamboo corals collected from intermediate water depths a calibration was calculated from a broadly distributed suite of isidella and keratoisis corals spanning a silicate and basw gradient n 33 corals 300 2800 m ba ca b a m b o o c o r a l mol mol 0 079 0 008 ba sw nmol kg 4 205 0 870 r 2 0 77 n 33 the strong linear correlation between ba cabamboo coral and basw suggests that coral ba ca is a reliable recorder of seawater barium and therefore silicate we find a distribution coefficient dba for ba cabamboo coral of 1 3 0 2 similar to that of other corals surface and deep sea dwelling and inorganic calcium carbonate precipitation experiments dba 1 2 1 5 this suggests that ba incorporation is primarily driven by cationic substitution in bamboo corals and holds promise as a globally applicable refractory nutrient proxy we find interannual decadal scale variability in a ba cabamboo coral timeseries from a california margin coral san juan seamount 1295 m these data suggest that additional high resolution ba cabamboo coral records may reveal a connection between regional scale intermediate water biogeochemistry and low latitude surface ocean atmospheric climate