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

diagenetic stabilization of the upper permian dalan formation persian gulf basin abstract the upper permian dalan formation is a supergiant gas reservoir in the persian gulf basin reservoir quality is controlled by the original facies type dolomitization and anhydrite cementation this study focuses on the texture petrographic analysis bulk stable isotope values and trace element composition in order to identify the original mineralogy of carbonate grains and cements and to assess the synsedimentary and diagenetic processes including the timing and setting of dolomitization the limestone data suggest that the initial precipitation of isopachous acicular to fibrous aragonite cements in the marine phreatic environment was followed by dissolution of aragonite grains and cements in the meteoric phreatic zone and neomorphism and low mg calcite cementation blocky and drusy crystals syntaxial overgrowths in the active freshwater phreatic zone the relatively pristine 18o and 13c values low mn and relatively high sr and na contents indicate that this meteoric diagenesis was relatively limited the remaining porous space was cemented by blocky calcite later during burial four types of dolomites are identified within a complex mixture of texturally and isotopically different dolomites dolomicrite dolomicrosparite dolosparite and saddle dolomite dolomicrite formed syndepositionally from the evaporated permian seawater or by reflux of dense evaporated brines during shallow burial the second major episode of dolomitization dolomicrosparite and dolosparite was driven by reflux of warmer and more saline fluids at greater depth which affected both previously non dolomitized and dolomitized sediments the final diagenetic stabilization during deep burial is associated with extensive pressure solution fracturing vein filling of calcite and dolomite cements and crystallization of saddle dolomite

multikilometer sized reefs built by foraminifera solenomeris from the early eocene of the pyrenean domain s france n spain palaeoecologic relations with coral reefs abstract solenomeris foraminifera reefs of the early ypresian pyrenean gulf were previously mistaken for red algal or incertae sedis algal reefs solenomeris has recently been referred to the acervulinid foraminifera these foraminifera buildups are described in detail and their palaeoecology is discussed the distribution of these reefs within the languedoc basin demonstrates their preference for bathymetric highs of external platforms in common with coral reefs to which they locally succeed during the early ypresian transgression all solenomeris reefs examined are located either at the outer periphery of a lagoon with small operculina or on the external margin of a carbonate platform characterized by various miliolida they extend into deeper waters than the associated coral reefs even in turbid environments unfavourable for encrusting coralline algae the reconstruction of the palaeoecology of solenomeris shows many similarities with corals however corals probably require higher light and oxygen levels especially when present near their northern limit the global distribution of solenomeris reefs can not be established until their correct identifications have been made instead of algal reefs

reduction of oceanic temperature gradients in the early eocene southwest pacific ocean abstract we present a southwest pacific ocean paleothermometry transect using new and existing foraminiferal mg ca data from six eocene locations from eastern new zealand to southwestern campbell plateau spanning 10 of paleolatitude 43 to 53 s sea surface and seafloor temperatures sst and sft have been calculated taking into account the partition coefficients of calcite and paleogene mg ca sw ratios and used to determine values for the power component h of this relationship in foraminiferal calcite from paired proxy 18 o and mg ca records from canterbury basin this study presents the first eocene paleotemperature record for the east coast basin and in so doing shows the absence of a meridional temperature gradient over 10 of latitude during the early eocene climatic optimum eeco and provides evidence for a very weak to absent gradient from the equatorial pacific to 53 s at this time of extreme global warmth the application of a new subsurface tex 86 calibration correlates remarkably well with mg ca seafloor temperature trends from the continental slope setting 86 is recording an upper ocean subsurface temperature record rather than simply sst values sst sft gradients demonstrate a notable reduction decreasing to 3 5 c across the eeco the comparable ocean temperatures of the east coast basin canterbury basin and dsdp site 277 during this time support the intensification of a proto east australian current eac explaining the distribution of tropical sea temperatures extending into the high latitude southwest pacific ocean during the eeco seafloor temperatures 1000 m paleodepth likely correspond to a northern intermediate water source during the early eocene before switching to a cooler southern derived source in the middle to late eocene

dolomitization a critical view of some current views the principal models in vogue today for dolomitization are the mixing zone and the sabkha models despite the wide acceptance of these models there has been little critical assessment of their validity such an assessment is the objective of the present paper a close look at the dorag mixing zone model badiozamani 1973 reveals several serious weaknesses 1 the range of freshwater seawater mixtures that meet the dorag requirement for dolomitization shrinks to a small window if the geologically more realistic disordered dolomite is used in the calculations instead of the ordered dolomite on which the model is based 2 in none of the known modern coastal mixing zones in limestone or lime sediments has replacement by dolomite been observed 3 in a number of dolomites interpreted to be of mixing zone origin dolomite has precipitated without dissolution of the calcite substrate evidence that negates the fundamental premise of the dorag model in addition to these weaknesses isotope and trace element data used to identify mixed water dolomite are inadmissible because 1 isotopic fractionation factors for dolomites remain unresolved 2 isotope values uncorrected for temperature for a host of dolomites interpreted to be of different origins overlap 3 nonisomorphous trace elements such as na in dolomite cannot on theoretical grounds be relied on to identify dolomitizing fluids similar overall objections can be brought against folk and land9s 1975 schizohaline version of mixing zone dolomitization in summary mixing zone models have such weak underpinnings that they should be questioned as viable explanations for massive dolomitization contemporaneous dolomite formation in modern sabkhas is well documented but the important question of whether the mechanism of dolomite formation is replacement or direct precipitation remains to be resolved in the well studied sabkha at abu dhabi brine chemistry changes have been used as evidence of a replacement origin for the dolomite but it is shown here that this evidence is far from unequivocal an alternative origin of direct precipitation of dolomite is offered an origin in keeping with dolomite precipitation known from other modern sabkhas and saline lakes and in line with our laboratory experience with dolomite synthesis moreover it is suggested here that in general contemporaneous dolomite will form at low temperatures only by direct precipitation a mechanism that requires special conditions of highly super saturated waters of high mg ca ratio and elevated co 3 hco 3 concentrations this may explain why modern dolomite is mainly restricted to evaporitic environments a bias not shared by ancient dolomites in contrast replacement dolomite appears to require at low temperatures long reaction times or 10 4 yr a requirement that is mainly to be met in large regional groundwater flow systems both marine and nonmarine a third dolomitization model considered here is that of baker and kastner 1981 based on the experimental finding that sulfate ions inhibit or retard dolomitization a number of modern sedimentary dolomites are not in accord with this model in that they are forming from brines with large sulfate concentrations 2 to 70 times that of seawater thus the baker kastner model should be held in abeyance until these serious contradictions are resolved the current emphasis on mixing zone and sabkha dolomitization has diverted attention from other promising avenues of approach to the dolomite problem four of these avenues each of which deemphasizes the special water approach are briefly addressed and are as follows 1 influence of temperature and time 2 mass transfer processes 3 burial diagenesis of epigenetic dolomites 4 fluid inclusion studies at elevated temperatures the dolomite problem essentially disappears ordered dolomite can be made in the laboratory in days at 100 degrees c what is more at temperatures above 60 degrees c ca rich waters become dolomitizing fluids which makes most natural subsurface waters capable of dolomitization at low temperatures time may be the key element so that seawater will become a major dolomitizing fluid only where stable circulation systems such as kohout convention can drive seawater through carbonate platforms for many thousands to millions of years this paper has tried to show that currently favored models of dolomitization carry serious uncertainties enough to warn us to look more critically at the validity of these models and also it is hoped enough to spur new efforts to find new solutions to the problems of dolomitization

temporal variation in calcification in marine cyanobacteria periods of widespread abundance of calcified cyanobacteria in marine environments are here termed cyanobacterial calcification episodes cces intense such episodes occurred in the cambrian early ordovician late devonian and mid late triassic mild episodes occurred during the early carboniferous and jurassic early cretaceous possible episodes during parts of the silurian and permian await confirmation cyanobacterial calcification is not obligate but is dependent upon environmental factors favouring carbonate precipitation cyanobacterial calcification episodes are therefore interpreted as reflecting periods of increased marine carbonate precipitation this is supported by the general abundance of marine carbonate cements and oolites during cyanobacterial calcification episodes cyanobacterial calcification episodes correspond with phanerozoic periods for which elevated global temperatures have been inferred they do not appear to correlate closely with inferred changes in aragonite calcite facilitation the sandberg curve and p co2 through time it is concluded that variations in the precipitation rates of abiotic and quasi abiotic marine carbonates through time have been controlled primarily by temperature the mineralogy of these precipitates appears instead to have been mainly influenced by p co2 and the mg ca ratio also linked to sea level through plate tectonic processes thus the controls on rate and mineralogy of precipitation were independent of one another

depositional environment sequence stratigraphy and geochemistry of lower cretaceous carbonates fahliyan formation south west iran abstract the fahliyan formation is a carbonate sequence of lower cretaceous berriasian hauterivian age and was deposited in the zagros sedimentary basin iran in this investigation the fahliyan formation at the type section and in the subsurface has been studied facies analysis and petrographic studies led to the recognition of 10 microfacies that were deposited in three facies belts lagoon shoal and open marine the observed facies patterns indicate a carbonate rimmed shelf depositional environment based on field observations microfacies analysis and sequence stratigraphic concepts two third order sequences in the type section and three third order sequences in the subsurface section were identified the transgressive deposits display a predominance of deep subtidal facies while highstand deposits show shallow subtidal facies some petrographic evidence such as an abundance of aragonite skeletal and non skeletal components shows that this formation was deposited in a sub tropical environment with original aragonite mineralogy geochemical evidence such as high sr na ratios also support original aragonite mineralogy 18o and 13c values suggests that alteration occurred during burial diagenesis in a closed system with low water rock interaction palaeotemperature calculation based on the heaviest oxygen isotope value in micritic samples of the fahliyan limestone shows that ambient water temperature was around 24 c during the deposition of this formation

the late paleozoic to mesozoic evolution of the eastern margin of the central asian orogenic belt in china abstract the north east central asian orogenic belt caob in china records terminal closure of the paleo asian ocean in the mid to late permian along the solonker xar moron changchun suture this marks the end of the overall northward movement of the chinese blocks from a peri gondwana position toward siberia and a switch in tectonic processes to those dominated by activity associated with the paleo pacific plate to the east four distinct changes in tectonic regime can be recognised here in the late paleozoic to early mesozoic i north south compression resulted in orogenesis and gave way to post collisional extension at 260 250 ma with the emplacement of a type granites ii almost coeval with this there was an the onset of east west extension from 250 to 225 ma along the extreme eastern margin of the caob when a seaway opened between the songliao and jiamusi khanka blocks iii the onset of westerly directed compression associated with subduction of the paleo pacific plate from 210 ma resulted in re amalgamation of the jiamusi khanka block with the caob by 190 180 ma and the massive generation of jurassic i type granitoids throughout the region finally iv a change to east west extension from 140 ma onward resulted from roll back of the paleo pacific plate this latter event was accompanied by the emplacement of s type granitoids and the development of sedimentary basins and core complexes it also accompanied a more widespread thinning or delamination of the lithosphere across most of north east china during the cretaceous

geochemistry of campanian maastrichtian brachiopods from the rordal 1 core denmark differential responses to environmental change and diagenesis abstract past marine environmental conditions can be reconstructed from geochemical signatures of both benthic and planktic organisms and particularly brachiopods have been extensively used for this purpose however it is seldom possible to investigate the links between environmental conditions and shell geochemistry in monospecific records over extended periods of time here we present geochemical data from the 100 m thick brachiopod rich upper campanian upper maastrichtian chalk 73 8 68 6 ma of the rordal 1 drill core northern denmark two species that lived attached to small substrate argyrotheca bronnii roemer and gisilina jasmundi steinich and one secondarily free living species magas chitoniformis schlotheim have been studied for element concentrations as well as c and o isotope signatures each species has a unique chemical signature with m chitoniformis showing lowest mg and mn concentrations a bronnii the highest mn concentrations and g jasmundi the highest sr concentrations all three species display decreasing mg ca ratios throughout the studied interval and distinct mn enrichments in the campanian maastrichtian boundary cmb interval in the campanian part of the succession the three species are slightly enriched in 13 c median 13 c values of 0 0 to 0 5 and 18 o median 18 o values of 0 3 to 0 6 with respect to coeval chalk in the course of the maastrichtian the two attached species acquire progressively lighter isotopic compositions with a bronnii reaching 13 c and 18 o values 1 0 lower than coeval chalk the secondarily free living species m chitoniformis on the other hand becomes isotopically heavier and reaches 13 c and 18 o enrichments of 1 0 at the top of the core the observed differences between the species illustrate species specific signatures of biomineralisation diagenesis and response to environmental change this geochemical complexity illustrates that a comprehensive geochemistry based picture of the late cretaceous chalk sea can only be painted using detailed multi species and multi proxy datasets

time specific aspects of facies state of the art examples and possible causes abstract the term time specific facies tsf was introduced to the scientific community by the late otto h walliser to refer to unique facies typical of particular narrow intervals some of which were related to bioevents in some senses however the concept was recognized much earlier and is even engrained in the very names of some geologic periods the concept of time specific facies is expanded slightly herein to include distinctive or unique regional to global characteristics of the sedimentary record that characterize particular intervals of geologic time the recognition of time specific and widespread processes in the sedimentary record is a critical step in unraveling the interplay between processes of differing scale these range from very short term but widespread facies that overlap with event deposits to general facies types that may persist for intervals up to 10s of millions of years in duration this paper briefly summarizes the history of development of the tsf concept provides examples to illustrate a few of the key aspects of time specific facies and offers a few tentative explanations for this phenomenon among the factors that control tsfs abrupt changes in redox conditions and early diagenetic mineralization sedimentary condensation often associated with abrupt sea level change altered climate and paleoceanography and biotic evolution and extinction seem to be most critical and permit a preliminary genetic classification of tsfs inevitably however many tsfs reflect multiple effects and some remain largely unexplained

dolomitization a critical view of some current views perspectives abstract the principal models in vogue today for dolomitization are the mixing zone and the sabkha models despite the wide acceptance of these models there has been little critical assessment of their validity such an assessment is the objective of the present paper a close look at the dorag mixing zone model badiozamani 1973 reveals several serious weaknesses 1 the range of freshwater seawater mixtures that meet the dorag requirement for dolomitization shrinks to a small window if the geologically more realistic disordered dolomite is used in the calculations instead of the ordered dolomite on which the model is based 2 in none of the known modern coastal mixing zones in limestone or lime sediments has replacement by dolomite been observed 3 in a number of dolomites interpreted to be of mixing zone origin dolomite has precipitated without dissolution of the calcite substrate evidence that negates the fundamental premise of the dorag model in addition to these weaknesses isotope and trace element data used to identify mixed water olomite are inadmissible because 1 isotopic fractionation factors for dolomites remain unresolved 2 isotope values uncorrected for temperature for a host of dolomites interpreted to be of different origins overlap 3 nonisomorphous trace elements such as na in dolomite cannot on theoretical grounds be relied on to identify dolomitizing fluids similar overall objections can be brought against folk and land s 1975 schizohaline version of mixing zone dolomitization in summary mixing zone models have such weak underpinnings that they should be questioned as viable explanations for massive dolomitization contemporaneous dolomite formation in modern sabkhas is well documented but the important question of whether the mechanism of dolomite formation is replacement or direct precipitation remains to be resolved in the well studied sabkha at abu dhabi brine chemistry changes have been used as evidence of a replacement origin for the dolomite but it is shown here that this evidence is far from unequivocal an alternative origin of direct precipitation of dolomite is offered an origin in keeping with dolomite precipitation known from other modern sabkhas and saline lakes and in line with our laboratory experience with dolomite synthesis moreover it is suggested here that in general contemporaneous dolomite will form at low temperatures only by direct precipitation a mechanism tha requires special conditions of highly super saturated waters of high mg ca ratio and elevated co3 hco3 concentrations this may explain why modern dolomite is mainly restricted to evaporitic environments a bias not shared by ancient dolomites in contrast replacement dolomite appears to require at low temperatures long reaction times 104 yr a requirement that is mainly to be met in large regional groundwater flow systems both marine and nonmarine a third dolomitization model considered here is that of baker and kastner 1981 based on the experimental finding that sulfate ions inhibit or retard dolomitization a number of modern sedimentary dolomites are not in accord with this model in that they are forming from brines with large sulfate concentrations 2 to 70 times that of seawater thus the baker kastner model should be held in abeyance until these serious contradictions are resolved the current emphasis on mixing zone and sabkha dolomitization has diverted attention from other promising avenues of approach to the dolomite problem four of these avenues each of which deemphasizes the special water approach are briefly addressed and are as follows 1 influence of temperature and time 2 mass transfer processes 3 burial diagenesis of epigenetic dolomites 4 fluid inclusion studies at elevated temperatures the dolomite problem essentially disappears ordered dolomite can be made in the laboratory in days at 100 c what is more at temperatures above 60 c ca rich waters become dolomitizing fluids which makes most natural subsurface waters capable of dolomitization at low temperatures time may be the key element so that seawater will become a ma or dolomitizing fluid only where stable circulation systems such as kohout convention can drive seawater through carbonate platforms for many thousands to millions of years this paper has tried to show that currently favored models of dolomitization carry serious uncertainties enough to warn us to look more critically at the validity of these models and also it is hoped enough to spur new efforts to find new solutions to the problems of dolomitization

mg isotopic systematics during early diagenetic aragonite calcite transition insights from the key largo limestone abstract the seawater magnesium mg isotopic composition 26mgsw can be applied to quantify marine mg cycle in earth s history however reconstruction of 26mgsw by using marine carbonate has been challenged by the large range of variation in mg isotopic composition of carbonate 26mgcarb such variation on the one hand reflects e g the mineralogy temperature and precipitation rate dependent isotopic fractionation during ca carbonate precipitation on the other hand the pristine seawater record could be modified in carbonate diagenesis during which less stable carbonate minerals would spontaneously convert to more stable mineral phases in the modern ocean with high mg ca molar ratio 5 aragonite precipitation is favored however aragonite is thermodynamically less stable than low mg calcite at ambient surface environment resulting in the spontaneous transition from aragonite to low mg calcite in the earliest stage of diagenesis i e the aragonite calcite transition as a common process in the modern ocean mg isotopic fractionation in aragonite calcite transition may provide valuable constraints on the variation of 26mgcarb in this study we measured mg isotopic compositions of pleistocene key largo limestone florida which has been experiencing the aragonite calcite transition during early diagenesis the key largo limestone samples consist of a mixture of calcite and aragonite 26mg of aragonite 26mgarag shows higher and more stable values while calcite has lower yet more variable mg isotopes 26mgcal we suggest a model conceptualizing a water film attached to the mineral surface in which the aragonite calcite transition initiates with aragonite dissolution and the mg exchange with external fluid can be variable followed by mg isotopes fractionate during low mg calcite precipitation in this model 26mgcal is controlled by 1 the chemical composition of water film which is dependent on the mineralogical composition of aragonite i e mg content and 26mgarag the composition of external fluid i e fresh water seawater or mixed fresh water and seawater and the mixing ratio between dissolved aragonite and external fluid and 2 the isotopic fractionation during calcite precipitation because the isotopic fractionation in calcite is sensitive to the rate of calcite precipitation that is dependent on the calcite saturation state of solution therefore 26mgcal could be highly heterogeneous depending on the aragonite dissolution and calcite precipitation processes further complicating the interpretation of carbonate data thus the process controlled mg isotopic fractionation should be taken into consideration when reconstructing 26mgsw by using carbonate sediments rocks

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

a coral reef in the telkwa range british columbia the earliest jurassic example an end triassic mass extinction profoundly affected reef ecosystems that flourished in the late triassic tethys seaway the collapse of late triassic coral sponge reefs was followed by an early jurassic hettangian sinemurian perturbation interval with a near global absence of reefs and sharp reductions in diversity a jurassic sinemurian reef in the hazelton group of central british columbia appears to fill the gap its paleoecology and composition show it to be the first large framework example in north america and perhaps the world it demonstrates that the reef building triassic coral phacelostylophyllum survived the extinction event and was constructing reefs in early jurassic time during a global reef eclipse the reef is a 48 m thick bioherm that grew within the island arc complex of stikinia following a decrease in volcanism reef building began with bivalves growing upon water lain tuffs the reef was dominated by large dendroid phaceloid corals primarily phacelostylophyllum rugosum a spe

sedimentary carbonates through phanerozoic time plate tectonic processes play a critical role in the origin and distribution of sedimentary carbonates through phanerozoic time the phanerozoic age distribution of sedimentary properties like calcite dolomite ratio inferred ooid and cement mineralogy and survival rate of continental carbonates is cyclic the cycles appear to be coupled to plate tectonic processes that give rise to global sea level change and changes in the properties of the ocean atmosphere system first order changes in sea level are driven by the accretion of mid ocean ridges high accretion rate high sea level low accretion rate low sea level although correlations between sea level and sedimentary carbonate properties are not strong high sea level over an extended period of time appears to be correlated with low calcite dolomite ratios lack of inferred aragonite ooids and cements and maxima in the survival rate of continental carbonates the opposite is true for extended periods of low mid ocean ridge accretion rates and global sea levels the lack of strong correlations may reflect an insufficient data base and the possibility of lags between sea level change and change in carbonate properties furthermore the survival rate of continental carbonates appears to be affected by differential cycling and therefore may not be directly related to accumulation rate it appears that the environmental conditions for early dolomitization and calcite ooid and cement formation are best met during extended times of high sea level when atmospheric co2 levels are high and the saturation state of seawater with respect to carbonate minerals relatively low during low sea levels early dolomitization is less favored and aragonite precipitates are more abundant because of low atmospheric co2 levels and enhanced seawater carbonate saturation states differential cycling has modified the phanerozoic sedimentary carbonate mass age distribution because of erosion of younger units within continental carbonate cycles it may be difficult to derive an unequivocal record of the partitioning of carbonate between the deep sea and shallow water realms of deposition during the phanerozoic this difficulty must be considered in further quantification of geochemical models describing the geologic history of atmospheric co2 and climate change

dynamic topography and long term sea level variations there is no such thing as a stable continental platform abstract globally uniform i e eustatic sea level trends with time scales approaching 100 myr have been inferred from both seismic and backstripping stratigraphic analysis at a small set of geographic sites that are presumed to lie on stable continental platforms and passive continental margins characterized by simple thermal subsidence histories e g the new jersey margin the western african margin we demonstrate using mantle flow simulations based on high resolution seismic tomography that both the new jersey margin and the conjugate western african margin have been subject to orders of 100 m of dynamic i e flow induced topography change over the last 30 myr we also show that the changing pattern of downwelling mantle flow associated with plate subduction is a significant contributor to the background eustatic sea level trend which is also of order 100 m during the 30 myr time window therefore late cenozoic variations of dynamic topography on these passive margin sites are comparable to the eustatic sea level changes and can partially mask the latter furthermore even if the observed trend could be accurately corrected for local dynamic topography variation the residual eustatic signal does not merely reflect changes in mean spreading rates at mid ocean ridges we conclude that the observed long term sea level variations at so called stable sites cannot be interpreted as eustatic moreover previous analyses that have used long term sea level trends as a proxy for spreading rates and geochemical fluxes must be revisited

gold behavior in supergene profiles under changing redox conditions the example of the las cruces deposit iberian pyrite belt the las cruces deposit is in the eastern end of the iberian pyrite belt sw spain it is currently being mined by cobre las cruces s a the main operation is focused on the supergene cu enriched zone initial reserves of 17 6 mt 6 2 cu an au ag pb rich gossan resource 3 6 mt 3 3 pb 2 5 g t au and 56 3 g t ag occurs in the upper part of the deposit the au grade ranges from 0 01 ppm to 100 ppm and occurs as three different au ore types 1 au mineralization in the upper part of the gossan linked to fe oxides lithofacies 2 au concentration in the lower part of the gossan associated with leached black shales and 3 au ore in the cementation zone related to subvertical fractures a hydroseparation device has been used to obtain heavy mineral concentrates from selected samples of different ore types reflected light microscopy scanning electron microscopy energy dispersive spectroscopy sem eds and electron probe microanalysis epma were used to study the separated au particles significant differences between the defined ore types include the au bearing lithologies mineral associations textural features particle sizes morphologies and fineness au rich minerals include native au au ag electrum and au ag hg amalgams gold bearing mineral associations include pb oxihalides fe oxides galena pyrite cinnabar and ag sulfosalts the au enrichment mechanism in the supergene profile involves 1 dissolution of au from the primary sulfides as chloride rich ionic complexes during the weathering of the deposit under subaerial exposure dissolved au is transported downward through the supergene profile under acidic and oxidized conditions 2 destabilization of the au complexes by fe controlled redox reactions as a consequence coarse grained high fineness au particles precipitated in association with fe oxyhydroxides this resulted in secondary concentration in the upper gossan and 3 after deposition of cover sediments took place a progressive change in the system conditions resulting in a later au remobilization as hydroxidehalide hydroxide thiosulfate and bisulfide complexes in the lowermost gossan and cementation zone the main pathways for migration of enriched fluids to the cementation zone are secondary permeability zones linked to alpine reactivated faults deposition of au seems to be related to fluid interaction with reductant lithologies including black shales and the primary sulfides

history of carbonate ion concentration over the last 100 million years abstract instead of having been more or less constant as once assumed it is now apparent that the major ion chemistry of the oceans has varied substantially over time for instance independent lines of evidence suggest that calcium concentration ca2 has approximately halved and magnesium concentration mg2 approximately doubled over the last 100 million years on the other hand the calcite compensation depth and hence the caco3 saturation has varied little over the last 100 my as documented in deep sea sediments we combine these pieces of evidence to develop a proxy for seawater carbonate ion concentration co32 over this period of time from the calcite saturation state which is proportional to the product of ca2 times co32 but also affected by mg2 we can calculate seawater co32 our results show that co32 has nearly quadrupled since the cretaceous furthermore by combining our co32 proxy with other carbonate system proxies we provide calculations of the entire seawater carbonate system and atmospheric co2 based on this reconstructed atmospheric co2 is relatively low in the miocene but high in the eocene finally we make a strong case that seawater ph has increased over the last 100 my

evolution of the mg ca ratio of cretaceous seawater implications from the composition of biological low mg calcite abstract for the evaluation of variations in the cretaceous seawater mg ca ratio 12 shells of rudist bivalves ranging in age from the late barremian 112 2 ma to the early campanian 81 4 ma have been analysed for intra shell variations in chemical mg sr fe mn and isotopic 18 o 13 c compositions of low mg calcite preservation of fibrous prismatic ultrastructure low fe and mn concentrations as well as sr concentrations within the range of marine biological calcite indicate only very minor diagenetic alteration in all studied shells mg concentrations and 18 o values show a more or less well defined inverse covariance this pattern is similar to the conditions observed in modern skeletal calcite and interpreted to result from a combination of a temperature effect and an unidentified metabolic control on the incorporation of mg into calcite average mg concentrations in rudist calcite are significantly lower than those of modern bivalves and increase from the barremian albian to the campanian while slopes of 18 o mg regressions are similar to those of modern bivalves assuming that the mg incorporation is linearly dependent on the mg ca ratio of seawater and that mg incorporation into calcite of modern bivalve mollusks follows the same metabolic pathway than in their extinct cretaceous relatives the mg ca molar ratio of cretaceous seawater increased from 1 in the late barremian to 3 in the early campanian this trend matches previous model predictions of seawater composition and experimental results from fluid inclusions in halite a very low mg ca ratio of seawater is confirmed here to have occurred before the onset of the significant mid cretaceous increase of seafloor production rates in the late barremian uncertainties in the secular variations of seafloor spreading are discussed as hydrothermal alteration of young oceanic crust is an important driver of changes in the seawater mg ca ratio

environmental factors influencing skeletal grain sediment associations a critical review of miocene examples from the western mediterranean the presence of foramol rhodalgal and bryomol skeletal grain associations in ancient shallow marine limestones is commonly interpreted as evidence for non tropical palaeoclimate despite temperature being only one of several factors influencing skeletal grain associations such interpretations neglect the multitude of factors other than temperature that influence carbonate producing biota these include nutrients water energy water transparency depth of the sea floor salinity oxygen ca2 and co2 concentrations mg ca ratio alkalinity substrate requirements competitive displacement as well as biological and evolutionary trends this uniformitarian approach also disregards the probability that conditions of present day biological systems may not be representative of past conditions of analogous systems here the importance of considering these other factors is illustrated through two examples of carbonate platforms in the western mediterranean these platforms are dominated by foramol rhodalgal and bryomol associations of miocene age in spite of having formed in tropical conditions the platforms discussed are 1 the lower tortonian ramp on menorca balearic islands and 2 the lower middle miocene ramps of the central apennines italy evidence for tropical conditions in the mediterranean during the period of growth of these platforms is provided by species of red algae and larger foraminifera by data from coeval continental basins and by global oxygen isotope data

the effects of magnesium to calcium ratios in artificial seawater at different ionic products upon the induction time and the mineralogy of calcium carbonate a laboratory study the effects of the mg2 ion concentration and the ionic products of carbonate upon the induction time for the onset of precipitation and the different mineralogies of calcium carbonates were studied it was shown that mg2 ions delay the spontaneous precipitation of calcium carbonate from supersaturated solutions e g seawater with respect to calcium carbonate mineral to such an extent that only biogenic removal of skeletal calcium carbonate is possible from the open ocean low concentrations of magnesium ions in solution favor calcite formation while aragonite is formed at high magnesium concentrations the mole of mgco3 in magnesian calcite increases with the increase of mg2 in solution and with the increase of co32 in the presence of mg2 in solution

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

benthic foraminiferal mg ca paleothermometry a revised core top calibration core top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium calcium mg ca to bottom water temperatures bwt benthic foraminifera collected from hawaii little bahama bank sea of okhotsk gulf of california ne atlantic ceara rise sierra leone rise the ontong java plateau and the southern ocean covering a temperature range of 0 8 to 18 c were used to revise the cibicidoides mg ca temperature calibration the mg ca bwt relationship of three common cibicidoides species is described by an exponential equation mg ca 0 867 0 049 exp 0 109 0 007 bwt stated errors are 95 ci the temperature sensitivity is very similar to a previously published calibration however the revised calibration has a significantly different preexponential constant resulting in different predicted absolute temperatures we attribute this difference in the preexponential constant to an analytical issue of accuracy some genera notably uvigerina show apparently lower temperature sensitivity than others suggesting that the use of constant offsets to account for vital effects in mg ca may not be appropriate downcore mg ca reproducibility as determined on replicate foraminiferal samples is typically better than 0 1 mmol mol 1 2 s e thus considering the errors associated with the cibicidoides calibration and the downcore reproducibility bwt may be estimated to within 1 c application of the revised core top mg ca bwt data to cenozoic foraminiferal mg ca suggests that seawater mg ca was not more than 35 lower than today in the ice free ocean at 50 ma

phosphorus phosphorites and skeletal evolution at the precambrian cambrian boundary clustering of sedimentary phosphate deposits around the precambrian cambrian boundary is related to a global phosphogenic event this event probably resulted from a complex interplay of factors and had a profound effect on the biota with high concentrations of phosphorus in the photic zone producing an increase in the total shallow marine biomass faunal diversification the precipitation of skeletal structures and explosive evolution

diagenesis and compositional partitioning of quaternary cool water carbonate aeolianites southeastern australia abstract middle to late pleistocene stranded carbonate sea beaches adjacent aeolian dunes and pleistocene aeolianites together with holocene marginal marine calcareous sediments across southeastern australia contain the longest record of such deposition in the modern world stretching back to at least 900 ky mis 23 the grains are were derived from a suite of cool water heterozoan carbonate sediments produced on the adjacent offshore shelf most modern shelf carbonate sediments in the region today are aragonite rich but the aragonite is presently slowly being dissolved on or just below the seafloor before the deposits enter the rock record beach dune sediments are derived mainly from the shallow 30 meters deep adjacent seafloor they are mollusk rich but with most bryozoan particles having been destroyed in the surf zone the mollusks are dominantly aragonite these nearshore sediments are swept onshore before any significant seafloor diagenesis can take place and so are compositionally different from the eventual aragonite poor open shelf sediments aragonite skeletal fragments in the dunes progressively dissolve with time under a semi arid climate and produce diagenetic low magnesium calcite meteoric cements a well known process common in tropical aragonitic pleistocene aeolianites the loss of metastable minerals with time is matched by a progressive and well understood change in stable isotopes such alteration in this environment however seems to take longer than in tropical carbonates with lithification herein not beginning until 200 ka and complete cementation being achieved in 450 ky thus neither aeolianites nor offshore marine carbonates record the composition of the original sediment aeolianites lack the important bryozoan constituents whereas neritic deposits lack the prolific mollusks this partitioning revealed for the first time answers the conundrum as to why some cool water neritic shelf and coastal sediments in the rock record are compositionally different

tectonic controls of phanerozoic sedimentary rock cycling the cyclic nature of the phanerozoic sedimentary rock distribution carbon sulphur coupling and material transfer among sedimentary reservoirs appears to be controlled by tectonic factors the distribution of preserved sedimentary mass in terms of rock mass remaining u geologic age shows a minimum c 300 350 ma ago which separates two subcycles of erosion and deposition of sedimentary rocks the older subcycle was interrupted because of the major continental collisions of the devonian and late carboniferous these collisions resulted in a reduction of outcrop areas of rocks of the older cycle relative to their masses leading to a decline in the probability of destruction and an increase in half life of these older sediments a strong correlation exists between the long term cyclicity in the phanerozoic global sea level curve and the distribution of carbon and sulphur among their major exogenic reservoirs this correlation is related to two principal tectonic modes of the phanerozoic oscillatory and submergent it is postulated that the submergent mode of active plate convergence obduction and subduction of sediments large ridge volume and high sea level gave rise to low erosion and sedimentation rates less restricted environments of carbonate deposition and relatively high atmospheric co 2 levels high temperatures resulting from an increased rate of production of co 2 from diagenetic and metamorphic reactions at subduction zones as sea level rose carbon was transferred from the sedimentary reservoir of reduced organic carbon to that of oxidized inorganic carbon in limestones whereas sulphur moved from the oxidized sulphate reservoir to the reduced sulphide reservoir as sea level fell reservoir transfers were opposite to those above culminating in the oscillatory mode of generally elevated continental interiors these reservoir transfers are consistent with secular changes observed in the distribution of 13 c and 34 s in sedimentary materials during the phanerozoic petrographic examination of phanerozoic oolite formations shows that ooids with preserved calcitic relict textures are characteristic of pre carboniferous carbonate rocks whereas ooids with relict textures indicative of initial aragonite mineralogy are dominant in rocks of younger age these changes in ooid mineralogy may be interpreted as reflecting changes in co 2 levels of the ocean atmosphere system consistent with the above tectonic considerations atmospheric co 2 levels were higher prior to carboniferous time favouring formation of calcitic ooids and skeletal parts after the carboniferous co 2 levels fell and aragonite and mg calcites of greater than 8 mol mg increased in abundance as precipitates

aragonitic algae in calcite seas effect of seawater mg ca ratio on algal sediment production abstract secular variation in seawater mg ca would have subjected the aragonite producing codiacean algae to two intervals of low mg calcite seas mmg ca mmg ca 2 seas since their origin in the ordovician it is asserted that the aragonite high mg calcite affinity of modern and recent tropical seas mmg ca 2 has enabled the aragonitic codiaceae to act as major carbonate sediment producers in these seas to test this assertion specimens of the sediment producing codiacean alga udotea flabellum were grown in artificial seawaters formulated at mmg ca ratios 1 0 2 5 5 2 that have occurred in the oceans throughout the geologic history of the codiaceae while the u flabellum algae produced exclusively aragonite in both the artificial boundary seawater mmg ca 2 5 and the artificial aragonite high mg calcite seawater modern seawater mmg ca 5 2 the algae produced a portion 25 3 of their caco3 as low mg calcite 4 mol mgco3 in the artificial calcite seawater mmg ca 1 0 suggesting that their caco3 polymorph control can be partially overridden by ambient seawater chemistry primary productivity calcification and linear growth of the algae decreased with reductions in ambient mg ca despite increases in absolute ca concentration of the seawater reduced calcification in the lower mg ca seawaters is probably due to kinetic difficulties of producing aragonite from seawater that favors the nucleation of calcite the decreased linear growth and primary production are likely associated with reductions in the ambient co2 available for photosynthesis resulting from the reduced calcification these findings support the assertion that the dominant ecological and sedimentological roles of codiacean algae in recent tropical seas is facilitated by a seawater mg ca ratio that favors the nucleation of aragonite over calcite furthermore producing aragonite in seawater that favors the nucleation of low mg calcite mmg ca

increased production of calcite and slower growth for the major sediment producing alga halimeda as the mg ca ratio of seawater is lowered to a calcite sea level abstract laboratory experiments were conducted to subject the calcareous alga halimeda a prolific producer of aragonite in the modern ocean to a variety of ambient mg ca ratios these experiments were based on three predictions 1 that halimeda would calcify at a lower rate when the ambient mg ca ratio was reduced from its high level in modern seawater 5 2 2 that this alga would grow more slowly under these conditions because its calcification yields as a byproduct co2 which is available for photosynthesis and 3 that the calcite content of halimeda s skeleton would increase as a percentage of total caco3 as predicted reduction of the mg ca ratio of ambient artificial seawater from its modern level to estimated early oligocene and early eocene levels 2 5 and 1 5 respectively resulted in progressively lower rates of calcification production of organic matter and linear growth for halimeda incrassata colonies the ambient mg ca ratio exerted a stronger influence over the rate of calcification than ca2 which in the geologic past has risen in seawater whenever the ambient mg ca ratio has declined thus although elevation of ca2 at such times would have promoted the calcification and growth of halimeda the concomitant decline of the mg ca ratio would have had a stronger negative effect in addition the percentage of skeletal material consisting of calcite rose from 8 in modern day seawater to 16 in artificial early oligocene seawater and 46 in artificial early eocene seawater magnesium was incorporated into this calcite as a function of the ambient mg ca ratio with a fractionation pattern differing only slightly from that of nonskeletal calcite halimeda exerts less biological control over its biomineralization than the related genera penicillus and udotea which in previous experiments produced only 22 25 of skeletal caco3 as calcite in seawater having a very low mg ca ratio 1 0 nonetheless it is likely that many taxa of green algae that produce little or no calcite today would have produced a substantial proportion of skeletal low mg caco3 as calcite in ancient seas such as those of the cretaceous whose mg ca ratios were close to unity

environmental change in the subtropics during the late middle eocene greenhouse and global implications 1 oxygen isotope records from odp site 1052 blake nose subtropical north atlantic ocean indicate significant short term high amplitude variability up to 1 4 in about 2500 to 4000 years during the late middle eocene 37 9 37 5 ma these variations reflect a combination of changes in sea surface temperature and the oxygen isotope composition of the regional seawater in order to independently evaluate the magnitude of sst changes at blake nose and better understand the nature of environmental change during the late middle eocene we present planktonic foraminiferal mg ca data combined with 18o data from the same samples the calculated mg ca paleotemperatures indicate a decrease in ssts over the study interval from 33 to 28 c at the same time that previously published foraminiferal 18ocalcite values from the same samples also decrease thus the 18ocalcite values must reflect a significant component of seawater 18o change in order to reconcile the opposite paleotemperature trends reflected by both proxies calculated 18oseawater values decreased from 3 at 37 83 ma to 2 at 37 6 ma the combined trends of the sst and 18oseawater cannot be explained by an increase of continental ice over this time interval instead the data favor an overall weakening of the hydrological cycle as global climate transitioned from the greenhouse to icehouse

marine carbon burial flux and the carbon isotope record of late cretaceous coniacian santonian oceanic anoxic event iii abstract episodes of widespread distribution of organic rich marine facies within relatively narrow stratigraphic intervals have been interpreted as oceanic anoxic events oaes there are a number of such intervals in the upper cretaceous some of which also exhibit significant positive excursions in carbon isotope records as a result a general model of the relationship between enhanced organic carbon burial and positive c isotope shifts has emerged carbon isotope stratigraphy has therefore developed the dual utility of a chronostratigraphic tool and a means to help identify and define intervals of exceptional organic matter burial and preservation however variations in regional carbon isotope records of globally documented events suggest that the relationship between organic carbon burial flux and magnitude of carbon isotope excursion may not be entirely straightforward for example strata of coniacian santonian age have long been recognized for enhanced organic content in many areas but the designation of oceanic anoxic event iii for this interval has been rather equivocal in the literature mostly due to the weak positive 13 c excursion 0 5 yet in some areas organic carbon accumulation rates for coniacian santonian strata are roughly double that of the older oae ii which is marked by a 2 4 shift in 13 c interestingly the burial flux of carbonate which leads to depletion rather than enrichment of the c isotope signal is also significantly elevated during coniacian santonian time in this study the role of variations in organic carbon and carbonate accumulation rates on carbon isotopic expression are explored through application of data on the composition accumulation rate and areal distribution of end member facies types to the development of a global carbon isotopic mass balance model the results are used to explore the hypothesis that net organic carbon burial during oae iii was not accurately represented in the carbon isotopic record these results have important implications for interpretation of c isotope records related to past perturbations of the global carbon cycle

experimental calibration of mg isotope fractionation between dolomite and aqueous solution and its geological implications abstract hydrothermal experiments at 220 160 and 130 c were performed to calibrate the mg isotope fractionation factor between dolomite and aqueous mg hydrothermal experiments included synthesis of dolomite using different starting materials as well as exchange experiments that used poorly ordered proto dolomite the morphology of synthesized dolomite was dependent on starting mineralogy suggesting that dolomite was synthesized by different pathways hydrothermally synthesized dolomite was initially fine grained disordered or poorly ordered dolomite that with time recrystallized to coarser grained ordered dolomite isotopic exchange was monitored using 87 sr 86 sr ratios and 25 mg tracers and these indicated near complete isotope exchange between dolomite and aqueous solutions at the end of most hydrothermal experiments the mg isotope fractionation factor between dolomite and aqueous solution obtained from synthesis and exchange experiments converged with time and was independent of dolomite morphology suggesting attainment of isotopic equilibrium combining results from synthesis and exchange experiments the temperature dependent mg isotope fractionation factor for ordered dolomite is 26 mg dolo aq 0 1554 0 0096 10 6 t 2 where t is in kelvin in contrast poorly ordered dolomite has a 26 mg dolo aq fractionation factor that is up to 0 25 lower than that of ordered dolomite and this is attributed to longer mg o bonds in imperfectly ordered dolomite the experimentally calibrated 26 mg dolo aq fractionation factors lie between those calculated by schauble 2011 and rustad et al 2010 the 26 mg dolo aq fractionation factor extrapolated to lower temperatures using the 26 mg t function of this study matches the 26 mg dolo aq fractionation factor obtained by modeling of mg isotope compositions of odp drill core samples this study shows that significant mg isotope fractionation occurs during dolomite precipitation these results collectively demonstrate that mg isotopes in dolomite are a useful tool for studying mg global cycling and dolomitization

zebra and boxwork fabrics in hydrothermal dolomites of northern canada indicators for dilational fracturing dissolution or in situ replacement zebra and boxwork fabrics in manetoe and presqu ile hydrothermal dolomites provide critical data for discrimination between hypotheses for their origin in a unique occurrence sets of weakly imbricated decimetre sized curvilinear lenticles of white dolospar are developed within sub metre sized tongues of greyish white dolomitized crinoidal packstone and grainstone this nascent zebra fabric has developed along wavy to nodular intra bed sedimentary partings primary bedding can be traced through dolomitized masses containing these fabrics into the surrounding undolomitized limestone all zebra and boxwork fabrics are confined within single beds consistent with an early burial time of origin no change in bed thickness occurs across zebra or boxwork fabrics within beds this indicates a dissolutional rather than a dilational origin for the creation of pore space partly cemented with white dolospar the dolomitized groundmass displays an abruptly gradational or sharp transition to centripetal saddle dolomite cement which partially to nearly completely occludes vugs circulation of geothermally heated hypersaline devonian elk point basinal sea water brines led to dissolution and replacive dolomitization of limestone adjacent to vugs and near contemporaneous precipitation of white dolospar within dissolutional vugs consistent with geochemical simulations the presence of downward extending galleries of white dolospar cemented solution collapse breccia provides further support for an interpretation of regional thermally driven convection of hydrothermal evaporative sea water brines across a broad area of northern canada the absence of gases under pressure in vacuoles within fluid inclusions from manetoe and presqu ile dolospars is also more consistent with a dissolutional and contemporaneous dolomitization origin for these fabrics rather than an origin involving dilational fracturing for space creation and dolospar precipitation the ubiquitous presence of zebra and boxwork fabrics in hydrothermal dolomite reservoirs indicates that they are not confined fault zones and instead occur wherever precursor limestones had relatively greater porosity and permeability prior to dolomitization

relic aragonite from ordovician silurian brachiopods implications for the evolution of calcification understanding the influence of aragonite calcite sea conditions on the evolution of biocalcification relies strongly on the correct interpretation of the original composition of calcareous taxa aragonite dissolves or inverts into calcite over geological time and its preservation is currently unknown to predate the pennsylvanian here we present direct evidence for the common occurrence of relic aragonite in ordovician and silurian trimerellid brachiopods thereby extending the known range of aragonite preservation by more than 130 million years together with associated hypercalcifying taxa of putatively original aragonite or high magnesium calcite composition and considerations of the temperature dependence of aragonite and calcite precipitation our results suggest that the evolution of aragonite biomineralization might have presented an adaptive advantage in shallow marine tropical waters of calcite seas a targeted search for paleozoic aragonite should both resolve the original composition of consistently recrystallized taxa and enable the reassessment of the aragonite calcite sea paradigm in a paleoenvironmental context