paleo seawater ree compositions and microbial signatures preserved in laminae of lower triassic ooids abstract signals indicative of paleo seawater rare earth element ree composition and microbial activity were identified in marine ooids from the lower triassic of south china using in situ laser ablation inductively coupled plasma mass spectroscopy la icp ms together with petrographic and isotope geochemical techniques quantitative trace element profiles were generated across successive growth laminae in the cortices of selected ooids the shale normalized ree and yttrium y data of these layers show 1 light rare earth element depletion mean la sn yb sn 0 36 0 14 2 positive la anomalies mean la la sn 2 02 1 25 and 3 high ratios of y ho mean 53 12 which are similar to modern seawater compositions and bahamian ooids these findings imply that ooids in the study samples faithfully record early triassic paleo seawater chemical signals such as ree y distributions petrographic observations revealed dark colored layers with intense fluorescence containing structures that resemble microbial filaments or extracellular polymeric substances these layers also possess more enriched ree compositions and higher concentrations of nutrient like elements e g zn and ba than adjacent recrystallized light colored laminae most ooid laminae contain negative ce anomalies indicative of a well oxygenated environment of formation but some laminae have minimal negative anomalies suggesting the influence of suboxic porewater conditions the present study provides a new perspective on the role of microbes in ooid genesis and on the utility of ooids as proxies for paleo seawater chemistry

aragonite crystal fans in neoproterozoic cap carbonates a case study from brazil and implications for the post snowball earth coastal environment abstract neoproterozoic cap carbonates are characterized by anomalous sedimentary features including sea floor precipitates represented by aragonite pseudomorph cement crusts and crystal fans these features are found in restricted periods of geological history and their generation in the context of the neoproterozoic has been attributed to very specific postglacial conditions leading to alkalinity oversaturation new sedimentary and geochemical results on well preserved neoproterozoic deposits of aragonite pseudomorph crystal fans at the base of the sete lagoas formation bambui group central brazil are reported the micrite settling facies shows the highest abundance of crystal fans arranged in centimeter scale layers interfingered with the micrite matrix this facies is interpreted as a result of postglacial calcium carbonate oversaturation in restricted areas characterized by marine dysoxic waters a numerical model constrains the kinetics of formation of aragonite crystals or micrite by calculating the induction times and precipitation rates of both carbonate species for postglacial conditions of elevated temperature and high atmospheric pco2 in these conditions the mg ca ratio of the neoproterozoic seawater is calculated at ca 1 2 alkalinity oversaturation is monitored by a variable evaporation degree aragonite formation is kinetically favored and the discrepancy between calcite and aragonite precipitation rate is greater as atmospheric pco2 hence alkalinity is higher these modeling conditions do not preclude the contribution of incomplete organic matter degradation to alkalinity as suggested by negative carbon isotope signatures in addition the large number of aragonite micrite pairs suggests a seasonal or paleoclimatic forcing other cases of abiotic aragonite precipitation through time are also briefly examined by comparison

rare earth patterns with positive cerium anomaly in alkaline waters from lake van turkey abstract the distribution of rare earth elements has been studied for aerobic alkaline ph 9 6 carbonate rich waters from lake van turkey shale normalized ree ree sn patterns display an almost linear increase from the light to the heavy rees and strong positive ce sn anomalies there exist neither positive nor negative gd sn anomalies the ree sn patterns are consistent with domination of ree speciation in solution by poly carbonato complexes generating enrichment of the heavy rees that is even more pronounced than that seen in seawater this is the first report of positive ce sn anomalies observed in ree sn patterns of aerobic natural waters these anomalies apparently result from stabilization of penta carbonato ce iv complexes in solution leading to enhanced abundances of ce in comparison with its trivalent ree neighbours thus in remarkable contrast to seawater positive ce sn anomalies may be general features of alkaline carbonate rich and aerobic lake waters

rare earth geochemistry of old phosphorites and probability of syngenetic precipitation and accumulation of phosphate1in memory of richard p sheldon1 abstract old vendian early cambrian phosphorites of the world demonstrate seawater like patterns in their rare earth element ree distributions but are depleted in heavy ree they also show a broad range of variation in total and elemental abundances primary bedded structureless phosphorites contain only 15 ppm total ree ree while granular pelletal varieties contain up to 650 ppm ree were incorporated into phosphate grains diagenetically during prolonged periods of transport and redeposition a higher surface mass ratio in pelletal phosphorites contributed to their enrichment in the ree s in primary bedded structureless phosphorites immediate burial of phosphate syngenetically precipitated and accumulated in situ at the sediment water interface prevented the later incorporation of the ree large deposits of vendian early cambrian phosphorites have originated by both processes primary bedded varieties occur in deeper water facies and granular phosphorites accumulated closer to the shore in terms of their ree geochemistry old granular phosphorites are almost indistinguishable from their phanerozoic counterparts indicating that both were deposited by the same mechanisms primary bedded structureless phosphorites were only deposited on a large scale at the beginning of the phanerozoic

microbial carbonates the geological record of the calcified bacterial algal mats and biofilms summary deposits produced by microbial growth and metabolism have been important components of carbonate sediments since the archaean geologically best known in seas and lakes microbial carbonates are also important at the present day in fluviatile spring cave and soil environments the principal organisms involved are bacteria particularly cyanobacteria small algae and fungi that participate in the growth of microbial biofilms and mats grain trapping is locally important but the key process is precipitation producing reefal accumulations of calcified microbes and enhancing mat accretion and preservation various metabolic processes such as photosynthetic uptake of co2 and or hco3 by cyanobacteria and ammonification denitrification and sulphate reduction by other bacteria can increase alkalinity and stimulate carbonate precipitation extracellular polymeric substances widely produced by microbes for attachment and protection are important in providing nucleation sites and facilitating sediment trapping microbial carbonate microfabrics are heterogeneous they commonly incorporate trapped particles and in situ algae and invertebrates and crystals form around bacterial cells but the main component is dense clotted or peloidal micrite resulting from calcification of bacterial cells sheaths and biofilm and from phytoplankton stimulated whiting nucleation interpretation of these texturally convergent and often inscrutable fabrics is a challenge conspicuous accumulations are large domes and columns with laminated stromatolite clotted thrombolite and other macrofabrics which may be either agglutinated or mainly composed of calcified or spar encrusted microbes stromatolite lamination appears to be primary but clotted thrombolite fabrics can be primary or secondary microbial precipitation also contributes to hot spring travertine cold spring mound calcrete cave crust and coated grain deposits as well as influencing carbonate cementation recrystallization and replacement microbial carbonate is biologically stimulated but also requires favourable saturation state in ambient water and thus relies uniquely on a combination of biotic and abiotic factors this overriding environmental control is seen at the present day by the localization of microbial carbonates in calcareous streams and springs and in shallow tropical seas and in the past by temporal variation in abundance of marine microbial carbonates patterns of cyanobacterial calcification and microbial dome formation through time appear to reflect fluctuations in seawater chemistry stromatolites appeared at 3450 ma and were generally diverse and abundant from 2800 to 1000 ma inception of a proterozoic decline variously identified at 2000 1000 and 675 ma has been attributed to eukaryote competition and or reduced lithification thrombolites and dendrolites mainly formed by calcified cyanobacteria became important early in the palaeozoic and reappeared in the late devonian microbial carbonates retained importance through much of the mesozoic became scarcer in marine environments in the cenozoic but locally re emerged as large agglutinated domes possibly reflecting increased algal involvement and thick micritic reef crusts in the late neogene famous modern examples at shark bay and lee stocking island are composite coarse agglutinated domes and columns with complex bacterial algal mats occurring in environments that are both stressed and current swept products of mat evolution ecological refugia sites of enhanced early lithification or all three

the carbonate signal and calcareous nannofossil distribution in an upper jurassic section balingen tieringen late oxfordian southern germany total abundance assemblage composition and the stratigraphic distribution of the six most abundant species of calcareous nannofossil were analysed in the upper oxfordian succession of balingen tieringen western swabian alb south germany this locality represents a deep shelf less than 200 m environment that is strongly influenced by its proximity to the jura shallow platform nannofossil abundance negatively correlates with carbonate content as well as with accumulation rate calcareous nannofossils thus did not produce the bulk of carbonates and their abundance was essentially controlled by the import of allochthonous carbonate mud gradual increase in carbonate content in the balingen tieringen succession can be related to an intensified carbonate mud export from the jura shallow platform to the swabian alb deep shelf during the late oxfordian changes in the nannofossil assemblage composition along the profile are interpreted as primary although a partial control by diagenesis on the assemblage can not be completely excluded the coccoliths lotharingius hauffii watznaueria britannica cyclagelosphaera margereli watznaueria barnesae watznaueria manivitae and the incertae sedis schizosphaerella spp display their highest relative abundance one after the other in a stratigraphic order this nannofossil succession parallels the gradual increase in allochthonous carbonate mud accumulation on the deep shelf as well as the gradual decrease in the intensity of siliciclastic input recorded on the jura shallow platform this suggests a climatic control by humidity on shallow platform carbonate production and export basinwards and on nutrient availability in deep shelf surface waters that itself controlled the nannofossil assemblage composition therefore the succession of highest relative abundance of l hauffii w britannica c margereli w barnesae w manivitae and schizosphaerella spp can represent a trophic preference continuum from more eutrophic to oligotrophic conditions

application of the ce anomaly as a paleoredox indicator the ground rules much attention has been paid in recent years to the potential application of the ce anomaly measured in various marine phases as a paleoceanographic indicator of widespread marine anoxia in this paper we present and discuss results from recent studies of present day rare earth element ree distributions and hence ce anomaly distributions in the marine environment which are particularly pertinent to paleoceanography subsequently we review and discuss the validity of the recent literature in which ce anomalies have been employed as paleoredox indicators

the assessment of ree patterns and 143nd 144nd ratios in fish remains abstract the ree content and isotopic composition of sr and nd have been determined in fish teeth ranging in age from the trias to the present and from various localities mostly around the atlantic these measurements have been carried out on selachian and teleost remains from the same locality in togo and show no appreciable difference which suggests with the help of a mass balance calculation of the ce anomaly that diagenetic effects are not responsible for the ree enrichment of biogenic phosphates one group of fossil teeth has about 3 times the ree abundances of shale and a shale normalized pattern with a minimum at sm it is thought to reflect deposition in the open sea environment a second group has ree concentration about 10 times higher than the first group with either a regular light ree enrichment or more frequently a maximum in the middle ree both being probably indicative of deposition in estuarine or near shore conditions the shape of the ree spectra and the size of the ce anomaly can be used semi quantitatively to determine the depth of deposition the results presented here on late cretaceous eocene fish teeth samples from morocco reflect an increasing influx of deep waters with a lowla yb ratio and strong negative ce anomaly which agrees well with the evolution of sediment chemistry and microfauna associations in contrast nd is typical of the water mass in which the fish debris decayed examples of nearly isolated basins identified with nd isotopes include the south atlantic prior to the lutetian nd 13 5 the miocene persian gulf nd 3 1 and bolivia during the late cretaceous nd 12 8 togo and guinea bissau results suggest that in the south atlantic the meridional oceanic circulation had not started before 45 ma ago combination of ree and nd data suggests that the assignment of jurassic cretaceous samples measured so far to open sea water masses is still ambiguous

evaluation of the application of rare earth elements to paleoceanography anomalous departures of rare earth elements ree from similarity of chemical behaviour are most evident in a comparison of ce with its neighbors under reducing conditions ce3 acts like other ree but oxidized ce4 is adsorbed on mn fe oxyhydroxides or organic particulates and consequently the remaining solution will tend to exhibit a negative ce anomaly in addition more subtle fractionations may emphasize the light or the heavy or the middle ree a pattern of ree may be recorded by immediate diagenesis on a suitable chemical substrate such as apatite fish debris conodonts carbonate or chert this record was originally thought to reflect the paleoredox conditions of primary deposition however any such primary record may be overprinted by late diagenetic alteration early analyses of ree in conodonts from a wide range of sediments suggested a prevalence of reducing conditions no ce anomaly in pre carboniferous oceans and more common oxidation negative ce anomaly in the late paleozoic however recent research by other investigators indicates that variations in cean are more diverse in origin and in particular many are distorted to an unknown extent by late diagenesis in any case it is now clear that geological age does not show a consistent relationship to the level of the ce anomaly the ce anomaly apparently does not play any regular role in the isotopic events that accompany prominent mass extinctions further research is required to understand and thus make useful the controls on the ce anomaly

the behavior of rare earth elements in seawater precise determination of variations in the north pacific water column abstract we present new highly precise and accurate data for ten rare earth elements rees in two water column profiles and in bottom waters from three additional localities in the north pacific our results presented here and in an earlier publication indicate that the water column in the western north pacific is stratified with respect to the isotopic composition of nd as well as nd la sm nd and er la both the nd isotopic and the ree data show that ree transport is strongly influenced by horizontal advection even in the sluggish circulation of the pacific in general rees increase in concentration with depth at mid latitude they reach a maximum concentration at about 3000 m and then decrease to the bottom at high latitude heavy rees reach a maximum concentration near 3000 m whereas light rees continue to increase in concentration with depth the deep water maximum and bottom water depletion is interpreted as an advective feature resulting from the flow of a lower concentration of rees in antarctic bottom water under a higher concentration of rees in the north pacific concentrations of rees do not show a linear relationship with those of si indicating that the ree cycle is not directly coupled to that of the si cycle ree element ratios i e nd la correlate with hydrographie properties which suggests that major features of the ree patterns may be conserved during lateral transport comparison of our ree data to those in previously published reports on pacific seawater shows that the identification of ree distributions affected by advection is only made possible by the high precision analysis we developed for this study the ce concentration we observe is relatively constant over 200 4500 m depth at both sites where we have complete profiles this unique constancy of ce is in contrast to the contiguous rees la and nd which show substantial concentration variations with depth

palaeoenvironmental control on sponge microbialite reefs and contemporaneous deep shelf marl limestone deposition late oxfordian southern germany abstract the late oxfordian bimammatum zone deep shelf deposits of southern germany are characterised by abundant reefs that laterally pass into marl limestone alternations the bioconstructions are made from three main components sponges microbialites and allochthonous sediment a detailed morphological analysis of sponge microbialite reefs in the plettenberg section swabian alb southern germany is combined with investigation of calcareous nannofossil assemblages in laterally correspondent marl limestone alternations in order to trace the evolution of palaeoenvironmental conditions during reef development fluctuations of caco3 content in deep shelf deposits provides evidence of a succession of small scale lithological units generally formed by five to six marl limestone couplets within a small scale lithological unit a close link is observed between growth patterns of sponge microbialite reefs and the changes in the nannofossil assemblage composition phases of expansion of the build ups correspond to carbonate deposits characterised by a relative dominance of large oligotrophic nannoplankton species large watznaueria britannica watznaueria manivitiae and schizosphaerella spp marly intervals reveal a high relative abundance of small sized taxa mainly lotharingius hauffii small w britannica and subordinated biscutum dorsetensis and bioconstructions show a net reduction in size or a total demise this suggests that the same palaeoenvironmental parameters controlled at the same time marl versus limestone deposition reef growth phases and calcareous nannofossil assemblage composition successive reef growth phases recognized within a bioherm are correlated to the limestone hemi couplets each reef growth phase is composed of several stacked elementary sequences comprising the following succession i sponge ii microbialites and iii carbonate mud in turn the microbialitic crust is formed of three successive microbial layers 1 a fine crust of dense to clotted micrite 2 a centimetre scale to multicentimetric columnar layer of clotted to peloidal micrite 3 a centimetre scale stromatolitic crust the passage from an initial dense microbial layer with numerous microencrusters to a final stromatolitic crust is interpreted as resulting from an increase of the microbial growth rate mainly driven by changes in the accumulation rate deep shelf deposits resulted from changes in platform carbonate production and export basinwards controlled both by sea level and climate changes climate controlled the intensity of carbonate production in shallow platform environments and export towards the deep shelf as well as the trophic conditions of the deep shelf marine waters low trophic conditions favoured platform carbonate production and export basinwards and a large development of the sponge microbialite reefs in the deep shelf however a high carbonate accumulation rate in the deep shelf was also commonly responsible for the demise of sponge microbialite reefs during unfavourable and higher trophic conditions during marl deposition reduced development and frequent demise of the sponge microbialite reefs is observed

growth dynamics and ecology of upper jurassic mounds with comparisons to mid palaeozoic mounds the mid palaeozoic including the late jurassic was a time of both widespread coral reef growth and pronounced mound formation a comparison of mound features and their general setting highlights despite all differences general similarities in overall growth dynamics mound formation was frequently driven by discontinuous patterns particularly by background sedimentation in many examples episodes of mound stabilisation by early lithification growth of microbolite crusts and winnowing of fines was followed by growth episodes of benthic fauna under reduced to negligible background sedimentation this pattern of variable sedimentation and organic buildups may have occurred in different orders and magnitudes inducing a fractal pattern in some mound complexes a composite approach in estimating growth rates of mounds demonstrates that highfrequency oscillations necessary for growth of most mounds might have ranged from a few thousand years to 4th and 5th order milankovich cycles that were superimposed by autocyclic factors d 2001 elsevier science b v all rights reserved

humans as geologic agents a deep time perspective humans move increasingly large amounts of rock and sediment during various construction activities and mean rates of cropland soil loss may exceed rates of formation by up to an order of magnitude but appreciating the actual importance of humans as agents of global erosion necessitates knowledge of prehistoric denudation rates imposed on land surfaces solely by natural processes amounts of weathering debris that compose continental and oceanic sedimentary rocks provide one such source of information and indicate that mean denudation over the past half billion years of earth history has lowered continental surfaces by a few tens of meters per million years in comparison construction and agricultural activities currently result in the transport of enough sediment and rock to lower all ice free continental surfaces by a few hundred meters per million years humans are now an order of magnitude more important at moving sediment than the sum of all other natural processes operating on the surface of the planet relationships between temporal trends in land use and global population indicate that humans became the prime agents of erosion sometime during the latter part of the first millennium a d

rare earth elements in river waters we measured rare earth element ree concentrations in river waters to characterize the suspended and dissolved river flux of the ree to the oceans the ree pattern of river suspended materials is sensitive to drainage basin geology a positive correlation is observed between la yb ratios and nd model ages for the rivers studied major rivers have light ree enriched patterns relative to the north american shale composite nasc with la yb n 1 6 2 7 river water dissolved material 0 2 m is heavy ree enriched relative to suspended material and the most pronounced negative ce anomalies occur in rivers of high ph light ree concentrations vary by approximately 3 orders of magnitude and are inversely related to ph and major cation concentrations from these data we estimate that typical major river runoff has heavy ree depleted suspended material with la yb n 1 9 we conclude that the terrigenous input to the oceans from major rivers is heavy ree depleted relative to shales from the available data average river water dissolved material appears to be heavy ree enriched with la yb n 0 4 estuarine removal processes lower the dissolved ree river flux by approximately 60 and result in a flux that is more heavy ree enriched with la yb n 0 2 calculated oceanic residence times with respect to river input range from 2300 to 21 000 years are shortest for ce and greatest for the heavy ree and la such long residence times may suggest the presence of additional sources of ree in seawater

the geochemistry of late archaean microbial carbonate implications for ocean chemistry and continental erosion history trace element concentrations and combined sr and nd isotope compositions were determined on stromatolitic carbonates microbialites from the 2 52 ga campbellrand carbonate platform south africa shale normalised rare earth element and yttrium patterns of the ancient samples are similar to those of modern seawater in having positive la and y anomalies and in being depleted in light rare earth elements in contrast to modern seawater and microbialite proxies the 2 52 ga samples lack a negative ce anomaly but possess a positive eu anomaly these latter trace element characteristics are interpreted to reflect anoxic deep ocean waters where unlike today hydrothermal fe input was not oxidised and scavenged and rare earth elements were not coprecipitated with fe oxyhydroxides the persistence of a positive eu anomaly in relatively shallow campbellrand platform waters indicates a dramatic reversal from hydrothermally dominated archaean to continental erosion dominated phanerozoic rare earth element flux ratio the dominant hydrothermal input is also expressed in the initial sr and nd isotope ratios there is collinear variation in sr nd systematics which range from primitive values 87sr 86sr of 0 702386 and end of 2 1 to more evolved crustal ratios mixing calculations show that the range in trace element ratios e g y ho and initial isotope ratios is not a result of contamination by trapped sediment but that the chemical and isotopic variation reflects carbonate deposition in an environment where different water masses mixed calculated nd flux ratios yield a hydrothermal input into the 2 52 ga oceans one order of magnitude larger than continental input such a change in flux ratio most likely required substantially reduced continental inputs which could in turn reflect a plate tectonic causation e g reduced topography or expansion of epicontinental seas

comparison of atlantic and pacific paleochemical records for the last 215 000 years changes in deep ocean circulation and chemical inventories abstract detailed cd ca and 13 c data have been obtained for benthic foraminifera from western north atlantic and equatorial pacific sediment cores in the modern ocean both tracers are closely linked to nutrient distributions the sedimentary records for both tracers indicate that bottom waters overlying the atlantic site have been nutrient depleted relative to those at the pacific site over the last 215 000 years from this evidence it is reasonable to infer that there has been a continuous net flux of nutrient depleted water from the western north atlantic into the pacific this exchange has undergone significant fluctuations with the export of nutrient depleted atlantic water diminishing by about a factor of two relative to the inflow from southern ocean sources over the last 215 000 years carbon isotope fluctuations in both regions are dominated by variable storage of isotopically light carbon on continents with a lesser contribution from these deep ocean circulation changes the cadmium signal in the north atlantic is dominated by changes in deep ocean circulation patterns cadmium shows less variability in the pacific which may reflect changes in the global average cadmium content or minor changes in deep pacific circulation patterns using these records to estimate global averages it appears that glacial ocean water had 22 more cd and 0 46 less 13 c than the modern ocean these numbers are estimates which may be revised as more data become available although they are not likely to be as much as 20 in error for cd or 0 2 for 13 c relative north atlantic deep water nadw formation rates are modulated with a significant 41 kyr periodicity linked to obliquity induced variations in high latitude insolation nadw lags 8 2 kyr behind insolation however

impact of the alluvial style on the geoarcheology of stream valleys abstract the extensive archeological record within river valleys provides an environment long favored for study by the archeologic community this record of human occupation varies with the alluvial style of the river resulting in each river valley having a unique archeological record controlled by three factors location of occupation sites preservation of those sites and recognition of the sites if problems of site preservation and recognition in a river valley can be recognized and addressed a better insight into settlement patterns and complex human environment interactions can result this study represents a synthesis of extensive published and secondary data sets pertaining to archaeology and alluvial geomorphology of the lower missouri red and mississippi rivers to examine the relationship of prehistoric site distribution with fluvial geomorphology the archeologic data are from published literature and government agencies the geomorphic data are from a variety of published and unpublished investigations including maps of alluvial geomorphology digital elevation models aerial photographs and topographic maps the data were input into spreadsheets and a gis for qualitative and quantitative analysis prehistoric human occupation of the narrow missouri valley floor is limited with only 0 061 recorded sites km2 additional sites are likely buried by thick vertical accretion sediment on the limited prehistoric portions of the floodplain and within alluvial colluvial fans along the valley margin non random preservation patterns such as the absence of sites from the youngest cultural period are attributed to shifts in settlement patterns in comparison to the lower missouri river valley prehistoric occupation of the lower red and mississippi rivers was much more extensive and the density of occupation was 0 274 sites km2 and 0 277 sites km2 respectively significant differences do exist in the age of sites and their relationship to different floodplain depositional environments many sites along the active meander belt of the red river were likely lost due to high rates of channel migration nevertheless intense occupation of paleo indian through caddoan groups assures that many significant sites have been preserved the wide valley and high rates of sedimentation suggest that many sites are likely buried particularly along natural levees flanking an older meander belt recorded sites are also present along streams that incise the terrace along the terrace margin and along small channels that cross the backswamp the spatial and temporal site distribution along the lower mississippi valley is distinct in comparison with the red river because the mississippi valley is wider the terraces are younger and less dissected and the floodplain has more relief and is not broadly inundated by floodwater with relatively low sediment concentrations most of the significant archaic through mississippian period floodplain sites are located along the surfaces of abandoned mississippi and distributary meander belts which aggraded above the adjacent backswamp and have rarely been influenced by flood sedimentation since abandonment abundant paleo indian through mississippian period sites are also widely distributed across undissected terraces only a few significant mississippian sites are present along the active meander belt and in the backswamp where flooding was common in comparison with the red river the archaeological record of the floodplain is less likely to be influenced by burial or erosion due to the mississippi river having lower rates of overbank sedimentation and channel migration respectively the variable alluvial styles of the lower missouri river lower red river and the lower mississippi river valleys presented varying opportunities and constraints to occupation and sustained settlement and resulted in widely varying archaeological patterns that are partly dependent upon the alluvial geomorphology

a mesozoic time scale we present an integrated geomagnetic polarity and stratigraphic time scale for the triassic jurassic and cretaceous periods of the mesozoic era with age estimates and uncertainty limits for stage boundaries the time scale uses a suite of 324 radiomenc dates including high resolution 40 ar 39 ar age estimates this framework involves the observed ties between 1 radiometric dates biozones and stage boundaries and 2 between biozones and magnetic reversals on the seafloor and in sediments interpolation techniques include maximum likelihood estimation smoothing cubic spline fitting and magnetochronology

rare earth element geochemistry of late devonian reefal carbonates canning basin western australia confirmation of a seawater ree proxy in ancient limestones rare earth element and yttrium ree y concentrations were determined in 49 late devonian reefal carbonates from the lennard shelf canning basin western australia shale normalized sn ree y patterns of the late devonian samples display features consistent with the geochemistry of well oxygenated shallow seawater a variety of different ancient limestone components including microbialites some skeletal carbonates stromatoporoids and cements record seawater like ree y signatures contamination associated with phosphate fe oxides and shale was tested quantitatively and can be discounted as the source of the ree y patterns co occurring carbonate components that presumably precipitated from the same seawater have different relative ree concentrations but consistent ree y patterns clean devonian early marine cements n 3 display ree y signatures most like that of modern open ocean seawater and the highest y ho ratios e g 59 and greatest light ree lree depletion average nd sn yb sn 0 413 sd 0 076 however synsedimentary cements have the lowest ree concentrations e g 405 ppb non contaminated devonian microbialite samples containing a mixture of the calcimicrobe renalcis and micritic thrombolite aggregates in early marine cement n 11 have the highest relative ree concentrations of tested carbonates average total ree 11 3 ppm stromatoporoid skeletons unlike modern corals algae and molluscs also contain well developed seawater like ree patterns samples from an estuarine fringing reef have very different ree y patterns with lree enrichment nd sn yb sn 1 possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged lree from a nearby riverine input source hence devonian limestones provide a proxy for marine ree geochemistry and allow the differentiation of co occurring water masses on the ancient lennard shelf although appropriate partition coefficients for quantification of devonian seawater ree concentrations from out data are unknown hypothetical devonian canning basin seawater ree patterns were obtained with coefficients derived from modern natural proxies and experimental values resulting devonian seawater patterns are slightly enriched in lree compared to most modem seawaters and suggest higher overall ree concentrations but are very similar to seawaters from regions with high terrigenous inputs our results suggest that most limestones should record important aspects of the ree geochemistry of the waters in which they precipitated provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high non seawater like ree contents hence we expect that many other ancient limestones will serve as seawater ree proxies and thereby provide information on paleoceanography paleogeography and geochemical evolution of the oceans copyright c 2004 elsevier ltd

diagenetic constraints on the use of cerium anomalies as palaeoseawater redox proxies an isotopic and ree study of cambrian phosphorites seawater rare earth element ree distributions show heavy ree enrichment and cerium depletion but these characteristics are only rarely found in ancient marine authigenic minerals such as carbonate fluorapatite and calcite this enigma may be due to changing ree distributions in seawater through time or to post depositional redistribution of ree differentiating between these two factors is however far from straightforward as their relative importance is likely to vary and evidence is often ambiguous in this article we present ree as well as strontium and sulphur isotope data for basal cambrian phosphorites of south china which confirm the emerging rule of thumb that granular phosphorites seldom reveal extreme departures from the seawater norm and tend to undergo therefore less diagenetic alteration of ree spectra than skeletal apatites and other phosphate types this study reveals stratigraphic trends in ce anomalies ce ce that could be taken to imply the preservation of a palaeoenvironmental signal however further investigation of our data shows that such trends in phosphorites can also be caused by post depositional alteration which tends to 1 increase ree contents 2 reverse ce depletion 3 alter eu anomalies and 4 concentrate preferentially the middle ree mree further alteration which may be due to weathering has led to hree depletion and positive la and y anomalies tetrad effect this is the first study where ceanom and phosphate bound sulphate s isotope values could be compared for one particular stratigraphic section which provides us with an additional tool for the interpretation of diagenetic redox conditions least altered phosphorites from meishucun that yield a strongly negative ceanom constrain early cambrian seawater 34s to about 33 we conclude that phosphorite ceanom primarily records variations in the local conditions of diagenesis while outlining some special cases in which diagenetic redox conditions may broadly reflect local bottom water redox conditions

facies distribution and coral microbialite reef development on a low energy carbonate ramp chay peninsula kimmeridgian western france abstract the chay peninsula western france succession corresponds to a kimmeridgian shallow and low energy ramp system that developed in the northeast of the aquitaine basin the sedimentation shows a transition from a carbonate dominated to a mixed carbonate siliciclastic depositional environment that takes place at the base of a major third order sea level transgression facies partitioning and coral microbialite reef levels i e reef windows suggest higher frequency fourth order sea level oscillations reef growth phases i e high frequency reef windows are interpreted to have been controlled by fifth order sea level oscillations in the mixed siliciclastic carbonate system successive prograding units of shoreface sediments pass into thick marl limestone alternations over a distance of tens of metres such remarkable short distance lateral facies variations suggest a complex sedimentary system made of juxtaposed deposits that rapidly shift through time terrigenous fluxes in modifying the light intensity and the nutrient level in the water column strongly controlled the facies distribution and notably the reef composition and growth identified coral genera suggest mixed photo heterotrophic mode of nutrition and low mesotrophic conditions in marine waters for each reef growth phase nutrient increase favoured large amounts of microbialites to develop forming a crust that entirely capped the coral reef surface thus high frequency fluctuations in nutrient input in tune with fifth or higher order sea level fluctuations controlled the reef development at a millennial scale the chay peninsula reef distribution and development provide insight into understanding the response of reef communities under climatically induced environmental changes

rare earth and trace elements of microbialites in upper jurassic coral and sponge microbialite reefs major trace y zr pb th and u rare earth element ree and sm nd isotope analyses were carried out on microbialites and detrital carbonate sediments collected in upper jurassic coral and sponge microbialite reef settings selected bioconstructions developed in various palaeogeographic settings and depositional environments on northwestern tethys and eastern atlantic margins pure carbonate lagoon carbonate dominated deep shelf to epicontinental basin and mixed carbonate siliciclastic shallow ramp and lagoon the proximity to terrigenous sources directly controlled ree patterns of carbonate samples lateral and intrareef sediments and to a lesser degree stromatolitic microbial crusts are more susceptible to contamination by terrigenous material than are microbialites of thrombolitic fabric in mixed carbonate siliciclastic settings microbialites display a flat shale normalized ree pattern in pure carbonate lagoonal settings microbialites have shale normalized ree patterns similar to those of modern seawaters with a negative ce anomaly ce ce up to 0 14 positive la and gd anomalies and light ree depletion relative to heavy ree these data imply that similar ree chemistry than modern seawater already occurred on the northwestern tethys margin at the upper jurassic strong negative ce anomalies b0 4 imply microbialite formation in well oxygenated seawaters both in coral reefs of pure carbonate lagoonal environments pagny sur meuse and sponge bioherms of deep shelf settings plettenberg absence of positive ce anomalies rules out an influence of alkaline and high ph seawaters thus ree patterns and nd isotopic signatures which are in perfect agreement with existing results for tethysian seawater confirm that microbialites can be used as proxies of palaeoenvironmental seawater chemical characteristics

rare earth element evolution of phanerozoic seawater recorded in biogenic apatites rare earth element ree contents of marine biogenic apatites have been shown to record seawater compositions a data base of available and newly acquired rare earth element ree contents of marine biogenic apatites has been created to assess the past seawater ree compositions to ensure that this data base contains only the pristine ree signals altered samples characterized by very low la sm n ratios where n stands for ree ratios normalized to the nasc composition gromet et al 1984 geochim cosmochim acta 48 1984 2469 acquired during apatite recrystallization are not included in the database these data reveal a change in the tethyan seawater composition between 110 and 80 ma after the end of the cretaceous the ree chemistry of seawater remains constant until present day this seawater composition change is likely due to concurrent changes in ree scavenging processes a strong correlation between decreasing sm yb n ratios and increasing ce anomalies for samples deposited during the 80 110 ma period is observed as ce anomalies are attributed to ocean water redox conditions changes in ree scavenging could reflect an evolution from stratified and poorly oxygenated waters towards well mixed and oxygenated waters this could have resulted from changing current patterns stemming from the contemporaneous opening of the atlantic ocean a major change in middle and late cretaceous oceanic circulation linked to plate tectonics would have favored the colonization of pelagic environments

the behavior of rare earth elements zr and hf during biologically mediated deposition of silica stromatolites and carbonate rich microbial mats abstract venere lake in the pantelleria island thermal system central mediterranean sea consists of a mix of seawater and hydrothermal volcanic fluids containing high levels of dissolved sio 2 close to the lake s thermal springs siliceous stromatolites are deposed under high bacterial activity conditions whereas roughly interlaminated ca carbonates and microbial mats are widely scattered in the lake the dissolved ree speciation in lake waters is dominated by ree co 3 2 ree co 3 and ree h 3 sio 4 2 complexes on the contrary the most abundant zr and hf species are hydroxyl and fluoride complexes the behavior of ree zr and hf in the venere lake waters is controlled by precipitation of amorphous silica carbonates and bacterial activity chondrite normalized ree patterns in stromatolites are characterized by positive la anomalies superchondritic y ho ratios and negative eu anomalies the eu depletion is also found in microbial mats where is associated to a chondritic y ho signature zr and hf differently behave in dissolved phase and in newly formed siliceous and carbonatic material hf reacts easily into amorphous silica surfaces whereas zr is preferentially partitioned onto phosphate binding sites on microbial cell surfaces similar to the observed behavior of heavy ree hree we suggest that the zr hf relationship reflect the interface processes between mineral phases and bacterial membranes or compounds produced by bacterial activity

impact of basin burial and exhumation on jurassic carbonates diagenesis on both sides of a thick clay barrier paris basin ne france several diagenetic models have been proposed for middle and upper jurassic carbonates of the eastern paris basin the paragenetic sequences are compared in both aquifers to propose a diagenetic model for the middle and late jurassic deposits as a whole petrographic optical and cathodoluminescence microscopy structural fracture orientations and geochemical 18o 13c ree studies were conducted to characterize diagenetic cements with a focus on blocky calcite cements and their connection with fracturation events four generations of blocky calcite cal1 cal4 are identified cal1 and cal2 are widespread in the dominantly grain supported facies of the middle jurassic limestones about 90 of the cementation whereas they are limited in the oxfordian because grain supported facies are restricted to certain stratigraphic levels cal1 and cal2 blocky spars precipitated during burial in a reducing environment from mixed marine meteoric waters and or buffered meteoric waters the meteoric waters probably entered aquifers during the late cimmerian jurassic cretaceous boundary and late aptian early cretaceous unconformities the amount of cal2 cement is thought to be linked to the intensity of burial pressure dissolution which in turn was partly controlled by the clay content of the host rocks cal3 and cal4 are associated with telogenetic fracturing phases the succession of cal3 and cal4 calcite relates to the transition towards oxidizing conditions during an opening of the system to meteoric waters at higher water rock ratios these meteoric fluids circulated along pyrenean oligocene and alpine fractures and generated both dissolution and subsequent cementation in oxfordian vugs in mud supported facies and in poorly stylolitized grainstones however these cements filled only the residual porosity in middle jurassic limestones in addition to fluorine inputs fracturation also permitted inputs of sulphur possibly due to weathering of triassic or purbeckian evaporites or h2s input during paleogene times

paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite abstract rare earth element concentrations in biogenic apatite of conodonts fish debris and inarticulate brachiopods were determined in over 200 samples from cambrian to modern sediments tests for experimental bias caused by the chemicals used to separate fossils from the rock matrix and for interlaboratory interexperiment or interspecies related variations clearly show that no resolvable fractionation of ree occurs incorporation of ree in biogenic apatite of recent fish debris occurs near the sediment water interface soon after deposition and reflects characteristics of seawater the original ree signature apparently survives subsequent burial and diagenesis cerium variations in fish debris from modern environments are controlled by redox potential ce is fractionated by co precipitation with metallic oxides under oxidizing conditions this fractionation produces a negative ce anomaly ce anom in seawater that is reflected in the sedimented fish debris conversely no fractionation of ce occurs under reducing conditions resulting in ce concentrations that are normal to enriched in anoxic seawater and fish debris deposited under local or basinwide anoxic conditions extrapolation of observations of the redox control of ce anom in modern oceans to fossil apatite indicates that anoxic conditions were prevalent in lower paleozoic and lower triassic oceans whereas in the upper paleozoic the world ocean was generally oxidizing

cemented mounds and hydrothermal sediments on the detachment surface at kane megamullion a new manifestation of hydrothermal venting 2 long lived detachment faults are now known to be important in tectonic evolution of slow spreading mid ocean ridges and there is increasing evidence that fluid flow plays a critical role in development of detachment systems here we document a new manifestation of low temperature hydrothermal venting associated with the detachment fault that formed kane megamullion 3 3 2 1 m y ago in the western rift valley wall of the mid atlantic ridge hydrothermal effects on the detachment surface include 1 cemented mounds of igneous rock and chalk debris containing hydrothermal mn oxides and fe oxyhydroxides and 2 layered deposits of similar fe mn minerals interbedded chalks mounds are roughly conical 1 10 m high and contain primarily basalts with lesser gabbro serpentinite and polymict breccia the layered fe mn rich sediments are flat bedded to contorted and locally are buckled into low relief linear or polygonal ridges we propose that the mounds formed where hydrothermal fluids discharged through the detachment hanging wall near the active fault trace hydrothermal precipitates cemented hanging wall debris and welded it to the footwall and this debris persisted as mounds as the footwall was exhumed and surrounding unconsolidated material sloughed off the sloping detachment surface some of the layered fe mn rich deposits may have precipitated from fluids discharging from the hanging wall vents but they also precipitated from low temperature fluids venting from the exposed footwall through overlying chalks observed natural disturbance and abnormally thin hydrogenous fe mn crusts on some contorted hydrothermal fe mn rich chalks on 2 7 ma crust suggest diffuse venting that is geologically recent results of this study imply that there are significant fluid pathways through all parts of detachment systems and that low temperature venting through fractured detachment footwalls may continue for several million years off axis

crystal chemical controls on rare earth element concentrations in fossil biogenic apatites and implications for paleoenvironmental reconstructions abstract fossil biogenic apatites display rare earth element ree patterns which have been proposed to reflect environmental and biological controls on past seawater composition these patterns can be separated in two groups 1 patterns that are similar to those of open ocean and epicontinental waters and 2 patterns that exhibit a strong enrichment in intermediate ree bell shaped patterns because ree trapping in biogenic apatites occurs mostly post mortem it is essential to understand the crystal chemical inorganic factors that can influence the fractionation of ree between apatite and water a model is proposed by which partition coefficients of ree between apatite and water for a substitution mechanism can be extrapolated from mineral melt partition data to seawater or sedimentary basin conditions these are compared with available experimental partition coefficients for ree adsorption mechanism and used to discuss ree patterns in fossil biogenic apatites calculations of ree patterns for apatites at equilibrium with water show that the bell shaped patterns in fossil apatites can be explained by fractionation with seawater or continental fluids at low temperature under crystal chemical control involving a substitution mechanism and in the context of extensive or late diagenesis in that case the equilibrium composition of the fluid cannot be unequivocally determined from observed ree concentrations in fossil apatites this type of sample is inappropriate to discuss the past environmental or biological controls on ree concentrations in the ocean other sample compositions suggest little to moderate alteration of the original oceanic to freshwater pattern through the adsorption mechanism in the context of weak or early diagenesis and may be used with caution for that purpose

stratigraphic control on mudrock chemistry kimmeridgian boulder bed succession ne scotland abstract a geochemical study of the fine grained background sediments to the boulder beds from the kimmeridgian 144 136 ma coastal outcrops around helmsdale ne scotland show that there is a stratigraphic change in the trace and rare earth element ree abundances from the oldest sediments of the helmsdale boulder beds mutabilis zone to the younger pectinatus zone there is an increase in rb and ba with a corresponding decrease in u v and the ree in the eudoxus zone element abundances are generally intermediate between the mutabilis zone and the pectinatus but the samples have la n yb n ratios which have most in common with the mutabilis zone this trend is interpreted as reflecting changing sediment input into the basin on the hanging wall of the helmsdale fault during the kimmeridgian as the footwall shelf was progressively denuded to remove initially older jurassic and then devonian sediments most of the ree characteristics are inherited from the source region with a provenance from river waters draining the hinterland

late jurassic coral microbial reefs from the northern paris basin facies palaeoecology and palaeobiogeography abstract during the late middle oxfordian patch reefs grew on the northern margin of the paris basin according to the facies analysis of the reef and inter reef sediments the environment was a warm clear and agitated sea with highly episodic sedimentation the bioherms were a short lived phenomenon during the third phase of regional reefal development sequence stratigraphically they are associated with a highstand system tract volumetrically and trophically dominant organisms were microbes now represented by massive clotted leiolite stalactitic hemispheroids with purely thrombolitic texture are restricted to open caves corals were of structural reef building importance due to their rapid upward growth the patch reefs are characterised by thickets of ramose corals which developed a very open framework in the vicinity of these patch reefs though in hydrodynamically higher energy environments grew thickets of more stoutly branched corals however they are rarely preserved in situ and are generally represented as abundant coral rubble the reef taxa are characterised by the notable absence of several groups e g oysters serpulids bryozoans pectinids occurring at other localities where reefs of similar age developed in similar environmental conditions the reefs also have strikingly modern aspects to them in particular the presence of cryptic elements within caves and a sponge dominated borer association dwellers belong to various life form types although encrusting taxa are exceedingly rare this may be explained by the presence of soft microbial films on most surfaces the palaeoecological analysis suggests that the major controls on faunal composition and high diversity were elevated nutrient levels highly episodic sedimentation and probably seasonal environmental disturbances structural and functional aspects of the reef community grazers trigger framebuilders borers trigger binders binders hamper borers allow ecological comparisons to be made with contemporaneous as well as recent reefs the unique combination of ecological factors resulted in a specialised previously undescribed community which differs from both tethyan and northern localities in various aspects these include cavities with cryptofauna prominence of grazing gastropods and high faunal diversity in a microbially dominated build up

rare earth element and nd isotopic variations in regionally extensive dolomites from the burlington keokuk formation mississippian implications for ree mobility during carbonate diagenesis abstract marine carbonates of the burlington keokuk fm miss of the midcontinent region have been subject to two major episodes of regionally extensive 100 000 km2 dolomitization previous studies of the cathodoluminescent petrography sr c and o isotopic compositions and sr fe mn and ca concentrations of burlington keokuk dolostones outline a diagenetic history in which lime mud was pervasively dolomitized by a seawater dominated fluid at many localities this early dolomite generation dolomite i was recrystallized by nonmarine diagenetic fluids at shallow burial depths to produce dolomite ii dolomites i and ii have similar rare earth element ree patterns and abundances and a narrow range of initial 143nd 144nd isotope ratios of 0 511906 0 000025 1 this consistency in the nd isotope ratios and ree patterns along with the presence of anomalously low abundances of cerium in the dolomites cherts glauconite pellets fish apatite and crinoids suggests that 1 seawater derived ree dominated the system and 2 the extensive water rock interaction that produced profound textural and compositional changes during the formation of dolomite ii did not significantly alter the ree patterns or nd isotopic signatures of the dolomites the results of quantitative modeling of isotopic and trace lement exchange during water rock interaction in carbonate systems indicate that extremely large water rock ratios are required to alter the ree signatures of diagenetic carbonates such large water rock ratios can reflect either 1 large extents of fluid flow during carbonate recrystallization or 2 minimal interaction between diagenetic fluids and host rocks during carbonate cement crystallization late vug filling calcite and dolomite have low sm nd and high ce nd n ratios relative to the dolostones such distinct ree signatures probably reflect limited interaction between late diagenetic fluids and burlington keokuk host rocks penecontemporaneous clastic sediments have similar initial 143nd 144nd isotope ratios 0 511857 0 511877 and lower sm nd ratios compared to the dolomites suggesting 1 a common crustal source of ree for the clastics and carbonates and 2 ree fractionation during the formation of carbonate apatite glauconite and other authigenic phases in the marine environment

shallow water redox conditions from the permian triassic boundary microbialite the rare earth element and iodine geochemistry of carbonates from turkey and south china redox sensitive elements serve as useful proxies of the oxygenation state of ancient environments but their interpretation may not always be straightforward to evaluate the inherent complexities rare earths and yttrium rey iodine and major element concentrations are determined in two carbonate sections spanning the permian triassic p tr transition in demirtas turkey and cili south china we use major oxides to identify non seawater rey sources such as siliciclastics fe oxides phosphates and diagenetic fluids additionally we employ y ho ratio la anomaly and light rare earth element depletion to identify which samples preserve a seawater like reysn distribution in contrast to past interpretations we find that the p tr boundary microbialites in both sections contain rey signatures indicative of deposition in an oxic environment these boundary microbialites have their base at the extinction horizon and are widespread within the tethyan region in the cili section the underlying permian limestone also preserves a seawater like rey signature with a negative ce anomaly this indicates that the water column was oxygenated both before and after the extinction event the permian limestone in the demirtas section does not preserve a seawater like reysn distribution so the absence of a ce anomaly cannot be used to distinguish prevailing redox conditions during deposition however in these samples we find the presence of a diverse permian benthic community sufficient to identify deposition in an oxic environment the geochemical evidence for a continuously oxic environment during the deposition of the boundary microbialite presented in this study strongly supports work done using ostracods as redox indicators within the boundary microbialite in south china the microbialite has been proposed as a disaster facies in part resulting from the exclusion of grazers although anoxia is one of the suggested mechanisms for the exclusion of grazers we find that it is not supported by geochemical and biotic evidence

secular change in northwestern tethyan water mass oxygenation during the late hauterivian early aptian abstract the mesozoic is punctuated by several extreme episodes of oxygen drawdown in the ocean known as oceanic anoxic events oae beside these discrete events little is however known about longer term oxygen level fluctuations and their controls a high resolution dataset of rare earth elements ree content in carbonate deposited in the vocontian basin se france has allowed to survey the evolution of the cerium anomaly ce ce during part of the early cretaceous latest hauterivian early aptian this ratio is used as a proxy for the degree of oceanic oxygenation the cerium anomaly is compared to the coeval evolution of relative sea level organic rich occurrences and nutrient level proxies in order to infer a cause and consequence relationship between these parameters and the evolution in sea water oxygenation the long term evolution of the cerium anomaly shows that northwestern tethyan water masses have evolved from less oxygenated during the latest hauterivian early barremian interval to more oxygenated during the late barremian earliest aptian time before being strongly oxygen depleted during the early aptian oae 1a time interval this trend is correlated with both the long term trend in nutrient levels as well as with the frequency of organic rich layers within the rock record on a medium term scale sub stage level there is a good correlation between the cerium anomaly and tectono eustatism as deduced by the mn content of the basinal carbonate and sequence stratigraphic observation on surrounding shallow water areas this suggests that sea level changes by altering ocean stratification and currents as well as modulating the amount of nutrient delivered from the continent exert control on oceanic oxygenation via changes in primary productivity

an early soda ocean in analogy to modern soda lakes commonly associated with volcanic regions it is postulated that the ancient sea had a high alkalinity a high ph and low ca and mg concentrations the change towards nacl dominance as observed in the present day ocean can best be explained by a series of mineral equilibria crustal differentiation and life processes in principle hydrothermal leaching of chlorine from the oceanic crust caused this ion to accumulate in the sea while at the same time dissolved carbonates became gradually removed by organisms and carbonates the switch from a soda to a halite ocean was accomplished 1 ga ago critical biochemical events marking the chemical evolution of the precambrian sea and their implications for the pco2 in air will be discussed

the geochemistry of rare earth elements in the seasonally anoxic water column and porewaters of chesapeake bay a twelve cruise time series study of a seasonally anoxic basin in chesapeake bay was carried out between february 1988 and february 1989 data from filtered bottom water and upper 0 1 cm porewater samples are presented this is the first study in which time series measurements have been employed to understand the low temperature geochemistry of rare earth elements rees the focus is on the coupling between redox reduction oxidation variations and ree cycling fractionation of trivalent rees and development of cerium anomalies the time series results demonstrate that rees have large seasonal cycles in both the water column and porewaters in response to the development of anoxia in the spring and reoxygenation in the fall the transition from oxic to suboxic to anoxic conditions results in the release of rees into the upper porewaters and bottom waters the release of rees and fe are coincident in the bottom waters while the release of rees lags fe by approximately 50 days in the upper porewaters this decoupling is explained in terms of a redox front which moves upward from the sediments to bottom waters during the development of seasonal anoxia the release of rees to the upper porewaters and bottom water are accompanied by 1 1 fractionation across the trivalent ree series and by 2 2 the preferential input of ce relative to its trivalent only ree neighbors ree iii fractionation is such that the relative rate of release increases from lu to la light ree middleree heavyree during reoxygenation removal of dissolved rees occurs from both the water column and upper porewaters and follows the same relative rates lree mree hree cerium removal occurs faster than its neighbor ree iii indicating a rapid oxidation of ce iii to ce iv

microbialites in a modern lagoonal environment nature and distribution tikehau atoll french polynesia abstract microbialites including stromatolitic structures gelatinous masses and mats develop in tikehau lagoon tuamotu french polynesia on the flanks and slopes of numerous pinnacles and motu islets between 0 and 25 m deep on coral colonies algal tufts or on lagoonal sediments individual stromatolitic structures consist of hemispherical domes and are produced by monospecific populations of filamentous cyanobacteria belonging to three distinctive phormidium species symploca and possibly to one new species of schizothrix gelatinous masses hanging from the ceiling of caverns are produced by phormidium laysanense microbial mats are well developed at all depths on pinnacle slopes and are produced by either monospecific or mixed cyanobacterial populations the study of micro and ultrastructure of stromatolites reveals that they result both from trapping and binding of sediments and from carbonate precipitation in addition to phototrophic biomineralization pervasive carbonate precipitation occurred in association with decaying organic matter the basic constructional elements of the precipitated carbonate consist of 0 1 0 2 m rounded bodies that form very fine anhedral to subhedral micrite their surfaces comprise extremely small carbonate granules 20 50 nm gradual changes ageing in the ultrastructure of carbonate precipitates include the precipitation of successive euhedral calcite layers around these grains widespread development of microbialites in this pristine lagoonal environment results from rapid blooms of microbial benthic communities possibly induced by temporary and local nutrient pulses nutrients seem to undergo a restricted circulation between the sediment and pinnacle reef frameworks pinnacles and reef islets are repeatedly affected by catastrophic storm events which cause redistribution of sediments and nutrients

geochemical study of coral skeletons from the puerto morelos reef southeastern mexico abstract geochemical analyses in coral skeletons have been used as a proxy of marine environmental conditions and to understand the mechanisms of adsorption of chemical elements into the coral skeletons and growth forms however little attention has been given to show the possible differences in the growth rates of corals based upon major trace rare earth element and microprobe analyses to examine the physical chemical conditions influencing those differences our goal is to show how branch and fan corals incorporate elements into their skeletons comparing them with their coral growth rates we determine the development of the skeletons of two branching acropora palmata acropora cervicornis and one fan shaped gorgonia ventalina colonies in the puerto morelos reef southeastern mexico based upon geochemical data and the influence of terrigenous input into the species mg and sr concentrations were the most statistically significant elements among the species studied suggesting that mg concentration in gorgonia ventalina is probably not linked to its growth rate mn content in the sea water is adsorbed by the three corals during past growth rates during high rainfall events sr concentration may be associated with the growth rate of acropora palmata little differences in the growth rate in acropora palmata may be associated with low rates of calcitization negligible changes in the sr concentration and little influence of temperature and water depth in its growth trace elements like cr co ni and v adsorbed by the corals are influenced by natural concentration of these elements in the sea water rare earth elements in the corals studied suggests abundant inorganic ions co32 with variable ph in modern shallow well oxygenated sea water lack of terrigenous input seawards is supported by geochemical geomorphological and biological evidences this study is an example of how geochemical data are useful to observe the differences in environmental conditions related to coral skeleton growth rates and morphology

rare earth elements and yttrium in seawater icp ms determinations in the east caroline coral sea and south fiji basins of the western south pacific ocean abstract using inductively coupled plasma mass spectrometry icp ms vertical profiles of yttrium and all the rare earth elements rees in seawater were obtained at three locations in the western south pacific the east caroline coral sea and south fiji basins based on the data we have analyzed the inter ree iii relationships and found that ree iii s heavier than dy and particularly close neighbors show strong coherencies in their oceanic behavior considering that the heavy ree iii s are less particle reactive than the light and middle ree iii s and that they have very tight correlations with regressions passing almost through the origin the neighboring element ratios of the heavy ree iii s behave virtually conservatively and are suitable as tracers of water masses the dy ho er system is practically good because its dynamic range signal to noise ratio is large in the ocean the highest ho dy ratios 0 31 are found in intermediate and deep waters throughout the western south pacific which overlie the antarctic bottom water with a low ho dy ratio 0 27 these high ho dy waters are probably formed in the polar and subantarctic frontal zone and advect northward ree iii data provide better insights into the deep water recirculation in the south pacific than those discussed based upon the regular oceanographic properties alone

rare earth elements in old biogenic apatites abstract the ree distributions in individual upper devonian conodonts have been measured by ion probe the patterns of all analyzed conodonts are enriched in middle ree eu gd and have a weak or no ce anomaly concentrations and la yb or la sm ratios vary very little within or among individuals from the same zone which suggests that uptake of labile ree from sediments was essentially quantitative therefore the ree signature of the primary carriers probably organic and oxyhydroxides particulates from marine suspensions was efficiently transferred to biogenic apatites and survived late diagenetic processes ree patterns of conodonts do not resemble those of present day seawater and post cretaceous biogenic phosphates which are typically depleted in nd and sm with a negative ce anomaly since ree distributions in the modern water column mimic those of nutrients we assume that in pre cretaceous seawater they were not controlled by surface biological activity we assume instead that ree in pre cretaceous seawater can be explained by mechanism of desorption adsorption on particle surfaces progressive extraction of lree from river water by oxyhydroxides leads to precipitates enriched in middle ree a simple quantitative model was calculated in order to illustrate the proposed mechanism

the ree and end of 40 70 ma old fish debris from the west african platform ree concentrations and nd isotopic compositions have been determined in late cretaceous early cenozoic fish debris from west african and israeli platform sediments and show a strong regional control independent of time except for those from the northern morocco it is suggested that although diagenetic fluids do not contribute ree s directly to the phosphatic debris they may significantly change the ce anomaly and the end t value of the epicontinental seas which in turn control the ree in marine phosphates it is shown that over the investigated period the north moroccan shelf seawater was progressively flushed by deep north atlantic water

rare earth element contents of jurassic fish and reptile teeth and their potential relation to seawater composition anglo paris basin france and england the rare earth element ree chemistry of jurassic shelf seawater from western europe anglo paris basin was investigated by analyzing the fish and reptile teeth deposited in shallow to deeper water 200 m environments ree patterns in apatites are controlled by the host sediments vertebrate teeth sampled from the siliciclastic sediments calcareous sandstones and shales show flat shale normalized ree patterns that reflect the dominant influence of the continental source from which the ree were derived carbonate deposits protected from the clastic sources contain fish and reptile teeth whose ree patterns reflect more accurately the ree composition of the overlying water column the ree patterns are similar through the bajocian to the oxfordian and are characterized by a depletion in heavy rare earth element dy ybn 1 8 5 0 compared to modern seawater compositions dy ybn 0 8 0 9 the fractionations among hree in the jurassic seawater are more efficient than in modern oceans and increases with depth instead of decreasing these hree removal processes operated as early as the paleozoic and disappeared during the late cretaceous the fractionation of hree relative to lree is correlated with the increasing depth of the basin as indicated by two independent criteria that are the sedimentary structures and the oxygen isotope composition of coexisting brachiopods the dy ybn ratio of the marine biogenic phosphates can be used as a proxy of paleo water depths at the scale of a water mass ce anomalies ce in biogenic apatite bearing limestones are variable and systematically negative relative to modern surface seawater and bathonian values mean ce 0 63 0 10 weak ce anomalies during the callovian mean ce 0 21 0 09 suggest the onset of more reducing conditions this redox change coincided with an increase of seawater temperatures as suggested by the oxygen isotope compositions measured on the same teeth we speculated that the callovian low ce could result from a decrease in the po2 due to the warming of seawater

mesozoic palaeoceanography of the north atlantic and tethys oceans summary the biogeography and preservation of calcareous nannofossil assemblages allow mapping of surface water fertility patterns and put constraints on carbonate dissolution in the global oceans of the middle cretaceous cyclic changes in carbonate dissolution and surface water biologic productivity in the cretaceous oceans were linked to oceanographic and climatic changes that had frequencies close to the milankovitch cycles tens of thousands to hundreds of thousand years evolution of calcareous nannoplankton during the jurassic and cretaceous periods occurred in two primary cycles of about 75 ma duration that were punctuated by major diversification events occurring every 15 30 ma that marked the beginning of periods of increased marine organic matter production and preservation stagnation events calcareous nannoplankton evolved largely in shallow seas during the rhaetian to kimmeridgian in the latest jurassic calcareous nannoplankton conquered the oceanic realm became major producers of pelagic carbonates and are thus responsible for the shift of carbonate deposition from shallow seas to the deep ocean in the late cretaceous chalk seas nannofossils replaced shallow water benthos as major carbonate producers warm climates due to high atmospheric co 2 concentrations and increased albedo during high sea level stands caused by global tectonic processes made these tiny creatures flourish during the late mesozoic

cerium a chemical tracer for paleo oceanic redox conditions abstract the ce anomalies found in marine carbonates provide a sensitive indicator for the study of paleo oceanic redox conditions the dependency of cce the observed ce concentration and cepo04 the activity of the cepo4 complex to the po2 ph and pco2 of seawater can be used for deciphering some aspects of the paleo ocean chemistry and is log c ce log cepo 0 4 13 2 0 25 log p o 2 3 0 ph 1 95 0 25 log p o 2 1 50 log p co 2 1 50 log ca the ph which is related to pco2 and po2 are major factors for controlling the ce concentration in seawater therefore ce anomalies ceas ce observed ce interpolated between la and pr or nd serve as indicators for ph or pco2 or po2 changes nearly uniform ce abundances found in pacific 5000 m water columns piepgras and jacobsen 1988 and the ceas in ichthyoliths can be explained using this model a general cea shift in sediments from d s d p holes 525a 530a b 516 516f suggest that the entire south atlantic water redox condition changed from reducing to oxidizing at 56 my in the north atlantic the galicia margin samples show a redox change between 132 148 my indicating active surface currents between the atlantic ocean and the shallow sea off the iberian peninsula the carbonate samples from d s d p hole 316 in the central pacific yielded an average cea of 0 15 0 01 which is 2 3 the ceas observed in deep pacific seawater by piepgras and jacobsen 1988 the relative enrichment of ce in these samples is ascribed to coprecipitation of ce oh 4 onto fe mn o coatings the striking similarities in the trace element profiles of ree sc hf th and ceas and the low u abundances 0 08 ppm in many marine carbonates indicate insignificant ce redox and trace elemental concentration changes for the pacific ocean over the past 95 my no significant ce redox change occurred in the pacific ocean within k t boundary one 240 my china limestone deposited under oxic sedimentary conditions yielded a cea of 0 53 calculations indicate a pco2 of 1 9 present value prevailed over the 240 my tethyan ocean u th ratios and low u concentrations are diagnostic indicators for obtaining reliable ceas in marine carbonates and perhaps for biogenic apatites and conodonts as well

nd isotopic composition of jurassic tethys seawater and the genesis of alpine mn deposits evidence from sr nd isotope data jurassic metabasalts metasediments and mn ores from the pennine realm of the alps were examined in order to establish the nd isotopic composition of the jurassic tethys seawater and to elucidate the genesis of the mn deposits the highly positive initial epsilon sub nd values 7 to 9 8 of the metabasalts and their low sup 87 sr sup 86 sr ratios 0 7028 to 0 7049 indicate that they originated from a depleted mantle the initial epsilon sub nd values of the cherts range between minus 5 and minus 9 the sm nd isotope data indicate that they are primary mixtures of basalt and continental detritus the smaller than 2 mu m fractions of the cherts and of a marble which probably represent the formerly authigenic material show initial epsilon sub nd values ranging between minus 5 9 and minus 6 6 the average initial sr isotopic composition of five mn ores is 0 70730 plus minus 22 identical to that of contemporaneous jurassic seawater the initial nd isotopic composition values of the mn ores are very homogeneous the average value of five ores a leachate and residue of one of them calculated for an age of 170 ma is 0 512082 plus minus 19 it is suggested that the ores together with the smaller than 2 mu mmore fractions of the sediments define the jurassic tethys seawater isotopic composition the resulting average sup 143 nd sup 144 nd initial value is 0 512089 plus minus 17 epsilon sub nd minus 6 5 plus minus 0 6 less

ca carbonates precipitation and limestone genesis the microbiogeologist point of view abstract experiments show that the production of carbonate particles by heterotrophic bacteria follows different ways in heterotrophy the passive carbonatogenesis is generated by modifications of the medium that lead to the accumulation of carbonate and bicarbonate ions and to the precipitation of solid particles it is induced by several metabolic pathways of the nitrogen cycle ammonification of amino acids degradation of urea and uric acid dissimilatory reduction of nitrates and of the sulphur cycle dissimilatory reduction of sulphates the active carbonatogenesis is independent of the mentioned metabolic pathways the carbonate particles are produced by ionic exchanges through the cell membrane following still poorly known mechanisms in autotrophy non methylotrophic methanogenesis and cyanobacterial photosynthesis also may contribute to the precipitation of carbonates autotrophic carbonates as carbonatogenesis is neither restricted to particular taxonomic groups of bacteria nor to specific environments it has been an ubiquitous phenomenon since precambrian times carbonatogenesis is the response of heterotrophic bacterial communities to an enrichment of the milieu in organic matter after a phase of latency there is an exponential increase of bacterial numbers together with the accumulation of metabolic end products these induce a ph increase and an accumulation of carbonate and hydrogenocarbonate ions in the medium this phase ends into a steady state when most part of the initial enrichment is consumed and there is a balance between death and growth in bacterial populations particulate carbonatogenesis occurs during the exponential phase and ends more or less after the beginning of the steady state the active carbonatogenesis seems to start first and to be followed by the passive one which induces the growth of initially produced particles in eutrophic conditions the first solid products are patches that appear on the surface of the bacterial bodies and coalesce until forming a rigid coating and or particles excreted from the cell all these tiny particles assemble into biomineral aggregates which often display precrystalline structures these aggregates grow and form biocrystalline build ups which progressively display more crystalline structures with growth in oligotrophic conditions the primary solid products are rapidly smoothed in the crystalline structure and leave no trace in present aqueous environments apart from deep ocean the potential efficiency of heterotrophic bacterial carbonatogenesis in ca carbonate sedimentation is much higher than autotrophic or abiotic processes it much more likely accounts for extensive apparently abiotic limestone formation than any of the latter as far as biodetrital particles are concerned it may be observed that the shells and tests of organisms are built from the activity of cellular organites which are nowadays considered by a number of biologists as endosymbiotic bacteria thus apart from probably mythical purely evaporitic and autotrophic ones most limestones must be considered as principally of heterotrophic bacterial origin as the carbon of limestones is issued from organic matter bacterial heterotrophic carbonatogenesis appears as a fundamental phenomenon in the relationships between atmosphere and lithosphere during the biogeological evolution of the earth

geochemistry of late archaean stromatolites from zimbabwe evidence for microbial life in restricted epicontinental seas we report comprehensive trace element and sr isotope data for microbial carbonates from the archaean mushandike limestone masvingo greenstone belt zimbabwe the stromatolites have very coherent ree y patterns and share the essential shale normalised characteristics of other archaean marine precipitates positive la and gd anomalies absence of a negative cc anomaly and a strongly superchondritic y ho ratio mixing models constrain the maximum amount of shale contamination to 0 25 1 and calculated detritus free carbonate ree y systematics require precipitation from seawater in terms of light ree over heavy ree depletion however the studied samples are very different from all other known archaean marine precipitates in shale normalised plots the mushandike samples yield a negative slope a very restricted regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss ree y data yields a pattern closely resembling typical shale normalised archaean marine chemical sediments the disappearance of a negative eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation sr isotope ratios are strongly correlated with trace element contents and ratios which explains the modest scatter in sr isotope ratios as representing minor clastic contamination importantly even the least contaminated samples have very radiogenic initial sr 87 sr 86 ratios 0 7184 implying sr input from an ancient high rb sr source such as the early archaean gneisses of south central zimbabwe a local ancient 3 5 3 8 ga source is also indicated by previously published pb isotope datasets for the mushandike stromatolites this is entirely compatible with the occurrence of 3 7 3 8 ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality comparison of the pb isotope ratios of the mushandike stromatolites with 2 7 and 2 6 ga old stromatolites from the neighbouring belingwe greenstone belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean the development of numerous basins on old continental crust with water masses variably restricted from the open ocean suggests a lack of strong vertical topography on this late archaean craton c 2004 elsevier b v all rights reserved

rare earth major and trace elements in chert from the franciscan complex and monterey group california assessing ree sources to fine grained marine sediments abstract rare earth element ree major and trace element analyses of 77 samples from the mesozoic franciscan complex and miocene monterey group of california usa indicate that magnitudes of the ce anomaly ce ce and total ree abundances sree in these rocks are controlled dominantly by a the amount of included metalliferous material b the amount of direct terrigenous input and c the overall burial rate the relative importance of these individual processes varies across an ocean basin in such a way that ree relative fractionations and sree correspond with its depositional environment our conclusions are supported by an extensive review of published ree data from various river coastal open ocean and ridge influenced waters as well as terrigenous pelagic and metalliferous sediment the chert sequences record deposition in spreading ridge open ocean basin and continental margin environments the relative importance of metalliferous and terrigenous influences and the role of scavenging from seawater may be estimated from a sample s inferred depositional distance km from the spreading ridge the major element chemistry and the stratigraphie context the ce ce values are low 0 29 in the vicinity of spreading ridges and trend to successively higher 1 values with decreasing metalliferous and increasing terrigenous influences other ree indicators ree lu n la n eu eu also respond to metalliferous and terrigenous influences near the spreading ridge chert ree appears determined by burial rate while shale ree responds to metalliferous abundance in open ocean and continental margin environments ree is controlled by sediment exposure time and therefore is related inversely to burial rate ree data are consistent with the major elements fe2o3 mno and al2o3 in reflecting the respective metalliferous and terrigenous sources p2o5 and cao do not vary with ce ce in any environment but cao shows a weak negative correlation with ree trace element trends e g v cr cu ge si rb sr y th u in general can similarly be accounted for in the context of depositional position relative to metalliferous and terrigenous inputs rees in chert appear less affected by post depositional processes than either major or trace elements indicating that rees are better tools for paleoceanographic or tectonic reconstructions that are based on chert chemistry this work complements recent efforts to elucidate the factors determining large scale ree distributions in marine sediments and has direct bearing on previous attempts to use the ce anomaly in older rocks and sediments as a recorder of secular variations and anoxic events in the overlying water column

rare earth geochemistry of phosphorites abstract the abundance of rare earth elements ree s in francolite increases with increasing age as a result of post depositional enrichment abundances are higher in pelletal samples than in non pelletal ones because the higher surface mass ratio of pelletal francolite promotes enrichment during diagenesis onshore francolite has higher ree abundances than that found offshore distribution patterns in francolite may be similar to those reported for open ocean water or shale depending upon the dominant source of the ree s different patterns result from weathering and deep burial diagenetic modification of the original patterns and abundances negative ce anomalies occur in francolites containing structural sulphur that is isotopically indistinguishable from seawater of the same age zero or positive anomalies occur in francolites which contain sulphur that is isotopically lighter than seawater

microbialite morphology structure and growth a model of the upper jurassic reefs of the chay peninsula western france abstract during the early kimmeridgian the northern margin of the aquitaine basin western france is characterised by a significant development of coral reefs the reef formation of the chay peninsula comprises two main reefal units in which the microbial structures can contribute up to 70 of framework the microbial crusts which played an important role in the stabilisation and growth of the reef body show the characteristic clotted aspect of thrombolitic microbialites corals are the main skeletal components of the build ups the bioconstructions of the chay area are thus classified as coral thrombolite reefs four main morpho structural types of microbial crusts are distinguished 1 pseudostalactitic microbialites on the roof of intra reef palaeocaves 2 mamillated microbialites found either on the undersides or on the flanks of the bioherms 3 reticular microbialites in marginal parts of the reefs and between adjacent bioconstructed units and 4 interstitial microbialites in voids of bioclastic deposits thrombolitic crusts developed on various substrates such as corals bivalves or bioclasts the thrombolites formed a dense clotted and or micropeloidal microbial framework in which macro and micro encrusters also occur variations in accumulation rate strongly influenced the reef morphology in particular its relief above the sediment surface the coalescence of the coral microbialite patches created numerous intra reef cavities of metre scale dimensions the direction of microbial growth which defined the macroscopic microbialite forms strongly depended on the position within the reef framework but was also controlled by water energy accumulation rate and light availability

sm nd in marine carbonates and phosphates implications for nd isotopes in seawater and crustal ages this study explores the possibility of establishing nd isotopic variations in seawater over geologic time calcite aragonite and apatite are examined as possible phases recording seawater values of nd modern biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have nd concentrations of from 0 2 to 70 ppb showing that primary marine caco 3 contains little ree and that nd ca is not greatly enhanced relative to seawater during carbonate precipitation very young marine limestone and dolomite containing no continental detritus have 200 ppb nd all the carbonates are lree enriched 0 16 sm nd 0 45 modern and very young atlantic and pacific carbonates have nd in the range of shallow atlantic and pacific seawater respectively implying that they derive their ree from local seawater the nd in well preserved carbonate fossils is 4 10 4 ppb much greater than in their modern counterparts but like the high values found for carbonates in other studies we believe the high ree contents at the 500 ppb level in some detritusfree carbonates are due to ree rich fe hydroxide in on the carbonate in favorable cases such material may record seawater nd values however introduction of extraneous ree may obscure the original isotopic composition of pure caco 3 because of its very low intrinsic primary ree abundance modern biogenic apatite is also shown to have very low ree content 150 ppb nd but appears to quickly scavenge ree from seawater inorganically precipitated apatite from phosphorites has high concentrations of seawater derived ree young phosphorite apatite from the atlantic and pacific oceans has nd in the range of the seawater from these oceans older apatite samples of similar age from different localities bordering common oceans record similar values of nd t sedimentary apatite has sr t values in good agreement with the curves for 87 sr 86 sr of seawater as a function of time individual conodonts from a single formation yield the same sr t and nd t other workers have shown that sedimentary apatite preserves seawater ree patterns these characteristics suggest that sedimentary apatite can be used to determine nd t in ancient seawater the seawater values so inferred range between 1 7 and 8 9 over the last 700 my and lie in the range of modern seawater showing no evidence for drastic changes high values of seawater nd t in the triassic and latest precambrian may correlate with the breakup of large continental landmasses the initial nd t 15 0 of a 2 ae old phosphorite implies the presence of 1 5 ae old continental crust at 2 ae ago the approach outlined here can be used to constrain the age of the exposed crust as a function of time

nature and environmental significance of microbialites in quaternary reefs the tahiti paradox drill cores from the bamer reef edge of tahiti exhibit 85 93 m thick coralgal sequences recording at least 13 500 years of continuous reef growth in optimal environmental conditions the cored reef sequences form an overall shallowingupward succession with assemblages of branching or massive colonies of porires at the base overlain by a robust branching community acropom gr dmmi robirstn heavily encrusted by coralline algae sessile vermetid gastropods and arborescent foraminifers which grew at depths less than 6 m microbialites generally form the last stage of encrustation of coral colonies or more commonly of related encrusting organisms thus appearing as a major structural component of the reef sequence where they may locally form 809 of the rock by volume they developed in an open cavity system of the reef framework with freely circulating normal marine water microbialites include laminated crusts and clotted micritic masses commonly associated in compound crusts probably feflecting differences in the composition of the involved biological communities and in biomineralization processes that controlled the accretion of the crusts the isotopic composition of the microbialites 2 05 to 3 92 i they underwent also indivitlual processes of biominrlali2ation besicles the overall decrease in lizht and enqy conditions rttlecting progressive burial by conil growth the widespread development of microbialites within the reef framework may be related to increased alkalinity and niitrient availability in interstitial waters due to temstrial groundwwr seepage and puiodic runoffs the tlevelopment of micrubialites in the cryptic niches of the reef framework ceased about 6000 years

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

nd isotope evidence for the evolution of the paleocurrents in the atlantic and tethys oceans during the past 180 ma the nd isotopic composition of atlantic and tethys seawater as deduced from marine phosphorites varied considerably during the past 180 ma the early tethys and central atlantic seawater from 180 to 160 ma ago early middle jurassic had a nd isotopic signature identical to that of the pacific end 6 suggesting that pacific seawater entered the newly forming tethys basin however with time continental runoff draining into the young basin became more important and led to a decrease in the nd isotopic composition and finally a decoupling from the pacific ocean during the late early cretaceous 120 90 ma ago atlantic and tethys seawater reached continental crust like nd isotopic composition values end 10 which could reflect high weathering rates induced by the warm and humid climate at that time in the time span between 80 and 50 ma late cretaceous early tertiary the nd isotopic composition of both tethys and atlantic seawater strongly increased towards pacific seawater values in the case of the atlantic ocean this change has been correlated with the opening of the south atlantic which enabled the more radiogenic pacific seawater to travel westwards around the southern edge of africa into the south and finally the north atlantic in the case of tethys seawater we have to assume that during this period large masses of pacific seawater entered the tethys again directly through the indian tethys seaway the renewed importance of this seaway might be related to the late cretaceous early tertiary first order global sea level highstand the most abrupt change towards lower more crust like values occurred in the early miocene 25 17 ma ago in the south and north atlantic as well as in the tethys during this period the143nd 144nd isotope ratios dropped from 0 5124 end 4 2 down to 0 5122 end 8 this change indicates a diminishing influx of pacif seawater into the atlantic and tethys oceans and can be correlated with the breakdown of the circum equatorial circulation patterns of the world oceans due to plate tectonics from 20 to 17 ma ago miocene the nd isotopic composition of the atlantic ocean increased again and reached values as high as 0 5123 end 6 6 whereas tethys seawater remained at low values this decoupling can be correlated with the incipient complete isolation of the tethys the nd isotopic composition was henceforth controlled by the continental runoff from surrounding land masses the major increase in the nd isotopic composition observed in the atlantic can be related to the opening of the drake passage and establishment of the circum antarctic current system this allowed pacific seawater to enter directly the south atlantic around antarctica a renewed drop in the nd isotopic composition of atlantic seawater during the late miocene can be related to the onset of north atlantic bottom water formation and its subsequent upwelling

discriminating stromatolite formation modes using rare earth element geochemistry trapping and binding versus in situ precipitation of stromatolites from the neoproterozoic bitter springs formation northern territory australia stromatolites consist primarily of trapped and bound ambient sediment and or authigenic mineral precipitates but discrimination of the two constituents is difficult where stromatolites have a fine texture we used laser ablation inductively coupled plasma mass spectrometry to measure trace element rare earth element ree y and th concentrations in both stromatolites domical and branched and closely associated particulate carbonate sediment in interspaces spaces between columns or branches from bioherms within the neoproterozoic bitter springs formation central australia our high resolution sampling allows discrimination of shale normalised ree patterns between carbonate in stromatolites and immediately adjacent fine grained ambient particulate carbonate sediment from interspaces whereas all samples show similar negative la and ce anomalies positive gd anomalies and chondritic y ho ratios the stromatolites and non stromatolite sediment are distinguishable on the basis of consistently elevated light rees lrees in the stromatolitic laminae and relatively depleted lrees in the particulate sediment samples additionally concentrations of the lithophile element th are higher in ambient sediment samples than in stromatolites consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites these findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment hence high resolution trace element ree y th geochemistry can discriminate fine grained carbonates in these stromatolites from coeval non stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation presumably within microbial mats biofilms rather than by trapping and binding of ambient sediment identification of the source of fine carbonate in stromatolites is significant because if it is not too heavily contaminated by trapped ambient sediment it may contain geochemical biosignatures and or direct evidence of the local water chemistry in which the precipitates formed

authigenic minerals from the paola ridge southern tyrrhenian sea evidences of episodic methane seepage abstract paola ridge along the nw calabrian margin southern tyrrhenian sea is one of the few reported deep sea sites of precipitation of authigenic carbonates in the tyrrhenian sea here the changing composition of the seeping fluids and the dynamic nature of the seepage induced the precipitation of pyrite siderite and other carbonate phases the occurrence of this array of authigenic precipitates is thought to be related to fluctuation of the sulfate methane transition zone smtz concretions of authigenic minerals formed in the near sub bottom sediments of the paola ridge were investigated for their geochemical and isotopic composition these concretions were collected in an area characterized by the presence of two alleged mud volcanoes and three mud diapirs the mud diapirs are dotted by pockmarks and dissected by normal faults and are known for having been a site of fluid seepage for at least the past 40 kyrs present day venting activity occurs alongside the two alleged mud volcanoes and is dominated by co2 rich discharging fluids this discover led us to question the hypothesis of the mud volcanoes and investigate the origin of the fluids in each different domed structure of the study area in this study we used stable isotopes carbon and oxygen of carbonates coupled with rare earth element ree composition of different carbonate and non carbonate phases for tracing fluid composition and early diagenesis of authigenic precipitates the analyses on authigenic precipitates were coupled with chemical investigation of venting gas and sea water authigenic calcite aragonite concretions from surficial sediments on diapiric structures have depleted 13c isotopic composition and slightly positive 18o values by contrast siderite concretions generally found within the first 6 m of sediments on the alleged mud volcanoes yielded positive 13c and 18o values the siderite ree pattern shows consistent lree light ree fractionation mree medium ree enrichment and positive gd and la anomalies as shown by the ree distribution the 13c depleted composition and their association with chemosymbiotic fauna calcite aragonite precipitated at time of moderate to high methane flux close to the seafloor under the influence of bottom seawater authigenic siderite on the other hand formed in the subseafloor during periods of lower gas discharges under prolonged anoxic conditions within sediments in equilibrium with 13c rich dissolved inorganic carbon dic and 18o rich water likely related to methanogenesis and intermittent venting of deep sourced co2

brucite microbialites in living coral skeletons indicators of extreme microenvironments in shallow marine settings brucite mg oh 2 microbialites occur in vacated interseptal spaces of living scleractinian coral colonies acropora pocillopora porites from subtidal and intertidal settings in the great barrier reef australia and subtidal montastraea from the florida keys united states brucite encrusts microbial filaments of endobionts i e fungi green algae cyanobacteria growing under organic biofilms the brucite distribution is patchy both within interseptal spaces and within coralla although brucite is undersaturated in seawater its precipitation was apparently induced in the corals by lowered pco2 and increased ph within microenvironments protected by microbial biofilms the occurrence of brucite in shallow marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates significantly the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies

carbonate stromatolites from a messinian hypersaline setting in the caltanissetta basin sicily petrographic evidence of microbial activity and related stable isotope and rare earth element signatures lower messinian stromatolites of the calcare di base formation at sutera in sicily record periods of low sea level strong evaporation and elevated salinity thought to be associated with the onset of the messinian salinity crisis overlying aragonitic limestones were precipitated in normal to slightly evaporative conditions occasionally influenced by an influx of meteoric water evidence of bacterial involvement in carbonate formation is recorded in three dolomite rich stromatolite beds in the lower portion of the section that contain low domes with irregular crinkly millimetre scale lamination and small fenestrae the dominant microfabrics are i peloidal and clotted dolomicrite with calcite filled fenestrae ii dolomicrite with bacterium like filaments and pores partially filled by calcite or black amorphous matter and iii micrite in which fenestrae alternate with dark thin wispy micrite the filaments resemble beggiatoa like sulphur bacteria under scanning electron microscopy the filaments consist of spherical aggregates of dolomite interpreted to result from calcification of bacterial microcolonies the dolomite crystals are commonly arranged as rounded grains that appear to be incorporated or absorbed into developing crystal faces biofilm like remains occur in voids between the filaments the dolomite consistently shows negative d 13 c values down to 11ae3 and very positive d 18 o mean value 7ae9 that suggest formation as primary precipitate with a substantial contribution of organic co2 very negative d 13 c values down to 31ae6 of early diagenetic calcite associated with the dolomite suggest contribution of co2 originating by anaerobic methane oxidation the shale normalized rare earth element patterns of sutera stromatolites show features similar to those in present day microbial mats with enrichment in light rare earth elements and m type tetrad effects enrichment around pr coupled to a decline around nd and a peak around sm and eu taken together the petrography and geochemistry of the sutera stromatolites provide diverse and compelling evidence for microbial influence on carbonate precipitation