controls of eustasy and diagenesis on the 238u 235u of carbonates and evolution of the seawater 234u 238u during the last 1 4 myr using a leaching protocol designed for the study of u isotopes in recent carbonates we measured the u isotope composition both 238 u 235 u and 234 u 238 u of modern and ancient corals n 6 a limestone and a dolostone as well as 43 shallow water carbonate sediments from the odp leg 166 site 1009 drill core on the slope of the bahamas platform although bulk corals record the seawater 238 u value within 0 02 differences of up to 0 30 in the 238 u of individual leachates suggest a control of the coral structure and a more positive 238 u 235 u ratio in the centers of calcification the drill core 238 u data shows that the 238 u 235 u ratio of shallow water carbonates is controlled mainly by 1 variations in sea level through the mixing of different amounts of platform derived sediments with 238 u 0 50 0 60 heavier than seawater and pelagic sediments with seawater like 238 u values 2 authigenic u enrichment via pore watercirculation and u reduction both on the platform and down to 5 m below the surface mbsf after deposition of the sediment and to a lesser extent by 3 early diagenetic processes i e carbonate dissolution and or recrystallization during sediment burial the global effect of these processes leaves the 238 u values of shallow water carbonates offset relative to that of seawater by carbonates sw 0 24 0 06 95 ci including all samples this shift can be used in seawater paleoredox reconstructions based on carbonates deposited on shallow water platform shelf and slope environments i e most of the carbonate sedimentary record prior to the mesozoic to account for the average effect of carbonate diagenesis assuming that the 238 u 235 u ratio of carbonate platform sediments directly records the seawater 238 u 235 u ratio would underestimate the extent of ocean seafloor anoxia by at least a factor 10 the rapid fluctuations in 238 u values due to sea level changes i is a factor that should be considered before interpreting 238 u variations as reflecting changes in oceanic paleoredox conditions and ii reinforces the need for statistically meaningful data sets the 234 u data suggest that the 234 u 238 u ratio of the seawater has remained within 20 of the modern seawater value during the last 1 1 4 myr furthermore we find that small scale 1 15 variations in seawater 234 u mirror sea level changes during the penultimate glacial interglacial period 140 to 200 ka thus confirming the record of lower 234 u sw during periods of low sea level stand and expanding it to at least the last two glacial interglacial events i e 0 23 ma such fluctuations in 234 u initial values should be taken into account when screening carbonate sediments u th ages on the basis of the initial 234 u 238 u ratios of the samples

neoproterozoic snowball earth simulations with a coupled climate ice sheet model ice sheets may have reached the equator in the late proterozoic era 600 800 myr ago according to geological and palaeomagnetic studies possibly resulting in a snowball earth but this period was a critical time in the evolution of multicellular animals posing the question of how early life survived under such environmental stress here we present computer simulations of this unusual climate stage with a coupled climate ice sheet model to simulate a snowball earth we use only a reduction in the solar constant compared to present day conditions and we keep atmospheric co2 concentrations near present levels we find rapid transitions into and out of full glaciation that are consistent with the geological evidence when we combine these results with a general circulation model some of the simulations result in an equatorial belt of open water that may have provided a refugium for multicellular animals

origin of giant wave ripples in snowball earth cap carbonate the most extreme climate transitions in earth history are recorded by the juxtaposition of neoproterozoic glacial deposits with overlying cap carbonate beds some of the most remarkable sedimentary structures within these beds are sharp crested trochoidal bedforms with regular spacing of as much as several meters that are often interpreted as giant wave ripples formed under extreme wave conditions in a nonuniform postglacial climate here we evaluate this hypothesis using a new bedform stability diagram for symmetric oscillatory fl ows that indicates that the fi rst order control on the formation of trochoidal rather than hummocky bedforms is sediment size not wave climate new measurements of bedform wavelengths and particle sizes from the ca 635 ma nuccaleena formation australia indicate that the giant ripples are generally composed of coarse to very coarse sand most are within the trochoidal bedform stability phase space for normal wave climates moreover numerical simulations of flover fi xed bedforms show that symmetric trochoidal ripples with a nearly vertical angle of climb may be produced over long time periods with variable wave climates in conjunction with rapid seabed cementation these data reveal that rather than extreme wave conditions the giant wave ripples are a consequence of the unusual mode of carbonate precipitation during a global carbon cycle perturbation unprecedented in earth history

tonian cryogenian boundary sections of argyll scotland abstract the tonian cryogenian system boundary is to be defined at a gssp global boundary stratigraphic section and point beneath the first evidence of widespread glaciation a candidate lies within the dalradian supergroup of scotland and ireland which is least deformed and metamorphosed in argyll western scotland we present new stratigraphic profiles and interpretations from the isle of islay and the garvellach islands update the chemostratigraphy of the appin group tonian carbonates underlying the thick ca 1 km glacigenic port askaig formation paf and demonstrate an environmental transition at the contact the appin group forms a regionally extensive 4 km thick succession of limestones shales and sandstones deposited on a marine shelf on islay the upper part of the lithostratigraphy has been clarified by measuring and correlating two sections containing distinctive stratigraphic levels including molar tooth structure oolite stromatolitic dolomite and intraclastic microbial mounds significantly deeper erosion at the unconformity at the base of the overlying paf is demonstrated in the southern section carbonate facies show a gradual decline in 13 c vpdb from 5 to 2 upwards in ne garbh eileach garvellach islands a continuously exposed section of appin group carbonates 70 m thick here designated the garbh eileach formation gef lies conformably beneath the paf the gef and the gef paf boundary relationships are re described with new sedimentological logs petrological and stable isotope data interstratified limestone and dolomicrosparite with 13 c of 4 to 7 a feature named the garvellach anomaly replacing the term islay anomaly are overlain by dolomite in which the isotope signature becomes weakly positive up to 1 upwards shallow subtidal conditions become peritidal upwards with evidence of wave and storm activity gypsum pseudomorphs and subaerial exposure surfaces are common near the top of the gef the basal diamictite d1 of the paf is rich in carbonate clasts similar to slightly deeper water parts of the underlying succession d1 is typically several metres thick with interstratified sandstone and conglomerate but dies out laterally scattered siliciclastic coarse sandstone to pebble conglomerate with dropstones associated with soft sediment deformation is interbedded with carbonate below and above d1 dolomite beds with derived intraclasts and gypsum pseudomorphs are found above d1 or equivalent position where d1 is absent published and new sr isotope studies including successive leach data demonstrate primary tonian 87 sr 86 sr values of 0 7066 0 7069 on islay decreasing to 0 7064 0 7066 in the younger gef limestones on the garvellachs with 1700 2700 ppm sr other typically tonian characteristics of the carbonates are the sr rich nature of limestones molar tooth structure and dolomitized peritidal facies with evidence of aridity seabed surveys suggesting uniformly dipping strata and shallow borehole core material illustrate the potential for extending the tonian record offshore of the garvellachs a candidate tonian cryogenian gssp is proposed on garbh eileach within the smooth 13 c profile at the cross over to positive 13 c signatures 4 m below the first occurrence of ice rafted sediment and 9 m below the first diamictite although lacking radiometric constraints or stratigraphically significant biotas or biomarkers the scottish succession has a thick and relatively complete sedimentary record of glaciation coherent carbon and strontium chemostratigraphy lateral continuity of outcrops and 100 exposure at the proposed boundary interval

zn sr isotope records of the ediacaran doushantuo formation in south china diagenesis assessment and implications abstract recent studies show that zinc isotopes could provide valuable clues to environmental change and biogeochemical cycle of the past oceans this study reports a modified procedure for leaching the carbonate fractions in sedimentary rocks a thorough evaluation of diagenetic effects and systematic variations of zn and sr isotope ratios in lower part of the ediacaran stratigraphic unit deposited in the aftermath of the marinoan glaciation in south china the influence of post depositional diagenesis on zn isotope compositions of the studied samples is assessed by comparing 66zn to other geochemical indexes 87sr 86sr 13c 18o and mn sr ratios in the five studied cap carbonate sections member i of the doushantuo formation dolostones from four sections have 66zn values positively correlated with 18o values and negatively correlated with 87sr 86sr ratios 0 7081 0 7204 these correlations suggest that these cap dolostone samples have been modified by post depositional diagenesis the light 66zn value 0 02 suggests that initial zn isotope ratios of cap dolostones could have been reset by hydrothermal fluids with relatively high zn concentration and low 66zn values by contrast carbonates from member ii of the doushantuo formation above cap dolostones are relatively pristine based on their low 87sr 86sr ratios 0 7079 0 7086 being indistinct from the proposed early ediacaran seawater 87sr 86sr values chemical and isotopic variations in these samples are interpreted to reflect primary signals that record paleo environmental changes of the early ediacaran ocean a rapid increase of 66zn from 0 3 to 1 1 occurs in the middle part of member ii accompanying by relatively invariant 87sr 86sr ratios that imply insignificant changes in input from continental weathering considering the limited change in atmospheric oxygen during this period the rapid 66zn raise indicates an increase in buried organic matters which is consistent with the coupled positive shift of 13ccarb as well as the fossil records found in the same strata these results provide insights into zn cycling in the post marinoan oceans and facilitate the application of zn isotopes in carbonates as a proxy for the fate of marine organic matter

magnesium isotope fractionation in biogenic and abiogenic carbonates implications for paleoenvironmental proxies abstract geochemical variations in marine biogenic carbonates that are preserved in the geological record serve as proxies of past environmental change however interpreting most proxies is complicated by biologically mediated vital effects highlighting the need to develop new tools for reconstructing paleoenvironmental change recently magnesium mg isotope variability in carbonates has been explored extensively to determine its utility as a paleoenvironmental proxy we review the results of these works which have yielded valuable information on the factors affecting mg isotope fractionation between carbonates and solution 26mgcarb sol in biogenic and abiogenic carbonate minerals strong evidence exists for a mineralogical control on 26mgcarb sol with the negative offset from 0 following the sequence aragonite 3 mol mol and saturation states 3 that are similar to seawater suggest that 26mgcarb sol has a temperature dependence of 0 01 c 1 and is insensitive to precipitation rate in contrast a significant precipitation rate dependence is observed in calcites precipitated from solutions with relatively low mg ca ratios

palaeomagnetism and magnetic anisotropy of late neoproterozoic strata south australia implications for the palaeolatitude of late cryogenian glaciation cap carbonate and the ediacaran system abstract the ediacaran global stratotype section and point gssp is defined near the base of the nuccaleena formation the cap carbonate overlying the terminal cryogenian glaciogenic elatina formation at a basin wide sequence boundary in the adelaide geosyncline south australia previous palaeomagnetic data for 205 specimens from the elatina formation yielded a structurally corrected mean declination d 208 3 and inclination i 12 9 95 4 2 palaeolatitude 6 5 2 2 and pole position at latitude p 47 3 s longitude p 359 3 e dp 2 1 and dm 4 2 new palaeomagnetic data for 141 specimens from the nuccaleena formation yield a structurally corrected mean direction of d 208 3 i 34 9 95 3 4 19 2 2 3 2 2 and pole position at p 32 3 s p 350 8 e dp 2 2 and dm 3 9 there is a substantial difference in inclination between the elatina and nuccaleena formations despite their juxtaposition positive fold tests for both formations seem to rule out remagnetisation of one or both formations fold tests on tepee like structures in the nuccaleena formation accord with the magnetisation having been acquired at or near the time the structures formed during early diagenesis magnetisation therefore variably lags deposition causing the three identified magnetostratigraphic horizons to appear highly bedding transgressive whereas local correlations may seem satisfactory regional correlations are not nevertheless the number and duration of polarity chrons at various localities appear valid implying that the nuccaleena formation accumulated over an interval of 10 5 years the question of compaction related inclination shallowing was addressed by examining the anisotropy of remanence using a superconducting 12 t magnet the effective flattening factors f determined were nuccaleena dolostones n 4 f 0 98 0 02 elatina tidal rhythmites n 6 f 0 97 0 01 elatina arenites n 9 f 0 92 0 02 the mean elatina inclination is corrected to 14 0 palaeolatitude of 7 1 and the mean nuccaleena inclination to 35 4 palaeolatitude of 19 6 inclination shallowing also was investigated using the elongation inclination method the distributions of directions for the elatina were somewhat skewed with respect to bedding possibly invalidating use of this method nevertheless for the elatina the method yields an inclination of 19 palaeolatitude of 10 for the nuccaleena the corrected inclination is 41 9 palaeolatitude of 24 these corrections do not materially alter the near equatorial palaeolatitude for the elatina formation which is supported by data for other neoproterozoic strata in southern australia however the substantial increase in palaeolatitude between the late cryogenian and the early ediacaran is maintained the sequence boundary below the nuccaleena formation is a disconformity to low angle unconformity that in places cuts deeply into the 1500 m thick late cryogenian glaciogenic succession and may represent a significant time gap marked by rapid polar wander such a hiatus may be an important factor in the juxtaposition of glacial deposits and cap carbonates

mineralogical constraints on the paleoenvironments of the ediacaran doushantuo formation assemblages of clay minerals are routinely used as proxies for paleoclimatic change and paleoenvironmental conditions in phanerozoic rocks however this tool is rarely applied in older sedimentary units in this paper the clay mineralogy of the doushantuo formation in south china is documented providing constraints on depositional conditions of the ediacaran yangtze platform that host the earliest animal fossils in the geological record in multiple sections from the yangtze gorges area trioctahedral smectite saponite and its diagenetic products mixed layer chlorite smectite corrensite and chlorite are the dominant clays through the lower 80 m of the formation and constitute up to 30 wt of the bulk rock saponite is interpreted as an in situ early diagenetic phase that formed in alkaline conditions ph 9 the absence of saponite in stratigraphically equivalent basin sections 200 400 km to the south indicates that alkaline conditions were localized in a nonmarine basin near the yangtze gorges region this interpretation is consistent with crustal abundances of redox sensitive trace elements in saponitic mudstones deposited under anoxic conditions as well as a 10 difference in the carbon isotope record between yangtze gorges and basin sections our findings suggest that nonmarine environments may have been hospitable for the fauna preserved in the yangtze gorges which includes the oldest examples of animal embryo fossils and acanthomorphic acritarchs

a chemostratigraphic overview of the late cryogenian interglacial sequence in the adelaide fold thrust belt south australia within the neoproterozoic sequence of the adelaide fold thrust belt south australia two of the most severe ice ages in earth history sturtian and marinoan are recorded in the glacigenic rocks which mark the base and top of the 4 5 km thick umberatana group the focus of the present chemostratigraphic study rock units from three drillholes and ten measured outcrop sections located in the southern and central flinders ranges and on the stuart shelf were sampled for isotopic analysis of their co existing calcite 13ccal dolomite 13cdol and kerogen 13corg strontium and sulphur isotopic analyses were also run on selected samples the sample sites are in tectonic domains where regional metamorphism has been insufficient to significantly alter the isotopic composition of the kerogen the resulting data when integrated with the lithostratigraphy of the umberatana group yield one of the most complete records of secular variation in the c isotope signature of the late cryogenian ocean between 750 and 680 ma its composite 13ccarb curve begins with a sharp positive excursion 3 to 1 5 in the dolomitic tindelpina shale which caps sturtian glacial diamictites wilyerpa formation then follows a steady climb through the shoaling upward tapley hill formation reaching 4 in the brighton limestone and culminating in a plateau of 13c enrichment within the platformal carbonates of the etina formation 8 to 10 the upper part of the temporal trend shows a decline to 6 to 7 in the stromatolite reef facies of the enorama shale and a dramatic drop to 8 to 9 5 followed by a recovery to 3 in the youngest carbonate unit trezona formation beneath the marinoan glacigenic elatina formation the latter is capped by a thin dolostone the nuccaleena formation which records a consistent up section decrease in 13c 1 to 3 superimposed on this overall pattern of c isotopic variation are second and third order fluctuations attributable to eustatic sea level change pyritic sulphur in the lower tapley hill formation 34s 9 to 40 is distinctly heavier than that in the underlying wilyerpa formation 4 to 20 minimum 87sr 86sr values obtained from the brighton limestone 0 7071 and etina formation 0 7076 are consistent with their late cryogenian age this sturtian to marinoan interglacial succession is more complete than equivalent sequences elsewhere and thus provides a useful reference for global chemostratigraphic correlation notable features of its c isotope curve are the strong post wilyerpa positive excursion also seen in key sections from svalbard and western mongolia the etina plateau of 13c enrichment which is remarkably similar to maxima in the terminal proterozoic c isotope records of western mongolia north western canada and brazil and the spectacular depletion of 13c in the lower trezona relative to similar carbonate facies in the underlying etina formation and enorama shale a preglacial offset in 13ccarb values of such proportions 14 is almost unprecedented except perhaps for that recently documented in the upper ombaatjie formation beneath tillites of the ghaub formation otavi group namibia it represents a key piece of evidence in the case presented by the proponents of a neoproterozoic snowball earth

zn isotopic evolution in early ediacaran ocean a global signature abstract the zn isotope composition of sedimentary archives reveals key biosphere lithosphere interactions throughout geologic history a recent zn isotope study of ediacaran cap carbonates from south australia revealed that the local isotopic profile reflects global changes in oceanic chemistry to examine this critical assumption this study investigates a high resolution zinc isotope profile of marinoan post glacial cap carbonates from the yangtze platform south china stratigraphic variations in zn isotope data from this study are similar to previously reported sections in south australia and south china the remarkable isotopic similarity between the two sections that were deposited on distant geographically separated continental blocks demonstrates that the zn isotopic variations reflect changing global signatures of the early ediacaran ocean this study highlights the value of zn isotopes in sediments as a global proxy for paleoceanographic studies we interpret the systematic stratigraphic changes in the zn isotope composition of the studied post glacial marinoan carbonates as a global oceanic trend controlled mainly by varying inputs and outputs of zn to the ocean decreasing 66zn values in the lowermost part of the section are attributed to the global precipitation of carbonate enriched in the heavier zn isotope a positive shift in the middle part of the section is explained by the non quantitative removal of isotopically lighter zn by sulfide minerals lower 66zn values in the uppermost part likely reflect the changing contributions of continental weathering and sulfide precipitation our data suggest that non quantitative removal of zn by sulfides is a previously unrecognized sink for zinc in the oceans

stratigraphic and tectonic implications of a newly discovered glacial diamictite cap carbonate couplet in southwestern mongolia we report here the discovery of a new end cryogenian glacial diamictite and an overlying basal ediacaran cap carbonate within the tsagaan oloom formation of southwestern mongolia the identifi cation of the cryogenian ediacaran boundary coupled with new 13 c chemostratigraphic profi les facilitates the integration of the neoproterozoic stratigraphy of mongolia with records elsewhere these correlations indicate that a previously unrecognized 16 cryogenian 13 c anomaly is present in the newly defi ned tayshir member informal of the tsagaan oloom formation furthermore chemostratigraphic and lithostratigraphic relationships suggest an 35 m y depositional hiatus below the phosphorite bearing zunne arts member informal of the upper tsagaan oloom formation and that subsidence renewed in the latest ediacaran early cambrian we propose that the lower 1500 m of the tsagaan oloom formation was deposited on a thermally subsiding passive margin after rodiniaage rifting whereas the zunne arts member and the overlying 1600 m of early cambrian strata were deposited in a foredeep basin that formed as the southern margin of the dzabkhan terrane was subducted beneath the khantayshir dariv arc

mechanisms of thermohaline mode switching with application to warm equable climates abstract a three box model of haline and thermal mode overturning is developed to study thermohaline oscillations found in a number of ocean general circulation models and that might have occurred in warm equable paleoclimates by including convective adjustment modified to represent the localized nature of deep convection the box model shows that a steady haline mode circulation is unstable for certain ranges of freshwater forcing vertical diffusivity a self sustained oscillatory circulation is found in which haline thermal mode switching occurs with a period of centuries to millennia it is found that mode switching is most likely to occur in warm periods of earth s history with relative to the present climate a reduced pole ndash uator temperature gradient an enhanced hydrological cycle and somewhat smaller values of oceanic diffusivities

persistence of a freshwater surface ocean after a snowball earth geochemical data from cap carbonates deposited above cryogenian glacial deposits have been widely used to infer the conditions that prevailed in the aftermath of snowball earth however the time scale over which these carbonates were deposited and the degree to which they record the chemistry of a globally well mixed ocean have remained poorly constrained during deglaciation a large volume of meltwater entered the ocean creating two distinct layers the fresh hot and light upper layer and the salty cold and dense lower layer here we estimate the ocean mixing time scale based on energetic constraints we find that the mixing time scale is 10 4 10 5 yr with a best estimate of 5 10 4 yr or up to 100 times longer than that of the modern ocean mixing of the surface temperature anomaly implies a delayed sea level rise of 40 50 m associated with pure thermal expansion this result reconciles geological geochemical and paleomagnetic data from basal ediacaran cap carbonates with physical oceanographic theory in particular our model suggests that 1 the cap dolostones formed predominantly in a freshwater environment 2 the waters in which the dolostones formed were not well mixed with saline deep water allowing for large geochemical differences between the cap dolostones and the deep ocean and 3 the cap carbonate sequences formed in a two phase transgression that lasted 10 4 yr which is consistent with both local sea level records and the preservation of magnetic excursions and reversals

extreme winds and waves in the aftermath of a neoproterozoic glaciation the most severe excursions in the earth s climatic history are thought to be associated with proterozoic glaciations according to the snowball earth hypothesis the marinoan glaciation which ended about 635 million years ago involved global or nearly global ice cover at the termination of this glacial period rapid melting of continental ice sheets must have caused a large rise in sea level here we show that sediments deposited during this sea level rise contain remarkable structures that we interpret as giant wave ripples these structures occur at homologous stratigraphic levels in australia brazil canada namibia and svalbard our hydrodynamic analysis of these structures suggests maximum wave periods of 21 to 30 seconds significantly longer than those typical for today s oceans the reconstructed wave conditions could only have been generated under sustained high wind velocities exceeding 20 metres per second in fetch unlimited ocean basins we propose that these extraordinary wind and wave conditions were characteristic of the climatic transit and provide observational targets for atmospheric circulation models

low latitude and multiple geomagnetic reversals in the neoproterozoic puga cap carbonate amazon craton palaeomagnetic study of the carbonates that ubiquitously cap glacial deposits may constrain the latitudinal extent of neoproterozoic glaciations and the duration of the greenhouse recovery we present the first palaeomagnetic data on the neoproterozoic cap carbonates covering the amazon craton which are folded along the paraguay belt samples collected at deformed beds along the paraguay belt present a single polarity secondary magnetization acquired by the end of the brasiliano orogeny 540 520 ma in the cratonic area a dual polarity component was isolated in dolostones at the base of the sequence the presence of a stratabound reversal stratigraphy along with high unblocking temperatures strongly suggest that this magnetization is primary this result implies a low palaeolatitude 22 6 5 for the amazon block just after deposition of puga diamictites in addition the presence of multiple reversals across the first 20 m of the cap carbonate sequence suggests that their sedimentation must have spanned hundreds of thousands of years at least

neoproterozoic cap dolostone deposition in stratified glacial meltwater plume abstract neoproterozoic cap carbonates host distinctive geochemical and sedimentological features that reflect prevailing conditions in the aftermath of snowball earth interpretation of these features has remained contentious with hypotheses hinging upon timescale and synchronicity of deposition and whether or not geochemical signatures of cap carbonates represent those of a well mixed ocean here we present new high resolution sr and mg isotope results from basal ediacaran cap dolostones in south australia and mongolia least altered sr and mg isotope compositions of carbonates are identified through a novel incremental leaching technique that monitors the purity of a carbonate sample and the effects of diagenesis these data can be explained by the formation of these cap dolostones involving two chemically distinct solutions a glacial meltwater plume enriched in radiogenic sr and a saline ocean residue with relatively lower 87sr 86sr ratios model simulations suggest that these water bodies remained dynamically stratified during part of cap dolostone deposition most likely lasting for 8 thousand years our results can potentially reconcile previous conflicts between timescales estimated from physical mixing models and paleomagnetic constraints geochemical data from cap carbonates used to interpret the nature of snowball earth and its aftermath should be recast in terms of a chemically distinct meltwater plume

aerobic microbial dolomite at the nanometer scale implications for the geologic record microbial experiments are the only proven approach to produce experimental dolomite under earth s surface conditions although microbial metabolisms are known to induce dolomite precipitation by favoring dolomite growth kinetics the involvement of microbes in the dolomite nucleation process is poorly understood in particular the nucleation of microbially mediated dolomite remains a matter for investigation because the metabolic diversity involved in this process has not been fully explored herein we demonstrate that halomonas meridiana and virgibacillus marismortui two moderately halophilic aerobic bacteria mediate primary precipitation of dolomite at low temperatures 25 35 c this report emphasizes the biomineralogical implications for dolomite formation at the nanometer scale we describe nucleation of dolomite on nanoglobules in intimate association with the bacterial cell surface a combination of both laboratory culture experiments and natural samples reveals that these nanoglobule structures may be 1 the initial step for dolomite nucleation 2 preserved in the geologic record and 3 used as microbial tracers through time and or as a proxy for ancient microbial dolomite as well as other carbonate minerals

stomatal response of swordfern to volcanogenic co2 and so2 from kilauea volcano 1 the experimentally determined relationship between atmospheric pco2 and plant stomata has been used to interpret large but transient changes in atmospheric composition such as may have resulted from the eruptions of flood basalt however this relationship has not been tested in the field i e in the vicinity of active volcanoes to examine the specific effects of volcanogenic emissions moreover the interpretation of paleoatmospheric pco2 from fossil stomatal data assumes that the stomatal response resulted solely from variation in pco2 and ignores the potential effect of outgassed so2 we hypothesize that volcanogenic so2 also has a significant effect on leaf stomata and test this hypothesis by measuring the stomatal index of the common swordfern nephrolepis exaltata in the plumes of the actively outgassing vents of kilauea volcano we find that compared to control locations stomatal index is lowest at sample sites in the plume of halema uma u crater where concentrations of both co2 and so2 are much higher than background however sites located directly in the plume of pu u o o where so2 levels are high but co2 levels are not also yield low values of stomatal index we propose that shifts in the stomatal index of fossil leaves may record transient atmospheric increases in both so2 and co2 such as may be caused by eruptions of flood basalts calculations of pco2 based on stomatal frequency are likely to be exaggerated

impact of diagenesis and low grade metamorphosis on isotope δ26mg δ13c δ18o and 87sr 86sr and elemental ca mg mn fe and sr signatures of triassic sabkha dolomites abstract dolomite is a common rock forming mineral in the geological record but its value as archive of ancient seawater 26 mg signatures and their variations in time is at present underexplored unknown factors include the sensitivity of 26 mg ratio to processes in the diagenetic and low grade metamorphic domain this paper documents and discusses the first detailed 26 mg data set from early diagenetic and burial dolomites samples come from the upper triassic hauptdolomit dolomia principale the dolomites italy and include coeval dolomicrites that underwent differential burial diagenesis and low grade metamorphosis in a temperature range between about 100 and more than 350 c magnesium isotope data are complemented by dolomite 13 c 18 o and 87 sr 86 sr isotope ratios as well as ca mg mn fe and sr elemental abundances and data on the dolomite crystal structure as indicated by dolomicrite 87 sr 86 sr ratios and petrographic evidence sabkha calcian d1 dolomites precipitated from evaporated seawater and stabilized at an early marine pore water diagenetic stage to d2 dolomites analysed here with increasing burial temperature dolomite 26 mg ratio scatter in the data set decreases with increasing mg ca ratio and degree of order specifically 26 mg ratio variability is reduced from 0 36 2 at burial temperatures beneath 100 c to about 0 14 2 at temperatures in excess of 350 c respectively with mean 26 mg values ranging constantly near 1 9 this suggests that at least for the rock buffered system investigated here dolomicrite 26 mg proxy data are conservative and preserve near pristine values even at elevated burial temperatures at present the main element of uncertainty is the mg isotope fractionation factor between evaporated seawater and dolomite a possible solution to this problem includes the compilation of data from modern sabkha environments including pore water and calcian dolomite 26 mg isotope signatures

microbial precipitation of dolomite in methanogenic groundwater we report low temperature microbial precipitation of dolomite in dilute natural waters from both field and laboratory experiments in a freshwater aquifer microorganisms colonize basalt and nucleate nonstoichiometric dolomite on cell walls in the laboratory ordered dolomite formed at near equilibrium conditions from groundwater with molar mg ca ratios of 1 dolomite was absent in sterile experiments geochemical and microbiological data suggest that methanogens are the dominant metabolic guild in this system and are integral to dolomite precipitation we hypothesize that the attached microbial consortium reacts with the basalt surface releasing mg and ca into solution which drives dolomite precipitation via nucleation on the cell wall these findings provide insight into the long standing dolomite problem and suggest a fundamental role for microbial processes in the formation of dolomite across a wide range of environmental conditions

a ubiquitous hydrothermal episode recorded in the sheet crack cements of a marinoan cap dolostone of south china implication for the origin of the extremely 13 c depleted calcite cement abstract sheet crack primarily filled with chalcedony quartz and calcite is a type of significant sedimentary structure in almost all documented cap carbonates in platform to slope settings which sharply overlie the global marinoan 635 ma glacial tillite the jiulongwan section located in the yangtze gorges areas south china is significant for the first discovery of extremely 13c depleted 13c down to 41 calcite cements in sheet crack structure jiang et al 2003a which provides direct evidence for the methane seep hypothesis kennedy et al 2001 focusing on the calcite cements in the same section bristow et al 2011 proposed a hydrothermal origin based on high temperatures 378 c determined by carbonate clumped isotope thermometry ccit in this study we provide evidence for the hydrothermal model using fluid inclusion technology fit to quartz cements in the jiulongwan section the widespread sheet crack structures in south china have uniform mineral paragenetic assemblages which apparently reflect three stages of a hydrothermal fluid activity including dolomitization at the early stage silicification comprising chalcedony and quartz at the middle stage and calcitization characterized by carbonaceous calcite filling preexisting voids at the late stage primary aqueous fluid inclusions from quartz crystals have homogenization temperatures of approximately 160 220 c mean 192 c n 31 while the salinity histogram contains two peaks at low salinity 6 3 8 3 wt nacl equiv and high salinity 18 0 20 8 wt nacl equiv reflecting precipitation caused by mixing of high and low salinity fluids a modified and detailed hydrothermal model is proposed indicating that the sheet crack structure resulted from successive thermal fluid activity after karstic dissolution due to postglacial isostatic rebound this model is compatible with the unified sequence of glacio eustatic events after the termination of marinoan glaciation zhou et al 2010 and the temperature results determined by ccit bristow et al 2011

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

the end triassic bivalve extinction event one of the most important episodes of mass extinction of animal groups in the whole of the phanerozoic took place in the latter part of the triassic but the time of major faunal turnover of the vertebrates preceded that of marine invertebrates by several million years as shown by ammonites brachiopods and conodonts decline from a carnian early norian diversity peak was followed by a significant extinction episode at the end of the period this pattern is confirmed at generic and subgeneric level by the bivalve molluscs probably the most abundant and diverse macroinvertebrate group this paper analyses the bivalves in detail and attempts to seek a relationship of the extinction event to environmental changes as recorded by late triassic facies stratigraphy of the youngest triassic is briefly discussed following a recent recommendation the rhaetian stage is dropped and the upper norian sevatian subdivided into three new ammonite zones it is suggested that the classic northwest european rhaetic correlates with the kossen and zlambach beds of the alps and corresponds at least approximately with the upper two of these zones it is estimated that nearly half the existing bivalve genera and nearly all the species failed to survive the end triassic extinction event the trigonioid unionoid and hippuritoid orders were especially strongly affected but most of the pholadomyoid genera survived three major ecological categories are distinguished a shallow neritic group to which most taxa belong a euryhaline group that could tolerate marginal marine and lagoonal conditions and a deep neritic group notably halobia and monotis all groups were strongly affected by the extinction but species of the deep neritic group were apparently the most susceptible seven biogeographic regions are distinguished for the purpose of analysis and it is shown that provinciality is slight but some important taxa are endemic to the tethyan and pacific regions endemic genera prove to have been much more subject to extinction than cosmopolitans there are very few places in the world with a more or less continuous marine sequence of deposits across the triassic jurassic boundary details are given of sections in the alps northwest europe and nevada and briefer mention made of others with regard to late triassic palaeogeographic changes those involving climate were neglibible but there was a more or less progressive regression of epicontinental seas following a ladinian early carnian transgressive maximum with a corresponding shallowing in the more continuously marine tethyan region that this first order effect was due to a eustatic lowering of sea level is fairly certain but the situation is less clear for second order transgressive regressive cycles the late late norian rhaetian cycle is probably however the results of a minor eustatic event by the end of the triassic the sea had regressed substantially and the mass extinction event is though to be bound up partly with this phenomenon and partly with the phase of widespread anoxicity that occurred during the succeeding hettangian transgression

field and laboratory tests for recognition of ediacaran paleosols abstract not a single paleosol had been described from rocks of ediacaran age until 2011 but 354 ediacaran paleosols have been described by 20 different authors since then some of these newly recognized paleosols have proven controversial so this paper reviews 20 distinct tests to determine whether a particular ediacaran bed could be a paleosol or not one problem has been that ediacaran paleosols are not precisely like modern soils because they lack root traces a diagnostic feature of silurian and geologically younger paleosols the principal problem for recognition of some ediacaran paleosols is the occurrence in them of megafossils assumed to have been marine although most of these fossils remain problematic for both biological and ecological affinities not all the tests discussed here are diagnostic of paleosols some are ranked permissive or persuasive permissive conditions for paleosols include ripple marks hummocky bedding pyritic limestones acritarchs or thalloid fossils low strontium isotopic ratios high 26 mg ratios and red color persuasive tests include loessites tsunamites desert playa minerals low boron content high 10 b isotopic ratios high carbon sulfur ratios and very low total reactive iron ratios diagnostic tests include matrix supported lapilli or crystal tuff parent materials ice wedges and other cryoturbation sepic birefringence fabrics evaporitic sand crystals and negative geochemical strain and mass transfer and highly correlated 13 c and 18 o like other geological periods the ediacaran is known from a variety of marine and non marine paleoenvironments

sr and mg isotope geochemistry of the basal ediacaran cap limestone sequence of mongolia implications for carbonate diagenesis mixing of glacial meltwaters and seawater chemistry in the aftermath of snowball earth abstract the seawater chemistry and oceanographic information associated with snowball earth are commonly inferred from the geochemistry of cap carbonates deposited on continental margins during and after deglaciation however interpretation of such records can be complicated by carbonate diagenesis and contamination from siliciclastic components in an attempt to disentangle these effects we studied the geochemistry of the post marinoan cap carbonate sequence from mongolia using a step leaching procedure which revealed that most samples are heterogeneous with respect to multiple geochemical signatures including trace element concentrations sr mg c and o isotopic signatures raising questions to previous studies applying carbonate bulk rock geochemistry for paleoenvironment reconstructions such sample heterogeneity can be explained by contamination from non carbonate phases and carbonate alteration after stepped leaching the least altered contaminated geochemical signatures for each sample were identified and the influences of carbonate diagenesis were evaluated our data indicate that mixing of glacial meltwater persisted to the maximum flooding surface within the cap carbonate sequence below which carbonates record significant mg and sr isotope fluxuations that are most readily interpreted in the context of the mixing of water masses having distinct isotopic compositions only limestones deposited above the maximum flooding surface formed in a well mixed ocean and exhibit mg and sr isotope values that record the integrated effects of snowball earth on ocean chemistry our study cautions against interpreting the geochemistry of cap carbonates in terms of whole ocean geochemical cycles

carbon isotopic composition of neoproterozoic glacial carbonates as a test of paleoceanographic models for snowball earth phenomena consistently positive carbon isotopic values were obtained from in situ peloids ooids and stromatolitic carbonate within neoproterozoic glacial successions in northern namibia central australia and the north american cordillera because positive values continue upward into the immediately overlying postglacial cap carbonates the negative isotopic excursions widely observed in those carbonate rocks require an explanation that involves a short term perturbation of the global carbon cycle during deglaciation the data do not support the ecological consequences of complete coverage of the glacial ocean with sea ice as predicted in the 1998 snowball earth hypothesis of p f hoffman et al in the snowball earth hypothesis the postglacial cap carbonates and associated 5 negative carbon isotopic excursions represent the physical record of co2 transfer from the high p co2 snowball atmosphere 0 12 bar to the sedimentary reservoir via silicate weathering in the snowball aftermath stratigraphic timing constraints on cap carbonates imply weathering rates of 1000 times preglacial levels to be consistent with the hypothesis the absence of sr isotopic variation between glacial and postglacial deposits and calculations of maximum weathering rates do not support a post snowball weathering event as the origin for cap carbonates and associated isotopic excursions

resetting of mg isotopes between calcite and dolomite during burial metamorphism outlook of mg isotopes as geothermometer and seawater proxy abstract magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates calcite due to its ubiquitous occurrence and the large mg isotope fractionation associated with the mineral has attracted great interests in applications of mg isotope geochemistry however the fidelity of mg isotopes in geological records of carbonate minerals e g calcite and dolomite against burial metamorphism remains poorly constrained here we report our investigation on the mg isotope systematics of a dolomitized middle triassic geshan carbonate section in eastern china magnesium isotope analysis was complemented by analyses of sr c o isotopic compositions major and trace element concentrations and petrographic and mineralogical features multiple lines of evidence consistently indicated that post depositional diagenesis of carbonate minerals occurred to the carbonate rocks magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high 26mg dolomite end member and a low 26mg calcite end member irrespective of sample positions in the section and calcite dolomite ratio in the samples by fitting the measured mg isotope data using a two end member mixing model an inter mineral 26mgdolomite calcite fractionation of 0 72 was obtained based on the experimentally derived mg isotope fractionation factors for dolomite and calcite a temperature of 150 190 c was calculated to correspond to the 0 72 26mgdolomite calcite fractionation such temperature range matches with the burial thermal history of the local strata making a successful case of mg isotope geothermometry our results indicate that both calcite and dolomite had been re equilibrated during burial metamorphism and based on isotope mass balance of mg the system was buffered by dolomite in the section therefore burial metamorphism may reset mg isotope signature of calcite and mg isotope compositions in calcite should be dealt with caution in studies of carbonate rocks with thermal history by contrast mg isotopes of dolomite are less prone to post depositional resetting due to a number of properties including high mg abundance and high thermodynamic stability and mg isotopes in dolomite may be a more robust recorder for original carbonate precipitates

condensation origin for neoproterozoic cap carbonates during deglaciation neoproterozoic deglacial stratigraphy is commonly characterized by a sharp contact separating glacial sediments from laminated capping carbonates this stratigraphic relation is generally assumed to have time significance and to reflect an abrupt shift from icehouse to greenhouse conditions in contrast to this sequence stratigraphic field studies of an ediacaran ca 635 ma glacial to postglacial transition in the amadeus basin of central australia reveal a complex deglacial stratigraphy in which more than 175 m of conglomerate sandstone marl and carbonate at the basin margin and portions of four unconformity bounded sequences pass basinward into no more than 3 m of laminated dolomicrite of typical cap carbonate facies the unconformities which are characterized by as much as several tens of meters of erosional relief oblique sections of incised valleys separate intervals of contrasting sediment provenance and are confidently mapped on the basis of both criteria comparable unconformities are absent in the overlying neoproterozoic succession which is 2 km thick and encompasses many tens of millions of years the amadeus basin cap carbonate was thus deposited during a protracted interval of multiphase cyclical transgression more similar to phanerozoic cyclical sea level rise than to the single catastrophic deglaciation and instantaneous precipitation invoked by popular current models to explain the classic cap carbonate the superposition of carbonate on glacial facies in distal sections evidently records condensation in the absence of siliciclastic sediment rather than abrupt shifts between glacial and tropical conditions facies lithologically similar to cap carbonates may be less obvious in phanerozoic successions because of a secular change in carbonate composition to reefal and deep sea pelagic deposits

bacterially induced dolomite precipitation in anoxic culture experiments to study the process of microbial mediated dolomite formation growth experiments were carried out with selected bacterial cultures under anoxic environmental conditions simulating those found in lagoa vermelha a hypersaline lagoon in brazil where dolomite precipitation occurs specifically we report the isolation of a particular strain of sulfate reducing bacteria lvform6 from lagoa vermelha sediment which apparently promotes the formation of nonstoichiometric dolomite sulfate reducing bacteria grown in a synthetic liquid medium produced dolomite during 30 days incubation at 30 c the precipitates have morphologies similar to those observed in lagoa vermelha sediment our results demonstrate that sulfate reducing bacteria can influence dolomite precipitation under controlled lowtemperature anoxic conditions and imply that anaerobic microorganisms can play an important role in carbonate sedimentation they may have been particularly significant in earth s earliest history when a more reducing atmosphere existed

could the late permian deep ocean have been anoxic models of ocean circulation and biogeochemical cycles are used to speculate about possible mechanisms of deep sea anoxia across the permo triassic boundary two modes of likely late permian ocean thermohaline circulation are identified a vigorous thermal mode driven by cooling in southern polar latitudes and a weaker haline mode driven by evaporation from the subtropics we find that the thermal mode typical of climates such as our own is unlikely to surpport deep sea anoxia the haline mode which might exist in warm climates with enhanced hydrological cycles can lead to significant but periodic depletion of oxygen in the panthalassic deep ocean however owing to the inherent instability of the haline mode a deep sea anoxia persisting for millions of years is not clearly supported by this study though mechanisms emerge which might be consistent with the observed record the enhanced hydrological cycle or reduced oceanic diapycnal mixing required to obtain the haline mode remain unconstrained for the late permian

aftermath of a snowball earth 1 using a simple 3 box model of the ocean atmosphere system we simulate the cycling of carbon and strontium in the aftermath of a global glaciation model simulations include the delivery of alkalinity to seawater from intense carbonate and silicate weathering under high pco2 conditions as well as ocean mixing air sea gas exchange and biological productivity the 13c of the first carbonate precipitated after the glaciation depends on the pco2 temperature the saturation state of the surface ocean and kinetic effects associated with mineral precipitation with no biological productivity the model produces 13c values between 1 and 3 consistent with observations this is in direct contradiction with arguments by kennedy et al 2001a who suggest that the 13c value of dissolved carbon in a snowball ocean and directly afterward must be 5 kennedy et al assume the carbon isotope cycle is in steady state which does not apply to a global glaciation and also neglect any effect of high pco2 on the carbonate chemistry of seawater a major difference between our findings and the qualitative predictions of hoffman et al 1998 is our interpretation of the cap dolostone as representing an interval dominated by carbonate weathering of exposed continental shelves as a result the 2 drop in the 13c observed in the cap dolostone is unlikely to be the product of rayleigh distillation of atmospheric co2 via silicate weathering instead we interpret the 2 drop in the 13c values as indicative of an increase in sea surface temperature which lowers the fractionation between co2 and carbonate kinetic isotope effects associated with rapid precipitation from a highly supersaturated surface ocean may also be important rayleigh distillation of atmospheric co2 via silicate weathering is a viable explanation for the continued drop in the 13c values in the limestone sequence above the cap dolostone with biological productivity and carbonate weathering driving a slow increase in 13c values once pco2 levels decline our study also simulates the cycling of strontium in seawater in contrast to the finding of jacobsen and kaufman 1999 and kennedy et al 2001a model simulations show a drop in 87sr 86sr of less than 0 001 during 5 million years of global glaciation and an increase of less than 0 001 over the entire episode of silicate weathering our calculations emphasize the importance of considering the changes in seawater chemistry due to high pco2 in evaluating the snowball earth hypothesis

the antimonio formation in sonora mexico and the triassic jurassic boundary the antimonio formation furnishes a record of sedimentation across the triassic jurassic system boundary and is one of a few stratigraphic sections globally that preserves latest triassic to hettangian ammonoids in stratigraphic succession the boundary falls near the middle of the formation within a 155 m thick stratigraphic section which is divided into five distinct sedimentary packages the laminated shales and siltstones in the middle of package 4 represent deposition in an anoxic or disaerobic setting although shales of package 4 themselves are poorly fossiliferous they are bounded below and above by triassic and jurassic biotas respectively the triassic jurassic system boundary should fall within or stratigraphically close to the laminated beds the transgressive regressive signature from the antimonio formation corresponds closely to that of the gabbs and sunrise formations in nevada and jointly shows eustatic regressive events at or near the beginning of the latest triassic crickmayi zone a

a two phase end triassic mass extinction abstract the end triassic mass extinction was one of the big five crises of the fossil record it affected diverse marine groups including bivalves brachiopods ostracods calcareous algae radiolarians and tetrapods and coincided with major changes in palynological assemblages the rapidity of the event has long been debated and here we show that it can be resolved into two distinct short lived extinction pulses separated by a several hundred thousand year interlude phase detailed collecting in the british isles shows the first extinction in the lower cotham member eliminated many bivalves and ostracods this event has been previously considered as the end triassic mass extinction horizon however a second extinction is also seen at the top of the langport member after a phase of recovery marked by diversity increase this younger crisis caused the loss of further bivalves ostracods and the last of the conodonts the two phases of marine extinctions coincide with marked turnovers amongst palynofloral assemblages with the interlude phase manifest as a fern spore dominated interval the polypodiisporites polymicroforatus abundance interval correlation of triassic jurassic boundary sections and their associated extinction record in europe has been controversial the most parsimonious correlation scheme assumes that a brief high amplitude negative excursion of 13corg values seen at the level of the first extinction phase in the uk is manifest in other european sections in the same way alternative correlation schemes require complex scenarios with extinction occurring in some areas as recovery is happening elsewhere in europe the first extinction coincides with regression whilst the second occurs at a flooding surface marked by the spread of anoxia the extinction history of the terminal triassic crisis is remarkably similar to that seen during other extinction events end ordovician permo triassic toarcian and suggests that if the ultimate driver of these crises large igneous province eruptions is the same then they show the same double punch eruption history separated by a more benign interval of a few hundred thousand year duration

continental weathering intensity during the termination of the marinoan snowball earth mg isotope evidence from the basal doushantuo cap carbonate in south china abstract the neoproterozoic global glaciations 720 635 ma represent the most severe icehouse climatic conditions in earth s history collectively known as the snowball earth events the snowball earth hypothesis hoffman et al 1998 proposed that the termination of the global glaciation was driven by the extremely high atmospheric pco2 level 300 times of present atmospheric level pal that was accumulated during the global glaciation by volcanic degassing for tens of million years because of extremely high temperature the deglaciation might associate with intense continental weathering that brought abundant bicarbonate and alkaline earth metals mg ca to the ocean resulting in the rapid precipitation of cap carbonate all over the world thus cap carbonate precipitation marks the termination of global glaciation the deglacial intense continental weathering has been recently supported by mg isotopes however the mg isotope data also indicate that the deglaciation might have significantly predated the cap carbonate precipitation and limited data suggest that the weathering intensity was already low during the cap carbonate precipitation in order to further test whether the cap carbonate precipitation was associated with low weathering intensity here we analyzed mg isotopic composition of siliciclastic component 26mgsil of the doushantuo cap carbonate in the yangtze block south china four cap carbonate sections the tongle tl drill core the fanyang fy section the wuluo wl drill core and the jiulongwan jlw section spanning from shelf to basin environments were analyzed 26mgsil ranges from 0 43 to 0 39 n 10 from 0 31 to 0 48 n 9 from 0 06 to 0 10 n 7 and from 1 42 to 0 03 n 8 for the jlw fy wl and tl samples respectively there are negative correlations between mg al and 26mgsil in jlw wl and tl the geochemical data indicate that the variation of 26mgsil might be attributed to authigenic clay formation during the cap carbonate precipitation the binary mixing model indicates that the isotopic compositions of terrestrial clays range from 0 to 0 3 comparable to the values of modern soil clays but significantly lower than the values of the upper nantuo formation up to 0 90 suggesting the moderate to low weathering intensity during the cap carbonate deposition our study suggests low atmospheric pco2 level during cap carbonate precipitation probably due to the consumption by intense continental weathering

sulfur cycling in the aftermath of a 635 ma snowball glaciation evidence for a syn glacial sulfidic deep ocean we have analyzed 34 s sulfate and pyrite 18 ocarbonate and 13 ccarbonate and major and trace elemental concentrations including extractable fe and mn phases in four sections of the maieberg formation the cap carbonate sequence to the marinoan glaciation in northern namibia 34 ssulfate profiles and other geochemical characteristics in the basal transgressive cap dolostone keilberg member are nearly identical in all sections and indicate deposition from a water mass with very low sulfate concentrations in the overlying interval that consists of rhythmites deposited during the transgressive high stand large geochemical disparities occur between sections that we interpret to have been deposited in open ocean versus restricted settings in the former a large negative shift in 34 ssulfate of 20 above the cap dolostone accompanies a change in mineralogy from dolomite to limestone a sharp decrease in 18 o and 13 c and a positive spike in fe and mn concentrations in the latter dolomite persists above the cap dolostone 34 ssulfate increases abruptly 18 o and 13 c are invariant and a spike in mn and fe concentrations is present but subtle these contrasting geochemical signatures in coeval sections can be explained by strong lateral chemical gradients that developed as cold euxinic deep water and a cap of warm oxic brackish water flooded the continental shelf during the post glacial transgression the geochemical di e rences between open ocean and restricted sections diminishes upsection presumably recording the gradual mixing and homogenization of the waters along the otavi platform

genesis of a giant paleoproterozoic strata bound magnesite deposit constraints from mg isotopes abstract giant strata bound magnesite deposits are absent in modern and most phanerozoic sedimentary environments but occur predominantly in precambrian strata these deposits may have formed directly through precipitation of evolved mg rich seawater in an evaporative shallow marine setting or alternatively by epigenetic hydrothermal replacement of the mg rich carbonate precursor to test these hypotheses we obtained the first mg isotope data from the world s largest strata bound magnesite deposit belt hosted by the ca 2 1 ga dashiqiao formation in northeast china the mg isotope compositions 26 mg of most magnesite ores in the huaziyu deposit are heavier 0 75 0 26 than most proterozoic sedimentary dolostones the mg isotope compositions and major and trace element data indicate that the magnesites are probably not of hydrothermal origin instead a mg rich carbonate precursor precipitated from evaporating seawater in a semi closed system diagenetic brines altered the mg rich carbonate precursor to magnesite subsequently recrystallization during regional metamorphism produced coarsely crystalline and saddle magnesite these interpretations are consistent with the geological features and other geochemical data element concentrations and c and o isotopes for the magnesite ores hence we interpret the formation of the huaziyu magnesite deposit to be dominated by evaporative sedimentation and brine diagenesis

dolomite occurrence evolution and economically important associations abstract dolomite is not a simple mineral it can form as a primary precipitate a diagenetic replacement or as a hydrothermal metamorphic phase all that it requires is permeability a mechanism that facilitates fluid flow and a sufficient supply of magnesium dolomite can form in lakes on or beneath the shallow seafloor in zones of brine reflux and in early to late burial settings it may form from seawater from continental waters from the mixing of basinal brines the mixing of hypersaline brine with seawater or the mixing of seawater with meteoric water or via the cooling of basinal brines bacterial metabolism may aid the process of precipitation in settings where sulfate reducing species flourish and microbial action may control primary precipitation in some hypersaline anoxic lake settings dolomite is a metastable mineral early formed crystals can be replaced by later more stable phases with such replacements repeated a number of times during burial and metamorphism each new phase is formed by the partial or complete dissolution of an earlier dolomite this continual re equilibration during burial detracts from the ability of trace elements to indicate depositional conditions and resets the oxygen isotope signature of the dolomite at progressively higher temperatures because subsurface dolomite evolves via dissolution and reprecipitation a bed of dolomite can retain or create porosity and permeability to much greater burial depths and into higher temperature realms than a limestone counterpart dolomitization also creates new crystals with new rhomb growth following the dissolution of less stable precursors repetition of this process without complete pore cementation can generate intercrystalline porosity a number of times in the rock s burial history intercrystalline porosity is a highly interconnected style of porosity that gives dolomite reservoirs their good fluid storage capacity and efficient drainage the fact that many dolomite reservoirs formed via brine reflux means that they sit beneath an evaporite seal in both platform and basinwide evaporite settings the same association of evaporites sulfate source and entrained hydrocarbons means that burial conditions are also suitable for thermochemical sulfate reduction and the precipitation of base metals this tends to occur at higher temperatures 60 c 80 c and so the resulting dolomites tend to be ferroan and consist of saddle shaped crystals

snowball earth termination by destabilization of equatorial permafrost methane clathrate the recovery from the marinoan snowball ice age of about 635 million years ago is one of the most severe climate change events known to have occurred on earth hypotheses accounting for the abruptness of deglaciation include ice albedo feedback deep ocean out gassing during post glacial oceanic overturn or methane hydrate destabilization martin kennedy and colleagues now report the broadest range of oxygen isotope values yet measured in marine sediments in methane seeps in marinoan deglacial sediments underlying a thin interval of carbonate these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise the range of values is likely the result of mixing between ice sheet derived meteoric waters and clathrate derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater their findings suggest that methane released from low latitude permafrost clathrates acted as a trigger and or strong positive feedback for deglaciation and warming this paper reports the broadest range of oxygen isotope values yet measured in marine sediments in methane seeps in marinoan deglacial sediments underlying a thin interval of carbonate these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise the range of values is likely the result of mixing between ice sheet derived meteoric waters and clathrate derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater the start of the ediacaran period is defined by one of the most severe climate change events recorded in earth history the recovery from the marinoan snowball ice age 635 myr ago ref 1 marinoan glacial marine deposits occur at equatorial palaeolatitudes2 and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about 5 and 15 parts per thousand respectively3 4 5 these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise1 3 4 this abrupt transition records a climate system in profound disequilibrium3 6 and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating phanerozoic deglaciation hypotheses accounting for the abruptness of deglaciation include ice albedo feedback3 deep ocean out gassing during post glacial oceanic overturn7 or methane hydrate destabilization8 9 10 here we report the broadest range of oxygen isotope values yet measured in marine sediments 25 to 12 in methane seeps in marinoan deglacial sediments underlying the cap carbonate this range of values is likely to be the result of mixing between ice sheet derived meteoric waters and clathrate derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater the equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day a pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions abrupt unidirectional warming cap carbonate deposition and a marine oxygen crisis our findings suggest that methane released from low latitude permafrost clathrates therefore acted as a trigger and or strong positive feedback for deglaciation and warming methane hydrate destabilization is increasingly suspected as an important positive feedback to climate change11 12 13 that coincides with critical boundaries in the geological record14 15 and may represent one particularly important mechanism active during conditions of strong climate forcing

fast or slow melting of the marinoan snowball earth the cap dolostone record article i nfo the end of the neoproterozoic era is punctuated by two global glacial events marked by the presence of glacial deposits overlaid by cap carbonates duration of glacial intervals is now consistently constrained to 3 12 million years but the duration of the post glacial transition is more controversial due to the uncertainty in cap dolostone sedimentation rates indeed the presence of several stratabound magnetic reversals in brazilian cap dolostones recently questioned the short sedimentation duration a few thousand years at most that was initially suggested for these rocks here we present new detailed magnetostratigraphic data of the mirassol d oeste cap dolostones mato grosso brazil and bomb spike calibrated ams 14 c data of microbial mats from the lagoa vermelha rio de janeiro brazil we also compile sedimentary isotopic and microbiological data from post marinoan outcrops and or recent depositional analogues in order to discuss the deposition rate of marinoan cap dolostones and to infer an estimation of the deglaciation duration in the snowball earth aftermath taken together the various data point to a sedimentation duration in the range of a few 10 5 years

variations in the marine ca cycle over the past 20 million years a 20 million year marine ca isotope record is constructed based on measurements of 36 nannofossil ooze samples from dsdp site 590 the ca isotopic composition d 44 ca relative to our bbulk earthq average of carbonate ooze samples varies between 0 2 and 0 9 and the inferred d 44 ca of seawater calcium varies between 1 1 and 0 4 modern seawater value is 0 95 on our scale fluctuations in the seawater ca isotope ratio occur in 2 to 4 million year intervals and indicate that the supply and removal of ca from the oceans are seldom in balance the ca isotope record is used to reconstruct past weathering fluxes and marine calcium concentrations the inferred marine concentration of ca fluctuates by about f20 on 2 4 million year time scales and by about f50 over the 20 million year record these variations are presumably superimposed on the previously inferred 100 million year variations the seawater ca concentration was about 0 5 times present at 20 ma and generally increased until 6 ma 1 7 times present local maxima in seawater calcium concentrations occur at 6 4 and 4 ma preceding periods of enhanced marine productivity and high mass accumulation rates at site 590 while the calculated calcium concentrations are sensitive to the assumed d 44 ca value for the weathering flux the 2 4 million year features of the derived

the magnesium isotope budget of the modern ocean constraints from riverine magnesium isotope ratios we have measured the magnesium mg isotope ratios in 45 rivers including 16 of the largest rivers in the world covering a range of geologic tectonic and climatic drainage basin environments the range in riverine 26mg is 2 5 half the variation in terrestrial rock although the mg isotopic composition of the source rock is important for small rivers at a global scale lithology is of limited significance for mg isotope ratios in rivers part of the variability at a global scale may be attributed to fractionation in the weathering environment the rivers analysed constitute 30 of the global mg riverine flux to the oceans and a flux weighted mg isotope composition of global runoff has been estimated at 1 09 even taking into account uncertainty this is distinct from seawater at 0 82 this difference arises either from the fractionation of mg isotope ratios in the ocean and or a mg budget which is not at steady state the difference is consistent with fractionation by carbonate precipitation in the simplest steady state scenario where the oceanic mass balance is maintained by riverine input and hydrothermal and dolomite output mg isotope ratios imply a minimum dolomite mg flux of 9 of the total output mg flux the implications of the distinct isotopic composition of the riverine flux from modern seawater is that the mg isotope ratio of seawater has probably varied outside of current analytical uncertainty mg isotope ratios may therefore provide a valuable new tracer in palaeo oceanography

late neoproterozoic cap carbonates mackenzie mountains northwestern canada precipitation and global glacial meltdown the 3 27 m thick cap carbonate overlying marinoan ice brook formation glacigene sediments and keele formation carbonate and terrigenous clastic rocks consists of two distinctive stratigraphic units a lower splintery buff weathering microcrystalline dolostone of extensive lateral uniformity comprises mm laminated peloidal sediment with local low angle hummocky like cross stratification micro ridges and synsedimentary tepees all elongated per pendicular to depositional strike this dolostone is unconformably overlain by an upper limestone that exhibits pro nounced facies variation from inboard peloidal lime grainstone and mudstone to shelf edge cementstone to outboard lime wackestone and mudstone calcite cementstones range from isolated crystal fans in laminated limestone to huge decimetre scale crystal arrays to hemispherical and elongate crystal stromatolites wholly composed of acicular crystals that form decametre scale reeflike structures crystal stromatolites are precipitates and replaced microbiolites that con structed biostromes and bioherms like those on many flat topped reef rimmed platforms the calcite crystals have all the physical and chemical attributes of neomorphosed aragonite this aragonite extensively replaced sediment and microbiolite just below the sea floor and grew upward into the overlying water column such interpreted massive synsedimentary replacement is rare in geological history and attests to the highly saturated state of the immediate postglacial ocean all sediment is interpreted to have been caco3 originally low and constant 18 o values reflect diagenetic modification of these carbonates although chemical attributes such as sr and c isotopes in some lithologies are near pristine lower dolostones virtually identical to most other coeval marinoan caps worldwide were part of a global precipitation event of remarkable similarity upper limestones are a more local phenomenon deposited during sea level rise in an aragonitic sea returning to equilibrium after global glaciation low 87 sr 86 sr ratios and varying 13 c values with carbonate sedimentary facies indicate that both units must have formed relatively rapidly prior to significant flu vioglacial runoff or that the influence of this runoff on the chemistry of seawater along continental shelves was mini mal the cap carbonate is thus interpreted to have formed in two steps 1 during initial marine ice melting accompanied by oceanic overturn and upwelling preceding continental margin rebound and 2 during initial stages of sea level rise accompanying continental deglaciation while confirming brief but extensive carbonate precipitation from an ocean highly perturbed by global glaciation the rocks also suggest that this event did not permanently affect either late neoproterozoic ocean chemistry or the contained marine biosphere 1262

zn isotope evidence for immediate resumption of primary productivity after snowball earth the ediacaran period began with the deglaciation of the ca 635 ma marinoan snowball earth and the deposition of cap dolostones on continental shelves worldwide during post glacial sea level rise these carbonates sharply overlie glacial sediments deposited at low paleolatitudes and preserve negative carbon isotope excursions the snowball earth hypothesis invokes an almost complete cessation of primary productivity in the surface ocean because assimilatory uptake of zn appears to fractionate its isotopes zn isotope ratios measured in carbonate precipitated in the surface ocean should track fluctuations in primary productivity here we report the first zn isotopic data together with carbon and oxygen isotopic profiles from a neoproterozoic cap dolostone the nuccaleena formation in the flinders ranges south australia we interpret the zn isotopic data in terms of a two stage evolution of the deglacial ocean slightly 66 zn enriched values at the base of the cap dolostone indicate immediate resumption of the biological pump upon melting of the surface ocean but this signal was diluted by intense surface runoff that drove 66 zn 66 zn 64 zn versus the jmc lyon reference values down to the composition of continentally derived zn a subsequent rise in 66 zn records a vigorous increase in primary production and export from a nutrient laden surface ocean

spatial variation of carbon isotopic compositions of carbonate and organic matter from the late ordovician sedimentary succession in the yangtze platform south china implications for sea level eustacy and shoaling of marine chemocline abstract spatial correlation of isotopic chemostratigraphy across ancient epeiric basins is of particular interest in the field of geology this study examines the carbon isotopic compositions of carbonate and organic matter from the late ordovician sedimentary succession in the yangtze platform including the linxiang lx formation deposited in the bottom and the tiezufeike tzfk daduhe ddh wufeng wf formations in the top paired 13ccarb and 13corg analyses of the upper ordovician strata on the yangtze platform were recorded and the results show that the rocks in the lx formation have high 13ccarb and 13corg values relative to those in the ddf tzfk wf formations additionally a variation of 2 was found between shallow and deep water settings during the late ordovician heavier 13ccarb and 13corg values are observed at the wukemuchang wkmc and wanhe wh sections representing the shallow regions of the yangtze platform relative to the tianjiawan tjw and tianba tb sections representing the deeper margin of the yangtze platform we suggest that the variations of 13c in carbonate and organic matter are related to the sea level eustacy and shoaling of marine chemocline 1 sea level rise driven decrease in local scale carbonate weathering 2 decreased decomposition of organic matter under anoxic conditions and 3 incorporation of non photosynthetic chemoautorophic bacteria living in deeper waters the 13c 13c 13ccarb 13corg values in both the wh and wkmc sections display an increasing trend upward from the lx formation to the overlying strata varying from 27 8 to 31 2 and from 28 1 to 31 1 respectively these increased 13c values are related to the enhanced nutrients and correspondingly high primary productivity and thus that the anoxic water conditions and high primary productivity may be the significant factors in the deposition of late ordovician black shales

magnesium isotope fractionation during dolostone weathering abstract the element mg and sr isotope ratios of a weathering profile from hubei china have been measured in order to document the behavior of mg isotopes during dolostone weathering the profile is developed in the joint system and the weathering intensity increases from the least weathered dolostone towards the joint plane according to the element and isotope ratios the weathering profile can be divided into the weakly and intensely weathered zones in the weakly weathered zone mg al atomic ratios decrease from 4 99 to 1 75 with increasing weathering intensity while ca al ratios slightly decrease from 13 70 to 9 02 these suggest massive loss of mg and simultaneous conservation of ca 26mg values in the weakly weathered zone slightly decrease from 1 90 to 2 22 lighter than the corresponding protolith 1 90 these element and isotope variations are likely caused by the cooccurrence of dolomite dissolution and calcite re precipitation suggesting that the fluids co existing with the dolostone are saturated with respect to calcite while not saturated with respect to dolomite by contrast both mg al and ca al ratios of intensely weathered samples display a decreasing trend towards the joint plane ranging from 1 62 to 0 16 and 10 24 to 2 05 respectively the significant loss of mg and ca indicates the considerable dissolution of both dolomite and calcite 26mg and 87sr 86sr values increase from 2 22 to 0 41 and from 0 71128 to 0 71368 respectively these observations demonstrate that the isotope compositions of the intensely weathered residues are dominantly controlled by the increasing silicate fractions after carbonate dissolution given that silicates have considerably high 87sr 86sr and 26mg values relative to the carbonates overall our study reveals large mg isotope fractionation during dolostone weathering the direction and extent of mg isotope fractionation are mainly governed by the dissolution and re precipitation of carbonate minerals which are further controlled by the fluid s saturation with respect to carbonate minerals calcite and dolomite therefore cautions should be taken when using whole rock mg isotope data of dolostones to trace paleoclimate change and dolostone genesis primary dolomite could be partially reserved in weakly weathered dolostones and step leaching experiments may help to reveal its bearing mg isotope signals

lithium and its isotopes in major world rivers implications for weathering and the oceanic budget abstract the outstanding problem in the lithium geochemical cycle is the lack of an isotopic mass balance in the ocean the 6li compositions of fresh basalts 4 the hydrothermal fluids derived from them average 9 and seawater significantly heavier at 32 are well understood but only very sparse river input data are available for li mass balance calculations in an attempt to rectify the situation we have measured the lithium concentrations and isotopic compositions of major world rivers draining representative geological terrains this helps both to constrain the river endmember and to understand the behavior of lithium isotopes in the continental weathering environment fluvial isotopic compositions display a very large range 6 0 to 32 2 there is no definitive relationship between 6li and lithology but in general rivers draining marine evaporites are 20 to 22 carbonates 26 to 32 black shales 26 shields 6 6 to 19 and mixed siliceous terrains 6 to 28 the flow weighted mean concentration of the measured rivers is 215 nm at 23 this updated riverine 6li value responsible for 30 of the global riverine discharge does not solve the isotopic imbalance if the measured li concentrations and isotopic compositions are representative of all rivers the presence of a yet unidentified sink with a higher fractionation factor 1 023 than determined for low temperature basalt alteration 1 019 is required for an isotopic steady state of li in the ocean authigenic clays are a possible candidate as clays are known to be enriched in both lithium and in the light isotope preferentially alternatively the hydrothermal flux must be much less than half of that estimated by the 3he inventory and the oceanic budgets for 87sr 86sr and mg the relationship of 6li to the major ions and 87sr 86sr suggests that the important processes affecting river dissolved lithium isotopic compositions are fractionation between solution and secondary minerals and thus the intensity of weathering

study of an ordovician carbonate with alternating dolomite calcite laminations and its implication for catalytic effects of microbes on the formation of sedimentary dolomite

siliciclastic prelude to elatina nuccaleena deglaciation lithostratigraphy and rock magnetism of the base of the ediacaran system

tracking physicochemical conditions of evaporite deposition by stable magnesium isotopes a case study of late permian langbeinites magnesium isotopic compositions of evaporite deposits may record information concerning brine evolution during deposition we report mg isotopic values delta mg 26 dsm3 measured from an evaporite deposit of langbeinite k2mg2 so4 3 found in the permian salado formation we used these data to model mg isotope fractionation between langbeinite and its parent brine in addition both measured and theoretical results are used to estimate precipitation temperature and interpret depositional environment the salado langbeinite delta mg 26 values are relatively low and fall within a relatively narrow range 4 12 0 03 parts per thousand to 3 81 0 07 parts per thousand equilibrium fractionation factors between langbeinite and aqueous mg2 solutions were calculated using quantum chemical density functional theory all computations were performed at the b3lyp 6 31 g d p level solvation effects were addressed using a solvent model water droplet approach and mineral structures were investigated using volume variable cluster models vvcm the equilibrium mg isotopic fractionation factors a between langbeinite and model brine solution we obtained are 1 0005 1 0004 and 1 0003 delta mg 26 langb water approximate to 10 3 ln alpha 0 473 parts per thousand 0 390 parts per thousand and 0 322 parts per thousand at 10 degrees c 25 degrees c and 40 degrees c respectively these relatively large equilibrium fractionation factors indicate significant mg isotope fractionation between langbeinite and its parent brine during precipitation as langbeinite preferentially incorporates the heavier mg 26 and mg 25 isotopes rayleigh distillation modeling of the salado langbeinite s relatively light mg isotopic composition requires delta mg 26 dsm3 values of 4 parts per thousand for the parent brine models favor a precipitation temperature as high as 40 degrees c under equilibrium conditions potential disequilibrium precipitation conditions suggested by mg isotopic data also imply rapid deposition in a hot arid sedimentary environment prevailing in the southwestern u s during the late permian

constraining magnesium cycling in marine sediments using magnesium isotopes abstract magnesium concentrations in deep sea sediment pore fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust to better characterize and differentiate these processes we have measured magnesium isotopes in pore fluids and sediment samples from ocean drilling program sites 1082 1086 1012 984 1219 and 925 that span a range of oceanographic settings at all sites magnesium concentrations decrease with depth at sites where diagenetic reactions are dominated by the respiration of organic carbon pore fluid 26mg values increase with depth by as much as 2 because carbonates preferentially incorporate 24mg low 26mg the increase in pore fluid 26mg values at these sites is consistent with the removal of magnesium in mg carbonate dolomite in contrast at sites where the respiration of organic carbon is not important and or weatherable minerals are abundant pore fluid 26mg values decrease with depth by up to 2 the decline in pore fluid 26mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore fluid the identity of this enriched magnesium sink is likely clay minerals using a simple 1d diffusion advection reaction model of pore fluid magnesium we estimate rates of net magnesium uptake removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites independent estimates of magnesium isotope fractionation during dolomite precipitation from measured 26mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites suggesting that local exchange of magnesium between sediment and pore fluid at these sites can be neglected our results indicate that the magnesium incorporated in dolomite is 2 0 2 7 depleted in 26mg relative to the precipitating fluid assuming local exchange of magnesium is minor at the rest of the studied sites our results suggest that magnesium incorporated into clay minerals is enriched in 26mg by 0 to 1 25 relative to the precipitating fluid this work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources sinks in low temperature aqueous systems

mg isotopic composition of carbonate insight from speleothem formation simultaneous high precision measurement of 24 mg 25 mg and 26 mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry mc icp ms relative to the international standard srm980 data are presented on low mg calcite speleothems and their associated host rocks and waters from four caves one in the french alps and three in israel covering various climate conditions in addition data are presented on three dolostones and three limestones from the himalaya the overall variation is 4 13x and 2 14x in n 26 mg and n 25 mg respectively this is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of mg is not unique each speleothem shows a characteristic range of n 26 mg values that are attributed to the isotopic composition of the local water differences between the isotopic composition of mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to mg isotopic fractionation during carbonate precipitation in the temperature range of 4 18 c the low mg calcite is enriched in light isotopes by 1 35x amu and the dependence on temperature has been found to be less than 0 02x amu c despite various geological settings the n 26 mg of the studied dolostones is 2 0 1 2x higher than the n 26 mg of the limestones all together these results suggest a strong mineralogical control and a weak temperature effect on the mg isotopic composition of carbonate a 2002 elsevier science b v all rights reserved

sequence stratigraphy and the interpretation of neoproterozoic earth history abstract the application of sequence stratigraphy to neoproterozoic successions is important for improving the resolution of time correlation within individual sedimentary basins and potentially at a global scale the methodology is illustrated in this paper by reference to two contrasting examples from the flinders ranges adelaide geosyncline of south australia where the younger part of the neoproterozoic to earliest cambrian succession 770 ma to 540 ma has been divided into thirteen unconformity bounded depositional sequences one of the most prominent sequence boundaries at or near the base of the wonoka formation is characterized by a series of buried canyons as much as 1 km deep high resolution sequence stratigraphic studies at umberatana syncline continue to support the view that the canyons were cut subaerially and filled by fluvial and shallow water sediments in contrast to the wonoka canyons sequence boundaries interpreted at the base of the nuccaleena formation seacliff sandstone and near the top of the abc range quartzite are relatively subtle with only limited evidence for erosion and valley incision four sequence boundaries at the level of the sturtian and marinoan varanger glacial deposits and in the vicinity of the precambrian cambrian boundary are thought to correlate with surfaces in the amadeus basin of central australia other prominent sequence boundaries including the wonoka canyons and surfaces within the upper part of the wonoka formation and at the base of the ediacara member of the rawnsley quartzite correspond with a relatively condensed section in the amadeus basin and their lateral persistence beyond the adelaide geosyncline is therefore difficult to evaluate given the lack of precision in biostratigraphy and isotope geochemistry in neoproterozoic rocks and in a marked departure from phanerozoic practice we recommend placement of a terminal proterozoic gssp at a sequence boundary a prime candidate in australia is the sequence boundary at the base of the nuccaleena formation seacliff sandstone immediately above the marinoan glacial rocks in the adelaide geosyncline and its likely correlative at or near the base of the gaylad sandstone in the amadeus basin

late triassic depositional environments and molluscan associations from west central nevada abstract the sequence of lithofacies and faunal associations described from the upper norian gabbs formation in nevada formed in response to the general late triassic regression this fauna because of its position at the triassic jurassic boundary should reflect the late triassic mass extinction event however the within habitat species diversity of these five bivalve ammonite associations is comparable to that of ecologically similar mesozoic deposit and suspension feeding associations the peculiar absence of gastropods is correlated with an abundance of small heteromorph ammonites suggesting a possible causal relationship

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

globally synchronous marinoan deglaciation indicated by u pb geochronology of the cottons breccia tasmania australia u pb zircon data from the uppermost cottons breccia representing the marinoan glacial postglacial transition on king island tasmania provide the first direct age constraint on the cryogenian ediacaran boundary in australia zircons in four samples from the topmost meter of the cottons breccia dated by sensitive high resolution ion microprobe exhibit two modes ca 660 ma and ca 635 ma the younger component predominates in the uppermost sample a possibly volcanolithic dolomitic sandstone apparently lacking glacially transported debris in the transition to cap carbonate chemical abrasion thermal ionization mass spectrometry ca tims u pb dating of euhedral zircons from that sample yields a weighted mean age of 636 41 0 45 ma equivalence to published tims ash bed dates from cryogenian ediacaran transitional strata in namibia 635 51 0 82 ma within glacial deposit and china 635 23 0 84 ma 2 m above glacial deposit supports correlation of those strata to the australian type sections and globally synchronous deglaciation at the end of the cryogenian period

magnesium isotope fractionation during precipitation of inorganic calcite under laboratory conditions abstract the mg isotope composition of biogenic and inorganic carbonate bears on paleoclimate and paleooceanography studies because of the potential for constraining temperatures so called vital effects and marine mg fluxes previous work has shown that marine organisms produce a wide range of mg isotope compositions that are species dependent where 26 24mgcarb sol fractionations vary from 1 to 5 e g hippler et al 2009 gca constraining mg isotope fractionation during inorganic carbonate precipitation is important because this serves as a baseline with which to compare biogenic samples as well as constrain mg cycling in natural environments we report mg isotope fractionation factors between mg bearing calcite and aqueous mg mg ca molar ratio between 3 1 and 13 1 from 20 free drift and one chemo stat experiment conducted at temperatures between 4 c and 45 c for solutions buffered at p co 2 between 0 038 and 3 pure caco3 seed crystals were used to promote the heterogeneous growth of carbonate from solution and to minimize kinetic isotope effects associated with nucleation and rapid precipitation from strongly super saturated solutions under these conditions calcite overgrowths that contained 0 8 14 9 mol mgco3 precipitated on the seed crystals the measured 26mg 24mg fractionation factors between mg calcite and solution 26mgcal sol are modestly correlated with temperature changing from 2 70 at 4 c to 2 22 at 45 c the fractionation factors are not correlated with experimental conditions chemo stat vs free drift mg content of the overgrowth p co 2 or the mg ca ratio of the solution the temperature dependence of the mg isotope fractionation is 26mgcal sol 0 158 0 051 106 t2 0 74 0 56 where t is temperature in kelvin fractionation of mg isotopes in calcite is much less sensitive to temperature than oxygen isotope fractionation which limits its application as a geothermometer in contrast the mg isotope fractionations for biogenically precipitated mg calcite vary greatly suggesting its potential to discern vital effects in natural samples finally the relatively small temperature effect on mg isotope fractionation greatly simplifies use of mg isotopes in modern or ancient marine systems to constrain mg fluxes including continental weathering

conservative behavior of mg isotopes in massive dolostones from diagenesis to hydrothermal reworking abstract mg isotopes in syndepositional dolomite have been suggested to be a potential proxy for understanding seawater chemistry however it is argued that the 26mg values of dolomite could be complicated by the effects of early diagenesis and later hydrothermal activities further investigations into the behaviors of mg isotopes in dolomitization systems are needed to resolve this controversy in the present study we investigated early ordovician dolostones from the tarim basin including diagenetically altered dolomites hydrothermally altered dolomites and well preserved dolostones that precipitated in the slope margin and interior of a carbonate platform different types of dolomites bulk dolostone and limestone were sampled by microdrilling for analyses of c o mg isotope compositions and ree concentrations the dolostone 13c values match those of coeval seawater and the ree distribution patterns in the dolostones are comparable with those in the limestones indicating that the dolostones originated from syndiagenetic dolomitization the 26mg values of the various syndiagenetic dolomites that formed in the slope margin and interior of the carbonate platform are similar averaging approximately 2 06 0 20 no stratigraphic variability in the dolomite mg isotopes can be discerned which implies that the mg isotope compositions of the porewater were homogeneous during massive dolomitization and remained in equilibrium with seawater additionally the 26mg values of the altered dolostone do not show correlations with diagenetic and hydrothermal signals demonstrating that dolomite mg isotopes are insensitive to postdepositional alteration given these facts we propose that mg isotopes in dolostones have conservative behaviors during diagenesis and late stage hydrothermal reworking

testing models for post glacial cap dolostone deposition nuccaleena formation south australia sedimentologically and geochemically distinctive carbonate sequences consistently drape the glacial deposits associated with the younger cryogenian ice age the presence of ice rafted debris in the basal dolostone implies that at least the lower portion of the cap sequence records deglaciation an isochronous model proposes that cap dolostones were deposited synchronously around the world regardless of water depth whilst a diachronous model proposes that deposition tracked glacioeustatic flooding during deglaciation the nuccaleena formation of the adelaide rift complex arc south australia exhibits many of the unique sedimentary features observed in other younger cryogenian cap dolostones around the world some bedforms are the product of wind driven oscillatory flow thus constraining post glacial dolostone deposition to 400 m these sedimentary features are absent in the deepest basinal facies in the northern arc suggesting that this region was below storm wave base even at the glacial sea level lowstand in the north flinders ranges there is a distinct relationship between lateral facies variability in the pre syn and post glacial sediments and the axes of 50 km scale structural folds the northern fold limbs are characterised by basinal facies whilst the southern limbs are associated with upper slope facies we interpret the abrupt facies transitions to reflect lower slope to upper slope shelf breaks across a series of linked south facing half grabens the majority of cap dolostone carbon isotope records show monotonic declines in 13c of 2 with starting points between 0 5 and 3 5 an isochronous model implies a 3 0 lateral gradient from platform to lower slope that varies dramatically on a short spatial scale and non systematically with palaeobathymetry if pre and syn glacial facies are used to infer palaeobathymetry and cap dolostones are deposited diachronously as sea level rises during deglaciation then 13c values becomes progressively lighter with time implying that cap dolostone deposition tracked the glacioeustatic sea level rise over a series of half grabens that deepened to the north the carbon isotope dataset cannot rule out uniquely isochronous or diachronous models given the high frequency spatial variability of 13c values temperature cannot be the dominant control on the isotopic variability of the cap dolostone