a whiff of oxygen before the great oxidation event high resolution chemostratigraphy reveals an episode of enrichment of the redox sensitive transition metals molybdenum and rhenium in the late archean mount mcrae shale in western australia correlations with organic carbon indicate that these metals were derived from contemporaneous seawater rhenium osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 8 million years ago ma molybdenum and rhenium were probably supplied to archean oceans by oxidative weathering of crustal sulfide minerals these findings point to the presence of small amounts of o 2 in the environment more than 50 million years before the start of the great oxidation event

molybdenum behavior during early diagenesis insights from mo isotopes 1 we present molybdenum isotope and concentration data from 14 sites in the eastern pacific from the central california to the peru margin the environments studied have been chosen to represent a broad range in oxidation reduction redox potential which provide a framework for the behavior of this redox sensitive element manganese rich hemipelagic sediments from the eastern tropical pacific have a mean characteristic mo isotope signature 98 95mo 0 49 0 04 two times the standard deviation of the mean 2 sdom with n 14 that reflects fractionation between ocean water and authigenic mo associated with mn oxides authigenic fe mo s deposits from reducing continental margin settings also have a characteristic mo isotopic signature 98 95mo 1 64 0 04 2 sdom with n 136 both of these values are in contrast to highly sulfidic 11 m h2saq restricted basin environments which contain mo isotope values analytically indistinguishable from seawater in terms of the mo isotope composition the modern oceanic mo sink is dominated by continental margin type environments where 98 95mo 1 6 and mn rich sediments where 98 95mo approximately 0 5 with a minor contribution from euxinic settings where h2saq 11 m

molybdenum and uranium geochemistry in continental margin sediments paleoproxy potential abstract we measured solid phase mo and u concentrations in marine sediments from the california mexico peru and chile margins to ascertain the behavior of mo and u during early diagenesis in continental margin settings at sites along the california mexico and peru margins where there are estimates of mass accumulation rates authigenic u accumulation rates range from 0 50 nmol m 2 day 1 at the california and mexico margin sites mo accumulation rates range from 0 to 134 nmol m 2 day 1 whereas at the peru margin site rates may be as high as 550 nmol m 2 day 1 we observe relationships between metal accumulation rates and the delivery and burial rates of organic carbon corg in the case of mo there appears to be at least two relationships between metal accumulation rate and organic carbon burial for most of the data presented in this manuscript continental margin sediments have a mo corg accumulation rate ratio of 20 mol mol 1 this value is significantly lower however than those reported for anoxic basins 100 mol mol 1 but is consistent with reported mo corg rain ratios from mexico margin sediment traps in contrast to mo there appears to be a single u corg burial ratio of 5 mol mol 1 which includes a range of environments from anoxic basins and open ocean sites we interpret the relationships between metal accumulation and organic carbon to indicate that the reactions that govern authigenic metal accumulation are primarily sensitive to the delivery and burial of organic carbon in these particular settings however we note that any relationship between metal accumulation and organic carbon could be indirect in the particular case of mo based on what is known about mo geochemistry from the literature it is possible that mo authigenesis is coupled to sulfur cycling in many of the environments covered by this study and that the observed association between mo and organic carbon burial is a consequence of the coupling between carbon and sulfur burial using the observed relationships between mo and corg burial as well as constraints from the mo isotope budget we estimate that continental margin sediments are an important sink for mo the magnitude of this sink 0 4 108 mol y 1 or larger may be as much as one quarter of the oceanic removal term and is likely to be larger than the modern anoxic basin sink

geochemical evidence for variations in delivery and deposition of sediment in pleistocene light dark color cycles under the benguela current upwelling system abstract distinctive light dark color cycles in sediment beneath the benguela current upwelling system indicate repetitive alternations in sediment delivery and deposition geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid pleistocene intervals from odp sites 1082 and 1084 concentrations of total organic carbon toc vary between 3 5 and 17 1 concentrations of caco3 vary inversely to toc and al which suggests that both carbonate dissolution and terrigenous dilution contribute to the light dark cycles opal concentrations are independent of both toc and caco3 therefore eliminating diatom production and lateral transport of shelf material as causes of the light dark cycles 13corg and 15ntot values do not vary across light dark sediment intervals implying that the extent of relative nutrient utilization did not change the stable 15ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the toc rich layers parallel changes in concentrations of indicator trace elements and toc imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen cu ni and zn are enriched in the darker sediment as a consequence of greater organic matter delivery redox sensitive metals vary due to loss mn and ba or enrichment mo under reducing conditions created by toc oxidation organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution sulfate reduction and the concentration of metals thus export production is considered ultimately responsible for the generation of the color cycles

natural mass dependent variations in the isotopic composition of molybdenum we present the first observations of natural mass dependent fractionation of the isotopic composition of molybdenum mo using multi collector inductively coupled plasma mass spectrometry variations in the isotopic composition of mo are reported as 97 95mo 97mo 95mo sample 97mo 95mo standard 1 1000 external analytical precision of 97 95mo is 1 between sediments deposited under anoxic conditions 97 95mo 1 02 to 1 52 relative to our in house standard and ferromanganese nodules 97 95mo 0 63 to 0 42 97 95mo of pacific ocean seawater 97 95mo 1 48 lies within the range of values for anoxic sediments closest to modern black sea anoxic sediments molybdenites from continental ore deposits have intermediate 97 95mo ranging from 0 26 to 0 09 variations in the abundances of 92mo 95mo 96mo 97mo and 98mo are consistent with mass dependent fractionation a sporadic unidentified interference occurs at mass 94 and 100mo is not measured we hypothesize that the 97 95mo offset between anoxic sediments and ferromanganese nodules results from mo isotope fractionation during inefficient scavenging of mo from seawater by mn oxides under oxic conditions the similarity in 97 95mo of anoxic sediments and seawater is consistent with the very efficient removal of mo from seawater under anoxic conditions in the presence of h2s the data can be interpreted in terms of a steady state mass balance between the mo flux into the oceans from the continents and the mo flux out of the oceans into oxic and anoxic sediments such an interpretation is quantitatively consistent with existing estimates of the removal fluxes of mo to anoxic and oxic sediments these findings suggest that 97 95mo in seawater may co vary with changes in the relative proportions of anoxic and oxic sedimentation in the oceans and that this variation may be recorded in 97 95mo of anoxic sediments hence the mo isotope system may be useful in paleoredox investigations

molybdenum evidence for expansive sulfidic water masses in 750 ma oceans abstract the ediacaran appearance of large animals including motile bilaterians is commonly hypothesized to reflect a physiologically enabling increase in atmospheric and oceanic oxygen abundances po 2 to date direct evidence for low oxygen in pre ediacaran oceans has focused on chemical signatures in the rock record that reflect conditions in local basins but this approach is both biased to constrain only shallower basins and statistically limited when we seek to follow the evolution of mean ocean chemical state through time because the abundance and isotopic composition of molybdenum mo in organic rich euxinic sediments can vary in response to changes in global redox conditions mo geochemistry provides independent constraints on the global evolution of well oxygenated environments here we establish a theoretical framework to access global marine mo cycle in the past from the abundance and isotope composition of ancient seawater further we investigate the 750 ma walcott member of the chuar group grand canyon which accumulated in a rift basin with open connection to the ocean iron speciation data from upper walcott shales indicate that local bottom waters were anoxic and sulfidic consistent with their high organic content up to 20 wt similar facies in phanerozoic successions contain high concentrations of redox sensitive metals but in the walcott member abundances of mo and u as well as mo toc 0 5 ppm wt are low 98 mo values also fall well below modern equivalents 0 99 0 13 versus 2 35 today these signatures are consistent with model predictions where sulfidic waters cover 1 4 of the global seafloor corresponding to a 20 80 fold increase compared to the modern ocean therefore our results suggest globally expansive sulfidic water masses in mid neoproterozoic oceans bridging a nearly 700 million year gap in previous mo data we propose that anoxic and sulfidic euxinic conditions governed mo cycling in the oceans even as ferruginous subsurface waters re appeared 800 750 ma and we interpret this anoxic ocean state to reflect a markedly lower atmospheric and oceanic o 2 level consistent with the hypothesis that po 2 acted as an evolutionary barrier to the emergence of large motile bilaterian animals prior to the ediacaran period

the behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic lake cadagno switzerland abstract molybdenum mo isotope studies in black shales can provide information about the redox evolution of the earth s oceans provided the isotopic consequences of mo burial into its major sinks are well understood previous applications of the mo isotope paleo ocean redox proxy assumed quantitative scavenging of mo when buried into sulfidic sediments this paper contains the first complete suite of mo isotope fractionation observations in a sulfidic water column and sediment system the meromictic lake cadagno switzerland a small alpine lake with a pronounced oxygen sulfide transition reaching up to h 2 s 200 m in the bottom waters or about 300 m total sulfide s 2 h 2 s hs s 2 we find that mo behaves conservatively in the oxic zone and non conservatively in the sulfidic zone where dissolved mo concentrations decrease from 14 nm to 2 8 nm across this transition dissolved mo in the upper oxic waters has a 98 mo oxic 0 9 0 1 which matches that of the riverine input 98 mo river 0 9 0 1 in the deeper sulfidic waters a subaquatic source delivers mo at 1 55 0 1 but the dissolved mo is even heavier at 98 mo sulfidic 1 8 sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in mo with depth with 98 mo values significantly fractionated at 0 8 to 1 2 both near the chemocline and in the deepest trap suspended particulates in the sulfidic waters carry lighter mo than the ambient dissolved mo pool by 0 3 1 5 sedimentary mo concentrations correlate with total organic carbon and yield mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area solid phase mo in the sediment shows a slightly positive 98 mo trend with depth from 98 mo 1 2 to 1 4 while the pore waters show dramatic enrichments of mo 2000 nm with a relatively light isotope signature of 98 mo 0 9 1 0 these data are explained if mo is converted to particle reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles isotope fractionation is expressed in the water column despite the high sulfide concentrations because the rate of mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation however elemental and isotopic mass balances show that mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water this efficient mo drawdown is expected to occur in settings where h 2 s is very much in excess over mo or in a restricted setting where the water renewal rate is slow compared to the mo burial rate we present a model for the mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems

primary and diagenetic controls of isotopic compositions of iron formation carbonates mineralogic chemical and isotopic compositions have been determined for 97 carbonate microbands in five core segments from the early proterozoic 2 5 ga dales gorge member of the brockman iron formation hamersley basin western australia samples were obtained both from banded iron formation bif macrobands 9 12 at paraburdoo on the southern margin of the basin and from bif macroband 13 at wittenoom 130 km nw at paraburdoo oxygen isotopic compositions of coexisting chert and magnetite microbands were measured and indicated final equilibration temperatures ranging from 60 160 degrees c this range is consistent with observed mineral assemblages and indicates a considerable temperature gradient across the basin cf t approximately 300 degrees c at wittenoom becker and clayton 1976 carbon isotopic compositions of carbonates are near 7 vs pdb at paraburdoo and 10 5 at wittenoom but the greater isotopic depletion at wittenoom appears related to primary or diagenetic processes not metamorphism contents of organic carbon are consistently low isotopic depletion is roughly correlated with iron abundance and together with petrographic observations and chemical balances is consistent with the model of bif deposition introduced by beukes et al 1990 primary siderite delta approximately 5 precipitated from an anoxic water column depleted in 13c additional depletion of 13c is associated with coprecipitation of iron oxides and organic carbon oxygen isotopic abundances of microbanded carbonates are similar to those under and overlying massive marine carbonates ranging from 17 6 to 21 0 vs smow 9 6 to 12 9 vs pdb millimeter scale variations in abundances of 13c and 18o are associated with diagenetic replacement of primary siderite by secondary ankerite and or magnetite it is shown that these isotopic variations cannot result from mineral dependent fractionations metamorphism or the influence of large volumes of water in an open system

mo total organic carbon covariation in modern anoxic marine environments implications for analysis of paleoredox and paleohydrographic conditions 1 sedimentary molybdenum mo s has been widely used as a proxy for benthic redox potential owing to its generally strong enrichment in organic rich marine facies deposited under oxygen depleted conditions a detailed analysis of mo s total organic carbon toc covariation in modern anoxic marine environments and its relationship to ambient water chemistry suggests that 1 mo s while useful in distinguishing oxic from anoxic facies is not related in a simple manner to dissolved sulfide concentrations within euxinic environments and 2 patterns of mo s toc covariation can provide information about paleohydrographic conditions especially the degree of restriction of the subchemoclinal water mass and temporal changes thereof related to deepwater renewal these inferences are based on data from four anoxic silled basins the black sea framvaren fjord cariaco basin and saanich inlet and one upwelling zone the namibian shelf representing a spectrum of aqueous chemical conditions related to water mass restriction in the silled basin environments increasing restriction is correlated with a systematic decrease in mo s toc ratios from 45 5 for saanich inlet to 4 5 1 for the black sea this variation reflects control of mo s by mo aq which becomes depleted in stagnant basins through removal to the sediment without adequate resupply by deepwater renewal the basin reservoir effect the temporal dynamics of this process are revealed by high resolution chemostratigraphic data from framvaren fjord and cariaco basin sediment cores which exhibit long term trends toward lower mo s toc ratios following development of water column stratification and deepwater anoxia mo burial fluxes peak in weakly sulfidic environments such as saanich inlet owing to a combination of greater mo aq availability and enhanced mo transport to the sediment water interface via fe mn redox cycling and are lower in strongly sulfidic environments such as the black sea and framvaren fjord these observations demonstrate that at timescales associated with deepwater renewal in anoxic silled basins decreased sedimentary mo concentrations and burial fluxes are associated with lower benthic redox potentials i e more sulfidic conditions these conclusions apply only to anoxic marine environments exhibiting some degree of water mass restriction e g silled basins and are not valid for low oxygen facies in open marine settings such as continent margin upwelling systems

biotic turnover driven by eutrophication before the sturtian low latitude glaciation a dramatic oceanic biotic shift from eukaryotic phytoplankton to bacteria occurred about 740 million years ago microfossil and geochemical data from the chuar group in the southwestern united states link this biotic turnover to widespread eutrophication of surface waters reconstructions of the diversity of precambrian microorganisms suggest a pronounced biotic turnover coinciding with the onset of neoproterozoic low latitude glaciation in which diverse assemblages of organic walled microfossils known as acritarchs were replaced by assemblages of simple smooth walled forms called leiosphaerids and the remnants of bacterial blooms1 2 3 4 this turnover has been interpreted as the mass extinction of eukaryotic phytoplankton1 2 3 4 and the subsequent proliferation of bacteria5 however the causes of this mass extinction and its exact temporal relationship to the glaciations remain unclear1 2 3 4 here we present palaeontological data from the 742 6 myr old chuar group from arizona which indicate that the biotic turnover occurred before the first low latitude sturtian glaciation constrained to be between 726 and 660 myr in age6 in our record the turnover is associated with the appearance of abundant and diverse protozoan fossils and a shift to rising total organic carbon suggestive of increased primary productivity spurred by the influx of nutrients this is followed by an increase in the ratio of highly reactive iron to total iron which we interpret as persistent water column anoxia we therefore conclude that the biotic turnover recorded in the chuar group was driven by widespread eutrophication of surface waters rather than low latitude glaciation

molybdenum isotope variations in molybdenite vapor transport and rayleigh fractionation of mo molybdenum isotopes in 20 molybdenite samples dated by the re os method and representing a range of geologic settings show mass dependent fractionation spanning 0 63 per atomic mass unit amu previous mo isotope data for molybdenite reveal variations in fractionation of 0 5 amu interpretation of these data is hampered however by limited sample numbers in each study lack of a common standard for interlaboratory comparison and limited range of geologic settings here we show that mo isotope compositions of molybdenites do not correlate with crystallization temperature age geographic distribution or geologic conditions rather rayleigh distillation may explain variations of as much as 0 34 amu in a single molybdenite occurrence exceeding the proposed variability in average continental crust vapor transport and rapid precipitation of mo in propagating fractures may account for isotope fractionation of mo and perhaps other metals at very small scales if so the average isotopic composition of mo at each molybdenite occurrence may be representative of bulk crust our results suggest that the isotopic composition of mo delivered to the oceans is uniform geographically and through geologic time

determination of molybdenum isotope fractionation by double spike multicollector inductively coupled plasma mass spectrometry 1 molybdenum isotopic compositions are precisely determined by mc icp ms measurements using a mo double spike the double spike is added prior to chemical purification so that laboratory and instrumental mass fractionations are separated from natural mass dependent fractionation fractionation is determined on four mo mass ratios providing an internal consistency check the external standard reproducibility is at 0 06 per mil on the 98mo 95mo ratio 2 standard deviation using a normal microconcentric nebuliser with a cyclonic spray chamber the minimum quantity of mo is 1 g for high precision results a hydrothermal molybdenite shows fractionation of 0 3 per mil on the 98mo 95mo ratio relative to our standard johnson matthey 1000 g ml 0 3 icp standard solution lot 602332b fine grained sediments show fractionation of 0 1 and 0 3 per mil on the 98mo 95mo ratio the observed mo isotope fractionation is small but resolvable with the presented high resolution technique

mid neoproterozoic biostratigraphy and isotope stratigraphy in australia abstract palynomorph and stromatolite assemblages from mid neoproterozoic strata of australia appear highly significant when collated with results obtained from isotope stratigraphy and allow correlation across the centralian superbasin and adelaide rift complex the majority of palynomorphs from the lower mid neoproterozoic 830 ma have limited biostratigraphic value although a few apparently have restricted ranges carbonates at this stratigraphic level contain the distinctive stromatolite acaciella australica and other taxa of the acaciella australica stromatolite assemblage these carbonates have 13ccarb values of between 4 and 0 and associated anhydrite has 87sr 86sr ratios of 0 7069 these depleted 13ccarb values are immediately preceded by values of 6 1 in the western officer and amadeus basins of the centralian superbasin similar c and sr isotopic features are seen in the similarly aged upper shaler supergroup of canada upper mid neoproterozoic 760 ma carbonates contain the distinctive stromatolite baicalia burra and other stromatolites of the baicalia burra stromatolite assemblage siliciclastic horizons in the same interval contain the acritarch cerebrosphaera buickii and have 13ccarb values of between 0 and 8 the highest mid neoproterozoic 13ccarb values of between 6 7 and 8 1 occur within the stratigraphic range of c buickii in australia in the western officer basin and adelaide rift complex the mid neoproterozoic 13ccarb peaks are preceded by values of ca 0 the apparently restricted range of c buickii in australia suggests the need for reinterpretation of the stratigraphic position of its occurrence in the svanbergfjellet formation akademikerbreen group spitsbergen which was previously considered a post sturtian glacial deposit

the molybdenum isotopic composition in river water constraints from small catchments we report molybdenum isotope compositions and concentrations in water samples from a variety of river catchment profiles in order to investigate the influence of anthropogenic contamination catchment geology within river precipitation and seasonal river flow variations on riverine molybdenum our results show that the observed variations in 98 95mo from 0 to 1 9 are primarily controlled by catchment lithology particularly by weathering of sulfates and sulfides erosion in catchments dominated by wet based glaciers leads to very high dissolved molybdenum concentrations in contrast anthropogenic inputs affect neither the concentration nor the isotopic composition of dissolved molybdenum in the rivers studied here seasonal variations are also quite muted the finding that catchment geology exerts the primary control on the delivery of molybdenum to seawater indicates that the flux and isotope composition of molybdenum to seawater has likely varied in the geologic past

the isotopic signature of the global riverine molybdenum flux and anoxia in the ancient oceans despite important biological and biogeochemical consequences of extensive ocean anoxic events their identification is controversial the marine isotope geochemistry of molybdenum can help quantify the past oxygenation state of the ocean if the riverine input of mo isotopes is known analysis of a set of rivers that account for 28 of global river runoff suggests more variable mo isotopic ratios in rivers that are also isotopically enriched in the heavy isotopes suggesting near total anoxia in the proterozoic ocean and during mesozoic ocean anoxic events despite its important biological and biogeochemical consequences1 2 3 the identification of extensive oceanic anoxia in the geological record is controversial in particular global anoxia is difficult to distinguish from spatially restricted anoxia in the deep ocean or in tectonically isolated basins such as the modern black sea the marine isotope geochemistry of molybdenum mo can help quantify the past oxygenation state of the ocean4 5 6 7 8 9 10 11 12 13 14 because to first approximation under oxic conditions lighter isotopes of mo are preferentially removed to sediments whereas in euxinic conditions quantitative removal leads to no fractionation however the isotopic composition of the mo input from rivers the main contributor of mo to the oceans is poorly constrained and had been assumed to be isotopically comparable to the narrow range found in a small dataset of continental rocks4 5 6 7 8 9 10 11 12 13 14 here we present an isotopic analysis of mo in a set of rivers that together account for 22 of the global riverine water discharge we find a broad range of variability in the mo isotopic composition of these rivers with almost all samples enriched in the heavy isotopes compared with continental rocks our data remove key uncertainties associated with the marine mo isotope budget14 and strongly suggest near total anoxia in the mid proterozoic ocean8 as well as during mesozoic ocean anoxic events13

neoproterozoic chuar group 800 742 ma grand canyon a record of cyclic marine deposition during global cooling and supercontinent rifting abstract chuar group sediments were deposited in a marine cratonic basin synchronously with marine deposition in other basins of western north america and australia the top of the chuar group is 742 ma thus this succession offers a potentially important record of global climatic and tectonic changes during the mid neoproterozoic a critical time leading to possible global glaciation during supercontinent rifting chuar group cycles and sequences may record glacioeustatic fluctuations during the climatic transition into the sturtian ice age 750 700 ma as well as extension related to the dispersal of rodinia the mid neoproterozoic chuar group 1600 m thick is predominantly composed of mudrock with subordinate meter scale beds of dolomite and sandstone facies analysis leads to the interpretation of a wave and tidal influenced marine depositional system diagnostic marine features include 1 marine fossils and high local pyrite content in the mudrock facies 2 mudcracked mud draped symmetric ripples and reverse flow indicators in the sandstone facies 3 facies associations between all facies and 4 no unequivocal terrestrial deposits chuar facies stack into 320 dolomite and sandstone capped meter scale cycles 1 20 m thick and non cyclic intervals of uniform mudrock facies 20 150 m thick nearly all cycles have mudrock bases indicating subtidal water depths dolomite capped cycles shallow to peritidal environments peritidal cycles some indicating subaerial exposure of varying degrees exposure cycles sandstone capped cycles shallow to peritidal environments with no evidence of prolonged exposure peritidal cycles non cyclic intervals represent the deepest water depths 10s of meters peritidal cycles and non cyclic intervals dominate the lower and middle chuar group in the upper chuar group the percentage of exposure cycles increases as does the thickness of individual cycles and non cyclic intervals and the degree of subaerial exposure in the cycle caps correlation of cycles across 10 km shows that many cycles are laterally continuous and some vary in thickness some thickness changes are coincident with local and regional extensional structures these cycle trends reflect a resolvable mixture of tectonic and climatic controls cycles are interpreted to be high frequency and glacioeustatically controlled based on comparison of cycle character and thickness to phanerozoic examples and lateral continuity of many cycles respectively cycles in the lower and middle chuar group show characteristics suggestive of low amplitude sea level changes similar to meter scale cycles from global greenhouse climates in the phanerozoic upper chuar group cycles show characteristics suggestive of moderate amplitude sea level changes similar to phanerozoic greenhouse icehouse transition climates indicating an increase in continental ice volume variability in cycle thickness and lateral pinching of some cycle caps is controlled by variable tectonic subsidence evidenced by thickening trends coincident with active rift related structures and also by variability in sediment supply the presence of dolomite caps in this otherwise siliciclastic succession is interpreted to be due largely to rapid changes in climate related to short term glacioeustatically controlled sea level changes four crude lithostratigraphic sequences 150 775 m thick are defined based on dolomite poor to dolomite rich stratigraphic intervals long term changes in cycle cap lithology may be driven by long term changes in climate similar to short term glacioeustatic controls on meter scale cycle cap lithology large scale thickness variability in these sequences is due to local differential tectonic subsidence

molybdenum isotope fractionation during adsorption by manganese oxides the isotopic composition of mo 97 95mo in seawater is 2 heavier than mo in marine ferromanganese crusts and nodules barling et al earth planet sci lett 193 2001 447 457 siebert et al earth planet sci lett 211 2003 159 171 to explore this phenomenon we have conducted an experimental investigation into the mass dependent fractionation of mo isotopes during adsorption onto mn oxyhydroxide two series of experiments were carried out a time series in which adsorption proceeded for 2 96 h and a ph series in which ph varied from 6 5 to 8 5 the extent of mo adsorption by mn oxyhydroxides decreases with increasing ph a trend typical of anion adsorption and takes 48 h to reach steady state lighter mo isotopes are preferentially adsorbed experimentally determined fractionation factors soln mnox exhibit no systematic variation with either time or experimental ph the mean soln mnox for all experiments is 1 0018 0 0005 2 s d comparison of the mo isotopic data for experimental solutions and mo adsorbed to mn oxyhydroxide with predictions for closed system equilibrium and rayleigh fractionation models indicates that isotope fractionation occurs as a result of closed system equilibrium exchange between dissolved and adsorbed mo the isotopic offset between dissolved and adsorbed mo is comparable to that observed between mo in seawater and mo in ferromanganese nodules and crusts it is therefore likely that adsorption of mo to mn oxyhydroxides is a significant factor in the fractionation of mo isotopes in the oceans

when do black shales tell molybdenum isotope tales molybdenum mo isotopes in ancient sediments are promising recorders of global ocean paleoredox conditions organic rich black shales can be used to reconstruct ancient ocean mo isotope compositions if these sediments record the isotopic composition of contemporaneous seawater comparison of 98 95 mo in two devonian shale sequences of similar age the new york oatka creek and geneseo formations reveals that this assumption cannot be applied to all organic rich shales although both sequences contain laminated intervals elevated organic carbon and enrichments of redox sensitive metals the mean 98 95 mo differs systematically between the formations by 0 59 independent paleoredox indicators reveal that portions of the oatka creek formation were deposited under pervasively euxinic anoxic and sulfidic conditions whereas conditions during deposition of the geneseo formation were intermittently euxinic to suboxic oxygen deficient but not sulfidic in the water column we infer that reconstruction of ancient ocean 98 95 mo from organic rich shales requires independent verification of persistent local euxinia with these considerations in mind our data point to 98 95 mo in the devonian oceans 0 6 lighter than in today9s oceans consistent with expanded anoxia

trace element and ree composition of a low temperature ridge flank hydrothermal spring abstract warm 25 c hydrothermal springs have been sampled on baby bare a basaltic outcrop on 3 5 ma old crust 100 km east of the endeavor segment of the juan de fuca ridge the source for these springs is a 62 to 64 c formation water that has cooled conductively as it ascends to feed the springs this water originated as bottom seawater that probably descended into basement 52 km to the southwest at another much larger outcrop called grizzly bare as this seawater flows towards baby bare it is heated and altered by reactions within basaltic basement and by diffusive fluxes to and from the overlying sediment concentrations of mn co ni zn cd and mo in the spring waters are greater than in bottom seawater indicating that the oceanic crust is a source for these elements to the oceans at least a portion of this increase probably results from the redox cycling of mn in sedimentary sources near the basement interface that produces a diffusive flux to basement formation waters additional removal of mo and inputs of the other five elements to two of the three springs are observed locally near sites of venting where density gradients can form shallow circulation cells within the sediment and diffusive exchange occurs concentrations of cu u v y and the rare earth elements rees excluding ce in these samples are less than in bottom seawater indicating that the oceanic crust is a net sink for these elements in this environment copper is probably removed into newly formed carbonate and or sulfide phases removal of the oxyanions u and v is consistent with a net removal of phosphate demonstrated previously for ridge flank hydrothermal systems similarly removal of y and the rees is associated with carbonate phosphate rich and oxide phases calculated maximum global chemical fluxes from warm ridge flank hydrothermal systems such as baby bare are insignificant relative to riverine fluxes for these elements except possibly for mn and mo the impact on global geochemical budgets for these elements from lower temperature

the geochemistry of redox sensitive trace metals in sediments abstract we analyzed the redox sensitive elements v mo u re and cd in surface sediments from the northwest african margin the u s northwest margin and the arabian sea to determine their response under a range of redox conditions where oxygen penetrates 1 cm or less into the sediments mo and v diffuse to the overlying water as mn is reduced and remobilized authigenic enrichments of u re and cd are evident under these redox conditions with the onset of sulfate reduction all of the metals accumulate authigenically with re being by far the most enriched general trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes oxic reducing where oxygen penetrates 1 cm and anoxic conditions using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations we calculate the area of sediments below 1000 m water depth in which oxygen penetration is 1 cm to be 4 of the ocean floor we conclude that sediments where oxygen penetrates 1 cm release mn v and mo to seawater at rates of 140 260 60 150 and 5 10 of their respective riverine fluxes using the authigenic metal concentrations and accumulation rates from this work and other literature these sediments are sinks for re cd and u with burial fluxes of 70 140 30 80 and 20 40 respectively of their dissolved riverine inputs we modeled the sensitivity of the response of seawater re cd and v concentrations to changes in the area of reducing sediments where oxygen penetrates 1 cm our analysis suggests a negligible change in seawater re concentration whereas seawater concentrations of cd and v could have decreased and increased respectively by 5 10 over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10 20 if the area increased by a factor of 3 the concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of cd ca and v ca ratios observed in foraminifera shells over the last 40 kyr this implies that the area of reducing sediments in the ocean deeper than 1000 m 4 has not been greater than twice the present value in the recent past

spatial variability in oceanic redox structure 1 8 billion years ago the deposition of iron formations ceased about 1 84 billion years ago reconstructions of ocean chemistry suggest that the advent of euxinic conditions along ocean margins preferentially removed dissolved iron from the water column in the form of the mineral pyrite inhibiting widespread iron oxide mineral deposition

basement rocks of the halmahera region eastern indonesia a late cretaceous early tertiary arc and fore arc halmahera is a k shaped island located at the junction of several major arc trench systems of the western pacific eastern indonesia region western halmahera is an active volcanic arc above a zone of intense seismicity which characterizes the north molucca sea eastern halmahera has a basement of dismembered ophiolitic rocks with slices of mesozoic and eocene sediments overlain unconformably by middle oligocene and younger sedimentary and volcanic rocks the mesozoic and eocene sediments reveal notable stratigraphical and petrological similarities to the marianas fore arc and the eastern halmahera basement complex is interpreted as a pre oligocene fore arc lacking an accretionary complex there is some evidence that the pre oligocene volcanic arc behind this fore arc now forms part of the basement of western halmahera the mesozoic and tertiary sediments were imbricated together with igneous and metamorphic rocks representing the deeper parts of the fore arc during the late eocene plate reorganization event recognized throughout the western pacific margins the eastern halmahera basement complex can be traced into eastern mindanao probably further northwards in the eastern philippines and may be related to similar terranes within and around the present philippine sea plate in contrast the southern part of the island of bacan at the southwestern end of the halmahera group has a basement of continental metamorphic rocks associated with a deformed ophiolitic complex quite different to the basement of eastern halmahera the metamorphic rocks are interpreted to be part of the north australian continental margin basement which is separated from the halmahera basement complex by a splay of the sorong fault system and the deformed ophiolite complex of bacan is suggested to represent magmatism in the fault zone

interactions between environmental change and shallow water carbonate buildup along the northern tethyan margin and their impact on the early cretaceous carbon isotope record 1 the evolution of the early cretaceous northern tethyan carbonate platform was not only influenced by changes in sea level detrital influx and surface water temperature but also by changes in trophic levels we distinguish between phases of carbonate production dominated by oligotrophic photozoan communities and by mesotrophic and eventually colder water heterozoan communities superimposed on this bimodal trend in platform evolution were phases of platform demise for which we provide improved age control based on ammonite biostratigraphy the initial phase of these episodes of platform demise corresponds in time to episodes of oceanic anoxic events and environmental change in general on the basis of a comparison between the temporal changes in an early cretaceous ammonite calibrated d 13 c record from southeastern france and coeval changes in the platform record we suggest that the history of carbon fractionation along the northern tethyan margin was not only influenced by changes in the oceanic carbon cycle such as in the rate of production and preservation of organic and carbonate carbon and in the size of the oceanic dissolved inorganic carbon reservoir but it was also influenced by the above mentioned changes in the ecology and geometry of the adjacent carbonate platform phases of photozoan carbonate production induced positive trends in the hemipelagic carbonate d 13 c record phases of heterozoan carbonate production pushed the d 13 c system toward more negative values platform drowning episodes implied an initial increase in d 13 c values followed by a longerterm decrease in d 13 c values

basinal restriction black shales re os dating and the early toarcian jurassic oceanic anoxic event 1 profiles of mo total organic carbon toc through the lower toarcian black shales of the cleveland basin yorkshire united kingdom and the posidonia shale of germany and switzerland reveal water mass restriction during the interval from late tenuicostatum zone times to early bifrons zone times times which include that of the putative early toarcian oceanic anoxic event the degree of restriction is revealed by crossplots of mo and toc concentrations for the cleveland basin which define two linear arrays with regression slopes ppm of 0 5 and 17 the slope of 0 5 applies to sediment from the upper semicelatum and exaratum subzones this value which is one tenth of that for modern sediments from the black sea mo toc regression slope 4 5 reveals that water mass restriction during this interval was around 10 times more severe than in the modern black sea the renewal frequency of the water mass was between 4 and 40 ka the mo toc regression slope of 17 applies to the overlying falciferum and commune subzones the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years the more restricted of the two intervals has been termed the early toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to nw europe crossplots of re os and mo against toc show similar trends of increasing element concentration with increase in toc but with differing slopes together with modeling of 187 os 188 os and d 98 mo the element toc trends show that drawdown of re os and mo was essentially complete during upper semicelatum and exaratum subzone times mo toc regression slope of 0 5 drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of re os and mo via a low salinity surface layer created isotopic excursions of up to 1 3 in d 98 mo and up to 0 6 for 187 os 188 os restriction thereby compromises attempts to date toarcian black shales and possibly all black shales using re os chronology and introduces a confounding influence in the attempts to use d 98 mo and initial 187 os 188 os for palaeo oceanographic interpretation

molybdenum isotope evidence for global ocean anoxia coupled with perturbations to the carbon cycle during the early jurassic relatively brief periods of severe paleoenvironmental change during the jurassic and cretaceous were associated with the widespread accumulation of organic rich marine deposits termed oceanic anoxic events oaes these intervals involved abrupt global warming of 5 10 c higher rates of continental weathering elevated extinction rates and large scale perturbations to the global carbon cycle the major oaes also overlapped temporally the emplacement of large igneous provinces however despite being known as oaes the extent of seawater anoxia at those times is undefined and the causative processes remain unclear here we show how changes in seawater molybdenum isotope ratios a proxy for seawater anoxia during the toarcian early jurassic oae define the onset and expansion of oxygen deficient conditions our data also place constraints on the areal extent of marine anoxia during the event and demonstrate that anoxia expanded and contracted periodically broadly in line with precession driven changes in 13 corg despite their intermittent occurrence over geological history oaes have an important contemporary relevance because the magnitude and high rates of environmental change then were broadly similar to those occurring at the present day