tracing euxinia by molybdenum concentrations in sediments using handheld x ray fluorescence spectroscopy hhxrf abstract elevated molybdenum mo contents in organic rich sediments are indicative of deposition from an anoxic and sulfide rich euxinic water column this can be used for tracing past euxinic conditions in ancient oceans from sedimentary archives conventional analytical detection of elevated molybdenum levels is however expensive and cannot be directly performed in the field here we show that handheld x ray absorption spectroscopy hhxrf on both rock powders and rock surfaces provides a powerful tool for laboratory or field based geochemical characterization of mo content and the tracing of euxinic depositional conditions we further present a sedimentary mo database compiled from over 300 globally distributed modern marine sites to show that modern euxinic marine basins are characterized by molybdenum enrichment 25 ppm relative to average crust 1 5 ppm and river suspended matter 3 ppm only mn oxide rich deposits from oxygenated deep sea settings match such high mo enrichments but these are easily distinguished from mo rich sediments from the continental shelves hence past and present organic rich sediments enriched in mo are indicative of at least intermittent water column euxinia we analyzed the molybdenum content of powdered and homogenized samples of holocene miocene triassic jurassic ordovician and cambrian age by hhxrf and inductively coupled plasma mass spectrometry icpms we further analyzed 2 certified nist standard references nist 2781 with mo 47 ppm and nist 2702 with mo 10 ppm for analytical control analytical precision 1 after 30 120 and 300 seconds of measuring time was 4 2 and 1 ppm with a respective detection limit of 11 5 3 ppm 3 noise level the data were accurate to within the given precision 1 after a daily calibration to samples covering a range of mo concentrations from 0 to 30 ppm hand held xrf equipment also allows mo measurements directly on fresh rock surfaces both in the field and under laboratory conditions rock samples from a cambrian drill core closely match icpms obtained mo concentrations from homogenous powders of the same rocks collectively our data show that hhxrf as a quick and reliable method for the precise and accurate quantification of molybdenum concentrations in both rock powders and at fresh rock surfaces the non destructive nature of the hhxrf measurements is combined with low per sample analytical costs minor sample preparation and easy applicability in the field

molybdenum isotope signatures in continental margin marine sediments abstract we present molybdenum isotope data for four sediment profiles from continental margin settings each profile has a distinctive average isotope composition ranging from 98 95 mo 0 5 to 1 3 relative to j and m laboratory standard this range lies between the modern ocean water value 2 3 and the values typical of mo adsorbed onto mn oxides 0 7 0 1 an important finding of this study is the apparent co variation between the mo isotope composition and the accumulation rate of authigenic mo under reducing conditions this relationship suggests that the chemical processes responsible for mo accumulation under reducing conditions produce an isotope signature in marine sediments in addition to the relationship between mo accumulation and the mo isotope signature there is also a relationship between these parameters and the rate of organic carbon oxidation and burial these relationships suggest that the mo isotope signature of reducing sediments may serve as a tracer for the cycling of organic carbon in continental margin sediments however additional data will be required to refine any such relationships

geochemistry of peruvian near surface sediments sixteen short sediment cores were recovered from the upper edge ueo within wo and below bo the oxygen minimum zone omz off peru during cruise 147 of r v sonne solids were analyzed for major trace elements total organic carbon total inorganic carbon total sulfur the stable sulfur isotope composition 34 s of pyrite and sulfate reduction rates srr pore waters were analyzed for dissolved sulfate sulfide and 34 s of sulfate in all cores highest srr were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and or diffusion of sulfate from bottom water 34 s of dissolved sulfate showed only minor downcore increases strong 32 s enrichments in sedimentary pyrite to 48 vs v cdt are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction manganese and co are significantly depleted in peruvian upwelling sediments most likely due to mobilization from particles settling through the omz whereas release of both elements from reducing sediments only seems to occur in near coastal sites cadmium mo and re are exceptionally enriched in wo sediments 600 m water depth high re and moderate cd and mo enrichments are seen in bo sediments 600 m water depth re mo ratios indicate anoxic and suboxic conditions for wo and bo sediments respectively cadmium and mo downcore profiles suggest considerable contribution to ueo wo sediments by a biodetrital phase whereas re presumably accumulates via diffusion across the sediment water interface to precipitation depth uranium is distinctly enriched in wo sediments due to sulfidic conditions and in some bo sediments due to phosphorites silver transfer to suboxic bo sediments is likely governed by diatomaceous matter input whereas in anoxic wo sediments ag is presumably trapped due to sulfide precipitation cadmium cu zn ni cr ag and t1 predominantly accumulate via biogenic pre concentration in plankton remains rhenium sb as v u and mo are enriched in accordance with seawater te availability lead and bi enrichment in ueo surface sediments is likely contributed by anthropogenic activity mining accumulation rates of toc cd mo u and v from peruvian and namibian sediments exceed those from the oman margin and gulf of california due to enhanced preservation off peru and namibia copyright 2004 elsevier ltd

controls on mo isotope fractionations in a mn rich anoxic marine sediment gullmar fjord sweden abstract molybdenum isotopes have emerged as an important tool for determining the spatial extent of past ocean redox conditions however our understanding of mo cycling and associated isotopic fractionations in modern and ancient continental margin sediments is limited restricting attempts to fully utilize the potential of mo isotopes this is particularly the case with regard to the relative significance of mo isotope fractionations associated with biogeochemical mn and fe oxide cycling under conditions of low dissolved sulfide to rectify this we have investigated sediments from gullmar fjord sweden which contain high concentrations of mn oxides and exhibit a strong redox zonation between mn and fe reduction a combination of dissolved and particulate mo isotope measurements with porewater and solid phase mn and fe characterization reveals that the main influence on porewater 98 mo compositions is exerted by adsorption and desorption processes during reductive dissolution of both mn and fe oxyhydr oxide minerals in areas enriched in mn oxides distinctively low solid phase 98 mo values are observed 1 0 and 0 4 which occur due to the large mo isotope fractionation associated with mo adsorption to mn oxides however where mn oxide concentrations are lower authigenic 98 mo is largely controlled by fe oxyhydr oxide minerals resulting in more positive 98 mo isotopic compositions 0 5 and 2 our results suggest that for modern anoxic marine sediments where deposition occurs beneath an oxic to suboxic water column 98 mo is dominantly controlled by the relative availability of mn and fe oxides and the production of dissolved sulfide

mobility of mo u as and sb within modern turbidites modern turbidites uranium molybdenum arsenic antimony we present and discuss porewaters and sediment data of mn fe mo u as and sb within four recent turbidites from the capbreton canyon sw france the deposition of turbidites on continental margins exerts strong influence on the fate of trace metals causing trace metal migration and or immobilization the down core distribution of the elements here depends entirely of ongoing diagenetic processes rather than the diffusion of o2 the persistence of fe mn oxides under anoxic conditions led to anoxic reoxidation of numerous species as nh4 reduced s compounds and trace metals metal oxides thus control the immobilization of mo and as in the solid phase and the remobilization of u and sb to the porewaters although the low sulphide production prevents anoxic authigenesis of mo and as reducing conditions below each horizon rich in mn fe oxides resulted in u and sb accumulation the exact mechanisms of sb immobilization are not known but it is most certainly different from that of as the profile shapes of mn and u were used to estimate the age of the turbidite deposits which cannot be determined by conventional radionuclide methods our interpretations however depend on calculations of diffusion coefficient particularly for u a simple diffusive model applied to mn suggested that the age of the latest deposit noted t1 was 22 months this date is close to the time elapsed between the core sampling and the last known turbiditic event in the capbreton canyon i e martin storm 18 months using the u data set and depending on diffusion coefficients used the estimated ages of the deeper layers were 4 7 yr for t2 and 7 5 14 yr for t3 the reliability and precision of this new approach to date sediments at short timescales is limited by the ignorance of a precise value for u diffusion coefficient reducing uncertainty on u diffusion coefficient will greatly support application of the proposed approach

nutrients as the dominant control on the spread of anoxia and euxinia across the cenomanian turonian oceanic anoxic event oae2 model data comparison 1 the cenomanian turonian oceanic anoxic event oae2 is characterized by large perturbations in the oxygen and sulfur cycles of the ocean potentially resulting from changes in oxygen supply via oxygen solubility and ocean circulation and in marine productivity we assess the relative impact of these mechanisms comparing model experiments with a new compilation of observations for seafloor dysoxia anoxia and photic zone euxinia the model employed is an intermediate complexity earth system model which accounts for the main ocean dynamics and biogeochemistry of the cretaceous climate the impact of higher temperature and marine productivity is evaluated in the model as a result of higher atmospheric carbon dioxide and oceanic nutrient concentrations the model shows that temperature is not alone able to reproduce the observed patterns of oceanic redox changes associated with oae2 observations are reproduced in the model mainly via enhanced marine productivity due to higher nutrient content responsible for 85 of the change higher phosphate content could have been sustained by increased chemical weathering and phosphorus regeneration from anoxic sediments which in turn induced an enhanced nitrogen nutrient content of the ocean via nitrogen fixation the model also shows that the presence of seafloor anoxia as suggested by black shale deposition in the proto north atlantic ocean before the event might be the result of the silled shape and lack of deep water formation of this basin at the late cretaceous overall our model data comparison shows that oae2 anoxia was quasi global spreading from 5 of the ocean volume before the event to at least 50 during oae2

anoxic vs dysoxic events reflected in sediment geochemistry during the cenomanian turonian boundary event cretaceous in the umbria marche basin of central italy abstract one of the most spectacular expressions of global oceanic anoxic events oaes of the cretaceous is the livello bonarelli of central italy deposited during the cenomanian turonian boundary event ctbe or oae2 at around 93 5 ma at furlo in the umbria marche basin in italy the bonarelli consists of approximately 1 m of c org rich shales interbedded with radiolarian rich layers and contrasts sharply with the extensive over and underlying siliceous limestones several minor c org rich intervals herein termed black levels average thickness 4 5 cm are interbedded within the scaglia bianca beneath the bonarelli x ray fluorescence and icp ms analyses show that these sediments consist of different mixing systems with three end members 1 sio 2 caco 3 scaglia bianca 2 average shale caco 3 black levels and 3 average shale sio 2 bonarelli given the sharp lithologic contacts and the little geochemical mixing between the groups these are thought to represent rapid switching events between sedimentary modes major element concentrations are generally low except for si and p owing to dilution by silica up to 96 and carbonates as al normalised ratios for elements such as ti or zr taken as proxies for higher energy environments are close to average shale values excess sio 2 is most likely linked to biogenic processes rather than quartz element al ratios of ti mg k rb and zr are fairly constant pointing to a mostly homogeneous source area the black levels and bonarelli are characterised by lower mg al ratios compared to the scaglia bianca sediments suggesting variability in chlorite input which could be linked with short term sea level drops indicated by ti al ratios the bonarelli sediments are severely depleted in mn which is indicative of oxygen depleted bottom water conditions and an open marine environment while the black levels appear to have been deposited in a much more restricted setting a model involving partial physical isolation of the furlo site by a sill coupled to omz variations by extra basinal forcing mechanisms is proposed to account for these conflicting data based on re mo ratios the bonarelli sediments were deposited under varying oxygen depletion levels from suboxic to anoxic while re mo ratios in the black levels show deposition under less oxygen deficient conditions most minor elements many of them redox sensitive or sulphide residing are strongly enriched in the c org rich sediments further documenting the absence of oxygen and potential availability of hydrogen sulphide in the water column at times while high zn concentrations suggest elevated submarine hydrothermal activity during this time interval ba is also present in very high concentrations up to 1 4 with an average weighed concentration of 0 6 for the entire bonarelli and is probably indicative of high paleoproductivity in this area this is further supported by high p concentrations hinting at nutrient availability at this site

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

rapid changes in the redox conditions of the western tethys ocean during the early aptian oceanic anoxic event the early aptian 125 to 121 ma records an episode of severe environmental change including a major perturbation of the carbon cycle an oceanic anoxic event oae 1a 122 5 ma a platform drowning episode and a biocalcification crisis we propose to trace changes in the oxygenation state of the ocean during the early aptian anoxic event using the redox sensitive trace element rste distribution phosphorus accumulation rates pars and organic matter characterization in three different basins of the western tethys the following sections have been investigated gorgo a cerbara central italy in the umbria marche basin glaise se france in the vocontian basin and cassis la bedoule se france located in the provencal basin in the gorgo a cerbara section rste distributions show a low background level along the main part of the section contrasted by different maxima in concentrations within the selli level in the glaise section the goguel level displays a weak increase in rste contents coeval with moderate toc values at cassis la bedoule no significant rste enrichments have been observed in sediments equivalent to the selli level these differences in the records of the geochemical proxies of the selli level or its equivalent indicate the deposition under different redox conditions probably related to the paleogeography our data indicate the development of anoxic euxinic conditions in the deeper part of the tethys during oae 1a whereas in the shallower environments conditions were less reducing moreover at gorgo a cerbara the selli level is characterized by rapid changes in the intensity of reducing conditions in the water column ocean eutrophication seems to be a major factor in the development and the persistence of anoxia as suggested by the par evolution higher par values at the onset of oae 1a suggest an increase in nutrient input whereas the return to lower values through the first part of the oae 1a interval may be related to the weakened capacity to retain p in the sedimentary reservoir due to bottom water oxygen depletion this general pattern is contrasted by the data of gorgo a cerbara where the sediments deposited during the oae 1a interval show p enrichments mainly authigenic p this is associated with maxima in toc values and corg ptot ratios suggesting that a part of the remobilized p was trapped in the sediments and as such prevented from returning to the water column

rhenium and molybdenum enrichments in sediments as indicators of oxic suboxic and sulfidic conditions of deposition abstract the trace elements re and mo both behave conservatively in seawater yet are strongly enriched in reducing sediments their potential for authigenic enrichment above crustal concentrations is greater than for many other elements due to the high ratio of metal sw metal crust we present sedimentary re and mo data from box and multi cores spanning a range of redox conditions from well oxygenated sites to locations with substantial sulfide concentrations at the oxic sites re and mo as expected accumulate at concentrations close to their crustal abundances re shows substantial enrichment in suboxic absence of o 2 and h 2 s sediments of the sea of japan in sediments within the oxygen minimum of the pakistan margin as well as in sediments underlying the sulfide bearing waters of the black sea and saanich inlet re enrichment occurs in these cores just below the depths of fe and u reduction only in the sediments underlying the sulfidic waters of the black sea and saanich inlet is there substantial authigenic mo accumulation absence of re and mo enrichments in sediment trap samples from the sulfide bearing basins suggests that the addition of both metals occurs at or below the sediment water interface the re and mo concentration profiles are modeled to hindcast the removal depth of re and mo in the sediments which along with the re mo ratio determine whether oxic suboxic or sulfidic conditions were present in the water column or in the sediments in the past using this approach historical redox conditions can be inferred even in environments such as continental margins where a substantial lithogenic component can obscure authigenic enrichments of other metals

molybdenum drawdown during cretaceous oceanic anoxic event 2 during the cretaceous greenhouse episodes of widespread ocean deoxygenation were associated with globally occurring events of black shale deposition possibly the most pronounced of these oceanic anoxic events oae s was the cenomanian turonian oae2 94 ma however although certain redox sensitive trace metals tend to be preferentially sequestered in sediments deposited under anoxic conditions with mo drawdown being specifically prone to euxinic settings these elements are generally somewhat depleted in sediments deposited during oae2 to understand the driving factors responsible for this depleted trace metal drawdown we have studied a low latitude section from the proto north atlantic ocean tarfaya s57 where existing biomarker and iron sulphur data point to a dominantly euxinic water column with periodic transitions to ferruginous fe rich water column conditions we utilise a variety of redox proxies fe speciation redox sensitive trace metals and mo isotopes which in combination allows us to evaluate the detailed nature of ocean redox conditions and hence controls on trace metal drawdown the results suggest that seawater 98mo values may have ranged between 0 6 and 1 1 during oae2 likely connected to changes in the local mo reservoir as a consequence of low and probably heterogeneous concentrations of mo in the ocean the very low mo toc ratios at tarfaya and elsewhere in the proto north atlantic may support a model in which deep water circulation was partially restricted within and between the north atlantic and other ocean basins we propose that the combination of a low and possibly heterogeneous 98mo of seawater mo together with low mo toc ratios points to a large decrease in the global oceanic mo reservoir during oae2 reflecting a major global scale increase in mo drawdown under persistent euxinic conditions 2016 elsevier b v

crustal velocities near coalinga california modeled from a combined earthquake explosion refraction profile crustal velocity structure for the region near coalinga california has been derived from both earthquake and explosion seismic phase data recorded along a nw se seismic refraction profile on the western flank of the great valley east of the diablo range comparison of the two data sets reveals p wave phases in common which can be correlated with changes in the velocity structure below the earthquake hypocenters in addition the earthquake records reveal secondary phases at station ranges of less than 20 km that could be the result of s to p wave conversions at velocity interfaces above the earthquake hypocenters two dimensional ray trace modeling of the p wave travel times resulted in a p wave velocity model for the western flank of the great valley comprised of a a 7 to 9 km thick section of sedimentary strata with velocities similar to those found elsewhere in the great valley 1 6 to 5 2 km sec b a middle crust extending to about 14 km depth with velocities comparable to those reported for the franciscan assemblage in the diablo range 5 6 to 5 9 km sec and c a 13 to 14 km thick lower crust with velocities similar to those reported beneath the diablo range and the great valley 6 5 to 7 30 km sec this lower crust may have been derived from subducted oceanic crust that was thickened by accretionary underplating or crustal shortening

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

development of a sequential extraction procedure for iron implications for iron partitioning in continentally derived particulates abstract the development of a sequential extraction procedure for iron in modern and ancient sediments is presented the scheme recognizes seven operationally derived iron pools 1 carbonate associated fe fe carb including siderite and ankerite 2 easily reducible oxides fe ox1 including ferrihydrite and lepidocrocite 3 reducible oxides fe ox2 including goethite hematite and akaganeite 4 magnetite fe mag 5 poorly reactive sheet silicate fe fe prs 6 pyrite fe fe py and 7 unreactive silicate fe fe u as such this is the first extraction scheme specifically developed to allow the separate identification of magnetite and the first to allow a complete evaluation of fe carbonate phases such as siderite and ankerite the scheme was developed following tests on pure mineral phases to evaluate the minerals solubilized by each technique and to determine optimum extraction times further tests on mixtures of pure minerals and on grain size separated sediments from two major us rivers and two glacial meltwaters validate the specificity of the scheme for different pools of iron minerals and demonstrate a high degree of reproducibility for each analytical stage the data obtained for the riverine and glacial sediments are additionally discussed in relation to the dominant modes of transport of different iron minerals in fine grained continental sediments

organic rich sedimentation at the cenomanian turonian boundary in oceanic and coastal basins in the north atlantic and tethys one of the most striking results of the deep sea drilling project is the proof that organic rich sediments have a widespread geographical distribution during the period from upper cenomanian to middle turonian such sediments were drilled at north atlantic dsdp sites 105 135 137 138 367 398 551 603 they are also present from outcrops or oil wells on the shelf of the african continental margin senegal tarfaya and agadir basins in the tethys former alboran block southern spain algeria tunisia and umbrian apennines italy and in the north sea although these sediments have different lithologies and depositional environments from shelf areas to the deep sea their study mainly based on organic geochemistry with additional data on sedimentology biostratigraphy and palaeo bathymetry suggests that a unique pulse of organogenic accumulation characterizes the cenomanian turonian boundary event ctbe the content and type of organic matter are related to the depositional environment and organic preservation the organogenic accumulation is distributed according to various trends off the african continental margin the organic content increases from onshore areas to the shelf casamance area and moreover increases also in deep sea areas with a gradual transition from terrestrial type iii to marine type ii the best preservation of the organic matter being in the deepest areas i e site 367 off the american continental margin site 603 shows the same toc and type of organic matter as at site 105 the ctbe is also well recorded in the northern part of the atlantic celtic margin north sea by a drastic lithological change black shales within chalks but the type of organic matter is mainly terrestrial in the tethyan area the organic matter is of marine origin and well preserved results are compared with those of pratt 1984 from the western interior basin of the usa different hypotheses to explain this synchronous widespread accumulation of organic matter are discussed 1986 the geological society

enhanced productivity led to increased organic carbon burial in the euxinic north atlantic basin during the late cenomanian oceanic anoxic event 1 three cenomanian turonian c t 93 5 ma black shale sections along a northeast southwest transect in the southern part of the proto north atlantic ocean were correlated by stable carbon isotope stratigraphy using the characteristic excursion in 13c values of both bulk organic matter om and molecular fossils of algal chlorophyll and steroids all three sites show an increase in marine organic carbon oc accumulation rates during the c t oceanic anoxic event oae the occurrence of molecular fossils of anoxygenic photosynthetic green sulfur bacteria lack of bioturbation and high abundance of redox sensitive trace metals indicate sulfidic conditions periodically reaching up into the photic zone before as well as during the c t oae during the c t oae there was a significant rise of the chemocline as indicated by the increase in concentrations of molecular fossils of green sulfur bacteria and mo al ratios the presence of molecular fossils of the green strain of green sulfur bacteria indicates that euxinic conditions periodically even occurred at very shallow water depths of 15 m or less during the c t oae however bottom water conditions did not dramatically change as indicated by more or less constant v al and zn al ratios at site 367 this suggests that the increase in oc burial rates resulted from enhanced primary productivity rather than increased anoxia which is supported by stable carbon isotopic evidence and a large increase in ba al ratios during the c t oae the occurrence of the productivity event during a period of globally enhanced organic carbon burial rates i e the c t oae points to a common cause possibly related to the formation of a deep water connection between north and south atlantic basins

trace metal evidence for changes in the redox environment associated with the transition from terrigenous clay to diatomaceous sediment saanich inlet bc abstract we measured the concentrations of redox sensitive trace metals mn v mo u cd and re in sediments from odp leg 169s hole 1033b in saanich inlet british columbia to determine changes in redox conditions associated with the onset of laminated sediments at 12 5 kyr the most striking result is a large peak in authigenic re along with detrital levels of mo at the glacial terrigenous clay diatomaceous sediment transition in contrast the underlying glacial terrigenous clay which extends throughout the bottom section of the core is chemically similar to detrital concentrations either cowichan river particulates or average shale values these data suggest a period of oxic bottom waters but reducing pore waters this could be due to the dramatic transformation of saanich inlet during the late deglaciation from an open bay to an inlet which restricted circulation and slowed bottom water oxygen renewal a peak and gradual increase in authigenic mn in younger sediments subsequent to the re peak suggests that increasingly oxic conditions followed the authigenic enrichment in re these conditions could be connected to the younger dryas cooling period which was coincident with an increase in well oxygenated upwelled waters on the west coast of north america that form the bottom waters of saanich inlet metal concentrations in a gray clay bed 11 kyr are similar to their concentrations in the glacial terrigenous clay implying that they have a common source authigenic enrichments of re with little authigenic mo and cd suggest that before the deposition of this bed bottom waters were oxic and pore water oxygen was consumed in the top centimeter or less laminations above the clay layer suggest anoxic conditions which are also indicated by higher authigenic mo and cd and slightly lower re mo ratios in these sediments the basin remained mostly anoxic after the gray clay was emplaced as seen by continuous authigenic enrichment of the redox sensitive trace metals these results are consistent with increased stratification of the water column brought about by an influx of fresh water to the basin by a large flood

basalt seawater interaction the plenus cold event enhanced weathering and geochemical change deconstructing oceanic anoxic event 2 cenomanian turonian late cretaceous oceanic anoxic event 2 cenomanian turonian ca 94 ma represents a major palaeoceanographic phenomenon that took place during an interval of extreme global warmth when large amounts of organic matter entered the marine burial record probably triggered by increased availability of nutrients for planktonic biota three sections eastbourne sussex uk raia del pedale campania italy and tarfaya morocco recording this event illustrate the influence on marine geochemistry of mafic volcanic rock seawater interaction anoxia to euxinia and re oxygenation and cooling during the so called plenus cold event the eastbourne section represents the organic lean epicontinental pelagic deposits of the english chalk the raia del pedale section represents a shallow water platform carbonate on the tethyan continental margin also largely devoid of organic matter and the tarfaya core represents an atlantic margin site where cyclically bedded organic rich sediments were well developed correlation between all three sections is readily achieved by biostratigraphy and carbon isotope stratigraphy 13ccarb and 13corg over the oceanic anoxic event 2 interval represented by a characteristic broad positive carbon isotope excursion the stratigraphic range of the plenus cold event defined by the presence in two discrete levels of boreal fauna and an excursion to heavier oxygen isotope values in the english chalk can be identified in raia del pedale and tarfaya by using the carbon isotope curve as a correlative tool similarly a section in southern france allows its co existing osmium isotope excursion to relatively unradiogenic values to be placed in the context of the oceanic anoxic event in all three analysed sections a fall to lower osmium isotope values clearly pre dated the onset of oceanic anoxic event 2 as defined by the initial rise in carbon isotope values allowing the putative magmatic mafic event as a trigger for the oceanic anoxic event an initial drop in sulphur isotope ratios 34scas at eastbourne correlates with the osmium isotope curve suggesting that isotopically light sulphur could have been derived from a mafic igneous source re oxygenation of sediments of all three investigated sections during the plenus cold event is variably illustrated by change in cerium calcium iodine calcium molybedenum calcium and uranium calcium ratios according to the redox behaviour of the elements in question and whether controls on seawater chemistry were local or global in nature changes in molybdenum isotope ratios from tarfaya and portions of the sulphur isotope curve from eastbourne and raia del pedale also indicate the probable presence of more oxygen rich bottom waters during the plenus cold event oxidation by such waters of previously deposited organic rich shales as well as loss of anoxic euxinic sinks is credited with temporarily enriching global seawater in a range of other redox sensitive trace metals for example v cr co ni cu zn and cd during ongoing basalt seawater interaction indicated by persistent relatively non radiogenic osmium isotope seawater values however early diagenetic enrichment of manganese in the english chalk over much of the oceanic anoxic event interval is broadly correlative in time with relatively low osmium isotope values in sections elsewhere a relationship that may be due to the lack of affinity of manganese with carbon rich shales hence allowing relatively elevated concentrations of the element in marine waters to persist during leaching of mafic rocks unlike other redox sensitive species the calcium isotope and lithium isotope ratios from eastbourne and raia del pedale indicate an increase in global weathering during the initial phase of oceanic anoxic event 2 and the shift in strontium isotopes and osmium isotopes to more unradiogenic values during the event suggests that not only construction but also destruction of one or more large igneous provinces was probably a proximal cause of this major palaeoceanographic phenomenon by elevating nutrient levels and planktonic productivity in large tracts of the world ocean globally widespread carbon burial and silicate weathering are both identified as important mechanisms for drawing down atmospheric carbon dioxide that in the absence of overwhelming volcanogenic replenishment of this greenhouse gas during the early phase of oceanic anoxic event 2 caused the plenus cold event

corrigendum to basin scale controls on the molybdenum isotope composition of seawater during oceanic anoxic event 2 late cretaceous geochim cosmochim acta 178 2016 291 306

paleoceanographic applications of trace metal concentration data abstract recent studies have identified a range of new applications of trace metal concentration data in the analysis of paleoceanographic systems in restricted anoxic marine systems trace metal toc ratios can provide insight into the degree of watermass restriction and estimates of deepwater renewal times in such systems secular changes in sediment trace metal ratios may provide evidence of the chemical evolution of basinal deepwaters in response to differential rates of trace metal removal to the sediment the degree of deepwater restriction in silled basins is generally controlled by eustatic elevations with higher lower sea levels resulting in lesser greater watermass restriction short term ca million year drawdown of the trace metal inventory of seawater has occurred repeatedly in conjunction with oceanic anoxic events which result in elevated rates of trace metal removal to widespread anoxic facies long term eon scale changes of the trace metal composition of seawater have occurred in response to secular changes in atmospheric oceanic redox conditions and their effects on trace metal cycling caution must be exercised in evaluating trace metal patterns in paleomarine systems however 1 hydrographic analyses based on trace metal toc relationships can be undertaken only on systems that had anoxic deepwaters and 2 the influence of redox variation on trace metal accumulation patterns outweighs that of hydrographic factors in some paleomarine systems

enrichment of redox sensitive trace metals u v mo as associated with the late hauterivian faraoni oceanic anoxic event the faraoni level is a short lived oxygen deficient event that took place during the latest hauterivian in order to improve our understanding of the palaeoenvironmental conditions that occurred during this event we have analysed the contents of several redox sensitive trace elements u v mo as co cd cu zn ni pb cr from bulk limestone samples of late hauterivian early barremian age from three reference sections u v mo and as show consistent and significant enrichments during the faraoni event whereas the other redox sensitive trace elements analysed here are not systematically enriched in order to explain this discrepant behaviour we propose that the faraoni level was deposited during a period of anoxic conditions near the sediment water interface the distinctive peaks in u v mo and as contents are traceable throughout the three studied sections and represent a good correlation tool which helps to identify the faraoni level and its equivalents in the western tethyan realm and outside of the tethys for example a peak in u contents in upper hauterivian sediments of the northwestern pacific realm odp leg 185 site 1149 may well be an expression of the faraoni event in this particular basin

the late frasnian kellwasser horizons of the harz mountains germany two oxygen deficient periods resulting from different mechanisms in the harz mountains germany three late devonian sections aeketal huhnertal and kellwassertal were analyzed for major and trace element concentration the inorganic geochemical data were used to determine the environmental conditions associated with the deposition of the two late frasnian black kellwasser horizons in a submarine rise environment low ti al and zr al values and slight enrichment in nutrient and organic matter related trace elements e g ba cu and ni suggest that the kellwasser horizons were deposited during two periods of minimum detrital input but relatively elevated primary production enrichments in u v and mo in both black kellwasser horizons and values of redox indices including u th v cr and ni co indicate oxygen restricted conditions prevailed during the late frasnian times under oxygen depleted conditions reductive diagenesis caused precipitation of iron sulphides such as pyrite that are observed with sem however variations in major and trace element concentrations are not similar in the two kellwasser horizons particularly regarding redox markers the lower kellwasser horizon seems to be more o2 depleted than the upper kellwasser horizon in some german sections on the basis of these results we propose that the two kellwasser horizons are not caused by identical conditions the lower kellwasser horizon results from increased primary productivity enhanced by land derived nutrient loading and which triggered the anoxic conditions recorded in drowned platform setting in contrast the upper kellwasser horizon results from the onset of oxygen impoverished bottom water in the deepest part of the ocean due to episodic water stratification during maximum frasnian flooding oxygen depleted water may have impinged shallower environment during the linguiformis transgressive pulse nutrients would have been released from organic matter decay under reducing conditions and brought up to the photic zone during episodic water mixing

significant increases in global weathering during oceanic anoxic events 1a and 2 indicated by calcium isotopes abstract calcium isotope ratios 44 42ca were measured in carbonate rich sedimentary sections deposited during oceanic anoxic events 1a early aptian and 2 cenomanian turonian in sections from resolution guyot mid pacific mountains coppitella italy and the english chalk at eastbourne and south ferriby uk a negative excursion in 44 42ca of 0 20 and 0 10 is observed for the two events these 44 42ca excursions occur at the same stratigraphic level as the carbon isotope excursions that define the events but do not correlate with evidence for carbonate dissolution or lithological changes diagenetic and temperature effects on the calcium isotope ratios can be discounted leaving changes in global seawater composition as the most probable explanation for 44 42ca changes in four different carbonate sections an oceanic box model with coupled strontium and calcium isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium isotope ratios the model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short lived to affect the oceanic calcium reservoir measurably a modelled increase in weathering flux on the order of three times the modern flux combined with increased hydrothermal activity due to formation of the ontong java plateau oae1a and caribbean plateau oae2 can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections this study presents the first major element record of a weathering response to oceanic anoxic events

cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode oceanic anoxic events oaes were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen deficient bottom waters oae2 occurring at the cenomanian turonian boundary about 93 5 myr ago is the most widespread and best defined oae of the mid cretaceous although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios the actual trigger mechanism corresponding closely to the onset of these episodes of increased carbon sequestration has not been clearly identified it has been postulated that large scale magmatic activity initially triggered oae2 refs 4 5 but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of oae2 has not yet been found here we report seawater osmium isotope ratios in organic rich sediments from two distant sites we find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of oae2 using a simple two component mixing equation we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin a approximately 30 50 fold increase relative to pre oae conditions furthermore the magmatic osmium isotope signal appears slightly before the oae2 as indicated by carbon isotope ratios suggesting a time lag of up to approximately 23 kyr between magmatism and the onset of significant organic carbon burial which may reflect the reaction time of the global ocean system our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of oae2 which may have triggered the subsequent deposition of large amounts of organic matter

sr ca variations in cretaceous carbonates relation to productivity and sea level changes abstract we present high resolution sr ca measurements on coccolith dominated pelagic carbonates of berriasian valanginian albian santonian and campanian maastrichtian age from dsdp sites and tethyan land sections carbonate sr ca varies by up to 80 over both long and short timescales and may reflect either temporal variations in seawater sr ca or variable sr partitioning in biogenic carbonates numerical models of seawater sr and ca budgets indicate that while sea level changes can cause comparably large variations in the seawater sr ca ratio the timing and pattern of predicted sr ca variations agrees poorly with the carbonate record reef crises unrelated to sea level changes may also elevate seawater sr ca and in some cases the record of reef crises corresponds to increasing carbonate sr ca changes in sr partitioning likely due to changes in calcareous nannoplankton productivity also appear to control carbonate sr ca in these records cretaceous carbonate sr ca broadly covaries with indicators of productivity derived from microfossil ecology recent studies in sediment core tops and cultures have shown that sr partitioning in coccolith carbonate is strongly influenced by changes in coccolithophorid growth and calcification rate where the effects of changing seawater sr ca can be constrained by independent geological data carbonate sr ca measurements could provide a valuable perspective on changes in the productivity of calcareous nannoplankton and variations in the carbonate and carbon cycle in the cretaceous

the carbon isotopic response of algae cyano bacteria archaea and higher plants to the late cenomanian perturbation of the global carbon cycle insights from biomarkers in black shales from the cape verde basin dsdp site 367 abstract the stable carbon isotopic compositions of free and sulfur s bound biomarkers derived from algae cyano bacteria archaea and higher plants and total organic carbon toc during the first phase of the late cenomanian turonian oceanic anoxic event oae were measured in black shales deposited in the southern proto atlantic ocean in the cape verde basin dsdp site 367 to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter the average positive isotope excursions of toc and biomarkers varied from 5 1 to 8 3 the 13c values were cross correlated to infer potential common sources of biomarkers this revealed common sources for c31 and c32 hopanes but no 1 1 relationship for pristane and phytane the correlation of 13ctoc with the 13c value of sulfur s bound phytane is the strongest this is because s bound phytane is derived from phytol that originates from all marine primary producers algae and cyanobacteria and thus represents a weighted average of their carbon isotopic compositions the 13c values of s bound phytane and c35 hopane were also used to estimate pco2 levels before the oae burial event pco2 levels are estimated to be ca 1300 ppmv using both biomarkers and the independent maximum rubisco fractionation factors at times of maximum organic carbon burial rates during the oae reconstructed pco2 levels are estimated to be ca 700 ppmv however compared to other c t oae sections the positive isotope excursion of s bound phytane is also affected by an increased production during the oae when we compensate for this we arrive at pco2 levels around 1000 ppmv a reduction of ca 25 this indicates that burial of organic matter can have a large effect on atmospheric co2 levels

rhenium osmium and molybdenum isotope systematics of black shales from the lower cambrian niutitang formation sw china evidence of a well oxygenated ocean at ca 520 ma abstract the early cambrian was a key period in earth s history and the reconstruction of ancient ocean chemistry on spatial and temporal scales can contribute to a better understanding of events during that period new early cambrian data for re os and mo isotopic compositions and redox sensitive elements rse are reported here for the niutitang formation se chongqin sw china a re os age of 520 30 myr model 3 2 n 21 mswd 62 and a 187os 188os i ratio of 0 79 0 11 were obtained consistent with previously reported data for equivalent strata from other areas separate regression of samples with 187os 188os i of 0 72 0 79 and 0 81 0 89 produce more precise ages of 520 1 9 5 myr model1 2 n 7 mswd 1 0 and 513 10 myr model 1 2 n 8 mswd 0 96 respectively suggesting heterogeneity in the primary source of os as the dominant cause of scatter and uncertainty high initial 187os 188os of 0 79 0 11 may indicate a high os input from oxidative weathering of upper continental crust for early cambrian ocean based on rse data such as mo u v enrichment and ni co v cr v v ni moef uef re mo ratios two geochemically distinct zones upper and lower can be delineated in the sedimentary sequence as reflected in drillcore sections the upper section n 9 is characterized by low total organic carbon toc contents mean 1 8 1 5 wt low rse contents mo 0 008 0 006 10 3 g g v 0 22 0 15 10 3 g g u 0 008 0 004 10 3 g g and low v cr 2 0 1 7 ni co 5 9 3 5 moef uef 2 6 1 8 and mo toc 6 0 3 9 ratios in contrast the lower core section n 13 is characterized by high toc contents 4 4 2 2 wt high rse contents mo 0 10 0 08 10 3 g g v 1 0 1 0 10 3 g g u 0 05 0 04 10 3 g g high v cr 6 5 ni co 24 14 moef uef 6 3 2 2 and mo toc 21 9 ratios uncertainties are 1sd here significantly decreasing trends of those redox proxies from lower to upper sections suggest that the depositional conditions evolved from anoxic euxinic to oxic condition all samples display extremely low re mo ratios of 0 2 10 3 1 9 10 3 indicating the absence of intermediate reducing conditions possibly reflecting rapid ocean oxygenation the mo isotopic composition in the sedimentary succession of the yc9 core exhibits a large variation with 98 95mo values of 0 04 2 00 upper section 98 95mo values display an opposite trend to mn content and negative correlation with mo toc ratios indicating mo fractionation associated with adsorption on mn oxides or oxyhydroxides lower section 98 95mo values are positively correlated with mo toc ratios and negatively with re mo ratios suggesting incomplete conversion of molybdates to tetrathiomolybdates under weakly euxinic conditions high 98 95mo of 2 00 and high average mo toc ratios of 21 10 6 g g wt were observed in euxinic shales in the niutitang formation suggesting extensive ocean oxygenation may have taken place at ca 520 ma

the mid cenomanian event prelude to oae 2 a detailed synthesis of litho and biostratigraphic investigations of the cenomanian pelagic limestones of the scaglia bianca formation in the umbria marche basin shows that the bonarelli level which is the regional sedimentary expression of the oae 2 represents the climax of a 2 myr long cycle of black shale deposition that began in the mid cenomanian planktonic foraminiferal rotalipora cushmani zone this long term cycle began with a prominent short term event named mid cenomanian event mce which is associated with several changes in the biotic and abiotic records in particular a comparison of the available litho bio and chemostratigraphic data from the umbria marche basin allows recognition of the mce based on a a significant change in the sedimentary and tectonic regimes b a reorganisation of planktonic foraminiferal assemblages c a major change in benthic foraminifera d a major turnover in the radiolarian assemblages e a 0 7 positive shift in the carbon isotope values and f a positive shift of carbonate sr ca ratio moreover the mce is preceded 400 kyr by a short term 0 5 negative excursion in the oxygen isotope record the above mentioned changes in carbon and oxygen isotope values can be confidently correlated over different basins and oceans and seem to occur in correspondence with a major sea level fall these lines of evidence define the mce as an outstanding event associated with large scale changes in the oceanic structure and palaeoclimate the mce and the subsequent cyclical deposition of organic rich beds serve as a case study to better understand differences and similarities between mesozoic black shales and cenozoic sapropels and related palaeoceanographic changes controlled by orbital climate cycles

diagenesis of oxyanions v u re and mo in pore waters and sediments from a continental margin this research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way we describe pore water and sediment measurements of iron fe manganese mn vanadium v uranium u rhenium re and molybdenum mo along a transect off washington state usa sediments become less reducing away from the continent and the stations have a range of oxygen penetration depths depth to unmeasurable o2 concentration varying from a few millimeters to five centi meters when oxygen penetrates 1 cm or less fe is reduced in the pore waters but reoxidized near the sediment water interface preventing a flux of fe 2 to overlying waters whereas mn oxides are reduced and mn 2 diffuses to overlying waters both re and u authigenically accumulate in sediments only at the most reducing location where the oxygen penetrates 0 3 cm below the sediment water interface does the surface 30 cm of sediments become reducing enough to authigenically accumulate mo stations in close proximity to the juan de fuca ridge crest are enriched in mn and fe from hydrothermal plume processes both v and mo clearly associate with mn cycling whereas u may be associating with either mn oxides and or fe oxyhydroxides rhenium is uncomplicated by adsorption to mn oxides and or fe oxyhydroxides and re accumulation in sediments appears to be due solely to the extent of reducing conditions therefore authigenic sediment re enrichment appears to be the best indicator for intermediate reducing conditions where oxygen penetrates less than 1 cm below the sediment water interface when coupled with negligible authigenic mo enrichment copyright 2005 elsevier ltd 1 introduction oceanic and atmospheric carbon cycles are strongly coupled with the ocean reservoir of dissolved inorganic carbon being 60 times larger than that of the atmosphere broecker and peng 1987 models that couple both ocean and atmosphere have been used to investigate why atmospheric carbon dioxide pco2 atm was reduced during the last glacial age and thus may be useful in predicting the environmental impact of future changes in pco2 atm some of these models require a large increase in organic carbon export through the more efficient use of nutrients to predict the lower pco2 atm observed during

molybdenum isotope fractionation in pelagic euxinia evidence from the modern black and baltic seas here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the black sea and two deeps of the baltic sea dissolved molybdenum in all water samples is depleted in salinity normalized concentration and enriched in the heavy isotope 98mo values up to 2 9 compared to previously published isotope data of sedimentary molybdenum from the same range of water depths furthermore 98mo values of all water samples from the black sea and anoxic deeps of the baltic sea are heavier than open ocean water the observed isotope fractionation between sediments and the anoxic water column of the black sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions an extrapolation to a theoretical pure mos42 solution indicates a fractionation constant between mos42 and authigenic solid mo of 0 5 0 3 measured waters with all thiomolybdates coexisting in various proportions show larger but non linear fractionation the best explanation for our field observations is mo scavenging by the thiomolybdates dominantly but not exclusively present in the form of mos42 the mo isotopic compositions of samples from the sediments and anoxic water column of the baltic sea are in overall agreement with those of the black sea at intermediate depth and corresponding sulphide concentrations the more dynamic changes of redox conditions in the baltic deeps complicate the black sea derived relationship between thiomolybdates and mo isotopic composition in particular the occasional flushing mixing of the deep waters affects the corresponding water column and sedimentary data 98mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations the results can be explained by non conservative behaviour of mo under suboxic to anoxic conditions in the shallow bottom parts of the basin most pronounced on the nw shelf of the black sea

the trace metal content of recent organic carbon rich sediments implications for cretaceous black shale formation organic carbon rich sediments are enriched in several redox sensitive and stable sulfide forming trace metals tm and form an important sink in global tm cycles in today s ocean such sediments are deposited in coastal upwelling areas like those in the gulf of california off peru or off the namibian coast and euxinic basins like the black sea in an attempt to distinguish both environments by their specific tm patterns some important conclusions may be drawn 1 the tm enrichment seen in both environments broadly is rather similar 2 upwelling sediments are often enriched in cd and p and depleted in co and mn 3 sapropels have a tendency towards higher enrichments in ba and mo s re as cu ni sb and fe reflecting the strong sulfidation in an anoxic water column 4 upwelling systems cover a broad range of environmental settings where the steepness of the slope the proximity of h2s to the sediment seawater interface and the intensity of bio accumulation and regeneration play an important role for tm accumulation 5 the tm content of anoxic basins is mainly controlled by tm availability in the water column and sedimentation rate 6 enhanced bio productivity is the main switch turning an oxygenated into an anoxic environment cretaceous black shales oae 2 exhibit tm signatures of both coastal upwelling areas and sapropels the strong enrichments in cd mo tl v cu ni bi and sb demonstrate that bio accumulation and presence of h2s in the water column and associated sulfidation processes persisted during this time interval in large parts of the proto atlantic the usefulness of ba as a paleoproductivity proxy is obscured by diagenesis the extreme accumulation in ag and zn requires either an additional tm source for instance hydrothermal input or a different tm seawater composition during the cretaceous the geochemical data suggest that the major driving force for the widespread occurrence of c t black shales seems to be the increase in volcanic activity and associated co2 input throughout the cretaceous the ocean atmosphere system operated in a mode different from today during this time interval after conversion of the nutrient co2 into organic matter the system switched back into the normal operational mode

sedimentary corg p ratios paleocean ventilation and phanerozoic atmospheric po2 the corg p ratios of organic rich facies tocn1 exhibit considerable variation through the phanerozoic from b10 1 in the permian phosphoria formation to n1000 1 in some devonian black shales relative to the composition of phytoplankton c p 106 1 which provide the bulk of organic c and p to organic rich marine sediments the range of phanerozoic sedimentary corg p ratios largely reflects the influence of benthic redox conditions on diagenetic pathways of c and p remobilization enhanced preservationoforganiccatlowerredoxpotentials combinedwithenhancedsedimentaryretentionofremineralizedorganicpathigher redox potentials results in a strong relationship between benthic redox conditions and sedimentary corg p ratios the strong secular coherence of the phanerozoic corg p record i e limited variation within narrow time slices suggests that these ratios are controlled primarily by factors influencing benthic redox conditions on a global scale such as atmospheric po2 inversion and scaling of the phanerozoic corg p record yields a new atmospheric po2 model that has strong similarities to existing models based on elemental and isotopic mass balances yet differs in some potentially significant respects in particular the new model suggests that atmospheric po2 wasmarkedlylowerduringtheearlytomiddlepaleozoicthanpreviouslyinferred duringmostofthedevonian atmospherico2levels mayhavebeensufficientlylow b13 astopreventthesustainedcombustionofplantmaterial thisfeatureofthemodelmayaccount for ananomalous gapinthefossilcharcoalrecordduringthedevonian theredox dependentburialofpintheoceanresults inpositive and negative feedback mechanisms that tend to stabilize atmospheric oxygen concentrations on geologic timescales temporal variations in the burial of p relative to c suggest that the strength of these feedback mechanisms varied over the phanerozoic 2007 elsevier b v all rights reserved

comment on molybdenum isotope evidence for widespread anoxia in mid proterozoic oceans arnold et al 1 1 reported mo isotope compositions of mid proterozoic black shale which were different from those of euxinic sediments in the black sea on the basis of a mass balance model calculation they claimed that the area of oxic sedimentation in the mid proterozoic oceans was

basin scale controls on the molybdenum isotope composition of seawater during oceanic anoxic event 2 late cretaceous abstract it is well established that the burial of organic carbon in marine sediments increased dramatically at a global scale at the cenomanian turonian boundary oceanic anoxic event 2 oae 2 94 myr ago late cretaceous many localities containing chemostratigraphic expressions of this event are not however enriched in organic carbon and point to a heterogeneous set of oceanographic and environmental processes operating in different ocean basins these processes are difficult to reconstruct because of the uneven geographical distribution of sites recording oae 2 thus limiting our understanding of the causes and palaeoceanographic consequences of the environmental changes that occurred at this time a new highly resolved molybdenum isotope dataset is presented from the cape verde basin southern proto north atlantic ocean and a lower resolution record from the tarfaya basin morocco the new data reveal periodic oscillations in the mo isotope composition of proto north atlantic ocean sediments from which coupled changes in the dissolved sulphide concentration and mo inventories of the basin seawater can be inferred the cyclic variations in sedimentary mo isotope compositions can be hypothetically linked to regional changes in the depth of the chemocline and in the rate of seawater exchange between basinal waters and global seawater the new data suggest that a global seawater mo isotope composition of 1 2 was reached very soon after the onset of oae 2 implying a rapid expansion of marine deoxygenation coeval with or slightly preceding enhanced global rates of organic carbon burial during oae 2 the modelled flux of mo into anoxic sediments is likely to have been 60 125 times greater than at the present day although the spatial extent of anoxia is unlikely to have been greater than 10 of the total seafloor

a euxinic southern north atlantic ocean during the cenomanian turonian oceanic anoxic event abstract during mid cretaceous times large amounts of organic carbon corg became sequestered in black shales possibly due to oceanic anoxic events characterized by the development of an extended oxygen minimum zone omz here we provide the first direct evidence for an open ocean omz in the cenomanian turonian c t southern north atlantic and in fact show that the base of the photic zone was euxinic as revealed by molecular fossils from photosynthetic green sulfur bacteria in c t black shales this together with evidence for bottom water anoxia and accumulation of redox sensitive trace metals and hydrogen rich organic matter indicates a continuously euxinic water column concurrent with the high corg accumulation rates which are 15 150 times greater in the southern than in the northern north atlantic and the low biological productivity this suggests that preservation controlled the accumulation of corg in c t black shales

organically bound iodine as a bottom water redox proxy preliminary validation and application abstract carbonate associated iodine i ca has been used as a proxy of local upper ocean redox conditions and has successfully demonstrated highly dynamic spatial and temporal patterns across different time scales of earth history to further explore the utility of iodine as a paleo environmental proxy we present here a new method of extracting organically bound iodine iorg from shale using volumes of samples on the order of tens of milligrams thus offering the potential for high resolution work across thin shale beds the ratio of iorg to total organic carbon i toc in modern surface and subsurface sediments decreases with decreasing bottom water oxygen which may be used to reconstruct paleo redox changes as a proof of concept we evaluate the i toc proxy in holocene sediments from the baltic sea landsort deep iodp 347 and discuss those data within a framework of additional independent redox proxies e g iron speciation and mo the results imply that i toc may be sensitive to hypoxic suboxic conditions complementary to proxies sensitive to more reducing anoxic euxinic conditions then we test the usage of i toc in sediments deposited during late cretaceous cenomanian turonian oceanic anoxic event oae 2 from 94 million years ago ma we generated i toc and iorg records from six oae 2 sections tarfaya morocco furlo central italy demerara rise western equatorial atlantic cape verde basin eastern equatorial atlantic south ferriby uk and kerguelen plateau southern indian ocean which provide a broad spatial coverage generally i toc decreases over the interval recorded by the positive carbon isotope excursion the global signature of oae 2 suggesting an expansion of more reducing bottom water conditions and consistent with independent constraints from iron speciation and redox sensitive trace metals e g mo relatively higher i toc values thus more oxic conditions are recorded at two high latitude sites for oae 2 supporting previous model simulations cgenie that indicated higher bottom water oxygen concentrations in these regions our results also indicate that organic rich and oxygenated seafloors are likely a major sink of iodine and correspondingly influence its global seawater inventory

contrasting molybdenum cycling and isotopic properties in euxinic versus non euxinic sediments and sedimentary rocks refining the paleoproxies abstract the redox sensitive transition element molybdenum is present in the earth s crust at trace concentrations but is abundant in seawater marine sediments and ancient sedimentary rocks these occurrences have led to the development of a suite of paleoredox proxies based on the bulk concentration of mo its isotopic composition and the covariation of mo with total organic carbon toc in ancient black shales however these proxies have almost exclusively targeted the identification and interpretation of euxinic environments where bottom waters are both anoxic and sulfidic here we present a discussion of the mo geochemistry of non euxinic sediments where hydrogen sulfide is sometimes present yet always restricted to pore waters we propose a new paleoredox application that uses mo concentrations to help distinguish between environments where sulfide was present in the bottom waters and environments where sulfide was restricted to pore waters under ideal conditions it is also possible to infer the presence of mn oxides recycling in non euxinic paleoenvironments based on the mo isotope composition of ancient black shales providing a critical constraint on bottom water oxygenation

environmental analysis of paleoceanographic systems based on molybdenum uranium covariation abstract modern low oxygen marine systems exhibit patterns of molybdenum uranium covariation that can be linked to specific attributes and processes of the depositional system including 1 variation in benthic redox conditions 2 the operation of particulate shuttles within the water column and 3 the evolution of watermass chemistry the importance of these factors in each depositional system can be assessed both from the degree of enrichment of authigenic molybdenum mo auth and uranium u auth and from the mo u auth ratio of the sediment relative to the seawater mo u molar ratio of 7 5 7 9 in open ocean systems with suboxic bottomwaters u auth enrichment tends to exceed that of mo auth owing to onset of u auth accumulation at the fe ii fe iii redox boundary resulting in sediment mo u auth ratios less than that of seawater as bottomwaters become increasingly reducing and at least occasionally sulfidic the rate of accumulation of mo auth increases relative to that of u auth and sediment mo u auth ratios equal or exceed that of seawater in restricted marine systems with permanently sulfidic deepwaters the relative enrichment of mo auth and u auth depends on additional factors in the cariaco basin which has an aqueous mo u ratio similar to that of seawater the operation of a particulate mn fe oxyhydroxide shuttle serves to accelerate the transfer of mo to the seafloor leading to strong enrichments in mo auth relative to u auth in the black sea the chemistry of the deep watermass has evolved to the point where its aqueous mo u ratio is only 0 04 that of seawater as a consequence of which sediments deposited under deepwater influence are depleted in mo auth relative to u auth these mo u covariation patterns can be used to gain a better understanding of the watermass attributes and processes of ancient low oxygen marine systems analysis of anoxic facies from two north american paleomarine systems the late pennsylvanian midcontinent sea lpms and the late devonian seaway lds reveals authigenic mo u relationships similar to those of the modern marine environments above implying similar redox and hydrographic controls the observed patterns are consistent with laterally unconfined circulation and strong watermass exchange within the lpms and with markedly restricted deepwater circulation in silled basins of the lds patterns of authigenic mo u covariation may prove useful in analysis of other paleoceanographic systems to reveal aspects of watermass composition and environmental dynamics

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

multiproxy reconstruction of oceanographic conditions in the southern epeiric kupferschiefer sea late permian based on redox sensitive trace elements molybdenum isotopes and biomarkers abstract the key drivers controlling the redox state of seawater and sediment pore waters in low energy environments can be inferred from redox sensitive trace elements rste molecular biomarkers and trace metal isotopes here we apply a combination of these tools to the upper permian kupferschiefer t1 from the thuringian basin deposited in the southern part of the semi enclosed kupferschiefer sea enrichment patterns of the rstes molybdenum mo and uranium u as well as biomarker data attest to the rapid development of euxinic conditions in basin settings during early t1 times which became progressively less extreme during t1 deposition the evolution of redox conditions in basinal settings and the associated delay in the onset of euxinia at more shallow marginal sites can be attributed to the interaction of sea level change with basin paleogeography euxinia in the southern kupferschiefer sea did not lead to near quantitative depletion of aqueous mo possibly due to short deepwater renewal times in the thuringian basin low aqueous h 2 s concentrations the continuous resupply of rste during transgression and declining burial rates of rstes throughout t1 times drawdown of rste is however indicated for euxinic lagoon environments moreover admixture of freshwater supplied to these lagoons by rivers strongly impacted local seawater chemistry the highest mo isotope compositions of 1 70 in basin sediments allow a minimum kupferschiefer sea seawater composition of 2 40 to be estimated this composition is similar to the 2 30 estimate for the late permian open ocean and confirms a strong hydrographic connection between the epeiric kupferschiefer sea and the global ocean the substantial variation in mo isotope signatures is paralleled by diagnostic shifts in biomarkers responding to oxygenation in different parts of the water column water column chemistry has been affected by variation in sea level hydrodynamic restriction riverine freshwater influx and evaporitic conditions in shallow lagoons elucidation of the relative role of each driving factor by a single geochemical proxy is not feasible but the complex scenario can be disentangled by a multiproxy approach

the late hauterivian faraoni oceanic anoxic event at rio argos southern spain an assessment on the level of oxygen depletion abstract an integrated study of multiple geochemical proxies toc 13ccarb trace metallic elements iron speciation on the late hauterivian faraoni oceanic anoxic event has been performed along the hemi pelagic section of rio argos south eastern spain in order to better constrain the environmental perturbations linked to this event in the subbetic domain in the studied section the toc is relatively low for the inorganic signal the trace metallic elements show contrasted record during the late hauterivian while detrital proxies th ti zr record rather constant signal the productivity cu ni p and redox u v mn fe proxies show noticeable variations the organic rich interval at the base of the faraoni horizon records higher values of cu ni and p as well as of u and v linked to bottom water oxygen depletion and enhanced primary productivity the rest of the faraoni horizon records punctual peaks of productivity and redox proxies but rather constant toc concentration as for organic and isotopic signals parts of inorganic signal linked to organic matter as those of productivity proxies have been probably reworked and partly influenced by carbonates however inorganic geochemical proxies are consistent suggesting rather oxygenated water masses associated with moderate productivity during the late hauterivian based on redox ratios u th vs v v ni fehr fet fepy fehr oxygen concentrations were determined and it clearly appears that only the organic rich interval at the base of the faraoni horizon might record ferruginous anoxic conditions compared to other hemi pelagic mediterranean regions the ultrahelvetic basin from switzerland and the vocontian trough from france the rio argos section shows good similarities concerning toc and 13ccarb signals suggesting moderate organic matter burial during the faraoni event in proximal environments the main difference concerns the redox variations contrary to italy and france sections where anoxic bottom water conditions persist up to the end of the faraoni event the rio argos section shows no truly anoxia onset except at the base of the faraoni horizon which we rather interpret as local intra basinal chemical variations

does large igneous province volcanism always perturb the mercury cycle comparing the records of oceanic anoxic event 2 and the end cretaceous to other mesozoic events mercury hg is increasingly being used as a sedimentary tracer of large igneous province lip volcanism and supports hypotheses of a coincidence between the formation of several lips and episodes of mass extinction and major environmental perturbation however numerous important questions remain to be answered before hg can be claimed as an unequivocal fingerprint of lip volcanism as well as an understanding of why some sedimentary records document clear hg enrichment signals whilst others do not of particular importance is evaluating the impact of different volcanic styles on the global mercury cycle as well as the role played by depositional processes in recording global hg cycle perturbations here new mercury records of cretaceous oceanic anoxic event 2 oae 2 94 ma and the latest cretaceous 67 66 0 ma are presented oae 2 is associated with the emplacement of multiple predominantly submarine lips the latest cretaceous with subaerial volcanism of the deccan traps both of these connections are strongly supported by previously published trends towards unradiogenic osmium os isotope values in globally distributed sedimentary records hg data from both events show considerable variation between different locations attributed to the effectiveness of different sediment types in registering the hg signal with lithologically homogeneous records documenting more clear hg enrichments than sections with major changes in lithology such as limestones to claystones or organic rich shales crucially there is no geographically consistent signal of sedimentary hg enrichment in stratigraphic records of either oae 2 or the latest cretaceous that matches os isotope evidence for lip emplacement indicating that volcanism did not cause a global hg perturbation throughout the entire eruptive history of the lips formed at those times it is suggested that the discrepancy between os isotope and hg trends in records of oae 2 is caused by the limited dispersal range of hg emitted from submarine volcanoes compared to the global scale distribution of os a similar lack of correlation between these two proxies in uppermost cretaceous strata indicates that although subaerial volcanism can perturb the global hg cycle not all subaerial eruptions will do so these results highlight the variable impact of different volcanogenic processes on the efficiency of hg dispersal across the globe factors that could influence the impact of lip eruptions on the global mercury cycle include submarine versus subaerial volcanism volcanic intensity or explosivity and the potential contribution of thermogenic mercury from reactions between ascending magma and surrounding organic rich sediments

phosphorus cycling from the margin to abyssal depths in the proto atlantic during oceanic anoxic event 2 abstract phosphorus p burial during the cenomanian turonian oceanic anoxic event oae 2 93 55 ma was studied using sediment records from four sites in the proto atlantic ocean the sites represent a variety of depositional settings from the continental margin and slope to the abyssal plain strong links between changing marine conditions during oae 2 and p cycling were observed in black shale sections on the continental margin and slope sedimentary p contents and p mars increased around the onset of oae 2 which may reflect enhanced productivity and p burial partly in the form of biogenic apatite fish debris during the main stage of oae 2 phosphorus was efficiently regenerated from the sediment resulting in p depleted sediments and high organic c corg total p ratios the increased availability of dissolved p may have helped to sustain high productivity during oae 2 the termination of oae 2 was associated with a strong recovery of p burial efficiency in the sediment sedimentary records from the two deep sites do not reveal such close links between different stages of oae 2 and the characteristics of p cycling here oae 2 was a period with maximum deposition of relatively thin black shale intervals that alternate with more oxic deep sea sediments the black shale layers record enhanced p regeneration from organic matter and in some cases p enrichment relative to the oxic sediments detailed chemical p fractionation was performed on sediment from all sites but the results were found to mostly reflect diagenesis and sample handling artifacts in these ancient sediments total p concentrations and the corg total p ratio appear to be the most robust indicators of p cycling and regeneration

a co2 decrease driven cooling and increased latitudinal temperature gradient during the mid cretaceous oceanic anoxic event 2 article i nfo the mid cretaceous is thought to be a greenhouse world with significantly higher atmospheric pco2 and sea surface temperatures as well as a much flatter latitudinal thermal gradient compared to the present this time interval was punctuated by the cenomanian turonian oceanic anoxic event oae 2 93 5 myr ago an episode of global massive organic carbon burial that likely resulted in a large and abrupt pco2 decline however the climatic consequences of this pco2 drop are yet poorly constrained we determined the first high resolution sea surface temperature sst record across oae 2 from a deep marine sedimentary sequence at ocean drilling program odp site 1276 in the mid latitudinal newfoundland basin nw atlantic by employing the organic palaeothermometer tex86 we found that ssts across the oae 2 interval were extremely high but were punctuated by a remarkably large cooling 5 11 c which is synchronous with the 2 5 5 5 c cooling in sst records from equatorial atlantic sites and the plenus cold event because this global cooling event is concurrent with increased organic carbon burial it likely acted in response to the associated pco2 drop our findings imply a substantial increase in the latitudinal sst gradient in the proto north atlantic during this period of global cooling and reduced atmospheric pco2 suggesting a strong coupling between pco2 and latitudinal thermal gradients under greenhouse climate conditions

lithium isotope evidence for enhanced weathering during oceanic anoxic event 2 the ocean anoxic event 2 oae2 about 93 5 million years ago was marked by high atmospheric co2 concentration rapid global warming and marine anoxia and euxinia the event lasted for about 440 000 years and led to habitat loss and mass extinction the marine anoxia is thought to be linked to enhanced biological productivity but it is unclear what triggered the increased production and what allowed the subsequent rapid climate recovery here we use lithium isotope measurements from carbonates spanning the interval including oae2 to assess the role of silicate weathering we find the lightest values of the li isotope ratio 7li during oae2 indicating high levels of weathering and therefore atmospheric co2 removal which we attribute to an enhanced hydrological cycle we use a geochemical model to simulate the evolution of 7li and the ca sr and os isotope tracers our simulations suggest a scenario in which the eruption of a large igneous province led to high atmospheric co2 concentrations and rapid global warming which initiated oae2 the simulated warming was accompanied by a roughly 200 000 year pulse of accelerated weathering of mafic silicate rocks which removed co2 from the atmosphere the weathering also delivered nutrients to the oceans that stimulated primary productivity we suggest that this process together with the burial of organic carbon allowed the rapid recovery and stabilization from the greenhouse state

inverse correlation between the molybdenum and uranium isotope compositions of upper devonian black shales caused by changes in local depositional conditions rather than global ocean redox variations abstract coupled mo u isotope data from the upper devonian kettle point formation ontario canada provide a cautionary tale regarding interpretation of global ocean redox conditions using data from euxinic black shales in the gore of chatham core the kettle point black shales have high mo concentrations 48 473 g g and consistently high mo u ratios 3 times the mo u ratio of modern seawater suggesting a euxinic depositional environment these shales yield an inverse correlation r 0 89 p

phosphorus and the roles of productivity and nutrient recycling during oceanic anoxic event 2 four sections documenting the impact of the late cenomanian oceanic anoxic event oae 2 were studied in basins with different paleoenvironmental regimes accumulation rates of phosphorus p bound to iron organic matter and authigenic phosphate are shown to rise and arrive at a distinct maximum at the onset of oae 2 with an associated increase in 13 c values accumulation rates of p return to preexcursion values in the interval where the 13 c record reaches its fi rst maximum an offset in time between the maximum in p accumulation and peaks in organic carbon burial hydrogen indices and corg preact molar ratios is explained by the evolution of oae 2 in the following steps 1 an increase in productivity increased the fl ux of organic matter and p into the sediments the preservation of organic matter was low and its oxidation released p which was predominantly mineralized 2 enhanced productivity and oxidation of organic matter created dysoxic bottom waters the preservation potential for organic matter increased whereas the sediment retention potential for p decreased 3 the latter effect sustained high primary productivity which led to an increase in the abundance of free oxygen in the ocean and atmosphere system after the sequestration of co 2 in the form of black shales this oxygen helped push the ocean back into equilibrium terminating black shale deposition and removing bioavailable p from the water column

a new particulate mn fe p shuttle at the redoxcline of anoxic basins abstract pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters intense element cycling favoured by elevated microbial activity causes steep gradients of physico chemical parameters nutrients and redox sensitive trace metals this study presents a conceptual model for authigenic particle formation at pelagic redoxclines which is based on the tight coupling of mn fe and p cycles besides the well known occurrence of mn oxides textural sem edx and geochemical icp oes icp ms analyses of particles from the redoxclines of the black sea and the baltic sea gotland basin landsort deep evidence the existence of earlier postulated fe oxyhydroxo phosphates and emphasize mixed phases consisting of mn oxides and fe oxyhydroxo phosphates as a new solid species most of the analyzed particles are star shaped of about 5 m in size and occur as single particles or aggregates without any morphological differences between mn oxides fe oxyhydroxo phosphates and mixed phases throughout the redoxcline these minerals show a general succession with maximum abundance of mn oxides above the redoxcline followed by mixed phases and almost pure fe phosphates within and below the redoxcline respectively molar fe p ratios of single particles argue against the formation of known pure fe phosphates like vivianite or strengite at the lower end of the redox transition zone but are consistent with recent experimental findings for colloidal p bearing hydrous ferric oxides moreover morphological similarities suggest the formation of irregular fe oxyhydroxo coatings due to oxidation of upward diffusing fe 2 by oxygen and stepwise replacement of mn iv by fe iii on sinking mno x particles followed by immediate adsorption or even co precipitation of phosphate batch type experiments using biogenic mno x particles demonstrate the efficient potential of fe 2 oxidation by sinking mno x particles when entering sulfidic waters mno x particles are progressively reduced leading to an increasing relative abundance of fe and p rich particles in deeper parts of the water column these particles are also reductively dissolved thereby releasing fe 2 and phosphate to the water column this mn fe p shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales furthermore the particulate mn fe p shuttle must have played an important role for the cycling of p and certain trace metals in ancient ocean basins e g during certain periods of cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic anoxic interfaces of aquatic ecosystems

anomalous molybdenum isotope trends in upper pennsylvanian euxinic facies significance for use of δ98mo as a global marine redox proxy abstract the use of molybdenum isotope data 98mo from organic rich shales to draw inferences concerning marine paleoredox conditions at a global scale is predicated upon the assumptions of 1 a residence time of mo in seawater much greater than the ocean mixing time and 2 quantitative removal of mo from a strongly euxinic h2s aq 11 m water column to the sediment thus preserving the seawater 98mo signature in this study we analyze mo isotopic variation in the hushpuckney shale a 73 cm thick unit representing the late transgressive to early regressive stages of a glacio eustatic cyclothem swope formation deposited in the late pennsylvanian midcontinent sea lpms of north america the hushpuckney can be subdivided into four stratigraphic zones of distinctive geochemical character zones i and iii which accumulated under weakly euxinic conditions acquired relatively high 98mo values 0 9 to 1 1 whereas zone ii which accumulated under intensely euxinic conditions acquired lower 98mo values 0 6 zone iv which accumulated under suboxic conditions in the water column acquired the heaviest 98mo values 1 1 to 1 8 these results contrast with the pattern of redox 98mo covariation in modern marine environments in which the heaviest 98mo values are found in the most intensely euxinic facies we evaluate three different hypotheses to account for the mo isotopic patterns of the hushpuckney shale one hypothesis seawater freshwater mixing is rejected owing to isotopic mass balance considerations a second hypothesis is a local control on 98mo by water column redox cycling of mn with particulate mn oxyhydroxides adsorbing isotopically light mo and transferring it to the sediment a process that was most active during deposition of zone ii the significance of this scenario is that euxinic black shales may not reliably record global seawater 98mo in areas where a mn particulate shuttle is operative a third hypothesis is based on rapid secular variation of the mo isotope composition of late pennsylvanian global seawater in order to account for 98mo trends within the hushpuckney shale seawater 98mo must have varied by 1 2 at a 100 kyr timescale which would have been possible only if the residence time of mo in late pennsylvanian seawater was

uranium and molybdenum isotope evidence for an episode of widespread ocean oxygenation during the late ediacaran period abstract to improve estimates of the extent of ocean oxygenation during the late ediacaran period we measured the u and mo isotope compositions of euxinic anoxic and sulfidic organic rich mudrocks orm of member iv upper doushantuo formation south china the average 238 u of most samples is 0 24 0 16 2sd relative to standard crm145 which is slightly higher than the average 238 u of 0 02 0 12 for restricted black sea deep water unit i euxinic sediments and is similar to a modeled 238 u value of 0 2 for open ocean euxinic sediments in the modern well oxygenated oceans because 238 u is preferentially removed to euxinic sediments compared to 235 u expanded ocean anoxia will deplete seawater of 238 u relative to 235 u ultimately leading to deposition of orm with low 238 u hence the high 238 u of member iv orm points to a common occurrence of extensive ocean oxygenation ca 560 to 551 myr ago the mo isotope composition of sediments deposited from strongly euxinic bottom waters h 2 s aq 11 m either directly records the global seawater mo isotope composition if mo removal from deep waters is quantitative or represents a minimum value for seawater if mo removal is not quantitative near the top of member iv 98 mo approaches the modern seawater value of 2 34 0 10 high 98 mo points to widespread ocean oxygenation because the preferential removal of isotopically light mo to sediments occurs to a greater extent in o 2 rich compared to o 2 deficient marine environments however the 98 mo value for most member iv orm is near 0 relative to standard nist srm 3134 0 25 suggesting extensive anoxia the low 98 mo is at odds with the high mo concentrations of member iv orm which suggest a large seawater mo inventory in well oxygenated oceans and the high 238 u hence we propose that the low 98 mo of most member iv orm was fractionated from contemporaneous seawater possible mechanisms driving this isotope fractionation include 1 inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater like 98 mo signature in sediments or 2 delivery of isotopically light mo to sediments via a particulate fe mn oxyhydroxide shuttle a compilation of mo isotope data from euxinic orm suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late neoproterozoic and early paleozoic time hence member iv does not capture irreversible deep ocean oxygenation instead complex ocean redox variations likely marked the transition from o 2 deficient proterozoic oceans to widely oxygenated later phanerozoic oceans

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

analysis of marine environmental conditions based onmolybdenum uranium covariation applications to mesozoic paleoceanography article i nfo article history accepted 13 september 2011 available online 17 september 2011 patterns of uranium molybdenum covariation in marine sediments have the potential to provide insights re garding depositional conditions and processes in paleoceanographic systems specifically such patterns can be used to assess bottom water redox conditions the operation of metal oxyhydroxide particulate shuttles in the water column and the degree of water mass restriction the utility of this paleoenvironmental proxy is due to the differential geochemical behavior of u and mo 1 uptake of authigenic u by marine sediments begins at the fe ii fe iii redox boundary i e suboxic conditions whereas authigenic mo enrichment re quires the presence of h2s i e euxinic conditions and 2 transfer of aqueous mo to the sediment may be enhanced through particulate shuttles whereas aqueous u is unaffected by this process in the present study we examine u mo covariation in organic rich sediments deposited mostly in the western tethyan region during oceanic anoxic events oaes of early jurassic to late cretaceous age our analysis generally confirms existing interpretations of redox conditions in these formations but provides significant new insights regard ing water mass restriction and the operation of particulate shuttles in depositional systems these insights will help to address contentious issues pertaining to the character and origin of mesozoic oaes such as the degree to which regional paleoceanographic factors controlled the development of the oaes

contemporaneous massive subaerial volcanism and late cretaceous oceanic anoxic event 2 abstract oceanic anoxic events oaes are geological time intervals characterized by extremely high burial rates of organic carbon that led to deposition of organic rich black shales in the global ocean it has been proposed that oceanic anoxic events are ultimately caused by massive volcanism associated with formation of large igneous provinces lips because of chronological similarities but no general consensus has developed yet to investigate the possibility of lip volcanism instigating oaes we measured stable isotopic compositions of bulk organic carbon 13 c org and lead pb isotopic compositions in the silicate sediment fraction across the bonarelli black shale italy a type stratigraphic section for the end cenomanian oae oae 2 94 ma ultra high resolution 13 c org records determined every 1 5 mm capture a 3 sharp negative shift at the base of the bonarelli at the same stratigraphic level pb isotopic compositions in the silicate sediment fraction exhibit significant shifts toward characteristic values of volcanic rocks from contemporaneous lips caribbean and madagascar flood basalts these data suggest a rapid substantial increase in the relative supply of silicate minerals from the two lips massive subaerial volcanism associated with lip formation provides a simple explanation for these two isotopic geochemical signals via release of a huge amount of carbon dioxide 10 5 gt co 2 and particulate materials into the atmosphere which resulted in a rapid negative shift of 13 c in sea water and changes in pb isotopic compositions in the silicate sediment fraction respectively we interpret that massive volcanism triggered significant climatic changes inducing biotic crises and oceanic anoxia

authigenic molybdenum isotope signatures in marine sediments we present new mo isotope data from the mexican continen tal margin that in conjunction with previous data allow us to propose a mechanistic description of the mo isotope system in ma rine sediments we hypothesize that there are unique environmen tally dependent mo isotope signatures recorded in marine sedi ments that reflect the mechanisms responsible for authigenic mo accumulation open ocean anoxic sites defined as having dissolved oxygen and sulfide concentrations near zero in the overlying water exhibit a 98 95 mo isotope signature of 1 6 we believe this val ue reflects mo sulfide formation via diagenetic processes within sediments quantitative formation of mo sulfide within the sulfidic water column of euxinic environments results in sediment isotope values similar to the modern seawater value 2 3 as typified by samples from the highly sulfidic black sea in contrast to these reducing settings manganese oxide rich sediments have measured mo isotope values that are more negative relative to seawater than any other sediment samples analyzed to date similar to fe mn crusts 0 7 most measured mo isotope compositions of marine sediments from open ocean settings appear to reflect a mix ture of lithogenic mo 0 0 and the mo signature of a specific authigenic mo accumulation mechanism we therefore suggest that mo isotopes may record unique signatures that reflect the domi nant chemical mechanism for mo sequestration into sediments

molybdenum isotope evidence for widespread anoxia in mid proterozoic oceans how much dissolved oxygen was present in the mid proterozoic oceans between 1 8 and 1 0 billion years ago is debated vigorously one model argues for oxygenation of the oceans soon after the initial rise of atmospheric oxygen 2 3 billion years ago recent evidence for h 2 s in some mid proterozoic marine basins suggests however that the deep ocean remained anoxic until much later new molybdenum isotope data from modern and ancient sediments indicate expanded anoxia during the mid proterozoic compared to the present day ocean consequently oxygenation of the deep oceans may have lagged that of the atmosphere by over a billion years

paleo redox conditions during oae 2 reflected in demerara rise sediment geochemistry odp leg 207 abstract cretaceous black shales deposited under severe oxygen depletion are carriers of proxy signals for paleoenvironmental conditions using high resolution patterns of iron and sulfur speciation stable sulfur isotope discrimination and trace element enrichment from black shale sequences of sites 1258 and 1260 we identified alterations of the depositional environment during the cenomanian turonian boundary event oae 2 in the southern north atlantic odp leg 207 demerara rise changes in redox conditions are suggested by high ratios of reactive to total iron which indicate that pyrite was formed both in the water column and within the sediment this corresponds to euxinic paleoenvironmental conditions with at least temporarily free dissolved sulfide in the water column a situation similar to the modern deep black sea in addition besides fixation of sulfide as iron sulfide organic matter acted as an important sulfur trap during early diagenesis stable sulfur isotope fractionation went through a minimum within the oae 2 interval indicating enhanced sulfur isotope discrimination during highest burial of organic matter om potentially due to lower burial efficiency of reduced sulfur and or a higher contributions from the oxidative part of the sulfur cycle e g in the water column or the surface sediments elevated fe al and co al values within the cenomanian turonian interval confirm euxinic conditions but at the same time require a zone where reducing but non sulfidic conditions prevail allowing reductive fe and co mobilization in oxygen depleted nearshore sediments the existence of an expanded oxygen minimum zone omz is demonstrated by extremely low mn al ratios a change in the trace metal tm inventory of seawater is postulated from a decline in seawater derived tm enrichment because hypoxic or even euxinic environments form an important sink for tm the enlargement of euxinic depositional areas at the global onset of black shale deposition during oae 2 have likely led to a drawdown of the seawater tm reservoir

sulfidity controls molybdenum isotope fractionation into euxinic sediments evidence from the modern black sea molybdenum mo isotope fractionation has recently been introduced as a new proxy in oceanography and biogeochemistry it is therefore fundamental to understand the processes controlling mo partitioning into modern marine environments this study identifies the availability of dissolved sulfide as the dominant control on overall mo removal from the water column in euxinic systems mo isotopic composition of surface sediments from different localities of the black sea demonstrates complete fixation of mo only below 400 m water depth above a critical concentration of 11 mol l 1 aqueous hydrogen sulfide in the bottom water the mo isotopic composition of these sediments reflects the homogeneous seawater isotopic composition of 2 3 in contrast significant mo isotope fractionation into less euxinic sediments is evident at shallower depths in the black sea as well as in temporarily euxinic deeps of the baltic sea consistent with the observed lower maximum sulfide concentrations in the respective water columns therefore mo isotope signatures in the modern black sea constrain the processes responsible for global mo removal from the ocean by euxinic sediments furthermore models of past ocean anoxia reconstruction have to consider that the seawater mo isotopic composition is not per se archived in euxinic sediments

the valanginian δ13c excursion may not be an expression of a global oceanic anoxic event abstract marine and terrestrial sediments of the valanginian age display a distinct positive 13 c excursion which has recently been interpreted as the expression of an oceanic anoxic episode oae of global importance here we evaluate the extent of anaerobic conditions in marine bottom waters and explore the mechanisms involved in changing carbon storage on a global scale during this time interval we asses redox sensitive trace element distributions rste uranium vanadium cobalt arsenic and molybdenum and the quality and quantity of preserved organic matter om in representative sections along a shelf basin transect in the western tethys in the polish basin and on shatsky rise om rich layers corresponding in time to the 13 c shift are generally rare in the tethyan sections and if present the layers are not thicker than several centimetres and total organic carbon toc contents do not surpass 1 68 wt palynological observations and geochemical properties of the preserved om suggest a mixed marine and terrestrial origin and deposition in an oxic environment in the polish basin om rich layers show evidence for an important continental component rste exhibit no major enrichments during the 13 c excursion in all studied tethyan sections rste enrichments are however observed in the pre 13 c excursion om rich barrande levels of the vocontian trough in addition all tethyan sections record higher mn contents during the 13 c shift indicating rather well oxygenated bottom waters in the western tethys and the presence of anoxic basins elsewhere such as the restricted basins of the north atlantic and weddell sea we propose that the valanginian 13 c shift is the consequence of a combination of increased om storage in marginal seas and on continents as a sink of 12 c enriched organic carbon coupled with the demise of shallow water carbonate platforms diminishing the storage capacity of 13 c enriched carbonate carbon as such the valanginian provides a more faithful natural analogue to present day environmental change than most other mesozoic oaes which are characterized by the development of ocean wide dysaerobic to anaerobic conditions

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

bottom water oxygenation history in southeastern arabian sea during the past 140 ka results from redox sensitive elements the concentrations of multiple redox sensitive elements such as re u mo cd v sb and tl were determined in sediments from the southeastern arabian sea 9 o 21 n 71 o 59 e to understand the bottom water oxygenation history throughout the past 140 ka the enrichment of redox sensitive elements re u cd and sb above average crustal abundances suggests that the last glacial maxima 17 48 ka stadials of marine isotope stage mis 5 5b and 5d and glacial termination gt ii 133 ka were associated with suboxic bottom water conditions sediments deposited during these suboxic conditions show the highest re content up to 54 ppb normalized to a carbonate free basis which is highly enriched over average continental crust 0 4ppb and these sediments appear to be the major sink for the global mass balance estimation marine isotope stages 1 3 4 and interstadials of mis 5 5a 5c 5e were all associated with near oxic conditions overall the lack of enrichment of mo and v above crustal abundance and a high re mo ppm ppm ratio avg 18 2x10 3 suggest that sediments of the southeastern arabian sea never contained free h2s during the last 140 ka these changes in the bottom water oxygen content can be related to the oceanic circulation pattern during this time and in part are reflected in relationships between the timing of redox changes and paleoproductivity proxies

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

patterns of local and global redox variability during the cenomanian turonian boundary event oceanic anoxic event 2 recorded in carbonates and shales from central italy careful evaluation of the local geochemical conditions in past marine settings can provide a window to the average redox state of the global ocean during episodes of extensive organic carbon deposition these comparisons aid in identifying the interplay between climate and biotic feedbacks contributing to and resulting from these events well documented examples are known from the mesozoic era which is characterized by episodes of widespread organic carbon deposition known as oceanic anoxic events this organic carbon burial typically leads to coeval positive carbon isotope excursions geochemical data are presented here for several palaeoredox proxies cr ti v mo zn mn fe speciation i ca and sulphur isotopes from a section exposed at furlo in the marche umbrian apennines of italy that spans the cenomanian turonian boundary here oceanic anoxic event 2 is represented by a ca 1 m thick radiolarian rich millimetre laminated organic rich shale known locally as the bonarelli level iron speciation data for thin organic rich intervals observed below the bonarelli level imply a local redox shift going into the oceanic anoxic event with ferruginous conditions i e anoxic with dissolved ferrous iron transiently developed prior to the event and euxinia i e anoxic and sulphidic bottom waters throughout the event itself pre oceanic anoxic event enrichments of elements sensitive to anoxic water columns were due to initial development of locally ferruginous bottom waters as a precursor to the event however the greater global expanse of dysoxic to euxinic conditions during the oceanic anoxic event greatly reduced redox sensitive trace metal concentrations in seawater pyrite sulfur isotopes document a positive shift leading into the oae carbonate i ca ratios were generally low suggesting locally reduced bottom water oxygen conditions preceding the event and relatively increased o2 concentrations post event combined the furlo geochemical data suggest a redox stratified water column with oxic surface waters and a shallow chemocline overlying locally ferruginous bottom waters preceding the event globally widespread euxinic bottom waters during the oceanic anoxic event followed by chemocline shallowing but sustained local redox stratification following the event this article is protected by copyright all rights reserved

sedimentary molybdenum cycling in the aftermath of seawater inflow to the intermittently euxinic gotland deep central baltic sea abstract molybdenum mo concentrations and isotope compositions in sediments and shales are commonly used as proxies for anoxic and sulfidic i e euxinic conditions in the water column of paleo marine systems a basic assumption underlying this practice is that the proxy signal extracted from the geological record is controlled by long term order of decades to millennia mo scavenging in the euxinic water column rather than mo deposition during brief episodes or events order of weeks to months to test whether this assumption is viable we studied the biogeochemical cycling of mo and its isotopes in sediments of the intermittently euxinic gotland deep in the central baltic sea here multiannual to decadal periods of euxinia are occasionally interrupted by inflow events during which well oxygenated water from the north sea penetrates into the basin during these events manganese mn oxyhydr oxide minerals are precipitated in the water column which are known to scavenge mo we present sediment and pore water mo and mo isotope data for sediment cores which were taken before and after a series of inflow events between 2014 and 2016 after seawater inflow pore water mo concentrations in anoxic surface sediments exceed the salinity normalized concentration by more than two orders of magnitude and coincide with transient peaks of dissolved mn a fraction of the mo liberated into the pore water is transported by diffusion in a downward direction and sequestered by organic matter within the sulfidic zone of the sediment diffusive flux calculations as well as a mass balance that is based on the sedimentary mo isotope composition suggest that about equal proportions of the mo accumulating in the basin are delivered by mn oxyhydr oxide minerals during inflow events and mo scavenging with hydrogen sulfide during euxinic periods since the anoxic surface sediment where mo is released from mn oxyhydr oxides are separated by several centimeters from the deeper sulfidic layers where mo is removed the solid phase record of mo concentration and isotope composition would be misinterpreted if steady state mo accumulation was assumed based on our observations in the gotland deep we argue that short term redox fluctuations need to be considered when interpreting mo based paleo records

trace element behavior and redox facies in core shales of upper pennsylvanian kansas type cyclothems the black shale submember of core shales of pennsylvanian kansas type cyclothems is highly enriched in redox sensitive trace elements tes relative to the overlying gray shale submember as well as to many other modern and ancient organic rich deposits controls on trace element behavior in the black shale can be inferred from trace element enrichment factors efs relative to gray shale and the relationship of tes to total organic carbon toc most tes conformed to one of two patterns 1 mo u v zn and pb exhibited moderate efs and strong covariation with toc in samples having 10 wt toc and 2 cu ni cr and co exhibited low efs and moderate to strong covariation with toc in all samples these patterns are inferred to represent different responses to benthic redox conditions the first pattern is characteristic of tes of strong euxinic affinity i e those taken up in solid solution by fe sulfide or involved in other reactions catalyzed by free h2s and resident mainly in authigenic phases whereas the second pattern is characteristic of tes of weak euxinic affinity i e those not strongly influenced by the presence of free h2s and resident mainly in the organic carbon or detrital fractions of the sediment these inferences allowed development of a multiproxy technique for assessing redox facies in black shale samples euxinic conditions were considered to have existed if at least two of four redox indicator trace elements mo u v zn showed euxinic levels of enrichment and nonsulfidic anoxic conditions were inferred otherwise the validity of the procedure is indicated by 1 agreement among all four redox indicators for a large majority of samples 69 of 185 2 among samples yielding a mixed redox signal a systematic sequence of te enrichment v zn mo u and 3 for tes of weak euxinic affinity reduced variance among samples representing each redox facies sequential enrichment may be a response to differential redox thresholds for accumulation e g v or postdepositional remobilization of trace elements e g u and may provide a basis for finer assessment of redox conditions in low oxygen paleoenvironments than permitted by simple classification schemes the multiproxy procedure for redox facies analysis developed in this study is likely to be more reliable than widely used single proxy indicators based on trace elements e g mo authigenic u or v v ni or c s fe systematics e g s toc or dop d 2004 elsevier b v all rights reserved

further evidence for the development of photic zone euxinic conditions during mesozoic oceanic anoxic events periods in earth history characterized by extensive organic carbon deposition so called oceanic anoxic events oaes are the subject of considerable scrutiny insight into the extent of anoxic conditions in the water column has been provided by the reported occurrence of derivatives of isorenieratene a carotenoid found only in green sulphur bacteria and thus indicative of photic zone euxinia i e a water column containing free h 2 s in north atlantic deep sea sediments deposited during the cenomanian turonian boundary oae2 bonarelli event in this study we have used the distributions of chlorophyll and bacteriochlorophyll degradation products maleimides 1 h pyrrole 2 5 diones and high molecular weight porphyrins to examine further the cenomanian turonian boundary oae2 as well as other oaes of the early toarcian posidonienschiefer event and early aptian selli event in particular methyl isobutyl me i bu maleimide on structural grounds appears to be diagnostic of green sulphur bacteria this compound occurs in five of seven examined marls that record the early toarcian oae marche umbria italy further expanding the geographical range of toarcian sediments where evidence for photic zone euxinic conditions has been found me i bu maleimide occurs in three of six black shales spanning the livello selli marche umbria italy the type locality for the aptian oae1a providing the first evidence for photic zone euxinic conditions during this event with respect to the cenomanian turonian oae maleimide evidence for photic zone euxinic conditions was found in all the north atlantic sites investigated including those characterized by relatively organic lean sediments several tethyan sites and one site off western australia these data indicate that euxinic conditions were common in the water column during mesozoic oceanic anoxic events

green rust formation controls nutrient availability in a ferruginous water column iron rich ferruginous conditions were a prevalent feature of the ocean throughout much of earth s history the nature of elemental cycling in such settings is poorly understood however thus hampering reconstruction of paleoenvironmental conditions during key periods in earth evolution this is particularly true regarding controls on nutrient bioavailability which is intimately linked to earth s oxygenation history elemental scavenging during precipitation of iron minerals exerts a major control on nutrient cycling in ferruginous basins and the predictable nature of removal processes provides a mechanism for reconstructing ancient ocean chemistry such reconstructions depend however on precise knowledge of the iron minerals formed in the water column here we combine mineralogical and geochemical analyses to demonstrate formation of the mixed valence iron mineral green rust in ferruginous lake matano indonesia carbonated green rust gr1 along with signifi cant amounts of magnetite forms below the chemocline via the reduction of ferrihydrite further we show that uptake of dissolved nickel a key micronutrient required for methanogenesis is signifi cantly enhanced during green rust formation suggesting a major control on methane production in ancient ferruginous settings

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

enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in mesozoic limestones and shales there have been many studies devoted to trace metals and their value in assessing the paleoredox conditions of ancient marine deposition among them molybdenum mo is frequently cited as an effective proxy for sediments and sedimentary rocks recently helz et al helz g r miller c v charnock j m mosselmans j l w pattrick r a d garner c d vaughan d j 1996 mechanisms of molybdenum removal from the sea and its concentration in black shales exafs evidences geochim cosmochim acta 60 3631 3642 and adelson et al adelson j m helz g r miller c v 2001 reconstructing the rise of recent coastal anoxia molybdenum in chesapeake bay sediments geochim cosmochim acta 65 237 252 suggested that mo does not behave conservatively in the water column when h2s reaches a threshold concentration above this concentration a switch operates and mo is scavenged by forming bonds with metal rich notably iron particles sulfur rich organic molecules and pyrite in this paper mo trapping by sulfur rich organic matter om in ancient marine deposits is emphasized the following mesozoic geological formations were selected for study because of their relatively high concentration of sulfurized om the akkuyu formation turkey the calcaires d orbagnoux france and kimmeridge clay uk and its timeequivalent in boulonnais france the kashpir oil shales russia and the la luna formation venezuela the sulfur rich om is identified by either measured organic s abundance or kerogen microscope observation our results show that mo is systematically more enriched relative to the other redox sensitive sulfide forming elements studied u v ni cu zn cr and mo enrichment is positively correlated with the amount of sulfurized om but not with pyrite abundance these results illuminate the role played by sulfurized om in geologic scale mo capture and retention but they also underline the role played by reactive iron significant om sulfurization is only possible when reactive iron is limited nevertheless pyrite formation though limited could act as an initial mo trap prior to mo uptake by om that is sulfurized after the pyritization step in future paleoenvironmental reconstructions attention must be paid to this enhanced mo enrichment in the presence of sulfurized organic matter in such cases the use of mo could lead to overestimation of the reducing conditions of the depositional environment

heterogeneous oxygenation states in the atlantic and tethys oceans during oceanic anoxic event 2 abstract the cenomanian turonian boundary ca 93 5 ma is marked by an episode of profound environmental change including a major perturbation of the carbon cycle and an oceanic anoxic event oae 2 here we present molybdenum mo isotope variations within the oae 2 interval for four sections from the western tethys furlo and la contessa and the north atlantic odp site 1276 and dsdp site 367 the main target of this study is to investigate the extent of reducing conditions truly global in extent or restricted to poorly ventilated restricted deep basins with particular reference to the relationship between the change in the oxygenation state of the ocean and the link to global perturbations of the carbon cycle recorded in carbon isotopes all four sections show fluctuations in the redox sensitive trace metal rste distribution suggesting rapid variations in local redox conditions ranging from anoxic to euxinic the rste enrichment factors efs also suggest different depositional conditions and paleoceanographic processes in the western tethys versus the north atlantic whereas the north atlantic sites show evidence of weak watermass restriction associated with the action of a particulate shuttle within the water column the efs of the tethyan sections are characteristic of unrestricted marine systems mo isotopes show surprisingly negative values through the tethyan sections at the onset of oae 2 an increasing trend in mo 98 is observed with values ranging from 0 6 to 0 6 during the second half of oae 2 the mo 98 curve shows a progressive shift towards more negative values in the north atlantic mo 98 signatures from odp site 1276 show a similar behaviour as observed in the western tethys at dsdp site 367 mo isotopes are generally heavier during oae 2 fluctuating around an average value of 1 1 this is consistent with fully euxinic conditions and the black shales deposited may have recorded the seawater signature during oae 2 the mo isotope signature is lighter than the modern ocean value 2 3 and suggests a higher proportion of bottom water euxinia 10 although this estimate is greater than the euxinic fraction in the modern ocean our results challenge the suggestion of a globally euxinic deep waters during oae 2 the variations in mo toc ratios within the north atlantic and tethys oceans are in good agreement with a general drawdown of mo within the oae interval suggesting a general increase in anoxic conditions during oae 2 our results highlight the role of local parameters in the development of euxinia even during period of widespread anoxia such as oaes

carbon isotope stratigraphy recorded by the cenomanian turonian oceanic anoxic event correlation and implications based on three key localities we present new detailed carbon isotope records for bulk carbonate total organic carbon toc and phytane from three key sections spanning the cenomanian turonian boundary interval eastbourne england gubbio italy tarfaya morocco with the purpose of establishing a common chemostratigraphic framework for oceanic anoxic event oae 2 isotope curves from all localities are characterized by a positive carbon isotope excursion of c 4 for toc and phytane and c 2 5 for carbonate although diagenetic overprinting appears to have obliterated the primary carbonate carbon isotope signal in at least part of the tarfaya section stratigraphically peak 13 c values for all components are followed by intervals of high near constant 13 c in the form of an isotopic plateau recognition of an unambiguous return to background 13 c values above the plateau is however contentious in all sections hence no firm chemostratigraphic marker for the end point of the positive isotopic excursion can be established the stratigraphically consistent first appearance of the calcareous nannofossil quadrum gartneri at or near the cenomanian turonian boundary as established by ammonite stratigraphy in conjunction with the end of the 13 c maximum characteristic of the isotopic plateau provides a potentially powerful tool for delimiting the stratigraphic extent and duration of oae 2 this oceanic anoxic event is demonstrated to be largely if not wholly confined to the latest part of the cenomanian stage

trace element abundances in the rock canyon anticline pueblo colorado marine sedimentary section and their relationship to caribbean plateau construction and oxygen anoxic event 2 1 rapid eruption of submarine lava flows during formation of the caribbean plateau correlates closely with ocean anoxic event 2 oae2 which bracketed the cenomanian turonian boundary 93 5 ma these events also correspond with a positive excursion in carbon isotopic composition of seawater hydrothermal activity associated with large scale submarine volcanism may have been responsible for this abrupt change in ocean chemistry we determined the distribution of major minor and trace element abundances in the rock canyon marine sedimentary section pueblo colorado after normalizing element concentrations to zr to remove the variable contribution of terrigenous material to these sediments we detected an interval of concentrated metal abundance anomalies that coincides with the abrupt beginning of the positive 13c isotope excursion the metal abundance anomalies indicate that intermittent hydrothermal activity in the form of both water rock exchange and magmatic degassing introduced large concentrations of trace metals into the cretaceous ocean at the same time that extinctions of benthic species turnover in plankton communities and increases in isotopically light organic carbon burial occurred the stratigraphic position of this interval of trace metal anomalies matches events associated with oae2 and indicates that intermittent hydrothermal activity on a massive scale triggered abrupt changes in carbon burial and deep ocean oxygen contents

secular variation in late cretaceous carbon isotopes a new δ13c carbonate reference curve for the cenomanian campanian 99 6 70 6 ma carbon stable isotope variation through the cenomanian santonian stages is characterized using data for 1769 bulk pelagic carbonate samples collected from seven chalk successions in england the sections show consistent stratigraphic trends and 13c values that provide a basis for highresolution correlation positive and negative 13cexcursions and inflection points on the isotope profiles are used to define 72 isotope events key markers are provided by positive 13c excursions of up to 2 the albian cenomanianboundary event mid cenomanian event i thecenomanian turonian boundary event the bridgewick hitch wood and navigation events of late turonian age and the santonian campanian boundary event isotope events are isochronous within a framework provided by macrofossil datum levels and bentonite horizons an age calibrated composite 13c reference curve and an isotope event stratigraphy are constructed using data from the english chalk the isotope stratigraphy is applied to successions in germany france spain and italy correlation with pelagic sections at gubbio central italy demonstrates general agreement between biostratigraphic and chemostratigraphic criteria in the cenomanian turonian stages confirming established relationships between tethyan planktonic foraminiferal and boreal macrofossil biozonations correlation of the coniacian santonian stages is less clear cut magnetostratigraphic evidence for placing the base of chron 33r near the base of the upper santonian is in good agreement with the carbon isotope correlation but generates significant anomalies regarding the placement of the santonian and campanian stage boundaries with respect to tethyan planktonic foraminiferal and nannofossil zones isotope stratigraphy offers a more reliable criterion for detailed correlation of cenomanian santonian strata than biostratigraphy with the addition of campanian 13c data from one of the english sections a composite cenomanian campanian age calibrated reference curve is presented that can be utilized in future chemostratigraphic studies the cenomanian campanian carbon isotope curve is remarkably similar in shape to supposedly eustatic sea level curves increasing 13c values accompanying sea level rise associated with transgression and falling 13c values characterizing sea level fall and regression the correlation between carbon isotopes and sea level is explained by variations in epicontinental sea area affecting organic matter burial fluxes increasing shallow sea floor area and increased accommodation space accompanying sea level rise allowedmore efficient burial ofmarine organic matter with the preferential removal of 12c from the marine carbon reservoir during sea level fall reduced seafloor area marine erosion of previously deposited sediments and exposure of basin margins led to reduced organiccarbon burial fluxes and oxidation of previously deposited organic matter causing falling 13c values additionally drowning of carbonate platforms during periods of rapid sea level rise may have reduced the global inorganic relative to the organic carbon flux further enhancing 13c values while renewed platform growth during late transgressions and highstands prompted increased carbonate deposition variations in nutrient supply changing rates of oceanic turnover and the sequestration or liberation of methane from gas hydrates may also have played a role in controlling carbon isotope ratios

reconstruction of water column anoxia in the equatorial atlantic during the cenomanian turonian oceanic anoxic event using biomarker and trace metal proxies abstract the occurrence of the biomarker lycopane and the enrichment patterns of redox sensitive trace metals in black shales from demerara rise western tropical atlantic reveal that bottom waters were anoxic during the upper cenomanian and lower turonian at this location bottom waters were clearly oxygen depleted already before oceanic anoxic event 2 oae 2 and continued to be so afterwards furthermore the presence of fossil derivatives of isorenieratene and chlorobactene pigments derived from green sulfur bacteria demonstrates that the waters at the base of the photic zone occasionally contained sulfide i e were euxinic before and after oae 2 low concentrations of derivatives of these pigments are present while much higher concentrations occur within the oae 2 section stratification of the water column must have been strong to sustain euxinic conditions in the photic zone for prolonged periods a substantial drop in the concentrations of isorenieratene and chlorobactene derivatives demonstrates that this stratification temporarily broke down during oae 2 a simultaneous decrease in sea surface temperatures suggests that local ventilation was instrumental in this re oxygenation event a rapid decrease in seawater derived trace metal burial rates at demerara rise occurring in phase with the onset of the anoxia related to oae 2 suggests an approximately synchronous onset of oae 2 in the proto north atlantic

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