late quaternary climate change from δ18o records of multiple species of planktonic foraminifera high resolution records from the anoxic cariaco basin venezuela seasonal trade wind induced upwelling along the southern margin of the caribbean sea occurs in response to the annual migration of the intertropical convergence zone laminated high deposition rate sediments of the cariaco basin a small anoxic basin on the venezuelan continental shelf clearly record large changes in the past intensity of this upwelling because sediments of the cariaco basin are largely unbioturbated they offer a natural opportunity to study the stable isotopic records of multiple planktonic foraminiferal taxa and to evaluate their sensitivity to both the modern hydrography and temporal changes in upwelling intensity and climate oxygen isotope data 18o from four dominant foraminiferal taxa are presented for the time period covering the last 28 kyr the 18o data from globigerina bulloides after correction for nonequilibrium precipitation are used as a monitor of sea surface conditions during the winter spring upwelling season the 18o data from white globigerinoides ruber are used as a measure of annual average conditions in the near surface while pink g ruber data are consistent with use as an index of endmember conditions during the summer fall nonupwelling season data from the deeper dwelling neogloboquadrina dutertrei yield information on conditions near the base of the local thermocline during the last glacial 18o data from g ruber and generally reduced interspecific differences indicate cooling of surface waters over the cariaco basin by up to 4 c this longer term cooling does not appear to be related to changes in upwelling intensity along the coast but may instead reflect more regional cooling of the larger caribbean superimposed on this pattern between 12 6 and 10 ka is a convergence of 18o data between g bulloides and n dutertrei implying much stronger upwelling during the last deglaciation this scenario is consistent with other evidence for high productivity at this time at 14 ka a sharp 18o depletion event observed in all taxa seems to have been produced by increased freshwater discharge to the southern caribbean suggesting either higher regional rainfall or the influence of glacial melting in the andes minimum 18o values of pink g ruber around 6 7 ka record warmer summer sea surface temperatures and or decreased salinity in the mid holocene

lack of enhanced preservation of organic matter in sediments under the oxygen minimum on the oman margin the impingement of oxygen minima on continental margins is widely thought to promote the accumulation of sedimentary facies enriched in well preserved organic matter it is shown here however that such a relationship does not clearly apply to the productive oman margin in the arabian sea which hosts one of the most severe oxygen minima in the oceans measurements made on the 0 1 cm depth interval from fourteen box cores collected from the outer shelf upper continental slope area off oman show that 1 1 deposited organic matter is overwhelmingly of marine origin 2 2 there is no significant correlation between the abundance of sedimentary organic carbon corg and the bottom water o2 concentration 3 3 there is no relation between the sedimentary corg n ratio and bottom water o2 4 4 there is no correlation between the hydrogen index hi of the organic matter and bottom water oxygen there are however significant correlations between the corg n ratio and the i corg cr al and zr al ratios as well as between the corg n ratio and the hydrogen index these relationships are interpreted as being the result of winnowing and attendant reworking which produce a progressive increase in the corg n ratio and a decrease in the hi and the i corg ratio as organic matter becomes progressively degraded commensurate rises in the cr al and zr al ratios result from the increased proportion of heavy minerals associated with winnowed lag deposits overall these data suggest that the bottom water oxygen concentration has little effect in governing either the distribution or the degree of preservation of organic matter on this margin thus the generally high but spatially variable corg content of the sediments on the oman margin may not reflect the occurrence of an oxygen minimum but instead be the result of a high settling flux of organic matter supported by monsoon driven upwelling and post depositional redistribution of the organic material by hydrodynamic influences

rates of formation of modern phosphorite off western mexico abstract phosphorite deposition represents a significant but poorly constrained sink in the marine p cycle this study establishes conclusively that phosphorite forms today throughout a widespread region along the upper continental slope off southern baja california mexico in this region o2 depleted 5 50 m bottomwater overlies the seafloor and a narrow range of suboxic to anoxic redox conditions prevail in the modern 0 18 000 yr old near surface 0 50 cm organic c rich 2 10 wt sediment interstitial gradients of total alkalinity ta and inferred effects of organic matter decay correlate directly with sedimentation rates calculated from 14c dating other porewater and solid phase data indicate that francolite currently precipitates authigenically at each of five study sites moderately high concentrations 20 100 m of dissolved inorganic phosphate dip produced in the upper 5 cm of sediment sustain francolite growth at slightly greater depths while the necessary f diffuses into the sediment from above neither organic matter decay nor fish bone dissolution seem capable of producing the steep near surface gradients of dip measured in this study at some sites dip production coincides spatially with the reversible production of dissolved fe2 but thorough evaluation of the possible link between these processes requires further study the mechanism responsible for the near surface enrichment of interstitial dip thus remains unidentified box cores from each site contain an unreworked sequence of up to six thin 1 3 cm discrete francolite rich horizons several of which qualify as true phosphorite 50 wt francolite estimated diffusional burial fluxes of inorganic p and f range respectively from 2 40 g cm 2 y 1 and 4 12 g cm 2 y 1 or the equivalent in francolite of 16 260 g cm 2 y 1 these present day accumulation rates lie within the range of those determined for several ancient phosphorite deposits and for the extensively studied region of modern phosphorite deposition off peru

rare earth elements in the permian phosphoria formation paleo proxies of ocean geochemistry abstract the geochemistry of deposition of the meade peak member of the phosphoria formation mpm in southeast idaho usa a world class sedimentary phosphate deposit of permian age that extends over 300 000 km2 is ascertained from its rare earth element ree composition ratios of ree al2o3 suggest two sources seawater and terrigenous debris the seawater derived marine fraction identifies bottom water in the phosphoria sea as o2 depleted denitrifying suboxic most of the time and seldom sulfate reducing anoxic this interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of cr ni v ni mo ni relative to their ratios in seawater for which marine cr v and mo can have a dominantly o2 depleted bottom water source and ni a photic zone largely algal source the water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column determined largely by primary productivity in the photic zone and the flux of oxidants into the bottom water via advection of seawater from the open ocean samples strongly enriched in carbonate fluorapatite the dominant ree host mineral have variable er sm tm sm and yb sm ratios their distribution may represent greater advection of seawater between the phosphoria sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient enriched water into the photic zone however the mean rate of deposition of marine ni a trace nutrient of algae and po43 a limiting nutrient indicate that primary productivity was probably high throughout the depositional history an alternative interpretation of the variable enrichments of er tm and yb relative to sm is that they may reflect temporally variable carbonate alkalinity of open ocean seawater in permian time a more strongly negative ce anomaly for all phosphatic units than the ce anomaly of modern pelletal phosphate is further indicative of an elevated o2 concentration in the permo carboniferous open ocean as proposed by others in contrast to the depletion of o2 in the bottom water of the phosphoria sea itself the oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated a shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction

sp coseismic signals observed on an electrodes array in an underground quarry electric self potentials sp and strains were measured on the surface of a pillar of the abandoned underground meriel limestone quarry france the time variations of strains and sp are interpreted in terms of crack instability the dynamic mapping technique shows that the most intensive sp variations corresponding to maximum stress variations estimated from strain data occur in the vicinity of active crack tips or crack intersections the location of these maxima changes with the stress distribution variations the synchronous stacking technique allows to detect significant pressure variations through electrodes installed in the fractured zone as well as through outside electrodes close to the medium discontinuities petrological boundaries and pillar edges

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

geochemical and paleoenvironmental record of the early to early late aptian major episodes of accelerated change evidence from sierra del rosario northeast mexico abstract the lower to lower upper aptian succession of northern mexico documents the drowning of the shallow water cupido cupidito carbonate platform system followed by deposition of the deep water sediments of the la pena formation using 13 c stratigraphy geochemical and mineralogical information coupled with previous microfacies paleontological and total organic carbon toc data from a stratigraphic section which includes such lithological change this study identifies distinctive episodes of accelerated global environmental change and determines the paleoenvironmental conditions conducive to the deposition of toc rich intervals within the cupidito unit the oceanic anoxic event 1a oae 1a is recorded near the base of the section and the intra furcata negative excursion in the topmost beds of the unit the upper part of the section within the la pena formation is correlatable with the noire level organic carbon rich intervals occur in the lower and middle part of the oae 1a upper part of the cupidito unit base of the la pena formation and in the noire level equivalent reducing conditions within the sediment and oxic dysoxic at the seafloor locally controlled persisted both before and during oae 1a interval in the cupidito lagoon oxygen depleted conditions dysoxic anoxic were more permanent and stronger during the deposition of the base of the la pena formation and the noire equivalent level it is proposed here that deposition of the lower middle part of the oae 1a and the base of the la pena formation was influenced by climate controlled increases in detrital and accompanying nutrient influx that supplied especially biolimiting nutrients fe p fostering marine productivity and toc burial upwelling of nutrient rich deeper waters and minor arrival of nutrients from runoff both account for the domination of radiolaria and organic carbon burial during the noire level equivalent record of the oae 1a time equivalent facies in the cupidito lagoonal sediments confirms the diachronism of the cupidito la pena flooding heterozoan carbonate production in the cupidito ramp was uninterrupted during and after oae 1a periodic arrival of detrital components and nutrients during warmer humid periods accelerated platform drowning which peaked during the diachronic deposition of the la pena formation

evidence for basin restriction during syn collisional basin formation in the silurian arisaig group nova scotia the arisaig basin in nova scotia canada provides a regional sedimentary record of an early silurian basin subsidence on the microcontinent of avalon the lower members of the arisaig group beechill cove and lower ross brook formations are likely to be deposited in a basin formed during syn to post collisional rifting subsidence driven by the collision of avalon and baltica the evolution of this constricted basin can be tracked by examining the geochemistry of the sedimentary rocks deposited within the basin here we report on the chemostratigraphy of the arisaig group a series of siliciclastics with a focus on understanding the redox chemistry during sedimentation the trace and major element geochemistry of this group provides insight into the oceanographic and geological processes that were influencing its depositional environment in particular concentrations of u v mo ni cd and pb indicate regional shifts in ocean redox state which serve as a proxy for changes in ocean circulation and regional tectonic activity we find evidence for anoxic conditions near the base of ross brook formation and attribute this anomaly in redox status to a significant change in physical mixing in the region trace element concentrations indicate that this anoxic event was associated with poor circulation rather than elevated productivity and organic matter burial based on these data we confirm that these sediments are deposited in a tectonically formed basin during a period of limited ocean circulation

the inorganic geochemistry of cretaceous black shales dsdp leg 41 in comparison to modern upwelling sediments from the gulf of california

organic matter apatite pyrite relationships in the botneheia formation middle triassic of eastern svalbard relevance to the formation of petroleum source rocks in the nw barents sea shelf abstract the middle triassic botneheia formation of eastern svalbard edgeoya and barentsoya comprises an organic carbon rich fine grained clastic succession 100 m thick that makes the best petroleum source rock horizon in the nw barents sea shelf the succession records a transgressive regressive interplay between the prodelta depositional system sourced in the southern barents sea shelf black shale facies of the lower and middle parts of the muen member and the open shelf phosphogenic system related to upwelling and nutrient supply from the panthalassic ocean phosphogenic black shale facies of the upper part of the muen member and the blanknuten member the relationships between organic matter authigenic apatite and pyrite in these facies allow to characterize the relative roles of redox conditions and oceanic productivity in the organic carbon preservation the accumulation of terrestrial and autochthonous marine organic matter in the black shale facies occurred under dominating oxic conditions and increasing upward productivity related to early transgressive phase and retrogradation of the prodelta system the phosphogenic black shale facies deposited in an oxygen minimum zone omz of the open shelf environment during the late transgressive to regressive phases under conditions of high biological productivity suppressed sedimentation rates and changing bottom redox the phosphatic black shales occurring in the lower and upper parts of the phosphogenic succession reveal depositional conditions indicative of the shallower part of omz including high input of autochthonous organic matter into sediment oxic to dysoxic episodically suboxic and or anoxic conditions intense phosphogenesis and recurrent reworking of the seabed the massive phosphatic mudstone occurring in the middle of the phosphogenic succession reflects the development of euxinia in the deeper part of omz during high stand of the sea high input of autochthonous organic matter in this environment was coupled with mineral starvation and intermittent phosphogenesis in mature sections in eastern svalbard the petroleum potential of the botneheia formation rises from moderate to good in the black shale facies and from good to very good in the phosphogenic black shale facies attaining maximum in the massive phosphatic mudstone

a modern vs permian black shale the hydrography primary productivity and water column chemistry of deposition the sediment currently accumulating in the cariaco basin on the continental shelf of venezuela has an elevated organic carbon content of approximately 5 is accumulating under o2 depleted bottom water conditions so42 reduction is composed dominantly of foraminiferal calcite diatomaceous silica clay and silt and is dark greenish gray in color upon lithification it will become a black shale recent studies have established the hydrography of the basin and the level of primary productivity and bottom water redox conditions these properties are used to model accumulation rates of cd cr cu mo ni v and zn on the seafloor the model rates agree closely with measured rates for the uppermost surface sediment the model is applied to the meade peak phosphatic shale member of the phosphoria formation a phosphate deposit of permian age in the northwest united states it too has all of the requisite properties of a black shale although the deposit is a world class phosphorite it is composed mostly of phosphatic mudstone and siltstone chert limestone and dolomite it has organic carbon concentrations of up to 15 is strongly enriched in several trace elements above a terrigenous contribution and is black the trace element accumulation defines a mean primary productivity in the photic zone of the phosphoria basin as moderate at 500 g m 2 year 1 organic carbon comparable to primary productivity in the cariaco basin the source of nutrient enriched water that was imported into the phosphoria basin upwelled into the photic zone and supported primary productivity was an o2 minimum zone of the open ocean the depth range over which the water was imported would have been between approximately 100 and 600 m the mean residence time of bottom water in the basin was approximately 4 years vs 100 years in the cariaco basin the bottom water was o2 depleted but it was denitrifying or no3 reducing rather than so42 reducing

tracing bottom water redox conditions during deposition of lower and upper jurassic organic rich sedimentary rocks in the lusitanian basin portugal insights from inorganic geochemistry abstract the lower jurassic agua de madeiros am fm and vale das fontes vf fm formations and the upper jurassic cabacos formation cab fm are considered the most important units with petroleum source rock potential in the lusitanian basin and the likely sources for its widespread hydrocarbon occurrences nonetheless the bottom water redox conditions during their deposition remain debatable to resolve this controversy we investigated whole rock inorganic geochemical data of the most significant organic rich levels of the am vf and cab fms cropping out at basin scale significant variations in toc ts and redox sensitive elements contents and their ratios are evident within and between the organic rich levels of the studied units a positive covariation between primary productivity proxies toc enrichment and paleo redox proxies for the lower jurassic units clearly suggest an interdependence between enhanced primary productivity organic matter accumulation and bottom water redox conditions for the am fm the paleo redox proxies indicate that the black shales deposition took place beneath bottom waters that ranged from suboxic to strongly euxinic conditions with a clear predominance of the latter a toc threshold of 6 7 wt clearly separates samples deposited under suboxic to anoxic conditions from those deposited under true euxinic conditions and is interpreted as the minimum amount of organic matter om accumulation within sediments required to sustain h2s production at rates that outpaced its consumption through precipitation of sulphides and or om sulphurization allowing the diffusion of h2s to the bottom waters for the vale das fontes fm the paleo redox proxies suggest a prevalence of suboxic to anoxic bottom waters despite all black shales displaying toc contents greater than the above threshold the less reducing conditions relative to the am fm euxinic black shales are attributed to i a larger proportion of continental om ii lower reactivity of the om reaching the sediment water interface decreasing oxygen consumption and iii higher availability of reactive iron increasing the buffer effect to h2s produced through om remineralization by sulphate reducing bacteria both units display mo ef vs u ef covariation patterns that deviate from the field of sediments deposited under unrestricted open marine conditions towards higher mo enrichment relative to that of u indicating an accelerated transport of aqueous mo to the sediments consistent with the operation of a metal oxyhydroxide particulate shuttle linked to mn and fe redox cycling within the water column in a weakly restricted basin the mo cot regression line slope indicates a moderate degree of bottom water mass restriction with mo aq concentration of 60 70 of the present day seawater value and bottom water renewal times of 10 20 years akin to the present day cariaco basin the redox conditions of the cab fm organic rich levels are dependent on the location of the depositional environment in the basin with deposition taking place beneath oxygenated bottom waters at cabo mondego and under suboxic conditions at vale de ventos and pedrogao the latter denoting a larger degree of oxygen depletion than the former in this context the overall potential for om preservation should increase from cabo mondego to vale de ventos and pedrogao

geochemical characteristics in the longmaxi formation early silurian of south china implications for organic matter accumulation abstract the organic rich early silurian sediments longmaxi formation on the yangtze platform are considered to be one of the main source rocks in south china in order to investigate the mechanism of organic accumulation multiple geochemical proxies including redox parameters s c and trace element ratios productivity indices p and ba contents and clastic influx indicator ti al ratios are presented here from the hehua section yichang hubei province the longmaxi sediments have high toc contents 3 00 10 85 avg 5 63 low pyrite sulfur contents 0 42 1 14 avg 0 59 high p 0 02 0 44 avg 0 12 and ba contents 576 65 2542 43 ppm avg 1592 17 ppm calculated s c th u ni co v cr and v v ni ratios are 0 05 0 24 avg 0 12 0 23 9 86 avg 2 30 2 65 46 24 avg 15 46 0 27 14 42 avg 3 75 and 0 36 0 96 avg 0 75 respectively s c and trace element ratios together with pyrite morphology suggest dysoxic anoxic conditions prevailed during deposition of the longmaxi intervals which was mainly caused by a worldwide marine transgression after the melting of gondwana glaciation productivity proxies indicate that the organic rich longmaxi sediments were deposited in moderate to high primary productivity water columns the consistent ti al ratios suggest a rather homogeneous nature for the detrital supply geochemical data provide a good constraint on the accumulation of organic matter and relevant oceanic environment anoxic conditions together with relatively high productivity were likely responsible for the accumulation of organic rich sediments during the longmaxi interval

palaeoecology and sedimentology of the dysaerobic bedford fauna late devonian ohio and kentucky usa abstract oxygen deficient biofacies models rely on lithologic and paleontologic attributes to identify distinctive biofacies interpreted to reflect levels of oxygenation in anaerobic dysaerobic and aerobic parts of a stratified water column this study of the bedford fauna from the bedford shale of ohio and kentucky and from adjacent black shale units reports faunal distributions different from those predicted by the accepted models this study suggests that although oxygenation was an important factor that determined the taxonomic makeup of the fauna bacterially mediated nutrient recycling and substrate characteristics were more important than oxygenation in determining faunal distribution in the dysaerobic zone

phosphate regeneration from sediments of the peru continental margin by dissolution of fish debris generally oxidative regeneration of phosphate from anoxic sediments is by microbially mediated sulfate reduction processes stoichiometric modelling of such reactions takes into consideration varying proportions of decomposable organically bound p to account for the ratios among nutrients in depth concentration profiles of near surface sediments new results of interstitial water composition from sediments underlying the water masses influenced by coastal upwelling of the eastern boundary current system off peru indicate that dissolution of phosphatic fish debris represents a mechanism for remineralization of phosphate comparable to or larger in magnitude than that by oxidative regeneration of organically bound p dissolved interstitial phosphate from fish debris is revealed by an excess amount of phosphate over that predicted from a simple stoichiometric oxidative regeneration model and by anomalously high dissolved interstitial fluoride concentrations phosphate flux estimates based on diffusion from the sediment suggest that this mechanism may generate up to 10 of the nutrient pool in the waters of the peru undercurrent partitioning of p among the two sources reveals further that fish debris phosphate is about four times more important than organically bound p in nutrient generation from sediments of the peru continental margin not only does this mechanism of regeneration affect the nutrient cycling but may also control widespread phosphorite formation in this area

molybdenum in the northeast pacific ocean1 the concentration of dissolved molybdenum has been determined in several profiles from the northeast pacific ocean the salinity normalized concentration is essentially constant in all open ocean samples 107 nm 1 2 5 nm the dissolved distribution is not significantly affected by biological cycling

organic carbon accumulation and preservation in surface sediments on the peru margin concentrations and characteristics of organic matter in surface sediments deposited under an intense oxygen minimum zone on the peru margin were studied in samples from deck deployed box cores and push cores acquired by submersible on two transects spanning depths of 75 to 1000 m at 12 and 13 5 s the source of organic matter to the seafloor in these areas is almost entirely marine material as confirmed by the narrow range of of organic carbon obtained in the present study 20 3 to 21 6 pdb and the lack of any relationship between pyrolysis hydrogen index and carbon isotope composition organic carbon contents are highest up to 16 on the slope at depths between 75 and 350 m in sediments deposited under intermediate water masses with low dissolved oxygen concentrations 5 mol kg even at these low concentrations of dissolved oxygen however the surface sediments that were recovered from these depths are dominantly unlaminated strong currents up to 30 cm s associated with the poleward flowing peru undercurrent were measured at depths between 160 and 300 m on both transects the seafloor in this range of water depths is characterized by bedforms stabilized by bacterial mats extensive authigenic mineral crusts and or thick organic flocs constant advection of dissolved oxygen although in low concentrations active resuspension of surficial organic matter activity of organisms and transport of fine grained sediment to and from more oxygenated zones all contribute to greater degradation and poorer initial preservation of organic matter than might be expected under oxygen deficient conditions dissolved oxygen concentrations ultimately may be the dominant affect on organic matter characteristics but reworking of fine grained sediment and organic matter by strong bottom currents and redeposition on the seafloor in areas of lower energy also exert important controls on organic carbon concentration and degree of oxidation in this region

the trace metal composition of suspended particles in the oceanic water column near bermuda trace metal partitioning between seawater and particles both suspended and sinking must be determined to understand and model oceanic trace metal scavenging processes in order to improve the oceanic particulate trace metal data base a newin situ pump was developed and deployed to collect suspended particles from 0 4000 m in the sargasso sea near bermuda these particles were analyzed for al fe mn co zn cu ni cd and pb major particulate carrier phases were estimated from ca opaline si and p cd is the only trace element of this group with a particulate maximum in near surface waters the other metals have low particulate concentrations mol l in near surface waters and increase with depth into the upper thermocline particulate al and fe are then uniform with depth below about 1000 m until increasing in the bottom nepheloid layer the remaining elements mn co zn cu ni and pb decrease from the mid thermocline values to lower and relatively uniform concentrations in deep waters the similarities among the vertical profiles for these metals suggest that authigenic mn oxides influence their uptake from the dissolved pool although an important or dominant role for other host phases specifically particulate organic matter is not ruled out by the data mean intermediate and deep water concentrations are al 3600 fe 1200 mn 146 co 1 5 zn 7 4 cu 15 ni 6 0 cd 0 06 and pb 2 1 pmol l these particulate al and mn values agree with previous measurements in this region but the other elements are lower by a factor of 3 fe co to 30 zn suggesting that earlier data were compromised by contamination the suspended metal data are used in a simple steady state two flux model to evaluate the role of suspended particles in determining the vertical flux of metals in the sargasso sea the model calculations indicate that removal of suspended particles in the deep 500 m water column contributes less than half of the total deep flux for all of the elements investigated except for cd this result implies that uptake of these metals onto particles in the deep central ocean is a minor factor in their oceanic mass balance if this finding is generally true for oligotrophic ocean environments whole ocean residence times for these elements must be governed largely by processes occurring either in near surface waters or at ocean margins

late paleozoic sedex deposits in south china formed in a carbonate platform at the northern margin of gondwana abstract sedex sulfide deposits hosted in black shale and carbonate are common in the south china block the dajiangping pyrite deposit is the largest of these deposits and is made up of stratiform orebodies hosted in black shales sandstone interlayered with stratiform orebodies contains detrital zircon grains with the youngest ages of 429 ma pyrite from the orebodies has a re os isochron age of 389 62 ma indicative of formation of the hosting strata and syngenetic pyrite ores in the mid late devonian the hosting strata is a transgression sequence in a passive margin and composed of carbonaceous limestone in the lower part and black shales in the upper part the ore hosting black shales have high toc total organic carbon mo as pb zn and cd indicating an anoxic euxinic deep basin origin the high redox proxies v v ni 0 6 and v cr 1 and the positive correlations of toc with mo and v in black shales are also consistent with an anoxic depositional environment the dajiangping deposit is located close to the ne trending wuchuan sihui fault which was active during the devonian the mid late devonian mineralization age and the anoxic euxinic deep basinal condition of this deposit thus imply that the formation of this deposit was causally linked to hydrothermal fluid exhalation in an anoxic fault bounded basin that developed in a carbonate platform of the south china block the regional distribution of many devonian stratiform carbonaceous sediment hosted sulfide deposits along the ne trending fault bounded basins in south china similar to the dajiangping deposit indicates that these deposits formed at a basin developed in the passive margin setting of the south china block during the devonian this environment was caused by the break up and northward migration of the south china block from gandwana

rare earth elements in foraminifera tests abstract the concentrations of nine rare earth elements ree la ce nd sm eu gd dy er and yb have been determined in mixed species assemblages of foraminifera tests taken from atlantic ocean sediment core tops reductive cleaning techniques have revealed that ree are present in three phases in foraminifera tests collected from sea floor sediments ree included in the foraminiferal calcite matrix termed lattice ree ree associated with an authigenic femn rich phase adsorbed onto the surface of the test following the death of the organism termed coating ree and ree associated with alumino silicate detritus termed detrital ree which commonly infills the test chambers after burial in the sediment the concentrations of ree in the nondetrital lattice plus coating and lattice phases have been measured in this study approximately 90 of the ree measured in the non detrital phase reside in the coating phase the remainder being present in the lattice phase these data have been used to investigate the relationship between the distribution of dissolved ree in the ocean and in the coating and lattice phases in addition to the ree the concentrations of mn fe cu al and po4 have been measured as an aid to characterisation of the various phases

rare earth elements in the phosphatic enriched sediment of the peru shelf abstract apatite enriched materials from the peru shelf have been analyzed for their major oxide and rare earth element ree concentrations the samples consist of 1 the fine fraction of sediment mostly clay material 2 phosphatic pellets and fish debris which are dispersed throughout the fine grained sediment 3 tabular shaped phosphatic crusts which occur within the uppermost few centimeters of sediment and 4 phosphatic nodules which occur on the seafloor the bulk ree concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction analysis of the fine grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale ree values the analysis of the fish debris suggested that the apatite fraction might have seawater values the seawater contribution of ree s is negligible in the nodules and crust in which the apatite occurs as a fine grained interstitial cement that is the concentration of ree s and the ree patterns are predominantly a function of the amount of enclosed fine grained sediment by contrast the ree pattern of the pelletal apatite suggests a seawater source and the absolute ree concentrations are relatively high the ree p 2 o 5 ratios of the apatite fraction of these samples thus vary from approximately zero in the case of the crust and nodules to as much as approximately 1 2 10 3 in the case of the pellets the range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the ree content of this authigenic fraction of the sediment pelletal glauconite was also recovered from one sediment core its ree concentrations closely resemble those of the fish debris

upper kellwasser carbon isotope excursion pre dates the f f boundary in the upper devonian lennard shelf carbonate system canning basin western australia abstract here we report four high resolution carbon isotope records in addition to trace element data for the frasnian famennian f f boundary interval in the lennard shelf carbonate system of the canning basin western australia this region lacks the characteristic black shale horizons associated with the global late devonian kellwasser extinction events yet still exhibits a trend in carbon isotope character similar to what has been reported from elsewhere in the world two positive 13c excursions with 3 4 amplitudes enrichments in select trace element ratios suggest that both excursions are related to periods of oxygen deprivation and perhaps increased biological productivity given the continuous and stratigraphically expanded nature of lennard shelf sections together with high density sampling constrained by both conodont biostratigraphy and magnetostratigraphy we observe that the upper kellwasser isotope excursion maximum 13c values and associated trace element enrichments occur distinctly lower than the f f boundary level these results have implications for the paleoenvironmental conditions leading up to the late devonian mass extinction in terms of ocean chemistry and circulation patterns this data set allows for a rare detailed look at the temporal relationship between the kellwasser events and the f f boundary and constrains the pattern of carbon isotope perturbations at the intra zonal scale

origins of metals and organic matter in the mecca quarry shale member and stratigraphically equivalent beds across the midwest samples of the middle pennsylvanian age mecca quarry shale member and stratigraphically equivalent beds from indiana illinois missouri and kansas have been analyzed for both inorganic and organic constituents trends for mo values reported by coveney and martin 1983 who found the highest tenors to be associated with the ancient shoreline in indiana have been confirmed regionally across the midwest similarly it has been found that cd v u se and sb are most concentrated near the shoreline whereas constituents such as ca and sr are richest offshore e g kansas organic matter analyses including pyrolysis gas chromatography show the eastern samples to be richest in total organic carbon and also in terrestrial organic matter unbuffered aqueous solutions containing powdered organic rich shales from indiana equilibrate to acid ph values ph 4 6 where mo is readily retained by organic matter laboratory experiments show the shales retain a capacity to fix mo from dilute solutions correlations between organic matter type and metal values such as those existing between mo and v and terrestrial organic matter in shale samples generally fit with the syngenetic model for metal fixation in near shore brackish waters proposed by coveney and martin 1983 however other evidence including the remnant activity of organic matter rich samples to fix metals suggests that nonsyngenetic agents such as basinal brines or meteoric fluids have probably augmented the metal contents of the deposits subsequent to sedimentation and diagenesis

a high resolution late quaternary upwelling record from the anoxic cariaco basin venezuela results are presented of a high resolution study of the planktonic foraminiferal faunas from two piston cores recovered from the cariaco basin in the southern caribbean sea the cariaco basin is a small anoxic marine basin on the northern continental margin of venezuela in an area today characterized by both seasonal trade wind induced upwelling and pronounced dry and wet seasons our data indicate that large changes in the intensity of upwelling and hence trade wind strength occurred in this region during the last glacial interglacial transition and throughout the holocene during the last glacial lowstand of sea level the cariaco basin was effectively isolated from the open caribbean along its northern margin by the then largely emergent tortuga bank oxic conditions existed in the deep cariaco basin at this time and surface productivity was low about 12 600 years ago the abrupt initiation of strong upwelling over the basin and the onset of permanent anoxia in the deep waters are coincident with the rapid rise of sea level that accompanied the peak interval of meltwater discharge from the laurentide ice sheet into the gulf of mexico strong upwelling between 12 600 and about 10 000 years ago may be related to intensified trade winds resulting in part from cooler sea surface temperatures in the caribbean and gulf of mexico after about 10 000 years ago upwelling intensity was reduced though highly variable a preliminary frequency domain analysis of the holocene portion of the cariaco basin time series suggests that solar forcing may explain a significant component of the century scale variability observed in the record of upwelling and trade wind strength

inorganic geochemistry of the type caradoc series sandbian to middle katian upper ordovician onny valley shropshire uk the geochemistry and petrology of the type section of the caradoc series in the onny valley indicate that it was deposited on a marginal basin continental shelf similar to the western side of the present sea of japan the lower beds form a transgressive regressive sequence in which the rocks become less mature upwards all the coarser sediments above the basal quartzites and conglomerates are greywackes in which the apparent muddy and ferrous matrix is due to the breakdown of unstable minerals and particles higher values of na 2 o and na k ratios are found in the coarser shallow water sandstones of the horderley sandstone formation and decrease markedly in the succeeding beds accompanied by an increase in k 2 o higher values of carbonate corrected and hence related other major and minor elements like sio 2 cao p 2 o 5 mno and most trace elements correlate with the transgressive systems and maximum flooding surfaces of the three sequences recognized where they are related to condensation at those horizons chemical indices of alteration cia suggest that the horderley sandstone formation underwent greater predepositional physical weathering than lower and higher beds which is compatible with the petrography and were deposited during a cool phase within overall warm sandbian katian times trace element ratios suggest an oxic to suboxic depositional environment

comment on redox cycling of rare earth elements in the suboxic zone of the black sea by c r german b p holliday and h elderfield

paleoproductivity in the southern peru chile current through the last 33 000 yr abstract based on a multiparameter approach including organic carbon biogenic opal carbonate and the species composition of planktic foraminifera this paper provides the first qualitative assessment of the history of paleoproductivity on glacial interglacial time scales in the southern peru chile current pcc off chile which belongs to the least studied parts of the world ocean during the last glacial maximum lgm highest relative paleoproductivity of the last 33 kyr indicated by high accumulation rates of organic carbon biogenic opal and carbonate has been found contrasted by lowest values during the early and middle holocene this shift from high to low productivity is accompanied by a major change in the species composition of planktic foraminifera from a dominance of neogloboquadrina pachyderma sin to the dominance of n pachyderma dex the temporal pattern of paleoproductivity off chile is very similar to the history of the continental paleoclimate in the region which is supposed to be driven by the position of the southern westerlies this observation points to a functional relationship between the position of the southern westerlies and the history of paleoproductivity off chile assuming that atmospheric and oceanographic circulation are closely linked a northward displacement of the antarctic circumpolar current during the lgm in line with the northward movement of the southern westerlies would bring the main nutrient source closer to our core sites resulting in increased productivity however based on the available data it is not clear if the higher productivity in the southern pcc during the lgm reflects generally higher productivity during this time or only a regional displacement of the main productivity centers

mineralogical composition and total organic carbon quantification using x ray fluorescence data from the upper cretaceous eagle ford group in southern texas six southern texas eagle ford cores were investigated to quantify mineralogical composition and total organic carbon toc machine learning of the x ray fluorescence xrf data set was conducted using neural network analysis to predict mineralogies for l1 l2 and l3 and toc for l1 l2 l3 iona 1 innes 1 and well x inees 1 and well x were used as blind tests to check the quality of the developed models the online neural designer software was used to perform the training process and develop models quantitative laboratory measured x ray diffraction xrd mineralogies and toc were used to conduct the training and develop high resolution semiquantitative models and the derived mineralogic and organic matter models were found to be promising the modeled mineralogy and toc represent continuous relative abundances which are far more significant than scattered individual xrd and toc point measurements the significance of this study is that it allows for the use of relatively inexpensive and nondestructive xrf analysis that requires minimal sample preparation to construct high resolution mineral abundances and toc content with modern advances in technology xrf can now be measured on drill cuttings in real time while drilling is occurring allowing operators to use the proposed method to construct semiquantitative mineralogical and toc models for evaluating placement of laterals in prospective intervals and designing completion techniques accordingly

paleoproductivity of the chang 7 unit in the ordos basin north china and its controlling factors abstract primary paleoproductivity provides basic organic matter for the formation of high quality hydrocarbon source rock a progressive method to quantitatively calculate paleoproductivity on the basis of total organic carbon toc has been proposed to evaluate the contribution of primary paleoproductivity to a hydrocarbon source rock with high organic matter abundance in this study pyrite contents organic maceral compositions and high resolution sedimentation rates srs were used to recover the amount of organic matter oxidation and to exclude the effect of terrestrial clastic input during the deposition of the chang 7 sediment multiple calculation methods were used to quantitatively reconstruct paleoproductivity and the results suggest that the ordos basin was a eutrophic lacustrine basin approximately 2 104 mg c cm 2 kyr 1 to 10 104 mg c cm 2 kyr 1 during the chang 7 stage compared with modern lake productivity the paleoclimatic analysis indicates that a warm humid paleoclimate was beneficial for increasing the weathering intensity which could have provided more nutrient inputs to the depositional environment with incoming terrestrial debris in addition the plate collision between the north china block and yangtze block generated moderate volcanic ash that spread to the study area and provided large amounts of essential nutrients for algae blooms moreover a brackish water condition promoted upward mixing of deep water which inhibited water mass stratification and then facilitated primary paleoproductivity in general the chang 7 high quality hydrocarbon source rock is a result of increased paleoproductivity resulting from suitable paleoclimate conditions brackish water masses and abundant essential nutrient inputs

iron limitation in the western interior seaway during the late cretaceous oae 3 and its role in phosphorus recycling and enhanced organic matter preservation the sedimentary record of the coniacian santonian oceanic anoxic event 3 oae 3 in the north american western interior seaway is characterized by a prolonged period of enhanced organic carbon oc burial this study investigates the role of fe in enhancing organic matter preservation and maintaining elevated primary productivity to sustain black shale deposition within the coniacian santonian aged niobrara formation in the usgs 1 portland core iron speciation results indicate the development of a reactive fe limitation coeval with reduced bioturbation and increased organic matter preservation suggesting that decreased sulfide buffering by reactive fe may have promoted enhanced organic matter preservation at the onset of oae 3 an fe limitation would also provide a feedback mechanism to sustain elevated primary productivity through enhanced phosphorus recycling additionally our results demonstrate inconsistencies between fe based and trace metal redox reconstructions iron indices from the portland core indicate a single stepwise change whereas the trace metal redox proxies indicate fluctuating redox conditions during and after oae 3 using fe speciation to reconstruct past redox conditions may be complicated by a number of factors including fe sequestration in diagenetic carbonate phases and efficient sedimentary pyrite formation in a system with limited fe supply and high levels of export production

geochemical investigation of the lower cambrian mineralised black shales of south china and the late devonian nick deposit canada abstract lower cambrian tommotian black shales of the niutitang formation south china host a thin accumulation 5 20 cm of ni mo platinum group elements pge au ni as zn cu v and rare earth elements ree of all known deposits the late devonian ni mo pge sulphide horizon in black shales of the nick deposit selwyn basin in canadian yukon presents the strongest similarity with the niutitang formation polymetallic layer in the present study samples of the mineralised layer and host shales in south china from two mine sites zunyi and sancha were investigated in order to further characterise the prevailing redox conditions and mechanisms involved in the metal concentration process at both sites additional comparison with the nick deposit mineralised layer was also undertaken bulk geochemical analysis including pge analysis were conducted on all samples along with m scale investigation of metal distributions and associations by x ray fluorescence xrf mapping and synchrotron xrf mapping the comparison of the two sites from south china highlights strong similarities in metal enrichment factors pge and ree distribution patterns are also highly similar and suggest a source from seawater strong variations in elemental distributions at m scale were observed at both sites most likely related to intense variations in redox conditions in the sediment the comparison with the nick deposit highlights a stronger enrichment in ni and zn in the nick deposit and a greater variety of minerals in the niutitang shales the pge and ree distributions of both the nick deposit and the niutitang shales however present highly similar patterns and support an origin from seawater the present study provides further insight into mineralisation style and processes in these mineralised black shales highlighting the importance of redox conditions and re emphasizing the role of organic matter in the formation of these mineralised layers

cambrian sphenothallus from guizhou province china early sessile predators abstract two species of sphenothallus cnidaria from cambrian rocks of eastern guizhou china are reported one species sphenothallus songlinensis n sp from the niutitang biota lower cambrian nangaoan stage represents the oldest reported example of the genus other specimens referred to sphenothallus taijiangensis are from the kaili formation lower cambrian duyuanian stage the new material adds to the record of sessile cnidarians an important group of predators from the early part of the cambrian occurrences of the genus in strata traditionally assigned to the lower cambrian show that sphenothallus was among the earliest animals to produce a biomineralized phosphatic skeleton

paleo environmental cyclicity in the early silurian yangtze sea south china tectonic or glacio eustatic control abstract the yangtze sea of the south china craton experienced strong environmental perturbations during the first 5 6 myr of the silurian the lower silurian lungmachi formation in the jiaoye 1 drillcore chongqing china records three sea level cycles stratigraphic sequences characterized by rapid deepening at the base of each cycle followed by slow shallowing each deepening event was associated with shifts toward higher marine productivity more intensely reducing bottomwater conditions reduced watermass restriction lower detrital input and enhanced siliciclastic weathering intensity we infer control by glacio eustasy in which deglacial sea level rises and concurrent climatic warming triggered the observed environmental changes shallowing was associated with renewed glaciation and characterized by the opposite set of conditions the results of this study thus provide evidence in support of continued continental glaciation during the early silurian i e following the termination of the major end ordovician hirnantian glaciation the study core also exhibits a long term shallowing trend through the entire lower silurian the origin of which may have been tectono epeirogenic uplift of the south china craton during the kwangsian orogeny

euxinia linked to the cambrian drumian carbon isotope excursion dice in australia geochemical and chemostratigraphic evidence abstract the cambrian drumian carbon isotope excursion dice event is a negative carbon isotope 13 c excursion it is associated with the first appearance datum fad of the agnostoid arthropod ptychagnostus atavus whose first appearance in the global boundary stratotype section and point gssp defines the base of the cambrian series 3 drumian stage although this isotopic event has been clearly identified in the great basin usa it has not been consistently reported in other areas of the world here we report a study integrating isotopic and geochemical data from middle cambrian series 3 sections from the northeastern georgina basin australia to investigate the occurrence of the dice event in australia and the paleoenvironmental conditions associated with this event the similarity between the isotopic excursions observed in the georgina basin 2 to 3 2 13 c excursion and that observed in the great basin 2 to 3 6 13 c excursion highlighted the presence of the dice in australia and emphasized the potential use of this event for refining global isotopic correlations the multi proxy correlation used in this study also showed a pulse of euxinia in association with the dice suggesting strongly euxinic conditions near the base of the drumian stage

geochemical relationships of late paleozoic carbon rich shales of the midcontinent usa a compendium of results advocating changeable geochemical conditions abstract previous studies have shown that pennsylvanian black shales of the midcontinent us possess a more complex geochemical history than was once thought vine and tourtelot econ geol 65 1970 253 and coveney and glascock appl geochem 4 1989 347 note that the widespread nature of metalliferous pennsylvanian black shales and the diverse geological environments across the midwestern us pose the likelihood that metals contained in the black shales are of complex origins detailed geochemical and statistical representations using characteristics of numerous black shale members have shown that water depth may not have been uniformly deep as previously inferred by numerous workers earlier suggestions that these black shales were associated exclusively with anoxic depositional conditions have been challenged by a more realistic theory of multifaceted fluctuating environmental conditions a wide range of major and trace element concentrations combined with widely varying characteristics and diverse types of organic matter indicate the presence of fluctuating geochemical settings the presumption is that numerous associated chemical reactions occurred syngenetically one geochemical index degree of pyritization dop suggests a dysaerobic to aerobic setting for many of the shales whereas some other geochemical proxies i e v v ni indicate punctuated episodes of bottom water anoxia schieber abstr programs geol soc am 33 6 2001 a102 notes that in some black shales pyrite enrichment due to intermittent organic reworking explains the high dop values once thought to equate with extreme euxinic depositional conditions it seems likely therefore that even during apparent euxinic periods as indicated by bulk geochemistry oxygen deprived events were apparently short lived the seemingly euxinic fingerprint as shown by geochemical characteristics may result through time averaging abstr programs geol soc am 33 6 2001 a102 of intermittent euxinic events providing a misleading indication of dominant euxinic conditions thus detailed microstratigraphic sampling is necessary to delineate short punctuated occurrences of intermittent sub oxic episodes the midcontinent pennsylvanian shales may reflect a complex array of bottom water oxygenation variations and water depth fluctuations in response to climatic and localized events hatch j r and leventhal j s 1992 relationship between inferred redox potential of the depositional environment and geochemistry of the upper pennsylvanian missourian stark shale member of the dennis limestone wabaunsee county kansas usa in meyers p a pratt l m nagy b eds geochemistry of metalliferous black shales chem geol 99 65 82 complicated by post depositional events appl geochem 4 1989 347 this research examines the previous exclusively anoxic origin for midcontinent pennsylvanian black shales from a geochemical perspective and offers an alternative supported by detailed statistical presentations with the hypothesis that events of anoxia were punctuated by short lived dysaerobic or even near oxic events

organic accumulation in lacustrine rift basin constraints from mineralogical and multiple geochemical proxies the lunpola basin in the central tibet is the highest petroliferous basin in the world the basin is a cenozoic lacustrine rift basin with widespread oil shale depositions which provide a valuable example for understanding the mechanisms of organic accumulation thirty five samples of oil shale and mudstone were collected from one of the organic rich oil shale intervals in the lunpola basin to discuss the controlling factors of organic enrichment in the investigated oil shale interval many redox proxies including v v ni ratios mo u covariations and pyrite framboid size distribution suggest anoxic conditions however the almost consistent variation patterns of toc p and mo contents indicate that organic matter accumulation was controlled mainly by primary productivity the relatively low sr ba average 0 74 and sr cu ratios average 4 75 suggest a warm humid climate during the oil shale deposition these conditions are suitable for living of organisms which would raise the initial productivity of lake and in turn could have led to the oxygen depleted conditions the detrital input together with fast sedimentary rate during the oil shale deposition would result in dilution of organic matter

an upwelling model for the phosphoria sea a permian ocean margin sea in the northwest united states the permian phosphoria formation a petroleum source rock and world class phosphate deposit was deposited in an epicratonic successor basin on the western margin of north america we calculate the seawater circulation in the basin during deposition of the lower ore zone in the meade peak member from the accumulation rates of carbonate fluorapatite and trace elements the model gives the exchange rate of water between the phosphoria sea and the open ocean to the west in terms of an upwelling rate 84 m yr 1 and residence time 4 2 yr of seawater in the basin these hydrographic properties supported a mean rate of primary productivity of 0 87 g m 2 d 1 of carbon in the uppermost few tens of meters of the water column the photic zone and denitrifying redox conditions in the bottom water below approximately 150 m depth high rain rates onto the sea floor of the organic matter that hosted the phosphate and several trace elements contributed to the accumulation of phosphorite chert and black shales and mudstones evaporation in the goose egg basin to the east of the phosphoria basin ensured the import of surface seawater from the phosphoria sea budgets of water salt phosphate and oxygen plus the minor accumulation of the biomarker gammacerane show that exchange of water between the two basins was limited possibly by the shallow carbonate platform that separated the two basins

early diagenesis of organic matter in peru continental margin sediments phosphorite precipitation abstract pore water chemistry total dissolved co 2 nh 4 no 3 no 2 po 4 si oh 4 ca mg fe mn so 4 h 2 s and f and titration alkalinity solid phase chemistry c org p org c tot n tot f si opal and s ii and sediment characteristics porosity dry bulk density and formation factors were determined on a centimeter scale spacing in the upper 20 40 cm of sediments under intense upwelling areas on the peru continental shelf these data demonstrate that carbonate fluorapatite cfa is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content up to 20 c org very high porosity 0 96 ml cm 3 and very low dry bulk density 3 dissolved phosphate concentrations at the sediment water interface range from 20 to 100 m orders of magnitude higher than bottom water concentrations and much higher than predicted from regeneration of organic matter the mechanism of this interfacial phosphate release is unclear but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments fluoride is incorporated into cfa by diffusion from the overlying seawater and carbonate ions are provided from pore water alkalinity magnesium concentrations in this reaction zone are not significantly different from those of seawater suggesting that magnesium depletion is not a necessary prerequisite for cfa precipitation the environment of precipitation is interface linked rather than driven by organic diagenesis of phosphorus deeper in the sediment most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region but almost all show the precipitation signature near the interface this interface linked early diagenetic porewater environment for the precipitation of cfa explains many of the geochemical characteristics of phosphorites and provides a testable model to compare the modern phosphogenic analog with ancient phosphorite deposits two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites