sedimentary pyrite formation an update sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time the amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter dissolved sulfate and reactive detrital iron minerals organic matter appears to be the major control on pyrite formation in normal non euxinic terrigenous marine sediments where dissolved sulfate and iron minerals are abundant by contrast pyrite formation in non marine freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic rich fresh water shales from marine shales under marine euxinic conditions sufficient h2s is produced that the dominant control on pyrite formation is the availability of reactive iron minerals calculations based on a sulfur isotope model indicate that over phanerozoic time the worldwide average organic carbon to pyrite sulfur ratio of sedimentary rocks has varied considerably high cs ratios during permo carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time low cs ratios compared to today during the early paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean the latter could have been due to lower oceanic oxygen levels and or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time

organic carbon burial rate and the molybdenum proxy theoretical framework and application to cenomanian turonian oceanic anoxic event 2 1 in this study the controls on organic carbon burial and molybdenum accumulation in ancient strata are investigated through an integration of biogeochemical modeling and data analysis critical aspects of the study are employment of a biogeochemical model for organic matter degradation to explore the controls on pore water sulfide generation and authigenic molybdenum accumulation and use of accumulation rate data for mo oc caco3 fe and ti to reconstruct organic matter remineralization processes the model results form a conceptual framework for the interpretation of primary production estimates and geochemical burial fluxes calculated on the basis of a high resolution orbital timescale for the cenomanian turonian c t oceanic anoxic event 2 interval in the western interior basin the results of this study suggest that the strong correlation between source rock development and intervals of transgression in the geologic record such as the c t could reflect a confluence of biogeochemical processes within sediments that obviates the need for large magnitude changes in primary production levels or oceanographic conditions such as prolonged periods of stable water column stratification

a study on the regulation of the concentrations of some trace metals rb sr zn pb cu v cr ni mn and mo in saanich inlet sediments british columbia canada abstract bulk metal concentrations were measured in the sediments of saanich inlet in an attempt to establish the occurrence of trace metal enrichment in the anoxic central basin ba ni v cr zn pb cu and mo were found to be enriched in the anoxic ooze over the possible contributions from lithogenic sources spatial and seasonal variations in the chemical composition of the settling particulates collected with interceptor traps gave further indications of the mode of incorporation of these metals biogenic ba and cr appeared to be associated with opaline silica although alternative explanations are also possible particularly for ba zinc seemed to be added to the sediment essentially in association with planktonic materials while cu required an additional source directly linked to the anoxic environment similarly ni v and mo were added to the anoxic sediments by reactions occurring at the sediment water interface in the nearshore environment studied here these metals particularly ni and mo were not associated to any significant extent with planktonic materials of all the elements analyzed mo showed the largest enrichment in the anoxic sediments of saanich inlet

oxygen minimum zone controlled mn redistribution in arabian sea sediments during the late quaternary 1 accumulation of labile mn is related to bottom water oxygen concentrations in this study we investigate the relation between oxygen minimum zone omz intensity and mn burial in arabian sea during the late quaternary mn carbonates in sediments of the deep arabian basin indicate that this part of the basin remained oxygenated for at least the last 185 kyr sequential leaching showed manganese carbonate enrichments with concentrations up to 3750 ppm in deep basin sediments these mn spikes must have formed diagenetically during periods of increased mn oxide fluxes to the deep basin associated with vertical extension of the omz this extension caused remobilization of mn oxides from a previously oxic slope resulting in increased mn accumulation in the deep basin mn relocation is evidenced by synchronous mn depletions in organic rich intervals in slope sediments mn records from the deep basin can thus be used as a qualitative proxy to reconstruct intermediate water oxygenation

early diagenesis in differing depositional environments the response of transition metals in pore water the cycling of fe mn ni co cu cr v and mo during early diagenesis was investigated in sediments from five different depositional environments in the california borderland dissolved o2 no3 no2 and so4 were also measured at each site to establish the position of redox boundaries pertinent to this study sites were chosen to allow the comparison of several parameters of potential importance to the cycling of these metals bottom water o2 concentration sediment redox conditions cycling of metal oxide carrier phases and the relative contribution of biogenic and terrigenous material to the detrital metal flux at 10 m oxygen and above the sequence of terminal electron acceptor utilization was typical of pelagic sediments differing only in scale under these conditions the recycling of mn oxides resulted in an enriched layer near the interface at bottom water 02 concentrations 5 m mn oxides are not recycled under these conditions fe oxides and so42 are important oxidants the depth of the zone of manganese oxidation with respect to the interface affects the efficiency of metal scavenging by manganese oxides trapping and recycling of ni and co with mn oxides results in remobilization from reducing sediments and enrichment in oxic sediments scavenging of these metals is favored by a deep oxic zone in the sediments in contrast cr v and mo appear to be transported to the sediments as reduced species and are released from the sediments by oxidation the source of the reduced species is assumed to be biogenic material the accumulation of these metals is favored by reducing conditions in the sediments cu is enriched in the sediments by transport with detrital biogenic material followed by adsorption onto sediment solids cu is released at the interface and rapidly removed onto the solids at all sites except the one pelagic site at the base of the slope the magnitude of cu released in the slowly accumulating pelagic sediment exceeds the cu binding capacity of the solids resulting in pore water cu concentrations in excess of 100 nm in general metal cycling associated with the early diagenesis of sediments was observed to decouple transport processes from burial processes for the transition metals measured in this study

multiple monsoon controlled breakdown of oxygen minimum conditions during the past 30 000 years documented in laminated sediments off pakistan abstract late holocene laminated sediments from a core transect centred in the oxygen minimum zone omz impinging at the continental slope off pakistan indicate stable oxygen minimum conditions for the past 7000 calendar years high sw monsoon controlled biological productivity and enhanced organic matter preservation during this period is reflected in high contents of total organic carbon toc and redox sensitive elements ni v as well as by a low diversity high abundance benthic foraminiferal buliminacea association and high abundance of the planktonic species globigerina bulloides indicative of upwelling conditions surface water productivity was strongest during sw monsoon maxima stable omz conditions reflected by laminated sediments were found also during warm interstadial events preboreal bolling allerod and dansgaard oeschger events as well as during peak glacial times 17 22 5 ka all ages in calendar years sediment mass accumulation rates were at a maximum during the preboreal and younger dryas periods due to strong riverine input and mobilisation of fine grained sediment coinciding with rapid deglacial sea level rise whereas eolian input generally decreased from glacial to interglacial times in contrast the occurrence of bioturbated intervals from 7 to 10 5 ka early holocene in the younger dryas 11 7 13 ka from 15 to 17 ka heinrich event 1 and from 22 5 to 25 ka heinrich event 2 suggests completely different conditions of oxygen rich bottom waters extremely low mass and organic carbon accumulation rates a high diversity benthic fauna all indicating lowered surface water productivity during these intervals the omz was very poorly developed or absent and a sharp fall of the aragonite compensation depth favoured the preservation of pteropods the abundance of lithogenic proxies suggests aridity and wind transport by northwesterly or northeasterly winds during these periods coinciding with the north atlantic heinrich events and dust peaks in the tibetan loess records the correlation of the monsoon driven omz variability in the arabian sea with the rapid climatic fluctuations in the high northern latitudes suggests a close coupling between the climates of the high and low latitudes at a global scale

late quaternary protoperidinium cysts as indicators of paleoproductivity in the northern arabian sea the reliability of organic walled cysts of the heterotrophic dinoflagellate protoperidinium as paleoproductivity indicators and the influence of bottom water oxygenation on cyst preservation is assessed by using arabian sea records of the past 125 kyr as a natural laboratory multidisciplinary geochemical micropaleontological and palynological datasets are integrated to analyze the relationship between protoperidinium cyst concentrations and other paleoproductivity proxies differential preservation potential is quantified in order to establish threshold oxidative degradation values for a possible application of quantitative protoperidinium cyst records in paleoenvironmental reconstructions results indicate that variations in protoperidinium cyst concentration closely correspond to other marine productivity and or upwelling proxies although oxygenation will lead to significant cyst degradation and thus decreased concentrations down core patterns in protoperidinium cyst concentration still primarily reflect changes in sea surface productivity in view of differential preservation among dinoflagellate cysts down core variations in relative abundance of protoperidinium should be treated with caution

minor elements in quaternary sediment from the sea of japan a record of surface water productivity and intermediate water redox conditions sediment of quaternary age from oki ridge 903 m depth in the sea of japan 3500 m deep records six episodes of high accumulation rates of cd cr cu mo ni u v and zn the high rates correspond to periods of sulfate reduction in the water column at the intermediate depth of oki ridge the intervening low values correspond to periods of denitrification and oxygen respiration the maxima have a period of 41 k y the youngest having an age of 1 10 ma the 41 k y cycle is similar to the cycle of 18 o values of open ocean plankton of the same age the similarity between the cycles of minor element accumulation in sea of japan sediment and 18 o values of atlantic ocean foraminifera indicates that redox changes in the water column of the sea of japan during the quaternary forced by major shifts in water column advection and minor shifts in photic zone productivity reflect global events

molybdenum accumulation in cariaco basin sediment over the past 24 k y a record of water column anoxia and climate molybdenum mo concentrations in a sediment core from the cariaco basin on the venezuelan continental shelf can be partitioned between a marine fraction and a terrigenous fraction the accumulation rate of the marine fraction of mo increased abruptly 15 000 calendar years ago 15 ka from 2 yr 1 to 4 g cm 2 yr 1 and then decreased abruptly at 9 ka the accumulation rate remained high throughout this 6 k y period but exhibited maxima at 15 14 and 12 5 ka corresponding in time to meltwater pulse ia into the gulf of mexico and the onset of the younger dryas cold event respectively the marine fraction of mo is interpreted in terms of redox conditions of bottom water as dictated by both the flux of settling organic matter and bottom water residence time correspondence between geochemical extremes in this core with changes in sea level and global climate demonstrates the high degree to which this ocean margin basin has responded to the paleoceanographic regime throughout the past 24 k y

temporal variability in the northern arabian sea oxygen minimum zone omz during the last 225 000 years the northern arabian sea is one of the few regions in the open ocean where thermocline water is severely depleted in oxygen the intensity of this oxygen minimum zone omz has been reconstructed over the past 225 000 years using proxies for surface water productivity water column denitrification winter mixing and the aragonite compensation depth acd changes in omz intensity occurred on orbital and suborbital timescales lowest o2 levels correlate with productivity maxima and shallow winter mixing precession related productivity maxima lag early summer insolation maxima by 6 kyr which we attribute to a prolonged summer monsoon season related to higher insolation at the end of the summer periods with a weakened or even non existent omz are characterized by low productivity conditions and deep winter mixing attributed to strong and cold winter monsoonal winds the timing of deep winter mixing events corresponds with that of periods of climatic cooling in the north atlantic region

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

manganese and iron in indian ocean waters abstract the first vertical profiles of dissolved mn and fe for the nw indian ocean are reported the area is characterized by seasonal upwelling and a broad oxygen minimum zone in intermediate waters the dissolved fe profile exhibits a maximum 5 1 nm in the oxygen minimum zone with low values both in surface waters 0 3 nm and deep waters around 1 nm mn concentrations in the surface waters are elevated 2 0 4 3 nm and decrease rapidly in an offshore direction below the first 25 m concentrations decrease dramatically 0 5 1 3 nm indicating removal by oxidation and particle scavenging further down various mn maxima are observed which can be related to hydrographic features sigma 1 1 intermediate water originating from the red sea lost its dissolved o2 while flowing northward along the omani coast and exhibits a strong mn maximum 4 6 6 5 nm coincident with the deep o2 minimum 2 2 at the two inshore stations in the gulf of oman this is overlain by relatively modest mn maxima 2 7 nm related to arabian gulf overflow water 3 3 finally the strong mn maxima 4 4 5 6 nm in the oxygen minimum zone at the two offshore stations are related to yet another watermass below these various maxima concentrations decrease gradually to values as low as 90 pm at 2000 meters depth towards the seafloor concentrations increase again leading to a modest bottom water maximum 0 7 1 5 nm the overall vertical distributions of mn and fe are strikingly similar also in actual concentrations to those previously reported for the eastern equatorial pacific an area also characterized by an extensive o2 minimum zone

redox sensitive element uptake in north east atlantic ocean sediments benthic boundary layer experiment sites regularly increasing radiocarbon age depth profiles and near constant sediment composition with depth have demonstrated that sediment accumulation has been relatively constant during the late holocene at two north east atlantic sites on rockall bank and feni drift uk benthic boundary layer experiment sites in such a quasi steady state situation the geochemical responses to early diagenesis of the redox sensitive elements cd mn mo re se and u are readily discerned through changes in element concentrations with depth collectively a colour change in the sediments surficial mnox enriched layers and 210pbexcess profiles allow an estimate of the mean position of the oxic post oxic boundary in the sediments at both sites this boundary is situated deeper than the 210pbexcess surface mixed layer but shallower than the 14c surface mixed layer which represent mixing on 102 and 103 year time scales respectively this implies that the well defined surface mnox enrichment and its associated 226ra and mo fractions must have been efficiently recycled first by downwards mixing into anoxic conditions and then by subsequent reduction and diffusive migration back up into oxic conditions this occurs in 40 years at the feni drift site and in 103 years at the rockall bank site authigenic enrichments of se cd and u are evident immediately below the oxic post oxic boundary although re enrichment does not occur until a few centimetres deeper the long term fluxes of authigenic se cd u and re uptake are evaluated with steady state assumptions while diffusion from bottom waters can supply sufficient se u and re an additional source likely corg is required for cd

comparative behavior of authigenic re u and mo during reoxidation and subsequent long term burial in marine sediments the trace element re is enriched in mildly reducing suboxic sediments close to or slightly later in the redox sequence than u and before reduction of mo in more reducing sulfidic sediments this work investigates the behavior of authigenic re during oxidation and long term burial in the sediments of several turbidites from the madeira abyssal plain exposure to bottom water o2 clearly remobilizes authigenic re as found in previous work but reimmobilization occurs in reducing sediments below the oxidation front over a depth range of 0 5 3 m the large spread of the re burndown peak must be kinetically controlled perhaps influenced by the corg content once reimmobilized however the authigenic re signal remains immobile for at least 3 4 myr authigenic u in contrast consistently forms peaks 0 5 m broad whereas authigenic mo is lost on oxidation and does not appear to be refixed unless authigenic pyrite is formed these results imply that any paleoenvironmental significance of authigenic re will be compromised in low sedimentation rate environments 10 cm kyr where there is significant exposure of authigenic re to bottom water o2 however authigenic re records from rapidly accumulating continental margin sediments with much less exposure to bottom water o2 still offer considerable potential as high fidelity recorders of past reducing conditions

geochemical characteristics of chilean upwelling sediments at 36 s abstract we examined the cycling of c s fe and the trace elements te ag cd mo mn re and se in chilean upwelling sediments from water depths of 127 2744 m at 36 s the sediments are clay rich with moderate total organic carbon toc and low biogenic caco3 contents for the shallow site within oxygen minimum zone omz which shows some thioploca biomass highest observed toc contents correspond to highest productivity induced toc flux and or enhanced preservation under o2 deficient conditions pyrite formation may be restricted by the concurrent presence of elemental s in thioploca and or the availability of reactive iron in the other sediments 370 m water depth pyrite formation is strongly restricted due to the low availability of metabolizable toc for sulfate reduction calculations of the degree of bacterially mediated remineralization suggest that more nitrogen than toc was remineralized by sulfate reduction than expected from redfield c n relationship manganese is significantly depleted due to reductive dissolution of mn hydr oxides within all sediments mo is only significantly enriched vs the lithogenic background in the shallow core implying anoxic conditions contents of re and mo as well as re mo ratios indicate suboxic conditions for the other cores cd and re contents decrease with increasing water depth reflecting decreasing reducing conditions in contrast authigenic ag contents increase with water depth suggesting enrichment controlled by seawater availability and or opaline input and not redox conditions elevated se contents in all cores may be either due to bio detrital input or diffusion from seawater accumulation rates of toc ts and te off chile are in the same order as those from the gulf of california and lower than those off peru distinct seasonality in upwelling and dilution of chilean sediments with terrigenous material lead to rather low metabolizable toc contents and lower te trapping capacity

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

inorganic geochemical indicators of glacial interglacial changes in productivity and anoxia on the california continental margin abstract evidence from sediments in cores collected from within the present oxygen minimum zone omz 600 1200 m on the central and northern california margins record several episodes during the last interstadial ois 3 ca 60 24 ka of deposition of laminated sediments containing elevated concentrations of several trace elements indicative of anoxic conditions e g mo ni zn and cu the presence of abundant well preserved organic matter as well as lack of bioturbation and the presence of elevated concentrations of mo and other trace elements all support the theory that the omz in the northeastern pacific ocean was more intense possibly anoxic at several times during the late pleistocene sediments of all ages in cores from the southern california margin contain elevated concentrations of mo suggesting that this area has always had higher rates of sulfate reduction than either the central or northern california areas most of the ba in sediments in all cores collected on the upper continental slope 200 2700 m off california and southern oregon is derived from detrital clastic material and this source did not change much in time however the amount of biogenic ba did vary with time and these variations closely follow the temporal variations in organic c corg mass accumulation rate using ba and corg mass accumulation rates as proxy variables for productivity all cores show that organic productivity under the california current upwelling system was highest during ois 3 and the holocene and lowest during the last glacial interval lgi ca 24 10 ka all paleoproductivity proxy variables indicate that the southern california area has always experienced higher productivity than other areas under the california current at least over the last 50 ky

geochemical and isotopic evidence for post glacial palaeoceanographic changes in saanich inlet british columbia abstract coring at site odp 1033b in saanich inlet recovered 59 4 m of mainly laminated olive grey diatom ooze and an underlying 55 15 m of massive grey to olive grey silty clay based on ams radiocarbon dating the boundary between the two units is between 11 000 and 13 800 calibrated years bp and represents the holocene pleistocene boundary the lower unit represents glaciomarine deposition whereas deposition of the upper unit began when the modern semi restricted physiography of the fjord was established following glacial rebound and highly productive marine conditions were established the glaciomarine clay is almost entirely terrigenous whereas the diatom ooze contains 2 3 wt organic c and 20 40 wt biogenous silica caco 3 contributions are minor but there are several peaks in carbonate abundance in the upper unit the isotopic composition of organic c and total n suggests that organic matter in the glaciomarine clay is dominantly terrestrial 13 c organic 15 n total ca 3 and in the diatom oozes it is mainly marine 13 c organic 22 and 15 n total ca 10 the heavy 15 n total values probably record a contribution of isotopically heavy nitrate to the surface waters of the inlet that is transported to british columbia bc coastal waters from the eastern tropical pacific by the california undercurrent major and minor elemental data suggest that the composition of the terrigenous material and its grain size has changed over the last 15 kyr and there are marked enrichments in several redox sensitive elements in the diatom oozes thus cu mn mo ni pb v and zn have higher concentrations in the upper unit br and i are also enriched because of their association with organic matter mn is enriched in the anoxic diatom oozes due to the presence of manganoan carbonate mn peaks generally corresponding with carbonate peaks formed in the sediment when deep water renewal caused precipitation of mn oxyhydroxides which dissolved in the anoxic sediment and was precipitated as a diagenetic phase the remaining metals are enriched because of their removal to the sediment as sulphides cu mo ni pb and zn or as particle reactive reduced species v cr enrichment is obscured by the presence of fe rich chlorite the lag in the enrichment of mo with respect to organic c in the sediments indicates that anoxia developed some time after marine production increased following the semi isolation of the fjord

geochemistry of recent toc rich sediments from the gulf of california and the black sea major and minor elements incl ag as ba cd co cr cu mn mo ni pb sr v zn have been determined in recent sediments from the gulf of california upwelling area and black sea sapropels in order to reinterpret their chemical composition in view of reliable seawater and plankton data the chemistry of the gulf of california sediments reflects regeneration processes which occur in the water column i e only a small fraction 10 of elements like cd which in seawater are coupled to the labile nutrients c n p is buried in the sedimentary column in contrast elements like the more resistant nutrients si undergo a deeper regeneration cycle ba several trace metals which are present in comparatively higher concentrations in seawater as mo u v and at the same time are reactive under reducing conditions and or are able to form stable sulfides are fixed in the sediments during early diagenesis the early diagenetic behavior of ba is closely related to bacterial sulfate reduction the formation of barite concretions is discussed anoxic conditions in the water column act as ideal traps for a number of redox sensitive and or stable sulfide forming elements a simple trace metal balance calculation shows that the chemical composition of black sea sapropels is controlled by fluvial and mediterranean seawater element input and the accumulation rate of terrigenous detrital material

instability of bottom water redox conditions during accumulation of quaternary sediment in the japan sea the concentrations of cd cr cu mo ni sb u v and zn were measured in early quaternary sediment 1 32 to 1 08 ma from the oki ridge in the japan sea the elements were partitioned between a detrital fraction composed of terrigenous and volcaniclastic aluminosilicate debris and a marine fraction composed of biogenic and hydrogenous debris derived from seawater the most important factors controlling minor element accumulation rates in the marine fraction were 1 primary productivity in the photic zone which largely controlled the flux of particulate organic matter bound minor elements settling through the water column and onto the seafloor and 2 bottom water redox which determined the suite of elements that accumulated directly from seawater this marine fraction of minor elements on oki ridge recorded six periods of high minor element abundance assuming a constant bulk sediment accumulation rate each period lasted roughly 5 000 to 10 000 years with a 41 000 year cycle accumulation rates of individual elements such as cd mo and u suggest sulfate reducing conditions were established in the bottom water during the 10 000 year periods accumulation rates of cr and v during the intervening periods are indicative of less reducing denitrifying conditions interelement ratios for example cu mo v cr and sb mo further reflect bottom water instability such that bottom water redox actually varied from sulfate reducing to denitrifying during the periods of highest minor element accumulation rates it varied from denitrifying to oxidizing during the intervening periods sediment lithology supports these interpretations of the minor element distributions the sediment is finely laminated for several of the periods represented by cd mo and u maxima and weakly laminated to bioturbated for the intervening periods the geochemistry of this sediment demonstrates the unambiguous signal of mo principally but of several other minor elements as well in recording sulfate reducing conditions in bottom water the forcing function that altered their accumulation that is that altered primary productivity and bottom water redox conditions is problematic currently held opinion suggests that o2 depletion was most strongly developed during glacial advances low sea level during such times is interpreted to have enhanced primary productivity and restricted bottom water advection

late pleistocene variability of the carbon isotopic composition of organic matter in the eastern mediterranean monitor of changes in carbon sources and atmospheric co2 concentrations the organic carbon isotopic record of the sapropels s1 and s3 s10 and intercalated marl oozes has been determined in a 12 m piston core from the eastern mediterranean the 13corganic values are systematically lighter mean 21 0 0 82 in all sapropels and heavier mean 18 8 1 07 in the marl oozes these differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the mediterranean there is no relationship between the corganic n ratios and the isotopic values and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter temperature effects on isotope fractionation are also discounted because the change in 13corganic values between glacial and interglacial horizons is in the opposite sense diagenesis which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances is unlikely to have caused the observed differences because this mechanism would cause an enrichment in 12c implying that all values were even heavier originally and there is no secular trend in the 13corganic record the observed differences in 13corganic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved co2 first freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the mediterranean to become lighter because of the 13c deficiency in fresh waters hence photosynthesis would have produced isotopically lighter organic material second changes in atmospheric pco2 between glacial and interglacial periods as shown by the vostok ice core caused marked changes in the concentration of free dissolved co2 in the mixed layer lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton whereas levels were less limiting during the interglacials concentrations of dissolved co2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated co2 to the mixed layer by upwelling and this could have further lightened the 13corganic values in the sapropels themselves carbon isotope records may provide an alternative method for estimating atmospheric pco2 levels over longer time periods than can be obtained from ice cores

rhenium in the black sea comparison with molybdenum and uranium rhenium concentrations were measured in the black sea to determine the behavior of this redox sensitive element in an anoxic basin under reducing conditions re is removed from solution leading to its depletion from black sea deep waters compared with uranium water column re and mo profiles show evidence of removal from mid depths suggesting that these elements are scavenged either in the water column or slope sediments to a greater degree than u black sea surface waters are enriched in re reflecting re in rivers draining into the northern black sea that are enhanced up to 80 fold over other large world rivers this enrichment is most likely anthropogenic and may be due to coal burning in the region a simple two box model is used to demonstrate that re concentrations in the black sea are not in steady state with respect to current riverine inputs and authigenic fluxes riverine inputs of u and mo are not as significant perhaps reflecting the fractionation of re from the other elements during a high temperature combustion process re2o7 is volatile above 270 c

sedimentary trace element records over the last 200 kyr from within and below the northern arabian sea oxygen minimum zone two piston cores pcs containing two full glacial cycles were retrieved at murray ridge one core pc463 contains sediment deposited at 920 mbsl within the other pc464 has sediment deposited at 1470 mbsl below the current oxygen minimum zone omz o2 2 m variations in the organic carbon oc content correlate well between the two cores high oc contents correspond with periods of high insolation and are accompanied by a stable and intensive omz the lithogenic fractions are similar and have a rather constant composition the v mn co cu se zn and sb contents in these fractions are in fair agreement with the values in standard shales ss the nicontent of the lithogenic fraction ishigherthanin ssdue to its high content in the regional eolian input andthe mo re andu contents are higher as a result ofsyngenetic and or diagenetic overprints in both cores mn and cohavea negative the other elements a positive correlation with oc four processes contributing to sedimentary enrichment in trace elements can be envisaged

a 225 kyr record of dust supply paleoproductivity and the oxygen minimum zone from the murray ridge northern arabian sea abstract analysis of a 15 m long sediment core recovered from the murray ridge northern arabian sea reveals a 225 000 year record of climate induced variations in surface water productivity mid water ventilation and dust input in the northern arabian sea productivity and dust input records closely resemble those from the owen ridge and oman margin also the phase lag of 10 kyr between maximum productivity and precession minimum is in phase with the summer monsoon upwelling record from the owen ridge and the oman margin this implies that the productivity variations in the northern arabian sea during the last 225 kyr are primarily controlled by changes in the indian ocean summer monsoon the winter monsoon obviously played a minor role in the productivity history of the northern arabian sea another result from this study is that the mg al record from the murray ridge nicely documents the post glacial flooding of the persian gulf which is the main glacial source for dolomite dust in this region finally it is concluded that the intensity of the omz co varies with surface water productivity being weak during periods of reduced summer monsoon especially during glacial periods

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

oxygenation history of bottom waters in the cariaco basin venezuela over the past 578 000 years results from redox sensitive metals mo v mn and fe we present results from analyses of the redox sensitive metals mo v mn and fe in sediment recovered from the cariaco basin ocean drilling program leg 165 site 1002 results are interpreted in the context of previous studies of 15n export production percent total organic carbon eolian input and hemipelagic deposition in the basin variations in redox metal ratios over the past 578 000 years were compared to variations in 18o at milankovitch frequencies and show a strong relationship between glacial interglacial cycles in sea level governed by the shallow sills encircling cariaco basin and bottom water oxygen content during 100 kyr and 41 kyr cyclicity enrichments of mo and v occur during highly productive interglacials indicating bottom water anoxia during glacials sediments are less depleted or enriched in mn and fe relative to the interglacials reflecting oxic conditions during 23 kyr and 19 kyr cyclicity however these redox metal patterns are not observed indicating that the cariaco basin responds differently to the higher frequency climate changes

the behavior of redox sensitive metals across a laminated massive laminated transition in saanich inlet british columbia abstract holocene laminated sediments in saanich inlet british columbia are interrupted by frequent non laminated massive layers these layers may be debris flows released by earthquakes or bioturbated sediments deposited during periods of relatively high bottom water oxygen concentration and or low surface productivity or both we determined the organic carbon content and the concentration of a suite of redox sensitive metals in bulk sediments at approximately 1 cm resolution across a laminated massive laminated interval odp leg 169s site 1033 hole b 4h4 54 74 cm to determine the redox conditions under which the massive layer was deposited our results indicate that this massive interval was deposited under anoxic bottom waters manganese al ratios are consistently low throughout the massive section while mo al cd al re al and u al ratios are enriched relative to their metal al ratios in detrital material represented by cowichan river suspended sediments the concentration of organic carbon in the lower portion of the massive layer is higher than in the upper portion which has a concentration similar to that in the overlying and underlying laminated sediments well defined peaks in mo al cd al and re al and a broad peak in u al occur in the lower portion of the massive layer the positions of the cd al re al and mo al peaks as well as the increase in organic carbon content with depth in the massive layer are best explained by a process of diagenetic redistribution of metals that occurred after the massive layer was emplaced

mobility of authigenic rhenium silver and selenium during postdepositional oxidation in marine sediments sedimentary records of redox sensitive trace elements hold significant potential as indicators of paleoceanographic environmental conditions records of re can reveal the intensity of past reducing conditions in sediments at the time of deposition whereas records of ag may record the magnitude of past diatom fluxes to the seafloor confidence in paleoenvironmental reconstruction from records of either metal however requires it to have experienced negligible redistribution since deposition this study examines diagenetic rearrangements of re and ag that occur in response to exposure to bottom water o2 in environments of low sedimentation rate including madeira abyssal plain turbidites and eastern mediterranean basin sapropels authigenic re was remobilized quantitatively by oxidation but poorly retained by the underlying sediments all records are consistent with previous work demonstrating that only a limited reimmobilization of re occurs preferentially in corg rich reducing sediments silver was also mobilized quantitatively by oxidation but it was subsequently immobilized more efficiently in all cases as sharp peaks immediately into anoxic conditions below active oxidation fronts and these peaks remain immobile in anoxic conditions during long term burial comparison of ag s and se records from various cores suggests that ag is likely to have been immobilized as a selenide a mechanism previously proposed for hg in similar situations mercone et al 1999 coexisting narrow peaks of ag and hg with se offer a means of assessing whether oxidative burndown has ever occurred at the top of corg and sulfide rich sedimentary units although these results suggest that caution must be used when inferring paleoenvironmental information from records of ag and re in cores with low sediment accumulation rates 5 cm ka 1 they should not affect the promise that authigenic ag and re records hold for paleoenvironmental reconstruction in sediments with higher accumulation rates and where anoxic conditions have been maintained continuously

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

trace metal fluxes to ferromanganese nodules from the western baltic sea as a record for long term environmental changes trace element profiles in ferromanganese nodules from the western baltic sea were analyzed with laser ablation inductively coupled plasma mass spectroscopy la icp ms and synchrotron based micro x ray radiation techniques fluorescence msxrf and diffraction mxrd at high spatial resolution in growth direction of the trace elements studied zn cu cd ni co mo ba zn showed the most significant enrichment with values in the outermost surface layers of up to six fold higher than those found in older core parts the high resolution zn profiles provide the necessary temporal resolution for a dating method analogous to dendrochronology profiles in various samples collected during two decades were matched and the overlapping sections used for estimation of the accretion rates assuming a continuous accretion of these relatively fast growing nodules on average 20 mm a 1 over the last century the zn enrichment was thus assessed to have commenced around 1860 70 in nodules from the kiel bight and in 1880 90 from mecklenburg bight reflecting the enhanced heavy metal emissions with rising industrialization in europe apart from the obvious success with zn only as and co show significant but only 1 5 fold enrichments in the most recent growth layers of the nodules other anthropogenic trace metals like cu and cdmore are not at all enriched which together with the distinct early diagenetic fe mn banding weakens the potential of the nodules for retrospective monitoring less

hemispherical variations in seismic velocity at the top of the earth s inner core knowledge of the seismic velocity structure at the top of the earth s inner core is important for deciphering the physical processes responsible for inner core growth1 2 3 previous global seismic studies4 5 6 7 8 9 have focused on structures found 100 km or deeper within the inner core with results for the uppermost 100 km available for only isolated regions10 11 12 here we present constraints on seismic velocity variations just beneath the inner core boundary determined from the difference in travel time between waves reflected at the inner core boundary and those transmitted through the inner core we found that these travel time residuals observed on both global seismograph stations and several regional seismic networks are systematically larger by about 0 8 s for waves that sample the eastern hemisphere of the inner core 40 e to 180 e compared to those that sample the western hemisphere 180 w to 40 e these residuals show no correlation with the angle at which the waves traverse the inner core this indicates that seismic anisotropy is not strong in this region and that the isotropic seismic velocity of the eastern hemisphere is about 0 8 higher than that of the western hemisphere

porphyroblast rotation and strain localization debate settled the topic of whether or not porphyroblasts rotate relative to a fixed external reference frame during deformation has engendered much debate mainly owing to the fact that pre deformational orientations of porphyroblasts and their inclusion trails can rarely be reconstructed in 20 years of

benthic foraminifera as proxies of organic matter flux and bottom water oxygenation a case history from the northern arabian sea abstract benthic foraminifera have been quantified in two sediment cores from a topographic high murray ridge in the northern arabian sea one core is from a station within the present day oxygen minimum zone omz the other from a station below the omz changes in the intensity of the omz linked to monsoonal climate variability had a strong impact on benthic foraminiferal composition and accumulation rates at the shallower omz station 920 m an intensification of the omz resulted in lower diversities and high dominances of low oxygen tolerant species the deeper station 1470 m was far less affected though at least once during the last 225 000 years the benthic faunal composition and accumulation rates show evidence for a deepening of the base of the omz to a level close to or even below 1470 m we suggest that percentages of miliolids can be used for rapid reconstruction of periods of increased ventilation in the northern arabian sea and are a promising proxy for tracing changes in bottom and pore water oxygenation in general omz conditions are characterised by high abundances of deep infaunal species and increased burial efficiency of organic matter the proportion of deep infaunal species appears to be a measure for the anoxic burial efficiency of organic matter and not a direct measure for the arriving flux at the seabed results furthermore show that benthic foraminiferal accumulation rates cannot be used as a proxy for surface water productivity under the prevalence of severe dysoxia