stable organic carbon isotope stratigraphy across oceanic anoxic event 2 of demerara rise western tropical atlantic ocean drilling program odp leg 207 recovered expanded sections of organic carbon rich laminated shales on demerara rise western tropical atlantic high resolution organic carbon isotope and total organic carbon toc records are presented which span the cenomanian turonian boundary interval ctbi including the oceanic anoxic event oae 2 from four sites oriented along a nw striking depth transect these records represent the first high resolution carbon isotope records across oae 2 from the south american margin of the tropical atlantic due to the scarcity of age significant fossils the main purpose of this study was to develop a detailed carbon isotope stratigraphy in order to correlate the ctbi across the depth transect and to tie this to biostratigraphically well defined sections in the western interior basin pueblo usa boreal shelf seas eastbourne england and western tethys oued mellegue tunisia all four sections studied document a 6 increase of 13corg values at the base of the ctbi which is followed by an interval of elevated 13corg values and a subsequent decrease our results supply an important stratigraphic base for subsequent paleoceanographic studies on late cenomanian to early turonian sediments from demerara rise and elsewhere

the cenomanian turonian oceanic anoxic event in the south atlantic new insights from a geochemical study of dsdp site 530a abstract one of the key objectives of deep sea drilling project dsdp leg 75 was to shed light on the underlying causes of cretaceous oceanic anoxia in the south atlantic by addressing two major hypotheses productivity productivity driven anoxia vs enhanced ocean stratification leading to preservation of organic matter and black shale deposition here we present a detailed geochemical dataset from sediments deposited during the cenomanian turonian c t transition and the global oceanic anoxic event 2 oae 2 at dsdp site 530a located off shore namibia southeast angola basin north of walvis ridge to characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting we have combined data derived from investigations on bulk organic matter biomarkers and the inorganic fraction the location of the c t boundary itself is biostratigraphically not well constrained due to the carbonate poor but organic matter rich facies of these sediments the bulk 13corg record and compound specific 13c data in combination with published as well as new biostratigraphic data enabled us to locate more precisely the c t boundary at dsdp site 530a the compound specific 13c record is the first of this kind reported from c t black shales in the south atlantic it is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other c t sections in order to discuss the paleoceanographic aspects and implications of the observations at dsdp site 530a in a broader context e g with regard to the potential trigger mechanisms of oae 2 global changes in black shale deposition and climate on a stratigraphic level an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox sensitive trace elements with the abundance of highly source specific molecular compounds these biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria chlorobiacea and are interpreted as paleoindicators for events of photic zone euxinia in contrast to a number of other oae 2 sections that are characterised by continuous black shale sequences dsdp site 530a represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re oxidation presumably leading to their progressive alteration into green shales the frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling

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

oceanic plateau formation a cause of mass extinction and black shale deposition around the cenomanian turonian boundary the cenomanian turonian boundary 90 4 ma represents a major period of worldwide environmental disturbance the physical manifestations of this are elevated atmospheric and oceanic temperatures a significant sea level transgression and a period of widespread anoxia leading to the formation of oceanic black shales and the extinction of 26 of all genera elevated 13 c values and enrichment of trace elements in cenomanian turonian boundary sediments combined with a reduction in 87 sr 86 sr also imply a severe environmental perturbation at this time oceanic crustal production rates reached their highest level of the last 100 million years this was principally caused by extensive melting of hot mantle plumes at the base of the oceanic lithosphere and the development of vast areas up to 1 10 6 km 2 of thickened oceanic crust in the pacific and indian oceans the anomalous volcanism associated with the formation of these oceanic plateaux may have been responsible for the environmental disturbances c 90 ma these eruptions would also have resulted in the emission of large quantities of co 2 into the atmosphere leading to global warming additionally the emission of so 2 h 2 s co 2 and halogens into the oceans would have made seawater more acidic resulting in the dissolution of carbonate and further release of co 2 this run away greenhouse effect was probably put into reverse by the decline of the anomalous volcanic activity and by increased co 2 driven productivity in oceanic surface waters leading to increased organic carbon burial black shale deposition anoxia and mass extinction in the ocean basins

slow drag in wet snow avalanche flow we report impact pressures exerted by three wet snow avalanches on a pylon equipped with piezoelectric load cells these pressures were considerably higher than those predicted by conventional avalanche engineering guidelines the time averaged pressure linearly increased with the immersion depth of the load cells and it was about eight times larger than the hydrostatic snow pressure at the same immersion depth the pressures were very similar for all three avalanches and no dependency between avalanche velocity and pressure was apparent the pressure time series were characterized by large fluctuations for all immersion depths and for all avalanches the standard deviations of the fluctuations were on average about 20 of the mean value we compare our observations with results of slow drag granular experiments where similar behavior has been explained by formation and destruction of chain structures due to jamming of granular material around the pylon and we propose the same mechanism as a possible microscale interpretation of our observations

the flux and mixing rates of antarctic bottom water within the north atlantic calculation was made of the northward flow of antarctic bottom water into the western north atlantic basin through a passageway approximately 300 km wide between the ceara rise and the mid atlantic ridge at about 4 n two moorings carrying four current meters each were placed in the region where currents were expected to be the greatest and were left for 360 days the current was not steady but exhibited large surges with approximately a 60 day time scale whose cause is unknown current meters in the fastest flowing region all exhibited a net northward flow it is estimated that approximately 0 8 106 m3 s 1 of water colder than 1 9 c potential temperature flowed on the average into the north atlantic with this number possibly being too small by 0 3 106 m3 s 1 or too big by 0 1 106 m3 s 1 depending upon estimates of the width of the region which the current meters sample however these numbers differ from geostrophic estimates of 1 98 106 m3 s 1 the disagreement coming almost entirely from the fact that the geostrophic estimates give a sizeable flux of water colder than 1 2 c while the current meters do not based upon the two different flux rates residence times and mixing coefficients are calculated for antarctic bottom water for each 0 1 c potential temperature interval from 1 0 c to 1 9 c finally some comments on the dynamics of the northward flow are made

remobilization of authigenic uranium in marine sediments by bioturbation uranium behaves as a nearly conservative element in oxygenated seawater but it is precipitated under chemically reducing conditions that occur in sediments underlying low oxygen bottom water or in sediments receiving high fluxes of particulate organic carbon sites characterized by a range of bottom water oxygen bwo and organic carbon flux ocf were studied to better understand the conditions that determine formation and preservation of authigenic u in marine sediments our study areas are located in the mid latitudes of the northeast pacific and the northwest atlantic oceans and all sites receive moderate 0 5 g cm2 kyr to high 2 8 g cm2 kyr ocf to the sediments bwo concentrations vary substantially among the sites ranging from 3 to 270 m a mass balance approach was used to evaluate authigenic u remobilization at each site within each region studied the supply of particulate nonlithogenic u associated with sinking particles was evaluated by means of sediment traps the diffusive flux of u into sediments was calculated from pore water u concentration profiles these combined sources were compared with the burial rate of authigenic u to assess the efficiency of its preservation a large fraction one third to two thirds of the authigenic u precipitated in these sediments via diffusion supply is later regenerated even under very low bwo concentrations 15 m bioturbating organisms periodically mix authigenic u containing sediment upward toward the sediment water interface where more oxidizing conditions lead to the remobilization of authigenic u and its loss to bottom waters

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

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

oscillating redox conditions in the vocontian basin se france during oceanic anoxic event 2 oae 2 abstract the cenomanian turonian boundary 94 ma was marked by an episode of widespread organic carbon burial largely associated with low oxygen concentrations in bottom oceanic waters named oceanic anoxic event 2 oae 2 in the vocontian basin se france the pont d issole section exposes a 22 m interval called niveau thomel the local sedimentary expression of the oae 2 characterized by levels of laminated dark shales with marine derived organic matter enrichments up to 2 5 wt an episodic disruption in total organic carbon toc enrichment is observed in bioturbated limestones within the niveau thomel reflecting bottom water reoxygenation associated to the plenus cold event oscillations in redox conditions during the oae 2 are evidenced by variations in the degree of pyritisation of the sediments reflecting suboxic to anoxic conditions associated with organic rich intervals these variations are additionally highlighted by enrichments in redox sensitive trace elements mo v zn in sediments containing at least 1 5 wt toc which may reflect a threshold between suboxic and anoxic conditions at pont d issole section low mn and fe concentrations in 0 3 wt toc samples mark a large o2 depletion in pore waters phosphorus released from the sediments under deoxygenated conditions could have contributed to sustain the primary productivity in the basin promoting further o2 consumption a large negative excursion in the sulfur isotopic composition of pyrite 34spy with minimum values down to 40 suggests that microbial sulfate reduction was non sulfate limited and was characterized by pyrite precipitation in an open system with regard to the marine sulfate reservoir this feature is probably linked to a higher sulfate availability within the vocontian basin due to important large igneous province outgassing at the onset of the oae 2

geochemistry of ferromanganese nodules from domes site a northern equatorial pacific multiple diagenetic metal sources in the deep sea abstract the major and minor element composition of ferromanganese nodules from domes site a has been determined by x ray fluorescence methods three phases appear to control the bulk compositions mn and fe oxyhydroxides and aluminosilicates relatively wide compositional variations are evident throughout the area nodules with high mn fe ratios high cu mg mo ni and zn concentrations and high todorokite mno 2 ratios have granular surface textures and are confined to an east west trending depression with thin quaternary sediment cover nodules with low mn fe ratios high concentrations of as ca ce co la p sr ti v y and zr and low todorokite mno 2 ratios have smooth surfaces and are confined to shallower areas with relatively thick quaternary sediment to the north and south of the depression all nodules in the area have compositions which are influenced by diagenesis but those with the most marked diagenetic signature high mn fe and cu ni ratios low ce la ratios and more todorokite are found in areas of very slow or non existent sedimentation many of these nodules are actually in contact with outcropping tertiary sediment this paradox may be resolved by postulating by analogy with some shallow water occurrences that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation the metals are supplied in a bottom flow probably antarctic bottom water which also erodes or prevents modern sedimentation in the depression nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying quaternary sediment apparently abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form

comparison of shear measurements and mixing predictions with a direct observation of diapycnal mixing in the atlantic thermocline four sets of velocity and density profiles have been measured with an autonomous profiler during an upper ocean intentional tracer sf6 diapycnal diffusivity measurement the north atlantic tracer release experiment natre the tracer was injected near 310 m depth in the canary basin two profile sets were collected 6 months after tracer release and two were collected i year after release all within the horizontal boundaries of the sf6 patch shear and strain can be combined with turbulent kinetic energy dissipation and diffusivity measurements published elsewhere to test existing expressions for dissipation and diffusivity due to shear induced turbulence these expressions arise from internal wave decay modeling one expression of dissipation parameterized in terms of shear based on stochastic nonlinear internal wave interaction has fared well empirically its extension to estimate diffusivity is evaluated shear variance of the first two data sets was about 1 6 times gm76 and 2 5 to 3 0 times gm76 in the later sets the average parameterized mixing estimate computed using all of the temporally limited shear measurements overestimates annual mean natre diffusivity 1 5 x 10 m 2 s by a factor of 1 2 a modified parameterization gives an underestimate to first order this supports the present understanding of open ocean diffusivity in terms of fine scale shear and internal wave decay that is the slow diapycnal mixing was not a consequence of unusually low shear adjustment of the shear induced mixing models to better fit the data is not warranted because of the lack of direct comparability between the various measurements the expected natural variability of the shear and sampling errors

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

sulfur isotopes track the global extent and dynamics of euxinia during cretaceous oceanic anoxic event 2 the mesozoic era is characterized by numerous oceanic anoxic events oaes that are diagnostically expressed by widespread marine organic carbon burial and coeval carbon isotope excursions here we present coupled high resolution carbon and sulfur isotope data from four european oae 2 sections spanning the cenomanian turonian boundary that show roughly parallel positive excursions significantly however the interval of peak magnitude for carbon isotopes precedes that of sulfur isotopes with an estimated offset of a few hundred thousand years based on geochemical box modeling of organic carbon and pyrite burial the sulfur isotope excursion can be generated by transiently increasing the marine burial rate of pyrite precipitated under euxinic i e anoxic and sulfidic water column conditions to replicate the observed isotopic offset the model requires that enhanced levels of organic carbon and pyrite burial continued a few hundred thousand years after peak organic carbon burial but that their isotope records responded differently due to dramatically different residence times for dissolved inorganic carbon and sulfate in seawater the significant inference is that euxinia persisted post oae but with its global extent dwindling over this time period the model further suggests that only 5 of the global seafloor area was overlain by euxinic bottom waters during oae 2 although this figure is 30 greater than the small euxinic fraction present today 0 15 the result challenges previous suggestions that one of the best documented oaes was defined by globally pervasive euxinic deep waters our results place important controls instead on local conditions and point to the difficulty in sustaining whole ocean euxinia

sulfur isotopic trends and pathways of iron sulfide formation in upper holocene sediments of the anoxic black sea down core trends for extents of iron sulfidation in upper holocene microlaminated deposits of the black sea abyssal plain imply that most of the pyrite in these sediments is formed in the sulfidic water column and or very close to the sediment water interface sulfur isotopic data for pyrite within microlaminated muds from two localities in the deep basin show striking uniformity between sites and down core with a mean 34scdt value of 37 2 0 9 1 n 18 these isotopic trends support the hypothesis of early pyrite formation isotopic compositions of pyrite sulfur in the microlaminated bottom sediments are similar to those reported for particulate reduced sulfur collected in middepth sediment traps and to 34s values for water column dissolved sulfide within a narrow zone immediately below the o2 h2s interface these three sulfur reservoirs are distinctly different from the isotopic composition of ambient dissolved sulfide of the deep water column 175 m with 34s values for the deep dissolved sulfide reservoir being consistently lower by 2 to 4 these isotopic relationships suggest that iron sulfidation is occurring dominantly within a narrow shallow region at the top of the sulfidic water mass isotopic data from a fine grained turbidite collected in the deep basin and from rapidly accumulating iron monosulfide rich muds on the anoxic upper slope are enriched in34s relative to the microlaminated deposits the enrichments on the basin margin reflect a large component of iron sulfide formed during rapid burial a broad suite of geochemical data including sulfur isotopic results are consistent with an upper slope sediment source for the ubiquitous muddy turbidites of the deep basin the collective effects of reworking transport and redeposition result in a complete conversion of avs to pyrite with little additional iron sulfidation this conclusion is supported by a detailed isotopic mass balance the present isotopic study also highlights fundamental differences in the reactivities of the iron reservoirs distributed throughout the anoxic basin sediments of the upper slope and the genetically linked turbidites of the deep basin show similar extents of iron sulfidation that are significantly lower than those of the microlaminated deposits of the deep basin floor suggesting dramatically shorter timescales of iron reactivity for the microlaminated sediments of the deep basin importantly isotopic patterns from the modern black sea should assist greatly in the recognition and interpretation of ancient anoxia in the stratigraphic record

strontium isotope stratigraphy in the upper cenomanian shallow water carbonates of the southern apennines short term perturbations of marine 87sr 86sr during the oceanic anoxic event 2 abstract strontium isotope stratigraphy of shallow water carbonates from the southern apennines italy indicates that the late cenomanian early turonian evolution of marine 87sr 86sr is not accurately depicted by the marine reference curve using the low mg biotic calcite of well preserved rudist shells as a study material and carbon isotope stratigraphy for correlation to the standard ammonite biozonal scheme of northern europe new 87sr 86sr values are proposed for four different stratigraphic levels the middle and uppermost part of the guerangeri zone the lower and upper part of the geslinianum zone the southern apennines data suggest that a sharp positive shift at the onset of oceanic anoxic event 2 precedes the well known sr isotope negative shift the positive shift is interpreted in terms of enhanced rates of chemical weathering driven by global warming forced by volcanogenic co2 outgassing a stratified ocean is invoked to reconcile the high gradient and the short lag time of the perturbation with estimates of present day total mass and residence time of strontium in the ocean the sharp switch to the negative shift is related to the collapse of water column density gradient driven by thermal instability during a late cenomanian cool event more active ocean circulation suddenly delivered to surface waters the signal of increased submarine volcanism that had accumulated in deep waters

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

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

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

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

comparison of deep ocean finescale shear at two sites along the mid atlantic ridge abstract four drifting floats were used to measure the magnitude of the vertical derivative of horizontal velocity in waters above the rough bathymetry of the mid atlantic ridge this derivative is typically the dominant component of the velocity gradient the shear two floats were at the site of the brazil basin tracer release experiment bbtre in the south atlantic and two were near the site of the guiana abyssal gyre experiment gage in the north atlantic floats operated for 1 year except for one bbtre float which operated for 100 days shear was measured over a vertical span of 9 5 m using drag elements that caused the floats to rotate slowly in response to shear for each float the first second and fourth moments of shear were elevated above levels associated with the garrett munk model internal wave spectrum three of the four floats were tracked as they moved over mountainous terrain allowing shear intensity to be measured as a function of height above the bottom a deep bbtre float showed enhancement of rms shear near the bottom floats at both areas provided measurements at 2000 m above the bottom with differing results the gage site had a lower fourth moment of shear diapycnal diffusivity proxy than the bbtre site however application of normalization factors accounting for differences between the sites in bottom roughness latitude dependent internal wave dynamics and tidal current speeds brings the results into agreement

vanadium accumulation in carbonaceous rocks a review of geochemical controls during deposition and diagenesis abstract published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks reduction adsorption and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon dissolved vanadate v v species predominate in oxic seawater and are reduced to vanadyl ion v iv by organic compounds or h 2 s vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle the large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff vanadium rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate rich units a correspondence between vanadium content and organically bound sulfur is consistent with high activities of h 2 s during sediment deposition excess h 2 s exited the sediment into bottom waters and favored reduction of dissolved v v to v iv or possibly v iii the stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic phosphate concentrated to more reducing euxinic conditions that favor vanadium accumulation during diagenesis some vanadium organic complexes migrate with petroleum out of carbonaceous rocks but significant amounts of vanadium are retained in refractory organic matter or clay minerals as carbon in the rock evolves toward graphite during metamorphism vanadium is incorporated into silicate minerals

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

reconstructing the rise of recent coastal anoxia molybdenum in chesapeake bay sediments abstract sporadic direct observations over a 50 yr period inadequately characterize the history of seasonal hypoxia and anoxia in chesapeake bay a large estuary threatened by eutrophication here we undertake a reconstruction of 20th century oxygen depletion in this estuary using mo concentrations in 210pb dated sediments cu concentrations are used to control for anthropogenic influences cores from the central channel display mild mo enrichments above crustal backgrounds up to 5 g g and strong cu enrichments up to 35 g g temporally cu enrichment mostly anthropogenic began earlier and stabilized in the last two thirds of the 20th century in contrast mo enrichment has grown during the last two thirds of the century molybdenum enrichment is mostly hydrogenic except in a section of the channel that receives additional mo from erosion of early miocene shore deposits two geochemical mechanisms promote mo enrichment manganese refluxing concentrates dissolved moo42 at the sediment water interface and sulfide substitution into moo42 produces thiomolybdates which can be fixed by particles the mo enrichment mechanisms operate primarily during periods when bottom waters are anoxic and thiomolybdate formation can occur near the sediment water interface this implies a temporal coupling between water column anoxia and mo fixation even though fixation occurs only within sediments the mo enrichment profiles suggest that chesapeake bay has experienced growing o2 depletion since the first half of the 20th century but especially after 1960

mixing in the main thermocline abstract a series of profiles of velocity microstructure along 152 e in the western north pacific ocean were collected in may june 1982 large averaged turbulent dissipation rates found in the main thermocline 400 to 1000 m were determined by a combination of large independent estimates of and a greater rate of occurrence of turbulent events in the main thermocline than elsewhere concurrently we find that averaged values of exhibit a positive dependence on the buoyancy frequency n and that form an is best fit by 1 when only the data below 400 m are considered of the more than 5000 m of data collected below 1000 m depth 12 showed measurable turbulence and dominated the depth averages a deep ocean estimate of an upper bound to the eddy coefficient for vertical diffusion k is 10 4 m2 s 1 and not significantly different from the value estimated by munk the inferred dependence of the mass flux with depth indicates the relative significance of vertical mixing in the main thermocli

finescale shear at 1660 and 2850 dbar over the mid atlantic ridge in the eastern brazil basin abstract two drifting shearmeter instruments have provided records of the magnitude of shear the magnitude of the vertical derivative of horizontal velocity measured over a 10 m aperture in the vicinity of the brazil basin tracer release experiment the floats drifted at roughly 1660 and 2850 dbar where the buoyancy frequencies were n 1 1 and 0 5 cph respectively two additional floats provided deep trajectories but no shear data the records of hourly mean values of shear magnitude with mean values denoted sh exhibit strong temporal variability with time scales comparable to those of fortnightly tidal modulation the deep record exhibits stronger mean sh near the seafloor than above with the exception of the bin closest to the seafloor sh from neither float correlates strictly with tidal forcing shallow sh varies in apparent response to atmospheric forcing the mean squared shear of the shallow record is 4 times the n dependent value associated with the garrett munk spectral model and that

hydrographic conditions of the devono carboniferous north american seaway inferred from sedimentary mo toc relationships abstract deepwater anoxia developed widely within a series of silled intracratonic basins in north america during the middle devonian to early carboniferous but the hydrographic factors contributing to this development are virtually unknown the present study demonstrates that the degree of enrichment of strongly hydrogenous elements such as molybdenum mo in the organic rich shales that accumulated in these basins has the potential to provide information about paleohydrographic conditions most of the study units 49 of 55 exhibit significant positive covariation between elemental mo and toc concentrations yet there is substantial variation in the statistical parameters that define these relationships specifically the regression lines characterizing mo toc covariation have slopes m ranging from 2 to 65 10 4 although a majority of the study units yield m values between 10 and 25 10 4 the parameter m exhibits systematic stratigraphic variation within individual basins and geographic variation among basins suggesting that mo toc relationships were controlled by slowly evolving watermass characteristics of the devono carboniferous north american seaway a recent study of modern anoxic silled basins algeo t j lyons t w 2006 mo total organic carbon covariation in modern anoxic marine environments implications for analysis of paleoredox and paleohydrographic conditions paleoceanography 21 pa1016 doi 10 1029 2004pa001112 demonstrated that m is closely linked to the degree of restriction of the subpycnoclinal watermass as reflected in aqueous mo concentrations mo aq and deepwater renewal times dw these relationships reflect control of sedimentary mo enrichment by both the amount of sedimentary organic matter i e host phase availability and the concentration of aqueous mo i e source ion availability when applied to black shales of the devono carboniferous north american seaway these relationships permit both qualitative and quantitative inferences regarding the degree of restriction of deepwaters in cratonic basins and the evolution of hydrographic conditions through time black shales associated with early stages of sea level rise commonly exhibit low m values 1000 yr higher sea level stands resulted in more open marine conditions and enhanced deepwater renewal leading to deposition of black shales with m values up to 65 equivalent to mo aq 70 of the normal seawater concentration and dw

litho bio and chemostratigraphy across the cenomanian turonian boundary oae 2 in the vocontian basin of southeastern france the oceanic anoxic event 2 oae 2 was one of at least two large oceanic anoxic events during the cretaceous period and it is characterized in the stratigraphic record by double positive peaks in the 13c curves of carbonate and organic carbon since the positive 13c shift is believed to have resulted from massive burial of isotopically depleted organic carbon generated globally in anoxic oceanic environments the positive 13c shift tend to coincide with widespread deposition of organic rich sediments in the case of oae 2 however the organic rich horizons do not accord exactly with the two intervals with positive 13c shifts at many sites such as pueblo tarfaya eastbourne and gubbio e g tsikos h jenkyns h c walsworth bell b petrizzo m r forster a kolonic s erba e premoli silva i baas m wagner t sinninghe dameste j s 2004 carbon isotope stratigraphy recorded by the cenomanian turonian oceanic anoxic event correlation and implications based on three key localities journal of the geological society london 161 711 719 the thomel level of the cenomanian turonian c t boundary in the vocontian basin southeastern france accumulated during the oae 2 and it is marked by frequent intercalations of black shale and organic rich marl detailed litho bio and chemostratigraphy analyses across the c t boundary in the vocontian basin indicate that the 13ccarbonate profile fluctuation across the thomel level corresponds well with changes in lithofacies total organic carbon toc and calcium carbonate caco3 abundance positive 13c excursions within the oae 2 correlate with basal and middle parts of the thomel level that are characterized by high toc low caco3 and predominantly contain organic rich sediments such as black shale and dark gray marl on the other hand negative 13c intervals within the oae 2 correspond with lower and upper parts of the thomel level that consist of marly limestone and limy marl with low toc and high caco3 values since the fluctuation of redox conditions during thomel level deposition in the vocontian basin coincides well with the global carbon burial rate indicated by its 13c profile the thomel level could be an ideal candidate for the reference section of the oae 2

geochemical and climatic effects of increased marine organic carbon burial at the cenomanian turonian boundary perhaps the most significant event in the cretaceous record of the carbon isotope composition of carbonate1 2 other than the 1 2 5 negative shift in the carbon isotope composition of calcareous plankton at the cretaceous tertiary boundary3 is the rapid global positive excursion of 2 13c enrichment which took place between 91 5 myr and 90 3 myr late cenomanian to earliest turonian c t boundary event 1 4 5 this excursion has been attributed to a change in the isotope composition of the marine total dissolved carbon tdc reservoir resulting from an increase in rate of burial of 13c depleted organic carbon which coincided with a major global rise in sea level5 during the so called c t oceanic anoxic event oae 6 here we present new data from nine localities which demonstrate that a positive excursion in the carbon isotope composition of organic carbon at or near the c t boundary7 8 is nearly synchronous with that for carbonate and is widespread throughout the tethys and atlantic basins fig 1 as well as in more high latitude epicontinental seas the postulated increase in the rate of burial of organic carbon may have had a significant effect on co2 and o2 concentrations in the oceans and atmosphere and consequent effects on global climate and sedimentary facies

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

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

the role of boundary mixing in the deep ocean recent laboratory studies demonstrate that mixing at the boundaries of stratified and rotating fluids can be described by a relatively simple parameterization these results are applied to the deep ocean and by using available field observations it is argued that mixing at the boundaries can lead to an apparent diapycnal diffusivity in the interior of the deep ocean whose magnitude has an upper bound of 3 10 5 m2 s 1

on the sources of north atlantic deep water abstract because the volumetric census of deep and bottom water in the north atlantic ocean consists of three isolated linear ridges along which heat and salt flow through the main volumetric mode and point of intersection it is possible to deduce the expected ratio of heat flux and ratio of salt fluxes measured in the denmark strait overflow off greenland and in the antarctic bottom water near the equator the weakly stratified layers of upper north atlantic deep water fall on the nearly linear ridge at temperatures above that of the mode there is an incompatibility between observed ratio and deduced ratio it is predicted that a remeasurement of the flux of antarctic bottom water near the equator will show that the previous determination of 4 n is unrepresentatively low

pyritization of trace metals in anoxic marine sediments the pyritization of reactive trace elements in different anoxic marine sediments was investigated to determine the importance of factors such as h2s reactive fe pyrite content and salinity in controlling this process the areas studied included anoxic sulfidic sediments baffin bay a hypersaline coastal lagoon from texas and green canyon a hemipelagic oil seepage area anoxic nonsulfidic sediments with high sedimentation rates atchafalaya bay mississippi delta system hemipelagic anoxic nonsulfidic sediments with low sedimentation rates gulf of mexico shelf and slope and orca basin an euxinic hypersaline basin and organic rich marsh sediments atchafalaya bay results indicate that the degree of trace metal pyritization dtmp of all trace metals except cd increased with increasing degree of pyritization dop irrespective of the type of sedimentary environment involved however for as hg and mo the dtmpdop values were generally above the 1 1 ratio line whereas the transition metals co cu mn and ni displayed a close to linear increase in dtmp with dop and moderate incorporation into pyrite chromium and the class b metals pb and zn were also gradually incorporated into the pyrite phase but without reaching the dtmp levels exhibited by the transition metals cadmium was not incorporated to a significant extent these results are consistent with the chemical attributes of these different classes of trace elements availability of dissolved trace metals and organic matter content are apparently important factors controlling the incorporation of co cr cu and ni into pyrite in anoxicsulfidic fe poor and h2s rich environments

sediment carbon nitrogen and phosphorus cycling in an anoxic fjord effingham inlet british columbia sediment geochemistry as well as benthic exchange of nutrients was investigated in effingham inlet a fjord located on the west coast of vancouver island in barkley sound the effect of bottom water oxygenation on sediment carbon nitrogen and phosphorus cycling was compared at sites overlain by oxic and anoxic bottom waters the sites separated by only 3 kilometers were similar in terms of key diagenetic parameters including mass accumulation rate and bulk sediment organic carbon content thus allowing a focus on diagenetic effects attributable to depositional oxygen availability benthic flux chamber incubations sulfate reduction rate measurements measurements of solid phase and pore water chemical profiles were compared for the sites these comparisons reveal that diagenetic processes in the site overlain by oxic waters act to retain more phosphorus in the sediment relative to the anoxic site differences in phosphorus benthic fluxes and burial between the two sites most likely result from differences in organic matter cycling under aerobic versus anaerobic conditions and are not strongly influenced by cycling of p associated with metal oxide phases

on the ratio of the mixing coefficients of heat and salt of antarctic bottom water in the north atlantic values of vertical eddy salt diffusivity and heat diffusivity for antarctic bottom water were estimated by whitehead and worthington 1982 from both current meter results and geostrophic calculations the ratios of the diffusivities have one impossible value of 0 858 for water colder than 1 1 c potential temperature for the geostrophic results this could be evidence against the geostrophic results however a small interpolation error in their tables 5 and 6 was uncovered the corrected ratio is 1 01 which is possible although very close to 1 and one other ratio is 0 98 thus geostrophic calculations cannot be ruled out but they lead to ratios very close to 1

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

a model for iron deposition to euxinic black sea sediments sulfur isotope and c s fe elemental data from the lower devonian siegenian emsian hunsruck slate of germany allow the conditions that led to the pyritization of soft bodied fossils to be determined the slates preserving pyritized soft tissues generally contain low concentrations of organic matter 0 3 0 4 percent c and pyrite sulfur 0 0 2 percent s respectively but are unusually rich in total and hcl extractable iron concentrations of iron are significantly lower in samples of the hunsruck slate from areas where fossils lack pyritized soft tissues the fossil pyrite is very enriched in s 34 compared to fine grained disseminated pyrite in the adjacent slates delta fossil sediment 10 to 50 permil suggesting that pyritization of the fossils persisted into later stages of authigenic mineralization pyrite formation in the sediments was limited by the low concentrations of metabolisable organic matter leaving residual sulfate and iron available for continued fossil pyritization in organic rich microenvironments a diffusion with precipitation model indicates that a critical control on the initial preservation of readily metabolisable soft tissue in this way is the presence of high concentrations of sediment iron capable of being solubilized during shallow burial diagenesis in association with low concentrations of metabolisable organic matter in the matrix pore waters rich in dissolved iron allow the sulfide generated by the decay of readily metabolisable soft tissue to be trapped efficiently within the carcass

a simulation of mid cretaceous climate a series of general circulation model experiments utilizing genesis have been completed for the mid cretaceous based on geography variable atmospheric carbon dioxide concentrations 2 to 6 times present day concentrations and variable poleward oceanic heat flux 6 to 1 2 1015 w increased from present day by combining all three major variables co2 geography and oceanic heat flux the distribution of mid cretaceous temperatures can be achieved in the simulations increased co2 is required to promote global warmth and increased oceanic heat flux is required to prevent the tropics from overheating with higher levels of co2 four times present day co2 with 1 2 1015 w provided the best match to the distribution of mid cretaceous data the best match to the cretaceous observations was achieved with a globally averaged surface temperature increase of 6 2 c at the lower end of past estimates of mid cretaceous warmth this value may be a better estimate of mid cretaceous global warming finally the model experiments can be used to provide a paleocalibration of the global warming expected for a doubling of atmospheric carbon dioxide the best estimates for the mid cretaceous appear to be a 2 5 to 4 0 c sensitivity in the mid to upper range of the sensitivity of current climate models used to assess future global change

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

shear and strain in santa monica basin by injecting a cloud of sf6 into santa monica basin at a depth of 790 m and observing its vertical spread ledwell and watson 1991 estimate the average diapycnal diffusivity between 750 and 850 m as kp 2 5 10 5 m2 m 1 this diffusivity is higher than inferred from microstructure measurements in the open ocean thermocline for typical internal wave levels gregg and sanford 1988 to examine shear and strain in the basin we dropped expendable current profilers xcps and calculated strain from conductivity temperature and depth ctd casts shear and strain are above the gm76 model spectrum garrett and munk 1975 cairns and williams 1976 and comparisons with published parameterizations indicate more than enough shear variance to account for the high diffusivity reported by ledwell and watson thus the eddy diffusivity in santa monica basin is not at odds with lower values estimated from microstructure measurements in the open ocean but is due to an elevated internal wave field the spectral shapes however differ from typical open ocean spectra

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

sulfur isotopic trends and iron speciation from the c 2 0 ga pilgujarvi sedimentary formation nw russia abstract sulfide sulfur isotope values and iron speciation data are reported here for sediments from the 2 0 ga old pilgujarvi sedimentary formation pechenga greenstone belt nw russia sulfides are abundant throughout the c 1400 m thick turbiditic sandstone siltstone shale succession and present as pyrite and pyrrhotite a stratigraphic trend is discernible with respect to sulfide mineralogy and sulfur isotopic compositions changing up section from highly to less variable and positive 34 s values the occurrence of pyrrhotite particularly high in the upper part of the section is thought to be the result of decomposition of pyrite during low grade metamorphism this is evidenced by the crystallographic habit and sulfur isotopic composition of the different sulfide minerals the 34 s of both sulfur species is quite variable in the lower part of the formation 9 5 to 18 7 while the upper part displays a smaller fluctuation in 34 s 4 4 13 3 the pyrrhotite is generally depleted in 34 s by approximately 3 6 average isotopic difference between pyrrhotite and pyrite compared to the pyrite this shift in the sulfur isotopic composition results from thermal decomposition of pyrite the overall spread in 34 s is indicative for the microbial reduction of sulfate but 34 s values suggest a sulfate limited environment in the upper part of the formation we note however that the sulfate limitation is restricted to the pore water realm caused by high sedimentation rates that inhibited a sufficiently high sulfate flux from the overlying water column into the sediment based on iron speciation data a previous characterization of the depositional environment as non euxinic can be specified more precisely we note that the siliciclastic succession of the pilgujarvi sedimentary formation was deposited under anoxic and ferruginous water column conditions derived from high ratios of fe hr fe t and low ratios of fe py fe hr

ocean stagnation and end permian anoxia ocean stagnation has been invoked to explain the widespread occurrence of organic carbon rich laminated sediments interpreted to have been deposited under anoxic bottom waters at the time of the end permian mass extinction however to a first approximation stagnation would severely reduce the upwelling supply of nutrients to the photic zone reducing productivity moreover it is not obvious that ocean stagnation can be achieved numerical experiments performed with a three dimensional global ocean model linked to a biogeochemical model of phosphate and oxygen cycling indicate that a low equator to pole temperature gradient could have produced weak oceanic circulation and widespread anoxia in the late permian ocean we find that polar warming and tropical cooling of sea surface temperatures cause anoxia throughout the deep ocean as a result of both lower dissolved oxygen in bottom source waters and increased nutrient utilization buildup of quantities of h2s and co2 in the late permian ocean sufficient to directly cause a mass extinction however would have required large increases in the oceanic nutrient inventory

a critical look at iron paleoredox proxies new insights from modern euxinic marine basins enrichments in reactive iron occur under euxinic marine conditions that is where dissolved sulfide is present in the water column these enrichments result primarily from the export of remobilized iron from the oxic shelf which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments strongly elevated ratios of highly reactive iron to total iron fehr fet and total iron to aluminum fet al and high degrees of pyritization dop are each products of this enrichment process these paleoredox proxies are among the most faithful recorders of ancient euxinia contrary to previous arguments iron enrichment is decoupled from biogenic sediment inputs but it does appear to be a uniquely euxinic phenomenon in other words we can rule out a major contribution from preferential physical transport of fehr rich detrital sediment to the deep basin which could also operate under oxic conditions furthermore enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins elevated fet al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net fehr addition these conclusions are supported by observations in the modern black sea orca basin and effingham inlet fet al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration however this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism resulting in only intermediate dop values for euxinic sediments and fet al ratios that mimic the oxic shelf such dilution effects are well expressed in black sea basinal turbidites and rapidly accumulating muds on euxinic basin margins under conditions of persistent euxinia varying extents of fehr enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation the magnitude of enrichment is a function of the source shelf to sink ocean basin areal ratio suggesting that iron proxies can also record ocean scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia for the first time manganese data are interpreted in light of the redox shuttle model as for the iron data the black sea orca basin and effingham inlet show enrichments in total manganese in the deep euxinic basin suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin the black sea data reveal iron and manganese enrichment across the broad deep euxinic basin suggesting efficient lateral transport and deep water mixing tied to the physical properties of the water column

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

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

the phosphorus cycle phosphogenesis and marine phosphate rich deposits abstract phosphorus in the form of phosphate is an essential nutrient and energy carrier on many different levels of life and a key element in mediating between living and lifeless parts of the biosphere one of the most important aspects of the phosphorus cycle is its vital role in governing productivity thereby interacting with the exogenic part of the carbon cycle which in turn is important in regulating earth s climate phosphorus is a prime element to be traced in earth s history because it allows for the reconstruction of long term feedback mechanisms between climate environment and ecology and of global change as such marine sedimentary phosphate deposits are particularly suited to study aspects of the phosphorus cycle because in the case of ubiquity their origin may result from a general acceleration of the global phosphorus cycle sources of sedimentary phosphate are microbial breakdown of buried organic matter and redox driven phosphate desorption from iron and manganese oxyhydroxides dissolved sea water phosphate represents an additional source which may become important in the formation of phosphatic hardgrounds the main locus of phosphogenesis is near the sediment water interface but phosphogenesis also occurs at greater sediment depths current induced winnowing and transport processes along the sea floor concentrate phosphate precipitates into deposits which exhibit internal stratification patterns typical for the prevailing hydraulic energy regime in a sequence stratigraphic context phosphate deposits preferentially occur along marine or maximum flooding surfaces consequent sedimentary reworking may result in the transfer of phosphates to highstand or lowstand deposits bio chemical weathering on continents represents the most significant source of bioavailable phosphorus this implies that long term changes in marine phosphorus levels and with these changes in marine ecology productivity rates and ratios of exported carbonate carbon and organic carbon are a response to changes in continental weathering rates a compilation of marine sedimentary phosphorus burial rates for the last 160 myr suggests that natural variations have occurred that span one order of magnitude for the late jurassic cretaceous and most of the paleogene the phosphorus cycle appears to have been accelerated in times of climate warming which was most likely due to the spreading of zones of humid climate and more intense continental weathering in the neogene the phosphorus cycle appears to have responded to changes in glacially induced weathering this suggests that uniform interpretations with respect to the emplacement of major phosphorite deposits should be treated with caution integrated analyses of the sedimentary and biogeochemical context of phosphorite occurrences may help to identify paleoenvironmental conditions as well as to improve our understanding of periods of enhanced phosphate accumulation periods which were usually characterized by steep gradients in the development of climate and environment with regard to the complexity of feedback mechanisms between the phosphorus cycle and the biosphere the present day input rates of phosphate into the world s oceans should be of great concern they are more than doubled by anthropogenic means and affect ecological systems on a rapidly increasing scale

tropical warming and intermittent cooling during the cenomanian turonian oceanic anoxic event 2 sea surface temperature records from the equatorial atlantic oceanic anoxic event 2 oae 2 occurring during the cenomanian turonian c t transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 myr however the impact of this major perturbation on and interaction with global climate remains unclear here we report new high resolution records of sea surface temperature sst based on tex86 and 18o of excellently preserved planktic foraminifera and stable organic carbon isotopes across the c t transition from black shales located offshore suriname french guiana demerara rise ocean drilling program leg 207 site 1260 and offshore senegal cape verde basin deep sea drilling project leg 41 site 367 at site 1260 where both sst proxy records can be determined a good match between conservative sst estimates from tex86 and 18o is observed we find that late cenomanian ssts in the equatorial atlantic ocean 33 c were substantially warmer than today 27 29 c and that the onset of oae 2 coincided with a rapid shift to an even warmer 35 36 c regime within the early stages of the oae a marked 4 c cooling to temperatures lower than pre oae conditions is observed however well before the termination of oae 2 the warm regime was reestablished and persisted into the turonian our findings corroborate the view that the c t transition represents the onset of the interval of peak cretaceous warmth more importantly they are consistent with the hypotheses that mid cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide co2 and that major oaes were capable of triggering global cooling through the negative feedback effect of organic carbon burial led co2 sequestration evidently however the factors that gave rise to the observed shift to a warmer climate regime at the onset of oae 2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 myr

the low temperature geochemical cycle of iron from continental fluxes to marine sediment deposition suspended sediments from 34 major rivers geographically wide spread and 36 glacial meltwater streams have been examined for their variations in different operationally defined iron fractions fehr iron oxides soluble in dithionite fepr iron soluble in boiling hcl but not in dithionite and feu total iron less that soluble in boiling hcl river particulates show a close association between fehr and total iron fet reflecting the effects of chemical weathering which derive oxide iron from and retain it in close association with total iron consistent with this continental scale average fehr fet ratios vary with runoff ratios average river runoff per unit area average precipitation per unit area by contrast the diminished effects of chemical weathering produce no recognizable association of fehr with fet in glacial particulates and instead both fepr and feu are closely correlated with fet reflecting essentially pristine mineralogy a comparison of the globally averaged compositions of riverine particulates and marine sediments reveals that the latter are depleted in fehr fepr and fet but enriched in feu the river and glacial particulate data are combined with estimates of authigenic hydrothermal atmospheric and coastal erosive iron fluxes from the literature to produce a global budget for fehr f e pr f e u and fet this budget suggests that the differences between riverine particulates and marine sediments can be explained by i preferentially removing fehr from the riverine particulate flux by deposition into inner shore reservoirs such as floodplains salt marshes and estuaries and ii mixing the resulting riverine particulates with fehr depleted glacial particulates preliminary measurements of inner shore sediments are consistent with i above phanerozoic and modern normal marine sediments have similar iron speciation characteristics which implies the existence of a long term steady state for the iron cycle this steady state could be maintained by a glacioeustatic feedback where fehr enriched riverine particulates are either more effectively trapped when sealevel is high small ice masses diminished glacial erosion or are mixed with greater masses of fehr depleted glacial particulates when sealevel is low large ice masses enhanced glacial erosion further important controls on the steady state for fehr operate through the formation of euxinic sediments and ironstones which also provide sealevel dependent sinks for fehr enriched sediment

pacific 187 os 188 os isotope chemistry and u pb geochronology synchroneity of global os isotope change across oae 2 studies of oae 2 sections beyond the atlantic ocean western interior seaway wis and european pelagic shelf are limited here we present initial osmium isotope stratigraphy 187os 188os osiosi from two proto pacific sites that span the cenomanian turonian boundary interval ctbi the yezo group yg section hokkaido japan and the great valley sequence gvs california usa to evaluate the 187os 188os seawater chemistry of the proto pacific additionally we combine new 206pb 238u zircon ca id tims geochronology from five volcanic tuff horizons of the yezo group section to test and facilitate inter basinal integration with the wis using radio isotopically constrained age depth models for both sections and quantitatively constrain the absolute timing and duration of events across the ctbi the yg shows an almost identical osiosi profile to that of the wis and very similar to that of other sites of the proto atlantic and european pelagic oceans turgeon and creaser 2008 and du vivier et al 2014 the characteristics of the osiosi profile are radiogenic and heterogeneous 0 55 0 85 prior to the oae 2 and synchronous with the inferred oae 2 onset the osiosi abruptly become unradiogenic and remain relatively homogeneous 0 20 0 30 before showing a gradual return to more radiogenic view the mathml sourceosi 0 70 throughout the middle to late oae 2 a206a206pb 238u zircon age of an interbedded tuff hk017 in the adjacent horizon to the first unradiogenic osiosi value constrains the age of the osiosi inflection at 94 44 0 14 ma94 44 0 14 ma this age including uncertainty agrees with the interpolated age of the same point in the osiosi profile 94 28 0 25 ma94 28 0 25 ma in the only other dated oae 2 section the wis indicating a coeval shift in seawater chemistry associated with volcanism at the oae 2 onset at the levels of temporal resolution ca 0 1 myr further prior to the onset of oae 2 an enhanced radiogenic inflection in the osiosi profile of the yg is correlative within uncertainty with a similar trend in the wis based on the u pb age depth model the interpolated ages 94 78 0 12 ma94 78 0 12 ma and 94 66 0 25 ma94 66 0 25 ma for this osiosi inflection in the yg and wis respectively indicate that palaeocirculation was sufficient to simultaneously influence transbasinal seawater chemistry in contrast the pre oae 2 osiosi profile for the gvs is disparate to that of the yg and those of the proto atlantic and european pelagic shelf locations we interpret the pre oae 2 heterogeneous osiosi values 0 30 0 95 to record a palaeobasin that was regionally influenced interchangeably by both unradiogenic hydrothermal flux and radiogenic continental flux os we conclude that the osiosi profiles from the proto pacific sections record both trends that are consistent globally oae 2 onset syn and post oae 2 but also show regional differences pre oae 2 between oae 2 sections worldwide as such the osiosi profiles coupled with u pb geochronology facilitate the correlation of oae 2 stratigraphy and demonstrate both regional and global ocean dynamics

intercalibration of radioisotopic and astrochronologic time scales for the cenomanian turonian boundary interval western interior basin usa we develop an intercalibrated astrochronologic and radioisotopic time scale for the cenomanian turonian boundary ctb interval near the global stratotype section and point in colorado usa where orbitally influenced rhythmic strata host bentonites that contain sanidine and zircon suitable for 40ar 39ar and u pb dating paired 40ar 39ar and u pb ages are determined from four bentonites that span the vascoceras diartianum to pseudaspidoceras flexuosum ammonite biozones utilizing both newly collected material and legacy sanidine samples of j obradovich comparison of the 40ar 39ar and u pb results underscores the strengths and limitations of each system and supports an astronomically calibrated fish canyon sanidine standard age of 28 201 ma the radioisotopic data and published astrochronology are employed to develop a new ctb time scale using two statistical approaches 1 a simple integration that yields a ctb age of 93 89 0 14 ma 2 total radioisotopic uncertainty and 2 a bayesian intercalibration that explicitly accounts for orbital time scale uncertainty and yields a ctb age of 93 90 0 15 ma 95 credible interval total radioisotopic and orbital time scale uncertainty both approaches firmly anchor the floating orbital time scale and the bayesian technique yields astronomically recalibrated radioisotopic ages for individual bentonites with analytical uncertainties at the permil level of resolution and total uncertainties below 2 using our new results the duration between the cenomanian turonian and the cretaceous paleogene boundaries is 27 94 0 16 ma with an uncertainty of less than one half of a long eccentricity cycle

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

trace metal records of regional paleoenvironmental variability in pennsylvanian upper carboniferous black shales abstract regional geochemical differences within a laterally continuous cyclic pennsylvanian upper carboniferous shale in midcontinent north america are interpreted in light of models of glacioeustatic forcing and new views on water column paleoredox stability and trace metal behavior in black shale environments specifically we characterize differences in transition metal fe mn mo v ni zn pb and u concentrations in black shales of the hushpuckney shale member of the swope limestone in iowa and equivalent black shale beds of the coffeyville formation in oklahoma although c s fe systematics and uniform 34 s depleted isotope ratios of pyrite indicate pervasive euxinic deposition anoxic and sulfidic bottom waters for these shales regional variations can be inferred for the efficiency of mo scavenging and for the rates of siliciclastic sedimentation as expressed in spatially varying fe al ratios black shales in iowa show mo enrichment roughly five times greater than that observed in coeval euxinic shales in oklahoma by contrast fe al ratios in oklahoma shales are as much as five times greater than the continental ratio of 0 5 observed in the over and underlying oxic facies and in the coeval black shales in iowa recent work in modern marine settings has shown that enrichments in fe commonly result from scavenging in a euxinic water column during syngenetic pyrite formation in contrast to fe the concentrations of other transition metals mo v ni pb zn u are typically more enriched in the black shales in iowa relative to oklahoma the transition metal trends in these paleozoic shales are reasonably interpreted in terms of early fixation in organic rich sediments due to euxinic water column conditions however regional variations in 1 rates of siliciclastic input 2 organic reservoirs including relative inputs of terrestrial versus marine organic matter and 3 additional inputs of metals to bottom waters from contemporaneous hydrothermal vents are additional key controls that lead to geographic variation in the extent of metal enrichments preserved in ancient organic rich sediments

redox sensitivity of p cycling during marine black shale formation dynamics of sulfidic and anoxic non sulfidic bottom waters abstract a high resolution geochemical record of a 120 cm black shale interval deposited during the coniacian santonian oceanic anoxic event 3 odp leg 207 site 1261 demerara rise has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo redox conditions high contents of organic matter sulfur and redox sensitive trace metals cd mo v zn as well as continuous lamination point to deposition under consistently oxygen free and largely sulfidic bottom water conditions however rapid and cyclic changes in deep ocean redox are documented by short term 15 20 ka intervals with decreased total organic carbon toc s and redox sensitive trace metal contents and in particular pronounced phosphorus peaks up to 2 5 wt p associated with elevated fe oxide contents sequential iron and phosphate extractions confirm that p is dominantly bound to iron oxides and incorporated into authigenic apatite preservation of this fe p coupling in an otherwise sulfidic depositional environment as indicated by fe speciation and high amounts of sulfurized organic matter may be unexpected and provides evidence for temporarily non sulfidic bottom waters however there is no evidence for deposition under oxic conditions instead sulfidic conditions were punctuated by periods of anoxic non sulfidic bottom waters during these periods phosphate was effectively scavenged during precipitation of iron oxyhydr oxides in the upper water column and was subsequently deposited and largely preserved at the sea floor after 15 25 ka sulfidic bottom water conditions were re established leading to the initial precipitation of cds zns and pyrite subsequently increasing concentrations of h2s in the water column led to extensive formation of sulfurized organic matter which effectively scavenged particle reactive mo complexes thiomolybdates at site 1261 sulfidic bottom waters lasted for 90 100 ka followed by another period of anoxic non sulfidic conditions lasting for 15 20 ka the observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface to mid waters from the south atlantic resulting in a lowering of the oxic anoxic chemocline in the water column alternatively sea water sulfate might have been stripped by long lasting high rates of sulfate reduction removing the ultimate source for hs production

carbon and oxygen isotope stratigraphy of the english chalk and italian scaglia and its palaeoclimatic significance a detailed carbon and oxygen isotope stratigraphy has been generated from upper cretaceous coastal chalk sections in southern england east kent culver cliff isle of wight eastbourne and seaford head sussex norfolk coast and the british geological survey bgs trunch borehole norfolk data are also presented from a section through the scaglia facies exposed near gubbio italian apennines wherever possible the sampling interval has been one metre or less both the chalk and scaglia carbon isotopic curves show minor positive excursions in the mid cenomanian mid and high turonian basal coniacian and highest santonian lowest campanian there is a negative excursion high in the campanian in chalk sections that span that interval the well documented cenomanian turonian boundary spike is also well displayed as is a broad positive excursion centred on the upper coniacian a number of these positive excursions correlate with records of organic carbon rich deposition in the atlantic ocean and elsewhere the remarkable similarity in the carbon isotope curves from england and italy enables cross referencing of macrofossil and microfossil zones and pinpoints considerable discrepancy in the relative positions of the turonian coniacian and santonian stages the oxygen isotope values of the various chalk sections although showing different absolute values that are presumably diagenesis dependent show nonetheless a consistent trend the east kent section which is very poorly lithified indicates a warming up to the cenomanian turonian boundary interval then cooling thereafter regional organic carbon burial documented for this period is credited with causing drawdown of co 2 and initiating climatic deterioration inverse greenhouse effect data from other parts of the world are consistent with the hypothesis that the cenomanian turonian temperature optimum was a global phenomenon and that this interval represents a major turning point in the climatic history of the earth

production and preservation of organic matter the significance of iron 1 iron fertilization has been previously recognized as a potential mechanism for enhanced organic matter burial in marine sediments however the singular view of iron as a control on primary production overlooks its role in sedimentary diagenesis a factor that must be evaluated when considering organic matter accumulation this study examines the role of iron as a buffer of pore water sulfide and its implications for marine organic matter burial biogeochemical model experiments indicate that dissolved sulfide buildup in surficial marine sediments is highly sensitive to reactive iron concentration a reduction in reactive iron concentration can initiate dissolved sulfide accumulation the consequences of which include inhibition of bioturbation bioirrigation a decrease in oxygen exposure time and enhanced organic matter burial alternatively an increase in reactive iron concentration can serve to decrease organic matter burial the coupling of iron and phosphorous cycling within marine sediments provides an important positive feedback and therefore this mechanism is designated the sulfide buffer phosphorous trap hypothesis given sufficient organic carbon supply carbonate rich and opal rich sediments should be especially prone to the development of sulfidic conditions because of a deficiency in terrigenous iron widespread chalk and marl deposition during the cretaceous in association with the evolutionary expansion of calcareous plankton may have predisposed many benthic marine environments to the accumulation of toxic hydrogen sulfide and fostered the development of oceanic anoxic events comparison of model results with proxy data from oceanic anoxic event ii middle cretaceous suggests a complex role of iron as a control on both organic matter production and preservation

mixing of a tracer in the pycnocline a patch of sulfur hexafluoride was released in may 1992 in the eastern north atlantic on an isopycnal surface near 300 m depth and was surveyed over a period of 30 months as it dispersed across and along isopycnal surfaces the diapycnal eddy diffusivity k estimated for the first 6 months was 0 12 0 02 cm2 s while for the subsequent 24 months it was 0 17 0 02 cm2 s the vertical tracer distribution remained very close to gaussian for the full 30 months as the root mean square rms dispersion grew from 5 to 50 m lateral dispersion was measured on several scales the growth of the rms width of the tracer streaks from less than 100 m to approximately 300 m within 2 weeks implies an isopycnal diffusivity of 0 07 m2 s at scales of 0 1 to 1 km larger than expected from the interaction between vertical shear of the internal waves and diapycnal mixing teasing of the overall patch initially about 25 km across into streaks with an overall length of 1800 km within 6 months supports predictions of exponential growth by the mesoscale strain field at a rate of 3 0 5 10 7 s 1 the rms width of these streaks estimated as 3 km and maintained in the face of the streak growth indicates an isopycnal diffusivity of 2 m2 s at scales of 1 to 10 km much greater than expected from internal wave shear dispersion the patch was painted in albeit streakily by 12 months confirming expectations from analytical and numerical models homogenization of the patch continued during the subsequent 18 months while the patch continued to spread with an effective isopycnal eddy diffusivity on the order of 1000 m2 s acting at scales of 30 to 300 km

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

internal tides in monterey submarine canyon abstract the m2 internal tide in monterey submarine canyon is simulated using a modified version of the princeton ocean model most of the internal tide energy entering the canyon is generated to the south on sur slope and at the head of carmel canyon the internal tide is topographically steered around the large canyon meanders depth integrated baroclinic energy fluxes are up canyon and largest near the canyon axis up to 1 5 kw m 1 at the mouth of the upper canyon and increasing to over 4 kw m 1 around monterey and san gregorio meanders the up canyon energy flux is bottom intensified suggesting that topographic focusing occurs net along canyon energy flux decreases almost monotonically from 9 mw at the canyon mouth to 1 mw at gooseneck meander implying that high levels of internal tide dissipation occur the depth integrated energy flux across the 200 m isobath is order 10 w m 1 along the majority of the canyon rim but increases by over an order of magnitude near the canyon head where internal ti

black shale deposition atmospheric co2 drawdown and cooling during the cenomanian turonian oceanic anoxic event 1 oceanic anoxic event 2 oae2 spanning the cenomanian turonian boundary ctb represents one of the largest perturbations in the global carbon cycle in the last 100 myr the 13ccarb 13corg and 18o chemostratigraphy of a black shale bearing ctb succession in the vocontian basin of france is described and correlated at high resolution to the european ctb reference section at eastbourne england and to successions in germany the equatorial and midlatitude proto north atlantic and the u s western interior seaway wis 13c offset between 13ccarb and 13corg is shown to be a good pco2 proxy that is consistent with pco2 records obtained using biomarker 13c data from atlantic black shales and leaf stomata data from wis sections boreal chalk 18o records show sea surface temperature sst changes that closely follow the 13c pco2 proxy and confirm tex86 results from deep ocean sites rising pco2 and sst during the late cenomanian is attributed to volcanic degassing pco2 and sst maxima occurred at the onset of black shale deposition followed by falling pco2 and cooling due to carbon sequestration by marine organic productivity and preservation and increased silicate weathering a marked pco2 minimum 25 fall occurred with a sst minimum plenus cold event showing 4 c of cooling in 40 kyr renewed increases in pco2 sst and 13c during latest cenomanian black shale deposition suggest that a continuing volcanogenic co2 flux overrode further drawdown effects maximum pco2 and sst followed the end of oae2 associated with a falling nutrient supply during the early turonian eustatic highstand

copper lead and zinc trapping in mediterranean deep sea sediments probable coprecipitation with mn and fe abstract in the deepest area of the western mediterranean sea between sardinia and minorca sediments are relatively rich in zn and fe on the periphery of this area the sediments are rather rich in cu pb and mn and to a lesser extent in zn in this last case the vertical profile of mn in the sediment suggests that the mn enrichment in the top level with an mn concentration of 1500 g g 1 is due to an ascending mn flux from deeper levels reducing for mn oxyhydroxides to the surficial 0 4 cm thick oxidizing sediment the concentrations of cu pb and zn dissolved in the surficial sediment pore waters are too low to allow direct precipitation of mere oxides or hydroxides of these metals but enrichment in the mn rich deep sea zone can be explained by a coprecipitation process during the precipitation of mn oxides or hydroxides since mn dissolved in surficial sediment pore water is present in an apparent slight oversaturation with respect to the solubility product in the deepest areas where zn seems to precipitate with fe hydroxides the surficial sediments appear to be too reducing to allow mn oxides to precipitate cu and pb are trapped not so well there calculations of chemical equilibria of the species concerned are consistent with these considerations since mn seems to be released from sediments in the deepest zone with total mn concentrations g g 1 it can be assumed that there the surficial sediments correspond nearly to a reducing medium for the mn oxides therefore the bottom seawaters of these deepest area of the western mediterranean sea seem to have rather low o 2 concentrations and to be only rarely renewed

sulfur isotope records around livello bonarelli northern apennines italy black shale at the cenomanian turonian boundary sulfur isotope ratios for carbonate hosted sulfate show a rapid increase 6 to 9 m y across the livello bonarelli black shale marche umbrian apennines of italy which was deposited at the cenomanian turonian boundary in the middle cretaceous 93 5 ma the increase suggests that rates of pyrite burial increased substantially over the event resulting in a decrease of 9 27 in the oceanic reservoir of so 4 2 the enhanced pyrite burial may have significantly increased the flux of oxygen to the atmosphere 9 27 10 18 mol m y furthermore removal of the large amount of iron associated with this process might have had a profound effect on iron cycle

authigenic molybdenum formation in marine sediments a link to pore water sulfide in the santa barbara basin pore water and sediment mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the santa barbara basin to examine the connection between authigenic mo formation and pore water sulfide concentration only at the deepest site 580 m where pore water sulfide concentrations rise to 0 1 mm right below the sediment water interface was there active authigenic mo formation at shallower sites 550 430 and 340 m where pore water sulfide concentrations were consistently 0 05 mm mo precipitation was not occurring at the time of sampling a sulfide concentration of 0 1 mm appears to be a threshold for the onset of mo fe s co precipitation a second threshold sulfide concentration of 100 mm is required for mo precipitation without fe possibly as mo s or as particle bound mo mass budgets for mo were constructed by combining pore water and sediment results for mo with analyses of sediment trap material from santa barbara basin as well as sediment accumulation rates derived from 210 pb the calculations show that most of the authigenic mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters there is however a non lithogenic particulate mo associated with sinking particles that contributes 15 to the total authigenic mo accumulation analysis of sediment trap samples and supernant brine solutions indicates the presence of non lithogenic particulate mo a large fraction of which is easily remobilized and perhaps associated with mn oxides our observations show that even with the very high flux of organic carbon reaching the sediment of santa barbara basin active formation of sedimentary authigenic mo requires a bottom water oxygen concentration below 3 mm however small but measurable rates of authigenic mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 mm indicating that the formation of authigenic mo occurred in the recent past but not at the time of sampling copyright 2000 elsevier science ltd

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

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

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

geochemical study of organic matter rich cycles from the kimmeridge clay formation of yorkshire uk productivity versus anoxia abstract in this contribution we study two meter scale cycles from the kimmeridge clay formation cored near marton yorkshire which shows cyclic organic matter om distribution our aim is to try to understand the factors responsile for om accumulation the first cycle called lower cycle shows a total organic carbon toc content between 1 and 10 whereas the second called upper cycle shows a toc content varying between 5 and 35 the geochemical composition major elements and trace elements the organic geochemistry toc hi palynofacies and mineralogy of the sediments have been determined in both cycles the cyclicity is expressed through variations in the nature and in the relative abundance of the various types of organic matter constituents furthermore dilution effects by inorganic components of the sediment cannot account for the toc cyclicity for lower cycle the mo v and u content is low and little variable as is the intensity of the oxidation which om suffered from this indicates that variations in phytoplanktonic productivity may be held responsible for the cyclicity in steady and mildly reducing redox conditions in the upper cycle cyclicity also appears to depend on productivity but variations in the concentration of mo v and u and in the oxidation state of the om suggest the environment was temporarily more reducing it is proposed that larger amounts of h 2 s were released into marine bottom waters as a result of initial om decomposition forced the oxic anoxic boundary to rise in the water column and thus favoured om storage the main driving force for variations in the om concentration was the productivity of organic matter walled phytoplankton redox conditions of the depositional environment could have had a positive action but only by acting as a positive feedback effect

a continental weathering control on orbitally driven redox nutrient cycling during cretaceous oceanic anoxic event 2 the cretaceous period 145 65 m y ago was characterized by intervals of enhanced organic carbon burial associated with increased primary production under greenhouse conditions the global consequences of these perturbations oceanic anoxic events oaes lasted up to 1 m y but short term nutrient and climatic controls on widespread anoxia are poorly understood here we present a high resolution reconstruction of oceanic redox and nutrient cycling as recorded in subtropical shelf sediments from tarfaya morocco spanning the initiation of oae2 iron sulfur systematics and biomarker evidence demonstrate previously undescribed redox cyclicity on orbital time scales from sulfidic to anoxic ferruginous fe rich water column conditions bulk geochemical data and sulfur isotope modeling suggest that ferruginous conditions were not a consequence of nutrient or sulfate limitation despite overall low sulfate concentrations in the proto north atlantic instead fluctuations in the weathering influxes of sulfur and reactive iron linked to a dynamic hydrological cycle likely drove the redox cyclicity despite the potential for elevated phosphorus burial in association with fe oxides under ferruginous conditions on the tarfaya shelf porewater sulfide generation drove extensive phosphorus recycling back to the water column thus maintaining widespread open ocean anoxia

ocean sound channel ray path perturbations from internal wave shear and strain the relative importance of internal wave strain and internal wave shear on perturbation of acoustic ray trajectories in the ocean is analyzed previous estimates based on the garrett munk internal wave spectral model are updated using data from recent field studies of internal waves estimates of the ratio of the rms shear effect to the rms strain effect based on data from the upper kilometer of ocean are as high as 0 25 0 4 exceeding the estimates of 0 08 0 17 stemming from the model increased strength of three phenomena that have shear to strain ratios higher than the internal wave average can cause this effect these are near inertial waves internal tides and vortical modes

benthic phosphorus regeneration net primary production and ocean anoxia a model of the coupled marine biogeochemical cycles of carbon and phosphorus we examine the relationships between ocean ventilation primary production water column anoxia and benthic regeneration of phosphorus using a mass balance model of the coupled marine biogeochemical cycles of carbon c and phosphorus p the elemental cycles are coupled via the redfield c p ratio of marine phytoplankton and the c p ratio of organic matter preserved in marine sediments the model assumes that on geologic timescales net primary production in the oceans is limited by the upwelling of dissolved phosphorus to the photic zone the model incorporates the dependence on bottom water oxygenation of the regeneration of nutrient phosphorus from particulate matter deposited at the water sediment interface evidence from marine and lacustrine settings modern and ancient demonstrates that sedimentary burial of phosphorus associated with organic matter and ferric oxyhydroxides decreases when bottom water anoxia dysoxia expands steady state simulations show that a reduction in the rate of thermohaline circulation or a decrease of the oxygen content of downwelling water masses intensifies water column anoxia dysoxia and at the same time increases surface water productivity the first effect reflects the declining supply of oxygen to the deeper parts of the ocean the second effect is caused by the enhanced benthic regeneration of phosphorus from organic matter and ferric oxyhydroxides sedimentary burial of organic carbon and authigenic calcium phosphate mineral francolite on the other hand is promoted by reduced ocean ventilation according to the model global scale anoxia dysoxia leads to a more efficient recycling of reactive phosphorus within the ocean system consequently higher rates of primary production and organic carbon burial can be achieved even when the continental supply of reactive phosphorus to the oceans remains unchanged

a model for uranium rhenium and molybdenum diagenesis in marine sediments based on results from coastal locations abstract the purpose of this research is to characterize the mobilization and immobilization processes that control the authigenic accumulation of uranium u rhenium re and molybdenum mo in marine sediments we analyzed these redox sensitive metals rsm in benthic chamber pore water and solid phase samples at a site in buzzards bay massachusetts usa that has high bottom water oxygen concentrations 230 300 mol l and high organic matter oxidation rates 390 mol c cm2 y the oxygen penetration depth varies from 2 to 9 mm below the sediment water interface but pore water sulfide is below detection release of rsm to pore waters during the remineralization of solid phases occurs near the sediment water interface at depths above the zone of authigenic rsm formation this release occurs consistently for mo at both sites but only in the winter for re in buzzards bay and intermittently for u at the buzzards bay site re removal to the solid phase extends to the bottom of the profile while the zone of removal is restricted to 2 9 cm for u and mo authigenic re formation is independent of the anoxic remineralization rate which is consistent with an abiotic removal mechanism the rate of authigenic u formation and its modeled removal rate constant increase with increasing anoxic remineralization rates and is consistent with u reduction being microbially mediated authigenic mo formation is related to the formation of sulfidic microenvironments the depth and extent of mo removal from pore water is closely associated with the balance between iron and sulfate reduction and the consumption of pore water sulfide via iron sulfide formation pore water rsm reach constant asymptotic concentrations in sulfidic sediments but only pore water re is constant at depth in buzzards bay the increases in pore water u at the buzzards bay site are consistent with addition via irrigation and subsequent upward diffusion to the removal zone deep pore water mo concentrations exceed its bottom water concentration due to irrigation induced oxidation and remobilization from the solid phase in sulfidic sediments there is no evidence for higher pore water u or mo concentrations at depth due to the absence of irrigation and or the presence of more stable authigenic rsm phases there are good correlations between benthic fluxes and authigenic accumulation rates for u and mo in sulfidic sediments however results from buzzards bay suggest irrigation ultimately results in the partial loss of u and mo from the solid phase with accumulation rates that are 20 30 of the modeled flux irrigation can augment re possibly u or compromise u mo authigenic accumulation in sediments and is important when determining burial rates in continental margin sediments

thermal evolution of cretaceous tethyan marine waters inferred from oxygen isotope composition of fish tooth enamels 1 the evolution of subtropical 30 35 n upper ocean temperatures through the cretaceous is inferred from the oxygen isotope compositions of 64 fish teeth enamel coming from the western tethyan platform mean 18o values of 22 at the berriasian valanginian boundary decrease with oscillations to 18 5 around the cenomanian turonian boundary and progressively increase to 21 5 by the end of the cretaceous the similarity of this oxygen isotope curve for bioapatites from platform environments with those for foraminifera and bulk carbonates that were deposited in deeper waters and at other paleolatitudes indicates that they record global climatic signals major cooling events at the million year scale can be distinguished 1 at the berriasian valanginian boundary and 2 during the earliest late valanginian a third cooling event is detected during the earliest aptian these events already proposed as icehouse interludes during the lower cretaceous are also recorded at subtropical latitudes a progressive warming is identified from the aptian to the cenomanian turonian interval that corresponds to a thermal optimum and then upper ocean temperatures decreased to the maastrichtian minimum isotopic temperatures range from 15 c to 28 c assuming a 18oseawater of 1 for an ice free world taking more realistic 18oseawater values of 0 for tropical waters during glacial periods within the berriasian valanginian interval and earliest aptian or with above average salinities possibly the maastrichtian temperatures are increased by 4 5 c temperature differences between climatic extremes of the valanginian and cenomanian turonian are estimated to have been 10 c latitudinal thermal gradients for the albian cenomanian turonian and maastrichtian were 0 2 0 3 c latitude and thus weaker than modern oceanic values at about 0 4 c latitude

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

doppler sonar observations of internal waves the wavenumber frequency spectrum abstract in may 1980 an 18 day sequence of velocity profiles of the top 600 m of the sea was collected off the coast of southern california the measurements were obtained using a pair of doppler sonars mounted on the research platform flip from these data estimates of the wavenumber frequency spectrum of the oceanic internal wavefield are obtained the spectra are characterized by a series of ridges which occur at near internal and tidal frequencies as well as higher harmonics and sums of these fundamentals the ridges run parallel to the wavenumber axis there is a pronounced near inertial spectral peak the near inertial motions are dominated by a few identifiable wave groups there is a net downward energy propagation in the near inertial frequency band the vertical wavenumber dependence of a the spectrum is decidedly asymmetric in this region the asymmetry extends to five times the inertial frequency making much of the so called continuum asymmetric a high wavenumber cutoff at approximately 60

orbital time scale and new c isotope record for cenomanian turonian boundary stratotype previous time scales for the cenomanian turonian boundary ctb interval containing oceanic anoxic event ii oae ii vary by a factor of three in this paper we present a new orbital time scale for the ctb stratotype established independently of radiometric biostratigraphic or geochemical data sets update revisions of ctb biostratigraphic zonation and provide a new detailed carbon isotopic record for the ctb study interval the orbital time scale allows an independent assessment of basal biozone ages relative to the new ctb date of 93 55 ma gts04 the d 13 corg data document the abrupt onset of oae ii significant variability in d 13 corg values and values enriched to almost 222 these new data underscore the difficulty in defining oae ii termination using the new isotope curve and time scale estimates of oae ii duration can be determined and exported to other sites based on integration of well established chemostratigraphic and biostratigraphic datums the new data will allow more accurate calculations of biogeochemical and paleobiologic rates across the ctb