eustatic sea level record for the cenomanian late cretaceous extension to the western interior basin usa a combination of biostratigraphic markers ammonites inoceramid bivalves and carbon isotope excursions is employed to establish a high resolution correlation between the middle to late cenomanian successions of the western interior basin usa and the anglo paris basin southern uk sequences identified from sedimentologic criteria in the pueblo succession and elsewhere in the western interior basin are shown to coincide precisely with globally recognized sea level events and were therefore under eustatic control this evidence refutes arguments that cenomanian sequences in the western interior basin were formed by local tectonic events the interaction of longer term tectonic movements and more rapid eustatic change may have simply enhanced the amount of erosion associated with sequence boundaries a crossplot of radiometric ages derived from north american bentonites against an orbitally tuned time scale developed in the anglo paris basin provides support for the argument that the sequences were controlled by the 405 k y long eccentricity cycle

origins and maturity of organic matter in mid cretaceous black shales from odp site 1138 on the kerguelen plateau abstract we have conducted elemental isotopic and rock eval analyses of cenomanian santonian sediment samples from odp site 1138 in the southern indian ocean to assess the origin and thermal maturity of organic matter in mid cretaceous black shales found at this high latitude location total organic carbon toc concentrations range between 1 and 20 wt in black to medium gray sediments deposited around the cenomanian turonian boundary results of rock eval pyrolysis indicate that the organic matter is algal type ii material that has experienced modest alteration important contributions of nitrogen fixing bacteria to the amplified production of organic matter implied by the high toc concentrations is recorded in 15n values between 5 and 1 and the existence of a near surface intensified oxygen minimum zone that favored organic carbon preservation is implied by toc tn ratios between 20 and 40 in contrast to the marine nature of the organic matter in the cenomanian turonian boundary section deeper sediments at site 1138 contain evidence of contributions land derived organic matter that implies the former presence of forests on the kerguelen plateau until the earliest cenomanian

de glauconiarum origine the glauconitic facies is widespread on present day continental shelves from 50 s to 65 n and at water depths between 50 and 500 m and is in particularly great abundance on the upper slope and outer shelf between 200 and 300 m it is also common in many ancient rocks of post late precambrian age it occurs as sand to pebble sized essentially green particles granular facies but also as a surface coating on particles and hardgrounds and as a diffuse impregnation film and diffuse facies we suggest the replacement of the term glauconite which has been interchangeably used to designate a morphological form and a specific mineral by glaucony facies and glauconitic smectite and glauconitic mica as end members of the glauconitic mineral family the widely accepted model of burst and hower for glauconitization requires a degraded micaceous 2 1 layer lattice structure parent clay mineral however detailed analysis of numerous samples of recent glaucony reveals that such a parent substrate is exceptional the model therefore requires modification generally the parent material is carbonate particles argillaceous kaolinitic faecal pellets infillings of foraminiferal tests various mineral grains and rock fragments that pass gradually into the commonly occurring green grains we show that the process of glauconitization is achieved by de novo authigenic growth of automorphous crystallites in the pores of the substrate accompanied by progressive alteration and replacement of the substrate it is this two fold evolution that causes the verdissement of granular substrates macrofossils and hardgrounds the authigenic mineral is an iron rich and potassium poor glauconitic smectite while new smectites are growing into the remaining pore space the earlier smectites are modified by incorporation of potassium producing decreasingly expandable minerals with a non expandable glauconitic mica as the end member this mineralogical diversity of the glauconitic mineral family explains the highly variable physical and chemical properties of glaucony four categories nascent little evolved evolved and highly evolved glaucony are distinguished glauconitization appears to be controlled by a delicate balance between degree of physical confinement of a particle and the amount of ionic exchange between the micro environment and ambient open marine sea water the optimum conditions for glauconitization are those of semi confinement as a result the interior of a grain is more glauconitized than its less confined periphery similarly for identical substrate types large grains 500 m provide more favourable substrates for glauconitization than lesser confined small grains on a larger scale the formation of glaucony is governed by the availability of iron and potassium and the balance between detrital influx and winnowing low accumulation rates expose grains to the open marine environment for sufficiently long times 105 106 years for highly evolved glaucony

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

orbital forcing of organic carbon burial in the proto north atlantic during oceanic anoxic event 2 the cenomanian turonian c t intervals at dsdp sites 105 and 603b from the northern part of the proto north atlantic show high amplitude short term cyclic variations in total organic carbon toc content the more pronounced changes in toc are also reflected by changes in lithology from green claystones toc 1 although their depositional history was different the individual toc cycles at sites 105 and 603b can be correlated using stable carbon isotope stratigraphy sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled the coinciding variations in hi oi 13corg and the abundance of marine relative to terrestrial biomarkers as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones indicate that these cyclic variations reflect changes in the contribution of marine organic matter om the cooccurrence of lamination enrichment of redox sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto north atlantic ocean water column was periodically euxinic from the bottom to at least the base of the photic zone 150 m during the deposition of the black claystones in contrast the green claystones are bioturbated are enriched in mn do not show enrichments in redox sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times indicating more oxic water conditions at the same time there is evidence e g abundance of biogenic silica and significant 13c enrichment for oc of phytoplanktic origin for enhanced primary productivity during the deposition of the black claystones we propose that increased primary productivity periodically overwhelmed the oxic om remineralisation potential of the bottom waters resulting in the deposition of om rich black claystones because the amount of oxygen used for om remineralisation exceeded the amount supplied by diffusion and deep water circulation the northern proto north atlantic became euxinic during these periods both sites 105 and 603b show trends of continually increasing toc contents and hi values of the black claystones up section which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine om during oceanic anoxic event 2 oae2

marine 187os 188os isotope stratigraphy reveals the interaction of volcanism and ocean circulation during oceanic anoxic event 2 high resolution osmium os isotope stratigraphy across the cenomanian turonian boundary interval from 6 sections for four transcontinental settings has produced a record of seawater chemistry that demonstrates regional variability as a function of terrestrial and hydrothermal inputs revealing the impact of palaeoenvironmental processes in every section the 187os 188os profiles show a comparable trend radiogenic values in the lead up to oceanic anoxic event 2 oae 2 an abrupt unradiogenic trend at the onset of oae 2 an unradiogenic interval during the first part of oae 2 and a return to radiogenic values towards the end of the event above the cenomanian turonian boundary the unradiogenic trend in 187os 188os is synchronous in all sections previous work suggests that activity of the caribbean lip large igneous province was the source of unradiogenic os across the oae 2 and possibly an instigator of anoxia in the oceans here we assess this hypothesis and consider the influence of activity from other lips such as the high arctic lip a brief shift to high radiogenic 187os 188os values occurred in the western interior seaway before the onset of oae 2 we evaluate this trend and suggest that a combination of factors collectively played critical roles in the initiation of oae 2 differential input of nutrients from continental and volcanogenic sources coupled with efficient palaeocirculation of the global ocean and epeiric seas enhanced productivity due to higher nutrient availability which permitted penecontemporaneous transport of continental and lip derived nutrients to trans equatorial basins

hydraulic control of flow over the sill in observatory inlet observations of density velocity and acoustic backscatter obtained over the sill in observatory inlet british columbia during the ebb tide illustrate several features of internal hydraulic control in a tidally forced stratified flow following high water slack the flow field was initially determined by critical control of the second internal mode at the sill crest as the flow speed increased a transition occurred and control changed to an approach control of the second internal mode located upstream of the sill crest whereas the critical control represents a minimum energy condition at the crest the approach control corresponds to a maximum energy condition upstream of the sill crest later when the ebb currents were just past their maximum values the control condition changed to critical control of the first internal mode the concept of approach control of flow over topography has not previously been discussed in the literature the data described here are believed to represent the first field observations of this phenomenon the changing hydraulic conditions are analyzed in terms of two and three layer hydraulic models model results are consistent with the evolution of the flow patterns although the model cannot reproduce the apparent hysteresis in the response after maximum ebb the concept of an approach control is demonstrated with a simple two layer laboratory model

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

organic matter provenance palaeoproductivity and bottom water anoxia during the cenomanian turonian oceanic anoxic event in the newfoundland basin northern proto north atlantic ocean abstract free and sulfur bound biomarkers in sediments deposited in the northern proto north atlantic newfoundland basin odp site 1276 during the cenomanian turonian oceanic anoxic event 2 oae 2 were studied the 13c records of phytane and lycopane confirmed the stratigraphic position of the positive carbon isotope excursion associated with oae 2 previously reported for total organic carbon toc and homohopane sediments before and after the oae 2 interval were poor in organic matter om and comprised numerous gravity flow deposits the interval itself was composed of pelagic sediments with occasionally a much higher toc content of up to 12 7 the oae 2 sediments were characterized by a low amount of terrestrial om since the dominant biological sources of the biomarkers were aquatic in origin high hopane pentamethylicosane pmi and squalane abundances in the om rich sediments pointed to a relatively high input of prokaryotes partly derived from cyanobacteria as suggested by the occasional occurrence of 2 methylhopanes pmi comprised both the regular and irregular isomer and changes in the 13c of pmi are thought to reflect contributions from methanogenic and methanotrophic archea the high relative concentration of lycopane indicated that bottom water conditions were anoxic during large parts of the oae 2 interval in one horizon trace amounts of isorenieratane provided evidence for the occasional occurrence of photic zone anoxia taken together the data imply that oceanic anoxia and probably also high productivity reached the northernmost part of the proto north atlantic during oae 2 albeit that photic zone anoxia was much less common than in the southern proto north atlantic

stepwise extinction of larger foraminifers at the cenomanian turonian boundary a shallow water perspective on nutrient fluctuations during oceanic anoxic event 2 bonarelli event a two step pattern in the extinction of larger foraminifers is recorded in the upper cenomanian shallow water carbonates of the southern apennines italy the first step eliminated the alveolinids the most extreme oligotrophs and reduced dramatically the diversity of larger foraminifers the second step wiped out the few survivors seemingly able to tolerate mesotrophic conditions leaving a disaster fauna dominated by small heterotrophs this pattern of extinction parallels the ecological succession of shallow water benthic foraminiferal assemblages along a gradient of increasing nutrient availability high resolution carbon isotope stratigraphy shows that the extinction of alveolinids was contemporaneous with the extinction of rotaliporid planktic foraminifers the drowning of certain tethyan carbonate platforms and an episode of thermal instability recorded in sea surface temperature in the open ocean ocean stratification during the first phase of oceanic anoxic event 2 would have promoted oligotrophic conditions in surface tropical waters and maximum diversity of larger foraminifers following this ocean overturning caused by surface water cooling is credited with delivering to shallow water environments the excess nutrient loads previously stored at depth triggering the environmental changes leading to stepwise extinction of larger foraminifers

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

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

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

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

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

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

obliquity forcing of organic matter accumulation during oceanic anoxic event 2 1 an analysis of orbitally influenced climate sensitive sedimentation is conducted across a meridional transect of the proto north atlantic to reconstruct the behavior of the carbon cycle and climate during oceanic anoxic event 2 oae 2 94 ma midlatitude to near equatorial sites spanning deep ocean to shelf environments are evaluated using a new inverse method for the identification and calibration of orbital influence in ancient strata the results yield consistent independent astrochronologies at each location compatible with the recently published radioisotopic astrochronologic time scale at the cenomanian turonian gssp and thus provide a unified high resolution temporal context for evaluation of the event the proto north atlantic astrochronologies document an amplification of obliquity power during oae 2 indicating that obliquity was the dominant pacemaker of organic matter accumulation by the latter portion of the event the strong obliquity signal suggests an influence of high latitude climate processes across midlatitude deep ocean to tropical shelf environments changes in oceanic circulation during oae 2 represent a likely mechanism for the propagation of a high latitude signal and proxy data from demerara rise reveal the development of a new intermediate water mass source synchronous with the record of obliquity amplification we hypothesize that a dense high latitude water mass displaced a pre existing nutrient rich anoxic deep water layer in the proto north atlantic augmented by enhanced volcanism driving an episode of high productivity that lasted 700 800 ka the development and intensification of the new intermediate deep water source was potentially driven by eustatic sea level rise which created expansive seaways in mid to high latitudes

syndepositional shallow water precipitation of glauconitic minerals abstract numerous studies have demonstrated that glauconitic minerals predominantly form in water depths of mid shelf to upper slope in modern oceans these areas tend to have slow sedimentation rates another commonly cited requisite for glauconitic mineral precipitation cambro ordovician strata from the southwestern us are rich in glauconitic minerals stratigraphic sedimentological and petrographic constraints indicate that the glauconitic minerals are autochthonous in marked contrast to the modern environments of deposition these cambro ordovician strata formed under very shallow water to tidal flat conditions the trough cross stratified deposits of the most glauconitic mineral rich accumulations glaucarenites indicate a high energy environment and probably a normal to high rate of sedimentation the presence of fibroradiated rims of glauconitic minerals on glauconitic mineral pellets echinoderm fragments and quartz grains demonstrates that the cambro ordovician glauconitic minerals precipitated on or in close proximity to the sea floor and prior to calcite precipitation consequently glauconitic minerals must have formed under markedly different conditions in the lower paleozoic than they do today thus the occurrence of glauconitic minerals in the rock record cannot be used a priori as an environmental indicator of either mid shelf and deeper water and or a slow rate of sedimentation

a southern hemisphere record of global trace metal drawdown and orbital modulation of organic matter burial across the cenomanian turonian boundary ocean drilling program site 1138 kerguelen plateau despite its assumed global nature there are very few detailed stratigraphic records of the late cenomanian to the early turonian oceanic anoxic event 2 from the southern hemisphere a highly resolved record of environmental changes across the cenomanian turonian boundary interval is presented from ocean drilling program site 1138 on the central kerguelen plateau southern indian ocean the new data lead to three key observations firstly detailed biostratigraphy and chemostratigraphy indicate that the record of oceanic anoxic event 2 is not complete with a hiatus spanning the onset of the event a decrease in glauconite and highly weathered clays after the onset of oceanic anoxic event 2 marks the end of the hiatus interval which can be explained by a relative sea level rise that increased sediment accommodation space on the kerguelen plateau margin this change in depositional environment controlled the timing of the delayed peak in organic matter burial during oceanic anoxic event 2 at site 1138 compared with other oceanic anoxic event 2 locations worldwide a second key observation is the presence of cyclic fluctuations in the quantity and composition of organic matter being buried on the central kerguelen plateau throughout the latter stages of oceanic anoxic event 2 and the early turonian a close correspondence between organic matter sedimentary elemental compositions and sediments recording sea floor oxygenation suggests that the cycles were mainly productivity driven phenomena available age control points constrain the periodicity of the coupled changes in sedimentary parameters to ca 15 to 50 ka suggesting a link between carbon burial and astronomically forced climatic variations precession or obliquity in the southern hemisphere mid latitudes both during and after oceanic anoxic event 2 fluctuations that were superimposed on the impact of global scale processes finally trace metal data from the non sulphidic black shale unit at site 1138 provide the first evidence from outside of the proto north atlantic region for a global drawdown of seawater trace metal mo inventories during oceanic anoxic event 2 this article is protected by copyright all rights reserved

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 cenomanian turonian boundary at eastbourne sussex uk a proposed european reference section the cenomanian turonian boundary ctb section at eastbourne sussex england is the thickest at outcrop in the anglo paris basin is rhythmic throughout rich in macro micro and nanno fossils and shows less diagenetic alteration than other sections in nw europe geochemical and biostratigraphic data are all related to detailed rhythmic lithostratigraphy allowing correlation with the global boundary stratotype section to within 20 000 years and accurate estimates of rates of changes very detailed stable isotope curves for oxygen and carbon are presented and show that the build up phase of the ctb carbon excursion had two portions separated by a trough patterns of occurrence of coarse fraction benthic foraminifera 250 mm show two peaks of extinction corresponding to the two build up phases of the carbon excursion benthic and planktic foraminifera ostracods and calcareous nannofossils all show declines in diversity and abundance across the ctb foraminifera also decline significantly in size key biomarker events for the ctb include first occurrences of the ammonites fagesia catinus and mammites nodosoides the bivalve mytiloides the planktic foraminifera helvetoglobotruncana praehelveticaand marginotruncana renzi and the calcareous nannofossils quadrum intermedium q gartneri and eprolithus octopetalus and last occurrences of the ammonite sciponoceras the planktic foraminifera rotalipora greenhornensis and r cushmani the calcareous nannofossils corolithion kennedyi axopodorhabdus albianus lithraphidites acutus rhagodiscus asperand microstaurus chiastius cyclostratigraphy allows very precise correlation of isotopic and bioevents with other sections in europe and north america eastbourne is recommended as a nw european standard section 1999 elsevier science b v all rights reserved

global enhancement of ocean anoxia during oceanic anoxic event 2 a quantitative approach using u isotopes during the mesozoic greenhouse world the oceans underwent several oceanic anoxic events oaes characterized by intervals during which organic rich black shales were deposited indicating strong oxygen depletion in the marine realm the cenomanian turonian oae2 ca 93 ma represents one of the most prominent events of the cretaceous with significant perturbations of the global carbon cycle although oae2 likely reached a global scale the spatial extent of seawater anoxia during this oae is poorly constrained here we demonstrate that variations in the 238u 235u isotope ratio 238u a newly developed paleoredox proxy can be used to quantify the extent of marine anoxia for black shales from the mid cretaceous oae2 we find a systematic shift toward lighter 238u and lower u concentrations as compared to modern equivalent organic rich sediments from the black sea this shift translates to a global increase of oceanic anoxia during oae2 by at least a factor of three as compared to the present day or to periods before and after oae2 the constant offset in u concentrations and isotope compositions of black shales throughout oae2 compared to modern black sea sediments indicates an enhancement of oceanic anoxic conditions already prior to the onset of oae2

seismic attenuation above 10 hz in southern california from coda waves recorded in the cajon pass borehole we estimate the attenuation around cajon pass southern california for frequencies above 10 hz and we find total q to exhibit only weak frequency dependence ranging from 800 at 10 hz to 1500 at 100 hz the intrinsic attenuation is approximately twice the level of the scattering attenuation measurements are made using earthquake seismograms recorded at 0 3 km depth using the multiple lapse time window method the results are not dependent on receiver depth and are consistent with previous estimates of q made from direct waves recorded at 2 5 km depth our q values are therefore thought to be representative of the seismogenic crust and the technique used is uncontaminated by the highly attenuating near surface at least above 10 hz we also calculate q from surface data between 1 and 10 hz and find a clear change in the frequency dependence of both intrinsic and scattering attenuation at 10 hz q exhibits strong frequency dependence below 10 hz 1 8 consistent with previous studies in active tectonic regions and only weak frequency dependence at higher frequencies 0 34 this change in behavior renders it unwise to extrapolate q measurements outside the frequency range from which they were derived for example in earthquake source studies possible factors responsible for the apparent change in frequency dependence of q are considered further work is required however to resolve the causes of this change

spatial extent and degree of oxygen depletion in the deep proto north atlantic basin during oceanic anoxic event 2 massive organic matter burial due to widespread ocean anoxia across the cenomanian turonian boundary event 94 ma resulted in a major perturbation of the global carbon cycle the so called oceanic anoxic event 2 oae2 the characteristics and spatial distribution of the oae2 deposits that formed in the deep basin of the proto north atlantic remain poorly described however here we present proxy data of redox sensitive trace elements e g mo fe al corg ptot and mn for oae2 sediments from five deep sea drilling project and ocean drilling program sites located in the deep proto north atlantic basin our results highlight that bottom waters in the entire deep proto north atlantic were anoxic during most of oae2 furthermore regressions of mo with total organic carbon content toc previously shown to document the degree of water mass restriction confirm that the water circulation in the proto north atlantic basin was severely restricted during oae2 comparison of these values to mo toc ratios in the present day black sea suggests a renewal frequency of the deep proto north atlantic water mass of between 0 5 and 4 ka compared to a maximum of 200 years for the present day northern atlantic the plenus cold event a cooler episode during the early stages of oae2 hypothesized to be caused by declining pco2 due to extensive burial of organic matter appears to have led to temporary re oxygenation of the bottom water in the deep proto north atlantic basin during oae2

late cretaceous eocene nannofossil and magnetostratigraphic correlations near gubbio italy abstract using a modified sample preparation technique we have been able to establish a detailed lower campanian to upper eocene nannofossil stratigraphy in the bottaccione and contessa highway sections near gubbio appearance and extinction levels of virtually all the commonly used calcareous nannofossil zonal markers have been recognized and can now be closely correlated with the planktonic foraminifera zonation and the magnetic reversal stratigraphy previously established in these sections comparisons with the nannofossil calibrations of the oceanic magnetic anomaly sequence in deep sea drilling project dsdp sites suggest that magmetic subchrons c17n and c25n are missing in the bottaccione section the observed variability of the relative stratigraphic position of most plankton events is confirmed to less than one magnetic subchron absolute abundance paleobiogeographic restriction and differential preservation render some of the traditionally used biostratigraphic events less reliable than others

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

the cenomanian turonian oceanic anoxic event ii palaeoceanographic controls on organic matter production and preservation correlation of the 13c spike with the well dated occurrences of strata rich in organic carbon detailed in schlanger et al this volume indicates that a global episode of intense organic carbon orgc burial took place during the latest cenomanian earliest turonian oceanic anoxic event oae a plenus through i labiatus macrofossil zones and upper r cushmani trz through w archecretacea prz foraminiferal zones over a period of no more than 1 million years m y the shape of the 13c curve indicates that rates of orgc burial gradually increased in the early part of the late cenomanian increased more rapidly in the later cenomanian and levelled off at peak values in latest cenomanian early turonian time during the maximum rate of orgc burial the 13c values decreased nearly to pre late cenomanian levels in the early to middle turonian the decrease in 13c reflects decreasing rates of orgc burial following the cenomanian turonian oceanic anoxic event as well as the probable oxidation and return of significant amounts of orgc to the oceans following regression and re oxygenation of much of the deeper water masses in contact with the seafloor

petrographic classification of oil shales abstract oil shales are a diverse group of rocks that contain mineral matter and organic matter the organic matter is derived from terrestrial lacustrine and marine organisms the maceral nomeclature system of the international committee for coal petrology used widely in coal petrography and petroleum source rock studies is suitable for describing the organic matter in oil shales provided the terminology for organic matter derived from algal precursors is divided into two submacerals telalginite and lamalginite macerals of the liptinite group including alginite are volumetrically important constituents of oil shales and are the major source of the shale oil that is formed during pyrolysis liptinite is easily characterized and quantified using fluorescence mode microscopy and thus the type and abundance of liptinite can be used as a basis for a petrographic classification of oil shales oil shales are grouped using the environmental of deposition as the discriminatory criterion into the three primary divisions of terrestrial lacustrine and marine oil shales type and abundance of liptinite is then used to subdivide these three groups into cannel coal torbanite lamosite further subdivided into rundle type lamosite and green river type lamosite marinite tasmanite and kuckersite

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

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

onset of the mid cretaceous greenhouse in the barremian aptian igneous events and the biological sedimentary and geochemical responses basalts and biostratigraphy dated at 125 120 ma from the ontong java and manihiki plateaus in the western pacific evidence the largest volcanic event in earth history in at least the past 160 m y the intervening nova canton trough rifted at about 121 118 ma and a number of guyots and seamounts formed concurrently or slightly later geological events that probably were responses to these volcanic tectonic events occurred in the following chronostratigraphic order biotic fluctuations began at about 122 5 ma at about 122 0 ma 87sr 86sr began to decline slowly metal concentrations of co mn pb yb and cu in sediments peaked at about 121 5 121 2 ma changes in planktonic communities and sedimentation culminated in a nannoconid crisis just prior to 120 5 ma and in the selli black shale oae la at about 120 5 119 5 ma a sharp drop in 13c occurred at the beginning of the selli event and rebounded into a longer positive excursion that reached a peak after the selli event at about 119 5 118 5 ma at 120 5 ma 87sr 86sr declined rapidly and reached a minimum at about 116 113 ma we speculate that the intensity of these latter responses suggests a corresponding peak in volcanic tectonic activity at about 121 119 ma

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

integrated quantitative stratigraphy of the cenomanian turonian bridge creek limestone member using evolutive harmonic analysis and stratigraphic modeling abstract secular changes in bulk sedimentation have a significant impact on the preservation of climatic signals in rhythmically bedded strata in this study a quantitative cyclostratigraphic methodology is developed to use these signal distortions as a means to reconstruct sedimentation the method exploits a moving window fourier technique that we designate evolutive harmonic analysis eha we calibrate this methodology to a specific set of geologic conditions i e changes in bulk sedimentation using a series of stratigraphic models and then apply the technique to the cenomanian turonian greenhorn formation of the western interior basin application of eha to strata that preserve a record of orbital forcing allows the reconstruction of a high resolution sedimentation history in which bulk sedimentation rates and hiatuses are quantified using the data on bulk sedimentation rate rates of accumulation for geochemical proxies representing detrital biogenic and authigenic contributions to the sediment can be calculated by integrating these quantitative assessments of siliciclastic dilution primary production and depositional redox conditions within a high resolution chronostratigraphic framework we are able to deconvolve secular trends in hemipelagic sedimentation during the late cenomanian early turonian in the western interior basin this integrated quantitative stratigraphic approach allows a reevaluation of hypotheses for the accumulation of excess organic matter in the western interior basin during the interval representing oceanic anoxic event ii

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

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

age and paleoenvironment of the cenomanian turonian global stratotype section and point at pueblo colorado biostratigraphy and stable isotopes indicate that the global stratotype section and point gssp at pueblo contains an essentially complete sedimentary record across the global ocean anoxic event oae 2 and the cenomanian turonian boundary the oae 2 d 13 c shift occurred over a period of about 90 ky and was accompanied by a major sea level transgression which at its peak was marked by an incursion of oxygen rich waters creating a benthic oxic zone that lasted about 100 ky a mid cenomanian d 13 c shift sea level transgression and faunal turnover occurred about 2 my before oae 2 d 18 o values of the planktic foraminifer hedbergella planispira and its relative abundance changes reveal cyclic variations in surface salinity due to alternating freshwater influx and marine incursions whereas dominance by the low oxygen tolerant heterohelix species indicates a well developed oxygen minimum zone omz for most of the middle to late cenomanian and early turonian profound faunal changes accompanied these oceanographic events including the extinction of 30 of the species assemblage and an equal gain in evolutionary diversification though the overall combined relative abundances of outgoing and incoming species were less than 2 and 4 respectively of the total assemblages the faunal turnover began with the sea level transgression and rapid increase in d 13 c values and accelerated with the influx of oxygen rich deep water increased water mass stratification and competition during the benthic oxic zone the incursion of oxygen rich deep waters at this time was also observed in morocco and may represent a global event of a still unknown source d 2003 elsevier b v all rights reserved

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

chemostratigraphy versus biostratigraphy data from around the cenomanian turonian boundary a detailed isotopic profile is presented for a stratigraphically expanded cenomanian turonian boundary section in chalk facies exposed at eastbourne sussex and compared with data from pueblo colorado in both sections macro and micropalaeontological markers first appearances and disappearances are well constrained and their relative positions and relationship to the structure of the carbon isotope curve are identical this consistent relationship between two independent phenomena one geochemical the other biostratigraphical is taken as evidence for the likely synchroneity of both the biostratigraphical markers and the carbon isotope excursion in these two areas this interpretation contrasts with suggestions made recently by other authors whose data have been taken to imply a lack of correlation between the carbon isotope excursion in europe and north america

black shale deposition on the northwest african shelf during the cenomanian turonian oceanic anoxic event climate coupling and global organic carbon burial high resolution geochemical records from a depth transect through the cenomanian turonian c t tarfaya basin northwest african shelf reveal high amplitude fluctuations in accumulation rates of organic carbon oc redox sensitive and sulphide forming trace metals and biomarkers indicative of photic zone euxinia these fluctuations are in general coeval and thus imply a strong relationship of oc burial and water column redox conditions the pacing and regularity of the records and the absence of a prominent continental signature suggest a dynamic depositional setting linked to orbital and higher frequency forcing determining the dominant frequency depends on the definition of the most pronounced oceanic anoxic event oae2 and its duration we propose that eccentricity is the main forcing factor at tarfaya and controlled fluctuations in wind driven upwelling of nutrient rich oxygen depleted intermediate waters from the adjacent atlantic and the periodic development of photic zone and bottom water euxinia on the mid cretaceous northwest african shelf accumulation records clearly identify the basin center as the primary site of sediment deposition with highest temporal variability and an up to six fold increase in oc burial from similar to2 g m 2 yr prior to the oae2 to similar to12 g m 2 yr during the oae2 photic zone and bottom water euxinia alternated with periods of greater oxygenation of the water column in response to climate forcing mass balance calculations imply that similar to2 of the overall global excess oc burial associated with the oae2 was deposited in the tarfaya basin an area that represented only similar to0 05 of the total global c t ocean floor in fact the lateral extent of similar black shales along the african continental margin indicates that this part of the ocean contributed significantly to the global increase in organic carbon burial during the oae2

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

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

riverine behaviour of uranium and lithium isotopes in an actively glaciated basaltic terrain this study presents u and li isotope and major and trace element data for the dissolved load suspended particulates and bedload for icelandic rivers draining predominantly basaltic catchments physical erosion rates range from 920 to 2084 t km2 yr with the higher values associated with glacier fed rivers chemical erosion rates range from 45 to 91 t km2 yr with lower rates being associated with glacier fed rivers uranium activity ratios 234u 238u are close to secular equilibrium in the suspended and bedloads but all dissolved load samples show values greater than unity ranging from 1 13 to 2 41 the highest 234u 238u values are found in glacier fed rivers and can be attributed to recoil effects as grinding by glaciers locally enhances rates of physical weathering activity ratios in glacial rivers decrease with distance from the glacial source due to input from non glacial tributaries which have high levels of dissolved uranium and lower activity ratios in contrast in non glacial rivers uranium activity ratios increase with distance downstream due to continued weathering in soils and of bedrock the 7li value of the suspended load is always lower than that of the bedload due to preferential retention of 6li in secondary minerals during weathering in turn the 7li value of the dissolved load is always greater than that of the bedload ranging from 17 0 to 43 7 7li for the dissolved load decreases with increasing levels of dissolved silicon and the saturation index of secondary minerals which suggests that 7li decreases with increasing chemical weathering there is no correlation between 7li values and uranium activity ratios for the dissolved load for non glacial rivers but for glacier fed rivers there is an increase in 7li with increasing 234u 238u suggesting that where physical comminution of mineral grains by glaciers is high chemical weathering is suppressed and vice versa

lithium isotope fractionation during continental weathering processes a comprehensive understanding of lithium isotope fractionation during terrestrial weathering is necessary in order to use lithium isotopes to trace chemical cycles climatic changes and igneous processes this study investigates lithium isotope fractionation in two laboratory experiments and by analyses of natural basalt weathering products partial dissolution of basalts in the laboratory does not result in fractionation of lithium isotopes but similar dissolution of a granite sample causes significant fractionation this may reflect dissolution of secondary minerals from the granite or differences in the li isotope composition of primary minerals in this more evolved igneous rock significant li isotope fractionation was also observed during sorption onto mineral surfaces in the laboratory although this was highly dependent on sample mineralogy no fractionation accompanies the outer sphere physisorption of li to smectite surfaces some fractionation accompanies sorption onto ferrihydrite and significant fractionation with 0 986 is seen during inner sphere chemisorption to gibbsite surfaces repeat experiments with varying amounts of sorption demonstrate that li remains in an exchangeable site on the gibbsite surface the extent of fractionation onto gibbsite observed in this study 13 is about half that required in order for clay surface removal to balance the ocean li isotope budget isotopic fractionation of li was found to occur on a 300 yr timescale in both cold and warm natural environments a minimally altered rock surface from iceland was found to be two lighter in 7li than the sample interior probably due to the preferential incorporation of 6li in clay or oxide rich alteration products on the sample surface soil samples from hawaii also demonstrate li fractionation during weathering in this environment rainwater 7li 10 contributes a significant flux of isotopically heavy li to the developing soil despite this soils have similar li isotope compositions to the primary basalt 7li 4 indicating that 6li is preferentially retained during weathering this conclusion is supported by isotopically heavy river water on hawaii 7li 22 and by the correlation between li concentration and 7li in the soil the lab and field based measurements of this study clearly demonstrate that lithium fractionates during weathering potentially providing information about the weathering environment now and in the past