chemical weathering indices applied to weathering profiles developed on heterogeneous felsic metamorphic parent rocks abstract chemical weathering indices are commonly used for characterizing weathering profiles by incorporating bulk major element oxide chemistry into a single metric for each sample generally on homogeneous parent rocks weathering indices change systematically with depth however the weathering of heterogeneous metamorphic rocks confounds the relationship between weathering index and depth in this paper we evaluate previously defined chemical weathering indices for their suitability in characterizing weathering profiles developed on felsic heterogeneous metasedimentary bedrock from coweeta hydrologic laboratory north carolina usa among the weathering indices evaluated here the weathering index of parker wip is the most appropriate for application to weathering profiles on heterogeneous and homogeneous parent rock because the wip includes only the highly mobile alkali and alkaline earth elements in its formulation it yields values that differ greatly from those of the parent rock in addition the wip allows for aluminum mobility unlike other weathering indices these characteristics combine to make the weathering index of parker the most applicable index for studying the weathering of heterogeneous metasedimentary rocks however the wip should be applied judiciously as alkali and alkaline earth metals may be readily depleted during weathering in addition to reflecting weathering the chemical index of alteration cia chemical index of weathering ciw plagioclase index of alteration pia and vogt s residual index v may be sensitive to subtle geochemical changes such as hydrothermal alteration along a fault and or alteration at the water table weathering indices that include iron in their calculations were not included in this study because they do not distinguish between ferric and ferrous iron the oxidation state and distribution of iron in a weathering profile is influenced by the proportion of oxidation states in the pre weathered metamorphic rock and interaction with groundwater during weathering

modeling phosphorus cycling and carbon burial during cretaceous oceanic anoxic events article i nfo in the greenhouse world of the cretaceous there were episodes of oxygen depletion in the deep ocean associated with enhanced organic carbon burial in sediments black shale formation in this study we use a box model of the oceanic phosphorus p organic carbon orgc and oxygen cycles to explore the hypothesis that variations in marine p availability control deep ocean oxygen depletion anoxia and the formation of black shales under cretaceous ocean conditions we find that for the cretaceous ocean with large continental shelves slow oceanic overturning and high sea surface temperatures oceanic anoxic events oaes can be triggered by enhanced p supply from land and that the system is particularly sensitive to oceanic mixing in our baseline scenario the deep sea becomes completely anoxic while the shelves attain only partial anoxia sedimentary burial differs between the shelves and open ocean while organic carbon burial is enhanced in both regions deep sea reactive p burial decreases dramatically under anoxia but not on the shelves where oxygen depletion is not complete furthermore our model results imply that oaes can be sustained by p recycling from sediments under low oxygen conditions ultimately however the feedbacks which result in the accumulation of atmospheric oxygen terminate the anoxic event atmospheric oxygen is modulated by land processes such as forest fires and oxidative weathering which limit the rise of atmospheric o2 our model findings are corroborated by p burial data from the geological record for oae2 approximately 94 myr bp through a sensitivity analysis we identify two necessary criteria for oaes low mixing of surface and deep waters poor ocean ventilation and enhanced sedimentary p recycling under low oxygen conditions when these criteria are met ocean anoxia is a robust result to a mild increase of continental supply of phosphorus under a wide range of environmental conditions

eccentricity paced monsoon like system along the northwestern tethyan margin during the valanginian early cretaceous new insights from detrital and nutrient fluxes into the vocontian basin se france high resolution changes in terrigenous and nutrient fluxes into the vocontian basin northwestern tethyan margin were investigated for the late berriasian late valanginian time interval in order to assess the precipitation patterns in the source areas and to evaluate the effect of orbital forcing on the strength of the hydrological cycle in this study new high resolution mineralogical bulk rock and clay fraction and geochemical phosphorus and oxygen isotope data are used from the astronomically calibrated orpierre section for the first time kaolinite detrital and phosphorus accumulation rates kar dar and par are calculated and compared to a set of 547 geochemical and 260 mineralogical published data from other vocontian sections it appears that three regional increases in the kar document three successive humid episodes during the valanginian this is confirmed by contemporaneous increases in dar and partly also in par which highlight higher terrigenous and nutrient fluxes to the vocontian basin during these episodes concomitant decreases in the 18owhole rock signals may reflect higher sea surface temperatures during the early valanginian and the early late valanginian transition the occurrence of the three humid episodes is interpreted to relate to an orbital paced monsoonal circulation pattern through seasonally reversing movements of air mass heat and precipitation over the northwestern tethyan margin in particular based on the correlation between the 405 kyr eccentricity cycles and the kar signal obtained at orpierre an eccentricity influenced monsoonal circulation is proposed as the possible forcing factor behind these climatic patterns the average duration between the climaxes of the three regional wetter episodes is approximately 2 43 myr the wetter and likely also warmer episode at the early late valanginian transition is in step with the onset of the weissert episode in this regard the intensification of monsoonal driven precipitations appears as a possible external forcing factor leading or at least accelerating the important perturbation in the global carbon cycle associated with the weissert episode

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

fluid inclusion evidence for impact heating at the siljan ring sweden the siljan ring in central sweden is a devonian impact crater of the complex type the 52 km wide crater occurs in precambrian dala series granites deep drilling in the crater provides samples from depths down to 6000 m these are supplemented by surface samples from the crater and surrounding regions secondary fluid inclusions occur in matrix quartz of nearly all granites examined most inclusions contain low salinity water and water vapor no ch sub 4 or h sub 2 has been detected in surface samples peak trapping temperatures are 327 342 sup 0 c on the crater s inner plateau and minimum trapping temperatures are 135 225 sup 0 c near the annular moat in the subsurface trapping temperatures distinguish two sample populations separated by a flat lying 60 m thick dolerite at 1200 m below sea level in the deep sample group below 1200 m estimated trapping temperatures increase with depth along gradients between 17 and 32 sup 0 c km from 250 300 sup 0 c just below the dolerite to 320 440 sup 0 c at 5711 m trapping temperatures in samples above 1200 m are hotter than would be predicted by extrapolation of the deep trends and are believed to reflect hydrothermal activity generated by impact heating this interpretation is supported by the presence of hotter temperatures of fluid inclusionmore trapping in samples from inside the crater compared to outside and by crosscutting relations which show that some fluid inclusion trails postdate impact related features such as planar elements in quartz impact heated fluids circulated through a circular domain of rock approximately 52 km wide and at least 1 2 km thick the large scale of this circulation system indicates that impact generated hydrothermal activity can be a significant mechanism for heat dissipation following bolide impacts on water bearing planets less

first archaeomagnetic field intensity data from ethiopia africa 1615 12 ad abstract first archaeointensity determinations have been obtained from ethiopia seven bricks 34 specimens from the dabsan archaeological remains were subjected to archaeointensity determination by means of classical thellier thellier experiment including tests for magnetic anisotropy and magnetic cooling rate dependency the age of the dabsan palace is well controlled by historical information between 1603 when land grants were conceded to the jesuits and the catholicism was established as the official religion in ethiopia and the age of the palace foundation in 1626 27 successful archaeointensity determinations were obtained in 27 specimens from five individual bricks revealing an average field value of 33 5 1 1 t which is 11 26 lower than expected values from global geomagnetic models based on historical and archaeomagnetic data global models for 1615 ad predict a low in central southern africa related to past location of the present southern atlantic anomaly saa our results suggest that the field intensity in central africa may have been slightly lower than global model predictions this would indicate that the low could be probably more extended towards central eastern africa or more intense than previously considered further data from this region are especially welcome to delineate the evolution of the saa

biogeochemical effects of atmospheric oxygen concentration phosphorus weathering and sea level stand on oceanic redox chemistry implications for greenhouse climates abstract understanding the key factors influencing the global oceanic redox system is crucial to fully explaining the variations in oceanic chemical dynamics that have occurred throughout the earth s history in order to elucidate the mechanisms behind these variations on geological timescales numerical sensitivity experiments were conducted with respect to the partial pressure of atmospheric molecular oxygen p o 2 the continental shelf area a cs and the riverine input rate of reactive phosphorus to the oceans r p the sensitivity experiment for atmospheric p o 2 indicates that pervasive oceanic anoxia and euxinia appear when p o 2 p o 2 are higher than a previous estimate of 50 pal present atmospheric level due to redox dependent phosphorus cycling the sensitivity experiment regarding the shelf area demonstrates that changes in the shelf area during the phanerozoic significantly affected oceanic oxygenation states by changing marine biogeochemical cycling a large continental shelf acts as an efficient buffer against oceanic eutrophication and prevents the appearance of ocean anoxia euxinia we also found that an enhanced r p is an important mechanism for generation of widespread anoxia euxinia via expansion of both the oxygen minimum zone and coastal deoxygenation although the critical r p value depends significantly on p o 2 a cs and the redox dependent burial efficiency of phosphorus at the sediment water interface our systematic examination of the oceanic redox state under cretaceous greenhouse climatic conditions also supports the above results

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

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

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

nitrogen isotopic composition of sediments from the eastern tethys during oceanic anoxic event 2 abstract low nitrogen isotopic compositions 15n have been reported in deposits from the proto north atlantic and western tethys during oceanic anoxic event 2 oae2 at the cenomanian turonian c t transition it has been proposed that the low 15n values may have resulted from enhancement of n2 fixation and or incomplete assimilation of the upwelled ammonium due to expansion of anoxic euxinic conditions however few 15n measurements are available for the sediments from the eastern tethys and the pacific and therefore the global significance of the n cycle and its environmental implications remains to be tested here we present 15n data from oae2 deposits in the gongzha section in the tingri area of southern tibet which was located on the southern margin of the eastern tethys during the mid cretaceous the 15n data reveal a large perturbation of the n cycle during oae2 the pronounced negative shift in 15n prior to oae2 as well as the persistent low 15n values during oae2 imply the significant contribution of n2 fixation the changes in the marine n cycle suggest that the expansion of an anoxic environment may also have occurred in the southern continental margin areas of eastern tethys the coincidence of the marine faunal turnover and the perturbation of the n cycle suggests that the expansion of anoxic water masses may have played an important role in the extinction of marine organisms across the c t boundary in eastern tethys

planktonic foraminifers across the bonarelli event oae2 latest cenomanian the italian record abstract a high resolution quantitative study of the planktonic foraminiferal assemblages across the bonarelli level oae2 latest cenomanian of italy from different areas and geological settings has allowed the recognition of several events and biotic changes including acmes and crises of different genera it provides evidence of a progressive and rapid change of palaeoenvironmental conditions reaching a climax coincident with the bonarelli event and of the subsequent gradual although not complete resumption of previous conditions the observed pattern is illustrated by marked changes in the assemblages that indicate five discrete phases of environmental perturbation within the marine ecosystem though there are several similarities our analyses highlight that each section has its own peculiarities clearly indicating more or less extreme environmental conditions

a discussion of anomalous quartz from the roter kamm impact crater namibia evidence for post impact hydrothermal activity this paper presents arguments against the statement made by koeberl et al 1989 to the effect that various differences between the quartz of the three quartz pebbles from the roter kamm impact crater namibia and the quartz of the pegmatites present in the basement rocks of this crater can be best interpreted as evidence that the pebbles were formed or recrystallized by a post impact hydrothermal system arguments are presented that suggest that the three quartz pebbles are most likely fragments of a preimpact vein quartz of hydrothermal origin

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

continental weathering and redox conditions during the early toarcian oceanic anoxic event in the northwestern tethys insight from the posidonia shale section in the swiss jura mountains abstract the geochemistry and mineralogy of organic rich sediments of the rietheim succession in northern switzerland were studied to evaluate the main impacts of the early toarcian oceanic anoxic event t oae 183 ma ago on the depositional environment in the nw tethys ocean the geochemical data obtained notably 13corg 13ccaco3 rock eval pyrolysis toccff support the hypothesis that the negative c isotope excursion at the onset of the t oae mainly reflects a major perturbation in the global carbon cycle rather than local environmental changes e g basinal restriction productivity rock eval pyrolysis and 13corg 15ntotal crossplots indicate that the organic matter was primarily of marine origin during the t oae and deposited in an epicontinental sea setting detrital proxies notably detritus index siliciclastic balance and ln al2o3 na2o suggest that the elevated pco2 levels and greenhouse climate prevailing during the t oae induced significant acceleration of the hydrologic cycle and an increase in continental chemical weathering rates redox sensitive proxies relative pyrite contents organic and sulfide balances v v ni ratios trace elements enrichment factors trace element toc co variation patterns and toc ptotal molar ratios indicate that the rietheim posidonia shale sediments accumulated under oxic to dysoxic bottom water conditions with more reducing conditions during the t oae anoxic and possibly euxinic these changes in redox conditions were probably induced by substantial thermohaline stratification driven by enhanced freshwater input and the recurrent influx of brackish arctic seawater into the nw tethys through the viking corridor in agreement with previous sedimentological and geochemical evidences from the nw tethys ocean in the studied succession such conditions were perhaps also responsible for sequestration of most of the regenerated p in the deeper water column by adsorption and or co precipitation into authigenic phases overall the major palaeoenvironmental changes documented in this study provide a robust example of earth s possible responses to the rapid onset of extreme greenhouse conditions

weathering and global denudation a negative correlation between sediment yield and weathering history as measured by the chemical alteration cia of the suspended sediment is observed for many of the world s major rivers and other regions of denudation the weathering history is a first order control on the sediment yield of such areas termed equilibrium denudation regions for other areas data scatter with either apparent increases or decreases of sediment yield for given cia values these areas are termed nonequilibrium denudation regions low sediment yields can be attributed to moderated erosion either natural or human induced and or the incorporation of unweathered glacial debris accelerated erosion resulting in high sediment yield is primarily human induced and results from cultivation and other land use each of these effects has a profound influence on global sediment discharge from the continents pre human suspended sediment discharge from the continents is estimated to be 12 6 times 10 15 g yr or about 0 6 the

evolution of mid cretaceous radiolarians in response to oceanic anoxic events in the eastern tethys southern tibet china abstract oceanic anoxic events oaes are well known from their widespread black shale and carbon isotopic excursions in the western and eastern tethys and atlantic ocean however the weakest link in the studies of the oaes is biological evolution sedimentological biostratigraphical and geochemical data from albian to coniacian strata in southern tibet recorded turnover events and fluctuations in diversity of the radiolarian fauna within the eastern tethys during oae 1d and oae 2 abundant radiolarian fossils were obtained from the gyabula formation with 93 species from 43 genera identified and assigned to the mid to upper cretaceous acaeniotyle umbilicata archaeospongoprunum tehamaensis crucella cachensis alievium superbum and dictyomitra formosa zones the association of carbon isotopic excursions black shale and radiolarian turnover indicates extensive changes in the ocean climate system nutrients are made increasing available to the marine plankton through submarine volcanic activity and rising sea level which were a likely cause of radiolarian turnover at or near the oaes active submarine tectonism volcanism leads to the expansion of the hypoxic zone and may cause many deeper dwelling forms to become extinct whereas most of the shallower dwelling radiolarians survive radiolarian evolution thus provides a useful record with which to seek understand relationships between climate paleoceanographic processes and plankton evolution

fluidization and hydrothermal alteration of the suevite deposit at the ries crater west germany and implications for mars the formation cooling and alteration of the impact ejecta deposits at the ries crater are an analog for impact processes and the formation of regoliths and soils on mars we have studied the suevite deposit an impact melt bearing breccia found outside of the crater rim this suevite contains large numbers of chimney like degassing pipes apparently formed by high gas pressures in the hot 500 c fluidized suevite immediately after deposition of the suevite the likely sources of the gas are volatiles from the melted and shocked basement inclusions the suevite outside of the crater rim contains about 15 wt clay indicating a large amount of alteration of the suevite the clay is an fe rich montmorillonite with less than 5 interstratified illite indicating that the temperature at which most of the alteration occurred was less than 100 130 c the duration of this low temperature period may have been extended by additional heating from the exothermal alteration reactions the surfaces of the degassing pipes are not altered to clays however but have a thin fe rich oxide or hydroxide coating the absence of alteration in the pipes suggests that the main alteration event outside the crater occurred under unsaturated conditions such that the walls of the pipes were dry suevite deposits are likely to exist on mars because of the presence of volatile rich target rock martian suevites may have also been fluidized and hydrothermally altered contributing significantly to the formation of the clay like phases inferred to exist in the martian soil

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

paleoclimatic control on the composition of the paleoproterozoic serpent formation huronian supergroup canada a greenhouse to icehouse transition unlike other feldspathic arenites in the 12 km thick huronian supergroup strata of the 250 350 m thick serpent formation contain abundant plagioclase deposited in a distal alluvial setting the serpent formation consists of arenites with minor shale and siltstone the plagioclase abundance could reflect unroofing of a unique source relative to other huronian units or could be due to less intense chemical weathering major trace and rare earth element ree geochemistry of the serpent formation are used to evaluate these two possibilities serpent formation source rocks form part of the archean superior province which mainly consists of tonalitic granitic and supracrustal assemblages and their metamorphosed equivalents in al2o3cao na2ok2o acnk space shales define a linear array which indicates that the unweathered source contained plagioclase and k feldspar in the ratio of 5 1 this particular array indicates that serpent fluvial systems tapped a variably weathered carapace developed on the superior province rather than purely fresh bedrock a modelled mixture of 80 tonalite and 20 granite group rocks reproduces ree and trace element characteristics of the serpent formation sandstones and shales average eu eu 0 87 lan smn 4 4 gdnybn 1 8 and th sc 1 65 mass balance considerations indicate that less than 5 supracrustal group rocks can be added at the expense of the granite group a unique source for serpent detritus is rejected because underlying and overlying units have approximately the same provenance composition plagioclase k feldspar ratios in serpent sandstones range from 2 1 to 1 2 which achieves mass balance among source mudstone and sandstone compositions when plotted in acnk space achievement of mass balance implies that sandstones and mudstones were derived from the same weathering profiles these findings indicate that plagioclase preservation in the serpent formation is related to less intense compared with other huronian arenites paleoweathering conditions probably a harbinger of the widespread continental glaciation recorded in the overlying gowganda formation

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

stratigraphy of the upper cretaceous and lower tertiary strata in the tethyan himalayas of tibet tingri area china the 1500 m thick marine strata of the tethys himalaya of the zhepure mountain tingri tibet comprise the upper albian to eocene and represent the sedimentary development of the passive northern continental margin of the indian plate investigations of foraminifera have led to a detailed biozonation which is compared with the west tethyan record five stratigraphic units can be distinguished the gamba group upper albian lower santonian represents the development from a basin and slope to an outer shelf environment in the following zhepure shanbei formation lower santonian middle maastrichtian outer shelf deposits continue pebbles in the top layers point to beginning redeposition on a continental slope intensified redeposition continues within the zhepure shanpo formation middle maastrichtian lower paleocene the series is capped by sandstones of the jidula formation danian deposited from a seaward prograding delta plain the overall succession of these units represents a sea level high at the cenomanian turonian boundary followed from the turonian to danian by an overall shallowing upward megasequence this is followed by a final transgression regression cycle during the paleocene and eocene documented in the zhepure shan formation upper danian lutetian and by upper eocene continental deposits the section represents the narrowing and closure of the tethys as a result of the convergence between northward drifting india and eurasia the plate collision started in the lower maastrichtian and caused rapid changes in sedimentation patterns affected by tectonic subsidence and uplift stronger subsidence and deposition took place from the middle maastrichtian to the lower paleocene the final closure of remnant tethys in the tingri area took place in the lutetian

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

ongoing cenomanian turonian heterozoan carbonate production in the neritic settings of peru abstract the present paper reports on the sedimentological and geochemical record of albian turonian neritic carbonates from the eastern subequatorial pacific domain in peru the focus is on one of the most extreme carbon cycle perturbations of the phanerozoic the oceanic anoxic event 2 late cenomanian early turonian thanks to the very expanded and well exposed sections in peru the oae2 interval was sampled at high temporal resolution for both bulk micrite and bulk organic matter carbon isotopes despite the scarcity of significant amounts of organic matter or evidence for oxygen deficiency the 13c curve matches well with global published high resolution data for coeval successions such as those reported from the english chalk and the portland 1 core biostratigraphic data and the detailed sequence stratigraphic interpretation of these sections are combined with the carbon isotope chemostratigraphy documented here applying the characteristic peak and trough chemostratigraphic terminology for oae2 a c the following main environmental and carbon isotope stratigraphic features are observed from the late albian to the early middle turonian in peru i an albian to early late cenomanian heterozoan ramp recording the pre oae2 13c excursions specifically the mid cenomanian event ii a late cenomanian trough of 13c values b showing a progressive deepening leading to the short lived establishment of middle ramp type sedimentation iii a late cenomanian to early turonian 13c plateau c characterised by benthonic inner ramp sedimentation during a sea level highstand phase iv a recovery of 13c values at the end of oae2 associated to a trophic change increased influx of argillaceous facies and reduced carbonate production v a early to middle turonian fluctuating 13c curve linked to a maximum flooding phase in the mammites nodosoides zone and carbonate production during the collignoniceras woollgari zone the data shown here are particularly relevant as they come from very expanded neritic sections in the sub equatorial eastern pacific many of the features recognized share important similarities with tethyan and atlantic sections whilst the ramp system as such did not suffer from a carbonate crisis during oae2 as recorded for instance in mexico and tibet

pitfalls of normalization of marine geochemical data using a common divisor abstract normalization of trace element contents of sediment through division by the content of an immobile element usually aluminum is common practice in marine geochemical studies this might appear to be a simple way of correcting for dilution by sedimentary phases barren of a particular trace element for instance carbonates or silica and for comparison with its content in a standard clay or shale the purpose of this paper is to revive the awareness of the pitfalls of this practice by giving numerical examples of the often unexpected results of normalization taking a statistical perspective it is first shown that uncorrelated variables acquire spurious correlations when normalized but normalization can also increase decrease change sign of or even blur the correlations between unmodified variables next a number of realistic scenarios are worked out to show that the correlations between normalized element contents still suffer from the closure effect only in a few simple cases it is possible to extract from the normalized data realistic estimates of trace element contents in distinct sedimentary phases such as organic matter this is ascertained from data on copper contents in sediment from the black sea and arabian sea when the coefficient of variation i e standard deviation divided by the mean of the aluminum data is relatively low and much lower than for the original values of the trace elements comparisons of correlations can equally well or even better be made on the basis of the unmodified values then the comparison of trace element data with their values for standard shales is discussed the inherent problem is that the composition of the commonly used standard shale and consequently the reference values of normalized elements are not necessarily representative of the local or regional sediments in the study area also this method falls short of identifying the processes responsible for enrichment or diminution in trace element contents finally consideration is given to some aspects of a proper use of al normalization

roter kamm impact crater namibia geochemistry of basement rocks and breccias abstract the roter kamm crater in the southern namib desert has previously been identified as an impact structure on the basis of crater morphology and the presence of impact melt breccias which contain shock metamorphosed quartz and lithic clasts to better define the variety of target rocks and breccias we studied the petrography and chemical composition of a new suite of twenty eight basement and breccia samples from the roter kamm crater based on chemical data for target lithologies and breccias we suggest that the crater was formed in a two layer target region an upper layer of gariep metasediments schist marble quartzite and sandstone overlying the crystalline basement of the namaqualand metamorphic complex the basement was also heavily intruded by coarse grained quartz veins and quartz and quartz feldspar pegmatites the clast population in the melt breccias indicates that impact induced melting involved mainly metasedimentary target rocks with rarely detected contributions from pegmatite and granite granodiorite three varieties of melt breccias can be defined 1 schistose 2 quartzitic melt breccias 3 true impact melt breccias these melt breccia types are chemically heterogeneous and even the impact melt breccias may have been produced in situ and not from a coherent melt body the shapes of the schistose melt breccias previously thought to be ejected impact breccias are most likely caused by erosion and these breccias are now interpreted to be locally derived the crater basement as exposed at the rim was structurally severely affected and at least locally considerable thermal energy was generated during formation of large volumes of cataclastic mylonitic and pseudotachylitic breccias analyses of mylonite and pseudotachylites from the crater rim as well as their respective host rocks show that these breccias were mainly formed from local material analyses of pseudotachylite like breccias indicate that these possible friction melts are generated by preferential melting of hydrous ferromagnesian minerals and feldspar similar to their tectonically produced counterparts although no significant fluid effects resulting from formation of mylonites or pseudotachylites are indicated several breccias compared to their host rocks do show evidence of severe chemical alteration chloritisation and sericitisation the presence of large vesicles filled with hydrothermal mineral assemblages in some schistose breccias and other petrographic and chemical data support the hypothesis of an impact induced hydrothermal event in the crater area

palaeoclimatic interpretation of high resolution oxygen isotope profiles derived from annually laminated speleothems from southern oman high resolution stable isotope profiles of three contemporaneously deposited stalagmites from a shallow cave in southern oman provide an annually resolved record of indian ocean monsoon rainfall variability for the past 780 years uranium series age dating and counts of annual growth bands enable an excellent age calibration although modern speleothems do not grow in perfect isotopic equilibrium oxygen isotope ratios 18o are a proxy for the amount of monsoon rainfall this is supported by the statistically significant correlation between 18o and the thickness of annual bands whereas 18o is inversely correlated with annual band thickness additionally overlapping 18o profiles are very similar in pattern and range indicating that sample specific noise did not blur the climatic signal the longest oxygen isotope profile derived from stalagmite s3 clearly shows the transition at 1320 ad from a generally wetter medieval warm period to a drier little ice age that lasted from approximately ad 1320 1660 in southern oman the decrease in monsoon rainfall since the 1960s is also obvious in meteorological records from northern africa and india indicating that our speleothem based rainfall records do not only reflect local monsoon rainfall variability

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

the cenomanian turonian eagle ford group of south texas insights on timing and paleoceanographic conditions from geochemistry and micropaleontologic analyses abstract the interbedded organic rich marls and limestones of the eagle ford group of south texas were deposited on the shelf of the central texas platform during the upper cenomanian through the turonian micropaleontological analyses of thin sections and residue samples from subsurface cores taken in atascosa and karnes counties yielded 13 biostratigraphic datums which were integrated with calcareous nannofossil datums stable carbon isotopic and bulk inorganic geochemical analysis to gain an understanding of the paleoceanographic conditions of the study area and their relationship to regional and global events the paired thin section residue sampling was necessitated by poor recovery of planktonic foraminifera in washed samples which were however abundant in most thin sections lower eagle ford marls were deposited under euxinic conditions produced by a stratified water column periodic enhanced water column mixing increased oxygen levels and surface water primary productivity which promoted calcite diagenesis and generation of limestones containing calcispheres and radiolaria an oxygenated bottom water mass entered the basin in the uppermost cenomanian prior to the onset of oceanic anoxic event oae 2 causing a spike in benthic foraminiferal diversity and decreasing preservation of organic matter although the lower portion of the upper eagle ford is age equivalent to oae2 as indicated by positive shift in 13corg it contains less organic matter and evidence of more oxygen than the lower eagle ford so deposition of the eagle ford black shales is not contemporaneous to oae2

ammonite biostratigraphy and organic carbon isotope chemostratigraphy of the early aptian oceanic anoxic event oae 1a in the tethyan himalaya of southern tibet abstract the early aptian oceanic anoxic event oae 1a is well known in the western tethys the north atlantic and the pacific ocean but has not been reported in the eastern tethys to date in this paper we present bulk organic carbon isotope data and ammonite biostratigraphy of a lower aptian succession from the gucuo area southern tibet these findings document the occurrence of the oae 1a for the first time from the eastern tethys the studied sequence can be attributed to the d forbesi and d deshayesi ammonite zones of the lower aptian the 13 c org data can be correlated with published early aptian carbon isotope records from the western tethys and the pacific a distinctive negative carbon isotope excursion of 2 4 in the upper part of the section corresponds to segment c3 of the oae 1a and the following positive excursion correlates to segment c4 the absolute values of the carbon isotope ratio in the gucuo area are higher than those of known sections in the western tethys and equatorial pacific we suggest that diagenetic alteration is the major cause of the higher absolute values in the gucuo area

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

the expression of the cenomanian turonian oceanic anoxic event in tibet the gongzha section of tibet china is located at the northern margin of the indian plate se tethys and is characterized by hemipelagic grey marls and marly limestones light grey limestones and silty limestones but no organic rich sediments high resolution biostratigraphy reveals an expanded cenomanian turonian ct boundary interval and the 13c record includes the main features of the classical positive carbon isotope excursion that characterizes the ct oceanic anoxic event the biotic response inferred from the foraminifera suggests that oxic to dysoxic conditions prevailed except for a short interval marked by peak abundance of heterohelix that indicates a significantly dysoxic environment during the 13c b peak excursion the overall decreasing trend in redox sensitive trace elements rste during the maximum 13c excursion confirms the absence of significant longer lasting anoxia in the gongzha section enrichments in rste are linked to phases of increased detrital input chemical weathering indices suggest that the upper cenomanian sediments accumulated under an increasingly hot and humid climate that culminated near the ct boundary in the early turonian lower weathering indices suggest a warm drier climatic regime with reduced continental runoff phosphorus mass accumulation rates show a significant peak at the onset of the positive 13c excursion followed by a decrease up to the basal turonian this pattern is positively correlated with the long term decrease in detrital index as also observed in numerous other ct boundary sections e g eastbourne pueblo and whadi el ghaib sinai long term phosphorus accumulation in the gongzha section is therefore associated with changes in detrital input the overall decreased detrital input can be explained by the increasingly remote continental sources due to the major transgression at the end of cenomanian coupled with changes in continental weathering intensity linked to increasingly more arid climate conditions

bioevents and redox conditions around the cenomanian turonian anoxic event in central mexico abstract the xilitla section of central mexico western margin of the proto north atlantic is characterized by pelagic sediments enriched in marine organic matter using biostratigraphic and radiometric data it was dated at the latest cenomanian earliest turonian transition we identified an interval coeval with the faunal turnover associated with the oceanic anoxic event 2 oae 2 recording the heterohelix shift and the filament event for the first time in mexico an integral analysis of sedimentary facies pyrite and geochemical proxies reveals vertically variable redox conditions with prevailing anoxic to dysoxic bottom waters along with phosphorous and manganese depletion the highest content of total organic carbon and of certain redox sensitive trace elements rstes is found during part of the anoxic event confirming more uniform and constant oxygen depleted conditions this interval is also characterized by a significant enrichment in biogenic barium and elevated toc ntot ratios suggesting a link between productivity and anoxia sulfur isotope fractionation has a maximum value within the anoxic event favored by the increase in the flux of organic matter and intensified through sulfur recycling highly bioturbated beds representing short lived episodes of oxic conditions are intermittent within the oae 2 and become more frequent in the early turonian this study proposes a model similar to that of modern upwelling regions high marine productivity controlled organic matter burial and oxygenation at the seafloor varying between anoxic laminated facies with small pyrite framboids and dysoxic conditions bedding parallel bioturbated facies with inoceramid bivalves and large pyrite framboids interrupted by short term well oxygenated episodes thoroughly bioturbated facies with common benthic foraminifera general low oxygen conditions led to the formation of glauconite and pyrite bacterially mediated the enrichment of redox sensitive trace elements in sediments cd zn v and cr scavenged by organic matter and ni mo pb co and re by pyrite and resulted in mn and p depletion

cenomanian turonian transition in a shallow water sequence of the sinai egypt environmental and depositional changes across the late cenomanian oceanic anoxic event oae2 in the sinai egypt are examined based on biostratigraphy mineralogy 13c values and phosphorus analyses comparison with the pueblo colorado stratotype section reveals the whadi el ghaib section as stratigraphically complete across the late cenomanian early turonian foraminifera are dominated by high stress planktic and benthic assemblages characterized by low diversity low oxygen and low salinity tolerant species which mark shallow water oceanic dysoxic conditions during oae2 oyster biostromes suggest deposition occurred in less than 50 m depths in low oxygen brackish and nutrient rich waters their demise prior to the peak 13c excursion is likely due to a rising sea level characteristic oae2 anoxic conditions reached this coastal region only at the end of the 13c plateau in deeper waters near the end of the cenomanian increased phosphorus accumulations before and after the 13c excursion suggest higher oxic conditions and increased detrital input bulk rock and clay mineralogy indicate humid climate conditions increased continental runoff and a rising sea up to the first 13c peak above this interval a dryer and seasonally well contrasted climate with intermittently dry conditions prevailed these results reveal the globally synchronous 13c shift but delayed effects of oae2 dependent on water depth

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

the cenomanian turonian extinction and oceanic anoxic event evidence from southern tibet deep shelf locations on the perigondwanan margin of southern tibet record a major extinction of foraminifera and calcareous nannoplankton in the latest cenomanian top of the rotalipora cushmani zone this is followed by a low diversity survival interval that straddles the cenomanian turonian boundary whiteinella archaeocretacea zone during which only low diversity surface water dwelling foraminifera and nannoplankton and microfilaments are present rapid recovery in the early turonian saw the appearance of new species the reappearance of many lazarus species and the reestablishment of a diverse community of planktonic foraminifera that included a range of shallow to deep water column dwellers the extinction and survival intervals coincide with the development of dysaerobic facies characterised by small sized burrows and moderately large sized framboid pyrite populations at no time does the water column appear to have become sulfidic this study indicates that the end cenomanian oceanic anoxic and extinction events were also manifested in moderately high southerly palaeolatitudes on the southern margin of the tethyan ocean thereby increasing the known extent of this global event albeit with the proviso that the anoxic event was a dysoxic one

upper cretaceous carbon and oxygen isotope stratigraphy of hemipelagic carbonate facies from southern tibet china a high resolution carbon isotope curve derived from upper cretaceous hemipelagic sediments cropping out at tingri southern tibet shows similarities to patterns established on other continents notably in the presence of a well defined positive excursion across the cenomanian turonian boundary where 13 c values exceed 3 5 from the upper turonian to the lower campanian 13 c values generally decline apart from a minor positive excursion in the middle coniacian a trend that departs from that recorded from europe relatively low 13 c values c 1 at the santonian campanian and campanian maastrichtian boundaries in tibet define a prominent broad positive excursion centred in the middle campanian and terminated by an abrupt fall towards the close of the stage when compared with data from europe and north africa the 13 c values of the tibetan section are generally lower by c 1 5 except for the middle campanian positive excursion where values 13 c c 2 are comparable with those documented from europe and north africa these differences are interpreted as reflecting variable mixing of water masses carrying different carbon isotope signatures such that areas close to the major sinks of marine organic carbon recorded higher 13 c values than those located in more distal regions oxygen isotope ratios albeit affected by diagenesis may record a palaeotemperature signal

the cenomanian turonian oceanic anoxic event i stratigraphy and distribution of organic carbon rich beds and the marine δ13c excursion marine strata deposited during late cenomanian and early turonian time display lithological faunal and geochemical characteristics which indicate that significant parts of the world ocean were periodically oxygen deficient at or very close to the cenomanian turonian boundary between 90 5 and 91 5ma ago oxygen deficiencies were particularly marked over a period of 1ma this short lived episode of oceanic oxygen deficiency has been termed the cenomanian turonian oceanic anoxic event oae the widespread distribution of anoxic sediments deposited synchronously during such a short lived event indicates that such sediments are not simply the product of coincidental local climatic or basinal water mass characteristics but are the result of a global expansion and intensification of the cenomanian turonian oxygen minimum zone related to feedback between sea level rise and regional palaeoceanography the palaeoceanography of the cenomanian turonian oae is discussed in detail in a companion paper by arthur et al 1987 from authors

middle and late cenomanian oceanic anoxic events in shallow and deeper shelf environments of western morocco the response of shallow water sequences to oceanic anoxic event 2 and mid cenomanian events 1a and 1b was investigated along the west african margin of morocco north of agadir azazoul and correlated with the deep water sequence of the tarfaya basin mohammed beach based on biostratigraphy mineralogy phosphorus and stable isotopes in the deeper mohammed beach section results show double peaks in 13corg for mid cenomanian events 1a and 1b rotalipora reicheli biozone lower cc10a biozone the characteristic oceanic anoxic event 2 13c excursion rotalipora cushmani extinction top of cc10a biozone and laminated anoxic black shale in the shallow environment north of agadir a fluctuating sea level associated with dysoxic brackish and mesotrophic conditions prevailed during the middle to late cenomanian as indicated by oyster biostromes nannofossils planktonic and benthonic foraminiferal assemblages anoxic conditions characteristic of oceanic anoxic event 2 for example laminated black shales did not reach into shallow water environments until the maximum transgression of the early turonian climate conditions decoupled along the western margin of morocco between mid cenomanian event 1b and the cenomanian turonian boundary as also observed in eastern tethys north of agadir alternating humid and dry seasonal conditions prevailed whereas in the tarfaya basin the climate was dry and seasonal this climatic decoupling can be attributed to variations in the intertropical convergence zone and in the intensity of the north east trade winds in tropical areas

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

large scale climatic fluctuations in the latest ordovician on the yangtze block south china likely under warm and humid conditions low cia values however indicate the near absence of chemical weathering thereby refl ecting cool and or arid conditions in this paper the paleo climatic changes during the ordovician silurian transition were reconstructed in the light of cia values derived from the chemical composition of fi ne grained siliciclastic rocks in the mid upper yangtze river region china the infl u ences of paleoclimatic changes on biota are also discussed abstract the ordovician silurian transition was a critical interval in earth s history marked by dramatic climatic oceanic and biological turnovers here we present the chemical index of alteration cia as a proxy of changes in intensity of chemical weathering and its varia tions across the ordovician silurian boundaries wufeng through guanyinqiao to longmaxi formations from wangjiawan and nanbazi on the yangtze block south china in order to explore the climatic changes our data show that the cia values of sediments commonly range from 75 to 90 in the wufeng and longmaxi formations indicating a high degree of chemical weathering and thus a hot and humid climate during deposition in contrast a sharp drop in cia values most 60 70 in the guanyinqiao formation or hirnantian suggests an overall cold and arid climate interrupted by several intervals of warm climate when deposited the temporal coincidence of two phases of massive biotic extinctions with the beginning and end of the cold climate epoch respectively suggests that the large climatic changes could be one of the main controls on the mass extinctions although other factors may also have played a role

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

climate driven paleolimnological change controls lacustrine mudstone depositional process and organic matter accumulation constraints from lithofacies and geochemical studies in the zhanhua depression eastern china abstract the influence of paleoclimate on the depositional process of lacustrine mudstone and organic matter accumulation is important to both paleoclimate reconstruction and hydrocarbon exploration here we study the lower third member es3l of the eocene shahejie formation in the zhanhua depression bohai bay basin eastern china in order to understand how paleoclimate influenced depositional processes and organic matter accumulation of lacustrine organic rich mudstone by combining detailed core descriptions and microscopic observations and high resolution mineralogical and geochemical analyses we identified two major lithofacies including massive calcareous mudstone and laminated calcareous mudstone from the luo 69 drilling core the sedimentologic observations and changes of geochemical proxies including detritus index ln al2o3 na2o b ga and v v ni suggest that the massive calcareous mudstone was deposited in a small shallow salt lake that was dysoxic anoxic and the paleoclimate in the lake catchment was cool and arid and the laminated calcareous mudstone was deposited in a large and deep stratified lake which has anoxic highly saline bottom and oxic less saline surface water and the lake catchment was more humid and warm the dominant lithofacies changed from laminated calcareous mudstone to massive calcareous mudstone in the studied core suggesting that the lake became shallower and smaller when the paleoclimate became cooler and drier through time such a climate trend may be a response to global cooling during the middle eocene the average total organic content toc in both lacustrine highstand and lowstand are comparable even though the lake water chemistry and amount of terrigenous input are different we infer that the accumulation of organic matter within the lacustrine highstand was controlled by the combination of primary productivity carbonate production and preservation in anoxic bottom water while accumulation within lacustrine lowstand was only controlled by primary productivity

anomalous quartz from the roter kamm impact crater namibia evidence for post impact hydrothermal activity abstract centimeter sized quartz pebbles have been found on the rim of the roter kamm impact crater the roter kamm crater has a diameter of about 2 5 km and is situated in the namib desert swa namibia because of the sand coverage impact products breccias impact melt shocked rocks are exposed exclusively in the form of ejecta on the crater rim the quartz pebbles were found close to the main deposits of the impact breccias and show signs of wind abrasion thin sections revealed that the pebbles consist of individual quartz domains that are up to 1 mm in size under crossed nicols polarized light all individual domains show extinction almost simultaneously within 2 which is a rare phenomenon microprobe studies neutron activation analyses and x ray diffractometry confirmed that the material consists of pure quartz the quartz contains three different types of fluid inclusions primary inclusions size about 5 10 m that record the formation conditions of the quartz very small m secondary inclusions associated with the grain boundaries and late inclusions of irregular size freezing point depression measurements of the primary inclusions indicate fluid salinities between 18 3 and 19 6 wt nacl homogenization temperatures t h for the primary inclusions range from 165 to 250 c the quartz and the primary inclusions may provide evidence for a post impact phase of extensive hydrothermal activity generated by the residual heat from the kinetic energy of the impact

record of latest barremian cenomanian environmental change in tectonically controlled depressions from the jura burgundy threshold jura mountains eastern france and western switzerland abstract the area of the western jura mountains constitutes the former jura burgundy threshold between the tethys ocean and the epicontinental paris basin sea during the barremian the area was covered by a shallow water urgonian carbonate platform tectonic processes influenced the architecture of the urgonian platform and were notably responsible for the formation of fault related depressions on top of the urgonian series which were subsequently transformed into incised valleys and then to marine depocenters their sedimentary infills are mostly represented by the perte du rhone formation and record stepwise environmental change on the innermost platform which was strongly influenced by the nearby landmass from the latest barremian onward sedimentation progressively changed from i predominantly oncoidal and detrital charophyte rich marly limestones to ii heterozoan marly limestones and marls followed by iii detrital sediments interspersed with numerous phosphatic conglomerates these changes are linked with the onset of the latest barremian taxy episode and with the following oceanic anoxic episodes oae s 1a to d in the neighbouring basins the sedimentary changes are associated with sedimentary sequences which formed during 2nd order transgressions and which express the effect of sea level fall followed by drowning events the presence of a rich ammonite fauna allowed a precise biostratigraphical dating of these events during the latest barremian to cenomanian time interval

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

δ13c values from the cenomanian turonian passage beds of southern tibet a group of bituminous sediments of mid cretaceous late cenomanian early turonian age are well exposed in the tingri gamba basin of southern tibet the characteristics of microfossils and geochemistry in the strata show that paleoceanographic environmental changes took place in the tethys himalayan sea the 13c profiles of southern tibet are characterized by a low high low cycle the maximum positive excursion of 2 0 occurs at the position just above the cenomanian and turonian boundary in tingri and 2 74 occurs underneath the cenomanian and turonian boundary in gamba the mid cretaceous in southern tibet is a short period of expansion of the tethys himalayan sea which brought about local sea level rise the positive excursion of 13c coincides with both global and local sea level rises the correlation of the 13c spike and well dated occurrence of layers rich in organic carbon indicate that intense orgc burial took place during the latest cenomanian to earliest turonian the positive 13c excursion reflects the burial of total dissolved carbon the positive excursion and excess carbon burial in southern tibet are coincident with the oceanic anoxic event during the time

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

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

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

al to oxide and ti to organic linkages in biogenic sediment relationships to paleo export production and bulk al ti abstract to increase our understanding of the mechanisms that control the distribution of al and ti within marine sediment we performed sequential extractions targeting the chemical signatures of the loosely bound exchangeable carbonate oxide organic opal and residual fraction of sediment from a carbonate dominated regime equatorial pacific and from a mixed opal terrigenous regime west antarctic peninsula we observe a systematic partitioning of al and ti between sediment phases that is related to bulk al ti we show that where we can quantify an alexcess component the dissolved al is preferentially affiliated with the oxide fraction resulting in al ti molar ratios of 500 3000 this is interpreted as the result of surface complexation in the water column of dissolved al onto oxyhydroxides we also observe a previously undetected tiexcess with as much as 80 of the total ti in the organic fraction which is most likely a function of metal organic colloidal removal from the water column in samples where the excess metals are obscured by the detrital load the al and ti are almost exclusively found in the residual phase this argues for the paired removal of al preferentially by the oxide component and ti preferentially by the organic component from the water column by settling particulate matter this research builds upon earlier work that shows changes in the bulk ratio of al to ti in carbonate sediment from the central equatorial pacific that coincide with changes in the sedimentary bulk accumulation rate bar the ratios that are observed are as much as three times higher than typical shale values and were interpreted as the result of scavenging of dissolved al onto particles settling in the water column because this non terrigenous alexcess accounts for up to 50 of the total sedimentary al inventory and correlates best with bar the bulk al ti may be a sensitive tracer of particle flux and therefore export production because we show that the excess metals are the result of scavenging processes the bulk al ti may be considered a sensitive proxy for this region

astronomical constraints on global carbon cycle perturbation during oceanic anoxic event 2 oae2 abstract oceanic anoxic event 2 oae2 was a major disturbance in global carbon cycling and transient climate disruption triggered by a pulse of volcanic co2 although this well studied perturbation to the ocean atmosphere system offers a unique opportunity to better understand abrupt climate change in response to co2 forcing the origin evolution and duration of the event are still debated due in large part to the temporal resolution of existing oae2 records and uncertainty over the duration of the overall perturbation and c cycle shifts within it here we report coupled magnetic susceptibility ms and carbon isotope time series of 2 5 to 5 0 5 kyr resolution from an expanded oae2 interval from southern tibet china ms cyclicity indicates short eccentricity modulation permitting the construction of a high precision orbital timescale which when integrated with the high resolution 13 c carb record fully constrains the timing and nature of onset through recovery of oae2 revealing finer scale structure than previously recognized abrupt coupled shifts in 13 c carb and ms and changing phase relationships in step with transitions between high and low long eccentricity indicate orbitally linked changes in marine carbon cycling and monsoon dynamics superimposed on repeated wholesale oceanographic changes in particular the high resolution tibetan record reveals dynamic shifts in the phasing relationship of ms and 13 c which suggests that the initiation of ocean anoxia was probably not orbitally forced this finding is in sharp contrast with the paradigm of orbitally forced ocean anoxia conversely the new record suggests that termination of anoxia was likely orbitally forced and superimposed on a dramatic oceanographic change