presence of an iron rich nanophase material in the upper layer of the cretaceous tertiary boundary clay abstract we report new geochemical evidence from ten cretaceous tertiary k t boundary sites in north america and europe indicating the presence of a material remnant of a large asteroid or comet that struck the earth at 65 0 ma mossbauer spectroscopic data reveals that a ubiquitous iron rich nanophase material exists at the uppermost part of the k t boundary layer in the western hemisphere and in europe marine and continental fine grained sedimentary rock the high surface to volume ratio of nanophase material suggests that it may be the carrier of the iridium abundance enhancement that marks the k t boundary even more provocative is the possibility that discovered nanophase material is for the most part composed of the vaporized impactor after the impact generated high temperature vapor plume rose and cooled above the atmosphere introduction in the last two decades an enormous amount of chemical and physical evidence has been gathered that supports the idea that a large asteroid or comet struck earth at

evidence for a rapid release of carbon at the paleocene eocene thermal maximum the paleocene eocene thermal maximum petm and associated carbon isotope excursion cie are often touted as the best geologic analog for the current anthropogenic rise in pco2 however a causal mechanism for the petm cie remains unidentified because of large uncertainties in the duration of the cie s onset here we report on a sequence of rhythmic sedimentary couplets comprising the paleocene eocene marlboro clay salisbury embayment these couplets have corresponding 18o cycles that imply a climatic origin seasonal insolation is the only regular climate cycle that can plausibly account for 18o amplitudes and layer counts high resolution stable isotope records show 3 5 13c decrease over 13 couplets defining the cie onset which requires a large instantaneous release of 13c depleted carbon during the cie a clear 13c gradient developed on the shelf with the largest excursions in shallowest waters indicating atmospheric 13c decreased by 20 our observations and revised release rate are consistent with an atmospheric perturbation of 3 000 gigatons of carbon gtc

an appalachian amazon magnetofossil evidence for the development of a tropical river like system in the mid atlantic united states during the paleocene eocene thermal maximum on the mid atlantic coastal plain of the united states paleocene sands and silts are replaced during the paleocene eocene thermal maximum petm by the kaolinite rich marlboro clay the clay preserves abundant magnetite produced by magnetotactic bacteria and novel presumptively eukaryotic iron biomineralizing microorganisms using ferromagnetic resonance spectroscopy and electron microscopy we map the magnetofossil distribution in the context of stratigraphy and carbon isotope data and identify three magnetic facies in the clay one characterized by a mix of detrital particles and magnetofossils a second with a higher magnetofossil to detrital ratio and a third with only transient magnetofossils the distribution of these facies suggests that suboxic conditions promoting magnetofossil production and preservation occurred throughout inner middle neritic sediments of the salisbury embayment but extended only transiently to outer neritic sediments and the flanks of the embayment such a distribution is consistent with the development of a system resembling a modern tropical river dominated shelf

magnetofossil spike during the paleocene eocene thermal maximum ferromagnetic resonance rock magnetic and electron microscopy evidence from ancora new jersey united states previous workers identified a magnetically anomalous clay layer deposited on the northern united states atlantic coastal plain during the paleocene eocene thermal maximum petm the finding inspired the highly controversial hypothesis that a cometary impact triggered the petm here we present ferromagnetic resonance fmr isothermal and anhysteretic remanent magnetization first order reversal curve and transmission electron microscopy analyses of late paleocene and early eocene sediments in drillcore from ancora new jersey a novel paleogeographic analysis applying a recent paleomagnetic pole from the faeroe islands indicates that new jersey during the initial eocene had a 6 9 degrees lower paleolatitude 27 3 degrees for ancora and a more zonal shoreline trace than in conventional reconstructions our investigations of the petm clay from ancora reveal abundant magnetite nanoparticles bearing signature traits of crystals produced by magnetotactic bacteria this result the first identification of ancient biogenic magnetite using fmr argues that the anomalous magnetic properties of the petm sediments are not produced by an impact they instead reflect environmental changes along the eastern margin of north america during the petm that led to enhanced production and or preservation of magnetofossils

mercury deposition through the permo triassic biotic crisis abstract a 6 7 million year record of marine sedimentation through the permo triassic biotic crisis shows notable shifts in mercury concentrations that varied over an order of magnitude 0 002 to 0 116 g g mercury concentrations correlate strongly with total organic carbon showing both parallel increasing and decreasing trends over geologic time scales results suggest that changes in bioproductivity strongly influence mercury sequestration into marine sediment this may provide insight to potential marine response to modern anthropogenic hg loading and supports models that suggest enhanced bioproductivity that due to recent climate has increased hg sequestration over time

rock magnetic criteria for the detection of biogenic magnetite abstract we report results on the magnetic properties of magnetites produced by magnetotactic and dissimilatory iron reducing bacteria magnetotactic bacterial mtb strains ms1 mv1 and mv2 and dissimilatory iron reducing bacterium strain gs 15 grown in pure cultures were used in this study our results suggest that a combination of room temperature coercivity analysis and low temperature remanence measurements provides a characteristic magnetic signature for intact chains of single domain sd particles of magnetite from mtbs the most useful magnetic property measurements include 1 acquisition and demagnetization of isothermal remanent magnetization irm using static pulse and alternating fields 2 acquisition of anhysteretic remanent magnetization arm and 3 thermal dependence of low temperature 20 k saturation irm after cooling in zero field zfc or in a 2 5 t field fc from 300 k however potentially the most diagnostic magnetic parameter for magnetosome chain identification in bulk sediment samples is related to the difference between low temperature zero field and field cooled sirms on warming through the verwey transition t 100 k intact chains of unoxidized magnetite magnetosomes have ratios of fc zfc greater than 2 where the parameter is a measure of the amount of remanence lost by warming through the verwey transition disruption of the chain structure or conversion of the magnetosomes to maghemite reduces the fc zfc ratio to around 1 similar to values observed for some inorganic magnetite maghemite greigite and gs 15 particles numerical simulations of fc zfc ratios for simple binary mixtures of magnetosome chains and inorganic magnetic fractions suggest that the fc zfc parameter can be a sensitive indicator of biogenic magnetite in the form of intact chains of magnetite magnetosomes and can be a useful magnetic technique for identifying them in whole sediment samples the strength of our approach lies in the comparative ease and rapidity with which magnetic measurements can be made compared to techniques such as electron microscopy

abrupt deep sea warming palaeoceanographic changes and benthic extinctions at the end of the palaeocene a remarkable oxygen and carbon isotope excursion occurred in antarctic waters near the end of the palaeocene 57 33 myr ago indicating rapid global warming and oceanographic changes that caused one of the largest deep sea benthic extinctions of the past 90 million years in contrast the oceanic plankton were largely unaffected implying a decoupling of the deep and shallow ecosystems the data suggest that for a few thousand years ocean circulation underwent fundamental changes producing a transient state that although brief had long term effects on environmental and biotic evolution

continental weathering and climatic changes inferred from clay mineralogy and paired carbon isotopes across the early to middle toarcian in the paris basin abstract lower toarcian strata lower jurassic have been extensively studied with a view to understanding the oceanographic climatic and biological processes that drove the earth s system into an oceanic anoxic event oae for this time period the evolution of the european marine seaways is now relatively well constrained owing to multiple geochemical studies but investigations regarding climatic trends in the continental realm remain sparse in the present study we test the clay mineralogy as a continental climate sensitive proxy in the well documented sancerre core southern paris basin we compare variations in the kaolinite content with p co 2 fluctuations derived from paired carbon isotopes 13 c 13 c carb 13 c org taking advantage of the detailed chemostratigraphic palaeoenvironmental and sequence stratigraphy frameworks established for this core material the results indicate a substantial decrease in kaolinite abundance at the end of the pliensbachian which is compatible with a long term diminution in continental weathering and an inferred temperature decrease the early toarcian prior to the carbon cycle perturbation and deposition of black shale facies remained relatively cold with minima in both the proportion of kaolinite and reconstructed p co 2 the mineralogical and geochemical responses across the prominent negative carbon isotope excursion cie itself are not univocal the first of four steps that compose the negative limb of the cie at sancerre is associated with decreased kaolinite and p co 2 and increased carbonate oxygen isotope ratios taken together these trends are compatible with a transient cooling phase immediately preceding the onset of black shale deposition conversely the subsequent steps are marked by substantial enrichment in kaolinite that matches increased osmium isotope ratios measured in yorkshire providing compelling evidence for rapid increases in continental weathering and riverine runoff forced by intensification of greenhouse conditions during the cie relaxation in the intensity of continental weathering as suggested by resumed low kaolinite abundance is seen immediately after the cessation of co 2 input after the fourth step of the cie the interval spanning the upper portion of the early toarcian and the middle toarcian records a subsequent long term increase in the proportion of kaolinite synchronous with significant clay enrichment of the sediment continued greenhouse conditions even after the recovery from the carbon isotope perturbation and regional black shale deposition are likely related to sustained co 2 emission by karoo ferrar volcanism through the considered interval

micromagnetic simulation of magnetofossils with realistic size and shape distributions linking magnetic proxies with nanoscale observations and implications for magnetofossil identification abstract we build micromagnetic models to investigate the magnetic properties of biogenic magnetite a common type of magnetic mineral that is responsible for recording a wide range of biological geophysical and geological processes on earth the geometry of modelled particles is based on realistic size and shape distributions from nanoscale observations systematic changes in microstructures of biogenic magnetite ensembles are built and their magnetic properties are calculated which enables a quantitative and separate assessment of the effect of crystal morphology and chain structures although the same particle size and shape distributions are used in all calculations simulation results document large variations in magnetic properties i e wide distributions of coercivity b c 10 60 mt coercivity of remanence b cr 14 81 mt dispersion parameter dp 0 1 0 5 and skewness values s 0 7 1 1 due to variable degree of anisotropy and magnetostatic interactions previously the commonly observed biogenic soft and biogenic hard components on biogenic magnetite bearing samples were often interpreted to reflect crystal morphologies and that the small dp values of coercivity distributions were an indication of narrow particle size distributions our simulations suggest that these speculations are not always the case and that magnetosome microstructures likely exert a dominant control over their magnetic properties our modelling results provide a new theoretical perspective on the magnetic properties of biogenic magnetite which is important for understanding magnetic proxy signals from magnetofossils in a wide range of environmental and geological settings and for the search for biogenic magnetite in terrestrial rocks and in extra terrestrial materials

detection of noninteracting single domain particles using first order reversal curve diagrams we present a highly sensitive and accurate method for quantitative detection and characterization of noninteracting or weakly interacting uniaxial single domain particles unisd in rocks and sediments the method is based on high resolution measurements of first order reversal curves forcs unisd particles have a unique forc signature that can be used to isolate their contribution among other magnetic components this signature has a narrow ridge along the hc axis of the forc diagram called the central ridge which is proportional to the switching field distribution of the particles therefore the central ridge is directly comparable with other magnetic measurements such as remanent magnetization curves with the advantage of being fully selective to sd particles rather than other magnetic components this selectivity is unmatched by other magnetic unmixing methods and offers useful applications ranging from characterization of sd particles for paleointensity studies to detecting magnetofossils and ultrafine authigenically precipitated minerals in sediments

detection of late cretaceous and cenozoic sequence boundaries on the atlantic coastal plain using core log integration of magnetic susceptibility and natural gamma ray measurements at ancora new jersey 1 magnetic susceptibility ms and natural gamma ray ngr were measured on middle miocene to cenomanian coastal plain strata from a continuously cored 356 m total depth 86 recovery borehole at ancora new jersey ocean drilling program leg 174ax these measurements were integrated with lithologic descriptions and a downhole ngr log a simple linear model explains most of the variation of the downhole ngr and the core ms as a consequence of the previously described lithologic variation spectral ngr at selected levels shows that ngr activity is mostly due to 40k associated with glauconite and mud sediment components that also tend to give high ms values abrupt deviations from the average values of ngr activity and ms determined by the linear model can be interpreted as due to singular lithologies for example an anomalous level with high ngr but not a parallel increase in ms was found at the navesink mount laurel formation contact and can be attributed to high uranium concentration in phosphorite most 27 of 33 of the sequence boundaries independently identified at the ancora site have sufficient lithological contrasts to be expressed in the ngr and or ms logs

fossil bacterial magnetite in deep sea sediments from the south atlantic ocean the magnetostratigraphy of deep sea sediment cores has proven to be a powerful and high resolution method of dating and comparing sedimentary records in contrast to this widespread application relatively few attempts have been made to analyse and identify the mineralogy grain size and origin of the carrier of the remanent magnetization1 2 it is widely assumed that dominant ferrimagnetic minerals in deep sea sediments are of lithogenic origin that is that they derive from oceanic or continental detritus volcanic ashfalls micrometeorites hydrothermal precipitation or chemical mineralization processes a very different view was taken by kirschvink and lowenstam3 who suggested that fossil remnants of magnetite mineralizing organisms in particular magnetotactic bacteria might play an important part in the magnetization of sediments deposited in certain detritus poor aquatic systems we have used rock magnetic diagnostic methods to characterize the magnetic phases in deep sea sediments from the south atlantic these phases were then extracted and studied with the electron microscope our results indicate that fossil bacterial magnetite is the main carrier of the natural remanent magnetization in sediments ranging in age from quarternary to eocene different types of bacterial magnetosomes were detected most of them occurring in chains of identical particles and nearly all of them falling into the theoretically determined4 size range of single domain magnetitite

magnetization of polar ice a measurement of terrestrial dust and extraterrestrial fallout abstract laboratory induced remanent magnetization of polar ice constitutes a measurement of the magnetization carried by the ferromagnetic dust particles in the ice this non destructive technique provides a novel kind of information on the dust deposited on the surface of polar ice sheets measurements made on ice samples from greenland north grip ice core and antarctica vostok and epica dome c ice cores allowed the recognition of a fraction of magnetic minerals in ice whose concentration and magnetic properties are directly related to that of insoluble dust the source of this fraction of magnetic minerals thus appears closely related to terrestrial dust transport and deposition and its magnetic properties are informative of the dust provenance areas the rock magnetic properties of the dust may reflect distinct changes of dust source areas from glacial to interglacial periods in agreement with and adding further information to the isotopic 87 sr 86 sr and 143 nd 144 nd analyses a second magnetic fraction consists of particles of nanometric size which are superparamagnetic at freezer temperature and whose concentration is independent of the mass of aerosol dust found in the ice the source of these nanometric sized magnetic particles is ascribed to fallout of meteoric smoke and their concentration in ice was found to be compatible with the extraterrestrial fallout inferred from ir concentrations the diameter of the smoke particles as inferred from magnetic measurements is in the range of about 7 20 nm

correlation between isotope records in marine and continental carbon reservoirs near the palaeocene eocene boundary changes in the isotope content of the large marine carbon reservoir can force shifts in that of the smaller carbon pools in the atmosphere and on land the carbon isotope compositions of marine carbonate sediments from the late palaeocene vary considerably exhibiting a sudden decrease close to the palaeocene eocene boundary which coincides with deep sea benthic extinctions1 and with changes in ocean circulation here we report that these fluctuations in the marine carbon isotope record are closely tracked by the terrestrial records provided by palaeosol carbonates and mammalian tooth enamel in using palaeosol carbonates to reconstruct the co2 content of the ancient atmosphere2 isotope shifts of this sort will have to be taken into account the sharp decrease in 13c 12c ratios in the late palaeocene provides a datum for precise correlation of marine and continental records and suggests that abrupt climate warming at this time may have played an important role in the evolution of land mammals

holocene paleointensities thellier experiments on submarine basaltic glass from the east pacific rise a complete description of the geomagnetic field requires both paleodirectional and paleointensity data although the paleointensity data base has grown steadily over the last three decades it remains limited in time and space the majority of data are of holocene age and come from europe furthermore it has been difficult to assess the reliability of the paleointensity determinations here we present paleointensity determinations on precisely dated holocene 0 to 3500 years old submarine basaltic glass from the east pacific rise 15 s to 22 s although hysteresis measurements and low temperature isothermal remanent magnetization irm acquisition experiments document a significant contribution of superparamagnetic grains high blocking temperatures above 400 c and curie temperatures between 490 c and 550 c indicate a single domain low ti magnetite as the carrier of the remanent magnetization this notion is further supported by the fact that saturation of remanence is achieved in moderate fields of about 200 300 mt submarine basaltic glass proves to be nearly ideal for paleointensity determinations in that it produces a high success rate for thellier experiments twenty six out of 30 samples resulted in acceptable paleointenisty determinations multiple experiments on splits from the same sample show good reproducibility the paleointensities for zero age glasses correspond precisely with the present field intensity at the site of recovery the results of the remaining samples range from 16 7 to 53 9 t with corresponding virtual axial dipole moments vadm of 3 61 1022 to 11 9 1022 a m2 the intensities vary rapidly with time excluding a westward drifting nondipole component as the source for these fluctuations basaltic glass is frequently recovered in both dredged and drilled material from the ocean floor the availability of submarine basaltic glass throughout the world oceans therefore holds great potential for a better distribution of paleointensity data through time and space

characterizing the superparamagnetic grain distribution f v hk by thermal fluctuation tomography 1 in 1965 d j dunlop showed that the joint distribution of particle volumes and microcoercivities f v hk0 can be determined for magnetically monomineralic thermally stable single domain ssd ensembles by taking advantage of the joint temperature and field dependence of relaxation time we have developed a procedure that follows dunlop s strategy to obtain f v hk0 for ensembles containing both superparamagnetic and ssd grains based on backfield remanence curves measured over a range of temperatures each point on the derivative curves represents the integrated contribution from grains that lie along a corresponding blocking contour on the neel plot a suitable set of such line integral samples can be used to reconstruct the f v hk0 distribution using the methods of tomographic imaging samples of the basal tiva canyon tuff have narrow size distributions of elongate ti poor titanomagnetite tomographic inversion of the low temperature backfield spectra yield sharply peaked f v hk0 distributions from which we calculate modal grain dimensions in good agreement with those observed by transmission electron microscopy analysis of synthetic samples containing bimodal populations clearly distinguishes the two modes because our simplified forward calculations incompletely account for the effects of orientation distribution the width of the coercivity distribution at each temperature is underestimated and consequently the inverse calculations yield grain distributions that are overly broad frequency and temperature dependent susceptibilities calculated for the inverted f v hk0 distributions accord fairly well with measured susceptibilities for the weakly interacting tiva canyon samples less well for a moderately interacting paleosol specimen and poorly for a strongly interacting ferrofluid

biogenic magnetite detrital hematite and relative paleointensity in quaternary sediments from the southwest iberian margin magnetic properties of late quaternary sediments on the sw iberian margin are dominated by bacterial magnetite observed by transmission electron microscopy tem with contributions from detrital titanomagnetite and hematite reactive hematite together with low organic matter concentrations and the lack of sulfate reduction lead to dissimilatory iron reduction and availability of fe ii for abundant magnetotactic bacteria magnetite grain size proxies arm and arm irm and s ratios sensitive to hematite vary on stadial interstadial timescales contain orbital power and mimic planktic 18 o the detrital biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages reflecting increased detrital magnetite input during times of lowered sea level coinciding with atmospheric conditions favoring hematitic dust supply magnetic susceptibility on the other hand has a very different response being sensitive to coarse detrital multidomain md magnetite associated with ice rafted debris ird high susceptibility and or magnetic grain size coarsening mark heinrich stadials hs particularly hs2 hs3 hs4 hs5 hs6 and hs7 as well as older heinrich like detrital layers indicating the sensitivity of this region to fluctuations in the position of the polar front relative paleointensity rpi records have well constrained age models based on planktic 18 o correlation to ice core chronologies however they differ from reference records e g piso particularly in the vicinity of glacial maxima mainly due to inefficient normalization of rpi records in intervals of enhanced hematite input

quantified abundance of magnetofossils at the paleocene eocene boundary from synchrotron based transmission x ray microscopy the paleocene eocene boundary 55 8 million years ago is marked by an abrupt negative carbon isotope excursion cie that coincides with an oxygen isotope decrease interpreted as the paleocene eocene thermal maximum biogenic magnetite fe3o4 in the form of giant micron sized spearhead like and spindle like magnetofossils as well as nano sized magnetotactic bacteria magnetosome chains have been reported in clay rich sediments in the new jersey atlantic coastal plain and were thought to account for the distinctive single domain magnetic properties of these sediments uncalibrated strong field magnet extraction techniques have been typically used to provide material for scanning and transmission electron microscopic imaging of these magnetic particles whose concentration in the natural sediment is thus difficult to quantify in this study we use a recently developed ultrahigh resolution synchrotron based full field transmission x ray microscope to study the iron rich minerals within the clay sediment in their bulk state we are able to estimate the total magnetization concentration of the giant biogenic magnetofossils to be only 10 of whole sediment along with previous rock magnetic studies on the cie clay we suggest that most of the magnetite in the clay occurs as isolated near equidimensional nanoparticles a suggestion that points to a nonbiogenic origin such as comet impact plume condensates in what may be very rapidly deposited cie clays

global and local forcing of early toarcian seawater chemistry a comparative study of different paleoceanographic settings paris and lusitanian basins 1 the early toarcian was characterized by two large perturbations to the carbon cycle a positive trend associated with increased organic matter burial and ocean anoxia and a pronounced negative carbon isotope excursion cie we contrast the geochemical evolution in the carbonate phases of two successions one from the paris basin sancerre core comprising black shales the other from the lusitanian basin peniche section with very minor lithological expression of bottom water anoxia our aim was to identify whether these carbon cycle perturbations were related and differentiate between the common global versus regional expressions of the biogeochemical response and ocean chemistry our results highlight contrasts in timing of different phases of anoxia in both locations through the widely documented negative cie widespread anoxic conditions were not a necessary prerequisite for generating a pronounced cie as required by the recycling so called kuspert model the production of carbonate simultaneously dropped during the 13c negative shift in both locations likely in response to lowered seawater saturation rate induced by substantial absorption of co2 from the atmosphere the recovery interval was accompanied by a rapid reestablishment of seawater alkalinity and primary and carbonate productivity in epicontinental seas as evidenced by high 13c and sr ca in contrast with the more open ocean regime in the lusitanian basin our results confirm that parallels can be draw between the ocean productivity response and feedback during the toarcian cie and the petm both events are characterized by ocean acidification and reduced pelagic calcification followed by a peak in nearshore coccolith productivity which could have helped the recovery from the perturbation

spinel bearing spherules condensed from the chicxulub impact vapor plume formation of the giant chicxulub crater off mexico s yucatan peninsula coincided with deposition of the global ir rich cretaceous tertiary k t stratigraphic boundary layer at ca 65 ma the boundary is marked most sharply by abundant spherules containing unaltered grains of magnesioferrite spinel here we predict for the first time the sequential condensation of solids and liquids from the plume of vaporized rock expected from oblique k t impacts we predict highly oxidizing plumes that condense silicate liquid droplets bearing spinel grains whose compositions closely match those marking the actual boundary systematic global variations in spinel composition are consistent with higher condensation temperatures for spinels found at atlantic and european sites than for those in the pacific

abrupt climate change and transient climates during the paleogene a marine perspective detailed investigations of high latitude sequences recently collected by the ocean drilling program odp indicate that periods of rapid climate change often culminated in brief transient climates with more extreme conditions than subsequent long term climates two examples of such events have been identified in the paleogene the first in latest paleocene time in the middle of a warming trend that began several million years earlier the second in earliest oligocene time near the end of a middle eocene to late oligocene global cooling trend superimposed on the earlier event was a sudden and extreme warming of both high latitude sea surface and deep ocean waters imbedded in the latter transition was an abrupt decline in high latitude temperatures and the brief appearance of a full size continental ice sheet on antarctica in both cases the climate extremes were not stable lasting for less than a few hundred thousand years indicating a temporary or transient climate state geochemical and sedimentolog

modeling topographical density for geoid determinationthis article is one of a series of papers published in this special issue on the theme geodesy in geoid computation effects of real three dimensional topographic masses on the earth s gravity field must be accurately quantified and in the stokes helmert scheme replaced with effects of those masses condensed on the geoid the most comprehensive modern schemes for evaluation of topographical effects account for terrain effects use a spherical model of topography and incorporate two dimensionally varying models of topographical mass density in this contribution we employ a three dimensionally varying model of topographical density we use newton s integration to determine the direct topographical effect dte on gravity and primary indirect topographical effect pite on gravity potential lastly we apply stokes integration to calculate the dte pite and secondary indirect topographical effect site on geoidal height we focus here on validation of our results and demonstration of our software s capabilities we present results for the simple geometrical shape of a disc under various rotati

massive dissociation of gas hydrate during a jurassic oceanic anoxic event in the jurassic period the early toarcian oceanic anoxic event about 183 million years ago is associated with exceptionally high rates of organic carbon burial high palaeotemperatures and significant mass extinction heavy carbon isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon which is isotopically light in contrast examples of light carbon isotope values from marine organic matter of early toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12c versus 13c refs 1 2 5 6 here however we report carbon isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic biospheric and atmospheric carbon reservoirs and that this occurred despite the enhanced burial of organic carbon we propose that as has been suggested for the late palaeocene thermal maximum some 55 million years ago the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental margin sediments

a case for a comet impact trigger for the paleocene eocene thermal maximum and carbon isotope excursion abstract we hypothesize that the rapid onset of the carbon isotope excursion cie at the paleocene eocene boundary 55 ma may have resulted from the accretion of a significant amount of 12c enriched carbon from the impact of a 10 km comet an event that would also trigger greenhouse warming leading to the paleocene eocene thermal maximum and possibly thermal dissociation of seafloor methane hydrate indirect evidence of an impact is the unusual abundance of magnetic nanoparticles in kaolinite rich shelf sediments that closely coincide with the onset and nadir of the cie at three drill sites on the atlantic coastal plain after considering various alternative mechanisms that could have produced the magnetic nanoparticle assemblage and by analogy with the reported detection of iron rich nanophase material at the cretaceous tertiary boundary we suggest that the cie occurrence was derived from an impact plume condensate the sudden increase in kaolinite is thus thought to represent the redeposition on the marine shelf of a rapidly weathered impact ejecta dust blanket published reports of a small but significant iridium anomaly at or close to the paleocene eocene boundary provide supportive evidence for an impact

first record of the early toarcian oceanic anoxic event from the southern hemisphere neuquen basin argentina abstract the first record of the early toarcian oceanic anoxic event c 183 ma from the southern hemisphere is described from the neuquen basin argentina identified chemostratigraphically on the basis of a relative increase in marine organic carbon and a characteristic negative carbon isotope excursion 13 c org in bulk rock and fossil wood the negative excursion of 6 in bulk organic carbon falling to 31 3 crosses the boundary of the tenuicostatum hoelderi andean ammonite zones equivalent to the tenuicostatum falciferum serpentinum zones of europe these data indicate that the early toarcian oceanic anoxic event was a global phenomenon supplementary material a detailed stratigraphic log chemostratigraphic data and nannofossil data are available at http www geolsoc org uk sup18411

magnetism and magnetic mineralogy of ash flow tuffs from yucca mountain nevada the magnetic susceptibility and remanent magnetization of an ash flow sheet are profoundly influenced by cooling history after emplacement spatial variations in these properties therefore provide a potentially useful tool for geological studies maxima and minima in measured along profiles at yucca mountain nevada identify persistent magnetic marker horizons within vitric portions of the tiva canyon and underlying topopah spring members of the paintbrush tuff the correlatable variations of with vertical position in these units exist over the 8 km of strike examined the observed stratigraphic changes in magnetic properties reflect variations in amounts and mineralogy of fe ti oxide phenocrysts and the presence shape size and mineralogy of magnetic fe oxide microcrystals that precipitated at high temperature after emplacement of each sheet vitrophyre near the top of the topopah spring member has a distinctive maximum in due to titanomagnetite phenocrysts susceptibility in the lower portion of the overlying tiva canyon member reaches maximum values of about 1 3 10 2 si near the base of the member beneath the columnarly jointed vitrophyre due to the presence of abundant superparamagnetic cubic fe oxide these elongate microcrystals are several tens of nm long and are typically deformed and tapered up section in the tiva canyon member the susceptibility decreases going to a minimum within the columnar vitrophyre at this stratigraphic level the precipitated fe oxides are larger and carry intense nrm of up to 30 a m is only 3 10 3 the whisker like microcrystals of fe oxide which typically nucleated on what appears to be chain silicate grew as needles up to 25 m in length the size variations of the precipitated fe oxides which were established using transmission electron microscopy tem and petrographic observation are consistent both with variations in magnetic susceptibility measured at the outcrop and with variations in the intensity of remanent magnetization several interpretations of the shape anisotropy of the precipitated feoxide are possible including growth by a dislocation mechanism additionally the observed elongation of precipitated microcrystals is consistent with theoretical predictions for growth in a uniaxial stress field susceptibility variations as established at the outcrop as well as in the borehole offer a potentially useful tool for stratigraphic correlation of ash flow sheets

evidence for abundant isolated magnetic nanoparticles at the paleocene eocene boundary new rock magnetic results thermal fluctuation tomography high resolution first order reversal curves and low temperature measurements for samples from the paleocene eocene thermal maximum and carbon isotope excursion in cored sections at ancora and wilson lake on the atlantic coastal plain of new jersey indicate the presence of predominantly isolated near equidimensional single domain magnetic particles rather than the chain patterns observed in a cultured magnetotactic bacteria sample or magnetofossils in extracts the various published results can be reconciled with the recognition that chain magnetosomes tend to be preferentially extracted in the magnetic separation process but as we show may represent only a small fraction of the overall magnetic assemblage that accounts for the greatly enhanced magnetization of the carbon isotope excursion sediment but whose origin is thus unclear

hydrothermal venting of greenhouse gases triggering early jurassic global warming abstract the climate change in the toarcian early jurassic was characterized by a major perturbation of the global carbon cycle the event lasted for approximately 200 000 years and was manifested by a global warming of 6 c anoxic conditions in the oceans and extinction of marine species the triggering mechanisms for the perturbation and environmental change are however strongly debated here we present evidence for a rapid formation and transport of greenhouse gases from the deep sedimentary reservoirs in the karoo basin south africa magmatic sills were emplaced during the initial stages of formation of the early jurassic karoo large igneous province and had a profound influence on the fate of light elements in the organic rich sedimentary host rocks total organic carbon contents and vitrinite reflectivity data from contact aureoles around the sills show that organic carbon was lost from the country rocks during heating we present data from a new type of geological structures termed breccia pipes rooted in the aureoles within the shale of the western karoo basin the breccia pipes are cylindrical structures up to 150 meters in diameter and are mainly comprised of brecciated and baked black shale thousands of breccia pipes were formed due to gas pressure build up during metamorphism of the shales resulting in venting of greenhouse gases to the toarcian atmosphere mass balance calculations constrained by new aureole data show that up to 1800 gt of co2 was formed from organic material in the western karoo basin about 15 times this amount of co2 27 400 gt may have formed in the entire basin during the intrusive event u pb dating of zircons from a sill related to many of the pipes demonstrates that the magma was emplaced 182 5 0 4 million years ago this supports a causal relationship between the intrusive volcanism the gas venting and the toarcian global warming

carbon isotopes rare earth elements and mercury geochemistry across the k t transition of the paraiba basin northeastern brazil the parao ba basin northeastern brazil is divided into three sub basins olinda alhan dra and miriri which encompass the formations beberibe coniacian santonian itamaraca campanian and gramame and maria farinha maastrichtian to danian respectively in the olinda sub basin the cretaceous palaeogene transition ktb has been recorded by the carbon ates of the gramame and maria farinha formations this study focus on the behaviour of c and o isotopes major and rare earth elements and mercury in carbonates from three drill holes in the olinda sub basin the climate was fairly cold during the marine transgression in which carbonates of the itamaracaformation were deposited a temperature and bioproductivity increase has been registered in the early maastrichtian gramame formation with a gradual fall during the rest of this period a positived 13 c 2 excursion near the ktb is followed by a drop to values around 1 immediately after this transition in one drill hole several negative d 13 c anomalies predate the ktb possibly related to either multiple impacts or volcanic activity that preceded this tran sition in two of the three drill holes the total mercury increases immediately after the ktb and in two of them mercury spikes four of them in one case precede this transition which has been interpreted as an indication that volcanic activity predated the transition rare earth element patterns support a marine origin for the carbonates in the campanian maastrichtian tran sition and ktb in the olinda sub basin in carbonates from one of the drill holes absent to weakly positive ce anomalies 20 1 and 0 002 in the ktb coincide with a fall in d 13 c values followed by an increase from 2 3 to 1 8 and back to 2 3 and in increment in mercury values from 0 4 to 2 7 ng g 21 the presence of pyrite nodules associated with a weakly negative eu anomaly point to slightly reducing conditions around the ktb

a carbon isotope perturbation at the pliensbachian toarcian boundary evidence from the lias group ne england a perturbation in the carbon isotope record at the time of the pliensbachian toarcian boundary 184 ma in the early jurassic is reported based on new data from yorkshire england two sharp 13 c org negative excursions each with a magnitude of 2 5 and reaching minimum values of 28 5 are recorded in the bulk organic matter record in sediments of latest pliensbachian to earliest toarcian age a similar pattern of negative carbon isotope excursions has been observed at the stage boundary in the sw european section at peniche portugal in 13 c carbonate 13 c wood and 13 c brachiopod records the isotopic excursion is of interest when considering the genesis and development of the later toarcian oceanic anoxic event oae as well as the second order global extinction event that spans the stage boundary furthermore the isotope excursion potentially provides a chemostratigraphic marker for recognition of the stage boundary which is currently achieved on the basis of different ammonite faunas in the nw european and tethyan realms

a biogenic origin for anomalous fine grained magnetic material at the paleocene eocene boundary at wilson lake new jersey 1 the paleocene eocene thermal maximum which occurred 55 5 ma was caused by a massive release of carbon as indicated by an 3 negative carbon isotope excursion recorded in the marine atmospheric and terrestrial reservoirs one suggested source for the carbon a cometary impactor is based on the sudden appearance and high concentration of single domain sd magnetite in paleocene eocene p e boundary cores from the north atlantic continental margin we evaluate the potential sources of sd magnetite at the p e boundary by presenting new magnetic hysteresis low temperature magnetic remanence and transmission electron microscopy data from the north atlantic coastal ocean our results show a similar increase in sd material but demonstrate that the magnetic material has a biogenic origin these findings indicate that the high concentrations of sd magnetite immediately above the p e boundary are the result of unusual accumulations and or preservation of magnetotactic bacteria such bacteria typically occupy the oxic anoxic transition zone near the sediment water interface or in the water column the high abundances of sd magnetite in sediments from across the shelf may be an artifact of nonsteady state redox conditions and exceptional preservation of sd magnetite it may also indicate that the oxic anoxic redox boundary shifted into the water column the latter explanation implies transient eutrophy of the coastal ocean in this region most likely due to seasonally enhanced runoff and increased stratification and nutrient loading

low temperature remanence in stable single domain magnetite 1 a numerical model is developed in order to simulate the loss of low temperature remanence while warming through the verwey transition we concentrate on the amount of remanence lost fc and zfc during field cooled and zero field cooled low temperature demagnetization curves for stable single domain ssd particles of 1 inorganic magnetite and 2 biogenic magnetite in the form of magnetosome chains the model predicts that delta ratios fc zfc for inorganic ssd magnetite increase from 1 to 1 6 with increasing aspect ratio and that magnetosome chains have elevated delta ratios of at least 2 0 disaggregated magnetosomes are predicted to behave similarly to inorganic acicular ssd magnetite the numerical results agree with experimental results

astronomical forcing and chronology of the early toarcian early jurassic oceanic anoxic event in yorkshire uk 1 during the early toarcian 183 ma ago a high rate of organic carbon burial globally over a brief interval of time has led to the recognition of a major oceanic anoxic event oae a pronounced negative excursion in the carbon isotope composition of marine organic matter marine carbonate and terrestrial plant material is a key feature of this event but the precise timescale and cause s of this isotopic anomaly are debated associated with the negative carbon isotope excursion is evidence for a coeval rise in seawater palaeotemperature an increase in continental weathering rates and the mass extinction of marine invertebrate species the early toarcian oae provides evidence for the earth s response during rapid climate change and critical to our understanding of the event is a high resolution timescale that allows us to quantify the rates duration and lead lag times of environmental processes in this study we present 2743 new high resolution organic carbon sulphur and carbonate concentration data from samples of well preserved organic rich mudrocks spanning the early toarcian oae in yorkshire uk we have used these data to document the geochemical changes and significantly extend and refine the astronomical timescale across this event our detailed analysis of the relationship between astronomical forcing and carbon isotope changes in both yorkshire and a section from peniche portugal indicates that astronomical forcing paced the timing of major shifts in 13c and hence climate in both sections our analyses also demonstrate that there was a marked increase in the relative strength of astronomical forcing recorded at the onset of the oae and that the recorded nature of astronomical forcing changed during the event both the yorkshire and peniche cyclostratigraphies suggest that one astronomical forcing parameter paced environmental change through the 13c event and that this parameter was obliquity or precession

enhanced magnetization of the marlboro clay as a product of soil pyrogenesis at the paleocene eocene boundary abstract the kaolinite rich marlboro clay was deposited on the inner shelf in the salisbury embayment of the u s atlantic margin at the onset of the carbon isotope excursion marking the 56 ma paleocene eocene boundary and is characterized by an anomalously high concentration of magnetic nanoparticles of enigmatic origin that give rise to notably intense bulk magnetization recent studies point to a magnetic assemblage that is dominated by single domain magnetite particles that tend to be isolated rather than arranged in chains the most distinguishing feature of magnetotactic bacteria fossils on the other hand it is very unlikely that the nanoparticles can be condensates of an impact plume given the meter scale thickness of the marlboro clay we obtained new data from a landward proximal site at wilson lake on the new jersey coastal plain and find that the abrupt increase in magnetite nanoparticles is virtually coincident stratigraphically with the recently reported impact spherule layer at the base of the marlboro clay in the same core yet the high field magnetic susceptibility a measure of total iron concentration and strontium isotope values on bulk sediment an indicator of sediment weathering provenance are not different in the marlboro clay from the immediately underlying vincentown formation we suggest that the distinctive magnetic properties of the marlboro clay originated from pyromagnetic soil enhancement by widespread wildfires on the adjoining drainage area the pyrogenetic products were soon washed from the denuded landscape and rapidly deposited as mud waves across the shelf becoming the marlboro clay a few percent of incinerated biomass ends up as calcite known as wood ash stone and can inherit its light carbon isotope composition disseminated wood ash stone entrained in the marlboro clay could contribute to the landward increase in amplitude of the carbon isotope excursion in bulk carbonate data a plausible trigger for the initial conflagration is a fireball from the impact of a sizable extraterrestrial object at moderate range

basinal restriction black shales re os dating and the early toarcian jurassic oceanic anoxic event 1 profiles of mo total organic carbon toc through the lower toarcian black shales of the cleveland basin yorkshire united kingdom and the posidonia shale of germany and switzerland reveal water mass restriction during the interval from late tenuicostatum zone times to early bifrons zone times times which include that of the putative early toarcian oceanic anoxic event the degree of restriction is revealed by crossplots of mo and toc concentrations for the cleveland basin which define two linear arrays with regression slopes ppm of 0 5 and 17 the slope of 0 5 applies to sediment from the upper semicelatum and exaratum subzones this value which is one tenth of that for modern sediments from the black sea mo toc regression slope 4 5 reveals that water mass restriction during this interval was around 10 times more severe than in the modern black sea the renewal frequency of the water mass was between 4 and 40 ka the mo toc regression slope of 17 applies to the overlying falciferum and commune subzones the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years the more restricted of the two intervals has been termed the early toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to nw europe crossplots of re os and mo against toc show similar trends of increasing element concentration with increase in toc but with differing slopes together with modeling of 187 os 188 os and d 98 mo the element toc trends show that drawdown of re os and mo was essentially complete during upper semicelatum and exaratum subzone times mo toc regression slope of 0 5 drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of re os and mo via a low salinity surface layer created isotopic excursions of up to 1 3 in d 98 mo and up to 0 6 for 187 os 188 os restriction thereby compromises attempts to date toarcian black shales and possibly all black shales using re os chronology and introduces a confounding influence in the attempts to use d 98 mo and initial 187 os 188 os for palaeo oceanographic interpretation

stepwise atmospheric carbon isotope excursion during the toarcian oceanic anoxic event early jurassic polish basin abstract during the mesozoic 250 64 ma intervals of about 0 5 myr were subject to severe environmental changes including high sea surface temperature and very low oxygen content of marine water these oceanic anoxic events or oaes occurred simultaneously with profound disturbance to the carbon cycle the carbon isotope anomaly in the early jurassic that marks the toarcian oceanic anoxic event t oae at 182 ma is characterized in marine sections by a series of dramatic steps towards lighter values herein we present new carbon isotope data from terrestrial organic matter phytoclast separates collected through a late pliensbachian middle toarcian coastal and marginal marine succession in the polish basin a setting where hinterland climate and sea level change are well recorded the results show that the shift to light carbon isotope values in the woody organic matter and therefore also in atmospheric carbon dioxide similarly occurred in major steps the steps are here correlated with those identified from marine organic matter where they have previously been attributed to 100 kyr eccentricity forcing of climate the results provide strong support for orbitally and climatically controlled release of isotopically light carbon from gas hydrates into the ocean atmosphere system in a series of rapid bursts additionally a link between the carbon isotope steps and shoreline movements can be demonstrated individual peaks of the negative excursion are mostly associated with facies indicative of sea level rise flooding surfaces however at the same time inferred higher atmospheric carbon dioxide content may be expected to have resulted in increased rainfall and temperature leading to accelerated weathering and erosion and consequently increased sediment supply progradation and regression causing some mismatches between isotope shifts and inferred sea level changes enhanced abundance of megaspores derived from hydrophilic plant groups and marked increase in kaolinite are coincident with the overall development of the negative isotope excursion the combined data suggest that each 100 kyr cycle in carbon isotope values was characterized by increasingly severe palaeoclimatic change culminating in extremely hot and humid conditions co incident with the peak of the final most negative carbon isotope excursion the chemostratigraphic correlation allows very precise dating of the late pliensbachian middle toarcian coastal and marginal marine sedimentary succession in the polish basin

evaluating the temporal link between the karoo lip and climatic biologic events of the toarcian stage with high precision u pb geochronology the karoo large igneous province k lip is considered to have substantially influenced global warming marine anoxia and concomitant marine extinction in the toarcian lower jurassic the sequence and duration of these events has been uncertain thus precluding direct comparison between sedimentary successions and the k lip two relatively narrow time intervals of the early toarcian one approximately within the lower portion of the h falciferum ammonite zone and the other near the pliensbachian toarcian boundary pl to b have received much attention because they are associated with carbon isotope excursions cies and marine extinctions potential causal mechanisms have been proposed such as the release of massive amounts of carbon to the atmosphere via a catastrophic magmatic intrusive episode related to the k lip here we test the timing with four new high precision ca id tims u pb zircon ages from the toarcian stage collected from tephra interstratified with ammonite bearing carbonates in southernmost peru we also present new u pb zircon and baddeleyite data from three sills and one rhyolite of the k lip in south africa our new data permit a substantial reinterpretation of the toarcian timescale the pliensbachian toarcian boundary pl to b a prominent global extinction level must be older than 183 5 ma on the basis of our oldest tephra the h falciferum cie equivalent to the so called toarcian oceanic anoxic event is bracketed by two ash fall bed dates between 183 22 0 26183 22 0 26 and 181 99 0 13 ma181 99 0 13 ma all 2 analytical and tracer errors the cie duration is estimated at approximately 300 ka on the basis of minimum error interpolation of ammonite zone boundaries the base of the h falciferum cie appears to correlate in time with the onset k lip sill emplacement dated by the oldest sill at 183 014 0 072 ma183 014 0 072 ma however sill emplacement appears to have lasted for a minimum of 2 million years at least until 181 31 0 19 ma181 31 0 19 ma which is in disagreement with a short duration of the h falciferum negative cie furthermore our data suggest that the timing of the main volume of the k lip may have been approximately 4 5 ma this prolonged and possibly pulsed magmatic activity of the k lip may be correlated with extinction pulses and climate changes in the middle and late toarcian stage each event occurring within a unique set of global environmental conditions

globally enhanced mercury deposition during the end pliensbachian extinction and toarcian oae a link to the karoo ferrar large igneous province the mesozoic era featured emplacement of a number of large igneous provinces lips formed by the outpouring of millions of cubic kilometres of basaltic magma the radiometric ages of several mesozoic lips coincide with the dates of oceanic anoxic events oaes as a result of these coincidences a causal link has been suggested but never conclusively proven this study explores the use of mercury as a possible direct link between the karoo ferrar lip and the coeval toarcian oae t oae mercury is emitted to the atmosphere as a trace constituent of volcanic gas and may be distributed globally before being deposited in sediments modern marine deposits show a strong linear correlation between mercury and organic matter content results presented here indicate departures from such a simple linear relationship in sediments deposited during the t oae and also during the pliensbachian toarcian transition an event that saw elevated benthic extinctions and carbon cycle perturbations prior to the t oae a number of depositional settings illustrate an increased mercury concentration in sediments that record one or both events suggesting a rise in the depositional flux of this element complications to this relationship may arise from very organic rich sediments potentially overprinting any hg toc signal whereas environments preserving negligible organic matter may leave no record of mercury deposition however the global distribution of coevally elevated hg rich levels suggests enhanced atmospheric mercury availability during the early toarcian potentially aided by the apparent affinity of hg for terrestrial organic matter although the relative importance of aquatic vs terrestrial fixation of hg in governing these enrichments remains uncertain a perturbation in atmospheric hg is most easily explained by enhanced volcanic output it is suggested that extrusive igneous activity caused increased mercury flux to the early toarcian sedimentary realm supporting the potential of this element as a proxy for ancient volcanism this interpretation is consistent with a relationship between lip formation and a perturbed carbon cycle during the pliensbachian toarcian transition and t oae the recording of these two distinct hg excursions may also indicate that the karoo ferrar lip released volatiles in temporally distinct episodes due either to multiple phases of magmatic emplacement or sporadic release of thermogenic gaseous products from intrusion of igneous material into volatile rich lithologies

the geochemistry of indian bole horizons palaeoenvironmental implications of deccan intravolcanic palaeosurfaces deccan intravolcanic bole horizons represent weathering products formed during major hiatuses of a major volcanic episode in these quiescent periods weathering processes pervasively altered the newly formed volcanic landscape and subsequent flows covered and effectively fossilized the resulting weathered palaeosurfaces the current work is a detailed geochemical study which examines patterns of element mobilization during these intravolcanic weathering events the bole horizons normally rest on top of altered basaltic lavas both boles and altered lavas represent a comparatively early stage in weathering because the content of chemically residual elements such as aluminium and iron are closer to fresh basalt than laterite nevertheless these is clear evidence for significant chemical alteration because the more mobile elements such as calcium and sodium have been substantially removed a chemically distinctive nature for some boles can be demonstrated from chondrite normalized ree plots and in these instances strontium and neodymium isotopic compositions demonstrate that the fine grained bole material is derived from a chemically distinct source in addition thin sections reveal that these fine grained portions commonly contains glass shards and occasionally fresh phenocrysts it is therefore suggested that many deccan boles are in fact weathered pyroclastic material and that the pyroclastic content of the basaltic succession may be greater than previously supposed a significant pyroclastic input during the deccan eruptions has important palaeoenvironmental implications for the fate of late cretaceous flora and fauna in peninsular india

extreme warming of mid latitude coastal ocean during the paleocene eocene thermal maximum inferences from tex86 and isotope data changes in sea surface temperature sst during the paleocene eocene thermal max imum petm have been estimated primarily from oxygen isotope and mg ca records generated from deep sea cores here we present a record of sea surface temperature change across the paleocene eocene boundary for a nearshore shallow marine section located on the eastern margin of north america the sst record as inferred from tex86 data indicates a minimum of 8 c of warming with peak temperatures in excess of 33 c similar ssts are estimated from planktonic foraminifer oxygen isotope records al though the excursion is slightly larger the slight offset in the oxygen isotope record may reflect on seasonally higher runoff and lower salinity

organic geochemistry of the early toarcian oceanic anoxic event in hawsker bottoms yorkshire england a comprehensive organic geochemical investigation of the hawsker bottoms outcrop section in yorkshire england has provided new insights about environmental conditions leading into and during the toarcian oceanic anoxic event t oae 183 ma rock eval and molecular analyses demonstrate that the section is uniformly within the early oil window hydrogen index hi organic petrography polycyclic aromatic hydrocarbon pah distributions and tricyclic terpane ratios mark a shift to a lower relative abundance of terrigenous organic matter supplied to the sampling locality during the onset of the t oae and across a lithological transition unlike other ancient intervals of anoxia and extinction biomarker indices of planktonic community structure do not display major changes or anomalous values depositional environment and redox indicators support a shift towards more reducing conditions in the sediment porewaters and the development of a seasonally stratified water column during the t oae in addition to carotenoid biomarkers for green sulfur bacteria gsb we report the first occurrence of okenane a marker of purple sulfur bacteria psb in marine samples younger than 1 64 ga based on modern observations a planktonic source of okenane s precursor okenone would require extremely shallow photic zone euxinia pze and a highly restricted depositional environment however due to coastal vertical mixing the lack of planktonic okenone production in modern marine sulfidic environments and building evidence of okenone production in mat dwelling chromatiaceae we propose a sedimentary source of okenone as an alternative lastly we report the first parallel compound specific c13 record in marine and terrestrial derived biomarkers across the t oae the c13 records of short chain n alkanes acyclic isoprenoids and long chain n alkanes all encode negative carbon isotope excursions cies and together they support an injection of isotopically light carbon that impacted both the atmospheric and marine carbon reservoirs to date molecular c13 records of the t oae display a negative cie that is smaller in magnitude compared to the bulk organic c13 excursion although multiple mechanisms could explain this observation our molecular petrographic and rock eval data suggest that variable mixing of terrigenous and marine organic matter is an important factor affecting the bulk organic c13 records of the t oae

black shales and carbon isotopes in pelagic sediments from the tethyan lower jurassic detailed sampling and analysis of jurassic pelagic limestones and marls from italy hungary and switzerland have enabled construction of an isotope stratigraphy across the pliensbachian toarcian boundary with resolution to the zonal level the oxygen isotope record is unremarkable the carbon isotopes however show two positive excursions one relatively minor during the pliensbachian margaritatus zone subnodosus subzone the other more major during the toarcian early falciferum zone where a maximum 13c value of 4 52 pdb is attained these intervals are known to be favoured periods of organic rich sedimentation in diverse parts of the globe and the isotopic excursions are interpreted as a response to abnormally high rates of storage of organic carbon in the sedimentary record a comparable phenomenon has been documented from the cenomanian turonian boundary in the cretaceous where it has been referred to the influence of an oceanic anoxic event some italian sections spanning this lower jurassic interval contain organic rich shales in the falciferum zone the isotopic signatures from their included locally manganiferous carbonate betray a considerable diagenetic overprint and they cannot therefore be incorporated in a composite isotopic curve carbon isotopes from the organic carbon itself are extremely negative falling to 33 pdb and in one section examined in detail correlate with the calcium carbonate content of the shales they may reflect a partial change to a non calcified planktonic biota during deposition of this lime poor interval possibly responding to upwelling and increased fertility of near surface waters the onset of upwelling may have been as early as spinatum tenuicostatum zone time that is at the pliensbachian toarcian boundary

the geochemical behavior and isotopic composition of hg in a mid pleistocene western mediterranean sapropel abstract the concentrations of mercury hg and other trace metals ni cu zn mo ba re u and the hg isotopic composition were examined across a dramatic redox and productivity transition in a mid pleistocene mediterranean sea sapropel sequence characteristic trace metal enrichment in organic rich layers was observed with organic rich sapropel layers ranging in hg concentration from 314 to 488 ng g avg 385 with an average enrichment in hg by a factor of 5 9 compared to organic poor background sediments which range from 39 to 94 ng g hg avg 66 comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers hg to the seafloor near complete scavenging of hg from the water column renders the sapropel hg isotopic composition representative of mid pleistocene mediterranean seawater sapropels have an average 202hg value of 0 91 0 15 n 5 1 sd and 199hg value of 0 11 0 03 n 5 1 sd background sediments have an average 202hg of 0 76 0 16 n 5 1 sd and 199hg of 0 05 0 01 n 5 1 sd which is indistinguishable from the sapropel values we suggest that the sapropel isotopic composition is most representative of the mid pleistocene tyrrhenian sea

the chon aike province of patagonia and related rocks in west antarctica a silicic large igneous province the field occurrence age classification and geochemistry of the mesozoic volcanic rocks of patagonia and west antarctica are reviewed using published and new information dominated by rhyolitic ignimbrites which form a bimodal association with minor mafic and intermediate lavas these constitute one of the largest silicic igneous provinces known equivalent in size to many mafic lips diachronism is recognized between the early middle jurassic volcanism of eastern patagonia marifil and chon aike formations and the middle jurassic earliest cretaceous volcanism of the andean cordillera el quemado ibanez and tobifera formations this is accompanied by a change in geochemical characteristics from relatively high zr and nb types in the east to subalkaline arc related rocks in the west although the predominance of rhyolites remains a constant factor all of the associated mafic rocks are well fractionated compared to direct mantle derivatives petrogenetic models favour partial melting of immature lower crust as a result of the intrusion of basaltic magmas possibly with some hybridisation of the liquids and subsequent fractionation by crystal settling or solidification and remelting the formation of large amounts of intracrustal silicic melt acted as a density barrier against the further rise of mafic magmas which are thus rare in the province

bolide summer the paleocene eocene thermal maximum as a response to an extraterrestrial trigger the standard paradigm that the paleocene eocene thermal maximum petm represents a threshold event intrinsic to earth s climate and connected in some way with long term warming has influenced interpretations of the geochemical climate and biological perturbations that occurred at this event as recent high resolution data have demonstrated that the onset of the event was geologically instantaneous attempts to account for the event solely through endogenous mechanisms have become increasingly strained the rapid onset of the event indicates that it was triggered by a catastrophic event which we suggest was most likely a bolide impact we discuss features of the petm that require explanation and argue that mechanisms that have previously been proposed either cannot explain all of these features or would require some sort of high energy trigger a bolide impact could provide such a trigger and in the event of a comet impact could contribute directly to the shape of the carbon isotope curve we introduce a carbon cycle model that would explain the petm by global warming following a bolide impact leading to the oxidation of terrestrial organic carbon stores built up during the late paleocene our intention is to encourage other researchers to seriously consider an impact trigger for the petm especially in the absence of plausible alternative mechanisms

metal emissions from kilauea and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes abstract measurements of a large suite of metals pb cd cu zn and several others and sulfur at kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily rare metals from this quiescently degassing volcano representative of an important type we have combined the kilauea data with data of recent studies by others emissions from volcanoes in the indonesian arc the large laki eruption of two centuries ago etna estimates of total volcanic emissions of sulfur to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes the new estimate is that volcanoes inject a substantially smaller mass of ordinarily rare metals into the atmosphere than was stated in a widely cited previous estimate j o nriagu a global assessment of natural sources of atmospheric trace metals nature 338 1989 47 49 our estimate which is an upper limit is an annual injection mass of about 10 000 tons of the metals considered versus the earlier estimate of about 23 000 tons also the proportions of the metals are substantially different in our new estimate

chains clumps and strings magnetofossil taphonomy with ferromagnetic resonance spectroscopy magnetotactic bacteria produce intracellular crystals of magnetite or greigite the properties of which have been shaped by evolution to maximize the magnetic moment per atom of iron intracellular bacterial magnetite therefore possesses traits amenable to detection by physical techniques typically narrow size and shape distributions single domain size and arrangement in linear chains and often crystal elongation past strategies for searching for bacterial magnetofossils using physical techniques have focused on identifying samples containing significant amounts of single domain magnetite or with narrow coercivity distributions searching for additional of traits would however increase the likelihood that candidate magnetofossils are truly of biological origin ferromagnetic resonance spectroscopy fmr is in theory capable of detecting the distinctive magnetic anisotropy produced by chain arrangement and crystal elongation here we present analyses of intact and lysed magnetotactic bacteria dilutions of synthetic magnetite and sedimentary samples of modern carbonates from the great bahama bank oligocene miocene deep sea muds from the south atlantic and pleistocene lacustrine deposits from mono basin california we demonstrate that fmr can distinguish between intact bacterial magnetite chains collapsed chains and linear strings of magnetite formed by physical processes we also show that sediments in which the magnetization is likely carried by bacterial magnetite have fmr spectra resembling those of intact or altered bacterial magnetite chains