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

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

influence of water column anoxia and sediment supply on the burial and preservation of organic carbon in marine shales abstract previous work has suggested that the laminated organic rich and bioturbated organic poor shales of the camp run member of the late devonian early mississippian new albany shale formed under anoxic and oxygenated bottomwater conditions respectively and that the interbedding of the two facies was due to the vertical oscillation of a water column anoxic oxic boundary where it impinged on the basin margin we have extended this analysis by examining the chemical and mineralogical differences between the two shale facies in a single borehole core by seeking evidence for deposition of the laminated shales under bottom water oxia or anoxia and by determining whether the laminated shales formed when the carbon supply to the sea floor was higher the results of this study show that the laminated and bioturbated shales are mineralogically and chemically distinct relative to al an index of the aluminosilicate content si ti fe p na ba co cr cu mo ni v zn and zr are all higher whereas mn ca mg and sr are lower in the laminated compared with the bioturbated shales the differences are due to a higher quartz feldspar titanite ilmenite and zircon content in the laminated shales probably indicating a coarser grain size and the greater abundance of manganoan calcite in the bioturbated shales dissolved oxygen was present in bottom waters during the deposition of some of the laminated shale intervals because of the presence of manganoan calcite a phase that can only form in sediments with an oxic surface in addition the organic matter preserved in the two shale types is isotopically different 13corganic values are 1 9z permil lighter on average in the laminated compared with bioturbated intervals possibly indicating a larger fraction of terrestrial organic matter in the latter 15n values are 1 9z permil lighter on average in laminated compared with bioturbated intervals possibly indicating a larger fraction of terrestrial organic matter in the latter 15n values are 1 9z permil lighter on average in laminated compared with bioturbated intervals suggesting that nutrient drawdown was less during the deposition of the organic rich laminated shales the chemical mineralogical and isotopic contrasts between the two shale facies of the camp run member indicate that the conditions of sedimentation were different during their deposition the difference was possibly related to variations in sea level which would have caused the camp run shoreline to move closer to and farther from the core site causing in turn the deposition of coarser and finer grained sediments that contained different mixtures of marine and terrestrial organic matter bottomwater conditions were anoxic during deposition of most laminated intervals bottom water anoxia or dysoxia led to decreased burial and preservation of the essential nutrient phosphorus in the laminated organic rich shales relative to the rocks deposited beneath better oxygenated bottomwaters increased availability of phosphorus in the water column on long timescales leads to increased productivity and a higher settling flux of organic matter causing bottom water oxygen levels to fall this is consistent with the nitrogen isotope evidence suggesting that production was probably higher during the deposition of the organic rich shales thus production variations coupled with enhanced sedimentary regeneration of phosphorus from sediments related to low oxygen bottom water concentrations provide a general mechanism for the formation of the alternating facies of this member of the new albany shale

relationships between sulphur organic carbon and iron in the modern sediments of the black sea abstract the ratio of sedimentary s to organic c has been used as a diagnostic criterion for recognizing anoxic environments in the sedimentary record here we examine the relationship between pyrite s and organic c in the modern unit 1 sediments of the black sea to re evaluate this suggested relationship in box cores from shallow oxic or near oxic water pyrite s contents ranging from 0 1 and 2 5 by weight do not correlate with organic c contents in cores from the deep anoxic basin pyrite s concentrations range between 1 0 and 2 5 and are linearly related to organic c contents with an intercept that is not significantly different from zero the s c ratio is around 0 31 in these sediments which is somewhat lower than the ratio of 0 36 considered to be characteristic of normal marine oxic sediments thus the black sea anoxic sediments appear to be depleted in s relative to organic c the degree of pyritization dop of the sediments may be a better measure of anoxic conditions of sedimentation the dop values measured here show that pyrite formation is fe limited the correlation between organic c and pyrite s probably being induced by a positive correlation between fine grained sediment components the original fe source for pyrite formation in the sediments and organic matter such fe limitation is probably characteristic of anoxic basins where pyrite formation can take place in the water column and fe oxyhydroxides do not accumulate in the surface sediments the results on the sample set examined here are at variance with earlier data and interpretations for the black sea in particular the suggested s enrichment of anoxic black sea sediments was not found because of fe limitation

can the aluminum and titanium contents of ocean sediments be used to determine the paleoproductivity of the oceans in the central equatorial pacific settling particles collected with sediment traps have al ti values greater than those of a typical crustal source the al ti values of the sediment trap material are not well correlated with either the flux of organic carbon or with total particle mass suggesting that this ratio cannot be used as a simple index of paleoproductivity however the al ti values of some trap samples are more than 3 times the ratio for typical crustal materials indicating a noncrustal source of excess al numerical analysis using linear programming indicates that the excess al is associated with opal and that this biological component carries as much as 1200 ppm of al because of the low particulate fluxes of lithogenic material in the equatorial pacific and the relatively high opal content of equatorial sediment trap material opal appears to be the predominant conveyor of al to the equatorial sediments our sediment trap al ti values are similar to ratios previously measured in equatorial sediments suggesting that measurements of this element pair in ocean sediments may be an indicator of opal rain to the seafloor the particle reactive nature of al and ti means their ratios in sediments may be relatively insensitive to opal preservation or other diagenetic processes however the al ti values of raining particles are highly sensitive to the relative proportion of opal and lithogenic material where opal lithogenic ratios are less than 20 the al ti values are indistinguishable from a crustal source ratio in addition the amount of excess al associated with opal in settling particles may be a function of the concentration of al in the water column and of the processes that fractionate dissolved al and ti these issues must be evaluated before the al ti values of ocean sediments can be used as a reliable proxy of opal flux to the seafloor

rhenium and molybdenum enrichments in sediments as indicators of oxic suboxic and sulfidic conditions of deposition abstract the trace elements re and mo both behave conservatively in seawater yet are strongly enriched in reducing sediments their potential for authigenic enrichment above crustal concentrations is greater than for many other elements due to the high ratio of metal sw metal crust we present sedimentary re and mo data from box and multi cores spanning a range of redox conditions from well oxygenated sites to locations with substantial sulfide concentrations at the oxic sites re and mo as expected accumulate at concentrations close to their crustal abundances re shows substantial enrichment in suboxic absence of o 2 and h 2 s sediments of the sea of japan in sediments within the oxygen minimum of the pakistan margin as well as in sediments underlying the sulfide bearing waters of the black sea and saanich inlet re enrichment occurs in these cores just below the depths of fe and u reduction only in the sediments underlying the sulfidic waters of the black sea and saanich inlet is there substantial authigenic mo accumulation absence of re and mo enrichments in sediment trap samples from the sulfide bearing basins suggests that the addition of both metals occurs at or below the sediment water interface the re and mo concentration profiles are modeled to hindcast the removal depth of re and mo in the sediments which along with the re mo ratio determine whether oxic suboxic or sulfidic conditions were present in the water column or in the sediments in the past using this approach historical redox conditions can be inferred even in environments such as continental margins where a substantial lithogenic component can obscure authigenic enrichments of other metals

deep water anoxia over the frasnian famennian boundary la serre france a tectonically induced oceanic anoxic event the frasnian famennian f f transition is well exposed in the basinal setting of la serre montagne noire france where oxygen deficient conditions prevailed in bottom environments in this paper we study the f f transition using inorganic geochemistry notably major elements redox sensitive and or sulphide forming trace metals and productivity proxies the results are compared with published data concerning the la serre section other f f sections and other geological formations also deposited in basinal settings the very high enrichment in redox and productivity tracers indicates that anoxic conditions prevailed across the f f boundary and that surface productivity was intense such deep water restricted conditions coupled with high productivity occurred in various places in late devonian oceans recycling alone cannot account for the intense nutrient supply and therefore the most probable source was via land runoff we discuss the eovariscan episode of uplift that stimulated rock weathering and hence long term nutrient supply to the seas

black shale deposition and faunal overturn in the devonian appalachian basin clastic starvation seasonal water column mixing and efficient biolimiting nutrient recycling integrated geochemical data suggest that black shale deposition in the devonian geneseo formation of western new york was initiated by the coincidence of siliciclastic starvation and the intensification of seasonal water column stratification and mixing once established however black shale deposition was maintained through efficient recycling of biolimiting nutrients which enhanced primary productivity recycling efficiency was achieved through a positive feedback loop of oscillating benthic redox conditions that enhanced n and p regeneration from sediments sustained high primary productivity by returning nutrients to the photic zone during mixing and ensured a downward flux of organic matter that drove or enhanced the episodic development of benthic anoxia during stratification this feedback was ultimately disrupted by rising siliciclastic influx which diluted organic matter and restored benthic redox stability the abrupt overturn of diverse long standing appalachian basin marine communities may have been the result of trophic resource destabilization during geneseo deposition

frasnian famennian biotic crisis undervalued tectonic control the prime cause of the late devonian kellwasser crisis culminating in a mass extinction event near the frasnian famennian f f boundary remains conjectural nevertheless rapid sea level fluctuations of uncertain origin during tectono eustatic highstand paired with repeated oceanic anoxia and climatic changes are usually thought at present to be one of the main immediate triggers the cathles hallam model of stress induced changes in plate density accompanying rapid rift formation furnishes an alternative for understanding the enigmatic sudden eustatic variations in the non glacial time late devonian tectonic extension causing rifting and volcanicity appears to be strongly marked in several regions of eurasia particularly in kazakhstan and eastern laurussia all larger devonian continents were more or less tectonically affected a subtle record of this tectonic rearrangement is implied even for distant and apparently quiet carbonate platforms in local extensional block faulting and tilting hydrothermal mineralisation geochemical anomalies and localized blooms of siliceous biota interpreting the late frasnian regressive transgressive pattern in terms of the cathles hallam tectono eustatic model two major rifting events are hypothesized one at about the beginning of the rhenana zone and a second principal pulse in the late linguiformis zone that encompassed the f f transition developing the veimarn milanovsky scenario of the global extensional pulse it is assumed that the key endogenous factors were related to episodic super plume activity the tectonically triggered changes climaxed in thermal and nutrient pulses and induced the stepdown ecosystem destabilization observed in the f f bio crisis minor cometary strike s might have eventually participated in this prolonged multicausal environmental stress mainly due to additional thermal shocks but perhaps effective on a regional scale only

pyrite framboid evidence for oxygen poor deposition during the permian triassic crisis in kashmir abstract the khunamuh formation of the guryul ravine section in kashmir provides one of the most detailed deep water records of the end permian mass extinction in perigondwanan palaeolatitudes examination of pyrite framboid size distributions and sediment microfabric reveals a distinct change in the uppermost permian strata from nonlaminated pyrite free silty mudstones to finely laminated silty shales rich in framboidal pyrite around 1 m above the base of the formation the size frequency distribution of the framboids is identical to populations from severely oxygen restricted modern depositional environments this change to dysoxic benthic conditions coincides with the rapid demise of diverse permian brachiopod and bryozoan assemblages thus the link between extinction and anoxia is clearly seen at guryul ravine and it provides an interesting contrast to other perigondwanan sections developed in shallower water where both the onset of anoxia and the extinction occurred somewhat later in the earliest triassic

the late devonian frasnian famennian f f biotic crisis insights from δ13ccarb δ13corg and 87sr 86sr isotopic systematics a severe biotic crisis occurred during the late devonian frasnian famennian f f transition f367 myr here we present d 13 ccarb d 13 corg and 87 sr 86 sr isotopic systematics from identical samples of two sections across f f boundary in south china which directly demonstrate large and frequent climatic fluctuations 200 kyr from warming to cooling during the f f transition these climate fluctuations are interpreted to have been induced initially by increased volcanic outgassing and subsequent enhanced chemical weathering linked to the rapid expansion of vascular plants on land which would have increased riverine delivery to oceans and primary bioproductivity and subsequent burial of organic matter thereby resulting in climate cooling such large and frequent climatic fluctuations together with volcanic induced increases in nutrient e g biolimiting fe toxin sulfide and anoxic water supply and subsequent enhanced riverine fluxes and microbial bloom were likely responsible for the stepwise faunal demise of f f biotic crisis d 2005 elsevier b v all rights reserved

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

silica secreting biota and mass extinctions survival patterns and processes abstract high survival and at least regional blooms of siliceous marine groups with coeval retreat of calcareous organisms is known from the frasnian famennian radiolarians silicisponges and end cretaceous diatoms radiolarians mass extinctions a strictly actualistic approach to the palaeoecology of silica secreting biota is of limited significance especially for silica enriched and oligotrophic palaeozoic epeiric seas and in particular during biotic turnovers adaptation among silica secreting marine plankton has led toward more efficient utilization of shrinking dissolved silica resources within surface waters of cenozoic oceans as shown by both radiolarians and diatoms this biosiliceous signal during the major biotic crises is mostly explained by a large scale increase in volcano hydrothermal activity during major plate boundary re arrangements triggering global ecosystem perturbations the cumulative stimulus favoured siliceous versus calcareous biota growth deposition and preservation because of 1 a higher rate of input of silica and other nutrients promoting eutrophication pulses 2 a punctuated or reversed greenhouse climatic effect episodically coupled with 3 vigorous oceanic circulation due to a variety of volcanogenic upwellings and turnovers siliceous communities adapted to more eutrophic conditions have thrived in the stressed niches on the other hand expanding anoxia and nutrification may lead to a stepwise loss of deep water niches and consequent selective decline of more specialized oligotrophic radiolarians and other pelagic biota by contrast siliceous faunas experienced severe non selective losses during the end permian mass extinction recorded as a chert gap thus the greatest environmental disaster of the phanerozoic was driven by a unique set of killing factors extremely effective for radiolarian productivity e g due to the combination of a drastic volcanic winter with expanding superanoxia

anisotropic p wave attenuation measured from a multi azimuth surface seismic reflection survey a system of aligned vertical fractures produces azimuthal variations in stacking velocity and amplitude variation with offset characteristics often reported in seismic reflection data for hydrocarbon exploration studies of associated attenuation anisotropy have been mostly theoretical laboratory or vertical seismic profiling based we used an 11 common midpoint long portion of each of four marine surface seismic reflection profiles intersecting each other at 45 within circa 100 m of a common location to measure the azimuthal variation of effective attenuation q 1eff and stacking velocity in a shallow interval about 100 m thick in which consistently orientated vertical fracturing was expected due to an underlying salt diapirism we found qualitative and quantitative consistency between the azimuthal variation in the attenuation and stacking velocity and published amplitude variation with offset results the 135 azimuth line showed the least apparent attenuation 1000 q 1eff 16 7 and the fastest stacking velocity hence we infer it to be closest to the fracture trend the orthogonal 45 line showed the most apparent attenuation 1000q 1eff 52 15 and slowest stacking velocity the variation of q 1eff with azimuth is well fitted by 1000q 1eff 34 18cos 2 40 giving a fracture direction of 140 23 1sd derived from bootstrapping fits to all 114 combinations of individual common midpoint azimuth measurements compared to 134 47 from published amplitude variation with offset data the effects of short window spectral estimation and choices of spectral ratio bandwidth and offset ranges used in attenuation analysis individually give uncertainties of up to 13 in fracture direction this magnitude of azimuthal variation can be produced by credible crack geometries e g dry cracks radius 6 5 m aspect ratio 3 10 5 crack density 0 2 but we do not claim these to be the actual properties of the interval studied because of the lack of well control and its consequences for the choice of theoretical model and host rock physical properties and the small number of azimuths available here

eutrophication by decoupling of the marine biogeochemical cycles of c n and p a mechanism for the late devonian mass extinction the late devonian mass extinction was unusually protracted and ecologically selective with preferential diversity losses among reefbuilding organisms and tropical shallow water faunas in general we have investigated the link between the extinction s unique characteristics and changes in biogeochemical cycling through analyses of the 13 c and c n p atomic ratios of organic matter buried across the kellwasser horizons in western new york state each horizon is characterized by 1 a long term 4 5 excursion in 13 c 3 of which occurs within the horizon and 2 a dramatic increase in the burial ratios of c n p from values of 100 15 1 to an average of 5000 170 1 on the basis of these results we propose that 1 increased efficiency of biolimiting nutrient recycling resulting from cyclic water column stratification and mixing promoted eutrophication during kellwasser deposition in new york and 2 the isotope excursions represent the composite effect of long term global organic c burial and local changes in photosynthetic c isotope fractionation related to nutrient availability this eutrophication model forges a mechanistic link between proposed late devonian climatic cooling and the selective demise of taxa likely to have been narrowly adapted to oligotrophic conditions

a modern vs permian black shale the hydrography primary productivity and water column chemistry of deposition the sediment currently accumulating in the cariaco basin on the continental shelf of venezuela has an elevated organic carbon content of approximately 5 is accumulating under o2 depleted bottom water conditions so42 reduction is composed dominantly of foraminiferal calcite diatomaceous silica clay and silt and is dark greenish gray in color upon lithification it will become a black shale recent studies have established the hydrography of the basin and the level of primary productivity and bottom water redox conditions these properties are used to model accumulation rates of cd cr cu mo ni v and zn on the seafloor the model rates agree closely with measured rates for the uppermost surface sediment the model is applied to the meade peak phosphatic shale member of the phosphoria formation a phosphate deposit of permian age in the northwest united states it too has all of the requisite properties of a black shale although the deposit is a world class phosphorite it is composed mostly of phosphatic mudstone and siltstone chert limestone and dolomite it has organic carbon concentrations of up to 15 is strongly enriched in several trace elements above a terrigenous contribution and is black the trace element accumulation defines a mean primary productivity in the photic zone of the phosphoria basin as moderate at 500 g m 2 year 1 organic carbon comparable to primary productivity in the cariaco basin the source of nutrient enriched water that was imported into the phosphoria basin upwelled into the photic zone and supported primary productivity was an o2 minimum zone of the open ocean the depth range over which the water was imported would have been between approximately 100 and 600 m the mean residence time of bottom water in the basin was approximately 4 years vs 100 years in the cariaco basin the bottom water was o2 depleted but it was denitrifying or no3 reducing rather than so42 reducing

carbon isotope geochemistry of the frasnian famennian transition abstract carbon isotope records for inorganic and total organic carbon toc as well as for individual organic biomarkers show two positive excursions in the late frasnian with comparable shape and amplitude in 13c the positive shifts in 13c can be correlated with the deposition of the kellwasser horizons the inorganic carbon isotope excursions are explained by an enhanced organic carbon burial that is expected to lower the concentration of oceanic dissolved co2 toc 13c values do not exhibit a larger shift than that recorded by inorganic carbon 13c values this is unexpected since a decrease in the dissolved co2 concentration should result in lower carbon isotope fractionation during photosynthesis ep 13c values of presumed algal biomarkers low molecular weight n alkanes pristane phytane although offset by 2 5 exhibit essentially identical records as toc and confirm this unexpected result it is proposed that high atmospheric and oceanic co2 concentrations during the devonian resulted in maximum photosynthetic fractionation any change in the co2 concentration would thus not affect ep as such 13c of primary organic carbon and 13ccarb will exhibit parallel excursions the data imply that carbon isotopes and the relationship between ep and co2 will not be effective to study changes in pco2 levels during the devonian since co2 concentrations were too high

early diagenetic pyrite morphology in a mudstone dominated succession the lower jurassic cleveland ironstone formation eastern england abstract diagenetic pyrite in the mudstones and ironstones of the lower jurassic cleveland ironstone formation of eastern england exhibits two distinct morphologies framboidal pyrite commonly associated with organic matter and euhedral pyrite associated with detrital clay pellets these two morphologies are mutually exclusive in occurrence framboidal pyrite is present in clay rich mudstones ooidal ironstones apatite rich units and some silt rich mudstones euhedral pyrite is present in silt rich and sand rich mudstones 34s isotopic analysis of six samples of pyrite suggests that both types of pyrite morphology precipitated during early diagenesis from porewaters with open access to overlying sea water although both probably acted as sites for continued pyrite precipitation during burial it is proposed that framboidal pyrite precipitated from iron dominated porewaters at sites of sulfide supply i e in the region of organic matter as a result of bacterial sulfate reduction where locally sulfide production rates were high enough for porewaters to reach supersaturation with respect to fes euhedral pyrite also precipitated from iron dominated porewaters but sulfide production rates from organic matter was such that fes saturation was not reached at the sites of sulfide production instead euhedral pyrite was precipitated directly from porewater when fes2 saturation was reached the control over pyrite morphology was probably the amount and reactivity of the organic matter within the deposited sediments the sand rich mudstones contained less reactive organic matter due to clastic dilution and deposition in shallower environments with o2 rich bottom waters the ironstones and apatite rich units were deposited under very low sedimentation rates and as a result organic matter contents were very low and iron reduction dominated early diagenesis which inhibited sulfate reduction the presence of minor framboidal pyrite within these units however suggests that sulfide reduction took place in micro environments during early diagenesis

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

anoxic events in the late frasnian causes of the frasnian famennian faunal crisis carbon isotope data collected from five frasnian famennian boundary sections in central europe show two positive 13 c excursions in the late frasnian 367 ma both anomalies coincided with the deposition of the bituminous lower and upper kellwasser horizons the carbon isotope patterns indicate two phases of enhanced burial and subsequent recycling of organic carbon a maximum formation of warm saline waters on the subtropical to tropical epicontinental shelves during late frasnian transgressive episodes may have induced oceanic oxygen deficits variations in the c org burial rates may have resulted in changes in the co 2 concentrations in the oceans and in the atmosphere culminating in global climatic changes we propose that the repeated co occurrences of sea level fluctuations anoxic conditions and global climatic changes during the late frasnian would affect especially the subtropical to tropical shallow water communities and reef ecosystems which were severely affected during the frasnian famennian faunal crisis

water column anoxia enhanced productivity and concomitant changes in δ13c and δ34s across the frasnian famennian boundary kowala holy cross mountains poland the investigation of the trace element and organic geochemistry of the frasnian famennian boundary section at kowala holy cross mountains poland shows that the lower water column was oxygen deficient during late frasnian and early famennian times the abundance and carbon isotopic composition of diaryl isoprenoids biomarkers indicative for green sulfur bacteria prove that euxinic waters reached into the photic zone at least episodically total organic carbon toc contents show two maxima that are time equivalent to the kellwasser horizons deposited in shallower water settings enhanced toc concentrations are explained by a higher primary productivity presumably as a consequence of an enhanced nutrient supply from the continent the increase in the abundance of hopanes and bituminite suggests that the bacterial contribution to toc increased at the frasnian famennian transition the sulfur isotopic composition of pyritic and organically bound sulfur shows a 27 excursion across the boundary the observation that the 34s values of organic bound sulfur closely resemble that of pyrite sulfur indicates a common sulfur source likely early diagenetic sulfide a change in the 13c of total dissolved inorganic carbon as a consequence of an enhanced burial of 12c enriched organic carbon is indicated by a 3 excursion measured for toc as well as for individual n alkanes and isoprenoids the burial of large amounts of organic carbon is expected to result in a decrease in pco2 and should affect the photosynthetic carbon isotope fractionation ep the fact that we observe no change in ep can be explained by the circumstance that ep was most probably at maximum values as a consequence of high atmospheric and oceanic dissolved co2 concentrations during the devonian

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

microfacies sequence stratigraphy and clay mineralogy of a condensed deep water section around the frasnian famennian boundary steinbruch schmidt germany abstract a multidisciplinary analysis microfacies sequential stratigraphy and clay mineralogy was made on frasnian famennian f f boundary strata of the steinbruch schmidt section in western germany three major microfacies are recognised their succession records a shallowing upward evolution from deep quiet and poorly oxygenated environments below the storm wave base to environments influenced by current activities close to the storm wave base the kellwasser horizons correspond to the deepest microfacies the shallowest microfacies correspond to fine grained calcareous tempestites or turbidites coming from a distant shelf of northwest germany the sequential pattern through the f f boundary shows the succession of seven systems tracts two sequence boundaries are located just above the lower kellwasser horizon and at the f f boundary itself these are underlined by hardgrounds suggesting time gaps the kellwasser horizons correspond to sea level highstands and the overlying beds record a transition from lowstand to transgressive systems tracts illite and kaolinite are the dominant clay minerals associated with mixed layers and traces of chlorite illite abundance is maximal during kellwasser horizons illite and kaolinite were probably inherited from a highly weathered source area although part of the illite is diagenetic kaolinite is the second most abundant clay mineral and is particularly well represented up to 50 between the kellwasser horizons an unusual clay assemblage of illite and mixed layers is associated with a bentonite layer kaolinite increases during times when thin tempestites or turbiditic microbioclastic layers come from a distant shelf during sea level falls the kaolinite percentage reaches its maximum at the top of the lowstand systems tract the high percentage of kaolinite suggests a hot wet climate and could be related to global warming

trace metal signatures of jurassic cretaceous black shales from the norwegian shelf and the barents sea abstract black shale samples of jurassic to cretaceous age recovered during the norwegian shelf drilling program between 1987 and 1991 from sites 7430 10 u 01 barents sea 6814 04 u 02 norwegian shelf near the lofoten and 6307 07 u 02 norwegian shelf near trondheim were analyzed for major and trace elements these laminated black shales are characterized by high total organic carbon toc and total sulfur ts contents as well as by significant enrichments in several redox sensitive and or sulfide forming trace metals ag bi cd co cr cu mo ni re sb tl u v and zn enrichment factors relative to average shale are comparable to those found in cenomanian turonian boundary event ctbe black shales and mediterranean sapropels the re content is high in the studied black shales with maximum values up to 1221 ng g re mo ratios averaging 2 3 10 3 are close to the seawater value high trace metal enrichments and re mo ratios close to the seawater value point to a dominantly anoxic and sulfidic water column during black shale formation interbeds with higher re mo ratios especially in high resolution sampled core sections point to brief periods of suboxic conditions additionally enhanced zn concentrations in the black shales from the barents sea support the assumption that hydrothermal activity was also high during black shale deposition trace metal signatures of black shales at different drill sites on a transect along the norwegian shelf are not only influenced by water depth but also by their location in the boreal realm metal enrichments are higher in the northern compared to the southern sites volgian tithonian 151 144 ma bp black shales exhibit elevated trace metal contents in comparison to their berriasian 144 137 ma bp counterparts this probably reflects a change in the circulation pattern during periods of black shale formation therefore different paleoceanographic conditions probably controlled by climatic change linked to the transgression of the paleo sealevel and the north atlantic opening may have developed from the volgian to the berriasian

the frasnian famennian boundary interval in the south polish moravian shelf basins integrated event stratigraphical approach abstract the late devonian mass extinction event near the frasnian famennian f f boundary has been analysed using conodont biostratigraphy and biofacies sedimentology magnetic susceptibility and geochemistry in reference sections of the south polish moravian shelf holy cross mountains cracow and brno areas high resolution biostratigraphic study revealed difficulties in the precise recognition of this natural stage boundary but confirmed the occurrence of a major third order sequence boundary in the f f transition in an active synsedimentary tectonic setting marked by erosional discontinuities hardgrounds and brecciation or omission surfaces conclusive evidence of an extraterrestrial impact has not been found among earth bound factors the main devastating role in the shelf habitats is ascribed to fluctuating anoxia and or nutrient dynamics in a disturbed greenhouse climatic setting the long term facies changes were determined by a conspicuous break in carbonate production accompanied by replacement of mature stromatoporoid coral reefs by pioneer shelly crinoid banks microbial mounds and localised oolitic bars the key f f passage interval was marked by intermittent but generally accelerated periplatform ooze debris input and severe storm events as well as by probably highly fluctuating oxygenation and biological overproduction best manifested in radiolarian silicisponge and cephalopod acmes eutrophication phenomena at least partly stimulated by various hydrothermal and volcanic processes were one of the major biogeochemical processes during this climax of the late devonian biotic crisis however significant oceanographic perturbations were also linked with the onset of the transgressive hypoxic upper kellwasser event still within the latest frasnian linguiformis zone i e well before the f f conodont collapse implied variations in the redox state of seawater through the kellwasser timespan probably in regionally highly variable temporal scales are in agreement with recent palaeoecological and biogeochemical inferences in particular suggesting recovering oxygenation just prior to the f f boundary in the other laurussian intrashelf basins all the data support a long time multicausal earth bound crisis instead a worldwide cosmic catastrophe

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

event stratigraphic markers within the kellwasser crisis near the frasnian famennian boundary upper devonian in germany abstract short time intervals of anomalous conditions often referred to as global events yield excellent tools for detailed stratigraphic correlations in addition to pronounced effects minor features may be applied for fine scale comparisons of rock sequences these include alternations within a given portion of rock or distinct layers at exactly the same position such marker horizons are often traceable over long distances recognition of these specific markers allows for a more detailed search for possible causes of anomalous events

frasnian famennian mass extinction and cold water oceans suturing of laurussia and africa elimination of easterly tropical currents and consequent equatorial diversion of cold and possibly dysaerobic waters are suggested as prime causes of the frasnian famennian late devonian extinction these are explained by using a new paleogeographic model evidence for stepdown extinctions that took place from givetian through frasnian time is taken particularly from atrypoid brachiopods one of the most abundant representatives of the global tropical shelly marine benthos during the middle and late devonian only 5 of 17 frasnian genera or subgenera of atrypoids are known to be present in late frasnian sediments and possibly only a single genus spinatrypa was present at the frasnian famennian boundary evidence for stepdown extinction from other invertebrate and vertebrate groups in general corroborates that provided by brachiopods

reactive iron in black sea sediments implications for iron cycling abstract the distribution of reactive iron in sediments of the northwestern shelf the shelf edge and the abyssal part of the black sea has been studied in the euxinic black sea iron sulfides pyrite and iron monosulfide are formed in the upper part of the anoxic water column and sink to the deep sea floor where they are buried in the sediment this flux of iron sulfides from the water column is reflected in enhanced concentrations of highly reactive iron and a high degree of pyritization 0 57 0 80 for the deep water sediments of the black sea the iron enrichment of deep water sediments is balanced by a loss of highly reactive iron from the oxic continental shelf calculations from a numerical diagenetic model and reported in situ flux measurements indicate that the dissolved iron flux out of the shelf sediments is more than sufficient to balance the enrichment in reactive iron in deep sea sediments and that the majority of the dissolved iron efflux is redeposited on the continental shelf this iron mobilization mechanism likely operates in most shelf areas but its net effect becomes only apparent when reactive iron is trapped in sulfidic water bodies as iron sulfides or when iron is incompletely oxidized in low oxygen zones of the ocean and transported over long distances

mass extinctions and sea level changes abstract review of sea level changes during the big five mass extinctions and several lesser extinction events reveals that the majority coincide with large eustatic inflexions the degree of certainty with which these eustatic oscillations are known varies considerably thus the late ordovician and end cretaceous extinctions are associated with unequivocal major regressions demonstrated from numerous widespread regions in contrast the multiple high frequency sea level changes reported for the frasnian famennian crisis based on the supposed depth preferences of conodont taxa have little support from sequence stratigraphic analyses which reveals the interval to be one of highstand the end permian mass extinction has long been related to a severe first order lowstand of sea level newell n d 1967 revolutions in the history of life geol soc am spec pap 89 63 91 based primarily on the widespread absence of latest permian ammonoid markers but field evidence reveals that the interval coincides with a major transgression newell s hypothesis that marine extinctions are related to shelf habitat loss during severe regression remains tenable for the end guadalupian and end triassic extinction events but not for other crises rapid high amplitude regressive transgressive couplets are the most frequently observed eustatic changes at times of mass extinction with the majority of extinctions occurring during the transgressive pulse when anoxic bottom waters often became extensive the ultimate cause of the sea level changes is generally unclear a glacioeustatic driving mechanism can only be convincingly demonstrated for the end ordovician and end devonian events at other times it is speculated that they may relate to the widespread regional doming and subsequent collapse caused by the impingement of superplumes and ultimate eruption on the base of the lithosphere

scavenged excess aluminum and its relationship to bulk titanium in biogenic sediment from the central equatorial pacific ocean we present results from chemical analyses of al and ti in surface sediment sampled along two cross equator latitudinal transects at 135w and 140w in the central equatorial pacific ocean although traditionally both al and ti are considered to reside exclusively within terrigenous phases in marine sediment these sediments present extremely high al ti ratios that are several times that of average shale and other potential crustal sources a sharp maximum in al ti is observed slightly south of the equator where sedimentary bulk accumulation rate bar is also highest reflecting elevated productivity in the overlying water caused by surface water divergence bulk al ti decreases sharply away 2 latitude to near crustal values at 4 north and south the latitudinal profiles of al ti are entirely unrelated to the concentration of the biogenic components as well as to the absolute accumulation of al and ti these results indicate the presence of a significant scavenged component of al sourced directly from seawater during particle settling the data from the two transects analytically and oceanographically confirms our earlier work that was based on the single 135w transect calculations of alexcess indicate that the highest al ti ratios correspond to 50 of the total al being unsupported by the small amount of terrigenous phases present these results are consistent with previous and ongoing studies of biogenic sediment suspended particulate matter and sediment trap material quantitative use of al as an index of terrigenous material may therefore lead to an overestimation by a factor of two of the true terrigenous load in marine sediment sedimentary rock and settling particles because bulk al ti appears to respond to sedimentary bar which in biogenic regimes is linked to surface water productivity downcore records of al ti in biogenic sediment may track productivity changes through time such al ti proxy records may be applicable in sediment of all ages unlike radionuclide tracers which are limited by radioactive decay to use over the past hundreds of kyr

an integrated assessment of a type euxinic deposit evidence for multiple controls on black shale deposition in the middle devonian oatka creek formation an integrated lithologic paleontologic and multi proxy geochemical study of the middle devonian oatka creek formation a black shale in the northern appalachian basin indicates that a number of different factors contributed to organic carbon rich black shale deposition conditions leading to this organic rich sedimentary deposit were ultimately controlled by a relative sealevel rise dominantly eustatic but with possible contributions from local tectonics which cut off the supply of carbonate to the basin geochemical proxy evidence such as mo ti fe ti corg spy and 34spy suggests that as sealevel continued to rise after the carbonate supply was cut off a threshold was crossed at which point conditions in the basin shifted from dominantly anoxic to dominantly euxinic anoxic sulfidic bottom waters concurrent with the shift to dominantly euxinic conditions the supply of siliciclastic sediments was cut off resulting in a condensed horizon as evidenced by the elemental ratios of si al and k fe mg and the relative concentration of eolian silt as determined petrographically and from scanning electron microscopy sediment starvation in the basin appears to have facilitated the biogeochemical re cycling of c n and p specifically the elemental ratios of c n and p and the stable carbon isotope composition of organic matter suggest that the preferential regeneration of p under anoxic conditions and of n during the oxic phase of oxic anoxic oscillation led to enhanced primary production in surface waters thereby maintaining euxinic conditions in the bottom waters through respiration of settling organic matter finally it is observed that though conditions in the basin seem to have remained consistently anoxic sulfidic for some time after the initial shift to euxinic conditions a progressive increase in siliciclastic sedimentation led to a corresponding decrease in the enrichment of various redox related elements illustrating the overriding control that sedimentation can have on geochemical proxy records

sedimentary geochemistry of manganese implications for the environment of formation of manganiferous black shales the sedimentary geochemistry of manganese is dominated by the redox control of its speciation higher oxidation states mn super 3 and super 4 occurring as insoluble oxyhydroxides in well oxygenated environments and the lower oxidation state mn super 2 being much more soluble in oxygen deficient settings its geochemical behavior is therefore quite different in oxic and anoxic environments and where oxic and anoxic conditions are juxtaposed mn is recycled between the two environments in modern marine sediments mn is present above its crustal abundance as an oxyhydroxide in all slowly accumulating pelagic sediments of the deep ocean and in surficial deposits of continental margin environments diagenetic recycling of mn in the latter causes surficial deposits to have larger mn enrichments than in many pelagic sediments bottom sediments of permanently anoxic basins show no enrichments and have mn concentrations that are controlled solely by the aluminosilicate fraction manganese carbonates kutnohorite and calcic rhodochrosite are found only in anoxic sediments accumulating beneath surface oxic horizons and therefore under oxygenated bottom waters in many nearshore environments such enrichments are due to delivery of mn by burial of surface oxyhydroxides into the subsurface anoxic environment where they are dissolved pore water mn levels can reach saturation with respect to a mixed mn ca carbonate phase in such sediments the diagenetic origin for these phases is shown by their carbon isotope compositions which typically indicate a carbon source from decomposing organic matter the presence of mn carbonates therefore signifies that the host sediment must have accumulated under oxygenated bottom waters on the basis of this information it is proposed that in contrast to several current explanations for the formation of mn carbonates kutnohorite and rhodochrosite in ancient organic rich shales limestone and marl sequences and in many mn ore deposits the occurrence of these mineral phases indicates that the sediments originally accumulated beneath oxygenated bottom waters by analogy with the present mn carbonates could not have formed in the bottom waters of anoxic basins these diagenetic phases however did form where mn was supplied at a high rate namely by the burial of oxyhydroxide enriched surface sediments to a subsurface anoxic environment this situation could only have occurred under oxygenated bottom waters the presence of mn carbonates in ancient black shales and in some carbonate rich rocks lends strong support to the notion that these rocks did not necessarily form in anoxic basins but owe their carbon richness to a high supply of organic matter to sediments deposited under oxygenated bottom waters probably in continental margin settings

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

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

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

multiple controls on the preservation of organic matter in devonian mississippian marine black shales geochemical and petrographic evidence geochemical and petrographic analysis of an interval of black shales between the huron shale member of the new albany shale upper devonian famennian and the sunbury shale lower mississippian tournaisian suggests that multiple controls influenced the accumulation of organic matter stratigraphic trends were determined following detailed analysis of a core from the central appalachian basin d6 montgomery county ky specifically c s fe relationships mo v v ni ni co and v cr were used to assess paleo redox conditions during sediment accumulation the role of clastic input was evaluated using ti al k al and si al and c p was used as a proxy for paleoproductivity the terrestrial to marine maceral ratio t m vitrinite plus inertinite alginite plus bituminite was used to evaluate changes in om source c s fe relationships and trace element ratios suggest anoxic conditions prevailed during deposition of much of the upper part of this interval however bottom water conditions were intermittently dysoxic during accumulation of the huron shale member and possibly dysoxic to marginally oxic during accumulation of the lowermost huron shale member productivity appears to have been an important factor in the accumulation of corg and high c p ratios are consistent with a productivity anoxia feedback mechanism in addition nutrients from increased terrestrial weathering may have contributed to enhanced productivity variations in sediment influx may also have influenced corg concentrations through sediment starvation one of the more significant observations in this work is an increase in terrestrial om inertinite and vitrinite up section which may reflect vegetative changes occurring on land during this time interval most of this increase is due to inertinite much of which appears to be fusinitic in origin and hence may be fossil charcoal this latter observation has implications for the expansion of land plants into drier niches and for late devonian atmospheric oxygen levels introduction of more resistant terrestrial om to anoxic basins may have been an important factor in the preservation of high carbon 10 intervals especially in the cleveland member of the new albany shale upper devonian famennian and the sunbury shale lower mississippian tournaisian

magnetostratigraphy susceptibility of the frasnian famennian boundary magnetosusceptibility event and cyclostratigraphy msec is used to establish a non polarity based magnetostratigraphy susceptibility mss between the stratotype region for the frasnian famennian f f boundary sequence in the montagne noire of southern france the eastern rheinisches schiefergebirge of germany belgium the eastern anti atlas of morocco and the arbuckle mountains of southern oklahoma usa despite differences of depositional environment the mss is remarkably consistent and can be described in the context of a hierarchy of magnetozones that allow the extension of correlation away from the montagne noire reference section the nature of the controls on the influx of iron into the marine system produces a natural hierarchy of at least seven orders or magnetozones designated msz1 msz2 msz3 msz4 msz5 msz6 and msz7 these are characterized in terms of the magnitude of their duration the mss reference section of choice for the f f boundary is the well known trench c at la serre lsc in the northeastern montagne noire of southern france the f f boundary is located at the lower boundary of magnetozone la serre i 3b at la serre as well as in all other sections studied msz4 and msz5 magnetozones are used to establish intra and inter regional correlation between the reference sequence and the other regions the base of the upper kellwasser event is as variable within the mss zonation as it is within the biostratigraphic zonation as is the position of the lower kellwasser event

climatically sensitive eolian and hemipelagic deposition in the cariaco basin venezuela over the past 578 000 years results from al ti and k al al ti and k al ratios in bulk sediment are used to interpret wind blown and hemipelagic sources of deposition to a 578 kyr record in the cariaco basin venezuela ocean drilling program site 1002 graphical and cross spectral analyses indicate that these ratios vary extremely closely with planktonic foraminiferal 18o with both ratios being significantly higher during interglacials and lower during glacials k al indicates that during glacials the lower sea level that results in relative basin isolation increases the relative proportion of kaolinite derived from local rivers draining the relatively humid venezuelan margin al ti decreases during glacials suggesting greater proportions of eolian rutile sourced from the northern sahara due to increased wind strength and or aridity this interpretation is consistent with previous studies of the chemistry and mineralogy of saharan derived eolian matter in the caribbean and with a mass balance determining the effect of changes in eolian rutile accumulation on the bulk sedimentary al ti ratio

mountain building enhanced continental weathering and organic carbon burial as major causes for climatic cooling at the frasnian famennian boundary c 376 ma the late devonian was a period of drastic environmental changes as exemplified by a major biotic crisis at the frasnian famennian boundary ffb and the onset in famennian times of glaciations across southern gondwana worldwide evidence for the coeval development of the major acadian eovariscan belt led us to propose a model relating the late frasnian famennian environmental perturbations to extensive continental uplift through two atmospheric co2 depleting mechanisms 1 the intensification of silicate weathering on the continental areas as attested by a major rise in the 87 sr 86 sr composition of sea water at the ffb and 2 the massive burial of organic carbon kellwasser events in partially confined basins due to the collisional induced reduction of equatorial oceanic communications between the palaeotethysian and panthalassic oceans this process is also suggested to have been controlled by an important primary productivity connected to an increased nutrient availability triggered by the enhanced continental run off

depositional conditions and organic matter preservation pathways in an epicontinental environment the upper jurassic kashpir oil shales volga basin russia abstract the middle volgian kashpir oil shales formation located on the russian platform is a lateral equivalent of the north sea and west siberian petroleum source rocks in the volga basin this formation is 6 m thick and shows alternations of marls and black shales the organic carbon content is often higher than 1 although bioturbation and benthos are abundant even in the black shales in the marls highly degraded organic matter om dominates while aliphatic sulphur rich om is dominant in the black shales the combination of sedimentological and geochemical studies allowed to determine that the redox conditions of the sediment regularly fluctuated from oxic to anoxic under relatively productive waters while climatic conditions were increasingly arid it is proposed that om deposition occurred in relation to the increasing aridity through the combination of recurrent disruption of salinity stratification and aeolian supply of iron which both promoted phytoplankton productivity

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

systematics of variations in excess al and al ti in sediments from the central equatorial pacific the proposal that the accumulation rate ar of scavenged al in central equatorial pacific sediments is controlled by bulk particle flux and therefore can be used as a paleoproduction proxy is tested by examining the relationship between al and ti using data on core wec8803b gc51 published by murray et al 1993 the downcore profile of the excess al ar follows the bulk ar consistent with the al scavenging hypothesis and is due to a relatively constant abundance of excess al down core however there have been large changes in the aluminosilicate ar to this region suggesting that changes in the al ti value do not solely trace variability in the delivery rate of scavenged al assuming that the excess al in this core is not the result of an analytical artifact we present an alternative to the al scavenging hypothesis that involves authigenic clay mineral formation or some other process causing the occurrence of excess al at a relatively constant abundance of the sediment this process may well be independent of bulk particle flux or paleoproduction

the global frasnian famennian kellwasser event during the uppermostp gigas conodont zone p linguiformis zone the stepwise frasnian extinction culminates in the global transgressive regressive frasnian famennian kellwasser event most pelagic organisms of the tropical marine environment are more or less affected by this mass extinction during the early upper devonian extinction rates are clearly related to the deposition of black shales and the storage of a great amount of organic carbon in the shelf sediments contemporaneous positive excursions of the 13c recorded from pelagic limestones of europe and australia prove a worldwide change in the co2 content of the oceans surface water which is in balance with the atmosphere if the climate is controlled by the co2 content of the atmosphere a cyclic operation process might have developed with the succession transgression high organic production deposition of organic carbon lowering of co2 in the atmosphere icehouse effect polar glaciation regression erosion of organic carbon and re supply of co2 to the ocean and atmosphere greenhouse effect deglaciation transgression during the change from a greenhouse to an icehouse effect an overturn of the anoxic oceans probably was one of the causes for the mass killing of low latitude marine organisms

trace elements as palaeoenvironmental markers in strongly mature hydrocarbon source rocks the cretaceous la luna formation of venezuela abstract the late cretaceous la luna formation is the main hydrocarbon source rock formation in venezuela in the lake maracaibo area the formation shows a steep maturation gradient affecting sedimentary organic matter om and clay minerals related to local burial history and thrusting events the influence of the gradient is examined through geochemical organic and inorganic and mineralogical investigations carried out on samples from five cored boreholes in the maracaibo basin the analytical procedure comprises rock eval pyrolysis vitrinite reflectance measurement palynofacies observation major and trace element content determination performed on bulk rock samples or after a sequential leach protocol dop calculation and the examination and analysis of clay mineral assemblages the maturation gradient seems to have had no effect upon the distribution of the trace elements referred to as proxy indicators for palaeodepositional conditions of om rich sediments ba p v mo ni co cu cd cr and mn consequently trace elements appear to be reliable palaeoenvironmental markers they indicate that during the la luna fm deposition the water column must have had variable conditions with high primary production near the surface and the correlative development of euxinic conditions at the bottom this provides further arguments for an upwelling system affecting the northern platform of south america during late cretaceous time the relative scarcity of reactive iron in the depositional environment must have taken an active part in a process involving sulphur and acting on the environmental conditions as well as on om vulcanisation this process favours aliphatic om storage and may be relevant for many other om rich facies or hydrocarbon source rocks

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

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

contrasting sulfur geochemistry and fe al and mo al ratios across the last oxic to anoxic transition in the cariaco basin venezuela an abrupt transition from oxic to anoxic sulfidic euxinic marine bottom waters occurred in the cariaco basin in response to increasing productivity resulting from the late pleistocene post glacial rise in sea level and corresponding increase in surface water nutrient availability the microlaminated sediments of the euxinic interval which span the last f14 5 ky suggest a predominance of water column syngenetic pyrite formation based on 1 high pyrite sulfur spy concentrations in the surficial sediment layers 2 values for degree of pyritization dop that generally do not increase appreciably with increasing burial 3 ratios of total iron fet to al that are elevated above the continental baseline recorded in the underlying oxic sediments and 4 spy isotope trends that largely mimic the d 34 shsof the modern water column intermediate dop values in the microlaminated deposits and fet al ratios that are slightly above continental levels indicate an iron reservoir controlled by scavenging during syngenetic pyrite formation in combination with intermediate rates of fe bearing siliciclastic accumulation as predicted from the relative rates of siliciclastic delivery fet al and dop data lie between end member values observed in the modern black sea as viewed broadly fet al and dop relationships in euxinic sediments reflect the balance between syngenetic fe scavenging and temporal and spatial gradients in siliciclastic input pyrite concentrations are generally low in the underlying oxic marine deposits because of limitations in the supply of organic carbon corg however the upper 80 cm of the fe rich corg poor bioturbated sediment show evidence for a strong diffusional hsoverprint from the overlying fe limited euxinic marine environment this post glacial transition manifests in pyrite overprints that are strongly 34 s depleted relative to those in restricted presently euxinic marine settings elsewhere in the world such as the black sea where the sedimentary sequence spanning the last glacial interglacial transition begins with a shift from freshwater to corg poor oxic marine deposition and thus dominantly sulfate diffusion trends for mo al ratios in the microlaminated sediments suggest that mo is enriched by roughly two orders of magnitude above the continental levels recorded in the oxic deposits organic matter plays a role by enhancing hsproduction and or by providing a substrate for mo scavenging significant mo enrichment via diffusion into the upper portion of the bioturbated zone was not observed despite hs rich pore waters as recorded in the heavy iron sulfide overprint we have

organic carbon sulphur and iron in recent semi euxinic sediments of kau bay indonesia kau bay island of halmahera eastern indonesia is a 470 m deep basin separated from the pacific ocean by a sill that is at present only 40 m below sea level during weichselian time the sea level dropped below the depth of the sill and freshwater sediments were deposited these sediments are rich in organic matter corg 2 6 wt with terrigenous isotope characteristics 13corg 28 to 30 and are also rich in sulphur s 4 wt this sulphur enrichment is interpreted to be a late diagenetic feature related to diffusion of dissolved sulphate and sulphide from the marine sediments into the freshwater sediments the sulphur in these sediments has a 34s value of 15 the overlying holocene sediments consist of marine muds deposited in alternating low oxygen and h2s bearing bottom waters the marine sediments are also rich in organic matter corg 2 6 wt but of mixed terrigenous and marine origin 13c 25 to 19 moreover the sulphur content of these holocene sediments is lower s 1 2 wt and isotopically lighter 34s 20 in addition to pyrite large amounts of acid volatile sulphur avs compounds accumulate in kau bay the reactive iron content of the sediment limits the amount of iron that is sulphidized while the supply of oxidants controls the limited conversion of avs to pyrite total and reactive iron contents are strongly correlated with the amount of terrigenous organic matter as a consequence of their common provenance and depositional histories the marine sediments in kau bay show no simple relation between organic carbon and sulphur

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

inorganic geochemistry of albian sediments from the lower saxony basin nw germany palaeoenvironmental constraints and orbital cycles abstract within the international albicore project upper albian sediments from a 245 m core kirchrode i drilled in hannover were studied by inorganic geochemical methods more than 650 samples minimum sample spacing 0 5 m were analysed for major and minor element concentrations this chemical database was used to reconstruct the depositional environment and to investigate the influence of high frequency milankovitch cycles on the chemical composition of the sediments the chemical composition of the sedimentary sequence is primarily controlled by variations in carbonate content corresponding to ca al ratios variations in both ti al and si al ratios are interpreted as fluctuations in detrital composition resulting from increases in smectite and quartz content in the upper section of the core high amounts of reactive iron but low pyrite concentrations the lack of enrichment of redox sensitive trace elements v cr and high mn concentrations indicate oxic bottom water conditions and the absence of an oxygen minimum zone for the upper albian at the kirchrode site the nutrient related trace elements ba p zn suggest a generally oligotrophic setting with slightly elevated productivity only in the uppermost upper albian only one layer was identified as containing volcanogenic material at 87 20 m this layer is characterised by elevated montmorillonite zr and nb mass balance calculations for the entire core suggest that the high mn values cannot be explained by riverine input alone therefore a coastal oxygen minimum zone south of the kirchrode site is postulated as an additional mn source cyclic variations in both carbonate content and al normalised concentrations of predominantly detrital elements like si and ti are seen in a 60 m interval 40 100 m where sedimentological palaeontological and geochemical data suggest stable depositional conditions although carbonate cyclicity cyclicity in detrital input and nutrient related element abundances do not correlate with each other three strong peaks in the results of spectral analysis of these chemical data for this interval appear to correspond to milankovitch frequencies in the eccentricity obliquity and precession bands

oxygen isotope evolution of biogenic calcite and apatite during the middle and late devonian oxygen isotope ratios of well preserved brachiopod calcite and conodont apatite were used to reconstruct the palaeotemperature history of the middle and late devonian by assuming an oxygen isotopic composition of 1 v smow for devonian seawater the oxygen isotope values of eifelian and early givetian brachiopods and conodonts give average palaeotemperatures ranging from 22 to 25 c late givetian and frasnian palaeotemperatures calculated from 18o values of conodont apatite are close to 25 c in the early frasnian and increase to 32 c in the latest frasnian and early famennian oxygen isotope ratios of late givetian and frasnian brachiopods are significantly lower than equilibrium values calculated from conodont apatite 18o values and give unrealistically warm temperatures ranging from 30 to 40 c diagenetic recrystallization of shell calcite different habitats of conodonts and brachiopods as well as non equilibrium fractionation processes during the precipitation of brachiopod calcite cannot explain the 18o depletion of brachiopod calcite moreover the 18o depletion of brachiopod calcite with respect to equilibrium 18o values calculated from conodont apatite is too large to be explained by a change in seawater ph that might have influenced the oxygen isotopic composition of brachiopod calcite the realistic palaeotemperatures derived from 18o apatite may suggest that biogenic apatite records the oxygen isotopic composition and palaeotemperature of palaeozoic oceans more faithfully than brachiopod calcite and do not support the hypothesis that the 18o 16o ratio of devonian seawater was significantly different from that of the modern ocean

influence of water column anoxia on the elemental fractionation of carbon and phosphorus during sediment diagenesis abstract organic carbon oxidation and benthic total phosphorus flux measurements from sites covering a range of bottom water oxygen concentrations have been compiled the data show that p regeneration relative to carbon oxidation is much more extensive in sediments overlain by oxygen depleted waters these results are consistent with studies showing that low oxygen bottom water concentrations correlate with reduced total phosphorus burial efficiencies and enhanced organic carbon burial efficiencies based on these observations a positive feedback is proposed between water column anoxia enhanced benthic phosphorus regeneration and marine productivity this feedback may help explain the widespread accumulation of organic rich marine sediments from anoxic waters observed in the geologic record

high resolution geochemistry and sequence stratigraphy of the hushpuckney shale swope formation eastern kansas implications for climato environmental dynamics of the late pennsylvanian midcontinent seaway abstract the hushpuckney shale member of the swope formation missourian stage eastern kansas is the core shale of a kansas type cyclothem formed during the late transgressive to early regressive phases of a late pennsylvanian glacio eustatic cycle coeval high frequency climato environmental dynamics of the midcontinent seaway are preserved in the kgs orville edmonds no 1a study core as centimeter scale variation in major components organic carbon authigenic sulfides and phosphate detrital siliciclastics organic macerals trace element redox proxies mo u v zn and ichnofabric features benthic o 2 levels declined sharply from the base of the black shale 0 cm went sulfidic at 4 cm and reached a redox minimum at 21 cm above this level redox potential gradually rose fluctuating between sulfidic and nonsulfidic conditions from 35 cm to the black shale gray shale contact at 52 cm onset of dysoxic conditions at that contact allowed establishment of a benthic community of soft bodied organisms comprised of deep tiered tracemakers tolerant of low o 2 conditions trichichnus and shallow tiered tracemakers favoring soupground helminthopsis or firmground substrates the zoophycos phycosiphon schaubcylindrichnus planolites association most geochemical records exhibit a low order cycle spanning the full 52 cm thickness of the black shale submember reflecting a dominant glacio eustatic control the base and top of the black shale submember record lateral migration of the pycnocline across the midcontinent shelf during the transgressive and regressive phases respectively the maximum flooding surface mfs is at 17 23 cm an interval containing the euxinic peak and characterized by high concentrations of illite representing a cratonic siliciclastic flux and terrestrial organic macerals the product of transient increases in humidity weathering rates and the export of coal swamp vegetation associated with the interglacial highstand of the swope cyclothem although a transgressive surface of maximum starvation sms cannot be confidently identified a phosphate rich regressive condensation surface at 28 34 cm records pycnoclinal weakening due to increased aridity associated with renewed southern hemisphere icesheet growth a correlative shift in dominance from terrestrial to marine derived organic macerals reflects increased upwelling of nutrient rich deepwaters and enhanced primary productivity penecontemporaneous paleogeographic and climatic factors e g semirestricted circulation monsoonal precipitation predisposed the midcontinent seaway toward sensitivity to high frequency climato environmental fluctuations which are preserved as 2 to 7 cm thick cycles in the study core the 52 cm thick black shale submember contains 12 such high order cycles which have an estimated average duration of 2 to 9 kyr implying a sub milankovitch band i e millennial scale climatic control the results of this study are relevant to the sequence stratigraphic interpretation of kansas type cyclothems the dynamics of gondwanan ice age glacio eustatic cycles and the development of boundary conditions for late pennsylvanian paleoclimate models

sulfur diagenesis and partitioning in holocene peru shelf and upper slope sediments abstract sediments of the peru margin were sampled in two transects across the shelf and upper slope 75 to 1000 m in october of 1992 this region is characterized by high surface water productivity and consequent high organic carbon fluxes low terrigenous inputs as well as an intense oxygen minimum zone omz impinging on the slope at depths between 75 and 550 m sediments analyzed in this study were collected from one ship deployed box core and five submersible deployed push cores organic carbon toc concentrations in surface sediments range from 1 to 18 on a dry weight basis formation of pyrite begins at the sediment water interface swi maximum concentrations of pyrite sulfur in the cores from this study range from 0 5 to 1 8 wt concentrations of pyrite are influenced by availability of reactive iron and an oxidant capable of converting avs to pyrite highly reactive iron is stripped from terrigenous detritus in the core of the omz some of this iron may contribute to glauconite formation in sediments near the base of the omz where it is concentrated into a glauconitic green sand as a result of reworking and winnowing in a shallow water site 109 m at the upper edge of the omz high concentrations of pyrite total iron and iron aluminum ratios indicate that easily reduced iron species are available for sulfidation at the swi pyrite formation at this site is nearly complete in the upper 4 cm of the sediment in contrast pyrite concentrations are slightly lower at the surface of two of the deeper water sites at 309 m in the center of the omz and to a lesser extent at 671 m at the bottom edge of the omz and appear to be influenced in part by availability of reactive iron concentrations of acid volatile sulfides avs are low in all sediments 0 04 wt but are slightly elevated in sediments from the center of the omz the ratio of organic sulfur s org to organic carbon toc at the sediment surface of the cores examined here is remarkably constant 0 012 0 002 and within the range observed in marine biota 0 01 to 0 02 suggesting that organic sulfur at the swi is dominantly biogenic although s org toc ratios increase downcore there is no clear correlation between concentrations of organic sulfur and organic carbon below the swi there is also no clear relation between concentrations of organic sulfur and total iron organic sulfur concentrations vary from site to site 0 06 to 0 33 wt but are relatively constant downcore at any given site maximum concentrations are in cores from the center of the omz

relationship between inferred redox potential of the depositional environment and geochemistry of the upper pennsylvanian missourian stark shale member of the dennis limestone wabaunsee county kansas u s a analyses of 21 samples collected from a core of the 52 8 cm thick stark shale member of the dennis limestone in wabaunsee county kansas demonstrate four cycles with two orders of magnitude variations in contents of cd mo p v and zn and order of magnitude variations in contents of organic carbon cr ni se and u the observed variability in amounts and or ratios of many metals and amounts and compositions of the organic matter appear related to the cause and degree of water column stratification and the resulting absence presence of dissolved o2 or h2s high cd mo u v zn and s contents a high degree of pyritization dop 0 75 0 88 and high high v v ni 0 84 0 89 indicate the presence of h2s in a strongly stratified water column intermediate contents of metals and s intermediate dop 0 67 0 75 and intermediate v v ni 054 0 82 indicate a less strongly stratified anoxic water column whereas low metal contents and low v v ni 0 46 0 60 indicate a weakly stratified dysoxic water column high p contents at the top of the organic matter rich intervals within the stark shale member indicate that phosphate precipitation was enhanced near the boundary between anoxic and dysoxic water compositions relatively abundant terrestrial organic matter in intervals deposited from the more strongly stratified h2s bearing water column indicates a combined halocline thermocline with the fresher near surface water the transport mode for the terrestrial organic matter the predominance of algal organic matter in intervals deposited from a less strongly stratified water column indicates the absence of the halocline and the presence of the more generally established thermocline relatively low amounts of degraded hydrogen poor organic matter characterize intervals deposited in a weakly stratified dysoxic water column the inferred variability in chemistry of the depositional environments may be related to climate variations and or minor changes in sea level during the general phase of deeper water deposition responsible for this widespread shale member

deep structure and evolution of the harz mountains results of three dimensional gravity and finite element modeling a new bouguer anomaly map is presented for the region of the entire harz mountains based on more than 60 000 gravity values the various gravity anomalies are discussed and interpretation is carried out by high resolution 3 d gravity modeling one of the main subjects of interest in the investigation is the northern boundary fault zone of the harz mountains separating the mesozoic sediments in the north from the palaeozoic rocks of the harz in the south dip and vertical displacement are determined for this fault zone mean values are 3400 m and 70 respectively gravity modeling shows that the brocken and the ramberg granites are distinctly different the brocken granite is shallow whereas the ramberg granite has a maximum depth of 8 5 km and a n s dimension of 37 km the prominent benneckenstein gravity high is explained by two different models one based on a granodioritic intrusion 2900 kg m3 with a center depth of 14 km and the other based on phyllites 2740 kg m3 on a depth of 3 4 km studies on the geodynamic evolution of the harz mountains are carried out using the finite element method on the basis of a 3 d model vertical displacements that can be related to horizontal forces are computed for the period of the variscan orogeny an uplift of 600 m in the harz area is calculated for late cretaceous and tertiary 400 m are determined the total amount of 1000 m is about 12 of the vertical displacement of the northern boundary fault zone of the harz mountains shown by the gravity modeling these results do not contradict geological ideas

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