a whiff of oxygen before the great oxidation event high resolution chemostratigraphy reveals an episode of enrichment of the redox sensitive transition metals molybdenum and rhenium in the late archean mount mcrae shale in western australia correlations with organic carbon indicate that these metals were derived from contemporaneous seawater rhenium osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 8 million years ago ma molybdenum and rhenium were probably supplied to archean oceans by oxidative weathering of crustal sulfide minerals these findings point to the presence of small amounts of o 2 in the environment more than 50 million years before the start of the great oxidation event

burial of organic carbon and pyrite sulfur in sediments over phanerozoic time a new theory in present day marine sediments almost all of which are deposited in normal oxygenated seawater rates of burial of organic carbon c and pyrite sulfur s correlate positively and bear a constant ratio to one another c s 3 on a weight basis by contrast calculations based on the isotopic model of garrels and lerman 1981 indicate that at various times during the phanerozoic the worldwide burial ratio must have been considerably different than the present day value this ratio change is caused by the requirement that increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur in order to maintain a roughly constant level of o2 in the atmosphere such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments as at present to non marine freshwater or to euxinic environments in the geologic past a shift to predominantly freshwater burial can help explain predicted high c s ratios in permo carboniferous sediments and a shift to euxinic environments can help explain predicted low c s ratios during the early paleozoic it is demonstrated that the three environments today exhibit distinguishably different average c s ratios

molybdenum and uranium geochemistry in continental margin sediments paleoproxy potential abstract we measured solid phase mo and u concentrations in marine sediments from the california mexico peru and chile margins to ascertain the behavior of mo and u during early diagenesis in continental margin settings at sites along the california mexico and peru margins where there are estimates of mass accumulation rates authigenic u accumulation rates range from 0 50 nmol m 2 day 1 at the california and mexico margin sites mo accumulation rates range from 0 to 134 nmol m 2 day 1 whereas at the peru margin site rates may be as high as 550 nmol m 2 day 1 we observe relationships between metal accumulation rates and the delivery and burial rates of organic carbon corg in the case of mo there appears to be at least two relationships between metal accumulation rate and organic carbon burial for most of the data presented in this manuscript continental margin sediments have a mo corg accumulation rate ratio of 20 mol mol 1 this value is significantly lower however than those reported for anoxic basins 100 mol mol 1 but is consistent with reported mo corg rain ratios from mexico margin sediment traps in contrast to mo there appears to be a single u corg burial ratio of 5 mol mol 1 which includes a range of environments from anoxic basins and open ocean sites we interpret the relationships between metal accumulation and organic carbon to indicate that the reactions that govern authigenic metal accumulation are primarily sensitive to the delivery and burial of organic carbon in these particular settings however we note that any relationship between metal accumulation and organic carbon could be indirect in the particular case of mo based on what is known about mo geochemistry from the literature it is possible that mo authigenesis is coupled to sulfur cycling in many of the environments covered by this study and that the observed association between mo and organic carbon burial is a consequence of the coupling between carbon and sulfur burial using the observed relationships between mo and corg burial as well as constraints from the mo isotope budget we estimate that continental margin sediments are an important sink for mo the magnitude of this sink 0 4 108 mol y 1 or larger may be as much as one quarter of the oceanic removal term and is likely to be larger than the modern anoxic basin sink

timing and patterns of the frasnian famennian event evidences from high resolution conodont biostratigraphy and event stratigraphy at the yangdi section guangxi south china abstract continuous centimeter scale sampling for conodonts with microfacies and carbon isotope analysis has been carried out across the frasnian famennian f f transition at the yangdi section guangxi south china the newly revised conodont biostratigraphy reveals a succession of six zones ranging from the upper palmatolepis rhenana zone to lower palmatolepis crepida zone in ascending order based on a detailed analysis of conodont abundance and diversity changes through the section two intervals involving significant conodont faunal changes were recognized in the uppermost palmatolepis linguiformis zone at the yangdi section the first conodont change occurred at the transition between the lower and upper pa linguiformis zone and is marked by the disappearance of pa linguiformis accompanied by the successive disappearances of pa eureka pa rhenana pa nasuta pa gigas ad ioides and ad nodosa the second conodont change appeared in a horizon equivalent to the uppermost upper kellwasser horizon ukh and is indicated by the elimination of nearly all frasnian palmatolepids ancyrodellids and polygnathids furthermore the second conodont change is coincident with the decimation of ostracods and tentaculitids and is synchronous with the turnovers of conodont biofacies in addition the onset of the 13 c carb perturbation is a little earlier than the second conodont change with the maximum amplitude of excursion right at the start of the famennian therefore we conclude that the second conodont change represents the f f mass extinction based on the temporal correlation among 13 c carb excursions pelagic faunal changes and conodont biofacies turnovers during the f f boundary interval according to the high resolution conodont biostratigraphy together with cyclostratigraphy the uppermost ukh and whole ukh contain 1 and 12 bundle cycles respectively thus the time span of the mass extinction and the entire upper kellwasser crisis lasted 16 18 kyr and 200 kyr respectively

anaerobic methane oxidation and a deep h2s sink generate isotopically heavy sulfides in black sea sediments the main terminal processes of organic matter mineralization in anoxic black sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2 4 m and methanogenesis below the sulfate zone the modern marine deposits comprise a ca 1 m deep layer of coccolith ooze and underlying sapropel below which sea water ions penetrate deep down into the limnic pleistocene deposits from 9000 years bp sulfate reduction rates have a subsurface maximum at the so42 ch4 transition where h2s reaches maximum concentration because of an excess of reactive iron in the deep limnic deposits most of the methane derived h2s is drawn downward to a sulfidization front where it reacts with fe iii and with fe2 diffusing up from below the h2s fe2 transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur the pore water gradients respond dynamically to environmental changes in the black sea with relatively short time constants of ca 500 yr for so42 and 10 yr for h2s whereas the fes in the black band has taken ca 3000 yr to accumulate the dual diffusion interfaces of so42 ch4 and h2s fe2 cause the trapping of isotopically heavy iron sulfide with 34s 15 to 33 at the sulfidization front a diffusion model for sulfur isotopes shows that the so42 diffusing downward into the so42 ch4 transition has an isotopic composition of 19 close to the 23 of h2s diffusing upward these isotopic compositions are however very different from the porewater so42 43 and h2s 15 at the same depth the model explains how methane driven sulfate reduction combined with a deep h2s sink leads to isotopically heavy pyrite in a sediment open to diffusion these results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth s history

natural mass dependent variations in the isotopic composition of molybdenum we present the first observations of natural mass dependent fractionation of the isotopic composition of molybdenum mo using multi collector inductively coupled plasma mass spectrometry variations in the isotopic composition of mo are reported as 97 95mo 97mo 95mo sample 97mo 95mo standard 1 1000 external analytical precision of 97 95mo is 1 between sediments deposited under anoxic conditions 97 95mo 1 02 to 1 52 relative to our in house standard and ferromanganese nodules 97 95mo 0 63 to 0 42 97 95mo of pacific ocean seawater 97 95mo 1 48 lies within the range of values for anoxic sediments closest to modern black sea anoxic sediments molybdenites from continental ore deposits have intermediate 97 95mo ranging from 0 26 to 0 09 variations in the abundances of 92mo 95mo 96mo 97mo and 98mo are consistent with mass dependent fractionation a sporadic unidentified interference occurs at mass 94 and 100mo is not measured we hypothesize that the 97 95mo offset between anoxic sediments and ferromanganese nodules results from mo isotope fractionation during inefficient scavenging of mo from seawater by mn oxides under oxic conditions the similarity in 97 95mo of anoxic sediments and seawater is consistent with the very efficient removal of mo from seawater under anoxic conditions in the presence of h2s the data can be interpreted in terms of a steady state mass balance between the mo flux into the oceans from the continents and the mo flux out of the oceans into oxic and anoxic sediments such an interpretation is quantitatively consistent with existing estimates of the removal fluxes of mo to anoxic and oxic sediments these findings suggest that 97 95mo in seawater may co vary with changes in the relative proportions of anoxic and oxic sedimentation in the oceans and that this variation may be recorded in 97 95mo of anoxic sediments hence the mo isotope system may be useful in paleoredox investigations

investigation of past archaeological landscapes using remote sensing and gis a multi method case study from mount ida crete spatial analysis in geoarchaeological applications can be improved by implementing a wider set of geoecological parameters in order to provide more precise results the aim of the paper is to show how geoscientific ground truth and techniques can be adopted for detailed archaeological studies using a comprehensive set of environmental variables that might have influenced ancient settlement patterns the project focuses on spatial patterns of archaeological sites as well as bronze age communication paths in central crete by applying a multi method approach surveying remote sensing dem analysis least cost analysis candidate site detection predictive modelling etc in contrast to conventional archaeological gis applications this enhanced strategy offers promising prospects regarding landscape and settlement modelling

diagenetic constraints on the use of cerium anomalies as palaeoseawater redox proxies an isotopic and ree study of cambrian phosphorites seawater rare earth element ree distributions show heavy ree enrichment and cerium depletion but these characteristics are only rarely found in ancient marine authigenic minerals such as carbonate fluorapatite and calcite this enigma may be due to changing ree distributions in seawater through time or to post depositional redistribution of ree differentiating between these two factors is however far from straightforward as their relative importance is likely to vary and evidence is often ambiguous in this article we present ree as well as strontium and sulphur isotope data for basal cambrian phosphorites of south china which confirm the emerging rule of thumb that granular phosphorites seldom reveal extreme departures from the seawater norm and tend to undergo therefore less diagenetic alteration of ree spectra than skeletal apatites and other phosphate types this study reveals stratigraphic trends in ce anomalies ce ce that could be taken to imply the preservation of a palaeoenvironmental signal however further investigation of our data shows that such trends in phosphorites can also be caused by post depositional alteration which tends to 1 increase ree contents 2 reverse ce depletion 3 alter eu anomalies and 4 concentrate preferentially the middle ree mree further alteration which may be due to weathering has led to hree depletion and positive la and y anomalies tetrad effect this is the first study where ceanom and phosphate bound sulphate s isotope values could be compared for one particular stratigraphic section which provides us with an additional tool for the interpretation of diagenetic redox conditions least altered phosphorites from meishucun that yield a strongly negative ceanom constrain early cambrian seawater 34s to about 33 we conclude that phosphorite ceanom primarily records variations in the local conditions of diagenesis while outlining some special cases in which diagenetic redox conditions may broadly reflect local bottom water redox conditions

iron stable isotopes beyond biosignatures abstract the stable isotope geochemistry of fe has attracted intense interest in the past five years this interest was originally motivated by the possible use of fe isotopes in biosignature applications particularly in sediments from the ancient earth or mars this application is still being developed with particular attention to fractionation mechanisms understanding such mechanisms should also provide new insights into the environmental biogeochemistry of fe at the same time the fe isotope system holds promise for other exciting frontiers including applications in oceanography solid earth geochemistry and biomedicine such applications will be increasingly attractive as fe isotope analysis becomes routine

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

a stable isotope study of pyrite formation in the late pleistocene and holocene sediments of the black sea the abundance and isotopic composition of total and pyrite sulphur have been determined in a core in the central black sea pyrite varies in concentration from roughly 2 wt in the sapropel unit 2 to 0 8 wt in the modern horizon unit 1 and ca 0 1 wt in the lowermost horizons of unit 3 lake beds an intermediate mud flow horizon and the upper part of the lake beds have similar values to those in the modern sediments the degree of pyritization dop is lowest 0 05 in the lower lake beds and highest 0 55 in unit 1 the sapropel has values of ca 0 48 34spyrite varies from a minimum of 37 in the sapropel to 33 in unit 1 up to 15 in the upper lake beds and 0 in the lower lake beds the unit 1 and sapropel values are similar to the 34s values reported by fry et al 1991 of dissolved sulphide immediately below the water column oxic anoxic interface 36 to 38 but significantly heavier than those in the deep waters of the basin ca 41 these results are interpreted as a reflection of the presence of four different types of pyrite in the sediments of the black sea 1 pyrite in units 1 and 2 that is formed within the upper part of the water column immediately below the oxic anoxic interface where 34s of dissolved sulphide is 36 2 pyrite in the mud flow layer lying between unit 1 and the sapropel unit 2 with a significantly heavier isotopic composition that was formed around the margins of the basin under conditions that were probably more closed with respect to dissolved sulphate than those in which the pyrite in units 1 and 2 were formed 3 pyrite in the upper part of the lake beds unit 3 that was formed under closed system conditions by reaction between excess reducible fe remaining in these freshwater sediments and downward diffusing sulphate and or sulphide from the overlying organic rich sapropel and 4 pyrite in the lower part of the unit 3 representing a phase formed from the ambient sulphate in the freshwaters of the late pleistocene lake the isotopic information supports earlier suggestions that pyrite in the modern sediments of the black sea forms mainly in the water column with only minor amounts forming in the sediment because of the severe fe limitation of the bottom sediments that accumulate 2 000 m below the main fe and hs reaction zone at the oxic anoxic interface at shallow depths in the water column

carbon sulfur iron systematics of the uppermost deep water sediments of the black sea box cores recovered during leg 4 of the 1988 r v knorr black sea oceanographic expedition from deep water regions of the basin were dominated by coccolith rich microlaminated unit 1 sediment and muddy gray turbidite layers both organic carbon oc and pyrite sulfur values for unit 1 display narrow ranges with mean concentrations of 5 3 1 1 1 wt and 1 3 0 3 wt respectively unit 1 is not enriched in pyrite s relative to sediments deposited under oxygenated bottom waters normal marine sediments with comparable oc concentrations carbon sulfur relationships evaluated on a calcium carbonate free basis to avoid spurious correlations resulting from dilution effects demonstrate that oc and pyrite s are essentially decoupled these observations combined with the persistence of elevated pore water sulfide to depth and a strong correlation between pyrite s and the detrital fe component argue strongly for limitation of pyrite formation in unit 1 by the availability of reactive fe unit 1 fe limitation is further indicated by degree of pyritization dop studies a measure of the extent to which the original potentially reactive fe has been transformed to pyrite these studies show sulfidation of reactive fe ranging from 57 to 78 with dop values independent of oc concentration unit 1 dop profiles suggest that the majority of the pyrite is formed in the sulfidic water column and or very close to the sediment water interface pyrite s concentrations of unit 1 when compared with the particulate reduced sulfur fluxes measured in time series sediment traps are compatible with predominantly water column pyrite formation because of the limitations in the supply of reactive fe associated with the comparatively high supply of oc the microlaminated sediment is characterized by c s ratios greater than those typical of holocene oxically deposited sediments the turbidite muds of the deep basin display high reduced s values relative to holocene normal marine sediments in samples with low oc concentrations low c s ratios this reflects pyrite formation under anoxic sulfidic bottom water conditions in a probable upper slope source region as well as during transport and final deposition intermediate dop values for the turbidites in part a product of their rapid rate of deposition reveal that fe limitation is ultimately not a factor and that further pyrite should form during burial however the very rapid rate at which unit 1 pyrite forms suggests fundamental differences between the overall reactivities of the fe phases associated with the microlaminated and turbiditic sediments the signature of water column anoxia with regard to sedimentary pyrite formation is clearly indicated by the high dop values of unit 1 and the comparatively high levels of s associated with the low concentrations of oc of the turbidite muds this agrees with similar conclusions based on studies of ancient sedimentary rocks

heavy sedimentary sulfur isotopes as indicators of super anoxic bottom water conditions iron monosulfides and pyrite total cr reducible s trs in the bottom sediments of the exceptionally sulfide rich euxinic fjord framvaren south norway are unusually enriched in 34 s most of these trss probably form in bottom waters where reactive detrital iron phases encounter isotopically heavy dissolved sulfide enrichment in 34 s in framvaren is a result of intense bacterial reduction of a sulfate reservoir whose exchange with the open sea is limited by shallow sills and a low salinity surface water layer 34 s enriched trs in the deposits of ancient euxinic environments is commonly interpreted as evidence for early diagenetic sulfide formation where residual less reactive iron phases were in contact with isotopically heavy dissolved sulfide sulfate depleted pore waters for prolonged periods during burial however the framvaren data indicate that isotopically heavy pyrite may form in relatively shallow 80 180 m super anoxic bottom water pools in contrast the presence of isotopically light pyrite does not indicate an absence of restricted conditions but only that most iron sulfide formation was completed before 34 s enriched sulfide could be encountered in the water column

glacial interglacial variations in production and nitrogen fixation in the cariaco basin during the last 580 kyr the effect of sea level change on nutrient supply to the anoxic cariaco demonstrates the fundamental importance of nitrogen n2 fixation and phosphate to oceanic production as n2 fixation produces biomass of low 15n and has been reported to be an important component of the nitrogen cycle in the modern cariaco basin we propose that it contributes to the light interglacial 15n 2 3 values observed in the ocean drilling program odp site 1002 sediment record during the glacials the sediments are bioturbated oxic conditions with low total organic carbon toc contents and sedimentary 15n values of 5 suggesting that nitrogen n2 fixation contributed little to the n nutrition of cariaco surface waters the most plausible explanation for the inferred glacial interglacial changes in n2 fixation in the cariaco is that they have occurred in response to variations in the n p ratio of the nutrient supply driven by changes in denitrification

pyrite and organic matter in phanerozoic normal marine shales data have been obtained from our own chemical analyses and from the literature for the concentrations of organic carbon c and pyrite sulfur s in over 600 samples of cambrian to recent normal marine shales normal marine refers to deposition in oxygenated bottom water as evidenced by the presence of benthic fossils and or indicators of bioturbation all samples were selected to minimize 1 1 loss of c and or s due to weathering at the outcrop by emphasizing the use of drill core material 2 2 analytical errors and non diagenetic effects by avoiding sediments low in c or s content such as sandstones 3 3 fe limitation of pyrite formation by avoiding limestones cherts and euxinic shales 4 4 metamorphic loss of c relative to s by avoiding rocks obviously subjected to even low grade metamorphism our results indicate that 1 there is generally a good positive linear correlation between organic c and pyrite s for normal marine shales of all ages and 2 the mean cs ratio for normal marine shales has varied over time devonian to tertiary shales exhibit mean cs weight ratios 1 8 0 5 somewhat lower than quaternary sediments meancs 2 8 this we believe is due to preferential c loss relative to s during biogenic methanogenesis plus diagenetic heating distinctly lower mean c s values for the cambrian and ordovician 0 5 0 1 cannot be explained solely in terms of diagenetic c loss and instead must represent low original ratios the low original ratios we suggest were due mainly to the absence of bacterially refractory organic matter added to the marine environment by rivers at that time because the major source of such material vascular land plants had not yet evolved this along with a possibly lower degree of bioturbation contributed to enhanced pyrite formation and preservation and thus lower early paleozoic cs ratios

molybdenum isotope fractionation during adsorption by manganese oxides the isotopic composition of mo 97 95mo in seawater is 2 heavier than mo in marine ferromanganese crusts and nodules barling et al earth planet sci lett 193 2001 447 457 siebert et al earth planet sci lett 211 2003 159 171 to explore this phenomenon we have conducted an experimental investigation into the mass dependent fractionation of mo isotopes during adsorption onto mn oxyhydroxide two series of experiments were carried out a time series in which adsorption proceeded for 2 96 h and a ph series in which ph varied from 6 5 to 8 5 the extent of mo adsorption by mn oxyhydroxides decreases with increasing ph a trend typical of anion adsorption and takes 48 h to reach steady state lighter mo isotopes are preferentially adsorbed experimentally determined fractionation factors soln mnox exhibit no systematic variation with either time or experimental ph the mean soln mnox for all experiments is 1 0018 0 0005 2 s d comparison of the mo isotopic data for experimental solutions and mo adsorbed to mn oxyhydroxide with predictions for closed system equilibrium and rayleigh fractionation models indicates that isotope fractionation occurs as a result of closed system equilibrium exchange between dissolved and adsorbed mo the isotopic offset between dissolved and adsorbed mo is comparable to that observed between mo in seawater and mo in ferromanganese nodules and crusts it is therefore likely that adsorption of mo to mn oxyhydroxides is a significant factor in the fractionation of mo isotopes in the oceans

when do black shales tell molybdenum isotope tales molybdenum mo isotopes in ancient sediments are promising recorders of global ocean paleoredox conditions organic rich black shales can be used to reconstruct ancient ocean mo isotope compositions if these sediments record the isotopic composition of contemporaneous seawater comparison of 98 95 mo in two devonian shale sequences of similar age the new york oatka creek and geneseo formations reveals that this assumption cannot be applied to all organic rich shales although both sequences contain laminated intervals elevated organic carbon and enrichments of redox sensitive metals the mean 98 95 mo differs systematically between the formations by 0 59 independent paleoredox indicators reveal that portions of the oatka creek formation were deposited under pervasively euxinic anoxic and sulfidic conditions whereas conditions during deposition of the geneseo formation were intermittently euxinic to suboxic oxygen deficient but not sulfidic in the water column we infer that reconstruction of ancient ocean 98 95 mo from organic rich shales requires independent verification of persistent local euxinia with these considerations in mind our data point to 98 95 mo in the devonian oceans 0 6 lighter than in today9s oceans consistent with expanded anoxia

on the coevolution of ediacaran oceans and animals fe speciation and s isotope of pyrite data from the terminal proterozoic sheepbed formation in canada and doushantuo formation in china reveal that ocean deep waters were anoxic after the global glaciations snowball earth ending 635 million years ago but that marine sulfate concentrations and inferentially atmospheric oxygen levels were higher than before the glaciations this supports a long postulated link between oxygen levels and the emergence of eumetazoa subsequent ventilation of the deep ocean inferred from shifts in fe speciation in newfoundland previously published data and western canada this report paved the way for ediacaran macrobiota to colonize the deep seafloors

comment on carbon isotope record of the early jurassic toarcian oceanic anoxic event from fossil wood and marine carbonate lusitanian basin portugal by hesselbo s jenkyns h c duarte l v and oliveira l c v hesselbo et al 2006 hereinafter hjdo06 present stable isotopic profiles through lower toarcian sediments at peniche portugal and interpret them as evidence of a massive injection to the atmosphere of isotopically light co2 derived from methane oxidation the atmospheric inputs supposedly gave rise to negative isotopic excursions in all carbon reservoirs the paper follows others proposing that environmental change in early toarcian time was driven by the release to the atmosphere of methane either from marine clathrates hesselbo et al 2000 kemp et al 2005 or from organic rich shales that were baked by karoo ferrar intrusions mcelwain et al 2005 the methane hypothesis was tested by van de schootbrugge et al 2005 who highlighted the existence of sections that lacked a negative excursion in ac in one or more sample media amongst them is the section on the coast of yorkshire uk used to erect the methane hypothesis by hesselbo et al 2000 which lacks a negative excursion in the c of belemnite calcite mcarthur et al 2000 van de schootbrugge et al 2005 as the excursion is not seen in these sections it cannot represent a global event and so could not have resulted from methane release which would have influenced all reservoirs of carbon new data are now provided by hjdo06 for a section peniche

tracking euxinia in the ancient ocean a multiproxy perspective and proterozoic case study the evolution and extinction of life are tied intimately to the oxygen state of the ocean and particularly to the presence of anoxic and h2s containing euxinic water on a global scale anoxia and euxinia were more common in the past relative to today s 0 5 euxinic seafloor we are able to constrain the distributions of these conditions through a combination of indirect numerical modeling methods and more direct geochemical proxies with particular emphasis on fe s mo analysis of fine grained siliciclastic rocks for the latter establishing the spatiotemporal pattern of oceanic redox is more difficult with very old rocks because of the limited availability of well dated well preserved materials that span shallow and deep environments across time lines despite these difficulties the multiple approaches synthesized in our case study point to global oxygen deficiency in the deep ocean and perhaps euxinia during most if not all of the proterozoic and likely extending into the early paleozoic

surface area control of organic carbon accumulation in continental shelf sediments the relationship between organic carbon oc and grain size found in most continental shelf sediments is here reinterpreted in terms of the surface area of the sediments cores from many north american shelf environments show downcore decreases in oc to similar refractory background concentrations if expressed relative to the surface area of the sediments this consistent concentration is 0 86 mg oc m 2 which is equivalent in concentration to a monolayer of organic matter coating all mineral surfaces a more global collection of sediment water interface samples show that this relationship is even more extensive with exceptions occurring in areas of very high riverine sediment input organic pollution or low oxygen water columns density separations indicate that organic matter is largely adsorbed to mineral grains the microtopography of surfaces was examined with n2 sorption and most surface area was found to be inside pores of 10 nm width these data lead to a hypothesis that organic matter is protected by its location inside pores too small to allow functioning of the hydrolytic enzymes necessary for organic matter decay such protection would likely work in concert with other protection mechanisms such as humification this consistent surface area correlation with oc concentration may explain control of spatial and temporal variations in oc burial rates by sedimentation rates the pore protection hypothesis provides a causal mechanism for this observed control

molybdenum isotope evidence for global ocean anoxia coupled with perturbations to the carbon cycle during the early jurassic relatively brief periods of severe paleoenvironmental change during the jurassic and cretaceous were associated with the widespread accumulation of organic rich marine deposits termed oceanic anoxic events oaes these intervals involved abrupt global warming of 5 10 c higher rates of continental weathering elevated extinction rates and large scale perturbations to the global carbon cycle the major oaes also overlapped temporally the emplacement of large igneous provinces however despite being known as oaes the extent of seawater anoxia at those times is undefined and the causative processes remain unclear here we show how changes in seawater molybdenum isotope ratios a proxy for seawater anoxia during the toarcian early jurassic oae define the onset and expansion of oxygen deficient conditions our data also place constraints on the areal extent of marine anoxia during the event and demonstrate that anoxia expanded and contracted periodically broadly in line with precession driven changes in 13 corg despite their intermittent occurrence over geological history oaes have an important contemporary relevance because the magnitude and high rates of environmental change then were broadly similar to those occurring at the present day