molybdenum isotope signatures in continental margin marine sediments abstract we present molybdenum isotope data for four sediment profiles from continental margin settings each profile has a distinctive average isotope composition ranging from 98 95 mo 0 5 to 1 3 relative to j and m laboratory standard this range lies between the modern ocean water value 2 3 and the values typical of mo adsorbed onto mn oxides 0 7 0 1 an important finding of this study is the apparent co variation between the mo isotope composition and the accumulation rate of authigenic mo under reducing conditions this relationship suggests that the chemical processes responsible for mo accumulation under reducing conditions produce an isotope signature in marine sediments in addition to the relationship between mo accumulation and the mo isotope signature there is also a relationship between these parameters and the rate of organic carbon oxidation and burial these relationships suggest that the mo isotope signature of reducing sediments may serve as a tracer for the cycling of organic carbon in continental margin sediments however additional data will be required to refine any such relationships

kibaran a type granitoids and mafic rocks generated by two mantle sources in a late orogenic setting burundi in the mesoproterozoic northeastern kibaran belt of burundi central africa two distinct late kibaran magmatic suites coexist both including a type granitoids they are located along the boundary zone between the kibaran mobile belt western internal domain and the archaean tanzanian craton overlain by mesoproterozoic foreland deposits eastern external domain intense deformation high temperature metamorphism and intrusion of abundant peraluminous anatectic crustal granites occur only in the former domain whereas the mesoproterozoic sedimentary cover of the latter is much less or even nearly undeformed nor metamorphosed the first late kibaran magmatism 350 km long kabanga musongati with an emplacement age of 1275 ma u pb on zircon is mainly composed of mafic and ultramafic layered rocks with subordinate a type acidic differentiates moderately enriched in incompatible elements initial isotopic ratios srlr 0 708 nd 8 indicate an old continental lithospheric mantle origin the emplacement of these late kibaran magmatic rocks was controlled by late lateral shear possibly contemporaneous with the latest intrusions of the kibaran peraluminous synkinematic granites of the western internal domain 1330 1260 ma the second late kibaran magmatism 40 km long gitega makebuko and bukirasazi alignment with an emplacement age of 1249 s ma u pb on zircon is limited in volume it is mainly granitic in composition a type can be strongly enriched in incompatible elements and comprises both syenites and mafic rocks initial isotopic ratios srlr 0 702 na 4 5 to 1 4 point to an oib type asthenospheric lower continental lithospheric mantle origin with only slight contamination by the lower crust during differentiation this group was also intruded during the late lateral shear in both groups liquid lines of descent can be reconstructed although some of the rocks have been strongly albitized this indicates that the granites are produced by differentiation of less evolved magmas and not by crustal anatexis upwelling of the asthenosphere along the tanzanian craton can generate by adiabatic pressure release the oibtype basic melts and provide the heat necessary to melt the continental lithospheric mantle sources this mechanism assigns a major role to a lithosphere scale late kibaran shear event occurring at the end of the regional compressive deformation between two rheologically contrasted domains ascent of the asthenosphere continental lithospheric mantle delamination and late orogenic extensional collapse of the western internal domain are suggested as a possible geodynamic model for the entire northeastern kibaran belt additional work is however necessary to test this model finally our results indicate that in the northeastern kibaran belt the kibaran orogeny ended at 1250 ma despite various reactivation events occurring later e g at 1137 ma

isotopic constraints on the genesis of the rogaland anorthositic suite southwest norway demaiffe d weis d michot j and duchesne j c 1986 isotopic constraints on the genesis of the rogaland anorthositic suite southwest norway in s deutsch and a w hofmann editors isotopes in geology picciotto volume chem geol 57 167 179 isotopic data were obtained on the sveconorwegian 1200 900 ma anorthosites and associated norites and charnockites of the rogaland igneous complex sw norway the isotopic data isr 0 703 0 7077 end 0 4 to 5 5 suf 4pb 1 8 1 8 2 so 5 2 to 6 6 c suggest an upper mantle origin for the parental magma of the anorthosites and related norites and jotunites or an origin in the lower crust by melting of mantle derived basic rocks shortly after their formation in two well documented cases the egersund ogna and the hidra bodies a progressive contamination by u depleted but not rb depleted lower crustal material is apparent during the differentiation process the late stage liquids have higher i up to 0 7086 lower but still slightly positive end less radiogenic pb isotopic composition the intrusive acidic rocks some of them of the charnockitic type display variable isotopic data is 0 7055 0 709 end 0 5 to 0 8 pb isotopic compositions comparable to that of some of the surrounding gneisses suggesting that there are in general no direct cogenetic relations between the anorthosites and the charnockites our data point to an origin of some of these acidic rocks by anatectic melting of the surrounding high grade metamorphic gneisses

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

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

a tale of shales the relative roles of production decomposition and dilution in the accumulation of organic rich strata middle upper devonian appalachian basin abstract a new consensus on the processes responsible for organic carbon burial in ancient epeiric seas has emerged more firmly grounded in the uniformitarian framework of modern oceanography and biogeochemistry this consensus recognizes the interdependent roles of sedimentation primary production and microbial metabolism in favor of earlier end member models e g production vs preservation in this study one of the classic stratigraphic sequences upon which the preservation end member was based is re interpreted in light of this new consensus the study employs an extensive new sedimentological biogeochemical database from cores drilled in western new york the database spans over 500 m and 15 my of devonian deposition in the appalachian basin and provides a framework for comparative study of organic matter burial the major conclusions are 1 few organic rich units were deposited under pervasive anoxic sulfidic water columns 2 establishment and breakdown of seasonal thermoclines on annual or longer timescales were the predominant mode of stratification and 3 under such conditions remineralization of bio limiting nutrients may have played a key role in organic matter burial by creating a eutrophication pump this pump may have augmented an already rising nutrient inventory such that productivity levels exceeded the threshold required for development of suboxic to anoxic conditions in sediments and episodically in bottom waters a final conclusion asserts that the master variable for organic matter accumulation was relative sea level change which exerted influence on clastic dilution preservation and production processes sea level rise events led to sediment starvation and organic carbon concentration in distal basin sediments as well as to decreased effectiveness of seasonal mixing and thus longer build up intervals for remineralized nutrients episodic mixing of nutrient enriched bottom waters led to enhanced production ultimately increased clastic sediment delivery and water column mixing during relative sea level fall diluted surface sediment organic content such that respiratory demand could be met by increased oxygen supply thus terminating deposition of strata enriched in organic carbon

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

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

new u pb zircon ages and the duration and division of devonian time newly determined u pb zircon ages of volcanic ashes closely tied to biostratigraphic zones are used to revise the devonian time scale they are 1 417 6 1 0 ma for an ash within the conodont zone of icriodus woschmidti i w hesperius early lochkovian 2 408 3 1 9 ma for an ash of early emsian age correlated with the conodont zones of po dehiscens lower po inversus 3 391 4 1 8 ma for an ash within the po c costatus zone and probably within the upper half of the zone eifelian and 4 381 1 1 3 ma for an ash within the range of the frasnian conodont palmatolepis punctata pa punctata zone to upper pa hassi zone u pb zircon ages for two rhyolites bracketing a palyniferous bed of the pusillites lepidophyta spore zone are dated at 363 8 2 2 ma and 363 4 1 8 ma respectively suggesting an age of363 ma for a level within the late famennian pa g expansa zone these data together with other published zircon ages suggest that the base and top of the devonian lie close to 418 ma and 362 ma respectively thus lengthening the period by20 over current estimates we suggest that the duration of the middle devonian eifelian and givetian is rather brief perhaps no longer than 11 5 myr 394 ma 382 5 ma and that the emsian and famennian are the longest stages in the period with estimated durations of15 5 myr and 14 5 myr respectively 1998 elsevier science b v all rights reserved

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

the crustal tongue melting model and the origin of massive anorthosites recent detailed field studies in several anorthosite complexes have shown that anorthosites are frequently associated with weakness zones in the crust which may have favoured their emplacement at mid crust levels recent experimental data have shown that the parent magma compositions of various anorthosite massifs lie on thermal highs in the relevant phase diagrams at 10 13 kbar indicating that these magmas cannot be derived by fractionation of peridotitic mantle melts but by melting of gabbronoritic sources in the lower crust at 40 50 km depths in the sveconorwegian province terne boundaries have been traced in deep seismic profiles to moho offsets or to tongues of lower crustal material underthrust to depths higher than 40 km in southern norway we suggest that a lithospheric scale weakness zone the feda transition zone has channelled the rogaland anorthosites through linear delamination asthenospheric uprise and melting of a mafic lower crustal tongue

igneous charnockites and related rocks from the bjerkreim sokndal layered intrusion southwest norway a jotunite hypersthene monzodiorite derived a type granitoid suite the upper part of the bjerkreim sokndal layered intrusion bksk introduction comprises a suite of charnockitic granitoids mangerite quartz charnockitic granitoids are a major component of mangerite and charnockite with some jotunites the petrology and anorthosite mangerite charnockite rapakivi granite geochemistry major and trace elements of eight main rock types amcg complexes and therefore play a crucial role in 88 samples are considered the rocks form a suite of k2o rich the formation and evolution of the proterozoic crust alkali calcic granitoids of a type deriving from jotunitic magma their origin has been long debated though intimately two trends of inferred liquids are distinguished the main liquid associated with massif anorthosites they are generally line of descent which passes from jotunites through two pyroxene considered to be derived from distinct parental magmas quartz mangerites to amphibole charnockites the second one which generated in different sources emslie 1978 1991 morse encompasses olivine bearing quartz mangerites and charnockites and 1982 duchesne 1984 wiebe 1992 ashwal 1993 it is rooted into mangeritic liquids comparison with the tellnes rock has however been recognized that some charnockitic series reveals that contamination by leucogranitic material has taken rocks could also be derived from an intermediate monplace simultaneously with fractional crystallization in both bksk zodioritic to ferrodioritic jotunitic magma duchesne trends zr rb cs and th are particularly sensitive to assimilation et al 1989 wilmart et al 1989 owens et al 1993 and the higher water content in bksk zircon and apatite have whose origin is also controversial the jotunitic magma saturated at the liquidus of quartz mangerite around 900 c close could either be derived from a crustal source by the to the fayalite magnetite quartz fmq buffer the two pyroxene partial melting of basic rocks duchesne et al 1989 quartz mangerites cannot have been equilibrated with the mangerite duchesne 1990 or be residual magmas after the forcumulates on which they rest a major influx of magma took place mation of massif anorthosites which have been conwhen mangeritic cumulates were being deposited it mingled and partly mixed with the resident contaminated magma taminated to various degrees by crustal material emslie et al 1994 the latter hypothesis seems to explain a large number of amcg complexes in the grenville and nain provinces and elsewhere accepting that some charnockites are derived from jotunites there is a logical

imaging downward granitic magma transport in the rogaland igneous complex sw norway combining geological mapping and petrological structural and geophysical gravity and seismic data already available for the late proterozoic rogaland igneous complex of norway allows the 3d shape of the bjerkreim sokndal layered intrusion to be modelled as a thick cumulate series capped by massive granitic rocks using the latter data along with the spectacular convergent linear flow pattern that covers both the cumulates and the felsic rocks of this chamber evidence is presented to show that the granitic material was downdragged through the sinking of its high density mafic floor into lower density anorthosites and granulitic gneisses this example illustrates that downward gravity driven flows of rocks were active in addition to upward flows in the building of the early crust up to late proterozoic times helping to explain the geochemical and structural complexities of the old crust

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

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

sources of iron for pyrite formation in marine sediments more than two hundred aerobic continental margin aerobic deep sea dysaerobic and anaerobic euxinic sediments have been examined for their variations in different operationally defined iron fractions each of which represents a different reactivity towards dissolved sulfide aerobic continental margin deep sea and dysaerobic sediments contain similar contents of highly reactive iron dithionite soluble iron plus pyrite iron poorly reactive iron iron soluble in hcl less that soluble in dithionite and unreactive iron total iron less that soluble in hcl by contrast non turbidite euxinic samples from the black sea as well as euxinic samples from the cariaco basin and framvaren are enriched in highly reactive iron these sediments contain a small lithogenous fraction and a large biogenous organic c rich fraction which decays by sulphate reduction in an iron rich water column to form pyrite rich sediment other anaerobic euxinic samples from the black sea orca basin and kau bay contain lower concentrations of biogenous sediment and are not therefore enriched in highly reactive iron degrees of pyritization dop for all the aerobic dysaerobic and anaerobic euxinix samples except those low in biogenous material are consistent with analogous ancient sediments and indicate that most pyrite formation occurs form the highly reactive iron fraction

the late devonian frasnian famennian event in south china patterns and causes of extinctions sea level changes and isotope variations abstract the frasnian famennian f f event may be recognized in various facies areas in south china in the pelagic cherty basin facies both lower and upper kellwasser events can seemingly be recognized in the deeper water carbonate facies the f f event level is well controlled in light of conodont biostratigraphy in the shallow water carbonate and mixed carbonate shale facies the f f boundary may be defined by clear taxonomic distinction in benthic fossils articulate brachiopods and corals as well as evidence from minor pelagic fossils post extinction recovery rate of benthic organisms differs in different facies settings and different taxonomic groups in open shallow water platform to inter platform depression areas brachiopods seem to recover quickly probably in the middle pa triangularis zone benthic ostracodes seem to recover at a later stage recovery of rugose corals did not happen until the uppermost famennian three steps of the f f mass extinction are postulated 1 extinction of diverse brachiopods including most atrypids 2 extinction of pelagic conodonts 3 extinction of both benthic faunas very abundant and diverse rugose corals and ostracodes and pelagic conodonts evidence of an end frasnian regression in south china is clear particularly in shallow water settings however in deeper water settings the picture is complicated with evidence of both sea level rise and fall in the latest frasnian it may be assumed from overall data so far known that crustal evolution itself and associated multiple volcanic hydrothermal activities may have mainly caused frequent and rapid climatically warming cooling alterations and sea level changes as well as marine ecologic collapse eutrophication microbial blooming seawater acidification and anoxia which may explain the f f extinction pattern in south china

shoshonitic liquid line of descent from diorite to granite the late precambrian post collisional tismana pluton south carpathians romania abstract the post collision late kinematic tismana pluton belongs to the shoshonitic series it is part of a late precambrian basement within the alpine danubian nappes of the south carpathians romania this pluton displays an exceptionally complete range of compositions from ultramafic to felsic rocks granites widespread mingling mixing relationships at all scales give rise to a variety of facies a liquid line of descent from the diorites to the granites is reconstructed by considering the variation in major and trace elements ree sr rb ba nb zr hf zn v co cr u th ga pb from 33 selected samples as well as mineral melt equilibrium relationships the first step of fractional crystallization is the separation from a monzodioritic parent magma of a peridotitic cumulate similar to the ultramafic rock found in the massif a possible contamination by lower crustal mafic component takes place at this stage the second step marks the appearance of apatite and fe ti oxide minerals as liquidus phases and the third step saturation of zircon mixing by hybridisation of magmas produced at different stages of the evolution along the liquid line of descent is also operating endo hybridisation as depicted by nd and sr isotopes fractional crystallization was combined to an important early contamination by a mafic lower crust in a deep seated magma chamber and to a later and mild contamination by a felsic medium crust in an intermediate chamber the mingling essentially occurred during the final emplacement in the high level magma chamber the monzodioritic parent magma identified by major and trace element modelling is shown by sr and nd isotopes to have its source in the lithospheric mantle or in a juvenile mafic lower crust derived from it the necessarily recent enrichment in k2o and associated elements of the lithospheric mantle is likely to be related to the preceding pan african subduction period the partial melting of this newly formed deep source has to be linked to a major change in the thermal state of the plate

the neoproterozoic pan african basement from the alpine lower danubian nappe system south carpathians romania abstract the south carpathians which were thrust to the moesian platform in the alpine orogeny late cretaceous to tertiary include the danubian nappe system the danubian pre alpine basement comprises two variscan nappes each one made up of partially retrogressed amphibolite facies rocks intruded by granitoids and capped by an ordovician devonian volcano sedimentary cover no lithological correlation can be established between the pre ordovician basements of these two units the metamorphic basement from the first variscan nappe the dr gsan group is composed of banded amphibolites with some augen and aluminous gneisses intruded by granodioritic to tonalitic plutons the banded structure of the amphibolites together with their geochemistry suggests a volcano sedimentary sequence zircon u pb data on an intercalated augen gneiss have given an age of 777 3 ma for the emplacement of the protolith of this gneiss nd model ages t dm for the amphibolites range from 717 ma to 817 ma at 777 ma nd values cluster is at 8 3 to 9 8 and sr initial ratios range between 0 7007 and 0 7023 indicating an oceanic origin without continental crust contamination major and trace elements from the dr gsan amphibolites consistently display an island arc signature with three differentiation trends evolving from an early tholeiitic trend to a more differentiated low k calc alkaline one the dr gsan terrane is similar to the early pan african juvenile terranes of the sahara the basement of the second variscan nappe the lainici p ius group is made up of metasedimentary rocks mainly quartzites marbles and graphitic mica gneisses cut by early leucogranitic dykes medium k calc alkaline and alkali calcic mainly granitic plutons and late medium k porphyry diorite dykes this magmatism can be bracketed between 588 ma and 567 ma u pb zircon ages the best preserved pluton tismana 567 ma old displays a composite alkali calcic very high k calc alkaline magmatic sequence ranging from gabbro diorite to monzogranite including an ultramafic pod ages and geochemical signatures resemble the saharan late pan african granitoids the existence of late precambrian partly juvenile terrains is thus confirmed within the basement of south carpathians which renders then a segment of the european alpine belt that can be successfully compared to the pan african trans saharan belt

a critical look at iron paleoredox proxies new insights from modern euxinic marine basins enrichments in reactive iron occur under euxinic marine conditions that is where dissolved sulfide is present in the water column these enrichments result primarily from the export of remobilized iron from the oxic shelf which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments strongly elevated ratios of highly reactive iron to total iron fehr fet and total iron to aluminum fet al and high degrees of pyritization dop are each products of this enrichment process these paleoredox proxies are among the most faithful recorders of ancient euxinia contrary to previous arguments iron enrichment is decoupled from biogenic sediment inputs but it does appear to be a uniquely euxinic phenomenon in other words we can rule out a major contribution from preferential physical transport of fehr rich detrital sediment to the deep basin which could also operate under oxic conditions furthermore enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins elevated fet al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net fehr addition these conclusions are supported by observations in the modern black sea orca basin and effingham inlet fet al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration however this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism resulting in only intermediate dop values for euxinic sediments and fet al ratios that mimic the oxic shelf such dilution effects are well expressed in black sea basinal turbidites and rapidly accumulating muds on euxinic basin margins under conditions of persistent euxinia varying extents of fehr enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation the magnitude of enrichment is a function of the source shelf to sink ocean basin areal ratio suggesting that iron proxies can also record ocean scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia for the first time manganese data are interpreted in light of the redox shuttle model as for the iron data the black sea orca basin and effingham inlet show enrichments in total manganese in the deep euxinic basin suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin the black sea data reveal iron and manganese enrichment across the broad deep euxinic basin suggesting efficient lateral transport and deep water mixing tied to the physical properties of the water column

some phase equilibrium constraints on the origin of proterozoic massif anorthosites and related rocks experimental data in the range of 1 bar to 13 kbar enable us to introduction map the liquidus equilibria relevant to proterozoic massif anorthere is hardly a consensus on the petrogenesis of thosites and related mafic rocks massif anorthosites are widely proterozoic massif anorthosites but many investigators believed to have formed by accumulation of plagioclase into highbelieve in a petrogenetic scheme that involves at least al basaltic liquids mantle derived basaltic liquids fractionating two major stages 1 extensive crystallization asat pressures sufficiently high 10 13 kbar to crystallize the highly similation of a mantle derived magma ponded at or aluminous orthopyroxene megacrysts typically observed in anorthosite near the base of the crust that produces suspensions of massifs reach plagioclase saturation at low normative silica contents plagioclase in fe rich high al gabbroic liquids followed peritectic like equilibria e g liq opx plag cpx sp by 2 intrusion of these suspensions into the mid upper and a thermal divide on the plagioclase pyroxene liquidus surface crust where they form complex magma chambers e g ensure that mantle derived liquids become nepheline normative with duchesne 1984 emslie 1985 ashwal 1993 wiebe further crystallization and crustal assimilation at depth such 1994 a key component of the scheme is the presence liquids cannot produce the full range of troctolitic noritic to trocin most massifs of high al orthopyroxene megacrysts tolitic gabbroic mineral assemblages observed in anorthosite massifs haom emslie 1975 that appear to preserve a record without extensive low pressure granite assimilation conversely the of the high pressure stage maquil duchesne 1984 array of plausible anorthosite parental liquids not only lies along longhi et al 1993 the structures of massifs vary from the trace of the plagioclase two pyroxene cotectic from 10 to 13 those that are composites of multiple diapiric intrusions kbar but also straddles the thermal divide on the plagioclase harp lake emslie 1980 rogaland duchesne 1984 pyroxene liquidus surface this condition requires mafic source to intrusive bodies with well developed layering of regions such as lower continental crust or foundered mafic plutons leucocratic troctolites and leuconorites or leucogabbros for liquids parental to massif anorthosites and associated mafic overlain by masses of anorthosite michikamau emslie intrusions 1970 laramie frost et al 1993 so there may be

geochemical constraints on the genesis of the tellnes ilmenite deposit southwest norway the ilmenite norite of the tellnes fe ti deposit in the aana sira massif type anorthosite is connected to a main dike which varies in composition from monzonorite to quartz mangerite fine grained satellite dikes also occur in the vicinity of the main dike a number of rock samples have been analyzed for 36 major and trace elements an rb sr whole rock isochron 12 samples gives an age of 930 ma initial sr isotope compositions of the ilmenite noritc the main dike and the satellite dikes are 0 7050 0 7069 and 0 7100 respectively thus precluding a comagmatic origin without invoking contamination the evolution of the main dike can be accounted for by a closed system fractional crystallization of a monzonoritic magma that is without progressive contamination which gave rise to a series of liquids prior to intrusion mass balance calculation permits a two stage process in which noritic cumulates were subtracted trace element behavior is also consistent with such a model the satellite dikes represent undifferentiated monzonorites with trace elements and isotopic ratios implying a source material quite different from that of the main dike monzonorite the orebody is made up of ilmenite norite and small amounts of more plagioclase rich rocks which plot on linear trends in variation diagrams it is interpreted as a noritic cumulate which was enriched in dense oxide rich magma before being emplaced as a crystal mush the parental magma was noritic in composition unsaturated in apatite and probably derived from the crystallization of the enclosing massif anorthosite it is not precluded either that it could have given rise to the main dike monzonoritic liquid after being contaminated by lower crustal material nevertheless as an alternative it is not possible to reject two distinct parental magmas for the orebody and the main dike they would have evolved in two separated magma chambers before the tapping of these chambers and simultaneous injection of their contents in the dike the main dike illustrates the process by which a quartz mangerite can derive from a monzonoritic magma and gives support to a comagmatic origin of charnockitic and monzonoritic rocks

authigenic molybdenum isotope signatures in marine sediments we present new mo isotope data from the mexican continen tal margin that in conjunction with previous data allow us to propose a mechanistic description of the mo isotope system in ma rine sediments we hypothesize that there are unique environmen tally dependent mo isotope signatures recorded in marine sedi ments that reflect the mechanisms responsible for authigenic mo accumulation open ocean anoxic sites defined as having dissolved oxygen and sulfide concentrations near zero in the overlying water exhibit a 98 95 mo isotope signature of 1 6 we believe this val ue reflects mo sulfide formation via diagenetic processes within sediments quantitative formation of mo sulfide within the sulfidic water column of euxinic environments results in sediment isotope values similar to the modern seawater value 2 3 as typified by samples from the highly sulfidic black sea in contrast to these reducing settings manganese oxide rich sediments have measured mo isotope values that are more negative relative to seawater than any other sediment samples analyzed to date similar to fe mn crusts 0 7 most measured mo isotope compositions of marine sediments from open ocean settings appear to reflect a mix ture of lithogenic mo 0 0 and the mo signature of a specific authigenic mo accumulation mechanism we therefore suggest that mo isotopes may record unique signatures that reflect the domi nant chemical mechanism for mo sequestration into sediments

molybdenum isotope evidence for widespread anoxia in mid proterozoic oceans how much dissolved oxygen was present in the mid proterozoic oceans between 1 8 and 1 0 billion years ago is debated vigorously one model argues for oxygenation of the oceans soon after the initial rise of atmospheric oxygen 2 3 billion years ago recent evidence for h 2 s in some mid proterozoic marine basins suggests however that the deep ocean remained anoxic until much later new molybdenum isotope data from modern and ancient sediments indicate expanded anoxia during the mid proterozoic compared to the present day ocean consequently oxygenation of the deep oceans may have lagged that of the atmosphere by over a billion years

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

the isotopic signature of the global riverine molybdenum flux and anoxia in the ancient oceans despite important biological and biogeochemical consequences of extensive ocean anoxic events their identification is controversial the marine isotope geochemistry of molybdenum can help quantify the past oxygenation state of the ocean if the riverine input of mo isotopes is known analysis of a set of rivers that account for 28 of global river runoff suggests more variable mo isotopic ratios in rivers that are also isotopically enriched in the heavy isotopes suggesting near total anoxia in the proterozoic ocean and during mesozoic ocean anoxic events despite its important biological and biogeochemical consequences1 2 3 the identification of extensive oceanic anoxia in the geological record is controversial in particular global anoxia is difficult to distinguish from spatially restricted anoxia in the deep ocean or in tectonically isolated basins such as the modern black sea the marine isotope geochemistry of molybdenum mo can help quantify the past oxygenation state of the ocean4 5 6 7 8 9 10 11 12 13 14 because to first approximation under oxic conditions lighter isotopes of mo are preferentially removed to sediments whereas in euxinic conditions quantitative removal leads to no fractionation however the isotopic composition of the mo input from rivers the main contributor of mo to the oceans is poorly constrained and had been assumed to be isotopically comparable to the narrow range found in a small dataset of continental rocks4 5 6 7 8 9 10 11 12 13 14 here we present an isotopic analysis of mo in a set of rivers that together account for 22 of the global riverine water discharge we find a broad range of variability in the mo isotopic composition of these rivers with almost all samples enriched in the heavy isotopes compared with continental rocks our data remove key uncertainties associated with the marine mo isotope budget14 and strongly suggest near total anoxia in the mid proterozoic ocean8 as well as during mesozoic ocean anoxic events13

pge re os and mo isotope systematics in archean and early proterozoic sedimentary systems as proxies for redox conditions of the early earth abstract re os data and pge concentrations as well as mo concentrations and isotope data are reported for suites of fine clastic sediments and black shales from the barberton greenstone belt south africa fig tree and moodies groups 3 25 3 15 ga the belingwe greenstone belt zimbabwe manjeri formation ca 2 7 ga and shales from the witwatersrand ventersdorp and transvaal supergroups south africa ranging from 2 95 to 2 2 ga moderately oxidizing conditions are required to mobilize re and mo in the environment mo fractionation only occurs in solution and these parameters thus have potential use as paleoredox proxies for the early earth pge re abundance patterns of barberton greenstone belt sediments are uniform and very similar in shape to those of komatiites this indicates 1 that the pge came from a source of predominantly ultramafic composition and 2 that pge were transported and deposited essentially in particulate form sediments from the younger belingwe greenstone belt show more fractionated pge re patterns and have re os ratios 10 to 100 higher than those of barberton sediments their pge abundance patterns and re os ratios are intermediate between those of the mid archean shales and neoproterozoic to recent black shales they reflect scavenging of re from solution in the sedimentary environment 98 95 mo values of black shales of all ages correlate with their concentrations the barberton greenstone belt samples have 1 3 ppm mo similar to a granitoid basaltic source this mo has 98 95 mo between 1 9 and 2 4 relative to present day mean ocean water molybdenum momo and is thus not isotopically fractionated relative to such a source similar to the pge this indicates transport in solid form sediments from the belingwe greenstone belt show in part enhanced mo concentrations up to 6 ppm and mo isotope fractionation 98 95 mo up to 1 4 relative to momo the combined pge re and mo data show mainly reducing conditions in the mid archean and suggest that by 2 7 ga the atmosphere and oceans had become more oxidizing substantially younger samples from the transvaal supergroup to ca 2 2 ga surprisingly have mainly low mo concentrations around 1 ppm and show no significant mo isotope fractionation relative to the continental source among possible explanations for this are a return to reducing atmospheric conditions after 2 7 ga reservoir effects or mo removal by sulfide precipitation following sulfate reduction in early proterozoic oceans

joining forces combined biological and geochemical proxies reveal a complex but refined high resolution palaeo oxygen history in devonian epeiric seas abstract two devonian black shale intervals were analysed using a carefully integrated palaeontological geochemical approach to interpret relative bottom water oxygen levels at a resolution and sensitivity possible only through the combined approach biological data presented as both trace and body fossil abundance and size suggest generally low bottom water oxygen conditions the frequently laminated sediments would be viewed traditionally as recording appreciable intervals of anoxic and or euxinic anoxic and h 2 s containing bottom waters the inclusion of parallel geochemical results however refines this perspective well established iron proxies for depositional redox tell us that anoxic and euxinic conditions were intermittent and short lived if present at all manganese and molybdenum data point to conditions with a likelihood of very low oxygen in bottom waters during intervals with high pore water concentrations of hydrogen sulphide near the sediment water interface these elevated sulphide concentrations under iron limited diagenetic conditions varied with organic content and may have further inhibited benthic colonization and an active infaunal community more specifically the combined palaeontological and geochemical data sets point to depleted bottom water oxygen contents with evidence for hydrogen sulphide limited dominantly or exclusively to the pore waters anoxia and euxinia if present occurred only intermittently and lasted only briefly perhaps on seasonal time scales tied to primary productivity cycles or climatically induced variation in water column stratification the time scales and mechanisms of rapid redox variation remain to be studied the details of such transitional and dynamic settings are best viewed from a multi proxy biogeochemical and palaeoecological perspective as an important byproduct geochemical methods refined in multi proxy studies of phanerozoic shales can then be extended with greater utility to precambrian strata without trace and body fossils

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

transient deep water oxygenation in the early cambrian nanhua basin south china abstract many late neoproterozoic to early cambrian fossils of multicellular eukaryotes including those of benthic animals are found preserved under anoxic and even euxinic bottom water conditions which is contradictory to the consensus that oxygen is essential to eukaryotes to investigate this conundrum we conducted an integrated study of iron speciation redox sensitive trace elements and mo isotopes 98 mo on the black shale interval of the lower cambrian hetang formation 535 521 ma at lantian south china in which benthic sponge fossils are abundant in the lower member lm but absent in the upper member um iron speciation data point to uniformly anoxic ferruginous conditions in the lm and euxinic conditions in the um whereas the trace element and 98 mo data show greater secular variation in redox conditions the lm shows higher mean trace element concentrations mo 108 ppm u 36 ppm v 791 ppm and lower and more variable 98 mo 0 13 to 1 76 relative to the um mo 45 ppm u 18 ppm v 265 ppm 98 mo 1 59 to 1 67 and ratios of redox sensitive trace element concentrations to total organic carbon are significantly more variable and higher on average in the lm relative to the um the appearance of sponge fossils and lower 98 mo values correlate strongly with gray i e lighter colored layers in the lm these patterns can best be interpreted as recording mainly euxinic conditions throughout deposition of the study units with more intense background euxinia in the lm relative to the um but also with frequent transient oxygenation events in the lm that do not appear in the um the transient oxygenation events of the lm led to the initial colonization of the deep nanhua basin by sponges and the termination of these events in the um caused sponge faunas to disappear until a general rise in o 2 levels later in the cambrian permitted their return to deeper water habitats our study also illustrates that multiple geochemical and paleobiological proxies exhibit different responses in poikiloredox environments i e characterized by small scale spatial and high frequency temporal variations which can lead to apparent contradictions between metazoan fossil occurrences and their inferred watermass redox conditions

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

unburrowed mudstones may record only slightly lowered oxygen conditions in warm shallow basins unbioturbated mudstones and highly bioturbated silty and sandy mudstones from the late albian of alberta canada are characterized by their ichnological foraminiferal and geochemical signatures a comparison of these data sets is undertaken to isolate the dissolved oxygen do conditions that led to the preservation of unbioturbated mudstones versus highly bioturbated silty and sandy mudstones highly diverse and abundant benthic foraminiferal assemblages coupled with conclusive geochemical signatures indicate that unbioturbated mudstones were deposited under oxic bottom waters the paucity of bioturbation in these rocks is attributed to the persistence of low oxic conditions 5 do 2 mg l 1 at the seafloor comparable to the present day gulf of mexico we assert that unbioturbated mudstone should not automatically be attributed to oxygen deficiency 2 mg l 1 instead it may reflect oxygenation sufficient to support benthic microfauna foraminifera but insufficient to sustain a diverse ecosystem of macrofauna burrowing fauna moreover we propose that the distribution of unburrowed mudstones deposited below low oxic waters is predictable a paucity of bioturbation is normal in shallow marine below fair weather wave base to 200 m water depth deposits of subtropical to tropical ocean basins and or semienclosed seaways

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

geochemical and multi isotopic 87sr 86sr 143nd 144nd 238u 235u perspectives of sediment sources depositional conditions and diagenesis of the marcellus shale appalachian basin usa abstract we investigate sediment sources depositional conditions and diagenetic processes affecting the middle devonian marcellus shale in the appalachian basin eastern usa a major target of natural gas exploration multiple proxies including trace metal contents rare earth elements ree the sm nd and rb sr isotope systems and u isotopes were applied to whole rock digestions and sequentially extracted fractions of the marcellus shale and adjacent units from two locations in the appalachian basin the narrow range of end values from 7 8 to 6 4 at 390 ma is consistent with derivation of the clastic sedimentary component of the marcellus shale from a well mixed source of fluvial and eolian material of the grenville orogenic belt and indicate minimal post depositional alteration of the sm nd system while silicate minerals host 80 of the ree in the shale data from sequentially extracted fractions reflect post depositional modifications at the mineralogical scale which is not observed in whole rock ree patterns limestone units thought to have formed under open ocean oxic conditions have 238u values and ree patterns consistent with modern seawater the 238u values in whole rock shale and authigenic phases are greater than those of modern seawater and the upper crust the 238u values of reduced phases the oxidizable fraction consisting of organics and sulfide minerals are 0 6 greater than that of modern seawater bulk shale and carbonate cement extracted from the shale have similar 238u values and are greater than 238u values of adjacent limestone units we suggest these trends are due to the accumulation of chemically and more likely biologically reduced u from anoxic to euxinic bottom water as well as the influence of diagenetic reactions between pore fluids and surrounding sediment and organic matter during diagenesis and catagenesis

extent and isotopic composition of fe and mo release from two pennsylvania shales in the presence of organic ligands and bacteria abstract isotopic fractionation of fe and mo during weathering could contribute toward the isotopic signatures of river and ocean waters to investigate weathering processes batch experiments were carried out at ph 6 under oxygenated conditions to investigate the influence of a nitrogen fixing soil bacterium and organic ligands on the extent and isotopic signature of fe and mo release from two pennsylvania shales with different mineralogies an olive to grey shale rose hill and a black shale marcellus results of these studies showed that fe and mo were mainly released from illite chlorite vermiculite and fe oxides in the rhs and from pyrite in the ms dissolution rates of the clays estimated from our batch experiments are broadly consistent with published estimates release of fe from both shales was only enhanced by the hydroxamate siderophore desferrioxamine b dfam in contrast none of the treatments enhanced release of mo furthermore release of this metal was measurable only for the black shale for both shales fe that was released in the presence of dfam was depleted in 56 fe as compared to the bulk rock in contrast leachate solutions were enriched in the heavier mo isotope as compared to the bulk marcellus in all experiments with and without organic ligands and the bacterium the isotopic fractionations in fe and mo are broadly consistent with previously reported fractionation effects during sorption onto precipitating fe mn oxides the observed mo isotope fractionation is also consistent with all published studies of rivers i e riverine mo is enriched in heavy mo isotopes the observed fe isotope fractionation is likewise consistent with published studies for some rivers i e riverine fe is sometimes depleted in 56 fe our experimental results are consistent with sorption of fe and mo onto fe oxyhydr oxides during weathering as a possible explanation for the isotopic signatures of these metals in many rivers

earthquake hazards rivers rifts and ruptures the southern san andreas fault is due for a large earthquake seismic images of sediments deposited in an ancient lake overlying the southern end of the fault indicate that episodic flooding may have triggered earthquakes in the past

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