a sulfate control on marine mid depth euxinia on the early cambrian ca 529 521 ma yangtze platform south china abstract given the high oxygen demands of complex metazoans a sound understanding of marine redox conditions is essential to reconstruct the factors that lead to the dramatic increases in ecosystem complexity and biological diversity in the early cambrian in this study we report new fe mo c s geochemical data from black shale rich strata of the early cambrian continental margin yangjiaping section in the yangtze platform south china integrated fe speciation and mo abundance data from the yangjiaping section in combination with previously reported data from shatan inner shelf songtao slope and longbizui basinal sections suggest mid depth euxinic waters coexisting with ferruginous deep waters and oxic surface waters this redox structure is similar to conditions previously suggested for the ediacaran yangtze platform and other proterozoic marine basins indicating that proterozoic layered ocean redox structure in some basins persisted into the early cambrian furthermore the fe mo data demonstrate that the mid depth euxinia was widespread during a marine transgression but shrank gradually along with widespread shelf oxygenation when the basin evolved into subsequent regression excess highly reactive iron fe hr in deep water with a hydrothermal origin may have had a control on the mid depth euxinia given geochemical and geological evidence for basinal hydrothermal activities on the other hand a sulfate limitation on bacterial sulfate reduction bsr and sulfide generation was suggested by a weak correlation r 2 0 22 between pyrite iron versus fe hr and total organic carbon toc form anoxic deep water sections and high toc averagely 6 in the deepest ferruginous water longbizui section furthermore a spatial gradient was observed in sulfur isotopic composition of pyrite averagely from 0 2 to 21 0 consistent with a lateral gradient of sulfate in concentration or and in isotope from shore to distal waters on the transgressive yangtze platform we accordingly proposed that two distinct sources riverine input and ocean reservoir provided sulfate for bsr dominantly in near shore and distal areas respectively and the euxinic retreat observed for the regression can be explained as a response to the progressive sulfate consumption of the ocean reservoir by intensive bsr and pyrite formation during preceding transgression therefore our results support a sulfate control on the spatiotemporal distribution of mid depth marine euxinia on the yangtze platform in early cambrian when complex metazoans rapidly evolved

tracing euxinia by molybdenum concentrations in sediments using handheld x ray fluorescence spectroscopy hhxrf abstract elevated molybdenum mo contents in organic rich sediments are indicative of deposition from an anoxic and sulfide rich euxinic water column this can be used for tracing past euxinic conditions in ancient oceans from sedimentary archives conventional analytical detection of elevated molybdenum levels is however expensive and cannot be directly performed in the field here we show that handheld x ray absorption spectroscopy hhxrf on both rock powders and rock surfaces provides a powerful tool for laboratory or field based geochemical characterization of mo content and the tracing of euxinic depositional conditions we further present a sedimentary mo database compiled from over 300 globally distributed modern marine sites to show that modern euxinic marine basins are characterized by molybdenum enrichment 25 ppm relative to average crust 1 5 ppm and river suspended matter 3 ppm only mn oxide rich deposits from oxygenated deep sea settings match such high mo enrichments but these are easily distinguished from mo rich sediments from the continental shelves hence past and present organic rich sediments enriched in mo are indicative of at least intermittent water column euxinia we analyzed the molybdenum content of powdered and homogenized samples of holocene miocene triassic jurassic ordovician and cambrian age by hhxrf and inductively coupled plasma mass spectrometry icpms we further analyzed 2 certified nist standard references nist 2781 with mo 47 ppm and nist 2702 with mo 10 ppm for analytical control analytical precision 1 after 30 120 and 300 seconds of measuring time was 4 2 and 1 ppm with a respective detection limit of 11 5 3 ppm 3 noise level the data were accurate to within the given precision 1 after a daily calibration to samples covering a range of mo concentrations from 0 to 30 ppm hand held xrf equipment also allows mo measurements directly on fresh rock surfaces both in the field and under laboratory conditions rock samples from a cambrian drill core closely match icpms obtained mo concentrations from homogenous powders of the same rocks collectively our data show that hhxrf as a quick and reliable method for the precise and accurate quantification of molybdenum concentrations in both rock powders and at fresh rock surfaces the non destructive nature of the hhxrf measurements is combined with low per sample analytical costs minor sample preparation and easy applicability in the field

identification of karst features using seismic p wave tomography and resistivity anisotropy measurements a football stadium with a capacity of a hundred thousand spectators is under construction over a karst terrain 10 km west of the old town of istanbul turkey a large cavity of approximately 30 m3 was detected beneath the sports field through a number of boreholes so that a geophysical survey was required to further investigate a portion of the sports field we utilized seismic refraction tomography and dc electrical method with rotated wenner array to delineate zones with solution voids and cavities total core recovery tcr was 5 15 from boreholes where zones with low velocities were identified through tomographic inversion whereas tcr values were above 60 in zones with higher velocities both low velocity zones in the tomographic images and increasing resistivity anisotropy with depth appear to indicate that the cavity extends toward the west and south at a depth of approximately 8 m although the southward and westward extension changes in character

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

carbon to phosphorus ratios in sediments implications for nutrient cycling defining the transformations of phosphorus p in sediments is critical to assessing the geochemical behavior of sedimentary p and the behavior of reactive p preactive poxide associated pauthigenic porganic relative to organic carbon corganic this study includes the determination of p components and corganic concentrations on samples from sites in the california current region ocean drilling program odp leg 167 sites 1010 1011 1012 1014 1016 and 1021 in the benguela current region odp leg 175 sites 1082 1084 and 1085 and on blake nose in the western atlantic odp leg 17 1b sites 1050 and 1052 sample depths range up to 650 m and ages range up to 65 ma our data demonstrate the transformation of labile forms of p porganic and poxide associated to pauthigenic throughout the sediment column in all redox states and at all sedimentation rates investigated until a substantial portion of reactive p is in the authigenic form 80 c p organic ratios are always greater than or equal to the redfield ratio in all of the sediments we studied sediments with corganic concentrations 2 wt have corganic preactive ratios less than the redfield ratio and corganic preactive ratios increase linearly with corganic consistent with degradation of corganic with age in general corganic preactive ratios for sediments with corganic concentrations 2 wt from a variety of redox states and sedimentation rates center around the redfield ratio although some ratios are as high as 3 times the redfield ratio however corganic preactive ratios up to 400 do not approach the high ratios observed for c p organic ratios up to 4500 because of the efficient transfer of labile forms of p to pauthigenic corganic preactive ratios better describe the geochemical behavior of sedimentary p

nd isotopic variations of phanerozoic paleoceans abstract the size of various phanerozoic paleoceans determined from paleogeographic maps provides a framework for assigningend measurements of primary authigenic marine minerals to individual paleoceans and for establishing theirend versus age curves we report newend data in the range from 80 to 750 ma for the largest phanerozoic and late precambrian paleocean the pacific panthalassa ocean ppo and limited data on some small paleozoic paleoceans these new data and all other published data on paleoceanend values are used to determine the trends through time ofend in seven phanerozoic paleoceans the variations in paleoceanend curves are due to changes in the rate of crustal additions and in paleoceanic geometry from these data we can calculate a meanend curve and a mean nd model age curve for phanerozoic seawater these curves show large variations with age and reflect the variations ofend in erosion products from the continents as a function of age the high erosion rates of young uplifted areas enhanceend and nd model age variations of phanerozoic seawater this makes it difficult to quantitatively recover crustal addition rates from these curves however it makes the episodic nature of continental additions more evident

boussinesq modeling of longshore currents 1 a time domain boussinesq model for nearshore hydrodynamics is improved to obtain the conservation of vertical vorticity correct to second order and extended for use on an open coast using longshore periodic boundary conditions the model is utilized to simulate surface waves and longshore currents under laboratory and field conditions satisfactory agreement is found between numerical results and measurements including root mean square wave height mean water level and longshore current one striking result of the simulations is the prediction of the strong longshore current in the trough shoreward of the bar as observed during the duck experiment on low frequency and incident band longshore and across shore hydrodynamics field campaign the model results give insight into the spatial and temporal variability of wave driven longshore currents and the associated vertical vorticity field under the phase resolving random wave forcing with wave current interaction numerical experiments are carried out to examine the response of the modeled longshore currents to the randomness of surface waves and the cross shore distributions of bed shear stress coefficient we find that both regular and irregular waves lead to very similar mean longshore currents while the input of monochromatic unidirectional waves results in much more energetic shear waves than does the input of random waves the model results favor whitford and thornton s 1996 finding that the bed shear stress coefficient for the area offshore the bar is larger than that in the trough as better agreement with the field data for both regular and irregular waves is found if such coefficients are used in the boussinesq model

assessing the utility of fe al and fe speciation to record water column redox conditions in carbonate rich sediments abstract geochemical proxies based on fe abundance fe al and fe speciation have been widely applied to marine sediments in order to unravel paleo depositional redox conditions though geological time to date however these fe proxies have only been calibrated in relation to modern and ancient fine grained siliciclastic marine sediments this clearly limits their use particularly in relation to carbonate rich sediments and rocks to address this we here explore the applicability of fe based redox proxies in carbonates through three approaches first we have compiled fe al data for modern marine sediments to investigate variability in fe enrichments as a function of carbonate content and depositional setting second we have expanded this approach with a compilation of new and existing fe speciation data for modern and ancient marine sediments deposited under oxic and euxinic anoxic sulfidic water column conditions finally we show new data from paired limestone and dolomite sample sets to demonstrate the potential significance of deep burial dolomitization on the fe speciation redox proxy modern marine sediments deposited under oxic conditions show no relationship between fe al and carbonate content these sediments have an average fe al ratio of 0 55 0 11 with some higher values potentially being attributable to steady state early diagenetic remobilization of fe towards the sediment water interface in contrast significant fe al enrichments occur as a consequence of water column fe mineral formation and deposition either under anoxic conditions or due to input of anoxic hydrothermal fluids into oxic seawater iron speciation data also show no direct correlation with carbonate content and instead three groups can be distinguished based on total fe fe t and organic c contents sediments deposited under oxic water column conditions with fe t 0 5 wt generally plot below the lower fe hr fe t siliciclastic reference threshold 0 38 for distinguishing anoxic environments regardless of carbonate content also consistent with siliciclastic calibrations carbonate rich sediments deposited under anoxic water column conditions tend to have fe hr fe t ratios 0 38 in contrast oxic carbonate rich sediments with low fe t hr fe t ratios suggesting that the use of fe speciation for such samples is not appropriate for evaluating water column redox conditions taken together our data suggest that an fe t content of 0 5 wt rather than carbonate content represents the most suitable basis for identifying whether carbonate rich sediments are appropriate for fe based redox proxy analyses analysis of burial dolostones suggests that the fe speciation proxy may also be compromised by deep burial dolomitization where there has been a source of mobile fe to enrich rocks during recrystallization however pre screening can identify such samples this new assessment expands the utility of fe based redox proxies to also incorporate appropriate carbonate rich rocks provided that care is taken to assess the possible impact of deep burial dolomitization

palaeoceanographic redox environments for the lower cambrian hetang formation in south china evidence from pyrite framboids redox sensitive trace elements and sponge biota occurrence abstract the lower cambrian hetang formation a black shale sequence contains a stone coal a flammable organic rich mudstone unit abundant pyrite framboids occur in this unit with the average mean sizes falling in a narrow range from 4 6 to 5 4 m and the maximum diameters being around 10 m the size distribution pattern of the pyrite framboids indicates a euxinic depositional environment the redox sensitive trace metals of the stone coal samples reveal a large enrichment of mo 10 180 times v 4 40 times u 10 60 times and ni 2 20 times compared to the average upper continental crust value consistent with an anoxic environment for their deposition the redox sensitive element ratios th u v v ni v cr indicate that the depositional environment for the lower part of the stone coal unit was the most anoxic and euxinic in contrast a sponge biota including eleven species of demosponges and hexactinellids and two undetermined forms indicate an oxic or dysoxic environment to reconcile these two facts we propose that although an anoxic euxinic environment predominated during the deposition of the lower cambrian hetang formation black shales occasional currents may also have brought free oxygen to the bottom water column to allow the growth of the sponges on the sea floor

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

paleoceanographic applications of trace metal concentration data abstract recent studies have identified a range of new applications of trace metal concentration data in the analysis of paleoceanographic systems in restricted anoxic marine systems trace metal toc ratios can provide insight into the degree of watermass restriction and estimates of deepwater renewal times in such systems secular changes in sediment trace metal ratios may provide evidence of the chemical evolution of basinal deepwaters in response to differential rates of trace metal removal to the sediment the degree of deepwater restriction in silled basins is generally controlled by eustatic elevations with higher lower sea levels resulting in lesser greater watermass restriction short term ca million year drawdown of the trace metal inventory of seawater has occurred repeatedly in conjunction with oceanic anoxic events which result in elevated rates of trace metal removal to widespread anoxic facies long term eon scale changes of the trace metal composition of seawater have occurred in response to secular changes in atmospheric oceanic redox conditions and their effects on trace metal cycling caution must be exercised in evaluating trace metal patterns in paleomarine systems however 1 hydrographic analyses based on trace metal toc relationships can be undertaken only on systems that had anoxic deepwaters and 2 the influence of redox variation on trace metal accumulation patterns outweighs that of hydrographic factors in some paleomarine systems

neoproterozoic to early cambrian small shelly fossil assemblages and a revised biostratigraphic correlation of the yangtze platform china abstract small shelly fossils ssfs occur widely on the yangtze platform and have great potential for biostratigraphic subdivision of pre trilobitic early cambrian strata based on the ssf record of the shallow water realm five biozones can be recognized for the meishucunian stage in ascending order the biozones are anabarites trisulcatus protohertzina anabarica assemblage zone paragloborilus subglobosus purella squamulosa assemblage zone watsonella crosbyi assemblage zone formerly heraultipegma yunnanensis zone poorly fossiliferous interzone sinosachites flabelliformis tannuolina zhangwentangi assemblage zone in addition one ssf biozone is recognized for the overlying qiongzhusian stage pelagiella subangulata taxon range zone the formerly used siphogonuchites triangularis paragloborilus subglobosus zone and heraultipegma yunnanensis zone are discussed and redefined approximately 80 species of ssfs were screened for their spatial and temporal distribution on the yangtze platform variations in lithofacies and biofacies can be recognized throughout the yangtze platform extending over an area of 2000 900 km in a deeper water shelf setting the first zone is represented by the protohertzina anabarica kaiyangites novilis assemblage zone while younger zones are not recognized in the southern region at the northern platform margin the qiongzhusian is represented by the ninella tarimensis cambroclavus fangxianensis assemblage zone and the rhombocorniculum cancellatum taxon range zone the southeastern shaanxi western hubei region followed a slightly different lithological and faunal development than the rest of yangtze platform indicating a stronger similarity with parts of east gondwana some taxa such as w crosbyi p subangulata r cancellatum microdictyon effusum a trisulcatus protohertzina unguliformis and p anabarica occur nearly worldwide and support an international correlation of early cambrian sequences between the yangtze platform and smaller west gondwanan blocks siberia newfoundland and australia the six investigated zones of the yangtze platform comprise an interval spanning the early nemakit daldynian to the late atdabanian early botoman stage on the siberian platform palaeobiogeographic analysis revealed a strong taxic similarity between the yangtze platform and the tarim platform a smaller number of species are shared with other west gondwanan platform fragments such as india and iran palaeobiogeographic results do not support the previously reported position of the south china block between australia and siberia during the early cambrian

nonlinear shear instabilities of alongshore currents over barred beaches the nonlinear dynamics of finite amplitude shear instabilities of alongshore currents in the nearshore surf zone over barred beach topography are studied using numerical experiments these experiments extend the recent study of allen et al 1996 which utilized plane beach constant slope topography by including shore parallel sandbars the model involves finite difference solutions to the nonlinear shallow water equations for forced dissipative initial value problems and employs periodic boundary conditions in the alongshore direction effects of dissipation are modeled by linear bottom friction forcing for the alongshore currents is specified using a model formulated by thornton and guza 1986 t g distinct classes of flows develop depending on the dimensionless parameter q the ratio of an advective to a frictional timescale for q greater than a critical value qc the flows are linearly stable for q qc q 0 the flow is unstable for small values of q equilibrated shear waves develop that propagate alongshore at phase speeds and wavelengths that are in agreement with predictions from linear theory for the most unstable mode at intermediate values of q unsteady vortices form and exhibit nonlinear interactions as they propagate alongshore occasionally merging pairing or being shed seaward of the sandbar at the largest values of q examined the resulting flow field resembles a turbulent shear flow a net effect of the instabilities at large aq is to distribute the time averaged alongshore momentum from local maxima of the t g forcing located over the sandbar and near the shore into the region of the trough the across shore structure of the time averaged alongshore current is in substantially better qualitative agreement with observations than that given by a steady frictional balance with t g forcing the results point to the possible existence in the nearshore surf zone of an energetic eddy field associated with instabilities of the alongshore current

biogeochemical cycling of cadmium isotopes along a high resolution section through the north atlantic ocean abstract cadmium cd is a bioactive trace element in the oceans with a nutrient like distribution that closely matches dissolved phosphate seawater dissolved stable cd isotope ratios 114cd are a relatively new parameter which show much promise for furthering our understanding of the biogeochemical cycling of cd in the oceans here we present a high resolution paired section of dissolved cd concentrations and dissolved 114cd from 21 open ocean stations along the us geotraces ga03 transect through the north atlantic ocean dissolved cd concentrations along the section are strongly influenced by water mass distribution and the cycling of cd the highest dissolved cd concentrations 400 540 pmol kg 1 are associated with antarctic sourced water masses whilst biological uptake in the surface ocean results in a strong vertical gradient in dissolved cd towards the surface reaching as low as 0 03 pmol kg 1 in western surface waters dissolved 114cd is also characterized by a vertical gradient from 0 2 in the deep ocean to 2 to 5 in the cd depleted surface ocean relative to nist srm 3108 this variability in 114cd can be ascribed to mixing of antarctic and north atlantic water masses together with fractionation due to in situ biological uptake of light cd in the very surface ocean subtle deviations from this overall pattern of dissolved cd concentration and dissolved 114cd are observed within low oxygen waters off north africa where a dissolved cd deficit relative to phosphate is associated with higher dissolved 114cd values together with elevated particulate cd and ba this suggests that cd sulfide precipitation is occurring within the water column of the north atlantic constituting a potentially important sink for isotopically light cd additionally the first measurements of dissolved 114cd within a hydrothermal plume at the mid atlantic ridge show that cd is scavenged from the dissolved phase leaving the remnant dissolved cd isotopically heavier constraining the significance of these marine sinks for dissolved cd is important not only for our understanding of the marine biogeochemical cycling of cd in the modern oceans but also for the successful application of the microfossil cd ca proxy and the development of 114cd as a tracer for past ocean biogeochemical cycling

sedimentary corg p ratios paleocean ventilation and phanerozoic atmospheric po2 the corg p ratios of organic rich facies tocn1 exhibit considerable variation through the phanerozoic from b10 1 in the permian phosphoria formation to n1000 1 in some devonian black shales relative to the composition of phytoplankton c p 106 1 which provide the bulk of organic c and p to organic rich marine sediments the range of phanerozoic sedimentary corg p ratios largely reflects the influence of benthic redox conditions on diagenetic pathways of c and p remobilization enhanced preservationoforganiccatlowerredoxpotentials combinedwithenhancedsedimentaryretentionofremineralizedorganicpathigher redox potentials results in a strong relationship between benthic redox conditions and sedimentary corg p ratios the strong secular coherence of the phanerozoic corg p record i e limited variation within narrow time slices suggests that these ratios are controlled primarily by factors influencing benthic redox conditions on a global scale such as atmospheric po2 inversion and scaling of the phanerozoic corg p record yields a new atmospheric po2 model that has strong similarities to existing models based on elemental and isotopic mass balances yet differs in some potentially significant respects in particular the new model suggests that atmospheric po2 wasmarkedlylowerduringtheearlytomiddlepaleozoicthanpreviouslyinferred duringmostofthedevonian atmospherico2levels mayhavebeensufficientlylow b13 astopreventthesustainedcombustionofplantmaterial thisfeatureofthemodelmayaccount for ananomalous gapinthefossilcharcoalrecordduringthedevonian theredox dependentburialofpintheoceanresults inpositive and negative feedback mechanisms that tend to stabilize atmospheric oxygen concentrations on geologic timescales temporal variations in the burial of p relative to c suggest that the strength of these feedback mechanisms varied over the phanerozoic 2007 elsevier b v all rights reserved

the origin of decoupled carbonate and organic carbon isotope signatures in the early cambrian ca 542 520 ma yangtze platform abstract the early cambrian ca 542 520 ma strata in south china record two prominent negative carbonate carbon isotope 13ccarb excursions of early nemakit daldynian n d and early tommotian ages across each of these excursions carbonate and organic carbon isotopes 13ccarb and 13corg are strongly decoupled regional correlation across a shelf to basin transect shows lateral heterogeneity of 13corg during the early middle n d but more homogenized 13corg values across the basin during the late n d and tommotian the temporal and lateral variations in 13corg suggest that decoupled 13ccarb and 13corg across the n d 13ccarb excursion were possibly caused by diagenetic alteration of organic matter and or amplification of detrital organic carbon isotope signature in low toc carbonates in contrast decoupled 13ccarb and 13corg of the upper n d and tommotian were likely resulted from chemoautotrophic methanotrophic biomass contribution to toc in organic rich black shale and carbonates the decoupled 13ccarb 13corg pattern from the lower n d strata ca 542 ma shows striking similarities with those from the basal ca 635 ma and upper ca 551 ma doushantuo formation in all three cases decoupled 13ccarb 13corg are seen in organic poor carbonates toc 0 1 and coupled 13ccarb 13corg occur in organic rich black shale and carbonates at the end of the negative 13ccarb excursion these similarities suggest that the shift from decoupled to coupled 13ccarb 13corg has no causal link with the terminal oxidation of a large oceanic doc reservoir given the pervasive anoxia euxinia in ediacaran early cambrian oceans local doc rich environments may have been common but a large oceanic doc reservoir capable of buffering the 13c of marine organic matter requires independent evidence

forcing of oceanic mean flows by dissipating internal tides we present a theoretical and numerical study of the effective mean force exerted on an oceanic mean flow due to the presence of small amplitude internal waves that are forced by the oscillatory flow of a barotropic tide over undulating topography and are also subject to dissipation this extends the classic lee wave drag problem of atmospheric wave mean interaction theory to a more complicated oceanographic setting because now the steady lee waves are replaced by oscillatory internal tides and most importantly because now the three dimensional oceanic mean flow is defined by time averaging over the fast tidal cycles rather than by the zonal averaging familiar from atmospheric theory although the details of our computation are quite different we recover the main action at a distance result from the atmospheric setting namely that the effective mean force that is felt by the mean flow is located in regions of wave dissipation and not necessarily near the topographic wave source specifically we derive an explicit expression for the effective mean force at leading order using a perturbation series in small wave amplitude within the framework of generalized lagrangian mean theory discuss in detail the range of situations in which a strong secularly growing mean flow response can be expected and then compute the effective mean force numerically in a number of idealized examples with simple topographies

high resolution organic carbon isotope stratigraphy from a slope to basinal setting on the yangtze platform south china implications for the ediacaran cambrian transition organic carbon isotope data from two slope to basinal sections across the ediacaran cambrian transition on the yangtze platform south china record secular variations in delta c 13 data supplement highly comparable organic carbon isotope profiles from time equivalent shallow shelf and slope settings no environmentally determined carbon isotope gradient across the yangtze platform is discernible suggesting that a transgressive anoxic event provided an isotopically homogenous carbon source for primary productivity that originated from the deeper part of an anoxic and or sulfidic basin c 2011 elsevier b v all rights reserved

contrasting molybdenum cycling and isotopic properties in euxinic versus non euxinic sediments and sedimentary rocks refining the paleoproxies abstract the redox sensitive transition element molybdenum is present in the earth s crust at trace concentrations but is abundant in seawater marine sediments and ancient sedimentary rocks these occurrences have led to the development of a suite of paleoredox proxies based on the bulk concentration of mo its isotopic composition and the covariation of mo with total organic carbon toc in ancient black shales however these proxies have almost exclusively targeted the identification and interpretation of euxinic environments where bottom waters are both anoxic and sulfidic here we present a discussion of the mo geochemistry of non euxinic sediments where hydrogen sulfide is sometimes present yet always restricted to pore waters we propose a new paleoredox application that uses mo concentrations to help distinguish between environments where sulfide was present in the bottom waters and environments where sulfide was restricted to pore waters under ideal conditions it is also possible to infer the presence of mn oxides recycling in non euxinic paleoenvironments based on the mo isotope composition of ancient black shales providing a critical constraint on bottom water oxygenation

environmental analysis of paleoceanographic systems based on molybdenum uranium covariation abstract modern low oxygen marine systems exhibit patterns of molybdenum uranium covariation that can be linked to specific attributes and processes of the depositional system including 1 variation in benthic redox conditions 2 the operation of particulate shuttles within the water column and 3 the evolution of watermass chemistry the importance of these factors in each depositional system can be assessed both from the degree of enrichment of authigenic molybdenum mo auth and uranium u auth and from the mo u auth ratio of the sediment relative to the seawater mo u molar ratio of 7 5 7 9 in open ocean systems with suboxic bottomwaters u auth enrichment tends to exceed that of mo auth owing to onset of u auth accumulation at the fe ii fe iii redox boundary resulting in sediment mo u auth ratios less than that of seawater as bottomwaters become increasingly reducing and at least occasionally sulfidic the rate of accumulation of mo auth increases relative to that of u auth and sediment mo u auth ratios equal or exceed that of seawater in restricted marine systems with permanently sulfidic deepwaters the relative enrichment of mo auth and u auth depends on additional factors in the cariaco basin which has an aqueous mo u ratio similar to that of seawater the operation of a particulate mn fe oxyhydroxide shuttle serves to accelerate the transfer of mo to the seafloor leading to strong enrichments in mo auth relative to u auth in the black sea the chemistry of the deep watermass has evolved to the point where its aqueous mo u ratio is only 0 04 that of seawater as a consequence of which sediments deposited under deepwater influence are depleted in mo auth relative to u auth these mo u covariation patterns can be used to gain a better understanding of the watermass attributes and processes of ancient low oxygen marine systems analysis of anoxic facies from two north american paleomarine systems the late pennsylvanian midcontinent sea lpms and the late devonian seaway lds reveals authigenic mo u relationships similar to those of the modern marine environments above implying similar redox and hydrographic controls the observed patterns are consistent with laterally unconfined circulation and strong watermass exchange within the lpms and with markedly restricted deepwater circulation in silled basins of the lds patterns of authigenic mo u covariation may prove useful in analysis of other paleoceanographic systems to reveal aspects of watermass composition and environmental dynamics

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

marine redox variations and nitrogen cycle of the early cambrian southern margin of the yangtze platform south china evidence from nitrogen and organic carbon isotopes the early cambrian is a crucial interval during which the marine environment encountered significant perturbations alongside key biological innovations the nitrogen isotopic composition of ancient sediments has the potential to record co variation between the marine ecosystem and environmental conditions here we report bulk nitrogen and organic carbon isotopic compositions accompanied by mo concentration data a proxy for redox conditions for a shelf marginal drill core section sancha and a deep basinal outcrop section yuanjia in hunan province south china for the cambrian fortunian stage variable delta n 15 bulk values 4 to 2 parts per thousand and low delta c 13 org values 35 parts per thousand to 33 from the yuanjia section indicate that anoxic waters shoaled into the photic zone with ammonia assimilation competing with anammox in the basinal area in the late cambrian stage 2 low delta n 15 bulk and delta c 13 org values together with high mo bulk concentrations delta n 15 bulk 5 to 0 parts per thousand delta c 13 org 33 5 to 31 0 parts per thousand 100 ppm mo bulk in sancha section and delta n 15 bulk 0 parts per thousand delta c 13 org similar to 33 parts per thousand 100 ppm mo bulk in yuanjia section reflect intense n 2 fixation accompanied by intermittent ammonia assimilation under expanded euxinic condition with shoaling chemocline possibly into the photic zone in the early cambrian stage 3 relatively high delta n 15 bulk values alongside positive delta c 13 org excursions at both sections indicate an increasing contribution from n 15 enriched nitrate assimilation and hence more oxic conditions shelf margin sediments from the middle and late parts of cambrian stage 3 are characterized bylaw delta n 15 bulk values similar to 0 parts per thousand being lowest in the basinal area 3 to 0 parts per thousand in combination with high mo bulk concentration 100 ppm and high mo tocbulk ratios averaging similar to 18 in deep basinal sediments these data suggest that the photic zone became anoxic again but that sulfidic conditions occurred in the basinal area only compared with stage 2 euxinia was less extensive during this interval with photosynthetic biomass dominating over chemoautotrophic biomass at both localities based on a combination of delta n 15 data from this study and published data from studies on contemporaneous sections in yunnan province and the three gorges area it is possible to reconstruct the spatial variability and temporal evolution of redox conditions in the various marine environments along the southern margin of the yangtze platform the basinal area appears to have been dominated by anoxia and intermittent euxinia in the photic zone during most of the early cambrian fortunian stage to stage 3 with the exception of more oxic conditions during early stage 3 on the platform oxygenated shallow water prevailed with the exception of the notable cambrian stage 2 anoxic event the outer shelf area experienced anoxia from stage 2 to stage 3 of the early cambrian although of possibly limited areal extent the high mo bulk concentrations and mo tocbulk ratios suggest that the south china basin was well connected with the considerably oxygenated open ocean and that the mean low delta n 15 bulk values similar to 1 6 parts per thousand from the basin may reflect generally lower delta n 15 composition for seawater nitrate in the early cambrian compared with modern value c 2015 elsevier b v all rights reserved

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

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

analysis of marine environmental conditions based onmolybdenum uranium covariation applications to mesozoic paleoceanography article i nfo article history accepted 13 september 2011 available online 17 september 2011 patterns of uranium molybdenum covariation in marine sediments have the potential to provide insights re garding depositional conditions and processes in paleoceanographic systems specifically such patterns can be used to assess bottom water redox conditions the operation of metal oxyhydroxide particulate shuttles in the water column and the degree of water mass restriction the utility of this paleoenvironmental proxy is due to the differential geochemical behavior of u and mo 1 uptake of authigenic u by marine sediments begins at the fe ii fe iii redox boundary i e suboxic conditions whereas authigenic mo enrichment re quires the presence of h2s i e euxinic conditions and 2 transfer of aqueous mo to the sediment may be enhanced through particulate shuttles whereas aqueous u is unaffected by this process in the present study we examine u mo covariation in organic rich sediments deposited mostly in the western tethyan region during oceanic anoxic events oaes of early jurassic to late cretaceous age our analysis generally confirms existing interpretations of redox conditions in these formations but provides significant new insights regard ing water mass restriction and the operation of particulate shuttles in depositional systems these insights will help to address contentious issues pertaining to the character and origin of mesozoic oaes such as the degree to which regional paleoceanographic factors controlled the development of the oaes

organic matter accumulation of late ordovician sediments in north guizhou province china sulfur isotope and trace element evidences abstract the organic rich upper ordovician sediments wufeng and guanyinqiao formations on the yangtze platform are considered to be one of the main source rocks here we present geochemical proxies including redox indicator s c ratios and sulfur isotopes and productivity indices toc mo and ba contents from nanbazi section in north guizhou province south china in order to investigate the mechanism of organic matter accumulation the geochemical data suggest a stagnant and anoxic environment predominated the yangtze sea during the wufeng period whereas ventilated and oxygenated marine conditions pervaded the yangtze sea during the guanyinqiao period variations in the concentration of toc mo and ba indicate that higher organic carbon export in the wufeng intervals than those in the guanyinqiao intervals these variations in redox and productivity during the late ordovician were associated with different mechanisms and forcing processes the abrupt change from anoxic to oxygenated condition at the beginning of the guanyinqiao was concomitant with the global glacial period likely resulted from the glacio eustatic sea level fall and subsequent circulation of cold dense oxygenated waters upon the shelf seabed the productivity variations were related to the change of nutrient supply which is consistent with volcanic activities and runoff to the yangtze sea redox changes together with primary productivity fluctuations could have played a significant role on the variation of organic matter accumulation during the late ordovician in south china

a laboratory study of longshore currents over barred and non barred beaches abstract a detailed description is given of the results of laboratory experiments on wave driven longshore currents on both barred and non barred beaches the objective is to examine the cross shore distribution of the longshore current velocities for purely wave driven currents with emphasis on the position of maximum current velocity with respect to areas where wave energy is dissipated unidirectional obliquely incident waves both regular and random were used the measurements were performed in a large wave basin with a pump recirculation system to create spatially homogeneous longshore currents the experiments yielded information on wave transformation set up of the mean water level and the cross shore distribution of wave driven longshore current velocity a number of cases are presented and compared with each other the measurements show that in the case of purely wave driven longshore currents the maximum current velocities occur close to areas where wave breaking is most intense the effect of mixing bottom friction and wave rollers on the longshore current velocity profile are examined in more detail with help of numerical modelling existing model equations based on the assumption of alongshore uniformity are used the results for the mean longshore current profile on a barred beach are in close agreement with the measurements

integrated ediacaran sinian chronostratigraphy of south china abstract the ediacaran period was a critical time in the history of life and earth understanding the complex interactions between geological and biological events during this interval requires high resolution chronostratigraphy thanks to its uniquely favorable palaeogeographic setting south china is an ideal region for constructing a framework for global chronostratigraphic correlation of ediacaran strata here continuous ediacaran successions contain both siliciclastic and carbonate rocks that range from shallow to deep marine and contain rich fossil assemblages showing a variety of preservation styles as part of the present study 62 reference sections distributed throughout the yangtze platform were investigated analyses of the sedimentary facies and sequence stratigraphy of more than 40 sections revealed four major sequences in the shallow marine facies three major sequence boundaries occur respectively in the middle and upper parts of the doushantuo formation and in the middle part of the dengying formation subdivision and correlation of the ediacaran successions of the yangtze platform based on sequence stratigraphy is congruent with the carbon isotope chemostratigraphy of 12 reference sections 1075 samples the sequence boundary sb2 in the middle part of the doushantuo formation is suggested here as the lower xiadongian upper yangtzean series boundary of the ediacaran which coincides with several globally recognizable events namely 1 the end of the neoproterozoic glaciations 2 the first appearance of animals 3 the sudden increase in the diversity of acanthomorphic acritarchs and 4 a negative 13 c excursion the ediacaran system of south china may be subdivided into five stages furthermore the criteria for defining these stages may be applicable throughout the world also the composite carbon isotope profile of the ediacaran of south china can be used as a global reference for chronostratigraphic subdivision and correlation in addition to the globally recognizable negative 13 c excursion in the cap carbonate at the base of the ediacaran the negative 13 c excursion in the uppermost doushantuo wonoka shuram interval represents another globally correlatable major excursion the positive 13 c excursion immediately following the uppermost doushantuo excursion and ending at 548 ma is also useful for global correlation current ediacaran chronostratigraphy and global correlations indicate that the upper doushantuo wonoka shuram negative 13 c excursion ranges from ca 560 ma to 551 ma and therefore coincides with the evolutionary renovation of life feedback between evolutionary innovation and geochemical cycling was the key mechanism for this unique and most strongly negative 13 c excursion in earth history our chronostratigraphic correlations also imply that the earliest known metazoan biotas namely the weng an and characteristic ediacaran biotas do not constitute two temporally separate evolutionary lineages as proposed previously but represent two parallel evolutionary pathways preceding the cambrian explosion of animal life

nitrogen and organic carbon isotope stratigraphy of the yangtze platform during the ediacaran cambrian transition in south china abstract n and corg isotope results are presented from six sections along a west east transect in the south china basin scb covering both shallow and deeper domains in order to investigate biogeochemical cycling stratigraphic correlation and isotope systematics over the crucial ediacaran cambrian transition 15n bulk values range between 3 and 7 while 13corg values range between 21 and 39 similar isotopic trends have been identified for both these proxies across the basin although hiatuses differences in depositional setting and syn depositional bacterial fermentation may have caused some inconsistencies a trend towards negative n isotope values can be recognized above the pc c boundary in both shallow and deeper basin realms across the yangtze platform this negative 15n excursion is probably a response to photic zone anoxia and intense nitrogen fixation assimilation by diazotrophic cyanobacteria and green purple sulfur bacteria gsb and psb the xiaotan section and a composite section from the yangtze gorges area show meaningful similarities in their nitrogen isotope trends interpreted as chemocline fluctuations in the water column that testify to rapid mixing of water overlying the shallow platform using carbon isotope stratigraphy we correlate boundary strata across the platform to test the wider significance of nitrogen isotopic variations increased bioturbation and food chain complexity across the ediacaran cambrian transition probably led to more frequent variations in nitrate isotope composition and related pool dimension during the early cambrian reflecting the beginning of a new more biologically controlled era

redox sensitivity of p cycling during marine black shale formation dynamics of sulfidic and anoxic non sulfidic bottom waters abstract a high resolution geochemical record of a 120 cm black shale interval deposited during the coniacian santonian oceanic anoxic event 3 odp leg 207 site 1261 demerara rise has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo redox conditions high contents of organic matter sulfur and redox sensitive trace metals cd mo v zn as well as continuous lamination point to deposition under consistently oxygen free and largely sulfidic bottom water conditions however rapid and cyclic changes in deep ocean redox are documented by short term 15 20 ka intervals with decreased total organic carbon toc s and redox sensitive trace metal contents and in particular pronounced phosphorus peaks up to 2 5 wt p associated with elevated fe oxide contents sequential iron and phosphate extractions confirm that p is dominantly bound to iron oxides and incorporated into authigenic apatite preservation of this fe p coupling in an otherwise sulfidic depositional environment as indicated by fe speciation and high amounts of sulfurized organic matter may be unexpected and provides evidence for temporarily non sulfidic bottom waters however there is no evidence for deposition under oxic conditions instead sulfidic conditions were punctuated by periods of anoxic non sulfidic bottom waters during these periods phosphate was effectively scavenged during precipitation of iron oxyhydr oxides in the upper water column and was subsequently deposited and largely preserved at the sea floor after 15 25 ka sulfidic bottom water conditions were re established leading to the initial precipitation of cds zns and pyrite subsequently increasing concentrations of h2s in the water column led to extensive formation of sulfurized organic matter which effectively scavenged particle reactive mo complexes thiomolybdates at site 1261 sulfidic bottom waters lasted for 90 100 ka followed by another period of anoxic non sulfidic conditions lasting for 15 20 ka the observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface to mid waters from the south atlantic resulting in a lowering of the oxic anoxic chemocline in the water column alternatively sea water sulfate might have been stripped by long lasting high rates of sulfate reduction removing the ultimate source for hs production

anoxia vs productivity what controls the formation of organic carbon rich sediments and sedimentary rocks discussion the prevailing explanation for the origin of organic rich sediments and rocks invokes deposition under conditions of anoxia however recent research suggests that high primary production and not water column anoxia provides the first order control on the accumulation of organic rich facies in the modern oceans oxygen minima do not appear to have any direct effect on carbon accumulation in continental margin or marginal sea environments sediments accumulating in the modern black sea the type euxinic basin are not particularly enriched in organic matter despite the presence of an anoxic water column although a sapropel containing extremely high carbon concentrations was deposited during the holocene at a time when the basin was oxic results of a recently published co pled ocean atmosphere model indicate that during the cretaceous thermohaline and surface circulation in the oceans was similar to or more intense than modern conditions despite the overall equable climate such conditions confound the idea that circulation in the cretaceous atlantic for example was punctuated by oceanic anoxic events brought about by more sluggish circulation sporadic temporal and spatial increases in primary production reflecting changes in the behavior and or state of the ocean atmosphere system constitute a more tenable explanation for the occurrence of modern and quaternary carbon rich sediments and cretaceous black shales consequently the fundamental control on the accumulation of carbon rich facies in the oceans and marginal seas is not the presence or absence of anoxia

further shrimp geochronology on the early cambrian of south china zircon 206pb 238u ages are reported for bentonites from two cambrian sections in south china the meishucun and the fandian the analyzed zircons vary widely in age because of the presence of detrital and altered grains spot ages were corrected for calibration drift during analysis and the age of reference zircon sl13 was calibrated as 580 ma against other standards using sims use of mixture modeling was essential to resolve the different age components and to identify the volcanic ages two age groups occur within the meishucun bed 5 bentonite of which the larger at 518 7 2 5 ma is interpreted as a post depositional zircon growth event and the other at 539 4 2 9 ma as the volcanic age bentonites from the meishucun bed 9 and its fandian equivalent have two age groups 526 5 1 1 ma and 540 2 1 0 ma we interpret the younger of these as the tuff magmatic age and the older as detrital small shelly fossils indicate meischucunian bed 5 is an equivalent of the late nemakit daldynian and its 539 4 2 9 ma age both closely times the base of the cambrian and is a maximum for the basal tommotian the 526 5 1 1 ma for bed 9 and its equivalents approximates the close of the tommotian

phosphorus phosphorites and skeletal evolution at the precambrian cambrian boundary clustering of sedimentary phosphate deposits around the precambrian cambrian boundary is related to a global phosphogenic event this event probably resulted from a complex interplay of factors and had a profound effect on the biota with high concentrations of phosphorus in the photic zone producing an increase in the total shallow marine biomass faunal diversification the precipitation of skeletal structures and explosive evolution

trace element behavior and redox facies in core shales of upper pennsylvanian kansas type cyclothems the black shale submember of core shales of pennsylvanian kansas type cyclothems is highly enriched in redox sensitive trace elements tes relative to the overlying gray shale submember as well as to many other modern and ancient organic rich deposits controls on trace element behavior in the black shale can be inferred from trace element enrichment factors efs relative to gray shale and the relationship of tes to total organic carbon toc most tes conformed to one of two patterns 1 mo u v zn and pb exhibited moderate efs and strong covariation with toc in samples having 10 wt toc and 2 cu ni cr and co exhibited low efs and moderate to strong covariation with toc in all samples these patterns are inferred to represent different responses to benthic redox conditions the first pattern is characteristic of tes of strong euxinic affinity i e those taken up in solid solution by fe sulfide or involved in other reactions catalyzed by free h2s and resident mainly in authigenic phases whereas the second pattern is characteristic of tes of weak euxinic affinity i e those not strongly influenced by the presence of free h2s and resident mainly in the organic carbon or detrital fractions of the sediment these inferences allowed development of a multiproxy technique for assessing redox facies in black shale samples euxinic conditions were considered to have existed if at least two of four redox indicator trace elements mo u v zn showed euxinic levels of enrichment and nonsulfidic anoxic conditions were inferred otherwise the validity of the procedure is indicated by 1 agreement among all four redox indicators for a large majority of samples 69 of 185 2 among samples yielding a mixed redox signal a systematic sequence of te enrichment v zn mo u and 3 for tes of weak euxinic affinity reduced variance among samples representing each redox facies sequential enrichment may be a response to differential redox thresholds for accumulation e g v or postdepositional remobilization of trace elements e g u and may provide a basis for finer assessment of redox conditions in low oxygen paleoenvironments than permitted by simple classification schemes the multiproxy procedure for redox facies analysis developed in this study is likely to be more reliable than widely used single proxy indicators based on trace elements e g mo authigenic u or v v ni or c s fe systematics e g s toc or dop d 2004 elsevier b v all rights reserved

new u pb zircon ages of the ediacaran cambrian boundary strata in south china the ediacaran cambrian transition is a critical interval marking drastic biological oceanic and geochemical co evolutions in geological history but it is poorly constrained geochronologically in south china we here present two new sets of sims u pb zircon ages from ediacaran cambrian boundary strata dengying liuchapo and niutitang formations deposited in the slope basin environments of carbonate platforms two weighted mean u pb ages of 542 1 5 0 ma and 542 6 3 7 ma in the basal and mid upper liuchapo formation respectively in slope and basinal settings provide the first direct age set for the ediacaran cambrian boundary in south china another two u pb ages of 524 2 5 1 ma and 522 3 3 7 ma from the base of the overlying niutitang formation indicate that this widespread unit in south china was deposited about 20 ma after the onset of the cambrian

marine productivity changes during the end permian crisis and early triassic recovery abstract the latest permian mass extinction lpme coincided with major changes in the composition of marine plankton communities yet little is known about concurrent changes in primary productivity earlier studies have inferred both decreased and increased productivity in marine ecosystems immediately following the end permian crisis here we assess secular and regional patterns of productivity variation during the crisis through an analysis of the burial fluxes of three elemental proxies total organic carbon toc phosphorus p and biogenic barium babio primary productivity rates appear to have increased from the pre crisis late permian through the early triassic in many parts of the world although the south china craton is unusual in exhibiting a pronounced decline at that time most of the 14 permian triassic study sections show concurrent increases in sediment bulk accumulation rates suggesting two possible influences linked to subaerial weathering rate changes 1 intensified chemical weathering resulting in an increased riverine flux of nutrients that stimulated marine productivity and 2 intensified physical weathering leading to higher fluxes of particulate detrital sediment to continental shelves thus enhancing the preservation of organic matter in marine sediments an additional factor especially in the south china region may have been the intensified recycling of bacterioplankton derived organic matter in the ocean surface layer reducing the export flux rather than primary productivity per se the ecosystem stresses imposed by elevated fluxes of nutrients and particulate sediment as well as by locally reduced export fluxes of organic matter may have been important factors in the 2 to 5 million year long delay in the recovery of early triassic marine ecosystems

surf zone longshore currents and random waves field data and models abstract analytic and numerical models for longshore currents generated by obliquely incident random waves am compared with field observations five days of observations were selected during which the waves were narrow banded in both frequency and direction in keeping with model assumptions the extensive measurements included radiation stress and wave directional spectra in 9 m depth and a closely spaced array of current and pressure sensors on a line perpendicular to shore the longshore current models are based on balancing the gradient of the radiation stress with the alongshore bed shear and reynold s stresses assuming stationary wave conditions and straight and parallel bottom contours the spatial variation of wave height required to determine the gradient of the radiation stress is modeled using linear random wave theory given hrms in 9 m depth the model predicts hrms at shoreward locations with an average error of less than 9 using a nonlinear bottom shear stress formulation and the meas

controls on organic matter accumulation on the early cambrian western yangtze platform south china abstract the origin of widespread organic rich shales on the early cambrian yangtze platform of nanhua basin south china has been attributed to high primary productivity to test this hypothesis we generated multiple paleoproductivity ocar and par paleoredox corg p ratios upwelling restriction coef mnef co ppm mn mo toc and cd mo ratios and terrigenous flux proxies al and unreactive fe feu for the lower cambrian niutitang formation in the outer shelf jinsha section which records a typical transition from the organic rich black shales to overlying organic lean mudstones or siltstones these new data were integrated with published paleoredox proxies iron speciation and redox sensitive trace metals for the same section our results suggest that the organic rich toc 4 6 1 8 lower member lm 0 37 m of the niutitang formation records ferruginous conditions high productivity levels and low siliciclastic fluxes and that the organic poor toc 0 1 0 1 upper member um 37 329 m was characterized by dominantly oxic conditions declining productivity levels and high siliciclastic fluxes our results suggest a redox shift from ferruginous to oxic conditions and enhanced terrigenous fluxes in response to falling sea level from the lm to the um secular variations in primary productivity and redox conditions are strongly correlated which is consistent with a positive feedback high primary productivity led to increasing water column anoxia which enhanced organic p recycling stimulating further productivity variations in primary productivity may reflect variable upwelling intensity in a semi restricted shelf setting linked to sea level changes taken together these findings suggest that a combination of primary productivity redox conditions and terrigenous fluxes driven by sea level changes played a key role in organic matter accumulation on the early cambrian western yangtze platform

a continental weathering control on orbitally driven redox nutrient cycling during cretaceous oceanic anoxic event 2 the cretaceous period 145 65 m y ago was characterized by intervals of enhanced organic carbon burial associated with increased primary production under greenhouse conditions the global consequences of these perturbations oceanic anoxic events oaes lasted up to 1 m y but short term nutrient and climatic controls on widespread anoxia are poorly understood here we present a high resolution reconstruction of oceanic redox and nutrient cycling as recorded in subtropical shelf sediments from tarfaya morocco spanning the initiation of oae2 iron sulfur systematics and biomarker evidence demonstrate previously undescribed redox cyclicity on orbital time scales from sulfidic to anoxic ferruginous fe rich water column conditions bulk geochemical data and sulfur isotope modeling suggest that ferruginous conditions were not a consequence of nutrient or sulfate limitation despite overall low sulfate concentrations in the proto north atlantic instead fluctuations in the weathering influxes of sulfur and reactive iron linked to a dynamic hydrological cycle likely drove the redox cyclicity despite the potential for elevated phosphorus burial in association with fe oxides under ferruginous conditions on the tarfaya shelf porewater sulfide generation drove extensive phosphorus recycling back to the water column thus maintaining widespread open ocean anoxia

new chronological constraints for cryogenian to cambrian rocks in the three gorges weng an and chengjiang areas south china abstract the neoproterozoic and cambrian were two of the most dramatic periods in the history of the earth because large multi cellular animals first appeared then in the so called cambrian explosion to better understand this event many paleontological and geochemical studies now focus on rocks in south china because of the fossiliferous succession and good exposure since the recognition of the yangtze gorges and chengjiang area as type localities of the sinian ediacaran and meishucunian early cambrian systems both sections have been intensively investigated in order to decipher the relationships between the evolution of life and surface environmental changes it is necessary to understand their paleontological geochemical and geo chronological constraints this study presents new chronological constraints for the cryogenian to cambrian rocks in the three gorges weng an and chengjiang areas south china we discovered two tuff layers one at the base of the shuijingtuo fm at three gorges and the other at the bottom of the dahai member in chengjiang in addition we collected sandstones from neoproterozoic strata in the three gorges chengjiang and weng an areas for provenance analysis zircons separated from the tuff layers provide new nano sims u pb ages of 526 4 5 4 ma at the base of the shuijingtuo fm and 523 9 6 7 ma at the bottom of the dahai member the tuffaceous beds occur at an unconformity and nodules are common in the three gorges meishucun and taoying sections indicating that major and relatively wide scale volcanic and sedimentological events occurred at ca 525 ma moreover carbonate carbon isotope chemostratigraphies at morocco siberia three gorges and meishucun display different characteristics during the tommotian one possibility is that the south china ocean was separated from an outer ocean at that time detrital zircons in sandstones have age populations at ca 2 7 1 8 1 6 1 0 and from 0 9 to 0 75 ga indicating that the paleo hinterland of the nanhua and kangdian rift basins was geologically complex despite the lack of ca 1 6 ga rocks in the yangtze and cathaysia blocks these data are nevertheless interpreted to indicate derivation of the zircons from basement rocks in the yangtze craton

benthic phosphorus regeneration net primary production and ocean anoxia a model of the coupled marine biogeochemical cycles of carbon and phosphorus we examine the relationships between ocean ventilation primary production water column anoxia and benthic regeneration of phosphorus using a mass balance model of the coupled marine biogeochemical cycles of carbon c and phosphorus p the elemental cycles are coupled via the redfield c p ratio of marine phytoplankton and the c p ratio of organic matter preserved in marine sediments the model assumes that on geologic timescales net primary production in the oceans is limited by the upwelling of dissolved phosphorus to the photic zone the model incorporates the dependence on bottom water oxygenation of the regeneration of nutrient phosphorus from particulate matter deposited at the water sediment interface evidence from marine and lacustrine settings modern and ancient demonstrates that sedimentary burial of phosphorus associated with organic matter and ferric oxyhydroxides decreases when bottom water anoxia dysoxia expands steady state simulations show that a reduction in the rate of thermohaline circulation or a decrease of the oxygen content of downwelling water masses intensifies water column anoxia dysoxia and at the same time increases surface water productivity the first effect reflects the declining supply of oxygen to the deeper parts of the ocean the second effect is caused by the enhanced benthic regeneration of phosphorus from organic matter and ferric oxyhydroxides sedimentary burial of organic carbon and authigenic calcium phosphate mineral francolite on the other hand is promoted by reduced ocean ventilation according to the model global scale anoxia dysoxia leads to a more efficient recycling of reactive phosphorus within the ocean system consequently higher rates of primary production and organic carbon burial can be achieved even when the continental supply of reactive phosphorus to the oceans remains unchanged

longshore current dislocation on barred beaches 1 we present a numerical investigation of longshore currents driven by breaking waves on barred beaches alongshore inhomogeneity in the wave envelope or bathymetry leads to the generation of strong dipolar structures when the waves are breaking the dynamics of these structures transfer momentum from the bar of the beach into the trough this study is pursued using a new model that allows long simulation times and realistic wave amplitudes we study two idealized settings that are expected to produce current dislocation as observed in field experiments in one setting the current maximum is dislocated in the other the current is diffused but the maximum is not shifted

increase of seawater mo inventory and ocean oxygenation during the early cambrian abstract the early cambrian radiation of macroscopic animals commonly referred as the cambrian explosion is one of the most important biological innovations in earth history because oxygen is a requirement for complex animal life it is generally accepted that ocean oxygenation may have been the environmental trigger for animal evolution but direct geochemical evidence supporting oxygen increase prior to the cambrian explosion remains sparse and insufficient to better understand the casual relationship between ocean oxygenation and animal evolution we have carried out a systematic analysis of redox sensitive trace element rste concentrations total organic carbon toc contents and pyrite morphology for the early cambrian niutitang formation of the hejiapu section northeastern guizhou province south china the new data in combination with previously published data from other sections show strong mo enrichments average of 88 ppm and high mo toc ratios average of 14 ppm wt in the euxinic black shales of the lower niutitang formation 520 ma indicating increase of the oceanic mo reservoir in the light of the positive correlation between sediment mo toc and aqueous mo in modern basins the early cambrian oceanic mo concentration is estimated as 50 nmol which is about half of the modern ocean mo concentration 105 nmol but is significantly higher than that of the mesoproterozoic oceans 10 20 nmol the marked increase in oceanic mo reservoir is therefore interpreted as recording significant rise of atmospheric oxygen and pervasive ocean oxygenation which may have facilitated the diversification of macroscopic metazoans during the early cambrian

numerical modeling of infragravity wave response during delilah 1 the nearshore circulation model shorecirc is applied to simulate the infragravity wave conditions at two intervals during the 1990 delilah campaign at duck n c the model has been extended to solve the energy equation for random short waves on the timescale of the wave groups which acts as a wave driver for the long wave model to simulate the wave conditions an algorithm has been derived which synthesizes a directional offshore wavefield from measured data including the bound directional low frequency components the model data comparison shows that the mean short wave transformation and mean longshore current are predicted well the structure of the infragravity spectrum as measured in the nearshore array is correctly represented albeit that the energy levels are underpredicted in most locations the 2 d frequency longshore wavenumber spectra show that the infragravity wave energy consists mostly of edge waves and that the computations qualitatively resemble the measurements it is shown that for 1 day bar trapped edge waves are present the model is also used to show that the influence of the longshore variability is small for this particular beach and that the directional spreading in the offshore wave field is critical in predicting the nearshore infragravity wave conditions correctly edge waves which propagate against the current are generated by the directionally broad short wave forcing and to a lesser extent by back scattering the nonlinear terms are relatively unimportant for the prediction of the infragravity wave climate the cross shore gradient of the onshore directed radiation stress is the most important of the forcing terms