annual biogenic particle fluxes to the interior of the north atlantic ocean studied at 34 n 21 w and 48 n 21 w abstract in order to clarify the annual quality quantity and export processes of biogenic particles from the euphotic zone to the deep ocean interior an array of automated time series sediment traps were deployed for 1 year from 4 april 1989 to 17 april 1990 at 34 n 21 w and 48 n 21 w as part of the joint global ocean flux program jgofs north atlantic bloom experiment nabe three sediment traps with 13 time series sediment collectors were placed at both stations approximately 1 and 2 km below the surface and 0 7 km above the bottom they collected settling particles during 26 14 day intervals for 376 days with an 20 day hiatus in september october 1989 for changeover of the trap moorings the collection periods of the six traps were synchronized forming a spatio temporal matrix of 156 samples the annual mass flux at about 2 km deep during this experiment was 22 and 27 g m 2 y 1 at the 34 and 48 n stations consisting of biogenic particles with traceable quantities of lithogenic particle flux the spring particle bloom characterized by the sedimentation of particles relatively enriched by norg began in january at the 34 n station and in march at the 48 n station the bloom continued for 4 5 and 3 months and provided 62 and 50 of the annual biogenic particle mass flux at 2 km at the 34 and 48 n stations the surface bloom penetrated to the ocean interior within a few weeks with apparently accelerated settling speed at deeper layers the order of susceptibility of biogenic elements to mineralization while settling in the 0 7 1 km a b water column was from least to most resistant p norg corg si and ca the c n p ratio at 0 7 km a b was 154 18 1 at the 34 n station and 148 18 1 at the 48 n station

balancing rare earth element distributions in the northwestern mediterranean sea abstract elemental concentrations of rare earth elements ree and isotopic compositions of neodymium end have been measured in three water column profiles in the north western mediterranean sea clear enrichments of ree are observed when comparing to adjacent atlantic waters suggesting ree inputs along the circulation in this area for the first time relative proportions of external sources including submarine groundwater discharges sgd have been quantified for the studied area atmospheric deposition is estimated to be the most important external source for all the ree with an average contribution of 44 followed by diffusion from porewaters which provide a 30 dissolved riverine fluxes account for 11 sgd for 10 and dissolution of remobilized surface sediments the remaining 6 mass balances accounting for seawater transport and identified external sources have been delineated for the three main water masses modified atlantic waters levantine intermediate waters and western mediterranean deep waters they show that the balances of ree in this area are dominated by seawater mass mixing superimposed on this hydrography ree vertical profiles are affected by external sources and biogeochemical cycling dissolved ree are correctly balanced in deep waters whereas substantial missing fluxes are identified in the surface and intermediate water masses additional net lree outputs and hree inputs are required in the surface waters while net output fluxes for all the ree are missing at intermediate waters the most likely process suggested here is an active reversible scavenging consistent with a stronger adsorption of lree compared to hree in the particular case of the redox sensitive cerium the most plausible mechanism to explain the net output missing fluxes is ce 3 removal by particle scavenging via oxidation to insoluble ce 4 estimated ce oxidation rates of 0 33 d 1 in surface waters agree well with previously published values exchange fluxes derived from the isotopic nd mass balance indicate higher nd scavenging in surface compared to intermediate waters

diagenetic cycling of arsenic in amazon shelf sediments in order to help elucidate major natural controls on the diagenetic behavior of as vertical profiles of total dissolved and solid phase as were measured in amazon shelf deposits a deltaic region little influenced by human activity arsenic distributions are typically characterized by subsurface porewater maxima and surficial solid phase enrichment maximum porewater as concentrations 2 4 m are an order of magnitude greater than levels reported in most other coastal marine environments and elevated concentrations extend several meters below the sediment surface dissolved as varies inversely with easily leachable as 40 140 nmol g 1 in the solid phase and directly with increases in solid phase fe ii these patterns reflect a strong redox coupling with fe whereby oxidized as is associated with fe oxyhydroxides in surface sediments then subsequently reduced and released upon burial in the extensive suboxic zone upward diffusion and intense physical reworking of sediments presumably releases the dissolved arsenic fraction to the water column or allows for re adsorption in surface sediments arsenic porewater concentrations generally increase away from the river in some cases regular seasonal variations are evident apparently corresponding to nonsteady state ingrowth of diagenetic profiles following extensive sediment reworking during rising river flow the massive cycling of as in amazon shelf sediments is likely due to the combined effects of intense chemical weathering in regions of the drainage basin production of oxides and a turbulent physical regime present on the shelf both of which promote sedimentary cycling of fe and coupled elements during early diagenesis

trace element signatures of chilean upwelling sediments at 36 s abstract with this contribution we continue the discussion on trace element te cycling in chilean upwelling sediments from within and below the oxygen minimum zone omz boning et al 2005 marine geology 220 1 21 low authigenic i e non lithogenic contents of te ag cd mo re and se were interpreted to result from the distinct seasonality in productivity induced organic flux bottom water oxygenation as well as dilution by terrigenous matter while all sediments were reducing enough to become depleted in mn highest enrichments in mo cd and re occur in sediments in contact with the omz here for a meaningful discussion total contents of as bi co cr cu ni pb sb tl v u and zn were corrected for the lithogenic background by determining te al ratios from local river samples the latter showed significantly lower te al ratios than average shale crust or andesite which are classically used for background correction hence the precise assessment of the lithogenic te contribution for the calculation of authigenic te contents allows to examine the source sink relationship of individual authigenic te for chilean sediments four te groups may be distinguished i mo re u and sb likely originate from sea water and accumulate via diffusive supply across the swi ii cd cr cu ni and zn require biologically induced pre concentration within biogenic material iii ag as se tl and v show an intermediate behaviour and iv bi and pb are contributed by anthropogenic activity highest enrichments in ni cu u as and v occur in sediments in contact with the omz the distinct depletion in co along with mn indicates the overall reducing but non sulfidic character of the chilean omz the degree of sedimentary sulfate reduction seems to be the most important control on chilean and peruvian near coastal enrichment of cd mo and u

geochemical and anthropogenic enrichments of mo in sediments from perennially oxic and seasonally anoxic lakes in eastern canada abstract we measured the vertical distributions of mo fe mn sulfide sulfate organic carbon major ions and ph in sediment porewater from one perennially oxic and three seasonally anoxic lacustrine basins in eastern canada as well as those of mo acid volatile sulfide fe mn al organic c 210pb and 137cs in sediment cores from the same sites the only input of anthropogenic mo to these lakes comes from atmospheric deposition the relatively monotonous distribution of mo in the porewater of three seasonally anoxic basins suggests that mo is not redistributed in the sedimentary column during periods of anoxia in contrast porewater mo profiles obtained at three sampling dates in a perennially oxic basin display sharp mo peaks below the sediment water interface indicating redistribution subsequent to deposition modeling of these latter porewater mo profiles with a diagenetic reaction transport equation coupled to comparisons among the various porewater and solid phase profiles reveal that mo is released at 1 2 cm depth as a consequence of the reductive dissolution of fe oxyhydroxides and scavenged both at the vicinity of the sediment water interface by re adsorption onto authigenic fe oxyhydroxides and deeper in the sediments where dissolved sulfide concentrations are higher the estimated rate constant for the adsorption of mo onto fe oxyhydroxides is 36 45 cm3 mol 1 s 1 diagenetic modeling indicates that authigenic mo in sediments of the perennially oxic basin represents about one third of the total solid phase mo in the first cm below the sediment water interface and only one tenth below this horizon if we assume that no authigenic mo is accumulated in the seasonally anoxic lake sediments we conclude that the sediment mo concentrations which are up to 3 16 times higher than the average lithogenic composition depending on the lake are mainly due to atmospheric deposition of anthropogenic mo and not to the formation of authigenic mo phases reconstructed historical records of the atmospheric mo deposition indicate maximum values in the 1970s and 1980s and significant decreases since then emissions to the atmosphere associated with the smelting of non ferrous ores and coal combustion appear to be the most important sources of anthropogenic mo

rare earth element concentrations and nd isotopes in the southeast pacific ocean 1 three vertical profiles of rare earth element concentrations and nd isotopic compositions have been measured in the remote southeast pacific ocean the three stations represent contrasting environments the oligotrophic center of the gyre station gyr the transition zone east of the south tropical front station egy and the peru chile upwelling marked by a pronounced oxygen minimum station upx rare earth concentrations display nutrient like vertical profiles except at upx where surface waters are enriched at this station nd isotopic compositions are clearly more radiogenic than in the open ocean suggesting that boundary exchange process is releasing lithogenic rare earth element from the volcanic andes unexpected radiogenic values end reaching 3 7 are also observed at 2000 m at station gyr in the upper circumpolar deep water that commonly have end values around 6 exchange processes related to hydrothermal activity are suspected to produce this increase in end in the vicinity of the east pacific rise these results provide some guidance for higher resolution studies planned in this region by the international geotraces program

reconstruction of palaeoenvironmental conditions of the vaca muerta formation in the southern part of the neuquen basin tithonian valanginian evidences of initial short lived development of anoxia abstract the vaca muerta formation is a famous source rock being largely present in argentina the formation was examined in the southern part of the neuquen basin through clay mineral assemblage composition as well as organic and inorganic geochemical characteristics in total 259 samples were analyzed on both sides of the huincul arch major e w structure that divided the southern part of the basin into two depocentres south to this structure picun leufu area the total organic carbon content toc can reach 20 but is generally ranging from 0 1 to 6 to the north covunco area average toc does not exceed 0 5 clay mineral assemblages indicate an evolution of the sources of clastic supply through time in response to evolving weathering erosion at the regional scale redox sensitive trace element distribution shows that the particulate iron shuttle process operated with an initially euxinic depositional environment that evolved rapidly to oxygenated seawater and suboxic sediments our results suggest an episodically restricted circulation pattern that occurred at the beginning of the deposition of the vaca muerta formation highest toc content

conjunctive use of spectral gamma ray logs and clay mineralogy in defining late jurassic early cretaceous palaeoclimate change dorset u k abstract detrital clay mineralogy is controlled by weathered source rock climate transport and deposition that in turn influence the spectral gamma ray sgr response of resultant sediments whilst a palaeoclimate signal in clay mineralogy has been established in some ancient successions the sgr response remains contentious largely because the data sets have yet to be collected at the same or appropriate vertical scales to allow comparison in addition the influence of organic matter on sgr is not always considered here we present clay mineralogical total organic carbon toc and sgr analyses from the late jurassic and early cretaceous of the wessex basin a period of previously documented palaeoclimate change the aim of this paper is to estimate the sensitivity of sgr as palaeoclimatic tool sgr and clay mineral data having been collected at the same sample points making this one of the most rigorous comparison of clay mineral and sgr to date overall the correlation between high thorium potassium or thorium uranium and kaolinite associated with a well established palaeoclimate change shows that elevated thorium may be used as a proxy for humid palaeoweathering as suggested by few previous studies

rare earth element fluxes and geochemical budget in the eastern equatorial pacific rare earth element ree patterns and flux measurements of sediment traps sediments and nodules from the eastern tropical pacific demonstrate the dominance of ree supply to the sea floor by particle settling quantitative partitioning of the particle flux reveals that biogenic debris is the major ree carrier in shallow depths however the labile particles are surpassed in importance by alumino silicate particles at greater depths regeneration of biogenic associated ree appears responsible for la ce variations in the particle flux with depth and provides the primary source of ree accreted by nodules

south pacific dissolved nd isotope compositions and rare earth element distributions water mass mixing versus biogeochemical cycling despite its enormous extent and importance for global climate the south pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography here we present the first detailed analysis of dissolved radiogenic nd isotopes end and rare earth elements rees in intermediate and deep waters of the mid latitude 40 s south pacific along a meridional transect between south america and new zealand the goal of our study is to gain better insight into the distribution and mixing of water masses in the south pacific and to evaluate the validity of nd isotopes as a water mass tracer in this remote region of the ocean the results demonstrate that biogeochemical cycling scavenging processes in the eastern equatorial pacific and release of lrees from the sediment clearly influence the distribution of the dissolved ree concentrations at certain locations nevertheless the nd isotope signatures clearly trace water masses including aaiw antarctic intermediate water average end 8 2 0 3 lcdw lower circumpolar deep water average end 8 3 0 3 npdw north pacific deep water average end 5 9 0 3 and the remnants of nadw north atlantic deep water average end 9 7 0 3 filtered water samples taken from the sediment water interface under the deep western boundary current off new zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process these data will serve as a basis for the paleoceanographic application of nd isotopes in the south pacific

the behavior of rare earth elements in seawater precise determination of variations in the north pacific water column abstract we present new highly precise and accurate data for ten rare earth elements rees in two water column profiles and in bottom waters from three additional localities in the north pacific our results presented here and in an earlier publication indicate that the water column in the western north pacific is stratified with respect to the isotopic composition of nd as well as nd la sm nd and er la both the nd isotopic and the ree data show that ree transport is strongly influenced by horizontal advection even in the sluggish circulation of the pacific in general rees increase in concentration with depth at mid latitude they reach a maximum concentration at about 3000 m and then decrease to the bottom at high latitude heavy rees reach a maximum concentration near 3000 m whereas light rees continue to increase in concentration with depth the deep water maximum and bottom water depletion is interpreted as an advective feature resulting from the flow of a lower concentration of rees in antarctic bottom water under a higher concentration of rees in the north pacific concentrations of rees do not show a linear relationship with those of si indicating that the ree cycle is not directly coupled to that of the si cycle ree element ratios i e nd la correlate with hydrographie properties which suggests that major features of the ree patterns may be conserved during lateral transport comparison of our ree data to those in previously published reports on pacific seawater shows that the identification of ree distributions affected by advection is only made possible by the high precision analysis we developed for this study the ce concentration we observe is relatively constant over 200 4500 m depth at both sites where we have complete profiles this unique constancy of ce is in contrast to the contiguous rees la and nd which show substantial concentration variations with depth

a new approach to the nd residence time in the ocean the role of atmospheric inputs concentrations of rare earth elements ree and nd isotopic ratios were analyzed for seawater filtered suspension and sediment trap samples collected in the tropical atlantic ocean eumeli program eutrophic mesotrophic and oligotrophic sites 20 n 18 21 w this is the first ree nd dataset on solution and different sized particles collected at the same site we present direct evidence of the nd isotopic exchange between particulate lithogenic fraction and seawater without significant mass transfer this exchange is probably one of the main factors that simultaneously constrains the nd concentration and isotopic ratio budget we propose a new approach to estimate the residence time of nd in the ocean nd based on isotopic exchange 200 yr nd 1000 yr the exchange requires a partial dissolution of lithogenic nd we estimate that the fraction of soluble nd proportion in atmospheric dust is of the order of 20 based on the isotopic ratios we suggest that the partial dissolution of atmospheric fallout is probably one of the main ree sources of the ocean

the isotopic composition of neodymium in the north pacific abstract we have determined the isotopic composition of neodymium in two water column profiles in the western north pacific and in bottom waters from three other locations in the north pacific the vertical profiles reveal that the water column is stratified with respect to isotopic composition mid depths associated with pacific deep water are uniform having nd 0 3 shallow waters are variable but deep waters are less radiogenic having md 0 4 4 to 5 in the western basin the more negative bottom waters in the western north pacific provide evidence for the advective transport of rare earth elements from antarctic sources to this region bottom waters in the eastern north pacific are more radiogenic nd 0 3 3 to 3 8 indicating very little transport of ree from antarctic sources to this basin overall the isotopic composition of nd in pacific bottom waters appears to be conservative when compared to the silica distribution in spite of evidence for nd removal the findings are generally compatible with other parameters such as temperature salinity and nutrient distributions the presence of nd isotopic signatures associated with antarctic sources in these waters provides evidence for a small component of rare earth elements of north atlantic origin in the bottom waters of the north pacific this is the first tracer evidence to corroborate the suggestion of reid and lynn 1971 that some of the temperature and salinity properties of the deep waters of the north pacific originated in the norwegian and greenland seas

the manganese and iron shuttle in a modern euxinic basin and implications for molybdenum cycling at euxinic ocean margins a meaningful application of mo as a paleo redox proxy requires an understanding of mo cycling in modern reducing environments stagnant euxinic basins such as the black sea are generally regarded as model systems for understanding euxinic systems during early earth history however drawing direct parallels between the black sea and open marine euxinic margins is somewhat complicated by differences in the seawater residence time between these two environments we report sediment and pore water mo u mn and fe data for a euxinic basin with a short seawater residence time the weakly restricted gotland deep in the baltic sea here prolonged periods of euxinia alternate with brief inflow events during which well oxygenated saline water penetrates into the basin during these inflow events dissolved mn and fe that has accumulated within the euxinic deep water can be oxidized and precipitated co variations of mo and u within the sediment suggest that these inflow and oxygenation events may favor mo accumulation in the sediment through adsorption to freshly oxidized mn and fe solid phases once mo is sequestered within the deeper euxinic water and sediments mo retention can be further facilitated by conversion to thiomolybdate species and interactions with organic matter and metal sulfides by comparing our data with those from previous studies where a mn and fe shuttle for mo has been demonstrated we identify two prerequisites for the occurrence of this mechanism first there must be a water column oxic anoxic redox boundary this provides a solubility contrast for mn and fe second the residence time of seawater in the system has to be short weeks to a few years the latter criterion can be met through regular inflow in weakly restricted basins or upwelling in oxygen minimum zones at open marine continental margins based on prior work we suggest that similar conditions to those currently represented by the gotland deep may have prevailed at euxinic ocean margins during the proterozoic a boundary between euxinic and oxic water masses overlying the continental shelf may have resulted in accelerated mo transport through the water column with mn and fe oxyhydr oxides we propose that this mechanism along with mo isotope fractionation during adsorption could contribute to the light mo isotope composition observed in open marine euxinic sediment facies of the proterozoic

rare earth elements of aeolian deposits in northern china and their implications for determining the provenance of dust storms in beijing this paper contributes to a better understanding of the source of dust storms in northern china and the relationship between these sources and other aeolian sediments in this region sediment samples in potential source areas were collected from the hunshandake sandy land heaven desert the loess deposits of the bashang area the mountainous basins and valleys north of beijing and from the badain jaran desert and hulunbaier sandy land fig 1 dust samples were collected in beijing during two dust storms in march 2002 and april 2006 the laboratory methods used in this study included measurements of abundance of trace elements in particular the rare earth elements rees mineral assemblages and grain size the ree contents eu and ce anomalies show clear differences between various deposits provenance is considered to be the key factor influencing ree patterns in the study areas the ree abundances and patterns indicate that the aeolian sand north of beijing such as in the heaven desert is mainly of local origin rather than from desert encroachment from the north the mineral grains carried in dust storms however are highly mixed and may come partly from local sources but mainly from distant desert regions in western china

iron isotope and trace metal records of iron cycling in the proto north atlantic during the cenomanian turonian oceanic anoxic event oae 2 1 the global carbon cycle during the mid cretaceous 125 88 million years ago ma experienced numerous major perturbations linked to increased organic carbon burial under widespread possibly basin scale oxygen deficiency and episodes of euxinia anoxic and h2s containing the largest of these episodes the cenomanian turonian boundary event ca 93 5 ma or oceanic anoxic event oae 2 was marked by pervasive deposition of organic rich laminated black shales in deep waters and in some cases across continental shelves this deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter enrichments of redox sensitive often bioessential trace metals including fe and mo indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production iron enrichments and bulk fe isotope compositions track the sources and sinks of fe in the proto north atlantic at seven localities marked by diverse depositional conditions included are an ancestral mid ocean ridge and euxinic intermittently euxinic and oxic settings across varying paleodepths throughout the basin these data yield evidence for a reactive fe shuttle that likely delivered fe from the shallow shelf to the deep ocean basin as well as 1 hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province s and 2 local scale fe remobilization within the sediment column this study the first to explore fe cycling and enrichment patterns on an ocean scale using iron isotope data demonstrates the complex processes operating on this scale that can mask simple source sink relationships the data imply that the proto north atlantic received elevated fe inputs from several sources e g hydrothermal shuttle and detrital inputs and that the redox state of the basin was not exclusively euxinic suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during oae 2

the trace metal content of recent organic carbon rich sediments implications for cretaceous black shale formation organic carbon rich sediments are enriched in several redox sensitive and stable sulfide forming trace metals tm and form an important sink in global tm cycles in today s ocean such sediments are deposited in coastal upwelling areas like those in the gulf of california off peru or off the namibian coast and euxinic basins like the black sea in an attempt to distinguish both environments by their specific tm patterns some important conclusions may be drawn 1 the tm enrichment seen in both environments broadly is rather similar 2 upwelling sediments are often enriched in cd and p and depleted in co and mn 3 sapropels have a tendency towards higher enrichments in ba and mo s re as cu ni sb and fe reflecting the strong sulfidation in an anoxic water column 4 upwelling systems cover a broad range of environmental settings where the steepness of the slope the proximity of h2s to the sediment seawater interface and the intensity of bio accumulation and regeneration play an important role for tm accumulation 5 the tm content of anoxic basins is mainly controlled by tm availability in the water column and sedimentation rate 6 enhanced bio productivity is the main switch turning an oxygenated into an anoxic environment cretaceous black shales oae 2 exhibit tm signatures of both coastal upwelling areas and sapropels the strong enrichments in cd mo tl v cu ni bi and sb demonstrate that bio accumulation and presence of h2s in the water column and associated sulfidation processes persisted during this time interval in large parts of the proto atlantic the usefulness of ba as a paleoproductivity proxy is obscured by diagenesis the extreme accumulation in ag and zn requires either an additional tm source for instance hydrothermal input or a different tm seawater composition during the cretaceous the geochemical data suggest that the major driving force for the widespread occurrence of c t black shales seems to be the increase in volcanic activity and associated co2 input throughout the cretaceous the ocean atmosphere system operated in a mode different from today during this time interval after conversion of the nutrient co2 into organic matter the system switched back into the normal operational mode

the profile of the rare earth elements in the canada basin arctic ocean we analyzed the dissolved rare earth element ree content of three water column profiles two shelf sites and one deep basin site in the canada basin in order to better constrain the behavior of rees in the arctic ocean dissolved concentrations of the rees in the surface are 1 3 to 1 9 times higher than deep water 500 m concentrations which are constant with depth la 19 23 pm nd 14 17 pm yb 4 0 4 3 pm the dominant source of rees to the surface waters of the canada basin is most likely pacific water flowing through the bering strait and chukchi sea and or the mackenzie river dissolved rees in the intermediate and deep waters are constant and appear to behave conservatively allowing us to investigate this aspect of ree behavior in the oceans calculated deep ocean residence times of the rees in the canada basin range from 450 700 years and match the age of these waters we postulate that these values are likely applicable to global deep ocean reservoirs and that observed deviations from this conservative value can help to constrain non conservative processes acting on the rees this article is protected by copyright all rights reserved

importance of vertical geochemical processes in controlling the oceanic profiles of dissolved rare earth elements in the northeastern indian ocean vertical profiles of dissolved rare earth elements rees were obtained in the bay of bengal and the andaman sea the ree concentrations at various depths in the bay of bengal are the highest in the indian ocean this is attributable ultimately to the large outflow of the ganges brahmaputra and irrawaddy rivers but the dissolved ree flux to surface waters alone cannot explain the large and near constant ree enrichment throughout the entire water column the underlying fan sediments serve as not a source but a sink for dissolved ree iii s absence of excess 228ra in the deep waters suggests that lateral input of dissolved rees from slope sediments is also small in these regions partial 0 3 dissolution of detrital particles which are carried by the rivers and lateral surface currents and subsequently settle through the water column appears to be a predominant source for the dissolved rees vertical profiles showing an almost linear increase with depth are common features for the light and middle rees everywhere but their concentration levels are variable from basin to basin and from element to element this suggests that their oceanic distributions respond quickly to the variation of particle flux and its ree composition through reversible exchange equilibrium with suspended and sinking particles much like the case for th the relative importance of the vertical geochemical processes of reversible scavenging over the horizontal basin scale ocean circulation with passive regeneration like nutrients decreases systematically from the light to the heavy rees using a model the mean oceanic residence times of rees in the bay of bengal are estimated to range from 37 years for ce to 140 1510 years for the strictly trivalent rees in the deep water of the andaman sea isolated from the bay of bengal by the andaman nicobar ridge maximum sill depth of 1800 m the ree concentrations are almost uniform presumably due to rapid vertical mixing the ree iii concentrations are similar to that of 1250 m depth water in the bay of bengal consistent with other oceanographic properties however the ree composition of the deep water appears to be altered slightly by preferential scavenging of the light ree iii at the bottom boundary of the basin

hydrographic conditions of the devono carboniferous north american seaway inferred from sedimentary mo toc relationships abstract deepwater anoxia developed widely within a series of silled intracratonic basins in north america during the middle devonian to early carboniferous but the hydrographic factors contributing to this development are virtually unknown the present study demonstrates that the degree of enrichment of strongly hydrogenous elements such as molybdenum mo in the organic rich shales that accumulated in these basins has the potential to provide information about paleohydrographic conditions most of the study units 49 of 55 exhibit significant positive covariation between elemental mo and toc concentrations yet there is substantial variation in the statistical parameters that define these relationships specifically the regression lines characterizing mo toc covariation have slopes m ranging from 2 to 65 10 4 although a majority of the study units yield m values between 10 and 25 10 4 the parameter m exhibits systematic stratigraphic variation within individual basins and geographic variation among basins suggesting that mo toc relationships were controlled by slowly evolving watermass characteristics of the devono carboniferous north american seaway a recent study of modern anoxic silled basins algeo t j lyons t w 2006 mo total organic carbon covariation in modern anoxic marine environments implications for analysis of paleoredox and paleohydrographic conditions paleoceanography 21 pa1016 doi 10 1029 2004pa001112 demonstrated that m is closely linked to the degree of restriction of the subpycnoclinal watermass as reflected in aqueous mo concentrations mo aq and deepwater renewal times dw these relationships reflect control of sedimentary mo enrichment by both the amount of sedimentary organic matter i e host phase availability and the concentration of aqueous mo i e source ion availability when applied to black shales of the devono carboniferous north american seaway these relationships permit both qualitative and quantitative inferences regarding the degree of restriction of deepwaters in cratonic basins and the evolution of hydrographic conditions through time black shales associated with early stages of sea level rise commonly exhibit low m values 1000 yr higher sea level stands resulted in more open marine conditions and enhanced deepwater renewal leading to deposition of black shales with m values up to 65 equivalent to mo aq 70 of the normal seawater concentration and dw

sedimentology and sequence stratigraphy of a tithonian valanginian carbonate ramp vaca muerta formation a misunderstood exceptional source rock in the southern mendoza area of the neuquen basin argentina abstract the vaca muerta formation early tithonian early valanginian is a rhythmic succession of marls and limestones cropping out in the neuquen basin west central argentina this lithostratigraphic unit was traditionally interpreted as basinal to slope deposits detailed facies analysis allows to differentiate seven facies associations representing basinal to middle ramp facies of a homoclinal ramp system prograding westward from the eastern margin and slope facies attributed to a distally steepened ramp system that progrades eastward from the andean volcanic arc in the west two sequence hierarchies are recognized five third order depositional sequences and fifteen fourth order high frequency sequences fluctuations in organic matter content within the vaca muerta formation suggest relationship with depositional sequences finding the highest values associated with transgressive system tracts this work represents an important advance in the understanding of the sedimentary and stratigraphic evolution of this exceptional unconventional reservoir our sequence stratigraphic approach contributes to the understanding of the relationship between organic matter facies and sea level changes

rare earth elements in foraminifera tests abstract the concentrations of nine rare earth elements ree la ce nd sm eu gd dy er and yb have been determined in mixed species assemblages of foraminifera tests taken from atlantic ocean sediment core tops reductive cleaning techniques have revealed that ree are present in three phases in foraminifera tests collected from sea floor sediments ree included in the foraminiferal calcite matrix termed lattice ree ree associated with an authigenic femn rich phase adsorbed onto the surface of the test following the death of the organism termed coating ree and ree associated with alumino silicate detritus termed detrital ree which commonly infills the test chambers after burial in the sediment the concentrations of ree in the nondetrital lattice plus coating and lattice phases have been measured in this study approximately 90 of the ree measured in the non detrital phase reside in the coating phase the remainder being present in the lattice phase these data have been used to investigate the relationship between the distribution of dissolved ree in the ocean and in the coating and lattice phases in addition to the ree the concentrations of mn fe cu al and po4 have been measured as an aid to characterisation of the various phases

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

rare earth elements rees in the tropical south atlantic and quantitative deconvolution of their non conservative behavior this study presents new concentration measurements of dissolved rare earth elements drees along a full depth east west section across the tropical south atlantic 12 s and uses these data to investigate the oceanic cycling of the rees enrichment of drees associated with the redox cycling of fe mn oxides is observed in the oxygen minimum zone omz off the african shelf for deeper waters a multi parameter mixing model was developed to deconvolve the relative importance of physical transport i e water mass mixing from biogeochemical controls on the dree distribution in the deep atlantic this approach enables chemical processes involved in ree cycling not apparent from the measurements alone to be distinguished and quantified results show that the measured dree concentrations below 1000 m are dominantly controlled 75 by preformed ree concentrations resulting from water mass mixing this result indicates that the linear correlation between drees and dissolved si observed in atlantic deep waters results from the dominantly conservative behavior of these tracers rather than from similar chemical processes influencing both drees and si minor addition of drees 10 of dnd and 5 of dyb is observed in the deep 4000 m brazil basin resulting from either remineralization of particles in situ or along the flow path greater addition of drees up to 25 for dnd and 20 for dyb is found at 1500 m and below 4000 m in the angola basin near the african continental margin cerium anomalies suggest that different sources are responsible for these dree addition plumes the 1500 m excess is most likely attributed to dree release from fe oxides whereas the 4000 m excess may be due to remineralization of calcite higher particulate fluxes and a more sluggish ocean circulation in the angola basin may explain why the dree excesses in this basin are significantly higher than that observed in the brazil basin hydrothermal venting over the mid atlantic ridge acts as a regional net sink for light rees but has little influence on the net budget of heavy rees the combination of dense ree measurements with water mass deconvolution is shown to provide quantitative assessment of the relative roles of physical and biogeochemical processes in the oceanic cycling of rees

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

study on vertical profiles of rare earth elements by using an ocean general circulation model 1 observed vertical profiles of rare earth elements rees in the north pacific ocean show a systematic change from lighter to heavier rees their source and sink consist of external fluxes coming from the surface and the bottom of the ocean and internal recycling within the ocean in order to evaluate the role of each source and sink in controlling the vertical profiles of rees we conduct numerical simulations of rees by using an ocean general circulation model these simulations demonstrate that the shape of their vertical profiles is not directly related to the external sources from river runoff atmospheric dust deposition and coastal regions but is sensitive to the internal recycling processes within the ocean nutrient like treatment where rees are removed at the surface and released in the deep ocean is suitable for simulating the vertical profiles of lighter rees but not for heavier rees when the irreversible scavenging is considered as a sink term and particle dissolution is taken into consideration as a source term the vertical profiles of heavier rees can be reproduced but those of lighter rees cannot the observed difference in the vertical profiles among rees can be reproduced only when the reversible scavenging process is incorporated into the model only the reversible scavenging process accounts for the observed vertical profiles of different rees in comprehensive manner

dissolved rare earth elements and hydrography in the sulu sea because most southeast asian basins are flushed rapidly by waters from the western pacific the effects of respiration and silica dissolution within those basins are hardly discernible based on general hydrographic and geochemical observations broecker et al 1987 however a different situation is expected for the sulu sea because its deep water is isolated from other deep sea basins by shallow sills of 400 m depth hence any heterogeneity of elemental distributions within the basin must be ascribed to vertical physical and biogeochemical processes we have obtained detailed vertical profiles of dissolved rare earth elements rees together with conductivity temperature depth ctd and hydrographic measurements in the sulu sea during the 1996 97 hakuho maru cruise vertical profiles clearly indicate that the ree iii s are enriched in the deep water due to regeneration and are involved in vertical biogeochemical cycling the light ree iii s la pr and nd showed a subsurface maximum at 500 m and a minimum 1500 m in depth none of the hydrographic properties or nutrients shows such features therefore the ree iii s and their elemental ratios may be useful as tracers of water masses the relationship of ree iii s versus dissolved si suggests that the ree iii s are regenerated in a delayed fashion relative to si and it is likely that their dissolution largely occurs at the bottom interface the mean residence time of the deep water is estimated to be 300 6 150 yr consequently the calculated benthic flux of ree iii s becomes roughly comparable with the river and atmospheric fluxes because of oxidation to ce iv the ce profile shows a decrease from 6 pmol kg at the surface to a constant value at 3 9 pmol kg below 1500 m unlike the other rees the rees in the sulu sea are enriched in the middle rees and ce relative to those of the north pacific deep water and must derive from local sources around the sulu sea copyright 1999 elsevier science ltd

composition of rare earth elements in settling particles collected in the highly productive north pacific ocean and bering sea implications for siliceous matter dissolution kinetics and formation of two ree enriched phases abstract settling particles were sampled monthly for 1 year using an automated time series sediment trap positioned at similar depths at two sites of high diatomaceous productivity in the north pacific ocean and bering sea the particles were analyzed for rare earth elements rees by inductively coupled plasma mass spectrometry icp ms with and without chemical treatment of the bulk samples to isolate siliceous fractions the ree composition of the bulk samples is explained largely by the contribution of two distinct components i carbonate with a higher ree concentration a negative ce anomaly and lighter ree lree enrichment ii opal with a lower ree concentration a weaker negative ce anomaly and heavier ree hree enrichment the siliceous fractions of settling particles are characterized by high si al ratios 30 190 reflecting high diatom productivity at the studied sites the la al ratio of the siliceous fraction is close to that of the upper crust but the lu al and lu la ratios are significantly higher than those of the upper crust or airborne particles indicating the presence of excess hrees in the siliceous fraction diatoms are believed to be important carriers of hrees the ce anomaly eu anomaly slope of the ree pattern and ree of the siliceous fraction vary exponentially with decreasing total mass flux they can be well reproduced according to the differential dissolution kinetics of elements in the order of ce

secular change in northwestern tethyan water mass oxygenation during the late hauterivian early aptian abstract the mesozoic is punctuated by several extreme episodes of oxygen drawdown in the ocean known as oceanic anoxic events oae beside these discrete events little is however known about longer term oxygen level fluctuations and their controls a high resolution dataset of rare earth elements ree content in carbonate deposited in the vocontian basin se france has allowed to survey the evolution of the cerium anomaly ce ce during part of the early cretaceous latest hauterivian early aptian this ratio is used as a proxy for the degree of oceanic oxygenation the cerium anomaly is compared to the coeval evolution of relative sea level organic rich occurrences and nutrient level proxies in order to infer a cause and consequence relationship between these parameters and the evolution in sea water oxygenation the long term evolution of the cerium anomaly shows that northwestern tethyan water masses have evolved from less oxygenated during the latest hauterivian early barremian interval to more oxygenated during the late barremian earliest aptian time before being strongly oxygen depleted during the early aptian oae 1a time interval this trend is correlated with both the long term trend in nutrient levels as well as with the frequency of organic rich layers within the rock record on a medium term scale sub stage level there is a good correlation between the cerium anomaly and tectono eustatism as deduced by the mn content of the basinal carbonate and sequence stratigraphic observation on surrounding shallow water areas this suggests that sea level changes by altering ocean stratification and currents as well as modulating the amount of nutrient delivered from the continent exert control on oceanic oxygenation via changes in primary productivity

accumulation of organic matter in the kimmeridge clay formation kcf an update fossilisation model for marine petroleum source rocks abstract a model for marine source rocks based on previous microtextural and molecular characterisation of the immature organic matter from the kcf uk is developed illustrating the relationship between the type of primary producers the nature of organic matter metabolisable or bioresistant delivered to the sedimentary environment and the mechanisms of organic matter fossilisation the fossilisation occurs because one of the following factors prevails a the inherited bioresistant character of the initial organic matter in the case of i a selective preservation sensustricto when both the biological structure and the molecular composition are well preserved and ii a re organisation of resistant bio macromolecules selectively preserved when only the molecular composition is conserved b the acquisition of bioresistance as in the case of iii natural vulcanisation which produces a homogeneous and nanoscopically amorphous organic matter the latter is hydrogen rich and its genesis depends on the rate of delivery of metabolisable organic matter to the oxic anoxic boundary this is determined by primary productivity controlled sinking rates and as a consequence by the occurrence in bottom waters of conditions promoting a prolific growth of sulphate reducers along with a somewhat limited supply of iron so that h 2 s is not entirely trapped as pyrite c the accumulation of hydrogen rich organic matter in such source rocks is not only due to the phytoplanktonic and micro algal origin of natural bio macromolecules but also to sulphate reduction which protects a part of the oil potential of deposited organic matter

arsenic in framboidal pyrite from recent sediments of a shallow water lagoon of the baltic sea arsenic is a redox sensitive element of environmental relevance and often enriched in iron sulphides because sediments from the achterwasser lagoon a part of the estuarine system of the river oder south west baltic sea show unexpectedly high pyrite concentrations of up to 7 5 wt they were used to investigate the influence of authigenic pyrite on the mobility and burial of as in the coastal environment micro x ray fluorescence measurements of 106 micrometre sized pyrite framboids from the anoxic sediments show highly variable as concentrations ranging from 6 to 1142 g g 1 even within a 1 cm thick layer the as concentration of different framboids varies greatly and no clear depth trend is visible throughout the 50 cm long sediment core pyrite can account for 9 to 55 average 22 of the total as budget of the sediments and the degree of trace metalloid pyritization for as ranges from 26 to 61 indicating that authigenic pyrite formation is an important process in the geochemical cycling of as in coastal sediments high resolution micro x ray fluorescence mapping of single pyrite grains shows that as is distributed inhomogeneously within larger framboids suggesting changing pore water composition during pyrite growth x ray absorption near edge structure spectra indicate that as is usually present as as i substituting s in the pyrite lattice however in samples close to the sediment water interface a considerable part of as is in higher valence states iii v this can be explained by frequent re suspension of the surficial sediments to the oxic water column due to wave action and subsequent re deposition leading to the adsorption of as oxyanions onto pyrite although reduced as i becomes more important in the deeper samples reflecting decreasing redox potential and a longer time since deposition the occurrence of oxidized as species asiii asv in pyrite in the anoxic part of the sediment suggests formation under dysoxic conditions

pyrite geochemistry in the toarcian posidonia shale of south west germany evidence for contrasting trace element patterns of diagenetic and syngenetic pyrites authigenic pyrite grains from a section of the lower toarcian posidonia shale were analysed for their trace element contents and sulphur isotope compositions the resulting data are used to evaluate the relationship between depositional conditions and pyrite trace element composition by using factor analysis trace elements in pyrite may be assigned to four groups i heavy metals including cu ni co pb bi and tl ii oxyanionic elements as mo and sb iii elements partitioned in sub microscopic sphalerite inclusions zn and cd and iv elements related to organic or silicate impurities ga and v results indicate that trace element contents in pyrite depend on the site and mechanism of pyrite formation with characteristic features being observed for diagenetic and syngenetic pyrites diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content and the degree of pyritization of these elements increases with increasing oxygen deficiency similar to the degree of pyritization of reactive fe the highest gradient in the increase of the degree of trace element pyritization with bottom water oxygenation was found for the elements ni cu mo as tl in contrast syngenetic pyrite formed within a euxinic water column typically is enriched in as mo and sb but is low in heavy metals and the geochemical variation reflects changes in sea water composition

a new particulate mn fe p shuttle at the redoxcline of anoxic basins abstract pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters intense element cycling favoured by elevated microbial activity causes steep gradients of physico chemical parameters nutrients and redox sensitive trace metals this study presents a conceptual model for authigenic particle formation at pelagic redoxclines which is based on the tight coupling of mn fe and p cycles besides the well known occurrence of mn oxides textural sem edx and geochemical icp oes icp ms analyses of particles from the redoxclines of the black sea and the baltic sea gotland basin landsort deep evidence the existence of earlier postulated fe oxyhydroxo phosphates and emphasize mixed phases consisting of mn oxides and fe oxyhydroxo phosphates as a new solid species most of the analyzed particles are star shaped of about 5 m in size and occur as single particles or aggregates without any morphological differences between mn oxides fe oxyhydroxo phosphates and mixed phases throughout the redoxcline these minerals show a general succession with maximum abundance of mn oxides above the redoxcline followed by mixed phases and almost pure fe phosphates within and below the redoxcline respectively molar fe p ratios of single particles argue against the formation of known pure fe phosphates like vivianite or strengite at the lower end of the redox transition zone but are consistent with recent experimental findings for colloidal p bearing hydrous ferric oxides moreover morphological similarities suggest the formation of irregular fe oxyhydroxo coatings due to oxidation of upward diffusing fe 2 by oxygen and stepwise replacement of mn iv by fe iii on sinking mno x particles followed by immediate adsorption or even co precipitation of phosphate batch type experiments using biogenic mno x particles demonstrate the efficient potential of fe 2 oxidation by sinking mno x particles when entering sulfidic waters mno x particles are progressively reduced leading to an increasing relative abundance of fe and p rich particles in deeper parts of the water column these particles are also reductively dissolved thereby releasing fe 2 and phosphate to the water column this mn fe p shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales furthermore the particulate mn fe p shuttle must have played an important role for the cycling of p and certain trace metals in ancient ocean basins e g during certain periods of cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic anoxic interfaces of aquatic ecosystems

the incorporation of rare earth elements in modern coral we report measurements of rare earth elements rees which show that these trace elements are being incorporated in modern coral in proportion to their seawater concentrations four bermuda north rock coral species diploria strigosa diploria labyrinthiformis montastrea annularis and porites astreoides and two tarawa atoll samples of the species hydnophora microconos were analyzed by ti idms following cleaning techniques to isolate the lattice bound rees based on the replicate analyses of the same piece of diploria strigosa excellent reproducibility was achieved the ree ca ratios 0 1 3 nmol mol of the bermuda and tarawa corals are similar to those of cd ca the trace metal with the lowest seawater concentration used in coral studies with the exception of ce the distribution coefficients e g dnd nd coral nd seawater ca seawater ca coral between bermuda coral lattice and sargasso seawater have fairly flat patterns across the ree series the values of d range from 1 to 3 like those reported for other trace elements in corals this suggests but does not prove that rees are incorporated in the aragonite lattice of these corals the shale normalized ree patterns of the tarawa corals also have seawater like distributions however no local seawater data are available to calculate values of d two bermuda species d labyrinthiformis and p astreoides have values of d for ce that are high with respect to the d values of la and nd implying that there is preferential uptake of ce into the lattice this may be related to the fact that ce is the only ree with an active redox chemistry in seawater there is considerable interest in using the chemical and isotopic composition of coral as indicators of climatic variations the combination of ree ca ratios and neodymium isotopic composition of coral has the potential to help understand important natural processes a primary application could be directed toward a tracer for river water discharge in tropical regions and by inference a proxy for rainfall climate variation and weathering history this application would exploit the fractionated composition of rees in river water as a terrigenous signature in coastal corals

from the subtropics to the central equatorial pacific ocean neodymium isotopic composition and rare earth element concentration variations 1 neodymium isotopic compositions end and rare earth element ree concentrations were measured for filtered surface to deep waters 112 samples in the southern tropical pacific the relatively detailed picture of these tracer distributions allowed us to refine the areas where oceanic end variations occur end values increase for most of the water masses flowing from samoa to the solomon sea and in the papua new guinea png area as already observed furthermore water masses arriving from the eastern equatorial pacific 200 550 m depth also revealed radiogenic values possibly acquired in the vicinity of the south american coasts and galapagos islands these end variations affect the whole water column the most likely process causing such variations is boundary exchange between the numerous radiogenic slopes margins located in this area and seawater flowing past dissolution of atmospheric deposition and or diffuse streaming of volcanic ash are also suggested to explain the radiogenic end observed at the surface in the png area interestingly a positive europium eu anomaly characterizes the normalized ree patterns of most of the studied water masses this anomaly is consistent with the ree patterns of sediment and rock samples that are potential sources for the local waters such consistency reinforces the hypothesis that lithogenic sources play a major role in the oceanic ree budget thanks to boundary exchange the data set presented here is a good basis for further sampling that will be realized in the framework of the ongoing geotraces program www geotraces org

variation of the distribution coefficients of rare earth elements in modern coral lattices species and site dependencies abstract rare earth element ree concentrations in the carbonate lattice of four species of coral have been analyzed and compared with the dissolved ree in ambient seawaters the corals were from two areas of different salinity marine 34 34 5 and bay 33 34 the measurement of ree in coral was carried out with inductively coupled plasma mass spectrometry icp ms after meticulous washing of coral samples digestion with acetic acid and preconcentration of ree the concentrations of ree in the two ambient seawaters were quite different being ten times higher in the bay area and enriched in light ree however the average distribution coefficients d s were almost identical in the two areas substantial distribution coefficient differences were observed among the four coral species and the magnitude of inter species variation in d was also species dependent theoretical calculations imply that ph variation could cause variations in d large enough to account for the small differences between the two areas

provenance of dust in the pacific ocean eolian dust preserved in deep sea sediment cores provides a valuable indicator of past atmospheric circulation and continental paleoclimate in order to identify the provenance of eolian dust nd and sr isotopic compositions and rb sr and rare earth element ree concentrations have been determined for the silicate fractions of deep sea sediments from the north and central pacific ocean different regions of the pacific ocean are characterized by distinct air borne inputs producing a large range in end 10 to 1 stsr 86sr 0 705 0 721 la yb 5 15 eun eu 0 6 1 0 and sr nd 4 33 the average nd isotopic composition of pacific deep sea sediments eno 6 is more radiogenic than the average from the atlantic ena 8 in contrast the average 1475m 14and ratio for pacific sediments 0 114 is identical to that of atlantic sediments and to that of global average riverine suspended material the values of ena and 147sm 144nd are positively correlated for the pacific samples but negatively correlated for atlantic samples reflecting a fundamental difference between the dominant components in the end members with radiogenic nd island arc components in the pacific and lree enriched intraplate ocean island components in the atlantic samples from the north central pacific have distinctive unradiogenic end values of 10 87sr 86sr 0 715 high la yb 12 and low eun eu 0 6 and sr nd 3 6 these data are virtually identical to the values for loess from asia and endorse the use of these sediments as indicators of asian paleoclimate and paleowind directions island arc contributions appear to dominate in the northwest pacific resulting in higher end 1 to 1 and lower 87sr 86sr 0 705 and la yb 5 sediments from the eastern pacific tend to have intermediate sr and nd isotopic compositions but regionally variable sr nd and ree patterns they appear to be derived from the west margin of the north and south american continents rather than from asia our results confirm that dust provenance can be constrained by isotopic and geochemical analyses which will facilitate reconstructions of past atmospheric circulation and continental paleoclimate

rare earth elements and yttrium in seawater icp ms determinations in the east caroline coral sea and south fiji basins of the western south pacific ocean abstract using inductively coupled plasma mass spectrometry icp ms vertical profiles of yttrium and all the rare earth elements rees in seawater were obtained at three locations in the western south pacific the east caroline coral sea and south fiji basins based on the data we have analyzed the inter ree iii relationships and found that ree iii s heavier than dy and particularly close neighbors show strong coherencies in their oceanic behavior considering that the heavy ree iii s are less particle reactive than the light and middle ree iii s and that they have very tight correlations with regressions passing almost through the origin the neighboring element ratios of the heavy ree iii s behave virtually conservatively and are suitable as tracers of water masses the dy ho er system is practically good because its dynamic range signal to noise ratio is large in the ocean the highest ho dy ratios 0 31 are found in intermediate and deep waters throughout the western south pacific which overlie the antarctic bottom water with a low ho dy ratio 0 27 these high ho dy waters are probably formed in the polar and subantarctic frontal zone and advect northward ree iii data provide better insights into the deep water recirculation in the south pacific than those discussed based upon the regular oceanographic properties alone

rare earth distributions with a positive ce anomaly in the western north atlantic ocean from the vertical distributions of the rare earth elements ree in the sargasso sea we now report the first profiles of pr tb ho tm and lu in seawater together with profiles for la ce sm eu and yb the first observations of positive ce anomalies in seawater are ascribed to reducing inshore sediments as a source for ce ref 1 all vertical profiles are consistent with adsorption of trivalent rare earths by settling particles possibly siliceous or calcareous followed by their release at or near the sea floor on dissolution of the carriers the very different ce profile demonstrates the additional effects of oxidation reduction reactions

rare earth elements of sinking particulate matter in the japan trench abstract settling particles were collected with time series sediment traps at four depths 1174 m 3680 m 5687 m and 8688 m moored at the deepest site water depth 9200 m of the japan trench for the period from march 5 1991 to march 2 1992 the composition of rare earth elements rees in the sinking particles selected for four seasons were measured to investigate the ree fractionation during scavenging and settling transport through the water column the ree particle associations were also investigated by sequential digestion with three chemical treatments acetic acid mild hcl hno3 and hf hno3 hclo4 the measured vertical particulate flux increased with depth suggesting that there is a significant addition of particles at least to the deeper traps from horizontal sources no systematic variation was observed in the ree concentration in the particles with respect to depth and season the shale normalized ree data show either flat or slightly heavy ree enriched patterns with a middle ree enrichment in which the maximum is usually centred at gd but sometimes at eu and a significantly positive ce anomaly the chemical digestion experiments indicated characteristic patterns for shale normalized rees the acetic acid leach showed a marked middle ree enriched pattern with a maximum at eu and distinctively negative ce anomaly the mild hcl hno3 leach had a middle ree enriched pattern with a maximum at gd but roughly no ce anomaly the residue showed a rather flat ree pattern with a marked positive ce and often middle ree enrichment with a maximum at gd these results are compared with those reported previously for sinking and suspended particles in other parts of the oceans it is suggested that rees adsorbed on the suspended particles are altered into some refractory phases prior to or during transport by settling the possibility exists that authigenic barite formed in the microenvironment around aggregates may effectively coprecipitate the rees attracted to the particle surfaces

diagenetic uptake of rare earth elements by bioapatite with an example from lower triassic conodonts of south china abstract the distribution patterns of rare earth elements rees are frequently used as proxies for ancient seawater chemistry or paleomarine environmental conditions however recent work has shown that diagenesis can lead to remobilization and inter elemental fractionation of rees and that these effects often occur in conjunction with redox reactions in sediment porewaters here we review existing literature on the diagenetic fluxes of rees in marine sediments and porewaters in order to systematize existing knowledge on this subject rees undergo significant redistribution among sediment phases during both early and late diagenesis as a consequence of adsorption and desorption processes remobilization of rees commonly leads to inter elemental fractionation variously leading to enrichment or depletion of the light middle or heavy ree fractions further ree remobilization can be facilitated by redox changes e g through reductive dissolution of host phases in suboxic and anoxic porewaters characteristic ree distribution patterns develop through these processes 1 a flat distribution signifying predominantly terrigenous siliciclastic influence 2 a middle ree bulge probably due to adsorption of light and heavy rees to mn and fe oxyhydroxides respectively and 3 heavy ree enrichment indicative of hydrogenous seawater influence note all patterns in this paper are normalized to the ree composition of average upper continental crust or ucc in the second part of this study we undertake an analysis of the ree distributions in conodonts and whole rock samples from west pingdingshan a permian triassic boundary section in south china using ree th and y ho ratios we show that almost all of the conodont samples have a strong diagenetic overprint and that the hydrogenous ree fraction is small and not isolatable furthermore the conodonts contain two diagenetic ree components one characterized by low ree 100 300 ppm high ree th ratios 1000 strong middle ree enrichment and eu eu ratios of 1 5 2 0 and the second by high ree 300 2000 ppm low ree th ratios 20 30 little or no middle ree enrichment and eu eu ratios of 1 0 the first component exhibits a pronounced middle ree bulge that represents an early diagenetic signature associated with suboxic conditions possibly related to adsorption of rees onto fe mn oxyhydroxides in the shallow subsurface environment the second component shows a flat ree distribution that is similar to both our whole rock samples and average ucc indicating derivation from rees released from detrital siliciclastics e g clay minerals probably at a range of burial depths from shallow to deep failure of the conodont samples to yield an isolatable hydrogenous component demonstrates that bioapatite does not always preserve a primary marine ree signature given that bioapatite rees have been widely used for this purpose often on the assumption of minimal or no diagenetic influence our findings are likely to necessitate a re evaluation of the results of many earlier studies in general we counsel caution in inferring a hydrogenous origin for rees in bioapatite owing to frequent diagenetic alteration of ree distributions

antimony and arsenic biogeochemistry in the western atlantic ocean the subtropical to equatorial atlantic ocean provides a unique regime in which one can examine the biogeochemical cycles of antimony and arsenic in particular this region is strongly affected by inputs from the amazon river and dust from north africa at the surface and horizontal transport at depth from highlatitude northern e g north atlantic deep water and southern waters e g antarctic bottom and intermediate waters as a part of the 1996 intergovernmental oceanographic commission s contaminant baseline survey data for dissolved as iii v as iii mono and dimethyl arsenic sb iii v sb iii and monomethyl antimony were obtained at six vertical profile stations and 44 sites alongthe 11 000 km transect from montevideo uruguay to bridgetown barbados the arsenic results were similar to those in other oceans with moderate surface depletion deep water enrichment a predominance of arsenate 85 as v and methylated arsenic species and as iii in surface waters that are likely a result of phytoplankton conversions to mitigate arsenate stress toxicity perhaps the most significant discovery in the arsenic results was the extremely low concentrations in the amazon plume as low as 9 8 nmol l that appear to extend for considerable distances offshore in the equatorial region the very low concentration of inorganic arsenic in the amazon river 2 8 nmol l about half those in most rivers is probably the result of intense iron oxyhydroxide scavenging dissolved antimony was also primarily in the pentavalent state 95 antimonate but sb iii and monomethyl antimony were only detected in surface waters and displayed no correlations with biotic tracers such as nutrients and chlorophyll a unlike as iii v s nutrient type vertical profiles sb iii v displayed surface maxima and decreased into the deep waters exhibitingthe behavior of a scavenged element with a strongatmospheric input while surface water sb had a slight correlation with dissolved al it is likely that atmospheric sb is delivered with combustion byproducts and not from mineral aerosols in the amazon plume antimony concentrations dropped substantially and an amazon river sample had a concentration 0 25 nmol l that was less than one fourth those found in other major rivers usingthese river data and estimates of atmospheric fluxes based on

early diagenesis of redox sensitive trace metals in the peru upwelling area response to enso related oxygen fluctuations in the water column pore water and solid phase data for redox sensitive metals mn fe v mo and u were collected on a transect across the peru upwelling area 11 s at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from 0 to 93 m by comparing authigenic mass accumulation rates and diffusive benthic fluxes we evaluate the respective mechanisms of trace metal accumulation retention and remobilization across the oxygen minimum zone omz and with respect to oxygen fluctuations in the water column related to the el nino southern oscillation enso sediments within the permanent omz are characterized by diffusive uptake and authigenic fixation of u v and mo as well as diffusive loss of mn and fe across the benthic boundary some of the dissolved mn and fe in the water column re precipitate at the oxycline and shuttle particle reactive trace metals to the sediment surface at the lower and upper boundary of the omz at the lower boundary pore waters are not sufficiently sulfidic as to enable an efficient authigenic v and mo fixation as a consequence sediments below the omz are preferentially enriched in u which is delivered via both in situ pre cipitation and lateral supply of u rich phosphorites from further upslope trace metal cycling on the peruvian shelf is strongly affected by enso related oxygen fluctuations in bottom water during periods of shelf oxygenation surface sediments receive particulate v and mo with metal oxyhydr oxides that derive from both terrigenous sources and precipitation at the retreating oxycline after the recurrence of anoxic conditions metal oxyhydr oxides are reductively dissolved and the hereby liberated v and mo are authigenically removed this alternation between supply of particle reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of v and mo compared to u on the peruvian shelf the decoupling of v mo and u accumulation is further accentuated by the varying susceptibility to re oxidation of the different authigenic metal phases while authigenic u and v are readily re oxidized and recycled during periods of shelf oxygenation the sequestration of mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions our findings reveal that redox sensitive trace metals respond in specific manner to short term oxygen fluctuations in the water column the relative enrichment patterns identified might be useful for the reconstruction of past omz extension and large scale redox oscillations in the geological record

dissolved rare earth elements distribution in the solomon sea abstract trace elements and isotopes teis were measured as part of the geotraces pandora cruise july august 2012 r v l atalante among them rare earth elements rees as pertinent tracers of land ocean inputs and water mass transformations this work discusses results of 19 dissolved ree dree profiles measured using a trispike method in the coral sea and inside and at the exits of the solomon sea a semi enclosed sea with complex topography and straits overall drees except the insoluble ce show nutrient like profiles i e depleted at the surface and enriched at depth illustrative nd concentrations range from 5 pmol kg at the surface to 25 pmol kg at 5000 m depth however local dree enrichments are observed mostly in the straits indispensable solomon and vitiaz straits and along the island coasts a box model allows calculating and discussing the fate of the drees in the different water layers flowing through the solomon sea finally subtle variations revealed by la ce eu anomalies and the normalized light versus heavy ree ratio expressed as ndn ybn allows the identification of specific mechanisms affecting the distribution of the different drees the positive eu anomaly observed in the surface layers reflects the basaltic origin of external inputs consistent with the intensive weathering and or volcanic activity affecting the surrounding islands these data also confirm that the distributions of heavy drees like yb are better correlated to the dsi concentrations than that of the other rees this article is part of a special issue entitled cycles of trace elements and isotopes in the ocean geotraces and beyond edited by tim m conway tristan horner yves plancherel and aridane g gonzalez

rare earth element ree silicic acid complexes in seawater to explain the incorporation of rees in opal and the leftover rees in surface water new interpretation of dissolved ree distribution profiles in light of a new finding that diatom opal carries rare earth elements rees at an amount exceeding that which would explain the rees si ratio in open ocean columns the complex formation of rees with silicic acid and subsequent incorporation of the complex into diatom opal has been explored reported complex formation constants of euh3sio42 and an empirical linear relationship of the constants with hydrolysis constants were employed in the species calculation the calculation reveals that ree silicic acid complex is the dominant species of dissolved rees especially in deep layers of the pacific and the atlantic oceans the degree of complex formation varies depending on dissolved silica concentration ph and pco2 assuming that only rees in the form of reeh3sio42 which is diffused advected from deep water to surface water together with dissolved silica are incorporated into diatom opal a ree incorporation theory has been developed the theory links the intake of rees and silica by diatoms in surface water and their concentrations in deep water and presents two distribution coefficients ds of rees in diatom opal conventional d against surface water and columnar d against deep water as functions of ph and dissolved silica concentration the theory successfully explains the significant ree concentration level leftover rees in the surface water of the oceans and reproduces a concentration of rees in diatom opal that is consistent with that observed in diatom opal in the north pacific ocean the ree composition of oceanic deep water is largely explained by two fractionation processes ree incorporation into opal and carbonate oxide scavenging of rees

in situ settling behavior of marine snow1 the settling velocities of undisturbed macroscopic aggregates known as marine snow were measured with scuba in surface waters off southern california and analyzed as a function of aggregate size mass and density the mean settling velocity was 74f39 m d l for aggregates ranging from 2 4 to 75 mm in maximum length sinking rates in the field varied exponentially with aggregate size and dry weight and were consistently up to four times slower than rates measured in the laboratory the excess densities of the 80 aggregates examined were calculated from volume and dry weight and ranged over four orders of magnitude with a median of 1 4 x 1o 4 g cm 3 aggregates of marine snow sank more slowly than predicted for either solid or porous spheres of equivalent volume and density although their velocities were within the range expected for equivalent sinking prolate ellipsoids no relationships between settling velocity and either excess density or particle shape were found drag coefficients of marine snow were also higher than predicted by theory for spheres of equivalent volume and density these deviations from theoretical expectations may be partially explained by errors in the estimation of the excess densities of aggregates variability in the densities of the heterogeneous primary particles comprising marine snow fecal pellets claymineral particlcs phytoplankton molts etc and the potential for buoyancy regulation by individual phytoplankton cells inhabiting aggregates make determination of excess density especially

biogeochemical implications from dissolved rare earth element and nd isotope distributions in the gulf of alaska dissolved rare earth element ree concentrations and nd isotope compositions were measured for surface waters and full water column profiles of the gulf of alaska goa and compared to water mass properties and circulation in order to better understand the mechanisms controlling the input and transport of rees in the ocean the rees display a typical open ocean range of concentrations i e la 12 66 pm lu 0 2 2 5 pm and depth distributions i e surface ocean depletion and enrichment with water depth nd isotope signatures are highly radiogenic as expected for the north pacific margin ranging from 3 8 to 0 2 epsilon nd the most radiogenic values were found in the coastal waters but also in the cores of eddies indicating efficient export of rees from the margins and across the mixed layer this is the first time that distinct nd isotope distributions in near surface waters can be directly assigned to offshore eddy transport a distinct mid depth similar to 2200 m nd isotope signal was found that most likely reflects advection of a water mass that formed through past down welling in the northern pacific subsurface nd isotope compositions appear to behave conservatively and can be explained through a ree distribution model proposed here this model is based on multivariate analysis of the rees and invokes two distinct pools of dissolved rees a passive pool complexed by carbonate ions and a bio reactive pool that is microbially manipulated the latter pool is only significant in the upper water column and most likely reflects the indirect effects of microbial cycling of iron our model of the open ocean ree distribution contributes to explaining the conservative nature of nd isotopes and provides a mechanism linking surface ocean and pore water ree dynamics

modeling of carbon cycling and biogeochemical changes during injection and recovery of reclaimed water at bolivar south australia 1 managed aquifer recharge is an increasingly popular technique to secure and enhance water supplies among a range of recharging techniques single well aquifer storage and recovery asr is becoming a common option to either augment drinking water supplies or facilitate reuse of reclaimed water for the present study a conceptual biogeochemical model for reclaimed water asr was developed and incorporated into an existing reactive multicomponent transport model the conceptual and numerical model for carbon cycling includes various forms of organic and inorganic carbon and several reactive processes that transfer carbon within and across different phases the major geochemical processes considered in the model were microbially mediated redox reactions driven by the mineralization of organic carbon mineral dissolution precipitation and ion exchange the numerical model was tested and applied for the analysis of observed data collected during an asr field experiment at bolivar south australia the model simulation of this experiment provides a consistent interpretation of the observed hydrochemical changes the results suggest that during the storage phase dynamic changes in bacterial mass have a significant influence on the local geochemistry in the vicinity of the injection extraction well farther away from the injection extraction well breakthrough of cations is shown to be strongly affected by exchange reactions and in the case of calcium by calcite dissolution

the geochemical balance of the rare earth elements and neodymium isotopes in the oceans profiles of ree concentrations and neodymium isotope measurements in the western indian ocean are consistent with published data from the other major oceans ree concentrations show a strong hydrographic control the influence of intermediate water masses is particularly significant surface water concentrations vary with salinity paniculate rees are less than 5 of dissolved concentration except for ce where up to 20 of total rees are present as 0 4 m particles in contrast to dissolved profiles concentration profiles of paniculate rees including ce all increase with depth ree concentrations correlate with silica over all but the deepest waters although in detail correlations are complex the neodymium isotopic composition of indian ocean seawater avg nd 0 8 3 is intermediate between that for the atlantic and pacific oceans comparison of ree data from the major oceans shows that the hrees behave more like si than do the lrees sm nd ratios are near constant for all oceans whereas ernd ratios vary between the atlantic indian and pacific oceans the fractionation of the rees in surface seawaters can be explained by fractionation factors relative to silica from 0 12 for la to 0 05 for er use of a seven box model shows that the interoceanic variations in neodymium isotopic compositions and nd concentrations cannot be reconciled unless particle water exchange is invoked the degree of exchange required is consistent with particle residence times of 1 10 yr

a 9 year time series of planktonic foraminifer fluxes and environmental change in the bering sea and the central subarctic pacific ocean 1990 1999 abstract a 9 year study of planktonic foraminifer fluxes was conducted in the bering sea station ab and in the central subarctic pacific station sa results clearly reflected variations of the water mass characteristics in the upper layers the 9 year means of total foraminifer fluxes were the same 1400 shells m 2 d 1 at both stations however total foraminifer flux at station ab tended to show its primary maximum during fall october december and its secondary maximum in spring april june whereas the primary maximum appeared in spring and the secondary maximum in fall at station sa seasonal variation was more apparent at hemipelagic station ab than at pelagic station sa planktonic foraminifers found at both stations were of six species neogloboquadrina pachyderma globigerina umbilicata globigerinita glutinata globigerina quinqueloba globorotalia wilesi and orbulina universa the foraminifer assemblages at the two stations reflected the temperature difference in the surface waters the variable g umbilicata tended to be high in the warm surface waters during the summers the temporal and geographical variation of g quinqueloba indicated that this taxon prefers regions with relatively low diatom fluxes a notable appearance of o universa occurred in 1997 at station sa during this period other measured biogenic particle fluxes such as those of diatoms were low this unusual 1997 event may be a reflection of global climatic change that happened to be observed in the central subarctic pacific ocean

rare earth element cycling in the pore waters of the bering sea slope iodp exp 323 abstract we studied the diagenetic behavior of rare earth elements rees in a highly productive passive margin setting of the bering sea slope site u1345 was drilled during the integrated ocean drilling program expedition 323 at a water depth of 1008 m currently in the center of an oxygen minimum zone pore water concentrations of fourteen rees were determined down to 140 meters below the seafloor mbsf the ree concentrations were higher in the pore water than the deep seawater indicating that there was significant liberation from the sediments during diagenesis there was a major peak at 10 mbsf that was more pronounced for the heavy ree hree this peak occurred below the sulfate methane transition zone 6 3 mbsf and coincided with high concentrations of dissolved iron and manganese at 2 mbsf there was a minor peak in ree and mn contents below 40 mbsf the ree concentration profiles remained constant the ce anomaly was insignificant and relatively constant paas normalized ce ce 1 1 0 2 throughout the depth profile showing that the ce depleted in seawater was restored in the pore water hree enrichment was observed over the entire 140 m except for the upper 1 m where a middle ree mree bulge was apparent ree release in shallow depths 2 4 mbsf is attributed to the release of light rees lrees and mrees during the organoclastic reduction of mn oxides in anoxic sediments the high hree concentrations observed at 10 mbsf can be attributed to the reduction of fe and mn minerals tied to anaerobic oxidation of methane or less significantly to ferromagnesian silicate mineral weathering the upward diffusion flux across the sediment water interface was between 3 for tm and 290 for ce pmol m 2 y 1

rare earth elements and nd isotopes tracing water mass mixing and particle seawater interactions in the se atlantic abstract distributions of dissolved and particulate rare earth elements rees and seawater neodymium isotopic composition e nd were established in samples from the bonus goodhope bgh ipy geotraces cruise in the se atlantic sector of the southern ocean 36 s 13 e to 57 s 0 feb mar 2008 close to the south african continent in the subtropical domain particulate rees show the highest concentrations and flat paas normalized patterns clearly tracing their lithogenic origin active cerium oxidation onto suspended particles is evidenced by the mirror image relationship of the cerium anomaly between dissolved and particulate phases unradiogenic dissolved neodymium in surface waters e nd 17 1 traces the influence of old sedimentary material brought by the agulhas current and rings to the cape basin area a mass balance calculation suggests that the release of nd from dissolution of lithogenic material corresponds to a remobilization of 154 10 6 t of sediment per year i e 5 of the total sediment delivered to the southeast african coast annually at open ocean stations both dissolved and particulate rees present negative cerium anomalies indicating that particles have acquired a marine signature the increasing ree concentrations with depth and the strong linear correlations of dissolved ree with silica indicate that surface removal and deep re mineralisation of rees are partially related to the biogeochemical cycle of silicate which involves biogenic silica diatoms combined with marine carbonates these authigenic phases could explain the observed ree patterns in suspended particles except for la we suggest that the positive la anomalies in both phases are linked to the oceanic barium cycle and the partial dissolution of barite crystals especially in the polar frontal zone the e nd composition behaves conservatively in intermediate and deep waters while input processes affect the isotopic signal of subtropical surface waters and weddell gyre bottom waters an indian ocean and an atlantic variety of aaiw have been isotopically differentiated e nd 9 3 0 3 and e nd 8 0 0 5 respectively homogeneous signatures characterize circumpolar waters e nd from 8 2 to 8 4 for cdw a binary mixing model has been used to assess the contribution of undiluted nadw reaching southern latitudes

particle settling rates increase with depth in the ocean abstract time and depth scales of particulate organic carbon degradation and caco3 and biogenic opal dissolution are critical to understanding the depth distribution of co2 and dissolved nutrients in the ocean the speed at which particles sink and the factors that control sinking speed are of primary importance to the distribution of oceanic nutrient concentrations and to the preservation of biogenic material in the sediment record sequencing sediment trap collectors deployed at us jgofs sites in the equatorial pacific and arabian sea provided a time series of particle fluxes from which particle settling rates were estimated a comparison of settling velocities obtained from 100 500 m pilskaln et al deep sea research 45 1998 1803 to settling velocities obtained for depths between 1000 and 3500 m indicate an increase of a factor of 2 10 between 100 and 2000 m and an increase of 15 60 between 2000 and 3500 m the increase in settling velocity in the deep ocean is generally correlated with the loss of corg with depth lithogenic content does not appear to impact particle settling rate variability in particle settling rate is systematically related to physical forcing of the surface ocean in the equatorial pacific but not in the arabian sea the increase in particle settling rate with depth likely influences the delivery of caco3 to the sea floor

provenance of late quaternary sediments on the southwestern slope of the ulleung basin east japan sea the provenance of fine grained sediments deposited since the late quaternary was recovered from drill site ubgh2 1 1 on the southwestern slope of the ulleung basin east japan sea based on geochemical analyses including rare earth elements rees the fine grained sediments could be interpreted as mixtures of sediments from china via various pathways and sediments discharged from the nakdong river nrs a comparison of variations in ree fractionation factor with marine isotope stages miss indicated that the provenance of the fine grained sediments on the southwestern slope of the ulleung basin was controlled by global eustatic sea level change during glacial periods most of the fine grained sediments were supplied via the atmospheric pathway by an intensified east asian winter monsoon and sediments from chinese rivers crs transported into the ulleung basin through the korea strait were limited due to the morphological characteristics of the korea strait and low sea level during interglacial periods the crs transported into the ulleung basin through the korea strait increased with sea level rise and eolian dust inputs decreased due to attenuated east asian winter monsoon simultaneously nrs also should have been deposited when sea level was higher than 40 m relative to present sea level during mis 1 and mis 5 in particular during mis 1 signals of nrs were revealed since 11 ka thus it can be suggested that the present coastal current system around the southeastern coast of korea became established by around 11 ka

dissolved rare earth elements in the south china sea geochemical characterization of the water masses we have measured the vertical profiles of dissolved rare earth elements rees and yttrium in the south china sea together with conductivity temperature depth and hydrographic measurements to compare with those in the western north pacific and the suiu sea although the south china sea is rapidly flushed by the pacific through the luzon strait with a sill depth of 2500 m broecker et al 1986 a unique ree pattern is developed within the sea the most striking difference exists in the dissolved ce profiles dissolved ce generally decreases from high values 6 9 pmol kg at the surface to a minimum of 3 pmol kg at around 300 500 m where the north pacific intermediate water penetrates in deepwaters of the north pacific and the sulu sea it remains at a relatively low and nearly constant concentration level of 5 pmol kg throughout the water column whereas in the south china sea it gradually increases with depth to a maximum of 12 9 pmol kg at 2500 m resembling the nutrient like profiles of other strictly trivalent rees and then sharply drops to a constant value of 6 pmol kg in the bottom water below 2900 m some lighter rees like pr nd and gd though to a much lesser extent also show similar concentration breaks at the sill depth but the other hydrographic properties like dissolved oxygen nutrients ph and alkalinity do not therefore dissolved rees may best be utilized to characterize the water masses two major sources for dissolved rees in the south china sea are fluvial and coastal input to the surface ocean and a bottom release into the deep water during the passage over the luzon strait redox chemistry including reduction of ce iv to ce iii in the pore water of hemipelagic sediments and subsequent release of dissolved ce iii to the overlying deep water may be involved in the latter the middle ree enriched patterns with a significant gd depression relative to that of the north pacific deep water are characteristic of the south china sea and prevail throughout the water column by physical circulation since the bottom water of the basin is also fed by the north pacific the dissolved ce iii must be oxidized through bacterial mediation and removed from the bottom water presumably by scavenging near at the sediment water interface along the slopes of the basin

major and trace element characterization of oceanic anoxic event 1d oae 1d insight from the umbria marche basin central italy abstract the pialli level in the umbria marche basin central italy correlates with the lowermost part of the positive carbon isotopic excursion characterizing the late albian early cenomanian oceanic anoxic event 1d oae 1d high resolution litho bio and chemostratigraphic data from the monte petrano and le brecce sections allow for a bed by bed comparison of the two successions and discriminate local from basin scale signals we present new x ray fluorescence icp ms and toc data for both the limestones and the pialli level shales integrated with available carbonate carbon isotopes and nannofossil temperature and nutrient indices data indicate a homogenous background sedimentation dominated by pelagic carbonates biogenic silica with little contribution by clays the limited variation in lithogenic elements points to an essentially homogeneous detrital source area with limited fluvial terrigenous input higher mn concentrations coupled with low enrichments in redox sensitive elements such as u fe s re mo ag suggest that the pialli level shales represent temporary suboxia without reaching anoxia furthermore p authigenic ba cd and ni enrichments together with nannofossil nutrient index indicate generally low primary productivity conditions along the entire succession with only minor increases for some of the black to dark grey shales of the pialli level the nannofossil temperature index highlights a warm climate during the oae 1d with the warmest conditions experienced during the deposition of the pialli level shales during the late albian the warm and humid climate was interrupted by brief episodes of relatively warmer and less saline surface waters ensuring slower rates of bottom water renewal and producing temporary suboxic conditions such paleoceanographic dynamics would be the continuation of episodic warmer and humid pulses characterizing the late albian interval in the umbria marche basin as such the pialli level can be considered the result of a last episode closing a cycle before the establishment of a steadier climate during the early cenomanian

discrimination of sediment provenance using rare earth elements in the ulleung basin east japan sea abstract in order to discriminate the origins of ulleung basin east japan sea sediments using rare earth elements rees sediments from 15 box cores and one piston core collected in the shelf slope and basin were analyzed for major elements al fe ca and mn and rees the major sedimentary components in this basin were presumed to be detrital materials from land even in the basin sediments based on al and organic contents carbon and opal post depositional recycling processes involving fe and mn were identified in the basin sediments thus the ce anomaly and the fractionation factors of light rees lrees and middle rees mrees relative to heavy rees hrees could not be used as provenance indicators in the deep basin sediments 2000 m of water depth based on a feasibility check using their covariation with fe and mn for the shelf slope and basin b sites near islands water depths of 1200 1800 m regions the eu anomaly lreen hreen and mreen hreen could be successfully used to discriminate possible provenances including nakdong river sediments nrs chinese river sediments crs ulleungdo volcanic rocks uvr and dokdo volcanic rocks dvr from the provenance indicators slope as well as the shelf sediments called the korea strait shelf mud kssm in the ulleung basin can be regarded as mixtures of nrs and crs with decreasing portions of nrs in the kssm with distance from the nakdong river basin b sediments were mixtures of uvr or dvr and crs these findings can be explained if sediments discharged from the nakdong river were transported and deposited kssm northward within the strong coastal front in normal periods and if sediment flumes from summer floods flowed out across the coastal front were carried with the tsushima warm current and then deposited in the slope area this study indicated that crs were very important detrital sediments and that ree compositions can be successfully used as a provenance indicator in even hemipelagic sediments close to land