seismic anisotropy of shales shales are a major component of sedimentary basins and they play a decisive role in fluid flow and seismic wave propagation because of their low permeability and anisotropic microstructure shale anisotropy needs to be quantified to obtain reliable information on reservoir fluid lithology and pore pressure from seismic data and to understand time to depth conversion errors and non hyperbolic moveout a single anisotropy parameter thomsen s parameter is sufficient to explain the difference between the small offset normal moveout velocity and vertical velocity and to interpret the small offset avo response the sign of this parameter is poorly understood with both positive and negative values having been reported in the literature is sensitive to the compliance of the contact regions between clay particles and to the degree of disorder in the orientation of clay particles if the ratio of the normal to shear compliance of the contact regions exceeds a critical value the presence of these regions acts to increase and a change in the sign of from the negative values characteristic of clay minerals to the positive values commonly reported for shales may occur misalignment of the clay particles can also lead to a positive value of for transverse isotropy the elastic anisotropy parameters can be written in terms of the coefficients w 200 and w 400 in an expansion of the clay particle orientation distribution function in generalized legendre functions for a given value of w 200 decreasing w 400 leads to an increase in while for fixed w 400 increases with increasing w 200 perfect alignment of clay particles with normals along the symmetry axis corresponds to the maximum values of w 200 and w 400 given by w max 200 10 8 2 and w max 400 3 2 8 2 a comparison of the predictions of the theory with laboratory measurements shows that most shales lie in a region of the w 200 w 400 plane defined by w 400 w 200 w max 400 w max 200

circulation mixing and production of antarctic bottom water abstract the antarctic source of bottom water to the abyssal layer of the world ocean is examined as well as its large scale flow pattern and ultimate entrainment rate into the deep water above we make use of the available high quality station data in the southern ocean to construct bottom maps of neutral density and mean property maps including chlorofluorocarbon cfc for the abyssal layer underneath a selected neutral density surface the maximum density at the sill depth of drake passage is used to distinguish between the voluminous deep water mass that is a continuous component of the antarctic circumpolar current from the relatively denser bottom water originated along the antarctic continental margins based on water density antarctic bottom water aabw is defined here generically to include all volumes of non circumpolar water of antarctic origin over the shelf regime multiple localized sources of specific aabw types contribute to the abyssal layer of the adjacent antarctic basins characteristics of these dense bottom waters reflect closely those observed on the parent shelf water mass spreading paths of newly formed deep and bottom waters over the slope regime and their subsequent oceanic circulation patterns are analyzed on the basis of global property maps for the aabw layer interior mixing and interbasin exchanges of aabw are deduced from mean characteristic curves following the southern streamline of the antarctic circumpolar current outflow and mixing of aabw from the weddell sea to the argentine basin is depicted using density and cfc distributions of two zonal hydrographic lines recirculation and mixing of deep and bottom waters within the weddell gyre are also detailed using a meridional section along the greenwich meridian the strength of all localized sources of aabw combined is estimated by two independent approaches an estimate of the total production rate of aabw is calculated based on the oceanic cfc budget for the aabw layer offshore of the 2500 m isobath the sum of all downslope inputs of well ventilated bottom water types underneath the top isopycnal must account for the measured cfc content in the bottom layer the resulting total aabw production rate is about 8 sv which is a conservative figure that neglects the loss of cfc bearing waters across the top isopycnal in recent years whereas about 9 5 sv is calculated assuming a well mixed bottom layer making use of their transient nature cfc distributions at the top of the aabw layer indicate that more direct and rapid entrainment of cfc rich bottom waters below occurs over localized areas with relatively strong upwelling rates and enhanced vertical mixing a second more ad hoc but independent oceanic mass budget of the bottom layer is also constructed a typical basin wide rate of deep upwelling of 3 10 7 m s 1 requires 10 sv 1 sv 106 m3 s 1 of newly formed aabw to sink down the slope around antarctica we have also formulated a spatial distribution of deep upwelling on the isopycnal at the top of the aabw it is expressed as a combination of wind topographic and turbulent components which in turn are functions of the isopycnal depth bottom depth and bottom layer thickness this non uniform upwelling field yields about 12 sv of aabw exported across the top isopycnal fortuitously the overall average of upward speed at the top isopycnal 3 7 10 7 m s 1 compares well with previous estimates of deep upwelling in the northern basins a series of likely sites for strong vertical entrainment of aabw are clearly identified in the modeled distribution of deep upwelling consonant with the observed cfc distributions on the top isopycnal altogether regions with relatively high upwelling rates 5 10 7 m s 1 occupy only a quarter of the total areal extent of the top isopycnal but they account for as much as 45 of the total vertical transport

climatic impact of glacial cycle polar motion coupled oscillations of ice sheet mass and rotation pole position precessional motion of earth s rotation axis relative to its orbit is a well known source of long period climatic variation it is less well appreciated that growth and decay of polar ice sheets perturb the symmetry of the global mass distribution enough that the geographic location of the rotation axis will change by at least 15 km and possibly as much as 100 km during a single glacial cycle this motion of the pole will change the seasonal and latitudinal pattern of temperatures we present calculations based on a diurnal average energy balance which compare the summer and winter temperature anomalies due to a 1 decrease in obliquity with those due to a 1 motion of the rotation pole toward hudson bay both effects result in peak temperature perturbations of about 1 celsius the obliquity change primarily influences the amplitude of the seasonal cycle while the polar motion primarily changes the annual mean temperatures the polar motion induced temperature anomaly is such that it will act as a powerful negative feedback on ice sheet growth we also explore the evolution of the coupled system composed of ice sheet mass and pole position oscillatory solutions result from the conflicting constraints of rotational and thermal stability a positive mass anomaly on an otherwise featureless earth is in rotational equilibrium only at the poles or the equator the two polar equilibria are rotationally unstable and the equatorial equilibrium though rotationally stable is thermally unstable we find that with a plausible choice for the strength of coupling between the thermal and rotational systems relatively modest external forcing can produce significant response at periods of 10 4 10 6 years but it strongly attenuates polar motion at longer periods we suggest that these coupled oscillations may contribute to the observed dominance of 100 kyr glacial cycles since the mid pleistocene and will tend to stabilize geographic patterns that are suitable to glaciations

redox chemistry of west antarctic peninsula margin surface sediments abstract continental margin sediments are commonly studied using trace metal enrichments as proxies for characterizing their modern redox conditions and tracking past changes in bottom water ventilation and marine primary productivity currently little is known about the sedimentary redox history of the continental shelf west of the antarctic peninsula yet environmental conditions in the antarctic peninsula region have changed rapidly in recent decades in response to global warming paleoclimate archives including bulk sediment trace metal enrichments can provide insight into both past and future environmental changes in this climatically sensitive region and characterization of redox conditions in surface modern sediments is essential for establishing a framework for paleoredox interpretations in this study we measured concentrations of trace metals ag cd re and mo and productivity proxies total ba organic carbon and biogenic silica in surface sediments from the marguerite bay gerlache strait and bransfield strait areas proxy concentrations suggest that sediments are generally suboxic due to seasonally high export of organic carbon from surface waters comparison of west antarctic peninsula trace metal al ratios to trace metal data from continental margins outside the antarctic region demonstrates that although the west antarctic peninsula water column differs from other locations e g it lacks a strong oxygen minimum zone sedimentary redox chemistry is similarly controlled by organic matter decomposition through slow recycling of highly seasonal export production falling through a cold water column

zonally asymmetric response of the southern ocean mixed layer depth to the southern annular mode interactions between the atmosphere and ocean are mediated by the mixed layer at the ocean surface the depth of this layer is determined by wind forcing and heating from the atmosphere variations in mixed layer depth affect the rate of exchange between the atmosphere and deeper ocean the capacity of the ocean to store heat and carbon and the availability of light and nutrients to support the growth of phytoplankton however the response of the southern ocean mixed layer to changes in the atmosphere is not well known here we analyse temperature and salinity data from argo profiling floats to show that the southern annular mode sam the dominant mode of atmospheric variability in the southern hemisphere leads to large scale anomalies in mixed layer depth that are zonally asymmetric from a simple heat budget of the mixed layer we conclude that meridional winds associated with departures of the sam from zonal symmetry cause anomalies in heat flux that can in turn explain the observed changes of mixed layer depth and sea surface temperature our results suggest that changes in the sam including recent and projected trends attributed to human activity drive variations in southern ocean mixed layer depth with consequences for air sea exchange ocean sequestration of heat and carbon and biological productivity

ultrasonic velocity and anisotropy of hydrocarbon source rocks an experimental study of the physical properties of black kerogen rich shales also including maturation analysis scanning electron microscope sem observations and physical modeling revealed fairly peculiar petrophysical parameters specifically these rocks have very low porosity and density but most importantly both p and s ultrasonic velocities normal to bedding are extremely low whereas they are much higher parallel to bedding giving rise to a strong anisotropy even at high confining pressures we found that these parameters primarily reflect kerogen content microstructure and maturation level of these rocks we found also that microcracks inferred from ultrasonic velocity measurements occur only in mature shales these microcracks are parallel to the bedding plane and further enhance strong intrinsic anisotropy notably at low effective pressure our results show that on a small scale kerogen rich shales are transversely isotropic rocks and can be effectively modeled using the thin laye

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

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

diagenetic behavior of barite in a coastal upwelling setting 1 multiproxy data from odp hole 1017e point conception california provide an excellent opportunity to examine the behavior of barium within a well characterized sedimentary system bariumexcess is generally considered to be a productivity proxy however in nearshore environments baexcess records can be compromised by both sediment provenance and barite remobilization for the last 60 kyr odp hole 1017e exhibits significant changes both in primary productivity driven by coastal upwelling and in the sediment redox chemistry of underlying sediments significant barite enrichment occurs at an active diagenetic front that marks the boundary between sulfate rich and sulfate poor pore waters this boundary also intersects a sediment facies change from deposition of relatively coarse grained sediment before 35 ka to an interval of fine grained organic rich sediment after i e interstadial event 8 changes in diffusion rates associated with the sediment facies change cause a strong but misleading correlation between a mobile zone of barite enrichment and rapid climate change thus within the baexcess record at odp hole 1017e is a history of redox chemistry that has corrupted the paleoproductivity record of babiogenic

the accumulation of silver in marine sediments a link to biogenic ba and marine productivity 1 the concentrations of ag and a suite of redox sensitive trace metals re cd and mo were measured in surface sediments from the western canadian mexican peruvian and chilean continental margins in all regions ag content increases from 80 ng g 1 i e lithogenic values on the shelf up to as high as 1483 ng g 1 on the lower slope however the trend of increasing ag with increasing water depth breaks down at deepwater sites 2500 m where only lithogenic concentrations are documented silver content does not correlate with the distributions of redox sensitive trace metals suggesting that sedimentary redox conditions are not the primary control on ag accumulation instead a positive correlation between ag and ba in surface and near surface sediments suggests that ag is scavenged by and delivered to the sediment with the organic particle flux scavenging probably results from the precipitation of ag2s within the organic particles due to the development of anoxia and sulfate reduction if this hypothesis is correct then ag has the potential to be a paleoproductivity proxy

ba distribution in surface southern ocean sediments and export production estimates 1 we present excess ba baxs data i e total ba corrected for lithogenic ba for surface sediments from a north south transect between the polar front zone and the northern weddell gyre in the atlantic sector and between the polar front zone and the antarctic continent in the indian sector focus is on two different processes that affect excess ba accumulation in the sediments sediment redistribution and excess ba dissolution the effect of these processes needs to be corrected for in order to convert accumulation rate into vertical rain rate the flux component that can be linked to export production in the southern ocean a major process affecting ba accumulation rate is sediment focusing which is corrected for using excess 230 th this correction however may not always be straightforward because of boundary scavenging effects a further major process affecting excess ba accumulation is barite dissolution during exposure at the sediment water column interface export production estimates derived from excess 230 th and barite dissolution corrected baxs accumulation rates i e excess ba vertical rain rates are of the same magnitude but generally larger than export production estimates based on water column proxies 234 th deficit in the upper water column particulate excess ba enrichment in the mesopelagic water column we believe export production values based on excess ba vertical rain rate might be overestimated due to inaccurate assessment of the baxs preservation rate barite dissolution has in general been taken into account by relating it to exposure time before burial depending on the rate of sediment accumulation however the observed decrease of excess ba content with increasing water column depth or increasing hydrostatic pressure illustrates the dependence of barite preservation on degree of saturation in the deep water column in accordance with available thermodynamic data therefore correction for barite dissolution would not be appropriate by considering only exposure time of the barite to some uniformly undersaturated deep water but requires also that regional differences in degree of undersatuation be taken into account index terms 1050 geochemistry marine geochemistry 4835 4850 4835 oceanography biological and chemical inorganic marine chemistry keywords excess ba sediment southern ocean export production

cadmium isotopic evidence for increasing primary productivity during the late permian anoxic event abstract earth s most extreme extinction event near the end of the late permian decimated more than 90 of all extant marine species widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe though the driving mechanisms that sustained such conditions are still debated of particular interest is whether water column anoxia was a consequence of a stagnant ocean or if it was controlled by increases in nutrient supply primary productivity and subsequent heterotrophic respiration testing these competing hypotheses requires deconvolving sedimentary bottom water redox conditions from changes in surface water productivity in marine sediments we address this issue by studying marine shales from east greenland and the mid norwegian shelf and combining sedimentary redox proxies with cadmium isotopic analyses sedimentary nitrogen isotopic data pyrite framboid analyses and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling and increasingly anoxic conditions with a strengthening upwelling in the greenland and norwegian sections respectively detailed analysis of sedimentary metal budgets illustrates that cd is primarily associated with organic carbon and records primary geochemical signatures thus enabling reconstruction of surface water nutrient utilization cadmium isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average cd 114 110 of 0 15 0 01 2 se n 12 rel nist srm 3108 indicative of incomplete surface water nutrient utilization up section the constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity and not oceanic stagnation to balance the larger nutrient fluxes to both study sites during the development of the late permian water column anoxia overall our data illustrate that if bottom water redox and upwelling can be adequately constrained cd isotopic analyses of organic rich sediments can be used to provide valuable information on nutrient utilization and therefore past productivity

some comparative marine chemistries of rhenium gold silver and molybdenum abstract four metals re au ag and mo whose dissolved forms in seawater can potentially be reduced to insoluble states have been measured in a variety of solids depositing under anoxic conditions hydrothermal sulfides coastal sediments and phosphorites for comparative purposes these elements have also been determined in ferromanganese minerals and pelagic sediments which have accumulated under oxidizing conditions rhenium appears to be a unique sentinel for identifying reducing depositional environments where enrichments of greater than three orders of magnitude above crustal concentrations are found molybdenum follows re in these sediments but mo is enriched also in those that accumulate under oxidizing conditions the reported mo crustal concentrations appear low in comparison to our measured sedimentary values gold and ag are concentrated in hydrothermal deposits and sulfides appear to be involved in the precipitation of these elements coastal sediments adjacent to a domestic outfall of los angeles california contain extraordinary high accumulations of anthropogenic au ag and pt the study seeks an understanding of the mobilities and sinks of these metals in the marine environment during the major weathering cycle further anthropogenic contributions to their sedimentary concentrations are identified

silicon dynamics within an intense open ocean diatom bloom in the pacific sector of the southern ocean abstract an intense diatom bloom developed within a strong meridional silicic acid gradient across the antarctic polar front at 61 s 170 w following stratification of the water column in late october early november 1997 the region of high diatom biomass and the silicic acid gradient propogated southward across the seasonal ice zone through time with the maximum diatom biomass tracking the center of the silicic acid gradient high diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of january 1998 ca 70 d driving the gradient over 500 km to the south of its original position at the polar front the bloom consumed 30 to 40 m si oh 4 in the euphotic zone between about 60 and 66 s leaving near surface concentrations our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around antarctica also occur in the deep ocean near the polar front the bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of antarctica implying a role for such blooms in the formation of those sediments comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the southern ocean which have been corrected for sediment focusing indicate a burial efficiency of 4 6 for biogenic silica that efficiency is considerably lower than previous estimates for the southern ocean

sedimentary patterns in the late quaternary southern ocean the spatial and temporal distribution of biogenic and lithogenic sediments in the late quaternary southern ocean reflects the zonal character of the antarctic circumpolar current and is basically controlled by glacial dynamics in antarctica sea ice distribution temperature gradients wind patterns and thermohaline ocean circulation carbonate patterns in most places reveal a decline in biogenic carbonate preservation during glacial periods mainly attributed to a reduced influx of north atlantic deep water and increased ocean stratification which modified deep water chemistry towards more corrosivity an important lithological feature of the southern ocean is the circumpolar opal belt which today is situated between the polar front and the seasonal sea ice limit to the south during the glacial periods the opal belt shifted to the north in response to a wider sea ice extension that reduced light availability and diatom productivity to the south biosiliceous productivity to the north likely was fueled by detrital iron supplied by aeolian dust input and or hemipelagic processes lithogenic fluxes generally increased during the glacial periods provenance studies on the origin and dispersal of detrital materials suggest combined effects of low sea level stands increased glaciogenic input and enhanced current transport to have caused elevated detrital fluxes the relative and absolute contribution of aeolian dust is difficult to decipher and awaits further clarification by integrated provenance studies of both marine sediments and more reference materials from the potential terrestrial source areas ice rafted debris ird represents a minor fraction of lithogenic sediments but can be used to infer both antarctic ice sheet dynamics and the fate of both sea ice and iceberg survival in the distal southern ocean future work should be concentrated on a better identification of ird origin in terms of volcaniclastic influences the distinction of east and west antarctic sediment sources and sea ice versus iceberg transportation

estimating physical parameters of cracked porous oil reservoirs by inverting shear wave splitting summary we present the problem of determining crack density porosity and permeability of cracked porous carbonate reservoirs by examining the origin of anisotropy considered from a physical model of porous reservoir rock with a system of vertical fluid filled cracks this stabilizes the non linear optimization inversion procedure and determines a set of significant reservoir parameters on a basis of qp qs1 and qs2 velocities measured in a vsp experiment

remobilization of barium in continental margin sediments abstract the rate of ba release from california continental margin sediments has been measured using an in situ benthic flux chamber and the range of values 25 50 nmol cm 2 y 1 is larger than any previously published benthic flux estimate for this element the magnitude of the ba flux suggests that a significant fraction of the ba raining from the euphotic zone is recycled at the seafloor ba si regeneration ratios from these margin sediments increase with depth demonstrating that ba is decoupled from si during the earliest stages of diagenesis on the other hand ba regeneration rates and caco3 dissolution rates covary the coupling between these two constituents is supported by the observation that the ba caco3 dissolution flux ratio 1 7 0 4 10 3 is independent of bottomwater depth even in sediments underlying the oxygen minimum zone along the continental margin furthermore this flux ratio is consistent with both the water column ba alkalinity ratio for the world s ocean as well as the ba caco3 ratio in sediment trap solid phases from the equatorial pacific 1 1 2 2 10 3 however the constancy of the ba alkalinity ratio over geologic time remains in question because the mechanism that controls this relationship remains a mystery our flux measurements suggest that diagenesis does not significantly influence the ba ca ratio in the upper 0 5 mm of pacific sediments thereby supporting the idea of using the ba concentration in surface dwelling benthic forams as a proxy for deep water chemical conditions lea and boyle 1989 1990 on the other hand we predict that if a foraminifer lives 0 5 mm or more below this interface then diagenetic effects could influence the ba ca ratio that foram species would record the carrier phase of the particulate ba reactive during early diagenesis does not appear to be organic matter oxyhydroxides or calcium carbonate but rather a mineral phase related to marine barite or perhaps celestite

effects of productivity glaciation and ventilation on late quaternary sedimentary redox and trace element accumulation on the vancouver island margin western canada variations in chalcophile and redox sensitive trace elements are examined at high resolution intervals from a 50 kyr long sediment core md02 2496 from the vancouver island margin enrichments of ag cd re u and mo above lithogenous levels signifying sedimentary suboxia and anoxia occurred during the early holocene and bolling allerod and during warm interstadial events of marine isotope stage mis 3 down core trace element profiles co vary with productivity proxy records opal caco3 and marine organic carbon and with sedimentary nitrogen isotope ratios which reflect variably enriched nitrate upwelled from intermediate waters that were transported northward from the eastern tropical north pacific the similarity of the md02 2496 record with records from the southern portion of the california current system ccs and to the greenland ice core oxygen isotope record during warm climate intervals suggests that sedimentary redox conditions along the california current responded to local productivity to north atlantic climate change and to tropical pacific surface water processes via long distance teleconnections concentrations of trace elements and productivity proxies were relatively depleted during the younger dryas cool stadial events of mis 3 and in two episodes of glaciomarine sedimentation from 14 7 to 30 5 kyr bp last glacial maximum lgm and from 44 to 50 4 kyr bp cordilleran ice sheet advancement onto the vancouver island continental shelf during the lgm led to intervals of increased terrigenous sedimentation and greatly reduced productivity not seen in the southern portion of the ccs and along with ventilation of north pacific intermediate waters resulted in brief sedimentary oxic conditions

silver in the western equatorial and south atlantic ocean vertical profiles of total dissolved 0 22 m silver concentrations in the equatorial and southwest atlantic ocean provide a new perspective on the processes controlling the element s external fluxes and internal biogeochemical cycling in the world ocean atmospheric inputs of natural and or industrial aerosols appear to elevate silver concentrations in remote surface waters in the south atlantic where silver is effectively scavenged onto and or bioaccumulated by plankton the subsequent remobilization of silver with depth is relatively coincident with that of silicate suggesting much of that silver is sequestered within a refractory organic phase associated with biogenic silica that silver is then remineralized and appears to be conservatively transported in subsurface water masses throughout the world ocean

effective elastic properties of solid clays clay minerals are perhaps the most abundant materials in the earth s upper crust as such their elastic properties are extremely important in seismic exploration seismic reservoir characterization and sonic log interpretation because little exists in the literature on elastic properties of clays we have designed a method of measuring effective elastic properties of solid clays clays without pores in this method clay minerals are mixed with a material with known elastic properties to make composite samples elastic properties of these clay minerals are then inverted from the measured elastic properties of the composite samples using the weighted hashin shtrikman average using this method we have measured 66 samples of 16 types of clays in this paper we present a comprehensive data set of elastic properties of solid clays that commonly occur in or are related to petroleum reservoirs although uncertainties up to 10 exist the data set reported here is by far the most comprehensive set of e

seismic anisotropy in sedimentary rocks part 2 laboratory data part one of this paper presents a method for measuring seismic velocities and transverse isotropy in rocks using a single core plug this method saves at least two thirds of the time for preparing core samples and measuring velocities in transversely isotropic ti rocks using this method we have measured velocity and anisotropy of many shale and reservoir rocks from oil and gas fields around the world we present some of the data in this paper which include seismic velocity and anisotropy in 17 brine saturated shale samples 1 gas and brine saturated coal sample 8 brine saturated sands 12 gas saturated sands 32 gas saturated carbonate samples and 25 brine saturated carbonate samples the results show that clays and fine layering in sedimentary rocks are the main causes of seismic anisotropy very little intrinsic anisotropy exists in unfractured reservoir rocks such as sands sandstones and carbonates under reservoir conditions in contrast all shales were found seismically anisotropic anisotr

benthic remineralization and burial of biogenic sio2 caco3 organic carbon and detrital material in the southern ocean along a transect at 170 west abstract we investigated the composition recycling and mass accumulation rates of sediments along a transect in the southern ocean located from 66 s to 57 s at 170 w this transect also corresponds to the location of a sediment trap mooring line the sediments at the seven sites studied range from largely terrigenous material to nearly pure 90 biogenic silica caco3 is a minor but persistent component at most sites mass accumulation rates have been determined on the basis of excess 230th in the sediments i e 230th normalized accumulation rates the influence of redistribution of sediments on the sea floor has been estimated from 14c analyses the recycling of material delivered to the sediments has been characterized on the basis of pore water studies that make extensive use of both in situ sampling and shipboard extractions the influence of the highly variable rates of input of particulate matter that characterize much of the southern ocean upon pore water gradients and fluxes across the sediment water interface has been considered we find only poor correspondence between bsio2 burial fraction burial particulate flux a quantifiable measure of preservation efficiency and bsio2 particulate rain along the transect however preservation does appear to be closely linked to a combination of sedimentation rate and particulate rain the burial fraction of bsio2 is small relative to benthic rain 5 19 despite the small fraction buried burial flux normalized to sedimentation rate 1 2 appears to provide a very consistent means of predicting benthic particulate rain over a large range of rain rates including data from a number of different studies and environments at sites with bsio2 rain 250 mmol m 2 yr 1 the average difference between predicted and observed rain is 25 30 such rain rates occur in many marine areas particularly the southern ocean with the result that this relationship potentially provides a means of estimating bsio2 benthic rain over prolonged periods in the past on the basis of readily measured sediment parameters at the southern most deep ocean station the particulate flux was characterized by an extremely high corg caco3 ratio 10 but this high ratio does not appear to have a substantial influence on caco3 burial caco3 is preserved in the sediments at this site despite a particulate flux with a 10 fold excess of corg above that required for complete dissolution in the sediments the unexpectedly high preservation of caco3 is due largely to the very steep corg oxidation rate profile at this site as a result a large fraction of the organic matter oxidized in the sediments does so in close proximity to the sediment water interface where most of the metabolic co2 is neutralized by co32 from the overlying water rather than by the dissolution of sedimentary caco3 diagenetic modeling indicates that at several of the stations the remineralization fluxes of carbonate species across the sediment water interface may not have been at steady state as a result of the highly pulsed nature of particulate rain in this environment we estimate that at the time of our sampling it is possible that near interface fluxes could have been a factor of 1 6 2 times the annual average at every site on the transect the burial fluxes of detrital material are substantially greater than the detrital particulate rain measured in the sediment traps by as much as a factor of 40 detrital burial is bimodal being greatest at the southern and northern extremes of the transect we postulate that the excess of burial over particulate rain in the south reflects the contribution of ice rafted debris at these high latitudes increases in the supply at the northern stations must have a different source we believe that the excess at these stations is material eroded from the sea floor to the west possibly on the campbell plateau and advected by currents to the northern portion of the transect at depths below the shallow traps

glacial enrichments of authigenic cd and u in subantarctic sediments a climatic control on the elements oceanic budget we examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic cd inventory thereby decoupling cd from po4 we suggest that the precipitation of cd sulfide in suboxic sediments is the single largest sink in the oceanic cd budget and that the accumulation of authigenic cd and u is tightly coupled to the organic carbon flux into the seafloor sediments from the subantarctic ocean and the cape basin south atlantic where oxic conditions currently prevail show high accumulation rates of authigenic cd and u during glacial intervals associated with increased accumulation of organic carbon these elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon a third core overlain by circumpolar deep water cpdw as are the other two cores but located south of the antarctic polar front shows an approximately inverse pattern to the subantarctic record the contrasting patterns to the north and south of the antarctic polar front suggest that higher accumulation rates of cd and u in subantarctic sediments were driven primarily by increased productivity this proposal is consistent with the hypothesis of glacial stage northward migration of the antarctic polar front and its associated belt of high siliceous productivity however the increase in authigenic cd and u glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts suggesting greater partitioning of organic carbon into the sediments during glacial intervals lower oxygen content of cpdw and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes higher glacial productivity in the cape basin record very likely reflects enhanced coastal up welling in response to increased wind speeds we suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum however our calculations suggest low sensitivity of seawater cd concentrations to glacial doubling of the extent of reducing sediments the model suggests that during the last 250 kyr seawater cd concentrations fluctuated only slightly between high levels about 0 66 nmol kg 1 on glacial initiations and reaching lowest values about 0 57 nmol kg 1 during glacial maxima the estimated 5 lower cd content at the last glacial maximum relative to modern levels 0 60 nmol kg 1 cannot explain the discordance between cd and 13c such as observed in the southern ocean this low sensitivity is consistent with foraminiferal data suggesting minimal change in the glacial cd mean oceanic content

the global ocean flux of particulate organic carbon areal distribution and magnitude the magnitude and distribution of the particulate organic carbon poc rain rate to the seafloor in the atlantic pacific and indian ocean basins between 61 n and 61 s has been estimated from benthic oxygen flux estimates for water depths 1000 m only the calculation utilizes the extensive data sets of sedimentary organic carbon caco3 and accumulation rate to extrapolate between individual benthic flux measurement sites using an empirically derived correlation between the seafloor oxygen flux and these parameters the poc flux through the 1000 m depth horizon was then estimated from published correlations between sediment trap determined fluxes and water depth total oxygen utilization in the deep ocean is estimated to be 1 2 1014 mol o2 yr 1 a value that agrees well with previous estimates which were based on surface water primary productivity sediment trap and depth relationships and with deep water respiration rates estimated from apparant oxygen utilization aou 14c relationships on the basis of the derived global ocean flux distribution it is concluded that 1 dissolved organic carbon doc inputs are not required to account for estimated deep water respiration rates 2 the majority of the poc input to the deep ocean occurs within 30 of the equator 3 the proportion of primary production that reaches the deep sea does not vary greatly with latitude 4 gyre and continental margin regions contribute roughly equally to the deep poc flux with a relatively minor contribution from the equatorial divergence region 5 of the estimated 7 2 1013 mol c yr 1 of poc that sinks below the 1000 m depth horizon 45 3 3 1013 mol c yr 1 reaches the seafloor where it is oxidized 6 when normalized to basin area average deep flux rates in the atlantic and pacific are similar while highest rates are observed in the indian ocean and 7 the results can be fully reconciled only if the benthic flux of doc is significantly less than the benthic o2 flux

230th normalization an essential tool for interpreting sedimentary fluxes during the late quaternary there is increasing evidence indicating that syndepositional redistribution of sediment on the seafloor by bottom currents is common and can significantly affect sediment mass accumulation rates notwithstanding its common incidence this process generally referred to as sediment focusing is often difficult to recognize if redistribution is near synchronous to deposition the stratigraphy of the sediment is not disturbed and sediment focusing can easily be overlooked ignoring it however can lead to serious misinterpretations of sedimentary fluxes particularly when past changes in export flux from the overlying water are inferred in many instances this problem can be resolved at least for sediments deposited during the late quaternary by normalizing to the flux of 230th scavenged from seawater which is nearly constant and equivalent to the known rate of production of 230th from the decay of dissolved 234u we review the principle advantages and limitations of this method notwithstanding its limitations it is clear that 230th normalization does provide a means of achieving more accurate interpretations of sedimentary fluxes and eliminates the risk of serious misinterpretations of sediment mass accumulation rates

influence of biological productivity on silver and redox sensitive trace metal accumulation in southern ocean surface sediments pacific sector abstract accurate interpretation of paleoproductivity proxies in the southern ocean requires ground truthing these proxies here the concentrations of total ba organic carbon c org and biogenic silica si bio along with other redox sensitive trace metals cd re and mo are compared with the distribution of silver ag in core top sediments from the pacific sector of the southern ocean conventional thinking holds that enrichment of trace metals should be muted or absent in southern ocean sediments despite high export of c org from surface waters because deposition under well oxygenated bottom waters inhibits accumulation of reduced metal phases while our data support this prediction detectable preserved vertical fluxes of ag cd and re exist beneath the opal belt and faithfully record surface productivity patterns therefore we suggest ag fluxes into southern ocean sediments occur via biodetritus associated with high export production rather than accumulation by redox driven diagenetic processes sedimentary ag concentrations are likely altered at the seafloor by biogenic particle remineralization due to high bottom water o 2 nevertheless zonal ag fluxes are similar to surface productivity patterns highlighting the potential of ag to serve as a proxy for diatom export production

selective organic matter preservation in burn down turbidites on the madeira abyssal plain 1 oxidized intervals of five organic rich madeira abyssal plain map turbidites deposited during the miocene pliocene and pleistocene all displayed comparable major loss of total organic carbon toc 84 3 1 accompanied by a negative isotopic 13c shift ranging from 0 3 to 2 9 major but significantly lower loss of total nitrogen ntot 61 7 1 also occurred leading to a decrease in toc relative to ntot c ntot and a 1 3 to 2 7 ntot isotopic 15n shift compound specific isotopic measurements on plant wax n alkanes indicate the terrestrial organic component in the unoxidized deposits is 13c enriched owing to significant c4 contribution selective preservation of terrestrial relative to marine organic carbon could account for the 13c behavior of toc upon oxidation but only if a 13c depleted component of the bulk terrestrial signal is selectively preserved in the process although the c ntot decrease and positive 15n shift seems inconsistent with selective terrestrial organic preservation results from analysis of a modern eolian dust sample collected in the vicinity indicate these observations are compatible regardless of the specific explanation for these isotopic observations however our findings provide evidence that paleoreconstruction of properties such as pco2 using the 13c of toc is a goal fraught with uncertainty whether or not the marine sedimentary record considered is contaminated with significant terrestrial input nonetheless despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation intensive organic geochemical proxies such as the alkenone unsaturation index u37k appear resistant to change and thereby retain their paleoceanographic promise

anisotropic effective medium modeling of the elastic properties of shales shales are complex porous materials normally consisting of percolating and interpenetrating fluid and solid phases the solid phase is generally comprised of several mineral components and forms an intricate and anisotropic microstructure the shape orientation and connection of the two phases control the anisotropic elastic properties of the composite solid we develop a theoretical framework that allows us to predict the effective elastic properties of shales its usefulness is demonstrated with numerical modeling and by comparison with established ultrasonic laboratory experiments the theory is based on a combination of anisotropic formulations of the self consistent sca and differential effective medium dem approximations this combination guarantees that both the fluid and solid phases percolate at all porosities our modeling of the elastic properties of shales proceeds in four steps first we consider the case of an aligned biconnected clay fluid composite composed of ellipsoidal inclusion

comparative behavior of authigenic re u and mo during reoxidation and subsequent long term burial in marine sediments the trace element re is enriched in mildly reducing suboxic sediments close to or slightly later in the redox sequence than u and before reduction of mo in more reducing sulfidic sediments this work investigates the behavior of authigenic re during oxidation and long term burial in the sediments of several turbidites from the madeira abyssal plain exposure to bottom water o2 clearly remobilizes authigenic re as found in previous work but reimmobilization occurs in reducing sediments below the oxidation front over a depth range of 0 5 3 m the large spread of the re burndown peak must be kinetically controlled perhaps influenced by the corg content once reimmobilized however the authigenic re signal remains immobile for at least 3 4 myr authigenic u in contrast consistently forms peaks 0 5 m broad whereas authigenic mo is lost on oxidation and does not appear to be refixed unless authigenic pyrite is formed these results imply that any paleoenvironmental significance of authigenic re will be compromised in low sedimentation rate environments 10 cm kyr where there is significant exposure of authigenic re to bottom water o2 however authigenic re records from rapidly accumulating continental margin sediments with much less exposure to bottom water o2 still offer considerable potential as high fidelity recorders of past reducing conditions

elastic properties of anisotropic synthetic calcite muscovite aggregates 1 a set of synthetic aggregates containing mixtures of calcite and muscovite were compacted with varying uniaxial loads ranging from 20 mpa up to 400 mpa their elastic properties have been measured using compressional and shear waves in confining hydrostatic pressures up to 475 mpa measured seismic velocities are shown to depend on 1 the ratio of calcite to muscovite 2 the uniaxial load used during sample manufacturing and 3 the porosity amount prior to velocity measurements the matrix framework may also affect the seismic velocities but this effect is not easily quantifiable in general measured seismic velocities decrease with increasing muscovite content and porosity elastic properties have been calculated based on texture measurements which were obtained by neutron diffraction the calculated velocities are based on the calcite and muscovite single crystal elastic tensors their orientation distribution functions and their modal fractions a large discrepancy is apparent between calculated and measured velocities where the former always overestimate the actual velocities shear waves display less of a difference between calculated and measured values than do compressional waves indicating that waves propagating by shearing are less affected by sample porosity and matrix framework a better agreement between measured and calculated seismic velocities arises when the initial porosity is taken into account using a differential effective medium model seismic anisotropy is evident from both measured and calculated velocities and is low for samples containing pure calcite but becomes prominent as the muscovite concentration increases the intensity of anisotropy further depends on the uniaxial load used during sample compaction and the initial porosity

geochemical characteristics of chilean upwelling sediments at 36 s abstract we examined the cycling of c s fe and the trace elements te ag cd mo mn re and se in chilean upwelling sediments from water depths of 127 2744 m at 36 s the sediments are clay rich with moderate total organic carbon toc and low biogenic caco3 contents for the shallow site within oxygen minimum zone omz which shows some thioploca biomass highest observed toc contents correspond to highest productivity induced toc flux and or enhanced preservation under o2 deficient conditions pyrite formation may be restricted by the concurrent presence of elemental s in thioploca and or the availability of reactive iron in the other sediments 370 m water depth pyrite formation is strongly restricted due to the low availability of metabolizable toc for sulfate reduction calculations of the degree of bacterially mediated remineralization suggest that more nitrogen than toc was remineralized by sulfate reduction than expected from redfield c n relationship manganese is significantly depleted due to reductive dissolution of mn hydr oxides within all sediments mo is only significantly enriched vs the lithogenic background in the shallow core implying anoxic conditions contents of re and mo as well as re mo ratios indicate suboxic conditions for the other cores cd and re contents decrease with increasing water depth reflecting decreasing reducing conditions in contrast authigenic ag contents increase with water depth suggesting enrichment controlled by seawater availability and or opaline input and not redox conditions elevated se contents in all cores may be either due to bio detrital input or diffusion from seawater accumulation rates of toc ts and te off chile are in the same order as those from the gulf of california and lower than those off peru distinct seasonality in upwelling and dilution of chilean sediments with terrigenous material lead to rather low metabolizable toc contents and lower te trapping capacity

accumulation of biogenic and lithogenic material in the pacific sector of the southern ocean during the past 40 000 years the 230th normalization technique was applied to surface sediments and down core records from the pacific sector of the southern ocean between 120 w and 170 w in order to reconstruct vertical rain rates corrected for lateral redistribution of sediment preserved rain rates of opal organic carbon and biogenic ba all indicate that biological productivity south of the antarctic polar front apf was much lower than today during the last glacial maximum lgm probably in response to increased ice cover however by analogy with modern opal fluxes south of the acc we show that year round ice cover is not a prerequisite for very low rates of opal accumulation available records from north of the apf indicate little to no change in opal export in contrast to records from the indian and atlantic sectors which show enhanced opal export north of the apf during the lgm glacial records from north of 66 s in the pacific all show lithogenic fluxes that were greater than today but significantly lower than lithogenic fluxes in the glacial atlantic and indian sectors together these new records from the pacific sector show that during the lgm the three basins of the southern ocean were significantly more differentiated than today the observed inter basin distribution of lithogenic fluxes and opal burial and the presumed geographical distribution of increased dust input to the southern ocean during the lgm are consistent with an atlantic indian pacific gradient in the degree of iron stimulated diatom productivity within the zone lying between the apf and the subantarctic front previous studies which focused primarily on the atlantic sector may have overestimated the glacial increase in the strength of the biological pump in the southern ocean

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

a new geochemical classification of sedimentary environments because of the relative constancy of ph in most subaqueous sediments and the general lack of measurability of eh these parameters are not practically useful for classifying sedimentary environments in their place a new classification is offered which derived from studies of modern sediments is based on the presence or absence of dissolved oxygen and dissolved sulfide in the sediments at the time of authigenic mineral formation sedimentary environments are first of all divided into oxic and anoxic depending upon the presence or absence of measurable dissolved oxygen anoxic environments in turn are divided into sulfidic and non sulfidic depending upon the presence of measurable dissolved sulfide anoxic nonsulfidic environments are further divided into postoxic or resulting from oxygen removal without sulfate reduction weakly reducing and methanic or resulting from complete sulfate reduction with consequent methane formation strongly reducing the environments are shown to succeed one another during early diagenesis in the order oxic post oxic sulfidic methanic iron and manganese minerals characteristic and stable in each environment are listed and discussed so that they may be used to distinguish the environments when studying the ancient geological record

ultrasonic velocities in cretaceous shales from the williston basin compressional and shear wave velocities were measured in the laboratory from 1 bar to 4 kbar confining pressure for wet undrained samples of cretaceous shales from depths of 3200 and 5000 ft in the williston basin north dakota these shales behave as transversely isotropic elastic media the plane of circular symmetry coinciding with the bedding plane for compressional waves the velocity is higher for propagation in the bedding plane than at right angles to it and the anisotropy is greater for the 5000 ft shale for shear waves the sh wave perpendicular to bedding and the sv wave parallel to bedding propagate with the same speed which is about 25 percent lower than that for the sh wave parallel to bedding in general compressional and shear velocities are higher for the indurated 5000 ft shale than for the friable 3200 ft shale all velocities increase with in increasing confining pressure to 4 kbar the 3200 ft shale exhibits velocity hysteresis as a function of pressure whereas this effect is a

geochemical signatures of redepositional environments the namibian continental margin abstract trace metal abundances in marine sediments have been used extensively to interpret periods of elevated primary productivity and ancient ocean redox conditions however sediment reworking that results in post depositional oxidation such as bio irrigation or lateral sediment transport through oxic water can modify the primary geochemical signal of the sediment which in turn may impact paleo redox and or productivity interpretations in the case of sediments on the namibian continental margin ncm lateral transport and redeposition contribute to the accumulation of organic matter on the margin slope to better constrain the geochemical effects of lateral transport on the ncm we examined the trace metal signature including solid phase fe mo v ni cu and ag and pore water fe mo and v in surface sediments up to 25 cmbsf along a transect from shelf to slope through the primary shelf and secondary upper slope depositional zones of the margin despite varying bottom water redox conditions ranging from seasonally anoxic upper shelf suboxic shelf break and oxic upper slope each site has elevated total organic carbon contents average toc content of 9 1 3 2 and 6 8 wt respectively due to high surface water primary productivity and lateral transport of organic rich material from the shelf to the upper slope our results show that the solid phase contents of the productivity proxies ni cu and ag parallel the organic carbon accumulations largely irrespective of the local redox conditions in contrast the solid phase contents of v mo and fe respond to the local bottom water redox conditions at each site being enriched under strongly reducing conditions and less enriched under oxic bottom waters despite enhanced toc at all three investigated sites thus the enrichment of trace metal and toc at each site on the ncm can not only be used to reconstruct primary depositional bottom water redox conditions but also to identify zones of sediment redeposition using an offshore transect allows for the identification of intense lateral transport and redeposition of organic rich sediments that are occurring along the margin the relative concentrations of both redox sensitive and productivity related trace metals suggest that the decoupling of trace metals and organic carbon enrichments occasionally observed in the geological record could be explained by the process of lateral transport and redeposition

mg ca temperature calibration for the benthic foraminifera melonis barleeanum and melonis pompilioides an important tool for deep sea temperature reconstruction is mg ca paleothermometry applied to benthic foraminifera foraminifera of the genus melonis appear to be promising candidates for temperature reconstructions due to their wide geographical and bathymetric distribution and their infaunal habitat which was suggested to reduce secondary effects from carbonate ion saturation co3 2 here we make substantial advances to previous calibration efforts and present new multi lab mg ca data for melonis barleeanum and melonis pompilioides from more than one hundred core top samples spanning in situ bottom temperatures from 1 to 16 c coupled with morphometric analyses of the foraminifer tests both species and their morphotypes seem to have a similar response of mg ca to growth temperature compilation of new and previously published data reveals a linear dependence of temperature on mg ca with a best fit of mg ca mmol mol 0 113 0 005 bwt c 0 792 0 036 r2 0 81 n 120 1 sd salinity bottom water co3 2 and varying morphotypes have no apparent effect on the mg ca temperature relationship but pore water co3 2 might have had an influence on some of the samples from the tropical atlantic

elastic moduli of anisotropic clay claymineralsareimportantcomponentsinshales controlling their elastic properties and anisotropy the elasticity of crystalline clay minerals differs significantly from that of clay in situ because of the ability of clay particles to bind water in the majority of published works only isotropic moduli for in situ clays are reported however anisotropy is inherent in the clay elasticity we develop an inversion technique for determination of thestiffnesstensorofinsituclayfromtheshale sstiffnesstensor as an example we obtain the stiffness tensor of a water clay composite from the data on the water saturated greenhorn shale sample whose clay composition consists of almost equal amounts of illite and smectite and comparable amounts of kaolinite and chlorite the stiffness tensor of the water clay composite is found for the greenhorn shale with step by step inversion based upon an effective medium theory the inversion uses a nonlinear optimization technique with bounds imposed on the estimated parameters in the inversion we apply different approaches of the effective medium theory using a published method referred to here as the generalized singular approximation gsa the gsa method makes it possible to take into account the microstructure of shales the resulting elasticity constants of the anisotropic transversely isotropic in situ clay composite are c11 23 7 c33 8 5 c44 0 8 c66 5 7 and c13 3 1 in gpa and the density equals 2 17 g cm 3 the thomsen parameters for the clay composite are 0 89 3 10 and 0 34 the elasticity constants found for this clay composite can be used in the theoretical analysis of shales that have a similar composition of clay but with different mineral compositions the inversion technique developed can be used for general shale water clay composites when the mineral composition and orientation of the clay platelets are known

what regulates rhenium deposition in euxinic basins abstract rhenium is greatly enriched in black shales and euxinic basin sediments relative to its crustal abundance the enrichment process is generally assumed to involve reduction of reo 4 the principal re species in seawater to an insoluble re iv oxide or sulfide in suboxic and anoxic environments the specific biotic or abiotic mechanism of reduction has so far defeated efforts to discover it here an alternative mechanism of fixing re in sediments is examined experimentally thiolation of reo 4 leading to particle reactive thioperrhenates re vii o n s 4 n or to re vii sulfide precipitates or coprecipitates using optical absorption methodology we obtain the first measurements of equilibrium constants for formation of reo 3 s and res 4 as well as a solubility constant for a colloidal re 2 s 7 polymer from these constants we conclude that most euxinic environments contain insufficient sulfide to stabilize thioperrhenates as major species similarly re 2 s 7 polymers are too soluble to form in near neutral ph waters although they might form in acidic mine waters or during supergene hypogene enrichment processes to explain remarkable similarities between mo and re vertical profiles in the black sea we propose that both elements become thiolated at surfaces of a fe mo s colloidal phase and consequently coprecipitate coprecipitation implies that the triggering mechanism for re removal from euxinic basins is neither reduction nor thiolation of reo 4 but instead saturation of sulfidic waters with the fe mo s phase coprecipitation favors removal of mo more than re from the aqueous phase explaining increasing aqueous phase re mo ratios as these elements are depleted from sulfidic waters the raleigh fractionation law describes the process well similar partition coefficients describe the evolution of re mo ratios quantitatively both in sulfidic black sea waters and in sulfidic hingham bay pore waters

a comparison between excess barium and barite as indicators of carbon export 1 since dymond et al 1992 proposed the paleoproductivity algorithm based on bio ba which relies on a strong correlation between ba and organic carbon fluxes in sediment traps this proxy has been applied in many paleoproductivity studies barite the main carrier of particulate barium in the water column and the phase associated with carbon export has also been suggested as a reliable paleoproductivity proxy in some locations we demonstrate that baexcess total barium minus the fraction associated with terrigenous material frequently overestimates babarite barium associated with the mineral barite most likely due to the inclusion of barium from phases other than barite and terrigenous silicates e g carbonate organic matter opal fe mn oxides and hydroxides a comparison between overlying oceanic carbon export and carbon export derived from baexcess shows that the dymond et al 1992 algorithm frequently underestimates carbon export but is still a useful carbon export indicator if all caveats are considered before the algorithm is applied babarite accumulation rates from a wide range of core top sediments from different oceanic settings are highly correlated to surface ocean 14 c and chlorophyll a measurements of primary production this relationship varies by ocean basin but with the application of the appropriate f ratio to 14 c and chlorophyll a primary production estimates the plot of babarite accumulation and carbon export for the equatorial pacific atlantic and southern ocean converges to a global relationship that can be used to reconstruct paleo carbon export index terms 3022 marine geology and geophysics marine sediments processes and transport 4267 oceanography general paleoceanography 4825 oceanography biological and chemical geochemistry keywords paleoproductivity barite export production excess barium marine sediments citation eagle m a paytan k r arrigo g van dijken and r w murray a comparison between excess barium and barite as indicators of carbon export paleoceanography 18 1 1021 doi 10 1029 2002pa000793 2003

vertical budgets for organic carbon and biogenic silica in the pacific sector of the southern ocean 1996 1998 abstract during the 1996 1998 antarctic environment and southern ocean process study aesops a component of us jgofs we obtained seasonal or longer term data sets on the rates of production vertical transport remineralization and burial of particulate organic carbon poc and biogenic silica bsio2 in the southern ocean at 170 w between 55 s and 68 s the aesops data records enable us to construct vertical c and si budgets for the water column and upper sediments with all estimates derived from direct measurement of the relevant fluxes we constructed annual c and si budgets for each of four ecologically distinct zonal bands within the system for both poc and bsio2 the greatest annual delivery to the sea floor 200 and 1400 mmol m 2 yr 1 respectively and burial 6 and 160 mmol m 2 yr 1 respectively were observed in the southern antarctic circumpolar current acc between 61 5 s and 65 5 s that pattern is consistent with our observation that a diatom bloom propagated southward through the southern acc during the spring and summer of 1997 1998 following the receding ice edge and that this bloom was the main source of both poc and bsio2 in the system on an annual basis in the other zones the annual fluxes of poc and bsio2 to the sea floor ranged from 19 to 67 of those in the zone traversed by the summer diatom bloom the higher benthic fluxes of both poc and bsio2 in the southern acc imply that blooms similar to the one we observed in 1997 1998 occur commonly in the southern acc and that their high productivity signature is transmitted to the sea floor the data show preferential preservation of bsio2 over poc throughout the water column and upper seabed in the four zonal bands we consider bsio2 and poc are produced in mole ratios of 0 1 0 4 exported from the upper 100 m in ratios of 0 2 0 6 arrive at 1000 m in ratios of 1 5 4 5 reach the sea floor in ratios of 2 2 7 6 and are buried in ratios of 11 6 28 despite the preferential preservation of bsio2 accumulation of opal rich sediments beneath the acc does not result from unusually efficient preservation of siliceous material the estimated bsio2 preservation efficiency burial production ranges from 1 2 to 5 5 indistinguishable from the global average of 3 instead opal rich sediment accumulation in this region reflects very high annual rates of bsio2 production in surface waters along with very low accumulation rates of other sedimentary components e g caco3 and detrital material the observed high ratios of bsio2 production to poc production in surface waters are consistent with the known tendency for the si c ratio of diatoms to increase when fe is low if greater fe availability during the last glacial maximum permitted diatoms in the southern ocean to grow with lower more normal si c ratios export of diatom produced poc could have occurred at 2 3 times its present rate a corresponding increase in opal export or opal sediment accumulation is unlikely because silicic acid is almost totally depleted north of 65 s under present conditions thus even large increases in poc production and export during glacial periods would not be reflected in the opal accumulation record

coastal zone color scanner pigment concentrations in the southern ocean and relationships to geophysical surface features the spatial and seasonal distributions of phytoplankton pigment concentration over the entire southern ocean have been studied for the first time using the coastal zone color scanner historical data set from october 1978 through june 1986 enhanced pigment concentrations are observed between 35 s and 55 s throughout the year with such enhanced regions being more confined to the south in the austral summer and extending further north in the winter north and south of the polar front phytoplankton blooms 1 mg m3 are not uniformly distributed around the circumpolar region instead blooms appear to be located in regions of ice retreat or high melt areas such as the scotia sea and the ross sea in relatively shallow areas e g the patagonian and the new zealand shelves in some regions of ekman upwelling like the tasman sea and near areas of high eddy kinetic energy such as the agulhas retroflection among all features examined by regression analysis bathymetry appears to be the one most consistently correlated with pigments correlation coefficient being about 0 3 for the entire region the cause of negative correlation with bathymetry is unknown but is consistent with the observed abundance of iron in shallow areas in the antarctic region it is also consistent with resuspension of phytoplankton cells by wind induced mixing especially in shallow waters on the other hand in the deep ocean especially at latitudes 30 in average pigment concentration over the entire region during different seasons indicates possible influence of time dependent parameters

hydrocarbon generation induced microcracking of source rocks laboratory measurements of ultrasonic velocity and anisotropy in kerogen rich black shales of varying maturity suggest that extensive bedding parallel microcracks exist in situ in most mature source rocks undergoing the major stage of hydrocarbon generation and migration given the normal faulting regime with the vertical stress being the maximum principal stress typical of most sedimentary basins this microcrack alignment cannot be accounted for using simplified fracture mechanics concepts this subhorizontal microcrack alignment is consistent with 1 a model of local principal stress rotation and deviatoric stress reduction within an overpressured formation undergoing hydrocarbon generation and with 2 a strong mechanical strength anisotropy of kerogen rich shales caused by bedding parallel alignment of kerogen microlayers microcracks originate within kerogen or at kerogen illite interfaces when pore pressure exceeds the bedding normal total stress by only a few mpa due to the extremely low fractu

elastic anisotropy modeling of kimmeridge shale 1 anisotropy of elastic properties in clay rich sedimentary rocks has been of long standing interest these rocks are cap rocks of oil and gas reservoirs as well as seals for carbon sequestration elasticity of shales has been approached by direct velocity measurements and by models based on microstructures here we are revisiting the classical kimmeridge shale studied by hornby 1998 by first quantifying microstructural features such as phase volume fractions grain shapes and grain orientations and pore distributions with advanced analytical methods and then using this information in different models to explain bulk elastic properties it is shown that by application of a self consistent algorithm based on eshelby s 1957 model of inclusions in a homogeneous medium it is possible to explain most experimental elastic constants though some discrepancies remain which may be due to the interpretation of experimental data using a differential effective medium approach an almost perfect agreement with experimental stiffness coefficients can be obtained though the physical basis of this method may be questionable the influence of single crystal elastic properties grain shapes preferred orientation and volume and shapes of pores on elastic properties of shale is explored

linking preferred orientations to elastic anisotropy in muderong shale australia the significance of shales for unconventional hydrocarbon reservoirs nuclear waste repositories and geologic carbon storage has opened new research frontiers in geophysics among many of its unique physical properties elastic anisotropy had long been investigated by experimental and computational approaches here we calculated elastic properties of cretaceous muderong shale from australia with a self consistent averaging method based on microstructural information the volume fraction and crystallographic preferred orientation distributions of constituent minerals were based on synchrotron x ray diffraction experiments aspect ratios of minerals and pores determined from scanning electron microscopy were introduced in the self consistent averaging our analysis suggested that phyllosilicates i e illite mica illite smectite kaolinite and chlorite were dominant with 70 vol the shape of clay platelets displayed an average aspect ratio of 0 05 these platelets were aligned parallel to the bedding plane with a high degree of preferred orientation the estimated porosity at ambient pressure was 17 vol and was divided into equiaxial pores and flat pores with an average aspect ratio of 0 01 our model gave results that compared satisfactorily with values derived from ultrasonic velocity measurements confirming the validity and reliability of our approximations and averaging approach

effects of porosity and clay content on wave velocities in sandstones the ultrasonic compressional vp and shear vs velocities and first arrival peak amplitude ap were measured as functions of differential pressure to 50 mpa and to a state of saturation on 75 different sandstone samples with porosities ranging from 2 to 30 percent and volume clay content c ranging from 0 to 50 percent respectively both vp and vs were found to correlate linearly with porosity and clay content in shaly sandstones at confining pressure of 40 mpa and pore pressure of 1 0 mpa the best least squares fits to the velocity data are vp km s 5 59 6 93 2 18c and vs km s 3 52 4 91 1 89c deviations from these equations are less than 3 percent and 5 percent for vp and vs respectively the velocities of clean sandstones are significantly higher than those predicted by the above linear fits about 7 percent for vp and 11 percent for vs which indicates that a very small amount of clay 1 or a few percent of volume fraction significantly reduces the elastic moduli of sandstones for shaly

authigenic cadmium enrichments in suboxic sediments precipitation and postdepositional mobility the postdepositional mobility of cd and u has been investigated in north atlantic turbidites in order to validate their utility as proxies of paleo organic carbon fluxes in this region pelagic sediments are interspersed with relatively organic rich turbidites following instantaneous emplacement of turbidite units an oxidation front progressively migrated downwards into the suboxic turbidite thereby leading to redistribution of authigenic phases according to their affinity to different redox conditions authigenic cd concentrations show a large peak at the redox boundary and are significantly lower in the oxidized portion than in the deeper unoxidized part of the turbidite this distribution indicates that cd has been continuously remobilized by the oxidation front thereby suggesting high sensitivity of the cd species to the redox state and an efficient immobilization mechanism for cd under reducing conditions we propose the precipitation of cds as a plausible mechanism for removal of cd in reducing sediments rather than adsorption onto mineral surfaces this proposal is consistent with porewater data indicating diffusion of cd toward and uptake by suboxic sediments solubility calculations suggest that precipitation of cds may occur in suboxic sediments in the presence of trace levels of h2s below routine detection limits there is no evidence for release of cd or u back into seawater upon oxidation of reducing sediments the strong coupling between precipitation of authigenic cd and u and the early diagenetic degradation of organic carbon offers the potential of reconstructing paleo productivity using records of cd and u however postdepositional redistribution of authigenic cd and u may significantly alter records of authigenic cd and u thereby rendering paleo productivity reconstructions uncertain we propose that the cd u authigenic ratio may provide a qualitative indicator to assess the relative role of steady state incorporation relative to transient burn down enrichments

assessing oxygen depletion in the northeastern pacific ocean during the last deglaciation using i ca ratios from multiple benthic foraminiferal species paleo redox proxies are crucial for reconstructing past bottom water oxygen concentration changes brought about by ocean circulation and marine productivity shifts in response to climate forcing carbonate i ca ratios of multiple benthic foraminifera species from odp hole 1017e a core drilled within the californian oxygen minimum zone omz on the continental slope are employed to re examine the transition from the well oxygenated last glacial into poorly oxygenated modern conditions the redox and export productivity history of this site is constrained by numerous proxies used to assess sensitivity of i ca ratios of benthic foraminifera to changes in bottom and pore water o2 concentrations reconstructed iodate io3 availability from the i ca ratio of epifaunal cibicidoides sp shallow infaunal uvigerina peregrina and deep infaunal bolivina spissa foraminifera the reconstructed io3 availability profile is used to determine the contribution of bottom water o2 relative to oxidant demand on pore water o2 concentrations these results suggest that high export productivity on the california margin drove pore low water o2 concentrations during the bolling in contrast low bottom water o2 concentrations at 950 m water depth only contributed to reduced sediments during the allerod increased contribution of modified north pacific intermediate water to the california current system ventilated the california omz during the late glacial and the younger dryas such that water overlying the site was oxygenated these results highlight the promising potential of this new proxy for understanding the relative influence of bottom water o2 concentration and pore water oxidant demand on omzs

texture and anisotropy analysis of qusaiba shales scanning and transmission electron microscopy synchrotron x ray diffraction microtomography and ultrasonic velocity measurements were used to characterize microstructures and anisotropy of three deeply buried qusaiba shales from the rub alkhali basin saudi arabia kaolinite illite smectite illite mica and chlorite show strong preferred orientation with 001 pole figure maxima perpendicular to the bedding plane ranging from 2 4 6 8 multiples of a random distribution m r d quartz feldspars and pyrite crystals have a random orientation distribution elastic properties of the polyphase aggregate are calculated by averaging the single crystal elastic properties over the orientation distribution assuming a nonporous material the average calculated bulk p wave velocities are 6 2 km s maximum and 5 5 km s minimum resulting in a p wave anisotropy of 12 the calculated velocities are compared with those determined from ultrasonic velocity measurements on a similar sample in the ultrasonic experiment which measures the effects of the shale matrix as well as the effects of porosity velocities are smaller p wave maximum 5 3 km s and minimum 4 1 km s the difference between calculated and measured velocities is attributed to the effects of anisotropic pore structure and to microfractures present in the sample which have not been taken into account in the matrix averaging

scavenging of 230th 231pa and 10be in the southern ocean sw pacific sector the importance of particle flux particle composition and advection abstract the scavenging of 230 th 231 pa and 10 be was studied in the pacific sector of the southern ocean along 170 w using measurements from surface sediments time series sediment traps and the water column all sediment traps collected an annual flux of 231 pa greater than the integrated rate of production by 235 u decay up to 5 5 times greater and a flux of 10 be greater than the global average deposition rate of 10 be up to 3 4 times greater fluxes of 230 th were on average close to the production rate in the overlying water column these large fluxes of 231 pa and 10 be and high unsupported 231 pa 231 th and 10 be 230 th ratios in the sediments are not associated with depletion of nuclides in the water column and therefore are not the result of the classical boundary scavenging mechanism we estimate that of the 231 pa and 230 th advected into the southern ocean as part of the large scale overturning circulation only those nuclides associated with the upper limb of this circulation i e those that pass through the surface as part of the wind driven ekman flow are scavenged efficiently the majority of the nuclides advected into the southern ocean and associated with the bottom water limb are not scavenged to the sediments of the southern ocean but are returned northward throughout the year the unsupported 231 pa 230 th and 10 be 230 th ratios of material reaching sediment traps at 1000 m at a given site increase with increasing particle flux this behavior is explained by a conceptual model in which th pa and be are scavenged reversibly by fine grained suspended particles at all depths while pa and be are in addition scavenged strongly by diatom rich aggregates in surface waters spatial variability in the annually averaged unsupported 231 pa 230 th and 10 be 230 th ratios of sinking particulate matter reflects primarily the variability in particle composition and in the ratio and quantity of nuclides upwelled to the mixed layer rather than variability in particle flux

an empirical method for estimation of anisotropic parameters in clastic rocks clastic sediments particularly shale exhibit transverse isotropic properties with the symmetric axis perpendicular to bedding vti these anisotropic rock properties are important in seismic imaging prestack seismic analysis and reservoir characterization laboratory tests are the main techniques used in measuring rock anisotropic properties vertical seismic profiling vsp and seismic refraction are the in situ techniques used to determine anisotropic parameters all of these methods provide significant insight to the anisotropic properties of the subsurface however limitations exist in the applications of these methods because of cost issues and restrictions on the number of measurements that can be conducted therefore new techniques that are cost effective easy to use and able to measure continuous anisotropic profiles are desirable this paper describes a methodology which involves the use of conventional rock properties to derive anisotropic rock properties

mathematical modelling of anisotropy of illite rich shale summary the estimation of illite rich shale anisotropy to account for the alignment of clays and gas or brine filled cracks is presented via mathematical modelling such estimation requires analysis to interpret the dominance of one effect over another this knowledge can help to evaluate the permeability in the unconventional reservoir stress orientation and the seal capacity for the conventional reservoir effective media modelling is used to predict the elastic properties of the illite rich shale and to identify the dominant contributions to the shale anisotropy we consider two principal reasons of the shale anisotropy orientation of clay platelets and orientation of fluid filled cracks in reality both of these two factors affect the shale anisotropy the goal of this study is first to separately analyse the effect of these two factors to reveal the specific features in p and s wave velocity behaviour typical of each of the factors and then consider a combined effect of the factors when the cracks are horizontally or vertically aligned to do this we construct four models of shale the behaviour of p and s wave velocities is analysed when gas and water filled cracks embedded in a host matrix are randomly oriented or horizontally or vertically aligned the host matrix can be either isotropic or anisotropic of vti symmetry in such a modelling we use published data on mineralogy and clay platelet alignment along with other micromechanical measurements in the model where the host matrix is isotropic the presence of a singularity point when the difference changes its sign in shear wave velocities is an indicator of brine filled aligned cracks in the model with the vti host matrix and horizontally aligned cracks filled with gas an increase in their volume concentration leads to that the azimuth at which the singularity is observed moves toward the symmetry axis in this case if the clay content is small around 20 per cent the singularity point may even vanish the thomsen parameters are helpful in fluid type indication in shale an indicator of gas filled aligned cracks is if aligned cracks in illite rich shale are brine filled negative value of indicates brine filled cracks in illite rich shale a shale with brine filled cracks exhibits higher vp vs ratio in the vertical direction as compared to the gas filled shale a disorientation of clay platelets and brine filled cracks may lead to that the singularity point is absent for brine saturated shale as well in this case one can also observe and decreased values of vp vs in the vertical direction as in the case of gas filled cracks in the presence of vertically aligned cracks shales exhibit distinctly revealed features of orthorhombic symmetry the results have important applications where seismic measurements are applied to predict the maturity state of the shale

biogenic opal in southern ocean sediments over the last 450 000 years implications for surface water chemistry and circulation we present records of biogenic opal percentage and burial rate in 12 piston cores from the atlantic and indian sectors of the southern ocean these records provide a detailed quantitative description of changing patterns of opal deposition over the last 450 kyr the striking regional coherence of these records suggests that dissolution in the deep sea and sediment pore waters does not obscure the surface productivity signal and therefore these opal time series can be used in combination with other surface water tracers to make inferences about the chemistry and circulation of the southern ocean under different global climate conditions three broad depositional patterns can be distinguished northernmost records 39 42 s latitude are characterized by enhanced opal burial during glacial periods and strong 41 kyr periodicity records from cores just north of the present antarctic polar front 46 49 s show even larger increases in opal burial rate during glacial intervals but have variance concentrated in the 100 and 23 kyr bands southernmost records 51 55 s are completely out of phase with those to the north with greatly reduced opal burial rates during glacial periods taken as a whole the opal records show no evidence for the increased total antarctic productivity predicted by recent geochemical models of atmospheric co2 variability the areal expansion of southern ocean sea ice over the present zone of high siliceous productivity provides one plausible explanation for the glacial interglacial opal patterns the excess silica not taken up in this zone during glacial periods would contribute to greater nutrient availability and thus higher productivity in the subantarctic region however local circulation changes may act to modify this basic signal possibly accounting for the observed differences in the opal variance spectra

glacial interglacial changes in sediment rain rate in the sw indian sector of subantarctic waters as recorded by 230th 231pa u and δ15n high resolution records of opal carbonate and terrigenous fluxes have been obtained from a high sedimentation rate core md84 527 43 50 s 51 19 e 3269 m by normalization to 230th this method estimates paleofluxes to the seafloor on a point by point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents we also measured sediment 15n to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations our results show that opal accumulation rates on the seafloor during the holocene and stage 3 based on 14c dating were respectively tenfold and fivefold higher than the vertical rain rates at this particular location changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230th disclose important variations in opal rain rates we found relatively high but variable opal paleoflux during stage 3 with two maxima centered at 36 and 30 kyr b p low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early holocene we interpret this record as reflecting variations in opal production rates associated with climate induced latitudinal migration of the southern ocean frontal system sediments deposited during periods of high opal paleoflux also have high authigenic u concentrations suggesting more reducing conditions in the sediment and high pa 231 th 230 ratios suggesting increased scavenging from the water column sediment 15n is circa 1 5 per mil higher during isotopic stage 2 and deglaciation the low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion this suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid leading to lower nitrate supply rates to surface waters

paleocurrent reconstruction of the deep pacific inflow during the middle miocene reflections of east antarctic ice sheet growth today the deep western boundary current dwbc east of new zealand is the most important route for deep water entering the pacific ocean large scale changes in deep water circulation patterns are thought to have been associated with the development of the east antarctic ice sheet eais close to the main source of bottom water for the dwbc here we reconstruct the changing speed of the southwest pacific dwbc during the middle miocene from 15 5 12 5 ma a period of significant global ice accumulation associated with eais growth sortable silt mean grain sizes from ocean drilling program site 1123 reveal variability in the speed of the pacific inflow on the timescale of the 41 kyr orbital obliquity cycle similar orbital period flow changes have recently been demonstrated for the pleistocene epoch collectively these observations suggest that a strong coupling between changes in the speed of the deep pacific inflow and high latitude climate forcing may have been a persistent feature of the global thermohaline circulation system for at least the past 15 myr furthermore long term changes in flow speed suggest an intensification of the dwbc under an inferred increase in southern component water production this occurred at the same time as decreasing tethyan outflow and major eais growth between 15 5 and 13 5 ma these results provide evidence that a major component of the deep thermohaline circulation was associated with the middle miocene growth of the eais and support the view that this time interval represents an important step in the development of the neogene icehouse climate

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

upper ocean eddy transports of heat potential vorticity and volume in the northeastern north atlantic vivaldi 1991 abstract mesoscale eddies in the northeast north atlantic were investigated using the seasoar towed ctd and adcp data from the 1991 vivaldi cruise these data cover an area of 1700 km 1500 km between 39 and 54 n and between 35 and 10 w to maximize statistical significance but retain the possibility of determining north south gradients statistics of eddy quantities were calculated separately for the northern and southern halves of the cruise area the mean flow in the south is essentially zero in the north the flow is dominated by the north atlantic current nac with a mean speed of 6 5 cm s 1 the eddy kinetic energy in the south 205 cm2 s 2 is however only slightly less than in the north 272 cm2 s 2 the eddy momentum transports or reynolds stresses u show a poleward decrease corresponding to an acceleration of the mean eastward flow associated with the nac of 0 03 cm s 1 day 1 the eddy heat transports u t are not significantly different from zero in the south but show a clear po

some correlations between the large scale meridional eddy momentum transport and zonal mean quantities abstract an empirical study has been made which compares the large scale meridional eddy momentum transport with some selected zonal mean quantities by calculating correlations between them as a function of time lag and latitude the basic dataset was the daily 200 mb geopotential and temperature grid analysis fields of the german weather service over an eight year period the results gave generally only small correlation values but show that a meridional covergence of the eddy transport leads to an increasing zonal mean wind or meridional curvature of the zonal wind component the correlation maxima are reached at a time lag of 2 days the same tendency can be recognized from an examination of the relation which green found between the convergence of momentum transport and the transport of sensible heat and potential vorticity an introductory discussion of two dimensional models is given which focuses on the methods of parameterizing the eddy transports

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

relationships between compressional wave and shear wave velocities in clastic silicate rocks new velocity data in addition to literature data derived from sonic log seismic and laboratory measurements are analyzed for clastic silicate rocks these data demonstrate simple systematic relationships between compressional and shear wave velocities for water saturated clastic silicate rocks shear wave veloci ty is approximately linearly related to compressional wave velocity and the compressional to shear velocity ratio decreases with increasing compressional velocity laboratory data for dry sandstones indicate a nearly constant compressional to shear velocity ratio with rigidity approximately equal to bulk modulus ideal models for regular packings of spheres and cracked solids exhibit behavior similar to the observed water saturated and dry trends for dry rigidity equal to dry bulk modulus gassmann s equations predict velocities in close agreement with data from the water saturated

particle fluxes to the interior of the southern ocean in the western pacific sector along 170 w abstract an array of five bottom tethered moorings with 19 parflux time series sediment trap at three depths 1 and 2 km below the surface and 0 7 km above the sea floor was deployed in the western pacific sector of the southern ocean along 170 w the five stations were selected to sample settling particles in the main hydrological zones of the southern ocean the sampling period spanned 425 days november 28 1996 january 23 1998 and was divided into 13 or 21 synchronized time intervals a total of 174 sequential samples were recovered and analyzed to estimate fluxes of total mass tmf organic carbon carbonate biogenic silica and lithogenic particles the fluxes of biogenic material were higher than anticipated challenging the notion that the southern ocean is a low productivity region organic carbon fluxes at 1 km depth within the polar frontal zone and the antarctic zone were relatively uniform 1 7 2 3 g m 2 yr 1 and about twice the estimated ocean wide average ca 1 g m 2 yr 1 carbonate fluxes were also high and uniform between the subantarctic front and ca 64 s 11 13 g m 2 yr 1 a large fraction of the carbonate flux in the antarctic zone was due to the presence of pteropod shells coccoliths were found only to the north of the polar front and calcium carbonate became the dominant phase in the subantarctic zone in contrast carbonate particles were nearly absent near 64 s latitudinal variations in biogenic silica fluxes were substantial the large opal flux 57 g m 2 yr 1 measured in the antarctic zone suggests that opal productivity in this region has been previously underestimated and helps to explain the high sedimentary opal accumulation often found south of the polar front unlike biogenic material fluxes of lithogenic particles were among the lowest measured in the open ocean 0 12 0 05 g m 2 yr 1 reflecting a very low dust input

the influence of crenulation cleavage development on the bulk elastic and seismic properties of phyllosilicate rich rocks abstract the anisotropy of seismic wave propagation is strongly influenced by the mineralogy and microstructure of rocks phyllosilicates are elastically highly anisotropic and are therefore thought to be important contributors to seismic anisotropy in the continental crust crenulation cleavage is one of the most common microstructural fabrics found in multiply deformed phyllosilicate rich crustal rocks we calculated the bulk elastic properties and resulting wave velocities for rock samples that preserved three different stages of crenulation cleavage development an initial planar foliation a moderately developed crenulation cleavage and a well developed crenulation cleavage mineral orientation maps were obtained using electron backscatter diffraction and calculations were made using asymptotic expansion homogenization combined with the finite element method the difficulties involved with sample preparation and data acquisition of phyllosilicate rich rock samples are also discussed we compare our results to more conventional methods for calculating an aggregate stiffness matrix from a mineral orientation map namely voigt and reuss averages these averages do not account for grain scale interactions and therefore deviate from the results calculated using asymptotic expansion homogenization our results show that the rocks characterized by a planar foliation and a moderately developed crenulation cleavage are highly anisotropic with p wave anisotropies up to 30 9 and s wave anisotropies up to 34 2 whereas the rock characterized by a well developed crenulation cleavage is only mildly anisotropic with a p wave anisotropy of 15 5 and s wave anisotropy of 10 7 progressive development of the fabric also causes the orientations of p and s wave velocity maxima and s wave polarization directions to change markedly despite the high anisotropy imparted by a planar schistosity the variety of folds and fabrics typically found in phyllosilicate rich rocks within larger scale crustal volumes will tend to mute the anisotropy possibly to the point of appearing nearly isotropic

is pore water oxygen content decoupled from productivity on the california margin trace element results from ocean drilling program hole 1017e san lucia slope california 1 trace element evidence from the california margin ocean drilling program hole 1017e shows significant changes in sediment redox chemistry at intermediate water depths over the last 60 kyr the influence of export production on intermediate water oxygen content can be distinguished from lateral ventilation through comparisons among proxies representing export production flux percent corg and sediment surface i br and pore water mo ag cd re and u oxygenation proxies sulfate reduction within the uppermost sediment column occurred during late quaternary interstadials and the holocene indicating reduced intermediate water ventilation however sulfate reduction was most intense during major interstadials when productivity was enhanced decoupling between export production and pore water oxygen content is demonstrated during deglaciation when the sediment pore water oxygen content increases without a corresponding reduction in export productivity thus both export production and intermediate water ventilation play a role in oxygen minimum zone processes on the california margin

trace metal evidence for a poorly ventilated glacial southern ocean abstract glacial benthic 13c and 14c measurements from the atlantic ocean have been interpreted to indicate the existence of a poorly ventilated southern ocean with greater co2 and nutrient contents compared to present enhanced storage of co2 in the deep ocean predicts that oxygen concentrations should have declined at the same time a prediction increasingly supported by evidence for oxygen depletion in the glacial southern ocean here we take a novel approach by using a suite of redox sensitive trace metals ag cd re and mo to show that southern ocean sediments from two cores in the atlantic sector were suboxic during and prior to deglaciation implying changes to ocean circulation and or elevated export production that significantly altered deep water chemistry in the cape basin enrichments of the authigenically deposited trace metal re are comparable to those found in oxygen minimum zones pointing to substantial decreases in oxygenation furthermore trace metal results suggest potential spatial heterogeneity in the glacial southern ocean and a more complicated oceanographic and oxygenation history than has previously been assumed

silver in the north pacific ocean 1 the distribution of silver in the north pacific determined using a suite of surface and subsurface samples was found to be controlled by both natural and anthropogenic processes within the water column silver was distributed as a typical nutrient type element as was previously observed in other oceanic waters however surface water concentrations of silver near japan were the highest ever measured for the open ocean up to 12 pm and are considered evidence of anthropogenic contamination since prevailing wind flow during this study was westerly this enrichment is attributed to aeolian fluxes of asian industrial aerosols to north pacific surface waters additional evidence of the impact atmospheric inputs of silver have on the north pacific water column is shown by comparisons of intermediate depth waters analyzed during this study and during a study carried out 20 years previously that indicate temporal increases in industrial silver fluxes to these waters measurements from this study also confirm that silver is significantly correlated with dissolved silica although the correlations are measurably different between the atlantic and pacific basins and that the ratio of silver to copper is diagnostic of individual water masses in the pacific and can be used as a geochemical tracer of ocean circulation overall data obtained during this study enable a complete preliminary survey of silver in the world ocean

mobility of authigenic rhenium silver and selenium during postdepositional oxidation in marine sediments sedimentary records of redox sensitive trace elements hold significant potential as indicators of paleoceanographic environmental conditions records of re can reveal the intensity of past reducing conditions in sediments at the time of deposition whereas records of ag may record the magnitude of past diatom fluxes to the seafloor confidence in paleoenvironmental reconstruction from records of either metal however requires it to have experienced negligible redistribution since deposition this study examines diagenetic rearrangements of re and ag that occur in response to exposure to bottom water o2 in environments of low sedimentation rate including madeira abyssal plain turbidites and eastern mediterranean basin sapropels authigenic re was remobilized quantitatively by oxidation but poorly retained by the underlying sediments all records are consistent with previous work demonstrating that only a limited reimmobilization of re occurs preferentially in corg rich reducing sediments silver was also mobilized quantitatively by oxidation but it was subsequently immobilized more efficiently in all cases as sharp peaks immediately into anoxic conditions below active oxidation fronts and these peaks remain immobile in anoxic conditions during long term burial comparison of ag s and se records from various cores suggests that ag is likely to have been immobilized as a selenide a mechanism previously proposed for hg in similar situations mercone et al 1999 coexisting narrow peaks of ag and hg with se offer a means of assessing whether oxidative burndown has ever occurred at the top of corg and sulfide rich sedimentary units although these results suggest that caution must be used when inferring paleoenvironmental information from records of ag and re in cores with low sediment accumulation rates 5 cm ka 1 they should not affect the promise that authigenic ag and re records hold for paleoenvironmental reconstruction in sediments with higher accumulation rates and where anoxic conditions have been maintained continuously

new insights into productivity and redox controlled trace element ag cd re and mo accumulation in a 55 kyr long sediment record from guaymas basin gulf of california a high resolution 55 kyr long record of chalcophile and redox sensitive trace element accumulation ag cd re and mo from md02 2515 western guaymas basin is investigated in conjunction with patterns in stratigraphy and productivity high opal concentrations 59 wt representing increased diatom production coincide with laminated sediments and dilute the concentrations of organic carbon corg and metals a similarity between opal and normalized corg ag and cd concentrations suggests delivery to the sediments by diatom export production while patterns in normalized re and mo accumulation suggest a different emplacement mechanism although mo enrichment in organic rich laminated sediments typically represents anoxic conditions at other locations mo and re in guaymas basin is enriched in nonlaminated and bioturbated sediments that are representative of oxygenated conditions adsorption onto fe and or mn oxyhydroxide surfaces during oxygenation inadequately explains both the re and mo enrichments thus recently published mechanisms invoking direct re and mo removal from the water column and bioturbation assisted irrigation of re into the sediments are used to explain the counterintuitive observations in guaymas basin the md02 2515 stratigraphic and proxy records are also different from other records in the northeast pacific in that there is little correspondence with greenland dansgaard oeschger interstadials there is some correlation with heinrich events suggesting that ventilation of intermediate waters and or reduced productivity may be important in controlling stratigraphy and trace element accumulation the results question whether md02 2515 records can be compared to northeast pacific open margin records especially before 17 kyr b p

velocity anisotropy in shales a petrophysical study using ultrasonic velocity and anisotropy measurements on a variety of shales with different clay and kerogen content clay mineralogy and porosity at a wide range of effective pressure we find that elastic anisotropy of shales increases substantially with compaction the effect is attributed to both porosity reduction and smectite to illite transformation with diagenesis a means of kerogen content mapping using velocity versus porosity crossplot for shales is shown matrix anisotropy of shales dramatically increases with kerogen reaching the maximum values of about 0 4 at total organic carbon toc 15 20 a strong chemical softening effect was found in shales containing even minor amounts of swelling smectite clay when saturated with aqueous solution this effect results in a significant p wave anisotropy reduction as compared to dry and oil saturated shales since mature black shales are normally oil wet this effect can only have a local significance restricted to the wellbore wall accurate measurements of phase velocities including velocities at a 45 direction to the bedding plane allow us to immediately calculate elastic stiffnesses and anisotropic parameters intrinsic high pressure properties of shales display an e 0 relation introduction of the bedding parallel microcracks in overpressured shales results in a decrease when fully fluid saturated and a increase when partially gas saturated with a characteristic effect on the shape of the p wave velocity surface at small angles of incidence filtering the contribution of the intrinsic anisotropy of shales it is possible to estimate the pore fluid phase microcrack density and aspect ratio parameters using seismic anisotropy measurements

prediction of sonic velocities in shale from porosity and clay fraction obtained from logs a north sea well case study abstractprediction of sonic velocities in shales from well logs is important for seismic to log ties if the sonic log is absent for a shaly section for pore pressure anomaly detection and for data quality control an anisotropic differential effective medium dem was used to simulate elastic properties of shales from elastic properties and volume fractions of silt and wet clay a hypothetical composite material that includes all clay minerals and water anisotropic elastic coefficients of the wet clay were assumed as a first order approximation to be linearly dependent on wet clay porosity wcp here by wcp we mean a ratio of a pore volume occupied by water to a total volume of the wet clay effects of silt inclusions on elastic coefficients of shales were taken into account by using the anisotropic differential effective medium model silt inclusions were modeled as spherical quartz particles simulated elastic coefficients of shales were used to calculate compressional and shear velocities and th

the geochemical cycle of rhenium a reconnaissance rhenium re is one of a suite of elements including uranium and molybdenum that display conservative behavior in seawater and are enriched in anoxic sediments the decay of187re to187os provides a geochronometer in ancient sedimentary rocks and gives rise to os isotopic variations in nature in order to better characterize its sources to seawater re was measured in three major rivers amazon orinoco ganges brahmaputra and some of their tributaries re concentrations span four orders of magnitude from 0 02 to 400 pmol kg with the highest concentrations found in rivers draining black shales in the venezuelan andes mainstream re levels in the three rivers are between 1 and 10 pmol kg with a flux weighted average of 2 3 pmol kg the residence time for re in the oceans is estimated to be 750 000 yr with respect to river inputs re profiles from the atlantic and pacific oceans confirm that re behaves conservatively in seawater with no significant uptake onto particles and or recycling within the water column this is also true in the anoxic water column of the black sea re removal into anoxic sediments occurs at or below the sediment water interface as demonstrated in sediment pore waters from chesapeake bay in oxic sediments re is not cycled with manganese oxides and it is not enriched in very slowly accumulating pelagic sediments with a large hydrogenous iron and manganese component or in manganese nodules burial of re in anoxic sediments which accumulate on 0 3 of the ocean floor removes approximately 50 of the riverine re flux to the oceans hence oceanic re concentrations may be very sensitive to changes in the area of anoxic sedimentation

circulation and seasonal evolution of polar waters south of australia implications for iron fertilization of the southern ocean abstract the southern ocean iron release experiment soiree was carried out in late summer february 1999 south of australia 61 s 140 e this region of the southern antarctic zone az s between the southern branch of the polar front pf and the southern front of the antarctic circumpolar current saacf is characterized by weak currents and is remote from the influence of sea ice or coastal waters the soiree site exhibits high nutrient concentrations year round phosphate nitrate and silicate remain above 10 m low chlorophyll accumulations

similar glacial and interglacial export bioproductivity in the atlantic sector of the southern ocean multiproxy evidence and implications for glacial atmospheric co2 we present time series of export productivity proxy data including 230thex normalized deposition rates rain rates of 10be dissolution corrected biogenic ba and biogenic opal as well as authigenic u concentrations which are complemented by rain rates of total detrital fe and sea ice indicating diatom abundances from five sediment cores across the atlantic sector of the southern ocean covering the past 150 000 years the results suggest that 10be rain rates and authigenic u concentration cannot serve as quantitative paleoproductivity proxies because they have also been influenced by detrital particle fluxes in the case of 10be and bulk sedimentation rates sediment focussing and deep water oxygenation in the case of u the combined results of the remaining productivity proxies of this study rain rates of biogenic opal and biogenic ba in those sections without authigenic u and other previously published proxy data from the southern ocean 231pa 230th and nitrogen isotopes suggest that a combination of sea ice cover shallow remineralization depth and stratification of the glacial water column south of the present position of the antarctic polar front and possibly fe fertilization north of it have been the main controlling factors of export paleoproductivity in the southern ocean over the last 150 000 years an overall glacial increase of export paleoproductivity is not supported by the data implying that bioproductivity variations in the southern ocean are unlikely to have contributed to the major glacial atmospheric co2 drawdown observed in ice cores