oxygenation episodes on the continental shelf of central peru remote forcing and benthic ecosystem response abstract the interplay between the oxygen minimum zone and remotely forced oxygenation episodes determines the fate of the benthic subsystem off the central peruvian coast we analyzed a 12 year monthly time series of oceanographic and benthic parameters at 94 m depth off callao central peru 12 s to analyze i near bottom oxygen level on the continental shelf in relation to dynamic height on the equator 095 w and ii benthic ecosystem responses to oxygen change macrobiotic infauna meiofauna and sulphide oxidizing bacteria thioploca spp shelf oxygenation episodes occurred after equatorial dynamic height increases one month before consistent with the propagation of coastal trapped waves several but not all of these episodes occurred during el ninos the benthic biota responded to oxygenation episodes by undergoing succession through three major ecological states under strong oxygen deficiency or anoxia the sediments were nearly defaunated of macro invertebrates and thioploca was scarce such that nematode biomass dominated the macro and meiobiotas when frequency of oxygenation events reduced the periods of anoxia but the prevailing oxygen range was 10 20 mol l 1 mats of thioploca formed and dominated the biomass finally with frequent and intense 40 mol l 1 oxygenation the sediments were colonized by macrofauna which then dominated biomass the thioploca state evolved during the 2002 2003 weak en while the macrofauna state was developed during the onset of the strong1997 1998 en repeated episodes of strong oxygen deficiency during the summer of 2004 in parallel with the occurrence of red tides in surface waters resulted in the collapse of thioploca mats and development of the nematode state ecological interactions may affect persistence or the transition between benthic ecosystem states

ekman modulation of the sea surface temperature on the eastern south pacific abstract nine years of data 1992 2000 were used to study the evolution of the sea surface temperature sst over the eastern south pacific our analysis shows that the variability in the sst on the interannual scale is attributed mainly to the equatorial el nino la nina events while cooling associated with the wind ekman drift is an important component of the annual cycle the anomalies at the interannual scale show up as a front that parallels the coast at the seasonal scale anomalous warming and cooling of coastal waters is strongly altered by the local effect of the wind driven ekman transport this latter effect is especially significant along the peruvian and northern chilean coast where wind induced upwelling and cooling is out of phase with other important annual forcings i e radiation and annual kelvin waves these local wind effects show up in the time latitude plots as a thinning of the warm water bands along the peruvian coast 10 s y 17 s and a thickening of the bands further south 18 s y 22 s three anomalous events that stand out clearly at the interannual scale are el nino 92 93 la nina 96 and el nino 97 98 their individual evolutions over time and along the coast are very different though the least intense of the three the 92 93 event had the longest duration the 96 event was the shortest in duration and its strongest anomaly occurred around the peruvian coast similar to the warm event of 92 93 the strongest event for the period occurred in 97 98 its warm anomaly showing strongly along the whole latitudinal extent of the study area contrary to what occurs at the seasonal scale the increase on east west ekman transport on the interannual scale seems to be in phase with other relevant cooling and warming mechanisms the interannual ekman anomalous transports are at their maximum near the peruvian northern chilean coast however they do not seem to alter the sst in a significant way a similar situation has been described for sea level data in the california current system i e interannual variability being associated mostly with variability of equatorial origin while seasonal variability is associated to both wind forced local variability and remotely forced variability j geophys res 94 1989 3159

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

authigenic uranium relationship to oxygen penetration depth and organic carbon rain we have measured u in benthic incubation chambers sediment pore waters and in sediments along the california continental margin sedimentary u uptake rates based on a combination of sediment pore water profiles and benthic incubation chambers generally agree with those predicted from sediment accumulation rate data this agreement supports the view that most of the continental margin sedimentary u is delivered by diffusion across the seawater sediment boundary the average rate of authigenic u accumulation for all the sites examined here is 0 2 nmol cm 2 y 1 which is consistent with published global estimates of sedimentary u uptake in addition the accumulation rate of u in sediments exhibits a nonlinear relationship with the oxygen penetration depth and a linear relationship with the organic carbon rain rate these relationships highlight the potential utility for the u accumulation rate as a proxy for these processes

early diagenesis in differing depositional environments the response of transition metals in pore water the cycling of fe mn ni co cu cr v and mo during early diagenesis was investigated in sediments from five different depositional environments in the california borderland dissolved o2 no3 no2 and so4 were also measured at each site to establish the position of redox boundaries pertinent to this study sites were chosen to allow the comparison of several parameters of potential importance to the cycling of these metals bottom water o2 concentration sediment redox conditions cycling of metal oxide carrier phases and the relative contribution of biogenic and terrigenous material to the detrital metal flux at 10 m oxygen and above the sequence of terminal electron acceptor utilization was typical of pelagic sediments differing only in scale under these conditions the recycling of mn oxides resulted in an enriched layer near the interface at bottom water 02 concentrations 5 m mn oxides are not recycled under these conditions fe oxides and so42 are important oxidants the depth of the zone of manganese oxidation with respect to the interface affects the efficiency of metal scavenging by manganese oxides trapping and recycling of ni and co with mn oxides results in remobilization from reducing sediments and enrichment in oxic sediments scavenging of these metals is favored by a deep oxic zone in the sediments in contrast cr v and mo appear to be transported to the sediments as reduced species and are released from the sediments by oxidation the source of the reduced species is assumed to be biogenic material the accumulation of these metals is favored by reducing conditions in the sediments cu is enriched in the sediments by transport with detrital biogenic material followed by adsorption onto sediment solids cu is released at the interface and rapidly removed onto the solids at all sites except the one pelagic site at the base of the slope the magnitude of cu released in the slowly accumulating pelagic sediment exceeds the cu binding capacity of the solids resulting in pore water cu concentrations in excess of 100 nm in general metal cycling associated with the early diagenesis of sediments was observed to decouple transport processes from burial processes for the transition metals measured in this study

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

remobilization of authigenic uranium in marine sediments by bioturbation uranium behaves as a nearly conservative element in oxygenated seawater but it is precipitated under chemically reducing conditions that occur in sediments underlying low oxygen bottom water or in sediments receiving high fluxes of particulate organic carbon sites characterized by a range of bottom water oxygen bwo and organic carbon flux ocf were studied to better understand the conditions that determine formation and preservation of authigenic u in marine sediments our study areas are located in the mid latitudes of the northeast pacific and the northwest atlantic oceans and all sites receive moderate 0 5 g cm2 kyr to high 2 8 g cm2 kyr ocf to the sediments bwo concentrations vary substantially among the sites ranging from 3 to 270 m a mass balance approach was used to evaluate authigenic u remobilization at each site within each region studied the supply of particulate nonlithogenic u associated with sinking particles was evaluated by means of sediment traps the diffusive flux of u into sediments was calculated from pore water u concentration profiles these combined sources were compared with the burial rate of authigenic u to assess the efficiency of its preservation a large fraction one third to two thirds of the authigenic u precipitated in these sediments via diffusion supply is later regenerated even under very low bwo concentrations 15 m bioturbating organisms periodically mix authigenic u containing sediment upward toward the sediment water interface where more oxidizing conditions lead to the remobilization of authigenic u and its loss to bottom waters

genesis of phosphorite crusts off peru abstract authigenic phosphorite crusts from the shelf off peru 9 40 s to 13 30 s consist of a facies with phosphatic coated grains covered by younger phosphatic laminite the crusts are composed of carbonate fluorapatite which probably formed via an amorphous precursor close to the sediment water interface as indicated by low f p2o5 ratios sr and ca isotopes as well as rare earth element patterns agreeing with seawater dominated fluids small negative ce anomalies and u enrichment in the laminite suggest suboxic conditions close to the sediment water interface during its formation increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and consequently point to episodical development of anoxic conditions during phosphogenesis the peruvian phosphorites formed episodically over an extended period of time lasting from middle miocene to pleistocene individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide rich phosphatic layers coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer phosphatic coated grains were later transported to the place of crust formation where subsequent laminite formation was favored under lower energy conditions a similar succession of phosphatic layers with varying contents of organic matter and sulfide rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains

concentration vertical flux and remineralization of particulate uranium in seawater abstract concentrations and fluxes of particulate u were measured throughout the water column at several locations in the atlantic and pacific oceans with in situ filtration systems and sediment traps the results indicate that dissolved u is fixed to particles in surface seawater organic matter appears to be the carrier phase formation of particulate authigenic u below the surface waters could not be detected authigenic u is remineralized within the bathypelagic layers at the open ocean sites studied in the panama basin an upwelling area with high biological productivity remineralization of authigenic u in the deep water column was not observed the rate of remineralization of authigenic u in the deep sea is insufficient to produce a measurable concentration gradient between surface and deep waters within the mixing time of the oceans formation of authigenic u in the water column in areas such as the panama basin is not a significant sink for u on an ocean wide basis

early diagenesis of trace metals cd cu co ni u mo and v in the freshwater reaches of a macrotidal estuary vertical profiles from the water column including the maximum turbidity zone mtz to the consolidated sediment were sampled in september 2000 in the freshwater reaches of the gironde estuary during a complete neap tide spring tide cycle the vertical distributions of dissolved major redox parameters and metals mn fe cd cu v co ni mo and u were determined reactive particulate metal fractions were also determined from selective leaching the studied system is characterized by density layers functioning at different time scales consisting of two mobile layers i e the liquid lm and the soft mud sm overlying consolidated sediments cs this results in a three zone diagenetic regime where 1 o2 dynamics are fast enough to show depletion in the rapidly mixed lm sequence tidal time scale 2 denitrification occurs on the weekly time scale mixing sm sequence and 3 the mn fe and sulfate cycling occurs in the cs layer annual time scale the studied trace metals show differential behavior during early diagenesis 1 cd cu and v are released into pore water preferentially from organic matter in the sm 2 co ni and u are released in the cs from mn and fe oxides during reductive dissolution and 3 mo from both processes transient conditions i e oscillations of redox fronts and reoxidation processes due to the dynamics of the mobile layers strongly influence the trace metal distributions as inducing resolubilization cd cu and mo in the cs authigenic metal phases accumulate either by direct precipitation with sulfides cu cd or co precipitation with fe sulfides mo microbially mediated reduction of fe oxides is proposed to control u removal from pore water by reduction of u vi to u iv at depth however a significant fraction of the trace metals is trapped in the sediment in exchangeable forms and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and or dredging activities

the diffusive tortuosity of fine grained unlithified sediments abstract use of fick s first law to estimate solute fluxes is arguably the most common and important calculation related to the geochemistry and environmental chemistry of fine grained unlithified sediments in such porous media the diffusion coefficient in this law must be reduced by the square of the tortuosity to account for the longer diffusive paths experimental methods to estimate tortuosity are specialized or time consuming and not routinely done an analysis of available data shows that tortuosity is accurately correlated to readily measured porosity values through the simple relation 2 1 l n 2

petrology and major element geochemistry of peru margin phosphorites and associated diagenetic minerals authigenesis in modern organic rich sediments abstract new petrographic and major element geochemical data from modern peru margin upper slope outer shelf phosphorites are presented which provide insight into their origin and paragenetic relationship with other authigenic minerals glauconite pyrite and dolomite occurring in organic rich sediments glauconites are precipitated relatively early following the partial reduction of ferric iron and following this process phosphate pyrite and then dolomite precipitation take place at progressively deeper levels in the sediment in association with microbial reduction of sulfate as in many ancient economic phosphorite deposits the phosphatic facies here consist of nodules crusts coatings and strata composed of phosphatic pelletal grains ooids structureless grains intraclasts clumps and biogenic grains in association with organic rich biosiliceous sediments all are considered to have formed within a few centimeters or within a few tens of centimeters below the sediment water interface important factors that influence which morphology will tend to develop include the amount of available pore space the presence of suitable nucleation sites the amount and size of siliciclastic detritus incorporated as inclusions and the relative solution chemistries of the precipitating solutions bacterial mediation may play an important but as yet unspecified role in the precipitation process textural data and factor analysis of chemical data suggest that structureless pellets are relatively inclusion free na f mg co3 substituted pore water precipitates whereas ooids are inclusion rich pore water precipitates poor in lattice substituted components variations in nodular cement birefringence and crystallinity are suggested to have been produced by similar lattice substitutions that directly reflect pore water carbonate ion concentrations and thus relative degrees of organic matter degradation phosphate and dolomite are intimately mixed yet mineralogically distinct phases in phosphatized dolomicrites depth stratified threshold carbonate ion concentrations may control the lower limit at which phosphatic minerals may precipitate below depths of a few centimeters excessive carbonate ion concentrations and diminished reactive iron and sulfate concentrations favor the development of dolomite while precluding further development of phosphatic minerals and pyrite periodic sediment reorganization bioturbation current winnowing and erosion mass wasting etc plays an important role in both concentrating pelletal grains and maintaining nodules and crusts at critical depth levels in the sediment as well as mixing ordered mineral parageneses into complicated sequences

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

reconstructing the rise of recent coastal anoxia molybdenum in chesapeake bay sediments abstract sporadic direct observations over a 50 yr period inadequately characterize the history of seasonal hypoxia and anoxia in chesapeake bay a large estuary threatened by eutrophication here we undertake a reconstruction of 20th century oxygen depletion in this estuary using mo concentrations in 210pb dated sediments cu concentrations are used to control for anthropogenic influences cores from the central channel display mild mo enrichments above crustal backgrounds up to 5 g g and strong cu enrichments up to 35 g g temporally cu enrichment mostly anthropogenic began earlier and stabilized in the last two thirds of the 20th century in contrast mo enrichment has grown during the last two thirds of the century molybdenum enrichment is mostly hydrogenic except in a section of the channel that receives additional mo from erosion of early miocene shore deposits two geochemical mechanisms promote mo enrichment manganese refluxing concentrates dissolved moo42 at the sediment water interface and sulfide substitution into moo42 produces thiomolybdates which can be fixed by particles the mo enrichment mechanisms operate primarily during periods when bottom waters are anoxic and thiomolybdate formation can occur near the sediment water interface this implies a temporal coupling between water column anoxia and mo fixation even though fixation occurs only within sediments the mo enrichment profiles suggest that chesapeake bay has experienced growing o2 depletion since the first half of the 20th century but especially after 1960

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

uranium removal in oceanic sediments and the oceanic u balance pore water uranium data from the nw atlantic ocean cariaco trench black sea and san clemente basin are used to calculate fluxes across the sediment water interface all samples were collected in situ and show depletions in pore water u relative to the overlying water concentration the uptake rate of u derived from pore water gradients reflects the redox environment with lowest fluxes 10 g cm 2 ky in oxic su ic sediments of the nw atlantic dominated by no 3 reduction and higher fluxes 25 70 g cm 2 ky in the anoxic sulfate reducing sediments of the cariaco trench black sea and san clemente basin the anoxic fluxes compare well with previous estimates based on solid phase data calculations indicate that the areally integrated removal of u into su ic hemipelagic sediments is of greater magnitude than that into anoxic sulfate reducing sediments these fluxes are discussed in the context of the oceanic u balance the removal of u in all oceanic sediments is estimated to account for about 65 of the riverine input and this sink plus removal of u in altered oceanic crust balances the most probable value for riverine input

the partition of vanadium and molybdenum between manganese oxides and sea water abstract the partition of v and mo between manganese oxides and sea water was investigated in the sea water supply system for aquaria at the marine science museum tokai university where both todorokite and birnessite are precipitated from aerated well sea water the distribution coefficient of v was an order of magnitude higher than that of mo assuming that the distribution coefficients can be applied to marine environments and that manganese oxides are precipitated from sea water the calculated contents of these oxyanionic elements in manganese oxides were comparable to those in marine manganese nodules

pyritization of trace metals in anoxic marine sediments the pyritization of reactive trace elements in different anoxic marine sediments was investigated to determine the importance of factors such as h2s reactive fe pyrite content and salinity in controlling this process the areas studied included anoxic sulfidic sediments baffin bay a hypersaline coastal lagoon from texas and green canyon a hemipelagic oil seepage area anoxic nonsulfidic sediments with high sedimentation rates atchafalaya bay mississippi delta system hemipelagic anoxic nonsulfidic sediments with low sedimentation rates gulf of mexico shelf and slope and orca basin an euxinic hypersaline basin and organic rich marsh sediments atchafalaya bay results indicate that the degree of trace metal pyritization dtmp of all trace metals except cd increased with increasing degree of pyritization dop irrespective of the type of sedimentary environment involved however for as hg and mo the dtmpdop values were generally above the 1 1 ratio line whereas the transition metals co cu mn and ni displayed a close to linear increase in dtmp with dop and moderate incorporation into pyrite chromium and the class b metals pb and zn were also gradually incorporated into the pyrite phase but without reaching the dtmp levels exhibited by the transition metals cadmium was not incorporated to a significant extent these results are consistent with the chemical attributes of these different classes of trace elements availability of dissolved trace metals and organic matter content are apparently important factors controlling the incorporation of co cr cu and ni into pyrite in anoxicsulfidic fe poor and h2s rich environments

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

suboxic trace metal geochemistry in the eastern tropical north pacific abstract we analyzed al ti fe mn cu ba cd u mo v and re in water column settling particulate and sediment 0 to 22 cm samples from the intense oxygen minimum zone omz of the eastern tropical north pacific near mazatlan mexico the goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique suboxic geochemical signature the water column was characterized by a mn maximum reaching 8 nmol kg 1 at 400 m concentrations of cu ba cd mo re u and v were unaffected by the low o2 conditions and were comparable to those of the open ocean sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin al ti and fe were mostly at least 79 lithogenic about 75 of the mn was nonlithogenic significant amounts at least 58 of cu ba cd and mo were nonlithogenic sediment geochemistry varied across the continental shelf and slope cadmium u and re have prominent maxima centered at 310 m with 12 3 ppm 10 9 ppm and 68 3 ppb respectively at the core top high values of mo averaging 6 8 ppm and v averaging 90 ppm are seen in omz surface sediment additional down core enrichment occurs for all redox sensitive elements in the top 10 cm for u mo v and re surface sediments are a poor indicator of metal enrichment comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition especially for cd u and mo we evaluated re mo and cd u ratios as tracers for redox environments rhenium and mo concentrations and re mo ratios do not lead to consistent conclusions concurrent enrichments of re and mo are an indicator of an anoxic depositional environment in contrast high re mo ratios are an indicator of suboxic conditions cadmium is enriched in surface sediments while u has considerable down core enrichment the concentrations of cd and u and the cd u ratio do not follow patterns predicted from thermodynamics though the water column is suboxic these four redox sensitive elements indicate that the sediments are anoxic the implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column

glacial interglacial variability in the eastern tropical north pacific oxygen minimum zone recorded by redox sensitive trace metals 1 changes in the intensity of the oxygen minimum zone omz in the eastern tropical north pacific over the past 140 kyr are recorded as enrichments and depletions of redox sensitive metals in sediments of two piston cores one within and one below the modern omz from the continental margin off mazatlan mexico 22 41 n 106 28 w concentrations of al 7 7 0 6 ti 0 37 0 03 fe 3 1 0 25 mn 320 31 ppm and ba 560 82 ppm in core nh15p within the omz at 420 m water depth were relatively constant over the last 110 kyr in contrast concentrations of cd 4 8 2 ppm cu 29 8 9 1 ppm u 9 1 3 7 ppm mo 12 1 5 0 ppm v 138 2 51 9 ppm and re 45 8 25 5 ppb were all at least 30 higher in interglacial stages compared to glacial stages concentrations of al 7 4 0 3 ti 0 35 0 03 fe 3 5 0 4 and mn 385 77 ppm in core nh22p below the omz at 2025 m water depth were comparable to those in core nh15p while concentrations of ba 1662 292 ppm were about a factor of three higher in contrast concentrations of cd 0 9 0 3 ppm u 6 6 0 9 ppm mo 3 2 1 2 ppm v 81 8 10 1 ppm and re 25 4 12 ppb were lower in sediments of comparable age than the concentrations of these same metals in the omz core and the differences in their concentrations over glacial interglacial cycles were less pronounced than those in shallower core comparison of the nonlithogenic fraction of metals in the sediments with their estimated contribution from plankton suggests that organic matter is probably the major source of cu ba and perhaps cd to the sediment whereas the indirect effects of organic carbon and low bottom water oxygen concentrations on sediment redox state appear to be more important controls on the distributions u re mo and v changes in the depth at which re and mo precipitated in the sediments and in the re mo ratio suggest that the redox state of the surface sediment and overlying water at both core depths varied over time re and mo removal depths were shallower and re mo ratios were lower at the omz site than in deeper water suggesting that a more reducing environment prevailed over time at the shallower site although the redox state of the waters and sediment at both sites varied over glacial interglacial cycles the omz likely was never anoxic in the last 140 kyr this variability in redox state could be attributed to changes in regional export productivity changes in ocean circulation or a combination of both processes a paleoproductivity reconstruction from biogenic ba data suggests that glacial productivity was considerable lower than it was during interglacial stages model results suggest that the oxygen penetration depth an indicator of sediment redox state changed less than 1 cm as a result of the change in productivity changes in oxygen penetration depth estimated from re and u removal depths are significantly larger suggesting that changes in ventilation are a more important control on sediment redox state overall trace metal results confirm the tight coupling between ocean circulation marine productivity and global change

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

climate response to orbital forcing across the oligocene miocene boundary spectral analyses of an uninterrupted 5 5 million year my long chronology of late oligocene early miocene climate and ocean carbon chemistry from two deep sea cores recovered in the western equatorial atlantic reveal variance concentrated at all milankovitch frequencies exceptional spectral power in climate is recorded at the 406 thousand year ky period eccentricity band over a 3 4 million year period 20 to 23 4 my ago ma as well as in the 125 and 95 ky bands over a 1 3 million year period 21 7 to 23 0 ma of suspected low greenhouse gas levels moreover a major transient glaciation at the epoch boundary approximately 23 ma mi 1 corresponds with a rare orbital congruence involving obliquity and eccentricity the anomaly which consists of low amplitude variance in obliquity a node and a minimum in eccentricity results in an extended period approximately 200 ky of low seasonality orbits favorable to ice sheet expansion on antarctica

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

enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in mesozoic limestones and shales there have been many studies devoted to trace metals and their value in assessing the paleoredox conditions of ancient marine deposition among them molybdenum mo is frequently cited as an effective proxy for sediments and sedimentary rocks recently helz et al helz g r miller c v charnock j m mosselmans j l w pattrick r a d garner c d vaughan d j 1996 mechanisms of molybdenum removal from the sea and its concentration in black shales exafs evidences geochim cosmochim acta 60 3631 3642 and adelson et al adelson j m helz g r miller c v 2001 reconstructing the rise of recent coastal anoxia molybdenum in chesapeake bay sediments geochim cosmochim acta 65 237 252 suggested that mo does not behave conservatively in the water column when h2s reaches a threshold concentration above this concentration a switch operates and mo is scavenged by forming bonds with metal rich notably iron particles sulfur rich organic molecules and pyrite in this paper mo trapping by sulfur rich organic matter om in ancient marine deposits is emphasized the following mesozoic geological formations were selected for study because of their relatively high concentration of sulfurized om the akkuyu formation turkey the calcaires d orbagnoux france and kimmeridge clay uk and its timeequivalent in boulonnais france the kashpir oil shales russia and the la luna formation venezuela the sulfur rich om is identified by either measured organic s abundance or kerogen microscope observation our results show that mo is systematically more enriched relative to the other redox sensitive sulfide forming elements studied u v ni cu zn cr and mo enrichment is positively correlated with the amount of sulfurized om but not with pyrite abundance these results illuminate the role played by sulfurized om in geologic scale mo capture and retention but they also underline the role played by reactive iron significant om sulfurization is only possible when reactive iron is limited nevertheless pyrite formation though limited could act as an initial mo trap prior to mo uptake by om that is sulfurized after the pyritization step in future paleoenvironmental reconstructions attention must be paid to this enhanced mo enrichment in the presence of sulfurized organic matter in such cases the use of mo could lead to overestimation of the reducing conditions of the depositional environment

a comparison of long coastal trapped wave theory with observations off peru abstract the agreement between coastal trapped wave theory and observation is studied for the case of observations made off peru during the 1977 cuea joint ii experiment wave properties are calculated using a numerical model with realistic horizontally uniform stratification and realistic bottom topography these properties are then explored as a function of the ratio of the first internal rossby radius of deformation to the shelf slope width the agreement of observed and calculated first mode free wave phase speeds 230 cm s 1 is excellent while modal structures agree more poorly a forced wave calculation using observed winds and currents as input is used to hindcast alongshore currents and sea level in the frequency band where smith 1978 observed free coastal trapped waves during 1977 the model suggests that most of the observed sea level and alongshore velocity fluctuations in the 5 10 day period band are due to free waves originating equatorward of 5 deg s while winds between 5 deg s and

uranium diagenesis in sediments underlying bottom waters with high oxygen content we measured u in sediments both pore waters and solid phase from three locations on the middle atlantic bight mab from the eastern margin of the united states a northern location on the continental shelf off massachusetts oc426 75 m water depth and two southern locations off north carolina en433 1 647 m water depth and en433 2 2648 m water depth these sediments underlie high oxygen bottom waters 250 270 m but become reducing below the sediment water interface due to the relatively high organic carbon oxidation rates in sediments en433 1 212 mol c cm2 y oc426 120 10 mol c cm2 y en433 2 33 mol c cm2 y pore water oxygen goes to zero by 1 4 1 5 cm at en433 1 and oc426 and slightly deeper oxygen penetration depths were measured at en433 2 4 cm all of the pore water profiles show removal of u from pore waters calculated pore water fluxes are greatest at en433 1 0 66 0 08 nmol cm2 y and less at en433 2 and oc426 0 24 0 05 and 0 13 0 05 nmol cm2 y respectively solid phase profiles show authigenic u enrichment in sediments from all three locations the average authigenic u concentrations are greater at en433 1 and oc426 5 8 0 7 nmol g and 5 4 0 2 nmol g respectively relative to en433 2 4 1 0 8 nmol g this progression is consistent with their relative ordering of reduction intensity with greatest reducing conditions in sediments from en433 1 less at oc426 and least at en433 2 the authigenic u accumulation rate is largest at en433 1 0 47 0 05 nmol cm2 y but the average among the three sites on the mab is 0 2 nmol cm2 y pore water profiles suggest diffusive fluxes across the sediment water interface that are 1 4 1 7 times greater than authigenic accumulation rates at en433 1 and en433 2 these differences are consistent with oxidation and loss of u from the solid phase via irrigation and or bioturbation which may compromise the sequestration of u in continental margin sediments that underlie bottom waters with high oxygen concentrations previous literature compilations that include data exclusively from locations where o2 bw 150 m suggest compelling correlations between authigenic u accumulation and organic carbon flux to sediments or organic carbon burial rate sediments that underlie waters with high o2 bw have lower authigenic u accumulation rates than would be predicted from relationships developed from results that include locations where o2 bw 150 m

a model for uranium rhenium and molybdenum diagenesis in marine sediments based on results from coastal locations abstract the purpose of this research is to characterize the mobilization and immobilization processes that control the authigenic accumulation of uranium u rhenium re and molybdenum mo in marine sediments we analyzed these redox sensitive metals rsm in benthic chamber pore water and solid phase samples at a site in buzzards bay massachusetts usa that has high bottom water oxygen concentrations 230 300 mol l and high organic matter oxidation rates 390 mol c cm2 y the oxygen penetration depth varies from 2 to 9 mm below the sediment water interface but pore water sulfide is below detection release of rsm to pore waters during the remineralization of solid phases occurs near the sediment water interface at depths above the zone of authigenic rsm formation this release occurs consistently for mo at both sites but only in the winter for re in buzzards bay and intermittently for u at the buzzards bay site re removal to the solid phase extends to the bottom of the profile while the zone of removal is restricted to 2 9 cm for u and mo authigenic re formation is independent of the anoxic remineralization rate which is consistent with an abiotic removal mechanism the rate of authigenic u formation and its modeled removal rate constant increase with increasing anoxic remineralization rates and is consistent with u reduction being microbially mediated authigenic mo formation is related to the formation of sulfidic microenvironments the depth and extent of mo removal from pore water is closely associated with the balance between iron and sulfate reduction and the consumption of pore water sulfide via iron sulfide formation pore water rsm reach constant asymptotic concentrations in sulfidic sediments but only pore water re is constant at depth in buzzards bay the increases in pore water u at the buzzards bay site are consistent with addition via irrigation and subsequent upward diffusion to the removal zone deep pore water mo concentrations exceed its bottom water concentration due to irrigation induced oxidation and remobilization from the solid phase in sulfidic sediments there is no evidence for higher pore water u or mo concentrations at depth due to the absence of irrigation and or the presence of more stable authigenic rsm phases there are good correlations between benthic fluxes and authigenic accumulation rates for u and mo in sulfidic sediments however results from buzzards bay suggest irrigation ultimately results in the partial loss of u and mo from the solid phase with accumulation rates that are 20 30 of the modeled flux irrigation can augment re possibly u or compromise u mo authigenic accumulation in sediments and is important when determining burial rates in continental margin sediments

k ar ages and the opening of the south atlantic ocean basaltic rock from the brazilian margin abstract new k ar ages for 13 samples of basalt gabbro wehrlite and trachyandesite drilled from the brazilian continental shelf and coastline yield information about the timing of the opening of the south atlantic and the nature of the crust seaward from the brazil margin the oldest basalt is 138 1 3 5 m y old and from offshore at 24 5 s it represents serra geral flood basalt on attenuated crust in the santos basin basalts from the coastline at 19 5 s are mixed with terrigenous graben sediments and their ages confirm that rifting was underway before 130 m y offshore sites in the campos basin 22 23 s 41 w have basalt ranging from 124 to 112 m y in age and mostly continental flood basalt in composition one 112 m y basalt however is morb like and could therefore represent oceanic lithosphere mixed with continental crust about 50 km from the shoreline at 22 5 s other samples reveal compositionally varied intraplate passive margin magmatism occurring 75 43 m y ago they correlate with profuse contemporary alkalic magmatism on the southeastern brazil coast and probably represent reactivation of zones of weakness i e fracture zone lineaments

redox dynamics in the chesapeake bay the effect on sediment water uranium exchange the effect of seasonal variations in productivity and redox dynamics on the sediment water exchange of uranium was investigated on a twelve cruise time series in the chesapeake bay the deep waters of the bay undergo seasonal anoxia in response to high primary productivity and water column stratification from late spring to early fall dissolved oxygen was used to monitor water column redox conditions and dissolved iron manganese and sulfide were measured to monitor sediment redox conditions dissolved 238u was measured in the water column and sediment porewaters to monitor water column sediment exchange uranium incorporation in bay sediments results from two distinct processes productivity dependent scavenging from the water column and redox dependent cycling of uranium between sediments and bottomwater uranium is removed from surface waters of the bay by scavenging with biodetritus during periods of high primary productivity bottomwater and sediment redox conditions determine whether this particle bound uranium is buried or released to overlying water particulate uranium is released to bottomwaters and porewaters during the degradation of biodetritus and oxidation of authigenic uranium low oxygen in bottomwaters in the summer results in minimal exchange of uranium between the sediments and bottomwater due to the stability of reduced u iv high bottomwater oxygen concentrations associated with bay turnover in the fall results in release of authigenic uranium by oxidation to the soluble vi form enrichment of uranium in fall bottomwater suggests that authigenic uranium is very labile when exposed to oxic environmental conditions this process is enhanced by physical mixing when anoxic sediments are resuspended into the oxic bottomwaters

sulfur diagenesis and partitioning in holocene peru shelf and upper slope sediments abstract sediments of the peru margin were sampled in two transects across the shelf and upper slope 75 to 1000 m in october of 1992 this region is characterized by high surface water productivity and consequent high organic carbon fluxes low terrigenous inputs as well as an intense oxygen minimum zone omz impinging on the slope at depths between 75 and 550 m sediments analyzed in this study were collected from one ship deployed box core and five submersible deployed push cores organic carbon toc concentrations in surface sediments range from 1 to 18 on a dry weight basis formation of pyrite begins at the sediment water interface swi maximum concentrations of pyrite sulfur in the cores from this study range from 0 5 to 1 8 wt concentrations of pyrite are influenced by availability of reactive iron and an oxidant capable of converting avs to pyrite highly reactive iron is stripped from terrigenous detritus in the core of the omz some of this iron may contribute to glauconite formation in sediments near the base of the omz where it is concentrated into a glauconitic green sand as a result of reworking and winnowing in a shallow water site 109 m at the upper edge of the omz high concentrations of pyrite total iron and iron aluminum ratios indicate that easily reduced iron species are available for sulfidation at the swi pyrite formation at this site is nearly complete in the upper 4 cm of the sediment in contrast pyrite concentrations are slightly lower at the surface of two of the deeper water sites at 309 m in the center of the omz and to a lesser extent at 671 m at the bottom edge of the omz and appear to be influenced in part by availability of reactive iron concentrations of acid volatile sulfides avs are low in all sediments 0 04 wt but are slightly elevated in sediments from the center of the omz the ratio of organic sulfur s org to organic carbon toc at the sediment surface of the cores examined here is remarkably constant 0 012 0 002 and within the range observed in marine biota 0 01 to 0 02 suggesting that organic sulfur at the swi is dominantly biogenic although s org toc ratios increase downcore there is no clear correlation between concentrations of organic sulfur and organic carbon below the swi there is also no clear relation between concentrations of organic sulfur and total iron organic sulfur concentrations vary from site to site 0 06 to 0 33 wt but are relatively constant downcore at any given site maximum concentrations are in cores from the center of the omz