fractionation of sulfur isotopes during bacterial sulfate reduction in deep ocean sediments at elevated temperatures abstract a numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid so 4 2 and 34 s data from four sites drilled during ocean drilling program odp leg 168 in the cascadia basin at 48 n where basement temperatures reach up to 62 c there is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures pore fluid 34 s data show the highest values 135 yet found in the marine environment the bacterial sulfur isotopic fractionation factor is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and rayleigh fractionation plots yield erroneous values for by as much as 15 in diffusive and advective pore fluid regimes model results are consistent with 1 077 0 007 with no temperature effect over the range 1 8 to 62 c and no effect of sulfate reduction rate over the range 2 to 10 pmol cm 3 d 1 the reason for this large isotopic fractionation is unknown but one difference with previous studies is the very low sulfate reduction rates recorded about two orders of magnitude lower than literature values that are in the range of mol cm 3 d 1 to tens of nmol cm 3 d 1 in general the greatest 34 s depletions are associated with the lowest sulfate reduction rates and vice versa and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates

ferromanganese oxide deposits from the central pacific ocean i encrustations from the line islands archipelago abstract chemical and mineralogical analyses of a well controlled suite of ferromanganese encrustations from the line islands archipelago central pacific suggest that they represent purely hydrogenous deposits i e they have formed through the slow accumulation of trace metal enriched oxides directly from the water column mineralogically they consist predominantly of mno2 and amorphous feoohxh2o compositionally they are similar to mno2 nodules from adjoining basinal areas but are enriched in both mn mean 20 4 max 29 3 and co mean 0 55 max 1 57 mno2 is the most important trace metal bearing phase strong associations are noted between it and co mo ni zn and cd whilst only be is associated specifically with feooh v sr and pb are partitioned between the authigenic oxide phases whilst ti most probably occurs as tio2xh2o cu is contained in both aluminosilicate contaminant phases and fe oxide phases these relations are considered to reflect the differing scavenging behaviour of mn and fe oxides in the water column crusts from 1 2 km are enriched in mn and the mn related elements and exhibit higher mn fe ratios than deeper crusts which are compositionally constant the higher mn fe ratios may result from a supply of mn from continental borderland sediments at these depths which is transported horizontally by advective diffusive processes since manganophile elements are enriched relative to mn in the 1 2 km crusts it is considered that the supply of mn is scavenged by existing oxides is oxidised and effectively occludes them a higher proportion of oxide particles thus exhibit mn oxide scavenging properties in the 1 2 km depth zone the increased vertical flux of mn resulting from the supply at 1 2 km is not reflected by higher mn fe ratios in deeper crusts so that the vertical flux of oxides is not simply related to the standing crop the mn fe ratios of the crusts thus reflect the composition of suspended oxides at similar depths

a 160 k y old record of el nino southern oscillation in marine production and coastal runoff from santa barbara basin california usa a 160 k y old laminated sediment record from the santa barbara basin california analyzed using scanning electron microscope techniques provides a history of interannual variability of marine production and coastal runoff we used backscatter electron imagery to measure the components of the varve these include a terrigenous lamina formed by seasonal runoff from winter rains together with a diatomaceous lamina that records marine production during the spring and early summer spectral analysis of terrigenous and diatomaceous laminae thickness reveals significant periodicities of 3 1 and 8 4 yr in the terrigenous series these are indistinguishable within the frequency resolution of the spectra from significant periodicities of 3 5 and 7 6 yr in the diatomaceous series the 3 1 and 3 5 yr periodicities record el nino modulation of coastal runoff and marine production the 8 4 and 7 6 yr periodicities are consistent with modulation by strong to very strong el nino events this is supported by the results of cross spectral analysis of the terrigenous and diatomaceous records which reveal inverse or antiphase relationships at 3 5 and 7 6 yr our work adds to a body of evidence that suggests that el nino has been a persistent feature of late quaternary climate variability

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

constraints on the lateral strength of slabs from three dimensional dynamic flow models if the viscosity of subducted lithosphere is described purely by temperature and pressure it should remain considerably more viscous than the surrounding material as it descends through the upper mantle many dynamic models of the long wavelength geoid associated with slabs require an increase in viscosity from the upper to the lower mantle but assume the perturbation to the lateral viscosity structure arising from the slabs themselves can be ignored previous studies indicate that strong and localized viscosity variations should have a dramatic influence on the geoid we present 3d finite element models of the regional geoid of the western pacific subduction zones slab buoyancies and viscosities are defined using the distribution of seismicity the geoid is very sensitive to the lateral strength of the slab very viscous slabs penetrating a low viscosity mantle generate significant 10 50 m long wavelength geoid lows opposite to the geoid high which is observed over slabs to obtain a geoid high comparable to that observed the lower mantle viscosity must be 60 200 times greater than the upper mantle viscosity and the slab must be in contact with the lower mantle these strict requirements suggest that slabs have been weakened and cannot act as stress guides from the deep mantle to the surface

trace metal signatures of eastern mediterranean sapropels abstract sapropel samples of pliocene to pleistocene age recovered during odp leg 160 from sites 964 ionian basin 969 mediterranean ridge 966 967 top and northern slope of the eratosthenes seamount south of cyprus and 968 cyprus margin were analysed for major and trace elements eastern mediterranean sapropels are characterized by high organic carbon and sulphur contents and by significant enrichments in several redox sensitive and or sulphide forming trace metals bi cd co cr cu mo ni re sb tl u v enrichment factors relative to average shale are comparable to those found in ctbe black shales the re content is extremely high in the sapropels studied with maximum values up to 1000 ng g re mo ratios averaging 2 7 10 3 are close to the seawater value high trace metal enrichments and re mo ratios close to the seawater value point to an anoxic water column during sapropel formation additionally enhanced ba concentrations in the sapropels support the assumption that bioproductivity was also high during these episodes trace metal signatures of sapropels originating from different drill sites on a transect across the eastern mediterranean are not only influenced by water depth but also by their location in the eastern mediterranean metal enrichments seem to be higher at the western sites compared with the eastern sites this probably reflects a change in the circulation pattern during periods of sapropel formation pliocene sapropels exhibit elevated trace metal contents in comparison with pleistocene examples therefore different palaeoceanographic conditions may have developed during the pleistocene compared with the pliocene altering palaeoceanography was probably controlled by climatic change which may be related to the onset of glaciation of the northern hemisphere decreasing summer precipitation throughout the late pliocene and the pleistocene may also have influenced sapropel deposition

stirring geochemistry in mantle convection models with stiff plates and slabs abstract numerical models of mantle convection are presented that readily yield midocean ridge basalt morb and oceanic island basalt oib ages equaling or exceeding the apparent 1 8 ga lead isotopic ages of trace element heterogeneities in the mantle these models feature high viscosity surface plates and subducting lithosphere and higher viscosities in the lower mantle the formation and subduction of oceanic crust are simulated by means of tracers that represent a basaltic component the models are run at the full mantle rayleigh number and take account of faster mantle overturning and deeper melting in the past more than 97 of the mantle is processed in these models including the expected excess density of former oceanic crust readily accounts for the depletion of morb source relative to oib sources a novel finding is of gravitational settling of dense tracers within the low viscosity upper mantle as well as at the base of the mantle the models suggest as well that the seismological observation of a change in tomographic character in the deep mantle might be explained without the need to postulate a separate layer in the deep mantle these results expand the range of models with the potential to reconcile geochemical and geophysical observations of the mantle

burial of organic carbon and pyrite sulfur in sediments over phanerozoic time a new theory in present day marine sediments almost all of which are deposited in normal oxygenated seawater rates of burial of organic carbon c and pyrite sulfur s correlate positively and bear a constant ratio to one another c s 3 on a weight basis by contrast calculations based on the isotopic model of garrels and lerman 1981 indicate that at various times during the phanerozoic the worldwide burial ratio must have been considerably different than the present day value this ratio change is caused by the requirement that increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur in order to maintain a roughly constant level of o2 in the atmosphere such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments as at present to non marine freshwater or to euxinic environments in the geologic past a shift to predominantly freshwater burial can help explain predicted high c s ratios in permo carboniferous sediments and a shift to euxinic environments can help explain predicted low c s ratios during the early paleozoic it is demonstrated that the three environments today exhibit distinguishably different average c s ratios

evidence from diatom bound nitrogen isotopes for subarctic pacific stratification during the last ice age and a link to north pacific denitrification changes higher diatom bound d 15 n 70 wt lower opal content and 1200 ppm lower biogenic barium taken together and with constraints on sediment accumulation rate these results suggest a reduced supply of nitrate to the surface due to stronger stratification of the upper water column of the bering sea during glacial times with more complete nitrate consumption resulting from continued iron supply through atmospheric deposition this finding extends the body of evidence for a pervasive link between cold climates and polar ocean stratification in addition we hypothesize that more complete nutrient consumption in the glacial age subarctic pacific contributed to the previously observed ice age reduction in suboxia and denitrification in the eastern tropical north pacific by lowering the nutrient content of the intermediate depth water formed in the subpolar north pacific in the deglacial interval of the bering sea record two apparent peaks in export productivity are associated with maxima in diatom bound and bulk sediment d 15 n the high d 15 n in these intervals may have resulted from greater surface nutrient consumption during this period however the synchroneity of the deglacial peaks in the bering sea with similar bulk sediment d 15 n changes in the eastern pacific margin and the presence of sediment lamination within the bering sea during the deposition of the productivity peaks raise the possibility that both regional and local denitrification worked to raise the d 15 n of the nitrate feeding bering sea surface waters at these times

occurrence of thick ethmodiscus oozes associated with a terminal mid pleistocene transition event in the oligotrophic subtropical south atlantic abstract within generally calcareous sediment sequences layers of variable thickness of the giant diatom ethmodiscus were found in five cores recovered in the subtropical south atlantic between 23 and 33 s from both sides of the mid atlantic ridge two types of oozes occur almost monospecific layers of ethmodiscus and layers dominated by ethmodiscus with several accompanying tropical subtropical oligotrophic water diatoms the two thickest ethmodiscus layers occur in geob3801 6 around 29 s and accumulated during late mis 14 and mis 12 respectively downcore concentrations of ethmodiscus valves range between 3 4 104 and 2 3 107 valves g 1 we discuss the ooze formation in the context of migration of frontal systems and changes in the thermohaline circulation the occurrence of ethmodiscus oozes in sediments underlying the present day pelagic low nutrient waters is associated with a terminal event of the mid pleistocene transition at around 530 ka when the ocean circulation rearranged after a period of reduced nadw production

pyritization processes and greigite formation in the advancing sulfidization front in the upper pleistocene sediments of the black sea pyritization in late pleistocene sediments of the black sea is driven by sulfide formed during anaerobic methane oxidation a sulfidization front is formed by the opposing gradients of sulfide and dissolved iron the sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content two processes of diffusion limited pyrite formation were identified the first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of fesn n 1 10 1 29 including greigite elemental sulfur and polysulfides formed from h2s by a reductive dissolution of fe iii containing minerals serve as intermediates to convert iron sulfides into pyrite in the second process a direct pyrite precipitation occurs through prolonged exposure of iron containing minerals to dissolved sulfide methane driven sulfate reduction at depth causes a progressive formation of pyrite with a 34s of up to 15 0 the s isotopic composition of fes2 evolves due to contributions of different sulfur pools formed at different times steady state model calculations for the advancement of the sulfidization front showed that the process started at the pleistocene holocene transition between 6360 and 11 600 yr bp our study highlights the importance of anaerobic methane oxidation in generating and maintaining s enriched layers in marine sediments and has paleoenvironmental implications

carbon and phosphorus cycling in anoxic sediments of the saanich inlet british columbia abstract uncertainty currently exists about the removal of carbon c and phosphorus p from the oceanic reservoir especially in low oxygen settings in this paper the cycling of c and p is examined in sediments from the anoxic saanich inlet cored by ocean drilling program odp leg 169s in 1996 at two sites although c org p org ratios are high and increase with depth in the saanich inlet this effect is due largely to a remobilization of p from an organic matter sink to an authigenic sink reducible sedimentary components act as temporary shuttles in this process even in this anoxic setting with the ultimate burial sink for the remobilized p being carbonate fluorapatite the effective c org p reactive molar ratio appears to be about 150 200 indicating some preferential loss of p compared to c during organic matter degradation but not approaching previously reported values of over 3000 in black shales reactive p accumulation rates in this basin range from 10 000 60 000 mol cm 2 kyr greatly exceeding the range of 500 8000 mol cm 2 kyr found in most continental margin settings including regions of modern phosphogenesis the initiation of marine sedimentation in the saanich inlet occurred after deglaciation and the high rates of p burial seen here may provide an end member example of the effects of sea level and margin sedimentation on the distribution of p within the marine p cycle

post depositional migration of elements during diagenesis in brown clay and turbidite sequences in the north east atlantic abstract two cores from a ne atlantic pelagic clay area of low accumulation rate each contain a single turbidite with different age thickness and composition diagenesis following introduction of exotic turbidite material into the pelagic clay sequence has resulted in distinctive colour changes the diagenetic process is thought to be driven by bacterially mediated organic oxidation and compositional differences in the turbidites and clays allow examination of the effects on metal concentrations of this process in one core a long turbidite section emplaced 330 000 years ago is overlain by clay organic oxidation has apparently proceeded from the turbidite top downwards and has maintained a u concentration peak below the oxidation front marked by a colour change the u source is believed to be u initially associated with the organic matter in the oxidised section of the turbidite vanadium and cu behave similarly but upward migration of the redox sensitive metals mn and ni is also seen in the second core an 8 cm turbidite section was emplaced about 170 000 years ago in a clay column in this case organic consumption now appears complete but evidence for diagenetic effects is found in a 16 cm compositional alteration halo of the underlying pelagic clay fe ii has been enriched and the hydrogenous component of mn co ni and cu removed from the pelagic clay to form the halo

anaerobic methane oxidation and a deep h2s sink generate isotopically heavy sulfides in black sea sediments the main terminal processes of organic matter mineralization in anoxic black sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2 4 m and methanogenesis below the sulfate zone the modern marine deposits comprise a ca 1 m deep layer of coccolith ooze and underlying sapropel below which sea water ions penetrate deep down into the limnic pleistocene deposits from 9000 years bp sulfate reduction rates have a subsurface maximum at the so42 ch4 transition where h2s reaches maximum concentration because of an excess of reactive iron in the deep limnic deposits most of the methane derived h2s is drawn downward to a sulfidization front where it reacts with fe iii and with fe2 diffusing up from below the h2s fe2 transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur the pore water gradients respond dynamically to environmental changes in the black sea with relatively short time constants of ca 500 yr for so42 and 10 yr for h2s whereas the fes in the black band has taken ca 3000 yr to accumulate the dual diffusion interfaces of so42 ch4 and h2s fe2 cause the trapping of isotopically heavy iron sulfide with 34s 15 to 33 at the sulfidization front a diffusion model for sulfur isotopes shows that the so42 diffusing downward into the so42 ch4 transition has an isotopic composition of 19 close to the 23 of h2s diffusing upward these isotopic compositions are however very different from the porewater so42 43 and h2s 15 at the same depth the model explains how methane driven sulfate reduction combined with a deep h2s sink leads to isotopically heavy pyrite in a sediment open to diffusion these results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth s history

redox zonation of elements at an oxic post oxic boundary in deep sea sediments abstract deep sea sediments generally provide limited evidence of redox control on the post depositional redistributions of elements this is because only a fraction of any element is reactive and observed elemental distributions are the result of a number of competing processes which are simultaneously active so that redox effects are not dominant a detailed investigation is reported of a core which is unusual in showing unequivocal evidence of direct redox control operating in a homogeneous environment that is relatively free from competing processes a progressive oxidation front has migrated slowly downwards into a uniform turbidite over a long period ca 250 ky the reactive fractions of several redox sensitive elements now show a remarkable degree of organisation around the redox boundary of this front with the different elements exhibiting individual responses solid phase enrichments are not coincident but are arranged in a clear succession of concentration peaks along the redox gradient from oxic to postoxic conditions the succession is mn i fe se and pt cu and pb v zn and sb and u the movement directions of most elements can be inferred from the peak shapes against the homogeneous turbidite background composition the system seems to have been essentially isolated within the sediment for most elements so that no loss or gain can be ascribed to redox processes exceptions are u and v which have been augmented by uptake from ocean bottom waters into the sediments by an efficient redox trap mechanism

similar rates of modern and last glacial ocean thermohaline circulation inferred from radiochemical data today the ocean thermohaline circulation transports half of the 231pa produced by radioactive decay in the atlantic ocean water column to the southern ocean this export respectively imparts low and high 231pa 230th ratios to the surface sediments of these oceans ocean sediments from the last glacial maximum bear a similar isotopic fingerprint implying that advection of north atlantic deep intermediate water into the circumpolar deep water of the southern ocean occurred at a similar or slightly higher rate during the last glacial period

the effects of chemical density differences on convective mixing in the earth s mantle subducted lithosphere and crust are chemically distinct from ambient mantle and some have hypothesized that the resulting anomalous buoyancy may affect mixing and in particular may cause chemical heterogeneity to persist to explore this effect two dimensional convective mixing calculations have been carried out boundary conditions mimicking features of plate kinematics have been imposed and negatively buoyant tracers placed beneath converging plate margins to simulate subduction the principal parameter of interest is the density anomaly ratio o t the ratio of the chemical to the thermal buoyancy for a density anomaly ratio appropriate to complete separation of the oceanic crust from the rest of the lithosphere it is marginally possible for the tracers to segregate into the warm region near the bottom and neutralize the thermal buoyancy there for internally heated flows and to segregate to the base of the uprising limbs of convection for bottom heated flows however for the more likely scenario of oceanic crust and lithosphere maintaining their layering after subduction there is neither segregation nor neutralization of thermal buoyancy the average residence time is the average time tracers remain in the box from subduction to sampling beneath ridges and could be increased by 4 from the passive case at the very most if the crust and lithosphere remain layered even in the more extreme case of separation of crust from lithosphere the residence times are only increased by 15 from the passive case

large scale mantle convection and the history of subduction a large scale pattern of mantle convention is evident in the shape of the earth s gravity field1 lateral variations in seismic velocity2 3 the distribution of hotspots4 and long wavelength bathv metric anomalies5 paradoxically these signals of mantle convection bear little resemblance to present day plate motions1 4 although they seem to be related to past subduction zone configurations6 here we quantify this relationship by correlating a time integrated history of subduction calculated in the hotspot reference frame for the past 180 myr with regions of the deep mantle inferred from other geophysical observations to be colder than average our results support suggestions6 9 that a direct relationship exists between large scale thermal heterogeneity in the lower mantle and subduction during the cenozoic and mesozoic

sulfur isotopic trends and pathways of iron sulfide formation in upper holocene sediments of the anoxic black sea down core trends for extents of iron sulfidation in upper holocene microlaminated deposits of the black sea abyssal plain imply that most of the pyrite in these sediments is formed in the sulfidic water column and or very close to the sediment water interface sulfur isotopic data for pyrite within microlaminated muds from two localities in the deep basin show striking uniformity between sites and down core with a mean 34scdt value of 37 2 0 9 1 n 18 these isotopic trends support the hypothesis of early pyrite formation isotopic compositions of pyrite sulfur in the microlaminated bottom sediments are similar to those reported for particulate reduced sulfur collected in middepth sediment traps and to 34s values for water column dissolved sulfide within a narrow zone immediately below the o2 h2s interface these three sulfur reservoirs are distinctly different from the isotopic composition of ambient dissolved sulfide of the deep water column 175 m with 34s values for the deep dissolved sulfide reservoir being consistently lower by 2 to 4 these isotopic relationships suggest that iron sulfidation is occurring dominantly within a narrow shallow region at the top of the sulfidic water mass isotopic data from a fine grained turbidite collected in the deep basin and from rapidly accumulating iron monosulfide rich muds on the anoxic upper slope are enriched in34s relative to the microlaminated deposits the enrichments on the basin margin reflect a large component of iron sulfide formed during rapid burial a broad suite of geochemical data including sulfur isotopic results are consistent with an upper slope sediment source for the ubiquitous muddy turbidites of the deep basin the collective effects of reworking transport and redeposition result in a complete conversion of avs to pyrite with little additional iron sulfidation this conclusion is supported by a detailed isotopic mass balance the present isotopic study also highlights fundamental differences in the reactivities of the iron reservoirs distributed throughout the anoxic basin sediments of the upper slope and the genetically linked turbidites of the deep basin show similar extents of iron sulfidation that are significantly lower than those of the microlaminated deposits of the deep basin floor suggesting dramatically shorter timescales of iron reactivity for the microlaminated sediments of the deep basin importantly isotopic patterns from the modern black sea should assist greatly in the recognition and interpretation of ancient anoxia in the stratigraphic record

the fall dump a new perspective on the role of a shade flora in the annual cycle of diatom production and export flux investigations of diatom fluxes recorded in laminated sediments using scanning electron microscope techniques together with evidence from sediment trap studies have contributed to a reappraisal of the annual cycle of diatom production and export flux we propose that where there is a strong seasonal thermocline and nutricline a number of diatoms hitherto regarded as typical sparse summer flora characteristic of oligotrophic waters are able to generate substantial production at depth these species including rhizosolenia spp stephanopyxis palmeriana thalassiothrix spp and some coscinodiscus spp may represent a shade flora that have adapted to grow in low light conditions and or to regulate their buoyancy to move between a deep nutrient source and the euphotic zone although rates of growth and primary production are substantially lower than species characteristic of spring bloom or upwelling conditions the total primary production integrated over the several month period of summer stratification may be as significant as the spring bloom or greater the term fall or autumn bloom as a counterpart of the spring bloom is therefore a misnomer whereas the spring bloom involves a rapid burst of reproduction and sedimentation the fall dump is the sedimentation of a long lived episode of production lasting the duration of the seasonal thermocline and triggered by the fall winter mixing that breaks down stratification the fall dump may produce as much or in some cases more export production than the spring bloom the results of this study suggest that a reorientation of thinking on diatom ecology and palaeoecology may be required

mixing by time dependent convection abstract two dimensional numerical flow models are employed to study the mixing of passive heterogeneities in the earth s mantle both simple kinematic models of time dependent flow and dynamic convection models are studied initially small blocks of tracers are inserted into the flow and their progressive dispersal is monitored through time some of the tracers also serve as infinitesimal strain markers three different regimes of mixing are observed a all heterogeneities are rapidly strained and stirred according to a turbulent mixing law where the size of a blob decreases exponentially with time b most heterogeneities are only slowly strained and possibly follow a laminar mixing law with a linear decrease with time of the size of a heterogeneity c the size reduction proceeds rapidly in part of the fluid but some poorly stirred islands persist for a long time all three regimes are found in various kinematic flow models while in the dynamic convection models only regime a is observed the effective strain rate in the exponential turbulent mixing law is more than an order of magnitude smaller than the average flow strain rate when the results from the dynamic convection models with variable viscosity are scaled to the upper mantle mixing over small length scales would be achieved after a few hundred million years for whole mantle convection with a significant increase of viscosity with depth mixing times could be in the order of 1 2 ga in the latter case it appears marginally possible that part of the isotopic heterogeneity observed in oceanic basalts has evolved within the convecting mantle rather than in physically separated reservoirs

preservation of particulate non lithogenic uranium in marine sediments particulate non lithogenic uranium pnu excess u above detrital background levels found in marine particulate matter is formed in surface waters throughout the ocean previous studies have shown that pnu is regenerated completely prior to burial of particles in sediments within well oxygenated open ocean regions however the fate of pnu has never been examined in ocean margin regions or in anoxic basins here we evaluate the preservation of pnu in ocean margin sediments and within semi enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments organic carbon fluxes at the sediment trap locations ranged from 0 1 to 4 3 g cm 2 kyr while the dissolved oxygen concentration in the water column ranged from 3 mt o 270 m preservation of pnu increases with decreasing dissolved oxygen concentration approaching 100 preservation at oxygen concentration 25 m pnu contributes as much as 40 to 70 of the total authigenic u in sediments in the santa barbara basin and seasonally anoxic saanich inlet and some 10 to 50 of the total authigenic u in sediments off the central california margin copyright 2002 elsevier science ltd

circulation in the glacial north atlantic inferred from grain size measurements records of nutrient proxies in marine sediments indicate that the nutrient distribution and hence circulation of the glacial north atlantic ocean was markedly different from that of today1 2 but these tracers are influenced by several biogeochemical factors unrelated to ocean circulation3 6 and thus do not provide a direct measure of the vigour of circulation distributions of grain size in marine sediments can provide such information owing to the sorting effects of currents7 8 if the characteristics of the input sediment flux are known here we present a record inferred from grain size measurements of variations in the relative strength of deep and intermediate currents in the eastern north atlantic over the past 25 000 years we find that glacial intermediate water flowed rapidly at depths of between 1 100 and 2 000 m in contrast deep water circulation was sluggish during the last glaciation but increased in strength shortly after the glacial maximum this would have resulted in increased heat flux to high latitudes and may have triggered sudden deglaciation deep current strengths declined again at the start of termination stage ia and during the younger dryas perhaps as a result of iceberg discharges the so called heinrich events9 10 a remarkably similar record of grain size variations has been found in the western north atlantic11 indicating that these changes in circulation are ocean wide

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 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

biogenic flux of al to sediment in the central equatorial pacific ocean evidence for increased productivity during glacial periods we examined the flux of al to sediment accumulating beneath the zone of elevated productivity in the central equatorial pacific ocean along a surface sediment transect at 135 w as well as downcore for a 650 kyr record at 1 3 n 133 6 w across the surface transect a pronounced broadly equatorially symmetric increase in al accumulation is observed relative to ti with al ti ratios reaching values 3 4 times that of potential detrital sources the profile parallels biogenic accumulation and the modeled flux of particulate 234th suggesting rapid and preferential adsorptive removal of al from seawater by settling biogenic particles normative calculations confirm that most al is unsupported by the terrigenous fraction the observed distributions are consistent with previous observations of the relative and absolute behavior of al and ti in seawater and we can construct a reasonable mass balance between the amount of seawater sourced al retained in the sediment and the amount of seawater al available in the overlying column the close tie between al ti and biogenic accumulation as opposed to concentration emphasizes that biogenic sedimentary al ti responds to removal transport phenomena and not bulk sediment composition thus in these sediments dominated by the biogenic component the bulk al ti ratio reflects biogenic particle flux and by extension productivity of the overlying seawater the downcore profile of al ti at 1 3 n displays marked increases during glacial episodes similar to that observed across the surface transect from a background value near al ti of average upper crust the excursions in al ti are stratigraphically coincident with maxima in both bulk and caco3 accumulation and the excess al appears to not be preferentially affiliated with opaline or organic phases consistent with the similar behavioral removal of al and 234th the latter of which responds to the total particle flux the al flux reflects carbonate accumulation only because carbonate comprises the dominant flux in these particular deposits these results collectively indicate that 1 al in biogenic sediment and settling biogenic particles is strongly affected by a component adsorbed from seawater therefore the common tenet that al is dominantly associated with terrestrial particulate matter and the subsequent use of al distributions to calculate the abundance and flux of terrestrial material in settling particles and sediment needs to be reevaluated 2 the al ti ratio in biogenic sediment can be used to trace the productivity of the overlying water providing a powerful new paleochemical tool to investigate oceanic response to climatic variation 3 the close correlation between the al ti productivity signal and carbonate maxima downcore at 1 3 n suggests that the sedimentary carbonate maxima in the central equatorial pacific ocean record increased productivity during glacial episodes

geoid anomalies in a dynamic earth in order to obtain a dynamically consistent relationship between the geoid and the earth s response to internal buoyancy forces we have calculated potential and surface deformation love numbers for internal loading these quantities depend on the depth and harmonic degree of loading they can be integrated as green functions to obtain the dynamic response due to an arbitrary distribution of internal density contrasts spherically symmetric self gravitating flow models are constructed for a variety of radial newtonian viscosity variations and flow configurations including both whole mantle and layered convection we demonstrate that boundary deformation due to internal loading reaches its equilibrium value on the same time scale as postglacial rebound much less than the time scale for significant change in the convective flow pattern by calculating relaxation times for a series of spherically symmetric viscous earth models for uniform mantle viscosity the geoid signature due to boundary deformations is larger than that due to internal loads resulting in net negative geoid anomalies for positive density contrasts geoid anomalies from intermediate wavelength density contrasts are amplified by up to an order of magnitude geoid anomalies are primarily the result of density contrasts in the interior of convecting layers density contrasts near layer boundaries are almost completely compensated layered mantle convection results in smaller geoid anomalies than mantle wide flow for a given density contrast viscosity stratification leads to more complicated spectral signatures because of the sensitivity of the dynamic response functions to model parameters forward models for the geoid can be used to combine several sources of geophysical data e g subducted slab locations seismic velocity anomalies surface topography to constrain better the structure and viscosity of the mantle

redox sensitive element uptake in north east atlantic ocean sediments benthic boundary layer experiment sites regularly increasing radiocarbon age depth profiles and near constant sediment composition with depth have demonstrated that sediment accumulation has been relatively constant during the late holocene at two north east atlantic sites on rockall bank and feni drift uk benthic boundary layer experiment sites in such a quasi steady state situation the geochemical responses to early diagenesis of the redox sensitive elements cd mn mo re se and u are readily discerned through changes in element concentrations with depth collectively a colour change in the sediments surficial mnox enriched layers and 210pbexcess profiles allow an estimate of the mean position of the oxic post oxic boundary in the sediments at both sites this boundary is situated deeper than the 210pbexcess surface mixed layer but shallower than the 14c surface mixed layer which represent mixing on 102 and 103 year time scales respectively this implies that the well defined surface mnox enrichment and its associated 226ra and mo fractions must have been efficiently recycled first by downwards mixing into anoxic conditions and then by subsequent reduction and diffusive migration back up into oxic conditions this occurs in 40 years at the feni drift site and in 103 years at the rockall bank site authigenic enrichments of se cd and u are evident immediately below the oxic post oxic boundary although re enrichment does not occur until a few centimetres deeper the long term fluxes of authigenic se cd u and re uptake are evaluated with steady state assumptions while diffusion from bottom waters can supply sufficient se u and re an additional source likely corg is required for cd

a deeper respired carbon pool in the glacial equatorial pacific ocean article i nfo atmospheric pco2 was approximately 80 ppm lower during the last glacial period than during pre industrial times identifying the fate of that carbon has been one of the great challenges in paleoceanography we present evidence from ten equatorial pacific ocean sediment cores to show that the deep pacific ocean likely stored more carbon during the last glacial period than the holocene the concentration of the redox sensitive metal uranium u in sediments was systematically greater during the last glacial period than during the holocene indicating more reducing conditions in glacial age sediments reconstructions of biogenic opal flux indicate that changes in u distribution were not the result of changes in biological productivity and the ensuing rain of organic carbon to the sea floor which also affects the redox conditions of the sediments together these results lead to the interpretation that bottom water in the equatorial pacific during the glacial period had significantly lower oxygen concentration than during the holocene and a correspondingly greater level of respired co2 this conclusion is supported by evidence for greater preservation of brassicasterol a biomarker produced by diatoms in glacial age sediments of the eastern equatorial pacific the presence of additional respired co2 in the glacial deep ocean would have lowered atmospheric pco2 by 1 increasing the total storage of co2 in the glacial ocean and 2 increasing ocean alkalinity following a transient carbonate dissolution event our results are consistent with recently published data from the north pacific ocean this suggests that increased carbon storage in the glacial deep pacific ocean was a basin wide phenomenon consistent with a large scale transfer of carbon to the deep ocean during glacial periods

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

isotope fractionation by sulfate reducing natural populations and the isotopic composition of sulfide in marine sediments isotope fractionations during sulfate reduction by natural bacterial populations were measured in seven different marine sediments and compared with the isotopic composition of solid phase sulfides in the same sediments the measured fractionations during sulfate reduction could explain only between 41 and 85 of the 34s depletion in the sedimentary sulfides this result directly demonstrates that the depletion of 34s in solid sulfides is an expression of the combined activity of sulfate reducing organisms with additional fractionations accumulated during the oxidative part of the sulfur cycle the only known process to significantly augment the fractionations created during sulfate reduction is the microbial disproportionation of the intermediate sulfur compounds elemental sulfur thiosulfate and sulfite in a simple model we show how important each of these disproportionation processes could be in generating the isotopic composition of sedimentary sulfides the sulfate reduction rates in the sediments studied varied by a factor of 1000 and did not correlate with the fractionation during sulfate reduction by contrast a correlation was observed between sulfate reduction rate and the extent of 34s depletion into sedimentary sulfides the most 34s depleted sulfides found in sediments supporting the lowest rates of sulfate reduction thus the fractionations imposed during the disproportionating processes are better expressed in sediments with low sulfate reduction rates the direct phototrophic oxidation of sulfide to sulfate with minimal fractionation may have been important in the sediments that had a high sulfate reduction rate

paleoecological significance of laminated diatomaceous oozes during the middle to late pleistocene north atlantic ocean iodp site u1304 abstract we examined diatom assemblages in a series of remarkable laminated diatomaceous ooze ldo horizons in the marine sediments from integrated ocean drilling program iodp site u1304 to reconstruct the middle to late pleistocene paleoceanographic evolution of the northern north atlantic ocean four confirmed diatom biohorizons combined with calcareous nannofossil and paleomagnetic stratigraphies established the chronological framework for the material the planktonic araphid needle like species thalassiothrix longissima was the greatest contributor to the ldo facies from the results of a principal component analysis using the percent abundances of 65 significant p 5 diatom taxa except for tx longissima which was extremely dominant in almost all horizons observed we identified two principal component pc axes taxa probably associated with the stratigraphic distribution of the major zonal marker neodenticula seminae ranging from 1 26 to 0 84 ma in this ocean loaded on pc1 with a high value pc2 was related to the ocean surface temperature the stratigraphic variability of the pc2 score indicated that switching between warm and cold water assemblages occurred concurrently with ldo deposition or extreme tx longissima dominance episodes in several horizons particularly after 0 84 ma suggesting that the subarctic convergence sac oceanic front passed over site u1304 during pleistocene glacial interglacial cycles our floral evidence supports the model of nearly monospecific ldo formation caused by the enhanced physical accumulation of particular diatoms such as tx longissima on the other hand nd seminae which probably contributes to spring phytoplankton blooms in the modern ocean was present only between 1 26 and 0 84 ma in this area thus we infer that the main contributor of export flux in the regional annual primary production cycle would have shifted drastically from one of a spring phytoplankton bloom leader nd seminae to minor but mass dump assemblages tx longissima etc in the mid pleistocene

brief interstadial events in the santa barbara basin ne pacific during the past 60 kyr the instability of the northern hemisphere glacial climate over the past 100 kyr has been revealed by at least 20 brief warm interstadial episodes called dansgaard oeschger events recorded in greenland ice cores1 3 and in north atlantic sedimentary records4 5 a few of these events have been recognized elsewhere6 8 here we describe a record of ocean oxygenation and circulation from the santa barbara basin in the northeast pacific ocean which correlates well with the greenland ice core records we see 19 of the 20 dansgaard oeschger events in the form of laminated sediments deposited under anoxic conditions and we can correlate at least 16 of these with the 17 ice core interstadials of the past 60 kyr thus these short term events were not restricted to the north atlantic region the events had substantial ecological and oceanographic effects in the santa barbara basin including changes in benthic faunal populations and in the age and composition of bottom waters similar ventilation changes have been seen in the gulf of california9 10 suggesting that these changes may have been widespread and synchronous along the northeast pacific margin these results suggest sensitivity of broad areas of the ocean atmosphere cryosphere system to short term climate change

migration of the antarctic polar front through the mid pleistocene transition evidence and climatic implications abstract the antarctic polar front is an important biogeochemical divider in the southern ocean laminated diatom mat deposits record episodes of massive flux of the diatom thalassiothrix antarctica beneath the antarctic polar front and provide a marker for tracking the migration of the front through time ocean drilling program sites 1091 1093 and 1094 are the only deep piston cored record hitherto sampled from the sediments of the circumpolar biogenic opal belt mapping of diatom mat deposits between these sites indicates a glacial interglacial front migration of up to 6 degrees of latitude in the early mid pleistocene the mid pleistocene transition marks a stepwise minimum 7 northward migration of the locus of the polar front sustained for about 450 kyr until an abrupt southward return to a locus similar to its modern position and further south than any mid pleistocene locus this interval from a 900 ka event that saw major cooling of the oceans and a 13c minimum through to the 424 ka mid brunhes event at termination v is also seemingly characterised by 1 sustained decreased carbonate in the sub tropical south atlantic 2 reduced strength of antarctic deep meridional circulation 3 lower interglacial temperatures and lower interglacial atmospheric co2 levels by some 30 per mil than those of the last 400 kyr evidencing less complete deglaciation this evidence is consistent with a prolonged period lasting 450 kyr of only partial ventilation of the deep ocean during interglacials and suggests that the mechanisms highlighted by recent hypotheses linking mid latitude atmospheric conditions to the extent of deep ocean ventilation and carbon sequestration over glacial interglacial cycles are likely in operation during the longer time scale characteristic of the mid pleistocene transition the cooling that initiated the 900 ka event may have been driven by minima in insolation amplitude related to eccentricity modulation of precession that also affected low latitude climates as marked by threshold changes in the african monsoon system the major thresholds in earth system behaviour through the mid pleistocene transition were likely governed by an interplay of the 100 kyr and 400 kyr eccentricity modulation of precession

sequential leaching of marine ferromanganese precipitates genetic implications abstract sequential leaching experiments were carried out on twenty one hydrogenetic crust samples from different locations in the central pacific and the results are compared with four crust and nodule samples of different genetic origin fe vernadite mno2 is the most important minor and trace metal bearing mineral phase and shows high concentrations of co ni cd ti ba zn and cu which are present in seawater mainly as hydrated and labile complexed cations elements forming carbonate and hydroxide complexes and oxyanions in seawater like pb mo v and minor proportions of cu and zn are bound in the fe00h fraction the ca carbonate phase and the residual fraction which consists of aluminosilicates and crystalline oxides show only minor heavy metal associations e g cu and zn only a small part of the high ti concentrations in hydrogenetic crusts is of detrital origin ti mainly forms a hydrogenetic phase probably consisting of ti02 2h20 intergrown with the amorphous fe00h phase analyses of different sample types and crust layers show that aging and diagenetic effects can change the phase associations of some elements the most notable change was observed for pb which during phosphatization of crusts is transferred from the mn fe oxide fraction to the apatite fraction a colloid chemical model for the hydrogenetic precipitation of ferromanganese crusts on seamounts is proposed in the first stage mn2 rich water from the oxygen minimum zone is mixed with oxygen rich deep water and oxidized mn iv and other metals like fe ti al and si form oxide and hydroxide colloids these form mixed colloidal phases and scavenge trace metals by sorptive processes which are dominated by coulombic and chemical interactions between colloid surfaces and dissolved metal species in stage two the colloidal phases precipitate on the substrate rocks of the seamounts as ferromanganese oxide encrustations incorporating the sorbed heavy metals into the mineral phases

inorganic geochemical indicators of glacial interglacial changes in productivity and anoxia on the california continental margin abstract evidence from sediments in cores collected from within the present oxygen minimum zone omz 600 1200 m on the central and northern california margins record several episodes during the last interstadial ois 3 ca 60 24 ka of deposition of laminated sediments containing elevated concentrations of several trace elements indicative of anoxic conditions e g mo ni zn and cu the presence of abundant well preserved organic matter as well as lack of bioturbation and the presence of elevated concentrations of mo and other trace elements all support the theory that the omz in the northeastern pacific ocean was more intense possibly anoxic at several times during the late pleistocene sediments of all ages in cores from the southern california margin contain elevated concentrations of mo suggesting that this area has always had higher rates of sulfate reduction than either the central or northern california areas most of the ba in sediments in all cores collected on the upper continental slope 200 2700 m off california and southern oregon is derived from detrital clastic material and this source did not change much in time however the amount of biogenic ba did vary with time and these variations closely follow the temporal variations in organic c corg mass accumulation rate using ba and corg mass accumulation rates as proxy variables for productivity all cores show that organic productivity under the california current upwelling system was highest during ois 3 and the holocene and lowest during the last glacial interval lgi ca 24 10 ka all paleoproductivity proxy variables indicate that the southern california area has always experienced higher productivity than other areas under the california current at least over the last 50 ky

a stable isotope study of pyrite formation in the late pleistocene and holocene sediments of the black sea the abundance and isotopic composition of total and pyrite sulphur have been determined in a core in the central black sea pyrite varies in concentration from roughly 2 wt in the sapropel unit 2 to 0 8 wt in the modern horizon unit 1 and ca 0 1 wt in the lowermost horizons of unit 3 lake beds an intermediate mud flow horizon and the upper part of the lake beds have similar values to those in the modern sediments the degree of pyritization dop is lowest 0 05 in the lower lake beds and highest 0 55 in unit 1 the sapropel has values of ca 0 48 34spyrite varies from a minimum of 37 in the sapropel to 33 in unit 1 up to 15 in the upper lake beds and 0 in the lower lake beds the unit 1 and sapropel values are similar to the 34s values reported by fry et al 1991 of dissolved sulphide immediately below the water column oxic anoxic interface 36 to 38 but significantly heavier than those in the deep waters of the basin ca 41 these results are interpreted as a reflection of the presence of four different types of pyrite in the sediments of the black sea 1 pyrite in units 1 and 2 that is formed within the upper part of the water column immediately below the oxic anoxic interface where 34s of dissolved sulphide is 36 2 pyrite in the mud flow layer lying between unit 1 and the sapropel unit 2 with a significantly heavier isotopic composition that was formed around the margins of the basin under conditions that were probably more closed with respect to dissolved sulphate than those in which the pyrite in units 1 and 2 were formed 3 pyrite in the upper part of the lake beds unit 3 that was formed under closed system conditions by reaction between excess reducible fe remaining in these freshwater sediments and downward diffusing sulphate and or sulphide from the overlying organic rich sapropel and 4 pyrite in the lower part of the unit 3 representing a phase formed from the ambient sulphate in the freshwaters of the late pleistocene lake the isotopic information supports earlier suggestions that pyrite in the modern sediments of the black sea forms mainly in the water column with only minor amounts forming in the sediment because of the severe fe limitation of the bottom sediments that accumulate 2 000 m below the main fe and hs reaction zone at the oxic anoxic interface at shallow depths in the water column

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

opal and organic carbon in laminated diatomaceous sediments saanich inlet santa barbara basin and the miocene monterey formation abstract laminated biosiliceous sediments from saanich inlet british columbia si the monterey formation california mf and santa barbara basin california sbb are organic rich and were studied to assess the suitability of si and sbb as modern analogs of the miocene mf and to explore the controls on distributions of opal and organic carbon to this end individual laminae and groups of laminae extracted from odp cores and outcrop samples were analyzed using a multi tracer geochemical approach total organic carbon opal c n ratios 13 c of organic matter om kerogen type and major and minor element abundances were measured si sediments are 52 84 detrital 15 45 opal and 1 2 organic carbon 13 c and c n ratios indicate a marine source of the om present in the sediments samples from the upper siliceous member of the mf are 6 41 detritus 28 87 opal and 1 5 organic carbon kerogen types c n ratios and 13 c data are suggest mixed but predominantly marine om sbb samples are 59 90 detritus 6 34 opal 3 22 calcite and 1 5 percent organic carbon si and sbb have similar bulk compositions with the exception of the presence of calcite in sbb samples mf sediments have significantly lower detrital and higher opal contents than si and sbb samples these large differences suggest that si and sbb are not appropriate modern analogs for the mf in si sediments organic carbon is concentrated in opal rich detritus lean laminae and intervals this distribution suggests that the coupling of opal and om created in the surface ocean by diatom productivity is preserved in the sediment record in the mf opal and toc are negatively correlated implying that the coupling of opal and organic carbon did not survive the processes of settling sedimentation diagenesis and or weathering this decoupling of organic carbon and opal in the mf is attributed to dilution of om by high opal flux rates and or the respiration and or redistribution of om during diagenesis and or weathering

geochemistry of recent toc rich sediments from the gulf of california and the black sea major and minor elements incl ag as ba cd co cr cu mn mo ni pb sr v zn have been determined in recent sediments from the gulf of california upwelling area and black sea sapropels in order to reinterpret their chemical composition in view of reliable seawater and plankton data the chemistry of the gulf of california sediments reflects regeneration processes which occur in the water column i e only a small fraction 10 of elements like cd which in seawater are coupled to the labile nutrients c n p is buried in the sedimentary column in contrast elements like the more resistant nutrients si undergo a deeper regeneration cycle ba several trace metals which are present in comparatively higher concentrations in seawater as mo u v and at the same time are reactive under reducing conditions and or are able to form stable sulfides are fixed in the sediments during early diagenesis the early diagenetic behavior of ba is closely related to bacterial sulfate reduction the formation of barite concretions is discussed anoxic conditions in the water column act as ideal traps for a number of redox sensitive and or stable sulfide forming elements a simple trace metal balance calculation shows that the chemical composition of black sea sapropels is controlled by fluvial and mediterranean seawater element input and the accumulation rate of terrigenous detrital material

temporal relationships of carbon cycling and ocean circulation at glacial boundaries evidence from high sedimentation rate south atlantic deep sea cores indicates that global and southern ocean carbon budget shifts preceded thermohaline circulation changes during the last ice age initiation and termination and that these were preceded by ice sheet growth and retreat respectively no consistent lead lag relationships are observed during abrupt millennial warming events during the last ice age allowing for the possibility that ocean circulation triggered some millenial climate changes at the major glacial interglacial transitions the global carbon budget and thermohaline ocean circulation responded sequentially to the climate changes that forced the growth and decline of continental ice sheets

pitfalls of normalization of marine geochemical data using a common divisor abstract normalization of trace element contents of sediment through division by the content of an immobile element usually aluminum is common practice in marine geochemical studies this might appear to be a simple way of correcting for dilution by sedimentary phases barren of a particular trace element for instance carbonates or silica and for comparison with its content in a standard clay or shale the purpose of this paper is to revive the awareness of the pitfalls of this practice by giving numerical examples of the often unexpected results of normalization taking a statistical perspective it is first shown that uncorrelated variables acquire spurious correlations when normalized but normalization can also increase decrease change sign of or even blur the correlations between unmodified variables next a number of realistic scenarios are worked out to show that the correlations between normalized element contents still suffer from the closure effect only in a few simple cases it is possible to extract from the normalized data realistic estimates of trace element contents in distinct sedimentary phases such as organic matter this is ascertained from data on copper contents in sediment from the black sea and arabian sea when the coefficient of variation i e standard deviation divided by the mean of the aluminum data is relatively low and much lower than for the original values of the trace elements comparisons of correlations can equally well or even better be made on the basis of the unmodified values then the comparison of trace element data with their values for standard shales is discussed the inherent problem is that the composition of the commonly used standard shale and consequently the reference values of normalized elements are not necessarily representative of the local or regional sediments in the study area also this method falls short of identifying the processes responsible for enrichment or diminution in trace element contents finally consideration is given to some aspects of a proper use of al normalization

carbon sulfur iron systematics of the uppermost deep water sediments of the black sea box cores recovered during leg 4 of the 1988 r v knorr black sea oceanographic expedition from deep water regions of the basin were dominated by coccolith rich microlaminated unit 1 sediment and muddy gray turbidite layers both organic carbon oc and pyrite sulfur values for unit 1 display narrow ranges with mean concentrations of 5 3 1 1 1 wt and 1 3 0 3 wt respectively unit 1 is not enriched in pyrite s relative to sediments deposited under oxygenated bottom waters normal marine sediments with comparable oc concentrations carbon sulfur relationships evaluated on a calcium carbonate free basis to avoid spurious correlations resulting from dilution effects demonstrate that oc and pyrite s are essentially decoupled these observations combined with the persistence of elevated pore water sulfide to depth and a strong correlation between pyrite s and the detrital fe component argue strongly for limitation of pyrite formation in unit 1 by the availability of reactive fe unit 1 fe limitation is further indicated by degree of pyritization dop studies a measure of the extent to which the original potentially reactive fe has been transformed to pyrite these studies show sulfidation of reactive fe ranging from 57 to 78 with dop values independent of oc concentration unit 1 dop profiles suggest that the majority of the pyrite is formed in the sulfidic water column and or very close to the sediment water interface pyrite s concentrations of unit 1 when compared with the particulate reduced sulfur fluxes measured in time series sediment traps are compatible with predominantly water column pyrite formation because of the limitations in the supply of reactive fe associated with the comparatively high supply of oc the microlaminated sediment is characterized by c s ratios greater than those typical of holocene oxically deposited sediments the turbidite muds of the deep basin display high reduced s values relative to holocene normal marine sediments in samples with low oc concentrations low c s ratios this reflects pyrite formation under anoxic sulfidic bottom water conditions in a probable upper slope source region as well as during transport and final deposition intermediate dop values for the turbidites in part a product of their rapid rate of deposition reveal that fe limitation is ultimately not a factor and that further pyrite should form during burial however the very rapid rate at which unit 1 pyrite forms suggests fundamental differences between the overall reactivities of the fe phases associated with the microlaminated and turbiditic sediments the signature of water column anoxia with regard to sedimentary pyrite formation is clearly indicated by the high dop values of unit 1 and the comparatively high levels of s associated with the low concentrations of oc of the turbidite muds this agrees with similar conclusions based on studies of ancient sedimentary rocks

on the emergence of plate tectonics at present young oceanic lithosphere is positively buoyant and it does not become negatively buoyant until it is older than about 20 m y if in the past the mantle was hotter the oceanic crust would have been thicker and the lithosphere9s age of neutral buoyancy greater on the other hand the hotter mantle would have had a lower viscosity and convected faster so the average age of oceanic plates at subduction would have been less than the present 100 m y at some time in the past average oceanic lithosphere would have only just become negatively buoyant as it reached a subduction zone it is estimated here that this condition occurred when the mantle was only about 50 c hotter than at present and as recently as 0 9 1 4 b y ago transformation of basaltic crust to eclogite might have enhanced the vigor of the plates but possibly only modestly and intermittently in earlier times plate tectonics could have operated but more slowly so that it could not by itself have accomplished the necessary rate of heat removal from the earth a different tectonic mode must also have operated perhaps subcrustal delamination or dripping plate tectonics would have gradually taken over from the earlier mode plumes are a omplementary mode of mantle convection driven by a lower thermal boundary layer and so they could have operated in conjunction with both regimes of the upper boundary layer

a dynamic concept for eastern mediterranean circulation and oxygenation during sapropel formation we propose that intermittent bottom water ventilation occurred throughout periods of sapropel deposition and that the recently reported sapropel interruptions represent centennial scale episodes of enhanced frequency intensity of that process in essence the modern high frequency variability in deep water formation affected by climatic variability over the northern basins on seasonal to longer time scales prevailed also at times of sapropel deposition although the overall ventilation state was much reduced this concept is supported by detailed multiple species isotope records for three aegean cores the presence of abundant globorotalia truncatulinoides within especially sapropels s7 and s8 in the western levantine basin observations of three rapid benthic repopulations within sapropel s6 in the deep western levantine basin a report of continuous benthic presence through sapropel s1 at intermediate deep locations offshore libya and further supporting information from the literature in the aegean records concomitant abundance of low oxygen tolerant benthic foraminifera and presence of the more oxyphilic benthic foraminifer uvigerina mediterranea with surface similar 13c values indicate repeated deep water re oxygenation events throughout the deposition of s1 the observations of a continuous benthic presence through s1 offshore from libya imply that no persistent anoxia developed at mid depth levels in that region which is far removed from direct deep ventilation influences the abundance of deep mesopelagic g truncatulinoides through several sapropels from the western levantine basin also suggests the presence of bio available oxygen at many hundreds of meters of depth moreover the rapid intermittent benthic repopulations within sapropels from the deep eastern mediterranean imply that bottom water anoxia was spatially restricted and or of a highly intermittent nature the short time scales of these repopulation events are incompatible with titration of an extensively anoxic water column and subsequent re establishment of water column anoxia we suggest that where anoxic azoic conditions were present they most likely were restricted to a veneer at the sediment water interface the extent of such an anoxic blanket depends on the balance between advective oxygen supply into the deep sea and biological and chemical oxygen demand the demand functions imply a decoupling of oxygenation from water mass advection allowing export production and corg posting rates to the sea floor to delimit the extent of the anoxic blanket in both space and time low productivity regions would develop no anoxic blanket allowing for the observed persistence of deep dwelling planktonic and bottom dwelling benthic faunas

excess aluminum in deep sea sediments of the central indian basin abstract the aluminum concentration in the marine sediments has long been considered an indicator of terrigenous abundance the al ti values 48 5 of the central indian basin subsurface siliceous sediment are up to three times that of post archean australian shale paas the estimation of structurally unsupported al al ex from six sediment cores suggests that an average of 40 of total al is from noncrustal sources higher al ti or al ex values are often but not exclusively associated with abundant volcanic unaltered glass shards electron microprobe analysis of 60 of these glass shards reveals that they are rhyolitic in composition and of youngest toba 74 ka origin from northern sumatra these glass shards have very high al ti ratio of 175 mean al ti values are also above the paas in sediment where glass shards are absent which could be due to scavenging of dissolved al by biogenic components

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

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

stirring and mixing in the mantle by plate scale flow large persistent blobs and long tendrils coexist the stirring of a small passive heterogeneity in an unsteady circulation is investigated by following the boundary of the heterogeneity the circulation mimics features of plate scale flow after initial release the heterogeneity is stirred and subsequently consists of at least one large blob connected to long but thin tendrils tendrils exponentially lengthen and exponentially thin with time as predicted by a turbulent mixing law but the width of blobs decays about 100 times more slowly the blobs mix slowly because they are smaller than the scale of flow and are sheared and occasionally unmixed by the laminar flow within the interiors of convection cells the decay time of 1 to 100 km sized heterogeneities is on the order of billions of years for whole mantle convection and thus is in accord with isotopic observations which indicate the mantle has chemical heterogeneities persisting for billions of years

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

mississippian barnett formation fort worth basin texas bulk geochemical inferences and mo toc constraints on the severity of hydrographic restriction abstract chemostratigraphic evidence from the barnett formation texas usa elucidates the restricted nature of the depositional environment in the fort worth basin during the early progression of the late paleozoic ouachita orogeny in accord with recent lithostratigraphic and petrographic studies stratigraphic bulk geochemical analyses reveal that the environment of deposition was anoxic to euxinic sediment starved with relatively high rates of organic matter accumulation using an environmental proxy developed from the sediment geochemistry of modern anoxic silled basins the stratigraphic concentrations of total organic carbon toc and molybdenum mo in the barnett formation reveal a high degree of subpycnoclinal water mass restriction and an extended timescale of deep water renewal of at least 8 103 years and potentially as long as 2 104 years an integrated assessment of elemental concentrations the degree of pyritization and toc s fe relationships reveals that severe fe limitation controlled pyrite formation and the large excess of sulfide in the overlying water column mineralogical and elemental constraints suggest that following sulfate reduction less easily bio extractable fe iii was bio reduced under methanogenic conditions consequently liberating fe ii which was subsequently incorporated into pore water formed dolomite i e organogenic dolomite the preserved mo toc toc s fe and fe bearing mineral relationships collectively indicate that the protracted turnover rate and persistent sediment starvation resulted in a biologically inhospitable environment that limited the microbial consumption rate of organic carbon

subducted slabs and the geoid constraints on mantle rheology and flow geoid anomalies are primarily the result of the density contrasts driving mantle convection and plate motion the total geoid anomaly resulting from a given density contrast in a convecting earth is affected by the mass anomalies associated with the flow induced deformation of the upper surface and internal compositional boundaries as well as by the density contrast itself these boundary deformations and hence the total gravity field depend on the radial distribution of effective viscosity if the internal density contrasts can be estimated as is the case for subducted slabs useful constraints can be placed on the depth and on the variation of viscosity with depth of the convecting system the degree 4 9 components of the observed long wavelength geoid are highly correlated with those predicted by a density model for seismically active subducted slabs the positive sign of the correlation requires that the effective viscosity increases with depth by a factor of 30 or more the amplitude of the correlation cannot be explained by the density contrasts associated with just the seismically active parts of subducted slabs however the amplitude can be explained if the density contrasts associated with subduction extend into the lower mantle or if old lithosphere is piled up at the base of the upper mantle beneath subduction zones to a thickness in excess of 350 km over horizontal distances of thousands of kilometers mantlewide convection in a mantle that has a viscosity increasing with depth provides a simple explanation of the long wavelength geoid anomalies over subduction zones

comment on mixing by time dependent convection by u christensen commentaire et reponse concernant l article de u christensen earth planet sci lett 95 382 394 1989

systematics of variations in excess al and al ti in sediments from the central equatorial pacific the proposal that the accumulation rate ar of scavenged al in central equatorial pacific sediments is controlled by bulk particle flux and therefore can be used as a paleoproduction proxy is tested by examining the relationship between al and ti using data on core wec8803b gc51 published by murray et al 1993 the downcore profile of the excess al ar follows the bulk ar consistent with the al scavenging hypothesis and is due to a relatively constant abundance of excess al down core however there have been large changes in the aluminosilicate ar to this region suggesting that changes in the al ti value do not solely trace variability in the delivery rate of scavenged al assuming that the excess al in this core is not the result of an analytical artifact we present an alternative to the al scavenging hypothesis that involves authigenic clay mineral formation or some other process causing the occurrence of excess al at a relatively constant abundance of the sediment this process may well be independent of bulk particle flux or paleoproduction

geochemical processing in a three dimensional regional spherical shell model of mantle convection 1 a three dimensional regional spherical model of processing of oceanic crust through subduction stirring and remelting confirms the main results from previous two dimensional models and from three dimensional models with low rayleigh number and only depth dependent viscosity the new model features high rayleigh number strongly temperature dependent viscosity a set of realistic surface plates and oceanic crust simulated by passive tracers it confirms that the processing timescale is the main determinant of the age distributions and mean ages of mid ocean ridge basalt morb and ocean island basalt oib samples and also of the present degree of processing of the mantle which is 99 in this model the melting depth decreases with time accounting for its temperature dependence and so the processing timescale increases with time an approximate processing theory reveals that morb and oib ages depend mainly on the recent processing timescale whereas the degree of processing depends mainly on the initial processing timescale

diatom mats in gulf of california sediments implications for the paleoenvironmental interpretation of laminated sediments and silica burial preservation of laminations in hemipelagic and pelagic sediments is routinely attributed to reduced oxygen conditions that inhibited benthic activity as such the degree of preservation of laminae is used commonly as a paleo oxygenation indicator recent evidence from deep sea pelagic sediments in the eastern equatorial pacific and north atlantic however demonstrates that preservation of laminae may occur by rapid deposition of ungrazed thalassiothrix longissima diatom mats that overwhelm the benthos in otherwise oxic bottom waters here we report that similar diatom mat laminae are common in hemipelagic sediments of the guaymas basin in the gulf of california have aided preservation of the laminated sediment sequence and have also enhanced opal burial examples of diatom mats influencing sediment preservation are also described from the northern california margin and from the miocene monterey formation southern california thus even in classical settings of laminated sediment occurrence caution needs to be taken in correlating degree of lamina preservation with paleo oxygen levels such studies must be underpinned by detailed microfabric and micropaleontological analyses

pyrite and organic matter in phanerozoic normal marine shales data have been obtained from our own chemical analyses and from the literature for the concentrations of organic carbon c and pyrite sulfur s in over 600 samples of cambrian to recent normal marine shales normal marine refers to deposition in oxygenated bottom water as evidenced by the presence of benthic fossils and or indicators of bioturbation all samples were selected to minimize 1 1 loss of c and or s due to weathering at the outcrop by emphasizing the use of drill core material 2 2 analytical errors and non diagenetic effects by avoiding sediments low in c or s content such as sandstones 3 3 fe limitation of pyrite formation by avoiding limestones cherts and euxinic shales 4 4 metamorphic loss of c relative to s by avoiding rocks obviously subjected to even low grade metamorphism our results indicate that 1 there is generally a good positive linear correlation between organic c and pyrite s for normal marine shales of all ages and 2 the mean cs ratio for normal marine shales has varied over time devonian to tertiary shales exhibit mean cs weight ratios 1 8 0 5 somewhat lower than quaternary sediments meancs 2 8 this we believe is due to preferential c loss relative to s during biogenic methanogenesis plus diagenetic heating distinctly lower mean c s values for the cambrian and ordovician 0 5 0 1 cannot be explained solely in terms of diagenetic c loss and instead must represent low original ratios the low original ratios we suggest were due mainly to the absence of bacterially refractory organic matter added to the marine environment by rivers at that time because the major source of such material vascular land plants had not yet evolved this along with a possibly lower degree of bioturbation contributed to enhanced pyrite formation and preservation and thus lower early paleozoic cs ratios

sulfur speciation in the upper black sea sediments abstract we report solid phase sulfur speciation of six cores from sediments underlying oxic suboxic and anoxic sulfidic waters of the black sea our dataset includes the five sulfur species pyrite sulfur acid volatile sulfides avs zerovalent sulfur s 0 organic polysulfides rsx humic sulfur together with reactive iron and manganese as quantified by dithionite extraction and total organic carbon pyrite sulfur was the major phase in all cores 200 400 mol g dry wt 1 except for the suboxic core however zerovalent sulfur and humic sulfur also reached very significant levels up to about 109 and 80 mol g dry wt 1 respectively humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where unit 1 type depositional conditions prevail elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments the accumulation of elemental sulfur to a level close to that of pyrite s in any part of central black sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build up of dissolved sulfide in the sediment this process also contributes to diagenetic pyrite formation whereas in the non turbiditic parts of the deep basin water column formed syngenetic pyrite dominates the sulfur inventory in slope sediments under suboxic waters organic sulfur humic sulfur organic polysulfides account for 33 42 of total solid phase s indicating that the suboxic conditions favor organosulfur formation our study shows that the interactions between depositional patterns unit 1 vs turbidite redox state of overlying waters oxic suboxic sulfidic and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite s

paleoproductivity and paleoredox conditions during late pleistocene accumulation of laminated diatom mats in the tropical west pacific paleoproductivity and paleoredox conditions were reconstructed in a sediment core in the parece vela basin of the eastern philippine sea the core consists of three units from youngest to oldest 1 laminated diatom mats ldm formed by ethmodiscus rex during the last glacial maximum similar to 18 28 kyr b p 2 diatomaceous clay dc and 3 pelagic clay pc elevated levels of export productivity during ldm deposition are indicated by high values for excess ba opal content and toc ti ratios estimated rates of organic carbon degradation ca 98 opal mass accumulation average 1322 g m 2 yr 1 and corrected organic carbon flux average 248 g m 2 yr 1 are comparable to high productivity regions of the modem ocean the ldm is also characterized by moderate enrichment of redox sensitive elements such as u mo cd and zn highly s 34 depleted pyrite sulfur isotopic compositions indicating bacterial sulfate reduction in a sulfate unlimited system and c s fe systematics reflecting limitation of pyrite formation by organic matter rather than reactive fe availability these features suggest mainly suboxic conditions in bottom waters but development of sulfidic anoxic conditions at or close to the sediment water interface association of intensified anoxia with productivity maxima indicates that export production was a more important control on bottom water redox conditions than lateral ventilation the dc and pc accumulated under oxic to suboxic conditions our observations suggest that redox environments during deposition of laminated marine sediments are more complicated and varied than previously thought and thus the use of sediment lamination as an indicator of anoxic bottom water conditions must be approached cautiously c 2012 elsevier b v all rights reserved

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

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

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

the behavior of redox sensitive metals across a laminated massive laminated transition in saanich inlet british columbia abstract holocene laminated sediments in saanich inlet british columbia are interrupted by frequent non laminated massive layers these layers may be debris flows released by earthquakes or bioturbated sediments deposited during periods of relatively high bottom water oxygen concentration and or low surface productivity or both we determined the organic carbon content and the concentration of a suite of redox sensitive metals in bulk sediments at approximately 1 cm resolution across a laminated massive laminated interval odp leg 169s site 1033 hole b 4h4 54 74 cm to determine the redox conditions under which the massive layer was deposited our results indicate that this massive interval was deposited under anoxic bottom waters manganese al ratios are consistently low throughout the massive section while mo al cd al re al and u al ratios are enriched relative to their metal al ratios in detrital material represented by cowichan river suspended sediments the concentration of organic carbon in the lower portion of the massive layer is higher than in the upper portion which has a concentration similar to that in the overlying and underlying laminated sediments well defined peaks in mo al cd al and re al and a broad peak in u al occur in the lower portion of the massive layer the positions of the cd al re al and mo al peaks as well as the increase in organic carbon content with depth in the massive layer are best explained by a process of diagenetic redistribution of metals that occurred after the massive layer was emplaced

isotopic composition and speciation of sulfur in the miocene monterey formation reevaluation of sulfur reactions during early diagenesis in marine environments the timing and pathways of early diagenetic sulfur transfer from dissolved species in pore waters to solid inorganic and organic compounds in sediments have been studied in the miocene monterey formation santa maria basin onshore california correlation between concentrations of total organic carbon toc and total sulfur ts in addition to concentrations of titanium aluminum total iron and reactive iron have been used to infer organic matter reactivity redox conditions and relative rates of clastic and biogenic input for each lithofacies isotopic compositions of six sulfur species acid volatile disulfide kerogen bitumen sulfate and elemental have provided information regarding relative timing of sulfur incorporation sulfate diffusivity in the upper centimeters of the sediments and the sources of sulfur for individual species isotopically the disulfide species expresses the greatest fractionation relative to estimated values of miocene seawater sulfate 22 cdt on average disulfide is depleted in 34s by 10 4 relative to kerogen and by 9 9 relative to acid volatile sulfide the 34s of bitumen shows no systematic change relative to 34skeregon suggesting the presence of migrated bitumen isotopic similarity of sulfate and elemental sulfur to sulfides and bitumen indicates that sulfate and elemental sulfur are chemical and or biological oxidation products derived from sulfides and bitumen consistent ordering of isotopic values for sulfur species disulfide acid volatile sulfide kerogen indicates that pyrite precipitated nearest to the sediment water interface under mildly reducing conditions and with little or no decrease in sulfate concentration relative to seawater enrichment of 34s in acid volatile sulfide and kerogen sulfur resulted from formation of these species at greater depths or in restricted micro environments under more reducing conditions and with low concentrations of porewater sulfate the formation of acid volatile sulfide after pyrite but during early diagenesis is significant because it implies more strongly reducing conditions than are generally recognized in deep water marine sediments

the influence of alteration on the engineering properties of dolerites the examples from the pindos and vourinos ophiolites northern greece abstract the influence of alteration on the physico mechanical properties of dolerites from the pindos and vourinos ophiolites northern greece is investigated quantitative petrographic analysis shows that the samples display various percentages of secondary minerals two new micropetrographic indices are calculated from the results of petrographic modal analysis for the engineering assessment of dolerites the micropetrographic strength index i ps and the replacement index i rep the samples are also tested to determine water absorption apparent density total porosity sand equivalent uniaxial compressive strength los angeles abrasion value aggregate impact value aggregate abrasion value and polished stone value the influence of alteration on the rock quality and especially the relationships between the proposed micropetrographic indices and the engineering parameters are determined using regression analysis and the derived equations were verified by the t test and the f test the relationships between the i ps and i rep indices and the engineering properties show that alteration products generally result in mechanically weaker rocks however the results of the physico mechanical tests indicate that dolerites retain their strength and durability due to the low proportions of soft minerals and microcracks along with the preservation of their igneous textures the polishing resistance is the only engineering parameter that is positively affected by alteration processes as expressed by the i ps index particularly the replacement of the primary mafic minerals by secondary minerals expressed by the i rep index can enhance the polishing resistance of dolerites when used in the wearing surface of a road the results also indicate strong positive correlations between the chlorite content and the water absorption and total porosity values

influence of water column anoxia on the burial and preservation of carbon and phosphorus in marine shales abstract organic p and organic c concentrations were measured in several well characterized phanerozoic marine shale sequences with the primary focus being the camp run member of the devonian mississippian new albany shale sequences were selected with close spatial association of bioturbated and laminated sediments which reflect deposition from oxic and anoxic waters respectively average organic c p mole ratios calculated from the data are 150 for bioturbated shales and 3900 for the laminated shales of the new albany differences in the extent and mechanisms of early diagenesis related to the oxygenation of waters at the sediment water interface can account for the c p ratios of buried organic matter low c p ratios of bioturbated sediments are attributed to 1 1 the increased ability of bacteria to store p in well oxygenated environments which leads to the production of low c p ratio bacterial biomass and 2 2 the extensive oxidation of sedimentary organic matter resulting in the formation of residual organic phases with low c p ratios high organic c p ratios of laminated sediments are explained by a combination of 1 1 the limited ability of bacteria to store p under anoxic conditions 2 2 extensive p regeneration from sedimentary organic matter 3 3 enhanced c preservation relative to the bioturbated shales it is also shown that relative to organic c laminated shales are not as effective a p sink as are bioturbated shales this provides a mechanism in anoxic environments for burying large quantities of organic matter without simultaneously sequestering the p needed to sustain further productivity

formation and preservation of greigite fe3s4 in sediments from the santa barbara basin implications for paleoenvironmental changes during the past 35 ka diagenetic processes are known to modify sedimentary records but they can also reveal important paleoenvironmental changes here we investigate variations in sedimentary iron diagenesis and depositional environments for the last 35 ka by analyzing the rock magnetic and geochemical properties of two sediment cores collected in the santa barbara basin california in organic rich sediments early diagenesis often leads to partial dissolution of detrital iron oxides and stepwise formation of authigenic pyrite fes2 the pyritization process takes place following several geochemical pathways sometimes involving intermediate iron sulfide species such as greigite fe3s4 sedimentary conditions in the basin appear to have recurrently favored preservation of greigite identified by its magnetic properties and inhibited its complete transformation into pyrite the holocene interval contains a series of centimeter thick greigite bearing layers that are associated with large flood deposits which are known in the basin as gray layers we propose that greigite preservation was enabled in these sediments by their relative enrichment in reactive iron over organic matter and or hydrogen sulfide because of their high ratio of terrigenous over organic material which limited pyritization reactions within the glacial deposits formation and preservation of meter thick greigite layers occurred in terrigenous rich and organic poor sedimentary layers and is proposed to result from a similar diagenetic process to that in the holocene greigite bearing layers dominance of reactive iron over organic matter and or hs the terrigenous enrichments in the glacial greigite bearing layers are probably related to climatic or sea level changes because they occur at times of massive iceberg releases in the north atlantic the so called heinrich events

high isotope fractionations during sulfate reduction in a low sulfate euxinic ocean analog a detailed record of the early earth sulfur s cycle is chronicled by the s isotope values of sulfide and sulfate preserved in the rock record interpretation of this record rests on our understanding of sulfur cycling in modern systems experiments and the resulting isotopic signatures very large fractionations in 34s of 70 are commonly measured between sulfide and sulfate in modern systems and in ancient sediments theoretical calculations suggest that sulfate reducing prokaryotes are capable of producing such large fractionations during the reduction of sulfate to sulfide although they have only been demonstrated to generate fractionations up to 48 here we report the first direct determination of 60 70 fractionations by natural populations of sulfate reducers these high fractionations occur under the relatively low sulfate conditions 1 1 2 mm of meromictic lago di cadagno in switzerland the major and minor isotopic composition of sulfide and sulfate in the lake water is consistent with sulfide produced by sulfate reduction with little evidence for modification by further oxidative sulfur cycling these observations help us to constrain the evolution of seawater sulfate concentrations

regular vs chaotic mantle mixing abstract most quantitative models of mantle mixing have been based on simulations of tracer advection by 2 d flows the present work shows that the mixing properties of 3 d time independent flows cannot be understood or extrapolated from previous 2 d models steady convective flows appropriate to simulate a uniform fluid with large viscosity are restricted to poloidal components they seem to have regular streamlines however the existence of plates on the earth s surface imposes the existence of a strong toroidal field flows where both poloidal and toroidal components are present can yield chaotic pathlines which are very efficient in mixing the mantle within areas of turbulent mixing where the stretching increases exponentially with time regular islands of laminar stretching persist in which unmixed material can survive our findings indicate that the intrinsic three dimensionality of convection coupled with plates as much as its time dependence must be included in numerical models to understand the mixing properties of the mantle as the viscosity is significantly larger in the lower mantle than in the upper mantle the toroidal component of the flow is confined to the upper mantle where a more thorough mixing should take place

sulphidic mediterranean surface waters during pliocene sapropel formation sapropels organic matter rich layers are common in neogene sediments of the eastern mediterranean sea the formation of these layers has been attributed to climate related increases in organic matter production1 2 3 and increased organic matter preservation due to oxygen depletion in more stagnant bottom waters2 3 here we report that eastern mediterranean pliocene sapropels4 contain molecular fossils of a compound isorenieratene known to be synthesized by photosynthetic green sulphur bacteria suggesting that sulphidic euxinic and therefore anoxic conditions prevailed in the photic zone of the water column these sapropels also have a high trace metal content which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column the abundance and sulphur isotope composition of pyrite are consistent with iron sulphide formation in the water column we conclude that basin wide water column euxinia occurred over substantial periods during pliocene sapropel formation in the eastern mediterranean sea and that the ultimate degradation of the increased organic matter production was strongly influential in generating and sustaining the euxinic conditions