controls of eustasy and diagenesis on the 238u 235u of carbonates and evolution of the seawater 234u 238u during the last 1 4 myr using a leaching protocol designed for the study of u isotopes in recent carbonates we measured the u isotope composition both 238 u 235 u and 234 u 238 u of modern and ancient corals n 6 a limestone and a dolostone as well as 43 shallow water carbonate sediments from the odp leg 166 site 1009 drill core on the slope of the bahamas platform although bulk corals record the seawater 238 u value within 0 02 differences of up to 0 30 in the 238 u of individual leachates suggest a control of the coral structure and a more positive 238 u 235 u ratio in the centers of calcification the drill core 238 u data shows that the 238 u 235 u ratio of shallow water carbonates is controlled mainly by 1 variations in sea level through the mixing of different amounts of platform derived sediments with 238 u 0 50 0 60 heavier than seawater and pelagic sediments with seawater like 238 u values 2 authigenic u enrichment via pore watercirculation and u reduction both on the platform and down to 5 m below the surface mbsf after deposition of the sediment and to a lesser extent by 3 early diagenetic processes i e carbonate dissolution and or recrystallization during sediment burial the global effect of these processes leaves the 238 u values of shallow water carbonates offset relative to that of seawater by carbonates sw 0 24 0 06 95 ci including all samples this shift can be used in seawater paleoredox reconstructions based on carbonates deposited on shallow water platform shelf and slope environments i e most of the carbonate sedimentary record prior to the mesozoic to account for the average effect of carbonate diagenesis assuming that the 238 u 235 u ratio of carbonate platform sediments directly records the seawater 238 u 235 u ratio would underestimate the extent of ocean seafloor anoxia by at least a factor 10 the rapid fluctuations in 238 u values due to sea level changes i is a factor that should be considered before interpreting 238 u variations as reflecting changes in oceanic paleoredox conditions and ii reinforces the need for statistically meaningful data sets the 234 u data suggest that the 234 u 238 u ratio of the seawater has remained within 20 of the modern seawater value during the last 1 1 4 myr furthermore we find that small scale 1 15 variations in seawater 234 u mirror sea level changes during the penultimate glacial interglacial period 140 to 200 ka thus confirming the record of lower 234 u sw during periods of low sea level stand and expanding it to at least the last two glacial interglacial events i e 0 23 ma such fluctuations in 234 u initial values should be taken into account when screening carbonate sediments u th ages on the basis of the initial 234 u 238 u ratios of the samples

mineralogy early marine diagenesis and the chemistry of shallow water carbonate sediments abstract shallow water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of earth s chemical and climatic history one of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post depositional diagenetic alteration in this study we use paired measurements of calcium 44ca 40ca or 44ca and magnesium 26mg 24mg or 26mg isotope ratios in sedimentary carbonates and associated pore fluids as a tool to understand the mineralogical and diagenetic history of neogene shallow water carbonate sediments from the bahamas and southwest australia we find that the ca and mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis the observed variability in bulk sediment ca isotopes is best explained by changes in the extent and style of early marine diagenesis from one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the fluid fluid buffered to one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the precursor sediment sediment buffered our results indicate that this process together with variations in carbonate mineralogy aragonite calcite and dolomite plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers 13c 18o major minor and trace elements in shallow water carbonate sediments in the geologic record our results also provide evidence that a large shallow water carbonate sink that is enriched in 44ca can explain the mismatch between the 44 40ca value of rivers and deep sea carbonate sediments and call into question the hypothesis that the 44 40ca value of seawater depends on the mineralogy of primary carbonate precipitations e g aragonite seas and calcite seas finally our results for sedimentary dolomites suggest that paired measurements of ca and mg isotopes may provide a unique geochemical fingerprint of mass transfer during dolomitization to better understand the paleo environmental information preserved in these enigmatic but widespread carbonate minerals

active circulation of saline ground waters in carbonate platforms evidence from the great bahama bank measurements of salinity temperature and ground water discharges within the great bahama bank provide evidence of active circulation of near normal ocean water beneath north andros island elevated salinity waters 38 42 derived by density refulx from the great bahama bank flow eastward beneath the island and mix with normal salinity cold ground waters 19 20 c from deeper than 250 m in the adjacent oceans east to west flow of water from the straits of florida may be driven by head differences generated by the florida current which impinges on the western margins of the platform alternatively density differences between the reflux and tongue of the ocean sea waters may cause more local circulation on the eastern flanks these flows have important diagenetic implications particularly in the explanation of pervasive secondary dolomitization widely reported at shallow depths in the bahamas

uranium and radium diffusion in organic rich sediments sapropels among the late quaternary mediterranean sapropels the s5 125 ka is one of the best preserved due to its high organic carbon content that has limited postdepositional oxidation the high uranium content in this sapropel 40 dpm g 1 makes this layer interesting for studying uranium series disequilibrium in organic rich sediments for this reason the present work provides isotopic measurements of the u decay series in a s5 sapropel by applying more precise mass spectrometric methods tims mc icpms and gamma spectrometry assuming that u in the sapropel mostly originated from seawater the 234u 238u 230th 238u 226ra 230th and 231pa 235u activity ratios show systematic deviations from the theoretical values for a closed system evolution of the u series over the 125 ka since sapropel formation the radiogenic 234urad and 226ra show clear evidence of migration in the sapropel with modeled diffusion coefficients of 7 1 1 1 10 12 cm2 s 1 and 1 6 0 2 10 10 cm2 s 1 respectively the diffusion of 234urad cannot explain the high 230th 238u and 231pa 235u activity ratios observed in the sapropel two possible mechanisms or a combination of both are proposed for explaining the irregular 230th 238u and 231pa 235u activity profiles in sapropel s5 the first one is an enhanced export flux of 230thxs and 231paxs excesses exceeding the production rate in seawater during the time of sapropel formation and the second one is diffusion of authigenic uauth in the sapropel however the ambiguous determination of 230thxs and 231paxs in the sapropel and the poorly understood processes that might lead to uauth migration in anoxic sediments still limit a final explanation for the deviation of 230th 238u and 231pa 235u activity ratios from their expected theoretical values

global ocean redox variations across the smithian spathian boundary linked to concurrent climatic and biotic changes abstract the smithian spathian boundary ssb was an interval characterized by a major global carbon cycle perturbation climatic cooling from a middle late smithian boundary hyperthermal condition and a major setback in the recovery of marine necto pelagic faunas from the end permian mass extinction although the ssb has been linked to changes in oceanic redox conditions key aspects of this redox variation e g duration extent and triggering mechanisms and its relationship to coeval climatic and biotic changes remain unresolved here we report a high resolution middle smithian to middle spathian u isotope 238u record based on marine carbonates of the zuodeng south china and jesmond british columbia sections to investigate the timing and global extent of ocean redox variation across the ssb our 238u record reveals values similar to or slightly heavier than modern seawater 0 39 during the middle smithian a rapid negative shift to highly negative values during the early late smithian a positive shift at the ssb and a rapid shift back to more negative values in the early middle spathian a simple u isotope mass balance modeling suggests that the global area of anoxic seafloor expanded strongly during the late smithian and the early middle spathian covering 11 of total seafloor area but that it contracted sharply during the ssb 2 the redox pattern documented by our 238u record shows a good first order correspondence to tropical sea surface temperature sst data for the smithian spathian in particular peak anoxia coincided with the middle late smithian boundary hyperthermal event and diminished anoxia with a pronounced decline in ssts at the ssb the temporal correlation between anoxia and low biodiversity levels of many marine clades e g conodonts and ammonoids during the late smithian indicates that oceanic anoxia may have played a role in the ssb biocrisis

glacial versus interglacial sedimentation rates and turbidite frequency in the bahamas the southern tongue of the ocean is a 1300 m deep flat floored basin in the bahamas that receives large amounts of sediment from the carbonate platforms surrounding it on three sides we have examined five 8 13 m long piston cores and determined bulk sedimentation rates turbidite frequency and turbidite accumulation rates for the past two glacial and interglacial periods the mean of bulk sedimentation rates is four to six times higher in interglacial periods average accumulation rates of recognizable turbidites are higher by a factor of 21 to 45 and interglacial turbidite frequency is higher by a factor of 6 to 14 sediment composition indicates that increased interglacial rates are due to higher accumulation of platform derived material additional data from other bahamian basins as well as published material from the caribbean strongly suggest that highstand shedding is a general trend in pure carbonate depositional systems carbonate platforms without a siliciclastic component export more material during highstands of sea level when the platform tops are flooded and produce sediment the response of carbonate platforms to quaternary sea level cycles is opposed to that of siliciclastic ocean margins where sediment is stored on the inner shelf during highstands and passed on to continental rises and abyssal plains during lowstands of sea level

numerical models of fluid flow in carbonate platforms implications for dolomitization abstract the role of fluid flow in dolomitization is evaluated through hydrologic simulations designed to capture and test numerically the essential elements of some common dolomitization models a two dimensional finite difference code bethke 1985 was used to simulate single phase flow of variable salinity fluids driven by compaction convection and topography in carbonate platforms and adjacent basinal sediments a simple hydrostratigraphic model consisting of a platform reef complex surrounded by basin filling shale was constructed to examine the magnitude and direction of compaction flow during the initial phase of subsidence most pore fluids in the shale migrate to the surface at velocities less than 0 1 mm yr and basin derived fluids are focused into the reef from only a limited distance of 10 km relatively porous and permeable basinal limestones and sandstones may act as conduits for updip fluid flow into the platform reef complex magnesium mass balance constraints coupled with hydrologic simulations suggest that burial compaction is not an efficient mechanism for regional dolomitization two layer hydrostratigraphic models involving variable salinity fluids show that evaporation of seawater results in downward and seaward fluid migration the magnitude of flow is a function of fluid density even fluids at salinities marginally elevated above normal seawater values are capable of penetration several hundreds of meters into the underlying sediments albeit at rates of less than 1 cm yr paleohydrologic simulations coupled with thermodynamic arguments support that reflux of surface derived waters evaporated past gypsum saturation is a viable dolomitization mechanism calculations utilizing rates of mg mass flux show that dolomitization of large carbonate platforms 10 km3 by fluids below halite saturation requires millions of years of reflux driven flow p thermal convection of seawater through carbonate platforms has been simulated by varying the basal heat flow the thermal pump produces a convection cell in which lateral and vertical flow achieve rates of 75 0 and 13 0 mm yr respectively the potential for dolomitization is high because a large reservoir of mg seawater is tapped elevated temperatures drive fluids further into the stability field for dolomite and kinetic inhibition of dolomite nucleation and growth is decreased simulations of high frequency glacio eustatic sea level oscillations suggest that a dynamic hydrologic regime may be established a sea level fall of 2 m lasting for 10 000 yr can drive lateral flow at rates up to 0 15 m yr dolomitization is possible because marine waters migrate through the carbonate platform in response to gradients of hydraulic head created by eustatic sea level fluctuations

early diagenetic processes in labrador sea sediments uranium isotope geochemistry the concentration and isotopic composition of u dissolved in pore waters from hemipelagic sediments of the labrador sea were determined by thermal ionization mass spectrometry in two 30 cm long box cores the present fluxes of seawater u that diffuses across the sediment seawater interface are on the order of 2 4 g cm2 ka this diffusion imposes decreasing gradients of dissolved u downwards but the u concentration in pore waters immediately below the surface is much lower than that of open ocean seawater this is a primary feature that cannot be explained by carbonate precipitation due to decompression during core retrieval more likely it reflects the presence of a stagnant benthic boundary layer above the sediment water interface in which molecular diffusion of u is slower than in the overlying turbulently mixed seawater and or of microzones near the interface where u is bioaccumulated uranium is adsorbed at depths onto the solid phase in response to changes in the redox conditions within the

u and th concentrations and isotope ratios in modern carbonates and waters from the bahamas the short residence times of th and pa in seawater make them very responsive to changes in the ocean environment we use a new multi ion counting technique to make th and pa isotope measurements in seawaters from a near shore environment in which oceanic chemical tracers are not overwhelmed by terrestrial inputs the bahamas an unusual feature of the bahamas setting is the shallow depth of water residing on the bank tops these waters have significantly lower 232th 230th 10 000 than those immediately adjacent to the banks 24 000 31 000 and a 231pa 230th near the production ratio 0 1 the change in 232th 230th and 231pa 230th on the bank tops is explained by almost quantitative removal of th and pa by scavenging and their replacement with a mixture of 230th and 231pa alpha recoiled from the underlying carbonates together with th from dust dissolution analysis of a water profile in the tongue of the ocean which separates the great and little bahama banks allows us to trace the movement of bank top water to depth a distinct minimum in both 232th 230th 13 000 and 231pa 230th 0 5 is observed at 430 m and is interpreted to reflect density cascading of bank top water with entrained carbonate sediment these results suggest that th and pa can be used as water mass tracers in near shore environments uranium concentration measurements on the same waters demonstrate that u is conservative across a range in salinity of 2 psu with a concentration of 3 33 ppb at a salinity of 35 the incorporation of u and th isotopes into marine carbonates has also been assessed by analyzing carbonate samples from the same location as these bahamas waters such incorporation is critical for u th geochronology u isotope analyses demonstrate that seawater 234u averages 146 6 and does not vary by more than 2 5 o and that carbonates capture this value additional high precision measurements 1 o on modern carbonates confirm that all oceans have identical 234u modern marine carbonates are shown to have 232th 230th ratios that reflect the local seawater in which they formed

clinoptilolite as a new proxy of enhanced biogenic silica productivity in lower miocene carbonate sediments of the bahamas platform isotopic and thermodynamic evidence abstract massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor mbsf in lower miocene well compacted carbonate periplatform sediments from the great bahama bank ocean drilling program odp leg 166 site 1007 the diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix as well as mg smectites in carbonate rich deposits the formation of the zeolite requires a supply of silica thus the objective of the study is to determine the origin of the silica supply its diagenetic evolution and consequently the related implications on interpretation of the sedimentary record in terms of local or global paleoceanographic change for lack of evidence for any volcaniclastic input or traces of si enriched deep fluids circulation an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow water carbonate sequences geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite as well as its contemporaneous formation with the carbonate deposition sr model ages of 19 6 23 2 ma the test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage seawater rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica which reacts with clay minerals the amount of silica opal a involved in the reaction has to be significant enough at least 10 wt to account for the observed content of clinoptilolite occurring at the most zeolite rich level modeling also shows that the observed amount of clinoptilolite 19 reflects an in situ and short term reaction due to the high reactivity of primary biogenic silica opal a until its complete depletion the episodic occurrence of these well lithified zeolite rich levels is consistent with the occurrence of seismic reflectors particularly the p2 seismic sequence boundary located at 1115 mbsf depth and dated as 23 2 ma the age range of most zeolitic sedimentary levels biostratigraphic ages of 21 5 22 ma correlates well with that of the early miocene glaciation mi 1 and mi 1a global events thus the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply or in other sensitive marine areas is potentially a significant new proxy for paleoproductivity and oceanic global events such as the miocene events which are usually recognized in deep sea pelagic sediments and high latitude deposits

the geochemistry of uranium and thorium in coastal marine sediments and sediment pore waters pore water profiles of uranium and thorium isotopes in the muddy sediments of buzzards bay ma permit an assessment of the effect of diagenetic redox reactions on the geochemical behavior of these elements uranium shows a pronounced minimum pore water concentration 1 2 dpm kg near the sediment water interface 0 3 cm which coincides with the pore water fe maximum u concentrations increase with depth to a broad maximum which is greater than the overlying seawater value then decrease laboratory sediment tank experiments maintained without macrofauna also show the near interface minimum and increase and sediment incubation experiments show removal of u from the pore water to a constant value by about 40 days the 234u238u activity ratio is equal to the seawater value in all samples oxidation state separations of pore water u in hcl solution using anion exchange demonstrate that u is present in the pore water as u vi the coincidence of the pore water uranium and fe maximum is consistent with the hypothesis of reduction of u vi to u iv and removal from solution at about the same depth or pe as fe is reduced increases in pore water u with depth appear to be related to release of authigenic seawater u vi to solution possibly as alkalinity and ph increase and organic matter with which the u is associated is oxidized lower concentrations at depth in the sediment column may be linked to increases of effective u reducing agents like hydrogen sulfide in the pore water or to the activities of macrofauna in contrast pore water profiles of the long lived th isotopes 232th and 230th show low activities 02 dpm kg and relatively little change with depth although values are greater than those in the overlying water solid phase activities are similarly constant with depth and the distribution may be controlled by a sorption equilibrium between pore water and the solid phase the short lived isotope 234th shows greatest pore water activities in the upper 5 cm and is present at virtually zero activities elsewhere in the sediment column the upper few centimeters of the sediment generally contain excess 234th scavenged from the overlying water column and distributed by bioturbation as well as pore water fe and mn profiles which show maxima indicating reduction and dissolution of fe and mn oxyhydroxides the pore water 234th profile can be explained by release of 234th from the solid phase as femn oxide surface coatings are reduced and dissolved

an early diagenetic deglacial origin for basal ediacaran cap dolostones abstract the beginning of the ediacaran period 635 ma is marked by conspicuous dolostone units that cap marinoan glacial deposits worldwide the extent and sedimentary characteristics of the cap dolostones indicate that anomalous carbonate over saturation coincided with deglacial sea level rise and ocean warming however the geochemical variability within cap dolostones both between continents across single continental margins and within individual stratigraphic sections has been difficult to reconcile with depositional models using a compilation of new calcium and magnesium isotope measurements in marinoan cap dolostone successions worldwide we show that the geochemical variability can be explained by early diagenetic dolomitization of aragonite along a spectrum of fluid and sediment buffered conditions dolostones from the outer platform formed under fluid buffered conditions whereas dolostones on the inner platform and foreslope environment formed under sediment buffered conditions this spatial pattern of dolomitizing conditions is consistent with buoyant recirculation of glacial seawater within carbonate platforms driven by the deglacial sea level rise and development of a meltwater surface ocean using a numerical diagenetic model to evaluate the geochemical differences between sediment and fluid buffered cap dolostone units we constrain the chemical and isotopic composition of both the dolomitizing fluid glacial seawater 13 c 0 2 the meltwater lens 13 c 11 and the primary aragonite sediment 13 c 6 to 3 these model end members do not imply that primary geochemical variability did not exist but demonstrates that it is not necessary to change the chemistry of seawater to explain the global stratigraphic variability in the geochemistry of basal ediacaran cap dolostones our results provide a novel framework for understanding the geochemical variability of cap dolostone units including large excursions in carbon isotopes and how this variability is the product of local diagenetic processes expressed globally in continental margin environments following the last snowball earth

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

gondwanatheria and multituberculata mammalia from the late cretaceous of madagascar in addition to four isolated mammalian teeth from the late cretaceous maastrichtian of madagascar described previously and allocated to gondwanatheria marsupialia and mammalia incertae sedis here i put on record five more specimens four of these a virtually complete lower molariform cheek tooth two fragmentary cheek teeth and a fragmentary lower incisor are referred to the sudamericidae gondwanatheria the internal structure of the hypsodont cheek teeth as revealed by micro computed tomography scans to simulate different stages of wear is highly variable limited knowledge of intra individual morphological and size variability in the dentition of sudamericids which are known almost exclusively from isolated teeth precludes a conclusive assessment of whether some or all of the new specimens belong to lavanify miolaka the only previously described sudamericid from madagascar or to a new taxon conservatively therefore pending the recovery of better material all four specimens are referred to sudamericidae gen et sp indet the fifth specimen a molar fragment is tentatively allocated to the multituberculata thereby adding to the controversial specimens that comprise the very sparse and questionable record of this clade on the southern supercontinent gondwana the new specimens do not provide any profound insight into the origins of the highly endemic and imbalanced extant mammalian fauna on madagascar rather they provide only more negative evidence like those previously described they do not represent the basal stocks of any of the five mammalian clades that live on the island today and therefore further support the growing consensus that representatives of the extant clades arrived in the cenozoic

high resolution characterization of the asian monsoon between 146 000 and 99 000 years b p from dongge cave china and global correlation of events surrounding termination ii abstract speleothem samples from hulu eastern china 32 30 n 119 10 e and dongge southern china 25 17 n 108 5 e caves provide a nearly continuous record of the asian monsoon over the last 160 ka wang y j cheng h edwards r l an z s wu j y shen c c dorale j a 2001 a high resolution absolute dated late pleistocene monsoon record from hulu cave china science 294 2345 2348 yuan d cheng h edwards r l dykoski c a kelly m j zhang m qing j lin y wang y wu j dorale j a an z cai y 2004 timing duration and transitions of the last interglacial asian monsoon science 304 575 578 we have obtained higher resolution data in the interval between 99 and 146 ka b p providing a detailed account of 18o variations over most of mis 5 and the latter portion of mis 6 precise 230th dating has replicated the chronology of the samples within error the higher resolution data set confirms the timing of asian monsoon termination ii the midpoint of the negative shift in 18o marking the onset of the last interglacial asian monsoon placing it at 129 0 0 9 ka b p the bulk of this transition 1 7 took place within approximately 70 years with the total range of the transition being 3 the most abrupt portion of the shift in 18o values 1 1 marking the end of the last interglacial asian monsoon occurred in 120 years the midpoint of which is 120 7 1 0 ka b p the dongge cave monsoon 18o record over late mis 6 exhibits a series of sub orbital millennial scale climate shifts that average 1 3 in magnitude and occur on average every 1 8 ky abrupt shifts in 18o of up to 1 also occurred throughout the last interglacial asian monsoon with periods at multi decadal to centennial timescales similar to the amplitude and periodicities of events found by dykoski et al dykoski c a edwards r l cheng h yuan d cai y zhang m lin y an z revenaugh j 2005 a high resolution absolute dated holocene and deglacial asian monsoon record from dongge cave china earth and planetary science letters 233 71 86 during the holocene in the dongge record these shifts cover more than 1 2 of the amplitude of millennial scale and multi centennial scale interstadial events during the last glacial period wang y j cheng h edwards r l an z s wu j y shen c c dorale j a 2001 a high resolution absolute dated late pleistocene monsoon record from hulu cave china science 294 2345 2348 and millennial scale and multi centennial scale interstadial events during the penultimate glacial period in china this study abrupt decadal to millennial scale climate events therefore appear to be a general feature of both glacial and interglacial climate we demonstrate that monsoon intensity correlates well with atmospheric ch4 concentrations over the transition into the bolling allerod the bolling allerod and the younger dryas in addition we correlate an abrupt jump in ch4 concentration with asian monsoon termination ii on the basis of this correlation we conclude that the rise in atmospheric co2 antarctic warming and the gradual portion of the rise in ch4 around termination ii occur within our weak monsoon interval wmi an extended interval of heavy 18o between 135 5 1 0 and 129 0 1 0 ka b p prior to asian monsoon termination ii and northern hemisphere warming antarctic warming over the millennia immediately preceding abrupt northern warming may result from the bipolar seesaw mechanism as such warming albeit to a smaller extent also preceded asian monsoon termination i the bipolar seesaw mechanism may play a critical role in glacial terminations

coupled uranium isotope and sea level variations in the oceans abstract globally rivers supply uranium to the oceans with excess 234 u relative to secular equilibrium and 234 u taken up by corals can be used for dating in addition the 234 u abundance in sea water at the time the coral was growing can be measured independently the veracity of u series ages used in determining past sea level variations is dependent on selecting pristine corals free from diagenetic alteration a quantitative test for alteration assumes invariant 234 u abundances in the oceans for at least the past half a million years and results from samples outside of a narrow range in modern ocean 234 u abundance are excluded from data sets here we have used previously published data to show that 234 u in the oceans appears to be variable and directly related to changes in sea level not only over long glacial interglacial timescales but also at very short centennial timescales most of the previously discarded data can be used to provide valuable additional sea level information the process permits a unique insight into the interplay between sources and sinks of uranium in the oceans mediated by sea level changes at rates far faster than previously thought possible similar rapid sea level forcing of other trace element abundances in the oceans is likely

accumulation of bank top sediment on the western slope of great bahama bank rapid progradation of a carbonate megabank high resolution seismic profiles and submersible observations along the leeward slope of western great bahama bank show large scale export of bank top sediment and rapid progradation of the slope during the holocene a wedge shaped sequence up to 90 m thick is present along most of the slope and consists of predominantly aragonite mud derived from the bank since flooding of the platform 6 8 ka total sediment volume of the slope sequence is 40 80 that of holocene sediment currently retained on the bank maximum rates of vertical accumulation and lateral progradation are 11 15 m ka and 80 110 m ka respectively 10 to 100 times greater than previously known for periplatform muds slope deposition of exported mud during sea level highs appears to have been a major mechanism for the westward progradation of great bahama bank throughout the quaternary this may provide a critical modern analogue for ancient progradational margins

quaternary aragonite cycles and oxygen isotope record in bahamian carbonate ooze carbonate ooze in bahamian troughs displays cyclic variation in the content of aragonite a 10 m core devoid of turbidites shows 3 5 cycles each defined by a sharp increase followed by a gradual decrease of aragonite the aragonite curve matches closely the oxygen isotope curve of planktic foraminifera from the same core aragonite highs correspond to light oxygen isotope values and thus to interglacial stages content of terrigenous material is low during interglacials and higher during glacial periods intermittent flooding and exposure of the bahama banks is most probably not the cause of the cycles because the latest increase in aragonite precedes bank flooding by 8 000 yr and because the cycles are distinctly asymmetric with rapid increase and gradual decrease of aragonitic content carbonate dissolution cycles tied to the glacial rhythm of earth9s climate are a more likely explanation of the variations in aragonite content

fluid flow through carbonate platforms constraints from 234u 238u and cl in bahamas pore waters the geometry timing and rate of fluid flow through carbonate margins and platforms is not well constrained in this study we use u concentrations and isotope ratios measured on small volumes of pore water from bahamas slope sediment coupled with existing chlorinity data to place constraints on the fluid flow in this region and by implication other carbonate platforms these data also allow an assessment of the behaviour of u isotopes in an unusually well constrained water rock system we report pore water u concentrations which are controlled by dissolution of high u organic material at shallow depths in the sediment and by reduction of u to its insoluble 4c state at greater depths the dominant process influencing pore water 234 u 238 u is alpha recoil in holocene sediments the increase of pore water 234 u 238 u due to recoil provides an estimate of the horizontal flow rate of 11 cm year but with considerable uncertainty at depths in the sediment where conditions are reducing features in the u concentration and 234 u 238 u profiles are offset from one another which constrains the effective diffusivity for u in these sediments to be1 2 10 8 cm 2 s 1 at depths between the holocene and these reducing sediments pore water 234 u 238 u values are unusually low due to a recent increase in the dissolution rate of grain surfaces this suggests a strengthening of fluid flow probably due to the flooding of the banks at the last deglaciation and the re initiation of thermally driven venting of fluid on the bank top and accompanying recharge on the slopes interpretation of existing chlorinity data in the light of this change in flow rate constrain the recent horizontal flow rate to be 10 6 3 4 cm year estimates of flow rate from 234 u 238 u and cl are therefore in agreement and suggest flow rates close to those predicted by thermally driven models of fluid flow this agreement supports the idea that flow within the bahamas banks is mostly thermally driven and suggests that flow rates on the order of 10 cm year are typical for carbonate platforms where such flow occurs 1999 elsevier science b v all rights reserved

algal uptake of u and some other metals implications for global geochemical cycling abstract freshwater green algae ankistrodesmus sp cultured in dilute solutions of metals chelated with edta revealed massive uptake of u examination of thames river waters and selected micro organisms of its aquatic ecosystem revealed an average dissolved u concentration of 1 46 ppb representing about twice the global mean riverine solute concentration of 0 6 ppb u suspended particulates principally algae contain u at 103 to 105 times that of their river habitat averaging 28 300 ppb u one community of the filamentous algae spirogyra sp contained intracellular crystals tentatively identified as the ca oxylate weddelite studies of algae from a variety of environments have shown large concentration factors for a wide range of elements algae from an acid u mine tailings site contain up to 2 7 u dry weight plus very high concentrations of other metals micro organisms may act as an important sink for metal solutes in the hydrosphere

control on 234u 238u in lake water a study in the dry valleys of antarctica abstract the 234 u 238 u ratio in surface waters is generally higher than secular equilibrium due to nuclide recoil during alpha decay of 238 u the size of the deviation from secular equilibrium contains information about the environment in which the water is found this potential tool for environmental reconstruction has previously been studied in rivers groundwater and sediment pore water here we conduct a first assessment of the controls on 234 u 238 u in lakewaters thirty three waters from glacial melt streams and lakes of the mcmurdo dry valleys antarctica were analysed for u concentration and isotope ratio glacial melt has a low u concentration and a 234 u 238 u identical to seawater suggesting that u in antarctic ice is largely sourced from sea salt aerosols stream waters have higher u concentration 0 009 to 1 282 ppb and 234 u 238 u 1 280 to 1 832 due to chemical weathering of sediment in stream channels and 234 u recoil from this sediment average 234 u 238 u is 1 502 close to the average of observations from other surface waters worldwide the absence of groundwaters in the dry valleys indicates that reasonably high 234 u 238 u ratios do not require groundwater sources of u so care should be taken before using high 234 u 238 u as an indicator of groundwater inputs to stream waters lakewaters have u concentrations ranging from 0 027 to 46 ppb i e up to 14 times the seawater concentration and 234 u 238 u from 1 05 to 4 50 young lakes have 234 u 238 u which reflects the sources of u in one case lake joyce a 234 u 238 u lower than seawater may suggest u sourced from melting of old ice in which 234 u excess has partially decayed in older lakes 234 u 238 u is significantly higher than that in the inputs due to addition of recoil 234 u from sediments underlying the lake the size of the deviation from secular equilibrium can only be explained however if recoil from a large area of sediment is considered this is reasonable for the two lakes with particularly high 234 u 238 u bonney vanda which are both relicts of much larger lakes present during the last glacial period on the basis of this study the addition of recoil 234 u to lake water is expected to be a general feature and to cause a noticeable increase in 234 u 238 u for lakes with a u residence time of more than a few thousand years

direct u th dating of marine sediments from the two most recent interglacial periods a knowledge of the age of marine sediments is necessary to determine the timing of events and rates of processes in the marine realm and the relationships among marine and other climatically sensitive records the establishment of an accurate chronology for pleistocene marine sediments beyond the range of radiocarbon dating approximately the past 45 kyr has therefore been a goal of palaeoceanographers for decades early attempts1 2 based on measurements of the radionuclides 230th and 231pa were beset with problems and subsequent studies focused on tying fluctuations in marine sediment oxygen isotope records to events such as the formation of coral reef terraces and changes in the earth s magnetic polarity3 4 and tuning the resultant chronologies to the earth s orbitally driven insolation variations5 8 but these chronologies especially the age and duration of the last interglacial period have been challenged by several studies9 12 raising questions about the fundamental cause of pleistocene climate fluctuations here we report the direct u th dating of aragonite rich marine sediments from the bahamas and present an accurately dated marine oxygen isotope record for the last two interglacials we obtain dates of 120 127 kyr bp for the last interglacial and 189 190 kyr bp for the late stage 7 interglacial these dates are in accord with the general theory of orbitally forced climate fluctuations and demonstrate the potential of our direct dating approach for developing an absolute chronology for the pleistocene marine oxygen isotope record

diagenetic effects on uranium isotope fractionation in carbonate sediments from the bahamas abstract uranium isotope variations 238u recorded in sedimentary carbonate rocks are a promising new proxy for the extent of oceanic anoxia through geological time however the effects of diagenetic alteration on the u isotopic composition in carbonate sediments which are crucial to understand the accurate reconstruction of marine 238u are currently poorly constrained here we examine the effects of the aragonite to calcite transition in the pleistocene key largo limestone of south florida and assess the effects of vadose meteoric phreatic meteoric and phreatic marine diagenesis on u isotope fractionation in carbonate sediments from the bahamas transect including the well studied clino unda and odp site 1006 drill cores our results suggest that early diagenetic processes in bahamas carbonate sediments fractionate u isotopes by an average of 0 27 0 14 1 sd heavier than contemporaneous seawater downcore variations of 238u in slope and basin sediments display little if any correlation with u concentration and common geochemical indicators of diagenesis 13c 18o mn sr mg ca sr ca enrichments of redox sensitive elements or rare earth elements anomalies we propose two possible mechanisms to interpret the positive change in the 238u during carbonate diagenesis authigenic enrichment of isotopically positive u iv in carbonates and preferential incorporation of isotopically positive aqueous u vi species into carbonates these processes likely operate during early syndepositional diagenesis on the banktop further diagenesis during deeper burial is limited by the low solubility of u iv under reducing pore water conditions the early diagenetic behavior of u isotopes in bahamas carbonate sediments is likely broadly representative of carbonate diagenesis in the geological past we suggest that the mean diagenetic offset determined in this study be applied when reconstructing seawater 238u from ancient carbonates furthermore early diagenesis induces significant statistical variability in sediment 238u values pointing to the need for large high resolution data sets in order to average out stochastic variations in individual bulk sediment samples

behaviour and mobility of u series radionuclides in madeira abyssal plain turbidites over the past 750 000 years the irregular u profiles developed in madeira abyssal plain turbidites shortly after emplacement are preserved thereafter in the sediments for at least 750 kyr and can be correlated between widely spaced cores such profiles at 22 29 m depth in units 650 730 kyr old have been exploited to study steady state diffusion of the longer lived u decay series radionuclides and to derive effective in situ diffusion coefficients applicable to post oxic conditions a model developed for comparison of parent daughter pair data 238u 234u 234u 230th 230th 226ra 226ra 210po confirms that the only nuclide to exhibit convincing evidence of migration is 226ra effective diffusion coefficients d in the range 6 10 9 1 10 9 cm2 s 1 have been calculated for 226ra in these sediments with between 35 and 70 of total 226ra available for pore water diffusion the symmetrical distribution of 226ra around the 230th peaks indicates that pore water advection is absent other nuclides which might be expected to show evidence of migration are 234u and 222rn although leaching experiments demonstrate that 234u is potentially preferentially mobile relative to 238u this is not observed in the sediments and suggests that the post oxic geochemical environment immobilises 234u a maximum possible d of 10 15 10 14 cm2 s for 234u can be derived 230th is not expected to diffuse in pore waters and this is confirmed by the maximum d of 10 14 5 10 13 cm2 s 1 found the profiles of 226ra and 210po show good agreement which indicates that diffusion of 222rn is limited by its short half life

u th systematics and ages of authigenic carbonates from hydrate ridge cascadia margin recorders of fluid flow variations uranium u concentrations and activity ratios 234u of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon rich fluids cold seeps at hydrate ridge off the coast of oregon usa the low u concentrations mean 1 3 0 4 g g and high 234u values 165 317 of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor their 230th 234u ages span a time interval from 0 8 to 6 4 ka and cluster around 1 2 and 4 7 ka in contrast chemoherm carbonates precipitate from marine bottom water marked by relatively high u concentrations mean 5 2 0 8 g g and a mean 234u ratio of 166 3 their u isotopes reflect the 234u ratios of the bottom water being enriched in 234u relative to normal seawater simple mass balance calculations based on u concentrations and their corresponding 234u ratios reveal a contribution of about 11 of sedimentary pore water to the bottom water from the u pore water flux and the reconstructed u pore water concentration a mean flow rate of about 147 68 cm a can be estimated 230th 234u ages of chemoherm carbonates range from 7 3 to 267 6 ka 230th 234u ages of two chemoherms alvin and se knoll chemoherm correspond to time intervals of low sealevel stands in marine isotope stages mis 2 4 5 6 7 and 8 this observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments the 18o pdb ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times deviations of the chemoherm 18o values from the marine 18o record can be interpreted as to reflect temporally and spatially varying bottom water and or vent fluid temperatures during carbonate precipitation between 2 6 and 8 6 c

use of u isotopes in exploring groundwater flow and inter aquifer leakage in the south western margin of the great artesian basin and arckaringa basin central australia abstract the distribution of uranium isotopes 238u and 234u in groundwaters of the south western margin of the great artesian basin gab australia and underlying arckaringa basin were examined using groundwater samples and a sequential extraction of aquifer sediments rock weathering the geochemical environment and recoil of daughter products control the 238u and 234u isotope distributions giving rise to large spatial variations generally the shallowest aquifer j aquifer contains groundwater with higher 238u activity concentrations and 234u 238u activity ratios close to secular equilibrium however the source input of uranium is spatially variable as intermittent recharge from ephemeral rivers passes through rocks that have already undergone extensive weathering and contain low 238u activity concentrations other locations in the j aquifer that receive little or no recharge contain higher 238u activity concentrations because uranium from localised uranium rich rocks have been leached into solution and the geochemical environment allows the uranium to be kept in solution the geochemical conditions of the deeper aquifers generally result in lower 238u activity concentrations in the groundwater accompanied by higher 234u 238u activity ratios the sequential extraction of aquifer sediments showed that recoil of 234u from the solid mineral phases into the groundwater rather than dissolution of or exchange with the groundwater accessible minerals in the aquifer caused enrichment of groundwater 234u 238u activity ratios in the boorthanna formation decay of 238u in uranium rich coatings on j aquifer sediments caused resistant phase 234u 238u activity ratio enrichment the groundwater 234u 238u activity ratio is dependent on groundwater residence time or flow rate depending on the flow path trajectory thus uranium isotope variations confirmed earlier groundwater flow interpretations based on other tracers however spatial heterogeneity and the lack of clear regional correlations made it difficult to identify recharge and inter aquifer leakage