the earth moon system during the late heavy bombardment period geochemical support for impacts dominated by comets the solid planets assembled 4 57 gyr ago during a period of less than 100 myr but the bulk of the impact craters we see on the inner planets formed much later in a narrow time interval between 3 8 and 3 9 gyr ago during the so called late heavy bombardment lhb it is not certain what caused the lhb and it has not been well known whether the impactors were comets or asteroids but our present study lend sup port to the idea that it was comets due to the earth s higher gravity the impactors will have hit the earth withtwice the energy density that they hit the moon and the bombardment will have continued on earth longer than on the moon all solid surface of the earth will have been completely covered with cra ters by the end of the lhb however almost nothing of the earth s crust from even the end of this epoch is preserved today one of the very few remnants though is exposed as the isua greenstone belt igb and nearby areas in western greenland during a field expedition to isua we sampled three types of metasedimentary rocks depos ited 3 8 billion years ago that contain information about the sedimentary river load from larger areas of surrounding land surfaces mica schist and turbidites and of the contemporaneous seawater bif our samples show evidence of the lhb impacts that took place on earth by an average of a seven times enrichment 150 ppt in iridium compared to present day ocean crust 20 ppt the clastic sediments show slightly higher enrichment than the chemical sediments which may be due to contamination from admixtures of mafic proto crustal sources we show that this enrichment is in agreement with the lunar cratering rate and a corresponding extra terrestrial lhb contribution to the earth s hadean eoarchean crust provided the bulk of the influx was cometary i e of high velocity and low in ci abundance but not if the impactors were meteorites i e had velocities and abundances similar to present day earth crossing asteroids our study is a first direct indication of the nature of the lhb impactors and the first to find an agreement between the lhb lunar cratering rate and the earth s early geochemical record and the corresponding lunar record the lhb comets that delivered the iridium we see at isua will at the same time have delivered the equivalent of a 1 km deep ocean and we explain why one should expect a cometary ocean to become roughly the size of the earth s present day ocean not only in terms of depth but also in terms of the surface area it covers the total impacting mass on the earth during the lhb will have been 1000 tons m

pseudotachylitic breccia from the dhala impact structure north central india texture mineralogy and geochemical characterization abstract pseudotachylitic breccia ptb occurs in a drill core from the crater floor of the 11 km diameter proterozoic dhala impact structure india ptbs were intersected in late archean granitoids between 348 15 m and 502 55 m depth in the mcb 10 drill core from the center of the dhala structure the breccias comprise both cataclastic matrix as well as melt breccias the presence of microlites and vesicles in the groundmass and a widely observed flow fabric in the ptb support the presence of melt in the groundmass of some samples clasts in ptb are derived from the archean granitoid basement ptb matrix the matrix of impact melt breccia also occurring between 256 50 m and 502 55 m depth and the target granitoids vary in terms of silica total alkali magnesium and iron oxide contents chondrite normalized ree patterns of ptb and target granitoids are similar but the elemental abundances in the ptb are lower the restricted size of ptb as veins and pods of up to 2 5 cm width their occurrence at varied depths over a core length of 150 m the clast population and the chemical relationships between ptb and their host rocks all suggest the derivation of these breccias locally from the fractured basement granitoids involving in situ melting we favor that this took place due to rapid decompression during the collapse and modification stage of impact cratering with locally additional energy input from frictional heating locally amphibolite and dioritic mylonite occur in the host granitoids and their admixture could have contributed to the comparatively more mafic composition of ptb alteration of these crater floor rocks could have involved preferential reduction of silica and alkali element abundances possibly due to impact induced hydrothermal activity at crater floor level this process too could have resulted in more mafic compositions

millennial scale changes in north atlantic circulation since the last glaciation ocean circulation is closely linked to climate change on glacial interglacial and shorter timescales extensive reorganizations in the circulation of deep and intermediate depth waters in the atlantic ocean have been hypothesized for both the last glaciation1 2 3 4 5 6 and the subsequent younger dryas cold interval3 6 7 8 9 10 but there has been little palaeoceanographic study of the subtropical gyres11 12 13 these gyres are the dominant oceanic features of wind driven circulation and as such they reflect changes in climate and are a significant control on nutrient cycling and possibly atmospheric co2 concentrations here we present cd ca ratios in the shells of benthic foraminifera from the bahama banks that confirm previous suggestions11 12 that nutrient concentrations in the north atlantic subtropical gyre were much lower during the last glacial maximum than they are today up to 50 lower according to our data these contrasting nutrient burdens imply much shorter residence times for waters within the thermocline of the last glacial maximum below the glacial thermocline nutrient concentrations were reduced owing to the presence of glacial north atlantic intermediate water a high resolution cd ca record from an intermediate depth indicates decreased nutrient concentrations during the younger dryas interval as well mirroring opposite changes at a nearby deep site3 9 together these observations suggest that the formation of deep and intermediate waters north atlantic deep water and glacial north atlantic intermediate water respectively wax and wane alternately on both orbital and millennial timescales

seasonal diurnal and storm scale hydrochemical variations of typical epikarst springs in subtropical karst areas of sw china soil co2 and dilution effects summary two year continuous ph conductivity temperature and water stage of the two typical epikarst springs nongla spring and maolan spring about 200 km apart in subtropical karst areas of sw china were presented our primary study objective was to understand how karst systems respond hydrochemically to recharge at different time scales and what the biogeochemical processes and controlling factors in the sw china epikarst environment are a thermodynamic model was used to link the continuous data to monthly water quality data allowing the calculation of co 2 partial pressures and calcite dolomite saturation levels on a continuous basis marked seasonal diurnal and storm scale variations were observed for ph conductivity co 2 partial pressures and calcite dolomite saturation indexes of the springs indicating that both springs are dynamic and variable systems however the coefficients of variation of these hydrogeochemical features tends to be in the order of seasonal storm scale diurnal the seasonal and diurnal variations of these features higher conductivity and lower ph in summer and at daytime lower conductivity and higher ph in winter and at nighttime tend to co vary with temperature which influences the production of co 2 in soils thus being the driving force for the variations soil co 2 effect the storm scale fluctuations occur during the spring summer rainy days due to the storm events depending on the rainfall intensities however there are differences in magnitudes and direction of the variations of these features at very high rainfall intensity the dilution effect dominates the variations characterized by the decrease in both conductivity and calcite dolomite saturation of the springs while soil co 2 effect determines the variations at lower rainfall intensity characterized by increase in co 2 partial pressure and conductivity but decrease in ph and calcite dolomite saturation in a word the hydrodynamic aspects together with hydrobiogeochemical characteristics need to be taken into account to correctly explain the hydrochemical variations of the epikarst springs results from the study demonstrate the need to redesign hydrogeochemical sampling strategies for epikarst springs in karst areas with monsoon climate like sw china i e with remarkable seasonal matching fluctuations in temperature rainfall and vegetation

neodymium isotopes in benthic foraminifera core top systematics and a down core record from the neogene south atlantic abstract records of the past neodymium nd isotope composition of the deep ocean can resolve ambiguities in the interpretation of other tracers we present the first nd isotope data for sedimentary benthic foraminifera comparison of the nd of core top foraminifera from a depth transect on the cape basin side of the walvis ridge to published seawater data and to the modern dissolved sio2 nd trend of the deep atlantic suggests that benthic foraminifera represent a reliable archive of the deep water nd isotope composition neodymium isotope values of benthic foraminifera from odp site 1264a angola basin side of the walvis ridge from the last 8 ma agree with fe mn oxide coatings from the same samples and are also broadly consistent with existing fish teeth data for the deep south atlantic yielding confidence in the preservation of the marine nd isotope signal in all these archives the marine origin of the nd in the coatings is confirmed by their marine sr isotope values these important results allow application of the technique to down core samples the new nd datasets along with ancillary cd ca and nd ca ratios from the same foraminiferal samples are interpreted in the context of debates on the neogene history of north atlantic deep water nadw export to the south atlantic in general the nd and 13c records are closely correlated over the past 4 5 ma the nd isotope data suggest strong nadw export from 8 to 5 ma consistent with one interpretation of published 13c gradients where the nd record differs from the nutrient based records changes in the pre formed 13c or cd ca of southern derived deep water might account for the difference maximum nadw export for the entire record is suggested by all proxies at 3 5 4 ma chemical conditions from 3 to 1 ma are totally different showing on average the lowest nadw export of the record modern day values again imply nadw export that is about as strong as at any stage over the past 8 ma

confirmation of a meteoritic component in impact melt rocks of the chesapeake bay impact structure virginia usa evidence from osmium isotopic and pge systematics the osmium isotope ratios and platinum group element pge concentrations of impact melt rocks in the chesapeake bay impact structure were determined the impact melt rocks come from the cored part of a lower crater section of suevitic crystalline clast breccia in an 823 m scientific test hole over the central uplift at cape charles virginia the 187os 188os ratios of impact melt rocks range from 0 151 to 0 518 the rhenium and platinum group element pge concentrations of these rocks are 30 270 higher than concentrations in basement gneiss and together with the osmium isotopes indicate a substantial meteoritic component in some impact melt rocks because the pge abundances in the impact melt rocks are dominated by the target materials interelemental ratios of the impact melt rocks are highly variable and nonchondritic the chemical nature of the projectile for the chesapeake bay impact structure cannot be constrained at this time model mixing calculations between chondritic and crustal components suggest that most impact melt rocks include a bulk meteoritic component of 0 01 0 1 by mass several impact melt rocks with lowest initial 187os 188os ratios and the highest osmium concentrations could have been produced by additions of 0 1 0 2 of a meteoritic component in these samples as much as 70 of the total os may be of meteoritic origin at the calculated proportions of a meteoritic component 0 01 0 1 by mass no mixtures of the investigated target rocks and sediments can reproduce the observed pge abundances of the impact melt rocks suggesting that other pge enrichment processes operated along with the meteoritic contamination possible explanations are 1 participation of unsampled target materials with high pge abundances in the impact melt rocks and 2 variable fractionations of pge during syn to post impact events

re os systematics in chondrites and the fractionation of the platinum group elements in the early solar system we have investigated the re os system for samples of whole rock metal and sulfide from ordinary chondrites using closed system analytical techniques we found complete exchange between sample and tracer isotopes for silicate containing samples and obtained precise and reliable re os concentration measurements results on two group iva iron meteorites and on a silicate rich iron steinbach iva an are consistent with the iva ivb isochron and support the previous observation that iva ivb irons may be slightly older than iiab irons data on whole rock fragments and metal rich separates from the st severin chondrite ll6 show a large range in 1870re 188 os and in 187 os 188 os which makes possible in principle the determination of a re os internal isochron on a chondrite for the first time this re os fractionation may be due to partial melting of fenis and macroscopic redistribution of metal and sulfide the st severin data show a good correlation line on a 187 re 187 os evolution diagram if this is considered to represent an internal isochron it gives an age t 4 68 0 15 ae 187 re 1 64 10 11 a 1 and an initial 187 os 188 os 0 0 0953 0 0013 this age is in agreement with but slightly older than the more precise 187 re 187 os age for the iiab irons as well as for irons from other groups t 4 61 0 01 ae a st severin sulfide nodule has very low re and os concentrations and shows a young re os model age 2 3 ae indicating recent element remobilization whole rock and metal rich separates of h group chondrites h3 to h6 yield restricted ranges in 187 re 188 os 0 42 0 47 and 187 os 188 os 0 128 0 133 there is a systematic difference between re os in the metal extracted from a chondrite and the bulk chondrite this shows that there is a small but significant re os fractionation within subsystems contained in the chondrites from whole rock samples of h group chondrites we calculate a mean 187 re 188 os 0 423 0 007 and 187 os 188 os 0 12863 0 00046 which may characterize the evolution of an average chondritic reservoir for re os the ordinary chondrite data plot close to the iiab isochron although the deviations found are larger than found for the irons the re os chronometer in iron meteorites is apparently controlled by the re os fractionation due to fractional crystallization of liquid metal re os ages of iron meteorites give the time of crystallization of metal segregations and cores of early planetary bodies in contrast the behavior in ordinary chondrites while also dominated by the metal phases must reflect fractionation and transport on a local macroscopic scale within the chondrites between the metal phases after aggregation due to partial melting of fenis or represent variable re os fractionation of the metal phases prior to the accretion of the chondrites however for st severin we attribute the major re os fractionation to early heating of the meteorite above the fe fes eutectic we do not consider that the re os fractionation observed in other chondrites is due to the redistribution of re and os during chondrite metamorphism including shock but it may plausibly represent earlier stages of re os fractionation for the different feni metal constituents prior to accretion

subsurface flow in a soil mantled subtropical dolomite karst slope a field rainfall simulation study abstract soil and epikarst co evolve resulting in complex structures but their coupled structural effects on hydrological processes are poorly understood in karst regions this study examined the plot scale subsurface flow characteristics from an integrated soil epikarst system perspective in a humid subtropical cockpit karst region of southwest china a trench was excavated to the epikarst lower boundary for collecting individual subsurface flows in five sections with different soil thicknesses four field rainfall simulation experiments were carried out under different initial moisture conditions dry and wet and rainfall intensities 114 mm h 1 high and 46 mm h 1 low on average the soil epikarst system was characterized by shallow soil overlaying a highly irregular epikarst surface with a near steady infiltration rate of about 35 mm h 1 the subsurface flows occurred mainly along the soil epikarst interface and were dominated by preferential flow the subsurface flow hydrographs showed strong spatial variability and had high steady state coefficients 0 52 and 0 36 for high and low rainfall intensity events irregular epikarst surface combining with high vertical drainage capacity resulted in high threshold rainfall depths for subsurface flows 67 mm and 263 mm for initial wet and dry conditions respectively the above results evidenced that the irregular and permeable soil epikarst interface was a crucial component of soil epikarst architecture and consequently should be taken into account in the hydrological modeling for karst regions

detection of a meteoritic component in ivory coast tektites with rhenium osmium isotopes measurement of rhenium re and osmium os concentrations and os isotopic compositions in ivory coast tektites natural glasses with upper crustal compositions that are ejected great distances during meteorite impact and rocks from the inferred source crater lake bosumtwi ghana show that these tektites incorporate about 0 6 percent of a meteoritic component analysis of elemental abundances of noble metals alone gives equivocal results in the detection of meteoritic components because the target rocks already have relatively large amounts of noble metals the re os system is ideally suited for the study of meteorite impacts on old continental crust for three reasons i the isotopic compositions of the target rocks and the meteoritic impactor are significantly different ii closed system mixing of target rocks and meteorites is linear on re os isochron diagrams which thus permits identification of the loss of re or os iii osmium isotopic compositions are not likely to be altered during meteorite impact even if re and os are lost

effect of the formation of the isthmus of panama on atlantic ocean thermohaline circulation the late cenozoic closure of the seaway between the north andsouth american continents is thought to have caused extensive changes in ocean circulation and northern hemisphere climate1 2 but the timing and consequences of the emergence of the isthmus of panama which closed the seaway remain controversial1 2 3 4 5 here we present stable isotope and carbonate sand fraction records from caribbean sediments which when compared to atlantic and pacific palaeoceanographic records indicate that the closure caused a marked reorganization of ocean circulation starting 4 6 million years ago shallowing of the seaway intensified the gulf stream and introduced warm and saline water masses to high northern latitudes these changes strengthened deep water formation in the labrador sea over the next million years as indicated by an increased deep water ventilation and carbonate preservation in the caribbean sea and favoured early pliocene warming of the northern hemisphere the evaporative cooling of surface waters during north atlantic deep water formation would have introduced moisture to the northern hemisphere although the pronounced intensification of northern hemisphere glaciation between 3 1 and 2 5 million years ago substantially lagged the full development of north atlantic deep water formation we propose that the increased atmospheric moisture content was a necessary precondition for ice sheet growth which was then triggered by the incremental changes in the earth s orbital obliquity

reduced north atlantic deep water flux to the glacial southern ocean inferred from neodymium isotope ratios the global circulation of the oceans and the atmosphere transports heat around the earth broecker and denton1 suggested that changes in the global ocean circulation might have triggered or enhanced the glacial interglacial cycles but proxy data for past circulation taken from sediment cores in the south atlantic ocean have yielded conflicting interpretations of ocean circulation in glacial times 13c variations in benthic foraminifera2 3 4 5 6 support the idea of a glacial weakening or shutdown of north atlantic deep water production whereas other proxies such as cd ca ba ca and 231pa 230th ratios show little change from the last glacial maximum to the holocene epoch7 8 9 here we report neodymium isotope ratios from the dispersed fe mn oxide component of two southeast atlantic sediment cores both cores show variations that tend towards north atlantic signatures during the warm marine isotope stages 1 and 3 whereas for the full glacial stages 2 and 4 they are closer to pacific ocean signatures we conclude that the export of north atlantic deep water to the southern ocean has resembled present day conditions during the warm climate intervals but was reduced during the cold stages an increase in biological productivity may explain the various proxy data during the times of reduced north atlantic deep water export

hydrochemical variations of epikarst springs in vertical climate zones a case study in jinfo mountain national nature reserve of china high temporal resolution 15 min measurements of stage ph electric conductivity temperature and other hydrochemical parameters of groundwater at two sites in the jinfo mountain nature reserve of china were collected using automatic data loggers bitan spring bs 700 m a s l sits in subtropical climate zone while shuifang spring ss 2 060 m a s l is located in plateau temperate climate the data show that hydrochemistry of epikarst springs at different altitudes is very sensitive to the changes of their physical environment especially two factors air temperature and soil co2 concentration springs at lower altitude are associated with higher air temperature and soil co2 concentration thus more likely leading to more active karst processes than those at higher elevation water temperature and ph of bs showed a noticeable diurnal circle with high values in daytime and low values at night the data also indicate that at least there are two effects that could impact the variations of groundwater hydrochemistry during flood pulse dilution effect and co2 effect

sedimentary fe mn oxyhydroxides as paleoceanographic archives and the role of aeolian flux in regulating oceanic dissolved ree in the marine environment authigenic ferromanganese fe mn oxides precipitate from seawater incorporating many dissolved trace elements such as nd pb whose isotopic composition is a direct proxy for ambient seawater thus isotopic studies of the fe mn oxyhydroxide component leached from sedimentary records can provide information on changes in erosional input or ocean circulation changes such studies may be complicated however by the presence of detrital material containing a fe mn oxide component which may mask the true seawater signal in addition the formation of fe mn oxyhydroxides in the marine environment remains poorly understood in particular the phase carbonates detrital particles that controls the delivery of authigenic fe mn oxides to the sediments has not yet been determined in this study we have analysed the ree and nd isotopic compositions of fe mn oxyhydroxide fractions dispersed in marine sediment cores from the cape and angola basins in the se atlantic cruise images ii for the angola basin deep sea core located at 1000 km south of the congo river mouth both the ree and nd isotopic compositions nd measured in recent fe mn oxyhydroxide fractions are typical of congo river borne fe mn oxides this shows that preformed fe mn oxides associated with detrital fractions can locally contaminate the seawater signal recorded by authigenic oxyhydroxides by contrast examination of ree distributions nd isotope data and mass accumulation rates in cape basin sediments shows paradoxically that the flux of fe mn oxides to sediments is controlled by aeolian particles from the nearby namib desert even though their ree and nd compositions point clearly to an authigenic origin it is proposed that partial dissolution of aeolian dust occurs in the water column releasing into solution its easily leachable fe mn component the dissolved fe2 and mn2 would then fuel the reprecipitation of authigenic fe mn oxyhydroxides scavenging additional dissolved trace elements from the ocean most probably from deep water masses in this case calculations suggest that aeolian deposition acts as a net sink for dissolved nd in the cape basin rather than a source and allows us to estimate the rate of removal of dissolved nd associated with atmospheric deposition yielding a global oceanic residence time for nd nd of between 500 and 1400 years

petrography and geochemistry of impactites and volcanic bedrock in the icdp drill core d1c from lake el gygytgyn ne russia the 3 6 ma old and 18 km diameter el gygytgyn impact structure in ne siberia was drilled in 2008 09 by icdp international continental scientific drilling program a 517 m long core hole d1c was drilled into the outer flank of the central uplift structure with an overall core recovery of approximately 63 thereby approximately 315 m lake sediments and approximately 202 m impactites were recovered here we present a detailed petrographic and geochemical assessment of the impact breccia and bedrock sections in this core the 97 m long lower bedrock unit 517 420 m below lake floor blf consists of an ignimbrite in the overlying upper bedrock unit 420 390 mblf the core recovered a sequence of similar ignimbrite and several decimeters of mafic rocks we interpret these units as rocks that are located close to their former preimpact position but have been somewhat rotated due to collapse of the central uplift i e it represents parautochthonous basement from about 390 to 328 mblf occurs a suevite package with an impact melt poor clast dominated matrix and lithic and mineral clasts that cover the entire range of volcanic target rocks known from the el gygytgyn region all stages of shock metamorphism unshocked to melted were observed in clasts and in microclasts of the matrix of suevite from different depths immediately below this package at the contact to the underlying bedrock occurs a 1 m wide sheared zone within vitrophyric ignimbrite which we consider the actual crater floor the uppermost approximately 12 m from 328 316 mblf depth seem to comprise reworked suevite consisting of a mixture of sediments and suevite with more and on average stronger shocked minerals than found in the main suevite unit this includes a small component of glassy spherules and impact melt fragments toward the top of this unit lake sediments progressively become the dominant material in this section we assume that this unit contains a fallback component from the ejecta plume that was mixed with the first sediments of the postimpact crater lake and possibly some rocks that slumped off the inner crater wall similar to a thin layer at the base of the sediment section of borehole lb 5a recovered in lake bosumtwi ghana

late quaternary paleoproductivity and deep water circulation in the eastern south atlantic ocean evidence from benthic foraminifera abstract two late quaternary sediment cores from the northern cape basin in the eastern south atlantic ocean were analyzed for their benthic foraminiferal content and benthic stable carbon isotope composition the locations of the cores were selected such that both of them presently are bathed by north atlantic deep water nadw and past changes in deep water circulation should be recorded simultaneously at both locations however the areas are different in terms of primary production one core was recovered from the nutrient depleted walvis ridge area whereas the other one is from the continental slope just below the coastal upwelling mixing area where present day organic matter fluxes are shown to be moderately high recent data served as the basis for the interpretation of the late quaternary faunal fluctuations and the paleoceanographic reconstruction during the last 450 000 years nadw flux into the eastern south atlantic ocean has been restricted to interglacial periods with the strongest dominance of a nadw driven deep water circulation during interglacial stages 1 9 and 11 at the continental margin high productivity faunas and very low epibenthic 13c values indicate enhanced fluxes of organic matter during glacial periods this can be attributed to a glacial increase and lateral extension of coastal upwelling the long term glacial interglacial paleoproductivity cycles are superimposed by high frequency variations with a period of about 23 000 yr enhanced productivity in surface waters above the walvis ridge far from the coast is indicated during glacial stages 8 10 and 12 during these periods cold nutrient rich filaments from the mixing area were probably driven as far as to the southeastern flank of the walvis ridge

identification of the projectile at the brent crater and further considerations of projectile types at terrestrial craters abstract impact melt samples from drill hole b1 59 at the 3 8 km diameter brent crater ontario have been analysed for siderophile trace elements indicative of meteoritic contamination samples from the basal melt zone at 823 857 m depth are enriched in ir os pd ni co cr and se over basement with the abundance pattern suggesting a chondritic projectile for brent from a ni cr correlation of 10 melt samples an l or ll chondrite is inferred the contribution of an ultramafic country rock alnoite in the melt is too small to significantly influence its ni cr ratio glass rich breccias from the allochthonous breccias filling the crater also contain a meteoritic component interelement ratios e g ni cr are however fractionated relative to the melt zone samples this as well as the low au content of all brent samples is probably a product of alteration additional data on impact melts from the 65 km diameter crater manicouagan still did not reveal a meteoritic component as also for the mistastin crater 28 km diameter where cr analyses set an upper limit of 1 of an achondritic projectile component in the melt irghizites tektite like glasses from the zhamanshin impact structure have been found to contain high ni and co concentrations and our data show that ir is also enriched it is however not possible to define the projectile type enrichment of an ivory coast tektite in ir is confirmed there are large differences in siderophile element concentrations among tektites with otherwise similar chemical composition there are now four known craters formed by chondrites clearwater east lapparjarvi wanapitei and brent with brent being the smallest of these for smaller craters the projectiles appear to be limited to iron or stony iron meteorites because of atmospheric destruction of relatively small stony meteorites it appears however that all major classes of meteorites are represented among the projectiles at terrestrial impact craters

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

the role of the subcutaneous zone in karst hydrology abstract the subcutaneous zone is the upper weathered layer of rock beneath the soil but above the permanently saturated phreatic zone it is of particular hydrological importance in karst because of its high secondary permeability arising from the considerable chemical solution in this zone however corrosional enlargement of fissures diminishes with depth thus permeability decreases in the same direction with the result that percolation is inhibited except down widened master joints and faults storage of water consequently occurs in this zone particularly after storms the upper surface of this suspended saturated layer in the subcutaneous zone is defined by a perched water table which slopes towards points of rapid vertical percolation the potential induces lateral water movement converging on the most permeable areas such as beneath dolines leakage from the subcutaneous store sustains slow percolation in the vadose zone cross correlation of rainfall with percolation rates in caves in new mexico u s a and new zealand reveal response lags of 2 14 weeks with no apparent relationship to depth below the surface other percolation sites show no correlation with rainfall interpreted as being a consequence of considerable friction in tight fissure networks the recognition of storage and rapid as well as very slow percolation from the subcutaneous zone requires re interpretation of the components of hydrographs from karst springs and of some conceptual models of karst aquifers the importance of subcutaneous storage in sustaining baseflow discharge at some sites must be recognised as must the contribution of subcutaneous water to flood hydrographs methods of estimating the volumes of subcutaneous and phreatic components of karst spring flood hydrographs are presented the paper concludes with a discussion of the significance of subcutaneous hydrologic processes for an understanding of karst geomorphology the desirability of explaining karst landform evolution in terms of hydrologic processes is stressed

highly siderophile elements re os ir ru rh pd au in impact melts from three european impact craters saaksjarvi mien and dellen clues to the nature of the impacting bodies twenty two large 10 g impact melt samples from three scandinavian craters i e saaksjarvi finland and mien and dellen sweden were analyzed for highly siderophile elements hse platinum group elements rh and au by the nickel sulfide technique in combination with neutron activation the ten impact melt samples from saaksjarvi are enriched in ir and other highly siderophile elements ir 2 48 0 73 ng g relative to average upper crust concentrations 0 03 0 02 ng g ir the twelve dellen and mien samples are marginally enriched in ir 0 48 0 23 ng g for dellen and 0 37 0 23 ng g for mien the amount of meteoritic component corresponds to 0 5 of a nominal ci component for saaksjarvi and about 0 1 for mien and dellen the saaksjarvi pattern is fractionated relative to ci chondrites normalized abundances increase from the refractory to the more volatile siderophile elements ir ni the trend is qualitatively similar to magmatic iron meteorites and corresponds to 0 4 of a nominal magmatic iron meteorite component tamarugal iiiab for mien and dellen no projectile assignment can be made all samples from the three impact craters have low osir ratios compared to chondritic ratios either the projectile had low osir ratios or os was lost during the impact as volatile oso4 based on the results of this study and on a compilation of literature data average upper crustal abundances of the highly siderophile elements in the target area baltic shield are estimated as 0 03 ng g for ir and os 1 1 ng g for ru 0 38 ng g for rh 2 0 ng g for pd 8 g g for co and 37 g g for cr these data are representative of the upper crust they allow for the first time reliable estimates of crustal abundances for rh and ru upper crustal abundances also show that ir and os are the most favourable elements for the identification of meteoritic signatures fractionated osir ratios in magmatic iron meteorites or potential losses of os during the impact leaves ir as the best indicator element for meteoritic contamination with ir extraterrestrial components as low as 2 104 ci may be identified

chromium isotopic studies of terrestrial impact craters identification of meteoritic components at bosumtwi clearwater east lappajarvi and rochechouart chromium isotopic compositions and elemental abundances in impact melt rock and impact glass samples from four terrestrial impact craters were measured to verify the presence of an extraterrestrial component and to identify the meteorite type of the impactor all meteorite classes have cr isotopic signatures that are different from those of terrestrial rocks thus precise measurements of cr isotopic abundances can unequivocally distinguish terrestrial from extraterrestrial materials for all four studied craters bosumtwi ghana clearwater east canada lappajarvi finland and rochechouart france we found positive 53cr excesses that eliminate carbonaceous chondrite projectiles because those would show apparent negative excesses and enstatite chondrites because of the magnitude of the excess in all four cases ordinary chondrites have been identified as the best fit for the data in the case of lappajarvi interelement correlations together with the cr isotope data make an h chondrite the most likely projectile whereas in the case of clearwater east both l or h chondrites are possible for bosumtwi and rochechouart the high indigenous contents of the siderophile elements and disturbances of the elemental abundances by weathering and hydrothermal alteration respectively do not allow further constraints to be placed on the type of ordinary chondrite involved in the impact

platinum group elements in impactites of the icdp chicxulub drill core yaxcopoil 1 are there traces of the projectile this study presents results of platinum group element pge analyses of impactites from the yaxcopoil 1 yax 1 and yucatan 6 drill cores of the 180 km diameter chicxulub crater these are the main elements used for projectile identification they were determined by nickel sulfide fire assay combined with inductively coupled plasma mass spectrometry the concentration of pge in the samples are low the concentration patterns of the suevite samples resemble the pattern of the continental crust we conclude that any meteoritic fraction in these samples is below 0 05 a syn and post impact modification of the pge pattern from meteoritic toward a continental crust pattern is very unlikely the globally distributed fallout at the cretaceous tertiary k t boundary however has high pge concentrations therefore the lack of a significant meteoritic pge signature in the crater is not an argument for a pge poor impactor taking the results of three dimensional numerical simulations of the chicxulub event into account the following conclusions are drawn 1 the main fraction of the impactor was ejected into and beyond the stratosphere distributed globally and deposited in the k t boundary clay and 2 the low amount of projectile contamination in the yax 1 lithologies may reflect an oblique impact however the role of volatiles in the mixing process between projectile and target is not well understood and may also have played a fundamental role

groundwater systems in bare and covered karst aquifers evidence from tracer tests hydrochemistry and groundwater ages the east guilin region contains a karst dominated hydrological system along the lijiang river the two main topographic characteristics of the basin are peak cluster depression and peak forest despite the fact that these areas represent adjacent units they have different groundwater movement patterns this study describes the groundwater and solute movement in the different hydrogeological sub regions via several techniques our results indicated that the topographic boundary between the peak cluster depression and the peak forest is clear however a transition zone exists between these topographic zones and it can be determined in terms of groundwater movement we employed several methods that are widely considered to be effective tracer tests were conducted in the transition zone hydrochemistry techniques were used in the peak forest and groundwater age dating based on cfcs was employed throughout the study area the main conduits could be found in the transition zone but the groundwater flow was much slower in the transition zone than in the mountain peak cluster area minor conduits also accounted for a high proportion of the total flow in the transition zone the solute migration within the plain which was determined by analyzing the nitrates was controlled by mixing and distance effects the maximum nitrate concentration was limited at the local scale the nitrate concentration gradient at the regional scale was not related to the groundwater movement indicating that the groundwater recharged in a dispersed manner and discharged at discrete locations along the river the age dating revealed that the groundwater was older in the plain than in the bare mountain zone this was due to the strong mixing of young and old water which was the result of the characteristics of the karst media in the aquifer our investigation of the groundwater system in a bare covered karst aquifer provides data for decision making in effective groundwater management

characterization of the dominant impactor signature for apollo 17 impact melt rocks abstract concentrations of the highly siderophile elements hse re os ir ru pt and pd and 187 os 188 os isotopic compositions are reported for seven apollo 17 impact melt rocks these data are used to examine the dominant chemical signature of the impactor that formed the melts six of the samples 72355 72435 72535 76035 76055 and 76135 have poikilitic textures one sample 73235 has an aphanitic texture data for the samples define linear correlations when ir is plotted versus other hse concentrations with y intercepts indistinguishable from zero for most hse in most rocks scatter about some of the trends and occasional trends with positive y intercepts indicate either mixing of additional components that are heterogeneously distributed within several rocks or modest fractionation of some hse by volatilization crystal fractionation or other processes during formation and evolution of the melt sheet there is no statistical difference between the aphanitic and poikilitic samples in terms of hse ratios after visible granulitic clasts were removed from aphanite 73235 hence earlier speculations that the two types of impact melt rocks at this site may have been generated by different impactors are not supported by our data most apollo 17 samples examined here and in prior studies are characterized by very similar hse signatures consistent with a common impactor these samples are characterized by elevated ru ir pd ir and re os relative to most chondrites collectively the data indicate that the impactor was characterized by the following hse ratios 2 re ir 0 093 0 020 os ir 1 03 0 28 ru ir 1 87 0 30 pt ir 2 36 0 31 pd ir 1 85 0 41 and present day 187 os 188 os of 0 1322 0 0013 the results most likely mean that the impactor was a body with a bulk composition that was just outside the range of meteoritic compositions currently sampled on earth

no major deglaciation across the miocene pliocene boundary integrated stratigraphy and astronomical tuning of the loulja sections bou regreg area nw morocco 1 an integrated high resolution stratigraphy and orbital tuning is presented for the loulja sections located in the bou regreg area on the atlantic side of morocco the sections constitute the upward continuation of the upper messinian ain el beida section and contain a well exposed continuous record of the interval straddling the miocene pliocene m p boundary the older loulja a section which covers the interval from 5 59 to 5 12 ma reveals a dominantly precession controlled color cyclicity that allows for a straightforward orbital tuning of the boundary interval and for detailed cyclostratigraphic correlations to the mediterranean the high resolution and high quality benthic isotope record allows us to trace the dominantly obliquity controlled glacial history our results reveal that the m p boundary coincides with a minor partly precession related shift to lighter interglacial values in d18o this shift and hence the m p boundary may not correlate with isotope stage tg5 as previously thought but with an extra weak obliquity controlled cycle between tg7 and tg5 consequently the m p boundary and basal pliocene flooding of the mediterranean following the messinian salinity crisis are not associated with a major deglaciation and glacio eustatic sea level rise indicating that other factors such as tectonics must have played a fundamental role on the other hand the onset of the upper evaporites in the mediterranean marked by hyposaline conditions coincides with the major deglaciation step between marine isotope stage tg12 and tg11 suggesting that the associated sea level rise is at least partly responsible for the apparent onset of intermittently restricted marine conditions following the main desiccation phase finally the loulja a section would represent an excellent auxiliary boundary stratotype for the m p boundary as formally defined at the base of the trubi marls in the eraclea minoa section on sicily

neodymium isotopes in planktonic foraminifera a record of the response of continental weathering and ocean circulation rates to climate change the neodymium nd isotope composition of ancient seawater is a potentially useful tracer of changes in continental inputs and ocean circulation on timescales of a few ka here we present the first nd isotope record for seawater using sedimentary foraminifera cleaned using standard oxidative reductive techniques the data along with mn ca ratios suggest that cleaned foraminifera provide a reliable record of nd in seawater and hold out the prospect of using nd in foraminifera to examine changes in seawater that accompany glacial interglacial climatic cycles the principal potential problem to be overcome with the use of forams as records of trace elements in ancient seawater is their diagenetic fe mn coatings these contain large amounts of nd and other trace elements but can be cleaned off using highly reducing reagents mn ca ratios for the majority of the cleaned sedimentary foraminifera analysed here lie within the range 10 100 mol mol that has yielded success in studies of transition elements in forams mass balance modelling suggests that for residual mn ca ratios 100 mol mol nd added to the foram in the coating will never shift the measured nd isotope composition significantly away from the seawater value acquired by the foram test in the water column additionally nd concentrations measured in cleaned sedimentary foraminifera are comparable with those for a modern sample that has never encountered diagenetic fluids finally core top planktonic foraminifera for two sites have nd isotope compositions that are identical to local surface seawater the data we present here for labrador sea forams over the past 2 5 m y are interpreted in terms of changes in the seawater isotopic composition the data show a pronounced shift from end values of 12 to 19 in the period 2 5 1 5 ma this change is interpreted to result from the initiation of northern hemisphere glaciation and the increased derivation of labrador sea nd via ice rafting from archaean terranes in central canada in combination with stable isotope and foraminiferal relative species abundance data the new nd data are consistent with the surface hydrography of the labrador sea being dominated by a fluctuating balance between cold polar waters containing unradiogenic nd and warm subtropical waters containing more radiogenic nd the major change in labrador sea nd that is observed in the past 2 5 ma can on its own account for the change in the nd isotope composition of north atlantic deep water over the same time period

pb pb age of earliest megascopic eukaryotic alga bearing rohtas formation vindhyan supergroup india implications for precambrian atmospheric oxygen evolution abstract though considered to be the earliest known well preserved megascopic body fossil of an eukaryotic alga grypania spiralis has not yet been dated directly and reliably in any of its four known locations in the world we report a pb pb isochron age of 1599 48 ma for the grypania bearing rohtas formation of the vindhyan supergroup central india besides being about 500 myears older than the previously inferred age for this formation this pb pb age together with close age constraints on the same fossil bearing horizons in jixian china and montana usa indicates that grypania bloomed on a global scale between 1 6 and 1 5 ga being an obligate aerobe the appearance of a much older grypania within one of the principal bif deposits near michigan usa has been linked to a significant jump in atmospheric oxygen between 2200 and 1900 ma inferred from geochemical evidence the long gap of 400 myears between the older and younger grypania occurrences could be due to reduction of atmospheric oxygen below the grypania survival threshold as a result of extensive bifs between about 1950 and 1850 ma

recent benthic foraminifera from the eastern south atlantic ocean dependence on food supply and water masses abstract sixty surface sediment samples from the eastern south atlantic ocean including the walvis ridge the angola and cape basins and the southwest african continental margin were analysed for their benthic foraminiferal content to unravel faunal distribution patterns and ecological preferences live stained with rose bengal and dead faunas were counted separately and then each grouped by q mode principal component analysis into seven principal faunal end members then multiple regression technique was used to correlate recent assemblages with available environmental variables and to finally differentiate between four principal groups of environmental agents acting upon the generation of benthic foraminiferal assemblages 1 seasonality of food supply and organic carbon flux rates together with oxygen content in the pore and bottom waters 2 lateral advection of deep water masses 3 bottom water carbonate corrosiveness and 4 energetic state at the benthic boundary layer and grain size composition of the substrate food supply and corresponding dissolved oxygen contents in the pore and bottom waters turned out to be the most important factors which control the distribution pattern of the recent benthic foraminifera at the continental margin in the zone of coastal upwelling and its mixing area benthic foraminiferal assemblages are dominated by stenobathic high productivity faunas characterized by elevated standing stocks low diversities and a large number of endobenthic living species at the continental shelf and upper continental slope the live assemblages are characterized by rectuvigerina cylindrica uvigerina peregrina s 1 uvigerina auberiana and rhizammina spp while the dead assemblages are characterized by cassidulina laevigata bolivina dilatata bulimina costata and b mexicana at the lower continental slope strong influence of high organic matter fluxes on the species composition is restricted to the area off the cunene river mouth where the live assemblage is dominated by uvigerina peregrina s 1 the corresponding dead assemblage by melonis barleeanum and m zaandamae in the adjacent areas of the lower continental slope the biocoenosis is characterized by reophax bilocularis and epistominella exigua which becomes dominant in the corresponding dead assemblage at the walvis ridge and in the abyssal angola and cape basins where organic matter fluxes are low and highly seasonal benthic foraminiferal assemblages reflect both the oligotrophic situation and the deep and bottom water mass configuration the top and flanks of the walvis ridge are inhabited by the rhizammina psammosphaera and r bilocularis live assemblages the corresponding dead assemblages are dominated by g subglobosa on the ridge top and e exigua on the flanks within the highly diverse e exigua dead assemblage several associated epibenthic species coincide with the core of nadw between about 1600 and 3700 m water depth these species include osangularia culter cibicidoides kullenbergi melonis pompilioides bolivinita pseudothalmanni and bulimina alazanensis the assemblages of the abyssal cape and angola basins are characterized by nuttallides umbonifer and a high proportion of agglutinated species these species are adapted to very low organic matter fluxes and a carbonate corrosive environment

182w and 187re 187os systematics of iron meteorites chronology for melting differentiation and crystallization in asteroids w isotopic compositions measured by n tims in five iron meteorite groups are used in conjunction with 187re 187os isotopic data to constrain the timing of metal segregation and crystallization respectively in the iron meteorite parent bodies fractionation of the parent isotope 182hf half life 9 2 ma from the daughter 182w likely occurred during segregation of metal from silicate in the iron meteorite parent bodies if w isotopic equilibrium was achieved between silicate and metal during metal segregation then the w isotopic compositions in the irons should record the timing of this event samples were taken from the five largest iron meteorite groups including the four magmatic groups iiab iiiab iva and ivb and the nonmagmatic iab iiicd group together these groups comprise approximately 90 by weight of iron meteorites classified so far with the exception of the iva group the groups have well defined 187re 187os isochron ages which are interpreted as the time of crystallization of the metal of their parent bodies within each magmatic group samples that crystallized both early and late in the sequence of each core were analyzed to evaluate possible evolution of the w isotopic composition during crystallization all the samples examined display very similar w values within a narrow range of compositions between 5 1 and 3 1 witzation began less than a few percent of additional metal was segregated to the cores moreover the average w values for the five groups have no resolvable difference ranging from 4 08 0 69 iva to 3 30 0 15 iab iiicd these data indicate that all of the iron meteorite parent bodies underwent metal segregation within 5 ma of each other apparently independent of their composition size and time of crystallization of the metal in all groups except the iiiab group there is a resolvable time interval between the timing of metal segregation as constrained by the w isotopic data and the initiation of core crystallization as given by the re os isotopic systematics

glacial interglacial variations in the neodymium isotope composition of seawater in the bay of bengal recorded by planktonic foraminifera this study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from odp site 758 in the southernmost reaches of the bay of bengal in the north east indian ocean cleaning experiments using oxidative reductive techniques suggest that diagenetic fe mn oxyhydroxide coatings can be effectively removed and that the measured nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated modern core top pulleniatina obliquiloculata and globorotalia menardii give end values of 10 12 0 16 and 10 28 0 16 respectively indistinguishable from recent direct measurements of surface seawater in this area a high resolution nd isotope record obtained from g menardii for the past 150 kyr shows systematic variations end 3 on glacial interglacial timescales the timing of those variations shows a remarkable correspondence with the global oxygen isotope record which suggests a process controlling the nd isotope composition that responds in phase with global climate cycles palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the indian subcontinent and a decrease in the flux of river water delivered to the bay of bengal thus changes in the riverine input of nd a change in either flux or composition most likely caused the isotope variations although changes in dust source or local ocean circulation may have also played a role these results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans and illustrate the potential of nd isotopes in foraminifera for high resolution palaeoceanographic reconstruction

delineating vulnerability of karst aquifers using hydrochemical tracers in southwestern china karst groundwater is particularly vulnerable to contamination long term hydrochemistry auto monitoring combined with laboratory analyses has shown that the chemograph demonstrates changes in the system in order to determine the primary groundwater vulnerability a relationship between hydrochemical changes and the origin of vulnerability in six karst spring catchments in southwestern china is discussed the reason and physical meaning of the hydrochemical changes in the spring are explained based on tracer tests and physical chemical process in the s31 spring the results prove that the hydrochemical changes show the origin of vulnerability and also can be its expression generally autogenic recharge in bare karst is concentrated in epikarst zone forming bypass flow and shaft flow which causes dilution of ca2 the chemograph reflects the percentage of concentrated and diffuse recharge the higher the ratio of concentrated recharge the higher the grade of groundwater vulnerability due to ca2 hco3 sec ph and temperature in water can change for kinds of reasons during their transport more karst systems with variable natural and human factors are discussed protective layer allogenic water recharge and transform of surface stream and subterranean river can change the origin shape of hydrochemical curve under this circumstance more indicators need to be monitored especially contaminant related ions such as nitrate in order to clearly understand the contribution of concentrated and diffuse recharge to water chemistry after comparing the traditional groundwater vulnerability assessment and the methods based on hydrochemical change rainfall protective layer epikarst transient storage and karst network should be more concerned when the work is done auto monitoring of karst is more and more popular in southwestern china therefore it is suggested that the hydrochemical methods should be used as a primary expression of vulnerability giving a direct reference for karst water management

isotopic evidence for the cretaceous tertiary impactor and its type high precision mass spectrometric analysis of chromium in sediment samples from the cretaceous tertiary k t boundary coincident with the extinction of numerous organisms on earth confirms the cosmic origin of the k t phenomenon the isotopic composition of chromium in k t boundary samples from stevns klint denmark and caravaca spain is different from that of earth and indicates its extraterrestrial source the chromium isotopic signature is consistent with a carbonaceous chondrite type impactor the observed differences in the chromium isotopic composition among various meteorite classes can serve as a diagnostic tool for deciphering the nature of impactors that have collided with earth during its history

acquisition of the neodymium isotopic composition of the north atlantic deep water the north atlantic deep water nadw neodymium isotopic composition nd ic is increasingly used in oceanography and paleoceanography to trace large scale circulation and weathering processes notably to investigate past variations of the global thermohaline circulation although the present day nadw nd ic is well characterized at nd 13 5 the acquisition of this isotopic signature in other words the causes of this value has so far been very sparsely documented such an understanding is however fundamental to the interpretation of paleo records nd ic and rare earth element concentrations were measured at 9 stations within the north atlantic subpolar gyre signature cruise summer 1999 the comparison of this data set with our understanding of water mass circulation provides a description of how the three layers constituting the nadw the labrador sea water lsw nd 13 9 0 4 north east atlantic deep water neadw nd 13 2 0 4 and north west atlantic bottom water nwabw nd 14 5 0 4 acquire their nd ic through distinct water mass mixings and lithogenic inputs these different mechanisms acting upon water masses from very diverse sources seem to bring the nd ic of the three nadw layers to values close together and similar to that of the nadw it is suggested that sediment seawater interactions significantly lower the neadw and nwabw nd ic along the south east greenland margin since these interactions do not significantly modify the nd content of these water masses sediment remobilizations leading to the nd ic variations are probably associated with nd removal fluxes from the water mass toward the sediment a process called boundary exchange on the other hand lsw seems to acquire its nd ic from the subpolar mode waters from which it is formed by deep convection and no other mechanism needs to be invoked its unradiogenic signature could ultimately be linked to fresh water runoff from the canadian shield these conclusions should allow more precise interpretations of paleoceanographic nd ic records taking into account the distinct histories of the three nadw layers including distinct water mass mixings and distinct lithogenic inputs

geochemistry of 2 63 2 49 ga impact spherule layers and implications for stratigraphic correlations and impact processes thin layers rich in spherules formed during impacts by large extraterrestrial objects have the potential to shed new light on impact processes and aid in the long distance stratigraphic correlation of precambrian successions seven formations in western australia and south africa clustered around the archean proterozoic boundary each contain a single spherule layer all of which were deposited between ca 2 49 and 2 63 ga analyses of 25 samples from 6 of the 7 spherule layers and 23 samples from closely associated strata free of spherules revealed an extraterrestrial component etc in all six layers based on pge ratios and or cr isotopic composition the amount of etc varies from marginally detectable to clear and obvious it generally amounts to ca a few percent both pge ratios and cr isotopic anomalies indicate most if not all of the impactors were ordinary chondritic in composition in contrast all spherule layers older than ca 3 0 ga that have been analyzed were produced by carbonaceous chondritic impactors normalized rare earth element patterns suggest most target rocks were basaltic in composition and variability in pge ratios favors ballistic emplacement of melt droplets rather than spherule formation via vapor condensation the geochemical data also provide a means to test proposed intra and intercontinental stratigraphic correlations cr isotopic compositions are consistent with the formation of the oldest layers on both continents by a single impact event about 2 63 ga in contrast clear geochemical differences between the middle layers both deposited ca 2 54 ga suggest they were not produced by the same impact event the youngest banded iron formation hosted layers on both continents have also been correlated but no geochemical data are available on the african layer to test this at present

neodymium in modern foraminifera from the indian ocean implications for the use of foraminiferal nd isotope compositions in paleo oceanography abstract the use of the nd isotope composition of planktic foraminifera as a proxy for sea surface water is based on the assumption that nd is incorporated during initial calcification and preserved after foraminifera death subsequent transport through the water column and storage in the sediment pile to test this assumption nd concentrations are reported from foraminiferal tests collected from 20 to 3045 m depth multinets and sediment traps from offshore somalia and in the somali basin of the indian ocean nd partition coefficients calculated for two species globigerinoides ruber and globigerina bulloides sampled in the uppermost water column 100 m are 16 52 the measured nd ca ratio of living foraminifera is 8 nmol mol which is 8 190 times lower than reported in cleaned foraminifera from sediment cores 61 1500 nmol mol moreover the nd content of foraminiferal tests varies markedly within the water column 8 220 nmol mol ca recording a positive correlation with mn content r2 0 91 the observed changes in the nd concentration after foraminiferal death appear to reflect nd addition from deeper in the water column and imply a major disturbance of the primary nd isotope composition formed at the surface the high nd ca reported for cleaned foraminifera from sediment cores are interpreted to be a consequence of current cleaning techniques although cleaning successfully removes organics and secondary mn coatings into solution any released rare earth elements ree are subsequently re adsorbed onto the calcite cleaning removes elements with a 2 valency state into solution e g cd and mn but more reactive elements with higher valency states e g ree3 th4 are re absorbed onto residual carbonate it is concluded that although foraminifera clearly record temporal variations in nd isotope composition the relationship between these variations and changes in the sea surface nd isotope composition has yet to be established unambiguously further work is required to rule out the possibility that the nd in foraminifera represents a mixed signal derived from surface sediments and bottom and pore waters

cadmium zinc copper and barium in foraminifera tests the concentrations of cadmium zinc copper and barium have been determined on 2 mg samples of single species foraminifera populations cleaning techniques were tested using north atlantic core tops and followed by a detailed downcore study for the last 30 000 years in south atlantic core v22 174 raw foram tests cleaned by crushing followed by ultrasonic removal of fine grained material and dissolved in a ph 5 5 acetate buffer contain appreciable amounts of trace elements associated with ferromanganese and alumino silicate contaminants a reductive complexing cleaning treatment reduces ferromanganese contamination by 1 2 orders of magnitude acetate buffers at ph 5 5 complex iron and raise the solubility of ferromanganese oxides these buffers are unsuitable for separating carbonate lattice bound trace elements from the fraction associated with ferromanganese phases improved mechanical and ultrasonic reductive cleaning combined with a mild dissolution in distilled water under 1 atm pco2 reduces contaminant levels another order of magnitude the cd and zn concentrations order 10 8 mole cd mole ca and 10 5 mole zn mole ca of species with low surface area show an increase with decreasing isotopic temperatures this increase is consistent with the increasing concentrations of these metals from low values in surface waters to higher values at depth the variance of cd and zn over the last 30 000 years in the central south atlantic is consistent with the probable variability of the dissolved trace elements at the calcification levels of the species analyzed cu and ba are irreproducible and probably sensitive to residual contaminant phases the trace element content of the tests differs from levels observed in a recent coprecipitation study foraminifera may be a significant vector in zinc cycling in the ocean

closure of the central american isthmus and its effect on deep water formation in the north atlantic modern ocean thermohaline driven circulation influences global climate by transporting heat to high latitudes1 2 and by affecting the exchange of co2 between ocean and atmosphere3 north atlantic deep water nadw plays a key role in this circulation and quaternary climate cycles have been linked to changes in nadw flow4 general circulation model simulations indicate that before closure some 3 4 million years ago of the central american isthmus the narrow strip of land linking north and south america the direct flow of low salinity water from the pacific to the atlantic ocean would have led to a smaller nadw flow5 6 sedimentation patterns7 and nutrient proxies8 11 support these model results by indicating an increase in nadw flow around the time of isthmus closure but these records do not allow changes in different nadw sources to be distinguished and the overall effect of closure on global ocean circulation is poorly known here we present nd pb and sr isotope records preserved by a hydrogenous ferromanganese crust from the nadw flow path in the western north atlantic ocean these records indicate that the isotopic signal associated with nadw strengthened around 3 4 million years ago showing that deep water that formed in the labrador sea made a gradually increasing contribution to nadw flow these data taken together with those from the central pacific ocean12 indicate an increased nadw flow since isthmus closure and suggest that the closure established today s general pattern of ocean circulation

actual timing of neodymium isotopic variations recorded by femn crusts in the western north atlantic hydrogenetic ferromanganese femn crusts from the western north atlantic record variations in the nd and pb isotopic composition of cenozoic deep water preserved during their growth the timing and cause of the most striking change have been the subject of debate some have proposed that the shift took place after 4 ma in response to the closure of the panama gateway others have argued that the major change in isotope composition occurred as early as 8 ma this study presents high resolution nd isotope records for crusts previously dated using 10be 9be chronology these data confirm that the shifts in nd occurred after 4 ma consistent with a likely relationship with the closure of the central american isthmus and intensification of northern hemisphere glaciation and in accordance with changes seen in other physical and chemical records these results illustrate the need for both a robust chronological framework and high resolution records before a reliable paleoceanographic interpretation can be made of the variations recorded by femn crusts

evolution of atlantic thermohaline circulation early oligocene onset of deep water production in the north atlantic the flow of deep water masses is a key component of heat transport in the modern climate system yet the role of deep ocean heat transport during periods of extreme warmth is poorly understood the present mode of meridional overturning circulation is characterized by deep water formation in both the north atlantic and the southern ocean however a different mode of meridional overturning circulation operated during the extreme greenhouse warmth of the early cenozoic during which time the southern ocean was the dominant region of deep water formation the combination of general global cooling and tectonic evolution of the atlantic basins over the past 55 m y ultimately led to the development of a mode of overturning circulation characterized by both southern ocean and north atlantic deep water sources the change in deep water circulation mode may in turn have affected global climate however unraveling the causes and consequences of this transition requires a better understanding of the timing of the transition new nd isotope data from the southeastern atlantic ocean indicate that the initial transition to a bipolar mode of deep water circulation occurred in the early oligocene ca 33 ma the likely cause of significant deep water production in the north atlantic was tectonic deepening of the sill separating the greenland norwegian sea from the north atlantic

late miocene through early pliocene deep water circulation and climate change viewed from the sub antarctic south atlantic benthic foraminiferal stable isotope records for the past 11 myr from a recently drilled site in the sub antarctic south atlantic site 1088 ocean drilling program leg 177 41 s 15 e 2082 m water depth provide for the first time a continuous long term perspective on deep water distribution patterns and southern ocean climate change from the late miocene through the early pliocene i have compiled published late miocene through pliocene stable isotope records to place the new south atlantic record in a global framework carbon isotope gradients between the north atlantic south atlantic and pacific indicate that a nutrient depleted watermass probably of north atlantic origin reached the sub antarctic south atlantic after 6 6 ma by 6 0 ma the relative proportion of the northernprovenance watermass was similar to today and by the early pliocene it had increased to greater than the modern proportion suggesting that thermohaline overturn in the atlantic was relatively strong prior to the early pliocene interval of inferred climatic warmth site 1088 oxygen isotope values display a two step increase between v7 4 ma and 6 9 ma a trend that parallels a published n 18 o record of a site on the atlantic coast of morocco this is perhaps best explained by a gradual cooling of watermasses that were sinking in the southern ocean i speculate that relatively strong thermohaline overturn at rates comparable to the present day interglacial interval during the latest miocene may have provided the initial conditions for early pliocene climatic warmth the impact of an emerging central american seaway on atlantic pacific ocean upper water exchange may have been felt in the north atlantic beginning in the latest miocene between 6 6 and 6 0 ma which would be v1 5 myr earlier than previously thought 9 2002 elsevier science b v all rights reserved

recently discovered 3 42 3 23 ga impact layers barberton belt south africa 3 8 ga detrital zircons archean impact history and tectonic implications the barberton greenstone belt bgb includes eight known layers containing spherical particles spherules that condensed from rock vapor clouds formed by the impact of large meteorites or asteroids 3 47 3 23 ga previous studies have inferred that the spherules represent bolides at least 20 70 km across spherule beds s1 s4 have been previously characterized in detail we provide here the first detailed analysis of more recently discovered beds s5 s8 all eight beds are composed of the same basic compositional and textural spherule types including nearly pure silica spherules representing nonaluminous melt precursors nearly pure phyllosilicate spherules representing mostly mafic and ultramafic liquids and compositionally mixed spherules evidence of spherule amalgamation and surface corrosion within the rock vapor clouds is developed in some beds bed s6 which occurs within a thick sequence of ultramafic volcanic rocks is overlain by a tsunami layer containing zircons as old as 3811 7 ma suggesting deep possibly impact related crustal uplift and erosion in distant areas the formation of at least 8 major impact layers representing bolides 20 70 km in diameter over an interval of 240 m y suggests impact rates greatly exceeding those of later geologic time and provides direct evidence that terrestrial bombardment by large bolides did not end abruptly at 3 8 ga but waned gradually until 3 0 ga or even later the coincidence of at least four large impact layers and the initiation of bgb deformation at 3 26 3 23 ga suggests that an impact cluster at this time may have disrupted a long lived earlier geodynamic system and triggered the development of a contrasting more modern plate tectonic regime

the dhala structure bundelkhand craton central india eroded remnant of a large paleoproterozoic impact structure the newly discovered dhala structure madhya pradesh state india is the eroded remnant of an impact structure with an estimated present day apparent diameter of about 11 km it is located in the northwestern part of the archean bundelkhand craton the pre impact country rocks are predominantly granitoids of 2 5 ga age with minor 2 0 2 15 ga mafic intrusive rocks and they are overlain by post impact sediments of the presumably 1 7 ga vindhyan supergroup thus the age for this impact event is currently bracketed by these two sequences the dhala structure is asymmetrically disposed with respect to a central elevated area cea of vindhyan sediments the cea is surrounded by two prominent morphological rings comprising pre vindhyan arenaceousargillaceous and partially rudaceous metasediments and monomict granitoid breccia respectively there are also scattered outcrops of impact melt breccia exposed towards the inner edge of the monomict breccia zone occurring over a nearly 6 km long trend and with a maximum outcrop width of 170 m many lithic and mineral clasts within the melt breccia exhibit diagnostic shock metamorphic features including multiple sets of planar deformation features pdfs in quartz and feldspar ballen textured quartz occurrences of coesite and feldspar with checkerboard texture in addition various thermal alteration textures have been found in clasts of initially superheated impact melt the impact melt breccia also contains numerous fragments composed of partially devitrified impact melt that is mixed with unshocked as well as shock deformed quartz and feldspar clasts the chemical compositions of the impact melt rock and the regionally occurring granitoids are similar the ir contents of various impact melt breccia samples are close to the detection limit 1 1 5 ppb and do not provide evidence for the presence of a meteoritic component in the melt breccia the presence of diagnostic shock features in mineral and lithic clasts in impact melt breccia confirm dhala as an impact structure at 11 km dhala is the largest impact structure currently known in the region between the mediterranean and southeast asia

an ordinary chondrite impactor for the popigai crater siberia with a diameter of 100 km popigai in northern siberia is the largest crater known in the cenozoic the concentrations in platinum group elements pge were analyzed in twenty samples of homogeneous impact melt collected in the northwestern flank of the crater to identify the composition of the projectile the method selected was preconcentration by nis fire assay followed by inductively coupled plasma mass spectrometry icp ms this technique measures all the pge except os and by using aliquots 10g the results are highly reproducible the major and trace element composition of the impact melt resembles that of gneissic lithologies of the anabar shield which are representative of the target rock the pge are enriched in the melt by factors of 3 to 14 compared to the main target lithology but the meteoritic contamination is only around 0 2 wt using plots of elemental ratios such as ru rh vs pt pd or ru rh vs pd ir the popigai impactor is clearly identified as an ordinary chondrite and most likely l chondrite this study indicates that pge elemental ratios allow discrimination of the type of impactor even in the case of low meteoritic contamination this study confirms that a significant fraction of the crater forming projectiles presently documented could have an ordinary chondrite composition their probable source the s type asteroids appears to form the majority of the bodies in the main asteroid belt and among near earth objects neos the ordinary chondrite origin of the popigai projectile supports an asteroidal origin for the late eocene impacts as a plausible alternative to the comet shower scenario proposed by farley et al 1998 copyright 2005 elsevier ltd

the use of foraminifera as a record of the past neodymium isotope composition of seawater 1 we present new isotopic data for sedimentary planktonic foraminifera as well as for potential water column and sedimentary sources of neodymium nd which confirm that the isotopic composition of the foraminifera is the same as surface seawater and very different from deep water and sedimentary nd the faithfulness with which sedimentary foraminifera record the isotopic signature of surface seawater nd is difficult to explain given their variable and high nd ca ratios ratios that are often sedimentary foraminifera ratios that are often much higher than is plausible for direct incorporation within the calcite structure we present further data that demonstrate a similarly large range in nd ca ratios in plankton tow foraminifera a range that may be controlled by redox conditions in the water column cleaning experiments reveal in common with earlier work that large amounts of nd are released by cleaning with both hydrazine and diethylene triamine penta acetic acid but that the nd released at each step is of surface origin while further detailed studies are required to verify the exact location of the surface isotopic signature and the key controls on foraminiferal nd isotope systematics these new data place the use of planktonic foraminifera as recorders of surface water nd isotope ratios and thus of variations in the past supply of nd to the oceans from the continents via weathering and erosion on a reasonably sure footing

temporal stability of the neodymium isotope signature of the holocene to glacial north atlantic the neodymium isotopic composition of marine precipitates is increasingly recognized as a powerful tool for identifying changes in ocean circulation and mixing on million year to millennial timescales unlike nutrient proxies such as 13 c or cd ca nd isotopes are not thought to be altered in any significant way by biological processes and thus they can serve as a quasi conservative water mass tracer however the application of nd isotopes in understanding the role of thermohaline circulation in rapid climate change is currently hindered by the lack of direct constraints on the signature of the north atlantic end member through time here we present the first results of nd isotopes measured in u th dated deep sea corals from the new england seamounts in the northwest atlantic ocean our data are consistent with the conclusion that the nd isotopic composition of north atlantic deep and intermediate water has remained nearly constant through the last glacial cycle the results address long standing concerns that there may have been significant changes in the nd isotopic composition of the north atlantic end member during this interval and substantiate the applicability of this novel tracer on millennial timescales for paleoceanography research

last glacial maximum paleochemistry and deepwater circulation in the southern ocean evidence from foraminiferal cadmium south atlantic benthic foraminiferal cd ca shows no glacial interglacial variation suggesting that the glacial contribution of north atlantic deep water to the southern ocean was not much different than at present in contrast cd ca in southeast indian ridge cores show lower glacial bottom water cd comparable to levels in intermediate depths of the north atlantic and significantly lower than in the deep south atlantic low glacial cd ca was also recorded in planktonic foraminifera suggesting a substantial decrease in the nutrient concentration of subantarctic surface water during the glacial maximum which most likely was caused by increased biological productivity the cd data are inconsistent with low glacial benthic foraminiferal 13c which suggest higher nutrient concentration we propose that the low cd ca in the southeast indian ridge records reflects a local source of nutrient depleted deepwater formed during the last glacial maximum by open ocean convection near the antarctic polar front downstream of the kerguelene plateau if this source was limited to the southeast indian basin then its impact on the overall chemistry of glacial circumpolar deepwater was rather small however if during glaciations open ocean convection became the dominant mode of bottom water formation it might have had a greater impact on cpdw chemistry

c o sr and pb isotope systematics of carbonate sequences of the vindhyan supergroup india age diagenesis correlations and implications for global events abstract the vindhyan supergroup of central india records a substantial portion of proterozoic time and contains some of the most disputed precambrian cambrian fossil discoveries despite the significance of these fossil finds many issues including reliable geochronology remained unresolved similarly the geochemical aspects of the sedimentary sequences and their implications to the evolution of proterozoic oceans have been studied only at a reconnaissance level here we report the results of the pb pb dating for the rohtasgarh limestone from the lower vindhyan supergroup giving an age of 1601 130 ma an estimate that is in accord with the recent u pb zircon dating of the lower vindhyan supergroup by rasmussen et al geology 30 2002 103 and ray et al geology 30 2002 131 sr isotope stratigraphy of carbonates from the upper vindhyan supergroup suggests a mid neoproterozoic 750 650 ma age for these formations this in turn argues for a long hiatus between the deposition of the lower and upper vindhyan supergroups our results conflict with the reports of cambrian age small shelly fossils and ediacaran fossils from the upper vindhyan rocks at the same time they suggest that the alleged trace fossils in the lower vindhyan rocks must be of paleoproterozoic age the most common 18 o values for calcitic components from limestone formations of the supergroup range from 10 to 7 similar to paleo neoproterozoic carbonates worldwide the modes of 13 c in the lower and upper vindhyan supergroups are 0 2 and 3 2 respectively again consistent with the worldwide dataset the secular patterns of carbon isotope trends do not support the earlier assumptions that the carbonate sequences at the southern margin correlate with those at the western or northern margins of the vindhyan basin c and sr isotope data provide new calibration points for the seawater evolutionary curves particularly for the paleoproterozoic for strontium isotopes the data from the lower vindhyan supergroup suggest that seawater departed probably less rapidly from mantle values than was previously believed

environmental and engineering problems of karst geology in china karst terrane is generally regarded as a fragile and vulnerable environment its underground drainage system can aggrevate both drought and flood problems the lack of filtration in an underground conduit makes waste disposal more difficult and the lack of soil cover in bare karstland can enhance deforestation moreover karst terranes are quite often haunted by a series of engineering problems such as water gushing into mines or transportation tunnels leakage from reservoirs and failure of building foundations in china there are more than 200 cases of karst collapse which include many thousands of individual collapse points some of these are paleo and natural collapses but most of them are modern collapses induced by human activities and they have caused serious damage many factors such as geologic structure overburden thickness and character lithologic features of karstified rock and intensity of karstification are related to development and distribution of modern collapses however china s karst is mainly developed in pre triassic old phase hard compact carbonate rock consequently most modern collapses have occurred only in the overlying soil so it is understandable that the fluctuation of the water table in the underlying karstified strata plays an important role in the process of collapse nevertheless there are different explanations as to how the groundwater activities can induce collapse

the osmium isotopic composition of the continental crust osmium isotopic compositions and concentrations have been determined for deltaic and continental shelf sediments from three major rivers the amazon changjiang and mississippi and for two loesses from the upper mississippi river valley the loesses have heavy mineral and clay compositions characteristic of mississippi river and delta sediment concentrations range from 15 to 120 pg os g and 187os 186os ratios range from 8 2 to 10 9 sediments which are polluted surface sediment from the changjiang estuary or which have scavenged metals from seawater gulf of mexico slope surface sediment and distal amazon shelf sediment have high osmium concentrations and less radiogenic isotopic compositions purely terrigenous sediments have 15 90 pg os g and 187os 186os 10 0 10 9 north american loess and mississippi delta sediment osmium isotopic compositions are indistinguishable we believe that 187os 186os 10 11 is a good average for currently eroding upper continental crust these sediments have neodymium isotopic compositions close to the global mean for river sediment terrigenous 187os 186os is significantly more radiogenic than seawater 187os 186os 8 6 requiring a nonriverine source of osmium to seawater terrigenous osmium is also significantly more radiogenic than bulk pelagic clay osmium we use the improved estimate of terrigenous 187os 186os to recalculate the flux of extraterrestrial osmium to pacific marine sediment if the residence age of osmium in an upper crustal region is similar to the neodymium model age of a sediment derived from that region a model dependent upper crustal 187re 186os ratio can be calculated for the model ages of the sediments analyzed in this study tdm 1 5 1 7 ga model 187re 186os ratios are 340 360 and can be used to correct for bias resulting from the preferential erosion of young crust the 187os 186os ratio of 2 2 ga crust with 187re 186os 400 is 14 2 we have also used the data from this study to estimate upper crustal osmium and rhenium concentrations of 50 pg g and 390 pg g respectively

manganese carbonate overgrowths on foraminifera tests below the zone where manganese is remobilized as mn2 aq reductively cleaned foraminifera in deep sea sediments have much higher mnca than those in core tops and sediment traps mnca ranges from less than 20 10 6 in and above the mno2 maximum to as high as 700 10 6 in reducing panama basin sediments the most plausible explanation for this enrichment is that the tests are coated with mn carbonate overgrowths these coatings can account for a significant proportion of the mn in reduced deep sea sediments uptake of manganous ion by carbonate may explain the absence of mn nodules in areas of high carbonate accumulation extreme degrees of overgrowth can alter foram trace element values but this artifact can be avoided by avoiding foraminifera with high mn ca

re os isotope and geochemical study of the vredefort granophyre clues to the origin of the vredefort structure south africa the origin of granophyric rock dikes the vredefort granophyre at the 2 ga vredefort structure in south africa has been controversial they have been interpreted as either impact melt or igneous intrusions most vredefort granophyre samples have considerably higher os contents than the country rocks and 187re 188os and 187os 188os ratios that scatter about a 2 ga isochron their initial 187os 188os ratios at 2 ga overlap the meteoritic data range indicating that all the granophyre samples contain some meteoritic os the re os isotopic composition of the granophyre is significantly different from that of local precursor rocks and indicates that up to 0 2 of a chondritic component could be contained in the granophyre our results confirm the interpretation that the vredefort granophyre represents an impact melt rock

crustal geodynamics from the archaean bundelkhand craton india constraints from zircon u pb hf isotope studies a comprehensive study based on u pb and hf isotope analyses of zircons from gneisses has been conducted along the western part babina area of the e w trending bundelkhand tectonic zone in the central part of the archaean bundelkhand craton 207 pb 206 pb zircon ages and hf isotopic data indicate the existence of a felsic crust at 3 59 ga followed by a second tectonothermal event at 3 44 ga leading to calc alkaline magmatism and subsequent crustal growth the study hence suggests that crust formation in the bundelkhand craton occurred in a similar time frame to that recorded from the singhbhum and bastar cratons of the north indian shield

the closing of a seaway ocean water masses and global climate change the late neogene witnessed various major paleoceanographic changes that culminated in intense northern hemisphere glaciation nhg the cause and effects of these changes are still debated we use a multiproxy approach to determine the relative timing of the closure of the panama gateway changes in atlantic circulation global cooling and ice sheet growth benthic foraminiferal mg ca records from a pacific and an atlantic site have been produced and are interpreted in terms of bottom water temperatures these mg temperature records are combined with published benthic 13c 18o and erosion records to reconstruct the flow of proto north atlantic deep water proto nadw over the past 12 ma the results suggest that between 12 5 and 10 5 ma and again between about 8 5 and 6 ma a nutrient depleted water mass that was colder by 1 2 c and fresher than the intervening deep water mass filled the atlantic basin this proto nadw became warmer by 1 c and saltier between 6 and 5 ma coincident with the restriction of surface water flow through the central american seaway the mg temperature records define a subsequent global cooling trend of 3 5 c between 5 ma and today early nhg in the late miocene was perhaps related to the formation of the relatively cold fresh proto nadw the formation of the warmer and saltier proto nadw in the early pliocene may have initially limited northern hemisphere ice growth however the increased moisture released at high northern latitudes associated with formation of warm proto nadw coupled with the global temperature decrease of deep and hence polar surface waters likely helped initiate the intense nhg of the plio pleistocene

late neogene history of deepwater ventilation in the southern ocean we compiled carbon isotope records from the north atlantic south atlantic and pacific oceans to estimate changes in vertical and interbasinal 13c gradients for the last 9 myr benthic 13c values of deep water in the south atlantic decreased in a series of steps at 7 2 75 and 1 55 ma away from the north atlantic and toward the pacific the benthic 13c of intermediate water in the south atlantic evolved differently from deep waters resulting in an increase in the intermediate to deep 13c gradient 13cid the 13cid increased in steps at 2 75 and 1 55 ma marking the development and intensification of a chemical divide in the atlantic ocean between well ventilated intermediate water and poorly ventilated deep water we suggest these changes in interbasinal and vertical gradients resulted from decreasing northern component water and reduced ventilation of southern component water scw the latter was caused by several interrelated processes in antarctic sources areas including increased sea ice cover enhanced surface water stratification decreased ekman induced upwelling and reduced vertical mixing across the thermocline because antarctic surface water processes and deepwater ventilation rates ultimately influence atmospheric co2 concentration these processes may have acted as a positive feedback that contributed to the major cooling steps in late neogene climate

diverse impactors in apollo 15 and 16 impact melt rocks evidence from osmium isotopes and highly siderophile elements abstract concentrations of highly siderophile elements hse and 187 os 188 os isotopic compositions for eleven impact related rocks from the apollo 15 and 16 landing sites are reported and combined with existing geochronological data to investigate the chemical nature and temporal changes in the large impactors implicated in the formation of the lunar basins data for the samples all define linear trends on plots of hse versus ir concentrations whose slopes likely reflect the relative hse compositions of the dominant impactors that formed the rocks the inferred imbrium basin impactor that generated apollo 15 impact melt rocks 15445 and 15455 was characterized by modestly suprachondritic 187 os 188 os ru ir pt ir and pd ir ratios diverse impactor components are revealed in the apollo 16 impact melt rocks the 187 os 188 os and hse ir ratios of the impactor components in melt rocks 60635 63595 and 68416 with reported ages 4 0 ga by contrast the impactor components in melt rocks 60235 62295 and 67095 with reported ages of 3 9 ga are characterized by suprachondritic 187 os 188 os and hse ir ratios similar to the apollo 15 impact melt rocks and may also sample the imbrium impactor three lithic clasts from regolith breccias 60016 and 65095 also with 3 9 ga ages contain multiple impactor components of which the dominant composition is considerably more suprachondritic than those implicated for imbrium and serenitatis apollo 17 impactors the dominant composition recorded in these rocks was most likely inherited from a pre imbrium impactor consideration of composition versus age relations among lunar impact melt rocks reveals no discernable trend virtually all lunar impact melt rocks sampled by the apollo missions as well as meteorites are characterized by 187 os 188 os and hse ir ratios that when collectively plotted define linear trends ranging from chondritic to fractionated compositions the impact melt rocks with hse signatures within the range of chondritic meteorites are interpreted to have been derived from impactors that had hse compositions similar to known chondrite groups by contrast the impact melt rocks with non chondritic relative hse concentrations could not have been made by mixing of known chondritic impactors these signatures may instead reflect contributions from early solar system bodies with bulk chemical compositions that have not yet been sampled by primitive meteorites present in our collections alternately they may reflect the preferential incorporation of evolved metal separated from a fractionated planetesimal core pre 4 0 ga ages for at least some impactor components with both chondritic and fractionated hse raise the possibility that the bulk of the hse were added to the lunar crust prior to the later stage basin forming impacts such as imbrium and serenitatis as proposed by fischer godde and becker 2012 for this scenario the later stage basin forming impacts were more important with respect to mixing prior impactor components into melt rocks rather than contributing much to the hse budgets of the rocks themselves

north atlantic thermohaline circulation during the past 20 000 years linked to high latitude surface temperature during a surface cooling event 10 000 to 12 000 years ago higher cd ca and lower 13c 12c ratios are observed in benthic foraminifera shells from rapidly accumulating western north atlantic sediments data from sediment cores show that marked nutrient depletion of intermediate waters occurs in association with reduced glacial north atlantic deep water flux it is proposed that cold high latitude sea surface temperatures enhance intermediate water formation at the expense of deep water formation

early archaean spherule beds in the barberton mountain land south africa no evidence for impact origin abstract detailed petrographical and geochemical studies are reported for several well documented occurrences of spherule rich layers in the barberton mountain land south africa which were previously inferred by lowe and co workers to be the result of early archaean meteorite impacts in contrast we made the following observations the textures of most spherules are not necessarily the result of impact but could instead be the product of radial or intersertal growth of crystals during secondary mineral formation there is no difference in the content of siderophile elements between spherule layers and layers devoid of spherules the siderophile element abundances are high where sulphide minerals e g pyrite gersdorffite and chalcopyrite and or chromite are present independent of the presence or absence of spherules high contents of e g ir up to 2700 ppb ni 0 96 wt and cr 1 6 wt were found in various samples abundances of these elements in chondritic meteorites are approximately 600 ppb 1 4 wt and 0 35 wt respectively resulting in respective meteoritic components in these samples of 450 70 and 460 we do not accept these high concentrations as primary meteoritic signatures impact melt rocks have typically 1 of a meteoritic component furthermore spherules of any kind are very rare in known impact deposits including the k t boundary if present at all they are not usually associated with any significant ir or pge anomaly the high abundances of the siderophile elements in some barberton samples and their enrichment in secondary minerals indicate that these elements have been remobilized and reconcentrated the pge interelement ratios have changed during remobilization as well thus the pge abundance patterns and ratios are not primary and cannot be used as an argument in favour of an impact origin either nickel rich cr spinels which are found in some of the barberton spherule samples have low fe 3 fe total ratios these ratios are incompatible with an extraterrestrial or impact origin because such impact derived spinels including those found at the k t boundary are highly oxidized and also have different chemical compositions there is also no indication of any evidence of shock metamorphism associated with the barberton spherule layers which is the commonly accepted definitive criterion for recognition of an impact origin this is unusual because such evidence is preserved even in heavily altered samples from deeply eroded archaean impact structures we conclude that while these spherule layers are clearly unusual and deserve further attention there is no convincing evidence for an origin by impact we suggest that they were formed by volcanic processes followed by extensive hydrothermal alteration

variations in the strontium isotopic composition of seawater during the neogene the authors report 261 strontium isotopic analyses of well preserved planktonic foraminifers from three deep sea drilling project sites 519 588 and 607 these samples cover the period from 24 ma to present with an average of approximately one sample per 100 ka the combination of high sample density and uniformity of analytical procedures has produced a well defined record of changes in the sup 87 sr sup 86 sr of seawater during the neogene the record can be viewed as a series of essentially linear segments with slopes ranging from as high as 6 times 10 sup minus 5 m y to as low as 0 m y the times associated with major inflections in the curve do not appear to correspond to simple geologic phenomena such as eustatic cycles but are probably controlled by a combination of tectonic and climatic factors that influenced the abundance and isotopic composition of terrestrial strontium input to the oceans the strontium isotopic data are consistent with a progressive increase in the chemical weathering rates of the continents during the neogene probably related to repeated glaciations increased exposure of continents by lowered sea level and increased continental relief resulting from high rates of tectonic uplift

contrasting meteoritic signatures within the clearwater east and clearwater west impact structures the view from osmium isotopes abstract osmium isotopes provide a powerful tool for identifying meteoritic signatures in impactites we apply the osmium isotope method to impact melt and country rocks from the clearwater east and clearwater west craters located in quebec canada impact melts from clearwater east have 187 os 188 os ratios of 0 1281 0 1285 these values indicate a significant meteoritic component which exceeds that in impact melts at all terrestrial craters studied to date except morokweng such findings align with earlier results from chromium isotopes and platinum group elements in contrast impact melts from clearwater west have 187 os 188 os ratios between 6 604 and 59 12 these highly radiogenic ratios are indistinguishable from the 187 os 188 os ratios in country rocks hence osmium isotopes provide no evidence for a meteoritic component in impact melts at clearwater west the clearwater craters formed in almost identical targets therefore target effects cannot readily explain the stark difference between the two clearwater craters if melt sheet heterogeneity is similar at the two craters the probability that melts at clearwater west host an undetected chondritic component is 1 may best explain the unusually strong meteoritic signature although the signature or its nondetection at each crater may be related to asymmetric preservation of the impactor component the results presented here provide further evidence that clearwater east and clearwater west were temporally separate impact events

north atlantic deep water export to the southern ocean over the past 14 myr evidence from nd and pb isotopes in ferromanganese crusts the intensity of north atlantic deep water nadw production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate here we present a new approach to reconstruct the overall strength of nadw export from the north atlantic to the southern ocean over the past 14 myr applying the deep water nd and pb isotope composition as recorded by ferromanganese crusts and nodules we present the first long term nd and pb isotope time series for deep southern ocean water masses which are compared with previously published time series for nadw from the nw atlantic ocean these data suggest a continuous and strong export of nadw or a precursor of it into the southern ocean between 14 and 3 ma an increasing difference in nd and pb isotope compositions between the nw atlantic and the southern ocean over the past 3 myr gives evidence for a progressive overall reduction of nadw export since the onset of northern hemisphere glaciation nhg the nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37 depending on location

hydrology of the karst aquifer at the experimental site of guilin in southern china abstract the experimental site of guilin is located near the village of yaji at the border of the lijiang plain province of guangxi southern china within upper devonian limestones and dolomitic limestones a karst has developed in accordance with intense fracturing resulting from mesozoic and tertiary tectonic episodes its morphology is characterized by two major types of karst a cone karst peak cluster area bounded by the lijiang plain which comprises a tower or mogote karst peak forest area groundwater discharges from a perennial spring discharge up to 7 m3 s 1 and three intermittent springs discharge less than 5 m3 s 1 some observation boreholes have been drilled on the peak cluster area dolines and on the lijiang plain in front of the spring tracing experiments in the dolines showed that the dolines are connected with the springs the apparent flow velocity ranges between 4 and 180 m h 1 analyses of storm responses of the perennial spring and the variability in time of 18o concentration pointed out the important role played by the flows occurring in the subcutaneous zone of the peak cluster area

preservation of seawater sr and nd isotopes in fossil fish teeth bad news and good news abstract we analyzed 87sr 86sr ratios in foraminifera pore fluids and fish teeth for samples ranging in age from eocene to pleistocene from four ocean drilling program sites distributed around the globe site 1090 in the cape basin of the southern ocean site 757 on the ninetyeast ridge in the indian ocean site 807 on the ontong java plateau in the western equatorial pacific and site 689 on the maud rise in the southern ocean sr isotopic ratios for dated foraminifera consistently plot on the global seawater sr isotope curve for sites 1090 757 and 807 sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values as are values for fossil fish teeth in contrast pore fluid 87sr 86sr values at site 689 are more radiogenic than contemporaneous seawater and the corresponding fish teeth also record more radiogenic values thus sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values furthermore there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve and the associated offset between the fish teeth and the seawater curve these data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange sr with its surroundings during burial and diagenesis therefore sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores but cannot be used to fine tune age models in contrast to the sr isotopic system our nd concentration data combined with published isotopic and rare earth element data suggest that fish teeth acquire nd during early diagenesis while they are still in direct contact with seawater the concentrations of nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids as a result nd isotopes are not altered during burial and later diagenesis therefore fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater nd isotopic compositions from the time of deposition

geochemistry of drill core samples from yaxcopoil 1 chicxulub impact crater mexico the chemical composition of suevites displaced cretaceous target rocks and impactgenerated dikes within these rocks from the yaxcopoil 1 yax 1 drill core chicxulub impact crater mexico is reported and compared with the data from the yucatn 6 y6 samples within the six suevite subunits of yax 1 four units with different chemical compositions can be distinguished a upper lower sorted and upper suevite depth of 795846 m b middle suevite depth of 846861 m c brecciated impact melt rock depth of 861885 m and d lower suevite depth of 885895 m the suevite sequence a b and d display an increase of the cao content and a decrease of the silicate basement component from top to bottom in contrast the suevite of y6 shows an inverse trend the different distances of the yax 1 and y6 drilling sites from the crater center 60 and 47 km respectively lead to different suevite sequences within the cretaceous rocks of yax 1 a suevitic dike depth of 916 m does not display chemical differences when compared with the suevite while an impact melt rock dike depth of 1348 m is significantly enriched in immobile elements a clastic breccia dike depth of 1316 m is dominated by material derived locally from the host rock while the silicate rich component is similar to that found in the suevite significant enrichments of the k2o content were observed in the yax 1 suevite and the impact generated dikes all impactites of yax 1 and y6 are mixtures of a crystalline basement and a carbonate component from the sedimentary cover an anhydrite component in the impactites is missing yax 1 or negligible y6

discovery of extraterrestrial component carrier phases in archean spherule layers implications for estimation of archean bolide sizes in the barberton greenstone belt bgb of south africa four distinct spherule horizons s1 s4 with ages between ca 3 5 and 3 2 ga are among the oldest records of large asteroid impacts on earth spherules in these layers are interpreted as molten impact ejecta condensation products from impact plumes or impact ejecta melted during atmospheric reentry past research has shown that some spherule layer samples from the bgb carry ultrahigh abundances of siderophile elements including platinum group elements pges in some cases as much as four times the chondritic abundances inferences for very large projectile sizes responsible for these impact layers have been made on the strength of these data drilling by the international continental scientific drilling program has yielded 4 new spherule layer intersections in a 22 cm long core segment scanning electron microscopy energy dispersive x ray spectrometry at high spatial resolution identified local areas of pge enrichment with ni rich chromium spinel ni cr spinel clusters they are associated with pge rich metal alloy and sulfarsenide phases 600 1400 nm in size the metal alloys are interpreted as primary objects that formed during the impact process pge sulfarsenides are the result of secondary alteration by s and as rich fluids thus a micronugget effect caused by pge phases and ni cr spinel is responsible for the anomalously high extraterrestrial component in some spherule layer samples this heterogeneous incorporation of meteoritic components due to primary heterogeneous fallout from the vapor plume must be taken into consideration in any attempt to estimate the global fallout of extraterrestrial components and thus to constrain projectile sizes

use of platinum group elements for impactor identification terrestrial impact craters and cretaceous tertiary boundary abstract this study presents the abundances of ru ir pt pd rh and au platinum group elements pge in the ejecta layer at the cretaceous tertiary boundary and melt rocks from east clearwater lake brent new quebec and lake wanapitei impact craters all believed to have been formed by the impact of chondritic projectiles the objective was to evaluate the pure application of pge interelement ratios e g ru ir for impactor identification to compare the utility of both melt rocks and ejecta deposits for this purpose and to expand the pge database for these craters the similarity of pge interelement ratios within the chondrite and iron meteorite groups precludes their use in the fine classification of impactors of this composition introduction of indigenous pge from country rock may contaminate the original meteoritic signature in addition the extent of pge fractionation during impact and melt sheet cooling and of post sedimentary pge remobilization must be evaluated in each case for east clearwater the pge chondrite normalized plot is flat indicating a chondritic impactor based on ru ir and cr ir ratios a cl or l chondrite is most likely however variation of ratios with depth in the core makes any fine classification of the projectile tenuous for the brent and new quebec craters the flat chondrite normalized pge plot indicates a chondritic impactor but finer classification is precluded by possible post syn depositional pge fractionation at lake wanapitei ni cr and cr ir ratios indicate a ll chondrite impactor wolf et al 1980 but sparse pge data for this chondrite type does not allow further classification of the projectile a flat chondrite normalized pge plot indicates a chondritic rather than an iron impactor at lake wanapitei the global ejecta layer at the cretaceous tertiary boundary has a chondritic pge signature but only when the integrated flux of pge on a global scale is considered individual sites may not show chondritic ratios due to differential pge remobilization resulting from local differences in depositional environment continental vs marine and to vaporization and or condensation pge fractionation occurring during impact the results for melt rocks and the k t ejecta deposit indicate that pge can be used for impactor identification but primarily in combination with other siderophile chalcophile meteoritic elements and their ratios

neogene evolution of atlantic thermohaline circulation perspective from walvis ridge southeastern atlantic ocean 1 we present new nd isotope records from walvis ridge ocean drilling program odp sites 1262 1264 southeastern atlantic spanning the past 24 ma to investigate the neogene evolution of atlantic thermohaline circulation the new data indicate that deepwater nd t values from odp site 1262 decrease from 11 0 at 10 6 ma to 12 5 by 7 3 ma this decrease parallels the nd isotope trends contained in fe mn crust records from the northwestern atlantic however the shift at odp site 1262 4755 m water depth occurred up to 6 ma earlier than the corresponding changes in crust records from the atlantic and earlier than any atlantic site shallower than 2700 m paleowater depth recent interpretations of the rapid decrease in fe mn crust nd nd t ssvalues invoke changes in weathering inputs to the labrador sea region rather than a fundamental change in deepwater convection in the labrador sea however the new evidence for significant depth stratification of the nd isotope signal in the southeastern atlantic between 10 6 and 7 3 ma suggests that the onset of deepwater convection in the labrador sea may have played a role in the deepwater decrease in nd isotopic composition climatic conditions during the middle to late miocene likely favored an increase in the importance of glacially induced mechanical weathering while at the same time promoting deep convection in the labrador sea

re os geochronology of organic rich sediments an evaluation of organic matter analysis methods rhenium and osmium in organic rich sedimentary rocks are dominantly hydrogenous but any nonhydrogenous component will influence the accuracy and precision of the re os date obtained to minimize the influence of any nonhydrogenous re and os we evaluate analysis of isolated organic matter from the whole rock together with whole rock analysis using a cro3 h2so4 digestion medium instead of inverse aqua regia for a black shale unit of the exshaw formation canada this unit previously returned a whole rock re os date of 358 10 ma model 3 geochim cosmochim acta 2002 using inverse aqua regia dissolution organic matter isolated from the whole rock matrix using the hf bf3 technique org geochem 20 1993 249 yields scattered data and a re os date of 449 220 ma model 3 mswd 616 the organic matter analyses show similar 187os 188os values but significantly lower 187re 188os values in comparison to the whole rock analyses we show that the re os systematics of organic matter are altered during chemical isolation and as such we suggest that the hf bf3 method should not be used for re os analysis of organic matter whole rock re os analysis using a cro3 h2so4 digestion medium yields significantly better regression analysis compared with the inverse aqua regia method and the re os data identify two distinct initial 187os 188os values for the sample set separate regressions of these data yield precise dates 366 1 9 6 mswd 2 2 and 363 4 5 6 ma mswd 1 6 model 3 which are indistinguishable from the age constraints for this formation 363 4 0 4 ma u pb monazite comparison of the re os dates obtained from aqua regia and cro3 h2so4 methods suggests that the former may contain nonhydrogenous re and os whereas the cro3 h2so4 method dominantly liberates hydrogenous re os from organic matter allowing for better stratigraphic age determinations and evaluation of the os isotope composition of seawater