strontium isotopes and rare earth elements as tracers of groundwater lake water interactions lake naivasha kenya abstract strontium isotope compositions and rare earth element ree concentrations are presented for groundwater and surface water samples collected from the lake naivasha watershed in the east african rift kenya the chief objective of the study is to test the suitability of rees in conjunction with sr isotopes as tools for investigating groundwater lake water interactions in general the ree concentrations and 87 sr 86 sr ratios support the authors earlier investigations where cl mass balance 18 o d and he isotopes were employed to study groundwater lake water interactions in the naivasha watershed the ree data suggest that a significant amount of the groundwater south of lake naivasha i e 50 85 consists of lake water recharge to the aquifer system specifically mixing calculations conducted using ree data of lake naivasha water and groundwaters indicate that between 70 and 85 of groundwater directly south of the lake is likely lake water these values are somewhat higher than the authors previous estimates determined with conservative stable h isotopes d 50 70 for both cases however the data demonstrate that water originating in lake naivasha contributes significantly to the underlying groundwater flow system hence supporting earlier evidence that the lake s freshness reflects rapid loss of water and dissolved solutes to the local groundwater system overall lake and groundwater sr isotope compositions support seepage of lake water into the underlying aquifer along the lake s south shore the 87 sr 86 sr data also provide additional insight into the geochemical evolution of waters of the lake naivasha watershed indicating that the initial source of sr to these waters is likely chemical weathering reactions involving basaltic rocks within the recharge zones of the watershed along the rift valley flanks furthermore with increasing residence time of groundwaters within the aquifer system and flow down and along the rift valley floor sr isotope compositions of groundwaters become more radiogenic reflecting rock water interactions with chemically differentiated and radiogenic peralkaline rhyolite volcanic rocks the importance of the longer aquifer residence times and radiogenic source rocks is especially apparent for geothermal waters of the olkaria geothermal field that have 87 sr 86 sr ratios i e 0 70747 similar to local comendites

the evolution of climatically driven weathering inputs into the western arctic ocean since the late miocene radiogenic isotope evidence highlights seawater hf nd pb isotopic evolution in the deep arctic ocean of the past 7 myr climatically driven changes in weathering inputs since 4 ma north american laurentide ice sheet runoff controlled the isotopic budget in the canada basin more congruent hf release due to glacial weathering conditions past arctic ocean water masses show larger isotopic differences than today abstract we present the first continuous records of dissolved radiogenic neodymium hafnium and lead isotope compositions of deep waters in the western arctic ocean spanning the time from the late miocene to the present the data were obtained from three hydrogenetic ferromanganese fe mn crusts recovered from seamounts along the northernmost edge of the northwind ridge in the canada basin from water depths of 2200 2400 and 3600 m dating the crusts using cosmogenic 10be documents undisturbed present day growth surfaces and yields growth rates between 27 and 2 2 mm myr the nd hf isotope time series of the three crusts show similar evolutions from endend ehf ehf of 8 5 4 in the oldest parts to 11 5 4 at the surfaces and a pronounced trend to less radiogenic values starting at 4 ma this coincided with a trend of the pb isotope evolution towards more radiogenic 206pb 204pb 207pb 204pb and 208pb 204pb it is inferred that climatically controlled changes in weathering regime and sediment transport along the north american continent were responsible for the major change of the radiogenic isotope composition of the arctic deep water adw in the canada basin based on these records we conclude that weathering inputs from the north american continent linked to enhanced glacial conditions started to increase and to influence the radiogenic isotope composition of adw 4 million years ago and were further intensified at 1 ma these new time series differ markedly from the radiogenic isotope evolution of arctic intermediate water recorded on the lomonosov ridge and suggest that much larger isotopic differences between the water masses of the arctic ocean than today prevailed in the past

constraining erosional input and deep water formation in the north atlantic using nd isotopes many marine radiogenic isotope records show both spatial and temporal variations reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents however changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater the provenance of physically weathered material in the labrador sea constrained through the use of ar ar ages of individual detrital minerals has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the labrador sea a simple box model approach for balancing observed nd isotope variations has been used to constrain the relative importance of localised input in the labrador sea and the subsequent mixing of labrador sea water into north atlantic deep water the long term pattern of erosion and deep water formation around the north atlantic seems to have been a relatively stable feature since 1 5 ma although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of hf and pb isotopes the modelled nd isotopes imply a relative decrease in water mass advection into the labrador sea between 2 4 and 1 5 ma accompanied by a decrease in the rate of overturning possibly caused by an increased freshwater input into the labrador sea

the distribution of rare earth and minor elements in manganese nodules and sediments from the equatorial and s w pacific abstract 62 manganese nodules and 17 associated sediments from the equatorial and s w pacific have been analyzed for a number of elements including the rare earth elements ree by instrumental neutron activation sc co as hf th and ree occur in higher concentrations in s w pacific than in equatorial pacific nodules reflecting the higher iron content of the s w pacific nodules these elements are probably incorporated nondiscriminantly into the iron oxyhydroxide structure by direct sorption from seawater because they are too large to be incorporated into the manganese oxide structure the highest ce la ratios are also found in the s w pacific nodules this may result from the fact that these nodules lie beneath the path of the fast flowing well oxygenated antarctic bottom water aabw which facilitates oxidation of ce to the tetravalent state if so this supports the idea that the ce la ratio of manganese nodules is an important redox indicator negative cerium anomalies were noted for nodules from areas f and g can be interpreted on the same model the ree contents in equatorial pacific siliceous oozes and s w pacific red clays are similar on a carbonate free basis the ce la ratio of the s w pacific red clays is however much higher than that of the equatorial pacific sediments possibly reflecting the preferential oxidation of ce to the tetravalent state beneath the aabw there appears to be no systematic relationship between the ree abundance in the nodules and their associated sediments although absolute ree abundances are higher in nodules than in their associated sediments nodules with the highest ce la ratios are however found on sediments with the highest ce la ratios the principal difference in the ree distribution pattern of the nodules and sediments lies in the well known cerium anomaly which is positive to slightly negative for nodules and always negative for sediments

isotopic abundances inferences on solar system and planetary evolution members of the royal swedish academy ladies and gentlemen in thinking over why i am here today i recalled the story of tom sawyer a character of mark twain s on a beautiful bright saturday morning when all of his friends were playing he appeared by the wall in front of his aunt s house with a bucket of whitewash paint and a long handled brush before him stood about thirty meters of continuous wooden fence three meters tall he dipped his brush and passed it over a plank and then repeated it then he stopped and compared the insignificant whitewashed streak with the far reaching continent of unpainted fence and became melancholy then he took up the brush again and went to work a friend came by and teased him for working on saturday when he could be swimming or playing tom said it wasn t so bad because a boy didn t get the chance to whitewash a fence every day tom took a new brush stroke at the fence and stepped back to note the beauty of the effect his friend got interested and then asked permission to make a stroke or two he then offered tom the core of an apple he had just started to nibble on tom told him that it was doubtful that his friend could help because this was the front fence and that a very good and sophisticated job had to be done possibly only but one child in a thousand possibly two thousand could do it well after this denial his friend just had to try and offered tom the whole apple for a chance to paint then more young friends came around to attempt this challenging task by the end of the afternoon tom was the wealthiest boy in town he had twelve marbles a key that didn t unlock anything a piece of blue glass to look through a tin soldier a dog collar but no dog and lots of other valuable things the fence had been coated three times and if he had not run out of whitewash tom would have bankrupted every kid in the village my presence here is due to an ability to attract young talent to help whitewash the fence the only difference is that we have just started on the job

nd and pb isotope time series from atlantic ferromanganese crusts implications for changes in provenance and paleocirculation over the last 8 myr high resolution nd and pb isotope time series for the last 8 myr are reported for four atlantic ferromanganese crusts dated by 10be 9be chronology these are compared to new high resolution and high precision pb isotope time series and recently published nd isotope time series for two previously studied crusts from the nw atlantic ocean these records allow a more detailed examination of atlantic deepwater variability over the time period of intensification of northern hemisphere glaciation nhg changes in the pb isotope time series started after 3 ma but were most dramatic over the last 1 8 myr coinciding with changes of pb isotopes in the arctic ocean this latter change post dates the intensification of nhg at 3 1 to 2 5 ma and reflects an increase in the input of material eroded from the archean shield of canada and greenland shifts in nd and pb isotope compositions in a crust from the blake plateau occur before 5 ma and most prominent at 8 ma suggest that water masses from either the pacific or southern ocean influenced the isotope composition of this crust the relatively high end values around 8 ma recorded by the blake plateau crust are explained by a contribution of eastward flowing pacific water through the panama gateway into the caribbean sea this high end signal decreased between 8 and 5 ma suggesting that the supply of pacific water into the caribbean became restricted this is earlier than the caribbean seawater salinity increase at 4 2 ma deduced from 18o data and may indicate that there was only a surface water connection between the caribbean and pacific between 5 and 4 2 ma the closure of the panama gateway to intermediate and deep water exchange 200 m depth apparently occurred much earlier than the intensification of northern hemisphere glaciation at 3 1 2 5 ma and cannot therefore have been a direct cause of this climatic change but may as recently argued only have been a necessary precondition

neodymium isotopes in seawater from the barents sea and fram strait arctic atlantic gateways abstract the neodymium concentration c nd and isotopic composition e nd in seawater have been determined in the water column at five sites in the barents sea fram strait area where most of the water exchange between the arctic ocean and the north atlantic takes place in the main arctic ocean inflow branch across the barents sea the concentration and isotopic composition c nd 15 5 pmol kg and e nd 10 8 are similar to those reported for the northeastern nordic seas which is consistent with this region being a source area for the arctic inflow due to the addition of nd from svalbard shelf sediments the c nd in the surface waters above 150 m in the fram strait inflow branch is higher by a factor of 2 and the e nd is shifted to lower values 11 8 in the stratified nansen basin where cold low salinity water overlies warmer atlantic water the c nd and e nd do not vary with the vertical temperature salinity structure but are essentially constant and similar to those of the atlantic inflow throughout the entire water column down to 3700 m depth which indicates that the nd is to a large extent of atlantic origin compared to the atlantic inflow water the nd in the major arctic ocean outflow the fram strait show higher c nd in the surface waters above 150 m and a higher e nd 9 8 throughout the entire water column down to 1300 m depth sources for the more radiogenic nd isotopic composition in deep water of the fram strait outflow most likely involve boundary exchange with sediments on the shelf and slope as the water passes along the canadian archipelago river water is a possible source in the surface water but it also seems likely that pacific water nd modified by interactions on the shelf is an important component in the fram strait surface outflow changes in the relative proportions of inflow of river water and flow of pacific water through the arctic ocean could thus influence the isotopic composition of nd in the north atlantic

nd isotopic excursion across cretaceous ocean anoxic event 2 cenomanian turonian in the tropical north atlantic late cretaceous fish debris from demerara rise exhibits a dramatic positive excursion of 8 nd units during ocean anoxic event 2 oae2 that is superimposed on extremely low nd t values 14 to 16 5 observed throughout the rest of the studied interval the oae2 nd excursion is the largest yet documented in marine sediments and the majority of the shift is estimated to have occurred over nd values on demerara rise are explained as the nd isotopic signature of the south american craton whereas eruptions of the caribbean large igneous province or enhanced mixing of intermediate waters in the north atlantic could have caused the excursion

cape in tropical cyclones abstractconvective available potential energy cape and the vertical distribution of buoyancy were calculated for more than 2000 dropsonde soundings collected by the noaa gulfstream iv aircraft calculations were done with and without the effects of condensate loading entrainment and the latent heat of fusion cape showed larger values downshear than upshear within 400 km of the center consistent with the observed variation of convective intensity the larger downshear cape arose from i higher surface specific humidity ii lower midtropospheric temperature and for entraining cape iii larger free tropospheric relative humidity reversible cape had only one half the magnitude of pseudoadiabatic cape as shown previously reversible cape with fusion closely resembled pseudoadiabatic cape without fusion entrainment had the most dramatic impact entraining cape was consistent with the observed radial distribution of convective intensity displaying the largest values downshear at inner radii with

the large scale evolution of neodymium isotopic composition in the global modern and holocene ocean revealed from seawater and archive data neodymium isotopic compositions 143nd 144nd or end have been used as a tracer of water masses and lithogenic inputs to the ocean to further evaluate the faithfulness of this tracer we have updated a global seawater end database and combined it with hydrography parameters temperature salinity nutrients and oxygen concentrations carbon isotopic ratio and radiocarbon of dissolved inorganic carbon archive end data are also compiled for leachates foraminiferal tests deep sea corals and fish teeth debris from the holocene period 10 000 years at water depths 1500 m property property plots show clear correlations between seawater end and the other variables suggesting that large scale water mass mixing is a primary control of deepwater end distribution at 200 m basin scale seawater t s end diagrams demonstrate the isotopic evolution of different water masses seawater and archive end values are compared using property property plots and t s end diagrams archive values generally agree with corresponding seawater values although they tend to be at the upper limit in the pacific both positive and negative offsets exist in the northern north atlantic applying multiple regression analysis to deep 1500 m seawater data we established empirical equations that predict the main large scale deepwater end trends from hydrography parameters large offsets from the predicted values are interpreted as a sign of significant local regional influence dominant continental influence on seawater and archive end is observed mainly within 1000 km from the continents generally seawater and archive end values form gradual latitudinal trend in the atlantic and pacific at depths 600 m consistent with the idea that nd isotopes help distinguish between northern southern sourced water contributions at intermediate and deep water depths

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

strontium dissolved and particulate loads in fresh and brackish waters the baltic sea and mississippi delta a study was conducted of the isotopic composition and concentration of sr and of major elements in dissolved and suspended loads of fresh and brackish waters the purpose was to establish the contributions of different parent rocks and minerals to sr during weathering and transport and to identify the role of fe mn oxyhydroxides in the redistribution of sr in the water column during the sedimentary cycle studies were conducted on a profile across an oxic anoxic boundary in the baltic and on rivers covering behavior over an annual cycle in general the 87sr 86sr ratios differ between particulate and dissolved loads with more radiogenic sr in the particulate loads these differences are attributed to differential weathering of minerals where high rb sr minerals dominate the particulate load and low rb sr the dissolved load there is broad correlation of 87 sr 86 sr with k al in the suspended load the differences in 87 sr 86 sr between suspended and dissolved load are highly variable and are related to the fe or mn concentration on the particulates in samples with high fe al the difference becomes small a good correlation was found between sr al and fe al or mn al in the particulates both in brackish and fresh waters sr is removed from solution both in rivers and in the baltic sea whenever there is formation of fe mn oxyhydroxide particulates this precipitation greatly diminishes the difference in isotopic composition of the dissolved and suspended loads as the particles containing fe mn oxyhydroxides settle they dissolve in anoxic zones and release sr this provides a mechanism for sr redistribution in the water column sr is thus only quasi conservative in environments where fe mn oxyhydroxides form or dissolve from consideration of the isotopic differences in sr between dissolved and suspended loads it follows that the net sr input depends upon weathering characteristics of the contributing mineral phases changes in weathering mechanisms due to climate change may cause sr isotopic shifts in the marine environment

the assessment of ree patterns and 143nd 144nd ratios in fish remains abstract the ree content and isotopic composition of sr and nd have been determined in fish teeth ranging in age from the trias to the present and from various localities mostly around the atlantic these measurements have been carried out on selachian and teleost remains from the same locality in togo and show no appreciable difference which suggests with the help of a mass balance calculation of the ce anomaly that diagenetic effects are not responsible for the ree enrichment of biogenic phosphates one group of fossil teeth has about 3 times the ree abundances of shale and a shale normalized pattern with a minimum at sm it is thought to reflect deposition in the open sea environment a second group has ree concentration about 10 times higher than the first group with either a regular light ree enrichment or more frequently a maximum in the middle ree both being probably indicative of deposition in estuarine or near shore conditions the shape of the ree spectra and the size of the ce anomaly can be used semi quantitatively to determine the depth of deposition the results presented here on late cretaceous eocene fish teeth samples from morocco reflect an increasing influx of deep waters with a lowla yb ratio and strong negative ce anomaly which agrees well with the evolution of sediment chemistry and microfauna associations in contrast nd is typical of the water mass in which the fish debris decayed examples of nearly isolated basins identified with nd isotopes include the south atlantic prior to the lutetian nd 13 5 the miocene persian gulf nd 3 1 and bolivia during the late cretaceous nd 12 8 togo and guinea bissau results suggest that in the south atlantic the meridional oceanic circulation had not started before 45 ma ago combination of ree and nd data suggests that the assignment of jurassic cretaceous samples measured so far to open sea water masses is still ambiguous

cycling of dissolved rare earth elements in chesapeake bay the measurement of dissolved rare earth elements ree in the surface waters water column of anoxic basins and pore waters in chesapeake bay has provided new insights to the biogeochemistry and estuarine chemistry of ree all dissolved ree from the riverine source show large scale removal in the lower salinity zone 0 10 the shale normalized pattern of dissolved susquehanna river water is opposite in form to that of surface sediments in the bay the former is enriched in heavy ree hree while the latter are enriched in light ree lree neither component has a flat pattern normally assumed for river transported ree to the ocean the dissolved lree i e la ce nd sm and eu are enriched 3 to 9 times in the oxygen depleted deep waters over their concentrations in the oxic surface waters in contrast hree er yb and lu are slightly depleted all ree concentrations in the two surface 0 2 cm pore waters are greatly enriched 8 17 times 43 times for ce relative to oxygen depleted bottom waters and have relative abundances opposite to those of their sediments while ce has a positive anomaly in the pore waters negative anomalies exist in the oxygen depleted bottom waters the ree are participating in a set of complex biogeochemical cycles within the water column and surface sediments fractionation of ree during these cycles leads to the preferential enrichment of lree in the seasonally oxygen depleted bottom waters it is proposed that this fractionation is coupled to redox cycles of mn and fe and the interaction of dissolved ree with suspended particles and surficial sediments

spatial distribution of dissolved neodymium and end in the bay of bengal role of particulate matter and mixing of water masses abstract the concentration and isotope composition of dissolved nd have been measured in the water column along an 87 e transect gio1 section of international geotraces program in the bay of bengal bob to investigate the effect of water mass mixing and nd release from particulate matter in determining these properties the concentration of nd in surface waters of the bob shows a north south decreasing non linear trend 46 to 22 pmol kg with salinity whereas its depth profiles typically show a high value in surface waters a minimum 15 to 23 pmol kg in the shallow subsurface 50 200 m followed by a gradual increase with depth the nd concentration of bob waters is generally higher than that in nearby oceanic basins on the other hand the e nd values in the bob are less radiogenic compared to those reported for other regions of the global oceans except baffin bay the north atlantic subpolar gyre and the niger delta margin and show a greater variation in the upper water column surface waters of the southernmost profile 6 n show a more radiogenic e nd value 8 which decreases to 15 in the northernmost profile 20 n close to the values for dissolved and particulate phases of the ganga brahmaputra g b rivers this latitudinal trend is most likely a result of variations in mixing proportion between the more radiogenic indonesian throughflow surface waters iw and unradiogenic bob low salinity water the former s signature being more clearly discernible in surface waters of the two southernmost profiles 6 n and 8 5 n attempts to balance the nd budget in the water column based on an inversion model suggest that in addition to water masses other source s is required the strength of which is estimated to vary from 1 to 65 of the measured nd concentration the calculations also show that the e nd of this additional source s has to be in the range of 16 2 typical of g b river sediments these observations coupled with the north south distribution of dissolved nd and e nd indicate that this additional source is release from particulate phases supplied by the g b river system the calculations also bring out the presence of hot spots of nd release excess nd near the sediment water interface along the northern slope of the bay indicating supply of nd from continental margin sediments this study underscores the significant role of dissolved particulate nd from the ganga brahmaputra river system in contributing to the dissolved nd budget of the global oceans

influence of the mediterranean outflow on the isotopic composition of neodymium in waters of the north atlantic the isotopic composition of neodymium in the water column of the eastern north atlantic near the strait of gibraltar has been determined for several depths the data show that the mediterranean outflow results in a significant shift in e nd 0 toward more radiogenic values of 143 nd 144 nd in the water column at a 1000 m depth this corresponds to a depth in the neighborhood of the salinity maximum associated with the mediterranean outflow the core of the mediterranean outflow gives e nd 0 9 8 as compared to e nd 0 12 in overlying and underlying waters demonstrating that the mediterranean waters are distinct from the atlantic from mixing considerations we estimate that pure mediterranean waters have e nd 0 6 possible sources of this relatively radiogenic nd could be from drainage of young continental terranes or the injection of remobilized nd from deep sea sediments that have a young radiogenic volcanic component new data from a depth profile in the western atlantic is presented comparison of nd data for the eastern north atlantic with that for the western north atlantic shows fundamental differences in the water column structures for e nd 0 while both regions show a pronounced maximum in e nd 0 the western basin maximum occurs at the near surface rather than at 1000 m in addition deep waters of the eastern basin are found to be more radiogenic than the western basin these differences indicate several sources of isotopically distinct nd in the north atlantic the deep waters of the north atlantic 1000 m have the lowest values of e nd 0 measured in the oceans we believe that the source of these low e nd 0 values which we associate with north atlantic deep water is either from freshwater drainage off the precambrian shields of north america and asia into the arctic ocean or from the injection of older continentally derived ree from deep sea sediments sm and nd concentrations are found to increase with depth and e nd 0 changes with depth indicating both vertical and lateral transport processes from different sources this suggests a surface source of nd and injection of ree into the water column from deep sea sediments or large scale bottom currents with high ree concentrations

neodymium isotope evolution of nw tethyan upper ocean waters throughout the cretaceous neodymium isotope compositions of twenty four fish teeth nineteen from the nw tethys and five from different locations within the tethys are interpreted to reflect the evolution of tethyan upper ocean water composition during the cretaceous and used to track changes in erosional inputs to the nw tethys and in oceanic circulation throughout the cretaceous the rather high end up to 7 6 of the nw tethyan upper ocean waters recorded from the late berriasian to the early aptian and the absence of negative excursions during this interval support the presence of a permanent westward flowing tethys circumglobal current tcc this implies that temperature variations during this time period inferred from the oxygen isotope analysis of fish tooth enamel were not driven by changes in surface oceanic currents but rather by global climatic changes the results presented here represent a significant advance over previously published cretaceous seawater nd isotope records our newly acquired data now allow the identification of two stages of low end values in the nw tethys during the early albian middle albian interval down to 10 and the santonian early campanian down to 11 4 which alternate with two stages of higher end values up to 9 during the late albian turonian interval and the maastrichtian used in conjunction with the oxygen isotope record the fluctuations of end values can be related to major climatic oceanographic and tectonic events that appeared in the western tethyan domain d 2005 elsevier b v all rights reserved

osmium isotope variations in the oceans recorded by fe mn crusts this study presents osmium os isotope data for recent growth surfaces of hydrogenetic ferromanganese fe mn crusts from the pacific atlantic and indian oceans in general these data indicate a relatively uniform os isotopic composition for modern seawater but suggest that north atlantic seawater is slightly more radiogenic than that of the pacific and indian oceans the systematic difference in the os isotopic composition between the major oceans probably reflects a greater input of old continental material with a high re os ratio in the north atlantic ocean consistent with the distribution of nd and pb isotopes this spatial variation in the os isotope composition in seawater is consistent with a residence time for os of between 2 and 60 kyr indian ocean samples show no evidence of a local source of radiogenic os which suggests that the present day riverine input from the himalaya tibet region is not a major source for os recently formed fe mn crusts from the tag hydrothermal field in the north atlantic yield an os isotopic composition close to that of modern seawater which indicates that in this area the input of unradiogenic os from the hydrothermal alteration of oceanic crust is small however some samples from the deep pacific 4 km possess a remarkably unradiogenic os isotope composition 187 os 186 os ratios as low as 4 3 the compositional control of os incorporation into the crusts and mixing relationships suggest that this unradiogenic composition is most likely due to the direct incorporation of micrometeoritic or abyssal peridotite particles rather than indicating the presence of an unradiogenic deep water mass moreover this unradiogenic signal appears to be temporary and local and has had little apparent effect on the overall evolution of seawater these results confirm that input of continental material through erosion is the dominant source of os in seawater but it is not clear whether global os variations are due to the input of mantle or meteoritic material or simply indicate that the continental source itself is not uniform 1999 elsevier science b v all rights reserved

weathering versus circulation controlled changes in radiogenic isotope tracer composition of the labrador sea and north atlantic deep water geological reconstructions and general circulation models suggest that the onset of both northern hemisphere glaciation 2 7 myr ago and convection of labrador sea water lsw were caused by the closure of the panama gateway 4 5 myr ago time series data that have been obtained from studies of ferromanganese crusts from the northwestern atlantic suggest that radiogenic isotopes of intermediate ocean residence time pb and nd can serve as suitable tracers to reconstruct these events however it has been unclear until now as to whether the changes that have been observed in isotope composition at this time are the result of increased thermohaline circulation or due to the effects of increased glacial weathering in this paper we adopt a box model approach to demonstrate that the shifts in radiogenic isotope compositions are unlikely to be due to changes in convection in lsw but can be explained in terms of increases of erosion levels due to the glaciation of greenland and canada furthermore we provide experimental evidence for the incongruent release of a labile fraction of strongly radiogenic pb and nonradiogenic nd from continental detritus eroding into the labrador sea this can be attributed to the glacial weathering of old continents and accounts for the paradox that one of the areas of the world most deficient in radiogenic pb should provide such a rich supply of radiogenic pb to the oceans an important general conclusion is that the compositions of radiogenic isotopes in seawater are not always a reflection of their continental sources perhaps more importantly the transition from chemical weathering to mechanical erosion is likely to result in significant variations in radiogenic tracers in seawater

rare earth element distribution in lake tyrrell groundwaters victoria australia abstract the rare earth element ree geochemistry of the saline to hypersaline acidic brines of lake tyrrell victoria australia were analyzed in order to determine the relative importance of concentration and modification processes in the lake system several types of brines were identified on the basis of different ree patterns and concentrations regional groundwater flowing into lake tyrrell yields the highest concentrations of ree while a transitional water group is identified on the basis of lower ree concentrations a third water group the reflux brine is characterized by extremely low ree concentrations the ree patterns suggest that ree are introduced to the lake tyrrell system by the regional groundwater which has concentrated ree from the aquifer material in its acidic waters eventually ree are removed from the evolving water mass as higher levels of ph are reached the data of the study strongly suggest that ree are scavenged from solution by fe oxyhydroxide phases which precipitate as the ph of the system rises water rock interactions probably control ph in the lake system and therefore ultimately control the concentration of ree in solution in this system our results are directly correlated with studies of hydrothermal vents and geothermal solutions which have shown the concentration of ree in solution to be dominantly controlled by ph

the isotopic composition of neodymium in the north pacific abstract we have determined the isotopic composition of neodymium in two water column profiles in the western north pacific and in bottom waters from three other locations in the north pacific the vertical profiles reveal that the water column is stratified with respect to isotopic composition mid depths associated with pacific deep water are uniform having nd 0 3 shallow waters are variable but deep waters are less radiogenic having md 0 4 4 to 5 in the western basin the more negative bottom waters in the western north pacific provide evidence for the advective transport of rare earth elements from antarctic sources to this region bottom waters in the eastern north pacific are more radiogenic nd 0 3 3 to 3 8 indicating very little transport of ree from antarctic sources to this basin overall the isotopic composition of nd in pacific bottom waters appears to be conservative when compared to the silica distribution in spite of evidence for nd removal the findings are generally compatible with other parameters such as temperature salinity and nutrient distributions the presence of nd isotopic signatures associated with antarctic sources in these waters provides evidence for a small component of rare earth elements of north atlantic origin in the bottom waters of the north pacific this is the first tracer evidence to corroborate the suggestion of reid and lynn 1971 that some of the temperature and salinity properties of the deep waters of the north pacific originated in the norwegian and greenland seas

chemical evolution of rare earth elements fractionation between colloidal and solution phases of filtered river water abstract within the dissolved fraction of connecticut river water there is large scale fractionation of rare earth elements between colloidal and solution phases colloidal particles carry a large part of the dissolved ree pool filtration through filters with progressively smaller pore size 0 45 0 22 and 0 025 m results in filtrates with lower absolute concentrations of ree and more fractionated compositions with decreasing pore size the filtrates have shale normalized abundances which become systematically more depleted in the lree relative to the hree hence both the solution and colloidal phases are significantly fractionated with respect to the dissolved fraction these conclusions are consistent with previous studies of ree in rivers estuaries and soils and with surface solution speciation models colloids play an important role in the aquatic geochemistry of rare earth elements they are responsible for the fractionation of ree during the estuarine removal of ree the removal of suspended and colloidal particles from river water leaves the solution phase of river water with compositions of ree as evolved as those of surface seawater hence the evolution of the composition of ree in river water and seawater is significantly influenced by colloid formation during chemical weathering on the continents

balancing the global oceanic neodymium budget evaluating the role of groundwater the distinctly different end 0 values of the atlantic indian and pacific oceans requires that the residence time of nd in the ocean i e nd be on the order of or less than the ocean mixing time of 500 1500 yr however estimates of nd based on river influxes range from 4000 to 15 000 yr thus exceeding the ocean mixing time in order to reconcile the oceanic nd budget and lower the residence time by roughly a factor of 10 an additional as yet unidentified and hence missing nd flux to the ocean is necessary dissolution of materials deposited on continental margins has previously been proposed as a source of the missing flux in this contribution submarine groundwater discharge sgd is examined as a possible source of the missing nd flux neodymium concentrations n 730 and end 0 values n 58 for groundwaters were obtained from the literature in order to establish representative groundwater values mean groundwater nd concentrations and end 0 values were used along with recent estimates of the terrestrial freshwater component of sgd 6 of river discharge on a global basis to test whether groundwater discharge to the coastal oceans could account for the missing flux employing mean nd concentrations of the compiled data base i e 31 8 nmol kg for all 730 analyses and 11 3 nmol kg for 141 groundwater samples from a coastal aquifer the global terrestrialderived sgd flux of nd is estimated to range between 2 9 10 7 and 8 1 10 7 mol yr these estimates are of the same order of magnitude and within a factor of 2 of the missing nd flux i e 5 4 10 7 mol yr applying the sgd nd flux estimates the global average end 0 of sgd is predicted to be 9 1 which is similar to our estimate for the missing nd flux 9 2 and in agreement with the mean s d end 0 measured in groundwaters i e end 0 8 9 4 2 the similarities in the estimated sgd nd flux and corresponding end 0 values to the magnitude and isotope composition of the missing nd flux are compelling and suggest that discharge of groundwater to the oceans could account for the missing nd flux future investigations should focus on quantifying the nd concentrations and isotope compositions of groundwater from coastal aquifers from a variety of coastal settings as well as the important geochemical reactions that effect nd concentrations in subterranean estuaries in order to better constrain contributions of sgd to the oceanic nd budget

isotopic composition of neodymium in waters from the drake passage the isotopic composition of neodymium has been determined in seawaters from the drake passage the antarctic circumpolar current which controls interocean mixing flows through this passage the parameter e nd 0 which is a function of the ratio of neodymium 143 to neodymium 144 is found to be uniform with depth at two stations with a value which is intermediate between the values for the atlantic and the pacific and indicates that the antarctic circumpolar current consists of about 70 percent atlantic water cold bottom water from a site in the south central pacific has the neodymium isotopic signature of the waters in the drake passage by using a box model to describe the exchange of water between the southern ocean and the ocean basins to the north together with the isotopic results an upper limit of approximately 33 million cubic meters per second is calculated for the rate of exchange between the pacific and the southern ocean concentrations of samarium and neodymium were also determined and found to increase approximately linearly with depth these results suggest that neodymium may be a valuable tracer in oceanography and may be useful in paleo oceanographic studies

evolution of deepwater mixing and weathering inputs in the central atlantic ocean over the past 33 myr the isotopic composition of nd in present day deep waters of the central and northeastern atlantic ocean is thought to fingerprint mixing of north atlantic deep water with antarctic bottom water the central atlantic romanche and vema fracture zones are considered the most important pathways for deep water exchange between the western and eastern atlantic basins today we present new nd isotope records of the deepwater evolution in the fracture zones obtained from ferromanganese crusts which are inconsistent with simple water mass mixing alone prior to 3 ma and require additional inputs from other sources the new pb isotope time series from the fracture zones are inexplicable by simple mixing of north atlantic deep water and antarctic bottom water for the entire past 33 myr the distinct and relatively invariable nd and pb isotope records of deep waters in the fracture zones appear instead to have been controlled to a large extent by contributions from saharan dust and the orinoco amazon rivers thus the previously observed similarity of nd and pb isotope time series from the western and eastern north atlantic basins is better explainable by direct supply of labrador seawater to the eastern basin via a northern pathway rather than by advection of north atlantic deep water via the romanche and vema fracture zones

a sr nd isotopic study of sand sized sediment provenance and transport for the san francisco bay coastal system abstract a diverse suite of geochemical tracers including 87sr 86sr and 143nd 144nd isotope ratios the rare earth elements rees and select trace elements were used to determine sand sized sediment provenance and transport pathways within the san francisco bay coastal system this study complements a large interdisciplinary effort barnard et al 2012 that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine coastal setting sand sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources fluvial and rock throughout the bay adjacent coast and beaches due to their intrinsic geochemical nature 143nd 144nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the pacific ocean for example nd isotopes confirm that the predominant source of sand sized sediment to suisun bay san pablo bay and central bay is the sierra nevada batholith via the sacramento river with lesser contributions from the napa and san joaquin rivers isotopic ratios also reveal hot spots of local sediment accumulation such as the basalt and chert deposits around the golden gate bridge and the high magnetite deposits of ocean beach sand sized sediment that exits san francisco bay accumulates on the ebb tidal delta and is in part conveyed southward by long shore currents broadly the geochemical tracers reveal a complex story of multiple sediment sources dynamic intra bay sediment mixing and reworking and eventual dilution and transport by energetic marine processes combined geochemical results provide information on sediment movement into and through san francisco bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system e g dike and dam construction as well as those which directly remove sediments from within the bay such as aggregate mining and dredging can have long lasting effects

major and trace elements of river borne material the congo basin the congo river basin is the second largest drainage basin in the world after the amazon the materials carried by its main rivers provide the opportunity to study the products of denudation of a large fraction of the upper continental crust of the african continent this paper presents the chemical composition of the different phases carried in the congo rivers and is followed by a companion paper devoted to the modelling of major and trace elements the congo river between bangui and brazzaville as well as its main tributaries including a few organic rich rivers also called black rivers were sampled during the 1989 high water stage the three main phases suspended load dissolved load and bedload were analysed for twenty five major and trace elements concentrations normalized to the upper continental crust show that in each river suspended sediments and dissolved load are chemical complements for the most soluble elements ca na sr k ba rb and u while these elements are enriched in the dissolved loads they are considerably depleted in the corresponding suspended sediments this is consistent with their high mobility during weathering another type of complementarity is observed for zr and hf between suspended sediments and bedload related to the differential velocity of suspended sediments and zircons which are concentrated in bedloads compared to other rivers absolute dissolved concentrations of ca na sr k ba rb and u are remarkably low surprisingly high dissolved concentrations are found in the congo waters for other trace elements e g rees especially in the black rivers on a world scale these concentrations are among the highest measured in rivers and are shown to be ph dependent for a number of dissolved trace elements the dissolved loads are systematically normalized to the suspended loads for each river in order to remove the variations of the element abundances owing to source rock variations normalized diagrams for rees are presented and extended to the other elements they strongly support the argument that the apparent higher solubility of trace elements in the congo waters is due to the presence in the dissolved load of a colloidal phase as a result of 0 2 m filtration an important result is that these colloids are strongly depleted in fe and al with respect to the other elements finally the comparison of the dissolved suspended and sandy transport fluxes of each element in the congo basin rivers shows that although the proportions of for example the rees in the dissolved loads of the majority of the congo basin rivers is close to 10 of the total transport flux up to 80 of the rees are transported by the so called dissolved load in the black rivers

water mass circulation on demerara rise during the late cretaceous based on nd isotopes abstract circulation in the north atlantic during the late cretaceous has implications for poleward heat transport and nutrient distribution during an extreme greenhouse interval with episodes of ocean anoxia nd isotopes of fossil fish teeth and debris represent one of the few water mass tracers that can be used to reconstruct deep ocean circulation we present nd isotopic data interpreted as bottom water values for 290 samples from three ocean drilling program sites on demerara rise sites 1258 1260 and 1261 along with 102 analyses from four other north atlantic sites cape verde goban spur bermuda rise and blake nose that provide additional geographic and bathymetric control our results confirm the presence of a water mass with low end values 14 to 17 that are believed to be influenced by continental material during local water mass formation at low latitudes this demerara bottom water dbw is the primary water mass in the region from the cenomanian to coniacian and from the late campanian through early maastrichtian following a hiatus of 10 my a positive 8 end unit excursion occurs during ocean anoxic event 2 oae2 that cannot be explained by changes in weathering inputs diagenesis or magmatic sources of nd instead it appears to represent an influx of bottom waters sourced from the tethys or north atlantic this replacement of dbw during oae2 argues for decreased production of dbw or enhanced production of tethys north atlantic waters during peak greenhouse conditions from the late campanian through early maastrichtian dbw becomes the only water mass recorded at demerara rise and it appears to expand to abyssal depths at cape verde in the campanian this water mass is ultimately replaced by waters that appear to be sourced from the north atlantic starting in the late maastrichtian observed variations in circulation in the tropical north atlantic during the late cretaceous can account for extensive deposition of black shales in the region prior to the hiatus as well as local warming during a global cooling event in the maastrichtian

the distribution of neodymium isotopes in arctic ocean basins nd concentration and isotope data have been obtained for the canada amundsen and makarov basins of the arctic ocean a pattern of high nd concentrations up to 58 pm at shallow depths is seen throughout the arctic and is distinct from that generally seen in other oceans where surface waters are relatively depleted a range of isotopic variations across the arctic and within individual depth profiles reflects the different sources of waters the dominant source of water and so nd is the atlantic ocean with lesser contributions from the pacific and arctic rivers radiogenic isotope nd signatures up to epsilon nd 6 5 can be traced in pacific water flowing into the canada basin waters from rivers draining older terrains provide very unradiogenic nd down to epsilon nd 14 2 that can be traced in surface waters across much of the eurasian basin a distinct feature of the arctic is the general influence of the shelves on the nd concentrations of waters flowing into the basins either from the pacific across the chukchi sea or from across the extensive siberian shelves water shelf interaction results in an increase in nd concentration without significant changes in salinity in essentially all waters in the arctic through processes that are not yet well understood in estuarine regions other processes modify the nd signal of freshwater components supplied into the arctic basin and possibly also contribute to sedimentary nd that may be subsequently involved in sediment water interactions mixing relationships indicate that in estuaries nd is removed from major river waters to different degrees deep waters in the arctic are higher in nd than the inflowing atlantic waters apparently through enrichments of waters on the shelves that are involved in ventilating the deep basins these enrichments generally have not resulted in major shifts in the isotopic compositions of the deep waters in the makarov basin epsilon nd similar to 10 5 but have created distinctive nd isotope signatures that were found near the margin of the canada basin with epsilon nd similar to 9 0 the deep waters of the amundsen basin are also distinct from the atlantic waters with epsilon nd 12 3 indicating that there has been limited inflow from the adjacent makarov basin through the lomonosov ridge c 2009 elsevier ltd all rights reserved

neodymium isotopes and concentrations in caribbean seawater tracing water mass mixing and continental input in a semi enclosed ocean basin we present the first full water column nd isotope end and concentration data for caribbean seawater as well as for stations close to the orinoco river mouth and in the florida straits the surface inflow into the southeastern caribbean via the guyana current is characterized by an endsignature of 10 9 which is a consequence of the mixing of relatively unradiogenic endsignatures 13 6 supplied by the orinoco river with contributions from the amazon river 10 despite the proximity to land sub surface and intermediate waters within the caribbean largely retain the endsignatures of their source water masses in the atlantic in contrast the deep waters of the caribbean show endsignatures at least 3 endunits more radiogenic than the inflowing upper north atlantic deep water unadw a endshift from 13 to 9 7 can be explained by addition of radiogenic nd to the deep caribbean through weathering inputs from land however in order to balance such large shifts in endwith at the same time modest increases in nd concentrations nd must also be removed from seawater within the basin it is suggested that the long residence time of deep waters in the caribbean allows significant interaction of seawater with sinking particles and seafloor sediments resulting in more radiogenic values these findings have implications for the use of endas a proxy for paleocirculation in restricted basins in which the residence times of the deep waters are long

radiogenic isotopic compositions of low concentration dust and aerosol from the gisp2 ice core abstract we have produced a record of radiogenic isotope compositions of particulate and soluble dust fractions from the gisp2 ice core from basal ice to the surface for each respective dust fraction we measured sr and nd isotope values to constrain the provenance of mineral dust and sea salt aerosol transported to the greenland ice sheet we have produced high precision measurements of end values on sub ng quantities of nd in ice core samples via tims with 1013 ohm resistors the range of measured end values of soluble material 12 9 2 6 to 7 3 0 9 is interpreted to represent sea salt aerosol based on sr isotope compositions that resemble seawater values 0 711007 0 000030 to 0 709416 0 000072 therefore the end potentially provides important insights to the atmospheric circulation patterns at high latitudes at least through mis 5 we compare end values of surface seawater from ocean basins and deltas at high latitudes to alternating relatively radiogenic and unradiogenic end at gisp2 we suggest these changes represent transitions between a climate system dominated by enhanced and persistent arctic oscillation positive anomalies as determined from sea level and ocean bottom pressure measurements and a state representative of modern atmospheric circulation which typically exhibits either negative anomalies or none altogether

patterns of ice rafted detritus in the glacial north atlantic 40 55 n the observation by heinrich 1988 that during the last glacial period much of the input of ice rafted detritus to the north atlantic sediments may have occurred as a succession of catastrophic events rekindled interest on the history of the northern ice sheets over the last glacial period in this paper we present a rapid method to study the distribution of these events both in space and time using whole core low field magnetic susceptibility we report on approximately 20 cores covering the last 150 to 250 kyr well defined patterns of ice rafted detritus appear during periods of large continental ice sheet extent although these are not always associated within their maxima most of the events may be traced across the north atlantic ocean for the six most recent heinrich layers hl two distinct patterns exist hl1 hl2 hl4 hl5 are distributed along the northern boundary of the glacial polar front over most of the north atlantic between 40 and 50 n hl3 is more restricted to the central and eastern part of the northern atlantic the nd sr isotopic composition of the material constituting different heinrich events indicates the different provenance of the two patterns hl3 has a typical scandinavia arctic icelandic young crust signature and the others have a large component of northern quebec and northern west greenland old crust material these isotopic results obtained on core su 9008 from the north american basin are in agreement with the study by jantschik and huon 1992 who used k ar dating of silt and clay size fractions of an eastern basin core me 68 89 these data confirm the large spatial scale of these events and the enormous amount of ice rafted detritus they represent

seasonal dissolved rare earth element dynamics of the amazon river main stem its tributaries and the curuai floodplain we present a comprehensive dissolved rare earth element ree data set for the amazon river and its main tributaries rio negro solimoes and madeira as well as the curuai floodplain the two year time series show that ree vary seasonally with discharge in each of the tributaries and indicate a hydrologically dominated control upper crust normalized ree patterns are relatively constant throughout the year with ce ce anomalies being positively related to discharge we propose revised annual dissolved ree fluxes to the surface atlantic ocean based on an integration of the seasonal data for nd 0 22 m this results in an average flux of 607 43 t yr which is at least 1 6 times larger than the previous estimate of 374 t yr 0 45 m based on low water stage data moreover during the high water season the maximum nd flux measures 1277 t yr 1 constituting 30 of the required flux to the atlantic ocean tachikawa et al 2003 consequently a smaller contribution of nd from atmospheric and river particle desorption is required than was previously suggested a mass balance of amazon tributaries and observed fluxes at obidos indicates that dissolved lree behave quasi conservatively conversely the hree mass balance presents a deficit during the high water stages which could be related to the passage of water through the floodplain system accompanied by solid dissolved phase transfer

high precision radiogenic strontium isotope measurements of the modern and glacial ocean limits on glacial interglacial variations in continental weathering existing strontium radiogenic isotope 87sr 86sr measurements for foraminifera over quaternary glacial interglacial climate cycles provide no evidence for variations in the isotope composition of seawater at the 9 13 ppm level of precision however modelling suggests that even within this level of uncertainty significant up to 30 variations in chemical weathering of the continents are permitted accounting for the longer term rise in 87sr 86sr over the quaternary and the apparent imbalance of sr in the oceans at the present day this study presents very high precision 87sr 86sr isotope data for modern seawater from each of the major oceans and a glacial interglacial seawater record preserved by planktic foraminifera from ocean drilling program odp site 758 in the north east indian ocean strontium isotope 87sr 86sr measurements for modern seawater from the atlantic pacific and indian oceans are indistinguishable from one another 87sr 86sr 0 7091792 0 0000021 n 17 at the level of precision obtained in this study 4 9 ppm 2 this observation is consistent with the very long residence time of sr in seawater and underpins the utility of this element for high precision isotope stratigraphy the 87sr 86sr seawater record preserved by planktic foraminifera shows no resolvable glacial interglacial variation 87sr 86sr 0 7091784 0 0000035 n 10 and limits the response of seawater to variations in the chemical weathering flux and or composition to 4 9 ppm or less calculations suggest that a variation of 12 around the steady state weathering flux can be accommodated by the uncertainties obtained here the new data cannot accommodate a short term weathering pulse during de glaciation although a more a diffuse weathering pulse accompanying protracted ice retreat is permissible however these results still indicate that modern weathering fluxes are potentially higher than average over the quaternary and such variations through glacial cycles can also account for the longer term rise in 87sr 86sr over this time interval the very high precision measurements made for the marine 87sr 86sr record in this study place clear limits on the magnitude and timing of changes in the chemical weathering flux during glacial interglacial cycles further constraints must be sought from even higher precision measurement or elements with shorter residence times in the ocean such as osmium os that have the capacity to respond to short term variations in input

a lead isotopic study of circum antarctic manganese nodules abstract lead isotope ratios in manganese nodules from the circum antarctic ocean display systematic geographical variations eastward in the direction of current movement from south of australia they progressively decrease in the pacific sector and into the western atlantic sector until 30 w from this longitude lead isotope ratios increase in the eastern atlantic sector and reach their highest values in the indian sector near 110 e south of western australia they abruptly decrease these two lead isotope domains correspond closely to the circum antarctic neodymium isotope domains previously recognized by albarede and goldstein 1992 however the intraocean isotopic variations are much clearer for pb than nd reflecting the shorter oceanic residence time of pb 102 y compared with nd 103 y and confirming that pb is a much more sensitive marine tracer throughout the circum antarctic ocean the lead isotopic changes follow the pattern of present day oceanic circulation the pb shows an overall continental signature which is strongest in the indian sector the most probable candidate as the source of the continental signal is north atlantic deep water nadw which enters the circum antarctic in the south atlantic as nadw mixes with circumpolar water lead isotope ratios increase eastward in the indian sector reflecting progressive loss of the pacific derived pb signal the abrupt decrease of lead isotope ratios between the indian and pacific sectors appears to be a consequence of addition of pacific seawater through the pacific lead isotope ratios gradually decrease eastward approaching values of east pacific rise metalliferous sediments ocean ridge basalts and south pacific mn nodules this trend results from an increasing influence of pacific ocean water containing a component derived from pacific volcanism the pacific signature persists into the argentine basin in the southwest atlantic ocean reflecting significant input of water from the drake passage northward into the atlantic the pacific pb component is seen in the atlantic and indian oceans near southern africa as well as in the atlantic and indian sectors of the circum antarctic lead and neodymium isotopes correlate in the atlantic indian sectors but not in the pacific sector reflecting differences in residence times and modes of water mass mixing the renewal of circum antarctic water occurs on a timescale which is short compared to the residence time of nd but long compared to pb as a result dissolved pb is subject to considerable changes over the timescale of circumpolar current movement while nd is less easily affected nadw is added locally in the south atlantic and moves eastward as a water mass as nadw mixes with circumpolar water cpw through the indian sector changes affecting nd pb in nadw and cpw occur in tandem and neodymium and lead isotopes are correlated through the pacific sector gradual addition of pacific seawater occurs over a large region and nd pb relationships are not coupled because simple isotopic mixing systematics are not conserved there neodymium and lead isotopes vary independently the consistency of lead isotope variations with present day ocean bottom water circulation is remarkable considering that the mn nodules as sampled reflect the integrated flux of pb over 105 106 y the oceanic mixing time is 103 y the residence time for pb is 102 y and the circulation time of the circumantarctic ocean is 30 y processes occurring over such different timescales can show such a relationship only if the system is stable over the longest time interval thus on average element sources and ocean circulation through the pleistocene have been similar to the present day despite significant perturbations during glacial periods

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

the formation of labrador sea water part i large scale processes abstract data obtained in the western labrador sea during march 1976 by hudson are analysed to show that new labrador sea water was being formed at this time on the basis of hydrographic and moored current meter data it is hypothesized that a 200 km scale cyclonic gyre forms in winter in the western labrador sea and that this gyre retains the developing deep mixed layers in this general area long enough for the transformation to labrador sea water to take place using a model it is demonstrated that water columns found along the western boundary of the labrador sea can be modified by cooling evaporation and mixing to form deep mixed layers with the properties of labrador sea water approximately 105 km3 of new labrador sea water was formed in 1976 an estimate that is consistent with earlier estimates of mean annual production rates this water 2 9 c 34 84 is some 0 6 c cooler and 0 06 fresher than that defined by lazier 1973 from his data collected in 1966 the variation of labrador sea water

rock anelasticity due to patchy saturation and fabric heterogeneity a double double porosity model of wave propagation heterogeneity of rock s fabric can induce heterogeneous distribution of immiscible fluids in natural reservoirs since the lithological variations mainly permeability may affect fluid migration in geological time scales resulting in patchy saturation of fluids therefore fabric and saturation inhomogeneities both affect wave propagation to model the wave effects attenuation and velocity dispersion we introduce a double double porosity model where pores saturated with two different fluids overlap with pores having dissimilar compressibilities the governing equations are derived by using hamilton s principle based on the potential energy kinetic energy and dissipation functions and the stiffness coefficients are determined by gedanken experiments yielding one fast p wave and four slow biot waves three examples are given namely muddy siltstones clean dolomites and tight sandstones where fabric heterogeneities at three different spatial scales are analyzed in comparison with experimental data in muddy siltstones where intrapore clay and intergranular pores constitute a submicroscopic double porosity structure wave anelasticity mainly occurs in the frequency range 104 107 hz while in pure dolomites with microscopic heterogeneity of grain contacts and tight sandstones with mesoscopic heterogeneity of less consolidated sands it occurs at 103 107 hz and 101 103 hz seismic band respectively the predicted maximum quality factor of the fast compressional wave for the sandstone is the lowest approximately 8 and that of the dolomite is the highest the results of the diffusive slow waves are affected by the strong friction effects between solids and fluids the model describes wave propagation in patchy saturated rocks with fabric heterogeneity at different scales and the relevant theoretical predictions agree well with the experimental data in fully and partially saturated rocks

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

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

behavior of sm and nd in a lateritic soil profile a study of lateritic soils and samples of ground and river waters was carried out in the nsimi zoetele a tropical watershed in the southern cameroon the nd isotopic compositions and concentrations of nd and sm were determined it was found that the nd isotopic composition of the river waters was much more radiogenic than the parent rocks and that the nd in the waters is not homogeneous but is carried by different dissolved and complexed components that are not isotopically homogenized the soil profile shows a regular increase in e nd going from the parent rock e nd 36 to e nd 18 near the top of the profile the nd transported in the river is thus not representative of the parent rock but reflects the results of differential weathering of constituent minerals and the redeposition of ree in phosphates and a significant contribution of radiogenic nd from dust the concentration of nd in the river water is far above that found in temperate climate rivers and thus this type of tropical river may play a dominant role in the marine nd and ree budget it is suggested that the correlation of ree with doc is related to doc fixing some dissolved ree but that the ree in solution is governed by other mechanisms no major shifts were found in sm nd however a regular progression from the parent rock through the lateritic profile was found the upper laterite profile shows large almost uniform depletions in all ree below tb and enrichment above complementary behavior was found in the lower part of the section the concentration of nd relative to the immobile elements zr and ti in the laterite is depleted by a factor of 10 th nd and sm are enriched in the lowest zone sampled and must reflect redeposition of ree from the upper part of the weathering section and is associated with phosphate formation it is concluded that the soil evolution involves both differential dissolution of primary phases from the parent rock significant to major input of ree from atmospheric dust from other regions and the formation of diagenetic phases particularly phosphates

neodymium isotopic composition and concentration in the western north atlantic ocean results from the geotraces ga02 section the neodymium nd isotopic composition of seawater is commonly used as a proxy to study past changes in the thermohaline circulation the modern database for such reconstructions is however poor and the understanding of the underlying processes is incomplete here we present new observational data for nd isotopes and concentrations from twelve seawater depth profiles which follow the flow path of north atlantic deep water nadw from its formation region in the north atlantic to the northern equatorial atlantic samples were collected during two cruises constituting the northern part of the dutch geotraces transect ga02 in 2010 the results show that the different water masses in the subpolar north atlantic ocean which ultimately constitute nadw have the following nd isotope characteristics upper labrador sea water ulsw end 14 2 0 3 labrador sea water lsw end 13 7 0 9 northeast atlantic deep water neadw end 12 5 0 6 northwest atlantic bottom water nwabw end 11 8 1 4 in the subtropics where these source water masses have mixed to form nadw which is exported to the global ocean upper nadw is characterised by end values of 13 2 1 0 2sd and lower nadw exhibits values of end 12 4 0 4 2sd while both signatures overlap within error the signature for lower nadw is significantly more radiogenic than the traditionally used value for nadw end 13 5 due to the dominance of source waters from the nordic seas nwabw and neadw comparison between the concentration profiles and the corresponding nd isotope profiles with other water mass properties such as salinity silicate concentrations neutral densities and chlorofluorocarbon cfc concentration provides novel insights into the geochemical cycle of nd and reveals that different processes are necessary to account for the observed nd characteristics in the subpolar and subtropical gyres and throughout the vertical water column while our data set provides additional insights into the contribution of boundary exchange in areas of sediment resuspension the results for open ocean seawater demonstrate at an unprecedented level the suitability of nd isotopes to trace modern water masses in the strongly advecting western atlantic ocean

rare earth elements and sr and nd isotopic compositions of dissolved and suspended loads from small river systems in the vosges mountains france the river rhine and groundwater abstract the aim of this study is to characterize the evolution of the rare earth elements ree in non mature streams from small catchment areas in the vosges mountains downstream to more mature plain rivers including the river rhine the dissolved load ree distribution patterns of the low ph vosges streams are very different from those of high ph plain rivers indicating that different physico chemical parameters control ree transport in these different water systems the plain rivers and groundwater show similar ree distribution patterns with a strong negative ce anomaly and heavy rare earth element hree enrichment in addition the river rhine has a positive gd anomaly which is of anthropogenic origin similar to the world s major rivers the light rare earth element lree enrichment in the plain rivers is mainly ph controlled their sm nd and 143 nd 144 nd isotope ratios are close to average continental crust values this is not the case for the less evolved non mature and low ph vosges streams their high sm nd and 143 nd 144 nd ratios but low 87 sr 86 sr ratios suggest that chemical alteration of accessory middle rare earth element mree enriched minerals such as apatites from rocks in the catchment area control the ree abundances of these waters a comparison of the dissolved load ree distribution patterns with those of the principal lithologies in the corresponding drainage basins illustrates that especially the eu anomalies of the vosges streamlets are strongly lithology dependent leaching experiments indicate that the suspended load is isotopically very inhomogeneous the ree distribution patterns of the suspended load leachates have no similarities with those of the corresponding dissolved load indicating that the leachable reservoir not only contains adsorbed ree but also ree from leachable mineral phases their 143 nd 144 nd sm nd and 87 sr 86 sr ratios support this suggestion being always higher and lower respectively than those of their corresponding dissolved loads they rather point to the presence of relic primary apatite in the leachable portion of the suspended load the flat paas normalized ree distribution patterns the high 87 sr 86 sr and low 143 nd 144 nd isotopic ratios of the corresponding residues suggest secondary silicate phases such as clay minerals in the residual phase of the suspended load leachates and corresponding residual phases define alignments in the sm nd isochron diagram whose slopes define ages ranging between 200 and 390 ma indicating that the mineral phases in the suspended load retain some memory of their primary precursor minerals in the hercynian granitic source rocks

ree fractionation during granite weathering and removal by waters and suspended loads sr and nd isotopic evidence very few studies deal with ree rare earth element mobility within the system soil soil solution streamwater in this article we try to characterize the fractionation and the migration of the ree in a granite derived soil system located in a small catchment of the vosges mountains icp ms and tims measurements were performed on both solid samples fresh granite soil and suspended load of the stream and waters soil solutions springwater and streamwater to determine their respective ree concentrations and sr and nd isotopic compositions the paas normalized ree pattern of the bedrock is characterized by a strong depletion in hree heavy ree and a negative eu anomaly 0 46 similarly the granite normalized ree distribution patterns of the soil samples show hree depletions that become more important with decreasing depth the correlative behavior between p2o5 th and ree with depth indicates that besides apatite other phosphate minerals such as monazite are the most important phases controlling the th and ree budget in the soil profile on the other hand at greater depth zircon seems to be another important mineral phase controlling especially the hree enrichment as shown by the positive relationship between zr content and the yb ho ratio different grain size fractions show similar ree distribution patterns and are only weakly fractionated compared with bulk soil sample however the finest fraction 0 20 m is more enriched in sr and ree suggesting a stronger concentration of ree carrying minerals in this fraction the suspended and dissolved load of the stream show as a whole an enrichment in hree if compared with the granite or with the different soil samples however compared with the uppermost soil samples the suspended load is significantly more enriched in hree its ree distribution pattern is more similar to that of the finest fraction of the deeper soil sample and to the fresh granite thus most probably the ree of the suspended load originated from a source with ree characteristics found in the deep soil horizons this source might have been situated in the uppermost soil profile which is actually ree depleted the weathering process can be compared with a leaching experiment where the waters correspond to the leachate and the soil to the residual phase of the granite the sr isotope data indicate that the suspended load originates from the finest soil fraction the sr and nd isotopic data of the suspended load suggest that it contains up to 3 sr and nd from apatite and up to 97 from feldspar most of the sr and nd in the waters originate from apatite leaching or dissolution

radiogenic isotopes systematics and applications to earth surface processes and chemical stratigraphy radiogenic isotopes have wide application to chemical stratigraphy geochronology provenance studies and studies of temporal changes in earth surface processes this paper briefly reviews the principles of radiogenic isotope geochemistry and the distribution of a number of elements of interest in the environment and then uses this information to explore the range of applications to chemical stratigraphy and other fundamental subjects of sedimentary geology many of these applications center on the reconstruction of secular variations in paleoseawater isotope signals these seawater isotope curves can be used for stratigraphic correlation and to assess changes through earth history in processes such as tectonic uplift climate change biogeochemical cycling ocean circulation crustal growth and surface water evolution understanding the modern biogeochemical cycle of the element isotope system of interest is essential for gaining the maximum information regarding the operation of ancient cycles the main sources of uncertainty for reconstructing seawater isotope curves involve diagenetic alteration sample impurities and errors in age assignments rigorous sample selection criteria and pretreatment methods are keys to reconstructing the most accurate seawater isotope curves applications are discussed for the rb sr sm nd la ce lu hf re os u th pb k ar and cosmogenic isotope systems d 2003 elsevier b v all rights reserved

rb sr and sm nd systematics of cherts and other siliceous deposits we have analyzed a suite of marine and lacustrine cherts to determine the concentration of rb sr sm and nd and the isotopic composition of sr and nd the samples ranged from pliocene to silurian in age and included nodular cherts in carbonates as well as bedded cherts massive samples were leached in acid to remove carbonate and both the leach and residue analyzed the residues contained 0 1 to 17 ppm rb and 0 5 to 20 ppm sr all samples have high rb sr ratios 0 1 to 0 8 and thus show enrichment of rb relative to sr of 6 to 60 times that of seawater the rb and sr in pegmatitic quartz are much lower by factors of 10 to 10 3 although these also may have high rb sr the site of rb and sr in the cherts was not established but appears to be correlated with al content the high rb sr ratios permit the use of cherts for dating in favorable circumstances the nd contents range from 9 to 1000 ppb with sm nd 0 16 to 0 19 typical of continental sources the initial 87 sr 86 sr ratio for a pacific deep sea chert is equal to that of associated carbonates and hence reflects the seawater environment in shelf and marginal basin environments the initial 87 sr 86 sr ratios of chert are distinctly more radiogenic than seawater this is most obvious where a substantial clay component is present but is observed even in samples with al 2o 3 contents less than 0 1 these results show the rb sr system in chert to be rather isolated from the associated carbonate with very little sr exchange this separate behavior appears to persist through both early and late recrystallization stages these data suggest that in many cases cherts are formed by dissolved sio 2 nucleating on clay like material which preserves the isotopic characteristics of the detrital source the detrital component required is less than 1 of the total chert in some cases it is possible that the cherts were formed from silica saturated waters from a nonmarine source possibly in coastal environments or during uplift these waters contained radiogenic sr in solution that was not exchanged with the carbonate matrix this latter mechanism is also indicated by oxygen isotopic studies knauth and epstein 1976 kolodny and epstein 1976 the nd isotopic signature of the deep sea samples reflects the seawater composition in agreement with the initial 87 sr 86 sr data on the same samples samples with excesses of 87 sr relative to seawater show low nd both sets of data thus indicating inheritance of an old detrital component the results demonstrate that the rb sr and sm nd systems may be used in elucidating the origin and evolution of cherts and that the rb sr system may be used for dating if consideration is given to the initial sr composition and to diagenetic changes this opens up numerous possibilities for sedimentological geochemical studies

neodymium budget in the modern ocean and paleo oceanographic implications the oceanic nd budget is calculated using a steady state 10 box model and a compilation of field data this is the first attempt to propose consistent estimates of the nd fluxes entering the ocean as well as indicating possible nd sources and the proportion of nd fluxes exchanged between dissolved and particulate fractions with presently available nd data the best estimates give a total nd influx of 9 x 10 9 g yr which leads to an oceanic nd residence time of 500 years from modeling tests we suggest that the authigenic nd scavenged by particulates is 100 remineralized in the deep ocean the total exchanged nd flux may be as high as 2 x 10 10 g yr the epsilon nd 0 values of the influxes are 22 11 1 and 4 for the north atlantic surface atlantic north pacific and surface indo pacific regions respectively atmospheric and riverine nd fluxes are insufficient to explain the magnitude and regional variability of calculated nd influxes and epsilon nd 0 we propose continental margins as an additional source supplying nd to the ocean using the model calibrated for nd we examine the sensitivity of deep water epsilon nd 0 to variations of nd inputs to the ocean deep water nd concentrations and epsilon nd 0 vary with the changes in nd influxes and their epsilon nd 0 as nd sources to the ocean may change during glacial interglacial periods the epsilon nd 0 shifts recorded in ferromanganese nodules and crusts do not necessarily reflect changes in paleoceanic circulation the effects of continental erosion should be considered in reconstructing patterns of ocean circulation using nd isotopes

decoupled sources of the 2 3 2 2ga yuanjiacun banded iron formation implications for the nd cycle in earth s early oceans abstract the recognized worldwide gap in bif deposition between 2 4 and 2 0 billion years ago has long been considered as an obstacle to fully determining the geochemical composition of seawater at that time however the recently dated 2 3 2 2 ga yuanjiacun banded iron formation bif in the north china craton ncc offers a possibility to redress these uncertainties shale normalized rare earth element yttrium ree y patterns of the bif and interlayered meta chert samples show features characteristic of other archean and paleoproterozoic bifs with hree enrichment relative to lree positive la and eu anomalies and superchondritic y ho ratios comparable to modern seawater very low al 2 o 3 e nd t 3 5 derived from interaction with a depleted mantle source and associated with high fe fluxes the second is ambient surface seawater e nd t 2 4 which obtained its signature through weathering of the nearby landmasses and associated with high si fluxes our findings suggest that the ree budget of the oceans prior to 2 3 ga was generally dominated by hydrothermal circulation of seawater through depleted mantle derived source rocks however where evolved local continental crust and or an enriched mantle source were present this positive mantle nd signal became discernible in the bifs by comparing the nd isotopic features of similar aged bifs and marine carbonates it is concluded that similar to modern oceans the early precambrian ocean was not well mixed with respect to its nd isotopic composition

response of beryllium and radiogenic isotope ratios in northern atlantic deep water to the onset of northern hemisphere glaciation we present time corrected ratios of cosmogenic 10 be to continent sourced 9 be from two fe mn crusts located in the northwest atlantic in the vicinity of the origins of northern atlantic deep water nadw these initial 10 be 9 be ratios represent those of the ambient seawater at the time of crust deposition and are constant through the last 7 ma previously published isotope records of radiogenic nd and pb isotopes in these crusts show a decrease in e nd and an increase in 206 pb 204 pb over the last 5 ma these changes are consistent with a gradual increase in the strength of nadw production an increase in the labrador sea component of nadw or an increased erosional input into the labrador sea since the residence time and thus the advective length scales of dissolved be in deep water lie between those of nd and pb records of 10 be 9 be should contrary to what has been observed vary in phase with those of nd and pb if these variations are accounted for by changes in paleo circulation the observed variations in radiogenic nd and pb isotopes are therefore most likely to be explained with an increase in the flux of terrigenous matter in the area of the labrador sea which was possibly associated with ice rafting and selective leaching of pb isotopes an increase of the labrador sea component that contributes to nadw is also a possibility but based on the 10 be 9 be data presented here large scale changes in the thermohaline circulation can be discounted as cause for the radiogenic tracer variations

rare earth distributions with a positive ce anomaly in the western north atlantic ocean from the vertical distributions of the rare earth elements ree in the sargasso sea we now report the first profiles of pr tb ho tm and lu in seawater together with profiles for la ce sm eu and yb the first observations of positive ce anomalies in seawater are ascribed to reducing inshore sediments as a source for ce ref 1 all vertical profiles are consistent with adsorption of trivalent rare earths by settling particles possibly siliceous or calcareous followed by their release at or near the sea floor on dissolution of the carriers the very different ce profile demonstrates the additional effects of oxidation reduction reactions

the sources and transport of sr and nd isotopes in the baltic sea we have determined the concentration and isotopic composition of sr and nd in waters from the baltic sea the baltic sea is an intracontinental stratified brackish water estuarine like system and the rivers emptying into it drain a suite of terranes ranging from proterozoic archean in the north to phanerozoic in the south the sampled brackish waters range in salinity from seawater sw at 35 289 to a minimum of 2 460 at the surface in the innermost part of the gulf of bothnia the sr concentrations show generally conservative behavior indicating a simple two component mixing however small deviations 3 70 from a perfect mixing line reveal that the imprints from rivers with different sr concentrations are preserved in the blending strontium concentrations from a depth profile across the redoxcline in the baltic proper indicate that vertical particle transport alters the sr concentration in the water our estimated concentration of sr in the average freshwater input to the baltic is 0 03 ppm which is only about 0 4 of the sw concentration the sr isotopic data range from e sr sw 0 in seawater to e sr bw sw 7 8 in the least saline baltic water bw sample in the gulf of bothnia the isotopic composition of sr versus 1 sr in the baltic sea follows an almost perfect mixing line which shows that seawater sr is mixed with much more radiogenic components calculated end member values of e sr sw for each sample show that the riverine input into the gulf of bothnia has e sr sw 120 200 and 10 50 e units in the baltic proper these values are in general agreement with direct measurements of river waters in each region however the calculated values in the gulf of bothnia are lower than the measured river water input in this region which indicates the presence of less radiogenic sr presumably originating from the river waters draining the southern part of the basin which are partially transported northward and mixed with sr from the gulf of bothnia rivers the nd concentration in the baltic sea is not conservative varying between 5 and 45 ppt with the highest concentrations in the bottom waters due to vertical particulate transport a plot of e nd o in baltic water yields a good correlation with the calculated freshwater end member e sr sw the data show that it is possible to unravel the different freshwater sources into the baltic and to identify the zones of particulate removal of both non conservative species such as the ree and of quasi conservative species such as sr the use of isotopic tracers in this estuarine environment may provide a much better insight into mixing and element transport it should also be possible to trace lateral movements of freshwater inputs

the ree and end of 40 70 ma old fish debris from the west african platform ree concentrations and nd isotopic compositions have been determined in late cretaceous early cenozoic fish debris from west african and israeli platform sediments and show a strong regional control independent of time except for those from the northern morocco it is suggested that although diagenetic fluids do not contribute ree s directly to the phosphatic debris they may significantly change the ce anomaly and the end t value of the epicontinental seas which in turn control the ree in marine phosphates it is shown that over the investigated period the north moroccan shelf seawater was progressively flushed by deep north atlantic water

evolution of nd and pb isotopes in central pacific seawater from ferromanganese crusts abstract hydrogenetic ferromanganese crusts incorporate elements from ambient seawater during their growth on seamounts by analysing nd pb and be isotope profiles within crusts it is possible to reconstruct seawater tracer histories depth profiles of 10be 9be ratios in three pacific ferromanganese crusts have been used to obtain growth rates which are between 1 4 and 3 8 mm ma nd and pb isotopes provide intact records of isotopic variations in pacific seawater over the last 20 ma or more there were only small changes in pb isotope composition in the last 20 ma this indicates a constant pb composition for the erosional sources and suggests further that erosional nd inputs may have been uniform too end values vary considerably with time and most probably reflect changes in ocean circulation the end values of the crusts not only vary as a function of age but also as a function of water depth from 25 to 0 ma crust va13 2 from 4 8 km water depth has a similar pattern of end variation to the two shallower crusts from 1 8 and 2 3 km but about 1 0 to 1 5 units more negative this suggests that end stratification in pacific seawater as demonstrated for the present day has been maintained for at least 20 ma each crust shows a decrease in end from 3 5 ma to the present which is interpreted in terms of an increase in the nadw component present in the pacific from 10 to 3 5 ma ago the crusts show an increase in end this suggests a decreasing role for a deep water source with end less than circum pacific sources in this regard the panamanian gateway restriction from 10 ma with final closure at 3 5 ma may have played an important role in reducing access of atlantic derived nd to the pacific

the geochemical balance of the rare earth elements and neodymium isotopes in the oceans profiles of ree concentrations and neodymium isotope measurements in the western indian ocean are consistent with published data from the other major oceans ree concentrations show a strong hydrographic control the influence of intermediate water masses is particularly significant surface water concentrations vary with salinity paniculate rees are less than 5 of dissolved concentration except for ce where up to 20 of total rees are present as 0 4 m particles in contrast to dissolved profiles concentration profiles of paniculate rees including ce all increase with depth ree concentrations correlate with silica over all but the deepest waters although in detail correlations are complex the neodymium isotopic composition of indian ocean seawater avg nd 0 8 3 is intermediate between that for the atlantic and pacific oceans comparison of ree data from the major oceans shows that the hrees behave more like si than do the lrees sm nd ratios are near constant for all oceans whereas ernd ratios vary between the atlantic indian and pacific oceans the fractionation of the rees in surface seawaters can be explained by fractionation factors relative to silica from 0 12 for la to 0 05 for er use of a seven box model shows that the interoceanic variations in neodymium isotopic compositions and nd concentrations cannot be reconciled unless particle water exchange is invoked the degree of exchange required is consistent with particle residence times of 1 10 yr

on the relationship between nd isotopic composition and ocean overturning circulation in idealized freshwater discharge events using a cost efficient climate model the effect of changes in overturning circulation on neodymium isotopic composition nd is systematically examined for the first time idealized sequences of abrupt climate changes are induced by the application of periodic freshwater fluxes to the north atlantic na and the southern ocean so thus mainly affecting either the formation of north atlantic deep water nadw or antarctic bottom water aabw variations in nd reflect weakening and strengthening of the formation of nadw and aabw changes in ndof end members are relatively small relationships between nd and the strength of nadw or aabw are more pronounced for aabw than for nadw atlantic patterns of variations in nd systematically differ between na and so experiments additionally the signature of changes in nd in the atlantic and the pacific is alike in na but opposite in so experiments discrimination between na and so experiments is therefore possible based on the atlantic pattern of variations in nd and the contrariwise behavior of nd in the atlantic and the pacific in further experiments we examined the effect of variations in magnitudes of particle export fluxes within the examined range and although settling particles represent the only sink of nd their effects on nd are relatively small our results confirm the large potential of nd as a paleocirculation tracer but also indicate its limitations of quantitative reconstructions of changes in the atlantic meridional ocean circulation

neodymium isotopic study of baffin bay water sources of ree from very old terranes water samples were collected from baffin bay and surrounding areas in order to evaluate this region as a potential source of nd from old continental material to atlantic water the isotopic data ranged from e nd 0 9 0 to 26 with most of the data around e nd 0 20 compared with values of north atlantic deep water nadw with e nd 0 13 5 the concentration of nd in baffin bay waters was as high as 6 10 12 g g compared with 2 5 10 12 g g for nadw the combination of low e nd and high nd concentration indicates that baffin bay may be a significant source of nd from very old crustal material a simple box model was used to evaluate the contribution to the nd budget of nadw and it was concluded that a substantial fraction of the nd from ancient crustal sources that is required to maintain the isotopic composition of nadw could be supplied by baffin bay outflow

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

new constraints on the pb and nd isotopic evolution of ne atlantic water masses 1 time series of lead pb and neodymium nd isotope compositions were measured on three ferromanganese crusts recording the evolution of ne atlantic water masses over the past 15 ma the crusts are distributed along a depth profile 700 4600 m comprising the present day depths of mediterranean outflow water and north east atlantic deep water a pronounced increase of the 206pb 204pb in the two deeper crusts starting at 4 ma and a decrease in 143nd 144nd in all three crusts took place between 6 4 ma and the present these patterns are similar to isotope time series in the western north atlantic basin and are consistent with efficient mixing between the two basins however the changes occurred 1 3 ma earlier in the eastern basin indicating that the northeastern atlantic led the major change in pb and nd isotope composition probably due to a direct supply of labrador seawater via a northern route the pb isotope evolution during the pliocene pleistocene can generally be explained by mixing between two end members corresponding to mediterranean outflow water and north east atlantic deep water but external sources such as saharan dust are likely to have played a role as well the pb isotope composition of the shallowest crust that grew within the present day mediterranean outflow water does not show significant pb isotope changes indicating that it was controlled by the same pb sources throughout the past 15 ma

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

the isotopic composition of nd in a boreal river a reflection of selective weathering and colloidal transport in this study the nd concentrations cnd from 18 months of weekly sampling of filtered water 90 dominated by a colloidal phase primarily composed of organic c and fe the end 0 and 147sm 144nd only vary within a narrow range 27 1 to 24 8 and 0 103 to 0 110 respectively with no obvious relationship to cnd and discharge the end 0 and 147sm 144nd in the river water is significantly lower than in the unweathered till and average bedrock in the catchment and show a closer resemblance with the isotopic characteristics found in humic substances and plant material these data show that the isotopic composition of nd exported from a large boreal drainage basin does not directly reflect that of the bulk bedrock in the catchment the isotopic composition is controlled by selective weathering and the nd transport is dominated by organic colloidal particles

neodymium isotopic composition of the mediterranean outflow and the eastern north atlantic the neodymium concentration and isotopic composition of the mediterranean outflow in the strait of gibraltar has been directly determined the outflow has a dissolved nd concentration of 23 pmoles kg with nd 0 9 4 these results are in clear disagreement with previous values inferred for the mediterranean this concentration and nd 0 do not sharply contrast with north atlantic deep water nadw values and can produce isotopic anomalies no larger than 1 unit in the north atlantic a new profile in the eastern north atlantic does not exhibit an nd 0 anomaly at the depth of the mediterranean water core in accordance with the above inferences while concentrations and nd 0 at this site indicate that nd is conservative in the deep eastern north atlantic a previously reported nd 0 anomaly in the eastern north atlantic originally associated with the mediterranean outflow has a different source the direct contribution of the mediterranean outflow to the nadw nd budget is small 10 of the high latitude sources however the outflow plus entrained water supply 30 of the total nd associated with northern latitude deep water sources concentrations of dissolved nd in the outflow are enriched compared to the atlantic inflow which has 16 pmoles kg with nd 0 11 8 the principal source of the excess dissolved nd is inferred to be partial dissolution of detrital particles simple mass balance calculations suggest that 0 6 of the nd associated with detrital river transported sediments and or 3 5 of the nd associated with eolian particles delivered to the mediterranean is mobilized during passage into the marine environment if general these mobilization efficiencies imply that the dissolution of detrital particles is a significant source of dissolved nd and other rare earth elements in seawater

rare earth element transport in the western north atlantic inferred from nd isotopic observations the isotopic composition of nd in the water column from several western north atlantic sites and formational areas for north atlantic deep water shows extensive vertical structure at all locations in regions where a thermocline is well developed large isotopic shifts 2 to 3 units are observed across the base of the thermocline regions without a thermocline are characterized by much more gradual shifts in isotopic composition with depth in general the data reveal an excellent correlation between the nd isotopic distribution in the western north atlantic water column and the distribution of water masses identified from temperature and salinity characteristics nadw as identified from t s properties is also characterized by a well defined isotopic composition having nd 0 13 5 0 5 this signature is associated with waters identified as nadw from high latitudes near formational areas in the labrador sea down to the equatorial region the isotopic signature of nadw would appear to be formed by a blend of more negative waters originating in the labrador sea nd 0 18 and more positive waters originating in the overflows from the norwegian and greenland seas nd 0 8 to 10 and is consistent with classical theories on the formation of nadw the isotopic signature of nadw is propagated southward to the equator where it is gradually being thinned out by mixing from above and below with more radiogenic nd associated with northward spreading antarctic intermediate and bottom waters the preservation of the isotopic signature of nadw over these large distances indicate that the ree undergo extensive lateral transport the isotopic composition of nd is largely conservative over the time scales of mixing within the atlantic in spite of the intrinsic nonconservative behavior of neodymium nd concentration gradients generally show surface waters to be depleted in nd relative to deep waters which must require vertical transport processes however isotopic differences in the water column preclude the local downward transport of ree from the surface into underlying deep waters as a simple explanation of the concentration gradient the apparent decoupling of ree in nadw from overlying local surface waters and the increasing concentration with depth provide a conflict with simple vertical transport mechanisms that is not yet resolved

zooming in on heinrich layers theories explaining the origin of the abrupt massive discharges of ice rafted detritus ird into the glacial north atlantic the heinrich layers hls generally point to the laurentide ice sheet as the sole source of these events until it was found that the irds also originated from icelandic and european ice sheets bond and lotti 1995 snoeckx et al 1999 grousset et al 2000 this apparent contradiction must be reconciled as it raises fundamental questions about the mechanism s of hl origin we have analyzed two 12 cm thick hls in an ultrahigh resolution mode 1 2 century intervals in a mid atlantic ridge piston core the 18o record n pachyderma left coiling reveals strong excursions induced by the melting of the icebergs these excursions are associated with a strong decrease in the amount of planktic foraminafersand with a 3 c cooling of the surface waters counts of coarse detrital grains reveal that ird are deposited according to a typical sequence 1 volcanic glass 2 quartz and feldspars 3 detrital carbonate that implies a chronology in the melting of the differentpan atlantic ice sheets sr and nd isotopic composition confirm that in both heinrich layers h1 and h2 precursor ird came from first europe iceland followed then by laurentide derived ird an internal cyclicity can be identified during h1 and h2 about four to six major abrupt discharges occurred roughly on a century timescale the 13c and 15n records reveal that dominant inputs of continent derived organic matter are associated with ird within the hls hiding the plankton productivity signal