li and δ7li in himalayan rivers proxies for silicate weathering this paper presents the first systematic survey of lithium and its isotopes in the dissolved load and suspended and bed sediments of tributaries of the ganges both before and after the monsoon locations were chosen in order to cover catchments draining both silicates and carbonates at high 2000 4000 m and low 550 1300 m altitudes modelling of the dissolved composition shows that the li ca ratio of the silicate endmember in himalayan rivers is at least an order of magnitude higher than that of the carbonate endmember most of the dissolved li 90 is derived from silicates even in carbonate dominated catchments while the sr isotope composition of the dissolved load reflects that of the bedrock the main control on its li isotope composition is fractionation during weathering fractionation between the dissolved and suspended load in silicate dominated catchments is greatest at high altitude and lower at low altitude where weathering is more intense tributaries draining silicates have lower dissolved 7li values by 2 3 to 4 2 following the monsoon when weathering is more intense because of higher runoff and elevated temperatures our data suggest that riverine li fluxes largely reflect silicate weathering rates while riverine 7li varies with weathering intensity as rivers presently contribute 50 of the li input to the oceans seawater li concentrations and 7li show potential as proxies for global silicate weathering processes

abstract a regional structural interpretation of the zagros mountain belt in northern fars and high zagros sw iran the structural style is controlled by the stratigraphic position of the decollement levels that varies with depth for the different areas of the 300 km long transect within the sedimentary pile the main decollement level is the hormuz salt sometimes this decollement level as well as pre hormuz sedimentary basins can be clearly observed on seismic lines paleozoic formations are therefore involved in the main structures the second decollement and disharmonic level is the evaporitic dashtak formation trias the difference in the tectonic style between northern fars in the southern part of the transect and high zagros in the northern part of the transect is partly due to the lateral facies changes in the triassic formations from evaporite to dolomite the shaly layers of the kazhdumi cretaceous and pabdeh gurpi late cretaceous early tertiary as well as gachsaran late miocene evaporitic layer can locally act as secondary decollement

construction of the cambrian and ordovician seawater 87sr 86sr curve abstract the estimated path of seawater 87 sr 86 sr during the cambrian and ordovician is based on 172 analyses the sample suite is largely from locations in oklahoma new york tennessee and texas where rocks of this age are widely exposed and well studied the oldest reliable samples examined in this study are of middle cambrian age and yield an 87 sr 86 sr near 0 70888 sw 19 the estimated ratio rises to near 0 70915 sw 8 in the lower upper cambrian the highest value during the phanerozoic and probably for all geologic time the estimated path drifts lower to near 0 70903 sw 4 at the cambrian ordovician boundary this further declines to near 0 70875 sw 32 at the end of the ibexian and reaches a value near 0 70821 sw 86 at the whiterockian mohawkian boundary the decline in the seawater 87 sr 86 sr continues into later mohawkian time to flatten abruptly near 0 70782 sw 125 this ratio is essentially constant through the latest ordovician the curve rises near to a ordovician silurian boundary value poorly constrained from our data near 0 70784 sw 123 the early paleozoic seawater curve shows the alternating dominance of continental and oceanic sources of sr continental sr dominated seawater from the beginning of the cambrian into late cambrian from that time as the cambrian transgression proceeded and radiogenic crystalline rocks were covered oceanic sr began to dominate sr from low ratio oceanic sources dominated through early mohawkian time an abrupt balance is struck between oceanic and continental sources to end the decline in the late ordovician and maintained until near the end of the ordovician the general curve shape follows the pattern suggested by proposed sealevel changes the rise and fall of seawater 87 sr 86 sr during the cambrian and ordovician characterized seawater variation during all the paleozoic

weathering processes and the composition of inorganic material transported through the orinoco river system venezuela and colombia abstract the composition of river borne material in the orinoco river system is related primarily to erosion regime which in turn is related to tectonic setting especially notable is the contrast between material derived from tectonically active mountain belts and that from stable cratonic regions for a particular morpho tectonic region the compositional suites of suspended sediment bed material overback deposits and dissolved phases are fairly uniform are are typically distinct from whose of other regions for each region a consistent set of chemical weathering reactions can be formulated to explain the composition of dissolved and solid loads in developing these formulations erosion on slopes and storage of solids in soils and alluvial sediments are important considerations compositionally verymature sediment is derived from areas of thick soils where erosion is transport limited and from areas where sediments are stored for extended periods of time in alluvial deposits compositionally immature sediments are derived from tectonically active mountain belts where erosion is weathering limited weathering limited erosion also is important in the elevated parts of the guayana shield within areas of sleep topography compared to the mountain belts sediments derived from elevated parts of the shield are more mature a greater degree of chemical weathering seems to be needed to erode the rock types typical of the shield the major element chemistry and mineral composition of sediment delivered by the orinoco river to the ocean are controlled by rivers that have their headwaters in mountain belts and cross the llanos a region of alluvial plains within the foreland basin the composition of sediments in rivers that drain the shield seems to be established primarily at the site of soil formation whereas for rivers that drain the mountain belts additional weathering occurs during s episodes of storage on alluvial plains as sediments are transported across the llanos to the main stem of the orinoco after mixing into the main stem there seems to be little subsequent alteration of sediment

mechanisms controlling the silicon isotopic compositions of river waters it has been proposed that silicon si isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions in this study the first seasonal variations of stable isotope compositions of dissolved riverine si are reported and compared with concomitant changes in water chemistry four different rivers in switzerland were sampled between march 2004 and july 2005 the unique high resolution multi collector icp ms nu1700 has been used to provide simultaneous interference free measurements of 28si 29si and 30si abundances with an average limiting precision of 0 04 on 30si this precision facilitates the clarification of small temporal variations in isotope composition the average of all the data for the 40 samples is 30si 0 84 0 19 1 sd despite significant differences in catchment lithologies biomass climate total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved si in each river is strikingly similar with means of 0 70 0 12 for the birs 0 95 0 22 for the saane 0 93 0 12 for the ticino and 0 79 0 19 for the verzasca however the 30si undergoes seasonal variations of up to 0 6 comparisons between 30si and physico chemical parameters such as the concentration of dissolved si and other cations the discharge of the rivers and the resulting weathering fluxes permits an understanding of the processes that control the si budget and the fate of dissolved si within these rivers the main mechanism controlling the si isotope composition of the mountainous verzasca river appears to be a two component mixing between the seepage of soil ground waters with heavier si produced by clay formation and superficial runoff associated with lighter si during high discharge events a biologically mediated fractionation can be excluded in this particular river system the other rivers display increasing complexity with increases in the proportion of forested and cultivated landscapes as well as carbonate rocks in the catchment in these instances it is impossible to resolve the extent of the isotopic fractionation and contributed flux of si contributed by biological processes as opposed to abiotic weathering the presence of seasonal variations in si isotope composition in mountainous rivers provides evidence that extreme changes in climate affect the overall composition of dissolved si delivered to the oceans the oceanic si isotope composition is very sensitive to even small changes in the riverine si isotope composition and this parameter appears to be more critical than plausible changes in the si flux therefore concurrent changes in weathering style may need to be considered when using the si isotopic compositions of diatoms sponges and radiolaria as paleoproductivity proxies

tertiary oxygen isotope synthesis sea level history and continental margin erosion tertiary benthic and planktonic foraminiferal oxygen isotope records are correlated to a standard geomagnetic polarity time scale making use of improved chronostratigraphic control and additional oligocene isotope data synchronous changes in both benthic and planktonic 18o values which occurred in the oligocene to miocene 36 5 2 ma are interpreted in part to represent ice growth and decay the inferred ice growth events correlate with erosion on passive continental margins as interpreted from seismic and chronostratigraphic records this association is consistent with a link between oligocene to miocene erosional events and rapid 15 m m y glacioeustatic lowerings of about 50 m high benthic foraminiferal 18o values suggest the presence of continental ice sheets during much of the oligocene to recent 36 0 ma substantially ice free conditions probably existed throughout the paleocene and eocene 66 36 ma the mechanisms and rates of sea level change apparently were different between the early and late tertiary with glacioeustatic changes restricted to the past 36 m y pre oligocene erosion on passive continental margins was caused by eustatic lowerings resulting from global spreading rate changes we apply a model which suggests that large areas of the continental shelves were subaerially exposed during such tectonoeustatic lowstands stimulating slope failure and submarine erosion the different mechanisms and rates of eustatic change may have caused contrasting erosional patterns between the early and late tertiary on passive continental margins this speculation needs to be confirmed by examination of data from several passive margins

geochemical assessment of the palaeoecology ontogeny morphotypic variability and palaeoceanographic utility of dentoglobigerina venezuelana to better understand the links between the carbon cycle and changes in past climate over tectonic timescales we need new geochemical proxy records of secular change in silicate weathering rates a number of proxies are under development but some of the most promising e g palaeoseawater records of li and nd isotope change can only be employed on such large samples of mono specific foraminifera that application to the deep sea sediment core archive becomes highly problematic dentoglobigerina venezuelana presents a potentially attractive target for circumventing this problem because it is a typically large 355 m diameter abundant and cosmopolitan planktic foraminifer that ranges from the early oligocene to early pliocene yet considerable taxonomic and ecological uncertainties associated with this taxon must first be addressed here we assess the taxonomy palaeoecology and ontogeny of d venezuelana using stable isotope oxygen and carbon and mg ca data measured in tests of late oligocene to early miocene age from ocean drilling program odp site 925 on ceara rise in the western equatorial atlantic to help constrain the depth habitat of d venezuelana relative to other species we report the stable isotope composition of selected planktic foraminifera species within globigerina globigerinoides paragloborotalia and catapsydrax we define three morphotypes of d venezuelana based on the morphology of the final chamber and aperture architecture we determine the trace element and stable isotope composition of each morphotype for different size fractions to test the validity of pooling these morphotypes for the purposes of generating geochemical proxy datasets and to assess any ontogenetic variations in depth habitat our data indicate that d venezuelana maintains a lower thermocline depth habitat at ceara rise between 24 and 21 ma comparing our results to published datasets we conclude that this lower thermocline depth ecology for the oligo miocene is part of an eocene to pliocene evolution of depth habitat from surface to sub thermocline for d venezuelana our size fraction data advocate the absence of photosymbionts in d venezuelana and suggest that juveniles calcify higher in the water column descending into slightly deeper water during the later stages of its life cycle our morphotype data show that 18o and 13c variation between morphotypes is no greater than within morphotype variability this finding will permit future pooling of morphotypes in the generation of the sample hungry palaeoceanographic records

arrested kinetic li isotope fractionation at the margin of the ilimaussaq complex south greenland evidence for open system processes during final cooling of peralkaline igneous rocks li contents li and isotopic composition 7 li of mafic minerals mainly amphibole and clinopyroxene from the alkaline to peralkaline ilimaussaq plutonic complex south greenland track the behavior of li and its isotopes during magmatic differentiation and final cooling of an alkaline igneous system li in amphibole increase from b10 ppm in caamphiboles of the least differentiated unit to n3000 ppm in na amphiboles of the highly evolved units in contrast li in clinopyroxene are comparatively low b85 ppm and do not vary systematically with differentiation the distribution of li between amphibole and pyroxene is controlled by the major element composition of the minerals ca rich and na rich respectively and changes in oxygen fugacity due to li incorporation via coupled substitution with ferric iron during magmatic differentiation 7 li values of all minerals span a wide range from 17 to 8 with the different intrusive units of the complex having distinct li isotopic systematics amphiboles which dominate the li budget of whole rocks from the inner part of the complex have constant 7 li of 1 8 2 2 2 n 15 this value reflects a homogeneous melt reservoir and is consistent with their mantle derivation in agreement with published o and nd isotopic data clinopyroxenes of these samples are consistently lighter with 7 liamph cpx as large as 8 and are thus not in li isotope equilibrium these low values probably reflect late stage diffusion of li into clinopyroxene during final cooling of the rocks thus enriching the clinopyroxene in 6 li at the margin of the complex 7 li in the syenites increases systematically from 2 to high values of 14 this coupled with the observed li isotope systematics of the granitic country rocks reflects post magmatic open system processes occurring during final cooling of the intrusion although the shape and magnitude of the li isotope and elemental profiles through syenite and country rock are suggestive of diffusion driven isotope fractionation they cannot be modeled by one dimensional diffusive transport and point to circulation of a fluid having a high 7 li value possibly seawater along the chilled contact in all this study

the fluvial geochemistry of the rivers of eastern siberia ii tributaries of the lena omoloy yana indigirka kolyma and anadyr draining the collisional accretionary zone of the verkhoyansk and cherskiy ranges fundamental to the global carbon cycle over geologic time scales is the control of atmospheric co2 by aluminosilicate weathering much of the information on the rates of this process comes from rivers in the tropics and subtropics to understand the possible climatic influences systematic studies are needed for the arctic subarctic regions this is the second in a series of papers addressing this problem by systematic studies of the pristine rivers of the russian far east the region to the east of the siberian platform huh et al 1998 is a geologically complex terrain formed by the mesozoic collision and accretion of the siberian and kolyma plates because of the arid continental climate it has not been glaciated in the recent past thus it is possible to study weathering processes in an arctic environment dominated solely by cryogenic interactions without contamination by heterogeneous components derived from scouring glaciers all the major rivers and their tributaries in this area have been sampled on expeditions to individual basins 100 samples on a reconnaissance basis at falling stage usually in july and august the total dissolved cation levels tz are moderate up to 3 100 eq and the major ion chemistry is indicative of ca aluminosilicate and carbonate weathering with significant contributions from black shales in some tributaries the si tz si na k and 87sr 86sr ratios indicate that the weathering is superficial i e only to cation rich secondary minerals the areal total dissolved solid fluxes range from 0 04 to 0 39 106 mol km2 yr up to an order of magnitude lower than for the amazon orinoco draining the andes in the tropics 0 6 4 1 106 mol km2 yr the co2 consumption by aluminosilicate weathering 18 230 103 mol km2 yr is also at the lower end of the range observed in the amazon orinoco headwaters 143 1 000 103 mol km2 yr however as the north american counterparts in similar latitudes and with comparable relief the mackenzie yukon and fraser draining the rockies also have high dissolved solids 0 2 2 9 106 mol km2 yr and co2 19 1 750 103 mol km2 yr fluxes these low values seem to be more a function of lithology than simply climate ice action in cold environments appears to overcome the inhibiting effects of the decreased temperatures and lack of precipitation in producing a high chemical yield but results in superficial weathering in the case of aluminosilicates

neogene himalayan weathering history and river87sr86sr impact on the marine sr record abstract clastic sediments in the bengal fan contain a neogene history of erosion and weathering of the himalaya we present data on clay mineralogy major element stable and radiogenic isotope abundances from lower miocene pleistocene sediments from odp leg 116 nd and sr isotope data show that the himalayan provenance for the eroded material has varied little since 17 ma however from 7 to 1 ma smectite replaces illite as the dominant clay while sediment accumulation decreased implying an interval of high chemical weathering intensity but lower physical erosion rates in the ganges brahmaputra gb basin o and h isotopes in clays are correlated with mineralogy and chemistry and indicate that weathering took place in the paleo gangetic flood plain the87sr86sr ratios of pedogenic clays vermiculite smectite record the isotopic composition of sr in the weathering environment and can be used as a proxy for87sr86sr in the paleo gb basin the sr data from pedogenic clays shows that river87sr86sr values were near 0 72 prior to 7 ma rose rapidly to 0 74 in the pliocene and returned to 0 72 in the middle pleistocene these are the first direct constraints available on the temporal variability of87sr86sr in a major river system the high87sr86sr values resulted from intensified chemical weathering of radiogenic silicates and a shift in the carbonate silicate weathering ratio modeling of the seawater sr isotopic budget shows that the high river87sr86sr values require a ca 50 decrease in the sr flux from the gb system in the pliocene the relationship between weathering intensity 87sr86sr and sr flux is similar to that observed in modern rivers and implies that fluxes of other elements such as ca na and si were also reduced increased weathering intensity but reduced sr flux appears to require a late miocene pliocene decrease in himalayan erosion rates followed by a return to physically dominated and rapid erosion in the pleistocene in contrast to the view that increasing seawater87sr86sr results from increased erosion mio pliocene to mid pleistocene changes in the seawater sr budget were the result of reduced erosion rates and sr fluxes from the himalaya

fluvial geochemistry of the eastern slope of the northeastern andes and its foredeep in the drainage of the orinoco in colombia and venezuela abstract the fluvial geochemistry of the tributaries of the orinoco draining the eastern branch of the northern andes in colombia and venezuela is determined by lithology and ranges from rivers dominated by aluminosilicate weathering mainly of shales and mafic rocks to those bearing the signatures of dissolution of marine limestones and evaporites and of continental playa deposits these left bank tributaries of the orinoco provide the overwhelming proportion of the suspended and dissolved loads transported by the main stem although feeding only half the discharge however due to the extreme severity of weathering on the guayana shield the right bank tributaries supply about half the silica and 40 of the k carried by the orinoco there is a similar partitioning between the andes and the lowlands in the amazon drainage in contrast the mackenzie which drains the northern extremity of the continental arc of the western americas is completely dominated by the weathering of limestones and evaporites and transports very little silica this again appears to be a reflection of lithology since the yukon in similar latitudes and terrain has silica concentrations comparable to the tropical systems in addition a conservative deconvolution of the data gives estimates of the net consumption of atmospheric co 2 by aluminosilicate weathering that follows the same pattern thus the available evidence from the western americas indicates that exposure and lithology rather than the climatic variables temperature and runoff dominate the weathering yields in active orogenic belts these observations contradict the conventional view of weathering processes and their controls and are at complete variance with the assumptions parameterised in most models of the geochemical cycle

lithium isotopes as a probe of weathering processes orinoco river abstract lithium isotopes have the potential to be effective tracers of weathering processes due to their large relative mass difference and therefore fractionation in this study an attempt is made to fill a major gap in the knowledge of li isotope fractionation during continental weathering and of the mechanisms involved finally the relationship between the suspended and dissolved material is made on a basin wide scale the orinoco basin provides a clear contrast in reaction limited and transport limited weathering regimes that has already been documented by a comprehensive study on its fluvial geochemistry edmond et al geochim cosmochim acta 60 1996 2949 2976 edmond et al geochim cosmochim acta 59 1995 3301 3325 conspicuous in our new results is the difference in 6li of the dissolved load between the andean 30 to 22 and shield 22 to 7 tributaries while the 6li of the suspended load is similar between the two to a first approximation during superficial weathering in high relief tectonically active terrains the dissolved load is high in li and isotopically heavy more negative 6li whereas in stable shield regions the concentrations are low and isotopically light in proportion to the increasing degree of weathering

himalayan tectonics weathering processes and the strontium isotope record in marine limestones the time evolution of the isotopic composition of seawater strontium the ratio of strontium 87 to strontium 86 over the last 500 million years has the form of an asymmetric trough the values are highest in the cambrian and recent 0 7091 and lowest in the jurassic 0 7067 superimposed on this trend are a number of smaller oscillations consideration of the geochemical cycle of strontium and the dynamics of weathering shows that only himalayan style continental collisions can influence the isotope ratio on the scale observed the contemporary himalayan orogeny is by far the largest since the late precambrian pan african event that produced the high in the cambrian

the osmium riverine flux and the oceanic mass balance of osmium the osmium concentration os and isotopic composition were determined in a set of 17 of the largest rivers of the world os varies between 4 6 and 52 1 pg kg and the 187os 188os ratio varies between 0 64 and 2 94 measurement of rainwater samples shows that there is no input of oceanic os to the continent through rain assuming a negligible anthropogenic os input in the dissolved load the natural average river water has an os concentration of 7 9 pg kg and a mean 187os 188os ratio of 1 54 the total riverine flux of os to the ocean is estimated to be 295 kg yr the dissolved os flux from island arcs and oceanic islands represents less than 5 of the total riverine flux and is not further considered the continental os flux to the ocean is then represented by the riverine flux as dissolved os from eolian dust and glacial sediments is negligible assuming steady state it is possible to estimate a maximum unradiogenic flux to the ocean of 126 kg yr cosmic dust or mantle derived and an oceanic residence time between 2 5 104 and 5 4 104 with a mean of 3 5 104 year the estimation of the flux of dissolved cosmic particles shows that their contribution to the seawater os would be 14 of the contribution of the unradiogenic component which means that the mantle derived flux should contribute a major part the first results on water from high temperature axial hydrothermal systems indicate that their input is probably negligible which would necessitate that dominant contribution from the low temperature alteration of the oceanic crust and or of the ultramafic exposures contributes dominantly to the input of unradiogenic os to the seawater we show that it would be necessary to leach 1 3 of the os contained in the volume of ultramafic exposures accessible to seawater to account for all of the unradiogenic component contribution another simpler but less likely possibility is that the dissolved cosmic dust represents the only source of dissolved unradiogenic os to the ocean in which case the riverine input represents 94 of the total dissolved flux to the ocean instead of 70 the modern global dissolved os flux to the ocean would then have a 187os 188os ratio of 1 44 instead of 1 06 and the system would be far from steady state

beryllium isotope geochemistry in tropical river basins abstract the distributions of beryllium 9 and beryllium 10 in rivers within the orinoco and amazon basins have been examined to extend our understanding of their geochemical cycles and to develop their use both in geochronometry and in studying erosional processes beryllium 9 the stable isotope is weathered from mineral lattices before entering the riverine dissolved or exchangeable phase the cosmogenic radioisotope 10be t 1 2 1 5 myr is produced primarily in the atmosphere and is brought into riverine systems via rainfall in dissolved or exchangeable form it may be used to examine the processes which affect beryllium partitioning between the dissolved and particulate phases ancillary data such as major ion distributions provide a basis for selecting regions in which riverine chemistry is dominated by a single geochemical process allowing examination of its effects on be distributions in isolation analyses of 9be in dissolved and suspended material from rivers with a wide range of chemical compositions indicate that its geochemistry is primarily controlled by two major factors 1 1 its abundance in the rocks of the watershed and 2 2 the extent of its adsorption onto particle surfaces the relative importance of these parameters in individual rivers is determined by the extent of interaction with flood plain sediments and the riverine ph this understanding of 9be geochemistry forms a basis for examination of the geochemical cycling of 10be in rivers which are dominated by interaction with sediments the riverine concentration of dissolved 10be is far lower than that in the incoming rainwater indicating that a substantial proportion of it is retained within the soils of the basin or is adsorbed onto riverine particles however in acidic rivers in which the stable dissolved be concentration is determined by the be level in the rocks of the drainage basin dissolved 10be has essentially the same concentration as in precipitation these observations imply that the soil column in such regions must be saturated with respect to 10be and that the ratio of the inventory to the flux does not represent an age as may be the case in temperate latitudes but rather a residence time

lithium isotopic composition and concentration of himalayan leucogranites and the indian lower continental crust abstract the lithium isotopic compositions of adakitic rocks and k rich volcanic rocks in southern tibet range from 1 3 to 7 5 and 4 9 to 3 5 respectively the subduction of the indian plate beneath the lhasa terrane means that traditional lithium isotopic compositions of various reservoirs are unable to explain the aforementioned 7 li data therefore it is necessary to determine the li isotopic compositions of the different geological endmembers underneath southern tibet here we report the lithium isotopic composition and concentration of indian upper and lower continental crust on the basis of whole rock major and trace element data and sr nd pb isotope data leucogranites from luozha and longzi are considered as representative of indian upper crust whereas two mica granites from quedang and dala and granulites and gneisses from nyalam are considered as representative of indian lower crust the li concentration of indian upper crust varies from 23 to 45 ppm with a mean of 34 ppm consistent with a weighted mean li concentration for the upper crust of 35 11 ppm in contrast the li abundance of indian lower crust is estimated to be 33 84 ppm with a mean of 58 ppm much higher than the average li concentration for the lower crust of 8 ppm because of the high modal abundance of biotite and muscovite the li isotopic compositions 0 9 to 5 6 of indian upper continental crust are relatively heavy compared with the average li isotopic composition of upper continental crust on the other hand the li isotopic compositions of indian lower continental crust 4 4 to 0 1 are lighter than those of indian upper continental crust the isotopically heavy signature of indian upper crust is produced by high 7 li fluids released from the indian lower crust slab whereas the lighter signature of indian lower crust is generated by the partial melting of residual indian lower crust slab during metamorphic dehydration of indian lower crust

lidar observations of gravity wave activity in the middle atmosphere over davis 69 s 78 e antarctica a 16 month series of lidar measurements in the stratosphere and mesosphere lower thermosphere mlt region over davis station 69 s 78 e in antarctica is used to study gravity waves the unprecedentedly large number of observations totaling 2310 h allows us to investigate seasonal variations in gravity wave activity in great detail in the stratosphere the gravity wave potential energy density gwped is shown to have a large seasonal variation with a double peak in winter and minimum in summer we find conservative wave propagation to occur between 29 and 41 km altitude in winter as well as in summer whereas smaller energy growth rates were observed in spring and autumn these results are consistent with selective critical level filtering of gravity waves in the lower stratosphere in the mlt region the gwped is found to have a semiannual oscillation with maxima in winter and summer the structure of the winter peak is identical to that in the stratosphere suggesting that the gravity wave flux reaching the mlt region is controlled by the wind field near the tropopause level

the fluvial geochemistry and denudation rate of the guayana shield in venezuela colombia and brazil abstract the guayana shield is composed of early to mid precambrian igneous and metamorphic basement rocks with a quartzitic platform cover the complete absence of limestones and evaporites allows a clear chemical expression in the stream data of the primary weathering of the basement in a humid tropical environment total erosion rates are extremely slow 10 m m y with equal contributions from the dissolved and suspended loads however the former is largely silica with ratios of si to total cation equivalents si tz ranging to in excess of three weathering is complete to kaolinite and gibbsite i e the environment is one of active laterisation with a penetration rate of the weathering front into the fresh substrate about twice the denudation rate in basins of relatively homogeneous lithology rb sr isochrons constructed from the river data agree with the whole rock ages from the drainages thus all the common refractory rb containing minerals k feldspar mica are completely dissolved the thick lateritic regolith that is accumulating as a result of this intense weathering is a common relict feature on other southern hemisphere shields in the absence of active tectonics or greatly accelerated mechanical erosion the weathering rates of these basement rocks must be quite insensitive to environmental change

alkali diffusion in plagioclase feldspar tracer diffusion kinetics at 1 atm pressure under dry conditions using 6li 41k and 87rb in four plagioclase feldspars have been determined diffusion profiles were measured using an ion microprobe sims the arrhenius parameters and 2 uncertainties for li k and rb respectively in albite are pre exponential factor log do 3 8 1 0 3 4 1 4 and 5 8 3 8 in m2 s and activation energies 146 14 296 30 and 283 85 kj mol the diffusion rate of k in albite at 700 c and 100 mpa water pressure equals that at 1 atm dry suggesting that diffusion of k is not dependent on water fugacity between 0 004 and 100 mpa the k diffusion rate depends on plagioclase anorthite content and is approximately 20 times slower in labradorite than albite li diffusion rates in albite and anorthite are identical a linear relation between log d for the alkalis measured and their ionic radius squared permits an estimate of cs diffusion kinetics diffusion rates are isotropic or nearly so in albite

lithium and its isotopes in major world rivers implications for weathering and the oceanic budget abstract the outstanding problem in the lithium geochemical cycle is the lack of an isotopic mass balance in the ocean the 6li compositions of fresh basalts 4 the hydrothermal fluids derived from them average 9 and seawater significantly heavier at 32 are well understood but only very sparse river input data are available for li mass balance calculations in an attempt to rectify the situation we have measured the lithium concentrations and isotopic compositions of major world rivers draining representative geological terrains this helps both to constrain the river endmember and to understand the behavior of lithium isotopes in the continental weathering environment fluvial isotopic compositions display a very large range 6 0 to 32 2 there is no definitive relationship between 6li and lithology but in general rivers draining marine evaporites are 20 to 22 carbonates 26 to 32 black shales 26 shields 6 6 to 19 and mixed siliceous terrains 6 to 28 the flow weighted mean concentration of the measured rivers is 215 nm at 23 this updated riverine 6li value responsible for 30 of the global riverine discharge does not solve the isotopic imbalance if the measured li concentrations and isotopic compositions are representative of all rivers the presence of a yet unidentified sink with a higher fractionation factor 1 023 than determined for low temperature basalt alteration 1 019 is required for an isotopic steady state of li in the ocean authigenic clays are a possible candidate as clays are known to be enriched in both lithium and in the light isotope preferentially alternatively the hydrothermal flux must be much less than half of that estimated by the 3he inventory and the oceanic budgets for 87sr 86sr and mg the relationship of 6li to the major ions and 87sr 86sr suggests that the important processes affecting river dissolved lithium isotopic compositions are fractionation between solution and secondary minerals and thus the intensity of weathering

himalayan uplift and osmium isotopes in oceans and rivers previous studies have shown that 187 os 188 os in seawater has become increasingly radiogenic over the last 40 ma in a manner analogous to strontium this rapid rise in the marine 187 os 188 os over the last 17 ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the himalayas and or selective weathering and erosion of highly radiogenic organic rich ancient sediments the key test of this hypothesis is the 187 os 188 os and the total osmium concentration of the himalayan rivers we report the concentration and isotopic composition of osmium in the ganges the brahmaputra and the indus rivers the 187 os 188 os of the ganges close to its source at kaudiyal 30 05 n 78 50 e is 2 65 and os 45 fm kg a second sample of the lower reaches of the ganges at patna 25 30 n 85 10 e gives 187 os 188 os 1 59 and os 171 fm kg the 187 os 188 os of the brahmaputra at guwahati 26 10 n 91 58 e is 1 07 and os 52 fm kg a sample of the indus besham 34 55 n 72 51 e has a 187 os 188 os of 1 2 and os 59 fm kg we infer that the himalayas do not provide either a high flow of osmium or a highly radiogenic osmium component to the oceans the overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the himalayas themselves appear not to be the dominant source

lithium isotopic composition of submarine basalts implications for the lithium cycle in the oceans abstract we have measured the li isotope composition of young pristine basalts from active ocean ridge crests of progressively older basalts along a dredging transect and a limited number of hydrothermally altered basalts the data significantly extend our limited knowledge of the isotopic abundance ratio of li in geological material fresh mid ocean ridge basalts have 6li values of between 3 4 and 4 7 relative to isotope standard l svec during low temperature weathering on the seafloor the isotopic composition of the rock becomes increasingly heavier due to addition of seawater li 6li 32 3 the oldest 46 m y and most altered rock studied has an isotopic composition of 14 a linear relationship exists between 6li and the inverse of li concentration suggesting that li in weathered basalts can be regarded as a two component mixture of basaltic li and seawater derived li that has been incorporated in alteration minerals most likely secondary clays such as smectite and phillipsite the inferred li isotopic composition of the alteration endmember indicates an apparent isotopic fractionation factor of 1 019 relative to the seawater source thus li uptake by secondary minerals from the low temperature weathering process and by analogy incorporation in similar authigenic minerals in marine sediments provides a mechanism for preferential removal of the lighter li isotope from ocean water however isotopic fractionation due to authigenic clay formation alone cannot account for the isotopic difference between seawater and its principal sources unless the hydrothermal flux is comparable to the river flux alternatively more important sinks of6li must exist if the steady state isotopic composition of li in ocean water is to be maintained

lithium isotopes as tracers of groundwater circulation in a peat land abstract water circulation in the peat bog of a maar depression in the massif central france was traced with lithium isotopes on water samples collected in the area from springs surface and groundwaters as well as on solid samples taken from peat bogs lithium contents fluctuate significantly in the groundwaters ranging from 0 01 mol l 1 in springs feeding the peat bog up to 28 mol l 1 in the groundwater collected in the peat bog lithium isotope compositions 7li are extremely variable within the site ranging from 12 in the stream draining the area up to a 7li rich value of 1226 in groundwater from the peat bog the 7li values in the streams agree with those reported in the literature for surface waters while those of groundwater are far beyond the range of values measured in nature in the present study we explain the extremely enriched 7li signature of the groundwaters by an external input due to ca amendment used in local agriculture the relationships between li content and ca mg and hco3 as well as the lack of a relationship between li and na plead in favour of 7li enriched carbonate amendments this hypothesis was tested by li isotope analyses on the peat and on several amendment samples carbonates and npk fertilizers confirming the potential role of amendments in the control of li isotopes in peat land groundwater and showing high 7li values in fertilizers application of 7li ratios to peat land waters provides a unique perspective on the hydrogeochemical dynamics at the scale of this site as the 7li values for the surface water were quasi constant throughout the survey period and the peat land groundwater does not supply the surface water runoff and may evolve as a stagnant system to conclude the water within the peat land exhibits very high 7li values consistent with artificially enriched 7li associated with ca amendments this study opens a new field for li isotope investigations in hydro systems and highlights the possibility of using li isotopes as environmental tracers

distribution of uranium and thorium series radionuclides in mineral phases of a weathered lateritic transect of a uranium ore body abstract a surficial weathered 400 m long profile of the ranger one ore body 3 northern territory australia has been characterised to a depth of 10 m in terms of the total uranium 238 u 234 u 232 th 230 th and 228 th distributions and measurements of other geochemically important elements the characterisation was limited to the 234 u 230 th and 228 th precipitation due to evaporation of ground and interstitial water and the adsorption of uranium and thorium within a time frame less than that required for 234 u 238 u and 230 th 234 u to achieve secular radioactive equilibrium the mineralogical composition of the soil is to some extent responsible for local variations in the measured properties the differences in chemical speciation and behaviour of uranium and thorium enhance the variability in the 230 th 234 u activity ratios the monsoonal climatic and hydrological variations intensify some of the observed effect

downstream and seasonal changes of lithium isotope ratios in the ganges brahmaputra river system the li isotope ratio 7li is expected to be a useful tracer of silicate weathering in river and groundwater systems which is an important contributor to the seawater compositional changes that accompany the evolution of the earth s surface environment to obtain accurate estimates of continental li fluxes to the ocean we determined 7li values of dissolved li in the lower ganges brahmaputra river system in both the dry and rainy seasons and in deep groundwater in the bengal basin dissolved li and 7li values in the lower reaches of the rivers 0 04 0 66 mol kg 1 and 19 1 to 34 2 respectively were predominantly derived from silicate weathering as is the case in the upper parts of these rivers we observed large changes in 7li over a distance of more than 1000 km downstream that were due mainly to rayleigh type removal of li from river water extremely high li concentrations 1 15 1 67 mol kg 1 and low 7li values 5 1 to 11 6 in groundwater samples indicate congruent isotope leaching and dissolution of silicate minerals in the deep aquifer where the water residence time is long in the rainy season li concentrations and 7li values were lower than in the dry season owing to the shorter residence time of river water and the substantial input of local subsurface flow through lowland alluvium these results suggest that accurate estimation of continental li fluxes to the ocean should take account of downstream and seasonal changes as well as aquifer depth variations in 7li values

lithium isotopic composition of central american volcanic arc lavas implications for modification of subarc mantle by slab derived fluids abstract li contents and isotopic compositions were determined for a suite of well characterized basaltic lavas from the central american volcanic arc cava variable li y 0 2 0 5 li sc 0 1 0 4 and 6 li values 2 6 to 7 7 attest to significant compositional heterogeneity in the subarc mantle within specific arc segments these parameters correlate strongly with each other and with a number of other constituents e g k rb ba b la 10 be 9 be 87 sr 86 sr u ce and 230 th 232 th among others these correlations are particularly strong for nicaragua samples coupling of this particular set of constituents is best explained in terms of addition of subduction components to the subarc mantle moreover their selective enrichment with respect to relatively fluid immobile incompatible elements signifies the dominance of fluid vs silicate melt transport of slab components to the subarc mantle several interesting nuances are revealed by the li data first although li and b are strongly correlated in both costa rica and nicaragua there are systematic along strike variations in li b that are consistent with these elements having different fluid release patterns from subducted slab segments for example li b is highest in costa rica where auxiliary evidence indicates higher subduction zone temperatures apparently b is preferentially depleted and li retained in the slab under warmer conditions the same relations are reflected in li 10 be and other subduction tracer systematics all of which point to larger subduction contributions below nicaragua yet even nicaragua lavas vary widely in levels of subduction enrichment high ti basalts from nejapa are the least enriched and have the highest 6 li 1 4 to 2 6 these values are greater than in fresh morb ca 4 and are not easily explained by additions of subducted li because most oceanic crustal rocks and marine sediments have lower 6 li than morb with typical values between 8 and 20 thus it appears the nejapa data may be representative of isotopically light mantle domains relatively light 6 li values in an undepleted spinel lherzolite 11 3 from zabargad is red sea and in primitive backarc basalts 1 6 to 0 5 from lau basin support this conclusion considering representative fluid and mantle endmember compositions the cava data are consistent with limited up to a few percent additions of slab derived fluids to a heterogeneous mantle containing variably depleted and enriched domains to form the respective magma sources in our view the subarc mantle is heterogeneous on a small scale but some arc sectors clearly received greater slab inputs than others

a possible link between the seawater osmium isotope record and weathering of ancient sedimentary organic matter the os isotopic composition of leachable os from a north pacific pelagic clay sequence pegram et al 1992 and bulk sediment samples of metalliferous carbonates deposited near the east pacific rise ravizza 1993 display similar patterns of temporal variation fig 1 this similarity indicates that the composite record of t87os 186os ratio variations reflects changes in the os isotopic composition of seawater temporal changes in the sr isotopic composition of seawater record changes in the relative rates of continental weathering and oceanic crustal alteration the os isotopic composition of seawater should be influenced by similar processes in both the rb sr and re os systems the continental crust is characterized by large time integrated parent daughter ratios compared to the deep earth imparting relatively radiogenic sr and os signatures to continental material however the seawater sr and os records are decoupled from one another over the past 27 ma from 27 to 15 ma 87sr 86sr increased rapidly while the 18vos 186os ratio of seawater remained nearly constant at 15 ma the 87os ts6os ratio of seawater began to increase rapidly but the rate

lithium isotope geochemistry of pore waters from ocean drilling program sites 918 and 919 irminger basin the distribution of li isotopes in pore waters to a depth of 1157 m below seafloor is presented for odp sites 918 and 919 in the irminger basin offshore greenland lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material as well as by very high accumulation rates in the upper section the lowering of the 87sr 86sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration the li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases these include cation exchange with nh4 and mobilization from sediments at depth in addition to the alteration of volcanic matter lithium isotopes are therefore a sensitive indicator of sediment water interaction 6li values of pore waters at these two sites vary between 42 and 25 at shallow depths 100 mbsf rapid decreases in the li concentration accompanied by a shift to heavier isotopic compositions indicate uptake of li into alteration products a positive anomaly of 6li observed at both sites is coincident with the nh4 maximum produced by organic matter decomposition and may be related to ion exchange of li from the sediments by nh4 in the lower sediment column at site 918 dissolved li increases with depth and is characterized by enrichment of 6li the li isotopic compositions of both the waters and the solid phase suggest that the enrichment of li in deep interstitial waters is a result of release from pelagic sediments the significance of sediment diagenesis and adsorption as sinks of oceanic li is evaluated the maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5 of the combined inputs from rivers and submarine hydrothermal solutions adsorption on to sediments can only account for 5 10 of the total inputs from rivers and submarine hot springs