solubility of silica polymorphs in electrolyte solutions ii activity of aqueous silica and solid silica polymorphs in deep solutions from the sedimentary paris basin abstract activity coefficient for aqueous silica in saline waters and brines from the paris basin was calculated using pitzer s specific interaction model quartz and chalcedony are the only reported authigenic silica minerals in the dogger aquifer of the paris basin france however the measured silica concentrations fall between those of these two phases the silica concentrations measured in dogger fluids seem to be controlled by a microcrystalline quartz phase with a grain size computed to be about 20 nm studies have shown that pressure can preserve small grain size for a long time at the geological scale the effective mechanism of pressure action is probably linked to the fact that pressure simultaneously favours dissolution at the grain contact inducing a quartz supersaturation and prohibits the increase in size of reprecipitated microcrystalline quartz grains this hypothesis is supported by other studies reported in the literature the proposed model which incorporates silica mineralogy and a precise calculation of aqueous silica activity allows us to explain measured silica concentrations in the deep sedimentary solutions of the dogger aquifers in the keuper brines silica solubility can in most cases be explained by an equilibrium with either chalcedony or quartz another application of the present work is shown by an example where we examined the importance of precisely evaluating the activity coefficient in basin characterisation as the goal of reservoir characterisation is to describe the spatial distribution of petrophysical parameters such as porosity permeability and saturations

variation of lithium isotope composition in the marine environment a preliminary report the li isotopic compositions of ocean waters lake water hydrothermal solutions altered and unaltered basalts have been determined using the technique of thermal ionization mass spectrometry of lithium tetraborate seawater appears to be homogeneous in li isotopic composition the mean delta sup 6 li value is minus 32 3 plus minus 0 5 per thousand relative to an isotopic standard three lakes studied lake tanganyika caspian sea and dead sea yield delta sup 6 li similar to the seawater isotopic composition a fresh basalt glass from 21 degree n east pacific rise displays a delta sup 6 li value of minus 4 7 per thousand a hydrothermal solution from a 21 degree n vent field has delta sup 6 li of minus 10 per thousand indicating incomplete extraction of li from the igneous minerals or partial retention in secondary phases the alteration margin of a basalt from the mid atlantic ridge has delta sup 6 li of minus 8 4 per thousand the isotope data of submarine basalts suggest preferential removal of sup 6 li from seawater into alteration minerals during low temperature weathering the delta sup 6 li values of two hydrothermal solutions from guaymas basin were found to be minus 5 per thousand and minus 10 per thousand the results can be interpreted as the net effect of li addition from basalt and sediments and incorporation in hydrothermal precipitates as the hydrothermalmore fluids interact with basin sediments the observed enrichment of sup 7 li in seawater relative to submarine hydrothermal solutions its principal li input is tentatively attributed to isotopic fractionation associated with low temperature alteration of sea floor basalt and incorporation in authigenic sediments it appears that the li isotope system may have characteristics that can resolve the mass balance of li in the ocean less

the relationship between riverine lithium isotope composition and silicate weathering rates in iceland abstract this study presents lithium isotope and elemental data for the dissolved phase and suspended and bedload sediments of the major icelandic rivers for the dissolved phase 7li values range between 10 1 and 23 8 while river sediments display lower and much more homogeneous values 7li 3 1 4 8 close to the composition of unweathered mid ocean ridge basalt morb high 7li values are associated with high k li na li and mg li ratios in waters draining mainly old and weathered basalt catchments whereas low 7li rivers are located in younger parts of the island simple mixing between precipitation li rich hydrothermal springs and basalt weathering is unable to explain the entire range of 7li values instead a simple model of li uptake by secondary minerals associated with clay water li isotope fractionation 7li ranging from 1 to 7 5 can explain both water and sediment 7li values a negative correlation is observed between basalt chemical erosion rates and 7li measured in icelandic rivers and an empirical law is inferred comparison with literature data suggests that this relationship may be applicable at a more global scale and if confirmed could be of particular use for estimating the evolution of continental weathering preserved in marine sedimentary records however more data are now needed for rivers draining silicates typical of the continental crust in order to refine large scale modelling

chemical multi isotopic li b sr u h o and thermal characterization of triassic formation waters from the paris basin this work reports chemical and isotope data and temperature estimates for seven water samples collected from triassic formations in the paris basin in france four samples were collected in the central part of the basin saline waters and three were collected at the edge of the basin near the recharge zone dilute waters the saline waters collected from the chaunoy and champotran boreholes have high salinities around 120 g l and very similar chemical and isotopic compositions the saline water sample from the la torche borehole has much higher salinity 168 g l and significantly different isotope characteristics the chemical geothermometers applied to these fluids from the centre of the basin give temperature values ranging between 80 and 100 c the fresh water samples collected at the edge of the basin have very different chemical and isotopic compositions these dilute water samples santenay and ch teauroux are shallow with colder temperatures of around 45 to 50 c the study of uranium activity ratios for these triassic formation waters allows us as a first approximation to estimate a mean apparent fluid circulation velocity of around 0 2 m yr which corresponds to a mean age slightly higher than 1 my for waters sampled in the chaunoy champotran and la torche fields in the centre of the basin the multi isotope characterization of triassic formation waters shows that our data are in agreement with literature values as concerns traditional isotope systematics delta18o deltad 87sr 86sr li and b isotope signatures in the centre of the paris basin are in a good agreement with a fluid signature derived mainly from water rock interactions involving clastic rocks with water essentially resulting from a seawater derived brine endmember diluted by meteoric waters the data reported in the present work for li and b isotopes could be used as a reference for future studies to characterize sandstone formation waters

boron isotope variations in nature a synthesis the large relative mass difference between the two stable isotopes of boron 10b and 11b and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes published 11b values relative to the nbs srm 951 standard span a wide range of 90 the lowest 11b values around 30 are reported for non marine evaporite minerals and certain tourmalines the most 11b enriched reservoir known to date are brines from australian salt lakes and the dead sea of israel with 11b values up to 59 dissolved boron in present day seawater has a constant world wide 11b value of 39 5 in this paper available 11b data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects including possible tracer applications of boron isotope geochemistry are summarized

transport of radionuclides in an unconfined chalk aquifer inferred from u series disequilibria abstract u series disequilibria measured in waters and rocks from a chalk aquifer in france have been used as an analog for long term radionuclide migration drill core samples from a range of depths in the vadose zone and in the saturated zone as well as groundwater samples were analyzed for 238 u 234 u 232 th and 230 th to determine transport mechanisms at the water rock interface and to quantify parameters controlling the migration of radionuclides isotope measurements in rocks were done by tims whereas 234 u 238 u and 230 th 232 th activity ratios in water samples were measured by multi collector icp ms both depletion and enrichment in 234 u relative to 238 u were observed in carbonate rock samples resulting from chemical weathering in the unsaturated zone and calcite precipitation in the zone of water table oscillation respectively the correlation between 230 th 232 th activity ratios and 87 sr 86 sr ratios found in the chalk samples indicates that thorium is mainly contained in a minor silicate phase whose abundance is variable in chalk samples water samples are all characterized by 234 u 238 u 1 resulting from recoil effect of 234 th groundwaters are characterized by a more radiogenic signature in 87 sr 86 sr than the rocks moreover 230 th 232 th activity ratios in the waters are lower than in the rocks and increase with distance from the water divide which suggests that th transport is controlled by colloids formed during water infiltration in the soil a 1 d transport model has been developed in order to constrain the u series nuclide transport considering a transient behavior of radionuclides in the aquifer and a time dependent composition for the solid phase this model permits a prediction of the time scale of equilibration of the system and an estimation of parameters such as weathering rate distribution coefficients and recoil fractions retardation factors of 10 35 and from 1 10 4 to 2 10 5 were predicted for u and th respectively and can be used to predict the migration of radionuclides released as contaminants in the environment at the scale of our watershed 32 km 2 a characteristic migration time from recharge to riverine discharge of 200 600 yr for u and 0 2 3 7 myr for th was obtained

noble gases in crude oils from the paris basin france implications for the origin of fluids and constraints on oil water gas interactions in order to investigate the potential of noble gases to trace the dynamics of oil reservoirs we have analysed the abundance and isotopic composition of all noble gases he ne ar kr and xe in crude oils from the paris basin france using a new extraction and purification procedure the main oil reservoirs are presently located in the jurassic dogger limestone and in the triassic keuper sandstone but hydrocarbons originated from a common source rock formation located in the interbedded liassic sequence despite this common origin the abundance and isotopic ratios of the noble gases differ between the dogger and the keuper the isotopic compositions of kr and xe are indistinguishable from that of air 3he 4he ratios higher than those predicted from radiogenic production in the sediments or in the crust are attributed to the occurrence of mantle derived 3he in the basin each sedimentary sequence is characterised by well defined and homogeneous 21ne 22ne and 40ar 36ar ratios which average 0 0306 0 0008 and 312 10 for the dogger and 0 0367 0 0012 and 664 30 for the keuper respectively the main source of radiogenic noble gases appears to be the continental crust underlying the basin with possible regional contributions of noble gas isotopes produced in the sediments the helium and argon isotopic ratios of the dogger oils are very similar to those observed in geothermal waters flowing in the dogger aquifer throughout the basin demonstrating that noble gases in oils derive from associated groundwaters oil reservoirs in the paris basin therefore accumulate noble gases from wide regions of the continental crust through cross formational flow of groundwaters and subsequent partitioning into oil this observation implies that noble gases cannot be directly used to date oils but can provide time constraints if 1 water oil interactions are quantified and 2 the residence time as well as the noble gas characteristics of associated groundwaters are known oil water gas partitioning processes are well recorded in the fractionation of noble gas elemental abundance two distinct processes have been identified 1 accumulation of atmosphere derived ang and radiogenic noble gases both initially dissolved in groundwaters resulting in a positive correlation between absolute amount of ang and the extent of heavy noble gas fractionation and 2 subsequent fractional degassing resulting in a negative correlation between ang abundance and heavy noble gas fractionation degassing is particularly evident for the keuper oils and might have occurred in the reservoirs following hydrodynamic gas stripping the ang abundance in the dogger reservoirs requires that about one order of magnitude more water than presently observed has interacted with the oil given current estimates of the residence time for groundwaters in the dogger aquifer the duration of oil water interaction is in qualitative agreement with a palaeocene oligocene age for the major episode of secondary oil migration in the paris basin high xenon contents in keuper reservoirs suggest that they have experienced hydrodynamic interactions between flowing waters and oils for long time and that the trias might have reached hydrostatic condition only recently

radiocarbon dating of groundwater of the aquifer confined in the lower triassic sandstones of the lorraine region france abstract blavoux b and olive ph 1981 radiocarbon dating of groundwater of the aquifer confined in the lower triassic sandstones of the lorraine region france in w back and r letolle guest editors symposium on geochemistry of groundwater 26th international geological congress j hydrol 54 167ndash 183 stable isotope and groundwater chemistry analyses on samples from about 40 boreholes in the lorraine region eastern france are used to evaluate the paleohydrological regime of the lower triassic sandstone aquifer in the study of the mechanisms of the general water dynamics of the aquifer at present in this sandstone aquifer the estimation of the 14 c activity a 14 in the total dissolved carbon tdc to 100 of modern carbon is justified by the absence of carbonates in the reservoir and by the 13 c contents in the tdc a significant relation could be determined between the 14 c activity in the tdc and 13 c a 14 7 7 13 59 6 this gradual enrichment of the tdc with 13 c results from the escape of the dissolved co 2 the meaning of the radiometric age is discussed as a function of piston and exponential type flows the study of the stable isotopes 18 o and 2 h revealed two water families the most recent waters have 18 o values higher by 1 0 than the more than 10 4 yr old waters this 1 0 discontinuity corresponds to the improvement of weather conditions during the holocene which amounts to 2 5 c the isochrons of the aquifer reveal the existence of hydrogeological sections bounded by faults where the rates of circulation are different

behavior of lithium and its isotopes during weathering of hawaiian basalt 1 we examined the pedogenic behavior of lithium li and its isotopes in hawaii by sampling same age lava flows under mean annual rainfall ranging from 18 to 300 cm lithium concentrations in these soils vary from 1 to 29 ppm whereas na k and ca are completely leached from the soil at the most humid and severely weathered site li mg si and al show significant retention due to their association with secondary clay minerals in these soils allochthonous li delivered in marine and mineral aerosol mixes with basalt derived li modifying the isotopic composition of the li pool the ability of soil to retain li is related to its effective cation exchange capacity which in turn is governed by rainfall and leaching intensity and their resulting effect on mineralogy lithium isotope ratios have a large range 7li of 0 4 to 14 well beyond the intershield or temporal variation of the lavas of hawaiian volcanoes 2 5 to 5 7 the most unweathered samples have 7li 5 6 comparable to that of mauna kea and mauna loa lavas the li concentrations and isotope ratios together suggest that in arid to subhumid sites there is a net addition of isotopically heavier lithium from marine aerosol but that under greater rainfall there is a net loss of li and isotopically light li is preferentially retained thus during incongruent weathering of primary minerals li especially 6li is adsorbed and sequestered by the clay mineral fraction of high cation exchange capacity soils in drier regions but lost from highly weathered low cation exchange capacity acidic soils in the wetter regions

stable isotope conservation and origin of saline waters from the middle jurassic aquifer of the paris basin france abstract seventy nine samples of formation water from geothermal boreholes oil field and ground water wells tapping the dogger middle jurassic limestone reservoir of the paris basin have been analyzed for their 2h 18o tds bromide and chloride contents geostatistical mapping of 2h and of 18o contents and their variations with chloride content indicate that both isotopes have a common origin and a similar behaviour within the aquifer the 2h and 18o values increase progressively from the outcrops toward a zone where temperature cl and tds values are high the 2h and 18o values are very uniform in this zone and do not show any relation with formation temperature in contrast to what is generally observed in other sedimentary basins a discussion of isotopes exchange with the carbonate matrix for oxygen and with h2s for deuterium shows that such processes are not controlling the heavy isotope contents of groundwaters this is attributed to the relatively short residence time of groundwaters in the aquifer both 2h and 18o contents of groundwater may thus be considered as conservative tracers in the dogger aquifer of the paris basin and their initial contents are modified only by fluid mixings complex mixing processes account for stable isotope composition tds cl and br values of the dogger fluids all mixtures include a brine component meteoric water percolated and dissolved halite in the triassic aquifer secondary brine this saline solution mixed with some residual primary brine then migrated via vertical faults into the dogger aquifer such migration is found to be in agreement with data from fluid inclusions in late carbonate cements from the liassic and dogger strata the requirement that these units were exposed implies that meteoric invasion could not have occurred before the tertiary successive mixings of the brine with several types of meteoric waters depleted in heavy isotopes account for the present isotope and chemical compositions of the dogger fluids

the chemistry of geothermal waters in iceland iii chemical geothermometry in geothermal investigations abstract new data from geothermal wells in iceland have permitted empirical calibration of the chalcedony and na k geothermometers in the range of 25 180 c and 25 250 c respectively the temperature functions are t c 1112 4 91 log sio 2 273 15 t c 933 0 993 log na k 273 15 concentrations are expressed in ppm these temperature functions correspond well with the chalcedony solubility data of fournier 1973 and the thermodynamic data for low albite microcline solution equilibria of heloeson 1969 a new co2 geothermometer is proposed which is considered to be useful in estimating underground temperatures in fumarolic geothermal fields its application involves analysis of co2 concentrations in the fumarole steam the temperature function which applies in the range 180 300 c is logco2 37 43 73192 t 11829 103 t2 0 18923t 86 187 logt where t is in k and co2 in moles per kg of steam

a lithium isotope study of hot springs and metabasalts from mid ocean ridge hydrothermal systems the li isotopic compositions of seawater and of fresh and altered basalts are distinct and therefore applicable to the study of the hydrothermal processes in the oceanic crust and the li balance in the ocean high temperature fluids from seven vents on the east pacific rise epr at 21 n and 11 13 n have 6li values ranging between 6 and 11 i e 3 7 heavier than fresh basalt values the intervent variations in li concentration and isotopic composition correlate well with water rock ratios no temporal change in the isotopic value was observed between 1981 and 1985 metabasalts show both li depletion and enrichment relative to fresh basalt they display light li isotopic values which reflect incorporation of li mobilized from fresh basalt from these observations we conclude that the li isotopic composition of submarine hot springs is controlled by a path dependent process involving dissolution of primary minerals and precipitation of li with alteration phases 6li values of fluids from the mid atlantic ridge 6 to 8 fall in the range of the epr indicating similar reaction controls at the two ridge systems the lack of 7li enrichment in the fluids from slower spreading ridges indicates that li is not recycled from older weathered crust thus the difference between the 3he and 87sr 86sr based hydrothermal flux and the crustal transfer rate of li cannot be reconciled by the inclusion of secondary li from older crust

behaviour of lithium and its isotopes during weathering in the mackenzie basin canada we report li isotopic compositions for river waters and suspended sediments of about 40 rivers sampled within the mackenzie river basin in northwestern canada the aim of this study is to characterize the behaviour of li and its isotopes during weathering at the scale of a large mixed lithology basin the mackenzie river waters display systematically heavier li isotopic compositions relative to source rocks and suspended sediments the range in delta li 7 is larger in dissolved load from 9 3 parts per thousand to 29 0 parts per thousand compared to suspended sediments from 1 7 parts per thousand to 3 2 parts per thousand which are not significantly different from delta li 7 values in bedrocks our study shows that dissolved li is essentially derived from the weathering of silicates and that its isotopic composition in the dissolved load is inversely correlated with its relative mobility when compared to na the highest enrichment of li 7 in the dissolved load is reported when li is not or poorly incorporated in secondary phases after its release into solution by mineral dissolution this counterintuitive observation is interpreted by the mixing of water types derived from two different weathering regimes producing different li isotopic compositions within the mackenzie river basin the incipient weathering regime characterizing the rocky mountains and the shield areas produces li 7 enrichment in the fluid phase that is most simply explained by the precipitation of oxyhydroxide phases fractionating li isotopes the second weathering regime is found in the lowland area and produces the lower delta li 7 waters but still enriched in li 7 compared to bedrocks and the most li depleted waters compared to na fractionation factors suggest that the incorporation of li in clay minerals is the mechanism that explains the isotopic composition of the lowland rivers the correlation of boron and lithium concentrations found in the dissolved load of the mackenzie rivers suggests that precipitation of clay minerals is favoured by the relatively high residence time of water in groundwater in the shield and rocky mountains li isotopes suggest that clay minerals are not forming and that secondary minerals with stronger affinity for li 7 appear although the weathering mechanisms operating in the mackenzie basin need to be characterized more precisely the li isotope data reported here clearly show the control of li isotopes by the weathering intensity the spatial diversity of weathering regimes resulting from a complex combination of factors such as topography geology climate and hydrology explains in fine the spatial distribution of li isotopic ratios in the large drainage basin of the mackenzie river there is no simple relationship between li isotopic composition and chemical denudation fluxes in the mackenzie river basin

temporal record of lithium in seawater a tracer for silicate weathering abstract this paper presents multi species records of the li ca ratio and li isotopic composition 7 li of planktonic foraminifera from the pacific and atlantic oceans for the past 18 ma the li ca record is corrected for interspecific offsets determined from recent holocene foraminifera interspecific offsets in 7 li are not significant despite different diagenetic histories the records produced from both oceans are remarkably consistent corrected planktonic foraminiferal li ca ratios range from 6 3 to 10 9 mol mol while planktonic foraminiferal 7 li ranges from 25 to 31 both records are interpreted in terms of long term changes in seawater li ca and 7 li enabling issues related to higher resolution variability in li ca and 7 li to be ignored by assuming that the hydrothermal flux of li into the oceans and the flux of li removed from the oceans during low temperature uptake by marine basalts and sediments have not changed significantly since 18 ma and using published records for the seawater calcium concentration the seawater li ca and 7 li records can be used to estimate global average river 7 li and li fluxes our records indicate that the river flux of dissolved li decreased between 16 and 8 ma while the 7 li value of the river input increased these data imply that both silicate weathering rates and weathering intensity decreased over this interval which may have been responsible for putative increases in levels of atmospheric co 2 in contrast the riverine flux of li has increased since 8 ma while its 7 li value has increased this implies that the silicate weathering rate has increased while weathering intensity has decreased since that time

rare earth elements neodymium and strontium isotopic systematics in mineral waters evidence from the massif central france abstract rare earth elements rees and sr and nd isotope distributions have been studied in mineralized waters from the massif central france the co 2 rich springs are characterized by a neutral ph 6 7 associated with total dissolved solids tds from 1 to 7 g l 1 the waters result from the mixing of very mineralized water pools thought to have equilibrated at a temperature of around 200 c with superficial waters these two mineral water pools evidenced by sr isotopes and dissolved rees could reflect 2 different stages of water rock interaction and an equilibrium with different mineral assemblages the concentrations of individual dissolved rees and total dissolved rees ree in the mineral waters examined vary over several orders of magnitude but are not dependent on the main parameters of the waters tds t c ph total organic c the dissolved ree concentrations presented as upper continental crust normalized patterns show hree enrichment in most of the samples the time evolution of ree patterns does not show significant fluctuations except in 1 borehole located in the limagne d allier area which was sampled on 16 occasions over an 18 month period ten samples are hree enriched whereas 6 samples show flat patterns the aqueous speciation of rees shows that co 2 3 complexes dominate 80 over the free metal f so 2 4 and hco 3 complexes the detailed speciation demonstrates that the fractionation of rees i e the hree enrichment in co 2 rich and ph neutral fluids is due essentially to the predominance of the co 2 3 complexes the sr isotopic composition of the mineral waters in the massif central shows different mixing processes in the cezallier area at least 3 end member water types exist the most dilute end member is likely to originate as poorly mineralized waters with minimal groundwater circulation two other mineralized end members are identified although the link between the geographical location of spring outflow and the mixing proportion between the 2 end members is not systematic the range in nd 0 for mineralized waters in the massif central correlates well with that of the known parent rocks except for 4 springs one way to explain the nd 0 in these instances is a contribution from drainage of volcanic rocks the isotopic systematics help to constrain the hydrogeological models for this area

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

behaviour of major elements and some trace elements li rb cs sr fe mn w f in deep hot waters from granitic areas abstract analyses of selected hot springs in more than sixty areas in granites from europe are presented concentrations of major elements and of some trace elements li rb cs sr fe mn w f in high ph waters are not significantly affected by processes during uprise from the deep reservoir to the surface re equilibrations mixing with surficial waters normalized to k or na concentrations of all other elements are related to the aquifer temperature the knowledge of aquifer temperature and total electric charge of mobile elements cl s possibly f allows us to predict both major elements within 50 and trace elements within a factor 2 or 3 concentrations in alkaline waters from granites

ground tilt changes in japan caused by the 2010 maule chile earthquake tsunami 1 oscillating ground tilt perturbations accompanied by the 2010 maule chile earthquake tsunami were observed over a broad inland area facing the pacific ocean coast in japan by a high density tiltmeter network through an analysis of ground tilt data observed at more than 500 stations we were able to obtain a detailed spatiotemporal distribution of the tsunami induced tilt changes and reveal a relationship between the tilt amplitude and the distance from the coast at distances of 1 km or less the peak tilt amplitudes were 5 10 2 rad and were almost constant with respect to the distance at distances greater than 3 km amplitudes were inversely proportional to the distance and reached 5 10 3 rad approximately 50 km away from the coast the dominant ground tilting directions were almost the same as the direction orthogonal to the coastline these observed ground tilt changes and their characteristics were successfully modeled with a loading deformation caused by sea level variations accompanied by the tsunami applying a two dimensional boxcar tsunami model to the observed data we estimated the water volume per unit length of coast for the maule earthquake tsunami to be 2 7 103 m3 m within the distance of 14 20 km seaward of the coastline

lithium and lithium isotope profiles through the upper oceanic crust a study of seawater basalt exchange at odp sites 504b and 896a abstract ocean drilling program odp hole 504b near the costa rica rift is the deepest hole drilled in the ocean crust penetrating a volcanic section a transition zone and a sheeted dike complex the distribution of li and its isotopes through this 1 8 km section of oceanic crust reflects the varying conditions of seawater alteration with depth the upper volcanic rocks altered at low temperatures are enriched in li 5 6 27 3 ppm and have heavier isotopic compositions 7li 6 6 20 8 relative to fresh mid ocean ridge basalt morb due to uptake of seawater li into alteration clays the li content and isotopic compositions of the deeper volcanic rocks are similar to morb reflecting restricted seawater circulation in this section the transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization li enrichment in this zone is accompanied by relatively light isotopic compositions 0 8 2 1 which signify influence of basalt derived li during mineralization and alteration li decreases with depth to 0 6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high temperature reaction zone rocks in the dike complex have variable isotopic values that range from 1 7 to 7 9 depending on the extent of hydrothermal recrystallization and off axis low temperature alteration hydrothermally altered rocks are isotopically light because 6li is preferentially retained in greenschist and amphibolite facies minerals the 7li values of the highly altered rocks of the dike complex are complementary to those of high temperature mid ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage the inventory of li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of li in the ocean on balance the upper 1 8 km of oceanic crusts remains a sink for oceanic li the observations at 504b and an estimated flux from the underlying 0 5 km of gabbro suggest that the global hydrothermal flux is at most 8 109 mol yr compatible with geophysical thermal models this work defines the distribution of li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle

lithium isotope systematics in a forested granitic catchment strengbach vosges mountains france abstract over the last decade it has become apparent that li isotopes may be a good proxy to trace silicate weathering however the exact mechanisms which drive the behaviour of li isotopes in surface environments are not totally understood and there is a need to better calibrate and characterize this proxy in this study we analysed the li concentrations and isotopic compositions in the various surface reservoirs soils rocks waters and plants of a small forested granitic catchment located in the vosges mountains strengbach catchment france ohge http ohge u strasbg fr li fluxes were calculated in both soil profiles and at the basin scale and it was found that even in this forested basin atmospheric inputs and litter fall represented a minor flux compared to input derived from the weathering of rocks and soil minerals which together represent a minimum of 70 of dissolved li li isotope ratios in soil pore waters show large depth dependent variations average dissolved 7 li decreases from 1 1 to 14 4 between 0 and 30 cm but is 30 7 at 60 cm this range of li isotopic compositions is very large and it encompasses almost the entire range of terrestrial li isotope compositions that have been previously reported we interpret these variations to result from both the dissolution and precipitation of secondary phases large isotopic variations were also measured in the springs and stream waters with 7 li varying from 5 3 to 19 6 7 li increases from the top to the bottom of the basin and also covaries with discharge at the outlet these variations are interpreted to reflect isotopic fractionations occurring during secondary phase precipitation along the water pathway through the rocks we suggest that the dissolved 7 li increases with increasing residence time of waters through the rocks and so with increasing time of interaction between waters and solids a dissolution precipitation model was used to fit the dissolved li isotopic compositions it was found that the isotopic compositions of springs and stream waters are explicable by an isotopic fractionation of 5 to 14 best fit 10 8 in agreement with li incorporation into clay in soil solutions it was found that isotopic fractionation during secondary precipitation is larger at least 23 suggesting a major role for different secondary phases such as iron oxides that maybe incorporate li with a higher isotope fractionation

geochemistry and origin of formation brines from the paris basin france 2 saline solutions associated with oil fields abstract oil fields from the paris basin are located in three geological levels dogger middle jurassic rhaetian and keuper upper triassic the origin of water and dissolved salts in saline solutions associated with oil is investigated using the hypothesis that cl and br are conservative in solution in a diagram of cl br ratios vs cl the points of the dogger and the keuper aquifers lie in the zone of primary brines whereas those of the rhaetian are located in the zone of secondary brines the na cl ratio is very high in all of the saline solutions suggesting either a relatively poorly evolved brine at the beginning of halite deposition or some halite dissolution all of the saline solutions especially those from the dogger aquifer are clearly diluted dilution by meteoric waters would not alter the cl br ratio high concentrations of lithium rubidium and boron are attributed to the presence of an extremely evolved brine of marine origin in mixtures of secondary brines formed by dissolution of halite and small amounts of sylvite and ca sulphate mass balance calculations of the excess of cl with respect to na k allows the fraction x of water derived from the primary brine to be calculated assumptions are that all na and k is derived from the secondary brine and that the cl content of the primary brine is constrained by bischofite saturation at 11 000 mmol kg 1 the typical proportion of water from the primary brine waters is 0 7 in the dogger formation and 2 4 in the keuper values of the concentration factor cf expressed as the ratio of the molal concentration of a conservative ion in the evolved brine to its concentration in seawater have been calculated for lithium solutions from the dogger and keuper aquifers have cfli values of 1 8 103 and of 7 7 103 respectively in the rhaetian aquifer the linear relationship between heavy isotope contents of the brine 2h and 18o and the cl content indicates a mixture of two water sources the first one is meteoric water as defined by the intersection of the formation water line with the global meteoric water line 2 h 65 18 o 9 3 the other end member is enriched in heavy isotopes and in cl and is attributed to seawater that has dissolved evaporites mainly halite however the presence of small amounts of an extremely evolved brine is required to account for the bromide lithium rubidium and boron contents of the formation brine from the rhaetian aquifer as this contribution is very limited in amount it cannot affect the heavy isotope content of the formation water mass balance equations are solved for ternary mixtures of meteoric water seawater and brine the same constraints as above no na and k supplied by the primary brine and clbrine 11 000 mmol kg 1 are applied it is also assumed that the seawater component has the same ionic contents as modern seawater and that the salt content of the meteoric component is negligible the fraction of primary brines is x 1 4 according to the cl balance this estimate agrees with that obtained from the lithium balance assuming that the primary brine component was the same as that of the keuper formation water mass balance calculations also indicate that the so42 content of the rhaetian formation water is exclusively due to the secondary brine component in the three saline solutions the very high ca2 contents and high ca 2 mg 2 ratios may be attributed to reaction of the very evolved brine free of so2 4 with gypsum or anhydrite the result is an exchange of mg2 for ca2 which causes a release of ca2 to the solution and a precipitation of secondary mg sulphate this process can also account for the high strontium contents of the analysed samples values of the ratio 87 sr 86 sr are very high in the keuper formation water due to close contact of the solutions with the granitic basement or with granite derived detrital deposits values in the rhaetian and dogger aquifers equal those of upper triassic marine deposits the stable isotope 34s and 18o content of the dissolved aqueous so2 4 indicates a triassic origin for the bulk of sulphate involved in the evolution of formation waters from the rhaetian and from the dogger all geochemical indicators thus show a vertical migration of triassic brines however aqueous so2 4 from the keuper has a permian isotopic signature suggesting a reworking in solution of salts from this period

in situ measurements of li isotopes in foraminifera in situ measurement of li isotope ratios in foraminifera has been developed using a cameca ims 1270 ion microprobe in situ 7li analyses have been performed in biogenic calcite of planktonic foraminifera from various locations results show that for west pacific mixed globigerinoides and globorotalia 22 s161 e the isotopic variability between tests and within a single test respectively is not significantly greater than estimated analytical uncertainty 1 5 mean 7li for several planktonic foraminifera tests corresponds to the seawater value strongly suggesting negligible li isotope fractionation relative to seawater as previously inferred by hall et al 2005 using thermo ionization mass spectrometer and multicollector inductively coupled plasma mass spectrometry techniques combined with scanning electron microscopy and ion microprobe imaging micron sized grains enriched in lithium silica and aluminum have been found in the foraminifera calcite matrix a simple mixing model shows that 0 3 2 wt of marine clays incorporated within the analyzed calcite would lower the foraminifera 7li value by 3 to 10 relative to the isotopic composition of the pure calcite by comparison no such grains have been detected in corals the presence of micron sized silicate grains embedded within the foraminifera calcite is consistent with the erez 2003 biomineralization model involving calcite precipitation from seawater vacuoles by contrast coral calcium carbonate is instead precipitated from ions which have been pumped or diffused through several membranes impermeable to micrometric grains ion microprobe in situ 7li measurements in biogenic calcite present new methods for investigating both biomineralization processes and the past record of the ocean composition by exploring geochemical variations at a scale that is smaller in space and in time

boron isotopic compositions of corals seawater or diagenesis record abstract the first analyses of modern and fossil corals calcite free using a positive ion cs2bo2 tims technique and a chemical procedure for b extraction are reported the 11b for modern corals fluctuates between 23 3 and 25 5 the range of variation of fossil corals from the last interglacial period is greater from 23 5 to 27 3 and the lowest 11b corresponds to the corals close to last glacial maximum boron concentrations show a variation from 49 to 58 ppm in the recent corals and from 39 to 52 ppm in ancient corals for the ancient corals linear correlations are observed in both 11b vs b concentration and 11b vs 1 b plots but these correlations are not observed for modern corals two interpretations are presented to account for these observations and to test the potential of 11b for reconstructing paleo ocean ph the first interpretation assumes a thermodynamic partitioning of b between seawater and carbonates and shows that both boron isotopic compositions and concentrations can be used to calculate the ph of seawater in which corals grow for our data such a model requires that both the ph and the co2 of the deglacial ocean was lower than present day values the second interpretation is based on the correlation observed for ancient corals between boron isotopic compositions and 1 b we suggest that the measured boron isotopic compositions of ancient corals are caused by the mixing of a primary aragonite the coral skeleton and secondary aragonite precipitated from 10b enriched reef pore fluids the characteristics 11b and b concentrations of the diagenetic aragonite and the fluids from which it precipitates can be constrained if this proves correct only the non recrystallised parts of ancient corals can be used for paleo ph reconstructions these recrystallisation processes did not affect the 234u 238u ratios of the corals

uranium series radionuclides in fluids and solids milk river aquifer alberta canada abstract samples from 21 wells completed in the milk river aquifer were sampled and analysed for u isotopes in general u concentrations decrease with distance from the recharge area groundwater samples can be delineated into a small oxic group u content 101t 5 mmol 1 and a more predominant anoxic group u content of 10 7 mmol 1 all groundwater samples were undersaturated with respect to the common u minerals such as uraninite coffinite and rutherfordine the dominant u complexes were uranyl carbonates the234u 238u activity ratios increased from 2 to 11 with distance downflow of the outcrop the highest activity ratio of 11 8 was measured at a well defined redox front whereupon a steady decrease downdip to 4 was observed this decrease was interpreted to be due to the decay of234u excess with age of the groundwater and due to u loss by sorption precipitation processes from solution to solid surfaces two u isotope dating models were used to estimate the age of the groundwater in the milk river aquifer model 1 is a simple model of downdip decay of234u excess in solution under steady state conditions model 2 is a phenomenological model for the evolution of u isotope groundwater composition downdip based on a transport dispersion equation incorporating radioactive decay and assuming that sorption processes are of first order kinetics both models were applied to the u isotope data collected along the same flow path in the aquifer they yielded flowrates of 0 1 0 2 m a and 0 2 0 6 m a respectively the latter range is in good agreement with flowrates of 0 3 m a obtained from hydraulic considerations the lower value derived from model 1 is interpreted in terms of u migration velocity rather than as groundwater flowrate model 2 was also applied to an additional flowpath the calculated flowrate range of 0 1 0 4 m a is in excellent agreement with the hydraulic model flowrate of 0 2 m a the main conclusion of this work is that u isotopes can be used for dating very old groundwaters provided the local hydrogeology and u geochemistry are understood well

geochemical evidence for efficient aquifer isolation over geological timeframes aquitards layers of rock having low permeability have been suggested as potential long term reservoirs for toxic materials such as nuclear or chemical waste but information about the isolation properties of aquitard layers is essential to evaluate whether they can indeed be used safely as reservoirs here we investigate the long term mobility of groundwaters between two aquifers surrounding an aquitard layer in the eastern recharge area of the paris basin france using helium isotopes as a geochemical tracer the deeper trias sandstone aquifer which lies above the crystalline basement accumulates radiogenic 4he and primordial 3he from large regions of the crust and mantle at rates comparable to the degassing of the whole crust1 and of mid ocean ridges2 we show that the overlying carbonate dogger aquifer which is separated from the trias aquifer by an aquitard layer consisting of a 600 m succession of shales and clays is stagnant and has been extremely well isolated from the trias over the past several million years this finding together with previous studies at the centre of the paris basin3 4 shows that diffusive mass transfer across aquitards is negligible and that cross formational flow in basins takes place preferentially in faulted areas

boron isotope geochemistry during diagenesis part ii applications to organic rich sediments the measured clay water isotope fractionation for boron was applied to natural organic rich sediments undergoing illitization two field areas were chosen that show illitization occurring over a range of temperatures 80 500 c samples representing diagenetic temperatures of illitization 80 200 c are from the gulf of mexico sedimentary basin at 4 to 6 km depth in the eocene wilcox fm and jurassic norphlet fm the higher temperatures of illitization 200 500 c occur in a contact metamorphic aureole of the cretaceous pierre shale near walsenburg colorado here the kinetics of the illitization reaction are more rapid than in a slowly subsiding sedimentary basin but the chemical and mineralogical variations are minimized as complete illitization occurs over a small lateral distance in a single bentonite layer these studies indicate that b isotopes provide a more sensitive indicator of fluid variations in sedimentary basins than o isotopes and that b isotope analyses of authigenic illite can be a valuable geochemical tracer of fluid rock interactions boron isotope ratios in authigenic illite pore filling and muscovite stylolites from reservoir sandstones in the gulf of mexico are distinct from adjacent illitic mudstones whereas the oxygen isotopic ratios show little variation fluids in equilibrium with the mudstones cannot precipitate the authigenic clays with higher d 11 b values measured in the hydrocarbon reservoirs this suggests that the reservoir fluids were not in communication with the adjacent mudstone pore fluids but were introduced from another source area perhaps carrying a b isotopic label derived from the hydrocarbon source region authigenic illite formed in the pierre shale meta bentonite shows large isotopic fractionations of boron 20 during illitization at high temperatures incorporation of 500 ppm b in illite formed at 500 c shows that illite is a host for b even at metamorphic temperatures by using the experimentally derived b isotope fractionation data for silicates the measured d 11 b values of i s could be predicted by using a rayleigh fractionation model oxygen isotopic variations were negligible over this temperature range and thus provide little information on the mechanism of illitization copyright 2001 elsevier science ltd

geothermal mineral equilibria the dominant reaction determining the chemistry of fluids in a geothermal system of the new zealand type consists of the conversion of primary plagioclase by co2 to calcite and clays with log pco2 15 26 7850 t 273 2 temperature t in c subsequent reactions involving secondary minerals control relative co2 h2s contents the distribution of mineral phases throughout a geothermal system reflects the stepwise conversion of thermodynamically unstable primary phases through a series of intermediate metastable phases to a thermodynamically stable secondary assemblage the relative stabilities of these phases was evaluated on the basis of their solubilities the least soluble aluminiumsilicate representing the thermodynamically most stable phase under a given set of conditions observed assemblages of secondary minerals in geothermal systems represent indicators allowing mineral fluidinteraction conditions to be evaluated on the basis of multi component mineral stability diagrams

geochemical and boron oxygen and hydrogen isotopic constraints on the origin of salinity in groundwaters from the crystalline basement of the alpine foreland abstract the b isotopic composition in combination with o and h isotopes and hydrochemical tracers is utilized to constrain the evolution of basement hosted groundwaters via water rock interactions and fluid infiltration from external sedimentary reservoirs two distinct groundwater types have been identified in the central european crystalline basement n switzerland sw germany 1 fresh groundwaters characterized by low values of 11b 3 5 to 0 6 18o 12 0 to 10 0 and d 86 8 to 71 9 and 2 brackish groundwaters with distinctly heavier b o and h isotopic compositions 11b 6 4 to 17 6 18o 9 4 to 5 6 d 67 6 to 60 8 fresh groundwaters show a systematic decrease in 11b related to an increase in b concentrations and degree of total mineralization along the pathway of groundwater migration which can only be interpreted in terms of leaching of crystalline host rocks a 11b value of 3 3 is inferred for the crustal b source mainly hercynian granites involved in the leaching process in agreement with the known 11b range of granitic rocks the evolution of brackish groundwaters derived from crystalline basement reservoirs with little water circulation is more complex as indicated by b o h stable isotope and hydrochemical e g b cl na cl and br cl constraints brackish groundwaters from the study area are influenced by admixture of sediment derived fluids which infiltrated from late paleozoic permo carboniferous and early mesozoic lower triassic sedimentary strata the data presented show that b isotopes are sensitive to mixing processes of fluids derived from different crustal reservoirs and hence may be utilized as a tracer for constraining the internal autochthonous vs external allochthonous origin of salinity in basement hosted groundwaters

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

impact of cretaceous sea level rise and anoxic events on the mesozoic carbonate platform of yugoslavia the adriatic dinaric carbonate platform of yugoslavia was influenced by rapid sea level rise and an oceanic anoxic event during the cenomanian turonian open marine biota such as planktonic foraminifera radiolarians and locally even ammonites associated with and bracketed by successions of typical shallow water carbonates indicate partial drowning of substantial areas of the platform during this time suggestive furthermore that the rate of increase of water depth was locally great enough to outpace carbonate production the presence of carbon rich and fish bearing platy limestones commonly cherty as an associated coeval facies indicates the development of anoxic or euxinic environments and the stromatolitic laminations in such rocks are attributed to the action of bacterial mats it is suggested that an extensive column of deoxygenated water developed in the neighboring marche umbrian adriatic deep water basin and was carried on to the carbonate platform during the cenomanian turonian transgression

lithium isotope geochemistry of sediments and hydrothermal fluids of the guaymas basin gulf of california abstract lithium isotopic compositions of hydrothermally altered sediments of deep sea drilling project dsdp site 477 477a as well as high temperature vent fluids of the guaymas basin have been determined to gain an understanding of lithium exchange during fluid sediment interaction at this sediment covered spreading center unaltered turbidite of the basin has a 6 li value of 10 5 7 heavier than fresh oceanic basalts contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value 8 below the sill sediments altered by a deep seated hydrothermal system show strong depletions in lithium while lithium isotopic compositions vary greatly ranging from 11 to 1 the shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals the complexity of the isotope profile is attributed to inhomogeneity in mineral composition the tortuous pathway of fluids and the temperature effect on isotopic fractionation the range of lithium concentration and 6 li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment free mid ocean ridge systems the lack of a distinct expression of sediment input is explained in terms of a flow through system with continuous water recharge the observations on the natural system agree well with the results of laboratory hydrothermal experiments the experimental study demonstrates the importance of temperature pressure water rock ratio substrate composition and reaction time on the lithium isotopic composition of the reacted fluid high temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as guaymas are a source of lithium to the ocean the ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones

basin scale evolution of formation waters a diagenetic and formation water study of the triassic chaunoy formation paris basin abstract formation waters and their movements within basins are commonly attributed with responsibility for patterns of cementation and porosity loss within reservoirs and aquifers it is thus important to understand when and how waters move in the subsurface we have studied the evolution and movement of formation water in the triassic chaunoy formation of the paris basin nw europe to define the way in which the water has evolved and to interpret water movement patterns using mineral isotope and fluid inclusion data in conjunction with detailed formation water analyses the chaunoy formation is cemented with different types of dolomite calcite and quartz cement we have studied the evolution of waters in terms of oxygen carbon and strontium isotopes and salinity connate waters were meteoric in origin but strongly influenced by the proximity of a playa lake input of palaeo meteoric water which entered the chaunoy via eastern halite bodies resulted in highly saline formation water for the majority of the chaunoy formation from about 100 ma until and for some time after maximum burial saline waters spread into the aquifer initially taking a west north west trajectory and then switching to a west south west pattern in the eocene following the alpine orogeny and localised uplift of the basin margin the southern portion of chaunoy received fresh low salinity meteoric water it is likely that formation water was lost from the chaunoy in a more central part of the basin via sub vertical cross formational flow to the mid jurassic dogger formation to accommodate the influx of fresh water

riverine behaviour of uranium and lithium isotopes in an actively glaciated basaltic terrain this study presents u and li isotope and major and trace element data for the dissolved load suspended particulates and bedload for icelandic rivers draining predominantly basaltic catchments physical erosion rates range from 920 to 2084 t km2 yr with the higher values associated with glacier fed rivers chemical erosion rates range from 45 to 91 t km2 yr with lower rates being associated with glacier fed rivers uranium activity ratios 234u 238u are close to secular equilibrium in the suspended and bedloads but all dissolved load samples show values greater than unity ranging from 1 13 to 2 41 the highest 234u 238u values are found in glacier fed rivers and can be attributed to recoil effects as grinding by glaciers locally enhances rates of physical weathering activity ratios in glacial rivers decrease with distance from the glacial source due to input from non glacial tributaries which have high levels of dissolved uranium and lower activity ratios in contrast in non glacial rivers uranium activity ratios increase with distance downstream due to continued weathering in soils and of bedrock the 7li value of the suspended load is always lower than that of the bedload due to preferential retention of 6li in secondary minerals during weathering in turn the 7li value of the dissolved load is always greater than that of the bedload ranging from 17 0 to 43 7 7li for the dissolved load decreases with increasing levels of dissolved silicon and the saturation index of secondary minerals which suggests that 7li decreases with increasing chemical weathering there is no correlation between 7li values and uranium activity ratios for the dissolved load for non glacial rivers but for glacier fed rivers there is an increase in 7li with increasing 234u 238u suggesting that where physical comminution of mineral grains by glaciers is high chemical weathering is suppressed and vice versa

behaviour of li isotopes during continental weathering the bidar laterite profile india weathering of large basaltic provinces is a major sink of atmospheric carbon dioxide and is also an important part of the geochemical cycle of many other elements this study aims to improve our understanding of basaltic weathering by analysis of trace elements and li isotopes in a lateritic profile developed upon the deccan traps flood basalt at its base the profile consists of unaltered basalt that has a li concentration and 7li value of 5 ppm and 2 5 respectively which is upwards progressively altered to a highly weathered laterite iron rich residuum at the surface high concentrations of fe2o3 85 wt at 11 m depth indicate the presence of a palaeowatertable the transition metals the rare earth elements rees and u are also strongly enriched in this horizon whereas fluid mobile elements such as li and rb are depleted relative to the precursor basalt and the bulk 7li value is very low 5 5 a high proportion of leachable li is found in this horizon and this is enriched in 6li relative to the bulk we suggest that leaching extracts the labile weathering products and these have high 6li as 7li has been preferentially mobilised during basalt weathering throughout the rest of the profile li concentrations and li isotope values are best explained by two component mixing between the precursor basalt and aeolian material with high li and low 7li mass balance calculations show that at least 50 of the li present in the profile could have been supplied by a mineral aerosol that has a 7li value between 0 and 1 3 the depth integrated 7li value of the profile is 0 6 which suggests that 7li has been preferentially leached from the aerosol after its deposition the source of this aeolian material is most likely to be ancient continental crust it is possibly derived from archaen proterozoic terrain to the south and southeast of the deccan and or material from central asia similar to that which forms chinese loess and which is supplied to the north pacific basin

lithium isotope fractionation during continental weathering processes a comprehensive understanding of lithium isotope fractionation during terrestrial weathering is necessary in order to use lithium isotopes to trace chemical cycles climatic changes and igneous processes this study investigates lithium isotope fractionation in two laboratory experiments and by analyses of natural basalt weathering products partial dissolution of basalts in the laboratory does not result in fractionation of lithium isotopes but similar dissolution of a granite sample causes significant fractionation this may reflect dissolution of secondary minerals from the granite or differences in the li isotope composition of primary minerals in this more evolved igneous rock significant li isotope fractionation was also observed during sorption onto mineral surfaces in the laboratory although this was highly dependent on sample mineralogy no fractionation accompanies the outer sphere physisorption of li to smectite surfaces some fractionation accompanies sorption onto ferrihydrite and significant fractionation with 0 986 is seen during inner sphere chemisorption to gibbsite surfaces repeat experiments with varying amounts of sorption demonstrate that li remains in an exchangeable site on the gibbsite surface the extent of fractionation onto gibbsite observed in this study 13 is about half that required in order for clay surface removal to balance the ocean li isotope budget isotopic fractionation of li was found to occur on a 300 yr timescale in both cold and warm natural environments a minimally altered rock surface from iceland was found to be two lighter in 7li than the sample interior probably due to the preferential incorporation of 6li in clay or oxide rich alteration products on the sample surface soil samples from hawaii also demonstrate li fractionation during weathering in this environment rainwater 7li 10 contributes a significant flux of isotopically heavy li to the developing soil despite this soils have similar li isotope compositions to the primary basalt 7li 4 indicating that 6li is preferentially retained during weathering this conclusion is supported by isotopically heavy river water on hawaii 7li 22 and by the correlation between li concentration and 7li in the soil the lab and field based measurements of this study clearly demonstrate that lithium fractionates during weathering potentially providing information about the weathering environment now and in the past