hydrothermal source of radiogenic sr to himalayan rivers 1 k 1 and cl 2 all of which are high in the hydrothermal waters cation concentrations decrease along the lesser himalayan reach of the river hot spring dissolved co2 has a d 13 c value to 15 9 indicating that metamorphic decarbonation reactions contribute co2 to the fluids hydrothermal co2 is partially neutralized in high temperature weathering reactions which generate alkalinity and yield abundant radiogenic sr radiogenic hydrothermal carbonate can form from these solutions and later weather releasing silicate sr but imparting carbonate characteristics to the overall water chemistry

silicate weathering rates decoupled from the 87sr 86sr ratio of the dissolved load during himalayan erosion this study establishes that carbonate weathering dominates the supply of sr with elevated 87sr 86sr ratios in the bhote kosi sun kosi river system central nepal a major himalayan tributary to the ganges the dissolved load of the bhote kosi sun kosi displays a rapid increase in the 87sr 86sr ratio in its lower section downstream of the main central thrust a feature common to other himalayan tributaries of the ganges mass balance analysis of the contributing sources to the dissolved load identifies the weathering of palaeoproterozoic impure carbonates comprised largely of dolomite and mica from the lesser himalaya as the most significant lithological control upon elevated 87sr 86sr ratios in situ laser ablation analysis of the dolomite component yields 87sr 86sr ratios of 0 93 to 1 11 indistinguishable from bulk rock this confirms the presence of a highly soluble source of radiogenic strontium and suggests that diffusive exchange during a protracted metamorphic history has homogenised sr isotopes between silicate and carbonate phases within the assemblage weathering of the carbonate component of such rocks has yielded unusually high 87sr 86sr at significant sr fluxes in the dissolved load approximately 60 of the impact of the bhote kosi sun kosi on the marine 87sr 86sr ratio can be traced to weathering of this carbonate since similar lithologies outcrop within the catchments of most himalayan tributaries that feed the ganges and brahmaputra rivers the presence of such radiogenic carbonates undermines the inference that the impact of these rivers on sr isotopes in seawater is indicative of high silicate weathering rates that result from the uplift of tibet and the himalaya

seismic evidence for sharp lithosphere asthenosphere boundaries of oceanic plates the mobility of the lithosphere over a weaker asthenosphere constitutes the essential element of plate tectonics and thus the understanding of the processes at the lithosphere asthenosphere boundary lab is fundamental to understand how our planet works it is especially so for oceanic plates because their relatively simple creation and evolution should enable easy elucidation of the lab data from borehole broadband ocean bottom seismometers show that the lab beneath the pacific and philippine sea plates is sharp and age dependent the observed large shear wave velocity reduction at the lab requires a partially molten asthenosphere consisting of horizontal melt rich layers embedded in meltless mantle which accounts for the large viscosity contrast at the lab that facilitates horizontal plate motions

accuracy of stable mg and ca isotope data obtained by mc icp ms using the standard addition method the standard addition method is evaluated to verify the accuracy and precision of mg and ca isotope data with complex matrices using the standard sample bracketing technique and analysis by mc icp ms the 44ca 42ca ratio of seawater expressed as 44 42ca relative to srm915a was determined as 0 93 0 03 95 confidence in agreement with estimates obtained by the double spike method using standard addition the seawater 26mg 24mg ratio expressed as 26mg relative to the dsm3 standard was determined as 0 80 0 06 95 confidence in agreement with previous estimates four terrestrial silicate rocks morb flood basalt glacial flour and granodiorite and olivine mineral separates from an island basalt are shown to exhibit no scatter within the error of the method averaging a 26mg of 0 20 0 05 95 confidence although a number of silicate rock data for mg isotope ratios have already been reported this is the first detailed effort to validate the accuracy of such data and test for residual analytical artifact after chemical purification of samples data regressions were evaluated statistically using the mean square weighted deviate mswd demonstrating that the uncertainty on individual data points are generally over estimated the external two standard deviation uncertainty on individual data points is estimated by monte carlo simulation as b0 075 about a factor of two improvement on early publications of mg isotope data the consistency of the standard addition estimates of 26mg in silicate rocks imply that if any residual matrix effects are present then they must be less than the spread of the data 0 11 given the diverse range of matrices in each of the samples the 26mg values of the silicate rocks suggest that mg isotope ratios in silicate material may only have a very restricted range the 26mg values of silicate material in the present study falls between the average values reported by teng et al teng f z wadhwa m helz r t 2007 investigation of magnesium isotope fractionation during basalt differentiation implications for a chondritic composition of the terrestrial mantle earth and planetary science letters 261 84 92 doi 10 1016 j epsl 2007 06 004 and wiechert and halliday wiechert u halliday a n 2006 non chondritic magnesium and the origins of the inner terrestrial planets earth and planetary science letters 256 360 371 doi 10 1016 j epsl 2007 01 007 and given the spread of published 26mg values for chondritic material a chondritic composition for terrestrial mg cannot be ruled out we suggest that some of the small discrepancies between our data and analysis of the same samples in earlier studies may have arisen because the chemical purification of mg prior to analysis can easily induce analytical artifact this method could be expanded to the isotope ratios of other elements which also rely on correcting for mass bias using the standard sample bracketing method where similar analytical discrepancies may also exist

magnesium isotope fractionation in biogenic and abiogenic carbonates implications for paleoenvironmental proxies abstract geochemical variations in marine biogenic carbonates that are preserved in the geological record serve as proxies of past environmental change however interpreting most proxies is complicated by biologically mediated vital effects highlighting the need to develop new tools for reconstructing paleoenvironmental change recently magnesium mg isotope variability in carbonates has been explored extensively to determine its utility as a paleoenvironmental proxy we review the results of these works which have yielded valuable information on the factors affecting mg isotope fractionation between carbonates and solution 26mgcarb sol in biogenic and abiogenic carbonate minerals strong evidence exists for a mineralogical control on 26mgcarb sol with the negative offset from 0 following the sequence aragonite 3 mol mol and saturation states 3 that are similar to seawater suggest that 26mgcarb sol has a temperature dependence of 0 01 c 1 and is insensitive to precipitation rate in contrast a significant precipitation rate dependence is observed in calcites precipitated from solutions with relatively low mg ca ratios

magnesium isotopic composition of the deep continental crust to constrain the behavior of mg isotopes during deep crustal processes and the mg isotopic composition of the middle and lower continental crust 30 composite samples from high grade metamorphic terranes and 18 granulite xenoliths were investigated the composites derive from eight different high grade metamorphic terranes in the two largest archean cratons of china including 13 ttg gneisses 5 amphibolites 4 felsic 4 intermediate and 4 mafic granulites they have variable bulk compositions with sio 2 ranging from 45 7 to 72 5 representative of the middle crust beneath eastern china the 26 mg values of these samples vary from 0 40 to 0 12 reflecting heterogeneity of their protoliths which could involve upper crustal sediments the granulite xenoliths from the cenozoic hannuoba basalts also have a diversity of compositions with mgo ranging from 2 95 to 20 2 these xenoliths equilibrated under high temperatures of 800 950 c corresponding to depths of the lower continental crust 30 km they yield a large 26 mg variation of 0 76 to 0 24 the light mg isotopic compositions likely result from interactions with isotopically light metamorphic fluids probably carbonate fluids together with previously reported data the average 26 mg values of the middle and lower continental crusts are estimated to be 0 21 0 07 and 0 26 0 06 respectively the bulk continental crust is estimated to have an average 26 mg of 0 24 0 07 which is similar to the average of the mantle the large mg isotopic variation in the continental crust reflects the combination of several processes such as continental weathering involvement of supracrustal materials in the deep crust and fluid metasomatism

riverine evidence for a fractionated reservoir of ca and mg on the continents implications for the oceanic ca cycle analysis of river water rock travertine and soil from the high altitude negligible vegetation setting of the southern tibetan plateau demonstrates that ca and mg isotope ratios are fractionated during weathering dissolved ca in the two rivers studied is derived primarily by limestone dissolution 44 42ca in the rivers averages 0 43 and is statistically distinct from limestone at 0 31 the range in 44 42ca in these small rivers is 0 43 equivalent to the entire range in 44 42ca recorded in marine carbonate over the last 80 ma precipitation of isotopically light travertine with a 44 42ca of 0 21 enriches solute ca in heavy isotopes the mg isotope composition of the rivers is intermediate between limestone and silicate rock averaging 1 5 silicate soil has a 26mg of 0 03 heavier than silicate rock by 0 5 these fractionations in the soil create a companion groundwater reservoir of heavy ca and light mg seasonal variations in ca and mg isotope ratios in the dissolved load are small but define an array which can be modelled as a mixture between a fractionated groundwater reservoir and surface runoff reflecting the isotopic composition of the lithology fractionation of ca during the weathering of the continents is of importance to the global cycle of ca the riverine input of ca to the oceans dominated by carbonate weathering is controlled not only by the composition of the primary continental crust but also by the size and composition of a fractionated reservoir on the continents the impact on the oceanic cycle of ca depends on the relative residence times of dissolved ca in the ocean and the storage time of fractionated ca

upper mantle seismic shear discontinuities of the pacific 1 shear wave impedance discontinuities are inventoried for eight paths connecting circum pacific earthquakes with seismic stations on hawaii and oahu in addition to the transition zone discontinuities we observe a consistent impedance decrease at a depth of 80 km that marks the transition from the fast seismic lid to the low velocity zone the interval over which this transition occurs is less than 30 km the requisite impedance decrease ascribed almost entirely to diminished velocities in the low velocity zone exceeds predictions for peridotite chemistries of appropriate lithospheric age in all cases the transition is better matched by lithosphere of roughly half of the true age four paths show clear evidence of the x discontinuity an impedance increase of 3 8 near 300 km depth the only viable explanations would require extensive eclogite or basalt depleted mantle in the upper mantle of the western pacific the impedance contrast of the 410 km discontinuity which depends on the modal fraction of mantle olivine does not signal the presence of either although a mixture of the two remains a possibility we find no evidence of a low velocity layer atop of the 410 km discontinuity if present it is either consistently thin 15 km highly variable in thickness topography in excess of 60 km or has little impedance contrast 2 3 with overlying mantle the apparent absence of melt atop the 410 km discontinuity an intermittent and weak 520 km discontinuity and a thinned transition zone are consistent with relatively dry conditions in the deep upper mantle of the central pacific

calcium isotope δ44 40ca variations of neogene planktonic foraminifera measurements of the calcium isotopic composition 44 40ca of planktonic foraminifera from the western equatorial pacific and the indian sector of the southern ocean show variations of about 0 6 over the past 24 myr the stacked 44 40ca record of globigerinoides trilobus and globigerina bulloides indicates a minimum in 44 40casw seawater calcium at 15 to 16 ma and a subsequent general increase toward the present interrupted by a second minimum at 3 to 5 ma applying a coupled calcium carbon cycle model we find two scenarios that can explain a large portion of the observed 44 40casw variations in both cases variations in the ca input flux to the ocean without proportional changes in the carbonate flux are invoked the first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux the second scenario generates an additional calcium flux from the exchange of ca by mg during dolomitization in both cases the calcium flux variations lead to drastic changes in the seawater ca concentrations on million year timescales our 44 40casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed

extracting mg isotope signatures of ancient seawater from marine halite a reconnaissance abstract the mg ca ratio of seawater fluctuated remarkably over the phanerozoic the processes that controlled the temporal variation in seawater mg ca ratio may also have caused the secular changes in mg isotope ratios of seawater therefore the mg isotope composition of seawater may be useful to understand the long term variation in seawater chemistry different sedimentary carbonates have been proposed as archives of ancient seawater mg isotope signatures but each type of carbonate has its limitations halite is a common mineral in evaporite deposits and their fluid inclusions may be used to infer the mg isotope composition of contemporary seawater in this study we developed a method to measure the isotope composition of mg in halite with an accuracy of better than 0 1 in 26mg the accuracy of the method was verified systematically using synthetic nacl solutions as well as holocene lacustrine halite samples from the dead sea the 26mg values of marine halite samples show a large variation ranging from 0 1 to 1 6 relative to the dsm3 international mg isotope standard the 26mg values of some ancient salt samples are lower than a published model curve for 26mg of seawater and such inconsistency could be explained by 1 isotopic evolution of brines due to mineral precipitation 2 entrapment of evaporite minerals into halite during halite precipitation or post depositional deformation 3 recrystallization and dissolution of pre existing mg minerals and 4 limitations of the model curve of seawater 26mg values collectively we suggest that mg isotopes in halite are a new geochemical proxy to study the secular variations in seawater chemistry syndepositional and post depositional processes of evaporite deposits our data highlight the importance of understanding the sedimentary background and textural details of evaporites for appropriate interpretations of mg isotope data from halite

massive magnesium depletion and isotope fractionation in weathered basalts abstract magnesium isotopes have been shown to fractionate significantly during continental weathering however the degree and direction of fractionation varies from one study to the next and the main factors that control mg isotope fractionation during weathering have yet to be delineated here we report mg contents and isotopic compositions for two 10 m deep drill cores through bauxites developed on columbia river basalts crbs samples from these two drill cores have very low mgo contents 0 12 0 25 wt and variable but high 26mg values from 0 1 to up to 1 8 the heaviest isotopic composition ever reported for mg relative to the average values of fresh crbs 26mg 0 23 0 07 and mgo 5 9 wt these features reflect the near complete loss of mg in the isotopically heavy regolith the most highly weathered bauxites at the tops of the profiles have the lowest 26mg values reflecting the addition of isotopically light eolian dust excluding these samples 26mg in bauxites displays a weak positive correlation with gibbsite abundance suggesting that gibbsite preferentially retains 26mg in the bauxites the integrated mg isotopic fractionation factors between bauxite and fluid 26mgbauxite fluid inferred from rayleigh fractionation calculations vary from 0 05 to 0 4 which is similar to the range inferred from previous studies of igneous rock weathering profiles though none of these previous studies found the extremely heavy 26mg and massive mg depletion seen here collectively studies of weathering profiles suggest loss of isotopically light mg from the continents which must contribute to the very light 26mg seen in river water and seawater

role of a low viscosity zone in stabilizing plate tectonics implications for comparative terrestrial planetology 1 earth s near surface layer its lithosphere is broken into quasi rigid plates that form the upper thermal boundary layer for mantle convection since the discovery of plate tectonics it has been widely conjectured but only recently demonstrated that this peculiar style of convection may be facilitated by an upper mantle low viscosity zone lvz over which the plates glide easily the lvz or asthenosphere concept dates from 19th century investigations of isostatic support of mountain belts and is supported by modern evidence for a seismic low velocity zone and by studies of postglacial rebound and dynamic compensation of the earth s gravity field here we show in both two dimensional 2 d cartesian and 3 d spherical earth models that combining a pronounced lvz and a plastic yield stress to allow localized weakening of the cold thermal boundary layer results in a distinctly plate tectonic style of convection with 30 toroidal surface motion for the 3 d case recycling of water into the upper mantle at subduction zones is a plausible cause of earth s lvz whereas venus is dry and lacks both an lvz and plate tectonics

mg isotope fractionation during calcite precipitation an experimental study abstract experimental precipitations of calcite and other carbonate minerals were performed under various conditions of ph temperature and solution mg ca to determine the mg partition coefficient and mg isotope fractionation fifteen experiments were performed at ph ranging from 7 41 0 07 to 8 51 0 39 temperature ranging from 16 2 0 7 to 26 5 0 3 c and mg ca solution ranging from 0 11 to 0 52 mol mol the apparent mg partition coefficient between calcite and solution d mg spans a large range of values from 0 018 0 014 to 0 15 0 11 and carbonate mg isotope fractionation 26 mg ranges from 2 53 0 25 to 1 33 0 14 and does not correlate with either ph or temperature the range in d mg and 26 mg suggests non equilibrium partitioning controlled by the processes of calcite growth i e mixing between calcite grown at equilibrium and fluid inclusions and entrapment of a surface mg rich calcite layer in isotopic equilibrium with the solution the equilibrium mg isotope fractionation between inorganic calcite and solution is estimated to be 2 13 0 24 additional mg elemental and isotopic fractionations are observed to occur during biogenic formation of calcite due to variable removal of mg by the organisms high mg calcite corals foraminifera of seawater mg from their calcification medium

boron and magnesium isotopic composition of seawater the isotopic systems of boron and magnesium are increasingly being used as proxies for a number of environmental variables and processes the isotopic composition of seawater for both systems plays a central role in these studies and is an important interlaboratory standard given the long residence times of both elements 10 7 years it is commonly assumed that seawater is isotopically homogenous for these systems yet no systematic studies currently exist here we present the b and mg isotopic composition of 26 28 seawater samples from a number of ocean basins that encompass a significant range in salinity 32 to 38 psu temperature 0 3 to 25 9c and water depth 0 to 1240 m we find no significant or systematic variation for either system in accordance with their long residence times we recommend that the mean values we report 11 b 39 61 0 04 2 s e n 28 25 mg 0 43 0 01 2 s e n 26 26 mg 0 82 0 01 2 s e n 26 be used in future studies involving mg and b isotopes copyright 2010 by the american geophysical union

the strontium isotopic budget of himalayan rivers in nepal and bangladesh abstract himalayan rivers have very unusual sr characteristics and their budget cannot be achieved by simple mixing between silicate and carbonate even if carbonates are radiogenic we present sr o and c isotopic data from river and rain water bedload and bedrock samples for the western and central nepal himalaya and bangladesh including the monsoon season central himalayan rivers receive sr from several sources carbonate and clastic tethyan sediments high himalayan crystalline hhc gneisses and granitoids with minor marbles carbonates and metasediments of the lesser himalaya lh and miocene recent foreland basin sediment from the siwaliks group and the modern flood plain in the tethyan himalaya rivers have dissolved sr 6 mol l and 87sr 86sr 0 717 with a large contribution from moderately radiogenic carbonate rivers draining hhc gneisses are very dilute with sr 0 2 mol l and 87sr 86sr 0 74 lesser himalayan streams also have low sr 0 4 mol l and are highly radiogenic 87sr 86sr 0 78 highly radiogenic carbonates of the lh do not contribute significantly to the sr budget because they are sparse and have very low sr in large rivers exiting the himalaya sr systematics can be modeled as a mixture between tethyan rivers where slightly radiogenic carbonates mean 87sr 86sr 0 715 are the main source of sr and lesser himalaya waters where extremely radiogenic silicates 0 8 are the main source of sr hhc waters are less important because of their low sr rivers draining the siwaliks foreland basin sediments have sr 4 mol l and 87sr 86sr 0 725 weathering of silicates in the siwaliks and the flood plain results in a probably significant radiogenic 0 72 0 74 input to the ganges and brahmaputra g b but quantification of this flux is limited by uncertainties in the hydrologic budget the g b in bangladesh show strong seasonal variability with low sr and high 87sr 86sr during the monsoon sr in the brahmaputra ranges from 0 9 mol l and 0 722 in march to 0 3 mol l and 0 741 in august we estimate the seasonally weighted flux from the g b to be 6 5 108 mol yr with 87sr 86sr 0 7295

isotope evidence for secondary sulfide precipitation along the marsyandi river nepal himalayas abstract we present sulfur and oxygen isotope data from 41 samples of dissolved riverine sulfate from along 65 km of the marsyandi river in the northern himalayas coupled sulfur and oxygen isotopic composition of riverine sulfate 34 s so 4 and 18 o so 4 respectively yield unique constraints on the source of sulfur to the river system the headwaters of the marsyandi river have light 34 s so 4 and 18 o so 4 which requires that the source of sulfate to the river is through the anoxic weathering of pyrite likely via fe3 the 34 s so 4 and 18 o so 4 of sulfate in tributaries to the marsyandi increase downstream which could result either from inputs from evaporites or bacterial sulfate reduction with subsequent sulfide precipitation in warmer and wetter catchments either of these processes could result in heavy 34 s so 4 and 18 o so 4 of the residual river sulfate elemental ratios such as sr ca and ca so4 suggest as previous studies have also concluded that evaporite weathering is not important in the marsyandi river we conclude that the isotope data is most consistent with the onset of bacterial sulfate reduction and secondary sulfide precipitation in the soils in the warmer and wetter downstream catchments our results have implications for understanding the source of sulfate to the ocean as well as the redox and acidity budget within rapidly eroding catchments

magnesium isotopic composition of igneous rock standards measured by mc icp ms to provide inter lab comparison for high precision mg isotope analysis mg isotope compositions expressed as 26mg relative to dsm 3 for commercially accessible peridotite basalt andesite and granite geo standards have been measured by multi collector inductively coupled mass spectrometry nu plasma using sample standard bracketing method there is a large tolerance of matrix cations during the measurement of mg isotopes as intensity ratios of 23na 24mg and 27al 24mg of about 20 only change the 26mg by less than 0 1 and low 55mn 24mg 0 1 and 58ni 24mg 0 01 do not cause significant mass bias either concentration match between samples and standards within 90 is adequate to obtain accurate isotope analysis which also mitigates the isobaric interference of 12c14n on 26mg organic matrix from chemical purification can cause significant analytical errors when the mass of mg processed is small the long term reproducibility of 26mgdsm 3 for samples with relatively higher mgo content is about 0 11 2sd and granites with lower mgo content is about 0 2 2sd although the standards in this study have wide ranges of major element compositions with sio2 from 40 to 70 wt and mgo from 0 75 to 49 6 wt they exhibit a variation of mg isotopic compositions with 26mg from 0 07 to 0 40 26mg do not correlate with sio2 or mgo contents suggesting homogenous mg isotope compositions in igneous rocks at the level of current precision relative to low temperature samples including sediments and riverine and sea waters our data do not support a non chondritic mg isotope composition of the earth

the gutenberg discontinuity melt at the lithosphere asthenosphere boundary the lithosphere asthenosphere boundary lab beneath ocean basins separates the upper thermal boundary layer of rigid conductively cooling plates from the underlying ductile convecting mantle the origin of a seismic discontinuity associated with this interface known as the gutenberg discontinuity g remains enigmatic high frequency ss precursors sampling below the pacific plate intermittently detect the g as a sharp negative velocity contrast at 40 to 75 kilometer depth these observations lie near the depth of the lab in regions associated with recent surface volcanism and mantle melt production and are consistent with an intermittent layer of asthenospheric partial melt residing at the lithospheric base i propose that the g reflectivity is regionally enhanced by dynamical processes that produce melt including hot mantle upwellings small scale convection and fluid release during subduction

significant increases in global weathering during oceanic anoxic events 1a and 2 indicated by calcium isotopes abstract calcium isotope ratios 44 42ca were measured in carbonate rich sedimentary sections deposited during oceanic anoxic events 1a early aptian and 2 cenomanian turonian in sections from resolution guyot mid pacific mountains coppitella italy and the english chalk at eastbourne and south ferriby uk a negative excursion in 44 42ca of 0 20 and 0 10 is observed for the two events these 44 42ca excursions occur at the same stratigraphic level as the carbon isotope excursions that define the events but do not correlate with evidence for carbonate dissolution or lithological changes diagenetic and temperature effects on the calcium isotope ratios can be discounted leaving changes in global seawater composition as the most probable explanation for 44 42ca changes in four different carbonate sections an oceanic box model with coupled strontium and calcium isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium isotope ratios the model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short lived to affect the oceanic calcium reservoir measurably a modelled increase in weathering flux on the order of three times the modern flux combined with increased hydrothermal activity due to formation of the ontong java plateau oae1a and caribbean plateau oae2 can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections this study presents the first major element record of a weathering response to oceanic anoxic events

an influence of extreme southern hemisphere cold surges on the north atlantic subtropical high through a shallow atmospheric circulation previous studies have attributed inter hemisphere influences of the atmosphere to the latitudinal propagation of planetary waves crossing the equator to the triggering of equatorial kelvin waves or to monsoonal circulation over the american atlantic sector such cross equatorial influences rarely occur during boreal summer due to unfavorable atmospheric conditions we have observed that an alternative mechanism provides an inter hemisphere influence when episodes of extreme cold surges and upper tropospheric westerly winds occur concurrently over southern hemisphere amazonia cold surges from extratropical south america can penetrate deep into southern amazonia although they do not appear to influence upper tropospheric circulation of the northern hemisphere extremely strong southerly cross equatorial advection 2 of cold and dense air in the lower troposphere can reach as least 10 n such cold advection increases the northward cross equatorial pressure gradient in the lower to middle troposphere thus shallow northerly return flow below 500 hpa this return flow and the strong lower tropospheric southerly cross equatorial flow form an anomalous shallow meridional circulation spanning from southern amazonia to the subtropical north atlantic with increased geopotential height anomalies exceeding 1 standard deviation to at least 18 n it projects onto the southern edge of the nash increasing its pressure and leading to equatorward expansion of nash s southern boundary these anomalies enhance the north atlantic subtropical high nash leading to its equatorward expansion these extreme cold surges can potentially improving the predictability of weather patterns of the tropical and subtropical atlantic including the variability of the nash s southern edge

ca isotope constraints on chemical weathering processes evidence from headwater in the changjiang river china abstract this study aims to clarify the relationship between chemical weathering of rocks and the carbon budget of rivers and better understand the weathering mechanisms of plateau watersheds we chose to study the jinsha river which originates from the tibetan plateau and also is in the upper reaches of the changjiang river analysis of hydrochemistry radiogenic strontium isotope and stable calcium isotopes were conducted of the jinsha river water samples which were collected along its mainstream and main tributaries in the summer the results show that the water chemistry of the mainstream waters is dominated by evaporite weathering which have low 87sr 86sr values 0 7098 0 7108 and wide range of sr contents 2 70 9 35 mol l in contrast tributaries of the jinsha river have higher 87sr 86sr 0 7090 0 7157 and lower sr contents 1 mol l moreover the ca isotopic compositions in the mainstream 0 87 1 11 are heavier than the tributaries 0 68 0 88 and could not be fully explained by the conventional mixing of different sources we suggest that secondary carbonate precipitation fractionates ca isotopes in the jinsha river and fractionation factors are between 0 99935 and 0 99963 at least 66 of ca was removed in the mainstream of the jinsha river through secondary mineral precipitation and the average value is 35 in the tributaries the results highlight that evaporite weathering results in more carbonate precipitation influencing ca transportation and cycling in the riverine system constrained by stable ca isotopic compositions and water chemistry

natural variations of δ30si ratios during progressive basalt weathering hawaiian islands abstract silicon stable isotopes can be used to trace the biogeochemical pathways of si as it moves from its continental sources to its sink in ocean sediments along the way si is incorporated into clay minerals taken up by plants where it forms plant opal and leached into rivers the major land to ocean conduit compared to igneous rocks the waters that drain continents are enriched in heavy si isotopes but the mechanisms that control fractionation have not been elucidated we studied si isotope fractionation along a 4 million yr basaltic soil chronosequence on the hawaiian islands using the natural context of these samples in combination with laboratory experiments we demonstrate that the isotopic composition of dissolved si in weathering systems is determined by the combined effects of rock disintegration clay mineral neosynthesis and si biocycling weathering preferentially releases 28si into solution whereas secondary mineral formation preferentially removes 28si from solution in humid environments leached soils have lost large amounts of this soluble si thus creating a net loss of 30si from the entire soil system as soils develop and greater fractions of si reside in neoformed clay minerals 30sibulk soil values change progressively toward more negative values basalt 30si values are about 0 5 but older soils have 30si values up to 2 5 the difference between the solid and solution 30si values remains more or less constant with progressive weathering and therefore soil water from older soils has a more negative 30si composition in the upper horizons of the hawaiian soils this weathering driven 30si shift is modified by the addition of unweathered primary minerals via dust carrying 30si values of about 0 5 and by biocycling of si via plants producing negative 30si values in phytoliths and positive 30si values in soil solutions derived from upper horizons due to the high concentrations of dissolved si in these near surface layers rivers have more positive 30si values than predicted based on the weathering status of the lower horizons when combined with published 30si values from large rivers worldwide we find that the results from hawaii point to weathering control of si isotopes delivered to the oceans and thus to an important continent ocean linkage that warrants further investigation

calcium isotopic fractionation in microbially mediated gypsum precipitates abstract gypsum caso4 2h2o precipitation experiments were carried out at low ph in the presence of the sulfur oxidizing bacterium acidithiobacillus thiooxidans the observed ca isotopic fractionation expressed as 44 40cas f 44 40casolid 44 40cafluid at the end of each experimental time period 50 to 60 days was 1 41 to 1 09 in the biotic experiments 1 09 in the killed control and 1 01 to 0 88 in the abiotic controls as there were no strong differences in the solution chemistry and the rate at which gypsum precipitated in the biotic and abiotic controls we deduce a biological ca isotope effect on the order of 0 3 the isotope effect correlates with a difference in crystal aspect ratios between the biotic experiments 8 05 3 99 and abiotic controls 31 9 8 40 we hypothesize that soluble and or insoluble organic compounds selectively inhibit crystal growth at specific crystal faces and that the growth inhibition affects the fractionation factor associated with gypsum precipitation the experimental results help explain ca isotopic variability in gypsum sampled from a sulfidic cave system in which gypsum crystals exhibiting a diversity of morphologies microcrystalline to cm scale needles have a broad range of 44 40ca values 1 2 0 4 relative to the limestone wall 44 40ca 1 3 in light of the laboratory experiments the variation in ca isotope values in the caves can be interpreted as a consequence of gypsum precipitation in the presence of microbial organic matter and subsequent isotopic re equilibration with the ca source

the calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance calcium isotope ratios relative to seawater were studied in natural waters in order to constrain the ca isotopic flux to the oceans and to discuss the oceanic ca budget this study includes the analysis of 1 ca isotopes in continental waters at the regional scale of the upper rhine valley and 2 the determination of the 44ca values of some major rivers and hydrothermal vents the data indicate that the global 44ca variability of the studied waters with a maximal range of 1 is limited and must be linked to mass fractionation processes at the scale of a small watershed aubure vosges france the 44ca river flux changes due to the variation of the proportion of waters resulting from chemical alteration of rocks and biologically fractionated soil solutions ca isotopes could therefore be an important tool to quantify the impact of the plants and the biosphere on the river water chemistry at the regional scale of the rhine valley as well as at the global scale of world rivers the 44ca variability of river samples ranges from 0 5 to 1 without any relationship with the lithology of the watershed or the climate similarly the 44ca value of hydrothermal vents is also uniform and close to the mean value of river waters consequently the 44ca flux to the ocean should remain rather constant through time with a mean of 1 1 0 2 this value confirms that the ca budget of the present day seawater is in steady state this was not necessarily the case in the past non steady state periods should have been due to intensity variations of incoming and outcoming ca fluxes rather than to the variations in their isotopic signatures

magnesium isotope analysis of olivine and pyroxene by sims evaluation of matrix effects abstract the performance of multi collector secondary ion mass spectrometry mc sims for mg isotope ratio analysis was evaluated using 17 olivine and 5 pyroxene reference materials rms the mg isotope composition of these rms was accurately and precisely determined by multi collector inductively coupled plasma mass spectrometry mc icp ms and these measured isotope ratios were used to evaluate sims instrumental mass bias as a function of the forsterite fo content of olivine the magnitude of the mg isotope matrix effects were 3 in 25mg and are a complex function of olivine fo content that ranged from fo59 3 to fo100 in addition to these mg isotope matrix effects si ion yields and mg si ion ratios varied as a complex function of the fo content of the olivine rms for example si ion yields varied by 33 based on the observations we propose instrumental bias correction procedures for sims mg isotope analysis of olivine using a combination of mg si ratios and fo content of olivine using this correction method the accuracy of 25mg analyses is 0 3 except for analysis of olivine with fo86 88 where instrumental biases and mg si ratios change dramatically with fo content making it more difficult to assess the accuracy of mg isotope ratio measurements by sims over this narrow range of fo content five pyroxene rms 3 orthopyroxenes and 2 clinopyroxenes show smaller ranges of instrumental bias 1 4 in 25mg as compared to the olivine rms the instrumental bias for the 3 orthopyroxene rms do not define a linear relationship with respect to enstatite en content that ranged from en85 5 96 3 the clinopyroxene rms have similar en and wollastonite wo contents but have 25mg values that differ by 0 5 relative to their 25mg values determined by mc icp ms these results indicate that additional factors e g minor element abundances likely contribute to sims instrumental mass fractionation in order to better correct for these sims matrix effects additional pyroxene rms with various chemical compositions and known mg isotope ratios are needed

the composition of the continental river weathering flux deduced from seawater mg isotopes this study establishes the magnesium isotopic composition of seawater and evaluates its constancy as a function of depth and geographic location it also provides results on the magnesium isotopic composition of river water samples draining specific lithologies in combination the results are used to obtain an average magnesium isotopic composition of 1 54 for the global continental weathering flux compared to the 2 value of the global ocean both relative to nist srm 980 analyses of modern and fossil carbonate secreting echinoderms suggest that these can serve as archives of seawater 26mg values it is demonstrated that these records of the magnesium isotopic composition of ancient oceans can be used to make important inferences about the relative contribution of different lithologies to the global continental weathering flux particularly carbonate versus silicate weathering preliminary results suggest that the composition of the continental weathering flux has not undergone dramatic changes during the phanerozoic

the isotopic composition of magnesium in the inner solar system abstract we report high precision mc icpms measurements of 25 mg 24 mg and 26 mg 24 mg isotope ratios for 14 meteorites both primitive and differentiated 5 lunar basalts and breccia samples 5 terrestrial basalts 1 dunite and 3 peridotites we estimate the 26 mg value of the bulk silicate earth bse at 0 54 0 04 2se w r t dsm3 carbonaceous and ordinary chondrites show an average 26 mg of 0 52 0 04 2se martian meteorites show a narrow range in 26 mg with an average 26 mg of 0 57 0 02 2se average 26 mg of pallasite olivines is 0 54 0 04 2se whereas that of lunar samples including ilmenite basalts olivine basalt and one crystalline breccia is 0 51 0 03 2se our data demonstrate that the overall stable mg isotopic composition of the inner solar system average 25 mg 0 273 26 mg 0 535 is homogeneous to within 0 04 for 26 mg 24 mg this value is indistinguishable from that of the bse and lunar samples demonstrating that the mg isotopic composition of the earth moon system is chondritic accurate determination of the mg isotopic composition of the rocky planets is important for mg isotope studies of surface processes on earth as well as for using mg isotope data to understand evaporation and condensation effects in the solar nebula consistent with a recent report we find that clinopyroxenes have higher 26 mg than co existing olivines and orthopyroxenes in mantle peridotites although the magnitude of this difference varies 0 08 to 0 2 such small mineral fractionations along with differences between components in primitive meteorites cais chondrules and matrix preclude the resolution of mass dependent fractionation differences smaller than about 0 05 between solar system objects we demonstrate that our results do not support the recent claims that i the earth moon system has a unique mg isotope composition different from chondrites or ii the higher 26 mg values up to 0 0 reported for chondrites achondrites terrestrial basalts and peridotites to address the issue of inter laboratory discrepancies on the mg isotopic composition of silicate rocks we have prepared 3 pure mg standards with wide ranging 26 mg 3 75 to 0 69 with respect to dsm3 as well as a large volume of homogenized olivine from the san carlos peridotite which will be available to the scientific community for future comparative studies

calcium isotopes in archaeological bones and their relationship to dairy consumption abstract the calcium isotope ratios 44 42 ca of bones from humans and fauna from three archaeological sites taforalt abu hureyra and danebury are evaluated in order to assess whether calcium isotope ratios of bones can be used to detect dairy consumption by adult humans at each site the fauna 44 42 ca is the same regardless of species while the humans have lower 44 42 ca than the local animals by 0 24 0 41 site means however we cannot ascribe this difference to dairy consumption given this human faunal difference also occurs in epipalaeolithic and mesolithic adult humans where dairy consumption is unlikely rather this difference appears to be a result of differences in metabolic processes or other aspects of diet between humans and fauna minimal isotopic change in sequential acid leaches of bone powders and consideration of the high calcium concentration in bone suggest that bone calcium isotope ratios are not substantially affected by diagenetic change

using mg isotope ratios to trace cenozoic weathering changes a case study from the chinese loess plateau abstract the magnesium isotope system is a useful tracer of weathering processes due to its sensitivity to secondary mineral formation we present elemental and isotopic data in bulk loess and paleosol sediments from the luochuan profile in the chinese loess plateau clp due to a relatively constant pre weathering mineralogy changes in the sediment chemistry with depth can be interpreted to reflect changes in weathering processes that are ultimately controlled by climate we find that the luochuan sediments are all enriched in light mg relative to the upper continental crust ucc 0 22 the isotopically light signature is a result of three way mixing between mg sourced from silicate calcite and dolomite changes in 26 mg between loess and paleosol reflect the higher weathering intensities during pedogenesis and corresponding loss of easily leachable calcite enriched in light mg isotopes from the loess layers this is confirmed by the results of a simple leaching procedure in which the leachate phase contains high ca concentrations and isotopically light 26 mg values of up to 2 any isotopic fractionation of mg imparted by isotopically heavy clay mineral formation appears to be insignificant and is obscured by the presence of detrital dolomite that is resistant to acid leaching and is isotopically light the isotopic composition of mg at luochuan broadly follows the magnetic susceptibility record in that loess layers are relatively isotopically light and have lower magnetic susceptibilities than their adjacent paleosol as such the changes in 26 mg values with depth do correspond to changes in chemical weathering however the driving factor behind these changing 26 mg values is carbonate preservation which in itself is not a highly sensitive paleoclimate proxy from a global perspective the 26 mg value of luochuan loess is similar to other loess sediments which are often isotopically light relative to the ucc we have recalculated the average 26 mg value of global loess sediments to be 0 58 1 18 this reflects the fact that 26 mg values in loess are highly heterogeneous and are generally enriched in 24 mg compared to typical ucc rocks due to preservation of high amounts of isotopically light carbonate minerals for this reason loess sediments cannot be used to approximate the isotopic composition of mg in the earth s crust

the geochemical behavior of mg isotopes in the huanghe basin china abstract the magnesium mg isotopic composition of river waters is mainly controlled by riverine mg sources and geochemical processes it is meaningful to characterize mg isotope behavior for us in understanding chemical weathering and other geochemical processes such as secondary mineral formation linked to environmental conditions the huanghe basin was chosen to investigate the behavior of mg isotopes during river erosion in temperate semiarid and arid climate dissolved mg shows a wide range of 26mg values ranging from 1 53 to 0 11 with most values being close to 1 09 by comparison most of the suspended loads are enriched in heavy mg isotope with 26mg values ranging from 2 00 to 0 62 which is controlled by mineralogy the mg isotopic composition in the upstream is mainly determined by the mixture between carbonate and silicate sources when the huanghe flows through the loess plateau the dissolved mg decreased due to the dissolution of easily dissoluble phases in loess such as mgcl2 or mgso4 carbonates weathering and evaporites dissolution are the major controlling factor of the evolution of mg isotopic composition in dissolved phase though evaporation related precipitation of secondary carbonates also influences the dissolved mg isotope composition in some tributaries the strong relationships between 26mg and ph temperature and 18o suggest that the mg isotope system bears significant information about the hydrogeochemical characteristics and climate conditions of the huanghe basin

magnesium isotopes in permafrost dominated central siberian larch forest watersheds abstract to unravel the mg isotope fractionation pathways within the continuous permafrost zone in the larch deciduous forest of central siberia we measured the mg isotopic composition of two large siberian rivers nizhnaya tunguska and kochechum which flow into the yenisey a small forested stream and the major fluid and solid sources of mg in the watershed atmospheric precipitates surface suprapermafrost flow interstitial soil solutions plant biomass litter and mineral soils the obtained results indicate a significant seasonal variation in riverine water mg isotope signatures during the winter baseflow the mg isotope composition of large rivers is significantly lighter than the source basaltic rocks and the atmospheric depositions these differences support the presence of fluids enriched in lighter mg isotopes such as those affected by the mineral precipitation of secondary silicates or fluids that dissolve sedimentary carbonate rocks during the spring flood and in the summer and fall seasons the river fluid 26 mg values increased by 0 2 0 3 and approached the mg isotope composition of the ground vegetation dwarf shrubs mosses and the soil organic horizon overall the riverine waters were 0 3 0 7 lighter than the unaltered bedrock and the deep minerals soil horizons the mg isotopic compositions of larix gmelinii organs i e stem wood roots and needles exhibit a low variability however an enrichment of 0 2 0 3 in the 26 mg of larch needles in the course of the growing season from june to september can be observed this enrichment most likely demonstrates uptake of isotopically heavier mg by the plant in addition to the progressive thawing of the mineral soil deepening of the active layer of the soil overall the mg isotope approach indicates the important contribution of vegetation larch needles mosses and dwarf shrubs to the riverine mg isotope signature and helps to reveal the contribution of isotopically light carbonate rocks in the large rivers of the central siberian plateau

a cenozoic record of seawater mg isotopes in well preserved fossil corals reconstructions of seawater mg isotopic composition 26 mg can provide novel insights into the processes that control the major ion chemistry of seawater over geologic time scales a key period of interest is the cenozoic ca 65 ma to today during which the mg ca ratio of seawater increased by a factor of 2 3 however two published records of seawater 26 mg over the cenozoic disagree making it difficult to draw conclusions about mechanisms driving seawater mg ca change over the past 65 m y here we present a new record of seawater 26 mg from a set of well preserved fossil corals ranging in age from paleocene to recent fossil coral 26 mg decreases by 0 3 between the early cenozoic and the oligocene then increases by 0 15 between the oligocene and present in strong agreement with the published record derived from bulk pelagic carbonate together with this existing record our fossil coral data suggest that the rise in mg seawater over the cenozoic was mainly driven by an increase in mg silicate weathering or a decline in mg uptake in marine silicates in contrast we suggest that changes in the rate of carbonate weathering and dolomite formation likely played a minor but not insignificant role in the global mg cycle over the cenozoic

determination of sr and ca sources in small tropical catchments la selva costa rica a comparison of sr and ca isotopes summary a comparative study of sr and ca isotopes was conducted to assess solute sources and effects of biogeochemical processes on surface water and groundwater in four small tropical catchments located at la selva biological station costa rica variable concentrations of dissolved sr 2 and ca 2 in the catchments are related to mixing of waters from different origin three catchments are influenced by high solute bedrock groundwater while another catchment is primarily supplied by local recharge 87 sr 86 sr ratios were employed to discriminate contributions from mineral weathering and atmospheric sources solutes in bedrock groundwater have a predominant geogenic origin whereas local recharge is characterized by low solute inputs from rainwater and minor in situ weathering releases from nutrient depleted soils bedrock groundwater contributes more than 60 of dissolved sr 2 to surface discharge in the salto saltito and arboleda catchments whereas the taconazo catchment receives more than 95 of dissolved sr 2 from rainwater 44 40 ca values of dissolved ca 2 vary greatly in the catchments mainly as a result of heterogeneous ca isotope compositions of the contributing sources based on differences in 44 40 ca values two distinct bedrock groundwaters discharging at the salto and the arboleda catchments are suggested effects of biological processes in the plant soil system on solute generation in the catchments are indicated by variable ca sr ratios however these effects cannot clearly be assessed by ca isotopes due to the strong heterogeneity of 44 40 ca values of ca 2 sources and high ca 2 concentrations in bedrock groundwater

behavior of lithium isotopes in the changjiang river system sources effects and response to weathering and erosion abstract lithium li concentrations and li isotopic compositions of the main channel of the changjiang river and its main tributaries were measured to better understand the geochemical behavior of li and its isotopic fractionation during weathering and erosion the li concentrations of the dissolved loads of the main channel range from 475 to 4570 nmol l and decrease from the upper reaches to the lower reaches values are clearly higher than those reported for many of the world s largest rivers samples with very high li concentrations are affected by the dissolution of evaporites in the headwater region the 7 li values of the particulate material has a narrow range 4 7 to 0 7 whereas the dissolved load has very variable 7 li 7 6 to 42 1 with values increasing from the upper reaches to the lower reaches after correction for contributions other than silicate weathering we show that the li isotopic compositions of the dissolved load reflect the balance between dissolution of primary minerals and preferential incorporation of the light isotope into secondary products of erosion which enrich the solution in 7 li the evolution of the isotopic composition from the upper reaches to the lower reaches is mainly controlled by the fraction of li incorporated adsorbed in onto secondary minerals and in fine by probably the difference in weathering regimes i e kinetic limited vs transport limited we also show that the magnitude of the apparent isotopic fractionation between the bedrock and dissolved li for example are not always only due to variation of the isotopic fractionation factor but might also be due to composition li content of the bedrock and mineralogical controls the composition of the eroded silicate crust estimated by a steady state mass balance reveals the important contribution of sedimentary rocks shales and highlights the effects of sedimentary recycling on the composition of the continental crust

strontium isotopic composition of the po river dissolved load insights into rock weathering in northern italy abstract strontium isotopic composition 87sr 86sr of river water provides insight on the nature of rocks involved in the weathering processes and important constraints for reconstructing silicate versus carbonate weathering in large scale basins new data presented in the context of a geochemical map of the po river basin highlight that the po river water evolves from the upper part of the catchment where 87sr 86sr approaching 0 7097 relates to the weathering of igneous and metamorphic silicate rocks to the middle part where less radiogenic compositions 87sr 86sr 0 7089 are driven by the confluence of the tributaries draining mesozoic carbonate rocks of the south alpine domain and from inflow of apennine streams characterized by less radiogenic sr signatures due to weathering of marly sediments and mafic magmatic rocks down flow the sr isotopic compositions of po river water rises at 0 7091 either by the confluence of the last apennine tributary panaro 87sr 86sr 0 7095 and or by the possible contribution from hyporheic exchanges po river isotopic signatures reveal slightly more radiogenic 87sr 86sr in comparison to other important alpine river systems e g danube rhine and rhone likely suggesting that silicate rocks are comparatively contributing more weathering byproducts in the po basin

seasonal sensitivity of weathering processes hints from magnesium isotopes in a glacial stream seasonal changes in river chemistry offer the potential to assess how weathering processes respond to changing meteorological parameters and ultimately how chemical weathering might respond to climatic parameters systematic seasonal variations in magnesium isotope ratios the 26mg 24mg ratio expressed as 26mg in per mil units are reported in stream waters from a mono lithological granitic weathering limited first order catchment from the swiss alps damma glacier rain ground and pore waters in addition to plants rocks mineral separates and soil are also reported the concentration response of the river waters is attenuated compared to the large changes in discharge however the systematic trends in the isotope data imply that either the source of the mg changes in a systematic manner or that the process by which mg is released into solution changes as a function of discharge the two first order observations in the data that need to be explained are 1 the systematic enrichment in 24mg in the stream waters compared to the granitic rocks they drain and 2 a systematic increase in 26mg in the waters during the summer melt season both observations which are similar to many other rivers draining silicate rock can either be accounted for by 1 conservative mixing between at least two different sources of mg in addition to precipitation inputs or 2 process related fractionation if the stream water compositions can be rationalised by multi component mixing there is at least one unidentified component with a 26mg 1 2 this is considered unlikely multiple physicochemical processes could fractionate mg isotope ratios such as 1 preferential leaching of 24mg 2 exchange of mg onto or from mineral surfaces and into interlayer sites of clays 3 uptake by plants and 4 26mg could be preferentially retained during the formation of secondary phases such as clays amorphous phases or oxides these processes are not mutually exclusive and distinguishing between them at a field scale is not trivial but significant biological uptake is improbable at this site unless there is a non identified external input of mg 26mg must be accumulating in solid phase residues in the catchment because of at least one physicochemical process such processes are likely well described at least in the first order by a rayleigh distillation model simple calculations illustrate how much 26mg would accumulate in the catchment per unit time in the first order the isotopic enrichments in the solids are so small that they would not be detectable for the time scales that are relevant to this field site in spite of the marked impact on the water chemistry the seasonal signal detected by mg isotope ratios is promising for using them with a better understanding of fractionation mechanisms to quantify how specific weathering processes impact upon both export fluxes and retention of elements within catchments

relative contributions of silicate and carbonate rocks to riverine sr fluxes in the headwaters of the ganges abstract exhumation of the himalayan tibetan orogen is implicated in the marked rise in seawater 87sr 86sr ratios since 40 ma however both silicate and carbonate rocks in the himalaya have elevated 87sr 86sr ratios and there is disagreement as to how much of the 87sr flux is derived from silicate weathering most previous studies have used element ratios from bedrock to constrain the proportions of silicate and carbonate derived sr in river waters here we use arrays of water compositions sampled from the head waters of the ganges in the indian and nepalese himalaya to constrain the end member element ratios the compositions of tributaries draining catchments restricted to a limited range of geological units can be described by two component mixing of silicate and carbonate derived components and lie on a plane in multicomponent composition space key elemental ratios of the carbonate and silicate components are determined by the intersection of the tributary mixing plane with the planes na 0 for carbonate and constant ca na for silicate the fractions of sr derived from silicate and carbonate sources are then calculated by mass balance in sr ca mg na composition space comparison of end member compositions with bedrock implies that secondary calcite deposition may be important in some catchments and that dissolution of low mg trace calcite in silicate rocks may explain discrepancies in sr ca na mg covariation alternatively composition dependent precipitation or incongruent dissolution reactions may rotate mixing trends on cation ratio diagrams however the calculations are not sensitive to transformations of the compositions by incongruent dissolution or precipitation processes provided that the transformed silicate and carbonate component vectors are constrained silicates are calculated to provide 50 of the dissolved sr flux from the head waters of the ganges assuming that discrepancies between ca mg na covariation and the silicate rock compositions arise from addition of trace calcite if the ca mg na mixing plane is rotated by composition dependent secondary calcite deposition this estimate would be increased moreover when 87sr 86sr ratios of the sr inputs are considered silicate sr is responsible for 70 16 1 of the 87sr flux forcing changes in seawater sr isotopic composition since earlier studies predict that silicate weathering generates as little as 20 of the total sr flux in himalayan river systems this study demonstrates that the significance of silicate weathering can be greatly underestimated if the processes that decouple the water cation ratios from those of the source rocks are not properly evaluated

weathering processes in the ganges brahmaputra basin and the riverine alkalinity budget abstract we present river chemistry data for a network of rivers draining the western and central nepal himalaya our sampling locations cover the system from the sources of rivers in tibet to the gangetic plain water samples were collected throughout the year including the monsoon season for rivers in nepal and for the ganges and brahmaputra in bangladesh rivers draining the north himalaya are characterized by low discharge under a cold and arid climate main stream waters have 13 c dic near 0 and high so42 so42 hco3 ratios xso4 with values around 40 eq and high cl ca is the dominant cation ca2 cations 55 to 75 eq after correction of sodium by chloride dissolved sulfate is produced in waters from the tethian sedimentary series whereas chlorine is related to thermal waters dissolved sulfate is primarily derived from sulfide oxidation rather than evaporite dissolution 13 c dic values of up to 3 9 show that metamorphic co2 is an important weathering agent rivers of the north himalayan basins have about 50 of their alkalinity derived from carbonate dissolution 20 from biogenic activity and 30 from metamorphic co2 on the south flank of the himalaya rivers are more depleted in 13 c and have on average lower xso4 most rivers have 13 c dic and xso4 values compatible with a simple mixing between soil co2 and sulfate derived from sulfide oxidation during the monsoon discharge increases by a factor 20 but the total dissolved concentration is only slightly reduced xso4 and 13 c decrease while ca cations increases implying enhanced dissolution of pedogenic calcite as a whole the g b riverine flux of alkalinity derived from silicate weathering is around 2 7 1011 mol year modest at the global scale sulphuric acid controls 20 30 of the weathering reaction in the brahmaputra and 6 to 9 in the ganges na and k balance 60 to 65 of the silicate derived alkalinity flux and the long term co2 consumption by ganges and brahmaputra is near 6 4 1010 mol year the flux of metamorphic co2 converted to alkalinity via weathering reactions is ca 1 1010 mol year

decoupling of erosion and precipitation in the himalayas the hypothesis that abrupt spatial gradients in erosion can cause high strain rates in active orogens has been supported by numerical models that couple erosional processes with lithospheric deformation via gravitational feedbacks1 2 3 most such models invoke a stream power rule in which either increased discharge or steeper channel slopes cause higher erosion rates spatial variations in precipitation and slopes are therefore predicted to correlate with gradients in both erosion rates and crustal strain here we combine observations from a meteorological network across the greater himalaya nepal along with estimates of erosion rates at geologic timescales greater than 100 000 yr from low temperature thermochronometry across a zone of about 20 km length spanning the himalayan crest and encompassing a more than fivefold difference in monsoon precipitation significant spatial variations in geologic erosion rates are not detectable decreased rainfall is not balanced by steeper channels instead additional factors that influence river incision rates such as channel width and sediment concentrations must compensate for decreasing precipitation overall spatially constant erosion is a response to uniform upward tectonic transport of greater himalayan rock above a crustal ramp

at the bottom of the oceanic plate according to the theory of plate tectonics huge plates below the pacific ocean are moving laterally at a speed of 10 cm year above a weak layer called the asthenosphere considering that the horizontal scale of a plate can be as large as 10 000 km the thickness is 100 km how such a thin plate maintains its rigidity while sometimes causing mega earthquakes at the edge is rather puzzling understanding what is happening at the bottom of the oceanic plate remains an open question even after some 40 years of success of plate tectonics in the past few years seismologists have reported sharp shallow seismic boundaries beneath oceanic basins that may define the bottom of the plate 1 3 on page 1480 of this issue schmerr 4 reports observations indicating the laterally varying nature of the bottom boundary of the oceanic plate

continental weathering intensity during the termination of the marinoan snowball earth mg isotope evidence from the basal doushantuo cap carbonate in south china abstract the neoproterozoic global glaciations 720 635 ma represent the most severe icehouse climatic conditions in earth s history collectively known as the snowball earth events the snowball earth hypothesis hoffman et al 1998 proposed that the termination of the global glaciation was driven by the extremely high atmospheric pco2 level 300 times of present atmospheric level pal that was accumulated during the global glaciation by volcanic degassing for tens of million years because of extremely high temperature the deglaciation might associate with intense continental weathering that brought abundant bicarbonate and alkaline earth metals mg ca to the ocean resulting in the rapid precipitation of cap carbonate all over the world thus cap carbonate precipitation marks the termination of global glaciation the deglacial intense continental weathering has been recently supported by mg isotopes however the mg isotope data also indicate that the deglaciation might have significantly predated the cap carbonate precipitation and limited data suggest that the weathering intensity was already low during the cap carbonate precipitation in order to further test whether the cap carbonate precipitation was associated with low weathering intensity here we analyzed mg isotopic composition of siliciclastic component 26mgsil of the doushantuo cap carbonate in the yangtze block south china four cap carbonate sections the tongle tl drill core the fanyang fy section the wuluo wl drill core and the jiulongwan jlw section spanning from shelf to basin environments were analyzed 26mgsil ranges from 0 43 to 0 39 n 10 from 0 31 to 0 48 n 9 from 0 06 to 0 10 n 7 and from 1 42 to 0 03 n 8 for the jlw fy wl and tl samples respectively there are negative correlations between mg al and 26mgsil in jlw wl and tl the geochemical data indicate that the variation of 26mgsil might be attributed to authigenic clay formation during the cap carbonate precipitation the binary mixing model indicates that the isotopic compositions of terrestrial clays range from 0 to 0 3 comparable to the values of modern soil clays but significantly lower than the values of the upper nantuo formation up to 0 90 suggesting the moderate to low weathering intensity during the cap carbonate deposition our study suggests low atmospheric pco2 level during cap carbonate precipitation probably due to the consumption by intense continental weathering

tomography reveals buoyant asthenosphere accumulating beneath the juan de fuca plate the boundary between earth s strong lithospheric plates and the underlying mantle asthenosphere corresponds to an abrupt seismic velocity decrease and electrical conductivity increase with depth perhaps indicating a thin weak layer that may strongly influence plate motion dynamics the behavior of such a layer at subduction zones remains unexplored we present a tomographic model derived from on and offshore seismic experiments that reveals a strong low velocity feature beneath the subducting juan de fuca slab along the entire cascadia subduction zone through simple geodynamic arguments we propose that this low velocity feature is the accumulation of material from a thin weak buoyant layer present beneath the entire oceanic lithosphere the presence of this feature could have major implications for our understanding of the asthenosphere and subduction zone dynamics

calcium isotopes in the marine environment and the oceanic calcium cycle abstract a systematic investigation of 44 ca 40 ca ratios in the oceanic ca cycle indicates that the average ca isotopic composition of input and output are quite different suggesting that the present ocean is not in a steady state our data show that sea water has uniform 44 ca 40 ca as expected from the long residence time of ca in the oceans it also exhibits the heaviest isotopic composition among all samples measured consistent with recent results by skulan et al 1997 and must be maintained at this value by strong biogenic isotope fractionation during the precipitation of caco 3 our measurements show that the riverine input is variable the most radiogenic river waters we have measured lowest 44 ca 40 ca are from ganges tributaries which also have high 87 sr 86 sr although there does not appear to be a systematic correlation between ca and sr isotopic compositions based on available data there is also significant isotopic variability among samples of caco 3 precipitated from the present ocean with coccolith oozes showing the most highly fractionated isotopic values relative to seawater among foraminifera ca isotopes exhibit species dependent fractionation effects but also appear to display systematic temperature dependent fractionation within inidividual species

the rapid resetting of the ca isotopic signatures of calcite at ambient temperature during its congruent dissolution precipitation and at equilibrium abstract this study provides direct experimental evidence of the resetting of the calcium ca isotope signatures of calcite in the presence of an aqueous fluid during its congruent dissolution precipitation and at equilibrium at ambient temperatures over week long timescales batch reactor experiments were performed at 25 c in aqueous nacl solutions air or co2 gas mixtures were bubbled through this fluid to fix ph during congruent calcite dissolution the fluid became enriched in isotopically heavy ca and the ca isotope composition continued to become heavier after the fluid attained bulk chemical equilibrium with the mineral the 44 42ca composition of the fluid was up to 0 8 higher than the dissolving calcite at the end of the dissolution experiments calcite precipitation was provoked by increasing the reactor fluid ph after chemical equilibrium had been attained via dissolution rayleigh isotope fractionation effects were observed immediately after the ph was increased and rapid calcite precipitation occurred however isotopic exchange continued after the system chemically equilibrated eradicating this rayleigh signal taken together these observations 1 confirm dynamic mineral fluid equilibrium i e dissolution and precipitation occur at equal non zero rates at equilibrium and 2 indicate that isotopic compositions of calcite can readily equilibrate even when this mineral is in bulk chemical equilibrium with its coexisting fluid this latter observation suggests the preservation of paleo environmental isotopic signatures in calcite may require a combination of the isolation of the fluid mineral system from external chemical input and or the existence of a yet to be defined calcite dissolution precipitation inhibition mechanism

variations in the marine ca cycle over the past 20 million years a 20 million year marine ca isotope record is constructed based on measurements of 36 nannofossil ooze samples from dsdp site 590 the ca isotopic composition d 44 ca relative to our bbulk earthq average of carbonate ooze samples varies between 0 2 and 0 9 and the inferred d 44 ca of seawater calcium varies between 1 1 and 0 4 modern seawater value is 0 95 on our scale fluctuations in the seawater ca isotope ratio occur in 2 to 4 million year intervals and indicate that the supply and removal of ca from the oceans are seldom in balance the ca isotope record is used to reconstruct past weathering fluxes and marine calcium concentrations the inferred marine concentration of ca fluctuates by about f20 on 2 4 million year time scales and by about f50 over the 20 million year record these variations are presumably superimposed on the previously inferred 100 million year variations the seawater ca concentration was about 0 5 times present at 20 ma and generally increased until 6 ma 1 7 times present local maxima in seawater calcium concentrations occur at 6 4 and 4 ma preceding periods of enhanced marine productivity and high mass accumulation rates at site 590 while the calculated calcium concentrations are sensitive to the assumed d 44 ca value for the weathering flux the 2 4 million year features of the derived

the magnesium isotope budget of the modern ocean constraints from riverine magnesium isotope ratios we have measured the magnesium mg isotope ratios in 45 rivers including 16 of the largest rivers in the world covering a range of geologic tectonic and climatic drainage basin environments the range in riverine 26mg is 2 5 half the variation in terrestrial rock although the mg isotopic composition of the source rock is important for small rivers at a global scale lithology is of limited significance for mg isotope ratios in rivers part of the variability at a global scale may be attributed to fractionation in the weathering environment the rivers analysed constitute 30 of the global mg riverine flux to the oceans and a flux weighted mg isotope composition of global runoff has been estimated at 1 09 even taking into account uncertainty this is distinct from seawater at 0 82 this difference arises either from the fractionation of mg isotope ratios in the ocean and or a mg budget which is not at steady state the difference is consistent with fractionation by carbonate precipitation in the simplest steady state scenario where the oceanic mass balance is maintained by riverine input and hydrothermal and dolomite output mg isotope ratios imply a minimum dolomite mg flux of 9 of the total output mg flux the implications of the distinct isotopic composition of the riverine flux from modern seawater is that the mg isotope ratio of seawater has probably varied outside of current analytical uncertainty mg isotope ratios may therefore provide a valuable new tracer in palaeo oceanography

ca cycling and isotopic fluxes in forested ecosystems in hawaii 1 biogeochemical processes fractionate ca isotopes in plants and soils along a 4 million year developmental sequence in the hawaiian islands we observed that plants preferentially take up 40ca relative to 44ca and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44ca in soil exchangeable pools our results imply moderate fluxes enriched in 44ca from strongly nutrient depleted old soils in contrast with high 40ca fluxes in young and little weathered environments in addition biological fractionation controls divergent geochemical pathways of ca and sr in the plant soil system while ca depletes progressively with increasing soil age sr ca ratios increase systematically sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial ca cycle ca isotopes in combination with sr ca ratios reveal more complex processes involved in the biogeochemistry of ca and sr

non biological fractionation of stable ca isotopes in soils of the atacama desert chile abstract we measured ca stable isotope ratios 44 40 ca in an ancient 2 my hyperarid soil where the primary source of mobile ca is atmospheric deposition most of the ca in the upper meter of this soil 3 5 kmol m 2 is present as sulfates 2 5 kmol m 2 and to a lesser extent carbonates 0 4 kmol m 2 in aqueous extracts of variably hydrated calcium sulfate minerals 44 40 ca e values vs bulk earth increase with depth 1 4 m from a minimum of 1 91 to a maximum of 0 59 the trend in carbonate 44 40 ca in the top six horizons resembles that of sulfate 44 40 ca but with values 0 1 0 6 higher the range of observed ca isotope values in this soil is about half that of 44 40 ca values observed on earth linear correlation among 44 40 ca 34 s and 18 o values indicates either a a simultaneous change in atmospheric input values for all three elements over time or b isotopic fractionation of all three elements during downward transport we present evidence that the latter is the primary cause of the isotopic variation that we observe sulfate 34 s values are positively correlated with sulfate 18 o values r 2 0 78 and negatively correlated with sulfate 44 40 ca e values r 2 0 70 if constant fractionation and conservation of mass with downward transport are assumed these relationships indicate a 44 40 ca fractionation factor of 0 4 in caso 4 the overall depth trend in ca isotopes is reproduced by a model of isotopic fractionation during downward ca transport that considers small and infrequent but regularly recurring rainfall events near surface low ca isotope values are reproduced by a rayleigh model derived from measured ca concentrations and the ca fractionation factor predicted by the relationship with s isotopes this indicates that the primary mechanism of stable isotope fractionation in caso 4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events

steady and non steady state carbonate silicate controls on atmospheric co2 two contrasting hypotheses have recently been proposed for the past long term relation between atmospheric co2 and the carbonate silicate geochemical cycle one approach berner 1990 suggests that co2 levels have varied in a manner that has maintained chemical weathering and carbonate sedimentation at a steady state with respect to tectonically controlled decarbonation reactions a second approach raymo et al 1988 applied specificlly to the late cenozoic suggests a decrease in co2 caused by an uplift induced increase in chemical weathering without regard to the rate of decarbonation according to the steady state first hypothesis increased weathering and carbonate sedimentation are generally associated with increasing atmospheric co2 whereas the uplift second hypothesis implies decreasing co2 under the same conditions an ocean atmosphere sediment model has been used to assess the response of atmospheric co2 and carbonate sedimentation to global perturbations in chemical weathering and decarbonation reactions although this assessment is theoretical and cannot yet be related to the geologic record the model simulations compare steady state and non steady state carbonate silicate cycle response the e fold response time of the co2 weathering feedback mechanism is between 300 and 400 ka the response of carbonate sedimentation is much more rapid these response times provide a measure of the strength of steady state assumptions and imply that certain systematic relations are sustained throughout steady state and non steady state scenarios for the carbonate silicate cycle the simulations suggest that feedbacks can maintain the system near a steady state but that non steady state effects may contribute to long term trends the steady state and uplift hypotheses are not necessarily incompatible over time scales of a few million years

magnesium isotope systematics of the lithologically varied moselle river basin france abstract magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the moselle basin northeastern france this small basin is remarkable for its well constrained and varied lithology on a small distance scale and this is reflected in river water sr isotope compositions upstream where the moselle river drains silicate rocks of the vosges mountains waters are characterized by relatively high 87sr 86sr ratios 0 7128 0 7174 in contrast downstream of the city of epinal where the moselle river flows through carbonates and evaporites of the lorraine plateau 87sr 86sr ratios are lower down to 0 70824 magnesium in river waters draining silicates is systematically depleted in heavy isotopes 26mg values range from 1 2 to 0 7 relative to the value presently estimated for the continental crust and a local diorite 0 5 in comparison 26mg values measured in soil samples are higher 0 0 this suggests that mg isotope fractionation occurs during mineral leaching and or formation of secondary clay minerals on the lorraine plateau tributaries draining marls carbonates and evaporites are characterized by low ca mg 1 5 3 2 and low ca sr 80 400 when compared to local carbonate rocks ca mg 29 59 ca sr 370 2200 similar to other rivers draining carbonates the most likely cause of the mg and sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer 26mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year from 1 4 to 1 6 and from 1 2 to 1 4 respectively within the range defined for the underlying rocks downstream of epinal the compositions of the moselle river samples in a 26mg vs 87sr 86sr diagram can be explained by mixing curves between silicate carbonate and evaporite waters with a significant contribution from the vosgian silicate lithologies 70 temporal co variation between 26mg and 87sr 86sr for the moselle river throughout year is also observed and is consistent with a higher contribution from the vosges mountains in winter in terms of runoff and dissolved element flux overall this study shows that mg isotopes measured in waters rocks and soils coupled with other tracers such as sr isotopes could be used to better constrain riverine mg sources particularly if analytical uncertainties in mg isotope measurements can be improved in order to perform more precise quantifications

δ44ca evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite abstract to improve understanding of ca isotope transport during water rock interaction on the continents we measured dissolved 44 ca values along a 236 km flow path in the madison aquifer south dakota where fluids have chemically evolved according to dolomite and anhydrite dissolution calcite precipitation and ca for na ion exchange over a timescale spanning 15 kyr we used a reactive transport model employing rate data constrained from major ion mass balances to evaluate the extent to which calcite precipitation and ion exchange fractionate ca isotopes elevated 44 ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and ca for na ion exchange respectively however for the bulk of the flow path 44 ca values evolve by mixing between anhydrite and dolomite dissolution with no fractionation during calcite precipitation under saturated conditions we attribute the absence of ca isotope fractionation to the long timescale of water rock interaction and slow rate of calcite precipitation which have enabled fluids to chemically and isotopically equilibrate with calcite we therefore conclude that the equilibrium ca isotope fractionation factor between calcite and water cal w is very close to zero to the extent that the madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium this study suggests that groundwater contributions to 44 ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination

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

magnesium isotope fractionation during low mg calcite precipitation in a limestone cave field study and experiments abstract the chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings despite intensive research including modelling and novel approaches speleothem data remain difficult to interpret a possible way foreword is to apply a multi proxy approach including non conventional isotope systems for the first time we here present a complete analytical dataset of magnesium isotopes 26 mg from a monitored cave in nw germany bunker cave the data set includes 26 mg values of loess derived soil above the cave 1 0 0 5 soil water 1 2 0 5 the carbonate hostrock 3 8 0 5 dripwater in the cave 1 8 0 2 speleothem low mg calcite stalactites stalagmites 4 3 0 6 cave loam 0 6 0 1 and runoff water 1 8 0 1 in the cave respectively magnesium isotope fractionation processes during weathering and interaction between soil cover hostrock and solute bearing soil water are non trivial and depend on a number of variables including solution residence times dissolution rates adsorption effects and potential neo formation of solids in the regolith and the carbonate aquifer apparent mg isotope fractionation between dripwater and speleothem low mg calcite is about 1000ln mg cc mg aq 2 4 a similar mg isotope fractionation 1000ln mg cc mg aq 2 1 is obtained by abiogenic precipitation experiments carried out at aqueous mg ca ratios and temperatures close to cave conditions accordingly 26 mg discrimination during low mg calcite formation in caves is highly related to inorganic fractionation effects which may comprise dehydration of mg 2 prior to incorporation into calcite surface entrapment of light isotopes and reaction kinetics relevance of kinetics is supported by a significant negative correlation of mg isotope fractionation with the precipitation rate for inorganic precipitation experiments

tracking physicochemical conditions of evaporite deposition by stable magnesium isotopes a case study of late permian langbeinites magnesium isotopic compositions of evaporite deposits may record information concerning brine evolution during deposition we report mg isotopic values delta mg 26 dsm3 measured from an evaporite deposit of langbeinite k2mg2 so4 3 found in the permian salado formation we used these data to model mg isotope fractionation between langbeinite and its parent brine in addition both measured and theoretical results are used to estimate precipitation temperature and interpret depositional environment the salado langbeinite delta mg 26 values are relatively low and fall within a relatively narrow range 4 12 0 03 parts per thousand to 3 81 0 07 parts per thousand equilibrium fractionation factors between langbeinite and aqueous mg2 solutions were calculated using quantum chemical density functional theory all computations were performed at the b3lyp 6 31 g d p level solvation effects were addressed using a solvent model water droplet approach and mineral structures were investigated using volume variable cluster models vvcm the equilibrium mg isotopic fractionation factors a between langbeinite and model brine solution we obtained are 1 0005 1 0004 and 1 0003 delta mg 26 langb water approximate to 10 3 ln alpha 0 473 parts per thousand 0 390 parts per thousand and 0 322 parts per thousand at 10 degrees c 25 degrees c and 40 degrees c respectively these relatively large equilibrium fractionation factors indicate significant mg isotope fractionation between langbeinite and its parent brine during precipitation as langbeinite preferentially incorporates the heavier mg 26 and mg 25 isotopes rayleigh distillation modeling of the salado langbeinite s relatively light mg isotopic composition requires delta mg 26 dsm3 values of 4 parts per thousand for the parent brine models favor a precipitation temperature as high as 40 degrees c under equilibrium conditions potential disequilibrium precipitation conditions suggested by mg isotopic data also imply rapid deposition in a hot arid sedimentary environment prevailing in the southwestern u s during the late permian

modeling novel stable isotope ratios in the weathering zone when rock is converted to weathering products the involved processes can be fingerprinted using the stable isotope ratios of metals for example li mg ca fe sr and metalloids b si here we construct a framework for interpreting these novel stable isotope ratios quantitatively in the compartments of the weathering zone in a geomorphic context the approach is applicable to any novel stable isotope system and is based on a simple steady state mass balance model that represents the weathering zone from the scale of a soil column to that of entire continents our model is based on the assumption that the two main processes associated with isotope fractionation are formation of secondary precipitates such as clays and uptake of nutrients by plants the model results show that the isotope composition of a given element in the weathering zone compartments depends on 1 the ratio between the release flux to water through primary mineral dissolution and the erosion flux of isotopically fractionated solid material consisting of secondary precipitates and organic matter 2 the isotope fractionation factors associated with secondary mineral precipitation and uptake by plants a relationship is established between isotope ratios isotope fractionation factors and indexes for chemical weathering such as chemical depletion fractions cdf and elemental mass transfer coefficients derived from simple elemental concentration measurements from this relationship isotope fractionation factors can be calibrated from chemical and isotope data measured on field material furthermore we show how the ratio of solid export to dissolved export of a given element from the weathering system can be estimated from the comparison of the isotope composition between bedrock water and sediment this calculation can be applied to samples from soils from rivers and from the sedimentary record and does not require knowing the isotope fractionation factors involved in the reactions finally we apply the model to the oceanic li isotope record reconstructed from marine carbonate sediments in order to discuss changes in global geomorphic regimes through the cenozoic

constraining magnesium cycling in marine sediments using magnesium isotopes abstract magnesium concentrations in deep sea sediment pore fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust to better characterize and differentiate these processes we have measured magnesium isotopes in pore fluids and sediment samples from ocean drilling program sites 1082 1086 1012 984 1219 and 925 that span a range of oceanographic settings at all sites magnesium concentrations decrease with depth at sites where diagenetic reactions are dominated by the respiration of organic carbon pore fluid 26mg values increase with depth by as much as 2 because carbonates preferentially incorporate 24mg low 26mg the increase in pore fluid 26mg values at these sites is consistent with the removal of magnesium in mg carbonate dolomite in contrast at sites where the respiration of organic carbon is not important and or weatherable minerals are abundant pore fluid 26mg values decrease with depth by up to 2 the decline in pore fluid 26mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore fluid the identity of this enriched magnesium sink is likely clay minerals using a simple 1d diffusion advection reaction model of pore fluid magnesium we estimate rates of net magnesium uptake removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites independent estimates of magnesium isotope fractionation during dolomite precipitation from measured 26mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites suggesting that local exchange of magnesium between sediment and pore fluid at these sites can be neglected our results indicate that the magnesium incorporated in dolomite is 2 0 2 7 depleted in 26mg relative to the precipitating fluid assuming local exchange of magnesium is minor at the rest of the studied sites our results suggest that magnesium incorporated into clay minerals is enriched in 26mg by 0 to 1 25 relative to the precipitating fluid this work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources sinks in low temperature aqueous systems

behavior of re and os during low temperature alteration results from himalayan soils and altered black shales re os analyses were performed on five soil profiles developed on silicate lithologies in the narayani drainage basin of the himalayas as well as on several altered black shales and associated alteration phases the results indicate that all of these samples have lost large amounts of re this re loss approached 100 in the black shale derived soils which also most probably lost substantial quantities of os the near constancy of os and re concentrations with depth indicates that this loss occurred quite early in the alteration process rather than progressively during the course of soil development a slight decrease in 187os 188os was observed toward the surface of the two black shale soil profiles possibly indicating a minor preferential mobility of radiogenic 187os for this lithology in the black shale derived saprolite and soils the loss of re and os was related to the loss of organic carbon the importance of this phase is underscored by the fact that organic material separated from a black shale sample accounted for nearly all of the os contained in the whole rock analysis of alteration phases from the surface of a weathered black shale showed that os liberated during alteration was partially reprecipitated in fe oxides with os isotopic compositions very similar to that of the original rock whereas re was removed with the fluid phase these results demonstrate the disproportionately large role that black shale weathering may play in determining the re and os contents of continental runoff and thus ultimately of seawater but they also emphasize the possible complexity of this process the data suggest that a large fraction of the os contained in black shales is released during chemical alteration which is apparently not the case for most other silicate rocks therefore the potential contribution of black shales to the dissolved os budget of runoff and river water may be even greater than that expected from the high os concentrations of these rocks the extent to which this os will affect the seawater os composition depends on how efficiently it is recaptured by secondary phases such as fe mn oxides in situ or during transport these results also underscore the high mobility of re with respect to os at every stage in the erosional process thus explaining the order of magnitude increase in re os ratio from the black shale source rocks to seawater

azimuthal anisotropy of the pacific region azimuthal anisotropy is the dependence of local seismic properties on the azimuth of propagation we present the azimuthally anisotropic component of a 3d sv velocity model for the pacific ocean derived from the waveform modeling of over 56 000 multi mode rayleigh waves followed by a simultaneous inversion for isotropic and azimuthally anisotropic vsv structure the isotropic vsv model is discussed in a previous paper a maggi e debayle k priestley g barruol multi mode surface waveform tomography of the pacific ocean a close look at the lithospheric cooling signature geophys j int 166 3 2006 doi 10 1111 j 1365 246x 2006 03037 x the azimuthal anisotropy we find is consistent with the lattice preferred orientation model lpo the hypothesis of anisotropy generation in the earth s mantle by preferential alignment of anisotropic crystals in response to the shear strains induced by mantle flow at lithospheric depths we find good agreement between fast azimuthal anisotropy orientations and ridge spreading directions recorded by sea floor magnetic anomalies at asthenospheric depths we find a strong correlation between fast azimuthal anisotropy orientations and the directions of current plate motions we observe perturbations in the pattern of seismic anisotropy close to pacific hot spots that are consistent with the predictions of numerical models of lpo generation in plume disturbed plate motion driven mantle flow these observations suggest that perturbations in the patterns of azimuthal anisotropy may provide indirect evidence for plume like upwelling in the mantle

experimental investigation of mg isotope fractionation during mineral dissolution and clay formation abstract silicate minerals are a major mg source to seawater through rivers and therefore it is important to determine the impact of dissolution and formation of mg rich primary and secondary minerals on the mg isotope signature of natural waters we dissolved biotite mineral in a plug flow reactor at controlled ph and t 25 c and synthesized to and tot phyllosilicates lizardite and kerolite respectively at t 90 150 and 250 c all leaching solutions during biotite dissolution are enriched in light isotopes compared to the biotite sample with a 1 1 range of 26mgbiotite solution at ph 1 mg isotopic steady state between the solution and biotite is established after 600 h while at ph 5 it is never reached even after 4 months a sequential leaching suggests that the solution 26mg values depend mostly on a balance between the relative proportions of labile and structural mg with different 26mg values ca concentrations and elementary ratios measured in output solutions during the incipient stage of dissolution indicate non negligible mg contribution from small amount of disseminated carbonate phases present within the biotite sample during synthetic clay formation both to and tot clays are significantly enriched in heavy isotopes and follow rayleigh fractionation equations for specific values of isotope fractionation factors at t 250 c a single isotope fractionation factor of 1 00059 0 00014 can explain the mg isotope evolution of both to and tot clays a similar isotope fractionation factor of 1 00054 0 00014 can be inferred from all tot synthesized at t 90 250 c a compilation of mg isotope fractionation factors during secondary phase formation highlights a difference between field and experimental investigations at low temperature more experiments are now necessary to determine the role of clay crystallochemistry at temperatures below 50 c

mg isotopic composition of carbonate insight from speleothem formation simultaneous high precision measurement of 24 mg 25 mg and 26 mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry mc icp ms relative to the international standard srm980 data are presented on low mg calcite speleothems and their associated host rocks and waters from four caves one in the french alps and three in israel covering various climate conditions in addition data are presented on three dolostones and three limestones from the himalaya the overall variation is 4 13x and 2 14x in n 26 mg and n 25 mg respectively this is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of mg is not unique each speleothem shows a characteristic range of n 26 mg values that are attributed to the isotopic composition of the local water differences between the isotopic composition of mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to mg isotopic fractionation during carbonate precipitation in the temperature range of 4 18 c the low mg calcite is enriched in light isotopes by 1 35x amu and the dependence on temperature has been found to be less than 0 02x amu c despite various geological settings the n 26 mg of the studied dolostones is 2 0 1 2x higher than the n 26 mg of the limestones all together these results suggest a strong mineralogical control and a weak temperature effect on the mg isotopic composition of carbonate a 2002 elsevier science b v all rights reserved

negligible temperature dependence of calcium isotope fractionation in 12 species of planktonic foraminifera the influence of temperature on calcium ca isotope fractionation during biomineralization was investigated through the paired analyses of d44 42ca via mc icp ms and d18o on the calcite tests of 12 species of planktonic foraminifera from coretop sediments samples were collected from a suite of box cores from sites between 608n and 308s in the north atlantic and west indian oceans spanning a range in sea surface temperature of 9 27 8c the d44 42casrm915a of the samples ranged from 0 21x to 0 81x over a range in the d18ovpdb of the foraminiferal calcite of between 2 3x and 2 1x the bulk of the species investigated produced calcite with an average calcite seawater ca enrichment factor e of 0 65f0 08x n 45 the globorotaliid species and a single globigerina bulloides sample were confined to the upper 0 4x of the observed range in d44 42ca values with the globorotaliids displaying a lesser degree of fractionation of 0 56f0 23x n 15 possibly as a result of physiological or metabolic processes such as the production of calcite crusts at depth leading to the depletion of internal stores of ca no significant correlation between temperature and ca enrichment factor was observed in any of the 12 species of foraminifera investigated the influence of temperature on e was close to zero for the combined non globorotaliid species 0 07f0 10 k e versus 1000 k 0 0008f0 0012x 8c1 the results suggest that the theoretically expected relationship between the ca enrichment factor and temperature can be obscured by as yet unquantified metabolic and physiological processes in nature these processes are particularly relevant to the globorotaliid species and g bulloides in this core top study consequently their effects must be better understood before laboratory determined temperature calibrations can be applied to downcore material with confidence provided that the effects of metabolic and physiological processes on e remain constant through time orbulina universa globigerinoides sacculifer neogloboquadrina pachyderma and globigerinella aequilateralis are suitable for the investigation of temporal changes in the calcium isotopic composition of seawater

magnesium isotopic fractionation in chondrules from the murchison and murray cm2 carbonaceous chondrites we present high precision measurements of the mg isotopic compositions of a suite of types i and ii chondrules separated from the murchison and murray cm2 carbonaceous chondrites these chondrules are olivine and pyroxene rich and have low 27 al 24 mg ratios 0 012 0 316 the mg isotopic compositions of murray chondrules are on average lighter d 26 mg ranging from 0 95 to 0 15 relative to the dsm 3 standard than those of murchison d 26 mg ranging from 1 27 to 0 77 taken together the cm2 chondrules exhibit a narrower range of mg isotopic compositions than those from cv and cb chondrites studied previously the least altered cm2 chondrules are on average lighter average d 26 mg 0 39 0 30 2se than the moderately to heavily altered cm2 chondrules average d 26 mg 0 11 0 21 2se the compositions of cm2 chondrules are consistent with isotopic fractionation toward heavy mg being associated with the formation of secondary silicate phases on the cm2 parent body but were also probably affected by volatilization and recondensation processes involved in their original formation the low al cm2 chondrules analyzed here do not exhibit any mass independent variations in 26 mg from the decay of 26 al with the exception of two chondrules that show only small variations just outside of the analytical error in the case of the chondrule with the highest al mg ratio a type iab chondrule from murchison the lack of resolvable 26 mg excess suggests that it either formed 1 ma after calcium aluminum rich inclusions or that its al mg isotope systematics were reset by secondary alteration processes on the cm2 chondrite parent body after the decay of 26 al

continental weathering following a cryogenian glaciation evidence from calcium and magnesium isotopes a marked ocean acidification event and elevated atmospheric carbon dioxide concentrations following the extreme environmental conditions of the younger cryogenian glaciation have been inferred from boron isotope measurements calcium and magnesium isotope analyses offer additional insights into the processes occurring during this time data from neoproterozoic sections in namibia indicate that following the end of glaciation the continental weathering flux transitioned from being of mixed carbonate and silicate character to a silicate dominated one combined with the effects of primary dolomite formation in the cap dolostones this caused the ocean to depart from a state of acidification and return to higher ph after climatic amelioration differences in the magnitude of stratigraphic isotopic changes across the continental margin of the southern congo craton shelf point to local influences modifying and amplifying the global signal which need to be considered in order to avoid overestimation of the worldwide chemical weathering flux

magnesium isotope fractionation during shale weathering in the shale hills critical zone observatory accumulation of light mg isotopes in soils by clay mineral transformation abstract magnesium isotopic ratios have been used as a natural tracer to study weathering processes and biogeochemical pathways in surficial environments but few have focused on the mechanisms that control mg isotope fractionation during shale weathering in this study we focus on understanding mg isotope fractionation in the shale hills catchment in central pennsylvania mg isotope ratios were measured systematically in weathering products along geochemical pathways of mg during shale weathering from bedrock to soils and soil pore water on a planar hillslope and to sediments stream water and groundwater on a valley floor significant variations of mg isotopic values were observed 26mg values 0 6 to 0 1 of stream and soil pore waters are about 0 5 to 1 lighter than the shale bedrock 26mg values of 0 4 consistent with previous observations that lighter mg isotopes are preferentially released to water during silicate weathering dissolution of the carbonate mineral ankerite depleted in the shallow soils but present in bedrock at greater depths produced higher mg2 concentrations but lower 26mg values 1 1 in groundwater 1 5 lighter than the bedrock 26mg values 0 2 to 0 4 of soil samples on the planar hillslope are either similar or up to 0 2 lighter than the bedrock hence a heavy mg isotope reservoir complementary to the lighter mg isotopes in soil pore water and stream water is missing from the residual soils on the hillslope in addition soil samples show a slight but systematic decreasing trend in 26mg values with increasing weathering duration towards the surface we suggest that the accumulation of light mg isotopes in surface soils at shale hills is due to a combined effect of i sequestration of isotopically light mg from soil water during clay dissolution precipitation reactions and ii loss of isotopically heavy particulate mg in micron sized particles from the hillslope as suspended sediments this latter mechanism is somewhat surprising in that most researchers do not consider physical removal or particles to be a likely mechanism of isotopic fractionation stream sediments 26mg values of 0 3 to 0 5 accumulated on the valley floor are 0 2 heavier than the bedrock and are thus consistent with that mobile particulates are the heavy mg isotope reservoir our study provides the first field evidence that changes in clay mineralogy lead to accumulation of lighter mg isotopes in residual bulk soils this example also demonstrates that transport of isotopically distinct fine particles from clay rich systems could be a new and important mechanism to drive the mg isotope compositions of silicate weathering residuals this mechanism drives fractionation in an opposite direction as might be expected from previous studies i e residual soils are driven to lighter mg values and sediments become isotopically heavier

boron and calcium isotope composition in neoproterozoic carbonate rocks from namibia evidence for extreme environmental change the level and evolution of atmospheric carbon dioxide throughout earth s history are key issues for palaeoclimate reconstructions especially during times of extreme climate change such as those that marked the neoproterozoic the carbon isotope ratios of marine carbonates are crucial in the correlation and identification of neoproterozoic glacial deposits and they are also used as a record for biogeochemical cycling and potential proxy for atmospheric pco2 likewise the boron and calcium isotope compositions of marine carbonates are potential proxies for palaeo seawater ph and the ratio of calcium fluxes into and out of seawater respectively and together they may be used to estimate atmospheric carbon dioxide here we use b and ca isotopes to estimate palaeoenvironmental conditions in the aftermath of a major neoproterozoic glaciation in namibia the validity of the b and ca isotope variation in the ancient marine carbonates is evaluated using the oxygen isotope composition of the carbonates and its correlation to the carbon isotope variation a negative 2 7 to 6 2 11b excursion occurs in the postglacial carbonates and is interpreted to reflect a temporary decrease in seawater ph associated variations in 44ca values ranging between 0 35 and 1 14 are linearly coupled with the carbon isotope ratios and imply enhanced postglacial weathering rates the reconstructed seawater ph and weathering profiles indicates that high atmospheric co2 concentrations were likely during the melt back of neoproterozoic glaciations and precipitation of cap carbonates however the b isotope trend suggests that these concentrations rapidly ameliorated and they do not co vary with 13c thus models attempting to link long lived negative 13c excursions to elevated pco2 need to be reconsidered

the significance of himalayan rivers for silicate weathering rates evidence from the bhote kosi tributary the significance of weathering by himalayan runoff for both the sr isotope marine record and the removal of atmospheric co2 through silicate dissolution has been examined by systematic sampling of dissolved loads and bedloads from the bhote kosi a tributary of the ganges that rises in tibet from tethyan sediment bedrock and traverses the major himalayan lithologies of eastern nepal before debouching onto the gangetic plains throughout the section the cation geochemistry of water samples is dominated by ca and mg ions suggesting that carbonates are the predominant lithology undergoing dissolution particularly within the lesser himalayas as the river transects the metasedimentary and granitic lithologies of the high himalayas the sr isotope ratio of the bedload rises rapidly closely reflecting the isotope geochemistry of the bedrock in contrast the 87sr 86sr ratio of the dissolved load remains roughly constant 0 719 0 723 downstream of the main central thrust where the river transects the carbonate bearing lithologies of the lesser himalayas the 87sr 86sr ratio of the dissolved load rises sharply 0 768 the relative contributions of silicate and carbonate weathering from each of the main himalayan units has been estimated from major cation sr concentration and sr isotope mass balance equations these calculations suggest that the high sr and high 87sr 86sr characteristics of riverine analyses arise initially from a component dissolved from the tibetan sedimentary series which is substantially enhanced by input weathering fluxes particularly as the river traverses the lesser himalayas whilst mechanical erosion is maximised within the high himalayan crystalline series as confirmed by 143nd 144nd ratios from the bedload at least 63 of the dissolved load is acquired by chemical weathering of bedrock lithologies and or of transported particulates within the lesser himalayas enhanced by higher ambient temperatures and slower discharge rates this may involve continued dissolution of the high himalayan crystalline series particulates in addition to lesser himalayan lithologies although himalayan rivers collectively have a major influence on the sr isotope marine record the high 87sr 86sr ratios of their dissolved load results from the mixing of a small component 90 of carbonate derived material some of which is characterised by a high 87sr 86sr ratio up to 0 8 elevated 87sr 86sr ratios in rivers are therefore not necessarily indicative of anomalously high dissolution rates of silicates

non chondritic magnesium and the origins of the inner terrestrial planets abstract high precision magnesium mg isotope data obtained using a large geometry high resolution mc icpms are reported for 9 carbonaceous and ordinary chondrites 9 eucrites and diogenites generally considered to originate from asteroid 4 vesta together with 4 martian meteorites and a variety of terrestrial and lunar materials the variation in mg isotopic composition found for mafic and ultramafic rocks mafic minerals and chondrites is smaller than reported previously the range of 26mg and 25mg of 0 6 and 0 3 defines a single mass dependent fractionation line consistent with a homogeneous mix of nucleosynthetic components data for the earth mars and vesta display no systematic mg isotopic differences despite large variations in the level of depletion in moderately volatile elements lunar mare basalts exhibit a significant range in 26mg 0 53 to 0 05 and 25mg 0 27 to 0 02 attributable to magmatic differentiation in the lunar magma ocean lmo lunar basalts derived from early segregated cumulates and thought to be the most primitive are on average slightly 0 17 26mg heavy relative to basalts from the earth mars and vesta however the difference is not well resolved more strikingly all differentiated planets and planetesimals as sampled have mg that is on average isotopically heavy compared with most chondrites analyzed thus far chondrules and cais also are generally heavy in terms of mg so this might reflect sorting of material in the proto planetary disk such an explanation would be similar to one previously proposed hewins r h and herzberg c t 1996 earth planet sci lett 144 1 7 to explain the non chondritic si mg of the earth in this model chondrule like objects separate from volatile rich planetary dust by accumulation in stagnant regions between eddies in the solar nebula small 1 km planetesimals formed by accumulation of such molten material then develop into planetary embryos and thence to larger terrestrial planets by combinations of runaway growth and collisions as such accumulation of molten chondrule like droplets provides an explanation that obviates some of the dynamic difficulties associated with the onset of planetary accretion the non chondritic mg isotopic composition of the earth is consistent with data for li and has important implications for earth s bulk composition and putative hidden reservoirs

magnesium retention on the soil exchange complex controlling mg isotope variations in soils soil solutions and vegetation in volcanic soils iceland understanding the biogeochemical cycle of magnesium mg is not only crucial for terrestrial ecology as this element is a key nutrient for plants but also for quantifying chemical weathering fluxes of mg and associated atmospheric co2 consumption requiring distinction of biotic from abiotic contributions to mg fluxes exported to the hydrosphere here mg isotope compositions are reported for parent basalt bulk soils clay fractions exchangeable mg seasonal soil solutions and vegetation for five types of volcanic soils in iceland in order to improve the understanding of sources and processes controlling mg supply to vegetation and export to the hydrosphere bulk soils 26mg 0 40 0 11 are isotopically similar to the parent basalt 26mg 0 31 whereas clay fractions 26mg 0 62 0 12 exchangeable mg 26mg 0 75 0 14 and soil solutions 26mg 0 89 0 16 are all isotopically lighter than the basalt these compositions can be explained by a combination of mixing and isotope fractionation processes on the soil exchange complex successive adsorption desorption of heavy mg isotopes leads to the preferential loss of heavy mg from the soil profile leaving soils with light mg isotope compositions relative to the parent basalt additionally external contributions from sea spray and organic matter decomposition result in a mixture of mg sources on the soil exchange complex vegetation preferentially takes up heavy mg from the soil exchange complex 26mgplant exch 0 50 0 09 and changes in 26mg in vegetation reflect changes in bioavailable mg sources in soils this study highlights the major role of mg retention on the soil exchange complex amongst the factors controlling mg isotope variations in soils and soil solutions and demonstrates that mg isotopes provide a valuable tool for monitoring biotic and abiotic contributions of mg that is bioavailable for plants and is exported to the hydrosphere

fractionation of fe isotopes by soil microbes and organic acids small natural variations in fe isotopes have been attributed to biological cycling however without understanding the mechanisms of fractionation it is impossible to interpret such variations here we show that the d 56 fe of fe dissolved from a silicate soil mineral by siderophore producing bacteria is as much as 0 8 lighter than bulk fe in the mineral a smaller isotopic shift is observed for fe released abiotically by two chelates and the magnitude of the shift increases with affinity of the ligand for fe consistent with a kinetic isotope effect during hydrolysis of fe at the mineral surface fe dissolved abiotically without chelates shows no isotopic shift the d 56 fe of the exchange fraction on soil grains is also lighter by 0 6 1 than fe from both hornblende and iron oxyhydroxides the kinetic isotope effect is therefore preserved in open systems such as soils when recorded in the rock record fe isotopic fractionation could document fe transport by organic molecules or by microbes where such entities were present in the geologic past

evidence for mass dependent isotopic fractionation of strontium in a glaciated granitic watershed abstract the stable isotope composition of strontium expressed as 88 86sr may provide important constraints on the global exogenic strontium cycle here we present 88 86sr values and 87sr 86sr ratios for granitoid rocks a 150 yr soil chronosequence formed from these rocks surface waters and plants in a small glaciated watershed in the central swiss alps incipient chemical weathering in this young system whether of inorganic or biological origin has no resolvable effect on the 87sr 86sr ratios and 88 86sr values of bulk soils which remain indistinguishable from bedrock in terms of sr isotopic composition although due in part to the chemical heterogeneity of the forefield the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of sr a low degree of chemical weathering is also implied by bulk soil chemistry the isotopic composition of sr in streamwater is more radiogenic than median soil reflecting the preferential weathering of biotite in the catchment streamwater 88 86sr values however are indistinguishable from bulk soil 88 86sr values implying that no resolvable fractionation of sr isotopes takes place during release to the weathering flux in the damma forefield analyses of plant tissue reveal that plants rhododendron and vaccinium preferentially assimilate the lighter isotopes of sr such that their 88 86sr values are significantly lower than those of the soils in which they grow additionally 88 86sr values of foliar and floral tissues are lower than those of roots contrary to observations for ca for which sr is often used as an analogue in weathering studies we suggest that processes that discriminate against sr in favour of ca due to the different nutritional requirement of plants for these two elements are responsible for the observed contrast

biological control of calcium isotopic abundances in the global calcium cycle measurements of 44ca 40ca expressed as 44ca were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature the results document a span of 4 in 44ca measured with the double spike technique to a precision of 0 15 volcanic rocks including basalt and rhyolite show little variability and cluster near 44ca 0 0 2 systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes and that biological fractionation is the primary generator of calcium isotopic fractionation in nature preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains calcium carbonate shells of marine microorganisms and deep sea carbonate ooze have 44ca about 1 0 lower than seawater this fractionation causes seawater to be enriched in heavy calcium 44ca 0 9 relative to igneous rocks marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level the calcium isotopic composition of living and fossil organisms may record information on diet and environment

increased mg release rates and related mg isotopic signatures during bacteria phlogopite interactions abstract phlogopite weathering experiments were carried out under aerobic conditions in a closed system to study mg isotopic fractionation during the dissolution and processes involved in the presence of bacterial strains four different bacterial strains with different metabolisms were chosen biotic experiments were performed in batch reactors at 24 c for 12 days in parallel abiotic phlogopite weathering experiments were also performed using organic and nitric acids citric and gluconic acids were used to model the effects of chelating agents produced by bacteria and nitric acid was used to model the effects of acidifying agents the results indicate that both decreases in ph and the production of metabolites during heterotrophic bacterial activities significantly accelerate the release of mg and si in solution also at a given ph the fraction of elements released in solution is greater in the presence of bacteria or citric acid compared to that released in the presence of nitric and gluconic acids magnesium isotopic analyses indicate that the solutions obtained using nitric acid and acidifying bacterial strains display on average 26mg values that are close to or slightly heavier by 0 4 than those of fresh phlogopite 1 2 0 08 in contrast in experiments performed with citric acid the mg leached into solution is slightly enriched in light isotopes by 0 3 relative to the initial phlogopite while its binding to organics is expected to be related to its preferential enrichment in heavy isotopes despite its small range of variations the 26mg values of solutions vary inversely with ph thus suggesting that secondary phases preferentially enriched in 26mg at the highest ph values may play a key role

reconciling the elemental and sr isotope composition of himalayan weathering fluxes insights from the carbonate geochemistry of stream waters determining the relative proportions of silicate vs carbonate weathering in the himalaya is important for understanding atmospheric co2 consumption rates and the temporal evolution of seawater sr however recent studies have shown that major element mass balance equations attribute less co2 consumption to silicate weathering than methods utilizing ca sr and 87sr 86sr mixing equations to investigate this problem we compiled literature data providing elemental and 87sr 86sr analyses for stream waters and bedrock from tributary watersheds throughout the himalaya mountains in addition carbonate system parameters pco2 mineral saturation states were evaluated for a selected suite of stream waters the apparent discrepancy between the dominant weathering source of dissolved major elements vs sr can be reconciled in terms of carbonate mineral equilibria himalayan streams are predominantly ca2 mg2 hco3 waters derived from calcite and dolomite dissolution and mass balance calculations demonstrate that carbonate weathering contributes 87 and 76 of the dissolved ca2 and sr2 respectively however calculated ca sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and pco2 gradients in the himalaya the state of calcite and dolomite saturation was evaluated across these gradients and the data show that upon descending through the himalaya 50 of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas co2 stream water ca mg and ca sr ratios decrease as the degree of supersaturation with respect to calcite increases and mg2 ca2 and hco3 mass balances support interpretations of preferential ca2 removal by calcite precipitation on the basis of patterns of saturation state and pco2 changes calcite precipitation was estimated to remove up to 70 of the ca2 originally derived from carbonate weathering accounting for the nonconservative behavior of ca2 during riverine transport brings the ca sr and 87sr 86sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock thereby permitting consistency between elemental and sr isotope approaches to partitioning stream water solute sources these results resolve the dissolved sr2 budget and suggest that the conventional application of two component ca sr and 87sr 86sr mixing equations has overestimated silicate derived sr2 and hco3 fluxes from the himalaya in addition these findings demonstrate that integrating stream water carbonate mineral equilibria divalent cation compositional trends and sr isotope inventories provides a powerful approach for examining weathering fluxes