a study of oxygen isotopic fractionation during bio induced calcite precipitation in eutrophic baldeggersee switzerland in order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences we undertook an extensive one year study march 1995 to february 1996 of water column chemistry and daily sediment trap material from a small lake in central switzerland comparisons between calculated equilibrium isotope values using the fractionation equation of friedman and o neil 1977 and measured oxygen isotope ratios of calcite in the sediment traps reveal that oxygen isotopic values of autochthonous calcite 18o are in isotopic equilibrium with ambient water during most of the spring and summer when the majority of the calcite precipitates in contrast small amounts of calcite precipitated in early spring and again in late autumn are isotopically depleted in 18o relative to the calculated equilibrium values by as much as 0 8 this seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations elevated ph 8 6 and increased co32 50 mol l in the surface waters the resulting weighted average 18o value for the studied period is 9 6 compared with a calculated equilibrium 18o value of 9 4 these data convincingly demonstrate that 18o of calcite are for the most part a very reliable proxy for temperature and 18o of the water

stable sr isotope sr ca mg ca li ca and mg li ratios in the scleractinian cold water coral lophelia pertusa the aragonitic skeletons of scleractinian cold water corals can serve as valuable archives in paleoceanographic studies the potential of 88 86sr sr ca mg ca li ca and mg li ratios of the cold water coral lophelia pertusa to record intermediate water mass properties has been investigated here we used samples from several locations along the european continental margin spanning a large temperature range from 6 to 14 c stable strontium isotope measurements were carried out with the recently developed double spike tims technique and our results differ from those obtained with less precise methods in contrast to the strong positive relationship with temperature of previous studies our results suggest that 88 86sr measured in scleractinian cold water corals is not controlled by seawater temperature but reflects the sr isotopic composition of seawater with an offset of 88 86sr 0 196 as found in previous studies the elemental ratios sr ca li ca and mg li measured in corals are significantly related to water temperature and do not correlate with salinity moreover sr ca ratios in l pertusa display the expected inverse correlation with temperature however the variance in the sr ca data severely limits the accuracy of paleotemperature estimates the li ca and mg ca ratios reveal other influences besides temperature such as ph and or growth or calcification rate however corresponding mg li ratios in l pertusa are more tightly related to temperature as they remove these secondary effects in particular the mg li ratio in l pertusa may serve as a new promising paleotemperature proxy for intermediate water masses our dataset represents the most extensive geochemical examination of l pertusa to date revealing a temperature sensitivity of 0 015 mol mmol c for mg li however using this temperature dependence and the precision of 5 3 2sd only temperature variations larger than 1 5 c can be resolved with 95 confidence

paleoclimate of the past 4000 years at lake turkana kenya based on the isotopic composition of authigenic calcite abstract authigenic calcite was analyzed for 13 c and 18 o in a 12 m long core from lake turkana that spans the last 4200 yr the 18 o record is interpreted to reflect lake level history and indicates high stands prior to 4000 yr b p from 1800 to 2000 yr b p and within the last century this coincides better with the history of lake level change reported for other lakes in africa than did the previous lake level curve for lake turkana based on 14 c dates of exposed shoreline deposits the 13 c curve roughly parallels the 18 o curve and may reflect the influence of the omo river plume both of the isotope records are strongly cyclic with periodicites common to both at 80 120 150 and 225 yr other somewhat longer periodicites are nearly equal in the two records and there is close agreement with previously published cycles based on carbonate and lamination thickness analyses in the same turkana core

evidence for stable sr isotope fractionation by silicate weathering in a small sedimentary watershed in southwestern taiwan abstract radiogenic sr isotopes 87 sr 86 sr are robust for provenance identification in hydrology affected mainly by the age of background lithologies and the degree of chemical weathering however there is limited knowledge concerning the fractionation mechanism of stable sr isotopes 88 sr 86 sr in rivers in this study river water was collected on a weekly to monthly basis throughout dry and wet seasons furthermore to study the variations of radiogenic and stable sr isotopes during intense weathering a major flooding event 2000 mm precipitation in three days typhoon morakot water was captured within a small drainage catchment system 161 km 2 along the hou ku river in southwestern taiwan for a better constraint on the end member compositions bedload sediments suspended particles and several host rocks were sampled for a systematic investigation the carbonate and silicate phases of these solids were chemically separated dissolved major elements indicate that the watersheds were predominated by silicate weathering stable sr isotopes show no significant variation 88 sr 0 24 0 31 temporally and spatially with an average of 0 28 additionally all solids showed lower 88 sr values than the river water while the host rocks had higher 88 sr values 88 sr 0 20 0 26 than the residual weathering products 88 sr 0 08 0 22 indicating preferential leaching of heavy sr into the hydrosphere and leaving light sr in the residual solids results of laboratory acid leaching experiments reveal that dissolution of high 88 sr value minerals occurred at an early stage of weathering the variation of weathering intensity does not alter stable sr isotopes in silicate weathering dominated river water which contains higher stable sr isotopes than the associated sediments the silicatic sedimentary rocks preferentially released higher stable sr isotopes into the hydrosphere during chemical weathering thus leaving lower stable sr isotopes in the residual solids

the origin and migration of mud volcano fluids in taiwan evidence from hydrogen oxygen and strontium isotopic compositions abstract mud volcanoes are important gateways for deep fluids to migrate upward and provide windows for studying fluid sediment interaction at depth fluids emitted from 40 terrestrial mud volcanoes were collected in southern and eastern taiwan to study their chemical compositions including h o and sr isotopes 87sr 86sr and 88 86sr relative to seawater the mud volcano fluids are depleted in cl mg so42 and d and are elevated in b ba li and 18o possibly due to water rock interaction and clay dehydration mainly smectite to illite transformation in the source region the distribution of sr in mud volcano fluids shows patterns associated with their localities and geological settings most fluids have higher 87sr 86s than seawater indicating water rock interaction at depth the low na 87sr 86s and high ca fluids emitted from eastern taiwan imply intense interaction with igneous basement most fluids have higher sr cl and lower 88sr than seawater except mud volcanoes in the northern chu kou fault which emit low sr cl and extremely high 88sr up to 0 82 fluids we performed laboratory carbonate precipitation experiments that indicate that these high sr isotope ratios are caused by co precipitation of carbonates from high alkalinity fluids mud volcano fluids in taiwan originate at depth and their chemical compositions are controlled by the host rock degrees of water rock interaction and clay dehydration but also are masked by retrograde progresses such as carbonate precipitation during migration our results show that an approach combining water isotopes d and 18o and strontium isotopes 87sr 86sr and 88 86sr provides a robust tool for tracing fluid sources and migration pathways in accretionary prisms

a new view of ridge segmentation and near axis volcanism at the east pacific rise 8 12 n from em300 multibeam bathymetry 1 new high resolution bathymetry for the east pacific rise between 8 n and 12 n was collected over a 6 km wide swath centered on the ridge axis using the 30 khz simrad em300 multibeam system the coverage area corresponds latitudinally to the designated ridge2000 integrated studies site iss for fast spreading ridges the em300 data gridded at 30 m latitude by 50 m longitude represent a greater than 4x improvement in horizontal resolution over previously available multibeam data and a 2x improvement in depth resolution the new bathymetry was used to update the locations and hierarchy of ridge offsets for this area among the many applications for this data it enables us to tabulate volcanoes half the size that could be previously detected the distribution of near axis volcanic cones 25 m high suggests that this population of small near axis cones results from low effusion rate eruptions of the ridge axis

dust transport and synoptic conditions over the sahara arabia deserts during the mis6 5 and 2 1 transitions from grain size chemical and isotopic properties of red sea cores abstract the red sea situated between the sahara and arabia deserts is a natural trap for fine grained particles transported by winds and floods from weathered materials in these deserts derived from the proterozoic crustal granitic and basaltic terrains and phanerozoic carbonates the accumulated fine particles provide valuable information on the climate conditions in the source regions and modes of atmospheric circulation over the red sea region here we report on the grain size mineralogy chemical composition and nd and sr isotope ratios of fine grained insoluble residues ir from acid leaching that were recovered from two deep sea cores kl23 and kl11 drilled in the northern and central red sea respectively we focus on the mis6 5 and mis2 1 transitions kl23 samples are closer to the sahara granitoids field and display significant variations during the mis6 5 transition between end of 7 to 2 and 87sr 86sr of 0 7096 to 0 7114 smaller variations occurred during the mis2 1 transition between end of 5 to 6 and 87sr 86sr of 0 7104 to 0 7118 the kl11 values are closer to the blue nile field which comprises mixtures of granitoid and basalt derived particles during the mis6 5 transition their end varies from 4 to 1 and in 87sr 86sr from 0 7059 to 0 7091 during periods equivalent to sapropels s5 and s1 both cores appear to converge to similar isotope ratios of e nd 2 and 87sr 86sr 0 7095 indicating derivation from the granitoid terrains of the arabian nubian shield occurring adjacent to the red sea and possibly distributed by runoff in terms of synoptic conditions the data indicate that during glacials dust was blown to the northern red sea from the northern sahara desert in association with the mediterranean winter cyclones and to the central red sea from the ethiopian plateau by southern winds that are associated with monsoonal circulation during interglacials especially sapropel intervals monsoonal rains caused erosion and flooding at the arabian nubian shield margins of the red sea during the heinrich events associated with the studied intervals h11 and h1 dust from mixed basaltic granitic terrains was blown from all of the regional sources in the red sea region reflecting severe regional aridity and transport of dust by regional winds when monsoonal activity and mediterranean cyclone activity were weak

determination of temperature dependent stable strontium isotope 88sr 86sr fractionation via bracketing standard mc icp ms stable strontium isotopes here 88sr 86sr are introduced as a new member of the nontraditional stable isotopes we have developed a bracketing standard method for the determination of 88 86sr using an axiom mc icp ms and normalizing to strontium srm nbs987 for individual measurements the external reproducibility is better than about 25 ppm 1 rsd for the iapso seawater standard a 88 86sr value of 0 381 0 010 2sem was determined for the first time a temperature dependent strontium isotope fractionation during calcium carbonate precipitation could be shown aragonite samples inorganically precipitated under temperature control between 10 and 50 c revealed a 88 86sr temperature dependency of 0 0054 5 c r2 0 987 in contrast for natural coral samples pavona clavus from a proxy calibration study 23 to 27 c we did determine 0 033 5 c r2 0 955 the processes causing this sixfold stronger temperature dependency for the natural coral samples have to be studied in more detail in future studies in a first approach the different slopes can be interpreted as effects of kinetic fractionation of strontium ions with or without a hydrate shell of 22 to 29 water molecules

88 sr 86 sr fractionation and calcite accumulation rate in the sea of galilee abstract this study used the sea of galilee lake kinneret northern israel as a natural laboratory to investigate the fractionation of the stable sr isotope ratio 88 sr 86 sr during precipitation of inorganic primary calcite from the lake s water it was found that the absolute value of the 88 sr 86 sr fractionation factor 88 86 sr increases as a function of calcite accumulation rate 88 86 sr 0 05 to 0 042 log r mol m 2 d 1 where r is the accumulation rate furthermore the 87 sr 86 sr and 88 sr 86 sr ratios in the freshwater and brines that enter the lake were used to calculate the contributions of these sources to the lake sr budget the 87 sr 86 sr and 88 sr 86 sr ratios were measured in primary calcite aragonite shells of live melanopsis lake water and various water sources to the lake while the lake s 87 sr 86 sr ratios are determined by the mixture of freshwater of the jordan river and saline springs the 88 sr 86 sr ratios of the lake reflect a more complex mass balance that includes the effect of isotopic fractionation associated with the precipitation of primary calcite data analysis suggests that long term accumulation of inorganic calcite depleted in the heavy isotope 88 sr results in an increase of the 88 86 sr value of the lake water by 0 05 in contrast to the primary inorganic calcite biogenic aragonite of the melanopsis shells show a rather constant 88 sr 86 sr water caco 3 fractionation of 88 86 sr 0 21 similar 88 86 sr values were reported for the precipitation of coralline and inorganic aragonite from seawater and the precipitation of inorganic calcite from various continental waters the 88 86 sr value of inorganic calcite is modulated by the rate of carbonate precipitation as noted above and shown by precipitation experiments massive precipitation of primary calcite with a wide spread of accumulation rates occurs during the spring phytoplankton bloom in lake kinneret the bloom dictates the degree of calcite saturation in the lake and hence the stable sr isotopic composition of the precipitating calcite the correlation between 88 sr 86 sr and the calcite accumulation rate can be therefore used as a tool to reconstruct environmental and ecological variations in the historical lake by analyzing the 88 sr 86 sr ratio in the primary caco 3 recovered from the lake s sedimentary archives

partitioning of strontium between calcite and fluid the sr ca ratio of biogenic carbonate is widely used as a proxy for paleotemperature this application is supported by empirical calibrations of sr ca as a function of temperature but it is also known that sr uptake in calcite gauged by kdsr is affected by other variables including bulk precipitation rate kdsr increases with increasing precipitation rate there are no data from controlled experiments specifically addressing the effect of radial growth rate of individual crystals on kdsr for this reason we conducted two series of experiments to explore sr partitioning at varying growth rates 1 growth from a cacl2 nh4cl srcl2 solution by diffusion of co2 from an ammonium carbonate source drift experiments and 2 drip precipitation of calcite on a substrate using a steady flow of cacl2 srcl2 and na2co3 solutions mixed just before passage through a tube and dripped onto a glass slide precoated with calcite cave type experiments the growth rates of individual crystals were determined by periodic monitoring of crystal size through time or roughly by comparison of the final size with the duration of the experiment electron microprobe analyses across sectioned crystals grown in the drift experiments show that the concentration of sr is high in the center where radial growth rates are highest and decreases systematically toward the edge the center to edge drop in sr concentration is a consequence of the slowing radial growth rate as individual crystals become larger in general high crystal growth rate v enhances sr uptake in calcite due to a type of kinetic disequilibrium we refer to as growth entrapment the apparent kdsr ranges from 0 12 to 0 35 as v increases from 0 01 nm s to 1 m s at 25 c

mapping and defining sources of variability in bioavailable strontium isotope ratios in the eastern mediterranean abstract the relative contributions of bedrock and atmospheric sources to bioavailable strontium sr pools in local soils was studied in northern israel and the golan regions through intensive systematic sampling of modern plants and invertebrates to produce a map of modern bioavailable strontium isotope ratios 87 sr 86 sr for regional reconstructions of human and animal mobility patterns the study investigates sources of variability in bioavailable 87 sr 86 sr ratios in particular the intra and inter site range of variation in plant 87 sr 86 sr ratios the range of 87 sr 86 sr ratios of plants growing on marine sedimentary versus volcanic geologies the differences between ligneous and non ligneous plants with varying growth and water utilization strategies and the relative contribution of atmospheric sr sources from different soil and vegetation types and climatic zones results indicate predictable variation in 87 sr 86 sr ratios inter and intra site differences in bioavailable 87 sr 86 sr ratios average of 0 00025 while the range of 87 sr 86 sr ratios measured regionally in plants and invertebrates is 0 7090 in pleistocene calcareous sandstone and 0 7074 in mid pleistocene volcanic pyroclast the 87 sr 86 sr ratios measured in plants growing on volcanic bedrock show time dependent increases in atmospheric deposition relative to bedrock weathering the 87 sr 86 sr ratios measured in plants growing on renzina soils depends on precipitation the spacing between bedrock 87 sr 86 sr ratios and plants is highest in wet conditions and decreases in dry conditions the 87 sr 86 sr ratios measured in plants growing on terra rossa soils is relatively constant 0 7085 regardless of precipitation ligneous plants are typically closer to bedrock 87 sr 86 sr ratios than non ligneous plants since the bioavailable 87 sr 86 sr ratios currently measured in the region reflect a mix of both exogenous and endogenous sources changes in the relative contribution of exogenous sources can cause variation over time precipitation the age of the bedrock and the overall sr concentration must to be taken into consideration when interpreting geographical variation in strontium isotopes throughout a region because these factors can change through time we recommend that sr data from time periods older than the holocene be interpreted with caution

the phanerozoic δ88 86sr record of seawater new constraints on past changes in oceanic carbonate fluxes the isotopic composition of phanerozoic marine sediments provides important information about changes in seawater chemistry in particular the radiogenic strontium isotope 87sr 86sr system is a powerful tool for constraining plate tectonic processes and their influence on atmospheric co2 concentrations however the 87sr 86sr isotope ratio of seawater is not sensitive to temporal changes in the marine strontium sr output flux which is primarily controlled by the burial of calcium carbonate caco3 at the ocean floor the sr budget of the phanerozoic ocean including the associated changes in the amount of caco3 burial is therefore only poorly constrained here we present the first stable isotope record of sr for phanerozoic skeletal carbonates and by inference for phanerozoic seawater 88 86srsw which we find to be sensitive to imbalances in the sr input and output fluxes this 88 86srsw record varies from 0 25 to 0 60 vs srm987 with a mean of 0 37 the fractionation factor between modern seawater and skeletal calcite 88 86srcc sw based on the analysis of 13 modern brachiopods mean 88 86sr of 0 176 0 016 2 standard deviations s d is 0 21 and was found to be independent of species water temperature and habitat location overall the phanerozoic 88 86srsw record is positively correlated with the ca isotope record 44 40casw but not with the radiogenic sr isotope record 87sr 86sr sw a new numerical modeling approach which considers both 88 86srsw and 87sr 86sr sw yields improved estimates for phanerozoic fluxes and concentrations for seawater sr the oceanic net carbonate flux of sr f sr carb varied between an output of 4 7x1010mol myr and an input of 2 3x1010mol myr with a mean of 1 6x1010mol myr on time scales in excess of 100myrs the f sr carb is proposed to have been controlled by the relative importance of calcium carbonate precipitates during the aragonite and calcite sea episodes on time scales less than 20myrs the f sr carb seems to be controlled by variable combinations of carbonate burial rate shelf carbonate weathering and recrystallization ocean acidification and ocean anoxia in particular the permian triassic transition is marked by a prominent positive 88 86srsw peak that reflects a significantly enhanced burial flux of sr and carbonate likely driven by bacterial sulfate reduction bsr and the related alkalinity production in deeper anoxic waters we also argue that the residence time of sr in the phanerozoic ocean ranged from 1myrs to 20myrs

the reconstruction of quaternary freshwater lakes from the chemical and isotopic composition of gastropod shells the dead sea rift israel abstract sr ca ba ca and 87sr 86sr ratios in fossil freshwater aragonitic gastropods melanopsis praemorsum and melanoides tuberculata have been used to reconstruct the water sources of quaternary lakes in the jordan river rift valley the reconstruction is based on the assumption that the same waurces which supply freshwater into the rift valley in the present i e carbonate water basaltic water and rift brines were active throughout the quaternary the distribution coefficients for sr and ba were obtained from live gastropods which were collected from modern water bodies in the region by using these distribution coefficients the composition of the ancient waters could be derived from the fossil shells chemistry altogether four ancient sites were sampled of which mishmar ha yarden and gesher benot ya akov formations are located in the upper jordan valley and erq el ahmar and ubeidiya formations are in its central part low salinity carbonate waters 300 mg l comprised the main h2o source into the hula basin in the upper jordan valley these solutions display a 87sr 86sr ratio of 0 7082 0 0002 which is significantly higher than the corresponding modern ratio 0 7070 suggesting that the ancient drainage system was initially fed by upper eocene carbonate aquifers and shifted later to a jurassic carbonate system the erq el ahmar lake in the central jordan valley was supplied by approximately equal proportions of carbonate and basaltic waters resulting in a water body of low salinity 300 mg l the water source of lake ubeidiya also in the central jordan valley was predominantly basaltic yet its chemistry bears a strong rift brine signature resulting in a salinity of about 1000 1300 mg l the values obtained are in good accord with the biological evaluation of the fossil biota

strontium stable isotopes fractionate in the soil environments abstract this study shows that the stable isotopic composition of strontium the 88sr 86sr ratio expressed as 88 86sr value relative to the nbs987 standard varies significantly in sedimentary terrestrial environments the abundances of 86sr 88sr isotopes were analyzed by mc icp ms nu plasma all studied rocks and waters show 88 86sr values that are distinctly different from the measured nbs987 standard yielding 0 01 0 05 all errors are reported as 2 modern corals from the northern gulf of aqaba red sea yielded significantly different value than seawater 88 86sr 0 22 0 07 compared to 0 35 0 06 respectively in an excellent correlation with the 88 86sr analyses reported by fietzke and eisenhauer fietzke j eisenhauer a 2006 determination of temperature dependent stable strontium isotopes 88sr 86sr fractionation via bracketing standard mc icp ms geochm geophys geosyst 7 no 8 on other coral samples all carbonate samples that originated in the marine environment corals porites and acropora from the northern gulf of aqaba cretaceous limestone and runoff from the judea mountains as well as lacustrine evaporitic aragonite dead sea and red sea and atlantic seawater yield an average 88 86sr value of 0 26 0 1 on the other hand secondary materials products of chemical weathering from the terrestrial environment of the judea mountain such as terra rossa soil and speleothem calcite that derives its sr from the above lying soil yielded significantly lower 88 86sr value of 0 17 0 06 this indicates that strontium isotopes fractionate in the soil environment calling for a possible development of strontium isotopes as a tracer for processes of chemical weathering and pedogenesis

calcium magnesium and strontium cycling in stratified hardwater lakes lake kinneret sea of galilee israel abstract in stratified hardwater lakes calcite crystallization in the epilimnion and partial dissolution in the hypolimnion play important roles in the cycling of ca2 in the water column mg2 and sr2 coprecipitate with this mineral to be released together with ca2 upon its dissolution here we focus on lake kinneret sea of galilee israel a stratified warm hardwater lake searching for an interpretable high resolution picture of the processes that drive ca2 mg2 and sr2 cycling in this and similar lakes elsewhere in total 1428 water samples were collected from the lake and another 81 samples were collected from the jordan river and two small streams discharging into it covering a full monomictic cycle from december 2001 through march 2003 particulate material was retrieved from sediment traps in the hypolimnion the water samples were analyzed for na k mg2 ca2 sr2 cl so42 hco3 and br and the trapped particulates were examined under sem and analyzed for their ca mg and sr content individual calcite crystals within the particulate material underwent la icp ms analysis for ca mg and sr downward transport of ca2 involves crystallization of calcite in the epilimnion followed by its settling through the water column followed by its partial dissolution in the hypolimnion magnesium and sr2 follow ca2 by coprecipitation in calcite and are released upon its dissolution in the hypolimnion upward cycling of the three solutes occurs through an admixture of the hypolimnetic water into the epilimnion during thermocline deepening terminated by overturn of the lake removal rates of mg2 and sr2 from the lake relative to that of ca2 and the water calcite distribution coefficients dmg and dsr were calculated from the analyses using 1 epilimnion water and bulk particulates 2 epilimnion water only and 3 epilimnion water and calcite crystals in the particulates the dsr values obtained were internally consistent 0 194 5 9 0 22 0 28 and 0 204 0 232 respectively however the dmg value for the bulk particulates 0 0477 was 6 times higher than that corresponding to calcite crystals included therein 0 00841 this difference is attributed to phytoplankton debris in the bulk particulates and should be of concern to geochemists using mg ca ratios in limestone to reconstruct ancient aquatic environments the cycling of ca2 mg2 and sr2 in the stratified lake is monitored by mg ca vs sr ca regression diagrams where each line represents the water column composition on a specific date the distance of the data points from the initial mixed lake coordinates reflects the fractionation of ca2 mg2 and sr2 after the onset of stratification the regression lines rotate in an orderly anticlockwise direction in response to the high calcite flux from the epilimnion in spring and the higher rate of mg2 replenishment than that of sr2 compensating for their loss in calcite the release of mg2 and sr2 from dissolving calcite in the hypolimnion at an mg sr ratio 7 5 eq eq much lower than that in the surrounding water 160 eq eq lends additional support to the anticlockwise rotation reversal of rotation occurs in summer when calcite crystallization and the freshwater supply slow down and brackish and saline water sources take control over the mg sr ratio in the lake subsequent turnover and mixing of the lake in winter reset the mg ca and sr ca ratios to their original values before the next stratification

strontium isotopic chemical and sedimentological evidence for the evolution of lake lisan and the dead sea precise strontium isotope ratios combined with chemical analyses and sedimentological information are used to monitor the water sources and the evolution of the dead sea and its late pleistocene precursor lake lisan 70 18 kyr b p the materials analyzed include bulk aragonite water leached soluble salts and residual aragonite and gypsum from the lisan formation in the perazim valley near the sw shore of the dead sea the residual aragonite and the associated soluble salts display systematic fluctuations in 17sr86sr ratios between 0 70803 and 0 70806 and from 0 70805 to 0 70807 respectively in individual soluble salt residual aragonite pairs the soluble salt displays a higher 87sr86sr ratio gypsum samples yield 17sr86sr ratios similar to the soluble salts from adjacent layers in the section this shows that in individual samples the source of sr in aragonite was distinct from that in soluble salts and the gypsum the sterility of the lisan sediments their strictly nonbioturbated fine lamination and their high content of chloride salts indicate that lake lisan was a saline or even hypersaline water body in the absence of alternative sources of hco3 and s042 the abundance of primary aragonite and gypsum in the lisan column reflects an import of very large volumes of freshwater into the otherwise saline lake resulting in a density stratification of this water body the history of the upper water layer and that of the lower brine is reflected in the chemical and strontium isotope composition of the aragonite and in that of the associated soluble salts and in the gypsum samples respectively whereas the bicarbonate and much of the ca2 required for aragonite crystallization were supplied by the freshwater the complementary ca2 and sr 2 were added by the lower brine the upper water layer of lake lisan acted as a so42 capacitor during the lake s rise periods it was removed therefrom as prominent gypsum beds upon climatic induced drier period mixing or even complete overturn of the lake the evolution of lake lisan took place between two distinct modes the first was characterized by an extensive supply of freshwater and resulted in a rise of the lake s level a density layered structure and precipitation of aragonite the second mode was marked by a diminishing freshwater input resulting in mixing or complete overturn of its water and precipitation of gypsum these two modes reflect the climatic evolution of the region in the late pleistocene which fluctuated between drier and wetter periods the transition to the holocene is accompanied by the dry up of lake lisan and its contraction to the present dead sea

crystal growth rate effect on mg ca and sr ca partitioning between calcite and fluid an in situ approach abstract partition coefficients of mg and sr kmg and ksr between calcite and fluid were determined in crystals grown under different rates v where v is defined as the crystal extension per unit of time nm s addition of rare earth elements ree into the fluid leads to ree preservation in the calcite this preservation allows for a direct determination of the values of v by measuring the widths of the ree spiked zones the edge to edge spot analyses of mg ca sr ca and ree ca in the individual crystals were conducted using secondary ion mass spectrometry sims the mg ca and sr ca ratios in the fluids from which calcites precipitated were also measured with inductively coupled plasma atomic emission spectroscopy icp oes this allowed for the first time to evaluate kmg in situ in the individual crystals without averaging the data from the multiple calcite crystals results show that ksr increases by a factor of six with increasing calcite growth rate from 0 001 to 4 nm s kmg decreases by a factor of three with the same increase of v values these ksr and kmg behaviors were described quantitatively using a growth entrapment model gem according to the gem simulations sr is enriched and mg is depleted in the near surface layer of calcite relative to the bulk lattice this distinct outermost region of the crystal may be fully or partially captured by its lattice during rapid growth this process causes disequilibrium partitioning of sr and mg through growth entrapment

reassessing the stable δ88 86sr and radiogenic 87sr 86sr strontium isotopic composition of marine inputs the stable strontium isotope system 88 86sr has recently been suggested to be a suitable proxy for determining variations in the strength of the marine carbonate system the principal output flux of oceanic sr however in order to be able to interpret carbonate driven variations in 88 86srseawater a robust understanding of 88 86srinput is required surprisingly only a limited amount of 88 86sr data currently exists for rivers and hydrothermal fluids thus this study assesses the variability of 88 86sr and 87sr 86sr in global rivers hydrothermal fluids and porewaters as well as minor marine sr sources such as continental dust rainwater and glacial ice our analyses broadly confirm the findings of krabbenhoft et al 2010 and reveal flux weighted 88 86srriverine and 87sr 86srriverine compositions of 0 32 and 0 71299 respectively the hydrothermal fluids analysed in this study are consistent with an end member 88 86srhydrothermal composition that is the same as the oceanic crust at 0 24 although three samples that display 88 86sr compositions offset from the seawater hydrothermal mixing trend suggest that the precipitation of alteration phases such as anhydrite may drive 88 86srhydrothermal to higher values porewater fluids obtained from sediment cores in the atlantic and pacific oceans have 88 86sr compositions within error of seawater 0 39 implying that the diagenetic flux of sr may not significantly affect the 88 86sr composition of seawater continental loess samples have 88 86sr compositions that are consistently lighter than or equal to terrestrial silicates with their tendency to lower values thought to reflect the preferential removal of heavier sr isotopes into solution during weathering finally rainwater and glacial ice samples have 88 86sr compositions that are also isotopically lighter than their associated water sources a factor that may be attributed to interaction with isotopically light loess and additional sr contributions from the bedrock together the principal marine inputs define flux weighted oceanic 88 86srinput and 87sr 86srinput compositions of 0 32 and 0 71161 these values are consistent with an elevated supply of riverine sr to the oceans due to increased post glacial weathering but require the enhanced weathering of exposed carbonate shelves during glacial periods or significant changes in the rate of carbonate burial to match observed changes in the 87sr 86sr ratio of seawater our results confirm that providing a diagenetically robust proxy can be found the 88 86sr and 87sr 86sr isotope systems should provide a useful proxy for investigating changes in the marine carbonate system through time

chemical tracing of salinity sources in lake kinneret sea of galilee israel lake kinneret is a freshwater lake in northern israel that receives a major part of its salt input from unmonitored springs that discharge through the lake s bottom we attempt to characterize the nature of these springs by estimating their chemical composition while the springs around lake kinneret are subject to wide spatial and temporal variations in their ionic concentrations specific sodium na potassium magnesium mg strontium bromine and lithium to chlorine cl ion ratios are almost constant within individual springs and spring groups the radium cl ratio and the d 18 o cl relationship confirm the notion that the spring waters result from recent mixing between saline brines and freshwater available compositional data from past years along with new analyses of the lake and its known springs allow identification of the salinity source that causes the observed deficit in the lake s salt budget e g 91 93 chloride the relative contributions from these saline springs are different for different ions this contribution is highest for bromide 95 decreases to 84 for na and is less than 50 for mg two independent approaches have been used for balancing the salts in the lake and they are as follows 1 an annual mass balance between salt removal and supply of the different ions assuming a steady state lake and 2 simulation of the lake s evolution from 1964 the beginning of salt removal from the lake via the salinity diversion channel until the present both methods predict very similar ionic ratios for the yet unknown average saline spring s testifying to the reliability of both approaches the ionic ratios so obtained closely resemble fuliya 6 tabgha type waters excluding the tiberias and eastern shore springs as significant salt sources this inferred composition of the average unmonitored springs depends strongly on present day diversion of saline springs this diversion thus prevents their flow into the lake the different ionic ratios that identify the various spring groups reflect the respective compositions of the brine pockets that feed them our simulation also shows that the layered structure of lake kinneret enhanced the evolution rate of the lake after the implementation of the salt diversion program in 1964 lake kinneret lk lake tiberias or the sea of galilee is a lake of immense historical and religious significance it is also the only freshwater lake in israel and the main water reservoir for the national water carrier nwc the water supply system that transfers freshwater to central and southern israel about 30 of the country s water supply was pumped from lk in 1995 furthermore with the water shortage in the middle east becoming more and more acute lk is also a waterbody of great political significance the lake is monomictic it is stratified between mid march and december the mixing of a fully stratified to a fully mixed lake takes about 4 5 months though it is a flowthrough lake it is significantly saltier than the jordan river which is its major water source table 1 the composition

strontium isotope fractionation of planktic foraminifera and inorganic calcite we have investigated the strontium isotope fractionation 88 86srcarb aq between inorganic calcite and aqueous sr2 ions by precipitation experiments at a constant temperature of 25 c and precipitation rates r ranging from 102 3 to 104 2 mol m2 h strontium isotope ratios were measured using the 87sr 84sr double spike technique it was found that strontium isotope fractionation in these calcites is strongly dependent on the precipitation rate view the mathml source the measured 88 86sr values are significantly correlated with previously measured 44 40ca and sr ca values of the same calcite samples 88 86srcarb aq 0 18 44 40cacarb aq 0 01 view the mathml source the slope of 88sr 86sr versus 44ca 40ca fractionation is 0 18 0 04 and compatible with a kinetic fractionation during dehydration of the strontium and calcium ions but not with isotope fractionation in a diffusive boundary layer using published equilibrium 44 40cacarb aq and view the mathml source values we estimate the equilibrium isotope fractionation of strontium to be very close to zero 88 86sreq carb aq 0 01 0 06 this estimate is confirmed by strontium isotope values of natural inorganic calcites that precipitated very slowly in basalts of the ocean crust the results from the inorganic calcites are used to explain strontium isotope fractionation of planktic foraminifera specimens of two warm water species globigerinoides ruber and globigerinoides sacculifer were picked from the holocene section of a caribbean sediment core we found no significant difference in 88 86sr between the two species in addition g ruber specimens from marine isotope stage 2 in the same core show 88 86sr values identical to the holocene specimens the strontium isotopes of both foraminifera species are strongly fractionated 88 86srcarb aq 0 248 0 005 when compared to published data of other major marine calcifiers applying the results from the inorganic precipitation experiments we find that the strong foraminiferal strontium isotope fractionation can be explained by calcification in a largely open system at high precipitation rates comparable in magnitude to rates known from scleractinian reef corals this interpretation is in good agreement with the kinetic calcification model for planktic foraminifera by kisakurek et al 2011 which was based on calcium isotopes and elemental sr ca ratios

technical specifications of low frequency radio identification bedload tracking from field experiments differences in antennas tags and operators abstract low frequency passive integrated transponders pit tags have been increasingly used for tracking bedload transport in gravel bed rivers prior studies have reported high recovery rates in small streams while recovery rates remained much lower in large systems in large part because of the limited reading distance of the tags

constraining the marine strontium budget with natural strontium isotope fractionations 87sr 86sr δ88 86sr of carbonates hydrothermal solutions and river waters we present strontium sr isotope ratios that unlike traditional 87sr 86sr data are not normalized to a fixed 88sr 86sr ratio of 8 375209 defined as 88 86sr 0 relative to nist srm 987 instead we correct for isotope fractionation during mass spectrometry with a 87sr 84sr double spike this technique yields two independent ratios for 87sr 86sr and 88sr 86sr that are reported as 87sr 86sr and 88 86sr respectively the difference between the traditional radiogenic 87sr 86sr normalized to 88sr 86sr 8 375209 and the new 87sr 86sr values reflect natural mass dependent isotope fractionation in order to constrain glacial interglacial changes in the marine sr budget we compare the isotope composition of modern seawater 87sr 86sr 88 86sr seawater and modern marine biogenic carbonates 87sr 86sr 88 86sr carbonates with the corresponding values of river waters 87sr 86sr 88 86sr river and hydrothermal solutions 87sr 86sr 88 86sr hydend in a triple isotope plot the measured 87sr 86sr 88 86sr river values of selected rivers that together account for not vert similar18 of the global sr discharge yield a sr flux weighted mean of 0 7114 8 0 315 8 the average 87sr 86sr 88 86sr hydend values for hydrothermal solutions from the atlantic ocean are 0 7045 5 0 27 3 in contrast the 87sr 86sr 88 86sr carbonates values representing the marine sr output are 0 70926 2 0 21 2 we estimate the modern sr isotope composition of the sources at 0 7106 8 0 310 8 the difference between the estimated 87sr 86sr 88 86sr input and 87sr 86sr 88 86sr output values reflects isotope disequilibrium with respect to sr inputs and outputs in contrast to the modern ocean isotope equilibrium between inputs and outputs during the last glacial maximum 10 30 ka before present can be explained by invoking three times higher sr inputs from a uniquely glacial source weathering of shelf carbonates exposed at low sea levels our data are also consistent with the weathering peak hypothesis that invokes enhanced sr inputs resulting from weathering of post glacial exposure of abundant fine grained material

controls on stable strontium isotope fractionation in coccolithophores with implications for the marine sr cycle abstract the controls on stable sr isotope fractionation into the calcite produced by the coccolithophore species emiliania huxleyi coccolithus pelagicus spp braarudii and gephyrocapsa oceanica are investigated each species has been cultured under controlled laboratory conditions at a range of temperatures 10 25 c to test the potential of 88 86 sr as a proxy for growth rate and or sea surface temperature coccolithophores are one of the most abundant pelagic calcifiers since sr substitutes to some degree for ca in their calcite coccoliths coccolithophores represent a significant output of sr from seawater potentially influencing the 88 86 sr mass balance in the modern oceans the coccoliths are investigated for their 88 86 sr sr ca and 18 o measured as function of temperature as temperature is increased all species show a negative stable sr isotopic fractionation related to a temperature controlled growth rate we infer the shift of 88 86 sr to lighter values as indicative of a kinetic control on the isotope fractionation revealing the potential of 88 86 sr as a proxy for growth rate which in these experiments is primarily dictated by temperature the results from these experiments indicate that coccolithophore calcite incorporates sr with a very light 88 86 sr isotope composition as low as 0

calcite precipitation rates in the field measurement and prediction for a travertine depositing stream abstract rates of calcite precipitation from a travertine depositing stream were determined from changes in stream composition between consecutive sampling points and were compared with rates predicted from a laboratory derived rate law plummer et al 1978 the agreement in rates was generally within an order of magnitude and routinely within a factor of 3 least agreement between measured and predicted rates was obtained for sections of flowpath where relatively little change in bulk chemical composition occurred which were the sections with the greatest mass transfer calculation error and for the stream segment including a waterfall which was the section with the greatest error in estimated surface area reaction rate obtained from the mass of calcite precipitated onto seed crystals placed in the stream significantly underestimated the mass transfer rate for the travertine depositing stream of warm river cave and falling spring creek virginia the coupling of equilibrium speciation models with mass balance calculations and simple field measurements allowed successful field based quantification of reaction rates

salinization and dilution history of ground water discharging into the sea of galilee the dead sea transform israel abstract the mechanism governing salinization of ground water discharging into the sea of galilee in israel has been the subject of debate for several decades because the lake provides 25 of the water consumed annually in israel correct identification of the salt sources is essential for the establishment of suitable water management strategies for the lake and the ground water in the surrounding aquifers existing salinization models were evaluated in light of available and newly acquired data including general chemistry and o h c and cl isotopes based on the chemical and isotopic observations the proposed salt source is an ancient intensively evaporated brine 21 to 33 fold seawater which percolated through the valley formations from a lake which had formed in the rift valley following seawater intrusion during the late miocene low na cl and high br cl values support the extensive evaporation whereas high ca cl and low mg cl values indicate the impact of dolomitization of the carbonate host rock on the residual solution based on radiocarbon and other isotope data the dilution of the original brine occurred in two stages the first took place 30 000 a ago by slightly evaporated fresh to brackish lake water to form the sea of galilee brine the second dilution phase is associated with the current hydrological regime as the sea of galilee brine migrates upward along the rift faults and mixes with the actively circulating fresh ground water to form the saline springs the spatially variable chemical and isotopic features of the saline springs suggest not only differential dilution by fresh meteoric water but also differential percolation timing of the original brine into the tectonically disconnected blocks registering different evaporation stages in the original brine consequently various operations to reduce the brine contribution to the lake may be differentially effective in the various areas

efficiency of natural calcite precipitation compared to lake marl application used for water quality improvement in an eutrophic lake abstract since the 1980s several in lake restoration methods for eutrophied lakes have been developed based on artificially induced calcite precipitation and lime additions the aim of these measures is to improve water quality and reduce the incidence of cyanobacterial blooms by increasing p adsorption and removal through natural calcite precipitation the authors compared the relative efficiencies of lake marl application and natural calcite precipitation in immobilizing p mn and fe in lake arendsee northeastern germany and their subsequent value as a tool for managing eutrophication microprobe investigations of element distributions in calcite minerals of laminae precipitated annually during several years before and two years following the restoration suggest that recently grown biogenic calcites were more efficient at the co precipitation and immobilization of p fe and mn the lake marl applied as 16 calcite water mixture proved unsuitable as a restoration tool because of its coarse grain size mainly in the range of 20 1000 m and associated organic matter which reduced its suspension time and sorption reaction rates in the water column in lake arendsee or in similar eutrophic hardwater lakes with fast internal p recycling by rapid degradation of autochthonous organic matter in the water column and at the sediment surface sedimentary toc tp ratios of 200 or more biogenic calcites provide almost permanent p fe and mn retention in the sediments the study shows that epilimnetic additions of pure caco 3 seed crystals comparable to natural calcite precipitation are the most effective for improving water quality small caco 3 crystals exhibit a larger reactive surface and thus incorporate adsorbed dissolved nutrients and trace metals more rapidly during growth however in lake water quality management strategies work best only if external point and non point nutrient sources are reduced or diverted

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

sources and transport routes of fine detritus material to the late quaternary dead sea basin abstract the sources and routes of transport of fine detritus material fdm to the lakes filling the late quaternary dead sea basin were studied by petrographic mineralogical grain size chemical and sr nd isotope analyses on sediments of the late quaternary lacustrine formations including river flood material dust and loess from the lake watershed the lacustrine formations comprise two sedimentary facies one that consists of alternating laminae of primary aragonite and silty detritus material aad facies and another that consists mainly of laminated detritus particles and generally lacks aragonite ld facies the aad facies characterizes the glacial intervals e g mis2 and 4 when lake levels were high while the ld facies characterizes interglacials e g mis1 5 and warmer glacial intervals e g mis3 when lake levels were low the detritus of both aad and ld facies show similar mineralogy mainly quartz and calcite grains with minor feldspars and clays but distinct grain sizes 8 10 m and 50 60 m respectively and distinct 87 sr 86 sr and end 0 711 0 712 and 7 to 8 versus 0 709 0 710 and 5 respectively the aad and ld fdm comprise desert dust of mixed granitic basaltic composition that was blown from the sahara desert and from the nile delta to the northern negev desert e g the loess deposits and the judean mountains bordering the dead sea basin mainly during glacial intervals along with enhanced mediterranean rain fronts the aad fdm reflects an enhanced transport of saharan granitic dust to the vicinity of the lake mainly during glacials the ld fdm was recycled from the loess surface cover of the negev desert mainly during interglacials and warm glacial intervals