Constraining the marine strontium budget with natural strontium isotope fractionations (Sr/Sr∗, δSr) 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 δ^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 (δ^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∗, δ^88/86Sr)_Seawater) and modern marine biogenic carbonates ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates) with the corresponding values of river waters ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River) and hydrothermal solutions ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd) in a triple isotope plot. The measured (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River values of selected rivers that together account for ∼18% of the global Sr discharge yield a Sr flux-weighted mean of (0.7114(8), 0.315(8)‰). The average (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd values for hydrothermal solutions from the Atlantic Ocean are (0.7045(5), 0.27(3)‰). In contrast, the (⁸⁷Sr/⁸⁶Sr∗, δ^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∗, δ^88/86Sr)_input and (⁸⁷Sr/⁸⁶Sr∗, δ^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.     

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio ⁸⁷Sr/⁸⁶Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.     

Hydrologic controls on radiogenic Sr in meltwater from an alpine glacier system: Athabasca Glacier,Canada

Filtered subglacial meltwater samples were collected daily during the onset of melt (May) and peak melt (July) over the 2011 melt season at the Athabasca Glacier (Alberta, Canada) and analyzed for strontium-87/strontium-86 (⁸⁷Sr/⁸⁶Sr) isotopic composition to infer the evolution of subglacial weathering processes. Both the underlying bedrock composition and subglacial water–rock interaction time are the primary influences on meltwater ⁸⁷Sr/⁸⁶Sr. The Athabasca Glacier is situated atop Middle Cambrian carbonate bedrock that also contains silicate minerals. The length of time that subglacial meltwater interacts with the underlying bedrock and substrate is a predominant determining factor in solute concentration. Over the course of the melt season, increasing trends in Ca/K and Ca/Mg correspond to overall decreasing trends in ⁸⁷Sr/⁸⁶Sr, which indicate a shift in weathering processes from the presence of silicate weathering to primarily carbonate weathering.Early in the melt season, rates of carbonate dissolution slow as meltwater approaches saturation with respect to calcite and dolomite, corresponding to an increase in silicate weathering that includes Sr-rich silicate minerals, and an increase in meltwater ⁸⁷Sr/⁸⁶Sr. However, carbonate minerals are preferentially weathered in unsaturated waters. During the warmest part of a melt season the discharged meltwater is under saturated, causing an increase in carbonate weathering and a decrease in the radiogenic Sr signal. Likewise, larger fraction contributions of meltwater from glacial ice corresponds to lower ⁸⁷Sr/⁸⁶Sr values, as the meltwater has lower water–rock interaction times in the subglacial system. These results indicate that although weathering of Sr-containing silicate minerals occurs in carbonate dominated glaciated terrains, the continual contribution of new meltwater permits the carbonate weathering signal to dominate.     

The isotopic composition of strontium in non-marine carbonate rocks: the Flagstaff Formation of Utah*

The isotopic composition of strontium in surface water in continental basins is determined primarily by the geology of the basin and to a lesser extent by climatic conditions. Consequently, the ⁸⁷Sr/⁸⁶Sr ratios of brines in such basins can change only as a result of changes in the geology or climate. This principle of isotope geology was studied by analysis of a suite of non-marine carbonate rocks from the Flagstaff Formation (Palaeocene-Eocene) of Utah. The samples were collected from a section in Fairview Canyon of Sanpete County. They include both limestone and dolomite and were selected to have low non-carbonate residues. The concentrations of strontium in calcites averages 383 ± 128 p.p.m., while those of dolomites increase from 354 ± 74 p.p.m. in the lower 43 m of section to a maximum of 2259 p.p.m. higher up. The increase in the strontium content of dolomite is interpreted as evidence for a change from steady-state to progressively more evaporitic conditions. Two dolomites have isotopic compositions of oxygen expressed as δ¹⁸O = -2.75‰ (relative to the PDB standard) and are enriched in ¹⁸O relative to two calcites whose average δ¹⁸O value is -9.9‰. The ⁸⁷Sr/⁸⁶Sr ratios of the carbonate minerals range from 0.70890 to 0.71260. These values are clearly greater than the ⁸⁷Sr/⁸⁶Sr ratio of marine carbonates of Early Eocene age which is 0.70744. The variation of the ⁸⁷Sr/⁸⁶Sr ratio in this section of the Flagstaff Formation is real and reflects the occurrence of geological events which changed the isotopic composition of Sr entering Lake Flagstaff. The non-carbonate fractions of six carbonate rocks and one sandstone fit a straight line on the strontium mixing diagram in co-ordinates of initial ⁸⁷Sr/⁸⁶Sr and 1/Sr concentration. These results suggest that the isotopic composition of strontium in Lake Flagstaff may have been modulated by periodic input of volcanogenic detritus of felsic composition.     

Isotopic evidence for the source of Ca and S in soil gypsum, anhydrite and calcite in the Atacama Desert, Chile

The origin of pedogenic salts in the Atacama Desert has long been debated. Possible salt sources include in situ weathering at the soil site, local sources such as aerosols from the adjacent Pacific Ocean or salt-encrusted playas (salars), and extra-local atmospheric dust. To identify the origin of Ca and S in Atacama soil salts, we determined δ³⁴S and ⁸⁷Sr/⁸⁶Sr values of soil gypsum/anhydrite and ⁸⁷Sr/⁸⁶Sr values of soil calcite along three east-west trending transects. Our results demonstrate the strong influence of marine aerosols on soil gypsum/anhydrite development in areas where marine fog penetrates inland. Results from an east-west transect located along a breach in the Coastal Cordillera show that most soils within 90 km of the coast, and below 1300 m in elevation, are influenced by marine aerosols and that soils within 50 km, and below 800 m in elevation, receive >50% of Ca and S from marine aerosols (δ³⁴S values > 14‰ and ⁸⁷Sr/⁸⁶Sr values >0.7083). In areas where the Coastal Cordillera is >1200 m in elevation, however, coastal fog cannot penetrate inland and the contribution of marine aerosols to soils is greatly reduced. Most pedogenic salts from inland soils have δ³⁴S values between +5.0 to +8.0‰ and ⁸⁷Sr/⁸⁶Sr ratios between 0.7070 and 0.7076. These values are similar to average δ ³⁴S and ⁸⁷Sr/⁸⁶Sr values of salts from local streams, lakes, and salars (+5.4 ±2‰ δ³⁴S and 0.70749 ± 0.00045 ⁸⁷Sr/⁸⁶Sr) in the Andes and Atacama, suggesting extensive eolian reworking of salar salts onto the surrounding landscape. Ultimately, salar salts are precipitated from evaporated ground water, which has acquired its dissolved solutes from water-rock interactions (both high and low-temperature) along flowpaths from recharge areas in the Andes. Therefore, the main source for Ca and S in gypsum/anhydrite in non-coastal soils is indirect and involves bedrock alteration, not surficially on the hyperarid landscape, but in the subsurface by ground water, followed by eolian redistribution of ground-water derived salar salts to soils. The spatial distribution of high-grade nitrate deposits appears to correspond with areas that receive the lowest fluxes of local marine and salar salt, supporting arguments for tropospheric nitrogen as the main source for soil nitrate.     

Determination of Radiogenic 87Sr/86Sr and Stable δ88/86SrSRM987 Isotope Values of Thirteen Mineral,Vegetal and Animal Reference Materials by DS‐TIMS

This work presents new ⁸⁷Sr/⁸⁶Sr and δ^88/86Sr_SRM987 isotopic values of thirteen mineral, vegetal and animal reference materials. Except for UB‐N, all our results are consistent with previously published data. Our results highlight intermediate precisions among the best presently published and a non‐significant systematic shift with the calculated δ^88/86Sr_SRM987 mean values for the three most analysed reference materials in the literature (i.e., IAPSO, BCR‐2 and JCp‐1). By comparison with the literature and between two distinct digestions, a significant bias of δ^88/86Sr_SRM987 values was highlighted for two reference materials (UB‐N and GS‐N). It has also been shown that digestion protocols (nitric and multi‐acid) have a moderate impact on the δ^88/86Sr_SRM987 isotopic values for the Jls‐1 reference materials suggesting that a nitric acid digestion of carbonate can be used without significant bias from partial digestion of non‐carbonate impurities. Different δ^88/86Sr_SRM987 values were measured after two independent Sr/matrix separations, according to the same protocol, for a fat‐rich organic reference material (BCR‐380R) and have been related to a potential post‐digestion heterogeneity. Finally, the δ^88/86Sr_SRM987 value differences measured between animal‐vegetal and between coral‐seawater reference materials agree with the previously published results, highlighting an Sr isotopic fractionation along the trophic chain and during carbonate precipitation.     

Sr and Nd isotopes as tracers in pedogenic studies: Evidence for Saharan dust contribution to the soils of Muravera (Sardinia,Italy)

Sr and Nd isotopes were applied to 5 soil profiles from the Muravera area, in south-eastern Sardinia.All the soils, which have developed during the Quaternary on the Lower Paleozoic metamorphic basement except for one on Eocene carbonates, are located far from major sources of pollution. Therefore, they are suitable for testing pedogenic processes and geochemical evolution to benefit for environmental studies.The Sr isotopic ratios range largely (δ⁸⁷Sr = 1.7–65.9‰), even in each soil profile. In particular, the observed increase of δ⁸⁷Sr with depth in the most of the metamorphic rock-based soils can be accounted for by the downward decrease of Sr contributions from organic matter and Saharan dust, both displaying lower isotopic ratios than the soil bedrocks. The carbonate rock-based soil exhibits δ⁸⁷Sr higher (1.7–18.1‰) than the bedrock, indicating a significant contribution of radiogenic Sr from the siliciclastic fraction of the soil, and probably from dust input. The Nd isotopic ratios are slightly variable through the profiles (ɛ_Nd from −7.8 to −14.5), confirming little mobility of Nd and Sm during the pedogenesis. Among the minerals present in the soils, phosphates, albite, and calcite are those important in providing low radiogenic Sr and Nd to organic matter of the soils.Lastly, this isotopic study has in particular allowed for evaluating the potential proportion of contribution of Saharan dust to south-eastern Sardinia, thus corroborating the findings of other studies related to soils from the central-western Mediterranean.     

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment,southwestern India

River water composition (major ion and ⁸⁷Sr/⁸⁶Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L⁻¹) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L⁻¹), with radiogenic ⁸⁷Sr/⁸⁶Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and ⁸⁷Sr/⁸⁶Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO₂/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO₂/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin.     

Natural variations of δSi ratios during progressive basalt weathering, Hawaiian Islands

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, δ³⁰Si_{bulk soil} values change progressively toward more negative values; basalt δ³⁰Si values are about −0.5‰, but older soils have δ³⁰Si values up to −2.5‰. The difference between the solid and solution δ³⁰Si values remains more or less constant with progressive weathering, and therefore, soil water from older soils has a more negative δ³⁰Si composition. In the upper horizons of the Hawaiian soils, this weathering-driven δ³⁰Si shift is modified by the addition of unweathered primary minerals via dust, carrying δ³⁰Si values of about −0.5‰, and by biocycling of Si via plants, producing negative δ³⁰Si values in phytoliths and positive δ³⁰Si 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 δ³⁰Si values than predicted based on the weathering status of the lower horizons. When combined with published δ³⁰Si 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.     

Carbon and Strontium Isotopes of Late Palaeozoic Marine Carbonates in the Upper Yangtze Platform,Southwest China

238 marine carbonate samples were collected from seven sedimentary sections ofthe entire late Palaeozoic (Permian, Carboniferous and Devonian) in the Upper Yangtze Plat-form, southwest China. Based on the absence of cathodoluminescence and very low Mn (gener-ally<50 ppm) contents of the samples, it is thought that they contain information on the orig-inal sea water geochemistry. The results of isotopic analyses of these samples are presented interms of δ~(13)C and ~(87)Sr/~(86)Sr ratios versus geological time. The strontium data, consistent withother similar data based on samples from North America, Europe, Africa and other areas inAsia, support the notion of a global consistency in strontium isotope composition of marinecarbonates. The strontium data exhibit three intervals of relatively low ~(87)Sr/~(86)Sr ratios in thelate Middle Devonian to early Late Devonian, Early Carboniferous and Early Permian, corre-sponding to global eustatic high sea level stands. The lowest ~(87)Sr/~(86)Sr ratio recorded in theLate Permian was probably caused by substantial basalt eruptions in the Upper Yangtze Plat-form at the time. Three corresponding periods of relatively high δ~(13)C values at roughly the samethe intervals were caused by a relatively high rate of accumulation of organic carbon duringsea level rises at these times. The deposition of coal was probably responsible for the increaseof sea water δ~(13)C at other times. The δ~(13)C values drop dramatically near theDevonian/Carboniferous, Carboniferous/Permian and Permian/Triassic boundaries, con-sistent with other similar data, which further support the notion that geological time boundariesare associated with mass extinction and subsequent rejuvenation.     

The geographic distribution of strontium isotopes in Danish surface waters - A base for provenance studies in archaeology, hydrology and agriculture

In this paper Sr isotope signatures are reported for 192 surface water (lakes/ponds and rivers/creeks) samples from within Denmark and an isotope distribution map is presented that may serve as a base for provenance applications, including archaeological migration studies, ground water - surface water - seawater interaction/contamination monitoring, and potentially for agricultural applications, including cases of authenticity proof for particular food products. The Sr isotopic compositions of surface waters range from ⁸⁷Sr/⁸⁶Sr = 0.7078 to 0.7125 (average 0.7096 ± 0.0016; 2σ). This average value lies above the range of ⁸⁷Sr/⁸⁶Sr values between 0.7078 and 0.7082 expected from Late Cretaceous to Early Tertiary (Oligocene) limestones which form the dominant bedrock type in a NW-SE trending belt in Denmark. The elevated ⁸⁷Sr/⁸⁶Sr signatures >∼0.7095 are explained by additions to the surface waters of radiogenic Sr predominantly derived from the near-surface weathering and wash-out of Quarternary glaciogenic tills and soils deposited and formed during and after the last two ice age stages (Saale and Weichsel). The Sr isotopic compositions and concentrations of the surface waters can, therefore, best be modeled by a two-component mixing involving carbonaceous bedrock and glaciogenic cover sediments as the two predominant Sr sources. A feasibility study for using Sr isotopic compositions of surface waters as a proxy for bio-available Sr signatures was conducted in a representative test area on Zealand (Land of Legends, Lejre) where there is no use and application of commercial fertilizers. It is demonstrated that the Sr isotopic signatures of lake waters from within this area are slightly higher (but statistically still indistinguishable) from the average value defined by snail shells and soil leachates considered to characterize the true bio-available Sr. In combination with results from other studies, this is interpreted to reflect the wash-out of Sr with a higher ⁸⁷Sr/⁸⁶Sr signature released by weathering in the topsoils into the saturated water tables, a component which is consequently not readily transferred into the shallow-rooting plants and into small herbivores feeding on them. Since drinking water is a likely important source of Sr uptake of humans and larger animals, the contention is that a surface water isotopic composition can potentially characterize the bio-available component relevant for human and carnivorous large animals. Spline functions and ordinary linear kriging were used for modeling the geographic distribution of bio-available Sr isotopes over territorial Denmark. As expected, based on the two-source mixing scenario, the water ⁸⁷Sr/⁸⁶Sr ratio contour maps (with some notable exceptions) neither mirror the pre-Quarternary bedrock geology nor a (Pleistocene) soil-type distribution map of Denmark.As a conservative suggestion, the use of the average ⁸⁷Sr/⁸⁶Sr ratio of 0.7096 ± 0.0015 (2σ) is recommended as an average for bio-available Sr from within Denmark (Bornholm excluded) for human and larger animals and as a confidence band for distinguishing “local” from “non-local” signatures in archaeological provenance studies. The study also reveals that the average ⁸⁷Sr/⁸⁶Sr ratio of ∼0.7088 defined from soil extracts and small herbivores lies approximately 0.15% lower than that defined by the surface waters. The authors recommend using this lower value as a “local”-“non-local” discriminator for food and plant authenticity control in agricultural applications.     

Strontium and oxygen isotopic systems in waters of mud volcanoes of the Taman Peninsula

Ten of eleven analyzed water samples from mud volcanoes of the Taman Peninsula are characterized by ⁸⁷Sr/⁸⁶Sr ratio within 0.70734–0.70957, which overlaps the values typical of the Mesozoic and Cenozoic sedimentary carbonates, but sharply differs from the value in the clayey sediments of the Maikop Group (0.7157 ± 0.0022). These data indicate that the strontium isotopic composition is mainly defined by carbonate reservoirs, with relatively little effect of elision solutions, input of which is noticeable only in the water of Gladkovsky Volcano (⁸⁷Sr/⁸⁶Sr = 0.71076). The high δ¹⁸O in mud volcanic waters (up to 14.2‰) can also be attributed to ionic exchange with sedimentary carbonates at temperatures around 150°C.     

A multi-isotope approach (O,H, C,S, B and Sr) to understand the source of water and solutes in some the thermal springs from West Coast geothermal area,India

The West Coast belt, consisting of nearly 60 thermal springs, is one of the most diversified geothermal fields in India. The present work describes the multi-isotopic (O, H, C, S, B and Sr) characterization of thermal waters carried out in the Tural-Rajwadi geothermal field, situated in southern sector of the west coast geothermal area. The aim of this study is to delineate the origin of thermal water as well as to ascertain the sources of carbon, sulphur, boron and strontium dissolved in those thermal springs. The stable isotopes (δ²H and δ¹⁸O) and tritium data indicate that these thermal springs are not recently recharged rain water rather, it contains very old component of water. Oxygen-18 shift is observed due to rock-water interaction over a long period of time. Carbon isotopic composition of DIC points out to the silicate weathering with soil CO₂ coming from C₃ type of plants whereas δ³⁴S of dissolved sulphate confirms the marine origin of sulphate. This marine signature is basically derived from paleo-seawater possibly entrapped within the flows. Boron isotopic data reveals that both the seawater and rock dissolution are the sources of boron in the thermal waters whereas high ⁸⁷Sr/⁸⁶Sr ratios (0.7220–0.7512) of the thermal waters conclusively establishes that archean granitic basement is the predominant rock source of strontium, not the Deccan flood basalts. In addition, like strontium, concentrations of lithium, rubidium and caesium are also governed by the rock-water interaction. Thus, the combined use of this multi-isotope technique coupled with trace element concentrations proves to be an effective tool to establish the sources of solutes in the thermal water.     

The Ediacaran radiogenic Sr isotope excursion in the Doushantuo Formation in the Three Gorges area,South China

The Ediacaran period was one of the most important times for the evolution of life. However, the scarcity of well-preserved outcrops of Ediacaran rocks still leaves ambiguity in decoding ambient surface environmental changes and biological evolution.The Ediacaran strata in South China are almost continuously exposed, comprise mainly carbonate rocks with subordinate black shales and sandstones, and they contain many fossils, suitable for study of environmental and biological changes in the Ediacaran. We conducted drilling through the Doushantuo Fm at four sites in the Three Gorges area to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected on the basis of microscopic observations and the geochemical signatures of Sr contents, Mn/Sr and Rb/Sr ratios, and δ¹⁸O values, with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS).The chemostratigraphy of the ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and two large positive shifts during Ediacaran time. The combination of the detailed chemostratigraphies of δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values and Mn and Fe contents enables us to decode the surface environmental changes and their causes in the Ediacaran. The first large positive excursion of ⁸⁷Sr/⁸⁶Sr occurred together with negative δ¹³C and positive δ¹⁸O excursions. The higher ⁸⁷Sr/⁸⁶Sr values indicate an enhancement of continental weathering, whereas the positive δ¹⁸O excursion suggests global cooling. Global regression due to global cooling enhanced the oxidative decay of exposed marine organic sediments and continental weathering. Accelerated influx of nutrients promoted primary productivity, resulting in oxidation of dissolved organic carbon (DOC), whereas active sulfate reduction due to a higher sulfate influx from the continents caused remineralization of the large DOC, both of which caused a negative δ¹³C anomaly. The 580 Ma Gaskiers glaciation accounts for the close correlation among the positive ⁸⁷Sr/⁸⁶Sr, negative δ¹³C and positive δ¹⁸O excursions.The second large positive shift of ⁸⁷Sr/⁸⁶Sr firstly accompanied a positive δ¹³C excursion, and continued through the Shuram δ¹³C negative excursion. The positive correlation of δ¹³C and ⁸⁷Sr/⁸⁶Sr values is consistent with an enhanced continental weathering rate due to continental collisions that built Trans-Gondwana mountain chains, and with a higher primary activity due to the enhancement of continental weathering and consequent higher nutrient contents in seawater. The accompanied increase in Mn and Fe contents implies a gradual decline of the seawater oxygen content due to more active aerobic respiration and oxidation of reductive materials flowing in the oceans. In the Shuram excursion, higher ⁸⁷Sr/⁸⁶Sr values and a transition from increase to decrease in Mn and Fe contents were accompanied by the large negative δ¹³C excursion. The higher ⁸⁷Sr/⁸⁶Sr values are the first compelling evidence for enhanced continental weathering, which was responsible for the large δ¹³C anomaly through the remineralization of the DOC by more active sulfate reduction due to a higher sulfate influx. Higher Mn and Fe contents in the early and middle stages of the excursion suggest a decline in the oxygen content of seawater due to oxidative decay of the DOC, whereas in the late stages the decrease in Mn and Fe contents is consistent with oceanic oxygenation.The emergence of Ediacara biota after the Gaskiers glaciation and the prosperity of the latest Ediacaran is concomitant with the formation of more radiogenic seawater with high ⁸⁷Sr/⁸⁶Sr values, suggesting that enhanced continental weathering, and the consequent higher influx of nutrients, played an important role in biological evolution.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Isotope hydrology of the Chalk River Laboratories site,Ontario, Canada

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 ± 12 g/cc and 1.32 ± 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (⁸⁷Sr/⁸⁶Sr) and uranium (²³⁴U/²³⁸U) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and −240 m elevation is relatively depleted in δ¹⁸O and δ²H perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. ²³⁴U/²³⁸U and correlation of ⁸⁷Sr/⁸⁶Sr with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions.     

Sr/Sr and Sr/Ca in speleothems for paleoclimate reconstruction in Central China between 70 and 280 kyr ago

Limestone cave deposits (speleothems) provide archives for past changes in regional climates over a range of timescales. While δ¹⁸O and δ¹³C in speleothem calcite have been commonly used for reconstruction of paleoclimates, we report here further efforts in the use of ⁸⁷Sr/⁸⁶Sr and Sr/Ca signals in speleothem calcite to deduce paleomonsoon variability near the Loess Plateau of central China. A two end-member mass-balance model of concentration and isotopic composition of strontium in a cave system is used to estimate variation of the ⁸⁷Sr/⁸⁶Sr ratio in sediments overlying a limestone cave. We show that this ratio reflects climate-driven variations in the provenance and the extent of chemical weathering of the epikarstic sediments. The measurements of ⁸⁷Sr/⁸⁶Sr made on a well-dated stalagmite, SFL, from Buddha Cave (33^o40N′ 109^o05′E) show ratios of 0.71092 to 0.71133 (±0.00001 as 2σ) during relatively cold periods (e.g., Marine Isotope Stage (MIS) 5b, 5d, and 8), lower than ratios of 0.71133 to 0.71194 during relatively warm periods (e.g., MIS 5a, 5c, 5e, and 7). As changes in the Sr/Ca ratio may affect speleothem ⁸⁷Sr/⁸⁶Sr, we show that the direct use of speleothem ⁸⁷Sr/⁸⁶Sr is less ideal than our modeled ⁸⁷Sr/⁸⁶Sr for the exogenic Sr source above the cave as a paleomonsoon proxy. Using the δ¹⁸O, δ¹³C, Sr/Ca, and ⁸⁷Sr/⁸⁶Sr records of the stalagmite, we reconstruct the variability of the East Asian monsoon for the time period between 70 and 280 kyr ago. The results show that summer monsoons were more intense during interglacial periods than during glacial periods.     

Strontium isotope composition of runoff from a glaciated carbonate terrain

The relationship between subglacial chemical weathering processes and the Sr isotope composition of runoff from Robertson Glacier, Alberta, Canada, is investigated. This glacier rests on predominantly carbonate bedrock of Upper Devonian age, but silicate minerals are also present. The provenance of solute in meltwaters is found to vary systematically with solute concentration and, by inference, subglacial water residence time. In dilute waters, the principal process of solute acquisition is calcite dissolution fueled by protons derived from the dissolution of CO₂ and subsequent dissociation of carbonic acid. At higher solute concentrations, dolomite dissolution coupled to sulfide oxidation is more important. Sr concentration is found to increase with total solute concentration in two separate meltwater streams draining from the glacier, but ⁸⁷Sr/⁸⁶Sr only increases in the eastern melt stream. Carbonate and K-feldspar sources are shown to dominate the Sr content of the western stream, irrespective of concentration. They also dominate the Sr content of the eastern stream at low and intermediate concentrations, but at higher concentrations, muscovite (with high ⁸⁷Sr/⁸⁶Sr) is also an important Sr source. This reflects the outcrop of muscovite-bearing lithologies in the catchment of the eastern stream and an increase in the rate of weathering of K-silicates relative to that of carbonates as more concentrated solutions approach saturation with respect to carbonates. Nonstoichiometric release of ⁸⁷Sr/⁸⁶Sr and preferential release of Sr over K from freshly ground K-silicate surfaces may also occur. This may help to explain the radiogenic nature of runoff from distributed subglacial drainage systems, which are characterized by long water:rock contact times and water flow through environments in which crushing and grinding of bedrock are active processes.Although the exchangeable Sr in tills has higher ⁸⁷Sr/⁸⁶Sr than local carbonate bedrock, only the more concentrated meltwaters from the eastern stream display similarly high values. The most dilute waters, which probably transport the bulk of the dissolved Sr flux from the glacier, have ⁸⁷Sr/⁸⁶Sr characteristic of local carbonate bedrock. Thus, the results suggest that although enhanced weathering of silicate minerals containing radiogenic Sr (such as muscovite) does occur in glaciated carbonate terrains, it is unlikely to contribute to any enhanced flux of radiogenic Sr from glaciated continental surfaces to the oceans.     

Water–granite interaction: Clues from strontium,neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the ⁸⁷Sr/⁸⁶Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed ⁸⁷Sr/⁸⁶Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.     

Rubidium,strontium and the isotopic composition of strontium in ultramafic nodule minerals and host basalts

The concentrations of rubidium and strontium and the isotopic composition of strontium have been determined in minerals separated from ultramaflc nodules occurring in late Tertiary and Quaternary basalts of wide geographic distribution. Clinopyroxene, orthopyroxene and olivine from each of three Iherzolite nodules show a relatively wide range of ⁸⁷Sr/⁸⁶Sr disequilibrium and none of the minerals is in isotopic equilibrium with its host basalt. In two cases there is a correlation between ⁸⁷Sr/⁸⁶Sr and ⁸⁷Rb/⁸⁶Sr ratios of the nodule minerals, indicating apparent isochron relationships which may represent relict mantle events. Clinopyroxene and olivine from each of two wehrlite nodules are not in isotopic equilibrium, although the magnitude of the disequilibrium is smaller than that observed in the Iherzolite nodules. None of these ultramafic nodules can be a crystal cumulate from its host basalt, and it is doubtful that any type of genetic relationship exists. The strontium isotopic disequilibrium between nodule minerals seems to be a primary feature inherited from past mantle histories.