Germanium-silicon fractionation in a tropical, granitic weathering environment

Germanium-silicon (Ge/Si) ratios were determined on quartz diorite bedrock, saprolite, soil, primary and secondary minerals, phytolith, soil and saprolite pore waters, and spring water and stream waters in an effort to understand Ge/Si fractionation during weathering of quartz diorite in the Rio Icacos watershed, Puerto Rico. The Ge/Si ratio of the bedrock is 2 μmol/mol, with individual primary mineral phases ranging between 0.5 and 7 μmol/mol. The ratios in the bulk saprolite are higher (∼3 μmol/mol) than values measured in the bedrock. The major saprolite secondary mineral, kaolinite, has Ge/Si ratios ranging between 4.8 and 6.1 μmol/mol. The high Ge/Si ratios in the saprolite are consistent with preferential incorporation of Ge during the precipitation of kaolinite. Bulk shallow soils have lower ratios (1.1-1.6 μmol/mol) primarily due to the residual accumulation of Ge-poor quartz.Ge/Si ratios measured on saprolite and soil pore waters reflect reactions that take place during mineral transformations at discrete depths. Spring water and baseflow stream waters have the lowest Ge/Si ratios (0.27-0.47 μmol/mol), reflecting deep initial weathering reactions resulting in the precipitation of Ge-enriched kaolinite at the saprolite-bedrock interface. Mass-balance calculations on saprolite require significant loss of Si and Al even within 1 m above the saprolite-bedrock interface. Higher pore water Ge/Si ratios (∼1.2 μmol/mol) are consistent with partial dissolution of this Ge-enriched kaolinite. Pore water Ge/Si ratios increase up through the saprolite and into the overlying soil, but never reach the high values predicted by mass balance, perhaps reflecting the influence of phytolith recycling in the shallow soil.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

Silicate and carbonate weathering in the drainage basins of the Ganga-Ghaghara-Indus head waters: Contributions to major ion and Sr isotope geochemistry

The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the⁸⁷Sr/⁸⁶Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between⁸⁷Sr/⁸⁶Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low⁸⁷Sr/⁸⁶Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and⁸⁷Sr/⁸⁶Sr in the headwaters on a basin-wide scale, however, the high⁸⁷Sr/⁸⁶Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of⁸⁷Sr/⁸⁶Sr and Ca/Sr data of the source waters show that they diverge from a low⁸⁷Sr/⁸⁶Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO₂ consumption rates and their global significance.     

Sr and Sr/Sr in the Yamuna River System in the Himalaya: sources, fluxes, and controls on sr isotope composition

Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Yamuna river headwaters and many of its tributaries (YRS) in the Himalaya. These results, with those available for major ions in YRS rivers and in various lithologies of their basin, have been used to determine their contributions to riverine Sr and its isotopic budget. Sr in the YRS ranges from 120 to 13,400 nM, and ⁸⁷Sr/⁸⁶Sr from 0.7142 to 0.7932. Streams in the upper reaches, draining predominantly silicates, have low Sr and high ⁸⁷Sr/⁸⁶Sr whereas those draining the lower reaches exhibit the opposite resulting from differences in drainage lithology. ⁸⁷Sr/⁸⁶Sr shows significant co-variation with SiO₂/TDS and (Na^* + K)/TZ⁺ (indices of silicate weathering) in YRS waters, suggesting the dominant role of silicate weathering in contributing to high radiogenic Sr. This is also consistent with the observation that streams draining largely silicate terrains have the highest ⁸⁷Sr/⁸⁶Sr, analogous to that reported for the Ganga headwaters. Evaluation of the significance of other sources such as calc-silicates and trace calcites in regulating Sr budget of these rivers and their high ⁸⁷Sr/⁸⁶Sr needs detailed work on their Sr and ⁸⁷Sr/⁸⁶Sr. Preliminary calculations, however, indicate that they can be a significant source to some of the rivers.It is estimated that on an average, ∼25% of Sr in the YRS is derived from silicate weathering. In the lower reaches, the streams receive ∼15% of their Sr from carbonate weathering whereas in the upper reaches, calc-silicates can contribute significantly (∼50%) to the Sr budget of rivers. These calculations reveal the need for additional sources for rivers in the lower reaches to balance their Sr budget. Evaporites and phosphorites are potential candidates as judged from their occurrence in the drainage basin. In general, Precambrian carbonates, evaporites, and phosphorites “dilute” the high ⁸⁷Sr/⁸⁶Sr supplied by silicates, thus making Sr isotope distribution in YRS an overall two end member mixing. Major constraints in quantifying contributions of Sr and ⁸⁷Sr/⁸⁶Sr from different sources to YRS rivers are the wide range in Sr and ⁸⁷Sr/⁸⁶Sr of major lithologies, limited data on Sr and ⁸⁷Sr/⁸⁶Sr in minor phases and on the behavior of Sr, Na, and Ca during weathering and transport.The Ganga and the Yamuna together transport ∼0.1% of the global Sr flux at the foothills of the Himalaya which is in the same proportion as their contribution to global water discharge. Dissolved Sr flux from the Yamuna and its mobilization rate in the YRS basin is higher than those in the Ganga basin in the Himalaya, a result consistent with higher physical and chemical erosion rates in the YRS.     

Sources of Sr and implications for weathering of limestone under tallgrass prairie, northeastern Kansas

Grasslands of north-central Kansas are underlain by carbonate aquifers and shale aquitards. Chemical weathering rates in carbonates are poorly known, and, because large areas are underlain by these rocks, solute fluxes are important to estimating global weathering rates. Grasslands exist where the amount of precipitation is extremely variable, both within and between years, so studies in grasslands must account for changes in weathering that accompany changes in precipitation. This study: (1) identifies phases that dominate chemical fluxes at Konza Prairie Biological Station (KPBS) and Long-Term Ecological Research Site, and (2) addresses the impact of variable precipitation on mineral weathering. The study site is a remnant tallgrass prairie in the central USA, representing baseline weathering in a mid-temperate climate grassland.Groundwater chemistry and hydrology in the 1.2 km² watershed used for this study suggest close connections between groundwater and surface water. Water levels fluctuate seasonally. High water levels coincide with periods of precipitation plus low evapotranspiration rather than during precipitation peaks during the growing season. Precipitation is concentrated before recharging aquifers, suggesting an as yet unquantified residence time in the thin soils.Groundwater and surface water are oversaturated with respect to calcite within limitations of available data. Water is more dilute in more permeable aquifers, and water from one aquifer (Morrill) is indistinguishable from surface water. Cations other than Ca co-vary with each other, especially Sr and Mg. Potassium and Si co-vary in all aquifers and surface water, and increases in concentrations of these elements are the best indicators of silicate weathering at this study site. Silicate-weathering indices correlate inversely to aquifer hydraulic conductivity.⁸⁷Sr/⁸⁶Sr in water ranges from 0.70838 to 0.70901, and it decreases with increasing Sr concentration and with increasing silicate-weathering index. Carbonate extracted from aquifer materials, shales, soil, and tufa has Sr ranging from about 240 (soil) to 880 ppm (Paleozoic limestone). ⁸⁷Sr/⁸⁶Sr ranges from 0.70834 ± 0.00006 (limestone) to 0.70904 ± 0.00019 (soil). In all cases, ⁸⁷Sr/⁸⁶Sr of aquifer limestone is lower than ⁸⁷Sr/⁸⁶Sr of groundwater, indicating a phase in addition to aquifer carbonate is contributing solutes to water.Aquifer recharge controls weathering: during periods of reduced recharge, increased residence time increases the total amount of all phases dissolved. Mixing analysis using ⁸⁷Sr/⁸⁶Sr shows that two end members are sufficient to explain sources of dissolved Sr. It is proposed that the less radiogenic end member is a solution derived from dissolving aquifer material; longer residence time increases its contribution. The more radiogenic end member solution probably results from reaction with soil carbonate or eolian dust. This solution dominates solute flux in all but the least permeable aquifer and demonstrates the importance that land-surface and soil-zone reactions have on groundwater chemistry in a carbonate terrain.     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

Ostracod Mg/Sr/Ca and 87Sr/86Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering

Jin, Z. D., Bickle, M. J., Chapman, H. J., Yu, J., An, Z., Wang, S. & Greaves, M. J. 2010: Ostracod Mg/Sr/Ca and ⁸⁷Sr/⁸⁶Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering. Boreas, 10.1111/j.1502‐3885.2010.00184.x. ISSN 0300‐9483 Lacustrine sediment serves as a valuable archive for tracing catchment weathering processes associated with past climatic and/or tectonic changes. High‐resolution records of fossil ostracod Mg/Ca, Sr/Ca and ⁸⁷Sr/⁸⁶Sr ratios from a lake sediment core from the central Tibetan Plateau reveal a temporal link between lake‐water chemistry and catchment weathering and distinct monsoonal oscillations over the early to mid‐Pleistocene. Between 2.01 and 0.95 Ma, lake‐water chemistry was dominated by a high proportion of carbonate weathering related to variations in the Indian monsoon, resulting in relatively low and constant ostracod ⁸⁷Sr/⁸⁶Sr but obvious fluctuations in Mg/Ca, Sr/Ca and δ¹⁸O. Across the mid‐Pleistocene transition (MPT), a significant increase in ⁸⁷Sr/⁸⁶Sr and frequently fluctuating ratios of ostracod Mg/Ca, Sr/Ca and δ¹⁸O are coincident with increases in both Chinese loess grain size and Arabian Sea lithogenic flux. This correlation indicates an increased glaciation and a strong monsoon seasonal contrast over the plateau. The increase in lake‐water ⁸⁷Sr/⁸⁶Sr across the MPT highlights a change in catchment weathering patterns, rather than one in climate‐enhanced weathering intensity, with an increased weathering of ⁸⁷Sr‐rich minerals potentially induced by marked extensive glaciation and strong seasonality in the central plateau.     

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.     

Sr fluxes and Sr/Sr characterization of river waters from a karstic versus granitic watershed in the Yangtze River

The watershed in the southern Jiangxi Province (Jiangxi Province is called simply Gan) (SGW) and the watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) are two subtropical watersheds of the Yangtze River in China. Both watersheds have similar latitudes and climate, but distinct differences in basin lithology. These similarities and differences provide a good natural laboratory in which to investigate weathering processes and Sr end-members in river waters. This work aims to identify and contrast the sources, fluxes and controls on Sr isotopic composition in the river waters of these two areas. Results showed that the ⁸⁷Sr/⁸⁶Sr in the SGW waters ranged from 0.716501 to 0.724931, with dissolved Sr averaging 27 μg l^− 1. Rhyolites and granites are two major sources for the dissolved Sr. The SGW waters receive 42% of their Sr from silicates weathering, 32% from carbonates and 3.2% from evaporites. ⁸⁷Sr/⁸⁶Sr in the CQW waters has a lesser variation from 0.707694 to 0.710039, but higher Sr contents (average of 208 μg l^− 1). Dolomite, limestone and dolomitic limestone are major sources of Sr in the waters. The CQW waters receive 69% of their Sr from carbonates, 1.7% from silicates and 0.9% from evaporites. The chemical erosion rate and Sr flux in the CQW are 122 t km^− 2 a^− 1 and 0.079 t km^− 2 a^− 1, respectively, which are higher than those of the SGW (56 t km^− 2 a^− 1 and 0.021 t km^− 2 a^− 1, respectively). These data suggest that the intensive carbonates weathering occurred in the karstic area in the upper-reach of the Yangtze River exert great influence on the high Sr concentration and low Sr isotopic ratios in the River.     

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

Patterns of Ca/Sr and Sr/Sr variation before and after a whole watershed CaSiO3 addition at the Hubbard Brook Experimental Forest, USA

Forty-one metric tons of the mineral wollastonite (CaSiO₃) was applied to an 11.8 hectare watershed at the Hubbard Brook Experimental Forest (HBEF; White Mountains, New Hampshire, USA) with the goal of restoring the Ca estimated to have been depleted from the soil exchange complex by acid deposition. This experiment provided an opportunity to gain qualitative information on whole watershed hydrologic flow paths by studying the response of stream water chemistry to the addition of Ca. Because the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of wollastonite strongly contrast that of other Ca sources in the watershed, the wollastonite-derived Ca can be identified and its amount estimated in various ecosystem components. Stream water chemistry at the HBEF varies seasonally due to shifts in the proportion of base flow and interflow. Prior to the wollastonite application, seasonal variations in ⁸⁷Sr/⁸⁶Sr ratios indicated that ⁸⁷Sr/⁸⁶Sr was higher during base flow than interflow, due largely to greater amounts of biotite weathering along deeper flow paths. After the application, Ca/Sr and ⁸⁷Sr/⁸⁶Sr changed markedly as the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr wollastonite dissolved and mixed with stream water. The Ca addition provided information on the response times of various flow paths and ion exchange processes to Ca addition in this small upland watershed. During the first year after the addition, wollastonite applied to the near stream zone dissolved and was partially immobilized by cation exchange sites in the hyporheic zone. In the second and third years after the addition we infer that much of this Ca and Sr was subsequently desorbed from the hyporheic zone and was exported from the watershed in stream flow. In the fourth through ninth years after the addition, Ca and Sr from wollastonite that had dissolved in upland soils was transported to the stream by interflow during wet periods when the ground water table was elevated. Between years three and nine the minimum annual Ca/Sr ratio (in late summer base flow) increased, providing evidence that Ca and Sr had increasingly infiltrated to the deepest flow paths. Strong seasonal variations in Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of stream water resulted from the wollastonite addition to upland forest soils, and these ratios have become sensitive to changing flow paths during the annual cycle. Most notably, high flow events now produce large excursions in stream geochemistry toward the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr ratios of wollastonite. Nine years after the application we estimate that ∼360 kg of Ca from wollastonite has been exported from the watershed in stream flow. The rate of export of Ca from wollastonite dissolution has stabilized at about 11 kg of Ca per year, which accounts for ∼30% of the dissolved Ca in the stream water. Given that 19 metric tons of Ca were applied to the watershed, and assuming this current rate of loss, it should take over 1000 years for this added Ca to be transported from the watershed.     

87Sr/86Sr isotope composition of bottled British mineral waters for environmental and forensic purposes

Mineral waters in Britain show a wide range of ⁸⁷Sr/⁸⁶Sr isotope compositions ranging between ⁸⁷Sr/⁸⁶Sr = 0.7059 from Carboniferous volcanic rock sources in Dunbartonshire, Scotland to ⁸⁷Sr/⁸⁶Sr = 0.7207 in the Dalradian aquifer of Aberdeenshire, Scotland. The ⁸⁷Sr/⁸⁶Sr composition of the waters shows a general correlation with the aquifer rocks, resulting in the waters from older rocks having a more radiogenic signature than those from younger rocks. This wide range of values means that the Sr isotope composition of mineral water has applications in a number of types of studies. In the modern commercial context, it provides a way of fingerprinting the various mineral waters and hence provides a method for recognising and reducing fraud. From an environmental perspective, it provides the first spatial distribution of bio-available ⁸⁷Sr/⁸⁶Sr in Britain that can be used in modern, historical and archaeological studies.     

Relative contributions of silicate and carbonate rocks to riverine Sr fluxes in the headwaters of the Ganges

Exhumation of the Himalayan-Tibetan orogen is implicated in the marked rise in seawater ⁸⁷Sr/⁸⁶Sr ratios since 40 Ma. However both silicate and carbonate rocks in the Himalaya have elevated ⁸⁷Sr/⁸⁶Sr ratios and there is disagreement as to how much of the ⁸⁷Sr flux is derived from silicate weathering. Most previous studies have used element ratios from bedrock to constrain the proportions of silicate- and carbonate-derived Sr in river waters. Here we use arrays of water compositions sampled from the head waters of the Ganges in the Indian and Nepalese Himalaya to constrain the end-member element ratios. The compositions of tributaries draining catchments restricted to a limited range of geological units can be described by two-component mixing of silicate and carbonate-derived components and lie on a plane in multicomponent composition space. Key elemental ratios of the carbonate and silicate components are determined by the intersection of the tributary mixing plane with the planes Na = 0 for carbonate and constant Ca/Na for silicate. The fractions of Sr derived from silicate and carbonate sources are then calculated by mass-balance in Sr-Ca-Mg-Na composition space. Comparison of end-member compositions with bedrock implies that secondary calcite deposition may be important in some catchments and that dissolution of low-Mg trace calcite in silicate rocks may explain discrepancies in Sr-Ca-Na-Mg covariation. Alternatively, composition-dependent precipitation or incongruent dissolution reactions may rotate mixing trends on cation-ratio diagrams. However the calculations are not sensitive to transformations of the compositions by incongruent dissolution or precipitation processes provided that the transformed silicate and carbonate component vectors are constrained. Silicates are calculated to provide ∼50% of the dissolved Sr flux from the head waters of the Ganges assuming that discrepancies between Ca-Mg-Na covariation and the silicate rock compositions arise from addition of trace calcite. If the Ca-Mg-Na mixing plane is rotated by composition-dependent secondary calcite deposition, this estimate would be increased. Moreover, when ⁸⁷Sr/⁸⁶Sr ratios of the Sr inputs are considered, silicate Sr is responsible for 70 ± 16% (1σ) of the ⁸⁷Sr flux forcing changes in seawater Sr-isotopic composition. Since earlier studies predict that silicate weathering generates as little as 20% of the total Sr flux in Himalayan river systems, this study demonstrates that the significance of silicate weathering can be greatly underestimated if the processes that decouple the water cation ratios from those of the source rocks are not properly evaluated.     

Crustal contamination versus enriched mantle: 143Nd/144Nd and 87Sr/86Sr evidence from the Italian volcanics

¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, and REE analyses are presented on a wide variety of Pliocene-Recent volcanic rocks from central Italy. ¹⁴³Nd/¹⁴⁴Nd varies from 0.51214–0.51289 and ⁸⁷Sr/⁸⁶Sr from 0.7255-0.7036; while the rare earth elements are characterised by light RE enrichment and a significant negative Eu anomaly. These Italian volcanics are tentatively subdivided into three zones: (1) N. Tuscany where the magmas are believed to reflect crustal anatexis. (2) A central zone in which hybrid (crust/ mantle) rocks have been recognised. (3) A southern zone, south of Rome, where mantle-derived magmas are identified which have been largely unaffected by interaction with continental crust. At Roccamonfina, in zone 3, Rb/Sr and Sm/Nd pseudo isochrons are observed but since the calculated ages are 0.5 and 2.0 b.y. respectively it is argued that a simple isochron model is not applicable and that the data are most easily explained by a recent mixing event within the upper mantle. It is envisaged that this occurred during metasomatism of the upper mantle source region by a fluid that had high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd and was enriched in K, Rb, and LREE's but relatively depleted in Sr²⁺ and Eu²⁺.     

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.     

Evidence of hydrological control of Sr behavior in stream water (Strengbach catchment,Vosges mountains,France)

Strontium and particularly ⁸⁷Sr/⁸⁶Sr ratios in stream water have often been used to calculate weathering rates in catchments. Nevertheless, in the literature, discharge variation effects on the geochemical behavior of Sr are often omitted or considered as negligible. A regular survey of both Sr concentrations and Sr isotope ratios of the Strengbach stream water draining a granite (Vosges mountains, France) has been performed during one year. The results indicate that during low water flow periods, waters contain lower Sr concentrations and less radiogenic Sr isotope ratios (Sr=11.6 ppb and ⁸⁷Sr/⁸⁶Sr=0.7246 as an average, respectively) than during high water flow periods (Sr= 13 ppb and ⁸⁷Sr/⁸⁶Sr=0.7252 as an average, respectively). This is contrary to expected dilution processes by meteoric waters which have comparatively lower Sr isotopic ratios and lower Sr concentrations. Furthermore, ⁸⁷Sr/⁸⁶Sr ratios in stream water behave in 3 different ways depending on moisture and on hydrological conditions prevailing in the catchment. During low water flow periods (discharge < 9 l/s), a positive linear relationship exists between Sr isotope ratio and discharge, indicating the influence of radiogenic waters draining the saturated area during storm events. During high water flow conditions, rising discharges are characterized by significantly less radiogenic waters than the recession stages of discharge. This suggests a large contribution of radiogenic waters draining the deep layers of the hillslopes during the recession stages, particularly those from the more radiogenic north-facing slopes. These results allow one to confirm the negligible instantaneous incidence of rainwater on stream water chemistry during flood events, as well as the existence in the catchment of distinct contributive areas and reservoirs. The influence of these areas or reservoirs on the fluctuations of Sr concentrations and on Sr isotopic variations in stream water depends on both moisture and hydrological conditions. Hence, on a same bedrock type, ⁸⁷Sr/⁸⁶Sr ratios in surface waters can be related to flow rate. Consequently, discharge variations must be considered as a pre-requisite when using Sr isotopes for calculating weathering rates in catchments, particularly to define the range of variations of the end-members.     

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.     

Input of Sr/Sr ratios and Sr geochemical signatures to update knowledge on thermal and mineral waters flow paths in fractured rocks (N-Portugal)

Strontium isotopes and other geochemical signatures are used to determine the relationships between CO₂-rich thermal (Chaves: 76 °C) and mineral (Vilarelho da Raia, Vidago and Pedras Salgadas: 17 °C) waters discharging along one of the major NNE–SSW trending faults in the northern part of mainland Portugal. The regional geology consists of Hercynian granites (syn-tectonic-310 Ma and post-tectonic-290 Ma) intruding Silurian metasediments (quartzites, phyllites and carbonaceous slates). Thermal and mineral waters have ⁸⁷Sr/⁸⁶Sr isotopic ratios between 0.716713 and 0.728035. ⁸⁷Sr/⁸⁶Sr vs. 1/Sr define three end-members (Vilarelho da Raia/Chaves, Vidago and Pedras Salgadas thermal and mineral waters) trending from rainfall composition towards that of the CO₂-rich thermal and mineral waters, indicating different underground flow paths. Local granitic rocks have ⁸⁷Sr/⁸⁶Sr ratios of 0.735697–0.789683. There is no indication that equilibrium was reached between the CO₂-rich thermal and mineral waters and the granitic rocks. The mean ⁸⁷Sr/⁸⁶Sr ratio of the thermal and mineral waters (0.722419) is similar to the Sr isotopic ratios of the plagioclases of the granitic rocks (0.71261–0.72087). The spatial distribution of Sr isotope and geochemical signatures of waters and the host rocks suggests that the thermal and mineral waters circulate in similar but not the same hydrogeological system. Results from this study could be used to evaluate the applicability of this isotope approach in other hydrogeologic investigations.     

Constraints on paleowater dissolved loads and on catchment weathering over the past 16 ka from Sr/Sr ratios and Ca/Mg/Sr chemistry of freshwater ostracode tests in sediments of Lake Constance, Central Europe

Sr isotope and Ca/Mg/Sr chemical compositions of freshwater ostracode tests separated from a sediment core represent the last 16 ka of sedimentation in Lake Constance, Central Europe. The chemical evolution of the paleowater's dissolved load of Lake Constance was estimated by correcting the ostracode data for Ca/Mg/Sr fractionation due to biogenic calcification. Since the Late Pleistocene deglaciation, the Ca/Sr molar ratios of paleowaters increased systematically from about 100 (a near marine signature) to about 200. Ca/Mg molar ratios varied in the range of 1–25. The ⁸⁷Sr/⁸⁶Sr ratios indicate Late Pleistocene paleowater compositions of 0.7086–0.7091, significantly more radiogenic than present day waters (0.7085). Sr isotopes and Ca/Mg/Sr chemical data together show that weathering of Mesozoic evaporites consistently dominated the dissolved Sr load (80–90%). Carbonate and silicate weathering were less important (1–10%). Trends of Sr dissolved loads were therefore not related to Mg which was mainly mobilized by carbonate weathering. Biotite weathering was an important source of radiogenic Sr in the paleowaters. The short-term release (duration about 600–800 years) of radiogenic Sr during glacier retreat started 15.2 ka ago and was due to enhanced biotite weathering at the glacier base. Long-term release of radiogenic Sr was due to biotite weathering in glacial soils and silicate rocks, and has gradually declined since the Late Pleistocene/Holocene transition.     

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.