Stable Sr Isotope Research Articles

Cross sections and isomer ratios in the Rb(n,$$\gamma $$) and Sr(n,$$\gamma $$) reactions

The neutron radiative capture cross sections have been measured for the stable isotopes of Rb (mass numbers 85, 87) and Sr (mass numbers 84, 86, 88) using the activation technique, by observing the $$\gamma $$ rays emitted in the decays of the radionuclides produced in neutron irradiation. Values are reported for both the thermal cross sections and the resonance integrals. Internal consistency of the deduced values has been obtained where possible by measuring several radioisotopes from the same sample as well as by irradiating at several different reactor sites that have different mixtures of thermal and epithermal neutrons. Experimental values of the thermal cross sections are compared with values calculated from the known resonances. Isomer ratios are deduced and compared with values calculated from a phenomenological model. Also reported are spectroscopic studies of Rb and Sr radionuclides leading to improved values for the energy of $$\gamma $$ rays emitted in the decays of $$^{{86}}\hbox {Rb}$$ , $$^{{{85g}}} \hbox {Sr}$$ , and $$^{\mathrm {89}}\hbox {Sr}$$ . The half-life of $$^{{{87m}}}\hbox {Sr}$$ has been remeasured in order to resolve the conflict between two precise but discrepant values reported in the literature.

Stable Ca and Sr isotopes support volcanically triggered biocalcification crisis during Oceanic Anoxic Event 1a

AbstractLarge igneous province (LIP) eruptions are hypothesized to trigger biocalcification crises. The Aptian nannoconid crisis, which correlates with emplacement of the Ontong Java Plateau and Oceanic Anoxic Event 1a (OAE 1a, ca. 120 Ma), represents one such example. The Ca isotope (δ44/40Ca) system offers potential to detect biocalcification fluctuations in the rock record because Ca isotope fractionation is sensitive to precipitation rate. However, other primary and secondary processes, such as input-output flux perturbations and early diagenesis, can produce similar signals. Here, we exploit emergent properties of the stable Sr isotope (δ88/86Sr) system to resolve the origin of δ44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ44/40Ca, δ88/86Sr, and 87Sr/86Sr records for Hole 866A of Ocean Drilling Program Leg 143 drilled in Resolution Guyot, mid-Pacific Ocean. The samples span ∼27 m.y. from the Barremian (ca. 127 Ma) to the Albian (ca. 100 Ma). The δ44/40Ca and δ88/86Sr secular trends differ from the 87Sr/86Sr record but mimic each other. δ44/40Ca and [Sr], as well as δ44/40Ca and δ88/86Sr, strongly correlate and yield slopes predicted for kinetic control, which demonstrates that variable mass-dependent fractionation rather than end-member mixing dominated the isotopic relationship between carbonates and seawater. Positive δ44/40Ca and δ88/86Sr shifts that begin before OAE 1a and peak within the interval are consistent with reduced precipitation rates. All results combined point to a cascade of effects on rate-dependent Ca and Sr isotope fractionation, which derive from the dynamic interplay between LIP eruptions and biocalcification feedbacks.

Impact of salinity and carbonate saturation on stable Sr isotopes (δ88/86Sr) in a lagoon-estuarine system

Local carbonate cycling in lagoon-estuarine systems, involving processes such as inorganic and biogenic carbonate precipitation/dissolution, represents an important but poorly constrained component of the coastal carbon budget. This study investigates the sensitivity of stable Sr isotope tracer (δ88/86Sr) with respect to carbonate saturation and salinity of local waters in the Coorong, Lower Lakes and Murray Mouth (CLLMM) estuary in South Australia. The CLLMM has an extensive range of salinity from fresh to hypersaline (from ∼0 to over 100 PSU), with corresponding variations in water chemistry and major ion composition that in turn controls mineral saturation states, and thus CaCO3 precipitation/dissolution in local waters. Here we use the novel δ88/86Sr tracer in tandem with the more established radiogenic Sr isotope ratio (87Sr/86Sr), where the latter is a robust proxy for Sr sources and thus water provenance. We also produced a geochemical (PHREEQC) model of calcium carbonate (CaCO3) saturation changes across this unique lagoon-estuarine system.The results indicate a systematically increasing trend of δ88/86Sr (from ∼0.25‰ to ∼0.45‰) with increasing salinity and CaCO3 (aragonite, calcite) saturation indices of the coastal waters, which in turn suggest an overall control of carbonate dissolution/precipitation processes on the stable Sr isotope composition in the CLLMM system. This was further corroborated by Ca isotope data (δ44/40Ca) published previously on the same samples from the Coorong, as well as a quantitative simulation of local carbonate removal in the lagoon based on Rayleigh modelling and Sr isotope data.Overall, our results confirm that a coupled Sr isotope approach (combining 87Sr/86Sr and δ88/86Sr) can be used to constrain not only the main water sources (continental versus marine Sr) but also local CaCO3 dissolution/precipitation processes, and thus inorganic carbon and coastal carbonate cycling in the CLLMM system. Finally, this coupled δ88/86Sr and 87Sr/86Sr approach can be potentially applied to fossil carbonate archives to reconstruct paleo-hydrology and salinity changes in the CLLMM and/or other carbonate-producing coastal systems.

Mass spectral database for TOF-SIMS of stable isotopes of Sr and Zr

Nuclear accidents (e.g., at the Chernobyl and Fukushima Daiichi nuclear power plants) release considerable amounts of radioactive pollutants into the environment. Radioactive particles in dust and soil can range from a few micrometers to several micrometers in size. Detection of these micrometer-sized particles requires a fast and effective analytical method. Because time-of-flight secondary ion mass spectrometry (TOF-SIMS) exhibits high spatial resolution and parallel detection capability, it is suitable for analyzing micrometer-sized radioactive particles. However, due to isobaric interferences, TOF-SIMS cannot effectively distinguish between isobaric elements such as 90Sr and 90Zr. Resonant ionization sputtered neutral mass spectrometry (R-SNMS) eliminates isobaric interferences and enables the measurement of isotope ratios of isotopes approaching the detection limit. However, R-SNMS cannot be performed independently because its results are based on the TOF-SIMS spectra. This study provides a database of reference spectra for Sr and Zr stable isotopes, which can act as important reference for further analysis of radioactive particles in environmental samples.

Strontium isotopes trace biological activity in the Critical Zone along a climate and vegetation gradient

Weathering and ecosystem nutrition are intimately linked through the supply of fresh mineral nutrients from regolith and bedrock (the “geogenic nutrient pathway”). However, the prominence of this link is dependent on the efficiency of nutrient recycling from plant litter (the “organic nutrient cycle”). Isotope ratios of strontium (Sr), an element that behaves similarly to Ca in ecosystems, confer two types of information: radiogenic Sr isotopes inform as to the sources of Sr and the degree of weathering, while stable Sr isotopes constrain partitioning between compartments of the Critical Zone (bedrock, water, secondary solids, and plants). To date, however, neither the reactions nor the mass balance between compartments that fractionate Sr isotopes, nor the fractionation factors involved, are well understood. Here, we present geochemical budgets of Sr (using radiogenic and stable Sr isotopes, and Ca/Sr ratios) at four sites along a substantial climate and primary production gradient in the coastal mountains of Chile. We found that Sr release through weathering is isotopically congruent, and released Sr is not strongly isotopically fractionated either during secondary mineral formation or transfer into the exchangeable pool. Despite this, the 88Sr/86Sr ratio of bio-available Sr, which should reflect the ratio of dissolved Sr, is higher than that of rock and regolith. We propose that this offset is caused by plants: while 88Sr/86Sr in plant organs at the four study sites systematically increased from roots towards their leaves, whole-plant Sr isotope compositions indicate preferential uptake of light Sr into plants (with a fractionation of up to −0.3‰ relative to the bio-available pool). Despite this strong biological fractionation, 88Sr/86Sr ratios in bio-available Sr do not covary with biomass production across our study sites, because with greater plant growth Sr is recycled more times after release by weathering – an isotope-neutral process. Rather, the loss of Sr from the ecosystem in solid organic material sets the isotope ratio of dissolved or bio-available Sr. Organic solids thus appear to constitute a significant export path of elements released during weathering, with the removal of solid plant debris reducing the recycling factor of Sr, and possibly that of other mineral nutrients too.

Characterizing nutrient pathways in Quebec (Canada) vineyards: Insight from stable and radiogenic strontium isotopes

Soils are a crucial interface of Earth's Critical Zone, responsible for the biogeochemical cycling of mineral nutrients. While the sources of essential nutrients such as Ca (and Sr) in plants have been widely studied, the processes by which these nutrients are transferred from the soil to the plants is less clear. We present new evidence for systematic nutrient fractionation between soils, grapes and wines from five vineyards from the Quebec terroir (Canada) using the novel stable Sr (δ88/86Sr) isotope system. We coupled this approach with traditional radiogenic 87Sr/86Sr measurements on the same samples (bulk soils, labile fraction of these soils, whole grapes, and wines) from five vineyards from the Quebec terroir (Canada) to ensure that variations in δ88/86Sr values were provoked by processes involved in Sr transfer instead of mixing between different sources. The δ88/86Sr values generally decrease from the bulk to the labile fractions of the soils to the grapes. A decrease in the difference between the soil fractions (Δ88/86Srbulk-labile) with increasing δ88/86Sr values in the labile fraction is interpreted to reflect increasing pedogenic mineral precipitation and higher soil fertility. The depleted δ88/86Sr values of the grapes are consistent with a preferential uptake of lighter isotopes by plants. This effect is magnified in soils showing higher secondary mineral precipitation. An increase in the δ88/86Sr values from the grapes to the wines reflects the separation of the skin/seeds and the juice (pulp enriched in 88Sr) in the winemaking process. This mixing relationship is supported by a correlation between the Sr concentrations and the δ88/86Sr values of the wines and grapes. These findings suggest promising new applications of stable Sr isotopes values for studying soil fertility and the impact of nutrient availability for plant growth in agricultural ecosystems as well as the impact of the maceration processes in the production of wine.The overall similarity of 87Sr/86Sr ratios of the labile soil fractions, grapes and wines from the same vineyard support the hypothesis of a same Sr source, from the soil solution to its transfer to the grape and wine and confirm the potential of the 87Sr/86Sr ratios as a proxy for geographic provenance of wine.However, slightly lower 87Sr/86Sr ratios in the grape pulps (by 0.00040 on average compared to the skins and seeds) suggest that the sources of nutrients available for plant uptake vary during the vegetative cycle. The grape seeds and skins formed in the early growth cycle are characterized by rapid growth due to enhanced rhizosphere activity (enhanced mineral dissolution) providing higher nutrient levels. The enhanced mineral solubility results in higher 87Sr/86Sr ratios in the skin and seeds derived from enhanced dissolution of 87Sr-enriched silicate minerals. In contrast, the pulp develops later in the growth cycle when rhizosphere activity and mineral solubility is reduced, resulting in a lesser contribution from silicate minerals and thus reflect a higher proportion of dissolved carbonate contributing to the lower 87Sr/86Sr ratios of the pulps.

Ultra-High Resolution Elemental/Isotopic Mass Spectrometry (m/Δm > 1,000,000): Coupling of the Liquid Sampling-Atmospheric Pressure Glow Discharge with an Orbitrap Mass Spectrometer for Applications in Biological Chemistry and Environmental Analysis.

Many fundamental questions of astrophysics, biochemistry, and geology rely on the ability to accurately and precisely measure the mass and abundance of isotopes. Taken a step further, the capacity to perform such measurements on intact molecules provides insights into processes in diverse biological systems. Described here is the coupling of a combined atomic and molecular (CAM) ionization source, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma, with a commercially available ThermoScientific Fusion Lumos mass spectrometer. Demonstrated for the first time is the ionization and isotopically resolved fingerprinting of a long-postulated, but never mass-spectrometrically observed, bi-metallic complex Hg:Se-cysteine. Such a complex has been implicated as having a role in observations of Hg detoxification by selenoproteins/amino acids. Demonstrated as well is the ability to mass spectrometrically-resolve the geochronologically important isobaric 87Sr and 87Rb species (Δm ~ 0.3mDa, mass resolution m/Δm ≈ 1,700,000). The mass difference in this case reflects the beta-decay of the 87Rb to the stable Sr isotope. These two demonstrations highlight what may be a significant change in bioinorganic and atomic mass spectrometry, with impact expected across a broad spectrum of the physical, biological, and geological sciences. Graphical Abstract "".

MEDICAL AND ECOLOGICAL ASPECTS OF ASSOCIATIONS BETWEEN HUMAN EXPOSURE TO TRACE CONCENTRATIONS OF STABLE BARIUM AND STRONTIUM AND FUNCTIONAL DISORDERS OF THE BODY. A REVIEW

A systematic analysis of the published results of studies on the effect of trace elements such as barium (Ba) and strontium (Sr) on functional systems of the human body. With sufficient intake of stable Sr isotopes, a decrease in pulse arterial pressure is observed in the morning, associated with a decrease in mortality among patients with ischemic heart disease and arterial hypertension. There is a statistically significant linear relationship between the ratio of the Ba and Sr content in the hair and the circadian heart rate index, that is associated with an increase in the incidence of thrombosis, particularly during treatment with the Strontium ranelate at therapeutic doses. A statistically significant negative correlation was found between the Ba tissue concentrations and the increase in the patient's age that is also associated with an increase in the risk of progressive degenerative brain disorders, as well as chronic obstructive pulmonary disease. The possible association of Sr and Ba tissue concentrations in the body with the risk of Kashin-Beck disease is discussed. For early detection of this disease in the population residing endemic areas and the areas of its sporadic cases, it is advisable to evaluate the function of active flexion of the distal joints of II - IV fingers of the hands in people aged 4 to 26 years with imaging the bone structure of these fingers in the people at risk within acceptable doses of radiation.

Controls on the solute geochemistry of subglacial discharge from the Russell Glacier, Greenland Ice Sheet determined by radiogenic and stable Sr isotope ratios

We used radiogenic and stable Sr isotope ratios (87Sr/86Sr and δ88/86Sr) to examine controls on solute acquisition in subglacial discharge from the Russell Glacier, a land-terminating lobe of the Greenland Ice Sheet (GrIS) located in western Greenland. The study focused on two melt seasons in 2014 and 2015. Subglacial discharge 87Sr/86Sr ratios are 13,000 ppm higher than those measured for bedload and suspended sediment digests, and are more similar to those of bedload sediment leachates. These results point to the preferential dissolution of minerals with high 87Sr/86Sr ratios. Analyses of mineral separates from bulk rocks demonstrate that biotite, chlorite, hornblende, and K-feldspar have relatively high 87Sr/86Sr ratios. Subglacial discharge δ88/86Sr values are ∼0.10‰ higher than those for bedload and suspended sediment digests. Isotope fractionation during secondary mineral formation and/or adsorption cannot account for the difference between subglacial discharge and bedrock δ88/86Sr values, as suspended and bedload sediment leachates and digests produced similar δ88/86Sr values and are within the range for bulk silicate Earth. Consistent with the interpretation of 87Sr/86Sr ratios, we attribute the difference to the preferential dissolution of minerals with high δ88/86Sr values. Mineral separates display a wide range of δ88/86Sr values (∼0.40‰). Those having high δ88/86Sr values include hornblende and K-feldspar, as well as apatite and titanite. Taken together, the preferential weathering of predominately silicate minerals explains the Sr isotope geochemistry of subglacial discharge.Subglacial discharge from the Russell Glacier feeds the proglacial Akuliarusiarsuup Kuua River (AKR). Along a 32 km transect of the AKR from the GrIS margin toward the coast, riverine 87Sr/86Sr ratios increase from ∼0.722 to ∼0.747 in an approximately step-wise pattern that corresponds to point-source inputs of additional subglacial discharge. Major cation concentrations and 87Sr/86Sr ratios minimally vary along lengths of the transect with no hydrological inputs. This suggests that proglacial chemical weathering is negligible and likely does not contribute significantly to GrIS solute fluxes.In general, this study supports the recent contention that silicate mineral weathering dominates the solute geochemistry of GrIS subglacial discharge in contrast to valley glaciers, which typically show substantial contributions from carbonate and sulfide weathering regardless of primary bedrock composition. Ice sheet subglacial chemical weathering may therefore have a greater impact on long-term atmospheric CO2 drawdown than previously realized.

The stable strontium isotopic composition of ocean island basalts, mid-ocean ridge basalts, and komatiites

The radiogenic 87Rb-87Sr system has been widely applied to the study of geological and planetary processes. In contrast, the stable Sr isotopic composition of the bulk silicate Earth (BSE) and the effects of igneous differentiation on stable Sr isotopes are not well-established. Here we report the stable Sr isotope (88Sr/86Sr, reported as δ88/86Sr, in parts per mil relative to NIST SRM 987) compositions for ocean islands basalts (OIB), mid-ocean ridge basalts (MORB) and komatiites from a variety of locations. Stable Sr isotopes display limited fractionation in a OIB sample suite from the Kilauea Iki lava lake suggesting that igneous processes have limited effect on stable Sr isotope fractionation (±0.12‰ over 20% MgO variation; 2sd). In addition, OIB (δ88/86Sr = 0.16–0.46‰; average 0.28 ± 0.17‰), MORB (δ88/86Sr = 0.27–0.34‰; average 0.31 ± 0.05‰) and komatiites (δ88/86Sr = 0.20–0.97‰; average 0.41 ± 0.16‰) from global localities exhibit broadly similar Sr stable isotopic compositions. Heavy stable Sr isotope compositions (δ88/86Sr > 0.5‰) in some Barberton Greenstone belt komatiites may reflect Archean seawater alteration or metamorphic processes and preferential removal of the lighter isotopes of Sr. To first order, the similarity among OIBs from three different ocean basins suggests homogeneity of stable Sr isotopes in the mantle. Earth's mantle stable Sr isotopic composition is established from the data on OIB, MORB and komatiites to be δ88/86Sr = 0.30 ± 0.02‰ (2sd). The BSE δ88/86Sr value is identical, within uncertainties, to the composition of carbonaceous chondrites (δ88/86Sr = 0.29 ± 0.06‰; 2sd) measured in this study.

Otolith mass marking techniques for aquaculture and restocking: benefits and limitations

The use of farmed and restocked fish to supplement the worldwide human consumption of fish, recreational fishing stocks, and conservation efforts, is growing at a rapid rate. Yet, monitoring the benefits of using hatchery-raised fish for supplementation is lacking, often due to hatcheries not marking or tagging all fish prior to release, despite a range of easy to apply, cost effective and accurate mass-marking methods being available to mark farmed and restocked fish en masse. Here we review otolith marking techniques that have the capability of mass marking millions of hatchery-reared fish that are, or could be, used for monitoring and compliance purposes. The otolith mass marking methods consist of otolith thermal marking and a range of otolith chemical marking methods (tetracyclines, alizarin compounds, calcein, strontium chloride, stable isotopes of Ba and Sr, and rare earth elements). We assessed and compared marking technique in terms of (1) ease of application, (2) cost of application, (3) mark retention and detectability, and (4) fish welfare. In addition, we determine the suitability of different otolith marking techniques for mass marking entire hatchery populations whether it be for restocking purposes, or for identifying and tracing escapees from aquaculture facilities. We conclude that although some techniques have restricted use due to regulations, the majority of otolith mass marking techniques are simple, easy to apply, cost effective and highly suitable for long term monitoring of hatchery produced fish.

Stable isotope fractionation of strontium in coccolithophore calcite: Influence of temperature and carbonate chemistry.

Marine calcifying eukaryotic phytoplankton (coccolithophores) is a major contributor to the pelagic production of CaCO3 and plays an important role in the biogeochemical cycles of C, Ca and other divalent cations present in the crystal structure of calcite. The geochemical signature of coccolithophore calcite is used as palaeoproxy to reconstruct past environmental conditions and to understand the underlying physiological mechanisms (vital effects) and precipitation kinetics. Here, we present the stable Sr isotope fractionation between seawater and calcite (Δ88/86 Sr) of laboratory cultured coccolithophores in individual dependence of temperature and seawater carbonate chemistry. Coccolithophores were cultured within a temperature and a pCO2 range from 10 to 25°C and from 175 to 1,240μatm, respectively. Both environmental drivers induced a significant linear increase in coccolith stable Sr isotope fractionation. The temperature correlation at constant pCO2 for Emiliania huxleyi and Coccolithus braarudii is expressed as Δ88/86 Sr=-7.611×10-3 T+0.0061. The relation of Δ88/86 Sr to pCO2 was tested in Emiliania huxleyi at 10 and 20°C and resulted in Δ88/86 Sr=-5.394×10-5 pCO2 - 0.0920 and Δ88/86 Sr=-5.742×10-5 pCO2 - 0.1351, respectively. No consistent relationship was found between coccolith Δ88/86 Sr and cellular physiology impeding a direct application of fossil coccolith Δ88/86 Sr as coccolithophore productivity proxy. An overall significant correlation was detected between the elemental distribution coefficient (DSr ) and Δ88/86 Sr similar to inorganic calcite with a physiologically induced offset. Our observations indicate (i) that temperature and pCO2 induce specific effects on coccolith Δ88/86 Sr values and (ii) that strontium elemental ratios and stable isotope fractionation are mainly controlled by precipitation kinetics when embedded into the crystal lattice and subject to vital effects during the transmembrane transport from seawater to the site of calcification. These results provide an important step to develop a coccolith Δ88/86 Sr palaeoproxy complementing the existing toolbox of palaeoceanography.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25°C in 0.01M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3−δ88/86Srfluid=−0.05±0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985±0.00003 corresponding to Δ88/86SrSrCO3-fluid = −0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7–8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

The radiogenic and stable Sr isotope geochemistry of basalt weathering in Iceland: Role of hydrothermal calcite and implications for long-term climate regulation

Several studies have examined the geochemistry of Icelandic rivers to quantify the relationship between basalt weathering and long-term climate regulation. Recent research has suggested that the chemical weathering of hydrothermal and metamorphic calcite contributes significant quantities of HCO3− to the Icelandic riverine flux (Jacobson et al., 2015). Because the HCO3− derives from volcanic CO2 that was sequestered in mineral form prior to atmospheric injection, the strength of the basalt weathering feedback occurring in Iceland may be lower than previously realized. To test these hypotheses, we analyzed the radiogenic and stable Sr isotope composition (87Sr/86Sr and δ88/86Sr) of the same suite of water, rock, and mineral samples as examined in Jacobson et al. (2015), and we developed a simple model of the long-term Ccycle that considers the transformation of volcanic CO2 to HCO3− during subsurface silicate weathering, which is a precursor to hydrothermal calcite formation.Interpretations based on 87Sr/86Sr and Ca/Sr ratios suggest that conservative, three-component mixing between basalt, calcite, and atmospheric deposition adequately explains river geochemistry. On average, the δ88/86Sr values of glacial and non-glacial rivers (0.414‰ and 0.388‰, respectively) are generally higher than those for basalt (0.276‰); however, calcite δ88/86Sr values (0.347‰) are also higher than those for basalt and span the range of riverine values. Thus, riverine δ88/86Sr values are also consistent three-component mixing between basalt, calcite, and atmospheric deposition. Isotopic fractionation is not required to explain riverine trends. Finally, model equations for the long-term Ccycle demonstrate that subsurface silicate weathering reduces the magnitude of the volcanic CO2 degassing flux, which in turn causes the atmosphere to stabilize at lower pCO2 values compared to the case where no subsurface silicate weathering occurs. However, the proportion of the net volcanic C flux introduced to the atmosphere-ocean system as HCO3− after subsurface silicate weathering does not regulate long-term climate. Because hydrothermal calcite simply sequesters some of this HCO3− and delays its transmission to the atmosphere-ocean system until it dissolves at the surface later in time, it can be concluded the weathering of hydrothermal calcite bearing non-atmospheric C also has no effect on long-term climate regulation. Icelandic riverine HCO3− fluxes should be corrected for the hydrothermal calcite weathering contribution prior to quantifying atmospheric CO2 consumption rates by basalt weathering at the Earth’s surface.

88Sr/86Sr fractionation and calcite accumulation rate in the Sea of Galilee

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 (88Sr/86Sr) during precipitation of inorganic (primary) calcite from the lake’s water. It was found that the absolute value of the 88Sr/86Sr fractionation factor, Δ88/86Sr, increases as a function of calcite accumulation rate (Δ88/86Sr [‰]=−0.05 to 0.042·log(R) [μmol·m−2·d−1], where R is the accumulation rate). Furthermore, the 87Sr/86Sr and 88Sr/86Sr 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 87Sr/86Sr and 88Sr/86Sr ratios were measured in primary calcite, aragonite shells of live Melanopsis, lake water and various water sources to the lake. While the lake’s 87Sr/86Sr ratios are determined by the mixture of freshwater of the Jordan River and saline springs, the 88Sr/86Sr 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 88Sr, results in an increase of the δ88/86Sr 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 88Sr/86Sr water-CaCO3 fractionation of Δ88/86Sr=−0.21‰. Similar Δ88/86Sr values were reported for the precipitation of coralline and inorganic aragonite from seawater and the precipitation of inorganic calcite from various continental waters. The Δ88/86Sr 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 Δ88Sr/86Sr 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 88Sr/86Sr ratio in the primary CaCO3 recovered from the lake’s sedimentary archives.

Effect of calcite precipitation on stable strontium isotopic compositions: Insights from riverine and pool waters in a karst cave

Radiogenic and stable Sr isotope ratios (87Sr/86Sr, δ88/86Sr) serve as potential tracers for evaluation of weathering sources and associated physicochemical processes in terrestrial environments. Despite carbonate weathering sourcing two-thirds of the total continental Sr flux to the ocean, however, few attempts have been aimed at studying stable Sr isotope fractionation in carbonate-dominated aquifers. Here we present a monthly-resolved monitoring dataset of major ion concentrations and Sr isotope ratios for karst riverine and pool waters at the Luofang Cave in the Central China to understand the potential controls responsible for water δ88/86Sr compositions under various climatic conditions. With the exception of some pool waters in the dry period, significantly heavier δ88/86Sr were detected in the riverine and pool waters (0.20‰ to 0.42‰) compared to bedrock δ88/86Sr (0.24‰ to 0.28‰), which can't be interpreted solely by lithology. A sequential leaching experiment of the local soils suggests limited stable Sr isotope fractionation during incongruent silicate mineral dissolution. Local plant utilization and biological activity in the soil overlying the cave are possible processes for causing the observed heavier δ88/86Sr in cave water. However, air partial pressure of CO2 in cave, monitoring water pH, and Sr isotopic mass balance calculations suggest that plant utilization is unlikely to be the primary control on the heavier water δ88/86Sr. On the other hand, significant stable Sr isotope fractionation was found between the cave dripping waters and calcite precipitates, and the Δ88/86Srcar-aq was estimated to be −0.15‰±0.07‰ (2SD). Precipitation of secondary calcites might be a potential process responsible for the heavier δ88/86Sr in the waters. The negative correlation between δ88/86Sr and Sr/Na ratios in the cave waters is consistent with a scenario of preferential incorporation of the light Sr isotope by solid phase. Furthermore, by combining the calcite saturation states and water pH, our results suggest that calcite precipitation is the most likely process controlling δ88/86Sr compositions in cave water. We demonstrate that secondary calcite precipitation in carbonate-dominated catchments could be important in controlling the riverine water δ88/86Sr compositions.

Geochemical evidence for initiation of the modern Mekong delta in the southwestern South China Sea after 8 Ma

Sedimentary records in the southwestern South China Sea reflect the evolving erosion and drainage systems that have operated in Southeast Asia during the Neogene. Analyses of the chemistry and clay mineral composition of sediments from International Ocean Discovery Program (IODP) Site U1433 allow us to examine these processes over the last 17Ma. Sediment older than 8Ma was deposited relatively slowly. Sr and Nd isotopes indicate a variable provenance with sequences of less and more altered material accompanied by strong changes in the proportion of smectite. Sediment flux was probably from Indochina, as well as from a more primitive volcanic source, most likely the Palawan ophiolite and/or Luzon. Sediments younger than 8Ma show a more stable Sr and Nd isotope character, indicating sources close to those seen in the modern Mekong River, although with some influx from smaller rivers draining the Indochina margin especially from 4 to 8 Ma. Our data are consistent with seismic estimates for an onset to the Mekong in its present location after 8Ma, following an avulsion from the Gulf of Thailand.

In situ Sr isotope analyses by LA-MC-ICP-MS of igneous apatite and plagioclase from magmatic rocks at the CPGeo-USP

ABSTRACT: This contribution describes the successful implementation of in situ Sr isotope analyses by LA-MC-ICP-MS at the CPGeo-USP. The choice for an analytical configuration using measurements of half-masses allows the accurate assessment of lanthanide interferences, permitting the determination of Sr isotopes in important REE-rich accessory phases, such as apatite. Likewise, the on-peak-zero method effectively corrects the background contribution (both from Kr and residual Sr contributions from previous ablations) to the signals of the unknown samples. The analytical campaigns resulted in an accuracy, in respect to reference TIMS values, better than 57 ppm (~ ±0.000057 2σ SD) for a modern coral and the Batjberg clinopyroxene which impart significant quality to our data. Similarly, the majority of the stable Sr isotope ratios are close to the accepted values, which also confirms the effectiveness of the method. The achieved accuracy allows the identification and investigation of spatially-controlled isotopic heterogeneities on the micrometric scale in several Sr-rich minerals (apatite, carbonates, plagioclase, and clinopyroxene) with important implications to the understanding of relevant geochemical processes, particularly AFC, source geochemical heterogeneities and magma-mixing.

Insights into combined radiogenic and stable strontium isotopes as tracers for weathering processes in subglacial environments

This study reports stable and radiogenic strontium isotope behaviour in the dissolved load and suspended sediments from the subglacial outflow of the Lemon Creek glacier (Juneau Ice Field, Alaska) over a single melt season. In situ measurements (discharge, total alkalinity, pH and conductivity) are combined with elemental concentrations, X-ray diffraction (XRD) analysis and radiogenic strontium isotope measurements to interpret the variations observed in stable strontium isotopic ratios.The stable Sr isotope composition (88Sr/86Sr ratio expressed as δ88/86Sr, ‰) of the dissolved load averages 0.31±0.05‰, and is heavier than both the suspended sediment 0.18±0.03‰, as well as local bedrocks ~0.20 to 0.26‰. We attribute the enrichment of heavier isotopes in the dissolved load to the uptake of lighter Sr isotopes by secondary weathering minerals, driving the dissolved load to heavier values. X-ray diffraction (XRD) analysis confirms the presence of clays in the suspended sediments and thermodynamic modelling suggests the presence of iron oxy-hydroxide phases. Although it is not possible to completely rule out the effect of dissolution of primary minerals in controlling Sr isotopic compositions of the dissolved load, our data indicate that the extent of secondary mineral formation likely plays a significant role. The preferential weathering of minerals such as biotite (consistent with the mineralogical assemblages found in the suspended sediments), as well as the potential presence of radiogenic calcites from metacarbonates (derived from the Yukon-Tanana terrain), may be driving the small seasonal shifts in 87Sr/86Sr of the dissolved load to more radiogenic compositions, from 87Sr/86Sr(DL)=0.71048 to 0.710647.Using the combination of stable and radiogenic strontium isotopes to investigate weathering processes shows that radiogenic Sr isotopes provide information regarding weathering of primary phases. While the stable Sr isotope data appear to record information regarding the extent of secondary mineral formation, where secondary minerals incorporate the light isotopes, driving the dissolved load to heavy values.

88Sr/86Sr fractionation in inorganic aragonite and in corals

Conflicting results have been reported for the stable Sr isotope fractionation, specifically with respect to the influence of temperature. In an experimental study we have investigated the stable Sr isotope systematics for inorganically precipitated and biogenic (coral) aragonite (natural and laboratory-cultured). Inorganic aragonite precipitation experiments were performed from natural seawater using the CO2 diffusion technique. The experiments were performed at different temperatures and different carbonate ion concentrations. 88Sr/86Sr of the inorganic aragonite precipitated in the experiments are 0.2‰ lighter than seawater, but showed no correlation to the water temperature or to CO32− concentration. Similar observations are made in different coral species (Cladocora caespitosa, Porites sp. and Acropora sp.), with identical fractionation from the bulk solution and no correlation to temperature or CO32− concentration. The lack of 88Sr/86Sr variability in corals at different environmental parameters and the similarity to the 88Sr/86Sr fractionation in inorganic aragonite may indicate a similar Sr incorporation mechanism in corals skeleton and inorganic aragonite, and therefore the previously proposed Rayleigh-based multi element model (Gaetani et al., 2011) cannot explain the process of Sr incorporation in the coral skeletal material. It is proposed that the relatively constant 88Sr/86Sr fractionation in aragonite can be used for paleo reconstruction of seawater 88Sr/86Sr composition. The seawater 88Sr/86Sr ratio reconstruction can be further used in calcite samples to reconstruct paleo precipitation rates.