Stable strontium (δ88/86Sr) and calcium (δ44/40Ca) isotope fractionation in coastal groundwater and its implications for the transport of dissolved cations to the ocean

Calcium and strontium isotope fractionation in aqueous solutions as a function of temperature and reaction rate; I. Calcite

Calcium and strontium isotope fractionation during precipitation from aqueous solutions as a function of temperature and reaction rate; II. Aragonite

ABSTRACTTranshumance and palaeodiet are two central themes in archaeology and using chemical analysis of bones and teeth to reconstruct trends and patterns in diet and mobility has become a cornerstone of bioarchaeology. This study has investigated strontium concentration ([Sr]), radiogenic (87Sr/86Sr) and stable strontium (δ88Sr) isotope systematics in a controlled feeding experiment on domestic pigs designed to simulate terrestrial versus marine protein consumption. The results of the radiogenic (87Sr/86Sr) analysis offer a validation of the strontium isotope methodology. The study confirms that the radiogenic strontium isotope composition of dental enamel does represent the radiogenic strontium isotope composition of the diet. The results of the δ88Sr analysis have revealed a distinct shift of 0.322 ± 0.060 ‰ towards isotopically light Sr with trophic level. The magnitude of this shift is consistent with the predictions from the analogous shift observed in calcium isotopes. This is the first time that trophic level fractionation in δ88Sr has been identified in a controlled setting. Although still in its infancy, δ88Sr analysis has great potential to inform on trophic level systematics, to investigate dietary trends in early life and is potentially useful in examining diagenetic alteration.

Strontium isotope fractionation of planktic foraminifera and inorganic calcite

Dietary preferences of extant reptiles can be directly observed, whereas diet reconstruction of extinct species typically relies on morphological or dental features. More specific information about the ingested diet is contained in the chemistry of hard tissues. Stable isotopes of calcium and strontium show systematic fractionations between diet and skeletal bioapatite, which is applied for diet and trophic-level reconstructions of extant and extinct vertebrate species. Here, we present the first comprehensive analysis of stable calcium and strontium isotopes of bones and teeth from 28 extant reptiles, including lepidosaurs and archosaurs (crocodilians) with distinct herbivorous to faunivorous feeding behaviour, establishing a dietary reference frame. Both calcium and strontium isotopes exhibit systematic offsets between dietary groups, with insectivores having the highest, herbivores intermediate and carnivores the lowest calcium and strontium isotope values. Although the isotopic trophic-level effect is similar to mammals, the absolute calcium isotope values in reptiles are more positive in each diet category. Combining isotopic data with dental microwear texture analysis enables a refined understanding of reptile feeding ecology and the identification of durophagous diets. This toolbox opens new possibilities for improved dietary reconstructions of extinct taxa, such as dinosaurs and other non-mammalian species in the fossil record.

Constraining rates of marine carbonate burial through geologic time is critical for interpreting reconstructed changes in ocean chemistry and understanding feedbacks and interactions between Earth's carbon cycle and climate. The Quaternary Period (the past 2.6 million years) is of particular interest due to dramatic variations in sea level that periodically exposed and flooded areas of carbonate accumulation on the continental shelf, likely impacting the global carbonate budget and atmospheric carbon dioxide. These important effects remain poorly quantified. Here, we summarize the importance of carbonate burial in the ocean-climate system, review methods for quantifying carbonate burial across depositional environments, discuss advances in reconstructing Quaternary carbonate burial over the past three decades, and identify gaps and challenges in reconciling the existing records. Emerging paleoceanographic proxies such as the stable strontium and calcium isotope systems, as well as innovative modeling approaches, are highlighted as new opportunities to produce continuous records of global carbonate burial.

Strontium isotope fractionation during precipitation of strontianite in aqueous solutions as a function of temperature and reaction rate

This study investigated whether stable strontium isotope (88Sr/86Sr) fractionation occurs during nutrient uptake by bean plants. Mung and soy beans were cultivated hydroponically using two nutrient solutions with different strontium (Sr) isotope compositions. The Sr and calcium (Ca) concentrations, 87Sr/86Sr ratios and δ88/86Sr values of the seeds, organs, initial nutrient solutions, and residual nutrient solutions were measured. The triple Sr isotope plot illustrates that bean sprout organs deviated considerably from the binary end-member mixing lines between intact bean seeds and the initial nutrient solutions, indicating fractionation of δ88/86Sr. In addition, the residual nutrient solutions had heavier δ88/86Sr values than the initial nutrient solutions, further supporting preferential uptake of lighter Sr isotopes by bean sprouts. This study indicates that stable Sr isotope fractionation occurs during nutrient uptake by bean plants, and that controlled hydroponic experiments are highly effective for observing this process.

Breakthrough mode liquid chromatography was employed to investigate calcium (Ca) isotope fractionation in methanol medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of Ca was observed in the frontal part of the respective Ca chromatograms. The values of the isotope fractionation coefficient (ϵ) were in the order of 10−3 at 25 °C. Use of methanol as solvent has little advantage over the aqueous system as far as the values of ϵ are concerned. However, a substantial improvement was observed concerning the adsorption capacity of the crown ether resin for Ca ions. Molecular orbital calculations supported the present isotopic results in a qualitative fashion.

Calcium isotope fractionation during the partial dissolution of artificial calcite

Weathering processes, catchment geology and river management impacts on radiogenic (87Sr/86Sr) and stable (δ88/86Sr) strontium isotope compositions of Canadian boreal rivers

Stable strontium isotopes (here 88Sr/86Sr) are introduced as a new member of the nontraditional stable isotopes. We have developed a bracketing standard method for the determination of δ88/86Sr using an AXIOM MC‐ICP‐MS and normalizing to strontium SRM NBS987. For individual measurements the external reproducibility is better than about 25 ppm (1σ RSD). For the IAPSO seawater standard a δ88/86Sr value of 0. 381 ± 0.010‰ (2SEM) was determined. For the first time a temperature‐dependent strontium isotope fractionation during calcium carbonate precipitation could be shown. Aragonite samples inorganically precipitated under temperature control between 10 and 50°C revealed a δ88/86Sr/temperature dependency of 0.0054(5)‰/°C (R2 = 0.987). In contrast, for natural coral samples (Pavona clavus) from a proxy calibration study (23 to 27°C) we did determine 0.033(5)‰/°C (R2 = 0.955). The processes causing this sixfold stronger temperature dependency for the natural coral samples have to be studied in more detail in future studies. In a first approach the different slopes can be interpreted as effects of kinetic fractionation of strontium ions with or without a hydrate shell of 22 to 29 water molecules.

In the southwest Japan forearc, slab‐fluids produced from subducted materials migrate to crustal levels and appear as deep‐seated brine. We have analyzed for the first‐time stable strontium isotopes in non‐volcanic spring water with high salinity, referred to as Arima‐type saline water that likely originate from slab‐fluid that upwelled along major faults. The stable strontium isotope compositions of the saline water are isotopically light (δ88/86Sr = 0.122–0.157‰) and different from those of local bedrock and near‐surface water. The light strontium‐enriched and radiogenic signature of the saline water reflects the primary characteristic of slab‐fluids without an isotopic overprint in the crust. The Arima‐type brines show signatures of slab‐fluids at forearc depth, which is different from the slab‐fluids at subarc depth estimated from arc lavas. The characteristic features of the Arima‐type brines are explained by a larger contribution of subducted sediments and strontium isotope fractionation during fluids generation at shallower depth.

In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The delta Ca-44/40 ratios of the southwestern Dongsha area samples ranged from 1.21aEuro degrees to 1.52aEuro degrees and the ratio of the Baiyun Sag sample was 1.55aEuro degrees of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The delta C-13 values of the carbonates of the southwestern Dongsha area varied between -49.21aEuro degrees and -16.86aEuro degrees of the Vienna PeeDee Belemnite (VPDB) standard and the delta O-18 values ranged from 2.25aEuro degrees to 3.72aEuro degrees VPDB. The delta C-13 value of the Baiyun Sag sample was 2.36aEuro degrees VPDB and the delta O-18 value was 0.44aEuro degrees VPDB. The delta C-13 values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of delta C-13 values suggesting a dominant methane carbon source for the light samples and mixtures of delta C-13 values for the heavier samples, with possibly an organic or seawater carbon source. The delta O-18 values indicated that there is enrichment in O-18, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high delta Ca-44/40 values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.

Recently, calcium isotope fractionation in the coccolithophore Emiliania huxleyi was shown to exhibit a significant temperature dependency. An important subsequent question in this context is whether the observed fractionation patterns are caused by temperature itself or related growth rate changes. In order to separate growth and calcification rate effects from direct temperature effects, batch culture experiments with the coccolithophore E. huxleyi were conducted under varying light intensities. Despite large changes in cellular growth and calcification rates, calcium isotope fractionation remained constant. Independence of calcium isotope fractionation on growth and calcification was also obtained in two additional sets of experiments in which growth rates changed in response to varying calcium concentration and seawater salinity. These experiments also showed no direct effects of calcium concentration and salinity on calcium isotope fractionation. Values for calcium isotope fractionation of E. huxleyi coccoliths fell within a range of −1.0 to −1.6 (1000 lnα), confirming earlier results. This range is similar to that observed in several foraminiferal species and coccolith oozes, suggesting a rather homogeneous calcium isotopic composition in marine biogenic calcite. Our data further show that the calcium isotope fractionation does not change with changing isotopic composition of seawater. This is a basic requirement for reconstructing the calcium isotopic composition of the ocean over time.