Stable Sr Research Articles

High H2O-Assisted Proton Conduction in One Highly Stable Sr(II)-Organic Framework Constructed by Tetrazole-Based Imidazole Dicarboxylic Acid.

Solid electrolyte materials with high structural stability and excellent proton conductivity (σ) have long been a popular and challenging research topic in the fuel cell field. This problem can be addressed because of the crystalline metal-organic frameworks' (MOFs') high structural stability, adjustable framework composition, and dense H-bonded networks. Herein, one highly stable Sr(II) MOF, {[Sr(H2tmidc)2(H2O)3]·4H2O}n (1) (H3tmidc = 2-(1H-tetrazolium-1-methylene)-1H-imidazole-4,5-dicarboxylic acid) was successfully fabricated, which was structurally characterized by single-crystal X-ray diffraction and electrochemically examined by the AC impedance determination. The results demonstrated that the σ of the compound manifested a positive dependence on temperature and humidity, and the optimal proton conductivity is as high as 1.22 × 10-2 S/cm under 100 °C and 98% relative humidity, which is at the forefront of reported MOFs with ultrahigh σ. The analysis of the proton conduction mechanism reveals that numerous tetrazolium groups, carboxyl groups, coordination, and crystallization water molecules in the framework are responsible for the high efficiency of proton transport. This work offers a fresh perspective on how to create novel crystalline proton conductive materials.

Pulsed field ablation for complex resistant atrial tachycardia recurring after radiofrequency ablation of persistent atrial fibrillation

Abstract Background There is a limited knowledge on immediate and long-term efficacy of pulsed field ablation (PFA) for residual atrial tachycardia (AT) recurring after persistent atrial fibrillation ablation (AF). Purpose To present immediate and medium-term outcome of PFA (Farapulse) for complex AT recurring after ≥1 radiofrequency ablation (RFA) of primary (longstanding) persistent AF. Methods In 5/2022-10/2023, 81 patients (64±8 years, 19 females) underwent PFA for complex AT in 83 PFA procedures after prior RFA procedure(s); in first (n=21), second (n=33), third (n=23), fourth (n=5), or fifth (n=1) repeat ablation procedure, respectively. Mapping/ablation strategy was directed by the CS activation/entrainment to: 1) no 3D mapping and direct PFA in left atrium (n=67); 2) PFA directly after 3D LA mapping (n=9); 3) PFA following RFA after 3D LA mapping (n=7). AT sources were classified as macroreentry (MRAT) (perimitral, roof-dependent, typical flutter) or localized (LOCAT) in case of smaller reentry or ectopic origin. Results At the procedure onset, persistent AT was present in 58 patients, in the remaining cases AT (n=21) or AF (n=4) were induced. AF eventually occurred at some time of procedure in another 10 patients and was terminated by ablation at LA ridge/CS/LOM region 8x, LA posterior wall 3x, LUPV 1x, RUPV 1x, and RA low lateral wall 1x. Only MRAT, only LOCAT, or both AT types were found at 34 (41%), 35 (42%), and 14 (17%) procedures, respectively. A total of 125 ATs was identified (1, 2, and 3 ATs in 52, 20, and 11 patients). MRAT (n=60) included 32 perimitral ATs, 20 roof-dependent ATs, and 8 typical flutters. LOCAT (n=65) included RUPV source (n=1), LA extraPV sources (n=59), and RA sources (n=5). SR was restored with a 5±7 PFA applications at the site of AF source, total of PFA deliveries was 71±27, and procedure and fluoroscopy times were and 89±37 and 9±5 minutes, respectively. In the 7 patients with initial ineffective 6, 6, 11, 5, 18, 10, and 2 minutes of RFA, the AT was converted into SR by subsequent 1, 4, 1, 13, 4, 24, and 20 PFA applications. All ATs were terminated and noninducibility was achieved in 82 (99%) and 74 (89%) procedures, respectively. In 52 patients with >3 month follow-up, 46 (88%) patients remain in stable SR (41 / 79%) off AAD); 3 and 3 patients have paroxysmal or persistent AT. Conclusion PFA with catheter Farapulse can affect complex/epicardial AT sources resistant to RFA in prior or present ablation procedure; however, there is a certain discrepancy between high efficacy in AT terminating and medium-term clinical outcome.

Equilibrium Fractionation of Stable Strontium Isotopes During Adsorption to Mn Oxides

AbstractUnderstanding the stable strontium isotope fractionation between seawater and ferromanganese crusts/nodules is crucial for reconstructing seawater Sr isotopic history. This study explores stable Sr isotope fractionation during adsorption to manganese oxides, as preliminary experiments indicated their higher Sr adsorption capacity compared to iron oxides. We observed that equilibrium in concentration and isotopic composition can be achieved within a day. The lighter isotope (86Sr) is preferentially adsorbed, with the fractionation extent showing no significant change with respect to reaction time, pH, or Sr concentration under low ionic strength conditions (−0.14‰). Equilibrium fractionation processes, rather than Rayleigh fractionation, more accurately represent the isotopic composition trends of dissolved and adsorbed Sr. Experiments in synthetic seawater demonstrated greater Sr isotope fractionation (−0.20‰) compared to low ionic‐strength solutions. This fractionation during adsorption by manganese oxides in synthetic seawater is consistent with the isotopic discrepancy between seawater and ferromanganese nodules, suggesting that Mn oxide adsorption is the primary mechanism for Sr accumulation in ferromanganese deposits. These results imply that ferromanganese deposit Sr isotopic compositions could be proxies for reconstructing seawater Sr isotopic history, which is influenced by carbonate burial and continental weathering, reflecting the global carbon cycle changes.

Fractionation Mechanism and Flux Estimation of Strontium Isotopes During Basalt Weathering

AbstractThe fluxes of metal cations and isotopes released by weathering of silicate rocks are crucial and a prerequisite for constraining geochemical fluxes to rivers and oceans. This study presents mineral and elemental compositions along with 87Sr/86Sr and δ88Sr data from a basaltic weathering regolith on Hainan Island, South China to elucidate Sr isotope fractionation and weathering fluxes. The 87Sr/86Sr ratios vary from 0.703936 to 0.706338 as a result of differential weathering of the minerals. δ88Sr values in the weathering regolith range from −0.29 to 0.37‰, with the majority of the weathering regolith having lower δ88Sr values than the parent rock. Sr is leached into the soil solution during plagioclase decomposition, while 86Sr is preferentially adsorbed on the surface of secondary minerals. As weathering progresses, smectite decomposes and kaolinite desorbs under weakly acidic conditions, releasing the previously adsorbed 86Sr into the soil solution. The differential weathering of kaolinite and smectite controls the δ88Sr values of the weathering regolith, with pH being an important determinant of isotope fractionation. Furthermore, Sr elemental fluxes (SrFlux) and Sr isotopic fluxes (δ88SrFlux) of this weathering regolith were calculated using a mass balance model, yielding mean values of 0.20 (mg cm−3 Myr−1) and 0.052 (‰ (mg cm−3 Myr−1)), respectively. The δ88SrFlux exhibits a nonlinear positive correlation with the Chemical Index of Alteration (CIA), indicating that enhanced weathering leads to significant stable Sr isotope fractionation at CIA values below 95%. Our research promotes the understanding of Sr recycling and the fractionation behavior of stable Sr isotopes during consecutive weathering.

Effect of terrestrial weathering on stable Sr and Ba isotope compositions of eucrites

Stable strontium and barium isotopes are potential tracers for understanding planetary differentiation and the nature of the building blocks of terrestrial planets. Strontium and barium are fluid-mobile elements, but it remains unclear how terrestrial weathering affects the Sr-Ba isotopes compositions in achondrites, thus hampering the utility of Sr-Ba isotopes in cosmochemistry. In this study, we conducted acetic acid leaching on three eucrites with varying weathering degrees (fall: Qiquanhu, hot desert find: Northwest Africa (NWA) 13583, and Antarctic find: Grove Mountains (GRV) 13001). Combined with detailed petrography observations and major and trace element analyses, we investigated the variations in Sr-Ba isotopes during terrestrial weathering. The degree of weathering follows an order of: NWA 13583 > GRV 13001 > Qiquanhu, evaluated based on several alteration signs, including: the presence of secondary carbonate, the enrichment of large ion lithophile elements (e.g., Sr, Ba, and U), and the Ce and Eu anomalies. The concentrations of Sr and Ba in the leachates of NWA 13583 show a good correlation with Ca, suggesting that the soluble Sr and Ba are derived from secondary carbonate. Differently, the concentrations of Sr and Ba in the leachates of Qiquanhu correlate with Al and Na, suggesting that the soluble Sr and Ba in Qiquanhu are derived from primary plagioclases. This also indicates that silicates dissolution may be inevitable in an acid leaching experiment for achondrites, even when using weak acetic acid. GRV 13001 shows no variation in Sr and Ba isotopes during leaching experiments. The δ138/134Ba in the leachate (0.26 ± 0.02 ‰) of Qiquanhu is higher than that of the residue (0.04 ± 0.03 ‰), reflecting that aqueous fluids preferentially uptake heavy Ba isotopes during plagioclase dissolution. Conversely, the leachate of NWA 13583 shows lower δ138/134Ba (-0.19 ± 0.05 ‰) than that of residue (-0.10 ± 0.03 ‰), reflecting the lighter Ba isotope composition in carbonate. Notably, the residue of NWA 13583 has δ138/134Ba ∼ 0.1 ‰ lower than those of Qiquanhu and GRV 13001. This discrepancy may reflect plagioclase dissolution during hot-desert weathering rather than magmatism on the parent body. Different from Ba isotopes, the δ88/86Sr of Qiquanhu shows tiny variation in the leaching experiment, suggesting that the dissolution of plagioclase may cause negligible Sr isotope fractionation. For NWA 13583, the δ88/86Sr of leachate is slightly heavier than that of leaching residue and bulk rock, reflecting the high δ88/86Sr in terrestrial fluids. Our results suggest that Ba and Sr isotopes of eucrites show different behaviors during terrestrial weathering. Sr isotopes show a smaller fractionation scale and may have greater resistance for terrestrial weathering than Ba isotopes.

Vertebral microchemistry as an indicator of habitat use of the oceanic whitetip shark Carcharhinus longimanus in the central and eastern Pacific Ocean.

The oceanic whitetip shark, Carcharhinus longimanus, is a highly migratory, epipelagic top predator that is classified as critically endangered. Although this species is widely distributed throughout the world's tropical oceans, its assumed mobility and pelagic behavior limit studies to derive required lifetime data for management. To address this data deficiency, we assessed variation in the habitat use of C. longimanus by oceanic region and over ontogeny through time series trace element and stable isotope values conserved along the vertebral centra (within translucent annulus bands) of 13 individuals sampled from the central and eastern Pacific Ocean. Elemental ratios of Mg:Ca, Mn:Ca, Fe:Ca, Zn:Ca, and Ba:Ca varied significantly among individuals from both sampling regions while principal component analysis of combined standardized elements revealed minimal overlap between the two areas. The limited overlap was also in agreement withstable isotope niches. These findings indicate that C. longimanus exhibit a degree of fidelity to sampling regions but also connectivity in a proportion of the population. The relatively stable Sr:Ca ratio supports its occurrence in oceanic environments. The decreasing trends in Ba:Ca, Mn:Ca, and Zn:Ca ratios, as well as in carbon and nitrogen isotope values along vertebral transects, indicate that C. longimanus undergo a directional habitat shift with age. Combined elemental and stable isotope values in vertebral centra provide a promising tool for elucidating lifetime data for complex pelagic species. For C. longimanus, management will need to consider subpopulation movement behavior in the Pacific to minimize the potential for localized depletions. Further work is now required to sample individuals across the entire Pacific and to link these findings with genetic and movement data to define population structure.

Study on Dynamic Column Behavior and Complexation Mechanism of DBS-Modified Crown Ether-Based Silica to 90Sr.

A crown ether-loaded hybrid adsorbent suitable for the separation and enrichment of strontium from high-level liquid waste was synthesized. 4',4'(5″)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its modifiers dodecyl benzenesulfonic acid (DBS) and 1-dodecanol were impregnated into silica-based polymer support. The hybrid adsorbent exhibited excellent Sr(II) selectivity ability, and effective chromatographic separation and recovery of Sr(II) from simulated high-level liquid waste could be achieved with a (DtBuCH18C6 + DBS + dodec)/SiO2-P packed column. The recovery rate of Sr(II) calculated based on the mass balance was approximately 99% and over 80% for the other coexisting metal ions. An appropriate increase in the concentration of Na-DTPA eluent was favorable to improve the efficiency of the elution process because of the increased complexation capacity of [DTPA]5- to Sr(II). The developed theoretical model can simulate the dynamic breakthrough curves of the material on the basis of short column data, thereby predicting the scale-up column of the practical operation. Density functional theory calculation was used to explore the action mechanism of DBS modifiers on the Sr(II) complexation process of crown ether groups. Two Sr(II) complexation isomeric models of DtBuCH18C6 were established, and the calculation results revealed a similar complexation ability. DtBuCH18C6 could form a stable Sr(II) complexation structure with DBS coordination, which further indicated that DBS could be a ligand to promote the Sr(II) adsorption ability of crown ether materials.

Analysing the behaviour of 90Sr and stable Sr in highly weathered soils: Soil to plant transfer factor and geochemical partitioning

Public concerns over environmental protection have increased after Fukushima accident. The soil-plant transfer factor (Fv) is a critical parameter for environmental risk assessment. 137Cs Fv values determined in acid Brazilian soils could be two orders of magnitude higher than Fv values measured in soils affected by the Chernobyl accident. This paper studied the behaviour of 90Sr in Brazilian soils where very few 90Sr Fv data is available. All classes of studied soils (Ferralsol, Acrisol and Nitisol) showed that more than 80% of total 90Sr in soils remains potentially mobile, mainly at the bioavailable phase, more than 2 years after soil contamination in an experiment conducted in lysimeters. Higher 90Sr Fv for maize and cabbage was observed in the acid soils with low content of exchangeable Ca, lower Fv values occurred at Nitisol, the subtropical soil type. It seems that the behaviour of 90Sr in these soils are mainly controlled by ionic competition mechanisms occurring for root uptake and sorption sites, with stable Sr and major nutrients (Ca, Mg and K). The mineralogy also seems to play a relevant role, since goethite rich clay soil presented 90Sr Fv values higher one or two orders of magnitude than 90Sr Fv values observed at clayed soil goethite rich with trace of vermiculite, for all studied crops. The high rate of 90Sr migration down the soil profiles observed for the studied soils during the 2 first years after contamination suggests a high rate of transfer to groundwater, even transfer to leafy crop group can be also a relevant pathway. In the present study, maize, among other plant species, presented the lowest Fv values, even when compared with maize cultivated in temperate soil. Our results suggest that stable Sr may not be a very good analogue of 90Sr for determining plant Fv values: geometric mean of stable Sr Fv for maize was Fvmaize = 6.3E-1 ± 2.1E0 (n = 8) and for 90Sr was Fvmaize = 1.8E-2 ± 2.5E0 (n = 16), geometric mean of stable Sr Fv for cabbage was Fvcabbage = 1.4E0 ± 3.9E0 (n = 17) and for 90Sr was Fvcabbage = 7.9E-1 ± 4.4E0 (n = 18).

Measurement of 90Sr and 87Sr/86Sr isotope ratio in Japanese cow milk sample using thermal ionization mass spectrometry

The pure beta emitter 90Sr (T1/2 = 28.8y) is a typical contaminant released by nuclear accidents and nuclear explosions. In the event of a nuclear disaster, it is crucial to identify radioactive pollutants quickly, to expedite the public's awareness of radiation exposure. In this work, a rapid 90Sr analysis protocol using thermal ionization mass spectrometry (TIMS) was developed for milk samples. With the improved sample preparation, Sr separation, and a newly developed TIMS method, 18 milk samples can be analyzed in less than 30 h and only 1 mL of cow milk is required for the complete analysis. The minimum detectable activity concentration of 90Sr is affected by the stable Sr concentration therefore, it is around 500 mBq·kg−1 (∼100ag·g−1). Additionally, 87Sr/86Sr isotope ratios (0.71518(9)–0.74132(4)) were determined for the first time in Japanese cow milk samples.

Identification of alkaline amendment sources (slash and burn versus marling) for cereal crops grown in the North of France: A multiple isotope approach (87Sr/86Sr, δ44/40Ca, δ88/86Sr)

Early farmers used at least two types of agrarian amendments that could raise pH and base saturation levels to allow the cultivation of cereals: marling and plant ash. Ash can be input in many different ways: felling and burning in place, transferring plant material from wastelands and spreading the ash, charring sod or peat blocks, burning stubble after harvest. Marling includes all the practices of amending limestone, from marl to chalky limestone composed of 99% CaCO3. In order to understand the evolution of these agricultural practices, it is important to identify which of the two techniques was used to amend cereal crops in the past. In order to test the potential of δ44/40Ca-δ88/86Sr-87Sr/86Sr multiple isotope approach for archaeological samples, we first applied the technique to currently grown crops, amended either with marl or with ash from freshly-cut and burned trees. We found that this approach makes it possible to discriminate cereal grains amended either by marling (less radiogenic Sr) or with tree ash (more radiogenic Sr). We also identified a positive correlation between stable Ca and Sr isotope values, suggesting that the Ca and Sr came from similar sources and had undergone similar mass-dependent isotopic fractionation mechanisms. Consequently, we later on mainly focused on stable and radiogenic Sr isotopes. Stable Sr isotope fractionation was also observed between different locations, different organs of a given cereal species and between different cereal types, but also within the same cereal species or the number of grains studied for a given locality, pointing to biological fractionation combined with source variation.

Phosphate (Bio)mineralization Remediation of 90Sr-Contaminated Groundwaters.

Historical operations at nuclear mega-facilities such as Hanford, USA, and Sellafield, UK have led to a legacy of radioactivity-contaminated land. Calcium phosphate phases (e.g., hydroxyapatite) can adsorb and/or incorporate radionuclides, including 90Sr. Past work has shown that aqueous injection of Ca-phosphate-generating solutions into the contaminated ground on both laboratory and field scales can reduce the amount of aqueous 90Sr in the systems. Here, two microbially mediated phosphate amendment techniques which precipitated Ca-phosphate, (i) Ca-citrate/Na-phosphate and (ii) glycerol phosphate, were tested in batch experiments alongside an abiotic treatment ((iii) polyphosphate), using stable Sr and site relevant groundwaters and sediments. All three amendments led to enhanced Sr removal from the solution compared to the sediment-only control. The Ca-citrate/Na-phosphate treatment removed 97%, glycerol phosphate 60%, and polyphosphate 55% of the initial Sr. At experimental end points, scanning electron microscopy showed that Sr-containing, Ca-phosphate phases were deposited on sediment grains, and XAS analyses of the sediments amended with Ca-citrate/Na-phosphate and glycerol phosphate confirmed Sr incorporation into Ca-phosphates occurred. Overall, Ca-phosphate-generating treatments have the potential to be applied in a range of nuclear sites and are a key option within the toolkit for 90Sr groundwater remediation.

Experimental and theoretical investigations of stable Sr isotope fractionation during its incorporation in aragonite

Strontium partitioning and isotope fractionation between aragonite and fluid have been determined experimentally at low values of the fluid saturation state (Ω) with respect to this mineral (1.1 ≤ Ωaragonite ≤ 2.2), and the measured isotope fractionation has been compared with the results of first-principles simulations. For the latter, Density Functional Theory (DFT) was used for estimation of the equilibrium Sr isotope fractionation between aragonite and Sr2+(aq). The obtained results suggest that, for values of Ωaragonite close to unity, the apparent distribution coefficient of Sr in aragonite (DSr,aragonite=XSrCO3XCaCO3(CaSr)fluid) exhibits values higher than one that rapidly decrease at increasing aragonite growth rate. Under equilibrium conditions (i.e. Ωaragonite=1) a DSr,aragoinite value of 2.7 can be extrapolated. Additionally, for aragonite growth rates rp ≤ 10−8.0±0.2 (mol/m2/s) the Sr isotope fractionation between aragonite and the fluid (i.e. Δ88/86Sraragonite-fluid) shows a constant value of −0.1±0.05‰, whereas it decreases to −0.40‰ when the growth rate increases to 10−7.7(mol/m2/s). The surface reaction kinetic model (SRKM) developed by DePaolo (2011) has been used to describe the dependence of DSr,aragonite and Δ88/86Sraragonite-fluid on mineral growth rate. In this model the best fit for DSr,aragonite and Δ88/86Sraragonite-fluid were 4 and −0.01‰, respectively, whereas the kinetic isotope fractionation factor for Δ88/86Sraragonite-fluid was −0.6‰. The results of first-principles calculations yield an equilibrium Sr isotope fractionation factor of −0.04‰ which is in excellent agreement with the experimental value of the present study. These results are the first experimental measurements of Sr isotope fractionation during inorganic aragonite precipitation as a function of growth rate and the first DFT calculations of Sr equilibrium fractionation in the aragonite-fluid system. The results of this study provide new insight into the mechanisms controlling stable Sr isotope composition in aragonite, which has implications for using Sr isotopes for paleo-reconstructions of natural archives, particularly those of abiogenic origin.

A highly stable Sr(II) dimer bearing phenyl carboxylate and N-containing ligands: Synthesis, crystal structure and proton conduction

Investigating the proton conductivity of crystalline materials based on supramolecular complexes holds important promise for application. Based on this, we prepared a novel three-dimensional supramolecular complex, [Sr2(dcba)4(phen)2(H2O)4] (1) based on a binuclear structural unit using the hydrothermal reaction of 3,4-dichlorobenzoic acid (H2dcba) and 1,10-phenanthroline (phen) with strontium chloride. Its crystal structure of 1 was first characterized, and its good H2O and thermal stability were further investigated, and its proton conductivity was temperature- and humidity-dependent. The analysis of the conductive mechanism indicated the presence of abound H-bonding networks within the solid-state structure, which facilitated the migration of protons.

Mechanisms Governing 90Sr Removal and Remobilisation in a VLLW Surface Disposal Concept

Flow-through columns were used to assess potential long-term trends in 90Sr biogeochemistry and transport in a Finnish near-surface very low-level waste (VLLW) repository concept. Experiments simulated the effects of water intrusion and flow through the repository barrier and backfill materials, examining impacts on 90Sr migration. Artificial rainwater containing 2.0 mg/L stable Sr (as a proxy for 90Sr) was pumped through column systems that had varying compositions from a matrix of rock flour (backfill material), bentonite (backfill/sealing material), and carbon steel (waste encapsulation material), for 295 days. Effluent geochemistry was monitored throughout. Sr retention behaviour in all column systems was broadly similar. Sr removal from influent rainwater was marked (~95% removed) at the beginning of the experiments, and this degree of removal was maintained for 20 days. Thereafter, Sr concentrations in the effluents began to rise, reaching ~2 mg/L by 295 days. Further, 56%–67% of added Sr was retained in the repository materials over the 295-day reaction period. Analysis of the effluents indicated that colloids did not form; as such, Sr output was likely to be aqueous Sr2+. Upon completion of the experiment, solid-associated Sr distribution and speciation in the columns were assessed through column sectioning and post-mortem analyses, which encompassed the following: total acid digests, sequential extractions, and XAS analysis. The total acid digests and sequential extractions showed that Sr was evenly distributed throughout the columns and that the majority (68%–87%) of solid-associated Sr was in the exchangeable fraction (MgCl2). This suggested that a major part of the solid-phase Sr was weakly bound to the column materials via outer-sphere sorption. Interestingly, a smaller amount of Sr (7%–23%) could only be extracted by aqua regia, suggesting that a proportion of Sr may bind more strongly to the barrier materials. XAS analysis of select samples confirmed that the dominant Sr phase was sorbed to the rock flour and bentonite, but not corroded carbon steel. Columns were also subject to remobilisation experiments using artificial rain- and seawater without added Sr. While rainwater remobilised Sr slowly, high-ionic strength seawater remobilised Sr at much higher rates in the systems containing bentonite. Interestingly, Sr was well retained in the rock flour-only system following rain and seawater intrusion. Overall, the results indicate that the column materials provide reactive surfaces for Sr removal should it be released from waste packages; however, the backfill and barrier materials have limited retention capacity, and the dominant sorption interaction is relatively weak. The safety case for the shallow disposal of radioactive waste should consider the possibility of seawater intrusion and that the bentonite-bound Sr was significantly more susceptible to remobilisation following seawater, despite retaining slightly more Sr during sorption experiments.

Direct Quantification of Attogram Levels of Strontium-90 in Microscale Biosamples Using Isotope Dilution-Thermal Ionization Mass Spectrometry Assisted by Quadrupole Energy Filtering.

Although thermal ionization mass spectrometry (TIMS) has been employed for the high-precision analysis of isotope ratios, direct quantification of artificial mono-nuclide in the environment is difficult by even using isotope dilution (ID) due to the coexistence of the great magnitude of natural stable nuclides or isobars. In traditional TIMS and ID-TIMS, a sufficient amount of stable Sr doped on a filament is required to realize a stable and adequate ion-beam intensity (i.e., thermally ionized beams). However, the background noise (BGN) at m/z 90, detected by an electron multiplier, disturbs 90Sr analysis at low concentration levels due to peak tailing of a significant 88Sr ion beam dependent on the 88Sr-doping amount. Here, TIMS assisted by quadruple energy filtering was successfully employed for the direct quantification of attogram levels of an artificial monoisotopic radionuclide strontium-90 (90Sr) in microscale biosamples. Direct quantification was achieved by integrating the ID quantification of natural Sr and simultaneous 90Sr/86Sr isotope ratio analysis. Additionally, the measurement amount calculated by the combination of the ID and intercalibration was corrected for the net result amount of 90Sr by subtracting dark noise and the detected amount derived from the survived 88Sr, which are equivalent with the BGN intensity at m/z 90. Background correction revealed that the detection limits were in the range of 6.15 × 10-2-3.90 × 10-1 ag (0.31-1.95 μBq), depending on the concentration of natural Sr in a 1 μL sample, and the quantification of 0.98 ag (5.0 μBq) of 90Sr in 0-300 mg/L of natural Sr was successful. This method could analyze small sample quantities (1 μL), and the quantitative results were verified against authorized radiometric analysis techniques. Furthermore, the amount of 90Sr in actual teeth was successfully quantified. This method will be a powerful tool for measuring 90Sr in the measurement of micro-samples, which are required to assess and understand the degree of internal radiation exposure.

An investigation of factors affecting high-precision Sr isotope analyses (87Sr/86Sr and δ88/86Sr) by MC-ICP-MS

The stable strontium (Sr) isotope system is being increasingly utilized to move forward our understanding of environmental, geological, and cosmological processes. Two analytical techniques are commonly used to measure stable Sr isotopes: 1) double-spike thermal ionization mass spectrometry (DS-TIMS) and 2) Zr-doped sample-standard bracketing multi-collector inductively coupled plasma mass spectrometry (Zr-doped SSB via MC-ICP-MS). Relative to DS-TIMS, Zr-doped SSB via MC-ICP-MS allows simultaneous determination of both 87Sr/86Sr and 88Sr/86Sr ratios, increasing measurement efficiency and sample throughput. However, several factors limit the analytical precision and accuracy of this technique, including matrix effects and potential intra- and inter-session offsets of measured isotope ratios. In this study, we evaluate potential causes for the observed offsets. We performed a series of experiments to assess the effect of different solution matrices and sources of contamination on Sr isotope measurements and to explore potential underlying mechanisms. Our tests show that incomplete Sr recovery during chromatographic separation, mismatches of Sr and Zr concentrations and acid molarity between samples and bracketing standards, and cation contamination all affect the precision and accuracy of Sr isotope measurements. We present evidence that analyses using our recommended updated preparation procedure for Zr-doped SSB via MC-ICP-MS can achieve a long-term reproducibility (2σSD: 87Sr/86Sr = ±0.000015 and δ88/86Sr = ±0.03 ‰) comparable to that of DS-TIMS.

Clean feed as countermeasure to reduce the 90Sr and 137Cs levels in fish from contaminated lakes

Glubokoye Lake situated within the Chernobyl Exclusion Zone is highly contaminated with respect to radioactive caesium and strontium isotopes, which also is reflected in the contaminated fish. To utilize the fish resources in contaminated lakes, the present work presents for the first time the effectiveness of using clean feed to counteract contamination of radionuclides in fish. The study is based on a series of repeated experiments with Prussian carp (Carassius gibelio (Bloch, 1782)) kept in cages in the contaminated Glubokoye Lake during summer 2018–2021. By the addition of clean feed, the activity concentration of 137Cs in fish muscle tissues was lowered with a factor of 2–5 due to biodilution. Surprisingly, additional clean feed did not lead to further decrease in the uptake of 137Cs in fish.In contrast to 137Cs, the addition of clean feed increased the 90Sr activity concentration in fish by a factor of 2–4 compared to fish fed with naturally occurring feed items. Radioactive strontium accumulated mainly in the fish bones and the muscle tissue level was 2 orders of magnitude lower, similar to the distribution observed for stable Sr. By utilizing a new kinetic model describing the dynamics of strontium isotopes in bone tissues of fish, predictions fitted well with site-specific data, taking growth rates and aging into account. Results showed that clean feeding can be used to counteract high activity concentration of 137Cs in fish due to biodilution, but cannot counteract bioaccumulation of 90Sr. Findings highlighted that it is essential to understand underlying factors influencing the uptake pathways for contaminants, as access to clean feed could increase the growth and thereby reduce the body activity concentration of dietary associated radionuclides such as 137Cs (biodilution), as well as increase the transfer of dissolved compounds such as 90Sr directly from water to fish.

Stable strontium isotope fractionation in hydroponically grown mung and soy bean sprouts

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.

90Sr and stable element levels in bones of brown bears: long-term trends in bear populations from Croatia and Poland.

The aim of this study was to investigate the temporal trends and geographical differences in 90Sr and stable element (Ba, Ca, Mn, Sr, Pb, Zn) levels in the bones of Croatian and Polish brown bear (Ursus arctos) populations. Experimental data suggest that in the decades after nuclear weapon tests and the Chernobyl accident, 90Sr bone activity concentrations decreased from 352 to 11Bqkg-1 in the Croatian bear population (period 1982-2015) and from 831 to 27Bqkg-1 in Polish bears (period 1962-2020). Calculated effective and ecological half-lives were 9 and 13years for Croatian bears, and 15 and 31years for Polish bears, respectively. Different temporal trends were noted in levels of Ba, Mn, Pb and Zn between the two countries with majority of bones having lower Pb, Sr and Zn in Croatian than in Polish bears. Estimated values for the soil-to-bear transfer of 90Sr were the same order of magnitude in the studied populations. Contrary to this, the estimated transfer of stable Sr was an order of magnitude lower for the Croatian bear population compared to Polish bears. The observed differences in soil-to-bear transfer between stable Sr and 90Sr found for Croatian bears might suggest the need for careful consideration on the use of stable Sr data as an analogue for 90Sr. To our knowledge, this is the first study that analysed 90Sr activity in tissue of brown bears. As such, it provides insight into the fate and behaviour of one of the most relevant anthropogenic radionuclides at the top of the food chain.

The Origin of the Black Shale Series and Bentonites from the Wufeng Formation in the Southwestern Upper Yangtze: Implications for the Convergence of the Yangtze and Cathaysia Blocks in the Late Ordovician

AbstractEarly Paleozoic black organic sediments and bentonites occur widely in the craton basin within the Yangtze block and are generally believed to be genetically related to a specific tectonic setting on the cratonic boundary. However, the intimate relationship between their origins and the dynamic mechanisms are unclear, as exemplified by the genesis of the black shale series and bentonites from the Wufeng Formation during the Ordovician–Silurian transition (OST). In order to reveal the relationship between the Wufeng Formation and the convergence of the Yangtze and Cathaysia blocks (i.e., the intracontinental Kwangsian Orogeny), two stratigraphic sections respectively in Zhaotong area (Northeast Yunnan) and Puyi area (Northwestern Guizhou) that were located in the semi‐restricted inner Yangtze Sea during the OST were systematically studied, on the basis of whole‐rock geochemical composition, pyrite δ34S (δ34Spy), total organic carbon (TOC), stable Sr isotope, pyrite framboid size distribution and zircon U‐Pb age, trace elements. The evidence shows that the paleo‐oceanic environment changed significantly at the turn of the early–late Katian and formed the black shale series in the Wufeng Formation. These acritarch assemblages were formed in the transition process of the Upper Yangtze Basin from passive continental margin basin to foreland basin during this interval. Based on previous research on the genetic relationship between black shale series and plate tectonic movement, a basin‐mountain evolution model suitable for South China in the Late Ordovician is presented. The two bentonites in the Wufeng Formation with U‐Pb ages of 445.5 ± 0.8 Ma and 441.9 ± 2.4 Ma primarily originated from the intermediate–acid volcanic eruption during the collision and convergence between the Yangtze and Cathaysia blocks in the Late Ordovician, the provenance region probably being located in the Jiangnan orogenic belt. Thus, we believe that the appearance of the black shale series and bentonite in the Wufeng Formation at the turn of the early–late Katian may represent the initiation of basin‐mountain transformation and the Kwangsian Orogeny in South China, which provides important evidence for the collision and convergence of the Yangtze and Cathaysia blocks in the Late Ordovician.