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The Sor and Gebba watershed plays a crucial role in the water resources of the Baro-Akobo River Basin. However, various factors have had a detrimental effect on the watershed. Unplanned groundwater extraction, wetland drainage, surface water pollution, and land use changes have all intensified due to population growth, urbanization, commercial farms, industrial development, poor water resources management, and improvements in living standards. This research utilized major hydrochemical ions and environmentally stable isotopes to elucidate the interaction between groundwater and surface water in the watershed, which are reliable tracers in various hydrologic processes. During the 2020 wet season and 2022 dry season, over 25 meteoric water samples were collected from different locations for hydrochemical and isotopic analysis. The hydrochemical analysis revealed that the dominant water type is Ca–Mg–HCO3−. Among the anions, HCO3− was the most dominant, followed by NO3−, Cl−, and SO42−, and those of cations Ca2+, followed by Na+, Mg2+, and K+. The spatial analysis of environmentally stable isotopes confirmed the interaction between groundwater and surface water in the watershed. The quality of groundwater is primarily influenced by rock-water interaction (Gibb's diagram) and, to some extent, by evaporation (Isotope study). A graph of the water samples closely aligned with the Addis Ababa-local meteoric water line indicates their meteoric origin. However, there was a slight deviation to the left due to the effects of distance and altitude. The isotopic correlation further supported the interaction between different water sources. [ABSTRACT FROM AUTHOR]

Mobile proximal gamma-ray spectrometry (GS) is an emerging approach to estimate soil texture directly in the field. It relies on gamma radiation emitted during the natural decay of potassium-40 (K-40) and other isotopes. The K-40 counts are correlated with total K content, mineralogical soil composition and therefore with soil texture. Yet, it is not clear if K fertilisation impacts the ratio of K-40 to total K which would necessitate to take the fertilisation history into account for soil sensing applications. To elucidate this question, a well-documented long-term experiment was selected. The soils of the Rengen grassland experiment (55 plots) were investigated for total K (XRF-K) and for K-40 via mobile proximal GS. No significant differences in XRF-K and K-40 were found between the treatments with and without K fertilisation, although formely published results point to negative and positive K balances, respectively. Fertiliser analysis revealed a ratio of K-40 to total K that was almost identical to the natural abundance of 0.0117%. It was concluded that it is not necessary to take K fertilisation history into account when predicting soil texture from mobile proximal GS on agricultural land for, e.g., precision farming purposes. [ABSTRACT FROM AUTHOR]

Aims: Forests with various mixed patterns often show large differences in water use strategies. However, mixed planting may enhance the drought resistance of the whole forest community. We evaluated whether mixed planting could enhance the drought resistance of Robinia pseudoacacia and Quercus acutissima under different seasons in the warm temperate zone of North China. Methods: Shallow-rooted R. pseudoacacia and deep-rooted Q. acutissima were studied to determine plant water use strategies under different seasons and planting methods. We measured hydrogen and oxygen isotope ratios of two species grown under pure and mixed planting methods, as well as those of the environment, including rainwater, soil water, and groundwater in spring, summer, and autumn. Results: Hydrogen and oxygen isotopic contents of soil water were significantly less than groundwater and significantly more than rainwater irrespective of the season. However, season was the key factor influencing the plant water use strategies. In spring and autumn, Q. acutissima used more groundwater while R. pseudoacacia used more soil water; in summer, both of the two species took more use of rainwater and soil water. Mixed planting significantly increased the proportion of groundwater use and the diversity of plant water use strategies of two species. Conclusion: Diversity of plant water use strategies facilitate the coexistence of two species with the same ecosystem irrespective of the changes in water availability in their respective root zones. Besides, mixed planting can enhance the drought resistance of the whole forest community via reducing competition for the seasonal changes in water resources. [ABSTRACT FROM AUTHOR]

Long-range transported atmospheric pollutants (or transboundary pollutants) include trace metals with isotope ratios and compositions that vary from those of domestic pollutants, which threaten mountain ecosystems. These differences can be applied as indices to evaluate the influence of transboundary pollutants on mountain ecosystems. Mosses play important ecological functions in mountains and are sensitive to atmospheric deposition. Therefore, using these indices for moss biomonitoring can provide a more accurate indication of ecosystem health. However, studies on indices that are appropriate for moss biomonitoring are limited. Here, the effectiveness of moss biomonitoring using trace metal indices was examined to evaluate transboundary pollutants in mountainous areas in Japan. Transboundary pollutants in these areas originate from mainland Asia and are characterized by high lead isotope ratios, lead-to-zinc (Pb/Zn) ratios, and arsenic-to-vanadium (As/V) ratios. Given that the abundance of transboundary pollutants decreases with distance from mainland Asia, these three indices are also expected to vary with distance. The Pb isotope ratios were found to decrease with distance from mainland Asia; in contrast, the Pb/Zn and As/V ratios did not display any notable relationship with distance. These results are likely attributed to biological and environmental factors that affect trace metal content in moss. Thus, moss Pb isotope ratios are useful indicators of transboundary pollutants in Japan's mountains, offering an important tool for comparable moss biomonitoring studies in East Asia. [ABSTRACT FROM AUTHOR]

This paper details the different steps for the isotopic determination of UAmO2 discs from analytical irradiation. MARIOS and DIAMINO irradiations were performed in materials testing reactors to study the behaviour of americium bearing blanket samples in regard of heterogeneous recycling in sodium-cooled fast reactor. Six irradiated discs were dissolved in hot cells and were analyzed to determine isotope ratios of uranium, plutonium, americium and neodymium. The ratios were measured combining chemical separations and TIMS analyses. Using the double isotope dilution methodology helps measuring 238Pu/238U, 241Am/238U and 148Nd/238U ratios with uncertainty about a few per mil (k = 2). [ABSTRACT FROM AUTHOR]

The most challenging problems in the field of chemico- and bioanalytical measurements are described. These problems are being solved, in particular, by participating in new international comparisons organized by the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology of the International Committee of Weights and Measures (CCQM CIPM). Solutions of these challenging problems are presented. The objectives and tasks of developing key comparisons in the following areas are described: isotopic measurements; determination of the purity of substances; organic analysis; bioanalytical measurements; measurements of aerosol particle parameters; measurements in the field of gas analysis and electrochemistry. It is shown that participation in international key comparisons allows obtaining valid and reliable results of measurements of the composition and properties of gas and liquid media, as well as solid substances and materials. [ABSTRACT FROM AUTHOR]

An analytical technique was developed to determine the age of uranium particles. After the chemical separation of uranium and thorium, the 230Th/234U ratio was measured using single-collector inductively coupled plasma mass spectrometry and a 233U-based reference material comprising a certain amount of 229Th as a progeny nuclide of 233U. The results allowed us to determine the purification age of two certified materials, i.e., U-850 and U-100, which was in good agreement with the reference purification age (61 y). Moreover, the age of a single U-850 particle was determined with a difference of − 28 to 2 years from the reference date. [ABSTRACT FROM AUTHOR]

The half-life of 243Am has been measured by an absolute and a relative method, i.e. by determining the specific activity of 243Am and the specific activity ratio with 241Am. A mixed 241,243Am reference material was produced and certified for its americium mass content and its isotope amount ratios. The characterisation of the mass content of 243Am was established by isotope dilution mass spectrometry using an 241Am spike, produced from highly enriched 241Pu material. The isotope amount ratios n(241Am)/n(243Am) and n(242mAm)/n(243Am) were measured by thermal ionisation mass spectrometry. Activity measurements were performed by alpha-particle counting at a defined solid angle, as well as high-resolution alpha-particle spectrometry. From the 243Am/241Am activity and isotopic amount ratios, a value of 16.988 (24) was derived for the 243Am/241Am half-life ratio. Using a value of 432.6 (6) a for the 241Am half-life, the corresponding 243Am half-life value, 7349 (15) a, is in good agreement with the result obtained from the absolute method, 7342 (14) a. The mean value, 7345 (14) a, agrees well with data from literature and lowers the relative standard uncertainty to 0.2%. [ABSTRACT FROM AUTHOR]

This study presents the development of an innovative experiment using a surrogate, for monitoring the depletion kinetics of plutonium dissolution residues in an irradiated fuel dissolution solution containing a high plutonium concentration. The surrogate, a (U,Pu)O2 compound, was synthesized from a plutonium having an isotopic composition different from the dissolution solution. This helps monitoring the plutonium residue depletion by TIMS measurements of the 240Pu/239Pu isotope ratio. Repeatability better than 83 ppm was achieved for the 240Pu/239Pu ratios in each aliquot of the dissolution profiles allowing qualitative and quantitative interpretation of the kinetic evolution that could not be reached by a conventional direct concentration determination. [ABSTRACT FROM AUTHOR]

In this study, we report the first independent measurements of lutetium isotopic composition using multi-collector ICPMS in four commercial lutetium materials, including a new NRC candidate lutetium isotopic reference material, LUIS-1. The regression model was used to correct for the instrumental isotopic fractionation (mass bias) using NIST SRM 989 isotopic rhenium as the primary calibrator. The regression model is based on a short 15-min measurement sessions at varying ICP plasma power. Isotope ratio of R176/175 = 0.026553(11)k = 1, corresponding isotopic abundances of x176 = 0.025866(11)k = 1, x175 = 0.974134(11)k = 1, and an atomic weight of Ar(Lu) = 174.966693(13)k = 1 were obtained for lutetium in LUIS-1. Uncertainty estimation was performed using a mixture of modeling approaches in accordance with the JCGM 100:2008 "Guide to the Expression of Uncertainty in Measurement" and its Supplement 1. The relative contribution of the rhenium primary standard to the combined uncertainty of 176Lu/175Lu isotope ratio was 15%. [ABSTRACT FROM AUTHOR]

Purpose: To evaluate the hydration of fat-free mass (FFM) in athletes and non-athletes.Methods: We analyzed the data of 128 healthy young adults (athletes: 61 men, 36 women; non-athletes: 19 men, 12 women) using the two-component (2C), 3C and 4C models. Under-water weighing or air-displacement plethysmography and deuterium dilution methods were used for estimating body density and total body water, respectively. The bone mineral content (BMC) was determined using whole-body scans by dual-energy X-ray absorptiometry.Results: There was no significant difference in FFM hydration between the athletes (men, 72.3 ± 1.3%; women, 71.8 ± 1.3%) and non-athletes (men, 72.1 ± 1.2%; women, 72.2% ± 1.0%) in the 3C model. The total mean FFM hydration (72.1% ± 1.3%) was similar to the corresponding value in the literature (~ 73%). The estimation error of the percentage fat by the 2C vs the 4C model was significantly and highly correlated with hydration (r = 0.96), BMC (r = - 0.70), and total body protein (r = - 0.86) in the 4C model FFM.Conclusion: Although FFM hydration was similar in athletes and non-athletes, it would be underestimated or overestimated when the 2C model is used for evaluation, and the biological FFM hydration value deviates from the 73% value inter-individually. Despite that this inter-individual variation in FFM hydration is low in terms of between-individual standard deviation (1.3%), the BMC and total body protein differ greatly in athletes, and when it affects FFM hydration, it may also affect the percentage fat measurement in the 2C model. Thus, FFM hydration would not be affected by FFM, percent body fat, or the athletic status. [ABSTRACT FROM AUTHOR]

Resonance ionization mass spectroscopy has proven to be a very efficient and selective method for the spatially resolved ultratrace determination of actinide contaminations, and the analysis of specific element and isotopic distributions on surfaces and environment particles. We report on the identification of highly element-selective optical excitation schemes identified for this purpose, with a particular focus on the precise determination of the isobaric ratios of 235U to 239Pu as well as 243Am to 241Pu. The chosen two-step ionization schemes were characterized with respect to their element selectivity on synthetic multi-element actinide mixtures, with an element ratio Pu : Am : U of 1 : 10 : 104, a composition which is typical, e.g., for spent nuclear reactor fuels. [ABSTRACT FROM AUTHOR]

Resonance ionization mass spectrometry is an ultra-sensitive and highly element selective tool for spectroscopy, ionization and detection of atoms and thus enables rare isotope determination. In combination with spatially resolved sputtering of neutrals by an initial ion beam, e.g. within a commercial secondary ion mass spectrometer, an isotope and isobar selective analysis technique with resolution on the micrometer scale for particles and surfaces is realized. Detection of minuscule amounts of specific actinides, e.g. of plutonium, in environmental and technical samples by this ultra-trace analysis technique requires detailed knowledge about the atomic physics of the element. Identification and characterization of the specific resonance ionization scheme applied within the particular geometry of the apparatus in use is needed. An analysis of the dependence of the specifications, specifically regarding the influence of the relative laser beam polarizations is presented here as an aspect, that could have a severe impact on isotope ratio precision and overall efficiency in the resulting ion signal. [ABSTRACT FROM AUTHOR]

In this study, the provenance of anthropogenic lead, a major pollutant of surface sediments, was determined in Huainan Panji coal mining area. The lead concentrations and the pollution degree were investigated by the enrichment factor. Tessier five-step morphology extraction method was used to discuss its potential hazard. By comparing the lead isotope ratios of surface sediments and surrounding potential polluted end-members, the lead isotope ternary mixture model was appropriated to explore the sources and relative contribution fractions. The results showed that: (1) The lead concentrations ranged from 31.44 to 64.07 mg/kg which was mild-moderate pollution. (2) The chemical forms of lead were residue state > iron-manganese oxidation state > exchangeable state > organic state > carbonate state. (3) The anthropogenic lead in surface sediments originated from soil, vehicle exhaust, coal gangue. And the relative contribution fractions were 51.70%, 30.90%, and 17.40%. [ABSTRACT FROM AUTHOR]

In this study, the microbial degradation of alpha-cypermethrin was investigated in 14 different soil samples by compound-specific stable isotope analysis. After 40 and 80 days of microbial degradation, the stable carbon isotope ratios of alpha-cypermethrin shifted from − 32.18 to − 31.87‰ ~ − 31.12 and − 31.45‰ ~ − 29.75‰ in the soils, respectively. The microbial degradation percentages of alpha-cypermethrin were calculated as 15.6~44.3% after 40 days of incubation and 33.3~73.9% after 80 days of incubation. The effects of physicochemical properties of soil samples were then explored on the microbial degradation of alpha-cypermethrin. The results revealed that the microbial degradation percentages were positively correlated with the contents of organic carbon in soils with Pearson correlation coefficients of 0.794 and 0.843 for 40 and 80 days of microbial degradation, respectively, indicating that the microbial degradation of alpha-cypermethrin was faster in the soil with higher content of organic carbon. Accordingly, soil-specific use should be considered in practical agricultural application of alpha-cypermethrin to reduce the residue of the pesticide. [ABSTRACT FROM AUTHOR]

Conditions of chemical separation of Al macroamounts and U microamounts, followed by atomic emission spectroscopic determination of the isotope composition and gravimetric content of U, were studied. An algorithm was developed for constructing calibration plots to determine the 235U/238U isotope ratio in various samples from nuclear fuel reprocessing. Optimum conditions of the spectral analysis for the U content were found by mathematical design of the experiment: NaCl content 2%, current 18 А, and exposure time 40 s. With the use of these conditions and of a specially developed form of carbon electrode, the uranium detection limit was decreased from 10-3 to 10-5%. [ABSTRACT FROM AUTHOR]

Surrogate nuclear explosive debris was synthesized and characterized for major, minor, and trace elemental composition as well as uranium isotopics. The samples consisted of an urban glass matrix, equal masses soda lime and cement, doped with 500 ppm uranium with varying enrichments. The surface and cross section morphology were measured with SEM, and the major elemental composition was determined by XPS. LA-ICP-MS was used to measure the uranium isotopic abundance comparing different sampling techniques. The results provide an example of the utility of LA-ICP-MS for forensics applications. [ABSTRACT FROM AUTHOR]

This paper describes an alternative approach to nuclear forensic analysis by employing time-of-flight (TOF) SIMS and sector-field (SF) SIMS collaboratively. A set of synthetic samples consisting of UO and other metal (Gd, Mo or Zr) oxide was analyzed by the both instruments. With TOF-SIMS, qualitative elemental analysis was possible in U-dominant or low-U samples. TOF-SIMS was also useful for investigating potential isobars for U isotopes induced by the other metals. To avoid the isobaric interferences, particle search and major U isotope analysis using SF-SIMS were performed by measuring UO instead of U, and thus the effects of interference were reduced. [ABSTRACT FROM AUTHOR]

A diffusive gradient in thin films (DGT) technique, based on a strongly basic anion exchange resin (Amberlite IRA-400), was successfully tested for S/S analysis in labile soil sulfate. Separation of matrix elements (Na, K, and Ca) that potentially cause non-spectral interferences in S/S analysis by MC ICP-MS (multi-collector inductively coupled plasma-mass spectrometry) during sampling of sulfate was demonstrated. No isotopic fractionation caused by diffusion or elution of sulfate was observed below a resin gel disc loading of ≤79 μg S. Above this threshold, fractionation towards S was observed. The method was applied to 11 different topsoils and one mineral soil profile (0-100 cm depth) and compared with soil sulfate extraction by water. The S amount and isotopic ratio in DGT-S and water-extractable sulfate correlated significantly ( r = 0.89 and r = 0.74 for the 11 topsoils, respectively). The systematically lower S/S isotope ratios of the DGT-S were ascribed to mineralization of organic S. [ABSTRACT FROM AUTHOR]

Stable isotope composition of precipitation from Pamba River basin, Kerala, India, is evaluated to understand the role of spatial and temporal variations on rainwater isotope characteristics. Physiographically different locations in the basin showed strong spatial and temporal variations. δ O varied from −7.63 to −1.75 ‰ in the lowlands; from −9.32 to −1.94 ‰ in the midlands and from −11.6 to −4.00 ‰ in the highlands. Local Meteoric Water Lines (LMWL) for the three regions were determined separately and an overall LMWL for the whole of the basin was found to be δ H = 6.6 (±0.4) δ O+10.4 (±2.0). Altitude effect was evident for the basin (0.1 ‰ for δ O and 0.8 ‰ for δ H per 100 m elevation), while the amount effect was weak. The precipitation formed from the marine moisture supplied at a steady rate, without much isotopic evolution in this period may have masked the possible depletion of heavier isotopes with increasing rainfall. Consistently high d-excess values showed the influence of recycled vapour, despite the prevailing high relative humidity. The oceanic and continental vapour source origins for the south-west and north-east monsoons were clearly noted in the precipitation in the basin. Rayleigh distillation model showed about 30% rainout of the monsoon vapour mass in the basin. [ABSTRACT FROM AUTHOR]

An analytical technique was developed by a combination of single particle dissolution, chemical separation of uranium, plutonium and americium with extraction chromatography using UTEVA resins and measurement with inductively coupled plasma mass spectrometry. This method was applied to plutonium isotope ratio analysis of individual U-Pu particles with U/Pu ratios ranging from 1 to 70. Consequently, Pu/Pu, Pu/Pu and Pu/Pu isotope ratios were successfully determined, while it was impossible to determine Pu/Pu ratios due to the high process blank values on m/z 238. [ABSTRACT FROM AUTHOR]

Age of individual uranium-plutonium (U/Pu) mixed particles with various U/Pu atomic ratios (1-70) were determined by inductively coupled plasma mass spectrometry. Micron-sized particles were prepared from U and Pu certified reference materials. The Pu reference was stored for 4-6 years since the last purification (July 14, 2008). The Pu purification age was obtained from the Am/Pu ratio which was calculated from the product of three measured ratios of Pu and Am isotopes in the eluted fractions. These ratios were measured by a high-resolution inductively coupled plasma mass spectrometer equipped with a desolvation system. Femto-gram to pico-gram quantities of Am, U, and Pu in a sample solution were sequentially separated on a small anion-exchange column. The Am/Pu ratio was accurately determined by spiking pure Am into the sample solution. The average determined age for the particles for the five independent U/Pu ratios was in good agreement with the expected age with high accuracy (difference age 0.27 years) and high precision (standard deviation 0.44 years). The described analytical technique can serve as an effective tool for nuclear safeguards and environmental radiochemistry. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

We present major element and actinide composition data from a population of fallout glass samples produced from a single near-surface nuclear detonation. Glass major element compositions indicate that composition of local geology is a primary control on bulk fallout chemical composition. Uranium isotope compositions indicate that vaporized, residual fuel was incorporated into the melts prior to solidification, likely within seconds, and are consistent with two-component mixing between naturally-occurring uranium and residual uranium fuel. Model ages of the residual fuel in fallout are systematically inaccurate, biased towards older ages, and are consistent with two-component mixing between naturally-occurring daughter nuclides in local sediment and decay-derived daughter nuclides from residual nuclear fuel. Multiple processes such as mixing, agglomeration of melted sediment-derived droplets, and incorporation of condensates must all occur within the timescale between sediment melting and melt solidification. [ABSTRACT FROM AUTHOR]

A Peltier-cooled silicon drift detector was successfully applied for conversion electron spectrometry. The energy resolution of the detector for 45 keV electrons was 0.50 keV (FWHM). The approximate thickness of the dead layer was determined to be 140 ± 20 nm Si equivalent. The relative efficiency of the detector was verified to be approximately constant in the energy range of 17-75 keV. This is concordant with the high transparency of the thin dead layer and the sufficient thickness of the detector (450 μm) to stop the electrons. The detector is suitable for use in plutonium analysis of chemically prepared samples. Moreover, it was demonstrated that conversion electron spectrometry is better than alpha spectrometry in preserving its capability to determine the Pu/Pu isotopic ratio as a function of sample thickness. The investigated measurement technique can be considered a promising new tool in safeguards, complementary to existing methods. [ABSTRACT FROM AUTHOR]

The desire for more rapid and sensitive analytical determinations of actinides in the environment is being addressed in our laboratory through the development of electrochemically modulated separations (EMS) coupled to multiple ion counting inductively coupled plasma mass spectrometry (MIC-ICP-MS). This work is focused on the characterization of EMS separations of U and Pu in swipe materials. EMS provides electrochemically controlled surface complexation of either U(IV) or Pu(IV), depending on the potential applied to an anodized glassy carbon electrode. The accumulation and rinse yields ~90 % recovery efficiency, matrix elimination, and analyte concentration of the selected actinide. All this is performed solely under the control of the applied potential. Once isolated, the concentrated actinide is released into a ~1 μL volume of dilute (0.5 M) HNO, resulting in a volumetrically concentrated transient signal that is ideal for multiple ion counting detection. Coupled with a Thermo Fisher Scientific Neptune Plus MIC-ICP-MS, atom utilization efficiencies are normally 1 %, comparable to the gold standard thermal ionization mass spectrometry (TIMS), but only requiring 20 min for separation and analysis; whereas TIMS requires >50 h for off-line separation, filament preparation, and isotopic analysis. Method and analytical figures of merit will be highlighted. [ABSTRACT FROM AUTHOR]

We employed femtosecond Laser Ablation Multicollector Inductively Coupled Mass Spectrometry for the determination of uranium isotope ratios in a series of standard reference material glasses (NIST 610, 612, 614, and 616). The uranium in this series of SRM glasses is a combination of isotopically natural uranium in the materials used to make the glass matrix and isotopically depleted uranium added to increase the uranium elemental concentration across the series. Results for NIST 610 are in excellent agreement with literature values. However, other than atom percent U, little information is available for the remaining glasses. We present atom percent and isotope ratios for U, U, U, and U for all four glasses. Our results show deviations from the certificate values for the atom percent U, indicating the need for further examination of the uranium isotopes in NIST 610-616. [ABSTRACT FROM AUTHOR]

This work describes the utilization of the laser ablation sector field inductively coupled plasma mass spectrometry (LA-SF-ICP-MS) technique for the determination of uranium isotopic composition in a highly enriched uranium sample. The measurements were performed on a continuous ablation with low energy density and defocusing, which demonstrated to be the optimum to reach the best signal stability. The measurements were improved by adjusting the following parameters: RF power, laser beam diameter, defocusing of laser beam, laser energy, laser energy density, auxiliary gas and sample gas. The U/U isotope ratio with its respective uncertainty was 16.36 ± 0.15 and its precision was 1.12 % relative standard deviation. The uncertainties were estimated following the ISO GUM, with a confidence level of 95.45 % ( k = 2.00). When compared the isotope abundances to the Round Robin Exercise Number 3's average results a difference of 0.46 % has been found and when compared to supplier's value, the difference was 0.41 %. The results presented by the measurements revealed that the LA-ICP-MS technique offers a rapid and accurate alternative to measure uranium isotope ratios without any sample preparation, since it allows carrying out the measurements straight on the sample. Moreover, it preserves the testimony-very important for safeguards and nuclear forensics purposes. [ABSTRACT FROM AUTHOR]

After the nuclear accident at TEPCO's Fukushima Dai-ichi power station in March, hydrogen explosions and reactor building explosion resulted in releases of radionuclides in the environment. Severe radioactive cesium and iodine contaminations have been observed in fallout deposition samples and soils in the East Japan. Radioactive cesium, iodine, uranium, and transuranic radionuclides were set as the monitoring targets in food safety tests. However, so far, only radioactive cesium and iodine were daily measured and reported by the Ministry of Health, Labour, and Welfare. The tedious and time consuming conventional alpha spectrometric method hampered the emergency monitoring U contamination in foods. In this work, we propose a simple and rapid analytical method for U and U/U isotope ratio analysis in fresh vegetables. This method was applied to the emergency monitoring of radioactive contamination after the nuclear accident at TEPCO's Fukushima Dai-ichi power station. The results showed no U contamination in fresh vegetables collected in Chiba and Ibaraki prefectures in April and May, 2011. [ABSTRACT FROM AUTHOR]

The kinetics of zinc absorption, metabolism and excretion is extensively studied by nutritionists. Stable isotopes of zinc can be used to identify body zinc compartments that have different turnover kinetics. Since the compartments might belong to physiological subsections of different organs, there is a need for microsampling analysis to determine isotope ratios of the trace element zinc in tissue samples. Here, we study the feasibility to use laser ablation coupled to quadrupole ICP-MS for the determination of zinc tracers given to rats at different time points with the aim to generate isotope ratio bioimages of heart tissue. A double tracer (Zn and Zn) experiment with rats was designed to label the exchangeable zinc pool as well as the stable zinc pool. The isotope ratios determined by laser ablation ICP-MS were evaluated by additional measurements of tissue digests. Accumulated tracers which made up more than 0.1% of total zinc could be identified in the tissues of the treated rats. It was established that at least 50 measurements from the microsampling were necessary to distinguish between controls and a tracer treated rat resulting in reduced resolution of the bioimage. With the parameters used, features in the tissue thin sections of at least 250 μm in size are necessary to detect the incorporation of a tracer. When different time points have to be measured, higher precisions are required and therefore a larger area needs to be ablated (1 mm). Using the bioimages and pool measurements from one physiological feature, it was possible to show that the aorta cell walls incorporate the zinc tracer at the different time points. [ABSTRACT FROM AUTHOR]

High-performance liquid chromatography linked to isotope ratio mass spectrometry (HPLC- co-IRMS) via a Liquiface© interface has been used to simultaneously determine C isotope ratios of glucose (G), fructose (F), glycerol (Gly) and ethanol (Eth) in sweet and semi-sweet wines. The data has been used the study of wine authenticity. For this purpose, 20 authentic wines from various French production areas and various vintages have been analyzed after dilution in pure water from 20 to 200 times according to sugar content. If the C isotope ratios vary according to the production area and the vintage, it appears that internal ratios of C isotope ratios ( $$ {R_{{{}^{{13}}{\text{C}}}}} $$) of the four compounds studied can be considered as a constant. Thus, ratios of isotope ratios are found to be 1.00 ± 0.04 and 1.02 ± 0.08 for $$ {R_{{{}^{{13}}{{\text{C}}_{{{\text{G/F}}}}}}}} $$ and $$ {R_{{{}^{{13}}{{\text{C}}_{{{\text{Gly/Eth}}}}}}}} $$, respectively. Moreover, $$ {R_{{{}^{{13}}{{\text{C}}_{{{\text{Eth/Sugar}}}}}}}} $$ is found to be 1.15 ± 0.10 and 1.16 ± 0.08 for $$ {R_{{{}^{{13}}{{\text{C}}_{{{\text{Gly/Sugar}}}}}}}} $$. Additions of glucose, fructose and glycerol to a reference wine show a variation of the $$ {R_{{{}^{{13}}{\text{C}}}}} $$ value for a single product addition as low as 2.5 g/L. Eighteen commercial wines and 17 concentrated musts have been analyzed. Three wine samples are suspicious as the $$ {R_{{{}^{{13}}{\text{C}}}}} $$ values are out of range indicating a sweetening treatment. Moreover, concentrated must analysis shows that C isotope ratio can be also used directly to determine the authenticity of the matrix. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared. [ABSTRACT FROM AUTHOR]

The article discusses the study which explores the contamination of lead (Pb) isotopes found in the hair of women in Japan during the twentieth century. It notes that the vintage hair samples had the highest Pb concentration which indicates environmental contamination. Moreover, it emphasizes that Pb isotope ratios in 1960 is heavily affected by gasoline.

The measurement of fission product cesium isotopes 135Cs and 137Cs at low femtogram (fg) 10−15 levels in ground water by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) is reported. To eliminate the natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10 cps/fg. The three sigma detection limit for 135Cs was 2 fg/mL (0.1 μBq/mL) and for 137Cs 0.9 fg/mL (0.0027 Bq/mL) measured from the standard with analysis time of less than 30 min/sample. Cesium detection and 135/137 isotope ratio measurement at very low femtogram levels using this method in a spiked ground water matrix is also demonstrated. [ABSTRACT FROM AUTHOR]

Depth profiles potassium and its isotope ratio (40K/K) were investigated in several forest soils from different geological and climatic backgrounds. The ratio was found not to be constant (0.0117%) but varied appreciably from 0.0085% to 0.0167% among different soils. Possible factors affecting variability of 40K/K values were considered by a multivariate factor analysis which suggested that aqueous parameters like humidity and pH might be a controlling factor in the surface soils. The amount (and probably chemical forms) of iron oxide may be another one influencing 40K/K values in mineral components at deeper portions. [ABSTRACT FROM AUTHOR]

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80–120-μm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-μm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. 34S/32S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both 34S/32S isotope amount ratios and δSV-CDT values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and δ34SV-CDT values are plotted for comparison. Slight variations of <1.2‰ were detected in the hair strands from UK residents whereas the traveler presented a variation of >5‰. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. [ABSTRACT FROM AUTHOR]

Bradykinin and substance P have been derivatised with cyclic diethylenetriaminepentaacetic anhydride (cDTPA) and subsequently labelled with natural and isotopically enriched Eu3+. This enabled the detection and relative quantitation of the peptides using element-selective detection by high-performance liquid chromatography inductively coupled plasma mass spectrometry (LC–ICP–MS). Relative quantitation was achieved by differentially labelling two peptide sources, after derivatisation with cDTPA, using natural and enriched 151Eu respectively. The 151Eu:153Eu isotope ratio was measured and used to calculate the original peptide ratio. The measured ratios came within 5.2% of the known ratio. Derivatisation and chelation reactions were additionally confirmed using LC–ESI–MS. [ABSTRACT FROM AUTHOR]

The analytical performance of five sample introduction systems, a cross flow nebulizer spray chamber, two different solvent desolvation systems, a multi-mode sample introduction system (MSIS), and a hydride generation (LI2) system were compared for the determination of Se isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS). The optimal operating parameters for obtaining the highest Se signal-to-noise (S/N) ratios and isotope ratio precision for each sample introduction were determined. The hydride generation (LI2) system was identified as the most suitable sample introduction method yielding maximum sensitivity and precision for Se isotope ratio measurement. It provided five times higher S/N ratios for all Se isotopes compared to the MSIS, 20 times the S/N ratios of both desolvation units, and 100 times the S/N ratios produced by the conventional spray chamber sample introduction method. The internal precision achieved for the 78Se/82Se ratio at 100 ng mL−1 Se with the spray chamber, two desolvation, MSIS, and the LI2 systems coupled to MC-ICP/MS was 150, 125, 114, 13, and 7 ppm, respectively. Instrument mass bias factors (K) were calculated using an exponential law correction function. Among the five studied sample introduction systems the LI2 showed the lowest mass bias of −0.0265 and the desolvation system showed the largest bias with −0.0321. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

The 234U/238U isotope ratio has been widely used as a tracer for geochemical processes in underground aquifers. Quadrupole-based inductively coupled plasma mass spectrometry (ICP-MS) equipped with a high-efficiency nebulizer and a membrane desolvator was employed for the determination of 234U/238U isotope ratios in natural water samples. The instrumental limit of detection for 234U was at the low pg L−1 level with very low sample consumption. Measurement precision (234U/238U) was 3–5% for bottled mineral water with elevated uranium concentration (>1 μg L−1). For the analysis of groundwater samples from the Almonte-Marisma underground aquifer (Huelva, Spain), uranium was stripped from stainless steel planchets that had previously been used as radiometric counting sources for alpha-particle spectrometry. Potential spectral interferences from other metals introduced during the dissolution were investigated. Matrix-matched blank solutions were needed to subtract the background on 234U due to the formation of platinum argides, and to allow for mass bias correction and background correction. The Pt appears to be an impurity present in the stainless steel, either as a minor component by itself or after extraction from the anode and a subsequent uranium electrodeposition. The 234U/238U isotope ratio data were in very good agreement with those of alpha spectrometry, while precision was improved by a factor of up to 10 and counting time was reduced down to ~20 min (10 replicate measurements). [ABSTRACT FROM AUTHOR]

The article presents abstracts of several studies on environmental geochemistry. Some of the abstracts presented include "Biogeochemical Cycling of Nutrients in Karstic Catchments, Southwestern China: Linkages to Changes of Eco-Environments," by Congqiang Liu and "Emerging Organic Contamination in China," by Guibin Jiang and colleagues.

Compound-specific stable isotope analysis (CSIA) using gas chromatography-isotope ratio mass spectrometry (GC/IRMS) has developed into a mature analytical method in many application areas over the last decade. This is in particular true for carbon isotope analysis, whereas measurements of the other elements amenable to CSIA (hydrogen, nitrogen, oxygen) are much less routine. In environmental sciences, successful applications to date include (i) the allocation of contaminant sources on a local, regional, and global scale, (ii) the identification and quantification of (bio)transformation reactions on scales ranging from batch experiments to contaminated field sites, and (iii) the characterization of elementary reaction mechanisms that govern product formation. These three application areas are discussed in detail. The investigated spectrum of compounds comprises mainly n-alkanes, monoaromatics such as benzene and toluene, methyl tert-butyl ether (MTBE), polycyclic aromatic hydrocarbons (PAHs), and chlorinated hydrocarbons such as tetrachloromethane, trichloroethylene, and polychlorinated biphenyls (PCBs). Future research directions are primarily set by the state of the art in analytical instrumentation and method development. Approaches to utilize HPLC separation in CSIA, the enhancement of sensitivity of CSIA to allow field investigations in the µg L-1 range, and the development of methods for CSIA of other elements are reviewed. Furthermore, an alternative scheme to evaluate isotope data is outlined that would enable estimates of position-specific kinetic isotope effects and, thus, allow one to extract mechanistic chemical and biochemical information. [ABSTRACT FROM AUTHOR]

The use of stable isotope tracers in human studies is a rapidly growing research field that benefits from the many new developments in inorganic mass spectrometric instrumentation and from the better availability of mass spectrometric techniques to nutritional scientists during the last three decades. Traditionally, thermal ionization mass spectrometry (TIMS) has been the preferred technique for these studies, but the development of new inductively coupled plasma mass spectrometric (ICPMS) techniques with better isotope-ratio measurement and interference-removal capabilities (e.g. single and multi-detector ICPMS and reaction/collision cell ICPMS) has enabled broader use of ICPMS for determination of stable isotope tracers in nutritional research. This review discusses the current and future use of ICPMS in stable isotope tracer studies in humans. [ABSTRACT FROM AUTHOR]

Capillary gas chromatography coupled to an inductively coupled plasma mass spectrometer with multiple-collector detection (GC–ICP–MCMS) has been used to assess the precision and instrumental mass bias in sulfur isotope-ratio determination for the gaseous sulfur species SF6. The isotopic composition of the compound was certified by the institute for reference materials and measurements (IRMM, Belgium) and is available as PIGS 2010. Integration of the peaks (peak half-width 1.4 s) was performed using a special peak-integration method based on definition of the integration area by assessment of a uniform isotope-ratio area within the chromatographic peak. Instrumental mass bias was determined to be approximately 12% per mass unit and proved to be stable in the concentration range measured. Replicate injections of 2, 10, 20, and 30 ng (as S) SF6 diluted in argon gave precision for the 32S/34S ratio from 0.6% RSD for 2-ng injections to 0.03% RSD for 30-ng injections. The 32S/33S and 33S/34S isotope-ratio precision was better than 0.4% RSD for injections of 10 ng (as S) and higher. Detection limits were in the absolute pg range for all measured sulfur isotopes. [ABSTRACT FROM AUTHOR]

In this paper isotope ratio mass spectrometry is used to determine the methane (CH4) oxidation fraction in the rhizosphere of intact rice plant-soil systems. Earlier studies on quantification of the methane oxidation were based on inhibition or incubation procedures which strongly interfered with the plant-soil system and resulted in a large variability of the reported fractions, while other studies considered stable isotopes at natural abundance levels to investigate methanotrophy in the rhizosphere of rice. The current work is the first that used 13C-labelled CH4 as additive and calculated the oxidation fraction from the ratio between the added 13C-labelled CH4 and its oxidation product 13CO2. Both labelled gases could be distinguished from the natural abundance percentages. The oxidation fraction for methane was found to be smaller than 7%, suggesting that former approaches overestimate the methane oxidation fraction. [ABSTRACT FROM AUTHOR]

The trophic interaction in the pelagic food web of oligotrophic-dystrophic Lake Shirakoma-ike was investigated by a stable isotope technique. Carbon and nitrogen isotope analyses revealed the trophic interaction among Piona carnea (a water mite), Chaoborus sp. (a phantom midge), Daphnia longispina (a cladoceran), and Acanthodiaptomus pacificus (a calanoida copepoda). The δ13C values for estimating the relative contributions of D. longispina and A. pacificus to carnivores were used, and they were also used for the constraint of the trophic enrichment factor of δ15N. Both Chaoborus sp. and P. carnea were suggested to consume D. longispina and A. pacificus at almost the same ratio (1 : 1). However, both carnivores preferred A. pacificus to D. longispina, because D. longispina was much more abundant in the lake than A. pacificus. Omnivory of P. carnea was also analyzed by the mixing model. [ABSTRACT FROM AUTHOR]

Literature from the first half of this century reports concern for toxicity from topical use of boric acid, but assessment of percutaneous absorption has been impaired by lack of analytical sensitivity. Analytical methods in this study included inductively coupled plasmamass spectrometry which now allows quantitation of percutaneous absorption of 10B in 10B-enriched boric acid, borax and disodium octaborate tetrahydrate (DOT) in biological matrices. In vitro human skin percent doses of boric acid absorbed were 1.2 for a 0.05% solution, 0.28 for a 0.5% solution, and 0.70 for a 5.0% solution. These absorption amounts translated into flux values of, respectively, 0.25, 0.58, and 14.58 μg/cm 2/h, and permeability constants ( Kp) of 5.0 x 10 -4, 1.2 x 10 -4, and 2.9 x 10 -4 cm/h for the 0.05%, 0.5%, and 5.0% solutions. The above in vitro doses were at infinite, 1000 μL/cm 2 volume. At 2 μL/cm 2 (the in vivo dosing volume), flux decreased some 200-fold to 0.07 μg/cm 2/h and Kp of 1.4 x 10 -6 cm/h, while percent dose absorbed was 1.75%. Borax dosed at 5.0%/1000 μL/cm 2 had 0.41 percent dose absorbed, flux at 8.5 μg/cm 2/h, and Kp was 1.7 x 10 -4 cm/h. Disodium octaborate tetrahydrate (DOT) dosed at 10%/1000 μL/cm 2 was 0.19 percent dose absorbed, flux at 7.9 μg/cm 2/h, and Kp was 0.8 x ICH cm/h. These in vitro results from infinite doses (1000 μL/cm 2) were a 1000-fold greater than those obtained in the companion in vivo study. The results from the finite (2 μL/cm 2) dosing were closer (10-fold difference) to the in vivo results. General application of infinite dose percutaneous absorption values for risk assessment is questioned by these results. [ABSTRACT FROM AUTHOR]

Literature from the first half of this century reports concern for toxicity from topical use of boric acid, but assessment of percutaneous absorption has been impaired by lack of analytical sensitivity. Analytical methods in this study included inductively coupled plasma-mass spectrometry, which now allows quantitation of percutaneous absorption of 10B in 10B-enriched boric acid, borax, and disodium octaborate tetrahydrate (DOT) in biological matrices. This made it possible, in the presence of comparatively large natural dietary boron intakes for the in vivo segment of this study, to quantify the boron passing through skin. Human volunteers were dosed with 10B-enriched boric acid, 5.0%, borax, 5.0%, or disodium octaborate tetrahydrate, 10% in aqueous solutions. Urinalysis, for boron and changes in boron isotope ratios, was used to measure absorption. Boric acid in vivo percutaneous absorption was 0.226 (SD = 0.125) mean percent dose, with flux and permeability constant ( Kp) calculated at 0.009 μg/cm 2/h and 1.9 x 10 -7 cm/h, respectively. Borax absorption was 0.210 (SD = 0.194) mean percent dose, with flux and Kp calculated at 0.009 μg/cm 2/h and 1.8 x 10 -7 cm/h, respectively. DOT absorption was 0.122 (SD = 0.108) mean percent, with flux and Kp calculated at 0.01 μg/cm 2/h and 1.0 x 10 -7 cm/h, respectively. Pretreatment with the potential skin irritant 2% sodium lauryl sulfate had no effect on boron skin absorption. These in vivo results show that percutaneous absorption of boron, as boric acid, borax, and disodium octaborate tetrahydrate, through intact human skin is low and is significantly less than the average daily dietary intake. This very low boron skin absorption makes it apparent that, for the borates tested, the use of gloves to prevent systemic uptake is unnecessary. These findings do not apply to abraded or otherwise damaged skin. [ABSTRACT FROM AUTHOR]

The features of a combustion with elementary fluorine for the case of compact SiC ceramics and model substances for boron containing ceramics (H3BO3 and Na2B4O7) were investigated with the aim of their decomposition and analysis. On-line detection of the gaseous decomposition products by quadrupole mass spectrometry using electron impact ionisation was studied. Limitations by blanks and transport interferences were investigated. Standard addition as well as the isotope dilution technique were used for calibration in the case of B, C and W at the trace and major component level. [ABSTRACT FROM AUTHOR]

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