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Saffron is regarded as the most expensive spice, mainly because of its laborious harvest. Only a few countries dominate the global saffron market, with Iran producing by far the most saffron, and the saffron production of all other countries thus being much smaller. However, the respective national production (not only of saffron) is usually preferred by local consumers with respect to foreign products and often has a higher price. Cases of saffron with mislabeled geographic origin have repeatedly occurred. Thus, to protect local saffron production, control of the declared geographic origin is required. In the present case, differentiation of the geographic origin by 87Sr/86Sr is performed. The results show the saffron of several countries of origin to vary within the range of marine carbonates; however, saffron samples of Moroccan and Indian origin mainly show elevated 87Sr/86Sr values. Within the Indian saffron samples, one sample from Kishtwar Valley can be differentiated from the Kashmir saffron samples. The results are thus promising, especially when using the combination of Sr and Rb concentrations to differentiate geographic origin whenever the regions are of homogenous bedrock geology within and of different geology between the regions. However, the reported findings need to be checked and confirmed by further and additional saffron samples. [ABSTRACT FROM AUTHOR]

BACKGROUND: Marine sedimentary carbonate rock is an important carrier for recording seawater information. The Sr isotope composition (87Sr/86Sr) of carbonate rocks can reflect the relative contribution of the continental crust and mantle to the Sr isotope composition of seawater. The long-term variation trend of Sr isotope composition in geological history can be used to interpret global tectonic events, weathering rate changes, biogeochemical cycles, and determine the age of marine sedimentary strata. However, the carbonate rocks likely contain non-carbonate fractions to varying degrees, which lead to the whole rock Sr isotope composition being unequal to that of the primary carbonate fraction. In order to obtain the primary carbonate fraction that reflects the primitive seawater, an effective leaching method is required. OBJECTIVES: To identify experimental procedures and target leaching steps that can effectively extract representative primary carbonate fractions in carbonate rock samples of varying purity and variety. METHODS: Reference materials of dolostone and limestone (GBW03105a and ECRM-782-1) were selected to represent carbonate rock samples with high purity, and natural samples of limestone (C-3, purity: 85%) and dolostone (E-3, purity: 65%) were selected to represent samples with low purity. The leaching solution of all steps was measured for Ca and Mg contents by inductively coupled plasma-optical emission spectrometry (ICP-OES), for Sr, Mn and Al contents by inductively coupled plasma-mass spectrometry (ICP-MS). The Sr isotope was measured by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) after purification of the leaching solution. Through the utilization of various indicators, such as Sr/Ca and Mn/Sr, the targeted leaching steps were ascertained. RESULTS: (1) Factors affecting the Sr isotope composition of the primary carbonate fraction. The detection of Sr isotope composition of primary carbonate fraction is affected by the soluble and exchangeable Sr, resulting in higher 87Sr/86Sr values. Thus, the pre-leaching step is essential for the multiple-step leaching method. It is shown that an excess of 5% acetic acid can cause leaching of non-carbonate fraction of limestone and affect the Sr isotope composition of the primary carbonate fraction. (2) Comparison and selection of multiple-step extraction methods. (a) It is recommended to use the method proposed by Li, et al[29] for limestone samples. It was found that the carbonate of GBW03105a and C-3 dissolved in the target steps (A10-A11) proposed by Liu, et al[13] accounted for 46.51% and 39.49% of the total carbonate fraction. A large number of target carbonate was dissolved rapidly in these two steps without considerable differentiation. In the method proposed by Li, et al[29], GBW03105a and C-3 target steps (B7-B9) dissolved carbonate accounted for 26.41% and 30.31% of the total carbonate fraction. The target steps are close to the step of non-carbonate fractions dissolved in strong acid. For natural samples with complex mineral compositions, the method proposed by Li, et al[29] may have leached non-carbonate fractions, which resulted in a higher 87Sr/86Sr value for testing. Therefore, the more conservative method proposed by Li, et al[29] is recommended for leaching unknown limestone samples, and B7-B9 are the target steps for leaching representative primary carbonate fraction. (b) The method proposed by Liu, et al[13] is recommended for dolostone samples. Liu, et al[13] selected acetic acid with different concentration ranging from 0.25%-10% for leaching. The carbonate fraction is almost completely dissolved, and the lowest Sr isotope value measured is lower than the method proposed by Li, et al[29] . Hence, to choose the concentration of acetic acid from low to high for leaching is helpful to separate the target fractions of dolostone samples. The same concentration of acetic acid is chosen by the method of Li, et al[29], and the dissolution rate of samples with different purity began to slow down at A9, leaving about 30% of the carbonate fraction not leached. Thus, it is difficult to judge whether the target carbonate fraction using this method has been leached completely. For the multiple-step leaching of unknown dolostone samples, the method proposed by Liu, et al[13] is recommended here, and A14-A15 are selected as the target steps for leaching representative primary carbonate fraction. (3) Optimization of a multiple step leaching method. The insoluble powder in the leaching solution will be digested by the subsequent addition of nitric acid, which can affect the Sr isotope value of the target fraction. This study has found that the Al/Ca ratio in the acetic acid leaching part is lower than that in Li, et al[13] (Fig.3b), indicating that the filter can reduce pollution caused by the dissolution of non-target fractions. In addition, the preleaching steps can also be optimized. The experimental data showed that 5mL of 1mol/L ammonium acetate could be selected for pre-leaching to simplify the experimental procedure and shorten the processing time. CONCLUSIONS: Based on prior research, a focused multiple-step leaching method for carbonate rocks is proposed. Limestone samples (purity≥85%) are suitable for 9-step leaching with 1% acetic acid, and the target steps are L7-L9; dolomite samples (purity≥65%) are suitable for the 14-step leaching method with 0.25%-10% acetic acid, and the target steps are D13-D14. The Sr isotope value of the primary carbonate fraction of the European Committee for Steel Standardization (ECISS) dolostone reference material ECRM-782-1 has been reported for the first time, which is 0.707868±0.000034 (n=12, 2SD). In the future, the experimental methods will be further improved to encompass samples from diverse sources and varying purity, thereby ensuring the reliability and universality of the experimental approach. [ABSTRACT FROM AUTHOR]

We undertook Zr isotope measurements on zircon, titanite, biotite, amphibole, and whole rocks from the La Posta pluton (Peninsular Ranges, southern California) together with trace element analyses and U-Pb age measurements to understand the controls on Zr isotope fractionation in igneous rocks, including temperature, crystallization sequence, and kinetic effects. We find large (>0.6‰) Zr isotope fractionations (expressed as δ94/90Zr) between titanite and zircon forming at approximately the same temperature. Using equilibrium fractionation factors calculated from ionic and ab initio models, we infer the controls on Zr isotope evolution to include the relative order in which phases appear on the liquidus, with titanite fractionation resulting in isotopically lighter melt and zircon fractionation resulting in isotopically heavier melt. While these models of Zr fractionation can explain δ94/90Zr variations in zircon of up to ∼1.5‰, crystallization order, temperature and presence of co-crystallizing phases do not explain all aspects of the intracrystalline Zr isotopic distribution in zircons in the La Posta pluton or the large range of Zr isotopic values among zircons (>2‰). Without additional constraints, such as knowledge of co-crystallizing phases and a better understand of the true causes of Zr isotope fractionation, Zr isotopes in zircon remains an ambiguous proxy of magmatic evolution. [ABSTRACT FROM AUTHOR]

Most researchers assume minimal impact of pretreatment on strontium isotope ratios (87Sr/86Sr) for bones and teeth, and methods vary tremendously. We compared 14 pretreatment methods, including no prep other than powdering enamel, ashing, soaking in water, an oxidizing agent (bleach or hydrogen peroxide) or acetic acid (0.1 M, 1.0 M, and 1.0 M buffered with calcium acetate), and a combination of these steps. We prepared and analyzed aliquots of powdered molar enamel from three proboscideans (one modern captive Indian elephant, Elephas maximus indicus; one Pleistocene mastodon, Mammut americanum; and one Miocene gomphothere, Afrochoerodon kisumuensis). Each pretreatment was performed in triplicate and we measured 87Sr/86Sr, Sr concentration, and uranium (U) concentration, using the same lab space and instrumentation for all samples. Variability in 87Sr/86Sr and Sr and U concentrations was considerable across pretreatments. Mean 87Sr/86Sr across methods ranged from 0.70999 to 0.71029 for the modern tooth, 0.71458 to 0.71502 for the Pleistocene tooth, and 0.70804 to 0.70817 for the Miocene tooth. The modern tooth contained the least Sr and negligible U. The Pleistocene tooth contained slightly more Sr and measurable amounts of U, and the Miocene tooth had approximately 5x more Sr and U than the Pleistocene tooth. For all three teeth, variance in 87Sr/86Sr, Sr concentrations, and U concentrations among replicates was statistically indistinguishable across pretreatments, but there were apparent differences among pretreatments for the modern and Pleistocene teeth. Both contained relatively little Sr, and it is possible that small amounts of exogenous Sr from reagents, building materials or dust affected some replicates for some pretreatments. For the modern tooth, median 87Sr/86Sr varied considerably (but statistically insignificantly) across pretreatments. For the Pleistocene tooth, variability in median 87Sr/86Sr was also considerable; some pretreatments were statistically distinct but there were no obvious patterns among methods. For the Miocene tooth, variability in median 87Sr/86Sr was much smaller, but there were significant differences among pretreatments. Most pretreatments yielded 87Sr/86Sr and Sr concentrations comparable to, or lower than, untreated powder, suggesting selective removal of exogenous material with high 87Sr/86Sr. Further evaluation of the mechanisms driving isotopic variability both within and among pretreatment methods is warranted. Researchers should clearly report their methods and avoid combining data obtained using different methods. Small differences in 87Sr/86Sr could impact data interpretations, especially in areas where isotopic variability is low.

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Saffron is regarded as the most expensive spice, mainly because of its laborious harvest. Only a few countries dominate the global saffron market, with Iran producing by far the most saffron, and the saffron production of all other countries thus being much smaller. However, the respective national production (not only of saffron) is usually preferred by local consumers with respect to foreign products and often has a higher price. Cases of saffron with mislabeled geographic origin have repeatedly occurred. Thus, to protect local saffron production, control of the declared geographic origin is required. In the present case, differentiation of the geographic origin by 87Sr/86Sr is performed. The results show the saffron of several countries of origin to vary within the range of marine carbonates; however, saffron samples of Moroccan and Indian origin mainly show elevated 87Sr/86Sr values. Within the Indian saffron samples, one sample from Kishtwar Valley can be differentiated from the Kashmir saffron samples. The results are thus promising, especially when using the combination of Sr and Rb concentrations to differentiate geographic origin whenever the regions are of homogenous bedrock geology within and of different geology between the regions. However, the reported findings need to be checked and confirmed by further and additional saffron samples.

Abstract The increasing significance of barium (Ba) in environmental and geologic research in recent years has led to interest in the application of the Ba isotopic composition as a tracer for natural materials with complex matrices. Most Ba isotope measurement techniques require separation of Ba from the rest of sample prior to analysis. This paper presents a method using readily available materials and disposable columns that effectively separates Ba from a range of geologic and hydrologic materials, including carbonate minerals, silicate rocks, barite, river water, and fluids with high total dissolved solids and organic content such as oil and gas brines, rapidly and without need for an additional cleanup column. The technique involves off-the-shelf columns and cation exchange resin and a two-reagent elution that uses 2.5 N HCl followed by addition of 2.0 N HNO3. We present data to show that major matrix elements from almost any natural material are separated from Ba in a single column pass, and that the method also effectively reduces or eliminates isobaric interferences from lanthanum and cerium.

Multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS) are widely used for Fe isotope measurements. The latter may be perturbed by interferences (notably from Cr and Ni) and matrix effects (notably from major elements), caused by elements remaining in the samples after purification. We quantified some of these perturbations and our ability to correct them whenever possible, using Thermo Neptune and Neptune Plus MC-ICPMS with a 57-58Fe double-spike mass bias correction. 54Cr and 58Ni isobaric interference corrections were found to be extremely efficient up to Cr/Fe=0.12 and Ni/Fe=0.04 (g/g natural Fe). Matrix effects were found negligible up to at least Na/Fe=175, Mg/Fe=10, K/Fe=1.5, and Mo/Fe=75 (g/g natural Fe). 28Si2+ interference was found negligible up to Si/Fe=50. Finally, we found that calcium and aluminum could cause significant interferences (e.g., 40Ca16O and 27Al2+), for Ca/Fe ≥ 2.5 and Al/Fe ≥ 2.5. The perturbation intensity relative to the Ca/Fe ratio was found dependent on the measurement conditions (plateau width). While working with samples with potentially high calcium or aluminum contents (such as calcite minerals or tests, bones and teeth, or marine samples and crustal rocks), we recommend to carefully take into account Ca and Al while tuning the instrument and checking the measurement accuracy with isotopic standards (i.e., doping the isotopic standard with Ca and Al levels comparable to those of the samples).

An extensive dataset of major- and trace-element and B-isotope composition related to the compositional variation of the tourmalines from the S-type granite and pegmatite from the Upper Bonai and Gangpur Group granitoids, eastern India, is provided. The Gangpur Schist Belt, consisting of the Upper Bonai and Gangpur Group, lies at the eastern end of the Proterozoic Central Indian Tectonic Zone. An attempt to constrain the source of the boron isotope and describe the magmatic–hydrothermal evolution of the granite–pegmatite system is made. The tourmalines record generally low trace-element concentrations, with the exception of some elements such as Zn, Li, Ga, Mn and Ti. The Zn and Li concentration increases from the tourmalines in the granites to the tourmalines in the pegmatite. Trace-element compositions also vary slightly from the core tourmaline to the rim tourmaline. Tourmalines in granites/pegmatites are mostly Fe-rich schorl, and have S-type B-isotopic signature (δ11B = −10‰ to −12‰). Their chemistries reflect changing salinities of the granitic melts as well as vapour exsolution during progressive crystallization. This study indicates that the tourmalines in the pegmatites crystallized from evolved flux-element-rich (F, B, Li) melt, probably after the crystallization of granite-forming melt. [ABSTRACT FROM AUTHOR]

The increasing significance of barium (Ba) in environmental and geologic research in recent years has led to interest in the application of the Ba isotopic composition as a tracer for natural materials with complex matrices. Most Ba isotope measurement techniques require separation of Ba from the rest of sample prior to analysis. This paper presents a method using readily available materials and disposable columns that effectively separates Ba from a range of geologic and hydrologic materials, including carbonate minerals, silicate rocks, barite, river water, and fluids with high total dissolved solids and organic content such as oil and gas brines, rapidly and without need for an additional cleanup column. The technique involves off-the-shelf columns and cation exchange resin and a two-reagent elution that uses 2.5 N HCl followed by addition of 2.0 N HNO3. We present data to show that major matrix elements from almost any natural material are separated from Ba in a single column pass, and that the method also effectively reduces or eliminates isobaric interferences from lanthanum and cerium. [ABSTRACT FROM AUTHOR]

A simple and quick method for simultaneous purification of Cu, Zn and Mo and accurate and precise measurement of their isotopic composition in geological samples using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been developed. The method involves the use of a single chromatographic column filled with the anion exchange resin AG-MP-1 for complex matrix removal and further purification of these three elements. The external standard-sample-standard bracketing (SSB) procedure combined to internal standard addition was used for accurate mass bias correction and precise Cu, Zn and Mo isotopic ratio measurements. The method was applied to different geological materials, as granodiorite (GSP 2-USGS), limestone (JLS-1, Japan), Buffalo River Sediments (NIST SRM - 8704) and sediments from Amazon River Basin. The mean precision for these samples was: 0.08 ‰ for δ65/63Cu; 0.05 ‰ for δ66/67Zn and 0.04 ‰ for δ98/95Mo. The main advantage is that the proposed method is simple and rapid, and carries out the quantitative recovery of elements of different atomic masses and at very low concentration ranges, mainly for Mo. In addition, optimizations made the calibration and correction of instrumental mass bias easier, leading to consistent results with other methods that are currently published. The comparison of isotopic compositions of Cu and Mo obtained for granodiorite with respect to data reported in the literature demonstrate that the simpler and multi-element method developed in this study can be properly used within the required limits of accuracy as a multi-proxy tool in isotope geochemistry.

Analysis of naturally occurring isotopic variations is a promising tool for investigating Zn transport and cycling in geological and biological settings. Here, we present the recently installed double-spike (DS) technique at the MAGIC laboratories at Imperial College London. The procedure improves on previous published DS methods in terms of ease of measurement and precisions obtained. The analytical method involves addition of a 64Zn–67Zn double-spike to the samples prior to digestion, separation of Zn from the sample matrix by ion exchange chromatography, and isotopic analysis by multiple-collector inductively coupled plasma mass spectrometry. The accuracy and reproducibility of the method were validated by analyses of several in-house and international elemental reference materials. Multiple analyses of pure Zn standard solutions consistently yielded a reproducibility of about ±0.05‰ (2 SD) for δ66Zn, and comparable precisions were obtained for analyses of geological and biological materials. Highly fractionated Zn standards analyzed by DS and standard sample bracketing yield slightly varying results, which probably originate from repetitive fractionation events during manufacture of the standards. However, the δ66Zn values (all reported relative to JMC Lyon Zn) for two less fractionated in-house Zn standard solutions, Imperial Zn (0.10 ± 0.08‰: 2 SD) and London Zn (0.08 ± 0.04‰), are within uncertainties to data reported with different mass spectrometric techniques and instruments. Two standard reference materials, blend ore BCR 027 and ryegrass BCR 281, were also measured, and the δ66Zn were found to be 0.25 ± 0.06‰ (2 SD) and 0.40 ± 0.09‰, respectively. Taken together, these standard measurements ascertain that the double-spike methodology is suitable for accurate and precise Zn isotope analyses of a wide range of natural samples. The newly installed technique was consequently applied to soil samples and soil leachates to investigate the isotopic signature of plant available Zn. We find that the isotopic composition is heavier than the residual, indicating the presence of loosely bound Zn deposited by atmospheric pollution, which is readily available to plants. Figure Zinc isotope ratio pools of bulk soil and the associated acid leach (estimated plant available pool) as measured by double-spike MC-ICPMS. δxZnLyon-JMC=(Rsample/RJMC-Lyon -1)x103, where Rsample and RJMC-Lyon denote the xZn/64Zn isotope ratio of the sample and standard (JMC-Lyon), respectively, and where x denotes either 66 or 68.

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]

The Acasta Gneiss Complex (AGC) of the Northwest Territories, Canada, contains some of the oldest evolved terrestrial crust and has a sustained record of more than a billion years of magmatism (>4.0–2.9 Ga). These rocks provide an opportunity to investigate the nature of continental crust formation on the early Earth. Because complexities in zircons and bulk rocks are characteristic of the early Earth record—including the AGC—strategies are needed to extract accurate and meaningful age and isotopic information. In order to evaluate the accuracy of the early Earth Hf isotope record, we examined AGC zircons from a range of lithologies using paired chemical abrasion isotope dilution U-Pb age and solution Lu-Hf isotope analysis and compared these with previous results obtained using laser ablation split-stream (LASS) analysis. We describe an approach whereby LASS is used to identify rocks with the least complex zircons, and, when appropriate, solution methods are then used to refine the age and Hf isotopic composition to the highest precision. This two-pronged analytical approach results in a more robust determination of the age and Hf isotopic record of complex rocks and zircons and allows identification of complexity in the Hf isotopic record that would not be apparent by solution analysis alone, thereby refining the record of magmatic evolution on the early Earth. Despite the better precision, solution techniques are unsuitable for rocks with complexly zoned zircons. In particular, zircons from the two oldest AGC rocks in this study have positive initial ε Hf values when determined by solution analysis (+2.8 and +4.9 at 4.0 and 3.9 Ga, respectively) but have negative ε Hf values when determined by LASS (−3.4 and −4.7, respectively). This is attributable to the presence of later radiogenic overgrowths on the zircon grains which are incorporated in solution analyses but can be avoided using LASS. This provides important clarity to the AGC Hf isotope record. In total, all but one of the AGC rocks we analyzed, including the oldest samples, have negative ε Hf values and indicate derivation from an enriched reservoir; none of these samples—in contrast to whole rock Nd isotope compositions—have sufficiently positive ε Hf values to indicate their derivation from a depleted mantle reservoir. Despite the presence of ancient AGC crust, there is no record of corresponding mantle depletion. This implies that extraction of Hadean crust in this region did not happen in sufficient volume to result in widespread mantle depletion in the AGC source by the Eoarchean. Our results underscore the importance of identifying different components in ancient zircons—and the rocks that contain them—and accurately determining the age and isotopic composition of those components. This is critically important for clarifying the record of the formation of enriched crust and development of the depleted mantle in Earth's early history. [ABSTRACT FROM AUTHOR]

A micro‐invasive technique is presented that enables pigment sampling from individual layers of a painting cross‐section by obtaining a furrow 10–50 μm wide of chosen length. Combined with increased sensitivity of lead (Pb) isotope analysis using multicollector inductively coupled plasma mass spectrometry (MC‐ICPMS) equipped with a 1013 Ω resistor or a Pb double‐spike technique, the amount of Pb needed for isotopic analysis is drastically reduced, while maintaining a relative 2 SD precision for 206Pb/204Pb of < 0.02%. The methodology proved able to characterize Pb isotope differences within paint layers. [ABSTRACT FROM AUTHOR]

Methods are presented for rapid determination of relative efficiencies of Faraday cups in a multicollector array with movable cups and of Daly or electron multiplier detector dead time and gain values. The Faraday calibration approach is based on measuring the same isotopic ratio in two sequences with different collector configurations having one collector in common. Changes in thermal fractionation during the two measurement sequences are monitored using the same two collectors. Since the relative efficiencies are determined by measuring the same ratio in different cups corrected for time‐dependent changes in fractionation, it is unnecessary to use a standard of known composition and calculations are simple, not requiring the solution of multiple equations. Determination of dead time and gain values for a Daly detector are shown based on multidynamic measurements of masses 207, 206, and 208 from Pb standard SRM982 in two sequences consisting of L1‐Daly‐H1 and Daly‐H1‐H2. This provides two equations that can be solved for Daly dead time and gain. This method uses static measurements and is therefore insensitive to signal instability. It also does not require use of a standard of known isotopic composition. The potential of using known cup efficiencies to help determine absolute isotopic abundances is discussed. [ABSTRACT FROM AUTHOR]

We present an in-situ method for Th and U isotope measurements by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) to determine possible age inversions of stalagmites, using a 213 nm Nd:YAG laser connected to an MC-ICPMS. Due to the low ion beam intensity of 230Th (20–120 counts per second, cps), we carefully optimized the operating parameters to get highest possible ion beam intensities, i.e., laser fluence (25 J cm−2), spot size (110 μm), pulse repetition rate (20 Hz), scan speed (4 μm s−1), integration time (1000 s), and He and Ar gas flow (∼0.9 L min−1 and ∼0.6 L min−1 respectively). A precision (2 relative standard error, 2RSE) of better than 1.8% was obtained for a single 230Th/238U measurement performed on a stalagmite from Hϋttenblӓserschachthöhle, western Germany, having U concentrations of 2–7 μg g−1 and with 230Th beam intensity of less than 100 cps. Compared to previous studies (Hoffmann et al., 2009), this is the about same precision, however at lower U concentrations. The data are corrected and calibrated by two factors (F1 and F2) for 230Th/238U and 234U/238U, respectively, using a carbonate material (flowstone in secular equilibrium). We obtained an age uncertainty (2 SE, 2σ) of ca. 9 ka at ca. 215 ka. Most data agree with solution MC-ICPMS results obtained on the same sample within their uncertainties. The reproducibility of the LA-MC-ICPMS age data is within 4.5% (2RSE) as determined from 3 to 4 repeated analyses. With a spot size of 110 μm and spatial resolution of about 400 μm or higher, it is possible to see much more details in thin growing layers than conventional solution analysis, where mixed layer sampling cannot be avoided. Potential age inversions in small regions are revealed, which cannot be detected by solution analysis due to the insufficient spatial resolution.

We present new Hf isotopic data of magmatic zircons from the Eastern Srednogorie zone. The data outline two clear temporal trends: rising initial εHf from the initiation of the magmatism at ~95 Ma to 81 Ma, followed by a rapid decline in the initial εHf in the 81-78 Ma time period. The first trend highlights the increasing participation of mantle melts in the formation of magmatic products in the East Balkan and Strandzha regions, which is likely dictated by the southward retreat of the subducting slab. This trend is also evident in published Hf isotopic data on zircons from Central Srednogorie zone. The second trend of rapidly decreasing initial εHf of zircons is interpreted to reflect increased proportion of lower crustal melts in an intra-arc rift extensional environment (the Yambol-Burgas region) between 81 and 78 Ma; this trend is not observed in the Central Srednogorie zone. [ABSTRACT FROM AUTHOR]

There is a renewed interest in K isotope geochemistry driven by the advances in analytical precision and it is emerging as a useful tracer in a variety of disciplines ranging from Earth sciences to biology. However, high-quality K isotopic data for reference materials are still limited but highly needed. Here, we report high-precision stable K isotopic compositions (δ41K) for 23 commercially available international reference materials, including igneous, sedimentary, and metamorphic rocks, as well as an in-house seawater standard. Potassium in digested samples was separated by cation-exchange chromatography with Bio-Rad AG50W-X8 (200–400 mesh) resin in 0.5 N HNO 3 media. Potassium isotopes were measured on a Nu Plasma II high-resolution MC-ICPMS. The reproducibility of K isotopic analysis, based on over one year of measurements of pure K solutions and rock standards, was ≤0.06‰ (95% confidence interval). Synthetic solutions made by mixing single element standards to represent various rock matrices confirmed the accuracy of our methods. The 23 reference materials have δ41K values ranging from −0.562‰ to −0.253‰ and the seawater standard has a much higher δ41K value of 0.143‰. The comprehensive dataset presented here provides a reference for quality control and inter-laboratory comparison of high-precision K isotopic analyses for future studies. [ABSTRACT FROM AUTHOR]

Abstract Multiple-collector inductively coupled plasma mass spectrometric (MC-ICPMS) techniques, with high-precision and high-throughput capabilities, have been applied to 230Th/U geochronology since the late 1990s. Significant effort has been dedicated to refining such techniques, but few studies have emphasized the development of data processing schemes. This study presents a convenient data-processing protocol that allows users to easily transform measured MC-ICPMS data to accurate 230Th/U ages, accounting for most sources of analytical uncertainty. This protocol comprises two interactive programs UTh_Review and UTh_Reduction, written with the MATLAB programming language. UTh_Review is designed to graphically present raw data of ion beam intensities and filter out outliers. UTh_Reduction enables data reduction, age calculations and data storage. This newly-developed protocol was validated by long-term measurement of δ234U in the Harwell uraninite isotope reference solution (HU-1) and an inter-laboratory comparison of 230Th/U dating of stalagmite. This methodology of data processing can easily be modified to fit previously published U Th data acquisition strategies. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Energy filters are critical for measurement of U-series nuclides by plasma mass spectrometry. • New compilation for 226Ra concentrations in rock standard reference materials. • Accuracy of isotope dilution is limited by the spike calibration standards. • 210Pb can be measured by plasma mass spectrometry. Abstract Application of retardation filters has revolutionized the use of multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) for the measurement of U-series disequilibria. Here, we present an evaluation of the application of retardation energy filters coupled with ion counting detectors for the measurement of U-series disequilibria by MC-ICPMS. We show that: 1) The RPQ minimizes backgrounds caused by ions experiencing irregular flight paths at high masses of uranium series nuclides. This reduced background is important for low count rate measurements and has enabled us to develop an improved method for the determination of 226Ra/228Ra ratios using a dual SEM/RPQ collector block. 2) Systematic biases exist for isotope ratios of 234U/238U and 230Th/232Th without the use of RPQs; thus, the RPQ is important for measurement of both of these isotope ratios. 3) That the RPQ makes possible 210Pb measurements in geologic samples using MC-ICPMS, but that this application is limited to samples that have low common Pb, such as carbonates and silica sinter. Additionally, we present mass spectrometric and gamma counting data for U-Th-Ra disequilibria in rock standard reference materials including AGV-2, AThO, BCR-1, BCR-2, BHVO-2, BIR-1a, DTS-1, PCC-1, RGM-2, TML, and W-2a. Comparing this new data with values from published literature enables us to provide consensus or recommended values for U, Th, and 226Ra concentrations and 230Th/232Th ratios for each of these standards. We note that this is the first compilation of recommended radium concentrations for rock standard reference materials. [ABSTRACT FROM AUTHOR]

Abstract A new multi-isotope plutonium standard for isotopic ratio measurements with Accelerator Mass Spectrometry (AMS) was created by gravimetric mixing of different single-isotope standards provided by IRMM (Pu-239, Pu-240, Pu-242, Pu-244). This standard material has been measured at the AMS facilities at Canberra (Australia), Cologne (Germany), Caserta (Italy), Sevilla (Spain) and Zurich (Switzerland). Additionally, the material was characterized using a Neptune MC-ICPMS (multi-collector inductively coupled plasma mass spectrometry) at the joint Cologne-Bonn isotope facility. The results of this laboratory intercomparison are presented and consensus values for the isotope compositions of the standard material are proposed. [ABSTRACT FROM AUTHOR]

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Zirconium plays a major role in geochemistry as it is the major cation of zircons - the oldest preserved minerals on Earth. While Zr isotopic anomalies in meteorites have been widely studied, mass dependant Zr stable isotope fractionation during geological processing has been untouched. Here, we report Zr stable isotopic data for terrestrial igneous rocks and present a novel method for the determination of Zr stable isotope ratios within natural geological materials using ion exchange, double-spike, multiple-collector inductively coupled mass spectrometry (MC-ICPMS). Zirconium is isolated from the rock matrix via a chromatographic separation protocol using a first pass column with AG1-X8 anion exchange resin, and a second pass column containing Eichrom® DGA resin. A 91 Zr– 96 Zr double-spike was created from enriched single 91 Zr and 96 Zr isotope spikes. Samples were combined with the Zr double-spike at a 43:57 spike:sample [Zr] ratio, prior to dissolution and column chemistry. After column chemistry the purified sample solutions were analysed on a Thermo Scientific Neptune Plus MC-ICPMS and the data was reduced using IsoSpike , with the final Zr isotope data being reported as the per mil deviation of the 94 Zr/ 90 Zr from the IPGP-Zr standard (δ 94/90 Zr IPGP-Zr ). The δ 94/90 Zr IPGP-Zr of six igneous standard reference materials: two basalts (BHVO-2 and JB-2), one andesite (AGV-2), two granites (GA and GS-N) and a serpentinite (UB-N) as well as one individual zircon grain (Plešovice zircon), are presented using this method. Sample measurements are presented with an analytical uncertainty of ±~0.05‰ (2 sd ) for δ 94/90 Zr IPGP-Zr and these rocks exhibit isotopic variations of ~0.15‰ for δ 94/90 Zr IPGP-Zr . These results demonstrate that natural variations of Zr isotopes occur within terrestrial igneous rocks, and are resolvable with this method. Finally the variation of δ 94/90 Zr IPGP-Zr values observed within the magmatic rock reference materials is correlated ( R 2  = 0.78; n  = 5) with SiO 2 , suggesting that Zr isotopes could serve as a sensitive tracer of magmatic processes. [ABSTRACT FROM AUTHOR]

Small-scale W isotope variations in ancient and modern terrestrial rocks provide insights into Earth's accretion and early differentiation history as well as the long-term evolution of the Earth's mantle. Tungsten isotope studies on such rocks have exploited advances in mass spectrometry, both NTIMS and MC-ICPMS, which now permit the determination of W isotope ratios at unprecedented precision. While W isotope studies performed in different labs by MC-ICPMS and NTIMS generally exhibit excellent agreement, obtaining accurate W isotope data at this level of precision remains analytically challenging. For example, a recent NTIMS study reported a relatively large, +24 ppm excess in 182 W/ 184 W for a Phanerozoic sample from the Ontong Java Plateau (OJP), but no such 182 W/ 184 W anomaly was found in another study by MC-ICPMS. The present study aims to resolve the discrepancy between these two previous studies, and more generally to evaluate the agreement between different recent W isotope studies by NTIMS and MC-ICPMS. To this end, we report new W isotope data for OJP drill core samples obtained by MC-ICPMS. The OJP samples analyzed here exhibit no resolvable 182 W/ 184 W excess relative to the standards and most terrestrial rocks. Moreover, the OJP samples as well as the terrestrial rock standards analyzed here exhibit small but variable W isotope variations for ratios involving 183 W, producing coupled variations in both ‘radiogenic’ ( i.e. , 182 W/ 183 W) and ‘non-radiogenic’ ( i.e. , 183 W/ 184 W) ratios. These W isotope variations are analytical in origin, induced during sample preparation, and very likely caused by a nuclear field shift isotope fractionation affecting primarily the odd isotope ( 183 W). The recently reported 182 W excess for an OJP sample may result from this nuclear field shift effect, as the NTIMS analyses had to rely on a double normalization involving the 183 W/ 184 W ratio. More generally, these results demonstrate that using 183 W data from any MC-ICPMS or NTIMS study requires a careful quantification of any potential analytical 183 W effect. Nevertheless, once such effects are taken into account, then both 182 W/ 184 W and 183 W/ 184 W can accurately be determined to a very high level of precision. [ABSTRACT FROM AUTHOR]

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100–3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes. [ABSTRACT FROM AUTHOR]

Ambient air particulate matter (< 2.5 μm in diameter) samples were collected on two different filter types in 2014 and 2015 over 24 h periods and analyzed for reactive mercury (gaseous oxidized mercury + particulate bound mercury) concentrations and lead isotopes to determine sources of pollution to three sites in Nevada, USA. Two sites were located on the western edge of Nevada (Reno, urban, 1370 m and Peavine Peak, rural, high elevation, 2515 m); the third location was ~ 485 km east in rural Great Basin National Park, NV (2061 m). Reactive mercury samples were collected on cation exchange membranes simultaneously with lead samples, collected on Teflon membranes. Lead isotopic ratios have previously identified trans-Pacific lead sources based on the 206/207 and 208/207 lead ratios. Influence from trans-Pacific air masses was higher from March to June associated with long-range transport of pollutants. Spring months are well known for increased transport across the Pacific; however, fall months were also influenced by trans-Pacific air masses in this study. Western North American background ozone concentrations have been measured and modeled at 50 to 55 ppbv. Median ozone concentrations at both rural sites in Nevada were within this range. Sources leading to enhancements in ozone of 2 to 18 ppbv above monthly medians in Nevada included emissions from Eurasia, regional urban centers, and global and regional wildfires, resulting in concentrations close to the USA air quality standard. At the high elevation locations, ozone was derived from pollutants being transported in the free troposphere that originate around the globe; however, Eurasia and Asia were dominant sources to the Western USA. Negative correlations between reactive mercury and percent Asian lead, Northern Eurasia and East Asia trajectories indicated reactive mercury concentrations at the two high elevation sites were produced by oxidants from local, regional, and marine boundary layer sources. [ABSTRACT FROM AUTHOR]

High-purity N was used to increase the mobile phase flow rate during ion purification of ion-exchange resin. This was performed to improve the efficiency of isotope separation and purification, and to meet the efficiency requirements of rapid multiple-collector-inductively coupled plasma mass spectrometry (MC-ICPMS) analysis. For Cu isotope separation, our results indicated that at a gas flow rate >60 mL/min, the separation chromatographic peaks broadened and the recovery rate decreased to <99.2%. On the other hand, no significant change in the Cu peaks was observed at a gas flow rate of 20 mL/min and the recovery rate was determined to be >99.9%. The Cu isotope ratio, measured by the standard-sample bracketing method, agreed with reference data within a ±2 SD error range. The separation time was reduced from the traditional 10 h (without N) to 4 h (with N), indicating that the efficiency was more than doubled. Moreover, Sr and Nd isotope separation in AGV-2 (US Geological Survey andesite standard sample) accelerated with a 20 mL/min gas flow, demonstrating that with the passage of N, the purified liquid comprised Rb/Sr and Sm/Nd ratios of <0.000 049 and <0.000 001 5, respectively. This indicated an effective separation of Rb from Sr and Sm from Nd. MC-ICPMS could therefore be applied to accurately determine Sr and Nd isotope ratios. The results afforded were consistent with the reference data within a ±2 SD error range and the total separation time was shortened from 2 d to <10 h. [ABSTRACT FROM AUTHOR]

In this study, a new analytical procedure based on isotachophoresis (ITP) coupled to a multi collector inductively coupled plasma mass spectrometer named Stop-Flow-ITP-MC-ICPMS is developed for exhaustive and high-precision multi-elemental isotopic characterization. We demonstrate that Stop-Flow-ITP makes it possible to stop the analytes migration several times for a duration compatible with the detector configuration changes without losing the separation performance. With this procedure, isotope ratio measurements of four lanthanides of interest for nuclear applications (Nd, Sm, Eu and Gd) were obtained with a reproducibility better than 0.4% in a single analysis with only 20 ng of each element. A nebulization interface between ITP and MC-ICPMS composed of a dual inlet spray chamber and a multiple flow stream valve made it possible to perform isotopic reference standard injections for on-line mass bias correction by the sample standard bracketing approach. The flexibility of the Stop-Flow-ITP-MC-ICPMS procedure opens the way to online determination of isotope ratio measurements of multiple analytes present in a sample in a single analysis. [ABSTRACT FROM AUTHOR]

The Okinawa Trough, a back-arc basin formed by extension within the continental lithosphere, is one of the most significant ocean basins between the East China Sea and the Pacific Ocean. In an attempt to constrain the U content and the 234 U/ 238 U of seawater, five depths vertical seawater profiles from the Okinawa Trough, two from the Indian Ocean and one from the South China Sea were investigated by MC-ICPMS. The method allows us to contribute most reliable uranium isotopic measurement in seawater and greatly reduces sample size. Results showed that the U contents of seawater profiles for Okinawa Trough were from 3.153 to 3.235 ppb, with an average value of 3.186 ± 0.040 (2σ, n = 37), Indian Ocean were from 3.255 to 3.283 ppb with a mean value of 3.272 ± 0.018 (2σ, n = 19), and South China Sea were from 3.253 to 3.271 averaging 3.263 ± 0.018 (2σ, n = 3) ppb. Similarly, we obtained δ 234 U values of 146.1 ± 1.2, 145.1 ± 1.4, and 145.8 ± 0.5‰ for Okinawa Trough, Indian Ocean and South China Sea, with a mean of 145.7 ± 1.0‰, in good agreement with previous reports within the error limits. With two-ml samples in the Okinawa Trough, it gives a mean δ 234 U of 145.8 ± 1.0‰ which is identical to that observed for 7-ml seawater within the 95% confidence level. These results suggest that the distribution of δ 234 U is homogeneous in the Okinawa Trough and followed U conservative behavior. We also obtained average δ 234 U values of 146.9 ± 2.1‰ (2σ, n = 6) for Acropora coral from the Xisha Islands in the South China Sea. All results show no marked differences with the open ocean and provide significant geochemical information for the study of environmental change in the East China Sea. [ABSTRACT FROM AUTHOR]

In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = −13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. [ABSTRACT FROM AUTHOR]

Molluscs incorporate negligible uranium into their skeleton while they are living, with any uranium uptake occurring post-mortem. As such, closed-system U-series dating of molluscs is unlikely to provide reliable age constraints for marine deposits. Even the application of open-system U-series modelling is challenging, because uranium uptake and loss histories can affect time-integrated uranium distributions and are difficult to constrain. We investigate the chemical and isotopic distribution of uranium in fossil Tridacna gigas (giant clams) from Marine Isotope Stage (MIS) 5e (128–116 ka) and MIS 11 (424–374 ka) reefs at Huon Peninsula in Papua New Guinea. The large size of the clams enables detailed chemical and isotopic mapping of uranium using LA-ICPMS and LA-MC-ICPMS techniques. Within each fossil Tridacna specimen, marked differences in uranium concentrations are observed across the three Tridacna growth zones (outer, inner, hinge), with the outer and hinge zones being relatively enriched. In MIS 5e and MIS 11 Tridacna , the outer and hinge zones contain approximately 1 ppm and 5 ppm uranium respectively. In addition to uptake of uranium, loss of uranium appears prevalent, especially in the MIS 11 specimens. The effect of uranium loss is to elevate measured [ 230 Th/ 238 U] values with little effect on [ 234 U/ 238 U] values. Closed-system age estimates are on average 50% too young for the MIS 5e Tridacna, and 25% too young for the MIS 11 Tridacna . A complex, multi-stage uptake and loss history is interpreted for the fossil Tridacna and we demonstrate that they cannot provide independent, reliable geochronological controls on the timing of past reef growth at Huon Peninsula. [ABSTRACT FROM AUTHOR]

Exposure to the neurotoxic element lead (Pb) continues to be a major human health concern, particularly for children in US urban settings, and the need for robust tools for assessment of exposure sources has never been greater. The latest generation of multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) instrumentation offers the capability of using Pb isotopic signatures as a tool for environmental source tracking in public health. We present a case where MC-ICPMS was applied to isotopically resolve Pb sources in human clinical samples. An adult male and his child residing in Milwaukee, Wisconsin, presented to care in August 2015 with elevated blood lead levels (BLLs) (>200 μg/dL for the adult and 10 μg/dL for the child). The adult subject is a gunshot victim who had multiple bullet fragments embedded in soft tissue of his thigh for approximately 10 years. This study compared the high-precision isotopic fingerprints (<1 ‰ 2σ external precision) of Pb in the adult's and child's whole blood (WB) to the following possible Pb sources: a surgically extracted bullet fragment, household paint samples and tap water, and a Pb water-distribution pipe removed from servicing a house in the same neighborhood. Pb in the bullet and adult WB were nearly isotopically indistinguishable (matching within 0.05-0.56 ‰), indicating that bullet fragments embedded in soft tissue could be the cause of both acute and chronic elevated blood Pb levels. Among other sources investigated, no single source dominated the child's exposure profile as reflected in the elevated BLL. [ABSTRACT FROM AUTHOR]

In this work the applicability of Ion Chromatography (IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) for on-line magnesium isotope ratio analysis was explored. Various instrumental setups were employed to enable continuous magnesium separation from the sample matrix by IC followed by MC-ICPMS. The performance of two separation columns IonPac CS16 (ID 5 mm or ID 3 mm) connected with appropriate CERS 500 suppressors (4 mm or 2 mm) using dry and wet plasma conditions was compared. With the use of ID 3 mm column and 2 mm suppressor it was possible to apply dry plasma mode with Aridus II desolvation system. Mass discrimination and instrument drift were corrected by sample-standard bracketing method using the 26 Mg/ 24 Mg isotope ratio of DSM-3 as standard. Good accuracy and high precision of the magnesium isotope ratio (generally 0.15‰ (2 SD)) were achieved for wet and dry plasma modes; both were comparable to off-line Mg separation and continuous measurement. The sensitivity of MC-ICPMS measurements with dry plasma was 25 times higher in comparison to wet plasma conditions. Robustness and applicability of the method was demonstrated for matrix-rich natural water and rock samples magnesium isotope analysis. [ABSTRACT FROM AUTHOR]

Double spiking is conventionally used to make accurate determinations of natural mass-dependent isotopic fractionations for elements with four or more stable isotopes. Here we document a methodology which extends the effective application of double spiking to three isotope systems. This approach requires making a mixture with isotope ratios that lie on a ‘critical curve’ where the sample – double-spike mixing line and the tangent to the instrumental mass-bias curve are coincident. Inversion of the mixing equations for such a mixture leads to a solution for the sample fractionation which is independent (to first order) of the uncertainty in the instrumental mass-bias and, hence, independent of any mass-dependent artefacts in the measurement such as those produced by residual matrix not completely removed by prior chemical purification. In practice, mixtures can be made which yield an accuracy conservatively estimated to be ∼ 0.005‰/amu. The precision of the method is explored as a function of double-spike composition for Mg, Si and K isotope systems. We show that for Mg and Si measurement precision is not compromised by the compositions of viable critical mixtures nor by uncertainty magnification during inversion of the equations. Thus, double spiking provides a valuable means to obtain robust, high precision isotopic measurements of Mg and Si. For K, however, the low abundance of 40 K in the optimal critical mixture places a significant practical limitation on the application of double spiking to analyses of this element. [ABSTRACT FROM AUTHOR]

Using zinc (Zn) and lead (Pb) isotopes is a powerful tool to track metal pollution in environment. In this study we have developed the coupling between DGT passive samplers and multi-collector ICP-MS to measure Pb and Zn isotopic ratios in dilute aqueous solutions. The benefits of this coupling are multiple: the use of DGT device allows achieving an isotopic composition of natural water integrated over time and to pre-concentrate metals in situ. This development will greatly facilitate the field collection of samples and their preparations in cleanroom prior to their isotopic analyses. To test the capability of DGT samplers a series of experiments was achieved in cleanroom and in experimental pilot simulating a water flow. These tests have shown that there is no fractionation of Pb isotopes due to the use of DGT within the reported precision of MC-ICPMS measurements. For Zn, the diffusion process through a membrane, inherent to the use of DGT device, induces a fractionation between the isotopic composition obtained by the DGT and the natural composition. However, this bias can be easily corrected by using a simple relation independent of the time of exposure and the thickness of diffusion layer. The coupling DGT passive samplers and multi-collector ICP-MS is suitable to determine the Pb and Zn isotopic compositions in natural waters and offers new perspectives to track the anthropic pollutions in the hydrosphere. [ABSTRACT FROM AUTHOR]

The high-precision isotopic characterization of actinides and fission products in nuclear samples is fundamental for various applications such as the management of spent nuclear fuel or the validation of neutronic calculation codes. However multi-elemental isotope ratio measurements by mass spectrometric techniques are hampered by the presence of both spectral and non-spectral interferences as complex sample matrices are encountered in such topics, but also due to the lack of high precision mass spectrometers able to cover the entire mass spectrum. This work describes a new LC-MC-ICPMS approach allowing simultaneous high-precision and multi-elemental isotope ratio measurements of four fission products of interest for nuclear issues (Nd, Sm, Eu, Gd) within a single elution run. Variable motorized Faraday cup configurations were successively used during a specifically designed elution procedure in order to take into account the non-natural Nd, Sm, Eu, Gd isotopic compositions encountered in irradiated nuclear samples. This new method, involving the relevant isotopic reference standard injection timings for on-line mass bias corrections, was validated by the analysis of a simulated fission product fraction from a 235 U-irradiated target. Reproducibilities better than 2‰ (k=2), comparable to those obtained by off-line measurements and the classic sample-standard bracketing mass bias correction approach, were obtained for all isotope ratios, except those involving isotopes with a transient signal peak apex lower than 100 mV, for which the reproducibilities were comprised between 2‰ and 6‰. [ABSTRACT FROM AUTHOR]

The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy – hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors – each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96 Zr/ 90 Zr (2 σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support these conclusions but exclude a CI- and enstatite chondrite-like composition for Theia. Thus, the impactor Theia most likely had a Zr isotope composition close to that of the Earth, and this suggests that a large part of the inner solar system (or accretion region of the Earth, Theia and enstatite chondrites) had a uniform Zr isotope composition. [ABSTRACT FROM AUTHOR]

Lead isotope analysis was combined with an investigation of style and technology in a study of pewter mounts from the Viking ship burial at Gokstad, Norway. The different methods reinforced one another and yielded a detailed picture of a ninth-century working process, demonstrating the potential of applying lead isotope analysis to artefact studies independent of the question of provenance. They provided evidence of the mounts being produced as a set, and signs of mixing demonstrate that it is important to be cautious when discussing provenance. England and Melle, France are indicated to be the most likely origin of the lead. [ABSTRACT FROM AUTHOR]

Isotopic compositions of B and Sr in rocks and sediments can be used as tracers for plant provincial sources. This study aims to test whether tea leaf origin can be discriminated using B/B and Sr isotopic composition data, along with concentrations of major/trace elements, in tea specimens collected from major plantation gardens in Taiwan. The tea leaves were digested by microwave and analyzed by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The data showed significant variations in Sr/Sr ratios (from 0.70482 to 0.71462), which reflect changes in soil, groundwater or irrigation conditions. The most radiogenic tea leaves were found at the Taitung garden and the least radiogenic ones were from the Hualien garden. The δB was found to change appreciably ( δB = 0.38-23.73 ‰) which could be due to fertilizers. The maximum δB was also observed in tea samples from the Hualien garden. Principal component analysis combining Sr/Sr, δB and major/trace elements results successfully discriminated different sources of major tea gardens in Taiwan, except the Hualien gardens, and this may be due to rather complicated local geological settings. [ABSTRACT FROM AUTHOR]

Determining the 129I concentration, a long-lived radionuclide present in spent nuclear fuel, is a major issue for nuclear waste disposal purpose. 129I also has to be measured in numerous environmental, nuclear and biological samples. To be able to accurately determine the 129I concentration, an analytical method based on the use of a multicollector-inductively coupled plasma mass spectrometer (MC-ICPMS) combined with an isotope dilution technique using an 127I spike, was developed. First, the influence of different media (HNO3, NaOH and TMAH) on natural 127I signal intensity and stability and on memory effects was studied. Then an analytical procedure was developed by taking into account the correction of blanks and interferences. Tellurium was chosen for instrumental mass bias correction, as no certified standards with suitable 127I/129I ratio are available. Finally, the results, reproducibility and uncertainties obtained for the 129I concentration determined by isotope dilution with a 127I spike are presented and discussed. The final expanded relative uncertainty obtained for the iodine-129 concentration was lower than 0.7% ( k = 1). This precise 129I determination in association with further activity measurements of this nuclide on the same sample will render it possible to determine a new value of the 129I half-life with a reduced uncertainty (0.76%, k = 1). [ABSTRACT FROM AUTHOR]