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Measurements of zirconium isotopes provide insights into the formation of planetary bodies, dating nuclear explosions, or maintenance of nuclear reactors. Although many comparative measurements for the isotopic composition of zirconium have been performed using mass spectrometry, there is a lack of zirconium isotopic reference materials and only a single calibrated measurement has been reported to date by total evaporation thermal ionization mass spectrometry (TE-TIMS). In this study, we report an independent measurement of full zirconium isotopic composition in a new zirconium isotopic reference material by multicollector inductively coupled plasma MS using the regression method and two independent certified isotopic reference materials, NIST SRM 984 Rb and NIST SRM 987 Sr. Our results agree well with the recent TE-TIMS measurements and suggest a revision of the standard atomic weight of zirconium.

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.

230Th/U dating can provide high-precision age constraints on Quaternary hydrothermal sulfides. However, low content of U and Th often involves extraction chemistry for the separation and enrichment of U and Th, but these chemical processes are very complex. We developed a simplified procedure consisting of total sample dissolution and single-column extraction chemistry, which can reduce the time and improve the accuracy of the dating. Concentrated HCl-HF followed by HNO3 was added to ensure complete dissolution. A single column filled with 0.4 mL of AG 1-X8 anion resin was used, then 8 M HNO3, 8 M HCl and 0.1 M HNO3 were used to elute most of the matrix metals, Th and U. This process provided more than 95% recoveries for U and Th, and negligible blanks. Meanwhile, Pb and Bi interferences were tested and showed no effect on the U and Th isotope ratio. The 230Th/238U activity of the Geological Survey of Japan geochemical reference material JZn-1 in secular equilibrium was determined and showed a radioactive equilibrium (1.00 ± 0.01, n = 5, all errors 2σ) and an in-house standard QS-1 was consistent to 0.0078 ± 0.0001 (n = 8, ±2σ) with an average age of 705 ± 10 yrs BP (n = 8, ±2σ). The technique greatly shortens the sample preparation time and allows more concise and effective analysis of U-Th isotopes. It is ideally suited for the high-precision 230Th/U dating of Quaternary submarine hydrothermal sulfides and sulfides from other settings.

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).

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. Supplementary Information The online version contains supplementary material available at 10.1186/s12932-021-00077-z.

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.

The heterogeneity of lead isotope ratios of lead white paints within individual paintings is evaluated. The analyses of five different 17th-century Dutch paintings, sampled in different locations, identifies the presence of isotopic heterogeneity in lead white within a single painting. Pure pigment in the form of cones of 16th-century Venetian lead white, in contrast, was found to be isotopically homogeneous. The study evaluates the origins of the increased heterogeneity of lead isotope ratios in the evolution from the pure pigment to the artwork.

The capabilities of Cu isotope ratio measurements are often restricted by the small volumes of sample available and/or their low Cu concentration. In this work, an analytical approach was developed for performing Cu isotopic analysis via multi-collector ICP-mass spectrometry (MC-ICP-MS) at ultra-trace level using Ga as an internal standard for mass bias correction. The minimum concentration of Cu required for accurate and precise isotope ratio measurements was established to be 20 mu g L-1 with wet plasma conditions and 5 mu g L-1 with dry plasma conditions. The use of Ga as an internal standard for mass bias correction provided several advantages compared to Ni, i.e. improved internal precision on delta Cu-65 values and lower blank levels. Ga can also be used at a 4- fold lower concentration level than Ni. However, in wet plasma conditions, the signals of (ArO2H+)-Ar-36-O-16-H-1 and (ArNO+)-Ar-40-N-15-O-16 interfered with the signals of Ga-69(+) and Ga-71(+), respectively, while in dry plasma conditions, realized by the use of a desolvation unit, Ga-69(+) suffered from spectral interference from (ArN2H+)-Ar-40-N-14-H-1. These interferences were resolved by using medium mass resolution. For validation purposes, the approach was applied to commercially available blood and serum samples. The delta Cu-65 values for the samples measured at a concentration level of 5 mu g L-1 Cu and 5 mu g L-1 Ga using dry plasma conditions were in good agreement with those obtained for isotope ratio measurements at the "standard" concentration level of 200 mu g L-1 Cu and 200 mu g L-1 Ni using wet plasma conditions. In addition, the delta Cu-65 values obtained for micro-samples of serum/blood (volume of 100 mu L) were in good agreement with the corresponding ones obtained using the "standard" volume for isotopic analysis (500 mu L).

New Tl, Pb, and Cd concentration and Tl, Pb isotope data are presented for enstatite as well as L- and LL-type ordinary chondrites, with additional Cd stable isotope results for the former. All three chondrite suites have Tl and Cd contents that vary by more than 1-2 orders of magnitude but Pb concentrations are more uniform, as a result of terrestrial Pb contamination. Model calculations based on Pb isotope compositions indicate that for more than half of the samples, more than 50% of the measured Pb contents are due to addition of modern terrestrial Pb. In part, this is responsible for the relatively young and imprecise Pb-Pb ages determined for EH, L, and LL chondrites, which are hence only of limited chronological utility. In contrast, four particularly pristine EL chondrites define a precise Pb-Pb cooling age of 4559 +/- 6Ma. The enstatite chondrites (ECs) have highly variable epsilon Cd-114/110 of between about +3 and +70 due to stable isotope fractionation from thermal and shock metamorphism. Furthermore, nearly all enstatite meteorites display epsilon Tl-205 values from -3.3 to +0.8, while a single anomalous sample is highly fractionated in both Tl and Cd isotopes. The majority of the ECs thereby define a correlation of epsilon Tl-205 with epsilon Cd-114/110, which suggests that at least some of the Tl isotope variability reflects stable isotope fractionation rather than radiogenic ingrowth of Tl-205 from Pb-205 decay. Considering L chondrites, most epsilon Tl-205 values range between -4 and +1, while two outliers with epsilon Tl-205-10 are indicative of stable isotope fractionation. Considering only those L chondrites which are least likely to feature Pb contamination or stable Tl isotope effects, the results are in accord with the former presence of live Pb-205 on the parent body, with an initial Pb-205/Pb-204=(1.5 +/- 1.4)x10(-4), which suggests late equilibration of the Pb-Tl system 26-113Ma after carbonaceous chondrites (CCs). The LL chondrites display highly variable epsilon Tl-205 values from -12.5 to +14.9, also indicative of stable isotope effects. However, the data for three pristine LL3/LL4 chondrites display an excellent correlation between epsilon Tl-205 and Pb-204/Tl-203. This defines an initial Pb-205/Pb-204 of (1.4 +/- 0.3)x10(-4), equivalent to a Pb-205-Tl-205 cooling age of 55+12/-24Ma (31-67Ma) after CCs.

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%.

Despite the numerous important applications of hafnium isotopes in geological science, and the advances in multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS), hafnium still lacks calibrated measurements of its isotope ratios and, in turn, isotopic abundances and atomic weight. In this study, we determined the isotopic composition of hafnium in four commercial hafnium reagents, including a commonly used hafnium standard (JMC-475) and a NRC candidate isotopic reference material (HALF-1) by MC-ICPMS. The state-of-the-art regression model with NIST SRM 989 isotopic rhenium as calibrator was used to correct instrumental isotopic fractionation without reliance on other hafnium standards, normalizing isotope ratios, or exponential mass-bias fractionation model.

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.

International audience; The ancient rock paintings drawn with ochre on the limestone cliffs at 15 sites in Cangyuan County, in southwestern China, contain more than 1200 identifiable figures. The paintings portray scenes of daily life in a remote mountainous area. The inhabitants probably led a sedentary life of animal herding and cultivation and in the scenes they are engaged in activities such as dancing, hunting and fighting. These rock paintings have been known more than 50 years, and have been registered by the State Council of China as major cultural relics under national protection since 2001, but their ages have remained uncertain. In this study, we carried out MC-ICPMS U-series (n = 57) and AMS 14C (n = 4) dating of the carbonate accretions associated with the rock paintings at eight sites. Among them, 25 samples overlying pigment and 14 samples underlying pigment with insignificant initial 230Th contamination yielded highly precise U-series ages. The samples overlying pigment provided reliable minimum ages of 3760, 2920, 2680 and 1110 yr BP for the dated motifs at Sites 2, 7, 14, and 11, respectively. The age ranges for the underlying carbonate accretions overlap those of the overlying ones, from ~3800 to ~3200 yr BP at Site 2 and from ~3000 to ~2700 yr BP at Site 7, suggesting that rock painting was a long-lasting tradition in this region. The combination of all of the reliable U-series dates enables us to constrain the time interval of the main rock painting phase to ~3800–2700 yr BP, which is coeval with the regional late Neolithic culture.

Increasing numbers of studies use zinc (Zn) and lead (Pb) isotopic compositions to track anthropogenic pollutions in surface water and groundwater. However, given the low content in Pb and Zn in natural waters, we are often restricted for analysis by MC-ICPMS. One solution is to use passive Diffusive Gradients in Thin films (DGT) samplers for in-situ pre-concentration of these metals. The technique of DGT is a useful tool for in situ measurements of metals concentration in surface waters. In these devices, labile fractions of metals are fixedin a layer of chelex resin after diffusion through a polyacrylamide gel. The goal of this study is to validate the use of DGT samplers to determine the isotopic signature of dissolved metals. We focused our work on Zn and Pb isotopic systems. First, this development was tested under laboratory conditions using mineral water (Volvic) spiked in Zn and Pb.The second experiment was performed in 3 PVC columns simulating piezometer systems with 3 different water flow rates (1, 2 and 4 meters/day). Two protocols were used to extract metals from chelex resin: the “classical” protocol in one step and a more recent protocol in three steeps.For Zn isotopes, a fractionation of 0.06‰ between dissolved and adsorbed metal is measured, likely related to diffusion processes. However, in agreement with systematics of diffusion-driven fractionation in solution, this Zn fractionation is systematic, and can therefore be corrected. Despite a recovery yield of 80% the extraction protocol 1, commonly used, does not induce isotopic fractionation. Moreover, this protocol provides a weak amount of metal pollution compared to protocol 2. In the case of Pb, no measurable fractionation could be observed within the reported precision of MC-ICPMS measurements. The tests performed in an experimental system simulating a piezometer suggest that DGT samplers are suitable for studies of the Zn and Pb isotopic composition in water with a low water flow rate.

© 2017 Elsevier B.V. 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.

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 230 Th (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 230 Th/ 238 U measurement performed on a stalagmite from Hϋttenblӓserschachthohle, western Germany, having U concentrations of 2–7 μg g −1 and with 230 Th 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 ( F 1 and F 2 ) for 230 Th/ 238 U and 234 U/ 238 U, 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.

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 40K in the optimal critical mixture places a significant practical limitation on the application of double spiking to analyses of this element.

The copper axe blade discovered in the pile dwelling site of Zug-Riedmatt is one of the few Neolithic copper axe blades in Europe that can be dated with certainty. The blade’s form and its metal composition suggest that it is connected both to the south – more specifically to Copper Age cultures in northern Italy and southern Tuscany – and to the copper axe of the famous ice mummy of Tisenjoch (called ‘the Iceman’ or ‘Ötzi’). We were able to confirm this connection to the south by measuring the lead isotope composition of the blade, which traces the blade’s origin to Southern Tuscany. Due to these links to the south, the copper axe blade of Zug-Riedmatt can be described as a key to understanding Neolithic metallurgy north of the Alps in the second half of the fourth millennium BC. As the classification of the blade will have far-reaching consequences in regard to chronology and cultural history, we have decided to make the results of our analyses available as quickly as possible – even if this means that for now we can only discuss some basic results and assumptions about the blade’s context., Archäologische Informationen, Bd. 40 (2017): Archäologische Informationen

An interdisciplinary study, involving geologists, chemists and pedologists, started aiming at identifying a "Geo-Pedo-Fingerprint" (GPF) univocally linking the wine to its origin, namely, the Piedirosso vineyards growing in the Campi Flegrei volcanic area. The focal point of this research was the characterization of the whole parent material-soil-vineyard-wine system, achieved by correlating the elemental pattern - with special reference to micro-nutrients and Rare Earth Elements (REEs) - and Sr isotopic ratios, to identify a reliable and convenient 'GPF', as a guaranteed indicator of wine provenance. A representative soil/Piedirosso vineyard system was identified and characterized. Samples from each soil horizon as well as from vine branches, leaves, grapes and wine were collected and analyzed. All samples were analyzed by multi-collector inductively coupled mass spectrometry (MC-ICPMS) to determine their 87Sr/86Sr isotopic composition, by ICP-Quadrupole MS to measure multi-elemental composition including REE, and by X-Ray Powder Diffraction (XRPD) for the quantitative evaluation of the mineral phases occurring in soil samples.Statistical analysis (Hierarchical Cluster Analysis, Factor Analysis) revealed the existence of separate correlations of element distribution between: i) soil, as nutrient pool source, and vegetative compartments, i.e. branches and leaves, as biochemical yards for nutrient elaboration and marshaling, ii) vegetative compartments and the productive compartment, i.e. grapes as the metabolic outcome of the vine, and, iii) the productive compartment and its artifact produced by man, i.e. wine. However, no sequential correlation of elements from soil to wine did appear, likely because clusters of elements were discriminated due to the varying takeup and fractionation processes in plants, as well as during vinification processes. Therefore, none of the investigated elements was a liable 'GPF' as a candidate tracer from soil to wine.In contrast, the use of a petrogenetic tracer such as 87Sr/86Sr isotopic composition provided satisfactory responses. In fact, the values of such a ratio within the entire studied chain vary in a very small range from 0.7076 to 0.7084, thus falling within the typical range for volcanites of Campi Flegrei (0.7065-0.7086). These results currently represent the only study focusing on a geotracer, such as the 87Sr/86Sr isotopic ratio, linked with a pedological survey to identify the volcanic Campanian wine-producing chains from soil parent material-to-wine. © 2013 Elsevier B.V.

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 96Zr/90Zr (2σ 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. ISSN:0012-821X ISSN:1385-013X

International audience

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.

International audience; In the general frameworks of the nuclear fuel cycle and environmental research field, the Cs isotopic composition must be known with high precision and accuracy. The direct determination of Cs isotopes by mass spectrometry techniques is generally hampered by the presence of Ba isobaric interferences however. Here we present a new method which takes advantage of the collision-reaction cell based Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) and allows to analyse Cs isotopes in the presence of Ba without prior separation step. The addition of N2O gas in the cell leads to an antagonistic behavior of Cs+ and Ba+ as the latter reacts with the gas to form BaO+ and BaOH+ products whereas Cs+ remains unreactive. The efficiency of the method was demonstrated for an UOx sample by comparing the results obtained (1) from the measurements of pure Cs fractions and (2) from Fission Products fractions containing more than 30 ionisable elements in addition to Cs, Ba, and where U and Pu were previously removed by using ion exchange resin. An excellent agreement is achieved between each set of experiments with an external reproducibility always better than 0.5% (RSD, k=2). This study confirms the strong potential of collision–reaction cell to measure Cs isotopes in presence of interfering Ba, precluding therefore former systematic chemical separations.

This paper reviews the problems encountered in eleven studies of Sr isotope analysis using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) in the period 1995-2006. This technique has been shown to have great potential, but the accuracy and precision are limited by: (1) large instrumental mass discrimination, (2) laser-induced isotopic and elemental fractionations and (3) molecular interferences. The most important isobaric interferences are Kr and Rb, whereas Ca dimer/argides and doubly charged rare earth elements (REE) are limited to sample materials which contain substantial amounts of these elements. With modern laser (193 nm) and MC-ICPMS equipment, minerals with500 ppm Sr content can be analysed with a precision of better than 100 ppm and a spatial resolution (spot size) of approximately 100 microm. The LA MC-ICPMS analysis of 87Sr/86Sr of both carbonate material and plagioclase is successful in all reported studies, although the higher 84Sr/86Sr ratios do suggest in some cases an influence of Ca dimer and/or argides. High Rb/Sr (0.01) materials have been successfully analysed by carefully measuring the 85Rb/87Rb in standard material and by applying the standard-sample bracketing method for accurate Rb corrections. However, published LA-MC-ICPMS data on clinopyroxene, apatite and sphene records differences when compared with 87Sr/86Sr measured by thermal ionisation mass spectrometry (TIMS) and solution MC-ICPMS. This suggests that further studies are required to ensure that the most optimal correction methods are applied for all isobaric interferences.

Engineered CeO2 nanoparticles (NPs) are becoming increasingly prevalent in consumer products and this has raised concerns about the unknown behaviour and fate of such materials in the environment. Analytical limitations have hampered the detection of CeO2 NPs in natural systems at environmentally relevant levels. This study presents data on the inherent stable isotope composition of commercially available purified Ce materials with a particular focus on CeO2 NPs. The aim of this investigation is to determine whether CeO2 NPs posses a distinct isotopic signature that may be exploited for their detection in natural systems. To achieve this, suitable stable isotope measurement protocols were developed for the precise determination of the 142Ce/140Ce isotope ratio by multiple collector ICP-MS using Ba for external normalisation of the instrumental mass bias. The data presented show that precisions of ±0.01‰ (2se) and ±0.04‰ (2sd) can be routinely achieved with these techniques. The results also demonstrate that commercially available CeO2 NPs do not have a distinct Ce isotope composition that may be exploited for the purpose of stable isotope tracing.

International audience; To improve the precision of isotope analyses of low ion intensities using the Faraday detection system, amplifiers equipped with 10(12) Omega resistors (hereafter 10(12) Omega amplifiers) have been developed. While the behavior of these amplifiers for steady signals has been well investigated, there is no ample evidence regarding the use of 10(12) Omega amplifiers for transient signal acquisition. In this work, we investigated the simultaneous use of amplifiers equipped with 10(12) Omega and 10(11) Omega resistors for transient signal acquisition. Using the equation describing the relationship between the input ion current and the output voltage in the amplifiers, we showed how the transient signal duration influences the accuracy of the isotope ratio measurements. In particular, lead transient signals were investigated using a Neptune Plus MC-ICPMS and Pb-204 and Pb-206 isotopes were measured using 10(12) Omega and 10(11) Omega amplifiers, respectively. The Pb-204/Pb-206 isotope ratio showed an important drift due to a large time lag between 10(12) Omega and 10(11) Omega amplifiers. The time lag was quantified (0.175(3) s) and the isotopic drift was corrected using a method of internal signal synchronization. The Pb-204/Pb-206 drift corrected data obtained from the 10(12)-10(11) Omega amplifier configuration were compared to the data obtained from 10(11)-10(11) Omega amplifiers. Our results point out that for low transient signal intensities (

The 182Hf-182W chronometer and, more generally, tungsten (W) isotopes are commonly used to address several scientific problems in cosmochemistry and, more recently, in geochemistry. They are, for instance, very useful tools for dating the first stages of our solar system history (radiochronometer), but also for studying the effects of galactic cosmic rays interacting with planetary or asteroidal surfaces (cosmogenic effects), or for glancing at the stellar environment of our nascent solar system (nucleosynthetic anomalies). On Earth, they have recently been used to test the Late Veneer hypothesis and to look for geochemical signatures dating back from before this late event. All these scientific problems use isotope signatures that are called “mass-independent” because they affect more some isotopes than others, independently of their masses.In this work, I propose new applications for the W isotopes system. I present an innovative method for measuring the “mass-dependent” fractionation of W stable isotopes, i.e. the fractionation induced by geological processes on asteroids, planetesimals, planets and their natural satellites, or in terrestrial environments: melting, crystallization, metamorphism, alteration, hydrothermal fluid circulations, contamination, mixing and much more.This new approach has been applied to a series of terrestrial and extraterrestrial samples (ordinary and carbonaceous chondrites, eucrites, iron meteorites). The measured isotope compositions range from -0,03 to +0,57 ‰ par atomic mass unit. It seems that alteration processes disturb the 182Hf-182W clock. As a consequence, 182Hf-182W ages measured on extensively altered samples could be apparent ages and have no chronological meaning.In order to better understand the effects of aqueous alteration on the H-W system, we set up a series of experiments in which we simulated the lixiviation of terrestrial samples (lherzolite and dunite) under controlled atmosphere, in both closed and semi-opened systems. These experiments were compared with PHREEQC geochemical modeling results. Experiments show a significant difference between the behaviors of Hf and W in solution, W being much more mobile than Hf. This is in line with our observations on altered carbonaceous chondrites: alteration may fractionate the Hf/W ratio, thus disturbing the Hf-W system and its associated radiochronometer.Having shown the effects of aqueous alteration on the Hf-W system, we chose to study an unaltered CR chondrite: these samples are of high interest for our knowledge of the early solar system, as they are considered as very pristine while presenting some clues of the earliest steps of differentiation. We studied the Tafassasset meteorite, generally considered as an anomalous and unaltered CR chondrite. We combined various analyses on this sample: 182Hf-182W chronology, micro-tomography, mineralogy and modeling of the thermal evolution of its parent body. This meteorite happened to be a partially differentiated primitive achondrite that accreted early in our solar system history, ca. one million years after CAIs.; Le chronomètre 182Hf-182W (hafnium-tungstène) et les isotopes du tungstène (W) sont aujourd’hui couramment utilisés en cosmochimie, et de plus en plus en géochimie. Ils servent notamment à dater les premières étapes de formation de notre système solaire (radiochronomètre), mais aussi à étudier l’effet des rayonnements cosmiques sur la matière (effets cosmogéniques) ou encore à retracer l’environnement stellaire de notre soleil au moment de sa formation (anomalies nucléosynthétiques). Sur Terre, ils sont utilisés depuis peu pour tester l’hypothèse du « Late Veneer » (vernis tardif) et pour rechercher des signatures géochimiques datant d’avant ce vernis tardif. Toutes ces signatures isotopiques sont dites « indépendantes de la masse » parce qu’elles affectent plus ou moins les différents isotopes, sans lien avec leurs écarts de masses.Ce travail propose une nouvelle application de l’analyse des isotopes du W. Une méthode analytique innovante est présentée pour le fractionnement « dépendant de la masse », c’est-à-dire le fractionnement des isotopes stables induit par les processus géologiques sur les astéroïdes, les planétésimaux, les planètes et leurs satellites naturels ou encore dans les environnements terrestres : fusion, cristallisation, métamorphisme, altération, hydrothermalisme, contamination, mélanges et bien d’autres.Le fractionnement des isotopes stables du W a été mesuré pour une série d’échantillons terrestres et surtout extraterrestres (chondrites ordinaires, chondrites carbonées, eucrites, météorites de fer). La gamme de variations observées va de -0,03 à +0,57 ‰ par unité de masse atomique. Nous avons mis en évidence que l’altération perturbait le chronomètre 182Hf-182W, les âges des échantillons altérés pouvant n’être que des âges apparents.De façon à mieux comprendre l’effet de l’altération sur le système Hf-W, nous avons mis en place des expériences de lixiviation de roches terrestres (lherzolite et dunite) sous atmosphère contrôlée, en système fermé et en système semi-ouvert. Nous avons complété ces expérimentations par des modélisations numériques à l’aide du logiciel PHREEQC. Les expériences montrent une grande différence de comportement de l’Hf par rapport au W en solution, confortant ce qui avait été observé dans les météorites : le W est beaucoup plus mobile que le Hf, ce qui fractionne le rapport Hf/W de l’échantillon. Ainsi, l’altération perturbe le système Hf-W et le radio-chronomètre associé.Enfin, ayant constaté ces effets de l’altération, nous avons choisi d’étudier une chondrite CR non altérée. En effet ces échantillons sont considérés comme parmi les plus primitifs du système solaire, et présentent des indices d’un début de différenciation. Nous avons donc étudié en détail la météorite de Tafassasset, une CR anormale, non altérée mais très métamorphisée, sur laquelle nous avons réalisé un ensemble d’analyses (182Hf-182W, minéralogie, micro-tomographie X, modélisation de l’évolution du corps parent). Cette météorite s’est révélée être en fait une achondrite primitive partiellement différenciée, et formée très précocement dans l’histoire du système solaire : elle s’est accrétée ~1 Ma après la formation des CAI.

The 182Hf-182W chronometer and, more generally, tungsten (W) isotopes are commonly used to address several scientific problems in cosmochemistry and, more recently, in geochemistry. They are, for instance, very useful tools for dating the first stages of our solar system history (radiochronometer), but also for studying the effects of galactic cosmic rays interacting with planetary or asteroidal surfaces (cosmogenic effects), or for glancing at the stellar environment of our nascent solar system (nucleosynthetic anomalies). On Earth, they have recently been used to test the Late Veneer hypothesis and to look for geochemical signatures dating back from before this late event. All these scientific problems use isotope signatures that are called “mass-independent” because they affect more some isotopes than others, independently of their masses.In this work, I propose new applications for the W isotopes system. I present an innovative method for measuring the “mass-dependent” fractionation of W stable isotopes, i.e. the fractionation induced by geological processes on asteroids, planetesimals, planets and their natural satellites, or in terrestrial environments: melting, crystallization, metamorphism, alteration, hydrothermal fluid circulations, contamination, mixing and much more.This new approach has been applied to a series of terrestrial and extraterrestrial samples (ordinary and carbonaceous chondrites, eucrites, iron meteorites). The measured isotope compositions range from -0,03 to +0,57 ‰ par atomic mass unit. It seems that alteration processes disturb the 182Hf-182W clock. As a consequence, 182Hf-182W ages measured on extensively altered samples could be apparent ages and have no chronological meaning.In order to better understand the effects of aqueous alteration on the H-W system, we set up a series of experiments in which we simulated the lixiviation of terrestrial samples (lherzolite and dunite) under controlled atmosphere, in both closed and semi-opened systems. These experiments were compared with PHREEQC geochemical modeling results. Experiments show a significant difference between the behaviors of Hf and W in solution, W being much more mobile than Hf. This is in line with our observations on altered carbonaceous chondrites: alteration may fractionate the Hf/W ratio, thus disturbing the Hf-W system and its associated radiochronometer.Having shown the effects of aqueous alteration on the Hf-W system, we chose to study an unaltered CR chondrite: these samples are of high interest for our knowledge of the early solar system, as they are considered as very pristine while presenting some clues of the earliest steps of differentiation. We studied the Tafassasset meteorite, generally considered as an anomalous and unaltered CR chondrite. We combined various analyses on this sample: 182Hf-182W chronology, micro-tomography, mineralogy and modeling of the thermal evolution of its parent body. This meteorite happened to be a partially differentiated primitive achondrite that accreted early in our solar system history, ca. one million years after CAIs.; Le chronomètre 182Hf-182W (hafnium-tungstène) et les isotopes du tungstène (W) sont aujourd’hui couramment utilisés en cosmochimie, et de plus en plus en géochimie. Ils servent notamment à dater les premières étapes de formation de notre système solaire (radiochronomètre), mais aussi à étudier l’effet des rayonnements cosmiques sur la matière (effets cosmogéniques) ou encore à retracer l’environnement stellaire de notre soleil au moment de sa formation (anomalies nucléosynthétiques). Sur Terre, ils sont utilisés depuis peu pour tester l’hypothèse du « Late Veneer » (vernis tardif) et pour rechercher des signatures géochimiques datant d’avant ce vernis tardif. Toutes ces signatures isotopiques sont dites « indépendantes de la masse » parce qu’elles affectent plus ou moins les différents isotopes, sans lien avec leurs écarts de masses.Ce travail propose une nouvelle application de l’analyse des isotopes du W. Une méthode analytique innovante est présentée pour le fractionnement « dépendant de la masse », c’est-à-dire le fractionnement des isotopes stables induit par les processus géologiques sur les astéroïdes, les planétésimaux, les planètes et leurs satellites naturels ou encore dans les environnements terrestres : fusion, cristallisation, métamorphisme, altération, hydrothermalisme, contamination, mélanges et bien d’autres.Le fractionnement des isotopes stables du W a été mesuré pour une série d’échantillons terrestres et surtout extraterrestres (chondrites ordinaires, chondrites carbonées, eucrites, météorites de fer). La gamme de variations observées va de -0,03 à +0,57 ‰ par unité de masse atomique. Nous avons mis en évidence que l’altération perturbait le chronomètre 182Hf-182W, les âges des échantillons altérés pouvant n’être que des âges apparents.De façon à mieux comprendre l’effet de l’altération sur le système Hf-W, nous avons mis en place des expériences de lixiviation de roches terrestres (lherzolite et dunite) sous atmosphère contrôlée, en système fermé et en système semi-ouvert. Nous avons complété ces expérimentations par des modélisations numériques à l’aide du logiciel PHREEQC. Les expériences montrent une grande différence de comportement de l’Hf par rapport au W en solution, confortant ce qui avait été observé dans les météorites : le W est beaucoup plus mobile que le Hf, ce qui fractionne le rapport Hf/W de l’échantillon. Ainsi, l’altération perturbe le système Hf-W et le radio-chronomètre associé.Enfin, ayant constaté ces effets de l’altération, nous avons choisi d’étudier une chondrite CR non altérée. En effet ces échantillons sont considérés comme parmi les plus primitifs du système solaire, et présentent des indices d’un début de différenciation. Nous avons donc étudié en détail la météorite de Tafassasset, une CR anormale, non altérée mais très métamorphisée, sur laquelle nous avons réalisé un ensemble d’analyses (182Hf-182W, minéralogie, micro-tomographie X, modélisation de l’évolution du corps parent). Cette météorite s’est révélée être en fait une achondrite primitive partiellement différenciée, et formée très précocement dans l’histoire du système solaire : elle s’est accrétée ~1 Ma après la formation des CAI.

The 182Hf-182W chronometer and, more generally, tungsten (W) isotopes are commonly used to address several scientific problems in cosmochemistry and, more recently, in geochemistry. They are, for instance, very useful tools for dating the first stages of our solar system history (radiochronometer), but also for studying the effects of galactic cosmic rays interacting with planetary or asteroidal surfaces (cosmogenic effects), or for glancing at the stellar environment of our nascent solar system (nucleosynthetic anomalies). On Earth, they have recently been used to test the Late Veneer hypothesis and to look for geochemical signatures dating back from before this late event. All these scientific problems use isotope signatures that are called “mass-independent” because they affect more some isotopes than others, independently of their masses.In this work, I propose new applications for the W isotopes system. I present an innovative method for measuring the “mass-dependent” fractionation of W stable isotopes, i.e. the fractionation induced by geological processes on asteroids, planetesimals, planets and their natural satellites, or in terrestrial environments: melting, crystallization, metamorphism, alteration, hydrothermal fluid circulations, contamination, mixing and much more.This new approach has been applied to a series of terrestrial and extraterrestrial samples (ordinary and carbonaceous chondrites, eucrites, iron meteorites). The measured isotope compositions range from -0,03 to +0,57 ‰ par atomic mass unit. It seems that alteration processes disturb the 182Hf-182W clock. As a consequence, 182Hf-182W ages measured on extensively altered samples could be apparent ages and have no chronological meaning.In order to better understand the effects of aqueous alteration on the H-W system, we set up a series of experiments in which we simulated the lixiviation of terrestrial samples (lherzolite and dunite) under controlled atmosphere, in both closed and semi-opened systems. These experiments were compared with PHREEQC geochemical modeling results. Experiments show a significant difference between the behaviors of Hf and W in solution, W being much more mobile than Hf. This is in line with our observations on altered carbonaceous chondrites: alteration may fractionate the Hf/W ratio, thus disturbing the Hf-W system and its associated radiochronometer.Having shown the effects of aqueous alteration on the Hf-W system, we chose to study an unaltered CR chondrite: these samples are of high interest for our knowledge of the early solar system, as they are considered as very pristine while presenting some clues of the earliest steps of differentiation. We studied the Tafassasset meteorite, generally considered as an anomalous and unaltered CR chondrite. We combined various analyses on this sample: 182Hf-182W chronology, micro-tomography, mineralogy and modeling of the thermal evolution of its parent body. This meteorite happened to be a partially differentiated primitive achondrite that accreted early in our solar system history, ca. one million years after CAIs.; Le chronomètre 182Hf-182W (hafnium-tungstène) et les isotopes du tungstène (W) sont aujourd’hui couramment utilisés en cosmochimie, et de plus en plus en géochimie. Ils servent notamment à dater les premières étapes de formation de notre système solaire (radiochronomètre), mais aussi à étudier l’effet des rayonnements cosmiques sur la matière (effets cosmogéniques) ou encore à retracer l’environnement stellaire de notre soleil au moment de sa formation (anomalies nucléosynthétiques). Sur Terre, ils sont utilisés depuis peu pour tester l’hypothèse du « Late Veneer » (vernis tardif) et pour rechercher des signatures géochimiques datant d’avant ce vernis tardif. Toutes ces signatures isotopiques sont dites « indépendantes de la masse » parce qu’elles affectent plus ou moins les différents isotopes, sans lien avec leurs écarts de masses.Ce travail propose une nouvelle application de l’analyse des isotopes du W. Une méthode analytique innovante est présentée pour le fractionnement « dépendant de la masse », c’est-à-dire le fractionnement des isotopes stables induit par les processus géologiques sur les astéroïdes, les planétésimaux, les planètes et leurs satellites naturels ou encore dans les environnements terrestres : fusion, cristallisation, métamorphisme, altération, hydrothermalisme, contamination, mélanges et bien d’autres.Le fractionnement des isotopes stables du W a été mesuré pour une série d’échantillons terrestres et surtout extraterrestres (chondrites ordinaires, chondrites carbonées, eucrites, météorites de fer). La gamme de variations observées va de -0,03 à +0,57 ‰ par unité de masse atomique. Nous avons mis en évidence que l’altération perturbait le chronomètre 182Hf-182W, les âges des échantillons altérés pouvant n’être que des âges apparents.De façon à mieux comprendre l’effet de l’altération sur le système Hf-W, nous avons mis en place des expériences de lixiviation de roches terrestres (lherzolite et dunite) sous atmosphère contrôlée, en système fermé et en système semi-ouvert. Nous avons complété ces expérimentations par des modélisations numériques à l’aide du logiciel PHREEQC. Les expériences montrent une grande différence de comportement de l’Hf par rapport au W en solution, confortant ce qui avait été observé dans les météorites : le W est beaucoup plus mobile que le Hf, ce qui fractionne le rapport Hf/W de l’échantillon. Ainsi, l’altération perturbe le système Hf-W et le radio-chronomètre associé.Enfin, ayant constaté ces effets de l’altération, nous avons choisi d’étudier une chondrite CR non altérée. En effet ces échantillons sont considérés comme parmi les plus primitifs du système solaire, et présentent des indices d’un début de différenciation. Nous avons donc étudié en détail la météorite de Tafassasset, une CR anormale, non altérée mais très métamorphisée, sur laquelle nous avons réalisé un ensemble d’analyses (182Hf-182W, minéralogie, micro-tomographie X, modélisation de l’évolution du corps parent). Cette météorite s’est révélée être en fait une achondrite primitive partiellement différenciée, et formée très précocement dans l’histoire du système solaire : elle s’est accrétée ~1 Ma après la formation des CAI.

The 182Hf-182W chronometer and, more generally, tungsten (W) isotopes are commonly used to address several scientific problems in cosmochemistry and, more recently, in geochemistry. They are, for instance, very useful tools for dating the first stages of our solar system history (radiochronometer), but also for studying the effects of galactic cosmic rays interacting with planetary or asteroidal surfaces (cosmogenic effects), or for glancing at the stellar environment of our nascent solar system (nucleosynthetic anomalies). On Earth, they have recently been used to test the Late Veneer hypothesis and to look for geochemical signatures dating back from before this late event. All these scientific problems use isotope signatures that are called “mass-independent” because they affect more some isotopes than others, independently of their masses.In this work, I propose new applications for the W isotopes system. I present an innovative method for measuring the “mass-dependent” fractionation of W stable isotopes, i.e. the fractionation induced by geological processes on asteroids, planetesimals, planets and their natural satellites, or in terrestrial environments: melting, crystallization, metamorphism, alteration, hydrothermal fluid circulations, contamination, mixing and much more.This new approach has been applied to a series of terrestrial and extraterrestrial samples (ordinary and carbonaceous chondrites, eucrites, iron meteorites). The measured isotope compositions range from -0,03 to +0,57 ‰ par atomic mass unit. It seems that alteration processes disturb the 182Hf-182W clock. As a consequence, 182Hf-182W ages measured on extensively altered samples could be apparent ages and have no chronological meaning.In order to better understand the effects of aqueous alteration on the H-W system, we set up a series of experiments in which we simulated the lixiviation of terrestrial samples (lherzolite and dunite) under controlled atmosphere, in both closed and semi-opened systems. These experiments were compared with PHREEQC geochemical modeling results. Experiments show a significant difference between the behaviors of Hf and W in solution, W being much more mobile than Hf. This is in line with our observations on altered carbonaceous chondrites: alteration may fractionate the Hf/W ratio, thus disturbing the Hf-W system and its associated radiochronometer.Having shown the effects of aqueous alteration on the Hf-W system, we chose to study an unaltered CR chondrite: these samples are of high interest for our knowledge of the early solar system, as they are considered as very pristine while presenting some clues of the earliest steps of differentiation. We studied the Tafassasset meteorite, generally considered as an anomalous and unaltered CR chondrite. We combined various analyses on this sample: 182Hf-182W chronology, micro-tomography, mineralogy and modeling of the thermal evolution of its parent body. This meteorite happened to be a partially differentiated primitive achondrite that accreted early in our solar system history, ca. one million years after CAIs.; Le chronomètre 182Hf-182W (hafnium-tungstène) et les isotopes du tungstène (W) sont aujourd’hui couramment utilisés en cosmochimie, et de plus en plus en géochimie. Ils servent notamment à dater les premières étapes de formation de notre système solaire (radiochronomètre), mais aussi à étudier l’effet des rayonnements cosmiques sur la matière (effets cosmogéniques) ou encore à retracer l’environnement stellaire de notre soleil au moment de sa formation (anomalies nucléosynthétiques). Sur Terre, ils sont utilisés depuis peu pour tester l’hypothèse du « Late Veneer » (vernis tardif) et pour rechercher des signatures géochimiques datant d’avant ce vernis tardif. Toutes ces signatures isotopiques sont dites « indépendantes de la masse » parce qu’elles affectent plus ou moins les différents isotopes, sans lien avec leurs écarts de masses.Ce travail propose une nouvelle application de l’analyse des isotopes du W. Une méthode analytique innovante est présentée pour le fractionnement « dépendant de la masse », c’est-à-dire le fractionnement des isotopes stables induit par les processus géologiques sur les astéroïdes, les planétésimaux, les planètes et leurs satellites naturels ou encore dans les environnements terrestres : fusion, cristallisation, métamorphisme, altération, hydrothermalisme, contamination, mélanges et bien d’autres.Le fractionnement des isotopes stables du W a été mesuré pour une série d’échantillons terrestres et surtout extraterrestres (chondrites ordinaires, chondrites carbonées, eucrites, météorites de fer). La gamme de variations observées va de -0,03 à +0,57 ‰ par unité de masse atomique. Nous avons mis en évidence que l’altération perturbait le chronomètre 182Hf-182W, les âges des échantillons altérés pouvant n’être que des âges apparents.De façon à mieux comprendre l’effet de l’altération sur le système Hf-W, nous avons mis en place des expériences de lixiviation de roches terrestres (lherzolite et dunite) sous atmosphère contrôlée, en système fermé et en système semi-ouvert. Nous avons complété ces expérimentations par des modélisations numériques à l’aide du logiciel PHREEQC. Les expériences montrent une grande différence de comportement de l’Hf par rapport au W en solution, confortant ce qui avait été observé dans les météorites : le W est beaucoup plus mobile que le Hf, ce qui fractionne le rapport Hf/W de l’échantillon. Ainsi, l’altération perturbe le système Hf-W et le radio-chronomètre associé.Enfin, ayant constaté ces effets de l’altération, nous avons choisi d’étudier une chondrite CR non altérée. En effet ces échantillons sont considérés comme parmi les plus primitifs du système solaire, et présentent des indices d’un début de différenciation. Nous avons donc étudié en détail la météorite de Tafassasset, une CR anormale, non altérée mais très métamorphisée, sur laquelle nous avons réalisé un ensemble d’analyses (182Hf-182W, minéralogie, micro-tomographie X, modélisation de l’évolution du corps parent). Cette météorite s’est révélée être en fait une achondrite primitive partiellement différenciée, et formée très précocement dans l’histoire du système solaire : elle s’est accrétée ~1 Ma après la formation des CAI.

The Loire River in Central France is approximately 1010 km long and drains an area of 117 800 km2. Upstream, the Loire river flows following a south to north direction from the Massif Central down to the city of Orléans, 650 km from its source. The Loire River is one of the main European riverine inputs to the Atlantic Ocean. Over time, its basin has been exposed to numerous sources of anthropogenic metal pollutions, such as metal mining, food industry, agriculture and domestic inputs. The Loire River basin is thus an excellent study site to develop new isotope systematics for tracking anthropogenic sources of metal pollutions. We have chosen to analyze the isotope composition of cadmium (Cd), zinc (Zn), mercury (Hg) and lead (Pb). These heavy metals have been chosen for their toxicity, even at low levels, to humans. The main goal of this study is to characterize 1) the sources and behavior of these heavy metals in the aquatic environment, and 2) their spatial distribution using a multi-isotope approach. Sources responsible for the release of Pb-Zn-Cd-Hg in the Loire basin were sampled and analysed for their concentrations and corresponding isotope compositions. We also analyzed river waters and suspended solids samples, known to play an important role in the transport of heavy metals through river systems. Biota samples (mussels, oysters), as natural accumulators of metal pollutants, were also analyzed. All trace elements were analysed in the BRGM laboratories using a Q-ICPMS. Pb-Zn-Cd isotope compositions were measured using a Neptune MC-ICPMS at the BRGM. Hg isotope compositions were measured at the U. of Illinois using a Nu Plasma MC-ICPMS. To analyse Zn and Cd, we carried out a two-steps analytical development: 1) a chromatographic separation, followed by 2) analysis on the MC-ICPMS. The results showed that, on their own, each of these isotope systematics reveals important information about the geogenic or anthropogenic origin of these metals. Considered together, they are however providing a more integrated understanding of the overall budgets of these pollutants at the scale of the Loire River Basin.

International audience; Estimating global fluxes of precious metals is key to understanding early monetary systems. This work adds silver (Ag) to the metals (Pb and Cu) used so far to trace the provenance of coinage through variations in isotopic abundances. Silver, copper, and lead isotopes were measured in 91 coins from the East Mediterranean Antiquity and Roman world, medieval western Europe, 16th-18th century Spain, Mexico, and the Andes and show a great potential for provenance studies. Pre-1492 European silver can be distinguished from Mexican and Andean metal. European silver dominated Spanish coinage until Philip III, but had, 80 y later after the reign of Philip V, been flushed from the monetary mass and replaced by Mexican silver.

von Patrick Galler Zsfassung in dt. Sprache Wien, Univ. für Bodenkultur, Diss., 2008

Massenabhängige Variationen der Cd Isotopenzusammensetzung in Gesteinen und Steinmeteoriten wurden mit MC-ICPMS (multiple collector inductively coupled plasma mass spectrometry) präzise und akkurat bestimmt. Aus den Daten ergibt sich, dass anorganische geologische Prozesse, im Gegensatz zu Verdampfungs- und Kondensationsprozessen, nicht zu grossen Cd Isotopenfraktionierungen führen. Messungen an primitiven und differenzierten Steinmeteoriten ermöglichten daher neue Einblicke in Verdampfungs- und Kondensationsprozesse bei der Entstehung des Sonnensystems. Anhand von Cd Verdampfungsexperimenten wird gezeigt, dass präzise Messungen von Massenabhängigkeiten Aussagen über Fraktionierungsmechanismen erlauben. Durch die Auswertung von Nd Isotopendaten zeigte sich, dass die instrumentelle Massendiskriminierung mit dem ?generalized power law? präzise beschrieben werden kann.

The need for performing isotope ratio measurements by MC-ICPMS on samples only available in small sizes and not allowing any dilution requires the development of sample introduction systems that can run below 10 μL min−1 sample flow rate (continuous mode). With a torch integrated sample introduction system (TISIS), optimisation of the running conditions involves the study of the temperature of the spray chamber (TSC). This paper investigates the consequences of changing TSC up to 100 °C and the sample flow rate down to 5 μL min−1 on mass discrimination effects. The validity of the exponential model commonly used to correct for these effects was tested for strontium isotopic measurements. Two categories of processes favouring the heaviest isotopes were envisaged: at plasma stage – “mechanism 1”, and within the ion beam – “mechanism 2”. The extraction potential applied inside the interface (HV1) was progressively increased, and results obtained for a range of approximately ±5 to 6 V around HV1 = 4004 V at 15 μL min−1 and TSC = 40 °C were used as reference. The intensity of mass discrimination effects increased at 15 μL min−1 and TSC = 60 or 100 °C, and decreased at 5 μL min−1 and TSC = 40 °C. At TSC = 100 °C (15 μL min−1) or at 5 μL min−1 (TSC = 40 °C) the stability of mass discrimination effects and the average efficiency of the exponential model were particularly degraded. The contribution of mechanism 1 (and its influence on mechanism 2) seemed to be the determining factor. At TSC = 100 °C the hypothesis made was the acceleration of the solvent evaporation process inside the TISIS, leading to variations in the characteristics of the tertiary aerosols. And the consequence was an increase of the plasma mass discriminative effects (ion diffusion) reinforced by the extra energy made available to the plasma ions. At 5 μL min−1, changes in the plasma composition arising from the reduction of the water load in combination with the ion production at an earlier stage within the plasma followed by the processes of ion diffusion were also hypothesized as possible causes for the inadequacy of the exponential model.

International audience; 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 (R) DGA resin. A Zr-91-Zr-96 double-spike was created from enriched single Zr-91 and Zr-96 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 Zr-94/Zr-90 from the IPGP-Zr standard (delta Zr-94/90(IPGP-Zr)). The delta Zr-94/90(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 (Plesovice zircon), are presented using this method. Sample measurements are presented with an analytical uncertainty of +/- similar to 0.05% (2sd) for delta Zr-94/90(IPGP-Zr) and these rocks exhibit isotopic variations of similar to 0.15% for delta Zr-94/90(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 delta Zr-94/90(IPGP-Zr) values observed within the magmatic rock reference materials is correlated (R-2 = 0.78; n = 5) with SiO2, suggesting that Zr isotopes could serve as a sensitive tracer of magmatic processes.