Determination of Precise and Accurate 51V/50V Isotope Ratios by Multi‐Collector ICP‐MS,Part 2: Isotopic Composition of Six Reference Materials plus the Allende Chondrite and Verification Tests

We present the first measurements of vanadium (V) stable isotopes for six reference materials – USGS PCC‐1, BHVO‐2, BCR‐2, BIR‐1a, GSP‐2 and AGV‐2 – plus the widely available carbonaceous chondrite Allende. We present standard addition and matrix spiking tests to assess the robustness and reproducibility of our data. Standard addition utilised an enriched ⁵⁰V solution designated VISSOX (Vanadium Isotope Standard Solution OXford). We further assessed the veracity of the method by spiking collected sample matrices with the same amount of a V standard solution, whose isotopic composition was defined as 0‰. Standard addition and matrix spiking tests recorded no appreciable artificial isotope fractionation. We estimate that the best currently attainable long‐term reproducibility of stable ⁵¹V/⁵⁰V isotope measurements in complex matrices is 0.15‰, which is in the same order as the reproducibility achievable with standard solutions. Finally, a large range of ～ 1.2‰ in stable V isotopic composition was documented, with ～ 0.5‰ of that variation in high temperature igneous materials alone. The range and resolving power of V stable isotopes, with respect to igneous material, compared favourably with the magnitude of fractionation reported for other non‐traditional stable isotope systems, which bodes well for the utility of this new system.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

A Case Study of Spectral and Non‐Spectral Interferences on Copper Isotope Measurements by Multi‐Collector ICP‐MS (Wet Plasma)

Mathematical modelling was combined with experimental Cu isotope measurements to demonstrate the effect of the sample matrix in changing the absolute and relative abundances of spectral interferences from Ti and Cr species. This unforeseen non‐spectral effect, evidenced by variable inaccuracies of the different Zn‐normalised Cu isotope ratios, was investigated by comparing real sedimentary samples and artificial solutions intended to match the Cu:Ti:Cr ratios of the real samples after (one or two step) chromatographic processing. Artificial solutions showed positive bias in δ⁶⁵Cu_X/Y with the magnitude depending on (a) the ^6XZn/^6YZn ratio used for normalisation, (b) the Ti/Cu ratio and (c) the transmission coefficient of the TiO species. In contrast, real samples showed different δ⁶⁵Cu_X/Y patterns and displayed a more complex population of Ti and Cr oxides and hydroxides, giving rise to positive and negative inaccuracies that were two to six times higher compared with the artificial samples. The results evidence contrasting behaviour of Ti and Cr when forming polyatomic species in the plasma and stress that artificial solutions may fail to predict how residual elements interact with the analyte/dopant pair during MC‐ICP‐MS analyses. More importantly, the study shows that all Zn isotope ratios do not have the same merit in correcting for mass bias in the presence of matrix elements and should all be monitored to verify the absence of spectral interferences for Cu isotope measurements. In this respect, accurate Cu data could be generally obtained by a two‐step chromatographic purification providing a minimum reduction of ~ 21000 and ~ 3000 times the initial amounts of Ti and Cr, respectively.     

Precise Determination of Silicon Isotopes in Silicate Rock Reference Materials by MC‐ICP‐MS

A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g^‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ³⁰Si and δ²⁹Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ³⁰Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ²⁹Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ³⁰Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ³⁰Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

Determination of Cr,Cu, Ni,Sn, Sr and Zn Mass Fractions in Geochemical Reference Materials by Isotope Dilution ICP‐MS

Isotope dilution (ID) mass spectrometry is a primary method of analysis suited for the accurate and precise measurement of several trace elements in geological matrices. Here we present mass fractions and respective uncertainties for Cr, Cu, Ni, Sn, Sr and Zn in 10 silicate rock reference materials (BCR‐2, BRP‐1, BIR‐1, OU‐6, GSP‐2, GSR‐1, AGV‐1, RGM‐1, RGM‐2 and G‐3) obtained by the double ID technique and measuring the isotope ratios with an inductively coupled plasma‐mass spectrometer equipped with collision cell. Test portions of the samples were dissolved by validated procedures, and no further matrix separation was applied. Addition of spikes was designed to achieve isotope ratios close to unity to minimise error magnification factors, according to the ID theory. Radiogenic ingrowth of ⁸⁷Sr from the decay of ⁸⁷Rb was considered in the calculation of Sr mass fractions. The mean values of our results mostly agree with reference values, considering both uncertainties at the 95% confidence level, and also with ID data published for AGV‐1. Considering all results, the means of the combined uncertainties were < 1% for Sr, approximately 2% for Sn and Cu, 4% for Cr and Ni and almost 6% for Zn.     

New Thorium Isotope Ratio Measurements in Silicate Reference Materials: A‐THO,AGV‐2, BCR‐2, BE‐N,BHVO‐2 and BIR‐1

A two‐step Th isolation protocol, involving micro‐columns of TRU‐Spec extraction chromatography material and AG1 resin, was evaluated. The MC‐ICP‐MS procedure included ²³²Th tailing characterisation and correction, and calibrator bracketing using an in‐house standard solution (ThS1) to correct for instrumental mass bias and Faraday cup to secondary electron multiplier relative gain. Repeated analyses of reference solutions (UCSC Th ‘A’, WUN, OU Th ‘U’, IRMM‐36) were consistent with published data. Six reference materials (A‐THO, BCR‐2, AGV‐2, BHVO‐2, BE‐N and BIR‐1) were processed. The average ²³⁰Th/²³²Th values obtained for these samples are in excellent agreement with published data. In addition, we report the first ²³⁰Th/²³²Th values for BE‐N and BIR‐1. The intermediate precisions for rock samples ranged from ± 0.24 to ± 0.49% (2 RSD) and were similar to those achieved for synthetic solutions, thereby supporting the overall validity of the chemical separation, data acquisition and reduction procedures. Counting statistics on the ²³⁰Th isotope was the most significant source of uncertainty. The intermediate precision of the mean ²³⁰Th/²³²Th for the Th‐depleted BIR‐1 (5.64 × 10^?6 ± 0.27%, 2 RSD) is in the range of the analyses of other reference materials analysed in this study.     

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.     

Determination of the Tin Stable Isotopic Composition in Tin‐bearing Metals and Minerals by MC‐ICP‐MS

This study uses MC‐ICP‐MS for the precise analysis of the stable tin isotopic composition in ore minerals of tin (cassiterite, stannite), tin metal and tin bronze. The ultimate goal is to determine the provenance of tin in ancient metal objects. We document the isotope compositions of reference materials and compare the precision of different isotope ratios and the accuracy of different procedures of mass fractionation correction. These data represent a base with which isotopic data of future studies can be directly compared. The isotopic composition of cassiterite and stannite can be determined after reduction to tin metal and bronze, respectively. Both metals readily dissolve in HCl, but while the solutions of tin metal can be directly measured, the bronze solutions must be purified with an anion exchanger. The correction of the mass bias is best performed with an internal Sb standard and an empirical regression method. A series of Sn isotope determinations on commercially available mono‐element Sn solutions as well as reference bronze materials and tin minerals show fractionations ranging from about ?0.09‰ to 0.05‰/amu. The combined analytical uncertainty (2s) was determined by replicate dissolutions of reference materials of bronze (BAM 211, IARM‐91D) and averages at about 0.005‰/amu.     

Investigating the Influence of Non‐Spectral Matrix Effects in the Determination of Twenty‐Two Trace Elements in Rock Samples by ICP‐QMS

The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, ¹¹³In and ²⁰³Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.     

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

High‐Precision Barium Isotope Measurements of Carbonates by MC‐ICP‐MS

This study presents a high‐precision method to measure barium (Ba) isotope compositions of international carbonate reference materials and natural carbonates. Barium was purified using chromatographic columns filled with cation exchange resin (AG50W‐X12, 200–400 mesh). Barium isotopes were measured by MC‐ICP‐MS, using a ¹³⁵Ba–¹³⁶Ba double‐spike to correct mass‐dependent fractionation during purification and instrumental measurement. The precision and accuracy were monitored by measuring Ba isotope compositions of the reference material JCp‐1 (coral) and a synthetic solution obtained by mixing NIST SRM 3104a with other matrix elements. The mean δ^137/134Ba values of JCp‐1 and the synthetic solution relative to NIST SRM 3104a were 0.21 ± 0.03‰ (2s, n = 16) and 0.02 ± 0.03‰ (2s, n = 6), respectively. Replicate measurements of NIST SRM 915b, COQ‐1, natural coral and stalagmite samples gave average δ^137/134Ba values of 0.10 ± 0.04‰ (2s, n = 18), 0.08 ± 0.04‰ (2s, n = 20), 0.27 ± 0.04‰ (2s, n = 16) and 0.04 ± 0.03‰ (2s, n = 20), respectively. Barium mass fractions and Ba isotopes of subsamples drilled from one stalagmite profile were also measured. Although Ba mass fractions varied significantly along the profile, Ba isotope signatures were homogeneous, indicating that Ba isotope compositions of stalagmites could be a potential tool (in addition to Ba mass fractions) to constrain the source of Ba in carbonate rocks and minerals.     

Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC‐ICP‐MS

Although initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass‐dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two‐stage chromatography procedure, Ni isotope ratios were measured by MC‐ICP‐MS and were corrected for instrumental mass bias using a double‐spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous‐ and mantle‐derived rocks displayed a restricted range of δ^60/58Ni values between ?0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO‐1), coal (CLB‐1) and a metal‐contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite‐hosted Ni‐rich sulfides varied from ?0.10 to ?1.03‰.     

Spectrophotometric Determination of Gold (III) after Liquid–Liquid Extraction and Selective Pre‐concentration with a Novel Dibenzo‐18‐Crown‐6 Derivative

A selective and sensitive method for the extraction and spectrophotometric determination of gold with N,N′‐6,7,9,10,17,18,20,21‐octahydrodibenzo[b,k][1,4,7,10,13,16] hexaoxacyclo‐octadecine‐2,13–diylbis(2‐chloroacetamide) (ODBOCA) is described. The ODBOCA–Au(III) complex was extracted from a slightly acidic aqueous solution (pH 5) into a chloroform layer and then the absorbance of the extract was measured using a UV–Vis spectrophotometer with 1.0 cm quartz cells at 540 nm. An enrichment factor of 200 was achieved. In the chloroform medium at 540 nm, the molar absorptivity and Sandell’s sensitivity were 4.12 × 10³ l mol^?1 cm^?1 and 0.048 μg cm^?2, respectively. Beer’s law was obeyed in the range of 0.5–15 μg ml^?1 in the measured solution. The relative standard deviation for ten replicate samples at the 1.0 μg ml^?1 level was 3.0%. The limit of detection, based on 3s, was 0.5 μg l^?1 in the original sample. The effects of pH, ligand concentration and shaking time were studied. The ratio of the metal ion to ligand molecules in the complex was found to be 1:2 according to the Job Method. The effects of interference by a number of metal ions were investigated. The method was verified with certified reference materials and spiked tests, and quantitative recovery values were obtained. The method was fast, accurate, selective and precise, and was applied to the determination of gold in water and ore with good results.     

Accurate and Precise Silicon Isotope Analysis of Sulfur‐ and Iron‐Rich Samples by MC‐ICP‐MS

Silicon isotope determination of sulfur‐rich samples by MC‐ICP‐MS can be challenging because cation‐exchange chromatography used for Si purification does not efficiently remove anionic sulfur species. Results for pure Si standard solutions with addition of sulfate showed shifts of up to +1.04 ± 0.10‰ (2s) in δ³⁰Si. Doping of both standard solutions and samples with S to a fixed S/Si ratio can eliminate the relative change in instrumental mass fractionation due to variable S/Si in samples and also boosts the relative sensitivity of Si by up to 66%. Moreover, Fe hydroxide precipitation during sample processing adsorbs Si resulting in isotopic fractionations. Tests using Fe‐rich samples showed that this could be a major factor for observed shifts in δ³⁰Si. Acidification of the sample and standard solutions to a pH < 1 aggressively dissolved any Fe hydroxide precipitates, even in relatively Fe‐rich samples such as chondrite meteorites. The pH values of the sample solutions were subsequently adjusted to a range of 2–3 by adding ultra‐pure NaOH solutions. The combination of sulfur doping and the pH adjustment protocol ensured a full recovery of Si and proved to be an efficient and reliable method for Si isotope determination of S‐ and Fe‐rich materials.     

Chemical Separation of Tungsten and Other Trace Elements for TIMS Isotope Ratio Measurements Using Organic Acids

One requirement for isotope ratio measurement results with small measurement uncertainties is that the element of interest is effectively separated from the sample matrix. Efficient chemical separation of W from matrix components, especially Ti, can be challenging, particularly for large test portion masses (> 1 g). We present a new W separation procedure that takes advantage of the distinct complexation behaviour of Ti and W with citrate ligand in a moderately low pH, oxidising solution. This preparation procedure can reduce the Ti/W ratio of large (4–10 g) basaltic (i.e., high‐matrix) test portions by a factor of 10⁵, relative to their original compositions, in a two‐step separation procedure. The procedure additionally provides a separate, well‐purified Mo fraction. We show that optimal separation requires precise selection of reagent concentrations and sample load. The procedure was employed to determine the μ¹⁸²W composition of BHVO‐2 as ?6.7 ± 4.2 (2 standard deviation, 2s). The principles derived from this method may prove useful for chemical separation of other elements used for geochemical and cosmochemical applications given an appropriate selection of organic acid. Future successful applications of this method may reveal that the use of organic acids as procedural reagents is a currently under‐utilised tool for efficient chemical separation protocols.     

A New Method for Low‐Temperature Decomposition of Chromites and Dichromium Trioxide using Bromic Acid Evaluated by Chromium Isotope Measurements

In recent years, routine application of the stable isotope determination of chromium (Cr) in environmental and health protection research has led to the search for simpler chromite decomposition techniques. As the range of Cr isotope abundance ratios in nature is very narrow, conventional chromite decomposition techniques are no longer suitable, due to the relatively high risk of contamination during laboratory procedures. We have developed a protocol for the decomposition of chromites based on oxidation by bromic acid at room temperature. The procedure takes 15 d and requires two doses of bromic acid during the reaction period (day 1 and 8), due to the limited stability of the reagent. Chromium extracted by alkaline oxidative fusion and by bromic acid decomposition yielded statistically indistinguishable δ⁵³Cr values, measured by multi‐collector inductively coupled plasma‐mass spectrometry following addition of a ⁵⁰Cr‐⁵⁴Cr double‐spike.     

Zinc Isotopic Compositions of NIST SRM 683 and Whole‐Rock Reference Materials

In this study the homogeneity of the zinc isotopic composition in the NIST SRM 683 reference material was examined by measuring the Zn isotopic signature in microdrilled sample powders from two metal nuggets. Zinc was purified using AG MP‐1M resin and then measured by MC‐ICP‐MS. Instrumental mass bias was corrected using the “sample‐standard bracketing” method and empirical external normalisation with Cu doping. After evaluating the potential effects of varying acid mass fractions and different matrices, high‐precision Zn isotope data were obtained with an intermediate measurement precision better than ± 0.05‰ (δ⁶⁶Zn, 2s) over a period of 5 months. The δ⁶⁶Zn_JMC‐Lyon mean values of eighty‐four and fourteen drilled powders from two nuggets were 0.11 ± 0.02‰ and 0.12 ± 0.02‰, respectively, indicating that NIST SRM 683 is a good isotopic reference material with homogeneous Zn isotopes. The Zn isotopic compositions of seventeen rock reference materials were also determined, and their δ⁶⁶Zn values were in agreement with most previously published data within 2s. The δ⁶⁶Zn values of most of the rock reference materials analysed were in the range 0.22–0.36‰, except for GSP‐2 (1.07 ± 0.06‰, n = 12), NOD‐A‐1 (0.96 ± 0.03‰, n = 6) and NOD‐P‐1 (0.78 ± 0.03‰, n = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.     

High‐Precision Measurement of Molybdenum Isotopic Compositions of Selected Geochemical Reference Materials

Here we describe high‐precision molybdenum isotopic composition measurements of geological reference materials, performed using multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS). Purification of Mo for isotopic measurements was achieved by ion exchange chromatography using Bio‐Rad AG^® 1‐X8 anion exchange resin. Instrumental mass bias was corrected using ¹⁰⁰Mo‐⁹⁷Mo double spiking techniques. The precision under intermediate measurement conditions (eighteen measurement sessions over 20 months) in terms of δ^98/95Mo was 0.10‰ (2s). The measurement output was approximately four times more efficient than previous techniques, with no compromise in precision. The Mo isotopic compositions of seven geochemical reference materials, seawater (IAPSO), manganese nodules (NOD‐P‐1 and NOD‐A‐1), copper‐molybdenum ore (HV‐2), basalt (BCR‐2) and shale (SGR‐1b and SCo‐1), were measured. δ^98/95Mo values were obtained for IAPSO (2.25 ± 0.09‰), NOD‐P‐1 (?0.66 ± 0.05‰), NOD‐A‐1 (?0.48 ± 0.05‰), HV‐2 (?0.23 ± 0.10‰), BCR‐2 (0.21 ± 0.07‰), SCo‐1 (?0.24 ± 0.06‰) and SGR‐1b (0.63 ± 0.02‰) by calculating δ^98/95Mo relative to NIST SRM 3134 (0.25‰, 2s). The molybdenum isotopic compositions of IAPSO, NOD‐A‐1 and NOD‐P‐1 obtained in this study are within error of the compositions reported previously. Molybdenum isotopic compositions for BCR‐2, SCo‐1 and SGR‐1b are reported for the first time.