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1.
This study presents two matrix‐matched reference materials developed for petroleum Re‐Os measurements. We present the Re and Os mass fractions and 187Re/188Os and 187Os/188Os values (ratio of the number of atoms of the isotopes) for repeatedly measured aliquots (ca. 120–150 mg test portions) of the NIST Research Material 8505 (RM 8505) crude oil, and its asphaltene and maltene fractions, and ~ 90 g of homogeneous asphaltene powder isolated from this oil. Measurements were performed using the Carius tube‐isotope dilution negative‐thermal ionisation mass spectrometry methodology. The RM 8505 crude oil contains 1.98 ± 0.07 ng g?1 Re and 25.0 ± 1.1 pg g?1 Os, with Re‐Os isotope amount ratios of 452 ± 6 for 187Re/188Os and 1.51 ± 0.01 for 187Os/188Os (n = 20, 95% conf.). The homogeneous asphaltene sample contains 16.52 ± 0.10 ng g?1 Re and 166.0 ± 0.9 pg g?1 total Os, and possesses isotope amount ratios of 574 ± 3 for 187Re/188Os and 1.64 ± 0.01 for 187Os/188Os (n = 24, 95% conf.). The intermediate precision of these data makes the RM 8505 whole oil and the (~ 90 g) homogenised asphaltene appropriate petroleum matrix‐matched reference materials for Re‐Os measurements. The asphaltene fraction of the oil is the main carrier of Re and Os of the RM 8505 whole oil, and caution is suggested in using asphaltene and maltene fractions of a single oil for Re‐Os geochronology.  相似文献   

2.
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.  相似文献   

3.
Properly combining highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding 187Os/188Os and 186Os/188Os measurements of rocks requires efficient digestion of finely‐ground powders and complete spike‐sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF‐desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014) Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8 to > 18% m/m, or as mass fractions, < 8 to > 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR‐1, BHVO‐2, TDB‐1). To investigate the effect of HF‐desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a ‘standard acid digestion’ (2:1 mixture of concentrated HNO3 and HCl), and a standard acid digestion, followed by HF‐desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF‐desilicification. Desilicification procedures using HF do not improve liberation of the HSE from Azores basalts, or some RMs (e.g., WPR‐1). We conclude that HF‐desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re‐Pt‐Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF‐desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured 187Os/188Os or 186Os/188Os.  相似文献   

4.
Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm3). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS 187Os/189Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM 187Os/189Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.  相似文献   

5.
To evaluate the homogeneity of geological reference material BIR‐1a (basalt; United States Geological Survey, USGS) for Re‐Os isotopic studies at the 0.2–1.0 g test portion size level, sixty‐three precise measurement results of Re and Os mass fractions and isotope amount ratios were obtained over an 18‐month period. These data reveal that the reference material has higher Re (0.691 ± 0.022 ng g?1, 2s, n = 63) and lower Os mass fractions (0.343 ± 0.089 ng g?1, 2s, n = 63) than UB‐N (serpentinite, CRPG) and is homogeneous in 187Os/188Os isotope amount ratio (0.13371 ± 0.00092, 2s, n = 63) at the 0.2–1.0 g test portion size level. The results are essentially consistent with previous views indicating that BIR‐1a gives precise measurement results for Re‐Os isotope amount ratio measurements at the 1 g test portion size level (Ishikawa et al., Chemical Geology, 2014, 384, 27–46; Meisel and Horan, Reviews in Mineralogy and Geochemistry, 2016, 81, 89–106). Based on these new Re‐Os data and previous studies, we propose BIR‐1a as a useful reference material that can be used in method validation and quality control and interlaboratory comparisons for studies dealing with mafic geological samples at test portion sizes of > 0.4 g.  相似文献   

6.
The characterisation of relative copper isotope amount ratios (δ65Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ65Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ65Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ65Cu. Additionally, four reference materials (with published δ65Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g?1 to 497 µg g?1 and δ65Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.  相似文献   

7.
In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.  相似文献   

8.
To precisely determine the abundances of fifty‐two elements found within natural water samples, with mass fractions down to fg g?1 level, we have developed a method which combines freeze‐drying pre‐concentration (FDC) and isotope dilution internal standardisation (ID‐IS). By sublimation of H2O, the sample solution was reduced to < 1/50 of the original volume. To determine element abundance with accuracy better than 10%, we found that for solutions being analysed by mass spectrometry the HNO3 concentration should be > 0.3 mol l?1 to avoid hydrolysis. Matrix‐affected signal suppression was not significant for the solutions with NaCl concentrations lower than 0.2 and 0.1 cg g?1 for quadrupole ICP‐MS and sector field ICP‐MS, respectively. The recovery yields of elements after FDC were 97–105%. The detection limits for the sample solutions prepared by FDC were ≤ 10 pg g?1, except for Na, K and Ca. Blanks prepared using FDC were at pg‐levels, except for eleven elements (Na, Mg, Al, P, Ca, Mn, Fe, Co, Ni, Cu and Zn). The abundances of fifty‐two elements in bottled drinking water were determined from five different geological sources with mass fractions ranging from the fg g?1 to μg g?1 level with high accuracy.  相似文献   

9.
In recent years, the 187Re–187Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(187Os/188Os) expressed as 187Os/188Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of 190Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H2O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of 187Os/188Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting 187Os/188Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.  相似文献   

10.
A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO3 and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with 193Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g?1 for Ru, 0.008 ng g?1 for Rh, 0.045 ng g?1 for Pd, 0.009 ng g?1 for Os, 0.006 ng g?1 for Ir and 0.016 ng g?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.  相似文献   

11.
This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., 109Ag1H+, 94Zr16O+, 94Mo16O+ and 70Zn40Ar+) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10?5 and In/Cd ≤ 10?3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ114/110Cd. The δ114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of ?0.251 to 0.632‰, the δ114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from ?0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes.  相似文献   

12.
A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A 100Mo‐97Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ98/95Mo, 2s) by MC‐ICP‐MS. The mean δ98/95MoSRM 3134 (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.  相似文献   

13.
In this study, the USGS black shale reference material SBC‐1 was investigated as a matrix‐matched reference material for both intra‐laboratory calibration and inter‐laboratory comparison of high‐precision Re‐Os dating for organic‐rich sedimentary rocks. This reference material was analysed for Re‐Os isotopic composition by three digestion protocols – inverse aqua regia, CrO3‐H2SO4 and H2O2‐HNO3. The results for SBC‐1 obtained by inverse aqua regia digestion yielded similar Re mass fractions but slightly (~ 5%) higher Os mass fractions and lower 187Os/188Os values than the CrO3‐H2SO4 and H2O2‐HNO3 digestions. The data set of inverse aqua regia digestion exhibited strong correlations in plots of 187Os/188Os vs. 1/192Os and 187Os/188Os vs. 187Re/188Os, which may signify the incorporation of detrital Re and Os into organic matter in the Re‐Os system. Similar correlations were also observed for the CrO3‐H2SO4 digestion data set, but not for that of H2O2‐HNO3. The data indicate that there is an amount of non‐hydrogenous Os in SBC‐1 and that CrO3‐H2SO4 and H2O2‐HNO3 digestions would minimise liberation of the non‐hydrogenous Os component. We propose that SBC‐1 may be a more suitable reference material to monitor the influence of detrital Re and Os on Re‐Os isochron age data, especially for samples with less organic matter and more siliceous detritus.  相似文献   

14.
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 δ137/134Ba 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 δ137/134Ba 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.  相似文献   

15.
A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl4 method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO3‐H2SO4 as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.  相似文献   

16.
We present an improved method for the determination of the boron isotopic composition of volcanic glasses with boron concentrations of as low as 0.4–2.5 μg g?1, as is typical for mid‐ocean ridge basalt glasses. The analyses were completed by secondary ion mass spectrometry using a Cameca 1280 large‐radius ion microprobe. Transmission and stability of the instrument and analytical protocol were optimised, which led to an improvement of precision and reduction in surface contamination and analysis time compared with earlier studies. Accuracy, reproducibility (0.4–2.3‰, 2 RSD), measurement repeatability (2 RSE = 2.5–4.0‰ for a single spot with [B] = 1 μg g?1), matrix effects (? 0.5‰ among komatiitic, dacitic and rhyolitic glass), machine drift (no internal drift; long‐term drift: ~ 0.1‰ hr?1), contamination (~ 3–8 ng g?1) and machine background (0.093 s?1) were quantified and their influence on samples with low B concentrations was determined. The newly developed set‐up was capable of determining the B isotopic composition of basaltic glass with 1 μg g?1 B with a precision and accuracy of ± 1.5‰ (2 RSE) by completing 4–5 consecutive spot analyses with a spatial resolution of 30 μm × 30 μm. Samples with slightly higher concentrations (≥ 2.5 μg g?1) could be analysed with a precision of better than ± 2‰ (internal 2 RSE) with a single spot analysis, which took 32 min.  相似文献   

17.
The homogeneity and Ar‐dating suitability of the GL‐O reference material were re‐evaluated to determine whether this material is sufficiently homogeneous to be suitable for the calibration of modern high sensitivity instruments. Based on new micro‐analyses and noble gas determinations, our contribution reveals several kinds of inhomogeneity at the grain scale: disparity in the glauconitisation among and within the pellets, variable occurrence of a phosphatic component within pellets (1% m/m on average), and rare occurrences of calcite and detrital grains. Measurements on test portions of ≤ 1 mg reflect such heterogeneity with variability in 40Ar* content that exceeds analytical uncertainty, including a few highly anomalous values. The lesser evolved glauconite population yielded 40Ar* contents ~ 15% lower than the value of 24.8 nl g?1 recommended by Odin et al. (1982, Numerical dating in stratigraphy. Wiley (Chichester, UK), 123–148). But the measured concentrations of 40Ar* converge towards the aforementioned value as test portion mass increased to > 3 mg. A few rare 3 mg experiments still yielded 40Ar* contents lower than the recommended value (down to 24.0 nl g?1), and we recommend using more conservative minimum masses of 5–10 mg. A further purification step for GL‐O or the intercalibration of its powder version could be considered to diminish the size of the test portions and the intensity of the measured signals.  相似文献   

18.
A double‐spike method in combination with MC‐ICP‐MS was applied to obtain molybdenum (Mo) mass fractions and stable isotope compositions in a suite of sedimentary silicate (marine, lake, stream, estuarine, organic‐rich sediment, shales, slate, chert) and carbonate reference materials (coral, dolomite, limestones, carbonatites), and a manganese nodule reference material, poorly characterised for stable Mo isotope compositions. The Mo contents vary between 0.076 and 364 μg g?1, with low‐Mo mass fractions (< 0.29 μg g?1) found almost exclusively in carbonates. Intermediate Mo contents (0.73–2.70 μg g?1) are reported for silicate sediments, with the exception of chert JCh‐1 (0.24 μg g?1), organic‐rich shale SGR‐1b (36.6 μg g?1) and manganese nodule NOD‐A‐1 (364 μg g?1). The Mo isotope compositions (reported as δ98Mo relative to NIST SRM 3134) range from ?1.77 to 1.03‰, with the intermediate precision varying between ± 0.01 and ± 0.12‰ (2s) for most materials. Low‐temperature carbonates show δ98Mo values ranging from 0.21 to 1.03‰ whereas δ98Mo values of ?1.77 and ?0.17‰ were obtained for carbonatites CMP‐1 and COQ‐1, respectively. Silicate materials have δ98Mo values varying from ?1.56 to 0.73‰. The range of δ98Mo values in reference materials may thus reflect the increasingly important relevance of Mo isotope investigations in the fields of palaeoceanography, weathering, sedimentation and provenance, as well as the magmatic realm.  相似文献   

19.
We present in this article a rapid method for B extraction, purification and accurate B concentration and δ11B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ11B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g?1 of total salts or 25 μg g?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ11B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).  相似文献   

20.
We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl4 solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.  相似文献   

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