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1.
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 δ60/58Ni 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‰.  相似文献   

2.
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,= 16) and 0.02 ± 0.03‰ (2s,= 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,= 18), 0.08 ± 0.04‰ (2s,= 20), 0.27 ± 0.04‰ (2s,= 16) and 0.04 ± 0.03‰ (2s,= 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   

3.
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 δ66ZnJMC‐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‰, = 6) and NOD‐P‐1 (0.78 ± 0.03‰, = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.  相似文献   

4.
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   

5.
Chromium (Cr) isotopes have been widely used in various fields of Earth and planetary sciences. However, high‐precision measurements of Cr stable isotope ratios are still challenged by difficulties in purifying Cr and organic matter interference from resin using double‐spike thermal ionisation mass spectrometry. In this study, an improved and easily operated two‐column chemical separation procedure using AG50W‐X12 (200–400 mesh) resin is introduced. This resin has a higher cross‐linking density than AG50W‐X8, and this higher density generates better separation efficiency and higher saturation. Organic matter from the resin is a common cause of inhibition of the emission of Cr during analysis by TIMS. Here, perchloric and nitric acids were utilised to eliminate organic matter interference. The Cr isotope ratios of samples with lower Cr contents could be measured precisely by TIMS. The long‐term intermediate measurement precision of δ53/52CrNIST SRM 979 for BHVO‐2 is better than ± 0.031‰ (2s) over one year. Replicated digestions and measurements of geological reference materials (OKUM, MUH‐1, JP‐1, BHVO‐1, BHVO‐2, AGV‐2 and GSP‐2) yield δ53/52CrNIST SRM 979 results ranging from ?0.129‰ to ?0.032‰. The Cr isotope ratios of geological reference materials are consistent with the δ53/52CrNIST SRM 979 values reported by previous studies, and the measurement uncertainty (± 0.031‰, 2s) is significantly improved.  相似文献   

6.
Molybdenum concentration and δ98/95Mo values for NIST SRM 610 and 612 (solid glass), NIST SRM 3134 (lot 891307; liquid) and IAPSO seawater reference material are presented based on comparative measurements by MC‐ICP‐MS performed in laboratories at the Universities of Bern and Oxford. NIST SRM 3134 and NIST SRM 610 and 612 were found to have identical and homogeneous 98Mo/95Mo ratios at a test portion mass of 0.02 g. We suggest, therefore, that NIST SRM 3134 should be used as reference for the δ–Mo notation and to employ NIST SRM 610 or 612 as solid silicate secondary measurement standards, in the absence of an isotopically homogeneous solid geological reference material for Mo. The δ98/95MoJMC Bern composition (Johnson Matthey ICP standard solution, lot 602332B as reference) of NIST SRM 3134 was 0.25 ± 0.09‰ (2s). Based on five new values, we determined more precisely the mean open ocean δ98/95MoSRM 3134 value of 2.09 ± 0.07‰, which equals the value of δ98/95MoJMC Bern of 2.34 ± 0.07‰. We also refined the Mo concentration data for NIST SRM 610 to 412 ± 9 μg g?1 (2s) and NIST SRM 612 to 6.4 ± 0.7 μg g?1 by isotope dilution. We propose these concentration data as new working values, which allow for more accurate in situ Mo determination using laser ablation ICP‐MS or SIMS.  相似文献   

7.
The demand for large and reliable data sets on isotopic composition has increased in geochemistry and environmental sciences over recent years. We present an automated ion chromatographic separation method using a robotic pipetting arm, termed ‘ChemCobOne’, to reduce sample separation time. Its performance was tested for lithium isotope separation in geological reference materials using a single‐step separation with HCl (0.2 mol l?1) and a 2 ml resin volume. This refined lithium purification method does not forfeit precision, accuracy or purity compared with manual sample processing. In addition, a δ7Li value for NASS‐6 of 30.99 ± 0.50‰ (2s) (95% CI = 0.14‰, n = 44) was determined and the first δ7Li values for the granite rock reference material GS‐N (?0.57 ± 0.25‰ (2s), 95% CI = 0.15‰, n = 15), and for the soil reference material NIST SRM 2709a (?0.37 ± 0.67‰ (2s), 95% CI = 0.15‰, n = 63) are proposed.  相似文献   

8.
We report mass‐independent and mass‐dependent Ca isotopic compositions for thirteen geological reference materials, including carbonates (NIST SRM 915a and 915b), Atlantic seawater as well as ten rock reference materials ranging from peridotite to sandstone, using traditional ε and δ values relative to NIST SRM 915a, respectively. Isotope ratio determinations were conducted by independent unspiked and 43Ca‐48Ca double‐spiked measurements using a customised Triton Plus TIMS. The mean of twelve measurement results gave ε40/44Ca values within ± 1.1, except for GSP‐2 that had ε40/44Ca = 4.04 ± 0.15 (2SE). Significant radiogenic 40Ca enrichment was evident in some high K/Ca samples. At an uncertainty level of ± 0.6, all reference materials had the same ε43/44Ca and ε48/44Ca values. We suggest the use of δ44/42Ca to report mass‐dependent Ca isotopic compositions. The precision under intermediate measurement conditions for δ44/42Ca over eight months in our laboratory was ± 0.03‰ (with n ≥ 8 repeat measurements). Measured igneous reference materials gave δ44/42Ca values ranging from 0.27‰ to 0.54‰. Significant Ca isotope fractionation may occur during magmatic and metasomatism processes. Studied reference materials with higher (Dyn/Ybn) tend to have lower δ44/42Ca, implying a potential role of garnet in producing magmas with low δ44/42Ca. Sandstone GBW07106 had a δ44/42Ca value of 0.22‰, lower than all igneous rocks studied so far.  相似文献   

9.
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.  相似文献   

10.
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   

11.
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 δ98/95Mo 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. δ98/95Mo 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 δ98/95Mo 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.  相似文献   

12.
The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.  相似文献   

13.
Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ18O values were determined by CO2 laser fluorination. The average δ18O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.  相似文献   

14.
The commonly used, but no longer available, reference materials NIST SRM 976 (Cu) and ‘JMC Lyon’ (Zn) were calibrated against the new reference materials ERM®‐AE633, ERM®‐AE647 (Cu) and IRMM‐3702 (Zn), certified for isotope amount ratios. This cross‐calibration of new with old reference materials provides a continuous and reliable comparability of already published with future Cu and Zn isotope data. The Cu isotope amount ratio of NIST SRM 976 yielded δ65/63Cu values of ?0.01 ± 0.05‰ and ?0.21 ± 0.05‰ relative to ERM®‐AE633 and ERM®‐AE647, respectively, and a δ66/64ZnIRMM‐3702 value of ?0.29 ± 0.05‰ was determined for ‘JMC Lyon’. Furthermore, we separated Cu and Zn from five geological reference materials (BCR‐2, BHVO‐2, BIR‐1, AGV‐1 and G‐2) using a two‐step ion‐exchange chromatographic procedure. Possible isotope fractionation of Cu during chromatographic purification and introduction of resin‐ and/or matrix‐induced interferences were assessed by enriched 65Cu isotope addition. Instrumental mass bias correction for the isotope ratio determinations by MC‐ICP‐MS was performed using calibrator‐sample bracketing with internal Ni doping for Cu and a double spike approach for Zn. Our results for the five geological reference materials were in very good agreement with literature data, confirming the accuracy and applicability of our analytical protocol.  相似文献   

15.
To enable quality control of measurement procedures for determinations of Mg isotope amount ratios, expressed as δ26Mg and δ25Mg values, in Earth‐surface studies, the δ26Mg and δ25Mg values of eight reference materials (RMs) were determined by interlaboratory comparison between five laboratories and considering published data, if available. These matrix RMs, including river water SLRS‐5, spring water NIST SRM 1640a, Dead Sea brine DSW‐1, dolomites JDo‐1 and BCS‐CRM 512, limestone BCS‐CRM 513, soil NIST SRM 2709a and vegetation NIST SRM 1515, are representative of a wide range of Earth‐surface materials from low‐temperature environments. The interlaboratory variability, 2s (twice the standard deviation), of all eight RMs ranges from 0.05 to 0.17‰ in δ26Mg. Thus, it is suggested that all these materials are suitable for validation of δ26Mg and δ25Mg determinations in Earth‐surface geochemical studies.  相似文献   

16.
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   

17.
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   

18.
Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g?1, SiO2 from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.  相似文献   

19.
Recent analytical developments in germanium stable isotope determination by multicollector ICP‐MS have provided new perspectives for the use of Ge isotopes as geochemical tracers. Here, we report the germanium isotope composition of the NIST SRM 3120a elemental reference solution that has been calibrated relative to internal isotopic standard solutions used in the previous studies. We also intercalibrate several geological reference materials as well as geological and meteoritic samples using different techniques, including online hydride generation and a spray chamber for sample introduction to MC‐ICP‐MS, and different approaches for mass bias corrections such as sample–calibrator bracketing, external mass bias correction using Ga isotopes and double‐spike normalisation. All methods yielded relatively similar precisions at around 0.1‰ (2s) for δ74/70Ge values. Using igneous and mantle‐derived rocks, the bulk silicate Earth (BSE) δ74/70Ge value was re‐evaluated to be 0.59 ± 0.18‰ (2s) relative to NIST SRM 3120a. Several sulfide samples were also analysed and yielded very negative values, down to ?4.3‰, consistent with recent theoretical study of Ge isotope fractionation. The strong heavy isotope depletion in ore deposits also contrasts with the generally positive Ge isotope values found in many modern and ancient marine sediments.  相似文献   

20.
Chalcopyrite is an important sulfide mineral in many types of ore deposits, but matrix‐matched chalcopyrite reference materials for microanalysis are lacking. A new natural chalcopyrite‐bearing specimen (HTS4‐6) was analysed in this study to investigate its potential as a reference material for microbeam sulfur isotope ratio measurement. Detailed textural examination and major element determination showed that the HTS4‐6 chalcopyrite grains have no growth rim or zoning. A total of 607 sulfur isotope ratio spot measurements with secondary ion mass spectrometry (SIMS) conducted on the cruciform sections, and over 120 randomly selected grains yielded highly consistent sulfur isotope ratio. The intermediate measurement precision for four measurement sessions of the 34S/32S measurement results was better than 0.39‰ (2s). Randomly selected chalcopyrite grains of HTS4‐6 were further analysed by LA‐MC‐ICP‐MS, which gave a mean δ34S value of +0.58 ± 0.38‰ (2s, n = 95). The maximum variance (expressed as intermediate precision from SIMS and LA‐MC‐ICP‐MS measurements) is not worse than 0.39‰ (the SIMS value), indicating that HTS4‐6 chalcopyrite is a potential reference material for in situ microbeam sulfur isotope measurements. The mean δ34S value determined by gas source isotope ratio mass spectrometry (GS‐IRMS) is +0.63 ± 0.16‰ (2s, n = 23), consistent with that derived by LA‐MC‐ICP‐MS, and can represent the recommended value for this potential reference material.  相似文献   

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