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• We report in situ S isotope analysis for multiple types of sulfides by LA-MC-ICPMS. • In situ S isotope analysis is applied to the study of the Erlihe Zn-Pb ore deposit. • Sulfur of the massive ores is likely sourced from the TSR process for the deposit. Sulfur isotopic composition is useful for tracing sources of ore-forming materials. In situ sulfur isotope analysis by laser ablation coupled with multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) has an advantage over traditional bulk analysis in tracing sources of sulfur in an ore deposit that has complex mineral types and multiple ore-forming processes. However, in using this method, matrix effects exist widely for sulfides from ore deposits. In this work, matrix effects of different sulfides were examined by matrix-unmatched tests, in which the δ34S values of different types of sulfides were calibrated against a laboratory pyrite standard. The results show that the δ34S values of pyrrhotite, chalcopyrite, molybdenite, sphalerite, and arsenopyrite are in agreement with the reference values, suggesting that the matrix effect was negligible. However, a significant matrix effect occurred in the analyses of Ag 2 S and galena, leading to significant deviations in δ34S values of up to 1.2‰ and 3.2‰, respectively. The matrix effect occurred not only during the laser ablation stage but also during the transition of ions into the mass spectrometer, resulting in significant space charge effects caused by heavy-mass elements. Thus, pyrite can be used as an external bracketing standard for sulfides that do not have a heavy-mass matrix. Based on our matrix-effect study, the following available external standards were selected for the in situ sulfur isotope analysis of complex-type minerals from the Erlihe Zn-Pb deposit. The coarse-grained sphalerite grains (Sph1) and euhedral to subhedral pyrite grains (Py1) from massive ores have δ34S values ranging from 9.2‰ to 18.1‰. Such heavy sulfur isotopic compositions indicate the derivation of sulfur from the deposits of seawater sulfate, related to a thermochemical reducing process. Fine-grained sphalerite (Sph2) and pyrite (Py2) from vein and disseminated ores coexist with pyrrhotite and chalcopyrite, and have relatively light sulfur isotopic compositions, with δ34S values of about 7‰. The slightly positive δ34S values are similar to those of sulfides from sulfide-rich quartz veins, which contain δ34S values of about 4‰, and granodiorite rocks, with δ34S values of about 6‰. Based on previous studies, the light sulfur of the late-stage sulfides may have resulted from a metamorphic or magmatic hydrothermal event during the Indosinian orogeny. In situ sulfur analysis by LA-MC-ICPMS provides new evidence for sources of sulfur from each stage of mineralization in the Erlihe deposit, suggesting that this is a promising method for studying complex ore deposits. [ABSTRACT FROM AUTHOR]

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

Lead isotopic compositions of international silicate glasses, feldspar and copper-based samples are obtained using femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry (fLA-MC-ICPMS). Some international glass standards for the microanalysis are applied to evaluate the method reported here. The Pb isotopic composition of these NIST glasses (SRM 610, 612, 614), USGS (BHVO-2G, BCR-2G, BIR-1G and GSD-1G) and MPI-DING glasses (GOR132-G, KL2-G, T1-G, StHs60/80-G) agree well with recommended values in 2 s error. One of 15 copper-based metals is found to have homogenized Pb isotope data and can be used as an external calibration standard and quality control sample for chalcopyrite, ancient coins, etc., to trace the genesis of metal deposit and culture exchange among different dynasties (GBW02137, 208Pb/ 204Pb = 37.9661 ± 0.0005 (2 s), 207Pb/ 204Pb = 15.5770 ± 0.0002 (2 s), 206Pb/ 204Pb = 17.7462 ± 0.0002 (2 s)). We also prepared a feldspar glass to serve as the external calibration standard/QC for Pb isotope analysis using fLA-MC-ICPMS. [ABSTRACT FROM AUTHOR]

A new matrix‐matched reference material (NWU‐Brt) with sulfur isotope ratios resembling those of natural barites has been developed for in situ S isotope measurements by laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS). A 100 g quantity of natural barite crystal was milled to ultra‐fine particles and sintered to a solid block using a fast hot‐pressing sintering technique (FHPS). We report δ34S ratios determined by isotope ratio mass spectrometry (IRMS), solution nebuliser multi‐collector inductively coupled plasma‐mass spectrometry (SN‐MC‐ICP‐MS) and LA‐MC‐ICP‐MS, involving up to six participating laboratories. The homogeneity of δ34S ratios of the synthesised barite was tested by LA‐MC‐ICP‐MS with an analytical spot size of 53 μm. The LA‐MC‐ICP‐MS results show that NWU‐Brt demonstrates a satisfactory homogeneous composition and is an appropriate material for calibrating δ34S ratios in barite. IRMS and SN‐MC‐ICP‐MS produced mean δ34S values of +14.17 ± 0.42‰ (2s) and +14.27 ± 0.23‰ (2s), respectively. The results of LA‐MC‐ICP‐MS analyses are consistent with the IRMS and SN‐MC‐ICP‐MS ratios within uncertainty. Overall, our results confirm the suitability of NWU‐Brt for the calibration of δ34S ratios in barite using LA‐MC‐ICP‐MS. [ABSTRACT FROM AUTHOR]

This study compares three zircon synthesis techniques (synthesis, high-temperature and high-pressure sintering and fast hot-pressing sintering) for the preparation of reference materials for Hf isotope analysis of zircon by laser ablation multi-collector inductively-coupled plasma mass spectrometry (LA-MC-ICP-MS). Ultrafine milled zircon powder particles doped with Yb2O3 produced by wet milling were used to synthesize zircon samples by using high-temperature and high-pressure sintering and fast hot-pressing sintering techniques. Li–Mo flux was necessary to obtain synthetic zircon grains. Zr signals for synthetic zircon grains and high-temperature and high-pressure sintered zircon are consistent with those of natural zircons but higher than that of fast hot-pressing sintered zircon, indicating that high-temperature and high-pressure sintered zircon has approximated the theoretical maximum density due to high pressure. The Hf isotopic compositions of high-temperature and high-pressure sintered and fast hot-pressing sintered zircon are comparable to those of the initial starting materials, whereas the Hf isotopes in synthetic zircon grains deviate slightly from those of the initial Hf solution. Compared with Hf isotope ratios obtained by SN-MC-ICP-MS, all preparation techniques give reliable LA-MC-ICP-MS results, suggesting that all synthetic zircon samples have great potential as both tools for in situ method development and isotopic reference materials. [ABSTRACT FROM AUTHOR]

Sulfur isotopes are important tracers in various geochemical processes. A matrix-matched reference material is essential for in situ sulfur isotope ratio measurement in sphalerite (ZnS), an abundant zinc sulfide in base metal deposits. In this study, natural sphalerite powders (GBW07270) were ground into ultra-fine powders and then sintered by using a plasma-activated sintering (PAS) method at 1000 °C and 50 MPa for 10 minutes. The synthesized sphalerite has a smooth surface and dense structure, making it suitable for laser ablation analysis. To investigate whether the PAS-synthesized sphalerite is an appropriate matrix-matched reference material for in situ sulfur isotope determination, a large number of in situ S isotope measurements were performed on the PAS-synthesized sphalerite by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). The LA-MC-ICP-MS results are highly consistent and yield a mean δ34SV-CDT value of −5.44 ± 0.20‰ (2SD, n = 1008), which agrees well with that measured by gas source isotope ratio mass spectrometry (GS-IRMS). Therefore, the PAS-synthesized sphalerite has a homogeneous sulfur isotopic composition and is a suitable matrix-matched reference material available for in situ S isotope measurements of sphalerite. [ABSTRACT FROM AUTHOR]

In this study, lead isotopic ratios in bronze artifacts were non-matrix-matched determined directly by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). We evaluated the necessity of matrix matching for lead isotope ratio analyses of bronzes by adopting thallium solution to correct mass discrimination during mass spectrometer measurements. Lead isotope ratios of four bronze reference materials were measured by fsLA-MC-ICP-MS to determine the quality of data when calibrating samples with standards having different physical characteristics and chemical compositions. The average 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, 208 Pb/ 204 Pb, 207 Pb/ 206 Pb and 208 Pb/ 206 Pb ratios determined by fsLA-MC-ICP-MS were within 0.06% of that by solution nebulizer MC-ICP-MS (SN-MC-ICP-MS). The results indicate that accurate lead isotopic compositions could be obtained by fsLA-MC-ICP-MS technique after non-matrix-matched standards calibration. Additionally, the lead isotopic compositions are presented for five Chinese bronze reference materials using fsLA-MC-ICP-MS. Homogeneity of lead isotope distribution was expressed as the RSD range from 0.010% to 0.017% for 208 Pb/ 204 Pb, 207 Pb/ 204 Pb, 206 Pb/ 204 Pb ratios. Therefore, the five bronze materials could potentially serve as external calibration standards and quality control samples for in situ lead isotope measurements of ancient bronze artifacts. The fsLA-MC-ICP-MS technique could be applied to differentiate the high radiogenic lead in bronze artifacts from common lead. [ABSTRACT FROM AUTHOR]

A new natural chalcopyrite reference material TC1725 is prepared for in situ Cu isotope measurement by femtosecond laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (fsLA‐MC‐ICP‐MS). Detailed textural examination and major element determination suggest the TC1725 chalcopyrite grains have no growth rim or zoning. The chalcopyrite grain is homogeneous with respect to Cu isotopes based on a large number of measurements performed by bulk solution nebuliser (SN)‐MC‐ICP‐MS, single‐grain SN‐MC‐ICP‐MS and fsLA‐MC‐ICP‐MS. The traditional bulk isotope analyses by SN‐MC‐ICP‐MS yielded a mean δ65Cu value of −0.06 ± 0.03‰ (2s, n = 132). Randomly selected single chalcopyrite grain of TC1725 determined by SN‐MC‐ICP‐MS without column chromatography gave a mean δ65Cu value of −0.06 ± 0.04‰ (2s, n = 188). The intermediate measurement precision for four measurement sessions was better than 0.04‰ (2s), suggesting TC1725 chalcopyrite is suitable as a microanalysis reference material for Cu isotope measurement. The mean δ65Cu value determined by fsLA‐MC‐ICP‐MS analyses on different individual chalcopyrite mounts and strips was −0.06 ± 0.03‰ (2s, n = 393), consistent with the bulk isotope composition within uncertainty. The recommended mean δ65Cu value for this chalcopyrite reference material is −0.06 ± 0.03‰ (2s, n = 132) as determined by bulk SN‐MC‐ICP‐MS. [ABSTRACT FROM AUTHOR]

A method was developed for the rapid in situ analysis of major and trace elements and Pb isotopes in silicate glass samples that combines laser ablation quadrupole and multi-collector inductively coupled plasma mass spectrometry (LA-Q-ICP-MS/MC-ICP-MS). Major, trace elements, and Pb isotope ratio compositions were clearly affected by laser conditions. Using a laser spot size of 160 μm, a laser ablation frequency of 15 Hz, an energy density 18 J/cm, and a 1: 9 ratio of laser ablation aerosol to the corresponding makeup gas, we obtained accurate major and trace element contents and Pb isotope ratios. Using Ca as the internal standard element, and GSE-1G and NIST 610 as the external standards for calibration, element contents generally matched the preferred values within 15%. Higher relative errors for some elements (e.g., Cr, Ga, Ge) may have been caused by lower than recommended values in some standards. The exponential law correction method for Tl normalization, with optimum adjusted Tl ratio, was utilized to obtain Pb isotopic data with good precision and accuracy. Pb isotopic ratios of the glass reference materials were in good agreement with the reference or published values to within 2 s measurement uncertainties, and the analytical precision was better than 0.17% (e.g., Pb/Pb). The developed method is a simple, reliable, and accurate technique for determining major, trace elements, and Pb isotope compositions of silicate glasses and minerals within a single ablation event. [ABSTRACT FROM AUTHOR]

In this study, a method for solidifying sulfide and sulfate nanoparticulate powder to prepare bracketing standards and samples for in situ S isotopic analysis using laser ablation multicollector inductively coupled plasma–mass spectrometry (LA-MC-ICP–MS) was developed. Sulfide or sulfate powder was transformed into a stable and mechanically resistant target by mixing it with epoxy resin. Using this method, seven bracketing standards with diverse matrix minerals (pyrite, chalcopyrite, sphalerite, galena, arsenopyrite, barite, and gypsum) were synthesized in the form of resin-preserved powders (RPPs). The effects of ablation behavior, powder particle size, and homogeneity on the S isotopic ratios in these RPPs were rigorously evaluated. The precision of the δ34S VCDT sulfur isotopic results obtained by LA-MC-ICP–MS was better than 0.47‰ (2SD uncertainty, n ≥ 20 over 4 months) for the S-bearing mineral RPPs. Finally, the in situ S isotope results of the seven RPPs measured by LA-MC-ICP–MS were consistent with the values obtained using solution nebulizer (SN)-MC-ICP–MS. The isotopic composition and homogeneity of a range of sulfide mineral RPPs (seven minerals referred to above) were characterized for use as potential reference materials. Our method provides the opportunity to prepare bracketing standards and samples for in situ S isotope analysis for a wide range of sulfur-bearing materials and is particularly appropriate for geologic samples with complex matrices and for which high spatial resolution in situ microbeam analysis is critical. More importantly, this method provides new prospects for the preparation of homogenized reference materials from natural minerals that are urgently needed for matrix-matched calibration and quality control of LA-ICP–MS geochemical and isotope data. [Display omitted] • A method for preparing bracketing S isotope standard has been developed. • Seven bracketing standards with diverse S matrices were synthesized in RPPs. • The precision of δ34S VCDT obtained were better than 0.47‰ for the S-bearing RPPs. • The S-bearing mineral RPPs solidifying method is reliability and robustness. • Isotopic composition and homogeneity of 7 RPPs were characterized for use as RMs. [ABSTRACT FROM AUTHOR]