Matrix-matched Reference Materials Research Articles

Rapid Sintering Method for Preparing Matrix-Matched Reference Materials in LA-MC-ICP-MS - An Example of Hafnium.

Matrix effects can significantly bias Hf isotopic ratios in situ Hf isotope analyses using laser ablation (LA-) multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS), necessitating the use of matrix-matched reference materials for accurate microanalysis. This work introduces a novel fast hot-pressing (FHP) sintering method to produce such reference materials efficiently for in situ analysis. By optimizing sintering temperatures, FHP technology enables the rapid preparation of in situ analysis reference materials with dense structures and homogeneous Hf isotopic compositions. The Hf isotope compositions of the FHP-sintered cassiterite and rutile were assessed using femtosecond LA-MC-ICP-MS, with results consistent with those determined by MC-ICP-MS. The homogeneity tests reveal minimal heterogeneity among the sintered sample tablets, suggesting their potential as reference materials for in situ Hf isotopic determination in cassiterite and rutile. The FHP method offers a rapid, cost-effective alternative to traditional preparation methods, producing large quantities of reference materials with compact structures. This procedure provides great promise for the synthesis of various isotope matrix-matched reference materials.

Consideration of spectral interference in total reflection X-ray fluorescence analysis using a limited number of calibration samples: Case study of ocean polymetallic nodules

A novel approach for quantitative analysis in total-reflection X-ray fluorescence (TXRF) which can be employed for the samples with complex matrices inducing overlapping spectral signals in the scenario of limited availability of standard samples is proposed. The approach is based on the least squares (LS) decomposition of real spectra into the weighted sum of simulated individual element subspectra and requires only a single sample of matrix-matched reference material. Oceanic polymetallic nodules and crusts, having complex mineral matrix and containing high concentrations of overlapping elements, were chosen to demonstrate the feasibility of the approach in quantification of 11 elements. The comparison of the results obtained with LS decomposition, internal standard and linear calibration with three standard samples was performed. It was demonstrated that the performance of the proposed approach and of the linear calibration was better than that of internal standard for most of the elements; however, the proposed method requires only a single standard sample.

Untargeted Metabolomics for Inborn Errors of Metabolism: Development and Evaluation of a Sustainable Reference Material for Correcting Inter-Batch Variability.

Untargeted metabolomics has shown promise in expanding screening and diagnostic capabilities for inborn errors of metabolism (IEMs). However, inter-batch variability remains a major barrier to its implementation in the clinical laboratory, despite attempts to address this through normalization techniques. We have developed a sustainable, matrix-matched reference material (RM) using the iterative batch averaging method (IBAT) to correct inter-batch variability in liquid chromatography-high-resolution mass spectrometry-based untargeted metabolomics for IEM screening. The RM was created using pooled batches of remnant plasma specimens. The batch size, number of batch iterations per RM, and stability compared to a conventional pool of specimens were determined. The effectiveness of the RM for correcting inter-batch variability in routine screening was evaluated using plasma collected from a cohort of phenylketonuria (PKU) patients. The RM exhibited lower metabolite variability between iterations over time compared to metabolites from individual batches or individual specimens used for its creation. In addition, the mean variation across amino acid (n = 19) concentrations over 12 weeks was lower for the RM (CVtotal = 8.8%; range 4.7%-25.3%) compared to the specimen pool (CVtotal = 24.6%; range 9.0%-108.3%). When utilized in IEM screening, RM normalization minimized unwanted inter-batch variation and enabled the correct classification of 30 PKU patients analyzed 1 month apart from 146 non-PKU controls. Our RM minimizes inter-batch variability in untargeted metabolomics and demonstrated its potential for routine IEM screening in a cohort of PKU patients. It provides a practical and sustainable solution for data normalization in untargeted metabolomics for clinical laboratories.

LEAD-LEAD DATING REVEALS PERMIAN REMOBILIZATION OF NIOBIUM MINERALIZATION AT BAYAN OBO

Abstract The Bayan Obo deposit hosted by the H8 unit is a world-class rare earth element (REE) deposit with considerable niobium (Nb) and iron (Fe). Permian granites are widely exposed in the mining area and have a close spatial association with the Nb mineralization. Whether the granites contributed Nb or only remobilized existing mineralization is important for understanding the controls of ore formation. Previous studies have mostly focused on the REEs, whereas research on Nb has been limited. This is due mainly to the difficulty of accurately determining the age of the Nb mineralization because of the fine-grained and texturally complex nature of the Nb-bearing minerals and their exceptionally low U content. Although microbeam techniques show promise in tackling the aforementioned challenges, their application is hampered by matrix effects caused by the diverse composition of Nb-bearing minerals. Here we report the application of a high-precision secondary ion mass spectrometry (SIMS) Pb-Pb isochron approach that enables young samples (i.e., <500 Ma) to be dated without matrix-matched reference materials. A variety of Nb-bearing minerals from eastern Bayan Obo were analyzed, yielding Pb-Pb isochron ages of 276 ± 10 Ma (pyrochlore, 394–6,864 ppm U in the rim and 6,563–19,858 ppm in the core), 277 ± 36 Ma (fersmite, 18–61 ppm U; fergusonite-Ce, 45–95 ppm U), and 257 ± 46 Ma (aeschynite, 342–1,006 ppm U). In combination with the deposit geology and petrographic observations, these ages link the Nb mineralization to ~270 Ma granites. As these granites are not particularly rich in Nb, skarn formation during granite emplacement is interpreted to have remobilized the existing Nb mineralization, which increased the grain size of the Nb-bearing minerals—a key factor facilitating their extraction. Our study shows that high-precision SIMS Pb-Pb analysis holds promise for directly dating mineralization without matrix-matched reference materials. It also emphasizes the need to consider the role of the Nb remobilization at Bayan Obo and elsewhere.

Laser ablation (in situ) Lu-Hf geochronology of epidote group minerals

Epidote group minerals, including allanite, clinozoisite and epidote are common in a range of metamorphic, igneous and hydrothermal systems, and are stable across a wide range of pressure–temperature (P–T) conditions. These minerals can incorporate substantial amounts of rare earth elements (REEs) during their crystallisation, making them potential candidates for Lu–Hf geochronology to provide age constraints on various geological processes. Here we report on a first exploration into the feasibility of in situ Lu–Hf geochronology for epidote group minerals from various geological settings and compare the results with age constraints from other geochronometers. Magmatic allanite samples from pegmatites and monzogranites in the Greenland anorthosite complex, Coompana Province and Qingling Orogen provided dates consistent with magmatic events spanning from c. 2660 to 1171 Ma. In the Qingling pegmatites, a younger phase of hydrothermal allanite was dated at c. 215 Ma, consistent with the timing of regional REE mineralisation. Allanite from the Yambah Shear Zone, Strangways Metamorphic Complex, yielded Lu–Hf age of c. 430 Ma. It predates the garnet and apatite growth at c. 380 Ma, suggesting the Lu–Hf system can be preserved in allanite during prograde amphibolite-facies metamorphism. Additionally, Lu–Hf dates for hydrothermal clinozoisite and epidote are consistent with the timing of hydrothermal alteration and mineralisation in a range of settings, demonstrating the utility of the technique for mineral exploration. Despite the current lack of matrix-matched reference materials, the successful application of laser ablation Lu–Hf geochronology to epidote group minerals offers valuable geochronological insights into various geological processes that can be difficult to access through other geochronometers.

A corundum reference material for oxygen isotope analysis by secondary ionization mass spectrometry

A synthetic laser ruby crystal (HD-LR1) is introduced as a new matrix-matched reference material for secondary ionization mass spectrometry (SIMS) analysis of oxygen isotopes in corundum.

A study on a natural pyrite sample as a potential reference material for simultaneous measurement of sulfur and iron isotopes using fs-LA-MC-ICP-MSs

A natural pyrite sample has been meticulously examined and identified as a promising reference material. It is ideally suitable for the simultaneous measurement of S and Fe isotopic compositions in pyrite samples using LA-MC-ICP-MS.

MAP-2 apatite: A new young age reference material for U–Pb dating with LA-ICPMS analysis

Apatite is an essential mineral for geochronology and geochemistry. Precise and accurate U–Pb Laser ablation (LA)-inductively coupled plasma mass spectrometry (ICPMS) dating of apatite requires suitable matrix-matched reference materials (RMs), but young RMs (<30Ma) are lacking from existing apatite RMs. We provided a gem-quality apatite MAP-2 collected from Myanmar and subjected it to detailed chemical composition and U–Pb dating analyses to assess its homogeneity and suitability as a reference material for LA-ICPMS age determination. The results of comprehensive analyses of multiple methods show that the MAP-2 apatite is largely free of inclusions and is relatively homogenous in chemical and isotopic content. Notably, MAP-2 apatite could be the youngest apatite U–Pb dating reference material (about 22 Ma) with relatively high U contents range from 161 μg g−1 to 231 μg g−1 and an average of 210 μg g−1. The isotope dilution-thermal ionization mass spectrometry (ID-TIMS) U–Pb measurements yielded weighted mean isotopic ratio values of 0.00345 ± 0.00003 for 206Pb/238U, 0.0243 ± 0.0039 for 207Pb/235U, 0.0512 ± 0.0082 for 207Pb/206Pb and the weighted mean 206Pb/238U ages of 22.18 ± 0.22 Ma (2SD, MSWD = 0.01, n = 6) as the recommended reference value. LA-ICPMS analyses yielded 207Pb-corrected weighted mean 206Pb/238U age of 22.0 ± 0.1/0.2 Ma (2SD, MSWD = 4.2, n = 232) and the results are consistent with ID-TIMS data within the limits of the ID-TIMS analytical uncertainly, which indicates that MAP-2 apatite has the potential as a reference material for microbeam determination of U–Pb ages.

A systematic evaluation of titanite reference materials for optimizing trace element and U[sbnd]Pb analysis by LA-ICP-MS

Titanite (CaTiSiO5) is a commonly occurring and versatile accessory mineral with broad applications in petrochronology. In situ U-Pb and trace element analyses via SIMS and LA-ICPMS are routinely performed using a matrix-matched reference material for U-Pb and standard glasses (non-matrix matched reference material) for elemental abundance determination. We report U-Pb isotopic ratios and major and trace element concentrations for three titanite samples (Ecstall, McClure and FCT) which are commonly used as reference materials in petrochronology studies. In addition, we characterize two new samples which can potentially serve as matrix-matched reference materials for titanite trace element geochemistry (BLR-2 and BRA-1). Based on electron microprobe analysis, samples BLR-1 and BLR-2 are homogeneous and suitable for use as a primary reference material for trace element concentrations. Whereas Ecstall, McClure, and FCT titanite reference materials show high intra-grain heterogeneity, yielding relative standard deviations for most trace elements between 5% and 40%, with higher standard deviations for U of 70% for Ecstall (n = 26), 265% for McClure (n = 22), and 202% for FCT (n = 26). Therefore, we suggest that these grains are unsuited to serve as reference materials for trace element quantification. The BRA-1 titanite has low trace element concentrations and is chemically heterogeneous (total REE abundances of 40 ppm for the rim and 95 ppm for the core of the grain), thus is not suitable for standardization of chemical composition using LA-ICPMS. It is commonly asserted that a matrix-matched standardization provides a more robust downhole fractionation correction compared to a non-matrix matched standardization. However, it remains unclear which standardization approach (matrix-matched vs non-matrix matched/glass) is more accurate for titanite trace element quantification. To resolve this, we tested several standardization approaches for trace element quantification, comparing matrix-matched (BLR-1) and non-matrix-matched (NIST612) standardizations with different internal elemental standards (IES; Ca, Si and Ti) and without internal standardization (semi-quantitative). To provide an independent constraint on the accuracy of the various trace element standardization techniques we compared results to trace element concentrations obtained via solution Q-ICPMS on crushed BLR-2 and BRA-1 aliquots. The matrix-matched standardization using Si as the IES yields the best reproducibility of trace element concentrations followed by the matrix-matched reduction using Ti as the IES. Moreover, the matrix-matched semi-quantitative correction yielded the lowest weighted percentage of difference compared to reference trace composition quantified by solution ICPMS. Finally, in this contribution we also benchmark sampling-size for precise U-Pb dating of common-Pb rich phases like titanite.

A newly synthesized reference material for in situ sulfur isotope measurement of sphalerite using laser ablation MC-ICP-MS

The PAS-synthesized sphalerite has a homogeneous sulfur isotopic composition and is suitable to be a matrix-matched reference material for in situ S isotope measurements of sphalerite.

High-precision ID-TIMS U-Pb geochronology of perovskite (CaTiO3) from the Ice River Complex, Southeastern British Columbia

Uranium‑lead perovskite in situ geochronology has become a cornerstone technique for determining the emplacement timing of alkaline, ultrapotassic, and silica-undersaturated igneous rocks, kimberlites, and carbonatites. Accurate in situ dates are dependent on the availability of matrix matched mineral reference materials which themselves are chemically well characterized and dated accurately to the highest possible precision. When dating perovskite to high precision, such as by isotope dilution thermal ionization mass spectrometry (ID-TIMS), appropriately accounting and correcting for the quantity and isotopic composition of Pb incorporated into the crystal upon crystallization (Pbi) is a large source of uncertainty and potential inaccuracy. Unfortunately, although ultra-high precision perovskite dates are attainable with modern mass spectrometry techniques, the accuracy of applied Pbi compositions, which can be a considerable percentage of total Pb in a crystal, has not kept pace, resulting in percent level inaccuracy on precisely measured isotopic ratios.In an effort to characterize the age and initial Pb isotopic composition of a readily available, relatively pure perovskite endmember (93–98%) which will be useful as a matrix matched age reference material for in situ U-Pb geochronology, we date crystals isolated from three samples from the Ice River Complex (samples 81IR6, I90.3, and I92.30) by ID-TIMS and evaluate their suitability as known-age reference materials. We directly determine the isotopic composition of Pbi in each sample by ID-TIMS measurement of cogenetic low 238U/204Pb (μ < 500) phlogopite, apatite, and/or clinopyroxene. Using these initial common Pb isotopic compositions, which are significantly more radiogenic than those predicted by age appropriate Pb evolution models, we obtain ultra-precise weighted-mean 206Pb/238U perovskite dates of 355.83 ± 0.14, 355.04 ± 0.15, and 357.34 ± 0.12 Ma on the three Ice River samples, respectively. These dates are consistent with the relative emplacement ages previously established for units in the Ice River layered ultramafic series based on field relationships. They also demonstrate the feasibility of attaining accurate perovskite dates in instances when maximum precision is critical by utilizing ID-TIMS analysis of cogenetic low uranium phases for direct measurement of Pbi.

In situ LA-ICPMS U–Pb dating of sulfates: applicability of carbonate reference materials as matrix-matched standards

Abstract. Recent developments in analytical capabilities in the field of in situ laser ablation mass spectrometry (LA-ICPMS) have expanded the applications of U–Pb geochronometers in low-U minerals such as carbonates or garnets. The rapid evolution of the technique relies on well-characterized matrix-matched reference materials. In this article, we explore the suitability of using carbonate as an “almost-matrix-matched reference material” for in situ U–Pb dating of sulfates. For such purpose, we have used the astrochronologically dated gypsum and anhydrite samples deposited during the Messinian Salinity Crisis (5.97–5.33 Ma) and compared these dates with the U–Pb ages obtained by LA-ICPMS. Although the majority of the samples failed due to the elevated common Pb content and low 238U/204Pb ratios, five of the samples showed a higher dispersion on U/Pb ratios. The obtained dates in four of these samples are comparable with the expected ages, while another gave an unexpected younger age, each of them with 6 %–11 % of uncertainty. The pit depth of the spots showed that the sulfates ablate similar to carbonates, so the offset due to the crater geometry mismatch or downhole fractionation can be assumed to be negligible. To sum up, the bias between the U–Pb and expected cyclostratigraphic ages, if any, is included in the uncertainty, and thus the results obtained here suggest that carbonate reference material is currently the best option for standardization of in situ U–Pb sulfate analyses.

Real matrix-matched standards for quantitative bioimaging of cytosolic proteins in individual cells using metal nanoclusters as immunoprobes-label: A case study using laser ablation ICP-MS detection

The persistent lack of adequate matrix-matched reference materials still hinders the quantitative analysis of elements and biomolecules in biological samples by LA-ICP-MS. This fact is especially critical in cell cultures due to their complex matrix. In this work, we propose a novel matrix-matched calibration strategy, which fully mimics the matrix of cultured cells, by using the same cell line of the sample to create laboratory standards. As a model case, the quantitative imaging of two cytosolic proteins (MT2A and APOE) in individual HRPEsv cells was performed by LA-ICP-MS, both in cells subjected to inflammation with cytokine Interleukin-1α (IL-1α) and controls (CT). A single biomarker strategy using Au nanoclusters (AuNCs) as specific antibody labels was employed for the analysis of the selected proteins in individual cells by LA-ICP-MS. HRPEsv cells supplemented with suspensions containing nude AuNCs was employed to generate single-cell laboratory standards (HRPEsv cells@AuNCs). The preparation and characterization of the single-cell laboratory standards by both ICP-MS and LA-ICP-MS were optimized as well as the data treatment protocol required for obtaining the quantitative distribution of the proteins in individual cells. The mass of APOE and MT2A per cell in CT and IL1α−treated HRPEsv cells analysed by LA-ICP-MS using the proposed matrix-matched calibration were successfully corroborated with commercial ELISA kits. In addition, quantitative real time polymerase chain reaction (qPCR) analyses were performed to study the proteins gene expression.

Quantitative Depth Profiling Using Online-Laser Ablation of Solid Samples in Liquid (LASIL) to Investigate the Oxidation Behavior of Transition Metal Borides.

The increased demand for sustainability requires, among others, the development of new materials with enhanced corrosion resistance. Transition metal diborides are exceptional candidates, as they exhibit fascinating mechanical and thermal properties. However, at elevated temperatures and oxidizing atmospheres, their use is limited due to the fact of their inadequate oxidation resistance. Recently, it was found that chromium diboride doped with silicon can overcome this limitation. Further improvement of this protective coating requires detailed knowledge regarding the composition of the forming oxide layer and the change in the composition of the remaining thin film. In this work, an analytical method for the quantitative measurement of depth profiles without using matrix-matched reference materials was developed. Using this approach, based on the recently introduced online-LASIL technique, it was possible to achieve a depth resolution of 240 nm. A further decrease in the ablation rate is possible but demands a more sensitive detection of silicon. Two chromium diboride samples with different Si contents suffering an oxidation treatment were used to demonstrate the capabilities of this technique. The concentration profiles resembled the pathway of the formed oxidation layers as monitored with transmission electron microscopy. The stoichiometry of the oxidation layers differed strongly between the samples, suggesting different processes were taking place. The validity of the LASIL results was cross-checked with several other analytical techniques.

The analysis of volcanic brines by freezing stage tandem LIBS-ICP-MS

Volcanic crater lakes pose unique hazards to the local population both during eruption and quiescence. The composition of crater lake fluids is therefore commonly monitored to aid hazard prediction and mitigation. Some of these fluids, such as at Kawah Ijen in Indonesia and Poas in Costa Rica, are hyper-acidic, concentrated brines (SO4–5 wt%, Cl - 2.5 wt%, Al - 5000 ppm). Analysis of such fluids requires extreme dilution due to the high total dissolved element load, which risks contamination and precipitate formation. To circumvent this undesired sample preparation and speed up the turn-around time on the analysis, we tested approaches which involved freezing the fluids to −30 °C and analysing them by simultaneous Laser Ablation-Inductively Coupled Plasma Quadrupole Mass Spectrometry (LA-ICP-QMS) and Laser-Induced Breakdown Spectroscopy (LIBS). LIBS is highly matrix sensitive, requiring matrix-matched reference materials. At the same time, LA-ICP-MS owes its success to being relatively insensitive to the matrix after accounting for differences in ablation yield. Analysing the fluids as a solid and sampling them by laser circumvents the usual dilution step. Fluid reference materials were prepared by adding the elements of interest to one of the crater lake fluid samples at known, but varying concentrations and by stepwise dilution of one of these fluids. Differences in ablation yield, resulting mainly from variations in the coupling of the laser with the sample, were accounted for by adding a known quantity of lithium as an internal standard. Working curves for both ICP-MS and LIBS were obtained for Al, Mg, Fe, Ca, K, Na, S and Cl, yielding relative trueness values for 4 crater lake samples of known composition of Al-7%, Ca-5%, Fe-1%, K < 1%, Mg-4%, Na-5%, S-3%, and Cl-6% for ICP-MS and Al-2%, Ca-9%, Fe-17%, K-10%, Mg-4%, Na < 1%, S-8%, and Cl-9% for LIBS. For these elements, ranging in concentration from around 400 mg/kg to 25 g/kg, LIBS yielded similar trueness results to ICP-MS. LIBS calibration without an internal standard produces acceptable results for Li only, allowing the cryo-LIBS to analyse the major elements while optimising the ICP-MS for trace-element analysis and obtaining a full suite of elements simultaneously without the need for sample dilution.

APPLICATION OF TOTAL-REFLECTION X-RAY FLUORESCENCE SPECTROMETRY (TXRF) TO GEOLOGICAL OBJECTS: EXPERIENCE OF THE TXRF LABORATORY, CENTER FOR GEODYNAMICS AND GEOCHRONOLOGY

Unlike conventional X-ray fluorescence spectrometry, the total-reflection X-ray fluorescence spectrometry is not a widespread and routine method for analyzing solid samples with mineral matrix, but it has a great potential for geochemical, geological, and archaeological studies. Rapid multi-elemental analysis of very small sample amounts can be performed by the internal standard method which does not require the matrix-matched reference materials. This is an undoubted advantage of the TXRF method over the conventional X-ray fluorescence method, especially if there is a limited available sample amount and a lack of well-characterized reference materials. This paper presents our experience with the application of TXRF spectrometry in the elemental analysis of apatite, ceramics, sediments, ores, and nodules. Special attention has been paid to the sample preparation procedure because it is one of the main sources of errors in the analysis. Preparing thin homogeneous specimen from the solid sample with a complex mineral matrix is not easy. Sample preparation strategy should be chosen considering the features of an analytical object, the content of the elements to be determined, and the accuracy required for a reliable interpretation. Consideration is being given to the examples of the preparation of a suspension for rapid analysis of ores and sediments, and to the original techniques of chemical decomposition for apatite and ceramics.

Combining standard addition and isotope dilution in order to improve SI traceable LA-ICP-MS measurements

Like in the previously published LA-ICP-MS method, the sample itself acts as the perfectly matrix matched reference material, but the combination with isotope dilution improves the uncertainty and accuracy of the novel LA-ID-ICP-MS method.

Reactor fuel characterization: Evaluation of multiple techniques for expedited analysis of 235U/238U isotopic ratios in U-10Mo

Uranium (U) enrichment measurements for the U.S. High Performance Research Reactor (USHPRR) conversion program are needed to certify the fuel is <20% 235U (tolerance range: 19.55%–19.95%). The main thrust of this work was to determine whether thermal ionization mass spectrometry (TIMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) U isotopic measurements can be made without chemically separating U from molybdenum (Mo) and other trace metal impurities. Although the data TIMS produces is considered the most accurate and precise, it is not typically used for isotopic analysis of U alloyed with 10 wt% Mo (U-10Mo) materials because of the complex sample preparation required prior to analysis. Results indicate that relative uncertainties on measurements made on chemically separated and unseparated samples was less than 0.03% (2 standard deviations) for this sample set with <0.06% trace metal impurities with no observable biases stemming from the presence of 10% Mo. This methodology provides relief from the bottleneck of separations chemistry, which discourages the use of TIMS and MC-ICP-MS in the case of 235U/238U ratios for U-10Mo, and allows for more rapid, highly accurate and precise determination of the 235U content in final fuel foils by TIMS. Additionally, samples were isotopically characterized for laser ablation multi-collector inductively coupled mass spectrometry (LA-MC-ICP-MS) by both TIMS and MC-ICP-MS in order to utilize them as in-house matrix matched reference materials in the absence of a standard.

Beryl Reference Materials for In Situ Oxygen Isotope Determination

The mineral beryl (Be3Al2(SiO3)6) has the most abundant phase with industrial value for extracting a critical metal—beryllium. Due to multi-stage, fluid-induced growth, individual beryl grains may yield complex geochemical records, revealing variations in the oxygen isotopes of the fluids from which they crystallize. Secondary ion mass spectrometry (SIMS) with high sensitivity and high spatial resolution represents a good tool for in situ isotopic analysis. SIMS oxygen analyses require matrix-matched reference materials to calibrate instrumental mass fractionations during measurement. In this work, the oxygen isotope homogeneities of six beryl samples with different compositions (BS1, BS2, BS3, BS4, BS5, and BS6) were documented by SIMS. These samples’ recommended oxygen isotope compositions were characterized by laser fluorination isotope ratio mass spectrometry (IRMS). This study suggests that there is no matrix effect related to composition variation in beryl SIMS oxygen isotope analysis. The recommended δ18O values of the four reference materials, BS1, BS2, BS4, and BS5, were 15.01 ± 0.34‰ (2 standard deviations, 2 SD), 7.53 ± 0.16‰ (2 SD), 2.38 ± 0.14‰ (2 SD), and 10.72 ± 0.44‰ (2 SD), respectively. Therefore, BS1, BS2, BS4, and BS5 are recommended as suitable reference materials for in situ mineral beryl oxygen isotope microanalysis.

Cassiterite oxygen isotopes in magmatic-hydrothermal systems: in situ microanalysis, fractionation factor, and applications

Tin and tungsten are important metals for the industrializing society. Deciphering the origin and evolution of hydrothermal fluids responsible for their formation is critical to underpin genetic models of ore formation. Traditional approaches obtain isotopic information mainly from bulk analysis of both ore and gangue minerals, or less frequently from in situ analysis of gangue minerals, which either bear inherited complexities and uncertainties or are indirect constraints. Hence, directly obtaining isotopic information from ore minerals such as cassiterite by in situ techniques is warranted. However, this has been hampered by challenges from both analytical and applicational aspects. In this study, we first demonstrate a lack of crystallographic orientation effects during cassiterite ion microprobe oxygen isotope analysis. Along with our newly developed matrix-matched reference material, the Yongde-Cst, which has a recommended δ18O value of 1.36 ± 0.16‰ (VSMOW) as defined by gas source isotope ratio mass spectrometry, in situ oxygen isotope analysis of cassiterite now is possible. We further refine the oxygen isotope fractionation (1000 ln α) for quartz-cassiterite by first-principles calculations, which is given by the equation of 1.259 × 106/T2 + 8.15 × 103/T − 4.72 (T is temperature in Kelvin). The 1000 ln α for quartz-cassiterite has a sensitive response to temperature, and makes cassiterite-quartz an excellent mineral pair in oxygen isotope thermometry, as described by the equation of T (℃) = 2427 × (δ18Oqtz − δ18Ocst)−0.4326 − 492.4. Using the well-established 1000 ln α of quartz-water, 1000 ln α of cassiterite-water is derived as 2.941 × 106/T2 − 11.45 × 103/T + 4.72 (T in Kelvin), which shows a weak response to temperature. This makes cassiterite an ideal mineral from which to derive δ18O of fluids as robust temperature estimates are no longer a prerequisite. We have applied oxygen isotope analysis to cassiterite samples from six Sn(-W) deposits in China. The results show considerable variability in δ18O values both within a single deposit and among studied deposits. Combining the δ18O of cassiterite samples and the equilibrium oxygen isotope fractionation, we find that the δ18O values of ore-forming fluids show a strong magmatic affinity with variable but mostly no to low degree involvements (~0-10%) of meteoric water, hence our results invite a reassessment on the extent and role of meteoric water in Sn-W mineralization. This study demonstrates that in situ oxygen isotope analysis of cassiterite is a promising tool to refine sources of ore-forming fluids, and to decode hydrothermal dynamics controlling tin and tungsten mineralization.