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

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

Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials

We present new reference values for nineteen USGS, GSJ and GIT‐IWG rock reference materials that belong to the most accessed samples of the GeoReM database. The determination of the reference values and their uncertainties at the 95% confidence level follows as closely as possible ISO guidelines and the Certification Protocol of the International Association of Geoanalysts. We used analytical data obtained by the state‐of‐the‐art techniques published mainly in the last 20 years and available in GeoReM. The data are grouped into four categories of different levels of metrological confidence, starting with isotope dilution mass spectrometry as a primary method. Data quality was checked by careful investigation of analytical procedures and by the application of the Horwitz function. As a result, we assign a new and more reliable set of reference values and respective uncertainties for major, minor and a large group of trace elements of the nineteen investigated rock reference materials.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

Determination of Boron Concentration in Geochemical Reference Materials Extracted by Pyrohydrolysis and Measured by ICP‐MS

This article presents new boron concentrations for nine geochemical reference materials (GS‐N, FK‐N, GL‐O, BX‐N, DT‐N, AN‐G, GH, Mica‐Fe, Mica‐Mg). After extraction by a modified pyrohydrolysis technique, boron concentrations were measured by ICP‐MS. The blank levels for the whole procedure were 0.091 ± 0.020 ng ml^?1 or 14 ± 5 ng of boron in total. The method was first validated by measuring nine reference materials with known boron concentrations. The determined boron concentrations are all within the range of recommended or published values, which means that the yields were 100%, and show precisions below 10% for samples containing over 2 μg g^?1 of boron.     

Iron Isotopic Compositions of Geological Reference Materials and Chondrites

High‐precision iron isotopic compositions for Fe‐bearing geological reference materials and chondrites with a wide range of matrices (e.g., silicates, oxides, organic‐bearing materials) are reported. This comprehensive data set should serve as a reference for iron isotopic studies across a range of geological and biological disciplines for both quality assurance and inter‐laboratory calibration. Where comparison is available, the iron isotopic compositions of most geological reference materials measured in this study were in agreement with previously published data within quoted uncertainties. Recommendations for the reporting of future iron isotopic data and associated uncertainties are also presented. Long‐term repeat analyses of all samples indicate that highly reproducible iron isotopic measurements are now obtainable (± 0.03‰ and ± 0.05‰ for δ⁵⁶Fe and δ⁵⁷Fe, respectively).     

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

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

An Intercomparison Study of the Germanium Isotope Composition of Geological Reference Materials

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 δ^74/70Ge values. Using igneous and mantle‐derived rocks, the bulk silicate Earth (BSE) δ^74/70Ge 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.     

Calibration of the New Certified Reference Materials ERM‐AE633 and ERM‐AE647 for Copper and IRMM‐3702 for Zinc Isotope Amount Ratio Determinations

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 δ^65/63Cu values of ?0.01 ± 0.05‰ and ?0.21 ± 0.05‰ relative to ERM^®‐AE633 and ERM^®‐AE647, respectively, and a δ^66/64Zn_IRMM‐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.     

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

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

High‐Precision Iron Isotope Analysis of Geological Reference Materials by High‐Resolution MC‐ICP‐MS

We report high‐precision iron isotopic data for twenty‐two commercially available geological reference materials, including silicates, carbonatite, shale, carbonate and clay. Accuracy was checked by analyses of synthetic solutions with known Fe isotopic compositions but different matrices ranging from felsic to ultramafic igneous rocks, high Ca and low Fe limestone, to samples enriched in transition group elements (e.g., Cu, Co and Ni). Analyses over a 2‐year period of these synthetic samples and pure Fe solutions that were processed through the whole chemistry procedure yielded an average δ⁵⁶Fe value of ?0.001 ± 0.025‰ (2s, n = 74), identical to the expected true value of 0. This demonstrates a long‐term reproducibility and accuracy of < 0.03‰ for determination of ⁵⁶Fe/⁵⁴Fe ratios. Reproducibility and accuracy were further confirmed by replicate measurements of the twenty‐two RMs, which yielded results that perfectly match the mean values of published data within quoted uncertainties. New recommended values and associated uncertainties are presented for interlaboratory calibration in the future.     

Potential Orthopyroxene,Clinopyroxene and Olivine Reference Materials for In Situ Lithium Isotope Determination

Over 1400 electron probe and 700 ion probe microanalyses were performed on eleven mineral separates to evaluate their potential as reference materials for in situ Li isotopic determination. Our results suggest the homogenous distributions of major elements, Li and its isotopes for each sample. Hence, these samples are suitable to be used as reference materials for in situ measurements of Li abundance and Li isotopes by secondary ion mass spectrometry (SIMS) or laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). These samples have the advantage of mitigating probable matrix effects during calibration owing to the wide range of compositions. The effect of composition on the δ⁷Li of olivine measured by SIMS is a linear function of composition, with δ⁷Li increasing by 1.0‰ for each mole per cent decrease in forsterite component.     

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

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

Preparation of Four Chromium Ore Reference Materials

The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr₂O₃ ranged from 17.59 to 57.80% m/m. The contents of FeO and CO₂ were taken as reference values.     

Lithium Isotope Composition of Ultramafic Geological Reference Materials JP‐1 and DTS‐2

An organic solvent‐free two‐step column procedure is presented that provided robust, high yield and super clean separation of Li from silicate rock sample matrices. The measured δ⁷Li value for BHVO‐2 of +4.29 ± 0.23‰ (1s) is comparable with the reported values. The δ⁷Li values for GSJ JP‐1 (+3.14 ± 0.41‰, 1s) and USGS DTS‐2 (+4.91 ± 0.34‰, 1s) presented here provide new reference values for ultramafic rock reference materials.     

New Chinese National Reference Materials for Hydrogen and Oxygen Isotopes in Water

The Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences recently prepared four certified reference materials for hydrogen and oxygen stable isotopes in water, which are called ‘China Standard Water' (CSW)‐HO1–HO4 (hereafter referred to as HO1–HO4). These reference materials are intended for calibration purposes and provide reference values of their relative difference in ²H/¹H and ¹⁸O/¹⁶O isotope‐amount ratios expressed in delta notation, normalised to the VSMOW–SLAP scale. The certified values of the reference materials were determined by an interlaboratory comparison of results from eleven participating laboratories. This paper describes in detail the production and certification procedure of the four reference materials. The first analytical data for the reference materials are also provided using a variety of analytical techniques, namely CO₂–H₂O equilibration and laser spectroscopy for δ¹⁸O and Cr reduction, as well as H₂–H₂O equilibration, laser spectroscopy, and high‐temperature conversion for δ²H. The reference values for materials HO1–HO4 and their associated uncertainties are assigned.     

A Review of the IAG GeoPT™ and Certification Programmes,their Protocols,and the Differences between the Original and Potential Modifications to the Certification Protocol

The IAG conducts two programmes, the GeoPT ^? proficiency test and a certification programme that are closely interconnected. Both support the quality control/quality assurance activities of geochemical laboratories. Each derives an estimate of ‘true value’ for a number of samples, but arrives at that estimate, and its uncertainty, differently. This review discusses the history of the two programmes and compares the ‘true values’ and their uncertainties obtained through each. It then considers ‘fitness‐for‐purpose’ issues related to both GeoPT ^? and certification uncertainties. Issues related to potential modification of the IAG protocol for certification are also considered.     

Magnesium Isotopic Compositions of International Geological Reference Materials

Magnesium isotopic compositions are reported for twenty‐four international geological reference materials including igneous, metamorphic and sedimentary rocks, as well as phlogopite and serpentine minerals. The long‐term reproducibility of Mg isotopic determination, based on 4‐year analyses of olivine and seawater samples, was ≤ 0.07‰ (2s) for δ²⁶Mg and ≤ 0.05‰ (2s) for δ²⁵Mg. Accuracy was tested by analysis of synthetic reference materials down to the quoted long‐term reproducibility. This comprehensive dataset, plus seawater data produced in the same laboratory, serves as a reference for quality assurance and inter‐laboratory comparison of high‐precision Mg isotopic data.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

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 δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo 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.     

Precise and Accurate Doping of Nanoporous Silica Gel for the Synthesis of Trace Element Microanalytical Reference Materials

This study presents an experimental procedure to fabricate high‐purity silica glass containing a selected element at a specified mass fraction. The procedure was used to prepare glasses doped with trace‐level mass fractions of Ti with the goal of improving analytical confidence when measuring trace elements in quartz. Systematic tests were performed to determine the ideal conditions and procedures for doping nanoporous silica gel with the highest efficiency of dopant recovery. Silica gel was cleaned in concentrated HCl, immersed in a non‐polar doping medium at a controlled pH and doped with precise quantities of ICP‐MS standard solution. Using liquids composed of longer chain molecules as the doping medium diminishes recovery, suggesting that large molecules could obstruct nanopores to inhibit capillary uptake of the dopant. A control experiment using crystalline quartz reinforced the effectiveness of nanoporous silica gel for doping with trace‐level precision. Layered aggregates of silica gel doped with different Ti mass fractions were hot‐pressed to create multi‐layered reference materials that were analysed with multiple techniques at a variety of spatial scales. Analyses at the intra‐grain scale (cathodoluminescence scanning electron microscopy, electron probe microanalysis), at the single grain scale (SIMS), at the sample layer scale (EPMA, laser ablation‐ICP‐MS) and at the bulk scale (ICP‐OES) demonstrated acceptable homogeneity at sample volumes characteristic of most microanalysis techniques and show that nanoporous silica gel holds promise as a highly retentive doping substrate for preparing reference materials for laser‐, electron‐ and ion‐beam microanalysis.