Flux‐Free Fusion of Silicate Rock Preceding Acid Digestion for ICP‐MS Bulk Analysis

We present a new method for the decomposition of silicate rocks by flux‐free fusion in preparation for whole‐rock trace element determination (Sc, Rb, Sr, Y, Zr, Nb, Cs, Ba, rare earth elements and Hf) that is especially applicable to zircon‐bearing felsic rocks. The method was verified by analyses of RMs of mafic (JB‐1a, JB‐2, JGb‐1) and felsic rocks (JG‐3, JR‐3, JSd‐1, GSP‐2, G‐2). Pellets of powdered sample (up to 500 mg) without flux were weighed and placed in a clean platinum crucible. The samples were then fused in a Siliconit® tube furnace and quenched to room temperature. The optimum condition for the fusion of granitic rock was determined to be heating for 2–3 min at 1600 °C. The fused glass in the platinum crucible after heating was decomposed using HF and HClO₄ in a Teflon® beaker. Decomposed and diluted sample solutions were analysed using a quadrupole inductively coupled plasma‐mass spectrometer. Replicate analyses (n = 4 or 5) of the RMs revealed that analytical uncertainties were generally < 3% for all elements except Zr and Hf (～ 6%) in JG‐3. These higher uncertainties may be attributed to sample heterogeneity. Our analytical results for the RMs agreed well with recommended concentrations and recently published concentrations, indicating complete decomposition of our rock samples during fusion.     

Simultaneous Determination of Major and Trace Elements in Fused Volcanic Rock Powders Using a Hermetic Vessel Heater and LA‐ICP‐MS

Fused glass prepared without the addition of a flux is generally more homogeneous than a pressed powder pellet and thus ideal for analysis of bulk samples by LA‐ICP‐MS. In this work, a new glass‐making method using a boron nitride crucible was developed to prepare homogenous glass samples from silicate rock powder. The apparatus consisted of a small boron nitride vessel with net volume of about 34 mm³ and two molybdenum strips. Applying the summed metal oxide normalisation technique, both major and trace element contents in the fused glass were measured by LA‐ICP‐MS. Analyses of five geochemical reference materials (spanning the compositional range basalt–andesite–rhyolite) indicated that the measured SiO₂, Al₂O₃ and P₂O₅ contents matched the preferred values to within 5%, and the other major elements generally matched the preferred values to within 8%. Except for the transition metals, the measured trace element contents generally matched the preferred values to within 10%. Compared with the iridium heater method developed by Stoll et al. (2008), element volatilisation during high‐temperature melting was effectively suppressed in our method, but metal segregation caused by reduction of BN may cause loss of Cr, Ni and Cu. Although analysis with a large spot size has the advantage of improving counting statistics, matrix effects induced by mass loading of the ICP may hamper the accurate determination of some elements.     

An Evaluation of the Inter‐Method Discrepancies in Ferromanganese Nodule Proficiency Test GeoPT 23A

Round 23 of the GeoPT international proficiency testing scheme included the ferromanganese nodule powder FeMn‐1 which was distributed as an additional sample (23A). The aim of this initiative was to assess overall analytical performance for such a challenging oxide matrix with a view to the possible certification of such a material in accordance with ISO Guide requirements. To investigate inter‐method discrepancies, precision data and the method means for the most frequently used analytical methods (XRF, ICP‐MS and ICP‐AES) and sample preparation techniques were calculated and then compared using statistical tests of equivalence. For most major elements, XRF and ICP‐AES data dominated and these were found to give equivalent results. In contrast, for most trace elements significant discrepancies were detected between data obtained by different analytical methods. Possible causes are discussed with a view to attributing their origin to calibration strategy, sensitivity or interferences. It is assumed that the unusual oxide matrix generated unexpected interferences and thus method bias. Discrepancies observed between data from different analytical methods provide valuable information for the participating analysts, helping them to avoid systematic errors and thus minimising bias. They also suggest actions necessary to improve results for any future certification of such a material.     

Comparison of Fused Glass Beads and Pressed Powder Pellets for the Quantitative Measurement of Al,Fe, Si and Ti in Bauxite by Laser‐Induced Breakdown Spectroscopy

Due to matrix interference and sample particle size effects, some of the most important and difficult issues in laser‐induced breakdown spectroscopy (LIBS) analysis are the calibration and quantitative measurement of a complex matrix. This study proposes the use of borate fusion as an alternative sample preparation procedure for the quantitative measurement of Al, Fe, Si and Ti in bauxite by LIBS. Analytical calibration curves were made using bauxite certified reference materials (CRM), and the precision and accuracy of the methods were evaluated by analysing an additional bauxite CRM, using two different approaches: pressed powder pellets and fused glass beads. The borate fusion method was the most suitable sample preparation technique, since particle size effects and matrix interference could be minimised, obtaining better linearity on the analytical calibration curves (r²), and more accurate and more precise results for bauxite analysis.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

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.     

Determination of Mercury in One Hundred and Sixteen Geological and Environmental Reference Materials Using a Direct Mercury Analyser

The mercury content of 116 reference materials (RMs) from ten international organisations was determined in this study, which focused on variability within and between batches of RMs. Direct mercury analysis (DMA) was applied to RMs having Hg contents between 1 and 6300 ng g^?1 and provided good precision and accuracy. Accuracy was demonstrated by the agreement of our results with certified values, while replicates were made to establish the precision. Low within‐batch variability was noted, with precision from 0.1 to 23% (n = 3–5) apparently depending on Hg content and homogeneity, whereas systematic offsets were detected among several batches. Thanks to the analysis of different batches; the homogeneity or heterogeneity of several RMs was shown, and thus, suitable RMs for quality control for Hg determinations could be recommended.     

Forty‐Nine Major and Trace Element Concentrations Measured in Soil Reference Materials NIST SRM 2586, 2587, 2709a, 2710a and 2711a Using ICP‐MS and Wavelength Dispersive‐XRF

Excellent agreement was noted in the concentration of major and trace elements in five NIST (National Institute for Science and Technology) soil reference materials (NIST SRM 2586, 2587, 2709a, 2710a and 2711a) between measurement results from wavelength dispersive‐XRF and ICP‐MS from two independent laboratories, and NIST certificate of analysis and literature data. We describe the variability in concentrations of up to forty‐nine elements (plus loss on ignition) and provide values for up to twenty‐one elements previously uncharacterised by NIST in these soil RMs. The additional characterisation provided in this investigation can be utilised to reduce the measurement bias of custom calibration routines and improve the quality of control checks developed using these NIST RMs.     

Abundances of Sulfur,Selenium, Tellurium,Rhenium and Platinum‐Group Elements in Eighteen Reference Materials by Isotope Dilution Sector‐Field ICP‐MS and Negative TIMS

Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of ¹⁸⁷Os/¹⁸⁸Os. All concentrations were obtained from the same aliquot after HCl‐HNO₃ digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.     

Precise Determination of Silicon Isotopes in Silicate Rock Reference Materials by MC‐ICP‐MS

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.     

Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re‐Pt‐Os Isotope Systematics in Mafic‐Ultramafic Rocks

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

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.     

Determination of Total Sulfur in Fifteen Geological Materials Using Inductively Coupled Plasma‐Optical Emission Spectrometry (ICP‐OES) and Combustion/Infrared Spectrometry

A method for the determination of total sulfur in geological materials by inductively coupled plasma‐optical emission spectrometry (ICP‐OES) is described. We show that good results were obtained using this method even for sample types with very low (< 20 μg g^?1) sulfur concentration (e.g., peridotite). Sulfur was determined in fifteen geological reference materials with different sulfur contents. For reference materials with certified sulfur contents, the ICP‐OES method gave results in excellent agreement with certified values, and uncertainties better than 4% RSD. ICP‐OES results for sulfur in other reference materials yielded RSDs better than 10%, where S concentrations were > 100 μg g^?1 (except for diabase W‐2a, 16% RSD). Reference materials with lower sulfur contents (< 40 μg g^?1) showed much higher RSDs (17–18%). Except for RMs with certified values for sulfur, most data obtained by the combustion infrared detection method generally showed higher concentrations than those measured by ICP‐OES and a better RSD (≤ 8% for all materials except DTS‐2b).     

Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

Determination of Trace Elements in Geological Reference Materials G‐3, GSP‐2 and SGD‐1a by Low‐Dilution Glass Bead Digestion and ICP‐MS

We present a revised alkali fusion method for the determination of trace elements in geological samples. Our procedure is based on simple acid digestion of powdered low‐dilution (flux : sample ≈ 2 : 1) glass beads where large sample dilution demanded by high total dissolved solids, a main drawback of conventional alkali fusion, could be circumvented. Three geological reference materials (G‐3 granite, GSP‐2 granodiorite and SGD‐1a gabbro) decomposed by this technique and routine tabletop acid digestion were analysed for thirty trace elements using a quadrupole ICP‐MS. Results by conventional acid digestion distinctly showed poor recoveries of Zr, Hf and rare earth elements due to incomplete dissolution of resistant minerals. On the other hand, results obtained by our method were in reasonable agreement with reference data for most analytes, indicating that refractory minerals were efficiently dissolved and volatile loss was insignificant.     

Provisional Elemental Values for IAEA‐Sewage Sludge by Instrumental Neutron Activation Analysis

The International Atomic Energy Agency (IAEA) organised a proficiency test (PT), IAEA‐CU‐2010‐02, for the determination of elements in sewage sludge. The PT sample was analysed by semi‐absolute standardless k₀‐instrumental neutron activation analysis (k₀‐INAA). Results for seven elements (As, Co, Cr, Fe, Hg, Se, Zn) were submitted to the IAEA by our laboratory. All of our results were scored ‘acceptable’ by the ‘result evaluation criteria’ adopted by the IAEA. The same analytical methodology produced quantitative results for twenty‐six additional elements. In total, thirty‐six elements were determined with uncertainty varying from 4 to 11%. This paper presents the provisional mass fractions of twenty‐six additional elements (Ag, Al, Br, Ca, Ce, Cl, Dy, Eu, Ga, Hf, I, K, La, Mg, Mn, Na, Rb, Sb, Sc, Sm, Ta, Tb, Th, V, U, W) not reported by the IAEA. The analytical methodology was discussed with important sources of spectral, nuclear and fission‐product interferences. It was shown that the important components of uncertainties were the k₀ factor, Q₀ factor, detector efficiency, mass and counting statistics. The methodology was validated by analysing the IAEA‐S7 reference material.     

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.     

Spatial Geochemistry: A Characterisation of Heterogeneity in Reference Materials

Geochemical reference materials (RMs) for microbeam techniques are typically characterised by averages and dispersion statistics (e.g., standard deviation, variance) that are calculated for a number of measurements (beam shots). It is proposed that the mapping of RMs will add spatial information that better characterises the grouping and magnitudes of the heterogeneities and provides the information necessary to define a minimum analytical mass. A simple mathematical solution is proposed, which can be easily computed and understood. The analogous notions to sill and range from geostatistics are applied to the minimum analytical mass versus the relative standard deviation. To assess grouping and magnitudes of the heterogeneities, a ‘proximity number’ is computed for each average value ± ‘n’ standard deviations (magnitude). Different chemical anomalies have been simulated to demonstrate the behaviour of the proximity number. To further test the proposed spatial geochemistry concept, sulfide‐ and oxide‐bearing RMs have been selected because many are crippled with nugget effect. They have been mapped with a micro‐XRF apparatus, and results are presented for CHR‐Bkg, CHR‐Pt+, MASS‐1, MASS‐3, WMS‐1 and WMS‐1a. MASS‐1 and MASS‐3 are the most suitable RMs for microbeam techniques. Spatial geochemistry offers a new approach to better characterise reference materials.     

Rapid Determination of Trace and Ultra Trace Level Elements in Diverse Silicate Rocks in Pressed Powder Pellet Targets by LA‐ICP‐MS using a Matrix‐Independent Protocol

A simple, single sample preparation involving pressed rock powder pellets was utilised to determine the trace and ultra trace abundances of petrogenetically important elements including high field‐strength elements and REEs by laser ablation‐ICP‐MS. One of the elements predetermined by XRF spectrometry served as an internal standard. The influence of sample preparation parameters (grain size, pellet compactness and amount of binding media) on analytical performance was also investigated, including sample homogeneity issues at the laser sampling scale. Line scanning with a high repetition frequency (20 Hz) and large beam diameter (200 μm) ensured ablation from a larger sample surface area, eliminating issues related to sample heterogeneity. A median grain size of about 10 μm for silicate rock powders was found to be sufficiently representative at this scale of laser sampling. Granitic rocks or samples containing resistant minerals such as zircon needed extra grinding to achieve grain sizes down to < 5 μm for better precision for elements that are concentrated in these phases. Using ¹³⁷Ba as an internal standard, reasonable accuracies within 15–20% for most of the high mass trace elements were achieved; in the case of low mass elements, it may deviate up to 40%. Precision of measurements rarely exceeded 15% RSD.     

Determination of Mercury in Thirty‐three International Stream Sediment and Soil Reference Samples by Direct Mercury Analyser

Mercury was determined in thirty‐three international stream sediment and soil reference samples (eleven Chinese soils, GSS‐1 to GSS‐11; twelve Chinese stream sediments, GSD‐1A to GSD‐12; four Canadian stream sediments STSD‐1 to STSD‐4; South African stream sediments, SARM‐42, SARM‐46 and SARM‐47; Japanese stream sediments, JSd‐1 to JSd‐3) by direct mercury analyser. Samples were taken in 500 μl quartz boats, placed in an auto sampler and processed (drying time 60 s at 300 °C; decomposition time 120 s at 850 °C; waiting time 45 s). The instrument was calibrated in the low (0‐50 ng) and high ranges (50‐500 ng) with two reference materials GSS‐5 and GXR‐2 (USGS). Using the calibration line, reference samples were analysed for Hg. The results of the determinations agreed with the recommended values of RMs in all cases except JSd‐1. The RSD calculated for the RMs was found to be within 20%. The detection limit was 1 ng g^?1.