Quantitative micro‐X‐ray fluorescence scanning spectroscopy of wet sediment based on the X‐ray absorption and emission theories: Its application to freshwater lake sedimentary sequences

Micro‐X‐ray fluorescence scanning spectroscopy of marine and lake sedimentary sequences can provide detailed palaeoenvironmental records through element intensity proxy data. However, problems with the effects of interstitial pore water on the micro‐X‐ray fluorescence intensities have been pointed out. This is because the X‐ray fluorescence intensities are measured directly at the surfaces of split wet sediment core samples. This study developed a new method for correcting X‐ray fluorescence data to compensate for the effects of pore water using a scanning X‐ray analytical microscope. This involved simultaneous use of micro‐X‐ray fluorescence scanning spectroscopy and an X‐ray transmission detector. To evaluate the interstitial pore water content from the X‐ray transmission intensities, a fine‐grained sediment core retrieved from Lake Baikal (VER99‐G12) was used to prepare resin‐embedded samples with smooth surfaces and uniform thickness. Simple linear regression between the linear absorption coefficients of the samples and their porosity, based on the Lambert–Beer law, enabled calculation of the interstitial pore spaces and their resin content with high reproducibility. The X‐ray fluorescence intensities of resin‐embedded samples were reduced compared with those of dry sediment samples because of: (i) the X‐ray fluorescence absorption of resin within sediment; and (ii) the sediment dilution effects by resin. An improved micro‐X‐ray fluorescence correction equation based on X‐ray fluorescence emission theory considers the instrument's sensitivity to each element, which provides a reasonable explanation of these two effects. The resin‐corrected X‐ray fluorescence intensity was then successfully converted to elemental concentrations using simple linear regression between the data from micro‐X‐ray fluorescence scanning spectroscopy and from the conventional analyzer. In particular, the calculated concentration of SiO₂ over the depth of the core, reflecting diatom/biogenic silica concentration, was significantly changed by the calibrations, from a progressively decreasing trend to an increasing trend towards the top of the core.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

Spectrophotometric Determination of Gold (III) after Liquid–Liquid Extraction and Selective Pre‐concentration with a Novel Dibenzo‐18‐Crown‐6 Derivative

A selective and sensitive method for the extraction and spectrophotometric determination of gold with N,N′‐6,7,9,10,17,18,20,21‐octahydrodibenzo[b,k][1,4,7,10,13,16] hexaoxacyclo‐octadecine‐2,13–diylbis(2‐chloroacetamide) (ODBOCA) is described. The ODBOCA–Au(III) complex was extracted from a slightly acidic aqueous solution (pH 5) into a chloroform layer and then the absorbance of the extract was measured using a UV–Vis spectrophotometer with 1.0 cm quartz cells at 540 nm. An enrichment factor of 200 was achieved. In the chloroform medium at 540 nm, the molar absorptivity and Sandell’s sensitivity were 4.12 × 10³ l mol^?1 cm^?1 and 0.048 μg cm^?2, respectively. Beer’s law was obeyed in the range of 0.5–15 μg ml^?1 in the measured solution. The relative standard deviation for ten replicate samples at the 1.0 μg ml^?1 level was 3.0%. The limit of detection, based on 3s, was 0.5 μg l^?1 in the original sample. The effects of pH, ligand concentration and shaking time were studied. The ratio of the metal ion to ligand molecules in the complex was found to be 1:2 according to the Job Method. The effects of interference by a number of metal ions were investigated. The method was verified with certified reference materials and spiked tests, and quantitative recovery values were obtained. The method was fast, accurate, selective and precise, and was applied to the determination of gold in water and ore with good results.     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

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.     

Determination of Gold in e‐Waste Dust Samples and Geological Matrices by ICP‐MS after Extraction by an HClO4‐HBr‐HI‐Aqua Regia Mixture

This study describes two methods (Procedures‐1 and ‐2) for the direct extraction of Au by an inorganic acid mixture (HClO₄‐HBr‐HI‐aqua regia) from complex sample matrices. Standard PTFE jars at 200 °C were used to decompose test portions of 0.5–1 g, with subsequent precise and accurate analysis by ICP‐MS without any other preconcentration or separation. Procedure‐1 decomposed samples effectively without the necessity of leaching with HF and was developed for dust samples from e‐waste (electronic waste) processing; however, testing on geological reference materials showed very good results. The analyses of replicate decompositions (n = 5) from both procedures yielded very good precision (< 5% RSD) for most of the reference materials. The accuracy achieved was better than ± 10%, with the exception of NIST SRM 2782 data from Procedure‐1. Two unknown samples of dust from e‐waste processing (P‐1 and VM‐1) exhibited elevated concentrations of Au (21.31–61.64 μg g^?1) with precision better than 10% (n = 5). The proposed techniques are simple, sensitive and sparing in the use of chemicals, and are designed for a variety of e‐waste dust samples. No significant influences were observed for the predicted spectral interferences on mass ¹⁹⁷Au.     

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.     

New ICP‐MS Results for Trace Elements in Five Iron‐Formation Reference Materials

Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.     

Classical and New Procedures of Whole Rock Dissolution for Trace Element Determination by ICP‐MS

Sample digestion is a critical stage in the process of chemical analysis of geological materials by ICP‐MS. We present a new HF/HNO₃ procedure to dissolve silicate rock samples using a high pressure asher system. The formation of insoluble AlF₃ was the major obstacle in achieving full recoveries. This was overcome by setting an appropriate digestion temperature and adding Mg to the samples before digestion. Sodium peroxide sintering was also investigated and the inclusion of a heating step to the alkaline sinter solution improved the recoveries of thirteen elements other than the lanthanides. The results of these procedures were compared with data sets generated by common acid decomposition techniques. Forty‐one trace elements were determined using an ICP‐QMS equipped with a collision cell. Under optimum conditions of gas flow and kinetic energy discrimination, polyatomic interferences were eliminated or attenuated. The measurement bias obtained for eight reference materials (BCR‐2, BHVO‐2, BIR‐1, BRP‐1, OU‐6, GSP‐2, GSR‐1 and RGM‐1) and intermediate precision (RSD) were generally better than ± 5%. The expanded measurement uncertainties estimated for two certified reference materials were mostly between 7 and 15%. New data sets for the reference materials are provided, including constituents with previously unavailable values and also for the USGS candidate reference material G‐3.     

An Acetic Acid‐Based Extraction Protocol for the Recovery of U,Th and Pb from Calcium Carbonates for U‐(Th)‐Pb Geochronology

A new method for the simultaneous recovery of U, Th and Pb from ca. 0.5 g calcium carbonate samples for the purpose of U‐(Th)‐Pb geochronometry is presented. The protocol employs ion‐exchange chromatography. Standard anion exchange resin (AG 1‐X8 100–200 mesh) was used as the static phase, and 90% acetic acid was used as the mobile phase to elute the unwanted matrix components; dilute nitric acid was used to elute the U, Th and Pb. Blanks of 1.8 pg Th, 6.4 pg Pb and 8.4 pg U were obtained. The protocol was evaluated by determining the isotopic composition of U‐Th‐Pb separates obtained from an in‐house reference material (prepared from a natural speleothem) by MC‐ICP‐MS. An independently dated speleothem was also reanalysed. Based on these tests, the extraction protocol had an acceptable blank and produced a Pb separate sufficiently free of matrix‐induced instrumental biases to be appropriate for U‐Th‐Pb chronology.     

New Thorium Isotope Ratio Measurements in Silicate Reference Materials: A‐THO,AGV‐2, BCR‐2, BE‐N,BHVO‐2 and BIR‐1

A two‐step Th isolation protocol, involving micro‐columns of TRU‐Spec extraction chromatography material and AG1 resin, was evaluated. The MC‐ICP‐MS procedure included ²³²Th tailing characterisation and correction, and calibrator bracketing using an in‐house standard solution (ThS1) to correct for instrumental mass bias and Faraday cup to secondary electron multiplier relative gain. Repeated analyses of reference solutions (UCSC Th ‘A’, WUN, OU Th ‘U’, IRMM‐36) were consistent with published data. Six reference materials (A‐THO, BCR‐2, AGV‐2, BHVO‐2, BE‐N and BIR‐1) were processed. The average ²³⁰Th/²³²Th values obtained for these samples are in excellent agreement with published data. In addition, we report the first ²³⁰Th/²³²Th values for BE‐N and BIR‐1. The intermediate precisions for rock samples ranged from ± 0.24 to ± 0.49% (2 RSD) and were similar to those achieved for synthetic solutions, thereby supporting the overall validity of the chemical separation, data acquisition and reduction procedures. Counting statistics on the ²³⁰Th isotope was the most significant source of uncertainty. The intermediate precision of the mean ²³⁰Th/²³²Th for the Th‐depleted BIR‐1 (5.64 × 10^?6 ± 0.27%, 2 RSD) is in the range of the analyses of other reference materials analysed in this study.     

A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

Reassessment of HF/HNO3 Decomposition Capability in the High‐Pressure Digestion of Felsic Rocks for Multi‐Element Determination by ICP‐MS

Complete dissolution is essential to obtain accurate analytical results for geological samples. Felsic rocks are known to be very difficult to dissolve because of the presence of refractory minerals such as zircon. In this study, we undertook a systematic evaluation of the effect of the HF/HNO₃ ratio, digestion time, digestion temperature, digested test portion mass and the presence of insoluble fluorides on analytical results for the felsic rock GSP‐2 using high‐pressure HF and HF/HNO₃ digestion. Digestion in mixtures of HF and HNO₃ acids is a commonly used method of dissolution for geological samples. However, our results clearly indicate that adding HNO₃ inhibited the digestion capabilities of HF for refractory minerals such as zircon. It took 8–12 hr for Zr to be completely recovered in GSP‐2 at 190 °C, whereas it needed about 36 and 72 hr at 160 and 140 °C, respectively. White precipitates were observed in the final solution for test portion mass > 100 mg, irrespective of which of the five different digestion solutions was used (1 ml HF, 2 ml HF, 1 ml HF + 0.5 ml HNO₃, 1 ml HF + 1 ml HNO₃ and 1.5 ml HF + 1.5 ml HNO₃). Environmental scanning electron microscopy showed that these precipitates were mainly composed of AlF₃. Instead of further HCl, HNO₃ or HClO₄ attack, we propose that using ultra‐fine samples and a small sample size is a good way to avoid the formation of insoluble residues (e.g., fluorides). To further investigate the precision and accuracy of the proposed method (using HF alone as the digestion solution during the first acid attack step), a suite of silicate rock reference materials was analysed. Most of the results were found to be in reasonable agreement with the reference values, with a relative error of < 10%.     

Accurate and High‐Precision Determination of Boron Isotopic Ratios at Low Concentration by MC‐ICP‐MS (Neptune)

We report an approach for the accurate and reproducible measurement of boron isotope ratios in natural waters using an MC‐ICP‐MS (Neptune) after wet chemistry sample purification. The sample matrix can induce a drastic shift in the isotopic ratio by changing the mass bias. It is shown that, if no purification is carried out, the direct measurement of a seawater diluted one hundred times will induce an offset of ?7‰ in the isotopic ratio, and that, for the same concentration, the greater the atomic mass of the matrix element, the greater the bias induced. Whatever the sample, it is thus necessary to remove the matrix. We propose a method adapted to water samples allowing purification of 100 ng of boron with a direct recovery of boron in 2 ml of 3% v/v HNO₃, which was our working solution. Boron from the International Atomic Energy Agency IAEA‐B1 seawater reference material and from the two groundwater reference materials IAEA‐B2 and IAEA‐B3, was chemically purified, as well as boron from the certified reference material NIST SRM 951 as a test. The reproducibility of the whole procedure (wet chemistry and MC‐ICP‐MS measurement) was ± 0.4‰ (2s). Accuracy was verified by comparison with positive‐TIMS values and with recommended values. Seawater, being homogeneous for boron isotope ratios, is presently the only natural water material that is commonly analysed for testing accuracy worldwide. We propose that the three IAEA natural waters could be used as reference samples for boron isotopes, allowing a better knowledge of their isotopic ratios, thus contributing to the certification of methods and improving the quality of the boron isotopic ratio measurements for all laboratories.     

Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

Determination of Platinum‐Group Elements in Geological Samples by Isotope Dilution‐Inductively Coupled Plasma‐Mass Spectrometry Combined with Sulfide Fire Assay Preconcentration

A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO₃ and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with ¹⁹³Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g^?1 for Ru, 0.008 ng g^?1 for Rh, 0.045 ng g^?1 for Pd, 0.009 ng g^?1 for Os, 0.006 ng g^?1 for Ir and 0.016 ng g^?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.     

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.     

Determination of Bromine and Iodine Speciation in Drinking Water Using High Performance Liquid Chromatography‐Inductively Coupled Plasma‐Mass Spectrometry

A specific method for the determination of bromine and iodine species in drinking water was developed by using high performance liquid chromatography‐ICP‐MS. An ICS‐A23 ion chromatography column was chosen for the separation of species, with the mobile phase being 0.03 mol l^?1 ammonium carbonate at a flow rate of 0.8 ml min^?1. The detection limits for BrO₃^?, Br^?, IO₃^? and I^? were 0.032, 0.063, 0.008 and 0.012 μg l^?1, respectively. Spectroscopic interferences were only observed in blank samples and mainly resulted from the argon‐potassium polyatomic ion (⁴⁰Ar³⁹K⁺). However, this interference was negligible because of the elution and complete separation from that of iodinate under optimised conditions. The method developed was successfully applied to twenty‐two samples of drinking water obtained from a supermarket. Results indicated that 36.4% of the samples had BrO₃^? concentrations exceeding the Chinese national limit for drinking water of 10 μg l^?1.     

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.