Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

High Sensitivity Analysis of Trace Element-Poor Geological Reference Glasses by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS)

Fifty-two trace elements in NIST SRM 614, 616 and MPI-DING BM90/21-G glass reference materials as well as in NIST SRM 612, USGS BCR2-G and other MPI-DING reference glasses (KL2-G, GOR132-G, GOR128-G, ATHO-G, Tl-G, StHs6/80-G and ML3B-G) were determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Accurate ultra-low trace element abundances in the NIST SRM 614, 616 and BM90/21-G reference glasses down to lower ng g⁻¹ levels were determined with relative standard deviations (RSD) of less than 10%. Limits of detection using He as carrier gas were up to two times lower than with Ar and were 0.004 to 0.12 μg g⁻¹ for elements of lower mass numbers (amu < 85) and 0.002 to 0.06 μg g⁻¹ for elements having amu < 85. The measured concentrations generally agree within 15% with previous studies except for B in NIST SRM 614 and 616, which appears to be heterogeneously distributed, and Co, Zn, Ga and Ag in NIST SRM 616 for which the existing data set is too small to evaluate the discrepancies. New values for As (0.593 μg g⁻¹), Ag (0.361 μg g⁻¹) and Cd (0.566 μg g⁻¹) in NIST SRM 614 and new values for Na (94864 μg g⁻¹) and As (0.276 μg g⁻¹) in NIST SRM 616 are reported.     

Determination of Selenium Concentrations in NIST SRM 610, 612, 614 and Geological Glass Reference Materials Using the Electron Probe, LA-ICP-MS and SHRIMP II

A combination of EMPA, sensitive high resolution ion microprobe (SHRIMP II) and/or LA-ICP-MS techniques was used to measure the concentration of selenium (Se) in NIST SRM 610, 612, 614 and a range of reference materials. Our new compiled value for the concentration of Se in NIST SRM 610 is 112 ± 2 μg g⁻¹. The concentration of Se in NIST SRM 612, using NIST SRM 610 for calibration, determined using LA-ICP-MS (confirmed using SHRIMP II) was 15.2 ± 0.2 μg g⁻¹. The concentration of Se in NIST SRM 614, using LA-ICP-MS was 0.394 ± 0.012 μg g⁻¹. LA-ICP-MS determination of Se in synthetic geological glasses BCR-2G, BIR-1G, TB-1G and the MPI-DING glasses showed a range in concentrations from 0.062 to 0.168 μg g⁻¹. Selenium in the natural glass, VG2, was 0.204 ± 0.028 μg g⁻¹.     

Total Sulfur Concentration in Geological Reference Materials by Elemental Infrared Analyser

Total sulfur is an analyte for which there are few determinations published, despite the fact that it is a very important element (e.g., a major element in most ores, an important gas constituent in global warming, an active participant in acid drainage). Most geological reference materials have very poor quality sulfur results, that is with relative standard deviations (RSD) in the range of 30–50%, even for concentrations over 100 μg g⁻¹ S, which compromises their use as calibrators. In order to provide modern results with low RSD, sulfur was determined in twenty-nine geological reference materials with a state-of-the-art elemental S/C analyser using metal chips (certified reference materials with a traceability link) and analytical grade sulfur for high concentration samples. Analytical parameters (sample mass, crucible degassing, calibration strategy, etc.) were optimised by testing. Our results agreed with reference material values provided by issuing bodies. Results for CCRMP SY-2 (129 ± 13 μg g⁻¹ S), which has been proposed as a sulfur reference material, were in agreement with the proposed modern value of 122 ± 3.7 μg g⁻¹ S.     

Simultaneous Determination of Total Carbon, Nitrogen, Hydrogen and Sulfur in Twenty-seven Geological Reference Materials by Elemental Analyser

The contents of total carbon, hydrogen, nitrogen and sulfur in twenty-seven geological reference materials, issued by five producer organisations (USGS, CCRMP, ANRT, NIST and GSJ) were determined using an automated simultaneous elemental analyser following combustion. In order to complete gasification of C and N in some geological materials, the combustion temperature needed to be greater than 1150 °C. The calibrator prepared from known amounts of reagent material was not adopted for more than 1.2% m/m of H. Unrealistically high values in certain materials supposed to contain less than 1000 μg g⁻¹ S may be due mainly to memory effects. The limit of detection was 50 μg g⁻¹ for C and N, 500 μg g⁻¹ for H and 1000 μg g⁻¹ for S. Although the blank value of C and N was always stable and less than one third of the detection limit, it had a slightly higher value for N and S. By repeating long-term analysis, high reproducibility for each of the four elements was verified. The method has been applied satisfactorily to a variety of geological reference materials, and recommended values for C, H and N for most of the reference materials studied have been tabulated.     

Determination of Selenium Concentration in Sixty Five Reference Materials for Geochemical Analysis by GFAAS after Separation with Thiol Cotton

Selenium has been determined in sixty five geological reference materials of different origins by graphite furnace atomic absorption spectrometry. Samples were decomposed with a mixture of nitric and hydrofluoric acids. Selenium was reduced to Se^IV with hydrochloric acid, and then fixed and separated from the matrix on thiol cotton. After digestion of the thiol cotton in hot nitric acid, the Se concentration was measured using palladium and magnesium nitrates as a matrix modifier. The limit of determination was 0.02 μg g⁻¹, the precision of the results (relative standard deviation of 3 to 8 replicates) varied from 2.6 to 17.7% with an average of 7.9% in the range 0.02-42.7 μg g⁻¹ and was similar to the value obtained for synthetic samples. Our results are in good agreement with available literature values.     

Preparation and Certification of Re-Os Dating Reference Materials: Molybdenites HLP and JDC

Two Re-Os dating reference material molybdenites were prepared. Molybdenite JDC and molybdenite HLP are from a carbonate vein-type molybdenum-(lead)-uranium deposit in the Jinduicheng-Huanglongpu area of Shaanxi province, China. The samples proved to be homogeneous, based on the coefficient of variation of analytical results and an analysis of variance test. The sampling weight was 0.1 g for JDC and 0.025 g for HLP. An isotope dilution method was used for the determination of Re and Os. Sample decomposition and pre-concentration of Re and Os prior to measurement were accomplished using a variety of methods: acid digestion, alkali fusion, ion exchange and solvent extraction. Negative thermal ionisation mass spectrometry and inductively coupled plasma-mass spectrometry were used for the determination of Re and ¹⁸⁷Os concentration and isotope ratios. The certified values include the contents of Re and Os and the model ages. For HLP, the Re content was 283.8 ± 6.2 μg g⁻¹, ¹⁸⁷Os was 659 ± 14 ng g⁻¹ and the Re-Os model age was 221.4 ± 5.6 Ma. For JDC, the Re content was 17.39 ± 0.32 μg g⁻¹, ¹⁸⁷Os was 25.46 ± 0.60 ng g⁻¹ and the Re-Os model age was 139.6 ± 3.8 Ma. Uncertainties for both certified reference materials are stated at the 95% level of confidence. Three laboratories (from three countries: PR. China, USA, Sweden) joined in the certification programme. These certified reference materials are primarily useful for Re-Os dating of molybdenite, sulfides, black shale, etc.     

Characterisation of Two New Reference Materials: STL-1, the Stewart Lepidolite and ZA-1, the Zapot Amazonite

The analysis of granitic pegmatites still remains a challenge because suitable natural reference materials are scarce or not available. Two new reference materials were prepared at the Smithsonian Institution, to provide an avenue to pursue the geochemical analysis of micas and feldspars in granitic pegmatites: STL-1, the Stewart lepidolite (NMNH 174041) and ZA-1, the Zapot amazonite (NMNH 174042). STL-1 was prepared from lepidolite collected from the lithium-rich Stewart pegmatite, San Diego County, California (33°22'52'N, 117°03'41'W). ZA-1 was prepared from an amazonite from the topaz-bearing Zapot pegmatite, Mineral County, Nevada, (38° 41'N, 118 °33'W). The results of this study indicated that STL-1 and ZA-1 are homogeneous and could be used as reference materials that would allow the expansion of calibration curves in XRF analysis up to 16000 μg g⁻¹ for Rb, 2000 μg g⁻¹ for Cs and 100 μg g⁻¹ for Tl. STL-1 and ZA-1 also contain unusually high concentrations of Ga and Tl, and STL-1 of Nb.     

Trace Element Analysis of NIST SRM 614 and 616 Glass Reference Materials by Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry

Fifty elements in NIST SRM 614 and 616 glass reference materials were determined by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). The values determined for NIST SRM 614 agreed well with the NIST-certified and information values (mean relative difference ± 3.6%), except for B, Sc and Sb. The values determined for NIST SRM 616 agreed with the NIST-certified and information values within a mean relative difference of ± 1.5%, except for B, Sc and Ga. In addition, at an 80 μm sampling scale, NIST SRM 614 and 616 glass discs were homogeneous for trace elements within the observed precisions of 5 and 15% (mean), respectively. Detection limits were in the range 0.01 - 0.3 μg g⁻¹ for elements of lower mass numbers (amu < 80) and 1 - 10 ng g⁻¹ for heavy elements (amu > 80). Detection at the sub ng g⁻¹ level is possible for most of the heavy elements by using an ablation pit size larger than 10 0 μm.     

Trace Element Data for Gold, Iridium and Silver in Seventy Geochemical Reference Materials

New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g⁻¹ were obtained. For Au and Ir concentrations above 10 ng g⁻¹, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g⁻¹ the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g⁻¹ to 6 μg g⁻¹. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

New ID-TIMS, ICP-MS and SIMS Data on the Trace Element Composition and Homogeneity of NIST Certified Reference Material SRM 610-611

We present new concentration data for twenty four lithophile trace elements in NIST certified reference material glasses SRM 610-SRM 611 in support of their use in microanalytical techniques. The data were obtained by solution ICP-MS and isotope dilution TIMS analysis of two different sample wafers. An overall assessment of these new results, also taking into account ion probe studies that have been published in the literature, shows that these wafers can be considered to be homogeneous. Therefore, individually analysed wafers are believed to be representative of the entire batch of the SRM 610-611 glasses. Possible exceptions are the alkali metals (and a few volatile or non-lithophile trace elements). The analysed concentrations range between 370 μg g⁻¹ (Cs) and 500 μg g⁻¹ (Sr) and agree well with published values. On the basis of our new data and data recently published in the literature we propose "preferred average" values for the elements studied. These values are, within a few percent, identical to those proposed by other workers.     

Boron Determination in Twenty One Silicate Rock Reference Materials by Isotope Dilution ICP-MS

The concentration of boron was determined in twenty one geochemical reference materials (silicate rocks) by isotope dilution inductively coupled plasma-mass spectrometry. Boron was extracted from the rocks using HF digestion, suppressing boron volatilisation through boron-mannitol complexation. Sample solutions, in a diluted HCl matrix, were analysed by ICP-MS without any separation of boron from the matrix elements. The results obtained were in agreement with the literature data and indicate that using the described procedure, trace amounts of boron can be very easily determined in complex matrices with rapidity and precision. With the instrumentation and reagents used in this study, this procedure can be used for the determination of 0.5 μg g⁻¹ boron in a 15 0 mg silicate rock sample. Replicate analyses of the twenty one geochemical reference materials (GRM), ranging in boron concentration from 1.35 to 15 7 μg g⁻¹, yielded precisions (relative standard deviation) varying between 0.9 and 9.8%.     

Determination of Molybdenum in Fifty Three Geochemical Reference Materials by Flameless Atomic Absorption Spectrometry

The molybdenum (Mo) contents of fifty three geochemical reference materials issued by ANRT, GIT-IWG, NIST and GSJ, have been determined by atomic absorption spectrometry, using a graphite furnace atomiser, after extraction of Mo dithiol with isoamyl acetate. Detection limits for this method (0.01 μg g⁻¹) are ten times smaller than for most classical methods. The agreement between the present results and published data is satisfactory.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

Chemical Characterisation of NIST Silicate Glass Certified Reference Material SRM 610 by ICP-MS, TIMS, LIMS, SSMS, INAA, AAS and PIXE

National Institute of Science and Technology (NIST) silicate glass SRM 610 is widely used as a certified reference material for various micro-analytical techniques such as SIMS or laser ablation ICP-MS. SRM 610 has been nominally doped with sixty one trace elements at the 500 μg g⁻¹ level, but certified concentration data exist for only a few of these elements. This study reports concentration data for fifty nine trace elements obtained by ICP-MS, SSMS, LIMS, TIMS, INAA, AAS, and PIXE analyses of two different SRM 610 wafers. Most elements fall within a 10% band around a median value of about 440 μg g⁻¹. The REE concentrations are shown to be constant to 3% (1 σ), thus emphasizing the value of SRM 610 as a reference material for REE analyses.
Comparison of our values with published data suggests that different SRM 610 wafers are, within errors, chemically identical for most elements. Exceptions to this general rule appear to be restricted to elements which were partly lost during the production of the glass, e.g. Ag and Br. On the basis of six independent determinations of Rb concentrations, which are systematically lower by a few percent than the reported NIST value, we argue that the certified Rb concentration may not be representative for all distributed SRM 610 wafers.     

Trace Determination of Strontium and Barium in River Waters by Inductively Coupled Plasma-Atomic Emission Spectrometry Using an Ultrasonic Nebulizer

Inductively coupled plasma-atomic emission spectrometry in conjunction with an ultrasonic nebulizer was employed for the determination of Sr and Ba in river waters at parts per billion (μg l⁻¹) levels without pre-concentration. The ultrasonic nebulizer, equipped with a desolvation system, enhanced the analytical sensitivity by ten to twenty fold compared to conventional pneumatic nebulizers. The detection limits for Sr and Ba, ascertained from blanks and reference samples made in 0.05% NaCl solution, were 0.045 μg l⁻¹ and 0.16 μg l⁻¹ respectively. The accuracy of measurements, based on analyses of solutions of reference materials (G-2 and W-1) and multielement commercial standards (Merck®), was ± 10%. Replicate analyses of samples and reference samples showed measurement precision to be to be better than ± 5%, which is adequate considering that the concentration of Sr and Ba in river waters varies by one to two orders of magnitude.     

Determination of Beryllium and Zirconium In 45 Geochemical Reference Samples By Inductively Coupled Plasma Emission Spectrometry

The beryllium and zirconium contents of 45 geochemical reference samples have been determined by inductively coupled plasma after fusion of the samples with lithium metaborate and dissolution of the melt in dilute nitric acid. The method described here is rapid and sample preparation straightforward. Good agreement is shown with previously published results for these two elements. A correction has to be made for an interference due to vanadium in determining the beryllium content, and there is a slight interference due to yttrium in the determination of zirconium. The detection limit for beryllium is about 0.2 μg g^-1 and for zirconium about 15 μg g^-1 in the sample.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.