Trace Element Analysis of Natural Gold by Laser Ablation ICP-MS: A Combined External/Internal Standardisation Approach

For the trace element analysis of gold by laser ablation ICP-MS, external calibration samples of differing matrix composition have been used in previous studies. Data presented here suggest that even for calibration samples and unknowns with closely-matched matrices, discrepancies arise due to variations in the coupling behaviour of the laser with the sample at different power deliveries, and can lead to erroneous trace element determinations. Internal standardisation for gold is complicated because Au and Ag, the most common major elements, do not have minor isotopes that can be used as internal standards. This problem was overcome for natural gold samples by using an external calibration sample only for the major elements Au and Ag, then defocussing the ion path and using ¹⁰⁷Ag in each sample as an internal standard against which μg g^-1 levels of Te, Sb, Hg, Bi, and Cu were determined. The results suggest that trace elements can occupy lattice sites in gold rather than occurring only as micro-inclusions of other phases. The analytical approach taken here may be used in trace element analysis where adequate external calibration samples are not readily available.     

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.     

Zircon U–Pb age, trace element and Hf isotope composition of Kongling terrane in the Yangtze Craton: refining the timing of Palaeoproterozoic high-grade metamorphism

U–Pb age, trace element and Hf isotope compositions of zircon were analysed for a metasedimentary rock and two amphibolites from the Kongling terrane in the northern part of the Yangtze Craton. The zircon shows distinct morphological and chemical characteristics. Most zircon in an amphibolite shows oscillatory zoning, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high formation temperature, high trace element contents, clear negative Eu anomaly, as well as HREE-enriched patterns, suggesting that it is igneous. The zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2857 ± 8 Ma, representing the age of the magmatic protolith. The zircon in the other two samples is metamorphic. It has low Th/U ratios, low trace element concentrations, variable HREE contents (33.8 ≥ Lu_N≥2213; 14.7 ≤ Lu_N/Sm_N ≤ 354) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.000030–0.001168). The data indicate that the zircon formed in the presence of garnet and under upper amphibolite facies conditions. The metamorphic zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2010 ± 13 Ma. These results combined with previously obtained Palaeoproterozoic metamorphic ages suggest a c. 2.0 Ga Palaeoproterozoic collisional event in the Yangtze Craton, which may result from the assembly of the supercontinent Columbia. The zircon in two samples yields weighted mean two-stage Hf model ( T _DM2) ages of 3217 ± 110 and 2943 ± 50 Ma, respectively, indicating that their protoliths were mainly derived from Archean crust.     

Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.     

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.     

Quantitative aspects of Mn-activated cathodoluminescence of natural and synthetic aragonite

The cathodoluminescence analyses of the trigonal carbonates calcite and dolomite have been applied intensively in sedimentary petrology for a long time and the properties of these minerals are well-known, but much less attention has been paid to aragonite. In this study, the cathodoluminescence behaviour and the trace element composition of natural and synthetic aragonite have been studied employing trace element analyses (proton induced X-ray emission) and luminescence spectroscopy. Aragonite doped with Mn²⁺ has been synthesized in a NH₄⁺–Mg²⁺–Ca²⁺–Cl⁻ solution in contact with a CO₂–H₂O–NH₃ atmosphere. The low effective distribution coefficients indicate a rapid growth of the crystals of millimetre size which occurred within hours or days. The natural aragonite samples contain Mn, Fe and Sr in different concentrations. The Mn-bearing aragonites exhibit a bright green luminescence which is caused by a strong emission band at 575 nm with a half-width of about 84 nm. The luminescence intensity shows a strong positive correlation with Mn in aragonite when Fe and Mn do not exceed 2000 p.p.m. The intensity is depressed if the concentration of these elements exceeds the critical values. In the shell of a recent Unio sp., the luminescence intensity deviates from the linear correlation, although the trace element contents are not too high; this is probably an effect of quenching by organic material between the crystallites of the biogenic aragonite.     

Heavy Mineral Placer Deposits of Ekakula Beach, Gahiramatha Coast, Orissa, India

Abstract: Ilmenite, hematite, garnet, monazite, zircon, rutile, magnetite, sillimanite, pyroxene and amphibole from the beach sands of Ekakula, Gahiramatha coast, Orissa, India are reported here for the first time. Their total concentration varies from 26. 4 to 100%. Ilmenite, monazite and zircon are between 100 and 300 um in size and are well rounded in shape. Ilmenite-hematite intergrowth is common. Ilmenite has 50. 02–54. 73% TiO₂, 42. 42–46. 90% FeO (total Fe) and small amounts of Al, Mn, Mg, Ca, Ba, Si, V, Cr, and Zn. The bulk samples contain 10. 63–41. 42 % TiO₂, 6. 15–26. 07 % FeO, 5. 86–16. 75 % Fe₂O₃, 7. 41–61. 74 % SiO₂, 1. 39–12. 83% A1₂O₃, 0. 32–4. 97% CaO, 0. 53–4. 24% P₂O₅, 0. 17–3. 27% MgO, 0. 15–2. 97% Na₂O, 0. 07–2. 34% K₂O, and 0. 05–0. 71% V₂O₅ together with appreciable amounts of La, Ce, Pr, Nd, Sm, Eu, Y, U, Th, Zr, and trace amounts of Pb, Zn, Cu, Ni, Co, and Cr. Khondalite, charnockite, calc-silicate granulite, leptynite, migmatite, gneiss, basic granulite and pegmatite of the Eastern Ghats appear to be the major source for the above heavy mineral assemblages. The samples are amenable to gravity and magnetic methods of beneficiation.     

Trace Element Analysis of Fused Whole-Rock Glasses by Laser Ablation-ICP-MS and PIXE

The concentrations of fifty trace elements, including relatively volatile elements and transition metal elements, in fused glasses of Geological Survey of Japan rock reference materials GSJ JR-2, JA-1, JA-2, JB-1a, JB-3, JGb-1 and JF-1 were determined by particle (proton) induced X-ray emission (PIXE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The fused glasses were prepared by rapid fusion and subsequent quenching in welded platinum capsules and were found to be homogeneous for major elements and for trace elements with concentrations of more than 1 μg g^-1 within the observed precision (± 10% mean) on a 70 μm sampling scale. The values obtained by PIXE and LA-ICP-MS for the transition elements (Cr, Mn, Fe, Ni and Cu), the relatively volatile elements (Zn, Ga, Rb and Pb) and the refractory elements (Y, Zr, Nb and Th) with concentrations greater than a few μg g^-1 showed good agreement (within 10 % relative difference). The values for almost all the elements detected at concentrations higher than 1 μg g^-1 as determined by LA-ICP-MS also agreed well with the reference values (mean relative difference < ± 10%), except for B and Cu. The good agreement confirmed the appropriateness of the NIST SRM 600 series glass calibration reference material for LA-ICP-MS analysis of glasses with variable major-element compositions for almost all elements. The concentrations of Cu in all the samples were lower than the reference values, which was attributed to adsorption of the transition metals onto the platinum capsule during preparation.     

1994 REPORT ON WHIN SILL DOLERITE WS-E FROM ENGLAND AND PITSCURRIE MICROGABBRO PM-S FROM SCOTLAND: ASSESSMENT BY ONE HUNDRED AND FOUR INTERNATIONAL LABORATORIES

This compilation report describes the field location, mineralogy, preparation and homogeneity testing of two new GIT-IWG reference materials: Whin Sill dolerite (WS-E) from England and Pitscurrie microgabbro (PM-S) from Scotland. The elemental composition of these two new reference materials has been established by an international cooperative analysis programme involving participation by 104 laboratories. A full assessment of these analytical results is presented, from which working values have been derived for the major elements as well as for 45 trace elements in WS-E and 44 trace elements in PM-S. Furthermore, isotopic ratios are presented for both samples, particularly for ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd.     

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 the Quartz Reference Material UNS-SpS and in Natural Quartz Samples by ICP-MS

A procedure for the digestion and analysis of quartz samples was developed to measure trace element concentrations in natural quartz. The certified glass sand reference material UNS-SpS was chosen to assess the precision, accuracy and detection limit of the analytical method. Quartz was digested with HF/HNO₃ in a closed glassy carbon vessel and analysed by means of quadrupole ICP-MS with external calibration. Analyte concentrations of the sand UNS-SpS were compared with certified and other values from the literature. The abundances of a number of elements (Pr, Gd, Ho and Er) in the reference material are reported here for the first time. The procedure was then applied to three quartz samples from different geological settings to show that trace element data by ICP-MS can distinguish the origin of the sample.     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

Preparation of a Synthetic Titanite Glass Calibration Material for In Situ Microanalysis by Direct Fusion in Graphite Electrodes: A Preliminary Characterisation by EPMA and LA-ICP-MS

This paper describes a technique for the preparation of a titanite (CaTiSiO₅) glass calibration material for use in in situ microanalysis of major, minor, and trace elements in geological materials. The starting composition was a titanite matrix doped with minor and trace elements at ∼ 200 μg g^-1. The elements Sc, Y, REEs, Th and U were added in the form of nitrates in solution, and the elements V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Hf and W were added as solid oxides. The synthetic titanite glass was produced by direct fusion by resistance heating in graphite electrodes at 1600-1700 °C, and quenched in air. Backscattered electron images indicate good homogeneity, with no signs of separate phases or vesicles, and analysis of the major elements Ca, Ti and Si by electron microprobe showed relative standard deviations between 0.5 and 0.7%, based on six independent measurements. Deviations from nominal concentrations for Ca, Si and Ti were measured to -1.2, -3.3 and -0.8%, respectively. The homogeneity of the trace elements in the glass was assessed by LA-ICP-MS analyses, using NIST SRM 610, 612 and 616 as external calibrators, and Ca as the internal standard element. Determinations were made both with a quadrupole mass spectrometer and a sector field instrument, and both raster and spot modes of analysis were used. For the majority of doped elements, precision was better than 10%, and relative deviations from nominal values were, with few exceptions, between 5 and 10%.     

Analyse des Standards de L'U.S.G.S. : GXR-1 a GXR-6 par Activation Neutronique et Fluorescence X

Six roches standards de I'USGS : GXR-1 à GXR-6 ont été analysées par activation neutronique instrumentale (INAA) pour le dosage de 17 éléments traces et par fluorescence X (XRF) pour les autres éléments difficiles à doser par activation neutronique. Les travaux précédemment publiés par Gladney et al. ont été pris comme référence en particulier les valeurs recommandées (R.V.) qui sont généralement en bon accord avec nos résultats. Quelques remarques et corrections sont proposées pour expliquer certaines disparités.
Six United States Geological Survey's (USGS) Geochemical Exploration References Samples (GXR) have been analyzed by instrumental neutron activation analysis (INAA) for the determination of seventeen trace elements and by X-ray fluorescence spectrometry (XRFS) for other trace elements difficult to determine by INAA. Our results compare favourably with the values recommended by E.S. Gladney et al. Some suggestions and corrections are proposed to explain some discrepancies.     

Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

Geochemistry of granitoids and their minerals from Rebordelo–Agrochão area, northern Portugal

Deformed Hercynian peraluminous granitoids ranging from tonalite to granite crop out in the Rebordelo–Agrochão area, northern Portugal and some of them contain tonalitic and granodioritic enclaves. Variation diagrams of major and trace elements of the rocks, biotites and sphenes show fractionation trends. The most- and the least-deformed samples of granite and their biotites also define fractionation trends. There is decrease in all rare earth element (REE) contents and increase in the Eu anomaly in REE patterns from the most- to the least-deformed samples of granite. All the granitoids define a whole-rock Rb–Sr errorchron. A whole-rock Rb–Sr isochron for the least-deformed samples of granite yields an age of 357±9 Ma and an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7087±0.0007. Geochemical modelling suggests that the tonalitic magma evolved by AFC (fractional crystallization of magnesiohornblende, plagioclase, quartz, biotite and ilmenite, and assimilation of metasediments) to originate tonalitic and granodioritic enclaves, granodiorite and granite. δ¹⁸O values support this mechanism. The tonalite is hybrid and derived by interaction of a mantle-derived magma and crustal materials.     

Preliminary Investigation into the Use of a High Resolution Inductively Coupled Plasma-Mass Spectrometer with Laser Ablation for Bulk Analysis of Geological Materials Fused with Li2B4O7

The paper presents preliminary results of the use of a high resolution double-focussing, magnetic sector inductively coupled plasma-mass spectrometer (HR-ICP-MS) with ultraviolet laser ablation (LA) for the bulk analysis of geological materials fused with Li₂B₄O₇. Detection limits are based on data from precision measurements of a fused SiO₂ sample of high purity, and sensitivity data (cps/μg g^-1) obtained on the Reference Material (RM) Syenite SY-2. For many trace elements, the detection limits are better than 0.05 μg g^-1 using a sample to flux weight ratio of 1:7.
Calibration curves, which are based entirely on RMs, are established for Hf, Ta, Tb, Tm and Lu. They indicate that, even at this early stage in the development of the technique, data accurate to ˜ 25% can be collected. It is concluded that the method may prove to be a valuable supplement to XRF for low level element concentration measurements; it is also very practical, as the same sample discs can be used for both XRF and LA-ICP-MS analyses.     

Trace Element Determination of Single Fluid Inclusions in Quartz by Laser Ablation ICP-MS

Single fluid inclusions in quartz from a Pb-Zn-Ag carbonate replacement deposit were selected for trace element determination by laser ablation ICP-MS. Spikes in element intensities were noted between first breached fluids versus subsequent analyses, suggesting that accurate element concentrations may not be determined in smaller fluid inclusions when only one analysis is obtained before the fluid is exhausted. Elemental concentrations in the fluid inclusions were determined by external standardisation using solutions sealed in microcapillary tubes. Standards and single natural inclusion analyses give repeatabilities (%RSD) of ˜ 20% for Rb and Sr. Rubidium and strontium concentrations range from 0.56-5.07 μg ml^-1 and 1.12-27.4 μg ml^-1, respectively, whereas Zn and Ag are below detection limits (< 10 ng ml^-1). The results suggest that nearly all Zn and Ag are removed by the time hydrothermal fluids precipitate gangue minerals.     

An Ion Chromatography Method for the Determination of Major Anions In Geothermal Water Samples

A single-column suppressed ion chromatography technique was employed for the simultaneous determination of major and trace anions in sulfaterich groundwater samples. An analytical column, a self regenerating suppressor and sodium carbonate as the eluent were used to separate the anions. Method detection limits for the anions of interest were 10.4, 15.9, 36.8, 62, 60, 61 and 67 μg l⁻¹ for F⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, PO₄³⁻ and SO₄²⁻ respectively. The precision of the method was tested at five different concentration levels for each anion reference sample to evaluate the effectiveness of the method for groundwater analysis. Recovery studies were performed between two successive months by adding reference samples to the geothermal groundwater and drinking water samples. Precision was also assessed as the relative standard deviation of both repeatability (within-day) and reproducibility (between-day and different concentrations) for groundwater samples. Standard deviation and RSD values of 220 groundwater samples acquired over 8 months were evaluated. The suppressed ion chromatography technique was found to be a suitable method for determining major anions in sulfate-rich geothermal water samples.     

Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.