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.     

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.     

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.     

Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

A Preliminary Study on the Preparation of Four Pacific Ocean Polymetallic Nodule and Sediment Reference Materials: GSPN-2, GSPN-3, GSMS-2 and GSMS-3

The research project for the preparation of two polymetallic nodule (GSPN-2, GSPN-3) and two marine sediment (GSMS-2, GSMS-3) reference materials was completed in 1996. The samples were collected from the Eastern and Central Pacific Ocean and prepared to less than 74 μm fine powder. The homogeneity of the materials was tested by X-ray fluorescence spectrometry. The relative standard deviations (RSD %) of measurements of selected elements in samples taken from thirty bottles selected at random were less than 0.5%. Thirty four laboratories worldwide participated in the collaborative analysis programme. The number of elements or constituents analysed was seventy nine for nodules and eighty one for sediments. Among those, sixty three elements were certified in each sample. The sum of major elements or components is 99.7% for GSPN-2, 99.5% for GSPN-3, 99.8% for GSMS-2 and 99.8% for GSMS-3.     

Determination of Multiple Trace Element Compositions in Thin (> 30 μm) Layers of NIST SRM 614 and 616 Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS)

To understand and/or avoid small-scale chemical heterogeneities within geological materials prepared as normal thin sections, in situ multiple trace element determination coupled with the simultaneous microscopic observation of the sample during analysis is preferable. We have examined fifty trace elements in thin (< 30 μm) layers of the NIST SRM 614 and 616 glass reference materials by LA-ICP-MS using different pit diameters and internal standard elements (Ca and Si). Compositional heterogeneities of Tl, Bi, As and Cd were found in NIST SRM 614 and 616 at the spatial resolution of ca. 10 0 μm. Except for these elements, the RSDs of six determinations for most elements were better than 10% in NIST SRM 614 when ablation diameters were < 50 μm. The measured concentrations for most elements in NIST SRM 614 and 616 agree with previous values in the literature at the 95% confidence level with the exception of W and Bi. New LA-ICP-MS data for K, As and Cd are also reported. The results support the view that the latest LA-ICP-MS is a powerful and flexible analytical technique for the determination of multiple ultra-trace element compositions in geological materials prepared as normal thin sections of the type that has been used for polarising optical microscopic observations since the end of the 19th century.     

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.     

Determination of Major/ Minor and Trace Elements in Seamount Phosphorite by XRF Spectrometry

In this paper, a method developed to determine the major, minor and trace elements, including carbon and the four halogens, in seamount phosphorite involving a modern XRF spectrometry technique is described. Ultra-fine (99% v/v < 40 μm) powder samples (4 g) were directly pressed into pellets (Φ= 30 mm). For elements having an analytical line lower in energy than the energy of Fe Kα line absorption edge, the inter-element absorption-enhancement effects were corrected using an influence coefficient method. For the other elements, the matrix effects were corrected using the ratio of element peak to Rh Kα Compton peak (for I, Rh K|3 Compton peak was used instead). The relative standard deviation was smaller than 1.0% for the major elements (except C, Na and Cl). The detection limit levels of C, F, Cl, Br and I were 30, 20, 0.8, 0.2 and 0.3 (μg g⁻¹ respectively for 100 s count time of background. The accuracy of this method was tested by evaluating determinations on three certified reference materials. The direct analysis of major and minor elements in geological materials by pressed pellet without any chemical procedures makes XRF spectrometry a particularly environment-friendly analytical technique.     

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.     

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.     

Preparation of Five China Sea and Continental Shelf Sediment Reference Materials (MSCS-1–5) with Ultra-Fine Particle Size Distributions

We report the preparation and characterisation of five sediment reference materials MSCS-1–5 from the China Sea and continental shelf. The raw samples were individually collected from the East China Sea and the South China Sea. They were first ground by ball mill to a homogenous powder of -200 mesh (< 74 μm). Then, half of each sample was further processed by an ultra-fine powder processing technique, a jet mill, to form a powder with an average particle size of < 4 μm (about 800 mesh). The homogeneity was tested by high-precision WD-XRF and the precision was found to be less than 1% RSD, which is compatible with the precision range for modern analytical techniques. An F-test showed that all five samples were homogeneous. Twelve laboratories participated in the cooperative study and sixty constituents were determined. Between fifty and fifty-two analytes were characterised as recommended values in MSCS-1–5 in compliance with Chinese national norms. The sum of the major and minor elements or components in the five reference materials MSCS-1–5 was 99.91%, 99.86%, 100.43%, 100.12% and 99.66%, respectively.     

Speciation of Chromium in Artificially Contaminated Soil Reference Material GSJ JSO-2 Using XANES and Chemical Extraction Methods

The oxidation states of chromium in GSJ JSO-2 (artificially contaminated soil) and three other geochemical reference materials (GSJ JSO-1, JLS-1 and JMS-1) were observed using X-ray near edge structure (XANES). For comparison, other artificially contaminated soil materials (mimic-JSO-2) were prepared by adding Cr(VI) into JSO-1. Their oxidation states of chromium were determined using XANES. The chromium contents were 1118 μg g^-1 for JSO-2, 1352 μg g^-1 for mimic-JSO-2 and 69-113 μg g^-1 for the other reference materials. Most chromium was present as hexavalent in mimic-JSO-2. No hexavalent species were detected in other samples. These results for chromium oxidation state in JSO-2 and mimic-JSO-2 obtained with XANES resembled those obtained from a chemical extraction method. The present JSO-2 has no trace of Cr(VI), although Cr(VI) was added as a major species during preparation. On the other hand, the content of Cr(VI) obtained in mimic-JSO-2 agreed with the original Cr(VI) content. A time-elapse study showed that Cr(VI) contents in mimic-JSO-2 decreased gradually to 70% of the original abundance during 240-day preservation in dry conditions. Moreover, the abundance of Cr(VI) decreased markedly to 15% after 240 days in the wet mimic-JSO-2 containing 20% m/m of water. These experiments suggested that soil humidity enhanced the reduction of Cr(VI) and that Cr(VI) was reduced even in dry conditions. Consequently, it is reasonable to infer that Cr(VI) doped into JSO-2 was completely reduced to Cr(III) during the preservation period of 5 years. The certification of the long-term stability of the chemical form in reference materials will be much more important in future.     

Analysis of Re, Au, Pd, Pt and Rh in NIST Glass Certified Reference Materials and Natural Basalt Glasses by Laser Ablation ICP-MS

A new technique for the in situ analysis of Re, Au, Pd, Pt and Rh in natural basalt glass by laser ablation (LA)-ICP-MS is described. The method involves external calibration against NIST SRM 612/613 or 614/615 glass certified reference materials, internal standardisation using Ca, and ablation with a 200 μm wide beam spot and a pulsed laser repetition rate of 50 Hz. Under these conditions, sensitivities for Re, Au, Pd, Pt and Rh analyte ions are ˜ 5000 to 100,000 cps/μg g^-1. This is sufficient to make measurements precise to ˜ 10% at the 2-10 μg g^-1 level, which is well within the range of concentrations expected in many basalts. For LA-ICP-MS calibration and a demonstration of the accuracy of the technique, concentrations of Re, Au, Pd, Pt and Rh in the NIST SRM 610/611 (˜ 1 to 50 μg g^-1), 612/613 (˜ 1 to 7 μg g^-1), 614/615 (˜ 0.2 to 2 μg g^-1) and 616/617 (˜ 0.004 to 2 μg g^-1) glasses were determined by solution-nebulisation (SN)-ICP-MS. Using the 612/613 or 614/615 glasses as calibration standards, LA-ICP-MS measurements of these elements in the other NIST glasses fell within ˜ 15% of those determined by SN-ICP-MS. Replicate LA-ICP-MS analyses of the 612/613 and 614/615 glasses indicate that, apart from certain anomalous domains, the glasses are homogeneous for Re, Au, Pd, Pt and Rh to better than 3.5%. Two LA-ICP-MS analyses of natural, island-arc basalt glasses exhibit large fractionations of Re, Au and Pd relative to Pt and Rh, compared to the relative abundances in the primitive mantle.     

Determination of Chlorine Contents in Geological Survey of Japan Reference Materials by Prompt Gamma Neutron Activation Analysis

We determined chlorine contents in nine GSJ (Geological Survey of Japan) reference materials (JB-1, 1a, 2, 3; JA-1, 2, 3; JR-1, 2) by prompt gamma neutron activation analysis, employing the standard addition method. Pressed powder disks of each reference material were used for neutron irradiation and gammaray measurement, after known quantities (25-200 μl) of sodium chloride solution were added. The influence of the nearby sodium peak overlap was checked, and fluctuations in the chlorine count rate were corrected using silicon as an internal standard. The slopes of calibration lines for seven reference materials (JB-1, 2, 3; JA-1, 2, 3; JR-2) and SiO₂ powders fall within 5% error, and their chlorine values were obtained from the intercepts. Chlorine contents in JB-1 a and JR-1 were also determined by using the calibration lines. Our chlorine values ranged from 26.1 to 934 μg g-¹, which agrees well with the previously reported values.     

Ion Chromatographic Determination of Fluorine and Chlorine in Silicate Rocks Following Alkaline Fusion

A simple and accurate method to determine fluorine and chlorine contents in small amounts (∼ 30 mg) in rock has been developed using ion chromatography after extraction by alkaline fusion. Powdered sample was mixed with sodium carbonate and zinc oxide at a mass ratio of 1:3:1, and was fused in an electric furnace at 900 °C for 30-40 minutes. An aqueous solution obtained by dissolving the fused silicate rock was diluted to the appropriate concentration of sodium carbonate (< ∼ 24 mmol l^-1) to minimise the tailing effect on F^- during ion chromatography caused by the large amount of carbonate species originating from the flux. Fluorine and chlorine contents were then determined by a standard additions method. Based on the relative standard deviation of the backgrounds, detection limits of both fluorine and chlorine were ∼ 4 μg g^-1, when 30 mg test portions were fused and diluted by a factor of 1200. We also report new fluorine and chlorine contents in nine GSJ (Geological Survey of Japan) reference materials, including peridotite (JP-1), granite (JG-1a), basalts (JB-1b, 2 and 3), andesites (JA-1 and 2) and rhyolites (JR-1 and 2). Fluorine and chlorine contents in the reference materials in this study were consistent with previously reported values. Reproducibilities were < 10 % for samples with F and Cl concentrations of > 20 μg g-1 and < 20 % with F and Cl < 20 μg g^-1.     

An experimental study of Ostwald ripening of olivine and plagioclase in silicate melts: implications for the growth and size of crystals in magmas

We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An₆₅)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t ^1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t ^1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 10⁵ years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 10³ years; a mean grain size of 3 mm is reached in 10⁵ years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.     

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.     

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.     

Characterisation of the Sarcheshmeh copper mine tailings,Kerman province,southeast of Iran

Mineral processing operation at the Sarcheshmeh porphyry copper mine has produced huge quantities of tailings materials containing sulphide minerals in particular pyrite. These tailings materials were geochemically and mineralogically characterised to assess pyrite and chalcopyrite oxidation, acid mine drainage generation, and trace element mobility to lead development of a proper remediation plan. Five vertical trenches up to 4.2 m deep were excavated from the tailings surface, and 70 solid samples were taken in 0.3 m intervals. The samples were first mineralogically analysed. Pyrite was the main sulphide mineral found in the tailings. The gangue minerals include quartz ± muscovite–illite ± chlorite ± albite ± orthoclase ± halite. The samples were geochemically analysed for total concentrations of 62 elements, paste pH, SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. The maximum concentrations of SO₄ ^2? (1,300, 1,170, 1,852, 1,960 and 837 mg/L) were observed at a depth of 0.9 m in profiles A, B, C, D and E, respectively. The tailings have a high acid-producing potential and low acid-neutralising potential (pyrite 4–6 wt %, calcite 1 wt %). Fe₂(SO₄)₃, CuSO₄, MgSO₄ and MnSO₄ were the dominant secondary sulphate minerals in the tailings. The lowest pH values (2.9, 3 and 3) were measured at a depth of 0.3 m in the profiles A, B and C, 3.9 at a depth of 0.6 m in the profile D and 3 at a depth of 0.9 m in the profile E. The upper portions of the profiles C (1.8 m) and D (2.1 m) were moderately oxidised, while oxidation in the profiles A, B and E did not extend more than 1.2, 1.2 and 1.5 m beneath the tailings surface. Zn, Pb, Rb, U, Hf, Nd, Zr and Ga show almost a constant trend with depth. Cd, Sr, Th, La and Ce increased with increasing depth of the tailings materials while, Co, V, Ti, Cr, Cu, As, Mn, Ag, Mo and Ni exhibit initially a decreasing trend from tailings surface to the depths that vary between 0.9 and 1.2. They then remained constant with the depth. The results show pyrite and chalcopyrite oxidation at surface layers of the tailings and subsequent leaching of the oxidation products and trace elements by infiltrated atmospheric precipitation.     

Application of High Spatial Resolution Laser Ablation ICP-MS to Crystal-Melt Trace Element Partition Coefficient Determination

In this contribution we evaluate the capabilities of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) using a 12 μm spot size. Precision, accuracy and detection limits were assessed on the USGS BCR-2G reference material. We demonstrate that the 12 μm LA-ICP-MS analyses of experimentally-grown amphibole and garnet are in excellent agreement with secondary ion mass spectrometry (SIMS) trace element determinations on the same crystals. The 12 μm spot size configuration was subsequently used to determine trace element crystal-melt partition coefficients (D_c/m) for a wide range of trace elements in amphibole in equilibrium with a basanitic melt. The following strategy to determine accurately and evaluate D_c/m is proposed. One or more major elements determined previously by electron probe microanalysis (EPMA) was used to ensure consistency between EPMA and the composition of the aerosol produced by the laser ablation. Measured D_c/m values were successively evaluated using the lattice strain model. The use of this strategy significantly improved the precision and accuracy of D_c/m determination when a LA-ICP-MS configuration with a high spatial resolution was employed.