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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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5.
Procedures for sampling, sample preparation and ICP-MS analysis of endemic sponges from Lake Baikal have been developed. Sample decomposition was carried out using an open acid decomposition with ultrasound treatment. The distribution of nineteen elements (Mg, Al, P, Ca, Ti, Mn, Co, Ni, Cu, Rb, Sr, Y, Cd, Ba, La, Ce, Pb, Th and U) in different parts of a sponge's body (outer and inner layers and layers adjacent to the substratum) was studied. Detection limits were determined; these ranged from 0.013 to 4.12 μg g-1 for trace elements and from 23 to 130 μg g-1 for biogenic elements. The degree of elemental uptake by living substances is discussed with regard to the environment.  相似文献   

6.
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.  相似文献   

7.
We present a new method that determines precisely and accurately rare earth elements (REE) at the sub-ng g-1 level in ultramafic rocks based on acid dissolution and quadrupole ICP-MS with systematic interference corrections on each sample. The method is demonstrated by analyses of the international geochemical reference materials, PCC-1 (peridotite), DTS-1 (dunite) and DTS-2 (dunite) provided by the United States Geological Survey (USGS), and JP-1 (peridotite) issued by the Geological Survey of Japan (GSJ). Detection limits, as rock equivalent, were calculated to be 0.01-0.08 ng g-1 for our instrument, which is sufficiently low compared to the REE concentrations of ultramafic rocks. In addition, procedural blanks of the proposed method were 0.2-5 pg, which is negligible even for the ultra-low level REE determinations. Reproducibility obtained from separate dissolutions and measurements of USGS DTS-2 and GSJ JP-1 was 3-6%, which corresponds to the high-precision data obtained by ID-TIMS or magnetic sector field ICP-MS with a desolvating nebuliser. The REE data determined exhibit smooth chondrite-normalised REE patterns for all of the tested geochemical reference materials, and the abundances are in good agreement with recently published data.  相似文献   

8.
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.  相似文献   

9.
Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l−1. Bromine and I were measured by ICP-MS with detection limits of 1 μg l−1 for Br and 0.1 μg l−1 for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg−1 for F and Cl, 15 mg kg−1 for S, 0.2 mg kg−1 for Br and 0.02 mg kg−1 for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H2O degassing, reduction on zinc at 1000 °C and H2 manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.  相似文献   

10.
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.  相似文献   

11.
The microanalytical capability of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to determine ultra trace elemental concentrations has been demonstrated by the analysis of two low concentration glass standard reference materials, NIST SRM 614 and 616. Results for fifty two elements at concentrations in the low ng g-1 range are compared with those determined using secondary ion mass spectrometry (SIMS). Both techniques provide results at these concentrations that generally agree within 95% confidence limits, demonstrating the accuracy for ultra-trace level of in situ determinations by the two techniques. At concentrations of less than 20 ng g-1 in NIST SRM 616, an accuracy and precision of better than 10% has been obtained for most mono-isotopic rare earth elements, when a spot size of 50 μm is used. Limits of detection for selected elements were as low as 0.5 ng g-1.  相似文献   

12.
The platinum-group elements (PGE) and gold have been determined in twenty international rock reference materials by inductively coupled plasma-mass spectrometry (ICP-MS) after pre-concentration by a nickel sulfide fire assay. It was possible to achieve determination limits for a 50 g sample that ranged from 1 pg g-1 (Rh) to 23 pg g-1 (Au). Compared to published certified and recommended values for rock reference materials, the trueness of the method was found to be good. However, in some cases we observed large deviations for all elements in the sub 10 ng g-1 range within individual reference sample splits. Our results show that the PGE and Au are inhomogeneously distributed in the reference materials analysed here, where they are present in low concentrations, using 50 g test portions.  相似文献   

13.
Refinements have been made to achieve over 99% yield in the conversion of CO to CO2 in order to improve the reproducibility and accuracy of δ18 O measurements in sulfates. BaSO4 (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO2; the former gas was simultaneously converted to CO2 by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ18 O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO2 produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO2 equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from 18O/16O of the working calibrator we used CO2 gas prepared from ocean water sulfate for this purpose. The calibrated δ18 O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.  相似文献   

14.
A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO3 in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO3. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)2, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO3 and a buffer solution of NH4Cl/NH4OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)3, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g−1. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.  相似文献   

15.
We present boron isotope and concentration data from magmatic (komatiitic to rhyolitic) and sedimentary geological silicate and artificial glass reference materials that cover a wide spectrum of boron isotope compositions and boron concentrations. Boron isotope compositions were determined by TIMS (Cs2BO2+ -graphite and BO2- method) and boron concentrations by ICP-AES. Boron concentrations ranged from 7 to 159μ g-1 and agree within 14% with published values. Based on replicate analyses of individually prepared sample aliquots an overall external reproducibility of better than 10% was determined. The obtained δ11B values ranged from -12.6 to +13.6% and were reproducible within 1.1 % (2 RSD; excluding NTIMS) on the basis of individually prepared sample aliquots. The δ11B values of JA-1 (+5.3%), JB-3 (+5.9%) and JR-2 (+2.9%) overlap the published data within analytical uncertainty. For the first time δ11B values for the TB (-12.6%) and the MPI-DING glasses GOR-128-G (+13.6%), GOR-132-G (+7.1 %) and StHs6/80-G (-4.5%) are reported. The δ11B values obtained by the Cs2BO2+ -graphite and the BO2- method as well as the majority of δ11B values obtained using different sample preparation methods agree within analytical uncertainty. Therefore, we conclude that none of these analytical methods introduce any systematic error on the obtained δ11B values.  相似文献   

16.
A precise and simple method for the determination of lithium concentrations in small amounts of silicate sample was developed by applying isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Samples plus a Li spike were digested with HF-HClO4, dried and diluted with HNO3, and measured by ICP-MS. No matrix effects were observed for 7Li/6Li in rock solutions with a dilution factor (DF) of 97 at an ICP power of 1.7 kW. By this method, the determination of 0.5 μg g-1 Li in a silicate sample of 1 mg can be made with a blank correction of < 1%. Lithium contents of ultrabasic to acidic silicate reference materials (JP-1, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 from the Geological Survey of Japan, and PCC-1 from the US Geological Survey) and chondrites (three different Allende and one Murchison sample) of 8 to 81 mg were determined. The relative standard deviation (RSD) was typically < 1.7%. Lithium contents of these samples were further determined by isotope dilution-thermal ionisation mass spectrometry (ID-TIMS). The relative differences between ID-ICP-MS and ID-TIMS were typically < 2%, indicating the high accuracy of ID-ICP-MS developed in this study.  相似文献   

17.
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.  相似文献   

18.
A procedure for the determination of chlorine by the isotope dilution technique (ID) using negative thermal ionisation mass spectrometry (N-TIMS) is described. Silicate samples of about 10 mg were spiked and decomposed with hydrofluoric acid, and chlorine was isolated by precipitation of silver chloride after neutralisation with Ca(OH)2. The ammonical solution of AgCl was then subjected to N-TIMS. Replicate analyses of rock reference materials, typically of JB-1 and JR-1, demonstrated the high quality of the analyses (precision for Cl was ± 1-2%). We present here the most precise data sets of chlorine concentrations in nine igneous rock reference materials, three basalts (JB-1, JB-2, JB-3), two andesites (JA-3, AGV-1), two rhyolites (JR-1, JR-2) and two granodiorites (JG-3, GSP-1). The chlorine concentrations found ranged from 152 μg g-1 in AGV-1 to 1008 μg g-1 in JR-1. Our results presented here are partly (but not completely) in agreement with recommended values, where they are available. The N-TIMS ID technique can thus be used as a means of determining low chlorine contents in silicate materials to high precision.  相似文献   

19.
Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO4 high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml−1 in solution (equivalent to 0.08 to 16.2 ng g−1 in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g−1) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g−1). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.  相似文献   

20.
We present an approach for tracing the fate of anthropogenic CO2, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ13C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO2 (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO2 concentrations in Atlantic surface waters, estimated from the δ13Corg of surface sediments, are compared to recently measured surface water [CO2 (aq)] values taken from literature. We obtain only a slight increase in [CO2 (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO2 released by human activities has been stored in Southern Ocean surface waters.  相似文献   

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