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1.
A method for the determination of major, minor and trace elements in silicate samples by ICP‐QMS and ICP‐SFMS applying isotope dilution‐internal standardisation (ID‐IS) and multi‐stage internal standardisation has been developed. Samples with an enriched isotope of 149Sm (spike) were decomposed by a HF/HCIO4 mixture and stepwise drying and finally diluted. In ID‐IS for trace element analyses by Q‐pole type ICP‐MS (ICP‐QMS), the Sm concentration was determined by ID, while other trace elements (Li, Be, Rb, Sr, Y, In, Cs, Ba, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, Bi, Th and U) were determined using the 149Sm intensity as an internal standard. Major and minor elements were determined by multi‐stage internal standardisation, with Na, Mg, Al, P, Ca, V, Mn, Fe and Co measured by sector magnetic field type ICP‐MS (ICP‐SFMS) at middle resolution (MR; M/AM =～ 3000) using Sr determined by ICP‐QMS in the sample as the internal standard. Potassium, Sc, Ni, Cu, Zn and Ga were measured at high resolution (HR; M/ΔM ～ 7500) using the Sr concentration obtained by ICP‐QMS or the Mn concentration obtained by ICP‐SFMS at MR as internal standard. The merit of ID‐IS is that accurate dilution of the sample is not required. Matrix effects on elemental ratios down to a dilution factor (DF) of 600 were not observed in either types of mass spectrometry. Pseudo‐flow injection (FI), where transient signals were integrated, was used in ICP‐QMS, while conventional continuous sample introduction was used in ICP‐SFMS, resulting in total required sample solutions of 0.026 ml and 0.08 ml, respectively. Detection limits were low enough to determine these elements in depleted ultramafic rocks, and typical reproducibilities for basalts were 3% (Li‐Be), 1% (Rb‐U), 5% (In, Tl and Bi), 7% (Sc‐Ga) and 3% (major elements). Carbonaceous chondrites including Orgueil (Cll), Murchison (CM2) and Allende (CV3), as well as reference materials, JB‐1, ‐2, ‐3, JA‐1, ‐2, ‐3 and JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 and DTS‐1 (USGS), were analysed to show the applicability of this method. Une méthode permettant la détermination des éléments majeurs, mineurs et en trace dans les echantillons silicates par ICP‐QMS et ICP‐SFMS a été développée. Elle combine la standardisation interne par dilution isotopique (ID‐IS) et la standardisation interne en deux étapes. Les échantillons, auxquels est ajouté un spike enrichi en 149 Sm, sont décomposés par une mixture HF/HCIO4′ séchés progressivement puis dilués. Dans la phase de standardisation interne par dilution isotopique avec un ICP‐MS à quadrupôle (ICP‐QMS), la concentration en Sm est déterminée par dilution isotopique tandis que les autres éléments en trace (Li, Be, Rb, Sr, Y, In, Cs, Ba, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, Bi, Th et U) sont déterminés en utilisant le signal de 149 Sm comme standard interne. Les éléments majeurs et mineurs sont déterminés par standardisation interne par étapes, avec Na, Mg, Al, P, Ca, V, Mn, Fe et Co mesurés par ICP‐MS à secteur magnétique (ICP‐SFMS) en résolution intermédiaire (MR; M/ΔM =～ 3000 en utilisant Sr, mesuré par ICP‐QMS comme standard interne. Les éléments K, Sc, Ni, Cu, Zn et Ga sont mesurés en Haute Résolution (M/ΔM ～ 7500) en utilisant comme standard interne, soit la concentration en Sr obtenue par ICP‐QMS soit la concentration en Mn obtenue par ICP‐SFMS en résolution moyenne. La technique de ID‐IS a l'avantage de ne pas nécessiter la connaissance exacte du facteur de dilution de l'Schantillon. Aucun effet de matrice sur la mesure de rapports élémentaires n'a été observé sur l'un ou l'autre des spectromètres de masse, ceci jusqu'à un facteur de dilution (DF) de 600. Les analyses par ICP‐QMS ont été effectuées par pseudo injection de flux (Fl) et intégration d'un signal transitoire tandis que les analyses par ICP‐SFMS l'ont été avec un système conventionnel d'introduction. Le volume total de solution d'échantillon nécessaire etait de 0.026 ml et 0.08 ml respectivement. Les limites de détection étaient suffisamment basses pour permettre la détermination de ces éléments dans des roches ultrabasiques et les reproductibilités pour les basaltes étaient de l'ordre de 3% (Li‐Be), 1 % (Rb‐U), 5% (In, Tl et Bi), 7% (Sc‐Ga) et 3% (tous les éléments majeurs). Des chondrites carbonées dont Orgueil (Cll), Murchison (CM2) et Allende (CV3) ainsi que des matériaux de référence JB‐1, ‐2, ‐3, JA‐1, ‐2, ‐3 et JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 et DTS (USGS) ont été analysés pour démontrer l'applicabilité de la méthode.  相似文献   

2.
We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission‐track (AFT) thermochronology by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP‐MS and laser ablation (LA) ICP‐MS were employed. Two apatite crystals are potential reference materials for LA‐ICP‐MS analysis: a 1 cm3 fraction of a Durango crystal (7.5 μg g?1 U) and a 1 cm3 Mud Tank crystal (6.9 μg g?1 U). The relative standard deviation (1 RSD) of the U concentration determined by ID‐ICP‐MS of both apatite crystals was ≤ 1.5%, whereas 1 RSD for the LA‐ICP‐MS results was better than 4%, providing sufficient homogeneity for fission‐track dating. The results on the U homogeneity for two different apatite samples are an important step towards establishing in situ dating routines for AFT analysis by LA‐ICP‐MS.  相似文献   

3.
Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g?1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from 7Li to 238U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties [2 relative standard error (RSE)] estimated in the range of 1–20%.  相似文献   

4.
We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected 206Pb/238U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam 206Pb/238U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean 176Hf/177Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf0 of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of 206Pb/238U and 176Hf/177Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic 176Hf/177Hf.  相似文献   

5.
This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., 109Ag1H+, 94Zr16O+, 94Mo16O+ and 70Zn40Ar+) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10?5 and In/Cd ≤ 10?3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ114/110Cd. The δ114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of ?0.251 to 0.632‰, the δ114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from ?0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes.  相似文献   

6.
To precisely determine the abundances of fifty‐two elements found within natural water samples, with mass fractions down to fg g?1 level, we have developed a method which combines freeze‐drying pre‐concentration (FDC) and isotope dilution internal standardisation (ID‐IS). By sublimation of H2O, the sample solution was reduced to < 1/50 of the original volume. To determine element abundance with accuracy better than 10%, we found that for solutions being analysed by mass spectrometry the HNO3 concentration should be > 0.3 mol l?1 to avoid hydrolysis. Matrix‐affected signal suppression was not significant for the solutions with NaCl concentrations lower than 0.2 and 0.1 cg g?1 for quadrupole ICP‐MS and sector field ICP‐MS, respectively. The recovery yields of elements after FDC were 97–105%. The detection limits for the sample solutions prepared by FDC were ≤ 10 pg g?1, except for Na, K and Ca. Blanks prepared using FDC were at pg‐levels, except for eleven elements (Na, Mg, Al, P, Ca, Mn, Fe, Co, Ni, Cu and Zn). The abundances of fifty‐two elements in bottled drinking water were determined from five different geological sources with mass fractions ranging from the fg g?1 to μg g?1 level with high accuracy.  相似文献   

7.
In this study, we report both 143Nd/144Nd and 147Sm/144Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured βSm and βNd (r2 = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. 143Nd/144Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of 143Nd/144Nd and 147Sm/144Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a 147Sm‐143Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.  相似文献   

8.
In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe2O3) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe2O3 were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.  相似文献   

9.
We present in this article a rapid method for B extraction, purification and accurate B concentration and δ11B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ11B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g?1 of total salts or 25 μg g?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ11B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).  相似文献   

10.
Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.  相似文献   

11.
Matrix‐matched reference materials are necessary for accurate microbeam U‐Pb dating and Hf isotopic determination. This study introduces the RMJG rutile as a new potential reference material, which was separated from Palaeoproterozoic pelitic granulites collected in Hebei Province, China. LA‐ICP‐MS measurements indicate the RMJG rutile has extremely low Th (< 0.003 ± 0.01 µg g?1) and common Pb contents, but high Hf (102 ± 34 µg g?1), U (61 ± 11 µg g?1), and radiogenic Pb (~ 20 µg g?1) contents. Moreover, the rutile yields relatively constant U‐Pb ages and Hf isotopic data. The LA‐ICP‐MS analyses suggest that this rutile has a concordant U‐Pb age with a statistical mean 206Pb/238U and 207Pb/235U ages of 1749.9 ± 32.1 Ma and 1750.0 ± 26.4 Ma, respectively (2s), which are statistically indistinguishable from its ID‐TIMS ages (1750.6 ± 8.4 and 1750.1 ± 4.7 Ma). Precise determination of the 176Hf/177Hf ratio by MC‐ICP‐MS in solution mode (0.281652 ± 0.000006) is in good agreement with the statistical mean of the LA‐MC‐ICP‐MS measurements (0.28166 ± 0.00018). Therefore, the limited variations of RMJG U‐Pb age and Hf isotopic composition together with its extremely low common Pb and high Hf, U and Pb contents make it an ideal calibration and monitor reference material for LA‐ICP‐MS measurements.  相似文献   

12.
Molybdenum concentration and δ98/95Mo values for NIST SRM 610 and 612 (solid glass), NIST SRM 3134 (lot 891307; liquid) and IAPSO seawater reference material are presented based on comparative measurements by MC‐ICP‐MS performed in laboratories at the Universities of Bern and Oxford. NIST SRM 3134 and NIST SRM 610 and 612 were found to have identical and homogeneous 98Mo/95Mo ratios at a test portion mass of 0.02 g. We suggest, therefore, that NIST SRM 3134 should be used as reference for the δ–Mo notation and to employ NIST SRM 610 or 612 as solid silicate secondary measurement standards, in the absence of an isotopically homogeneous solid geological reference material for Mo. The δ98/95MoJMC Bern composition (Johnson Matthey ICP standard solution, lot 602332B as reference) of NIST SRM 3134 was 0.25 ± 0.09‰ (2s). Based on five new values, we determined more precisely the mean open ocean δ98/95MoSRM 3134 value of 2.09 ± 0.07‰, which equals the value of δ98/95MoJMC Bern of 2.34 ± 0.07‰. We also refined the Mo concentration data for NIST SRM 610 to 412 ± 9 μg g?1 (2s) and NIST SRM 612 to 6.4 ± 0.7 μg g?1 by isotope dilution. We propose these concentration data as new working values, which allow for more accurate in situ Mo determination using laser ablation ICP‐MS or SIMS.  相似文献   

13.
Here, we present determinations of thallium (Tl) concentrations in the USGS reference materials BIR‐1G, BHVO‐2G and BCR‐2G measured by solution ICP‐MS. The Tl content in these three glasses spans a range of about 2–230 ng g?1, which is similar to the values published for the respective powder materials. The determined range of Tl concentrations in these three glass reference materials makes them ideal for investigating Tl concentrations in basaltic and andesitic volcanic glasses. We also performed a series of laser ablation ICP‐MS measurements on the three samples, which show that this technique is able to determine Tl concentrations in glass samples with concentrations as low as 2 ng g?1.  相似文献   

14.
A specific method for the determination of bromine and iodine species in drinking water was developed by using high performance liquid chromatography‐ICP‐MS. An ICS‐A23 ion chromatography column was chosen for the separation of species, with the mobile phase being 0.03 mol l?1 ammonium carbonate at a flow rate of 0.8 ml min?1. The detection limits for BrO3?, Br?, IO3? and I? were 0.032, 0.063, 0.008 and 0.012 μg l?1, respectively. Spectroscopic interferences were only observed in blank samples and mainly resulted from the argon‐potassium polyatomic ion (40Ar39K+). However, this interference was negligible because of the elution and complete separation from that of iodinate under optimised conditions. The method developed was successfully applied to twenty‐two samples of drinking water obtained from a supermarket. Results indicated that 36.4% of the samples had BrO3? concentrations exceeding the Chinese national limit for drinking water of 10 μg l?1.  相似文献   

15.
An in situ, medium‐resolution LA‐ICP‐MS method was developed to measure the abundances of the first‐row transition metals, Ga and Ge in a suite of geological materials, namely the MPI‐DING reference glasses. The analytical protocol established here hinged on maximising the ablation rate of the ultraviolet (UV) laser system and the sensitivity of the ICP‐MS, as well minimising the production of diatomic oxides and argides, which serve as the dominant sources of isobaric interferences. Non‐spectral matrix effects were accounted for by using multiple external calibrators, including NIST SRM 610 and the USGS basaltic glasses BHVO‐2G, BIR‐1G and BCR‐2G, and utilising 43Ca as an internal standard. Analyses of the MPI‐DING reference glasses, which represent geological matrices ranging from basaltic to rhyolitic in composition, included measurements of concentrations as low as < 100 μg g?1 and as high as > 104 μg g?1. The new data reported here were found to statistically correlate with the ‘preferred’ reference values for these materials at the 95% confidence level, though with significantly better precision, typically on the order of ≤ 3% (2sm). This analytical method may be extended to any matrix‐matched geological sample, particularly oceanic basalts, silicate minerals and meteoritic materials.  相似文献   

16.
The low‐Sr content (generally < 100 μg g?1) in clinopyroxene from peridotite makes accurate Sr isotopic determination by LA‐MC‐ICP‐MS a challenge. The effects of adding N2 to the sample gas and using a guard electrode (GE) on instrumental sensitivity for Sr isotopic determination by LA‐MC‐ICP‐MS were investigated. Results revealed no significant sensitivity enhancement of Sr by adding N2 to the ICP. Although using a GE led to a two‐fold sensitivity enhancement, it significantly increased the yield of polyatomic ion interferences of Ca‐related ions and TiAr+ on Sr isotopes. Applying the method established in this work, 87Sr/86Sr ratios (Rb/Sr < 0.14) of natural clinopyroxene from mantle and silicate glasses were accurately measured with similar measurement repeatability (0.0009–0.00006, 2SE) to previous studies but using a smaller spot size of 120 μm and low‐to‐moderate Sr content (30–518 μg g?1). The measurement reproducibility was 0.0004 (2s, n = 33) for a sample with 100 μg g?1 Sr. Destruction of the crystal structure by sample fusion showed no effect on Sr isotopic determination. Synthesised glasses with major element compositions similar to natural clinopyroxene have the potential to be adopted as reference materials for Sr isotopic determination by LA‐MC‐ICP‐MS.  相似文献   

17.
The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, 113In and 203Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.  相似文献   

18.
Zircon crystals in the age range of ca. 10–300 ka can be dated by 230Th/238U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr2O3+) are critical for reliable determination of 230Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (230Th)/(238U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including 230Th) within the 238U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on 230Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).  相似文献   

19.
Mass fractions of S, Cu, Se, Mo, Ag, Cd, In, Te, Ba, Sm, W and Tl were determined by isotope dilution sector field ICP‐MS in the same sample aliquot of reference materials using HF‐HNO3 digestion in PFA beakers in pressure bombs and glassy carbon vessels in a high‐pressure asher (HPA‐S) for comparison. Additionally, Bi was determined by internal standardisation relative to Tl. Because isobaric and oxide interferences pose problems for many of these elements, efficient chromatographic separation methods in combination with an Aridus desolvator were employed to minimise interference effects. Repeated digestion and measurement of geological reference materials (BHVO‐1, BHVO‐2, SCo‐1, MAG‐1, MRG‐1 and UB‐N) gave results with < 5% relative intermediate precision (1s) for most elements, except Bi. Replicates of NIST SRM 612 glass digested on a hot plate were analysed by the same methods, and the results agree with reference values mostly within 2% relative deviation. Data for the carbonaceous chondrites Allende, Murchison, Orgueil and Ivuna are also reported. Digestion in a HPA‐S was as efficient as in pressure bombs, but some elements displayed higher blank levels following HPA‐S treatment. Pressure bomb digestion yielded precise data for volatile S, Se and Te, but may result in high blanks for W.  相似文献   

20.
An efficient, clean procedure for the measurement of element mass fractions in bulk rock nanoparticulate pressed powder pellets (PPPs) by 193 nm laser ablation ICP‐MS is presented. Samples were pulverised by wet milling and pelletised with microcrystalline cellulose as a binder, allowing non‐cohesive materials such as quartz or ceramics to be processed. The LA‐ICP‐MS PPP analytical procedure was optimised and evaluated using six different geological reference materials (JP‐1, UB‐N, BCR‐2, GSP‐2, OKUM and MUH‐1), with rigorous procedural blank quantification employing synthetic quartz. Measurement trueness of the procedure was equivalent to that achieved by solution ICP‐MS and LA‐ICP‐MS analysis of glass. The measurement repeatability was as low as 0.5–2% (1s, n = 6) and, accordingly, PPP homogeneity could be demonstrated. Calibration based on the reference glasses NIST SRM 610, NIST SRM 612, BCR‐2G and GSD‐1G revealed matrix effects for glass and PPP measurement with NIST SRM 61×; using basalt glasses eliminated this problem. Most significantly, trace elements not commonly measured (flux elements Li, B; chalcophile elements As, Sb, Tl, In, Bi) could be quantified. The PPP‐LA‐ICP‐MS method overcomes common problems and limitations in analytical geochemistry and thus represents an efficient and accurate alternative for bulk rock analysis.  相似文献   

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