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.     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

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.     

Precise Determination of Ultra-Low (sub-ng g-1) Level Rare Earth Elements in Ultramafic Rocks by Quadrupole ICP-MS

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.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

APPLICATION OF THE ICP-MS TECHNIQUE TO TRACE ELEMENT ANALYSIS OF PERIDOTITES AND THEIR MINERALS

Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, Pb, Sc and 14 REE in peridotites and their constituent minerals: garnet, clinopyroxene, orthopyroxene and olivine. Determination limits for most elements are 1–10 ppb (in the solid sample), with accuracy and precision comparable to those of thermal ionisation and spark-source mass spectrometry. New data on international standards PCC-1, DTS-1, UB-N and JP-1 are reported.     

Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

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.     

Determination of Molybdenum, Antimony and Tungsten at sub μg g−1 Levels in Geological Materials by ID-FI-ICP-MS

We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma-mass spectrometry with a flow injection system (ID-FI-ICP-MS). The chemical procedure requires HF digestion of the sample with a Mo-Sb-W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g⁻¹ level. Analysis of the silicate reference materials PCC-1, DTS-1, BCR-1, BHVO-1, AGV-1 from the US Geological Survey and JP-1, JB-1, -2, -3, JA-1, -2, and -3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

Determination of Chlorine in Nine Rock Reference Materials by Isotope Dilution Mass Spectrometry

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.     

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.     

Neutron Activation Determination of The Fourteen Rare-Earth Elements In Five Rock Standards

Five geochemical reference samples. Granite GA and Basalt BK from CRPG, Diorite DR-N and Serpentine UB-N from ANRT and Andesite AGV-1 from USGS were analysed for their rare-earth element (REE) contents. All the fourteen REE were determined using neutron activation analysis. The results are presented and compared with published data.     

高分辨电感耦合等离子体质谱法测定地球化学样品中钪钇和稀土元素

建立了高分辨电感耦合等离子体质谱法(HR-ICP-MS)测定地球化学样品中钪、钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥的分析方法。样品经氢氟酸-硝酸-硫酸-王水消解,试液直接用HR-ICP-MS测定钪、钇和14种稀土元素。用高分辨模式有效地避免了多原子离子及难熔氧化物离子对待测元素测定的干扰,为钪、钇和14种稀土元素选择了最佳的测定同位素和合适的分辨率;用地球化学标准物质制备的溶液优化仪器工作参数,确定了最佳的仪器测定条件。方法检出限(6σ)为0.003～0.013μg/g(稀释因子为1000),相对标准偏差(RSD,n=12)小于6%。方法经国家一级地球化学标准物质验证,测定值与标准值吻合。     

An Evaluation of Methods for the Chemical Decomposition of Geological Materials for Trace Element Determination using ICP-MS

Complete dissolution is essential to obtain accurate analytical results using ICP-MS. In this study, decomposition techniques (i.e. acid digestions using Savillex Teflon vials, a high pressure digestion system and microwave oven, a combined lithium tetraborate fusion - HF/HNO3 acid decomposition and sodium peroxide sinter) for the total dissolution of different types of geological reference materials have been investigated. Savillex Teflon vial HF/HNO3 digestion is effective for basaltic samples. The high pressure HF/HClO4 digestion (PicoTrace TC-805 digestion system, Bovenden, Germany) allows dissolution of basalts and ironstones. Granites and magnetite-rich samples can be dissolved using a high pressure HF/H₂SO₄ method. Geological samples cannot be effectively attacked by microwave acid digestion. A combined lithium tetraborate fusion - HF/HNO3 acid digestion method allows complete dissolution of many different types of geological materials; however, this method precludes the determination of volatile elements due to the high fusion temperature (1000 °C). A sodium peroxide sinter method at 480 °C has the potential for the rapid determination of Y, Sc and REE in different types of geological materials. However, the lack of ultra-pure reagents precludes the use of lithium tetraborate fusion and sodium peroxide sinter methods for the measurement of geological samples with low trace element abundances.     

Molybdenum Concentrations Measured in Eleven USGS Geochemical Reference Materials by Isotope Dilution Thermal Ionisation Mass Spectrometry

Molybdenum concentrations in eleven USGS geochemical reference materials AGV-1, BCR-1, BHVO-1, BIR-1, DNC-1, DTS-1, G-2, GSP-1, MAG-1, PCC-1 and W-2 were measured by isotope dilution thermal ionisation mass spectrometry (ID-TIMS). In every case but one, the concentrations determined in this study were significantly lower than the current consensus values. Molybdenum concentrations determined by ID-TIMS are inherently more accurate and precisions may be up to an order of magnitude higher than those measured by other analytical techniques.     

δ30Si and δ29Si Determinations on USGS BHVO-1 and BHVO-2 Reference Materials with a New Configuration on a Nu Plasma Multi-Collector ICP-MS

We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the ¹⁴N¹⁶O and ¹⁴N₂ interferences overlying the ³⁰Si and the ²⁸Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ³⁰Si and δ²⁹Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ³⁰Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ³⁰Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Determination of Rare Earth Elements and Y in Ultramafic Rocks by ICP-MS After Preconcentration Using Fe(OH)3 and Mg(OH)2 Coprecipitation

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%.     

Determination of Lithium Contents in Silicates by Isotope Dilution ICP-MS and its Evaluation by Isotope Dilution Thermal Ionisation Mass Spectrometry

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.     

Germanium Contents of USGS Standard Rocks by Flameless Atomic Absorption

Germanium in 13 USGS standard silicate rooks was determined by flameless atomic absoprtion using a procedure which permits the determination of 0.2 ppm of germanium in as little as 50 mg of sample. The mean germanium content found is (in ppm Ge) for the new USGS standards: BHVO-1, 1.60; SDC, 1. 51; STM-1, 1. 32; QLO-1, 1. 28; RGM-1, 1. 24; and for- the older USGS standards: W-l, 1.S3; BCR-1, 1.39; G-l, 1.19; GSP-1, 1.16; AGV-1, 1.06; G-2, 0.96; PCC-1, 0.80; DTS-1, 0.72.