Trace Element Determination by ICP‐AES and ICP‐MS: Developments and Applications Reported During 2006 and 2007

This review describes developments in trace element determination using inductively coupled plasma‐atomic emission spectrometry (ICP‐AES) and inductively coupled plasma‐mass spectrometry (ICP‐MS) that were reported in 2006 and 2007. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP‐MS and ICP‐AES instrumentation have largely been ignored. New advances in ICP‐MS and ICP‐AES were incremental over this period, partly because both techniques are now well‐established. A continuing shift towards the hyphenation of low‐flow separation techniques has sparked activity in the development of appropriate low‐flow interfaces, and papers discussing interference removal also contribute significantly to the volume of research for both ICP‐AES and ICP‐MS. Whereas the majority of new ICP publications concerned advances in ICP‐MS analysis rather than ICP‐AES, development for ICP‐AES still occurs in almost all areas, particularly in sample introduction and hyphenated techniques.     

In Situ Quantitative Measurement of Rare Earth Elements in Uranium Oxides by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Advances in the quantification of rare earth elements (REE) at the micrometric scale in uranium oxides by laser ablation‐inductively coupled plasma‐mass spectrometry are described. The determination of the best analytical conditions was tested using a uranium oxide (Mistamisk) the concentrations of REE in which were previously estimated by other techniques. Comparison between the use of U or Pb as an internal standard clearly showed a diameter‐dependent fractionation effect related to Pb at small crater diameters (16 and 24 μm), which was not found for U. The quantification of REE contents in uranium oxide samples using both matrix‐matched (uranium oxide) and non‐matrix‐matched (NIST SRM 610 certified glass) external calibrators displayed no significant difference, demonstrating a limited matrix effect for REE determination by LA‐ICP‐MS. Moreover, no major interferences on REEs were detected. The proposed methodology (NIST SRM 610 as external calibrator and U as internal standard) was applied to samples from uranium deposits from around the world. The results showed that LA‐ICP‐MS is a suitable analytical technique to determine REE down to the μg g^?1 level in uranium oxides at the micrometre scale and that this technique can provide significant insights into uranium metallogeny.     

Rapid Determination of Trace Element Compositions in Peridotites by LA‐ICP‐MS Using an Albite Fusion Method

A rapid sample preparation procedure is described to determine trace element compositions of peridotites using LA‐ICP‐MS. Peridotite powders were fused with albite in a molybdenum–graphite assembly to obtain homogeneous glasses. Best conditions for the fusion procedure (heating at 1500–1550 °C for 10–15 min with a sample‐to‐flux ratio of 1:2) were constrained with melting experiments on two USGS reference materials, PCC‐1 and DTS‐2B. Mass fractions of first series transition elements, Ba and Pb, in quenched glasses of PCC‐1 and DTS‐2B are consistent with published data within 10% RSD. Three spinel peridotite xenoliths from eastern China were analysed following both our method and conventional solution ICP‐MS. Compared with solution ICP‐MS, the relative deviations of our method for most elements were within 10%, while for the REE, Ta, Pb, Th and U, the relative deviations were within 20%. In particular, volatile elements (e.g., Pb and Zn) are retained in the glass. Compared with conventional wet chemistry digestion, our method is faster. Additional advantages are complete sample fusion, especially useful for samples with acid‐resistant minerals (spinel and rutile), and long‐term conservation of glasses allowing unlimited repeated measurements with microbeam techniques. The same approach can be used for analyses of other mantle rocks, such as eclogites and pyroxenites.     

感耦等离子体质谱法测定商代原始瓷中的稀土

以混合酸溶样电感耦合等离子体质普法测定了商代古陶瓷中稀土元素,采用Ｉｎ内标补偿测定信号所受的影响,同时讨论了干扰因素及其校正方法。方法经国家一级标准物质分析验证,其分析结果与标准植吻合;经１０次重复测定同一样品,方法的精密度ＲＳＤ在１．６％～７．３％。该方法已用于不同地区的商瓷样品中稀土的测定,并对古瓷的地球化学特征作了探讨。     

等离子体质谱法分析原油中超痕量稀土元素的研究

报道了用等离子体质谱仪测定原油中超痕量稀土元素的研究工作。试验了不同地区原油样品前处理的各种方法,确定以浓Ｈ２ＳＯ４为炭化剂,克服了原油样品炭化过程中试样膨胀外溢和跳溅诸问题。考察了共存元素的干扰情况,采用Ｒｅ内标补偿测定信号的影响。各稀土元素的检出限在０．９～１６．１ｎｇ／Ｌ,标准加入回收率为９９．８％～１０７．７％,方法精密度好,ＲＳＤ（ｎ＝１０）为４．３６％～１６．５３％。该方法已成功地用于不同地区原油样品的测定。     

Natural Titanite Reference Materials for In Situ U‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Titanite is a common accessory mineral that preferentially incorporates considerable amounts of U and light rare earth elements in its structure, making it a versatile mineral for in situ U‐Pb dating and Sm‐Nd isotopic measurement. Here, we present in situ U‐Pb ages and Sm‐Nd isotope measurement results for four well‐known titanite reference materials (Khan, BLR‐1, OLT1 and MKED1) and eight titanite crystals that could be considered potential reference material candidates (Ontario, YQ‐82, T3, T4, TLS‐36, NW‐IOA, Pakistan and C253), with ages ranging from ~ 20 Ma to ~ 1840 Ma. Results indicate that BLR‐1, OLT1, Ontario, MKED1 and T3 titanite have relatively homogeneous Sm‐Nd isotopes and low common Pb and thus can serve as primary reference materials for U‐Pb and Sm‐Nd microanalysis. YQ‐82 and T4 titanite can be used as secondary reference materials for in situ U‐Pb analysis because of their low common Pb. However, internal structures and mineral inclusions in YQ‐82 will require careful selection of suitable target domains. Pakistan titanite is almost concordant with an age of 21 Ma and can be used as a reference material when dating Cenozoic titanite samples.     

A Robust Procedure for High‐Precision Determination of Rare Earth Element Concentrations in Seawater

This study reports a robust procedure that permits precise measurement of all fourteen naturally occurring rare earth element (REE) concentrations, present at ng kg^?1 to sub ng kg^?1 levels, in ~ 100 ml seawater. This procedure is simple and can be routinely applied to measure seawater REEs with relatively high sample throughput. The procedure involves addition of a ¹⁴²Ce‐¹⁴⁵Nd‐¹⁷¹Yb‐enriched spike mixture, iron co‐precipitation, REE purification with chromatographic separation and the use of a magnetic‐sector‐field ICP‐MS (Element 2) coupled with a desolvating sample introduction system (Aridus 1). Critical steps of the procedure, including co‐precipitation pH and matrix removal, have been optimised through a set of experiments described here. The accuracy of the new procedure was assessed against a gravimetric mixture of REEs, and the precision was demonstrated by repeated measurement of two well‐mixed natural seawaters. Repeated analyses of these seawater reference materials (RMs), using ~ 100 ml seawater for each aliquot, indicate precision of 3% (1s) for the REEs. Measured REE concentrations of two uncertified seawater RMs (CASS‐4 and NASS‐5) are consistent with published values, and REE concentrations of the GEOTRACES intercalibration samples show good agreement with those reported by other participant laboratories. REE concentrations for other intercalibration samples (SAFe and Arctic PS70) are also reported.     

Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

Accurate Measurement of Rare Earth Elements by ICP‐MS after Ion‐Exchange Separation: Application to Ultra‐Depleted Samples

This study reports precise and accurate data for rare earth elements (REE) measured on eight geological reference materials, five enriched in REE (BE‐N, BHVO‐2, BR, BR‐24 and RGM‐1) and three very depleted in REE (BIR‐1, UB‐N and DTS‐2). Data were acquired by quadrupole ICP‐MS after isolation of the REE using an ion‐exchange chromatography procedure. All the measured REE abundances were similar within ≈ 5% (10% for the most REE‐depleted sample DTS‐2) to the high‐quality measurements previously published in the literature. We also show that by using an internal Tm spike, the reproducibility of the data was improved to ～ 1%. Applying this technique to the analysis of ultra‐depleted rock samples (sub ng g^?1), we show that significant improvements were obtained relative to the routine trace element measurement method. The chondrite‐normalised patterns were smooth instead of displaying irregularities. Although the classical method gives excellent results on REE‐rich samples, we believe that our technique improves the precision and accuracy of measurements for highly REE‐depleted rocks.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

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.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.     

Measurements of Rare Earth Element and Other Element Mass Fractions in Environmental Reference Materials (NIST SRM 1646a,NIST SRM 1400, IAEA‐395 and IAEA‐450) by INAA,ICP‐AES and ICP‐MS

INAA, ICP‐AES and ICP‐MS were used to elementally characterise four environmental reference materials – NIST SRM 1646a (Estuarine Sediment), NIST SRM 1400 (Bone Ash), IAEA‐395 (Urban Dust) and IAEA‐450 (Algae). An analytical scheme consisting of the three methods was first applied to NIST SRM 1646a to validate the methodology because it has been extensively analysed and has certified values for many elements. With repeated analyses of NIST SRM 1646a, the accuracy and measurement repeatability of the data obtained were evaluated based on two statistical calculations (zeta‐score and Horwitz ratio) and were observed to be good enough for the analytical scheme to be applied to similar sorts of environmental/geochemical samples. Applying the same approach to NIST SRM 1400, IAEA‐395 and IAEA‐450, enabled mass fractions of 29, 38 and 28 elements to be determined, respectively. Among these results, the data for rare earth elements are of particular interest, not only for IAEA‐450 but also for the other three reference samples. The data for Pr, Gd, Dy, Ho, Er and Tm in NIST SRM 1646a are newly reported in this study. By using small test portions (< 100 mg) for NIST SRM 1646a and IAEA‐395, and recommended minimum amounts for NIST SRM 1400 and IAEA‐450, sample homogeneity was evaluated.     

Investigation of Thulium and Other Rare Earth Element Mass Fractions in NIST SRM 1632a Bituminous Coal Reference Material by Quadrupole ICP‐MS

Inductively coupled plasma‐mass spectrometry after lithium metaborate fusion and digestion was used to measure the rare earth element (REE) mass fractions of several reference materials including NIST SRM 1632a, a historical bituminous Pennsylvania seam coal. While most of the REE mass fractions measured in this study were consistent with the published consensus data, the measured mass fraction of thulium for NIST SRM 1632a was consistently lower compared with the published data. Chondrite normalisation of the published consensus data for NIST SRM 1632a produced a positive thulium anomaly (Tm = 1.78), which is inconsistent with a terrestrial source of sediment. Normalisation of REE mass fractions collected in this study produced no significant Tm anomaly (Tm = 0.93), which agrees with the sedimentary depositional environment of coal. Therefore, a revised mass fraction of 0.16 mg kg^?1 Tm in NIST SRM 1632a is recommended.     

A Comparative Study of Five Reference Materials and the Lombard Meteorite for the Determination of the Platinum‐Group Elements and Gold by LA‐ICP‐MS

A range of independently characterised reference materials (RMs) for LA‐ICP‐MS, used for the determination of the platinum‐group elements (PGE) and Au in a sulfide matrix, were analysed and compared: 8b, PGE‐A, NiS‐3, Po727‐T1, Po724‐T and the Lombard meteorite. The newly developed RM NiS‐3 was used as the RM for the calibration of all LA‐ICP‐MS analyses and the measured concentrations of the other RMs compared against their published concentrations. This data were also used to assess the consistency of concentrations calibrated against the different RMs. It was found that Po727‐T1 and 8b produced results that were comparable, within uncertainty, for all elements. Po727‐T1 also produced consistent results with NiS‐3 for all elements. All other RMs showed differences for some elements, especially Ru in Po724‐T, and Os, Ir and Au in PGE‐A. The homogeneity of the PGE and Au in each RM was assessed, by comparing the precision of multiple LA‐ICP‐MS spot analyses with the average uncertainty of the signal. Po724‐T, Po727‐T1 and the Lombard meteorite were found to be homogeneous for all elements, but 8b, PGE‐A and NiS‐3 were heterogeneous for some elements. This is the first direct comparison between a range of independently characterised PGE and Au LA‐ICP‐MS RMs.     

In Situ Determination of First‐Row Transition Metal,Ga and Ge Abundances in Geological Materials via Medium‐Resolution LA‐ICP‐MS

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% (2s_m). This analytical method may be extended to any matrix‐matched geological sample, particularly oceanic basalts, silicate minerals and meteoritic materials.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Towards a Method for Quantitative LA‐ICP‐MS Imaging of Multi‐Phase Assemblages: Mineral Identification and Analysis Correction Procedures

Here, we present an approach to laser ablation ICP‐MS mapping of multi‐phase assemblages that permits the use of different internal standard elements, concentration values and reference materials for each mineral. In this way, we obtain not only broad pictures of elemental distributions within samples but can also extract high accuracy concentration data for any user‐selected region. This is accomplished by assigning regions of an image to corresponding mineral phases on a pixel‐by‐pixel basis. In this way, accurate trace element concentrations can be determined for each mineral phase, despite potential variations in their ablation characteristics. We present an example where elemental maps are constructed from ablation of a gabbroic sample that includes the phases apatite, amphibole and plagioclase. This work represents an important first step towards development of a method to produce highly accurate LA‐ICP‐MS elemental maps of multi‐phase samples.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).     

Determination of Trace Element Mass Fractions in Ultramafic Rocks by HR‐ICP‐MS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation

A procedure is described for the determination of thirty‐seven minor and trace elements (LILE, REE, HFSE, U, Th, Pb, transition elements and Ga) in ultramafic rocks. After Tm addition and acid sample digestion, compositions were determined both following a direct digestion/dilution method (without element separation) and after a preconcentration procedure using a double coprecipitation process. Four ultramafic reference materials were investigated to test and validate our procedure (UB‐N, MGL‐GAS [GeoPT12], JP‐1 and DTS‐2B). Results obtained following the preconcentration procedure are in good agreement with previously published work on REE, HFSE, U, Th, Pb and some of the transition elements (Sc, Ti, V). This procedure has two major advantages: (a) it avoids any matrix effect resulting from the high Mg content of peridotite, and (b) it allows the preconcentration of a larger trace element set than with previous methods. Other elements (LILE, other transition elements Cr, Mn, Co, Ni, Cu, Zn, as well as Ga) were not fully coprecipitated with the preconcentration method and could only be accurately determined through the direct digestion/dilution method.