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.     

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.     

Calcium Carbonate and Phosphate Reference Materials for Monitoring Bulk and Microanalytical Determination of Sr Isotopes

In situ laser ablation analyses rely on the microanalytical homogeneity of reference materials (RMs) and a similar matrix and mass fraction between unknown samples and RMs to obtain reliable results. Suitable carbonate and phosphate RMs for determination of Sr isotope ratios in such materials are limited. Thus, we determined ⁸⁷Sr/⁸⁶Sr ratios of several carbonate (JCt‐1, JCp‐1, MACS‐1, MACS‐3) and phosphate (MAPS‐4, MAPS‐5, NIST SRM 1400, NIST SRM 1486) international RMs using dissolved samples and two different multi‐collector inductively coupled plasma‐mass spectrometers (MC‐ICP‐MS). Our Sr isotope data are in agreement with published data and have an improved measurement precision for some RMs. For MACS‐1, we present the first ⁸⁷Sr/⁸⁶Sr value. We tested the suitability of these materials for microanalytical analyses by LA‐MC‐ICP‐MS, with two different laser ablation systems: a conventional nanosecond laser and a state‐of‐the‐art femtosecond laser. We investigated the RMs micro‐homogeneity and compared the data with our solution data. Both laser ablation systems yielded identical ⁸⁷Sr/⁸⁶Sr ratios within uncertainty to the solution data for RMs with low interferences of REEs. Therefore, these carbonate and phosphate RMs can be used to achieve accurate and precise results for in situ Sr isotope investigations by LA‐MC‐ICP‐MS of similar materials.     

Chemical Characterisation of Natural Ilmenite: A Possible New Reference Material

Seven ilmenite (FeTiO₃) megacrysts derived from alnöite pipes (Island of Malaita, Solomon Islands) were characterised for their major and trace element compositions in relation to their potential use as secondary reference materials for in situ microanalysis. Abundances of thirteen trace elements obtained by laser ablation ICP‐MS analyses (using the NIST SRM 610 glass reference material) were compared with those determined by solution‐mode ICP‐MS measurements, and these indicated good agreement for most elements. The accuracy of the LA‐ICP‐MS protocol employed here was also assessed by repeated analysis of MPI‐DING international glass reference materials ML3B‐G and KL2‐G. Several of the Malaitan ilmenite megacrysts exhibited discrepancies between laser ablation and solution‐mode ICP‐MS analyses, primarily attributed to the presence of a titano‐magnetite exsolution phase (at the grain boundaries), which were incorporated solely in the solution‐mode runs. Element abundances obtained by LA‐ICP‐MS for three of the ilmenite megacrysts (CRN63E, CRN63H and CRN63K) investigated here had RSD (2s) values of < 20% and therefore can be considered as working values for reference purposes during routine LA‐ICP‐MS analyses of ilmenite.     

Correlation and characterisation of individual glass shards from tephra deposits using trace element laser ablation ICP‐MS analyses: current status and future potential

Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) is a high spatial resolution analytical method which has been applied to the analysis of silicic tephras. With current instrumentation, around 30 trace elements can be determined from single glass shards as small as ～ 40 µm, separated from tephra deposits. As a result of element fractionation during the ablation process using a 266 nm laser, a relatively complex calibration strategy is required. Nonetheless, such a strategy gives analyses which are accurate (typically within ±5%) and have an analytical precision which varies from ～ ±2% at 100 ppm, to ～ ±15% at 1 ppm. Detection limits for elements used in correlation and discrimination studies are well below 1 ppm. Examples of the application of trace element analysis by LA‐ICP‐MS in tephra studies are presented from the USA, New Zealand and the Mediterranean. Improvements in instrumental sensitivity in recent years have the potential to lower detection limits and improve analytical precision, thus allowing the analysis of smaller glass shards from more distal tephras. Laser systems operating at shorter wavelengths (e.g. 193 nm) are now more widely available, and produce a much more controllable ablation in glasses than 266 nm lasers. Crater sizes of <10 µm are easily achieved, and at 193 nm many of the elemental fractionation issues which mar longer wavelengths are overcome. By coupling a short wavelength laser to a modern ICP‐MS it should be possible to determine the trace element composition of glass shards as small as 20 µm and, providing sample preparation issues can be overcome, the determination of the more abundant trace elements in glass shards as small as 10 µm is within instrumental capabilities. This will make it possible to chemically fingerprint tephra deposits which are far from their sources, and will greatly extend the range over which geochemical correlation of tephras can be undertaken. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

LA‐(MC)‐ICP‐MS Trends in 2006 and 2007 with Particular Emphasis on Measurement Uncertainties

Research in 2006 and 2007 dealing with laser ablation‐(multicollector)‐inductively coupled plasma‐mass spectrometry, LA‐(MC)‐ICP‐MS, involved studies concerned with optimising the technique itself, as well as applying the method to a variety of problems in the Earth sciences. The causes of elemental and isotopic fractionation produced during laser ablation continues to be of considerable interest, with evidence mounting that processes occurring both at the ablation site and in the argon plasma of the ICP are culpable. There is growing excitement in the use of femtosecond lasers for LA‐(MC)‐ICP‐MS, with the hope that they reduce or eliminate melting and non‐congruent volatilisation at the ablation site and thus approach stoichiometric sampling. Ablation chamber design emerged as a serious concern, particularly with respect to achieving the rapid washout needed for fine‐scale compositional mapping of geological objects. LA‐MC‐ICP‐MS provided data for a wide range of isotopic systems, especially hafnium, but also B, S, Mg, Cu, Fe, Sr, Nd, Pb and U. Measurement uncertainties in LA‐ICP‐MS were discussed by several researchers, and are critically reviewed here ‐ total uncertainties for trace element concentration measurements of silicates including errors on the calibration values of common reference materials are ～10% (95% confidence limits), though the precision of individual spot measurements (50 to 100 μm) is much better, ～1% RSD, using a 193 nm laser and a sector field‐ICP‐MS. LA‐ICP‐MS U‐Pb ages for zircon and other U‐rich accessory phases are claimed by most geoanalysts to have 2s uncertainties of ～0.7 and 1.3% respectively but the actual accuracy of the method is probably only as good as ～2% (2s), when uncertainties associated with laser‐induced Pb/U fractionation are included.     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

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.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

Evaluation of Major to Ultra Trace Element Bulk Rock Chemical Analysis of Nanoparticulate Pressed Powder Pellets by LA‐ICP‐MS

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.     

Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

The Preparation and Preliminary Characterisation of Three Synthetic Andesite Reference Glass Materials (ARM‐1, ARM‐2, ARM‐3) for In Situ Microanalysis

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%.     

Direct Quantitative Determination of Trace Elements in Fine‐Grained Whole Rocks by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Previous laser ablation‐ICP‐MS bulk analyses have been confined to volcanic glasses and glass disks or powder pellets similar to those used for XRF analysis. This study proposes a method to determine twenty trace elements (fourteen rare earth elements, Sc, Y, Zr, Nb, Hf and Ta) by LA‐ICP‐MS directly from polished thick sections and rock slabs of six fine‐grained crystalline and aphanitic rocks (five volcanic rocks and one pelitic tillite). Laser scanning of eight to ten 20 mm long linear tracks using a spot size of 160 μm, with a total ablated area of 26–32 mm², was performed. Quantification was carried out by (a) internal standardisation using Si and (b) without applying internal standardisation. In the latter method, external determination of one element in conventional LA‐ICP‐MS quantification is no longer needed. Although the fine‐grained rocks studied contained variable amounts of volatiles (up to 4%), this method gave results that agree within 10% relative with those obtained by internal standardisation using Si. Two USGS basalt glass reference materials (BCR‐2G and BHVO‐2G) were used for external calibration. The results and the associated trace element patterns and ratios of elemental pairs obtained from both methods of quantification showed good agreement with the results from solution nebulisation ICP‐MS within 20% (mostly within 10%) relative. Fine‐grained rocks are common and include volcanic, sedimentary and low‐grade metamorphic rocks (e.g., basalt, andesite, rhyolite, shale, mudstone, tillite, loess, pelite and slate) and their trace element contents and associated ratios are important geochemical tracers in studies focusing on the composition and evolution of the crust and mantle. Our method provides a simple and quantitative way to determine trace elements in fine‐grained rocks even with those displaying complex textures.     

Community‐Derived Standards for LA‐ICP‐MS U‐(Th‐)Pb Geochronology – Uncertainty Propagation,Age Interpretation and Data Reporting

The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess ²³⁰Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.     

Assessment of Nanosecond Laser Ablation Multi‐Collector Inductively Coupled Plasma‐Mass Spectrometry for Pb and Sr Isotopic Determination in Archaeological Glass: Mass Bias Correction Strategies and Results for Corning Glass Reference Materials

This work presents an evaluation of various methods for in situ high‐precision Sr and Pb isotopic determination in archaeological glass (containing 100–500 μg g^?1 target element) by nanosecond laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (ns‐LA‐MC‐ICP‐MS). A set of four soda‐lime silicate glasses, Corning A–D, mimicking the composition of archaeological glass and produced by the Corning Museum of Glass (Corning, New York, USA), were investigated as candidates for matrix‐matched reference materials for use in the analysis of archaeological glass. Common geological reference materials with known isotopic compositions (USGS basalt glasses BHVO‐2G, GSE‐1G and NKT‐1G, soda‐lime silicate glass NIST SRM 610 and several archaeological glass samples with known Sr isotopic composition) were used to evaluate the ns‐LA‐MC‐ICP‐MS analytical procedures. When available, ns‐LA‐MC‐ICP‐MS results for the Corning glasses are reported. These were found to be in good agreement with results obtained via pneumatic nebulisation (pn) MC‐ICP‐MS after digestion of the glass matrix and target element isolation. The presence of potential spectral interference from doubly charged rare earth element (REE) ions affecting Sr isotopic determination was investigated by admixing Er and Yb aerosols by means of pneumatic nebulisation into the gas flow from the laser ablation system. It was shown that doubly charged REE ions affect the Sr isotope ratios, but that this could be circumvented by operating the instrument at higher mass resolution. Multiple strategies to correct for instrumental mass discrimination in ns‐LA‐MC‐ICP‐MS and the effects of relevant interferences were evaluated. Application of common glass reference materials with basaltic matrices for correction of ns‐LA‐MC‐ICP‐MS isotope data of archaeological glasses results in inaccurate Pb isotope ratios, rendering application of matrix‐matched reference materials indispensable. Correction for instrumental mass discrimination using the exponential law, with the application of Tl as an internal isotopic standard element introduced by pneumatic nebulisation and Corning D as bracketing isotopic calibrator, provided the most accurate results for Pb isotope ratio measurements in archaeological glass. Mass bias correction relying on the power law, combined with intra‐element internal correction, assuming a constant ⁸⁸Sr/⁸⁶Sr ratio, yielded the most accurate results for ⁸⁷Sr/⁸⁶Sr determination in archaeological glasses     

Simultaneous Determination of Major and Trace Elements in Fused Volcanic Rock Powders Using a Hermetic Vessel Heater and LA‐ICP‐MS

Fused glass prepared without the addition of a flux is generally more homogeneous than a pressed powder pellet and thus ideal for analysis of bulk samples by LA‐ICP‐MS. In this work, a new glass‐making method using a boron nitride crucible was developed to prepare homogenous glass samples from silicate rock powder. The apparatus consisted of a small boron nitride vessel with net volume of about 34 mm³ and two molybdenum strips. Applying the summed metal oxide normalisation technique, both major and trace element contents in the fused glass were measured by LA‐ICP‐MS. Analyses of five geochemical reference materials (spanning the compositional range basalt–andesite–rhyolite) indicated that the measured SiO₂, Al₂O₃ and P₂O₅ contents matched the preferred values to within 5%, and the other major elements generally matched the preferred values to within 8%. Except for the transition metals, the measured trace element contents generally matched the preferred values to within 10%. Compared with the iridium heater method developed by Stoll et al. (2008), element volatilisation during high‐temperature melting was effectively suppressed in our method, but metal segregation caused by reduction of BN may cause loss of Cr, Ni and Cu. Although analysis with a large spot size has the advantage of improving counting statistics, matrix effects induced by mass loading of the ICP may hamper the accurate determination of some elements.     

Major and Trace Element Analysis of Silicate Rocks by XRF and Laser Ablation ICP-MS Using Lithium Borate Fused Glasses: Matrix Effects, Instrument Response and Results for International Reference Materials

Major and trace element compositions of fifteen silicate rock reference materials have been determined by a combined XRF and laser ablation ICP‐MS (LA‐ICP‐MS) technique on glasses prepared by fusing the sample with a lithium borate flux (sample:flux = 1:3). Advantages of this technique include the ability to measure major and trace element abundances on a single sample using a quick and simple preparation that attacks resistant phases such as zircon without the need for acid dissolution. The method is suitable for a wide variety of bulk compositions including mafic, intermediate and silicic rocks. Abundance‐normalized mass response patterns (the ratio of signal intensity to element concentration) of the LA‐ICP‐MS analyses vary systematically with major element composition, demonstrating the presence of a matrix effect that cannot be compensated by normalisation to a single internal standard element. Increasing the sampling distance between the ICP‐MS cone and the torch reduces the magnitude of this effect, suggesting that a mechanism related to residence time of ablated particles in the plasma may be at least partially responsible for the observed variations in mass response patterns. When using a matrix‐matched calibration, agreement of the LA‐ICP‐MS results with published reference values or those obtained by solution ICP‐MS is 10% relative. Analytical precision based on replicate analyses is typically 5% RSD. Procedural detection limits that include contributions from gas background and flux are 0.01‐0.1 μg g‐¹ for the heavy mass trace elements (Rb‐U). Major element analyses by XRF show excellent agreement with results obtained using a conventional heavy element absorbing flux. High quality major and trace element data for silicate rocks can be achieved by a combined XRF and LA‐ICP‐MS analysis of Li₂B₄O₇/LiBO₂ fused glasses provided an appropriate matrix‐matched calibration is adopted.     

A Comparison of In Situ Analytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits

Trace element concentrations in gold grains from various geological units in South Africa were measured in situ by field emission‐electron probe microanalysis (FE‐EPMA), laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and synchrotron micro X‐ray fluorescence spectroscopy (SR‐μ‐XRF). This study assesses the accuracy, precision and detection limits of these mostly non‐destructive analytical methods using certified reference materials and discusses their application in natural sample measurement. FE‐EPMA point analyses yielded reproducible and discernible concentrations for Au and trace concentrations of S, Cu, Ti, Hg, Fe and Ni, with detection limits well below the actual concentrations in the gold. LA‐ICP‐MS analyses required larger gold particles (> 60 μm) to avoid contamination during measurement. Elements that measured above detection limits included Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te, which can be used for geochemical characterisation and gold fingerprinting. Although LA‐ICP‐MS measurements had lower detection limits, precision was lower than FE‐EPMA and SR‐μ‐XRF. The higher variability in absolute values measured by LA‐ICP‐MS, possibly due to micro‐inclusions, had to be critically assessed. Non‐destructive point analyses of gold alloys by SR‐μ‐XRF revealed Ag, Fe, Cu, Ni, Pb, Ti, Sb, U, Cr, Co, As, Y and Zr in the various gold samples. Detection limits were mostly lower than those for elements measured by FE‐EPMA, but higher than those for elements measured by LA‐ICP‐MS.