GGR Biennial Review: Advances in Laser Ablation and Solution ICP-MS from 2008 to 2009 with Particular Emphasis on Sensitivity Enhancements,Mitigation of Fractionation Effects and Exploration of New Applications

Recent developments from 2008 to 2009 in ICP-MS engineering, methods and applications are reviewed here. Of particular emphasis are advances in: (a) maximising sensitivity and reducing elemental/isotopic fractionation during laser ablation processing; (b) developing new analytical techniques to measure major, minor and trace element abundances without depending on matrix-matched calibrating materials, pre-determined internal standard concentrations and/or multiple analytical methods; (c) applying in situ and solution-based ICP-MS techniques to the analysis of forensic materials for criminal and/or nuclear investigations; and (d) improving precision and limits of detection of laser ablation multi-collector ICP-MS measurements of (ultra) trace elemental and isotopic abundances.     

Trends in Analytical Developments and Earth Science Applications in LA-ICP-MS and LA-MC-ICP-MS for 2004 and 2005

This review of laser ablation-inductively coupled plasma-mass spectrometry includes research that employed quadrupole instruments, and single-collector and multicollector magnetic sector field instruments. The most important trend in 2004–2005 was the growing appreciation that small matrix effects in LA-(MC)-ICP-MS need to be addressed in order to produce highly precise and accurate data by the method. The issue is most acute for isotope ratio measurements that require standard-sample-standard bracketing but can also be important for certain elemental analysis. Matrix-dependent elemental and isotopic fractionations were studied from the standpoint of laser-sample interactions and the behaviour of laser-generated particles in the ablation cell, transfer tubing and ICP torch. Innovations in LA-(MC)-ICP-MS involved signal smoothing, in torch laser ablation, on-line isotope dilution and molecular oxide monitoring. Other important research was carried out on the calibration and homogeneity of various reference materials; and the exploration of mature ( in situ U-Pb geochronology) and emerging (apatite fission-track chronometry, U-Th/He thermochronology, boron/strontium/uranium-series isotopic microanalysis) applications in the Earth sciences.     

激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用

激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一。文章介绍了多种类型的质谱仪及其使用的激光器。用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍。文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量。     

Laser Ablation ICP-MS Developments and Trends for 2003

This annual review of laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) covers the year 2003. Significant advances were made in understanding laser-sample interactions. In particular, research defined the distribution of particle sizes produced by the interplay of laser wavelength, laser pulse width and the gas environment of ablation. A link between particle sizes and elemental and isotopic fractionation at both the ablation site and in the ICP was established. Experimental 15 7 nm and femtosecond laser systems were tested with promising results. The number of applications of LA-ICP-MS in geology and environmental Earth science continued to grow with particular interest in element concentration and isotope ratio profiling of materials, linking composition to time scales. In situ isotopic ratio measurements were increasingly made using multicollector magnetic sector ICP-MS instruments. Other applications of wide interest included bulk sampling of rocks and ores prepared as lithium borate glasses; low level analysis of platinum-group elements, rhenium and gold in sulfides, metal and silicates; in situ uranium-lead zircon geochronology; and melt and fluid inclusion analysis.     

Application of Laser Ablation ICP-MS to U-Th-Pb Dating of Monazite

Recent advances in laser ablation ICP-MS techniques allow accurate U-Th-Pb age dating of monazites that are as young as several tens of million years to a precision better than 2%. Accuracy of the age determinations has been improved by true real-time mass bias correction via nebulisation of a solution containing enriched ²³³U and natural Tl isotopes. The Tl-U tracer solution eliminates possible effects of variable sample matrices on the precision and accuracy of measured isotopic ratios. Mass bias corrections based on measured ²⁰⁵Tl/²³³U ratios in the tracer solution allow direct measurement of ²³⁵U in monazite. Combined with high-sensitivity laser ablation ICP-MS measurements, direct measurement of ²³⁵U particularly improves the precision of U-Pb dating of young monazites. Correction for laser-induced Pb/U and Pb/Th elemental fractionation is based on a mathematical treatment of time resolved count-rate data that is independent of laser ablation characteristics, does not require external standardisation and allows variable laser pit size or raster patterns for each measurement. The new procedures make the LA ICP-MS technique more flexible for in situ U-Th-Pb analysis.     

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.     

秦皇岛柳江地区长龙山组石英砂岩物质源区组成——来自碎屑锆石U-Pb-Hf同位素的证据

在秦皇岛市柳江地区出露最古老的沉积岩为青白口系长龙山组石英砂岩,该石英砂岩与下伏的新太古代钾质花岗岩呈不整合接触。LA-ICPMS锆石U-Pb测年显示该区长龙山组石英砂岩中碎屑锆石年龄分布在2635～2487Ma之间,其物质源区较单一。与北京—蓟县标准剖面相比,本研究区在较长的一段地质时期为古陆壳的剥蚀区,直至新元古代早期,又沉积了长龙山组滨海相碎屑岩。碎屑锆石Hf同位素组成显示,它们的源区物质虽然有不同程度的壳幔混合,但主要来自于古老的地壳物质再循环,暗示在～2.5Ga其碎屑物质源区的地壳已经达到一定的规模和厚度。     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

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.     

Matrix-independent Fe isotope ratio determination in silicates using UV femtosecond laser ablation

UV femtosecond laser ablation coupled to MC-ICP-MS provides a promising in situ tool to investigate elemental and isotope ratios by non-matrix-matched calibration. In this study, we investigate Fe isotope composition in siliceous matrices including biotite, hornblende, garnet, fayalite and forsterite (San Carlos Olivine), and an oceanic Fe–Mn crust using the iron reference material IRMM-014 for calibration. To test the accuracy of the laser ablation data, Fe isotope compositions were obtained independently by solution ICP-MS after chromatographic separation of Fe. Sample materials with low Cr content, i.e. biotite, hornblende, fayalite and the Fe–Mn crust, reveal δ^56/54Fe and δ^57/54Fe values that agree with those from solution ICP-MS data within the measured precision. For high Cr concentration (⁵⁴Cr/⁵⁴Fe >0.0001), i.e. in the garnet and forsterite sample, δ^56/54Fe and δ^57/54Fe values were derived from ⁵⁷Fe/⁵⁶Fe ratios as correction of the isobaric interference of ⁵⁴Cr on ⁵⁴Fe is unsatisfactory. This approach provides accurate results for both minerals. Moreover, the garnet crystal exhibits isotopic zonation with differences of 0.3‰ in δ^56/54Fe showing that substantial heterogeneities exist in high-temperature metamorphic minerals. Multiple analyses of homogeneous sample materials reveal a repeatability of 0.1‰ (2 SD) for δ^56/54Fe and 0.2‰ (2 SD) for δ^57/54Fe, respectively. This study adds to the observations of Horn et al. (2006) who have shown that the determination of Fe isotope ratios in various matrices including iron alloys, iron oxides and hydroxides, iron sulfide and iron carbonates can be performed with high accuracy and precision at high spatial resolution using UV femtosecond laser ablation ICP-MS. These results demonstrate that femtosecond laser ablation ICP-MS is a largely matrix-independent method, which provides a substantial advantage over commonly employed nanosecond laser ablation systems.     

GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

U–Pb dating of detrital zircons for sediment provenance studies—a comparison of laser ablation ICPMS and SIMS techniques

New developments in U–Pb dating of zircons by laser ablation (LA) ICPMS are described and, for the first time, a direct comparison of detrital zircons dated by LA ICPMS and SIMS methods is presented. True real-time mass bias correction is made by aspirating a Tl/U tracer at the same time as laser ablation. The method is similar to that described in Horn et al. (2000), except that enriched ²³³U rather than ²³⁵U is used in the tracer solution. Correction for laser-induced Pb/U elemental fractionation is based on a mathematical treatment of time-resolved data that is independent of laser ablation characteristics and does not require external standardisation. Internal corrections for mass bias and elemental fractionation eliminate the effects of variable sample matrix on isotopic ratios and improve the accuracy of U–Pb dating by laser ablation ICPMS. With the proper error propagation, the precision of U–Pb age determinations is only slightly worse than SIMS-based ion probe dating. However, LA ICPMS is capable of much more rapid analysis of the large number of zircons required for sediment provenance studies. There is excellent agreement between concordant laser ablation ICPMS and SIMS analyses of detrital zircons extracted from lower Silurian metasandstone from the Ulven Group (Skarfjell Formation) in the west Norwegian Caledonian nappes. Both LA ICPMS and SIMS U–Pb zircon ages indicate that sedimentary detritus of the Ulven Group was supplied from a terrain containing zircons of Archean, Proterozoic and early Ordovician age.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Isotope Ratio Determination in the Earth and Environmental Sciences: Developments and Applications in 2003

This annual review documents developments and applications in the field of isotope ratio determination, as reflected in the literature for the Earth and environmental sciences for the year 2003. Particular emphasis is placed upon the relationship between the two dominant analytical techniques-thermal ionisation mass spectrometry (TIMS) and multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS)-and the rapidly changing nature of their roles in isotope analysis. Additionally, the review covers developments in single-collector ICP-MS and TOF technologies, new sample preparation procedures and the characterisation of isotopic reference materials, together with fundamental investigations of mass spectrometer performance.     

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.     

一个新的矿物面扫描分析方法开发和地质学应用

LA-ICP-MS面扫描分析近些年来发展的新兴技术,相对于其他面扫描仪器,其具有样品制样流程简单、仪器购置和分析成本低、分析时间短、检测限低、多元素表面分析(5μm)、近乎无损等分析优势,在地球科学和生物学领域有着大量的应用。本文系统介绍了作者应用Photon Machines激光剥蚀系统与安捷伦ICP-MS新开发矿物元素面扫描分析方法。该方法基于近些年来开发的双室样品仓技术和Matlab软件,通过自主开发的LaIcpMsSoftware(LIMS)进行数据处理来完成的。本次研究开发的激光面扫描分析技术可以在短时间内(2小时)分析3mm×3mm区域,并同时给出多组元素(包括稀土元素等)在二维平面的分布特征。论文详细描述了LIMS工作原理和特点,相对于国外同类型软件,LIMS具有操作简单,并具有多种数据显示模式和剖面切割展示,元素比值面分布分析等优势,便于后期数据分析与解译。同时,还展示了对斜长石、白钨矿和石榴子石进行面扫描分析的初步结果。研究表明,通过LA-ICP-MS面扫描,可以获得比点分析更为准确的元素分布特征,并能够更为直观的展示不同元素在矿物分布特征和相关关系,更好的开展矿物地球化学研究。     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Magma homogenization during anatexis,ascent and/or emplacement? Constraints from the Variscan Weinsberg Granites

Recent studies have shown that melts and residues may not equilibrate during anatexis, and uncertainty exists about the scale on which magmas can be homogenized. This study of elemental and isotopic homogeneity of the South Bohemian Weinsberg granites (˜ 5000 km²) identifies three voluminous, relatively homogeneous magma batches. Each batch has different ⁸⁷Sr/⁸⁶Sr_init (0.7080, 0.7093 and 0.7106), but all equilibrated at ˜ 327–329 Ma, very similar to the time of monazite crystallization. The data cannot entirely prove melt/residue equilibration during anatexis. However, elemental and isotopic compositions imply magma generation by partial melting of heterogeneous South Bohemian crust and chemical differentiation subsequent to Sr-isotope equilibration. Assuming relatively rapid ascent and solidification rates, magma homogenization must have occurred mostly just after partial melting, during melt segregation and accumulation in the deeper crust with slow prograde heating. Models of rapid crustal heating and instantaneous melt extraction are incompatible with the data.     

Comparison of UV and IR Laser Ablation ICP-MS on Silicate Reference Materials and Implementation of Normalisation Factors for Quantitative Measurements

Direct analysis of geological reference materials was performed by LA-ICP-MS using two Nd:YAG laser systems operating at 266 nm and 1064 nm. The aim of this work was to compare UV and IR laser ablation and to assess the potential of the technique for the quantitative bulk analysis of rocks, sediments and soils. The laser sampling process was investigated and the analytical performance of both systems was compared. The influence of the laser operating conditions and the nature of the matrix on ICP-MS response factors calculated for major, minor and trace elements was evaluated. Under consistent laser settings, the response factors appeared to be matrix dependent. For a given matrix, the response factors were also significantly different for the two lasers. Normalisation with a single matrix element was effective only for matrices with similar mineralogy. When operating at 266 nm instead of 1064 nm, matrix effects could be reduced but not overcome. However, variations of the response factors between the different matrices appeared to be similar within distinct groups of elements, reflecting geochemical associations. When using multiple internal standards, matrix effects but also effects of the laser wavelength, could be fully compensated.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.