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.     

GGR Critical Review of Analytical Developments in 2003

The articles that comprise this critical review serve to draw attention to research papers published in specific fields of interest during 2003, provide critical comment on the relevance and importance of individual publications in these fields, and offer an overview of the comparative importance of advances in particular areas. In this way, these articles aim to assist experts in the field by keeping them informed of relevant recent publications, as well as providing an important resource for students or early career researchers who are embarking on studies in an area new to them. This year, five papers provide summaries of developments in bulk sample determinations employing (1) ICP-AES and ICP-MS (trace elements), (2) XRF and atomic absorption spectrometry and INAA, (3) isotope ratio measurements (TIMS, MC-ICP-MS, ICP-MS, ToF), as well as in situ measurements conducted using (4) secondary ion mass spectrometry and (5) laser ablation ICP-MS (trace element and isotope ratio determinations).     

GGR Critical Review of Analytical Developments in 2008–2009: An Introduction

This collection of articles represents the fourth in a series of reviews in which authors have aimed at capturing the key advances in a range of analytical fields ( Hergt et al. 2005, 2006, 2008 ). The publication period under review is 2008–2009 and the intention here is to provide readers with a summary of the most influential developments published during this period, across a broad range of topics appropriate to the Earth and environmental sciences. Most authors comment on the ways in which the emphases of research in their specific fields of examination have changed over time. All note an increase in rigour and focus on data quality. Whether advances have taken place in instrumentation, sample manipulation or data deconvolution, there are a large number of dedicated scientists out there contributing to the high quality of geochemical data employed in geological and environmental research.     

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.     

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.     

GGR Biennial Review: Advances in Geo‐SIMS during 2006–2007

Secondary ion mass spectrometry (SIMS or ion microprobe) remains one of the most powerful tools available to the analytical geochemist. Despite the impressive progress witnessed by other competing laboratory methods over recent years, SIMS remains unsurpassed in its combination of small sampling volumes with low analytical uncertainties. Although the current SIMS analytical design has existed for over three decades, the period 2006–2007 saw significant advances in instrumentation, analytical methodology and, not least, the characterisation of new reference materials upon which all analyses depend. As of the end of 2007 the SIMS geoscience literature was reporting total sampling masses down to the 10 fg range, spatial resolution of better than 100 nm and uncertainties on major element isotope ratio determinations of better than ± 0.2‰ (1s). This article intends to synthesise the progress made by the geo‐SIMS community during this two year period and will also highlight some specific research results that were only possible due to the unique capabilities provided by SIMS.     

GGR Biennial Critical Review: Analytical Developments Since 2010

Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition and interpretation, including access to better reference materials, can also be crucial components enabling important breakthroughs. This biennial review highlights key advances in either instrumentation or data acquisition and treatment, which have appeared since January 2010. This review is based on the assessments by scientists prominent in each of the given analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the most significant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has been formulated into a unified work, providing a single source covering a broad spectrum of geoanalytical techniques. Additionally, some themes that were not previously emphasised, in particular thermal ionisation mass spectrometry, accelerator‐based methods and vibrational spectroscopy, are also presented in detail.     

Isotope Ratio Determination in the Earth and Environmental Sciences: Developments and Applications in 2006–2007

This 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 years 2006 and 2007. The emphasis is predominantly on applications, reflecting the enormous diversity of problems to which isotopic analysis can now be applied, but viewed in the context of rapid uptake of new analytical technologies and significant new drivers of research output.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

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

NanoSr – A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g^?1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g^?1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction), as well as laser ablation and solution ICP‐MS in different laboratories. The ⁸⁷Sr/⁸⁶Sr ratio was determined by well‐established bulk methods for Sr isotope measurements and is 0.70756 ± 0.00003 (2s). The Sr isotope microhomogeneity of the material was determined by LA‐MC‐ICP‐MS, which resulted in ⁸⁷Sr/⁸⁶Sr ratios of 0.70753 ± 0.00007 (2s) and 0.70757 ± 0.00006 (2s), respectively, in agreement with the solution data within uncertainties. Thus, this new reference material is well suited to monitor and correct microanalytical Sr isotope measurements of low‐Sr, low‐REE carbonate samples. NanoSr is available from the corresponding author.     

Neutron Activation Analysis,Atomic Absorption and X‐Ray Fluorescence Spectrometry Review for 2006–2007

These mature analytical techniques do not show any change in publication level from the previous two years and AAS remains dominant in terms of the number of publications. The last two years have seen fewer technical improvements than in the previous review period. Some interesting papers dealing with uncertainty and quality assurance in INAA were published during 2006–2007. It is suggested that photon activation should be reconsidered because the source of electron accelerators has recently improved. A technique to preconcentrate Se for INAA determination has also been proposed. In the case of AAS, papers on analyte preconcentration continue to be more abundant than those relating to instrumental modification. Sample preparation for AAS is also active and ultrasound‐assisted leaching shows some promising applications. There were an unusual number of reviews concerned with AAS and those important to geological samples are cited here. A technique to preconcentrate Cr in water is presented and a new device to determine As and Se is showing some potential uses. Confocal X‐ray mapping continues to show interesting developments. One group developed a technique to perform XRF inside an oyster and an interesting application of μ‐XRF mapping of sediments is presented. Determination of platinum‐group elements (at μg g¹ concentrations) can be carried out very quickly with an improved XRF technique.     

GGR Biennial Critical Review: Analytical Developments Since 2012

Advances in the chemical, crystallographic and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware or to innovative approaches to data acquisition and/or its interpretation. This biennial review addresses key laboratory methods that form much of the foundation for analytical geochemistry; again, this contribution is presented as a compendium of laboratory techniques. We highlight advances that have appeared since January 2012 and that are of particular significance for the chemical and isotopic characterisation of geomaterials. Prominent scientists from the selected analytical fields present publications they judge to be particular noteworthy, providing background information about the method and assessing where further opportunities might be anticipated. In addition to the well‐established technologies such as thermal ionisation mass spectrometry and plasma emission spectroscopy, this publication also presents new or rapidly growing methods such as electron backscattered diffraction analysis and atom probe tomography – a very sensitive method providing atomic scale information.     

2004–2005 Analytical Developments in Secondary Ion Mass Spectrometry

This review of the literature from 2004 and 2005 concerning secondary ion mass spectrometry (SIMS) highlights the contribution the technique has made in the fields of petrology, geochronology, cosmochemistry and material sciences. In petrology, much research was devoted to the measurement of stable isotopes and trace elements by developments in multicollection acquisition, with emphasis on low atomic mass number elements. Elements studied in particular were S (in sulfides), O (in garnets), C (in sedimentary organic matter), Cl (in glasses) and Si. Novel applications of SIMS to geochronology have included the measurement of young zircon grains by the U-Pb and U-Th decay methods. An increasing number of studies have combined U-Pb geochronology with the measurement of trace elements or stable isotopes in zircon.     

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.     

Determination of In and Sn Mass Fractions in Sixteen Geological Reference Materials by Isotope Dilution MC‐ICP‐MS

Mass fractions of Sn and In were determined in sixteen geological reference materials including basaltic/mafic (BCR‐2, BE‐N, BHVO‐1, BHVO‐2, BIR‐1, OKUM, W‐2, WS‐E), ultramafic (DTS‐2b, MUH‐1, PCC‐1, UB‐N) and felsic/sedimentary reference materials (AGV‐2, JA‐1, SdAR‐M2, SdAR‐H1). Extensive digestion and ion exchange separation tests were carried out in order to provide high yields (> 90% for Sn, > 85% for In), low total procedural blanks (~ 1 ng for Sn, < 3 pg for In) and low analytical uncertainties for the elements of interest in a variety of silicate sample matrices. Replicate analyses (n = 2–13) of Sn–In mass fractions gave combined measurement uncertainties (2u) that were generally < 3% and in agreement with literature data, where available. We present the first high‐precision In data for reference materials OKUM (32.1 ± 1.5 ng g^?1), DTS‐2b (2.03 ± 0.25 ng g^?1), MUH‐1 (6.44 ± 0.30 ng g^?1) and PCC‐1 (3.55 ± 0.35 ng g^?1) as well as the first Sn data for MUH‐1 (0.057 ± 0.010 μg g^?1) and DTS‐2b (0.623 ± 0.018 μg g^?1).     

Development of Two New Copper Isotope Standard Solutions and their Copper Isotopic Compositions

In this study, two new laboratory reference solutions for testing Cu isotopic composition were established and investigated. Two commercially available pure copper products, copper plate and copper wire, were dissolved in 1000‐ml Teflon^® bottles, to produce 200 μg ml^?1 stock solutions (hereafter referred to as NWU‐Cu‐A and NWU‐Cu‐B), and cryogenically stored. The Cu isotopic compositions of the two samples were determined in three different laboratories using multi‐collector inductively coupled plasma‐mass spectrometry, and the Cu isotopic compositions obtained from the standard‐sample bracketing method were consistent within the two standard deviation (2s) range. The Cu isotopic compositions of the NWU‐Cu‐A and NWU‐Cu‐B standard solutions were δ⁶⁵Cu = +0.91 ± 0.03‰ (2s, n = 42) and δ⁶⁵Cu = ?0.05 ±0.03‰ (2s, n = 49), respectively, relative to the reference material NIST SRM 976.     

Determination of Gallium Isotopic Compositions in Reference Materials

The interest in the study of gallium (Ga) stable isotope fractionation in low‐ and high‐temperature environments has increased significantly in the last few years. However, a unified reference material (RM) is still lacking for the Ga isotope research community, which hinders interlaboratory comparison between different groups. Consequently, certification of Ga isotopic reference materials for interlaboratory comparison is of high priority. In this study, Ga isotope ratio data for ten geological RMs including silicates, shales and ferromanganese nodules, and two pure Ga RMs including NIST SRM 994 and NIST SRM 3119a reported by three different groups, were determined by MC‐ICP‐MS. Sample matrices of geological RMs were separated by a two‐column separation method with the use of AG MP‐1M and AG 50‐X8 resin, separately, and quantitative recoveries of > 99% Ga were obtained for all geological RMs. Instrumental mass bias was corrected by the combined calibrator‐sample bracketing and internal normalisation model. Validation of the proposed method was performed by analysing synthetic solutions. After normalisation of all available δ⁷¹Ga data of geological RMs to a single Ga RM, results obtained in our study are in agreement with previously reported results.     

Comment on: Mass Fractions of Forty‐Six Major and Trace Elements,Including Rare Earth Elements,in Sediment and Soil Reference Materials Used in Environmental Studies. Fiket et al. (2017), Geostandards and Geoanalytical Research, 41, 123–135

This paper is intended to be a constructive discussion of Fiket et al. (2017, Geostandards and Geoanalytical Research , 41 , 123–135), who dealt with the determination of major, trace and rare earth elements in several sediment and soil certified reference materials. In the present author's view, the paper by Fiket et al. (2017) suffers from a lack of reference to several publications in which somewhat similar results had already been reported. The present contribution therefore provides a comparison of previously published results with those of Fiket et al. for the CRMs soil NCS DC 77302 (GBW 07410), stream sediment NCS DC 73309 (GBW 07311), marine sediments MESS‐3 and NCS DC 75301 (GBW 07314) and estuarine sediment IAEA‐405. It is argued that this fuller consideration (a) allows critical evaluation of the quality of the results presented by Fiket et al. and (b) highlights the advantages of their work. Finally, attention is drawn to the (possible or real) problems that can arise during simultaneous determination of multiple trace elements.