GGR Biennial Critical Review: Analytical DevelopmentsSince 2010

Michael Wiedenbeck (1)*, Roxana Bugoi (2), M. John M. Duke (3), Tibor Dunai (4),Jacinta Enzweiler (5), Mary Horan (6), Klaus Peter Jochum (7), Kathryn Linge (8), Jan Ko�sler (9),Silke Merchel (10), Luiz F.G. Morales (1), Lutz Nasdala (11), Roland Stalder (12), Paul Sylvester (13),Ulrike Weis (7) and Arnaud Zoubir (14)

(1) Helmholtz–Zentrum Potsdam, Telegrafenberg, D-14473, Potsdam, Germany(2) National Institute for Nuclear Physics and Engineering, PO Box MG-6, RO-077125, Bucharest-M�agurele, Romania(3) SLOWPOKE Nuclear Reactor Facility, University of Alberta, Edmonton, Alberta, T6G 2G7, Canada(4) Institut f€ur Geologie und Mineralogie, Universit€at zu K€oln, Greinstrasse 4, D-50939, K€oln, Germany(5) Institute of Geosciences, University of Campinas – UNICAMP, PO Box 6152, 13083-970, Campinas, Sao Paulo, Brazil(6) Department of Terrestrial Magnetism, Carnegie Institution of Washington, 5241 Broad Branch Road NW, Washington, DC, 20015, USA(7) Max-Planck-Institut f€ur Chemie, Postfach 3060, D-55020, Mainz, Germany(8) Curtin Water Quality Research Centre, Curtin University, GPO Box U1987, Perth, Western Australia, 6845, Australia(9) Department of Earth Science and Centre for Geobiology, University of Bergen, Allegaten 41, N-5007, Bergen, Norway(10) Helmholtz–Zentrum Dresden–Rossendorf, Bautzner Landstraße 400, D-01328, Dresden, Germany(11) Institute of Mineralogy and Crystallography, University of Vienna, Althanstrasse 14, A-1090, Wien, Austria(12) Institute of Mineralogy and Petrography, University of Innsbruck, Innrain 52, A-6020, Innsbruck, Austria(13) Department of Earth Sciences, Memorial University of Newfoundland, 300 Prince Philip Drive, St. John’s, Newfoundland, A1B 3X5, Canada(14) ALPhANOV – Technology Center in Optics and Lasers, 351 cours de la Lib�eration, F-33400, Talence, France* Corresponding author. e-mail: michael.wiedenbeck@gfz-potsdam.de

Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribedto technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition andinterpretation, including access to better reference materials, can also be crucial components enabling importantbreakthroughs. 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 thegiven analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the mostsignificant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has beenformulated 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.

Keywords: TIMS, isotopic determination, geochronology, ICP-MS, laser ablation, mass spectrometry, ICP-AES, calibration,environmental sampling, FIB, 3D imaging, SIMS, particle search, AMS, ion beam analysis, radionuclides, Raman, FTIR, fastimaging, neutron activation, INAA, reference materials, microanalysis.

Received 20 Oct 12 – Accepted 26 Oct 12

Advances in thermal ionisation massspectrometry (contribution by M. Horan)

Thermal ionisation mass spectrometry (TIMS), a tech-nique that has been employed for nearly 100 years, uses aheated filament from which the element of interest is ionised.

A highly purified form of an element is loaded onto afilament, which is usually made of a refractory metal such asRe, Pt, Ta or W. Creation of the ionised species is a processspecific to the chemistry of the element in question, its formafter purification and the filament material. Most elementsare analysed by TIMS as positively charged ions formed by

Vol. 36 — N° 4 1212 P. 337 – 398

doi: 10.1111/j.1751-908X.2012.00218.x© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 3 7

electron donation to the filament, although some elementsmore easily form negatively charged oxides (N-TIMS) byelectron donation from an activator. While nearly everyelement can be ionised in a plasma, as used in aninductively coupled plasma-mass spectrometer (ICP-MS),only some elements ionise efficiently from the surface of a hotfilament. For those elements, though, TIMS provides amethod of isotopic determination that combines highsensitivity and high precision with low background andlow instrumental mass fractionation. These analytical advan-tages can be difficult to match by other methods.

Two commercially produced TIMS instruments are cur-rently available: the Triton manufactured by Thermo Scientificof Bremen, Germany, and the Phoenix and extendedgeometry Phoenix62 manufactured by Isotopx of Middle-wich, UK. Over the past 20 years or so, huge advances havebeen made in the capabilities of commercially availableTIMS by these companies and their predecessors. Moveablearrays of Faraday cups allow simultaneous collection of up tonine ion beams. Use of a Daly detector, unique to the Isotopxinstrument, or discrete dynode ion multiplier, in addition to theFaraday cups, increases the effective dynamic range ofmeasurements for those elements having large variations inisotope abundances (e.g., U, Th and Pb). Zoom opticsemploying additional electrostatic lenses before and after themagnet of the Triton can improve cup coincidence byminimising beam spread, which is particularly useful for multi-dynamic determinations of low-mass elements. To providebetter repeatability for static analyses, the amplifiers for theFaraday cups on the Triton instrument can be electronicallyrotated among the cups during determination. Laminated,fast-switching magnets allow more precise field control. Suchadvances have led to improvements in measurement repro-ducibility (‘external’ precision) of better than 5 ppm on aregular basis. Newer-generation mass spectrometers alsoallow easy switching between positive and negative ionbeams, which permits a wider range of elements to bemeasured. The option of simultaneous ion collection usingmultiple ion multipliers is offered, although there do notappear to be any TIMS papers published in the geologicalliterature yet that use this feature. Details of the developmentof detector systems for multi-collector mass spectrometers aregiven in Wieser and Schwieters (2005).

The analytical capabilities of the newer generation ofTIMS instruments have opened (or re-opened) discussions ofthe best strategies for achieving the lowest analyticaluncertainties and greatest accuracies for geological appli-cations. Important to any discussion of TIMS advances is thechoice of reference ‘zero points’ to which natural data arecompared. Noteworthy trends include the following: new

strategies for the use of double spiking to quantify mass-dependent fractionation; the application of static and multi-step schemes for data collection; a re-evaluation of theaccuracy of corrections for instrumental mass fractionationand isobaric interferences; and refinements of decayconstants or other constants used in data analysis. In recentyears, TIMS determinations have been applied to anincreasing number of elements important to geochronology,geochemistry, hydrology and cosmochemistry.

Determination of selected elements

Here we highlight some recent, significant advances inTIMS determination reported for specific elements. The intentof this review is not to provide a compendium of all uses ofTIMS for geological research, but instead to summariserecent approaches to analysis and problem-solving thathave general applicability.

Cadmium: Mass-dependent variations in Cd isotopecompositions in natural samples, including rocks and seawater, were constrained by TIMS analysis on a Triton massspectrometer (Schmitt et al. 2009, Abouchami et al. 2011).Samples were double-spiked with 106Cd-108Cd prior tochemical separation and ionised using Re filaments withsilica gel and H3PO4 activator. Optimal ionisation occurs atabout 1150 °C. Abouchami et al. (2011) report long-termreproducibility for 110Cd/112Cd of � 8 ppm (2s).

Calcium: Variations in the isotopic composition of Camay be caused by mass-dependent fractionation, by excess40Ca caused by decay of 40K or by the presence of non-solar nucleosynthetic components. To evaluate variations inradiogenic 40Ca in river waters and rocks, Caro et al.(2010) used a Triton mass spectrometer to achievemeasurement reproducibility (‘external precision’) of 0.35e-unit for 40Ca/44Ca ratios. A multi-dynamic data collectionroutine, using the zoom lenses to improve peak alignment,was run in low-resolution mode. Mass fractionation wascorrected using an exponential law; however, data thatshowed high degrees of fractionation were found to deviatesignificantly from the law and were not included in the finalevaluation. The amount of Ca loaded onto the filaments wastightly controlled at 5 lg, which was found to provide amore reproducible instrumental mass fractionation.

Studies that also measure mass-dependent fractionationof Ca in nature require the addition of a double-spikesolution to the sample prior to chemical separation. Using a43Ca-42Ca double-spike and a three-cycle multi-dynamiccollection routine, Holmden and B�elanger (2010) andHolmden et al. (2012) analysed 3–8 lg of Ca samples

3 3 8 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

using single Ta filaments with H2PO4 on a Triton instrument.They noted a long-term instrumental drift in measured ratiosof their double spike that they postulate to be the result of theablation by oblique impact of the Ca ion beams on thecarbon sides of the Faraday cup. Static data collection and a43Ca-46Ca double spike were used by Hindshaw et al.(2011). Farka�s et al. (2011) analysed Ca as the nitrate usinga Re triple filament assembly on an Isotopx IsoProbe-Tinstrument, using a 43Ca-48Ca double-spike and a two-sequence collection routine. For their study of Ca in terrestrialand meteoritic samples, Simon and DePaolo (2010) used a42Ca-48Ca double spike.

To quantify both the mass-dependent as well as themass-independent variations in Ca isotope compositions,Huang et al. (2012) analysed Ca from refractory inclusionsfrom meteorites using both double-spiked (using 43Ca-48Ca)and unspiked approaches. Double-spiked analyses pro-vided information about mass-dependent fractionation;radioactive decay and nucleosynthetic variations were thenconstrained by analysis of unspiked samples. Fantle andBullen (2009) provide a more detailed review of TIMSmethods for Ca determination and strategies for choosingdouble-spiked tracers and for reducing those data.

Chromium: Qin et al. (2010) evaluated mass-inde-pendent Cr isotopic compositions in meteorites on a Tritonmass spectrometer. After chemical separation of Cr, mostsamples were split among three or four filaments, eachcontaining about 1–2 lg of Cr loaded in HCl with silicagel and saturated boric oxide. Measurements were takenin static mode for approximately 6 hr per analysis; eachfilament was analysed two to three times leading to a totalof 6–10 determinations per sample. Qin et al. (2010)found that reference materials analysed in a three-stepmulti-dynamic routine (intended to eliminate cup bias) didnot show improved measurement reproducibility whencompared with static measurements. Furthermore, multi-dynamic analyses did not appear to offer advantageswhile imposing much longer analysis times, possibledistortions in ion optics resulting from the use of largezoom voltages and added bias from long amplifier decaytimes between steps. The mass-dependent fractionation ofCr, which may be induced during redox reactions, forexample, can be constrained by addition of a doublespike of 54Cr–50Cr prior to chemical separation of Cr andmeasurement by TIMS, using a sample loading procedureand static data collection scheme similar to that describedby Kitchen et al. (2012). Fantle and Bullen (2009) provideadditional discussion of sample loading procedures, Far-aday cup configurations and use of double spikes for Crdetermination.

Neodymium, high precision: Contrasting Nd isotopiccompositions of terrestrial and meteorite samples have notonly revised models for the earliest evolution of the Earth andsolar system (Boyet and Carlson 2005, Andreasen andSharma 2006, Rankenburg et al. 2006), but have also ledto further pressure towards improving in the quality of thehighest precision data. Measurements of the short-lived146Sm-142Nd system require hundreds of lg of purified Ndthat are analysed by TIMS using double Re filaments.Brandon et al. (2009) demonstrated that a three-stepmeasurement routine for Nd, which averaged isotope ratioscollected in different Faraday cups, provides more repro-ducible 142Nd data over multi-year periods and allows forbetter interlaboratory comparison. Carlson et al. (2007)used a two-step multi-dynamic routine in which ratios for142Nd/144Nd were calculated dynamically, so that differ-ences in Faraday cup efficiencies were eliminated. Static Ndcollection routines, by contrast, are invaluable when theneed is to maximise ion-counting statistics for low-abun-dance, sample-limited studies – for example, in analyses ofenstatite chondrites (Gannoun et al. 2011).

There is always the concern that inaccuracies in the massfractionation correction can yield apparent isotopic shifts ingeological samples. Upadhyay et al. (2008) and Andrea-sen and Sharma (2009) noted the apparent divergence ofNd isotope ratios measured in reference materials from theexponential mass fractionation law, which may beexplained by mixing of domains of variably fractionatedreservoirs of sample on the filament. Such mixing on thefilament, first described by Hart and Zindler (1989), wouldcreate a linear mixing between isotope ratios from differentlymass-fractionated domains, resulting in correlations betweenratios that remain after correction for exponential massfractionation.

A significant development within the 146Sm-142Ndsystem was reported by Kinoshita et al. (2012), who refinedthe decay constant for the short-lived 146Sm by suggesting ahalf-life of 68 � 7 Ma (1s), which is 30% shorter than thepreviously accepted half-life. Using the revised decayconstant, data for 146Sm-142Nd systematics in meteorites,lunar and Hadean terrestrial rocks yield a more compressedtimescale for the earliest mantle differentiation events and, insome cases, giving better convergence with 147Sm-143Ndand 207Pb-206Pb ages (Borg et al. 2011, Kinoshita et al.2012, O’Neil et al. 2012).

Neodymium, low abundance: Refinements in theprecise determination of low abundances of Nd areparticularly useful in the determination of Sm/Nd ages ofsingle minerals (Harvey and Baxter 2009). After chemical

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 3 9

purification, small samples of Nd (1–50 ng), along with anactivator solution of Ta2O5 in H3PO4, were dried onto singleRe filaments. Upon heating to 1500 °C, a 2–2.5 V beam of142NdO+ was produced and measured via static collectionwith amplifier rotation. No O2 was bled into the source.Correction for the oxide species used an oxygen isotopiccomposition obtained by separate measurement of PrO+

under the same mass spectrometric conditions as used forNdO. It is critical to remove potential interferences frommetallic Gd, Tb and Dy and from LaO+ and CeO+ duringchemical purification. Geological samples analysed usingthis method achieved a measurement reproducibility of� 10 to 20 ppm (2 RSD) for 143Nd/144Nd ratios with1–10 ng loads. This technique, combined with microdrillingand partial dissolution of garnet (Pollington and Baxter2011) can provide a high-resolution (HR) temporal record ofgarnet growth in tectonically evolving crust (Pollington andBaxter 2010).

Nickel: The presence and magnitude of Ni isotopicvariations in meteorites is a hotly debated topic, possiblyrecording radioactive decay of the short-lived 60Fe ornucleosynthetic variations in the isotopic composition of Ni.The earliest Ni isotopic determinations were by TIMS; morerecent data, however, have been provided by MC-ICP-MSor ion probe techniques, despite complex interferencespresent in this part of the mass spectrum (cf. Steele et al.2011). Chen et al. (2009) reported new Ni isotopicmeasurements by TIMS, using a chemical purificationmethod for Ni that improved yield and reduced possibleinterfering elements. V-shaped Re filaments were filled withsilica gel, boric acid, aluminium and 1 lg Ni. Nickel was runat 1000–1100 °C for 10–15 hr using amplifier rotationand a three-sequence collection scheme with zoom lensvoltages applied. The first sequence provided high-precisionNi isotope ratios; the second and third sequences were usedto monitor for potential interferences from Fe, Co, Cu and Zn.Ratios for 64Ni were not reported because correction for Znon 64Ni was at the 1 e unit level; measurement reproduc-ibility for 60Ni was � 0.1 e unit and for 61Ni � 0.5 e unit.

Osmium: Variations in osmium isotopic compositions interrestrial and meteoritic samples may result from radioactivedecay of 187Re and 190Pt to 187Os and 186Os, respectively(e.g., Ireland et al. 2011). Isotopic studies have revealedadditionally that some meteorites host Os having differingnucleosynthetic or cosmogenic components (Reisberg et al.2009, Yokoyama et al. 2011, Walker 2012). Recent workhas provided improved accuracy and uncertainties in Osisotope measurements, particularly of the less abundant186Os and 184Os isotopes. Osmium is measured by TIMS asthe negatively charged trioxide, by ionisation from platinum

filaments using Ba- as an electron emitter. For studies of Osisotopic variations within meteorites, Yokoyama et al. (2011)and Walker (2012) improved standard reproducibility of184Os/188Os from 1.1% to 0.27% e units by correcting forPtO-

2 using ion multiplier measurement of masses 230 and231 at the beginning of each block of Os data collection.Typical Pt interferences on 184Os were 0.1% to as much as0.5%. Consistent with Luguet et al. (2008), Reisberg et al.(2009) and Ireland et al. (2011), these studies found thatany possible Pt or W oxide interferences on 186Os trioxidewere much smaller than the measurement errors.

For the oxide correction, Luguet et al. (2008) andReisberg et al. (2009) used an oxygen compositionobtained by in-run determination of masses from239–242. Walker (2012) used the average oxygen isotopiccomposition of Nier (1950) for the oxide correction andremoved possible bias introduced by the oxygen correctionby re-normalisation of all measurements to the averageobtained for standards obtained during the period ofsample analysis. Instrumental mass fractionation should becorrected using 192Os/188Os for terrestrial samples (Luguetet al. 2008, Ireland et al. 2011) and for meteorites, whoseOs was affected by cosmic ray interaction (Walker 2012).For meteorite samples expected to show variations in r- ors-process nuclides, mass fractionation should be correctedusing 192Os/189Os, both of which have the smallestcontributions from the s-process (Reisberg et al. 2009,Yokoyama et al. 2011).

Tungsten: Over the past two decades, the short-lived182Hf–182W isotope system has been used to date earlysolar system processes, although most recent data havebeen obtained by multi-collector ICP-MS determinations.More recent advances in TIMS for the determination oftungsten isotopic signatures have allowed excess of 182W tobe resolved in some Archaean komatiites (Touboul et al.2012). Using a Triton instrument, W was ionised from Refilaments as the negatively charged trioxide species, using Laand Gd as electron emitters (Touboul and Walker 2012).The mass spectrometric data were collected by a two-line,multi-static scheme using amplifier rotation. Data were firstcorrected for oxide interferences and for mass fractionation,using a predefined oxygen isotope composition and bynormalising to 186W/184W or 186W/183W, using anexponential law. Small second-order correlations, most likelyreflecting mass-dependent fractionation of O isotopes, werethen corrected by normalising to 183W/184W using a linearlaw. This double normalisation on repeated measurementsof the reference material and on geological samples yieldedlong-term reproducibility of � 5 ppm (2s) for 182W/184W.Although large quantities of some rock types (up to 30–

3 4 0 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

50 g) must be processed to obtain the 1–2 lg of tungstenrequired for determination, this procedure provides a nearlyfivefold improvement in precision as compared with individ-ual analyses by MC-ICP-MS.

Uranium: Analytical methods for U–Pb age determi-nations in zircons have improved to the point where both theaccuracy and analytical uncertainties of the ages are limitedby even small uncertainties in the decay constants andisotopic composition of U. To address this issue, new TIMSstudies have assessed the variability of 235U/238U in naturalmaterials. More precise values for the synthetic uraniumreference materials, CRM U500 and IRMM 184, used forcomparison with natural variations, were measured againsta 233U–236U tracer with both Triton and Isotopx TIMS(Condon et al. 2010). The bulk Earth 238U/235U ratio wasrecently revised downward to 137.818 � 0.050 (2s),based on low uncertainty measurements of U-bearingminerals from a wide range of crustal and mantle-derivedrocks (Heiss et al. 2012). This study provided coherent resultsfrom both TIMS and MC-ICP-MS determinations of U in thesame samples, using the same 233U–236U tracer to controlfor instrumental mass fractionation. The change in terrestrial235U/238U, which is typically assumed and not directlymeasured in zircon geochronological studies, decreases theresultant U–Pb and 207Pb–206Pb dates, as shown inFigure 1.

A suite of annealed and chemically abraded (CA) zirconsamples, carefully selected to minimise discordant U–Pbsystematics and other sources of error, were used to improvethe precision of the decay constant (k) for 235U (Mattinson2010). The revised decay constant is consistent with theconclusion of Schoene et al. (2006) that the correct ratiobetween 238U and 235U decay constants was offset from theaccepted ratio by 0.09%. Combining the data of Mattinson(2010) with the 238U/235U ratios measured on the samesamples from Heiss et al. (2012) yields k235U that is wellwithin the uncertainty of the accepted value (Jaffey et al.1971), but more precise by about a factor of two. Heiss et al.(2012), however, cautioned against premature abandon-ment of the accepted value until isotopic tracers used inthese studies are better intercalibrated.

Choice of reference material for TIMS

A reference material for a given element to which datafor natural samples are compared should be easilyavailable and should ideally have an isotopic compositionthat is similar to the isotopic composition of the bulk Earth.Most, if not all, elements undergo mass fractionationin nature, in the laboratory, or during preparation of

commercial reference materials of high purity. Most datareduction procedures for TIMS analyses assume thatfractionation induced in the instrument is mass dependentand follows an exponential law. Indeed, any exponentialfractionation prior to mass spectrometry should also beremoved by this correction. High-precision isotope measure-ments, however, have shown that mass fractionation inducedoutside of the mass spectrometer, such as during chemicalpurification, may be decidedly non-exponential. Choosingthe correct reference material, therefore, is critical forinterlaboratory comparisons and for quantifying massfractionation in nature.

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Figure 1. Figures show the effect on age calculations

of using the consensus 238U/235U value (137.88),

compared with the value of 137.818 � 0.045 from

Heiss et al. (2012) for (a) 207Pb/206Pb dates; (b)207Pb/235U dates; and (c) 206Pb/238U dates. Grey

bands include the 2s uncertainty of the Heiss et al.

value. Figure after Heiss et al. (2012).

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 4 1

Cadmium isotope data historically have been norma-lised to several reference materials that are resolvably massfractionated relative to each other. To improve interlabora-tory comparisons, Abouchami et al. (2011) recommend useof NIST SRM 3108 Cd as the ‘zero delta’ isotope reference(see also the section on RMs, below).

Calcium isotope compositions are reported relative tothe average of a large, internally consistent database of‘normal’ planetary materials (Simon and DePaolo 2010).Comparisons of low uncertainty measurements of Careference materials by both TIMS and MC-ICP-MS supportthe use of NIST SRM 915b as a laboratory referencematerial because its isotope composition is most similar tothat of bulk Earth and because NIST SRM 915a, long usedfor isotopic studies, is no longer available (Schiller et al.2012).

Qin et al. (2010) found systematic offsets in 54Cr/52Crbetween their data set and that of Trinquier et al. (2007)that resulted from normalisation to a Cr reference solutiondesigned for ICP use, instead of the NIST SRM 3112a.Offsets between the isotope compositions of the tworeference standards were modelled well by linear depen-dence on mass, which was not removed by the exponentialcorrection during mass spectrometry. This observation isconsistent with that of Schoenberg et al. (2008). Normali-sation of Cr isotope data to NIST SRM 3112a wasrecommended for accurate comparisons of data betweendifferent laboratories.

A study by Wakaki and Tanaka (2012) of Nd, measuredby TIMS using a double spike, showed mass-dependentisotope fractionation of commercial Nd oxide reagents andthe long-used La Jolla Nd isotopic reference material,relative to the JNdi-1 Nd reference material, of up to 1.3 e

units/amu. The La Jolla results are particularly pertinent forcomparing low uncertainty data for 142Nd on naturalsamples, suggesting that these data always should benormalised to the JNdi-1 reference material (O’Neil et al.2009). Mass fractionation of Nd on ion exchange columnsduring chemical separation was also documented andprovides an additional caution about the interpretation ofresults obtained when yields are low (Wakaki and Tanaka2012).

Advances in plasma source massspectrometry (contribution by J. Ko�slerand P. Sylvester)

Inductively coupled plasma source-mass spectrometry(ICP-MS) was first applied in geoanalysis in the mid-1970s

to early 1980s (Gray 1975a, b, Houk et al. 1980, Gray andDate 1982, Houk and Thompson 1982). Unlike othertechniques of inorganic mass spectrometry, the ICP sourceoperates at atmospheric pressure, which makes it possible tocombine the mass spectrometer with diverse sampling andsample preparation devices (e.g., laser ablation, electrother-mal vaporisation (ETV) or liquid chromatography). Over theyears, this has resulted in development of numeroustechniques for elemental and isotopic determination ingeological and environmental materials that are capable ofa wide dynamic range of detection (major to sub-traceelement and isotope contents) at a diverse range of spatialresolutions (macroscopic bulk sampling to micrometre-scaleanalysis). Landmarks in the development and application ofICP-MS in the Earth sciences include the following: high-performance liquid chromatography coupled to ICP-MS fortrace metal speciation studies (Dean et al. 1987); determi-nation of platinum-group metals in nickel sulfide fire assaybeads of rock powders by ETV-inductively coupled plasma-mass spectrometry (Gr�egoire 1988); application of laserablation-ICP-MS for in situ elemental determination ingeological samples (Gray 1985, Jackson et al. 1992);development of data processing routines for laserablation-ICP-MS (Longerich et al. 1996); first successful insitu U–Pb zircon dating by laser ablation-ICP-MS (Hirata andNesbitt 1995); and application of multiple-collector ICP-MSto high-precision isotopic determination (Halliday et al.1998). Although the basic principles of ICP-MS instrumen-tation and the hyphenated techniques have not changedsignificantly over the last 20 years, the general trend istowards the development of faster and more sensitiveinstruments that are less biased by the effects of samplematrix, resulting in improved analytical uncertainties, accu-racy and spatial resolution.

Improvements in ICP-MS technology over the last2 years are mainly in the development of faster and morecompact detectors that are incorporated in multiple-collectorinstruments; further development and commercialisation oftime-of-flight (ToF) and Mattauch-Herzog designs with ICPion source; the development of the distance-of-flight (DoF)mass spectrometry; and introduction of the first commercialICP triple-quad mass spectrometer (ICP-QQQ-MS). Also,improvements in ion transmission due to the re-design of theICP interface and ion extraction region have built on thepreviously successful concepts of cone geometry (G€untheret al. 1996, Latkoczy and G€unther 2002) and improvedvacuum in the interface region (‘S-option’ of VG Elemental). Inthe domain of laser ablation analysis, there has been furtherdevelopment of short-pulse femtosecond lasers, dual-volumeablation cells and dedicated software for the processing oftime-resolved signals and elemental/isotopic mapping.

3 4 2 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

ICP-MS hardware developments

Ion detectors: The two ion detection modes employedin ICP-MS instruments include digital (pulse counting withdiscrete-dynode and continuous-dynode or channeltronmultipliers and Daly detectors) and analogue (with Faradayor multi-channel direct charge detectors, Figure 2). In single-collector ICP-MS instruments, the two-detector modes areused to expand the detection dynamic range. The twomanufacturers of sector field ICP-MS single-collector instru-ments (Thermo Scientific – Element XR and Nu Instruments –AttoM) now offer the option of a Faraday detector inaddition to the discrete dynode electron multiplier thatincreases the maximum quantifiable count rate from 109 to1012 cps. This allows for detection of low-level traceelements together with major elements during a single scanof the mass spectrum. However, this approach may bepoorly suited for applications that require acquisition of fasttransient signals (e.g., laser ablation analysis), wherepotential issues include spectral skew related to delay in

signal acquisition during detector switchover (on the order ofms), uncertainties with electron multiplier–Faraday cross-calibration and different response times of the two detectors(Longerich 2008). Use of the multi-detector mode on sectorfield single-collector ICP-MS instruments therefore seemsbetter suited for analyses where sample size is not a limitingfactor.

Recent years have seen mixed detector arrays on thetwo multiple-collector ICP-MS instruments currently on thecommercial market become more versatile. In addition to theThermo Scientific Neptune equipped with a standard arrayof nine moveable Faraday detectors connected to 1010,1011 or 1012 Ω amplifiers and up to eight channeltronsmounted to the side of the Faradays within the collectorarray, the newer Neptune Plus is available with compactdiscrete dynode (CDD) electron multipliers that can bespaced at 1 amu (e.g., for Os or Pb isotopic determination insmall samples). Only a few successful applications of isotopicdeterminations using multiple channeltrons have beenreported for geological materials (e.g., Souders and Sylvester2010). Compared with the channeltrons, the CDD multipliersare expected to have a wider dynamic range (over 106

compared with 105 for channeltrons), better long-termstability and a longer lifetime.

The Nu Plasma II (Nu Instruments) is equipped with 16fixed Faraday detectors and up to six discrete dynodeelectron multipliers, all of which can be fitted with deceler-ation filters to improve abundance sensitivity. With twoversions of detector configuration and a powerful zoom lens,the Nu Plasma II is more versatile than its predecessormodel, being capable of the simultaneous detection ofwider range of analytes and their interferences. Like theNeptune Plus, it has become a powerful tool for multipleion-counting measurements of small samples and transientsignals.

Time- and DoF mass spectrometry: Improvements insensitivity of the orthogonal ToF-ICP-MS have contributed toits more frequent use in geoanalysis. While comparable witha quadrupole ICP-MS in sensitivity (ca. 108 cps per lg g-1)and limits of detection (ng g-1 level) for many elements, theToF-ICP-MS is at least five times faster and suffers less from aspectral skew due to the near-simultaneous ion sampling.This makes it suitable for analysis of samples with limitedvolume and analytes with transient signal. Gonz�alez et al.(2012) explored the potential for bulk analysis of geologicalmaterials using femtosecond laser ablation-ToF-ICP-MS.

A complementary concept of the DoF mass spectrometryhas been recently demonstrated experimentally (Graham

(a)

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Figure 2. Common types of analogue and digital

detectors used with ICP-MS. (a) Faraday cup. When

incident ions produced in the ICP bombard the con-

ductive cup, an electrical current is produced, which is

proportional to the number of impinging ions (b)

discrete- and (c) continuous-dynode electron multipli-

ers. Secondary electron emission is used to multiply the

charges of the incident ion beam, increasing sensitivity

of the mass spectrometer dramatically.

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 4 3

et al. 2011, Enke et al. 2012). This technique determines themass to charge ratio from the distance travelled by each ionduring a fixed time period. The mass spectrum is thenrecorded with a position sensitive multi-channel detector.Although it has so far been tested only with a glowdischarge ion source, the DoF-MS may be coupled to an ICPion source in the near future, potentially offering better massresolving power compared with the ToF instruments.

Mattauch-Herzog ICP-MS: The continuing efforts todevelop a double-focusing sector field ICP-MS employing aMattauch-Herzog geometry (as opposed to the conven-tional Nier-Johnson geometry, Figure 3) and a detectorcovering a large mass range (e.g., Solyom et al. 2001,Schilling et al. 2009) have recently resulted in the firstcommercial product by Spectro Analytical Instruments. TheICP-MS utilises a single direct charge detector with 4800channels that is capable of fast and simultaneous detectionof the entire mass spectrum from Li to U with an average of20 channels per amu. Each channel can operate in twoamplification modes that allow measurement of a signalintensity range covering six orders of magnitude. With asensitivity similar to most of the quadrupole ICP-MS

instruments, the Spectro ICP-MS seems well suited forcommon geoscience applications (e.g., Resano et al.2012). However, the potential advantage of the fast dataacquisition for detection of transient signals by this Mattauch-Herzog ICP-MS remains to be tested more thoroughly,because dumping of the accumulated charge from theindividual channels may slow the detector response.

Triple-quad ICP-MS: The three most commonapproaches for handling polyatomic interferences in ICP-MSanalysis of complex geological, environmental and bio-logical samples (e.g., Ripley et al. 2011) have utilised(a) mathematical corrections (e.g., on-peak subtraction),(b) high mass resolution and (c) collision/reaction cellsplaced before the mass analyser. The major drawbacks ofusing collision and reaction cells in ICP-MS have been boththeir complexity and their poor control of the collisionreactions (e.g., Tanner et al. 2002). Removal of polyatomicinterferences in quadrupole ICP-MS utilised either a collisionmode (cell filled with an inert gas, usually helium) or areaction mode (cell filled with a reactive gas such as H2, O2

or NH3). Disadvantageously, the elimination of specificinterferences can often result in the formation of new

Energy slit

tilstixEtilsecnartnE

Nier-Johnson Geometry

rotcetedoTmaebnoI

Magneticanalyser

Electrostaticanalyser

(a)

Energy slit

Entrance slit

Ionbeam

To detector

MagneticanalyserElectrostatic

analyser

Mattauch-HerzogGeometry

31° 50'(b)

Figure 3. Schematic overviews of double-focusing, sector field mass spectrometers with (a) Nier-Johnson and (b)

Mattauch-Herzog geometries. The Mattauch-Herzog geometry produces a deflection of p/(4 √2) radians in a radial

electric field, followed by a deflection of p/2 radians in a magnetic sector of opposite curvature direction.

3 4 4 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

interferences from the reaction products. The reactive analyteis shifted to a new mass (away from the original interference)and may produce a new interference with another analyteor reaction product at a higher mass. Simplification of the ioncollision reactions by mass filtering the ion beam prior to thecollision and reaction cell can significantly improve theremoval of isobaric by-products. This technique is known astandem MS (MS/MS), and it has been long used inmolecular mass spectrometry. Recently, Agilent Technologiesintroduced a triple-quad arrangement in their new 8800ICP-QQQ-MS instrument. It consists of a quadrupole filterthat removes masses other than the analyte ions and theirpolyatomic interferences prior to the collision and reactioncell, which only acts as an interference filter. The thirdquadrupole then separates the ions based on their mass tocharge ratios. The technique has been successfully appliedto a variety of analytically challenging systems, including thefollowing: the determination of trace elements that suffer frominterferences in high-purity samples (e.g., Ge and As in HCl;V and Ti in H2SO4); to the low-level measurement ofselenium and arsenic in soils, rocks and plants that typicallysuffer from both polyatomic and doubly charged interfer-ences; and to the quantitative determination of S and P inproteins and peptides (Ferna ndez et al. 2012).

Design of ICP-MS interface and ion extractionregion: Recently reported improvements in instrument sen-sitivity by several ICP-MS manufacturers are attributed to newdesigns of the interface (cone shape, size and shape of thecone orifice, the juxtaposition of sample and skimmer cones)as well as improved vacuum in the interface region (e.g.,Ebert et al. 2012, Taylor and Farnsworth 2012). G€untheret al. (1996) and Latkoczy and G€unther (2002) reportedsimilar improvements as a result of using a smaller orifice inthe sample cone, a shorter distance between the sampleand skimmer cones and a high-capacity rotary pump in theinterface region of the ICP-MS. Although these new designsmay prove useful for improving instrument sensitivity inelemental ICP-MS determination, their use in isotope ratio ofICP-MS remains to be tested. The results of initial experimentson multiple-collector instruments suggest that some changesin interface design may affect oxide production rates,leading to non-exponential isotopic ratio biases, especiallyfor Nd isotopes (Newman et al. 2009, Newman 2012).

Laser sampling developments

Femtosecond laser ablation-ICP-MS: The increasinguse of short-pulse (femtosecond) laser ablation systems inICP-MS over the past 10 years has been driven by the effortto eliminate the effects of zone heating and laser-inducedplasma shielding that both contribute to non-stoichiometric

ablation and degraded accuracy and analytical uncertain-ties. The elimination of these two processes is related tominimising the laser pulse duration, which controls thedynamics of the ablation process (Koch and G€unther 2011).Laser ablation using short pulses (on the scale of hundreds offemtoseconds) should reduce fractionation effects duringphase transition from solid over liquid to gaseous orsuperheated liquid, as the energy starts to diffuse out ofthe irradiated volume or to interact with ejected material onlyon the picosecond timescale. However, most of the availablefemtosecond ablation systems suffer from substantial energyloss, beam profile distortion and pulse dispersion during thebeam delivery on the sample surface. As a result, theexpected benefits of femtosecond laser ablation-ICP-MSanalysis (in comparison with nanosecond ablation) havebeen only partly achieved. Studies of femtosecond laserablation over the past 2 years include the evaluation ofwavelengths from IR to UV for ablation of metals, alloys,silicates (e.g., zircon, glass), phosphates (e.g., monazite),oxides (spinel, quartz), sulfides and carbonates. Many ofthese studies report effects of non-ideal femtosecondablation and induced phase/chemical changes in thesamples (Glaus et al. 2010, Seydoux-Guillaume et al.2010, d’Abzac et al. 2011, 2012a, b) as well as thespatial decoupling of different types of aerosol (Koch et al.2010). However, the majority of studies conclude that,compared with nanosecond laser ablation, analysis of mostsample types using femtosecond laser ablation-ICP-MS isless matrix dependent and that non-matrix-matched cali-bration normally results in data with geologically usefulaccuracies and uncertainties (see review by Koch andG€unther 2011). The growing availability of several commer-cially produced femtosecond ablation systems to the geo-science community should further facilitate research into thefemtosecond ablation process and the effects of laserparameters on the quality of the ICP-MS data.

Developments in ablation cell design: Design of theablation cell is an important factor that impinges on memoryeffects, response rate and elemental fractionation duringlaser ablation-ICP-MS analysis. Improvements in the originalcylindrical ablation cell design have led to a variety of cellshapes and sizes that are available for modern laserablation systems. Surprisingly, few theoretical studies havebeen carried out to predict the behaviour of laser aerosolwithin the cell (e.g., Bleiner and G€unther 2001, Bleiner andBogaerts 2007, G€unther and Koch 2008, Koch et al.2008), and most of the development has been based onexperimental designs. The requirements vary with the specificapplications, but generally the ablation cell should have fastwashout, low memory, reduced elemental fractionation,simple sample handling, good illumination and sufficient

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 4 5

volume to contain several samples (or a large sample). Thishas led to development of various large format cells andcells with inserts (dual-volume cells) where the inner volumeis divided between the part that contains the samples and asmall ablation volume (typically 1–2 cm3). Such cells werefirst designed for laser ablation systems by Michael Shelley(Laurin Technic Pty Ltd) and used at the Australian NationalUniversity (Eggins et al. 2005) and recently adopted andmodified by several laser system manufacturers (e.g., M€ulleret al. 2009). Other recently developed specialised ablationcells include a large-volume cell for imaging of biologicalsamples or trace element determinations in climate archives,such as stalagmites (Fricker et al. 2011), and a cryo-cell fordirect chemical analysis of frozen ice cores at high spatialresolution (M€uller et al. 2011).

Software developments

Processing of time-resolved signals and laser ablationmapping: Since the last comprehensive review of softwaretools available for the processing of time-resolved laserablation-ICP-MS data (Sylvester 2008), there have beennotable developments particularly in 2D and 3D mappingof mineral and rock composition (e.g., Ulrich et al. 2009,�Selih and van Elteren 2011, Peng et al. 2012). Applicationof laser ablation-ICP-MS for elemental and isotopic map-ping has been made possible by the introduction of samplecells with low ablation volumes and fast response timeswhere the coordinates of the ablated area on the samplesurface can be matched with a specific part of the time-resolved signal. Iolite (http://www.iolite.org.au) is perhapsthe most advanced software presently available for reduc-tion in transient ICP-MS signals with applications in traceelement determination, U–Pb age dating (Paton et al. 2010)and composition mapping (Paton et al. 2011, Paul et al.2012). It has been written in Igor Pro, although its sourcecode is not available to users, its numerous modules forspecific tasks are user accessible and can be modified ornew modules can be developed. An alternative softwaresolution for 2D elemental mapping, written in the R freewarelanguage and which greatly facilitates data reduction andvisualisation of laser ablation-ICP-MS data, hasbeen reported in Rittner and M€uller (2012). Solari andTanner (2011) recently introduced UPb.age (http://www.geociencias.unam.mx/� solari/index_files/LEI/R_-_UPb.age_files/UPb_R_scripts.zip), a script also written in R freeware,which reads, corrects and reduces U–Pb isotopic dataobtained by several LA-ICP-MS instruments.

Developments in hyphenated techniques of plasmasource mass spectrometry over recent years have made useof the latest technology and software while emphasising the

flexibility of the instruments and increasing the automation ofthe analytical process. These advances will inevitably lead toa more widespread use of ICP-MS in Earth, environmentaland life sciences in the future. It can be anticipated thatemerging new instruments with unmatched sensitivity andspeed will soon allow the study of natural processes andcompositions of natural and synthetic objects at the sub-micrometre scale. Further improvements in ICP-MS sensitivityand laser ablation technology may enable analysis on thenm scale using the near-field technology that circumvents thediffraction-defined spot size limit of the conventional laserablation sampling (Koch and G€unther 2011). Plasma sourcemass spectrometry and laser ablation would then comple-ment existing ion and electron beam techniques of surfaceanalysis.

Advances in plasma source emissionspectroscopy (contribution by K. Linge)

As an established analytical technique, inductivelycoupled plasma-atomic emission spectrometry (ICP-AES) isroutinely used for geochemical analysis, but advances ininstrumentation are rare. Recently reported fundamentalstudies have focused on measurement protocols andremediation of matrix effects, while most analytical advancesare in the areas of improved sample pre-treatment, sampleintroduction and calibration. Of particular interest in thisbiennial review are reports of the determination of uraniumisotopes using ICP-AES (Mahani et al. 2010, Krachler andCarbol 2011). There is a continued expansion in the area ofsample pre-concentration, with few new hyphenated speci-ation methods reported. While this review has focused ondevelopments related to geochemical analysis, develop-ments in all research areas continue to be reported in long-running reviews of atomic spectrometry (Bings et al. 2010,Evans et al. 2010, 2011).

Measurement protocols

A study of the influence of acquisition/operating para-meters and sample introduction system confirmed thatflicker-noise-limited signals were necessary to compensatefor time-correlated signal fluctuations by internal standardi-sation (Grotti et al. 2010), with the best compensationachieved when RSD values of the reference and analyticallines were similar. A comparison of sample introductionsystems showed that analyte signal is limited by shot noise,rather than flicker noise, at low signal intensities. The besttime correlation was observed for ultrasonic nebulisation withdesolvation, where shot noise was a negligible contributionto signal. Internal standardisation was less effective forsample introduction systems characterised by lower flicker

3 4 6 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

noise levels. The theory was demonstrated by improvedrepeatability for samples with complex soil and sedimentmatrices, and the authors recommend that preliminaryexperiments should be undertaken during method devel-opment to ensure that signals are flicker noise limited andthat the RSD values of reference and analytical signals aresimilar.

A sampling rate of at least 2 Hz had to be used toobtain a representative signal for a short transient signal ina study using ICP-AES with charged coupled device (CCD)detection (Chaves et al. 2011). The difficulty of choosing anintegration time for unknown samples was partly alleviatedby monitoring two or more emission lines with differentsensitivities for each analyte or monitoring the spectral peakwith sufficient resolution to enable ‘wing integration’. Theseauthors used post-acquisition data processing in MATLABfor offline generation of 3D analyte spectrum, backgroundcorrection and signal integration. Determination of Al in twocertified reference materials (CRMs), one with low andanother with high Ca concentration, using ETV-ICP-AESshowed that accurate results could be obtained when anappropriate background correction was applied using the3D spectrum to compensate for the significant overlap ofthe Al analytical line and the ‘wing’ of the matrix-related Caline.

Isotopic determination by ICP-AES

The wavelength region around 424.4 nm offered thelargest spread between individual U signals (i.e., 233U, 235U,236U and 238U) for quantification of uranium isotope ratiosusing a commercially available HR ICP-AES scanning at pmresolution (Krachler and Carbol 2011). These authors foundthat the selection of the appropriate spectral backgroundand an accurate positioning of the peaks were essential forobtaining reproducible U isotope ratios. Abundances of235U (424.412 nm) and 238U (424.437 nm) were deter-mined in samples containing depleted, natural and slightlyenriched U, with measurement uncertainties between 1%and 5%, improving with higher abundance of 235U. Themeasured abundance of highly enriched 235U samples was1–4% lower than expected values, but could be correctedusing an empirically derived bias factor. This study showedthat HR-ICP-AES had poorer accuracy and precision thancommonly used MS-based techniques; however, U did notrequire separation from the matrix prior to determination,and there was no requirement to correct for mass biaseffects. Thus, ICP-AES may have use as a fast screening toolfor nuclear applications. An earlier study, using a commercialICP-AES instrument, which was unable to resolve the isotopesat 424.4 nm, employed partial least-squares regression

modelling to overcome spectral overlap (Mahani et al.2010). The regression model was developed using datafrom synthetic 235U and 238U mixtures. Predicted results fornatural and depleted samples were in agreement with TIMSanalysis.

Mitigation of interferences

Injection of a 5-ll sample into an air carrier gas streamwas found to both mitigate non-spectral interferencescaused by organic samples and petroleum products andalso to reduce plasma loading (Sanchez et al. 2010).Whereas ICP-AES sensitivities for continuous sample intro-duction changed significantly as a function of the solventvolatility, spray chamber configuration and temperature,injection of 5 ll ensured complete evaporation prior to theintroduction into the plasma, largely mitigating the effect ofsolvent on analyte transport.

Chan and Hieftje (2010) devised an algorithm thatidentifies matrix-effect-free crossover points within an ICP fromvertically resolved analyte emission profiles and described itin detail with illustrative examples. Crossover points wereidentified from relative intensity profiles of the original sampleand a diluted sample. Profile noise was smoothed via curvefitting with segmented polynomial regression, with thecrossover point determined by solving the algebraic differ-ence of these two polynomial segments. Accuracy could befurther improved by analysing a second dilution of thesample, producing three independent values for eachcrossover point. Chan and Hieftje (2010) also found thatthe analyte must be present at a concentration 100–200times greater than the detection limit for accurate results. Themethod is suitable for neutral atom emission lines and ionicemission lines, both with and without charge transfer.

ICP-AES sample pre-treatment and introduction

Nebulisation: A microwave-assisted liquid sampleintroduction system (MASIS) combined both microwave-based nebulisation and desolvation in a single TM010

microwave cavity (Grindlay et al. 2010). Optimum operat-ing conditions were obtained with increased microwavepower, matrix concentration and sample uptake rate anddecreased nebuliser nozzle inner diameter. Limits of detec-tion for the MASIS were typically five times better than eithera microwave-based thermal nebuliser or a microwave-based desolvation system and were up to 50 times betterthan conventional sample introduction using a concentricnebuliser and thermostatted cyclonic spray chamber. Allsample introduction systems tested have similar precision(2–5%), but the MASIS took longer to stabilise (3–10 min)

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 4 7

compared with the conventional system (≈ 10 s); its longerwashout time was attributed to its high inner volume.

Laser ablation-ICP-AES: A LA-ICP-AES method forprecise Sr/Ca and Mg/CA ratios in coral introduced theablated aerosol into a standard cyclonic spray chamber viaa tube inserted through the waste liquid tube (Deng et al.2010). Continuously mixing the dry aerosol with solutionaerosol produced more robust plasma conditions, minimisedmatrix differences between the ablated sample and aque-ous solutions and thereby enabled calibration with aqueousreference materials. Repeated measurements of a coral-likesynthetic reference provided uncertainties in RSD values of0.4% and 0.8% for Sr/Ca and Mg/Ca, respectively, which isbetter than previously reported by LA-ICP-MS; the superiordata quality can be attributed to both the ICP-AES instrumentset-up, including simultaneous collection of Sr, Ca and Mg,and the high-performance ArF excimer laser. While Sr/Caratios by LA-ICP-AES matched solution ICP-AES analysiswithin 2%, Mg/Ca ratios varied by up to 20%, which Denget al. (2010) attributed the mechanism by which Mg isincorporated in the coral skeleton.

Kn�apek et al. (2010) demonstrated heavy metal deter-mination (Cd, Cr, Cu) in highly saline matrices (e.g., seawater and waste waters) using electrodeposition followed bythe ablation of the electrode with a Nd:YAG laser. However,detection limits were high (0.05–1.9 mg l-1), and only Cdprovided quantitative recovery, meaning the quantification ofCu and Cr required a strategy based on standard addition.This approach was applied successfully to wastewatersamples and a spiked seawater matrix; however, thedetection limits were too high for the determination of Cd,Cr and Cu in real seawater samples. The practical use of theLA method in conjunction with ICP-AES appears limited tovery specific applications.

Particle analysis: The analysis of SiO2 and Au nano-and microparticles by ICP-AES using a commercial piezo-electric droplet dispenser that introduced monodispersedroplets into the plasma torch was reported by Garcia et al.(2010). Diluted particle suspensions were calibrated withmonodisperse droplets of Si and Au standard solutions ofknown concentration and diameter. The atomic line inten-sities recorded for particles agree with the intensities fromstandard solution droplets with the same analyte mass. Thismethod’s limit of detection was 200 and 470 nm particlediameters for Au and SiO2 spherical solid particles, respec-tively, corresponding to analyte masses of 80 fg (Au) and50 fg (Si). Analysis of a suspension containing spherical SiO2

particles of three different sizes suggested that it is possible todifferentiate between different-sized particles, as long as the

suspension was sufficiently dilute, and that the probability ofhaving more than one particle per droplet was negligible. Asecond study by the same authors (Murtazin et al. 2010)demonstrated that characterisation of particle size distribu-tion by this method could be affected by instrument noiseand that the relative mass distribution measured by ICP-AESwas typically larger than the absolute mass distributionmeasured by SEM.

Thermal vaporisation: An improved double-chamberETV system included a new inner chamber and quartzbottom plate below the carrier support gas inlet port, whichimproved vapour transport to the argon ICP and loweredvaporising temperature from 1300 to 1000 °C (Matsumotoet al. 2010). Under the optimised experimental conditions,the best attainable detection limit at the Cd II (214.438 nm)line was 2 pg in a 10-ll sample; this study went on to applythis strategy to the determination of Cd in zinc metal.

Chemical vapour generation: A review by Pohl andJamroz (2011) discusses recent innovations in chemicalhydride generation (HG), including sample introductioninterfaces for the simultaneous analysis of hydride- and non-hydride-forming elements, as well as expanding the scopeof chemical vapour generation to include the determinationof transition and noble metals. HG applied to slurry samplesis also becoming a popular means of avoiding time-intensive sample digestion procedures. The review by Pohland Jamroz (2011) also considers HG system design,chemical interferences, sample preparation and the perfor-mance characteristics achievable with ICP and microwave-induced plasma (MIP) instruments. A second review (Pohland Sturgeon 2010) of dual-mode sample introductionsystems for the simultaneous measurement of hydride- andnon-hydride-forming elements discusses the transition fromtraditional HG systems, employing a mixing coil and phaseseparator, to newer systems based on modified pneumaticnebulisers and spray chambers. While early systems wereonly used for HG elements, true dual-mode systems havenow been developed that are typically based on eithertandem nebulisation or on the modification of either thenebuliser or the spray chamber. Parameters critical toperformance include forward power, nebuliser/carrier gasflow rate, sample uptake rate, NaBH4 flow rate, andconcentration and sample pH. The limits of detection forhydride-forming elements are typically improved by at leastan order of magnitude, while for non-hydride-formingelements the limit of detection is equal or sometimes betterthan what is typically achieved using normal nebulisation.Such improvements in emission intensities are sometimesattributed to the positive influence of H2 on thermal processin the torch. The review by Pohl and Sturgeon (2010) also

3 4 8 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

covers spectral and non-spectral interferences and describesongoing developments focused on the generation of vapourphase species from photochemical reactions.

The simultaneous determination of hydride- and non-hydride-forming elements was achieved with a modifiedultrasonic nebuliser, for HG of As, Bi, Ge, Sb, Se, Sn andnebulisation of Ba, Ca, Fe, Li, Mg and Sr (Matusiewicz and�Slachci�nski 2010a). Two capillaries, placed on the vibratingquartz transducer plate of the nebuliser for introduction ofacidified sample and alkaline NaBH4, produced sampleand NaBH4 aerosol and in situ HG before transport to amicrowave induced plasma-AES instrument. The low flowrate (11 ll min-1) enabled analysis of volumes as small as10 ll, while interferences from transition metals werecorrected by the addition of thiourea. Detection limits forHG elements ranged from 1 to 7 lg l-1, while detectionlimits for nebulised element ranged from 7 to 40 lg l-1.Iodine vapour generation was also achieved by the sameauthors using a USN with three capillaries for introduction ofH2O2, H2SO4 and sample pre-treated with Fe and NaNO3

(Matusiewicz and �Slachci�nski 2010b). Again, the capillarieswere in direct contact with vibrating nebuliser surface,enabling mixing and dispersion before gas–liquid separa-tion with a cyclonic spray chamber. After optimisation, thedetection limit for a 15-ll min-1 sample flow rate was1.6 ng ml-1. Analysis of solid samples (e.g., NIST SRM 1549non-fat milk powder and NIST SRM 1566b oyster tissue) bythe method used tetramethylammonium hydroxide andsonication to ensure sample solubilisation and also toreduce iodine evaporation before reaching the USN.

Hashimoto et al. (2010) used KMnO4 and H2SO4 tooxidise chloride to chlorine gas, which dramaticallyincreased ICP-AES sample introduction efficiency to almost100%, increasing Cl sensitivity by twenty times comparedwith a typical nebulising system. Results obtained by the newmethod were confirmed using mineral drinking water andriver water, yielding results comparable with values obtainedfrom ion chromatography.

Photochemical vapour generation: Compared withchemical vapour generation, photochemical vapour gener-ation can provide better sensitivity, lower reagent use andfewer interferences. Zheng et al. (2010) describe a novelthin-film reactor utilising a thin film of sample pumped onto avertical quartz rod that allows the rapid escape of gener-ated hydrophobic species while simultaneously enablingvapour generation and gas–liquid separation. The rod washoused within a concentric quartz tube where a flow ofargon gas through this tube transported volatile species tothe ICP-AES. The sensitivity of As, Bi, Co, Fe, Hg, I, Ni, Sb, Sc

and Te was enhanced by between 1.3 (Co) and 250 (Sc)times.

High-yield production of Hg from solution was achievedusing a laboratory-built dielectric barrier discharge (DBD)vapour generation system (Wu et al. 2011). The DBD systemconsisted of a large quartz tube, functioning as a dielectricbarrier, and two copper wires as electrodes. While vapourgeneration efficiency from the DBD system alone was poorerthan other chemical vapour generation techniques (e.g.,SnCl2–HCl reduction, or alkali-induced vapour generation),efficiency was about two times better in the presence of 10%CH2O2. The addition of 10% CH2O2 also improved the Hgemission signal by thirty-eight times compared with conven-tional solution nebulisation. Wu et al. (2011) found nosignificant interferences from a range of nitrate salts, butvapour generation efficiency was reduced in the presence ofchloride ions, Au or oxidising substances. The detection limitunder optimised conditions was 0.09 lg l-1.

Solution cathode glow discharge (SCGD) was used toinduce advanced redox processes for the generation ofiodine vapour (Zhu et al. 2010). The SCGD produces highlyreactive chemical species, eliminating the need for redoxreagents and minimising contamination. The method wasable to vaporise both I- and IO3

-, although the mechanismof I vapour generation was not identified for either. Vapourgeneration occurred in both alkaline and acidic matrices,with best enhancement seen for HNO3 and H3PO4. Afteroptimisation, the SCGD method was found to be 30 timesmore sensitive than solution nebulisation. Addition of low-molecular-weight organic molecules (e.g., C2H6O,CH3COOH) increased vapour generation efficiency forKIO3, but decreased efficiency for KI, indicating that organiccompounds might cause interferences and that furtherinformation about the mechanisms of vapour generation isrequired. The detection limits for KI and KIO3 were 0.30 and0.43 lg l-1, respectively.

Online pre-concentration and flow injection: Onlinecloud point extraction for Pb was achieved using non-ionicmicelles of polyethyleneglycolmono-p-nonylphenyether(PONPE 7.5), which does not require heating or salting outagents to induce phase separation (Gil et al. 2010). Instead,the micelles were retained in a minicolumn filled withparticles of polytetrafluoroethylene, before elution usingHNO3. For the optimised method, Pb signals wereenhanced 150-fold, compared with conventional ICP-AES,with a limit of detection of 0.09 lg l-1.

Two methods using online minicolumns packed withethyl vinyl acetate – without modification or complexation,

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 4 9

and with ICP-AES detection – were reported for pre-concentration of Cu2+ (Escudero et al. 2010a) and Zn2+

(Escudero et al. 2010b). Enrichment factors of 54 and 44,corresponding to detection limits of 0.26 and 0.08 lg l-1,were achieved for Cu and Zn, respectively. However,differences in the optimised conditions for pH, sample flowrate, reconcentration time and eluent concentration suggestthat simultaneous Cu and Zn determination by the methodwould be compromised.

Speciation: Terol et al. (2010) reported the first cou-pling of high-temperature liquid chromatography (HTLC)with an ICP-AES, which provided several advantages overhigh-performance liquid chromatography, including shorteranalysis time and no need for a nebuliser. The HTLC systemincluded two separate injection ports: one port precedingthe column enabled separation of organic analytes beforeICP-AES detection by measuring carbon. A second port afterthe column enabled measurement of total metal concentra-tions by ICP-AES before elution of the first organic analyte.Separation, optimised at 150 °C, was completed within3 min. At high temperatures, an aerosol was automaticallygenerated at the end of a separation capillary, obviating theneed for a nebuliser, reducing peak broadening from deadvolume and improving detection limits. The best sensitivitywas achieved when the capillary was heated to 220 °C,although it was important to utilise a thermostaticallycontrolled spray chamber to cool aerosols to room temper-ature to maximise solvent removal and prevent plasmaoverloading. While peaks were 5% narrower with a single-pass spray chamber, the maximum sensitivity was achievedusing a cyclonic spray chamber. Detection limits were slightlyhigher for HTLC coupled to ICP-AES compared with couplingwith an evaporative light scattering detector. Using yttrium asan internal standard for the metals’ measurement, themethod was applied for the simultaneous analysis of metalsand carbohydrates in milk, cream, candy and beer withgood results. In addition to food analysis, the method holdspromise for the simultaneous determination of organiccompounds and metals in other fields. The authors notedthat high background signals for C and the potential formetal precipitation and retention in the high-temperaturecapillary still needed to be addressed.

Nanoparticles: Nanoparticles have a higher surfacearea to volume ratio than other materials that are commonlyused in solid phase extraction (SPE) methods, resulting in amore rapid extraction, a high extraction capacity and ahigher efficiency. However, this can lead to high back pres-sures in SPE column experiments and poor filtration in batchexperiments. For the pre-concentration of trace metals (Cd2+,Co2+, Cr3+, Ni2+, Pb2+ and Zn2+), using paramagnetic

Fe3O4 nanoparticles in conjunction with a magnetic fieldoutside the extraction container to collect solid phases priorto flow injection, ICP-AES avoided the need for filtration orcentrifugation (Faraji et al. 2010). The Fe3O4 nanoparticleswere coated with decanoic acid, and the trace metals werecomplexed with 1-(2-pyridilazo)-2-naphthol (PAN), wherethe adsorption of the PAN–metal complex onto the deca-noic acid coating was controlled by pH. A pH valuebetween 8 and 10 was required both to ensure nanopar-ticles did not become charged and for optimum adsorptionof the PAN–metal complex. Under optimised conditions,detection limits ranged from 0.2 to 0.8 lg l-1 and metalenrichment factors (116–150) were better than for otherrecently proposed SPE methods for trace heavy metals.

Nanometre mesoporous silica (MCM-41), functionalisedwith 2,4-dihydroxybenzaldehyde, gave quantitative recoveryof Be, compared with only 11% recovery for unmodifiedMCM-41 (Yousefi et al. 2010). The adsorption of Be on thefunctionalised MCM-41 was controlled by pH, with nointerference detected from common trace metals, alkaliand alkaline earth metals or anions at concentrations1000–10000 times higher than the Be concentration. Thedetection limit of the optimised method was 0.3 ng l-1,which is well below typical drinking water concentrationsand is better than other reported SPE-ICP-AES methods.

A new yeast strain (Yamadazyma spartinae), immobi-lised onto TiO2 nanoparticles and packed in a glass column,was used for offline pre-concentration of Cr, Cu, Fe, Mn, Niand Zn from water samples before ICP-AES (Baytak et al.2011). The best adsorption was at pH 8 for all elements,attributed to an overall negative charge on the yeast cellwalls. Adsorption was unaffected by 500 lg l-1 NaCl andKCl, 100 lg l-1 Ca(NO3)2 and 50 lg l-1 MgSO4,although it was not clear whether reduced adsorption wascaused by the cation or the anion. While the authorssuggested the column could achieve an enrichment factor of250 by pre-concentration of 500 ml of sample, testedsamples were typically 50 or 20 ml. The limit of detectionobtained from 50 ml of sample ranged from 0.1 to0.45 lg l-1.

Calibration

Mermet (2010), who reviewed calibration methods inatomic spectroscopy, argued that the uncertainty due toregression is a more appropriate measure of calibrationquality than the correlation coefficient, particularly for ICP-AES, where data must have a bias greater than 5% forR2 < 0.99. It is noted that a key assumption of least-squareslinear regression is that the standard deviation is constant for

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all concentrations used, which is not the case for ICP-AESwhere the analytical uncertainty is typically proportional tothe signal intensity. Therefore, Mermet (2010) argued thatweighting should be applied during regression, and anumber of tutorial examples are given to demonstrate theinfluence of the weighting procedure and weighting factor. Asingle regression line is unsuitable for calibration curves withnon-linearity at high concentrations. Bracketing or cutting thegraph in several parts was found to be more suitable in suchcases.

An ‘exact matching’ of both analyte and internalstandard mass fractions and of matrix composition wasshown to improve the relative expanded uncertainties ofICP-AES analysis (Winchester et al. 2010), particularly fordeterminations with subtle non-linear responses that werenot visually apparent. Small variations in acid composition orin the concentration of the easily ionisable element Na werealso shown to significantly influence signal response, therebyimpacting overall RSD. In particular, mass fractions of Na lessthan 4 mg kg-1 were shown to produce demonstrablesignal effects for the first time. The effect was morepronounced for poorly ionised elements such as P and Cu.A review of historic ICP-AES analyses performed at NIST withand without exact matching illustrated that the relativeexpanded uncertainties halved to approximately 0.1%when exact matching was used.

Statistical noise in the determination of Te, Bi and Sn byICP-AES was reduced using principal component regression,a composite calibration technique that uses between 7 and9 emission lines for each element, simultaneously collectedvia CCD detection (Reinsberg et al. 2011). The reduction innoise improved limits of detection by up to a factor of 2compared with those determined from the best singleemission line for each element. The method is particularlyuseful for determinations where internal standards are notable to correct for signal fluctuations. Reinsberg et al. (2011)applied this approach to the determination of Te, Bi and Snin small (0.1–5 mg) samples of thermoelectric materials. Themethod is potentially suitable for elements with numerousinterference-free spectral lines.

Tandem calibration, where two separate nebuliserssimultaneously introduce sample and calibration solutions,using high-efficiency nebulisers based on flow blurringtechnology, was used by �Angel Aguirre et al. (2010) to testonline calibration methods. Three different configurations (all400 ll min-1 total flow rate), varying by the longitudinalangle of introduction (0–30°), were compared with acommercial concentric nebuliser (1000 ll min-1). Bothonline and offline internal standardisation improved relative

error for all tested matrices from 14% to 3%, while standardaddition improved accuracy to 2%, albeit with poorerprecision. Online standard addition was found to require amathematical correction to compensate for the differenttransport efficiencies of the sample and standard solution.There was little difference in performance between onlineand offline modes, although the online methods werequicker and consumed less sample. The tandem nebuliserstypically had better precision than the concentric nebuliser,but poorer sensitivity due to low transport efficiency.

Advances in ion-based sampling:focus ion beam, secondary ion massspectrometry (contribution byL. Morales and M. Wiedenbeck)

In the realm of in situ analyses, ion beam–basedsampling techniques offer a number of distinct advantagesover photon- or electron-based methods. Modern ionsources can generate beams with diameters in the low lmto nm range. The strong interaction between ions emitted byan ion source operating at moderate potential and a solidmaterial means that most processes are confined to the topfew monolayers of the sample, thereby yielding excellentdepth resolution as compared with photon- or electron-based methods. This section highlights recent technologicaland methodological advances for two specific analyticalapproaches. First, in recent years, the application of focus ionbeam (FIB) technology has experienced massive growthwithin the geosciences. Below, we describe the capabilitiesof such instruments and highlight key methodologicaladvances of the past 2 years. Second, high spatial resolutionmaterial sampling using secondary ion mass spectrometry(SIMS) to sample a polished sample surface is a well-established laboratory technique. Nonetheless, significantadvances in instrumentation performance, analytical strate-gies and data evaluation approaches have appearedrecently; these are described below.

The focused ion beam method

For many years, the FIB technique has been widely usedin the semiconductor industry (e.g., Mengailis 1987); recently,it is witnessing rapid growth in the Earth and biologicalsciences as a tool for in situ analyses, enabling thedeposition and ablation of virtually any type of material(e.g., Wirth 2009). A FIB instrument resembles a scanningelectron microscope, but while the later one uses a focusedbeam of electrons to image the samples, the former uses afocused beam of ions. Nowadays, there are a number ofdevices that have both beams, which can be usedsimultaneously for different proposes. Used initially for milling

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 5 1

of lm-sized structures in integrated circuits, the techniqueevolved rapidly during the 1980s and began to be appliedin the sample preparation in the semiconductor industry andon the preparation of in situ transmission electron microscopy(TEM) samples. More recently, this technique started to beemployed for the analyses of geological materials, andalthough the major application of FIB in geosciences is stillthe preparation of TEM foils, there are an increasing numberof different purposes using this technique. Here, we presentsome of these innovative applications and the potentialapplications of FIB in geosciences.

Application of FIB to the study of microstructures:Microstructures of fine-grained geological materials such asclay-rich or strongly deformed rocks are normally difficult toanalyse by optical means due to the grain size; even at theSEM scale, the microstructural features are not self-evident.This problem results from the extreme difficulty of producingsmooth and clear surfaces at the nm scale by standardpolishing preparation methods due to the mechanicalinstability of some of the phases present in such specimens.

Normally Ga+ ions are used to sputter the target material,creating a trench with a length typically between 25 and70 lm, which is normal to the sample’s surface which canbe either a thin section or a smooth piece or rock/mineral.Because the interaction between the ion beam and thetarget occurs at the atomic scale, the sputtering of materialcan produce very smooth and clean surfaces even in ultra-fine-grained rocks such as shales (Wirth and Morales 2012),regardless of the mechanical behaviour of the phasespresent (Figure 4a, c). The efficiency of the sputtering processis a function of the accelerating voltage, beam currents andthe incidence angle of the beam where, in general, highbeam currents produce a high degree of Ga+ implantationinto the sample, producing thick layers of amorphousmaterial. Subsequently, this amorphous layer can beremoved by sputtering material with progressively low beamcurrents, thus performing a ‘polishing’ of the surface. Oncepolished, HR imaging down to few tens of nm can be carriedout with the electron source and secondary/backscatterelectron detectors. One of the main applications of thistechnique has been for the study of gas shales (Figure 4c),

Figure 4. Potential applications of the focused ion beam techniques include the (a) cutting and polishing of

minerals by sputtering the materials with an ion source for microstructural observations such as in symplectites

(sample courtesy by Patrick Remmert, GFZ); (b) Micromachining of minerals for diamond anvil cell high-pressure

experiments and the in situ coating to make the crystals partially non-transparent (in this example, single crystals of

MgO – sample courtesy by Hauke Marquardt, GFZ); (c) systematic sputtering of material at constant thickness and

imaging with the electron source of the SEM allows the acquisition of a stack of 2D pictures that can be used for 3D

microstructural modelling; (d) the external shape of the pyrite framboid shown in (c) appears in yellow, whereas part

of its nm-scale porosity appears in red (modified from Wirth and Morales 2012).

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specimens which can contain large volumes of gas enclosedin their pore space. The investigation of potential gasreservoirs requires the characterisation of the phases, grainsizes, the amount of organic matter and the porositydimensions at various scales. Standard imaging via opticaland SEM analyses did not reveal clearly the microstructuralaspect of these rocks, whereas FIB-based studies were ableto achieve these goals (Keller et al. 2011, Wirth andMorales 2012).

The 3D modelling of microstructures: The initial exca-vation of the trench normal to a polished sample surfacefollowed by two additional smaller cuts parallel to eachother and normal to both the sample surface and the initialtrench will define a three-dimensional volume. FIB sub-micrometre-scale 3D visualisation of such a volume ispossible by using ions to successively sputtering off thinslices of material from the front surface, followed by theacquisition of secondary electron images, repeating thisprocess until the entire volume has been consumed. Such aprocess of alternating between sputtering and imagingresults in a stack of 2D SEM images that can be displayed in3D by either a film-like animation of the successive picturesor a 3D modelling of specific features in those images(Figure 4c, d). Such nanotomography via coupled focusedion beam + scanning electron microscope has a number ofimportant applications. A recent study using the sequentialimaging of quartz grain boundaries from contact andregional metamorphic rocks shows that a large number ofgrain and phase boundaries (between quartz and feld-spars) in these rocks are opened on the nm scale (Kruhlet al. 2012). Segments of these open boundaries werefound to be crystallographically controlled, and in 3D, theyform channels where the grain boundary opens and closesas one progresses in the third dimension. These openingsare suggested to be caused by anisotropy of thermalcontraction at relatively low temperatures in quartz and mayboth allow fluid circulation and affect the physical propertiesof such metamorphic rocks at the macroscale. Additionally, itappears possible that such opened grain boundaries mightoccur in other phases such as calcite and amphiboles,resulting from other mechanisms. This remains a topic forfurther investigations.

Another application of these 3D methods is the charac-terisation of porosity in fine-grained sedimentary rocks(Figure 4d) and ultrastructures in microfossils (e.g.,Schiffbauer and Xiao 2009, Keller et al. 2011). Theevaluation of such lithologies either for exploration for oiland gas or for the disposal of radioactive wastes requires adetailed understanding on the mass transport processes,which are in turn directly related to the pore space geometry,

interconnectivity and distribution with the material beingstudied. A comparison between FIB nanotomography andgas absorption methods shows that the former is able todetect ≈ 20–30% of the total porosity revealed by the later.In addition, when porosity exceeds a length scale >15 nm,both methods are in good agreement, suggesting that thenanotomography can provide representative data of thedistribution of pores ranging between 10 and 100 nm(Keller et al. 2011).

Chemical composition and crystallographic orienta-tion: 3D chemical analyses employing a SEM/FIB systemgenerally utilises energy-dispersive X-ray spectrometers(EDX), which allow the quantification of major elementcompositions of different phases within an aggregate. Theacquisition of 3D composition maps follows the sameiterative process described previously, but with the EDXchemical mapping being conducted on the frontal surface ofthe target. This approach can be particularly useful when thephases of an aggregate do not have enough contrast for thesecondary and/or backscattered detectors. Although thismethod has yet to be applied in geological materials, it hasbeen shown to work well in the identification of differentphases in metal alloys (e.g., Lasagni et al. 2010), suggestingthat it could be applied to geomaterials. Similarly, if the SEMhas an electron backscattered (EBSD) detector, one canmeasure the crystallographic orientation of individual phaseson a surface after each milling step of a material. This resultsin a stack of 2D orientation maps that can be reassembled,generating a 3D volume. Beyond a simple bidimensionalcrystallographic orientation determination, all five parame-ters necessary to describe the complete orientation of grainboundaries in an aggregate along with the quantification ofgrain sizes and shapes can be recovered from 3D EBSDdata. As far as we are aware, this technique has only beenapplied to the study of metals and alloys (e.g., Zaefferer et al.2008, Calcagnotto et al. 2010). Such studies require thatthe EDS or the EBSD data to be collected from at least a fewhundred slices, which requires a very stable system, includingstable electrical and magnetic environmental fields, duringseveral hours of acquisition.

FIB micromachining of geological materials: Anotherforeseeable use of FIB technology in the geosciences is in thecutting and polishing of very small samples of natural andsynthetic materials. As an example, one of the few means ofconducting experiments under extreme pressure conditionsis based on the diamond anvil cell. Due to the very limitedspace in their pressure chambers, such devices commonlyaccommodate only lm-scale samples. Marquardt andMarquardt (2012) demonstrated that FIB technology is wellsuited for the preparation of samples with different

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 5 3

dimensions and shapes and with excellent surface qualitiesneeded for high-pressure experiments in diamond anvilcells. A second application of FIB-based machining involvesBrillouin scattering studies, which require well-polishedcrystal surfaces. Standard methods of cutting and polishingare limited to crystals of certain dimensions and mechanicalproperties; in general, materials with a strong mechanicalcleavage or other anisotropies are not suitable for standardpreparation methods. FIB instruments make possible the‘cutting’ and ‘polishing’ of such delicate samples in brittle ormetastable phases (Figure 4b), thereby expanding therange of materials that can be investigated by suchtechniques.

Secondary ion mass spectrometry

Starting roughly in the early 1970s, SIMS has been awell-established method in geochemistry. This high-endmethod employs a focused ion beam to sample selecteddomains from a well-polished sample surface. Ions gener-ated through the so-called ‘sputtering process’ are ejectedfrom the sample in vacuo, allowing them to be extracted byan accelerating potential for direct injection into a massspectrometer. As there is no need to transfer ions generatedat atmospheric pressures into a vacuum system, the methodis highly sensitive, commonly operating on total samplemasses in the low nanogram to picogram range. Commonapplications of SIMS in geochemistry involve trace elementquantification, isotope ratio determination and depth profil-ing, with the use for a variety of imaging applications alsoseeing growth in recent years. Noteworthy are recent SIMSoverview publications by Fayek (2009), Cherniak et al.(2010) and Zinner et al. (2011). A comprehensive review ofSIMS as a tool for fine-scale image acquisition in both thenatural and material sciences is reported by Senoner andUnger (2012).

Instrumentation developments: Commercial activity inthe field of magnetic sector SIMS instrumentation isdominated by two companies: Australian Scientific Instru-ments based in Canberra and Cameca based in Paris.Since 2010, both of these companies have begunmarketing improved designs of their instruments. In thecase of Australian Scientific instruments, the SHRIMP SI or‘Stable Isotope’ model has been released. Modificationsproviding enhanced performance beyond the earlierSHRIMP II model include improved source chamberpumping, improved primary beam focus providing asmaller beam diameter and modifications to the multi-collection system (Australian Scientific Instruments 2010).Also in the realm of large geometry SIMS instrumentation,Cameca is marketing the 1280-HR or ‘High Resolution’

model based on the earlier Cameca 1280 instrument. Keyimprovements offered by the new design include ion opticmodifications that fully eliminate all second-order aberra-tions, augmented instrument baking for improved flight tubevacuum, enlarged magnet pole pieces to suppress off-axisaberrations and an improved Hall probe and associatedelectronics (Ehrke et al. 2010, Peres et al. 2010). Theprimary goals for this package of modifications are toprovide better beak shape characteristics at high massresolving power and to allow improved sensitivity in multi-collection mode at moderate mass resolution. The 1280-HRdesign is intended to allow routine operating at a massresolution of M/ΔM > 20000 while retaining a flat toppeak in single-collector mode. The first such machine wasinstalled in Nancy, France, in 2010.

Away from the domain of large geometry SIMS instru-ments, Cameca has also introduced the IMS 7f-Auto, whichis a modified version of the earlier IMS 7f model. The mainimprovements of the new design are modified primarycolumn, extended computer automation and a motorisedsample storage chamber (on line product information fromwww.cameca.com); the overall goal of these modifications isto improve system stability while increasing sample through-put.

Sample preparation is a crucial factor in achieving high-precision SIMS isotope data. Key considerations, which areespecially relevant for d18O determinations, are sampleflatness and the proximity of the measurement position to thesample mount’s centre. In the case of the Cameca 1280and 1280-HR instruments, it is well established thatso-called ‘X-Y artefacts’ can impact data quality when theanalysis point is located at the periphery of the sample, aneffect attributed to a deformation of the high-voltageextraction field when one approaches the edge of thesample holder. A recent publication by Peres et al. (2012)describes a new sample holder design that allows analysesto be made over a much larger proportion of the surface ofa traditional 25.4-mm-diameter circular mount. A seconddescription for a modified sample holder design wasreported by Nakashima et al. (2011). The goal of theseauthors was to use a large geometry SIMS instrument tomeasure the D17O compositions of small extraterrestrialgrains, but were challenged by the need to embed singlegrains in individual epoxy mounts. Nakashima et al. (2011)developed metal disc designs that could accommodateeither three or seven small samples which could then beinserted into a single standard sample holder. Using aCameca 1280 instrument, these authors went on to validated18O SIMS measurements using this new design for thesample geometry.

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SIMS-based geochronology: As in past years, much ofthe geochemical work by the large geometry laboratorieshad focused on geochronological applications. The field ofU–Th–Pb zircon dating continues to thrive, although onlymodest advances have been reported here during the lastdecade. One trend that can be discerned is the combinationof the SIMS-based U–Pb zircon dating with hafnium isotopedeterminations conducted subsequently on the same crystaldomains by laser ablation. This analytical strategy has showngrowth in recent years; examples from the literature includepublications by Appleby et al. (2010), Whitehouse andKemp (2010), Gagnevin et al. (2011) and Mueller andWooden (2012). The additional information provided by theLA-ICP-MS Lu-Hf determinations, albeit on a significantlylarge sampling volume, has been found to be helpful bothfor modelling the nature of the precursor material which wasultimately led to zircon crystallisation and for better under-standing of the inheritance/crystallisation/Pb-loss histories ofcomplex zircon populations. A concurrent determination ofU-Pb and Lu-Hf signatures in zircon by SIMS has not yetbeen reported, meaning this strategy requires access tomultiple classes of instrumentation and is far from what couldbe considered routine. The key analytical challenge for SIMS,despite the high abundance of hafnium in zircon, isachieving the necessary low uncertainties on the176Hf/177Hf ratio, which often varies by as little 0.5‰ withina given zircon population.

Beyond the analysis of zircon, SIMS U–Th–Pb dating ofother minor mineral phases continues to attract interest. Onenoteworthy publication is by Hietpas et al. (2011), whocompared the detrital age spectra of zircons and monazitesin samples from the Appalachian foreland in the easternUnited States. They showed that the Th–Pb age spectrumfrom detrital monazite is distinct from that of the zirconextracted from the same sandstone specimen. They attributesuch differences to both the differing petrogenesis of the twophases as well as differences in physical properties thatmight influence the survival and depositional histories of thetwo phases within a clastic sedimentary environment.

The use of SIMS large geometry instruments for the U–Thdating of Quaternary materials has become an establishedtechnique. A recent review by Schmitt (2011) describes the U–Th in situ dating technique in detail. In a modification to thetraditional spot analysis approach, Zou et al. (2010)performed depth profile-like U–Th determinations on zirconusing a Cameca 1270 instrument. The objective of theseauthors was to document the presence of a circa 54 kaovergrowth component on their zircon population. This wasachieved by carefully mounting their zircon grains withnaturally occurring flat surfaces at the level of the face of their

sample mount. These zircons were then analysed by SIMS inan unpolished state; the total depth consumed through thisprocedure was approximately 3 lm.

A final geochronology paper of note is devoted to the40K-40Ca geochronometer. The mass difference betweenthese two species is small, requiring a mass resolving powerof M/ΔM > 28000, which is effectively out of range of allSIMS tools with the possible exception of the recentlycommissioned Cameca 1280-HR instrument. To overcomethis challenge, Harrison et al. (2010) applied the approachsuggested by Ottolini (2002), whereby the 40Ca2+ massstation at 20 Da is used. As a result of potassium’ssignificantly higher second ionisation potential, this massstation is largely free of the isobaric interference 40K2+, thusallowing measurements to be conducted at a relativelymodest mass resolving power of M/ΔM = 5000. Thefeldspar crystals investigated by Harrison et al. (2010)proved to have a quite complex post-magmatic history,making an exact assessment of this approach difficult.Nonetheless, it would seem that SIMS dating of lateProterozoic, K-rich, Ca-poor samples is possible using thisstrategy with an age uncertainty of <5%.

SIMS applications in oceanography and climatestudies: As compared with a decade ago, there has beena clear trend towards increased numbers of projects usingSIMS for environmental and low-temperature applications, ofwhich only a small sampling can be reported here. A studyof d11B in a single species of cultured foraminifera byRollion-Bard and Erez (2010) evaluated this archive as ameans for reconstructing ocean palaeo-pH. This work reportslarge variations in d11B values of up to 12‰ within singletests, despite a repeatability of better than � 1‰ (1s) fortheir analytical method, which might be attributed to vitaleffects that occur during biomineralisation. Rollion-Bard andErez (2010) concluded that size of the total range in d11Bvalues in a single specimen may correlate with seawater pH,providing a means of assessing pH of the environment inwhich the specimen grew.

A second trace element study of foraminifera tests as apalaeoenvironmental archive has been reported by Glocket al. (2012); these authors investigated the Mn/Ca and Fe/Ca contents of tests recovered from the Peruvian oxygenminimum zone as potential redox proxies. Despite havingachieved a beam diameter of <5 lm for their SIMS tool,Glock et al. (2012) demonstrated that diagenetic coatingsof the sample material impacted their data set. A detailedinvestigation into the optimal sample cleaning strategy,employing an extensive use of electron probe mapping,resulted in an improved protocol for suppressing the effects

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 5 5

of post-depositional alteration. Another similar SIMS investi-gation of the effects of diagenetic alteration, this time asapplied to the Sr/Ca sea surface temperature (SST) proxy incorals, has been reported by Sayani et al. (2011). Theseauthors showed that secondary aragonite contained in theirspecimens yielded relatively high Sr/Ca ratios, whereassecondary calcite formed from the dissolution of originalcarbonate yielded low Sr/Ca ratios as compared withpristine aragonite; both can lead to inaccurate SST estimates.Sayani et al. (2011) also conducted d18O gas sourceanalyses on 60–90 lg ‘bulk’ samples from the samematerial; this alternative SST proxy was found to be morerobust with regard to alteration-induced artefacts but waschallenged by the need to find much larger regions thatremained pristine. This suggests that d18O determination bySIMS may be the preferred strategy for pursing this type ofresearch.

The isotopic analysis of speleothems as a palaeoclimatearchive has continued to grow as a SIMS application.Orland et al. (2012) used confocal laser fluorescentmicroscopy to establish the geometry of fine-scale growthpatterns in their polished samples that, at least in part, areinterpreted as seasonal growth bands related to thevariability of organic acids within cave drip waters. Thisinformation was used both for targeting subsequent SIMSanalyses and for establishing D18O values between adja-cent light and dark fluorescent bands, interpreted asindicative of rainfall seasonality beyond the ‘baseline’isotopic composition recorded by the low fluorescing bands.This combination of microanalytical methods was found toconstrain both regional palaeoclimate patterns as well asprovide more local hydrological information at an annualtimescale resolution. Another investigation by Wynn et al.(2010) used SIMS-determined sulfur concentration and d34Svalues in speleothem collected from the European Alps as aan environmental monitoring tool applicable to the pastcentury. The data set reported by Wynn et al. (2010) recordsboth a steady increase in sulfur content and a decrease ind34S values until towards the end of the past century,interpreted as the result of human industrial activity. Signif-icant short-term excursions are superimposed on thesetrends, which have been interpreted as either due tochanges in the cave environment or due to short, discreetevents such as volcanic eruptions.

SIMS volatile element quantification: Sulfur concen-tration and isotopic composition studies continue to becommon SIMS themes beyond the monitoring of environ-mental pollution. A good introductory work on this topic hasrecently been published by Ripley et al. (2011), whocompared the merits and limitations of a wider variety of

analytical techniques as applied to this element. A novelapplication of SIMS d34S was reported by Reuschel et al.(2012), who investigated anhydrite and barite associatedwith early Proterozoic marine and clastic deposits from theFennoscandian Shield. Together with both bulk rock isotopedata and textural observations, these authors argue for theexistence of a sizeable sulfate marine reservoir havingalready been established at this point in time.

Sharp et al. (2010) applied both gas source and SIMSto investigate the d37Cl composition of lunar materials. Thesemeasurements revealed an extraordinarily large range ind37Cl compared with the total range seen on Earth. Theseauthors attribute this feature to the hydrogen-depletednature of the moon. In the absence of HCl as the dominantchloride species, volatile metal chlorides would be gener-ated during melting that are capable of generating largefractionation effects. Thus, Sharp et al. (2010) conclude thatthe very heavy d37Cl values, reaching 24.5‰ in the case ofone SIMS analysis of apatite, are evidence for a veryH-depleted system early in the evolution of the moon.

The geochemical cycling of hydrogen within the Earth’smantle is a fairly well researched topic. In contrast, untilrecently, the partition coefficient for halogens between meltsand key silicate phases have been poorly investigated.Publications reporting experimental studies of the partition-ing of F and Cl between basaltic melts and key silicatephases have been published by Dalou et al. (2012) andBeyer et al. (2012). In both cases, piston cylinder runs wereconducted on synthetic assemblages, resulting in intimatelyintergrown melt silicate assemblages, which could subse-quently be analysed using SIMS. The resulting data wereinterpreted in terms of melt viscosities, major elementcompositions of the mineral phases as well as subductionzone processes and the interaction of fluids within the mantlewedge. The fluxes of volatile elements, and in particular thatof CO2, within subduction zones were also investigated byWehrmann et al. (2011). These authors used SIMS toquantify the carbon concentration in olivine-hosted meltinclusions from the Central American Volcanic Arc; thispublication includes details about SIMS ion yields of aspectrum of volatile elements as a function of materialcomposition.

The quantification of hydrogen by SIMS has also beenreported by Hauri et al. (2011), who used a NanoSIMSinstrument to image hydrogen and other volatile elementdistributions in olivine-hosted melt inclusions recovered from aprimitive lunar magma. This unusual quantification strategywas required due to the small size of individual inclusions.These authors were able to demonstrate that the pre-eruptive

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magma possessed much higher water contents than isimplied by the degassed glass matrix of their lunar sample.

A modified approach for the determination of H/D ratiosin geological materials was reported by Liu et al. (2011a). Toimprove the sensitivity of their small geometry Cameca 7finstrument, these authors took advantage of the strongdifference in the energy distributions of the D+ and theisobaric interference 1Hþ

2 ion. By applying a 50 V energyoffset to their sample, Liu et al. (2011a) were able to increasethe sensitivity of their instrument by a factor of four, enabling aD/H determination in 12 min on samples containing 4% m/m H2O with a total uncertainty of around � 1‰ (1s).

SIMS particle search: SIMS has become a well-estab-lished tool for conducting particle search routines, especiallyas applied to the field of nuclear safeguards. In recent years,there has been much interest in the use of large geometrySIMS instruments for the automated screen of large numbersof environmental particles and for the subsequent detailedcharacterisation of any particles that have reported eitheranomalous isotopic compositions or the presence of syntheticisotopes. Since 2010, there have been two noteworthypublications related to this topic. Hedberg et al. (2011)provide a detail description of SIMS particle search, with acomparison of the relative capabilities of large vs. smallgeometry SIMS instruments. Improved software is describedwhich allows several million particles, distributed over thesurface of a single 25.4-mm-diameter mount, to be screenedfor a target property; it is also discussed how individualparticles can be relocated after an initial screening has beencompleted. A second report by Esaka et al. (2012) describesan alternative particle search strategy based on an initialidentification using fission track observations of irradiatedparticles contained in a polycarbonate film. Particlesenriched in uranium, as determined by the presence offission tracts in the etched polycarbonate, along with 25 lmof the surrounding film, were extracted from the sample. Theindividual particles where then extracted from the film matrixusing a plasma asher prior to isotopic determination using aCameca IMS 6f instrument. Esaka et al. (2012) went on tovalidate the isotopic results of their approach, and they alsodescribe some of the limitations imposed by isobaricmolecular interferences which their small geometry instru-ment was unable to mass resolve.

NanoSIMS advances: Over recent years, the sub-lmspatial resolution provided by Cameca’s NanoSIMS plat-form has been rapidly taken up by both the material scienceand natural science user communities, such that total sales ofthis tool have now outpaced those of the large geometrymachines. Within the geosciences, the main applications for

NanoSIMS remain the imaging or isotope ratio determina-tions on presolar grains. One area of strong growth is theapplication of the NanoSIMS tool to soil science research.Both Heister et al. (2012) and Mueller et al. (2012) reportNanoSIMS-based imaging studies of soils, providing exten-sive discussion of the strengths and limitations of theapproach. The novel approach by Mueller et al. (2012),involving a time series analysis over six days of a sampledoped with 13C and 15N isotopic tracers, is particularlynoteworthy. Such investigations are often based on highspatial resolution isotope ratio maps, for which ease of use ofthe data evaluation software can be a significant factor.Polerecky et al. (2012) describe an open-source softwarepackage developed by the Bremen NanoSIMS group that istailored to the requirements of NanoSIMS image processing,allowing the extraction of quantitative results from user-defined regions within such data sets.

Novel research strategies based on the high spatialresolution imaging capabilities provided by the NanoSIMSplatform are also appearing in the biological and palae-ontological literature. Kopp et al. (2011) employed Nano-SIMS – along with a broad spectrum of other analyticalapproaches – to understand the growth mechanisms incalcareous sponges. Here, NanoSIMS element distributionmaps were able to define important sub-lm chemicalvariations that had gone unresolved in earlier electron probeinvestigations, ultimately leading to a better understanding ofthe mechanisms by which this species generates its calcar-eous structures. In a novel application, Oehler et al. (2010)used the NanoSIMS technique to investigate organicmicrostructures in cherts from the 3 Ga Farrel Quartzite ofWestern Australia. C, N, O, Si and S distribution maps ofthese small features were interpreted as evidence for adiverse biological community having existed at this remotetime. In a similar study, Wacey et al. (2010) used aNanoSIMS instrument to investigate the d34S of fine-grainedpyrite from a 3.4 Ga sandstone from Western Australia.Despite the fact that such material commonly occurs only aspolycrystalline 10 lm large aggregates, their NanoSIMSinvestigation could unravel the complex isotopic signaturesof these assemblages. Their results, along with the spatialassociation of the pyrite with carbon- and nitrogen-richdomains, led Wacey et al. (2010) to conclude thatbiological processing of sulfur had taken place during themid-Archaean. A comparison with three-isotope sulfur datacollected using a 1280 SIMS instrument was able to verifythese analytical results.

Other SIMS investigations: In recent years, there havebeen two noteworthy publications that report on theperformance of multi-collector SIMS instruments as applied

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 5 7

to non-traditional stable isotope systems. Firstly, Villeneuveet al. (2011) investigated the magnesium isotope systemat-ics of chondrite-derived forsteritic olivines. Their multi-collection SIMS determinations were able to achieve arepeatability of � 0.025‰ (2s, n = 60) on the d26Mgvalues from their reference materials. Secondly, Marin-Carbonne et al. (2011) investigate the analytical perfor-mance of MC-SIMS for determining d56Fe in a broad suite ofFe-rich minerals. They report a repeatability of � 0.12‰ (1s,n = 12) for their method and also validated their approachagainst results obtained from MC-ICP-MS analyses.

In the field of SIMS imaging, Majzlan et al. (2010) reportoperating a small geometry SIMS instrument at massresolutionM/ΔM = 6400 for acquired scanning ion imagesof the gold distribution within arsenopyrite samples. Theycompared their SIMS images to Au distribution mapsacquired with synchrotron X-ray fluorescence mapping,concluding that SIMS performs well when characterisingsamples with homogeneous distributions, whereas the twomethods were comparable in their abilities to identifynanoparticulate Au hot spots in the samples. Surprisingly,different locations were observed by the two techniques forsuch hot spots when evaluating the same image field.

Kita et al. (2011) discuss limitations on the uncertaintiesof SIMS isotopic determinations with particular reference tod18O, d34S and d56Fe determinations. In particular, theseauthors discuss the importance of surface polish for goodrepeatability in their results and describe current under-standing of the influence of crystallographic orientation onion yields and isotope ratio determinations for all three ofthese elements.

Rollion-Bard and Marin-Carbonne (2011) assessed thesputtering behaviour of a broad spectrum of carbonatephases; they showed that Fe/Mg ratio of the material beinganalysed has a significant effect on the fractionation ofoxygen isotopes even at concentrations as low asMgO ≈ 1% m/m. Their results suggest that previous SIMSstudies that did not consider this effect might need to berevisited.

Advances in accelerator-based methods(contribution by R. Bugoi, T. Dunaiand S. Merchel)

Introduction to accelerator-based methods

Accelerator-based analytical methods, mainly accelera-tor mass spectrometry (AMS) and ion beam analysis (IBA),have been applied to numerous research projects from the

geosciences in recent decades. The number of theseapplications has risen enormously within the last years asdocumented by the increase in publications with respect tothe use of (in situ-produced) cosmogenic nuclides (Figure 5).There are mainly two reasons for this rise: (a) the increasingnumber of available facilities, and thus easier access, whichis the result of either the transformation of old acceleratorsformerly exclusively used for fundamental research such asnuclear physics or installation of dedicated geosciencemachines (Arnold et al. 2010, Klein et al. 2011); and (b)substantial funding of European and US networking projectssuch as CRONUS-Earth, CRONUS-EU and SPIRIT (Phillips2009, Stuart and Dunai 2009, M€oller 2011), focusing ontraining the next generation, reducing the overall uncertaintyof the analytical system, technical improvements by jointresearch activities and the promotion of transnational accessto accelerator facilities. Such combined efforts have led toseveral user workshops and special sessions on accelerator-based applications at most of the geosciences meetingssuch as AGU, EGU and Goldschmidt, which in turnincreased the awareness of these methods within thegeosciences community.

As this is the first GGR Biennial Review to include AMSand IBA, a short general introduction in both accelerator-based methods is given here. However, for a deeperunderstanding, the following review papers and books, mostfocusing on geosciences, are suggested: Dunai (2010)(AMS), Gosse and Phillips (2001) (AMS), Jeynes et al.(2012) (IBA), Litherland et al. (2011) (AMS), Muzikar et al.(2003) (AMS), Ryan (2004) (IBA), Wang and Nastasi (2010)(IBA) and Watt et al. (1987) (IBA).

Figure 5. Statistical evaluation of peer-reviewed

papers (Web of Knowledge) on the topic of cosmogenic

nuclides and its sub-group in situ cosmogenic nuclides.

3 5 8 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

The key element of both methods is a high-energyaccelerator with a terminal voltage from 0.2 to 14 MV.Therefore, AMS and IBA are very often performed at thesame facility. For AMS, samples containing long-livedradionuclides (Table 1) are mounted in a Cs sputter ionsource, where negative ions (molecules or elements) areextracted from the sample surface and inserted in a tandemaccelerator, where they gain MeV energies. By passingthrough matter (gas or foil) at the positively charged terminalin the middle of the accelerator, the negative ions lose someof their outer electrons and transmute into multiple positivelycharged ions and are then further accelerated towards theexit. Effectively, all molecules are destroyed by this strippingprocess. AMS is capable of measuring isotope ratios, that is,stable nuclides are usually measured in Faraday cups, whileradionuclides are detected using ionisation chambers. Usingsuch a set-up of two mass spectrometers in one, that is, onewith negative ions of keV energy, followed by high-energypositive ions of MeV energy after the accelerator, andcombined with several magnetic and electrostatic analysers,AMS can determine ratios as low as 10-16, thus providingthe lowest detection limit of all mass spectrometry methods.Very rarely, AMS has been also used for the detection ofstable elements. The most common terms for this are TraceElement AMS (TEAMS, e.g., Wallner et al. 2012) or if the Csbeam is focused and spatial resolution kept, Accelerator-SIMS or Super-SIMS (Matteson 2008). However, mainly dueto the background from the ion source, detection limits arenot as low for Super-SIMS as for ‘standard’ AMS, but still

some orders of magnitude better than is the case fortraditional dynamic SIMS.

For IBA techniques, employing a set-up very similar to theone mentioned previously, samples are not placed in the ionsource but at the end of the beam line near the detector(s).The specimens are bombarded with MeV ions such asprotons, deuterons, helium or 15N, generating – by interac-tions at atomic and nuclear levels – recoiled or scatteredparticles and electromagnetic radiation, which are subse-quently analysed. Using this approach, information aboutcomplex matrices, possibly in conjunction with spatial and/ordepth resolution, is gained. IBA, being the generic term ofseveral individual analytical methods, has demonstrated itsfull potential for geochemical applications due to thefollowing performance features as reported by Jeynes et al.(2012) and Ryan (2004):

1 Good imaging capabilities (spatial resolution of1 lm and even less) of the scanning nuclearmicroprobes based on a finely focused MeV ionbeam (Giuntini 2011, Ryan 2011);

2 Good sensitivity for trace elements (≈ lg g-1 level),due to the high cross-sections of particle-induced X-ray emission (PIXE);

3 Deep penetration of light ion beams (≈ 100 lm) –useful for probing buried structures, such as intact fluidand melt inclusions or microscopic precious metals orrare minerals;

4 Light element detection (≈ lg g-1 level) and depthprofiling by particle-induced gamma-ray emission(PIGE) and nuclear reaction analysis (NRA) withoutthe need for matrix-specific reference materials;

5 Hydrogen detection (≈ lg g-1 level) and profilingusing elastic recoil detection (ERD), proton–protoncoincident scattering or NRA without the need formatrix reference materials;

6 Rutherford backscattering spectrometry (RBS) providesdepth profiles for heavier elements without recourse toreference materials – useful for investigating diffusionprofiles and surface processes;

7 Ion beam–induced luminescence can provideimages of sample structures to guide IBA analysis,or zonation of certain ions, such as the rare earthelements (REE);

8 Channelling ion beams into single-crystalline sam-ples, applicable for probing the location of impuritiesin the crystal structure.

Most IBA techniques can be simultaneously employedfor acquiring complementary data and images. By properlychoosing measurement conditions, IBA techniques can be

Table 1.Major, long-lived radionuclides that can be rou-tinely measured by AMS, including their associatedhalf-lives

Radionuclide Half-life

10Be (1.378 � 0.012) Ma (Chmeleff et al. 2010,Korschinek et al. (2010)

14C (5730 � 40) a26Al (0.705 � 0.024) Ma36Cl (0.301 � 0.002) Ma41Ca (0.104 � 0.005) Ma

(0.0994 � 0.0015) Ma (J€org et al. 2012)53Mn (3.7 � 0.37) Ma59Ni (0.076 � 0.005) Ma55Fe (2.73 � 0.03) a60Fe (2.62 � 0.04) Ma129I (15.7 � 0.4) MaActinides e.g.,231Pa 0.03276 Ma233,234,235,236,238U 0.159–4468 Ma239,240,241,242,244Pu 14.3 a–80.8 Ma

References are given only for recent works.

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 5 9

performed in a non- or minimally-destructive mannerallowing for further complementary analyses. Only littlesample preparation is necessary for IBA analysis. And last,but not least, RBS, ERD, NRA and PIGE are well suited for thecertification of reference materials for other analyticalmethods as they can be executed as primary methods.

Starting with some general improvements of AMS andIBA with respect also to geosciences, here we place specialfocus on the booming applications of terrestrially producedcosmogenic radionuclides, leaving aside the overwhelmingmajority of radiocarbon dating work for archaeometrypurposes.

Quality assurance, uncertainties and dataprocessing

Following earlier round-robin work for 14C, 26Al and 129Ito allow for comparability and traceability of AMS results ona world-wide scale, two additional exercises with tenparticipants for 10Be (Merchel et al. 2012) and eightlaboratories for 36Cl (Merchel et al. 2011) have beensuccessfully performed. Both data sets show no difference inthe sense of simple statistical significance. However,multi-variate statistical investigations demonstrated certaininterlaboratory bias and an underestimation of uncertaintiesby some laboratories. Along similar lines, Richter et al.(2010a) reported about the preparation and certification ofa new series of gravimetrically prepared synthetic isotopereference materials (IRMM-075) with 236U/238U isotoperatios varying from 10-4 to 10-9, which is well suitable forTIMS, ICP-MS, AMS and resonance ionisation mass spec-trometry (RIMS) measurements.

As numerous geosciences applications of cosmogenicradionuclides need the conversion of isotope ratios into atime-related value (i.e., erosion/uplift/incision rate or expo-sure ages), the accurate knowledge of the half-life of theused radionuclide is essential. Within the CRONUS-EUproject, two attempts for a new determination of the 10Behalf-life, which had been lately in question, have beenconducted by Chmeleff et al. (2010) and Korschinek et al.(2010), which arrived at a common value of1.378 � 0.012 Ma. Interestingly, the latter study employedalso an IBA method, namely heavy-ion ERD using 127I ions of170 MeV as the incident beam. J€org et al. (2012) chose acombination of methods (i.e., liquid scintillation counting,TIMS and isotope dilution) which together provided thelowest uncertainty for a revised 41Ca half-life determination.Their new value of 0.0994 � 0.0015 Ma is in fact moreprecise while agreeing well within uncertainties with earlierdeterminations (see also Table 1). Half-lives of 53Mn and

60Fe are still under discussion. Re-measurements andre-evaluations are works in progress.

After spending significant efforts upgrading existingscaling models for the transformation from so-called‘production rates’ for terrestrial applications from onesampling site of known exposure (i.e., a calibration site) toanother unknown one, the latest focus of research had beenon the production rates themselves. Generally, productionrates are given in values of atoms per year per gram targetelement (Fe, Ca, K,…) or mineral (quartz) and normalised tosea level and high latitude (SLHL). The accurate knowledgeof a production rate is a prerequisite for all applicationsusing this value, thus both CRONUS projects spent consid-erable time and money on improving those values, espe-cially for the mostly widely used nuclides 10Be and 36Cl. Forexample, Schimmelpfennig et al. (2011) concentrated onnew determinations of 36Cl production rates for the two mostimportant target elements Ca and K, as literature values haddiffered considerably (up to a factor of two). In contrast tomost of the earlier works, they have investigated mineralseparates, Ca-rich plagioclase and K-feldspar, with lownatural chlorine isolated from independently dated lavaflows. Their new SLHL production rate values (42.2 � 4.8),36Cl atoms gCa-1 a-1 and (124.9 � 8.1) 36Cl atomsgK-1 a-1, agree well with the literature values from studiesusing samples containing little 35Cl. Argento et al. (2012)presented a pure physical calculation of production rates for36Cl from Ca and K, and 10Be, 26Al and 14C from SiO2.Several recent papers studying samples from New Zealand,Norway and Patagonia argued for the use of a local ratherthan a global average cosmogenic nuclide production ratefor, for example, 10Be (Putnam et al. 2010, Fenton et al.2011, Kaplan et al. 2011, Goehring et al. 2012). A rathernew member of the terrestrial cosmogenic nuclide group is53Mn that is, due to its very long half-life, well suited formonitoring long-lasting Earth surface processes. Thus, thework of Fujioka et al. (2010) on seven Brazilian haematitesleading to an estimation of a SLHL production rate of(103 � 19) 53Mn atoms gFe-1 a-1 is of utmost importanceas it validates the only previously published measurement.

Special precautions are advised by Braucher et al.(2011) for taking into account production at great depths,the effect of density uncertainties in cosmogenic 10Be depthprofiles (Rod�es et al. 2011) and using boulders for exposuredating (Heyman et al. 2011, Schmidt et al. 2011) of, forexample, depositional surfaces.

Hippe et al. (2012a) propose a different format to reportin situ 14C data. Currently, in situ data are reported in theformat customary for radiocarbon dating, which is a

3 6 0 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

measured fraction modern carbon, normalised to a d13C of25‰ Vienna Pee Dee Belemnite (VPDB) and AD 1950. Themain purpose of the d13C correction is to compensate fornatural isotopic fractionation that can be induced bybiochemical processes. Normalisation to AD 1950 accountsfor the anthropogenic release of ‘bomb’ 14C in theatmosphere. As both effects are not relevant for theproduction of in situ 14C in quartz, and confound theprocesses that lead to accumulation of in situ 14C inminerals, the authors suggest reporting the 14C/12C asmeasured by AMS relative to the used reference material.The proposed format is in line with the format and logic ofreporting data for all other longer-lived cosmogenic radio-nuclides measured by AMS.

Wittmann et al. (2012) investigated the dependence ofmeteoric 10Be concentrations on the particle size fromdetrital Amazon River bed sediment samples. Such variability(up to a factor of 20) would have a strong influence onbasin-wide erosion studies. They studied this effect bymeasuring 10Be/9Be ratios after selective chemical extrac-tion of reactive authigenic phases, that is, Fe–Mn-(hydr)oxides carrying most of the 9Be and 10Be. To overcome theproblem, they advise to normalise leached 10Be to leached9Be, that is, a ‘reactive’ 10Be/9Be ratio that is sizeindependent.

As a correct quantification of IBA data is highly depen-dent on the accuracy of the underlying nuclear data, researchis ongoing with respect to advances in the field of stoppingpower (e.g., Barradas et al. 2012, Zier et al. 2012) andcross-section measurements (e.g., Foteinou et al. 2011,Paneta et al. 2012) and their evaluation (Paul 2012).Additionally, the quantification of IBA data in general requiresthe use of computer simulation codes. Thus, Mayer et al.(2011) had a close look at the different types of availablecodes, discussing their advantages and weaknesses regard-ing the underlying physics and computing time requirements.The recent advances in the Guelph PIXE software packageGUPIX, one of the more widely used tools for the interpre-tation of PIXE spectra, were reported by Campbell et al.(2010). Among such advances are the extension of theproton upper energy limit to 5 MeV, thereby facilitating thesimultaneous use of PIXE with other IBA techniques, as well asthe design of a new batch mode handling ‘two-detectorPIXE’: one detector for major elements and the second onesimultaneously measuring trace elements. The alpha-particleX-ray spectrometer (APXS) for the Mars Exploration Rover,based on the simultaneous use of PIXE and X-ray fluores-cence, triggered the development of a new fitting code thatcombines a fundamental parameters approach with the useof reference materials (Campbell et al. 2011a, b). The

calibration of the APXS was made using homogeneous andstoichiometric materials, elements, oxides and chlorides, andsingle-phase minerals; accuracy was checked with a suite ofcertified geochemical reference materials. Some discrepan-cies were observed for certain elements in specific rock types,probably resulting from the mineral phase structure. Inparticular, it was concluded that trace element results shouldbe treated with caution. More accurate quantitative resultscan be obtained by subsequent sub-calibrations of the APXSusing reference materials ‘tuned’ to specific rock types. TheGeoPIXE software, developed by Ryan et al. (1990) andbased on the dynamic analysis method, allows the extractionof true elemental images from l-PIXE data. Traditionally usedfor treating the PIXE spectra of complex geological targets,including zoned samples, fluid and melt inclusions, andsamples in which secondary fluorescence effects are strong(e.g., heavy-element matrices), GeoPIXE was recentlyimproved to deal with large solid-angle detector arrays,such as the Maia detector (Ryan 2011).

Sample pre-treatment for AMS

In contrast to non-destructive IBA, chemical preparationof samples to be measured by AMS is a key issue. Itcommonly takes more time (some hours to several weeks)than the AMS measurement itself and is often equally cost-and manpower-intensive as running an accelerator facility.Thus, improvements in chemical processing of AMS samplesshould be seen as being as important as instrumentationdevelopments.

As Be is not very abundant in environmental samples,10Be AMS sample preparation usually needs to add stableBe as a carrier to allow for chemical and physicalmanipulation of the sample as Be(OH)2 and BeO. Incontrast, Lachner et al. (2012) have presented an optimisedtwo-step leaching procedure for the seawater-derivedisotopic signature of Be from a marine sediment for carrier-free 10Be/9Be measurements to determine sedimentationrates in the Arctic Ocean. They overcame several challengesin carrier-free AMS sample preparation, such as avoiding ofany contamination mainly from chemicals and handling with9Be. These authors report an elaborate procedure for theextraction of the authigenic Be component within thesediments while leaving detrital Be untouched. They alsohave identified certain discrepancies, which are not yetunderstood, between their carrier-free results and classicaldata. In contrast, the MALT group (Horiuchi et al. 2012)totally dissolved small amounts (1–10 mg) of sediments thatwere then spiked with normal amounts of 9Be (10–300 lg),thereby demonstrating that sophisticated chemical separa-tion of Be such as ion exchange can be avoided.

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 6 1

Moln�ar et al. (2012) tested simple methods without theneed for vacuum for the preparation of groundwatersamples (≈ 1 ml) for 14C measurements. While samplepreparation for classical radiocarbon dating generally aimsat minimising sample sizes (e.g., Druffel et al. 2010, Lieblet al. 2010), sample preparation for in situ-produced 14Cfrom gram amounts of quartz or olivine (e.g., Pigati et al.2010a) focuses more on topics such as lower analyticalblanks, higher yields and better reproducibility. Variouslaboratories report progress in the quest for reproducible,low-blank in situ 14C determination from minerals. Currently,most procedures used to liberate 14C from minerals employa lithium metaborate (LiBO2) flux to melt quartz in anoxidising atmosphere at ≈ 1100 °C (F€ul€op et al. 2010,Pigati et al. 2010b, Goehring et al. 2011); these procedureshave typical blank levels in the order of 150–350 9 103

atoms 14C and a blank variability of ≈ 10% correspondingto 10–20 9 103 atoms 14C. Hippe et al. (2012a) describean alternative approach involving a sub-solidus, flux-freedegassing of quartz samples at 1550–1600 °C in anoxidising atmosphere that results in much lower blanks thataround (40 � 12) 9 103 atoms 14C. This procedure alsohas up to 10% higher 14C yields than recent flux-basedprocedures on the same material (F€ul€op et al. 2010, Pigatiet al. 2010b). As variability in the blanks can be excluded, itis currently unclear whether this is due to an incompletedegassing of flux-derived melts or due to some hithertounrecognised effect(s). A very innovative approach is sug-gested by Longworth et al. (2012); they tested the direct 14Cdetermination in carbonate materials (as small as 0.06 mg),thus eliminating the time and expense of graphite prepara-tion. This approach seems very promising for high samplethroughput projects such as the analysis of deep-sea coralsand organisms forming carbonate skeletons.

Instrumentation advances

The use of helium as a stripper gas for AMS of heavyions, such as 41Ca, 129I and 236U, at low energies hasincreased the mean charge state while reducing scatteringlosses, both of which contribute towards a higher measure-ment efficiency (Vockenhuber et al. 2012). Using energies aslow as 0.75 MeV on the TANDY AMS system in Zürich,M€uller et al. (2010) developed 10Be measurements thatwere competitive with lager AMS systems in terms ofbackground and total analytical uncertainties. This novelstrategy could lead to a slashing of analytical costs, therebyboosting future accessibility for geosciences users andpromoting the further use of 10Be.

The VERA team (Steier et al. 2010, Martschini et al.2012) has invested significant effort in making 36Cl a routine

nuclide at their rather small 3 MV tandem accelerator,targeting even its use for exposure dating. They reduce thebackground from 36S through both conventional andinnovative techniques, such as exposing the target to alaser beam in the ion source. In cooperation with theG€oteborg University, they have also continued their work onselective laser photodetachment (Forstner et al. 2008) ofHfF5- /WF5- .

The Toronto-based IsoTrace Laboratory has also inves-tigated fluoride ions. They used their AMS as a high-sensitivity SIMS to determine the relative sputter yields ofMFn - (n = 0–8; M = element embedded or present asnatural impurity) from Cs+ sputtered PbF2 matrices (Zhaoet al. 2010). This strategy forms anions having higherelectron binding energies, while both increasing the spec-trum of analysable elements and, in some cases, suppressingisobar interferences (Kieser et al. 2012). IsoTrace has alsodeveloped further their radiofrequency quadrupole (RFQ)ion guides and ion-gas reaction cells for additional isobarsuppression (Eliades et al. 2010, Kieser et al. 2010, 2012).This system decelerates the radionuclides from keV to eVenergies, guides them through a single RFQ gas cell andre-accelerates them to MeV before analysis. Eliades et al.(2012) are optimistic that using this simple approach canlead to the AMS determination of 90Sr and 135,137Cs.

All 14C analytical facilities cryogenically clean theevolved gas liberated from minerals to obtain pure CO2.The CO2 is either graphitised (F€ul€op et al. 2010, Pigati et al.2010b, Goehring et al. 2011) or transferred directly as agas to the AMS for measurements (Fahrni et al. 2012, Hippeet al. 2012a). Using gas source AMS allows the carrier-freepreparation of samples, avoids graphitisation blanks andgenerally results in higher signal to noise ratios due to thehigher 14C/12C compared with strategies using a 12Ccarrier dilution component (Hippe et al. 2012a).

Ryan (2011) recently reviewed technological develop-ments of IBA aimed at improved detection and datacollection systems, software developments and advancedfocusing devices for the nuclear microprobes. Here, the newMaia detector and imaging system being integrated into thenuclear microprobe of the Commonwealth Scientific andIndustrial Research Organisation in Australia is attractingparticular attention. The large solid angle of this newdetector arrays offers great opportunities and challenges forquantitative l-PIXE analysis and elemental imaging, allow-ing the collection of larger amounts of data with real-timespectral deconvolution. It offers the potential of lowerdetection limits, improved data quality and 3D tomographicimaging techniques (Ryan 2011).

3 6 2 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

Two other technical developments in IBA aimed at betterimaging and chemical composition determinations in geo-logical samples recently have been reported. Firstly, aconfocal PIXE set-up established at the Jo�zef Stefan Institutein Slovenia (Grlj et al. 2011) provides the ability to probesmall volumes in geological samples (3D elemental micros-copy of particles). This arrangement was found to beespecially useful for the non-destructive depth profiling oflayered samples with a depth resolution of tens of lm oversome tens to hundreds of lm (i.e., beyond the range of RBS).Secondly, Kav�ci�c (2012) demonstrated that, compared withenergy-dispersive analyses, a wavelength-dispersive X-raydetection system allows substantially improved detectionlimits for the PIXE measurement of trace elements with atomicnumbers in the close vicinity of the Z of the matrix element.For example, it was shown that the PIXE determination of Pdand Cd in a silver matrix or of platinum-group elements(PGEs) in a gold matrix could be significantly improved usingthis approach. The same in vacuo WD X-ray detectionsystem, equipped with a cylindrically curved crystal inJohansson geometry and a compact position–sensitivePeltier cooled CCD detector, achieves an resolving powerof around 7000 (at 2–5 keV), thus making the chemicalspeciation analyses of light elements such as P, S and Clfeasible. Finally, Reis et al. (2011) have used a commerciallyavailable microcalorimeter-based, HR, EDX detector system,to show a clear separation of the Si-Ka and the Si-Kb groupsand secondary order radiative Auger emission satellites froman agate sample.

Applications in the geological sciences

In recent decades, the focus of AMS applications in thegeological sciences has shifted from extraterrestrial materialsto geomorphology/tectonics and climate research. However,recently, hot topics such as archaeometry and anthropologyhave emerged and are most promising for enlarging theAMS user community. Generally, three production mecha-nisms on Earth can be distinguished: (a) anthropogenicsources such as bomb-released nuclides, (b) so-called‘atmospheric or meteoric nuclides’ that are produced in theEarth’s atmosphere and (c) in situ-produced nuclides that areproduced directly in the investigated sample (e.g., quartz).Graly et al. (2010) reviewed the use of atmospheric 10Be asapplied to the study of soil age or isotope residence times forthe quantification of erosion and soil transport rates. As thesurface deposition of meteoric 10Be originates not only fromaerosols bearing atmosphere-produced 10Be, but also from10Be-bearing dust, the interpretation of measured meteoric10Be fluxes is rather complex (Graly et al. 2011). Records ofthe variability in atmospheric 10Be can also be used toreconstruct the ancient solar activity or significant changes in

the Earth’s magnetic field such as the Laschamp geomag-netic dipole low at ≈ 41 ka ago (M�enabr�eaz et al. 2011).In situ-produced nuclides have also been used to dateevents including volcanic eruptions, rock avalanches, tsuna-mis, meteor impacts, earth quakes and glacier movements.Furthermore, AMS-based applications for the study oferosion, uplift and river incision rates have become wellestablished.

PIXE in combination with the nuclear microprobeprovides an efficient tool for imaging the spatial variationsof different elements even down to low lg g-1 concentrationlevels. So-called ‘l-PIXE’ is routinely applied to the study ofgeological and extraterrestrial materials, providing a pow-erful tool for investigating geological processes. Using amulti-detector arrangement, PIXE has often been used inconjunction with simultaneous PIGE and RBS analyses for(semi-) quantitative determination of low-atomic-numberelements. Other IBA techniques are less commonly appliedto geoscience samples; however, some novel applicationsare presented below.

Geomorphology and tectonics: Dating rock falls is atypical application using in situ-produced nuclides. Akc�aret al. (2012) measured 10Be in quartz-rich boulders from theupper Ferret Valley, Mont Blanc Massif (Italy), which havebeen exposed to cosmic radiation either only since a historicrock fall in AD 1717 or which were from a pre-historicglacial deposit.

Calcite-rich samples from the Velino–Magnola fault, amajor active normal fault in Central Italy, have beenanalysed for 36Cl to determine the slip release pattern overthe last ≈ 15 ka (Schlagenhauf et al. 2011). The 36Clconcentrations measured in 376 samples showed that thefault broke in at least nine large earthquakes producingmaximum surface slip rates of 2–3 m per event. Theearthquakes occurred in two 5 to 6 ka-long supercycleswith an intervening 4 to 5 ka-long tectonic quiescent phase.Furthermore, Schlagenhauf et al. (2011) warn that thecurrent stage of relative quiescence might be followed bya phase of paroxysmal seismic activity within a few hundredyears.

Based on luminescence and 10Be data, Viveen et al.(2012) concluded that the Mi~no terraces (NW IberianAtlantic Margin) are fluvial terraces of a minimum age of650 ka rather than terraces incised into an older marineinfill. Denudation rates of the terraces are very low(<1.3 m Ma-1), while incision rates (calculated from terraceage and altitude) provide a proxy for the tectonic uplift ratesestimated at 70–90 m Ma-1.

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 6 3

In a study of the topographic development of the highplateau of southern Africa, considered to be either upliftingdue to mantle-driven dynamics or to have been stable sinceMesozoic rifting, rock uplift rates have been derived byErlanger et al. (2012) from the dating of fluvial and marineterraces. The Sundays River, near Port Elizabeth, has incisedat 16.1 � 1.3 m Ma-1 for the past ≈ 4 Ma, and a marineterrace near Durban yields a rock uplift rate of9.4 � 2.2 m Ma-1, which is inconsistent with a rapidNeogene uplift.

Valla et al. (2010) used in situ-produced 10Be data fromthe Gorge du Diable (French western Alps) to date andquantify bedrock gorge incision into a glacial hangingvalley. The gorge sidewalls and the active channel bed weresampled to derive both long-term and present-day incisionrates. Rapid incision (6.5–13 mm a-1) took place throughthe late Holocene (≈ 5 ka), whereas present-day incisionrates are significantly lower (0.5–3 mm a-1) within thegorge. The authors interpret their data as either delayedinitiation of gorge incision after final ice retreat from internalAlpine valleys at about 12 ka or as a post-glacial surfacereburial of the gorge.

With the improved ability to measure 14C in situ in rocks,novel applications, which make specific use of the short half-life of 14C compared with other in situ-produced cosmogenicnuclides, are emerging. In particular, Goehring et al. (2011)describe the development and application of the novel insitu cosmogenic 14C/10Be chronometer to date the recentlyexposed pro-glacial bedrock of the Rhone Glacier inSwitzerland. Their research clearly demonstrated that abra-sion rates beneath the Rhone Glacier increased with icespeed. In combination with 10Be and 26Al, Hippe et al.(2012b) used 14C to assess the timescales of sedimentstorage in hill slope and fluvial systems on the easternAltiplano of Bolivia.

Soil, loess and sand: Fallout from nuclear-weaponstests some decades ago has been proven to be a verysuitable tracer for the study of recent soil erosion andsediment accumulation rates. The tracer of choice is clearly239Pu due to the smaller sample size, shorter measuringtime, absence of background and superior statisticalprecision for 239Pu measured by AMS compared with, forexample, 137Cs measured by c-spectrometry (Tims et al.2010, Hancock et al. 2011). These advantages are evenmore obvious for studies in the Southern Hemisphere, whichhas been less influenced by fallout.

Graly et al. (2010) have assembled a large data set ofmeteoric 10Be soil measurements, allowing for an analysis of

the relationship between meteoric 10Be depth distributionand several other physical and chemical properties of soilsuch as grain size effects on adsorption, incorporation intoclays and oxyhydroxides during weathering, soil transport ofclays and oxyhydroxides through illuviation, and theisotope’s initial atmospheric source. Subsequent work hasaddressed the long-term delivery rates of meteoric 10Be toterrestrial soils from short-time measurements in precipitates(Graly et al. 2011).

The Namib Sand Sea, one of the world’s oldest andlargest sand deserts, has been investigated with respect toprovenance and migration history of its sand grains(Vermeesch et al. 2010). First, U–Pb geochronology ofdetrital zircons identified the primary source: The OrangeRiver at the southern edge of the Namib Desert. Second,burial ages calculated from cosmogenic nuclides 10Be, 26Aland 21Ne point to a residence time within the sand sea of>1 Ma. Thus, despite large climatic shifts in the Namibregion associated with Quaternary glacial–interglacialcycles, it seems that the actual Namib Sand Sea area hasnever been entirely sand free during this time.

To investigate the sources of 10Be in loess, Shen et al.(2010) determined 10Be in sand grains from deserts inwestern China (1.1–5.1 9 107 atoms g-1), from falling dust(1.3–2.8 9 108 atoms g-1) and from loess and palaeosols(1.4–4.5 9 108 atoms g-1). Thus, the investigated Chineseloess is composed of two components: locally precipitatedatmospheric 10Be and wind-blown 10Be adsorbed on thesurface of silt grains originating from the loess–deserttransitional zones. A loess profile from Donglingshan nearBeijing was selected for the study of loess formationprocesses and palaeoclimate variation (Ali et al. 2010) by10Be AMS along with other analytical techniques. Theseauthors were able to document a warm and humid periodfrom 2965 to 528 years BP.

External beam l-PIXE was used to investigate the levelsof nutrient elements, particularly P- and Br-rich fibrous peat-like inclusions, in plaggen soils from Shetland (Grime andGuttmann-Bond 2011). Plaggen soils are artificial agricul-tural soils created by using peat or turf as animal beddingspread onto fields to create rich and deep topsoil layer – atechnique used in northern Europe from the Middle Ages upto the 1960s. This study tried to provide a reliable methodfor distinguishing plaggen soil from manured soil, withimportant implications in landscape archaeology.

The characterisation of microscopic radioactive hotparticles containing actinide elements (mixed Pu and U)that resulted from the aircraft accidents in Palomares and

3 6 4 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

Thule was performed using either l-PIXE, RBS and confocalSR-l-XRF or High-Energy PIXE with 18 MeV protons(Jimenez-Ramos et al. 2010, Jim�enez-Ramos et al. 2012).These studies allowed the characterisation of the remainingfissile materials in the areas affected by two aircraft accidentsinvolving nuclear materials, information essential for the long-term impact assessment of contaminated soils. The mea-surement of the isotopes 239Pu and 240Pu by AMS in asediment core collected in a submarine canyon in theMediterranean coast confirmed that the weapon-gradeplutonium released on land during the Palomares accidentin 1966 has also found its way into the marine environment(Chamizo et al. 2010).

Ores, metal resources and biogenic activity: Lal et al.(2010) have performed detailed studies of the chemicalcomposition, cosmogenic 10Be and the radiogenic U and Thconcentrations of ironstones from six southern Californialocalities. The pebble-sized sandstone concretions, cemen-ted by iron and manganese oxides, are found in severalsemi-arid regions in the world; however, their formationmechanisms have not yet been unambiguously established.The described trace element enrichments (Mn, Zn, Mg, Ti, Fe)and the presence of bacterial fossils support the model thatthe ironstones are principally a product of bacterial activity,which concentrates dust leachates in a narrow layer withinthe beach ridges.

The mineralogy and geochemistry of Sn- and Ge-bear-ing copper ore from Barrig~ao re-mobilised vein deposit,Iberian Pyrite Belt, Portugal, was studied by Reiser et al.(2011) using l-PIXE. The content and distribution of Sn andGe in chalcopyrite is strongly correlated with Fe. Chemicalzonation related to re-mobilisation associated with mineralreplacement, resulted in a distinctive pattern of mineraldisequilibrium. Lead concentrations as high as 2% m/mhave been identified by SEM-EDX and l-PIXE in diageneticpyrite from the Silurian continental red bed-hosted cuprifer-ous Transfiguration deposit in the Quebec Appalachians,Gasp�e Belt, Canada (Cabral et al. 2011a). The Pbdistribution is highly heterogeneous, with plumbiferousdomains occurring as patches and concentric growth layersalternating with Mn- and Mo-bearing zones surrounded byAs- and Cu-rich RIMS. The plumbiferous pyrite from Trans-figuration has a light S-isotope composition that is charac-teristic of bacterial sulfate reduction and is, thus, interpretedas originating from Pb-tolerant bacterial activity in an ancientsedimentary system. The limitations of l-PIXE and l-XRF vs.SR-l-XRF for the determination of iodine in alluvial Pt–Pd–Hgnuggets were demonstrated by Cabral et al. (2011b). Evenat iodine concentrations as high as 10–120 lg g-1 in thedelicate morphological features from C�orrego Bom Sucesso,

Minas Gerais, Brazil, only SR-l-XRF allowed for detailedmapping of iodine, which was interpreted as due tobiogenic fixation in the aqueous alluvial milieu.

Marine environment and oceanography: A successfuldetermination of 36Cl/Cl in sea water was performed byArgento et al. (2010). Their value of (5 � 3) 9 10-16, whichis slightly lower than previous values published by Galindo-Uribarri et al. (2007), is in reasonable agreement withcalculated contributions from the three main sources: 40Arspallation in the atmosphere, capture of secondary cosmicray neutrons by dissolved 35Cl and river runoff that contains36Cl produced in situ over the surface of the continents. Asecond isotopic system, in the form of 236U, has shown largepotential as a new, conservative and transient tracer inoceanography. Depth profiles from the western equatorialAtlantic Ocean (Christl et al. 2012) and together with 137Csdata from the Japan/East Sea (Sakaguchi et al. 2012) havedocumented anthropogenic/fallout 236U at depths near tothe sea floor. The first 231Pa profile by AMS together with Thand U data by ICP-MS from a marine sediment core locatedin the large upwelling area off West Africa (Northern CapeBasin) yielded 231Pa/230Th ratios covering the past 30 ka(Christl et al. 2010). Lippold et al. (2012) validated theapplicability of 231Pa/230Th as a tracer for Atlantic over-turning by investigating down-core profiles from high particleflux areas of Namibia and Senegal that cover the past≈ 35 ka.

Atmospherically produced 10Be, incorporated into mi-crocrystalline calcian rhodochrosite nodules from Neogenesediments along the Galapagos Ridge, equatorial Pacific,showed that these nodules grew at rates reaching 1000times faster than those reported for Fe–Mn ones (Aldahanet al. 2010).

de Ronde et al. (2011) presented l-PIXE maps of S, Cu,Fe and Ba in Cu- and Zn-rich chimneys from the hydrother-mal system associated with the Brothers Volcano from theKermadec intraoceanic arc. The geochemical signature, theage of individual chimneys and sulfur isotopic signaturesprovided insights into the source of the hydrothermal fluids,their evolution over time and the influence of magmatic fluidson the formation of gold-rich massive sulfides. Yeats et al.(2010) performed trace element mapping by l-PIXE ofundersea sulfide chimney samples from the Rogers Ruinsand Fenway hydrothermal sites, Eastern Manus Basin,Papua New Guinea. The abrupt transition from dense Fe–Cu sulfide close to the fluid conduit to a much moreheterogeneous–porous outer phase was interpreted as amixing front between the hot acidic hydrothermal fluids (250–350 °C) and cool, deep-ocean water (3–4 °C) within the

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 6 5

chimney walls. The sequence of heavy-element enrichmentsacross this mixing zone was consistent with steep thermaland chemical gradients.

Gemstones, archaeometry and anthropology: Sur-face exposure dating using 36Cl has been indirectly used forarchaeometry purposes (Sadier et al. 2012). It has beendemonstrated that the cliff overhanging the Chauvet cavehas collapsed several times since 29 ka before the entrancewas finally blocked 21.5 � 1.0 ka ago. These dates agreewith the radiocarbon dates of the human and animaloccupancy, thus confirming that the Chauvet cave paintingsare the oldest yet discovered.

Applying the authigenic 10Be/9Be dating method tocontinental sediments deposited since the upper Miocene inthe northern Chad Basin, Lebatard et al. (2010) reportedthe expected regular decrease in the calculated ages as afunction of stratigraphic position for the period extendingfrom 8 Ma up to the Pleistocene. Under favourableenvironments, namely those that preserved closed systems,10Be/9Be dating of samples up to 14 Ma is possible,opening numerous applications in palaeoclimatology,palaeontology and palaeoanthropology.

Palaeomagnetic measurements and direct 26Al/10Beburial dating of six quartzite artefacts (Pappu et al. 2011)revealed that South India was already occupied duringthe Early Pleistocene by hominines, fully conversant with anAcheulian technology including handaxes and cleaversamong other artefacts. These ages (≈ 1.51 Ma) fromAttirampakkam show that the Acheulian in India is olderthan previously thought, and the authors advise thatevidence from other sites in South Asia should bereconsidered.

The investigation of archaeological materials of geolog-ical origin such as obsidian and gemstones has gainedmajor interest. Advances in elemental imaging of rocks andminerals were reviewed by Calligaro et al. (2011). The useof the AGLAE external nuclear microprobe for l-PIXE,combined with l-XRD and l-Raman spectroscopy, providedclear mineralogical fingerprints for unambiguous prove-nancing of ancient gemstones such as lapis lazuli and earlymediaeval garnets. A similar approach based on l-PIXE, SR-XRD and l-Raman spectroscopy was also used by Gliozzoet al. (2011) for the characterisation of archaeologicalgemstones from Vigna Barberini. In a quest for reconstructingancient trade routes, a systematic l-PIXE study of lazurite anddiopside phases from lapis lazuli from different quarries wasperformed by Re et al. (2011). Zhang et al. (2011) usedl-PIXE to characterise key elements such as Mg, Fe, Mn, Cr,

Co, Ni and Sr, in nephrite minerals from several geologicaldeposits forming two distinct dolomite and serpentinisedultramafic groups, thereby targeting the provenanceidentification of archaeological artefacts. NRA based onthe 9Be(a,nc)12C reaction has been successfully applied byGuti�errez et al. (2010) to analyse Be-treated gemstones(detected: 5–16 lg g-1; detection limit: 1 lg g-1). Thus, theyhave clearly demonstrated the advantage of the non-destructiveness of NRA over competing analytical methodssuch as LA-ICP-MS or laser-induced breakdown spectro-scopy (LIBS), when testing for the artificial treatment of naturalsapphires by diffusion of Be. For the purpose of provenanc-ing, obsidian samples from geological (Seelenfreund et al.2010) or archaeological (Gazzola et al. 2010, Poupeauet al. 2010, Quarta et al. 2011) settings have also been thefocus of numerous PIXE and PIGE investigations. A rather‘experimental’ approach for provenancing ancient ceramicswas tried by Sterba et al. (2012) using l-PIXE and LA-ICP-MS, who produced contemporary pieces of ceramic fromknown clays and tempers. Subsequently, the remainingtemper inclusions (e.g., quartz, feldspars) were analysed todeduce the original chemical composition of the clay matrix.

Glaciology and climate: Palaeo-erosion rates over thelast ca. 9 Myr have been calculated by Charreau et al.(2011) from in situ-produced cosmogenic 10Be concentra-tions measured in magnetostratigraphically-dated continen-tal quartzitic sediments from the Tianshan piedmont. Erosionrates of 0.1–1 mm a-1 were derived for most records.Maximum values of up to ca. 2.5 mm a-1 were detected forthe time period of 2.5–1.7 Ma, which correlates with theonset of Quaternary ice ages and suggests that globalclimate had a significant and transient impact on erosion.

Buizert et al. (2012) have combined cosmic ray scalingand production estimates with a two-dimensional ice flowmodel to study in situ-produced 14C at Taylor Glacier,Antarctica. They found that the thermal neutron production of14C in gas bubbles of glacial ice is negligible, but that solarmodulation and bedrock topography can significantly affectin situ 14C production. The exact knowledge of the in situproduction is essential as it is part of the overall 14Cinventory, which potentially can be used for ice dating,ablation rate estimates and palaeoclimatic reconstructions atice margin sites and blue ice areas.

The short-lived 32Si (t1/2 = 144 a) can be used fordating in the time range of 30–1000 a, therefore filling thegap between the shorter-lived or recently introducedisotopes from nature such as 210Pb and tritium or fromanthropogenic origin, mainly bomb-produced such astritium, 14C, 137Cs and 239Pu, and cosmogenic 14C

3 6 6 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

(Morgenstern et al. 2010). Preliminary 32Si AMS data ofsnow and ice samples from Mt. Cook National Park, NewZealand, have been shown to be reproducible andcomparable with results from mid-latitude snow samplesmeasured previously via the decay counting technique.Thus, 32Si as an ice core dating tool over the last thousandyears has potential; attempts to determine chronologiesfor both Alpine and Antarctic glaciers are alreadyunderway.

Extraterrestrial material: Due to their high radionu-clide concentrations, meteorites were among the firstgeological materials investigated by AMS. Scientific interestin these exciting and long-travelled materials is, of course,ongoing. A large body of meteorite research has made useof a combination of long-lived radionuclides quantified byAMS, stable isotope determinations made by noble gasmass spectrometry and Monte Carlo-based proton- andneutron-induced cross-section and final production ratecalculations (Leya and Michel 2011) to reconstruct theoverall history of such material that have experiencedprolonged cosmic radiation exposure. Using this multi-pronged strategy, the pre-atmospheric radii of originalmeteoroids and associated asteroids such as Vesta and2008 TC3 have been deduced and possible complexirradiations deciphered (Welten et al. 2010a, Beck et al.2012, Meier et al. 2012). Investigations on large meteoriteshowers from cold and hot deserts, that is, Antarctica,Arizona and Sahara (Welten et al. 2010b, 2011a, b), haveshown that the precursor meteoroid bodies have radii aslarge as 80–250 cm. In the rare case of observed falls, alsoshort-lived radionuclides measured by c-spectrometry yieldadditional information (e.g., the Bunburra Rockhole fallstudied by Welten et al. 2012). In contrast, the mediumlong-lived 14C isotope in combination with 10Be has beenvery useful for establishing the terrestrial age of meteoritesfound in hot deserts from Australia or Africa (Jull et al. 2010,Welten et al. 2011b). Going much further back in time,Herzog et al. (2011) measured the concentrations of 26Al,36Cl and 41Ca produced by 3He-induced nuclear reactionson Mg, Al and Ca to calculate the reaction rates for earlysolar system irradiation scenarios.

Nearly the same high interest in extraterrestrial materialis coming from the IBA side. �Smit et al. (2011) appliedexternal PIXE-PIGE and l-beam PIXE mapping on meteoritefragments of the observed fall from 2009 in Jesenice,Slovenia. Three different types of chondrules composed ofolivine/pyroxene and pyroxenes have been identified in thisordinary chondrite. Borysiuk et al. (2011) have investigatedthe possibility for measuring oxygen isotope ratios in fossilmeteorite samples by NRA as the variations in oxygen ratios

within meteoritic chromite grains would allow the determi-nation of the type of meteorite to which the grains originallybelonged to.

Developments in vibrationalspectrographic analyses (contribution byL. Nasdala, R. Stalder and A. Zoubir)

Vibrational spectroscopic techniques – including infraredabsorption spectroscopy, Raman spectroscopy and Brillouinspectroscopy (the latter not being covered in this chapter) –are the most valuable and versatile tools in the investigationof minerals, crystals and other geological materials. Thesetechniques probe samples based on minute interactions ofincident light and vibrating matter, making them highlysensitive to the local structure of the sample being studied.Vibrational spectroscopies are connected with a number ofanalytical advantages, including low demands on thesample preparation, the opportunity to perform analysesnon-destructively and their excellent volume resolution.Recent technical improvements have helped overcomeprevious problems such as insufficient signal sensitivity,accuracy and reproducibility, with a major focus on theimprovement of imaging/mapping techniques for the studyof distribution patterns and internal textures.

Infrared absorption spectroscopy

Infrared spectroscopy remains one of the most sensitivemethods for determining the speciation of volatile compo-nents (such as OH) at low concentrations. A novel analyticaltool, namely, a two-dimensional focal plane array (FPA)detector consisting of a large number of individual detectorsthat produce an IR image, has been introduced recently tothe Earth sciences (Della Ventura et al. 2010, Prechtel andStalder 2010). In contrast to the point-by-point mappingtechnique, where each analysis point has to be masked withan aperture and is measured sequentially, FPA imaging issimultaneous and the location of each analysed point isdetermined by the position of respective individual detector.Hence, no optical aperture is necessary to define theanalysed spot. As a consequence, the spatial resolutionachieved is only limited by the wavelength of the IR light (forinstance, 3.3 lm for light with a wavenumber of 3000 cm-1).

A FPA detector typically consists of 64 9 64 detectorsproducing an image of 4096 pixels, but larger formats suchas 256 9 256 are also available. When using a 64 9 64FPA format and a 159 objective, an area of 170 lm 9

170 lm size can typically be achieved within less than oneminute, with a pixel resolution of 2.7 lm. Larger areas can

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 6 7

be imaged by sequential analysis of several IR images, soeven mm2-sized sample areas can be imaged within areasonable time of about 20 min. Each analysis pointcontains full spectral information that can be visualised byspecific integration procedures, where an x–y view of peakareas, peak heights or their ratios can be plotted. Singlespectra from regions of interest can be extracted from the IRimage, and differences in spectra can be highlighted orused for refinement of a new integration strategy. Comparedwith IR mappings using synchrotron-based IR sources, theproduction of FPA-detector-based IR images is much lesscostly and requires considerably shorter analysis times. A FPAdetector may also be used in combination with other opticalcomponents (e.g., polarised measurements that providetextural information, Figure 6) and measurements in atten-uated total reflection (ATR) mode that provide information

about the surface of the sample (Figure 6b), accompaniedby an enhancement of the spatial resolution by the refractiveindex n of the ATR crystal (e.g., Germanium, n = 4 in the IRrange).

Examples for the successful use of fast IR images,generated using FPA-based systems, in the Earth sciencesinclude the characterisation of microscopic fluid and meltinclusions (Mormone et al. 2011), hydrous mineral lamellaein an anhydrous host mineral (Gose et al. 2011), thedocumentation of growth or diffusion-controlled zoning(Prechtel and Stalder 2010) and the documentation offine-grained, fabric textures. Study objects may be derivedfrom natural rocks (Figure 6a), high-pressure syntheses,industrial ceramics, as well as cultural heritage goods(Figure 6b).

Figure 6. Examples of spectroscopic micro-images. (a) Orientation dependence of the integral IR absorption in the

2700–3100 cm-1 range of a natural rhodochrosite (MnCO3) aggregate, measured in transmission mode with the

two polarisation directions of the electric field vector E marked with arrows. (b) FPA-ATR image of the integral

absorption in the 1040–1080 cm-1 range of a wollastonite (CaSiO3) needle in a historic plaster (age 550 a) from

the Finsterm€unz fortress, Austria (Diekamp et al. 2012). The diffuse change in the colour coding (note the needle’s

green rim) is due to the pixel resolution being better than the diffraction limit. (c) Fast Raman image (≈ 11000

spectra obtained in 9 min, using the SWIFT mode) of the phase distribution in a polished meteorite section (courtesy

of Horiba Scientific). (d) Transmitted-light photomicrograph and corresponding 3D Raman image of a multi-phase

inclusion in hydrothermal quartz from Sierra de Lujar, Granada, Spain (for sample details see B�eny et al. 1982; data

courtesy of RENISHAW plc).

3 6 8 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

Raman spectroscopy

Raman spectroscopy instrumentation: Raman spec-troscopy has seen considerable progress in the recent years, inparticular in the imaging domain. It is then no wonder thatRaman-based images have found an impressive array ofapplications (e.g., Fries and Steele 2010, Nasdala et al.2012). The two dominant players in high-end Ramanspectroscopy instrumentation, HORIBA Scientific and RENI-SHAW, continue their quest for faster imaging, with dataacquisition modes and software developments that enable2D and 3D Raman imaging significantly faster than previouslypossible. At Pittcon 2012, both companies released newsoftware optimised for fast imaging and data processing.

On the hardware front, HORIBA Scientific developed anew Raman imaging option to increase measurementspeed, allowing micro- or macro-Raman images to berecorded in record times. The SWIFT imaging mode is basedon detector-stage synchronisation: the stage moves contin-uously and spectra are acquired ‘on the fly’, with acquisitiontimes for a single point in the millisecond range. HR imagescontaining thousands of spectra can then be acquired inminutes, even seconds, instead of hours. RENISHAW’sStreamLine Plus Raman imaging combines advanced auto-mated optics and detector technologies, significantly reduc-ing measurement times over more conventional pointmapping, enabling large samples to be mapped at highresolution in practical timescales. RENISHAW claims imagingspeed improvement of 200-fold, opening the door to nearreal-time image display with live spectral analysis andimage display during data collection. These innovativeimaging modes also allow shorter laser beam exposure orlower power density on each point of the sample, decreas-ing the risk of laser-induced sample damage. With dataacquisition times in the millisecond range per spectrum, anenormous amount of data can now be acquired within timewindows that are compatible with high-definition 2D or 3Dimaging. Innovative scanning methods have also beendeveloped. Traditionally, Raman imaging is performed bymoving the sample with a translation stage while the laserspot remains fixed and recording a spectrum at every point.HORIBA Scientific recently introduced the DuoScan modulewhere a combination of two scanning mirrors, placed beforethe microscope, scan the laser beam across the samplefollowing a user-defined pattern. This both allows thecreation of variable-size laser macro spots (from 1 lm upto 300 lm) as well as Raman mapping without samplemechanical translation. The measurement remains fullyconfocal, without any loss of Raman collection efficiency,and allowing full analysis of large surfaces (up to 1 cm2).

Another significant technological advance is the imple-mentation of filters to access the low-frequency region of theRaman spectrum. Low-frequency vibrational modes canreveal details on conformational changes, subtle changes inlattice structure and even gaseous phase bond length –

parameters not easily accessible on traditional bench-topequipment. Until recently, if one wanted to measure spectralfeatures much lower than 100 cm-1, the only recourse wasto use a triple spectrograph, which is a more complicated,more expensive instrument with less optical throughput.Within the past year or two, Bragg filters have becomeavailable that allow measurement of Raman bands veryclose to the Rayleigh line on specially designed single-grating spectrographs (e.g., Rapaport et al. 2010). Theultra-low frequency (ULF) module available on the LabRAMHR, HORIBA’s flagship Raman product, allows Ramanspectroscopic information in the sub-100 cm-1 region, withmeasurements down to < 10 cm-1 routinely available(Figure 7). The high throughput of the LabRAM HR allowsmeasurements to be obtained in just a few seconds.Moreover, Stokes and anti-Stokes spectral features can bemeasured simultaneously, providing additional informationto the user.

Further technical developments are driven towards thedesign of spectrometer systems with short focal lengths thatare still powerful enough for fast phase identification. Suchsmall, transportable systems (e.g., Jehli�cka et al. 2011) can beused potentially by prospectors in the field. Also, several teamsworldwide continue to work on compact Raman systems forfuture extraterrestrial missions (e.g., Sharma et al. 2011).

Figure 7. Raman spectrum (633 nm excitation) of

L-cystine, measured with a single-stage spectrometer

equipped with ULF filter (spectrum courtesy HORIBA

Jobin Yvon).

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 6 9

Raman spectroscopy applications: Raman spectros-copy is used increasingly to study geological and relatedmaterials. Having been a rather special, rare techniquesome 20 years ago, Raman spectroscopy has now becomea widespread standard method in mineralogy and geolog-ical sciences. The scarceness of Raman systems in the pasthas been overcome; systems are now available at manyEarth sciences institutions. The dramatic growth in the use ofthe technique is documented by a continuous increase in thenumber of Raman-related SCI papers per annum. Existingtraining opportunities provided by university institutions andmanufacturers, however, do not yet meet the extensive needsof a fast-growing community of users. As a negative result,recent articles are increasingly affected by the publication ofunrecognised artefacts and misinterpretations (this problemhas been summarised and discussed at length in Nasdalaet al. 2012).

Applications of Raman spectroscopy in the Earthsciences can be assigned to two major groups. First, Ramanis used traditionally as a fingerprint technique for theidentification of fluid (e.g., Baumgartner and Bakker 2010,Frezotti et al. 2012) and solid inclusions, which may providevital data for interpreting the evolution of geologicalsamples. For instance, the detection of stishovite in an impactrock (St€ahle et al. 2011) has verified ultra-high pressureconditions during an impact event. Another growing field ofapplication is the fingerprint identification of mineral andother pigments in historic art objects (e.g., Muralha et al.2012, Ropret et al. 2012). Any result based on thecomparison of unknown with reference fingerprint patterns,however, depends on the quality (i.e., completeness andtrustworthiness) of the reference databases available; herethe situation remains somewhat unsatisfactory. Many Ramanlaboratories work on building up own reference databases,several of them providing their data online; here the externalusers always need to be vigilant of the possibility of incorrectentries. This is unfortunately also to some degree the case forthe main initiative in this field, the RRUFF project (www.rruf-f.info), where the reliability of recently added spectra seemsto decrease while their total number increases. RRUFF is,nevertheless, the most useful tool in the fingerprint analysis ofminerals. Second, Raman spectroscopy is used to characte-rise in detail minerals and other geological samples. Thisincludes the assessment of stress and disturbance of theshort-range order, as for instance stress around inclusions inhigh-pressure minerals due to heterogeneous volumeexpansion upon uplift (Howell et al. 2010), lattice distortion

Figure 8. Raman mapping applied to the study of

heterogeneous radiation damage within a single

crystal. Top, BSE image of a zoned zircon from Bancroft,

Ontario. A multitude of finger-like patches affected by

chemical alteration that emanated from fractures show

dark BSE (sample courtesy D. Moser and J.M. Hanchar;

image D. Rhede); for details see Nasdala et al.

(2010b). Bottom, Raman map of a small area visual-

ising the heterogeneous short-range order, based on

the damage-induced broadening of the antisymmetric

stretching of SiO4 tetrahedrons. Alteration patches are

much less radiation damaged compared with the

primary zircon.

Figure 9. Raman line scan of a natural, moderately

radiation-damaged zircon sample (Sri Lanka) after

irradiation with 8.8 MeV 4He ions (for details see

Nasdala et al. 2011). The additional, irradiation-

induced disorder, visualised by the increasing broad-

ening of the antisymmetric SiO4 mode (diamonds),

correlates well with the defect distribution predicted by

Monte Carlo simulation (dashed graph).

3 7 0 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

due to variations in the chemical composition (Ruschel et al.2012) or structural damage resulting from corpuscularirradiation (Figures 8 and 9). To study the latter on a morequantitative level, and to avoid analytical artefacts associ-ated with limits in depth resolution, Nasdala et al. (2010a)proposed that ion irradiation studies be performed onmicrometre-thin focused ion beam foils whose thicknessesare adjusted carefully according to the penetration depth ofthe ions irradiated. Another growing field of application isthe evaluation of the crystallinity/disorder of graphiticcarbon, with applications in geobiology (Papineau et al.2011), cosmochemistry (Wopenka 2012) and as a geo-thermometer for low-temperature metamorphic events (Lah-fid et al. 2010, Beyssac and Lazzeri 2012).

Instrumental neutron activation analysis(contribution by M.J.M. Duke)

The principles of neutron activation analysis (NAA) werefirst demonstrated and developed some 76 years ago byvon Hevesy and Levi (1936). However, it was not until thedevelopment of the nuclear reactor, providing an intensesource of neutrons, that the method could be appliedwidely. Since the late 1960s, the increased availability ofresearch reactors, together with the development ofsemiconductor detectors and complementary solid-stateelectronics and laboratory computers capable of collectingand processing complex spectra, has made NAA anextremely attractive analytical method, particularly in thegeosciences. When NAA is carried out on samples withouteither pre- or post-irradiation chemical separations, it isreferred to as instrumental neutron activation analysis(INAA). The sensitivity, good uncertainties, low contamina-tion risk, non-destructive and multi-elemental nature ofINAA make it a competitive means of analysis when accessis available to a nuclear reactor. The method is relativelyfree from matrix effects and offers a very wide dynamic, oranalytical, range.

In reviewing INAA-related papers published since thebeginning of 2010, the application of INAA continues todominate the NAA literature, with few notable methodolog-ical developments having been reported. Given the longhistory and maturity of INAA, this is not surprising. In theirevaluation of the thirteen Modern Trends in ActivationAnalysis (MTAA) meetings held over the past 50 years, deBruin and Bode (2012) clearly show a shift from a roughly1:1 ratio of NAA applications vs. method developmentcontributions prior to 1975 as compared with almost a 2:1ratio for the MTAA meetings held over the past 35 years.However, contributions at the 2011 MTAA-13 meetingshowed a shift back to the 1:1 ratio, and only time will tell

whether this is spurious or a true shift in the focus of thecommunity.

Assessment of the INAA papers published in the periodaddressed by this review shows an increase in the appli-cation of INAA in West Africa (e.g., Ghana and Nigeria), theMiddle East (e.g., Egypt and Syria) and Pakistan. With theexception of Egypt, each of these countries has a MiniatureNeutron Source Reactor (MNSR) that, depending upon thecountry in question, has been operational for between 8 and23 years. While this increase in the number of publications isobviously related to the ready availability and accessibility ofthe low-flux MNSR research reactors, this transition alsoprobably reflects the transition from new to more establishedand experienced facilities. Also, particularly in the WestAfrican examples, the value of INAA to resource-basedeconomies may be a significant factor for this growth incontributions from INAA.

A particularly significant NAA-related paper to bepublished in the review period, one which summarises theculmination of many years of work, is that of Greenberg et al.(2011) on NAA as a primary method of measurement. In aseries of three chapters, the authors present the case forNAA, based on the comparator method, as a primarymethod of measurement as defined by the ConsultativeCommittee on Amount of Substance – Metrology in Chem-istry (CCQM). While the CCQM has not yet formerly addedINAA to a list of primary methods of analysis, the President ofthe CCQM ‘…agreed that, although the CCQM no longerlisted “primary methods,” it was recognised that NAA hadclaims to a similar status to that of the five methods listedoriginally by the CCQM and that he would return to areconsideration of this list of techniques in the future’ (CCQM2008). As noted in Greenberg et al. (2011), it would beparticularly beneficial to have a primary method, in additionto isotope dilution mass spectrometry, for the preparationand characterisation of reference materials for inorganictrace element determination. It would appear that INAA,based on the comparator method, is on the brink of beingofficially classified as a primary method.

While many analytical techniques, particularly thoseused in the geosciences, focus on the analysis of either smallsample sizes (e.g., AAS, ICP-AES, ICP-MS) or on themicroscopic scale (e.g., EPMA, LA-ICP-MS, SIMS), the readeris reminded that NAA is a bulk sample analysis technique.Consequently, in comparison with many other analyticalstrategies, one area in which INAA continues to showsignificant promise and utility is in the analysis of large, oftenheterogeneous (particularly at the 100–200 mg samplesize), samples with masses in the range of tens to thousands

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 7 1

of grams. The analysis of such large samples, particularly fortheir trace element contents, using AAS, ICP-AES or ICP-MS iscompletely impractical. Large-sample INAA (LS-INAA) isfeasible on account of the highly penetrating nature ofneutrons and gamma rays and our thorough understandingof their interactions with matter. While the application of LS-INAA is not new, in the review period there are examples ofit being applied at additional reactor centres (e.g., Acharyaet al. 2010, Swain et al. 2012) for the analysis of largeand/or heterogeneous samples. Nyarko et al. (2011)describe the design and feasibility of a large-sampleirradiation site for a low-flux reactor, and Haddad andAlsomel (2011) examine and demonstrate LS-INAA of wasteproducts (ash, municipal waste and sewage) for thedetermination of Sb, Hg, Co, Zn, As, Cs, Sm, K, Sc, Ti, Mnand Br using photoneutrons generated by the interaction ofhigh-energy gamma rays emitted by fission products with thereactor Be reflector when the reactor is shutdown (subcritical).

The k0-method of NAA is essentially a flexible, single-comparator approach that combines the absolute capabil-ities of the technique with radionuclide-specific nuclearconstants that can be applied using site-specific parameters,such as reactor neutron flux and detector efficiencies(Rossbach and Blaauw 2006). Implementation of the k0-method of NAA in many laboratories around the world hasresulted in a preponderance of k0-NAA-related publicationson the implementation, application and refinement of the k0-standardisation method (e.g., Fadzil et al. 2011, Menezesand Ja�cimovi�c 2011). This trend is not expected to changein the near future. In describing the history and contributionsof NAA at the Jo�zef Stefan Institute (JSI) in Slovenia, Smodi�s(2012) outlines the implementation and development of thek0-method at JSI and in particular its application in thecharacterisation of a broad range of reference materials.

In conclusion, when discussing the future demand forgeological reference materials, Meisel and Kane (2011)noted that, while microanalytical techniques have becomethe major impetus in geochemical research, there stillremains geoanalytical interest and demand for bulk ele-mental analyses – INAA still has much to offer in this regard.

Reference materials for geoanalyticaland environmental research (contributionby J. Enzweiler, K.P. Jochum and U. Weis)

Reference materials (RMs) play an important role in allfields of geoanalytical and environmental research, as theyare necessary for calibration, quality control and assurance,method validation and to establish metrological traceabilityto measurements. This review gives an overview of the

literature in this field since 2010, augmenting reviews for the2-year periods 2004–2005 (Jochum and Willbold 2006),2006–2007 (Jochum and Brueckner 2008) and 2008–2009 (Jochum et al. 2010). It describes recent develop-ments in the production of new samples for bulk andmicroanalytical applications, in the preparation of newisotopic RMs, which are mainly necessary as ‘delta zero’materials for stable isotopic work, and in the certificationprocesses of RMs. Because this study contains manyabbreviations of RM names and RM providers, we havelisted these in Tables 2 and 3.

ISO Guidelines and the International Associationof Geoanalysts Protocol

The International Organization for StandardizationCommittee on Reference Materials (ISO/REMCO) works toestablish and update internationally agreed guidelinesconcerning terminology, production, certification, distributionand proper use of reference materials. ISO Guide 30(1992) contains definitions and terminology related to RMs,while the current ISO/REMCO definitions for RMs andCRMs were published in ISO Guide 30 Amd 1 (2008). RMis a material, sufficiently homogeneous and stable withrespect to one or more specified properties, which has beenestablished to be fit for its intended use in a measurementprocess. Certified RM (CRM) is a reference materialcharacterized by a metrologically valid procedure for oneor more specified properties, accompanied by a certificatethat provides the value of the specified property, itsassociated uncertainty, and a statement of metrologicaltraceability.

ISO Guide 31 (2000) describes the documentation thatshould accompany a RM, and ISO Guide 33 (2000)describes the uses of RMs. These three guides are underrevision. The last ISO/REMCO developments weredescribed by Emons et al. (2010, 2011) and reviewed byBotha (2010, 2012). Three ISO Guides are dedicated toassist in setting up a scheme to produce and certify RMs toensure that their quality meets the requirements of the endusers (Botha 2012). ISO Guide 34 (2009), the main guideof the series, covers the competence required from RMproducers and outlines the scheme of the work needed toproduce a CRM. It begins with planning, goes throughmaterial selection and its physical preparation, the homo-geneity, stability and characterisation studies, the assignmentof reference values, the emission of the certificate, materialdistribution and finally material maintenance. ISO Guide 35(2006) is dedicated to the certification of RM and is underrevision. Metrological traceability (Barwick and Wood 2010)and certified values with uncertainties determined according

3 7 2 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

Table 2.Details of discussed reference materials

Reference material Scientific interest

Provider Name Type of material

ANRT GS-N Rock powder (granite) Major and trace elements, Mg isotopesAWI PS1772-8 Diatom O isotopesBAM BAM-S005-A Soda lime glass Major and trace elementsBAM BAM-S005-B Soda lime glass Major and trace elementsBAM ERM-AE102a Boron solution B isotopesBAM ERM-AE104a Boron solution B isotopesBAM ERM-AE-120 Boron solution B isotopesBAM ERM-AE-121 Boron solution B isotopesBAM ERM-AE-122 Boron solution B isotopesBAM BAM-I012 Cadmium solution Cd isotopesBCR ERM-CC580 Estuarine sediment powder Trace elements, Hg isotopesCEREGE MSG60 Phytolith O isotopesCGL OShBo Rock powder (granite) Major and trace elements, different isotopesCGL GAS Rock powder (serpentinite) Major and trace elements, different isotopesCRPG GA Rock powder (granite) Major and trace elements, Mg isotopesDSM DSM3 Magnesium Mg isotopesGSJ JB-1 Rock powder (basalt) Major and trace elements, different isotopesGSJ JB-2 Rock powder (basalt) Major and trace elements, different isotopesGSJ JA-1 Rock powder (andesite) Major and trace elements, different isotopesGSJ JA-2 Rock powder (andesite) Major and trace elements, different isotopesHarvard University Harvard-JM Magnesium oxide Mg isotopesHarvard University Harvard-Spex Magnesium oxide Mg isotopesHarvard University Harvard-AA Magnesium Mg isotopesIAEA Sewage sludge Sewage sludge Trace elementsIAEA IAEA-B-1 Sea water B isotopesIAEA IAEA-B-2 Groundwater B isotopesIAEA IAEA-B-3 Groundwater B isotopesIAEA SMOW Virtual water RM O and H isotopesIAEA VSMOW Water (alias NIST SRM 8535), exhausted O and H isotopesIAEA VSMOW2 Water O and H isotopesIAEA SLAP2 Water O and H isotopesIAEA SLAP Water O and H isotopesIAPSO IAPSO Sea water Different isotopesIGGE GCr-1 Rock powder (chromium ore) Major elements, Cr, S, Ni, Co, P, Ti, Mn, VIGGE GCr-2 Rock powder (chromium ore) Major elements, Cr, S, Ni, Co, P, Ti, Mn, VIGGE GCr-3 Rock powder (chromium ore) Major elements, Cr, S, Ni, Co, P, Ti, Mn, VIGGE GCr-4 Rock powder (chromium ore) Major elements, Cr, S, Ni, Co, P, Ti, Mn, VIRMM ERM-AE633 Copper nitrate solution Cu isotopesIRMM ERM-AE647 Copper nitrate solution Cu isotopesIRMM IRMM-014 Iron Fe isotopesIRMM IRMM-3702 Zinc solution Zn isotopesIRMM IRMM-3100a Uranium solution U isotopesISS MURST-ISS-A3 Scallop (Adamussium colbecki) Trace elementsJMC Zn-Lyon JMC zinc solution, batch JMC-3-0749L Zn isotopesJMC JMC-Mo Molybdenum solution Mo isotopesJMC JMC Cd M€unster JMC cadmium solution, lot 502552A Cd isotopesJMC NZ JMC Cd JMC cadmium solution, lot 250421H Cd isotopesMPI-DING ATHO-G Glass (rhyolite) Major and trace elements, different isotopesMPI-DING BM90/21-G Glass (peridotite) Major and trace elements, different isotopesMPI-DING GOR128-G Glass (komatiite) Major and trace elements, different isotopesMPI-DING GOR132-G Glass (komatiite) Major and trace elements, different isotopesMPI-DING KL2-G Glass (basalt) Major and trace elements, different isotopesMPI-DING ML3B-G Glass (basalt) Major and trace elements, different isotopesMPI-DING StHs6/80-G Glass (andesite) Major and trace elements, different isotopesMPI-DING T1-G Glass (diorite) Major and trace elements, different isotopesMUN MunZirc0 Synthetic zircon Hf isotopes, REEMUN MunZirc1 Synthetic zircon Hf isotopes, REEMUN MunZirc2 Synthetic zircon Hf isotopes, REEMUN MunZirc3 Synthetic zircon Hf isotopes, REE

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 7 3

to the principles of the Guide to the Expression of Uncertaintyin Measurement (ISO Guide 98-3 2008) are requirementsfor a CRM. Guidelines for establishing metrological trace-ability of quantity values assigned to reference materials arecurrently being developed by an ISO/REMCO workinggroup. The new Guides 79 and 80 on RMs for qualitativeanalysis and in-house production of RM for quality control(QCM), respectively, are being prepared for the first time.

Historically, geochemical RMs were produced using thebest practices available (Kane 2010, Meisel and Kane2011). The necessity to follow and apply metrologicalprinciples motivated the International Association of Geoan-alysts (IAG) to elaborate a protocol for the certification ofgeochemical RMs, with procedures compliant to ISO/REMCO guidelines (Kane et al. 2003, 2007). The maingoal of the IAG certification programme is to achieve target

Table 2 (continued).Details of discussed reference materials

Reference material Scientific interest

Provider Name Type of material

MUN MunZirc4 Synthetic zircon Hf isotopes, REENBL NBL112a Uranium U isotopesNERC BFC Diatom O isotopesNIST NIST SRM 610 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 611 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 612 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 613 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 614 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 615 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 616 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 617 Silicate glass Major and trace elements, different isotopesNIST NIST SRM 951 Boric acid solution B isotopesNIST NIST SRM 8546 Silica sand (alias NBS28) O isotopesNIST NIST SRM 976 Copper Cu isotopesNIST NIST SRM 3120a Germanium solution Ge isotopesNIST NIST SRM 3134 Molybdenum solution Mo isotopesNIST NIST SRM 3108 Cadmium solution Cd isotopesNIST NIST SRM 3133 Mercury solution Hg isotopesNRCC SLRS-4 River water Trace elementsNRCC SLRS-5 River water Trace elementsNRCC NASS-5 Sea water Trace elements, Cd isotopesNRCG MCPt-1 Rock powder (seamount crust) PGE, trace elementsNRCG MCPt-2 Rock powder (seamount crust) PGE, trace elementsNRCG CGSG-1 Glass (alkali basalt) Major and trace elementsNRCG CGSG-2 Glass (syenite) Major and trace elementsNRCG CGSG-4 Glass (soil) Major and trace elementsNRCG CGSG-5 Glass (andesite) Major and trace elementsSMITHS Allende Rock powder (carbonaceous chondrite) Trace elements, different isotopesUM M€unster Cd Cadmium Cd isotopesU-Mich UM-Almad�en Mercury solution Hg isotopesUOX AA vanadium solution Vanadium solution V isotopesUSGS BCR-1 Rock powder (basalt) Major and trace elements, different isotopesUSGS BCR-2 Rock powder (basalt) Major and trace elements, different isotopesUSGS BHVO-1 Rock powder (basalt) Major and trace elements, different isotopesUSGS BHVO-2 Rock powder (basalt) Major and trace elements, different isotopesUSGS MACS-1 Carbonate pellet Trace elementsUSGS MACS-3 Carbonate pellet Trace elementsUSGS GSD-1G Synthetic basalt glass Major and trace elements, different isotopesUSGS DTS-1 Rock powder (dunite) Major and trace elements, different isotopesUSGS PCC-1 Rock powder (peridotite) Major and trace elements, different isotopesUSGS GSP-2 Rock powder (granodiorite) Major and trace elements, V isotopesUSGS SDO-1 Rock powder (shale) Major and trace elements, Mo isotopesUSGS BIR-1 Rock powder (basalt) Major and trace elements, different isotopesUSGS BIR-1a Rock powder (basalt) Major and trace elements, different isotopesUSGS AGV-1 Rock powder (andesite) Major and trace elements, different isotopesUSGS AGV-2 Rock powder (andesite) Major and trace elements, different isotopesUWO G95-25CL Phytolith O isotopes

3 7 4 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

uncertainties that are both metrologically valid and are fit forpurpose (Kane 2010). The characterisation of candidateRMs is mainly performed by experienced laboratories,selected on basis of their performance during the analysisof samples with similar matrix in the GeoPT ProficiencyTesting (PT) programme, which is regularly run by IAG. Kane(2010) exemplifies the calculation of combined uncertaintiesof certified values and also discusses the achievements andneeds of the IAG certification programme. Recently, it hasbecame apparent that the IAG protocol needs to undergorevision to comply with the new editions of ISO Guides 35and 34 (Meisel and Kane 2011). Participation in a PTscheme can be used for both quality control and forlaboratory accreditation purposes. Guidance for selecting,using and interpreting PT results was updated by EURA-CHEM (2011), reflecting the growing attention given to thisactivity.

Rock powders

Powdered rock RMs are the backbone of geoanalysis(Kane 2010). Inspection of the literature shows that mostgeochemists use these samples to demonstrate their dataquality. Since many years, the powdered rock RMs from theUSGS (e.g., BCR-1, BCR-2, BHVO-1, BHVO-2) and GSJ (e.g.,JB-1, JB-2, JA-1, JA-2) have been the most popular samples.However, the reference values of these valuable sampleshave not been certified according to recent ISO guidelines.

Since 1974, the CGL of Mongolia has been working onthe development and certification of RMs (Batjargal et al.2010). Among many other RMs, the CGL has prepared theserpentinite GAS and the alkaline granite OShBO. Recently,these RMs have been recertified following the IAG (Kaneet al. 2003, 2007) and ISO guidelines for certification (Kaneet al. 2009). These recertification efforts have increased thenumber of elements that were certified by CGL for OShBO,but not for GAS. Both samples are important for both qualitycontrol and quality assurance.

Only a small number of well-characterised RMs forchromite are currently available. For this reason, the IGGE,China, recently produced the four chromium ore RMs:GCr-1, GCr-2, GCr-3 and GCr-4 (Cheng et al. 2012).These samples were collected from chromite deposits inTibet and Inner Mongolia. They were found to be sufficientlyhomogeneous at the bulk scale to serve as certified RMs,such that Cheng et al. (2012) could present certified valuesfor eighteen components.

There are few RMs with low uncertainty data for PGEsthat can be used for quality control. Therefore, Wang et al.

(2011) produced the two cobalt-rich, seamount crust, ultra-fine RMs MCPt-1 and MCPt-2 at NRCG. The ultra-fineprocessing yielded powders with an average particle size ofabout 1.8 and 1.5 lm. The mass fractions of the PGEs –

except for Rh – were determined by isotope dilution-ICP-MS.Platinum was characterised as certified value, whereas theother five PGEs were classified as reference values with andadditional sixty-two elements being indicated as informationvalues. Minimum sampling mass for the determination ofPGEs was 1 g and for the other elements 2–5 mg.

Environmental samples

Environmental RMs comprise a large variety of matrices,such as soils, dust, sewage sludge, water and biologicalsamples. In the following section, some interesting papers willbe discussed, which have been published recently.

There is an increasing interest in sewage sludge, such asa fertiliser. In 2010, the IAEA organised a proficiency test(IAEA-CU-2010-02) for the determination of mass fractionsin sewage sludge. Wasim et al. (2012) participated in thisprogramme and presented the results for thirty-six elementsdetermined by INAA; most of them are not reported by theIAEA.

Natural river water RMs are useful samples for qualitycontrol of river water, seawater, snow or ice samples. Thecertified RM SLRS-4 distributed by the NRCC is such asample; however, it is now depleted. SLRS-5 is the replace-ment sample and was certified for twenty-two elements;however, in contrast to SLRS-4, no complete set of elementdata exist. Therefore, Heimburger et al. (2012) analysedSLRS-5 and presented the results for thirty-five additionalelements, including REE, Li, Cs, Ti, Th, Y and others, which areuseful in quality control procedures.

The need for monitoring of environmental contaminationin Antarctica requires the availability of certified RMs for anumber of pollutants in different Antarctic matrices (Caroliand Bottoni 2010, 2012). One of these candidates is theRM Adamussium colbecki MURST-ISS-A3 prepared by EC-JRC-IRMM and provided by ISS, because this scallop is asuitable bioindicator. Eighteen laboratories were involved inthe certification project from which Caroli and Bottoni (2010)presented certified mass fractions for the trace elements As,Cd, Cr, Cu, Fe, Mn, Ni and Zn.

Microanalytical RMs

Microanalytical RMs have gained a wide interest ingeoanalytical and environmental research due to the

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 7 5

increasing use of microanalytical techniques, such as LA-ICP-MS, SIMS, SR-XRF. Because of the multiplicity of kinds of solidgeological and biogenic materials, RMs of quite diversematrices are needed to address matrix effects. The USGShas prepared the two synthetic carbonate RMs MACS-1 andMACS-3, because many samples, such as corals, stalag-mites, shells and ostracods, have calcium carbonate matri-ces. Mertz-Kraus et al. (2009) and Chen et al. (2011)provided LA-ICP-MS and solution ICP-MS results of thesematerials. In a recent paper by Jochum et al. (2012), thepreliminary reference values from the USGS have beenpublished together with new LA-ICP-MS data, so that MACS-1 and MACS-3 are now well characterised.

The Lu–Hf isotopic system is a powerful tool forgeochronology investigations and a wide variety of terrestrial

and extraterrestrial minerals. In particular, zircon samples arewidely used for such studies. However, interferences of REEcan lead to incorrect Hf isotopic compositions using in situLA-MC-ICP-MS techniques, where such interferences areunavoidable and must be corrected. To get REE–Hf-dopedzircon crystals, Fisher et al. (2011) produced a series of fivesynthetic homogeneous zircon reference materials, MUNZir0–4, with different REE contents, which are extremely usefulfor in situ Hf isotope ratio measurements. In addition, areference value of 176Hf/177Hf = 0.282135 � 0.000007is given in this important paper.

There is a need for reference glasses of different rocktypes. Up till now, only the MPI-DING glasses cover the entirespectrum from ultramafic to highly siliceous compositions(Jochum et al. 2006). To supply the demand of naturalgeological reference glasses, the NRCG, Beijing, hasprepared four homogeneous ‘Chinese Geological StandardGlasses (CGSG)’: CGSG-1 (alkali basalt), CGSG-2 (syenite),CGSG-4 (soil) and CGSG-5 (andesite). The homogeneity ofthese glasses was investigated by Hu et al. (2011). Theauthors also provided preliminary reference values usinga variety of analytical techniques performed in nine labo-ratories.

The NIST SRM 610–617 reference glasses continue tobe widely used as calibration materials in microanalysis.These glasses have – with the exceptions of few elements –not been certified by NIST and were not designed formicro-analytical purposes. Because of the great need for thebest possible values for the NIST glasses, Jochum et al.(2011a) acted in a similar way as the IAG would proceed inrecertifying a RM. Possible element inhomogeneities werequantitatively determined using test portion masses between0.02 and 1 lg. New reference values for NIST SRM610–617 glasses were presented together with uncertain-ties at the 95% confidence level for bulk and microanalyticalpurposes. In contrast to former compilation procedures, thisapproach delivered data that consider present-day require-ments of data quality.

To expand the pallet of silicate RMs available formicroanalysis, Yang et al. (2012) tested the two soda limeBAM-S005-A and BAM-S005-B glasses from BAM, whichwere designed and certified for bulk analytical purposes,such as XRF. This study indicates that all major and traceelements are homogeneously distributed at micrometresampling scale with the exception of some trace elements(e.g., Cs, Cl, Cr, Mo, Ni), which had not been addressed inthe original certificate of analysis. Yang et al. (2012) alsodetermined the mass fractions of fifty major and traceelements. With the exceptions of Sr, Ba, Ce and Pb, the data

Table 3.List of reference material providers and theirabbreviated titles

Abbreviation Provider

ANRT Association Nationale de laRecherche Technique, France

AWI Alfred Wegener Institute, GermanyBAM Federal Institute for Materials

Research and Testing, GermanyBCR Community Bureau of References, BelgiumCEREGE Centre Europ�een et d’Enseignement des

G�eosciences de l’Environnement, FranceCGL Central Geological Laboratory, MongoliaCRPG Centre de Recherches Pétrographiques et

Géochemiques, FranceDSM Dead Sea Magnesium Ltd., IsraelGSJ Geological Survey of Japan, JapanHarvard University Harvard University, USAIAEA International Atomic Energy Agency, AustriaIAPSO International Association for the Physical Sciences

of the OceansIGGE Institute of Geophysical and Geochemical

Exploration, ChinaIRMM Institute for Reference Materials and Measurements,

BelgiumISS Istituto Superiore di Sanit�a, National Institute of

Health, ItaliaJMC Alfa Aesar Johnson Matthey, USAMPI-DING Max-Planck-Institut f€ur Chemie, GermanyMUN Memorial University of Newfoundland, CanadaNBL National Brunswick Laboratory, USANERC Natural Environment Research Council, UKNIST National Institute of Standards and Technology,

USANRCC National Research Council of Canada, CanadaNRCG National Research Centre for Geoanalysis, ChinaSMITHS Smithsonian Institution, USAUM Universit€at M€unster, GermanyU-Mich University of Michigan, USAUSGS United States Geological Survey, USAUWO University of Western Ontario, CanadaUOX University of Oxford, UK

3 7 6 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

for eighteen trace elements are within the uncertainties of thecertified values.

In recent years in situ isotopic determinations have grownin their importance as a tool in geochemistry. Jochum et al.(2011b) initialised an extensive isotopic study of USGS GSD-1G and the MPI-DING glasses ATHO-G, BM90/21-G,GOR128-G, GOR132-G, KL2-G, ML3B-G, StHs6/80-G,T1-G. Thirteen laboratories participated in this initiativeproviding data from high-precision bulk and microanalyticaltechniques. Together with previously published data, pre-liminary reference values and their uncertainties at the 95%confidence level were determined for H, Li, B, O, Si, Ca, Sr,Nd, Hf, Pb, Th and U isotopes using the recommendations ofthe IAG for certification of RMs. GSD-1G and the MPI-DINGglasses are therefore suitable RMs for major and traceelement as well as isotopic studies.

Isotope-specific reference materials

Variations in the isotopic composition of light elements(e.g., H, C, O, S) provide information about processes ofisotope fractionation in natural systems. Recent advances inmass spectrometry, in particular MC-ICP-MS, have alsoopened up new fields based on the measurement of theisotope fractionations of other ‘non-traditional’ stable iso-topes (e.g., Li, B, Mg, Si, Cd, Ca, Cr, Fe). Stable isotope dataare commonly reported as d-notation, which is the deviationof the isotope composition of a sample relative to acommonly agreed RM, the so-called ‘delta zero’ material.The use of common isotopic RMs is highly preferable tofacilitate easy comparison of data sets derived frommeasurements in different laboratories. For some isotopicsystems, there is already agreement as to which RMs shouldbe the common ‘delta zero’ material. However, especially forisotope systems involving non-traditional stable isotopes (e.g.,Zn, Mo, Cd), there is still a lack of suitable, commonly usedisotopic RMs as normalisation material to calculate d values.There is also a need for certified radioactive isotopic RMs,such as of uranium and thorium, for geochemical andenvironmental applications. Vogl and Pritzkow (2010)reviewed the work in this field from previous years anddescribed a possible strategy for a new programme onisotope RMs. Here we present some of the more significantadvances reported in this field over the recent few years.

Boron isotopes: The NIST SRM 951 boric acid solutionis generally used as ‘delta zero’ material for B isotopicmeasurements. Guerrot et al. (2011) reported an approachfor the accurate and reproducible measurement of boronisotope ratios in natural waters. They determined d11B valuesfor the three IAEA natural waters IAEA-B1 (sea water) and

IAEA-B2 and IAEA-B3 (groundwater) and proposed thatthese materials could be used as RMs for boron isotopes.Because there are but few isotopic RMs available, Vogl andRosner (2012) produced and certified two B isotopic RMs(ERM-AE102a and ERM-AE104a) and produced a furtherthree offset d11B RMs (ERM-AE120, ERM-AE121 and ERM-AE122) at BAM. The isotopic composition of all the materialswas adjusted by mixing B parent solutions enriched in either10B or 11B with a parent solution having a natural isotopiccomposition under full gravimetric control.

Oxygen isotopes: Investigations of oxygen isotopicfractionation is a widely used tool in geological, biologicaland environmental studies. Since 1961, the Standard MeanOcean Water (SMOW), a virtual water reference materialspecified relative to the RM NBS-1, has served as a ‘deltazero’ material. Later on, the Vienna Standard Mean OceanWater (VSMOW) was prepared by mixing 70 l of waters tomake its 18O/16O ratio as close as possible to that ofSMOW. Because VSMOW is now exhausted, the IAEAcreated VSMOW2, which was prepared by mixing lake andground waters, which Lin et al. (2010) analysed and foundto be indistinguishable from the precursor within analyticaluncertainties. They also detected no difference between theoxygen isotopic compositions of SLAP2, the new StandardLight Antarctic Precipitation water, and its precursor SLAP. Theresults are a confirmation of the successful isotopic matchingof VSMOW2 and SLAP2 to their precursors. For oxygenisotope measurements, the NBS 28 (NIST 8546) quartz isalso widely used. This RM has a d18O value that is muchlower than that of most biogenic opal. Therefore, Chapliginet al. (2011) organised an interlaboratory comparison usinghighly pure materials. Based on the results of the laborato-ries, they proposed for d18O analyses PS1772-8 (diatom),BFC (diatom), MSG60 (phytolith) and G95-25CL (phytolith)as RMs. These materials are very useful to calibrate the d18Ovalues of biogenic silica and are available on request fromthe relevant laboratories.

Magnesium isotopes: Magnesium isotope ratios arecommonly given as d25Mg and d26Mg values relative toDSM3, a magnesium solution from the Dead SeaMagnesium Ltd., Israel. Chakrabarti and Jacobsen (2010)have prepared three pure Mg RMs by dissolving largequantities (about 1 g each) of commercially available Mgoxides (Harvard-JM, Harvard-Spex) and pure Mg metal(Harvard-AA) and analysed them for their Mg isotopiccomposition. Because these solutions have a wide range intheir isotopic compositions (e.g., d26MgDSMS = -0.69 to-3.75‰), they are valuable for future interlaboratorycomparisons. DSM3 was also used as ‘delta zero’ materialin the investigation of Huang et al. (2011). These authors

© 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts 3 7 7

provided the Mg isotopic composition of a number ofgeological RMs, such as BCR-1, BCR-2, BHVO-1, DTS-1,PCC-1, GA and GS-N.

Vanadium isotopes: Nielsen et al. (2011) presentedthe first technique to obtain accurate, low uncertainty V stableisotope compositions. These authors expect that V isotopefractionation will be observed in many environments on Earthand in the solar system. As ‘delta zero’ material, they used awidely available Specpure Alfa Aesar standard solution. Thefirst measurements of V stable isotopes for six rock RMs (PCC-1, BHVO-2, BCR-2, BIR-1a, GSP-2, AGV-2) and the carbo-naceous chondrite Allende were reported by Prytulak et al.(2011). A large range reaching 1.2‰ in stable V isotopiccomposition was documented.

Iron isotopes: In their extensive study of Fe and Mgisotopic compositions of peridotite xenoliths of Eastern China,Huang et al. (2011) demonstrated their analytical perfor-mance by analysing the Fe isotopic compositions in the USGSRMs BIR-1, AGV-1 and BCR-2. As usual, the data werereported relative to the certified isotopic RM IRMM-014.

Copper isotopes: The copper metal NIST SRM 976 isgenerally used as the ‘delta zero’ material for Cu isotopedetermination. However, this RM is no longer available.Therefore, Moeller et al. (2012) recently calibrated NISTSRM 976 against the new IRMM RMs ERM-AE633 andERM-AE647. The d65/63Cu values of NIST SRM 976 relativeto ERM-AE633 and ERM-AE647 are (-0.01 � 0.05)‰ and(-0.21 � 0.05)‰, respectively.

Zinc isotopes: Most scientists use the Zn-Lyon, astandard solution from Johnson Matthey (batch 3-0749 L)as the ‘delta zero’ material. Because Zn-Lyon is running out,Moeller et al. (2012) calibrated this RM against IRMM-3702, obtaining a d66/67Zn value of (-0.29 � 0.05)‰.

Germanium isotopes: Germanium isotope composi-tions are used to study oceanic systems and environments. Asis also the case for many other isotope systems, for Ge, thereis a lack of a suitable and established ‘delta zero’ material.Therefore, Escoube et al. (2011) recently proposed the useof NIST SRM 3120a. The authors also intercalibrated severalgeological RMs as well as geological and meteoriticsamples using different analytical techniques and differentapproaches for mass bias corrections. The bulk silicate Earthd74/70Ge was re-evaluated to be (0.59 � 0.18)‰ relativeto NIST SRM 3120a.

Molybdenum isotopes: For Mo, there is no interna-tionally accepted isotopic RM available. For their investiga-

tions of black shales, Kendall et al. (2011) used the JMC MoSpecpure plasma standard solution. They also published ad98/95Mo value for the RM SDO-1. In a recent paper,Greber et al. (2012) determined d98/95Mo values for NISTSRM 610 and 612 (solid glasses), NIST SRM 3134 (liquid)and IAPSO seawater RMs by MC-ICP-MS. NIST SRM 610,612 and 3134 have identical and homogeneous98Mo/95Mo ratios at a test portion mass of 0.02 g.Therefore, Greber et al. (2012) proposed that NIST SRM3134 should be used as the ‘delta zero’ material and NISTSRM 610 or 612 as solid silicate RMs.

Cadmium isotopes: Until now, comparison of cad-mium isotope data sets collected in different laboratories hasbeen hampered by the lack of a common ‘delta zero’material. Abouchami et al. (2010) established three criteriafor a Cd isotope RM: (a) long-term supply from a large,homogeneous batch, (b) low elemental impurities and (c)isotopic composition close to that of the bulk silicate Earth.Because of their extremely fractionated Cd isotopes, the RMsBAM-I012 and ‘M€unster-Cd’ are unsuitable (Abouchamiet al. 2012). They strongly encouraged the adoption of NISTSRM 3108 Cd solution as ‘delta zero’ material in futurestudies. The isotope ratio of 114Cd/110Cd for NIST SRM3108 lies within ≈ 10 ppm Da-1 of best estimates for thebulk silicate Earth (Abouchami et al. 2012). Cadmiumisotope fractionation was used as a novel proxy for oceanbiological productivity in the Southern Ocean (Abouchamiet al. 2011), where the isotope data were referenced toNIST SRM 3108. Gault-Ringold and Stirling (2012) alsonormalised their measurements of some RMs (NZ JMC Cd,JMC Cd M€unster, BAM-I012, NASS-5) to the composition ofNIST SRM 3108.

Mercury isotopes: Liu et al. (2011b) used Hg isotopedeterminations to determine the potential Hg contaminationsources of the Pearl River Delta system by analysing typicalsediments of Dongjiang, China. They reported their data indelta notation and referenced them to NIST SRM 3133mercury standard solution. To demonstrate the quality of theirdata, Liu et al. (2011b) reported the results for the RMs ERM-CC580 and UM-Almad�en.

Uranium isotopes: IRMM in Geel, Belgium, recentlyprepared a certified RM, the so-called ‘Quad-IRM’ (Qua-druple Isotope RM) IRMM-3100a. This RM has the advan-tage that the isotopic composition was adjusted to be closeto n(233U)/n(235U)/n(236U)/n(238U) = 1/1/1/1 (Richteret al. 2011) and is therefore suitable for verifying theintercalibration of Faraday multi-collectors or multiple ion-counting detectors in TIMS and MC-ICP-MS instruments. Theuranium metal assay reference material, CRM 112-A from

3 7 8 © 2012 The Authors. Geostandards and Geoanalytical Research © 2012 International Association of Geoanalysts

NBL, has been widely used as a natural uranium isotopeRM, even though the material has yet to be certified.Mathew et al. (2012) analysed the dissolved metal bydifferent high-precision TIMS methods and determinedcertified values for 235U/238U and 234U/238U ratios. Theresults are in excellent agreement with the values found inthe IRMM measurement campaign (Richter et al. 2010a, b).

Medium-term trends for RMs

Inspection of the literature since 2010 shows thatconsiderable effort has been made to further improve thereliability of RMs by the application of certificationprocedures using ISO guidelines. However, althoughcurrently many well-characterised rock and microanalyticalRMs exist, there is a need for further homogeneous andcertified microanalytical samples, in particular for mineralanalysis, as well as for certified rock and environmentalRMs. For stable isotope ratio measurements, many so-called ‘delta zero’ isotopic RMs remain wanting; for somesystems, there is not yet any agreement for a common‘delta zero’ material. Progress has been recently made forCd, where NIST SRM 3108 seems to be the bestcandidate. The challenge for the future is to establishand certify new suitable isotopic RMs for geochemical andenvironmental applications, especially for non-traditionalisotope systems.

Acknowledgements

The TIMS section benefited from comments by T. Black-burn, R.W. Carlson, S.B. Shirey and R.J. Walker. For theaccelerator mass spectrometry and ion beam analysissection, F. Munnik, A. Renno and G. Rugel in Dresden arethanked for their critical reviews. Here, thanks also to themany colleagues (operators and users) from other acceler-ator facilities for discussion and suggestions that made thiscontribution more balanced.

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