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Total sulfur is an analyte for which there are few determinations published, despite the fact that it is a very important element (e.g., a major element in most ores, an important gas constituent in global warming, an active participant in acid drainage). Most geological reference materials have very poor quality sulfur results, that is with relative standard deviations (RSD) in the range of 30–50%, even for concentrations over 100 μg g−1 S, which compromises their use as calibrators. In order to provide modern results with low RSD, sulfur was determined in twenty‐nine geological reference materials with a state‐of‐the‐art elemental S/C analyser using metal chips (certified reference materials with a traceability link) and analytical grade sulfur for high concentration samples. Analytical parameters (sample mass, crucible degassing, calibration strategy, etc.) were optimised by testing. Our results agreed with reference material values provided by issuing bodies. Results for CCRMP SY‐2 (129 ± 13 μg g−1 S), which has been proposed as a sulfur reference material, were in agreement with the proposed modern value of 122 ± 3.7 μg g−1 S.

No abstract

The interest in selenium concentrations in whole rocks is growing, in part because it is a useful tool for base and precious metal exploration. Selenium is often neglected in whole rock geochemistry because of the inability of most laboratories to make reliable determinations of this element. A consequence of these difficulties is a paucity of assigned or certified values for Se in international geological reference materials, so that the “best practice” proposed by Kane and Potts (2007) to obtain robust values for such reference materials cannot be followed. In order to address this problem, we have determined Se by pre‐concentration on thiol‐cotton fibre followed by INAA (Se/TCF‐INAA technique) in twenty‐six international geological reference materials, and one quality control material (KPT‐1). These values were used, in conjunction with a set of published values, to estimate Se concentrations for these twenty‐seven reference samples. Robust statistics were developed for seven of the RMs, with standard deviations equal to or less than precisions calculated using the Horwitz function and so that consensus values could be proposed. For three of the RMs, the presence of outliers gave less robust results, and suggested values are proposed. For seventeen of the RMs, only information values are provided, because either insufficient determinations were available or because large standard deviations of the data were derived.

In the past, there has been little interest in the trace element characteristics of quartz, and in consequence little activity in the trace element characteristics of reference materials with high silicon content. The main purpose of this paper is to contribute to the characterisation of two international certified reference materials, BCS 313/1 from the Bureau of Analysed Samples, (BAS), UK and SRM 1830 from the National Institute of Standards and Technology (NIST), USA. BCS 313/1 was analysed by laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS), solution ICP‐MS and instrumental neutron activation analysis (INAA). NIST SRM 1830 was analysed by LA‐ICP‐MS and INAA. Analytical results are reported for more than forty elements, most of them for the first time. For most elements, the results obtained by the different methods agree within 15 % relative. The recent, heightened interest in quartz and in particular the precise determination of trace0element contents in natural quartz samples requires the use of well characterised reference materials such as BCS 313/1 and SRM 1830, to which this study is designed to contribute.

Geochemical reference materials (RMs) for microbeam techniques are typically characterised by averages and dispersion statistics (e.g., standard deviation, variance) that are calculated for a number of measurements (beam shots). It is proposed that the mapping of RMs will add spatial information that better characterises the grouping and magnitudes of the heterogeneities and provides the information necessary to define a minimum analytical mass. A simple mathematical solution is proposed, which can be easily computed and understood. The analogous notions to sill and range from geostatistics are applied to the minimum analytical mass versus the relative standard deviation. To assess grouping and magnitudes of the heterogeneities, a ‘proximity number’ is computed for each average value ± ‘n’ standard deviations (magnitude). Different chemical anomalies have been simulated to demonstrate the behaviour of the proximity number. To further test the proposed spatial geochemistry concept, sulfide‐ and oxide‐bearing RMs have been selected because many are crippled with nugget effect. They have been mapped with a micro‐XRF apparatus, and results are presented for CHR‐Bkg, CHR‐Pt+, MASS‐1, MASS‐3, WMS‐1 and WMS‐1a. MASS‐1 and MASS‐3 are the most suitable RMs for microbeam techniques. Spatial geochemistry offers a new approach to better characterise reference materials.

The Opatica plutonic belt, Abitibi greenstone belt, and Pontiac Subprovince represent a major proportion of the southeastern Superior Province, which was formed and accreted rapidly between approximately 2.9 and 2.8 Ga. Plutons in these belts are grouped into four types: (i) trondhjemite–tonalite–granodiorite (TTG) suite (2.82–2.69 Ga), (ii) monzodiorite (MZD) suite (2.697–2.669 Ga), (iii) late alkaline granitoid (ALK) suite (2.68–2.67 Ga), and (iv) anatectic granite and monzonite (ANA) suite (2.69–2.64 Ga). The four suites are represented in all belts and show similar petrography and geochemistry. In terms of Nd-isotope composition, the TTG, MZD, and ALK suites are typical of destructive plate margin magmatism and have + 1.4 < initial εNd < +3.7, values which are very similar to that of the Abitibi mantle (εNd + 2.5). The lower values for the ANA suites (εNd + 0.1 to + 2.4) result from recycling of crustal components. In the Opatica belt the ANA granitoids fall on the Nd-isotope evolution curve defined by the Opatica TTG plutons, and are thus considered to be melt products of this suite. However, Abitibi and Pontiac ANA suites show a larger range of εNd, from + 0.1 to + 2.4, compared with + 1.0 to + 1.3 for the Opatica, suggesting more heterogeneous crustal source rock. Recent geological mapping and geophysical studies associated with the Lithoprobe project have suggested that the Opatica belt represents a plutonic belt against which the Abitibi was accreted by subduction-related collision and that the Pontiac Subprovince is dominated by imbricated metasediments related to the final stages of collision in the Abitibi region. The Nd-isotope data provide support for these arguments. Early plutonic suites are mantle derived and related to arc-accretion processes. As the collision process progresses, a more evolved isotopic component is introduced, possibly in relation to sediment subduction into the mantle. Anatexis of the crust in the central Opatica belt and the core of the Pontiac Subprovince resulted in the formation of granites with a crustal signature for Nd isotopes.

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