BAM‐S005 Type A and B: New Silicate Reference Glasses for Microanalysis

To test whether the silicate reference glasses BAM‐S005‐A and BAM‐S005‐B from BAM (The Federal Institute for Materials Research and Testing, Germany) are suitable materials for microanalysis, we investigated the homogeneity of these reference glasses using the microanalytical techniques EPMA, LA‐ICP‐MS and SIMS. Our study indicated that all major and most trace elements are homogeneously distributed at micrometre sampling scale in both types of glass. However, some trace elements (e.g., Cs, Cl, Cr, Mo and Ni) seem to be inhomogeneously distributed. We also determined the composition of BAM‐S005‐A and BAM‐S005‐B. The EPMA data of major elements confirmed the information values specified by the certificate. With the exception of Sr, Ba, Ce and Pb, our trace element data by LA‐ICP‐MS were also in agreement with the certified values within the stated uncertainty limits. The reasons for the discrepancy in these four elements are still unclear. In addition, we report new data for twenty‐two further trace elements, for which the concentrations were not certified. Based on our investigation, we suggest that both of these materials are suitable for many microanalytical applications.     

TERMINOLOGY FOR GEOLOGICAL REFERENCE MATERIAL VALUES: A PROPOSAL TO THE INTERNATIONAL ORGANISATION FOR STANDARDISATION (ISO), PRODUCERS AND USERS

A new terminology is proposed for categorising values in geological reference materials based on the confidence that may be placed in an individual datum. This classification scheme is designed to be applicable to data derived from both cooperative analysis programmes and compilations of data published in the literature. Use of the following terminology is proposed: "certified value equivalent", "recommended value" and "provisional value", depending on the associated one sigma confidence limits and other analytical criteria listed in Table 1. To demonstrate the application to data that was originally assessed using different criteria and terminology, the proposed scheme has been used to reclassify data derived from the cooperative analysis program for USGS SDO-1 (Devonian Shale) and a compilation of published data for USGS G-1 (granite).     

GGR Biennial Review: Reference Materials in Geoanalytical and Environmental Research – Review for 2008 and 2009

This review gives an overview of the literature on reference materials of geochemical and environmental interest for the two-year period 2008–2009. Reference materials play an increasingly important role in all fields of geoanalytical research. This is demonstrated by the large number of publications containing data on reference materials. Although many reference materials exist, there is still a great need for certified samples, so-called delta zero materials for stable isotopic work and homogeneous microanalytical reference materials. This review focuses on six topics: developments of certification processes of reference materials mainly postulated in ISO guidelines and the IAG protocol, new developments of the GeoReM database, investigations of powdered rock reference materials, Chinese reference materials published in Chinese journals, microanalytical reference materials and isotopic reference materials.     

A Compilation of New and Published Major and Trace Element Data for NIST SRM 610 and NIST SRM 612 Glass Reference Materials

Microanalytical trace element techniques (such as ion probe or laser ablation ICP-MS) are hampered by a lack of well characterized, homogeneous standards. Two silicate glass reference materials produced by National Institute of Standards and Technology (NIST), NIST SRM 610 and NIST SRM 612, have been shown to be homogeneous and are spiked with up to sixty one trace elements at nominal concentrations of 500 μg g-1 and 50 μg g-1 respectively. These samples (supplied as 3 mm wafers) are equivalent to NIST SRM 611 and NIST SRM 613 respectively (which are supplied as 1 mm wafers) and are becoming more widely used as potential microanalytical reference materials. NIST however, only certifies up to eight elements in these glasses. Here we have compiled concentration data from approximately sixty published works for both glasses, and have produced new analyses from our laboratories. Compilations are presented for the matrix composition of these glasses and for fifty eight trace elements. The trace element data includes all available new and published data, and summaries present the overall average and standard deviation, the range, median, geometric mean and a preferred average (which excludes all data outside ± one standard deviation of the overall average). For the elements which have been certified, there is a good agreement between the compiled averages and the NIST data. This compilation is designed to provide useful new working values for these reference materials.     

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

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

地球化学与环境样品分析标准物质和GeoReM数据库

在地球化学和环境样品分析中,标准物质发挥着越来越重要的作用。尽管通常要求分析者必须提供量值溯源的测量过程的信息;但大多数论著都未给出标准物质的数据。文章强调标准物质在地球化学分析工作中的重要性,同时将地球化学与环境样品分析标准物质数据库GeoReM介绍给中国的地质分析工作者。GeoReM数据库收录了1880个地球化学和环境样品分析标准物质的定值数据、汇编数据、分析数据及其他相关信息,其中包括156个由中国制备的标准物质的数据。GeoReM数据库还给出了所收录标准物质推荐使用的首选值及其不确定度。尽管这些首选值大多都不是按照国际标准化组织的有关规定而确定的,但是它们的置信度高,因而被广泛应用于仪器校准和分析数据的质量监控。文章还指出要将中国研制的、发表在中文期刊上的标准物质也收录到GeoReM数据库中,这对于促进中国的相关研究,增加国际认可度具有重要意义。     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

The Reliability of Assigned Values from the GeoPT Proficiency Testing Programme from an Evaluation of Data for Six Test Materials that have been Characterised as Certified Reference Materials

Assigned values derived from the GeoPT proficiency testing programme were compared with certified values for six certified reference materials that have been used as test materials in the GeoPT programme. Statistical analysis showed that there were few significant differences between these sets of data and that these differences had no significant impact on the GeoPT assessment when fitness‐for‐purpose criteria were taken into account.     

Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

Homogeneity testing of microanalytical reference materials by electron probe microanalysis (EPMA)

Homogeneity testing of candidate reference materials requires distinguishing the effects of measurement uncertainty of the analytical method from true compositional variations within the material. Many in situ microanalytical techniques do not allow classical ANOVA homogeneity testing due to the infeasibility of truly replicated analyses on the same analysis volume. This also applies to the analysis of beam-sensitive and light element-bearing materials by electron probe microanalysis (EPMA). This reality has led me to reconsider the homogeneity index approach used in the testing of microanalytical reference materials by EPMA. Based on statistical considerations, I show that the homogeneity index is suitable for statistical significance testing using F and chi-squared statistics and allows estimating the contribution of compositional heterogeneity to the total uncertainty budget of the referenced values. However, there are problems of bias and masking of small compositional variations by measurement uncertainty. This contribution shows the strong impact of the total number of measurements on the resolution of a microanalytical homogeneity study and discusses how to quantify the relative contribution of heterogeneity to the total uncertainty budget. I present an example of EPMA to illustrate this approach and show some pitfalls and limitations in its application.     

Reference samples for use in analytical geochemistry: their availability, preparation, and appropriate use

A large number of certified and other reference samples are available for use in analytical geochemistry. Certified materials are preferred, but of much more limited availability than other reference samples for most geochemical applications. The availability of rock, sediment, soil, water, and plant reference samples is outlined; ore and mineral separate reference samples are not included in the discussion. The preparation of these materials, including the establishment of certified or recommended concentrations, is then reviewed. It is shown that comparable quality can be achieved for both certified and recommended concentrations, though it has not always been achieved in the past. Finally, the most appropriate ways to use reference samples in quality control and instrumental calibration are discussed.     

The GeoPT Proficiency Testing Programme as a Scheme for the Certification of Geological Reference Materials

ISO Guide 35:2017 provides, for the first time, an alternative way of characterising certified reference materials using proficiency testing. In this paper, the properties of assigned values derived from the well‐established GeoPT proficiency testing scheme are examined. This scheme, designed for laboratories that undertake the routine analysis of silicate rocks and related materials, routinely has over 100 participants contributing results. Following a detailed assessment of the metrological properties of GeoPT assigned values in relation to Guide 35 recommendations, it is demonstrated that these values may be regarded as certified values, provided a number of criteria are met. These criteria include the following: a demonstration of sufficient homogeneity of the candidate CRM; circulation, when judged to be appropriate, of an established matrix‐matched CRM for co‐analysis in that round; the robust statistical analysis of data sets using GeoPT established criteria; a decision whether assigning a value is justified (including a requirement of a minimum of fifteen valid results); and an expert group to manage the certification and the maintenance of appropriate records. In summary, the GeoPT proficiency testing scheme, subject to the arrangements summarised above, is considered to be competent for the certification of geological reference materials.     

MAJOR AND TRACE ELEMENT DETERMINATIONS ON NIST GLASS STANDARD REFERENCE MATERIALS 611, 612, 614 AND 1834 BY INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY

We report on the major and trace element composition and homogeneity of NIST (National Institute of Standards and Technology) glass standard reference materials 611, 612, 614, and 1834 for use as microanalytical trace element standards in laser ablation-inductively coupled plasma-mass spectrometry. The four analyzed NIST glasses were not designed as microanalytical standards, but their availability and careful preparation made them obvious candidates. Our data indicate that NIST 1834 is inhomogeneous on a scale of 100 mg with respect to several trace elements. Within analytical uncertainty, NIST 611, 612, and 614 are apparently homogeneous.     

光石沟晶质铀矿:一种潜在的铀矿物电子探针定量分析标准样品

电子探针定量分析是采用元素A在待测样品中的特征X射线强度与标准样品中元素A特征X射线强度相比较而进行的,要实现未知样品的元素定量分析必须要具有相应的标准样品,目前可用于铀元素分析的电子探针分析标准样品极少,且缺乏与天然矿物成分、结构近似的标准样品。国际和国内已经制定了电子探针标准物质研制的规范(GB/T 4930—2008/ISO14595:2003),按该规范规定的方法研究了产于陕西光石沟铀矿床的晶质铀矿,结果表明:这些晶质铀矿晶形发育好,颗粒大,具备良好的纯度、均匀性和稳定性。随机选择30个颗粒进行均匀性检测,UO₂和PbO在95%的置信区间的平均浓度不确定度分别为0.275%和0.060%,具备非常好的均匀性;该晶质铀矿在电子探针电子束长时间(如360s)轰击下和在自然条件下存放,均具有良好的稳定性;采用五家实验室化学分析定值方法确定了该晶质铀矿的化学成分,并计算了不确定度,主量元素UO₂为(86.80±0.36)%,PbO为(4.80±0.07)%,其他元素也给出了参考值。综合以上研究结果:产于光石沟铀矿床的晶质铀矿满足GB/T 4930—2008关于电子探针定量分析标准样品的各项判据,是一个潜在的适用于铀矿物化学成分电子探针定量分析使用的天然矿物标准样品。     

In situ Lu–Hf phosphate geochronology: Progress towards a new tool for space exploration

Geochronology is fundamental to understanding planetary evolution. However, as space exploration continues to expand, traditional dating methods, involving complex laboratory processes, are generally not realistic for unmanned space applications. Campaign-style planetary exploration missions require dating methods that can (1) rapidly resolve age information on small samples, (2) be applied to minerals common in mafic rocks, and (3) be based on technologies that could be installed on future rover systems. We demonstrate the application of rapid in situ microanalytical Lu–Hf phosphate geochronology using samples of pallasite meteorites, which are representative examples of the deep interiors of differentiated planetoids that are generally difficult to date. Individual pallasites were dated by laser ablation tandem mass-spectrometry (LA-ICP-MS/MS), demonstrating a rapid novel method for exploring planetary evolution. Derived formation ages for individual pallasites agree with traditional methods and have <2% uncertainty, opening an avenue of opportunity for remote micro-analytical space exploration.     

New ID-TIMS, ICP-MS and SIMS Data on the Trace Element Composition and Homogeneity of NIST Certified Reference Material SRM 610-611

We present new concentration data for twenty four lithophile trace elements in NIST certified reference material glasses SRM 610-SRM 611 in support of their use in microanalytical techniques. The data were obtained by solution ICP-MS and isotope dilution TIMS analysis of two different sample wafers. An overall assessment of these new results, also taking into account ion probe studies that have been published in the literature, shows that these wafers can be considered to be homogeneous. Therefore, individually analysed wafers are believed to be representative of the entire batch of the SRM 610-611 glasses. Possible exceptions are the alkali metals (and a few volatile or non-lithophile trace elements). The analysed concentrations range between 370 μg g⁻¹ (Cs) and 500 μg g⁻¹ (Sr) and agree well with published values. On the basis of our new data and data recently published in the literature we propose "preferred average" values for the elements studied. These values are, within a few percent, identical to those proposed by other workers.     

Chemical Characterisation of NIST Silicate Glass Certified Reference Material SRM 610 by ICP-MS, TIMS, LIMS, SSMS, INAA, AAS and PIXE

National Institute of Science and Technology (NIST) silicate glass SRM 610 is widely used as a certified reference material for various micro-analytical techniques such as SIMS or laser ablation ICP-MS. SRM 610 has been nominally doped with sixty one trace elements at the 500 μg g⁻¹ level, but certified concentration data exist for only a few of these elements. This study reports concentration data for fifty nine trace elements obtained by ICP-MS, SSMS, LIMS, TIMS, INAA, AAS, and PIXE analyses of two different SRM 610 wafers. Most elements fall within a 10% band around a median value of about 440 μg g⁻¹. The REE concentrations are shown to be constant to 3% (1 σ), thus emphasizing the value of SRM 610 as a reference material for REE analyses.
Comparison of our values with published data suggests that different SRM 610 wafers are, within errors, chemically identical for most elements. Exceptions to this general rule appear to be restricted to elements which were partly lost during the production of the glass, e.g. Ag and Br. On the basis of six independent determinations of Rb concentrations, which are systematically lower by a few percent than the reported NIST value, we argue that the certified Rb concentration may not be representative for all distributed SRM 610 wafers.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

Comparison of Synchrotron Radiation X-Ray Fluorescence with Conventional Techniques for the Analysis of Sedimentary Samples

A comparison is made of elemental analyses of sediment samples (lake bottom sediments and sediments from the petroliferous Bazhenovka Formation) by five competitive methods (synchrotron radiation X-ray fluorescence (SR-XRF), INAA, ICP-MS, AAS and traditional XRF). The object of this study was to identify the most suitable analytical techniques for applications in sedimentary geochemistry. Advantages and shortcomings of the five techniques were considered with respect to applications related to studies of palaeo-climate changes recorded in sedimentary cores from Lake Baikal and the geochemical stratigraphy of the Bazhenovka Formation, which is rich in organic material. We have concluded that SR-XRF was the best technique for producing extensive analytical data series, from the point of view of its speed, ease of application, cost, non-destructive nature and sensitivity, which allowed for the simultaneous determination of more than twenty elements of geochemical interest in small samples of sediments. An additional benefit of the method was demonstrated when used for the independent certification of geological reference materials. International reference samples BIL-1 and SDO-1 were certified by means of this method without use of reference materials. Analyses were based on the physics of the theory of energy transport.     

Report on the 2007 Recertification of the Certified Reference Materials GAS (Serpentinite) and OShBO (Alkaline Granite)

A report is presented on the recertification of two certified reference materials (CRMs) initially prepared and certified by the Central Geological Laboratory of Mongolia (CGL), namely serpentinite GAS and alkaline granite OShBO. Subsequent work done in collaboration with the International Association of Geoanalysts (IAG) followed the International Organisation for Standardisation (ISO) guidelines for certification (ISO Guide 35, 2006) more closely than had been possible originally. The certification protocol followed was that of the International Association of Geoanalysts (IAG). The recertification added to the number of elements that were certified for OShBO (from 21 to 30), but not for GAS (decreased from 15 to 12) because of the greater analytical difficulties posed by that sample matrix in meeting the more stringent metrological requirements for recertification. Further, the uncertainties for these values were established in accordance with the Guide to Measurement Uncertainty ; individual contributions of heterogeneity and bias are reported as appropriate for each of the certified constituents. Traceability of the certified values was demonstrated to the greatest possible extent, based on concurrent analyses of the matrix-matched existing CRMs, SW and GM, by all participating laboratories. The materials are now available from the CGL for use by laboratories in controlling data quality when analysing materials of similar matrices.