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1.
Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).  相似文献   

2.
We present a new method for the decomposition of silicate rocks by flux‐free fusion in preparation for whole‐rock trace element determination (Sc, Rb, Sr, Y, Zr, Nb, Cs, Ba, rare earth elements and Hf) that is especially applicable to zircon‐bearing felsic rocks. The method was verified by analyses of RMs of mafic (JB‐1a, JB‐2, JGb‐1) and felsic rocks (JG‐3, JR‐3, JSd‐1, GSP‐2, G‐2). Pellets of powdered sample (up to 500 mg) without flux were weighed and placed in a clean platinum crucible. The samples were then fused in a Siliconit® tube furnace and quenched to room temperature. The optimum condition for the fusion of granitic rock was determined to be heating for 2–3 min at 1600 °C. The fused glass in the platinum crucible after heating was decomposed using HF and HClO4 in a Teflon® beaker. Decomposed and diluted sample solutions were analysed using a quadrupole inductively coupled plasma‐mass spectrometer. Replicate analyses (n = 4 or 5) of the RMs revealed that analytical uncertainties were generally < 3% for all elements except Zr and Hf (～ 6%) in JG‐3. These higher uncertainties may be attributed to sample heterogeneity. Our analytical results for the RMs agreed well with recommended concentrations and recently published concentrations, indicating complete decomposition of our rock samples during fusion.  相似文献   

3.
The mercury content of 116 reference materials (RMs) from ten international organisations was determined in this study, which focused on variability within and between batches of RMs. Direct mercury analysis (DMA) was applied to RMs having Hg contents between 1 and 6300 ng g?1 and provided good precision and accuracy. Accuracy was demonstrated by the agreement of our results with certified values, while replicates were made to establish the precision. Low within‐batch variability was noted, with precision from 0.1 to 23% (n = 3–5) apparently depending on Hg content and homogeneity, whereas systematic offsets were detected among several batches. Thanks to the analysis of different batches; the homogeneity or heterogeneity of several RMs was shown, and thus, suitable RMs for quality control for Hg determinations could be recommended.  相似文献   

4.
Geochemical studies of geological samples require the precise determination of their major and trace element contents and, when measured, of their isotopic compositions. It is now commonly accepted that the accuracy and precision of geochemical analyses are best estimated by the concomitant analysis of international reference materials run as unknown samples. Although the composition of a wide selection of basalts is relatively well constrained, this is far from being the case for sedimentary materials. We present here a comprehensive set of major and trace element data as well as Nd, Hf, Sr and Pb isotopic compositions for thirteen commonly used international reference materials – eight magmatic rocks (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) and five sediments (JLk‐1, JSd‐1, JSd‐2, JSd‐3, LKSD‐1). We determined the concentrations of over forty elements in the magmatic rocks together with Sr, Nd, Hf and Pb isotopic compositions. Our trace element results were both accurate (difference ≤ 3%) and precise (reproducibility at 1s ≤ 3%) and the isotopic results were very similar to other published values. In contrast, we observed a significant chemical and isotopic variability in the sedimentary materials, which we attribute to mineral heterogeneities in the powders. Despite the limitation imposed by this heterogeneity, our work presents a complete set of data determined with a precision not yet achieved in the literature for sedimentary material. We also provide the first Nd, Hf and Pb isotopic measurements for the five sediments, which are commonly used by the geochemical community. Our study of both basalt and sediment reference materials represents a comprehensive and self‐consistent set of geochemical data and can therefore be considered as a reference database for the community.  相似文献   

5.
The 18 Chinese geochemical standard reference samples GSD 9-12 (stream sediments), GSS 1-8 (soils) and GSR 1-6 (rocks) were prepared after GSD 1-8 (stream sediments) for even wider and increasing needs of geology, exploration geochemistry and geochemical analysis. Usable values of 41 trace, minor and major elements of the 18 samples were published in 1984. In the following two years, efforts were concentrated on the determination of other elements, most of which are more difficult to determine accurately and hence not many data were available in the literature. At the same time, additional data on the 41 elements already evaluated were also submitted. In all, 155 234 results were available along with the 35 284 analytical data submitted. The processing of samples, the examination of sample homogeneity, the plan of collaborative analysis of the samples, and the criteria for defining the recommended values are described. The recommended or reference values of the 72 constituents, to-gether with the 35 284 analytical data of the 18 samples are published in this paper.  相似文献   

6.
Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l?1 for both F and Cl and 10 ng l?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg?1 for F and Cl and 2 μg kg?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg?1 for F and Cl, 100 μg kg?1 for Br and 25 μg kg?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.  相似文献   

7.
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8.
Manganese‐ and iron‐rich materials are of major geoscientific and economic interest, many of which contain microscopic features that provide valuable information. To obtain accurate results, a homogeneous microanalytical reference material for calibration is needed. Several researchers have used the Mn‐ and Fe‐rich RMs, JMn‐1, NOD‐A‐1, NOD‐P‐1 and FeMn‐1, for this purpose; therefore, they were tested in this study to determine their suitability for microanalysis. Their homogeneity was investigated by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) with two different types of lasers (nano‐ and femtosecond), with spot and line scan analyses and with different operating parameters, such as spot size, pulse repetition rate and fluence. As the established manganese nodule RMs revealed inhomogeneities for picogram to microgram test portions, we also investigated the new synthetic Fe‐ and Mn‐rich RM, FeMnOx‐1. FeMnOx‐1 was found to be homogeneous for large (ø 40 μm: 2% RSD repeatability) and small (ø 8–10 μm: 10% RSD repeatability) spot sizes. This homogeneity is in the range of the homogeneous NIST SRM 610 and GSE‐1G reference glasses. Furthermore, FeMnOx‐1 revealed a large‐scale homogeneity within uncertainties of a few per cent, using test portions in the ng range, when measuring four individual mounts of this material.  相似文献   

9.
Over 3 million samples were collected from southern China at a density of 1–2 stream sediment samples per square kilometre as part of the Regional Geochemistry National Reconnaissance (RGNR) programme of China initiated in the late 1970s. Approximately 5244 composite samples of stream sediments from twelve provinces of southern China were prepared from the original RGNR samples collected from a territory with an area of 2300000 km2 at a density of one composite sample per 1:50000 map sheet (about 400 km2). Seventy‐six elements were determined by the geoanalysis laboratory of Henan Province (platinum‐group elements) and by the Institute of Geophysical and Geochemical Exploration (IGGE) laboratory for the remainder. Internal quality and external quality control methods were applied to ensure that the analytical data were comparable. Statistics were used to derive the mean and background values and indicate the average concentrations of the seventy‐six elements. Comparisons were made against the mean values obtained from stream sediments, floodplain sediments, overall sediments and overall soils of the entire territory of China. The concentrations of Hg, Cd, rare earth elements and 24 other elements were higher than their background for the whole of China. In contrast, the concentration of Na2O, CaO, Ba and Sr were lower in the stream sediments in southern China than their whole China background.  相似文献   

10.
Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of 187Os/188Os. All concentrations were obtained from the same aliquot after HCl‐HNO3 digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.  相似文献   

11.
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.  相似文献   

12.
Pressed powder pellets and fused beads or glass disks are routinely used in X‐ray fluorescence spectrometry for the determination of major and trace elements, respectively, in geological materials. In order to evaluate the performance of these two sample preparation methods, we determined Ni and Cr concentrations of fourteen RMs from Japan, France and South Africa, and eighty‐five igneous and three sedimentary rock samples from Mexico in both powder pellets and glass beads. We also computed new values of statistical parameters for RMs from an outlier‐based multiple‐test method and compared them with the literature mean and confidence limit values. The results showed that the multiple‐test method provided more reliable central tendency and dispersion parameters for RMs than those obtained previously from the two or three standard deviation method, or from robust methods. The powder pellet and fused bead sample preparation methods provided consistent results for Ni and Cr at concentration levels > 50 μg g?1 in this application; for lower concentration levels, however, these methods showed somewhat greater differences. For quantitative comparisons, both ordinary and weighted least‐squares linear regression models were used to show that the two sample preparation methods provided generally unbiased results.  相似文献   

13.
In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.  相似文献   

14.
Eighteen Chinese geologic reference samples (stream sediments GSD 9–12, soils GSS 1–8, and rocks GSR 1–6) were analyzed by wavelength-dispersive X-ray fluorescence spectrometry (XRFS) for major elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P, and by energy-dispersive XRFS for trace elements Ba, Ce, Cr, Cu, La, Nb, Ni, Rb, Sr, Y, Zn, and Zr. Major element analysis followed gravimetric determination of loss on ignition, and samples were prepared by fusion with Li2B4O7. A loose-powder sample preparation was used for trace element analysis. The results reported in this study are, generally, in good agreement with concentrations compiled by X. Xie of the Geochemical Standard Reference Group and the Institute of Geophysical and Geochemical Exploration (People's Republic of China).  相似文献   

15.
We report high‐precision iron isotopic data for twenty‐two commercially available geological reference materials, including silicates, carbonatite, shale, carbonate and clay. Accuracy was checked by analyses of synthetic solutions with known Fe isotopic compositions but different matrices ranging from felsic to ultramafic igneous rocks, high Ca and low Fe limestone, to samples enriched in transition group elements (e.g., Cu, Co and Ni). Analyses over a 2‐year period of these synthetic samples and pure Fe solutions that were processed through the whole chemistry procedure yielded an average δ56Fe value of ?0.001 ± 0.025‰ (2s, n = 74), identical to the expected true value of 0. This demonstrates a long‐term reproducibility and accuracy of < 0.03‰ for determination of 56Fe/54Fe ratios. Reproducibility and accuracy were further confirmed by replicate measurements of the twenty‐two RMs, which yielded results that perfectly match the mean values of published data within quoted uncertainties. New recommended values and associated uncertainties are presented for interlaboratory calibration in the future.  相似文献   

16.
New Series of Rock and Sediment Geochemical Reference Materials   总被引：1，自引：0，他引：1  
Certified or reference values for sixty six to sixty seven elements and element oxides are given for geochemical reference materials recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), including limestone (GSR-13), granitic gneiss (GSR-14), amphibolite (GSR-15), lake sediment (GSS-9) and stream sediments (GSD-1a, GSD-13, GSD-14). These samples supplement the GSR 1-6, GSD1-8 and GSD 9-12 certified reference materials already prepared and characterized by the IGGE.  相似文献   

17.
In order to meet the needs of geochemical mapping and geochemical exploration, 125 geochemical reference materials have been successively prepared by the Institute of Geophysical and Geochemical Exploration (IGGE) since 1978. They include certified reference materials of stream sediments (GSD1-14), soils (GSS1-16; ASA 1–6, for analysis of available elements), various rocks (GSR1-6, GSR13-15), biological material (GSV1-4 and GSB 1–10), synthetic silicates (GSES I 1–11) and limestones (GSES II 1–9 for spectral analysis). They also include geochemical reference materials for ore analysis: Cu-Pb-Zn ores (GSO1-4), Cu-Pb-Zn concentrates (GSO5-7), platinum-group element (PGE) ores (GPt5-6 and GPt9-10), silver ores (GAg1-6) and geochemical reference materials for Au (GAu8-14) and PGE determination (GPt1-4, and GPt7-8). A multi-laboratory collaborative analysis scheme was adopted in the certification procedure of the IGGE. Dozens of competent laboratories with hundreds of senior analysts in China participated in the certification analysis. These samples have been supplied to more than thirty countries and more than 4000 customers from national industrial, agricultural, environmental, scientific and educational fields. Most of the geochemical reference materials are used for the calibration of measuring apparatus, evaluation of analytical methods, certification studies, quality control and laboratory accreditation programmes.  相似文献   

18.
Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO3 results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF3 precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH4HF2 open vessel digestion and (c) NH4F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF3 and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH4HF2 or NH4F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO3, the white precipitates and the semi‐transparent gels present in the NH4HF2 and NH4F digestion methods could be efficiently dissolved by evaporation with HClO4. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.  相似文献   

19.
A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ30Si and δ29Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ30Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ29Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ30Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ30Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.  相似文献   

20.
Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g?1, SiO2 from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.  相似文献   

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