Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Preservation of coal-waste geochemical markers in vegetation and soil on self-heating coal-waste dumps in Silesia,Poland

Occurrence and distributions of geochemical markers on vegetation and in soils covering two self-heating coal waste dumps were investigated with gas chromatography-mass spectrometry (GC–MS) and compared with those of bitumen expelled on the coal waste dump surface. Presence of biomarkers, alkyl aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and such polar compounds as phenols indicate that components of self-heating coal wastes indeed migrate to soils and plants surface and their characteristic fingerprints can be applied in passive monitoring to investigate migration of contaminants from self-heating coal wastes. Moreover, results allow to discriminate between the Upper- and Lower Silesian coal basins, notwithstanding value shifts caused by heating. Mechanisms enabling the migration of geochemical compounds into soils include mixing with weathered coal-waste material, transport in gases emitted due to self-heating and, indirectly, by deposition of biomass containing geochemical substances. Transport in gases involves mostly lighter compounds such as phenols, methylnaphthalenes, methylbiphenyls, etc. Distributions and values of geochemical ratios are related to differences in their boiling temperatures in the case of lighter compounds but preserve geochemical features in the case of heavier compounds such as pentacyclic trierpanes.     

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限(3s)为:LD(Nb)=0.08μg/g,LD(Ta)=0.04μg/g,LD(Zr)=0.5μg/g,LD(Hf)=0.04μg/g,精密度(RSD%,n=6)为:0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。     

高效液相色谱-离子阱质谱法测定海洋微藻藻粉中的8种脂溶性毒素

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS)测定海洋微藻藻粉中8种典型脂溶性毒素的分析方法。藻粉样品经超声细胞破碎后,采用超声波辅助提取法对藻毒素进行提取,用HPLC-ESI-IT-MS多反应离子监测(MRM)模式对各种毒素(包括大田软海绵酸(OA)、鳍藻毒素1(DTX-1)、扇贝毒素2(PTX-2)、虾夷扇贝毒素(YTX)、原多甲藻酸1(AZA1)原多甲藻酸2(AZA2)、罗环内酯毒素(SPX),米氏裸甲藻毒素(GYM))进行测定。8种脂溶性藻毒素均在线性范围内线性关系良好(R2均在0.991以上),检出限均介于0.085～1.315 pg之间,加标回收率在88.5%～111.4%之间,方法重复性相对标准偏差(RSD)在4.82%～10.17%范围。应用该方法对利玛原甲藻干藻粉中的毒素进行了测定,分析结果良好,说明本方法是海洋微藻藻粉中脂溶性藻毒素测定的有效方法。     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

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).     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

粉末压片-X射线荧光光谱法测定盐湖样品中的主次元素

采用粉末样品压片制样,利用波长色散X射线荧光光谱仪对盐湖样品中K、Ca、Na、Mg、Cl、SO_4~(2-)等6个主次元素(组分)含量进行测定。使用化学定值得到的样品作为人工标样,其值作为标准样品参考值,建立了X射线荧光光谱法测定盐湖样品中主次元素的方法。经验证,该分析方法的准确度完全能够满足化学分析的要求,其相对标准偏差RSD7%,分析元素结果与化学法结果的相对误差均小于5%。     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

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.     

ASTER mapping of gypsum deposits of Thumrait region of southern Oman

This study demonstrates the use of ASTER data for the mapping of gypsum deposits and associated geological formations that occurred in the Thumrait region of southern Oman. The measurement of spectra over samples of gypsum in the 1,300–2,500 nm wavelength using a PIMA spectrometer showed the presence of distinct absorptions at 1400–1600, 1750, 1940, 2,100, and 2,400 nm characteristics to O? H stretching, H₂O combinations, and S? O bending overtones and stretching, respectively. Studying the unique spectral absorption characters of gypsum samples, we developed a false color composite (FCC) and an image by decorrelation stretch using the spectral bands 7, 3, and 2 of ASTER. The results FCC showed the regions of gypsum occurrences, and the decorrelated image discriminated the gypsum occurrences from other geological formations of the area. The study of surface mineralogy of the region using the VNIR‐SWIR bands by the spectral angle mapper method showed the presence of sulfate, carbonate, and clay minerals of the geological formations in the study area. We compared the results of ASTER with the results obtained using spectral bands 12, 8, and 4 of Sentinel‐2A processed by the same methods. The study showed that the spectral bands of ASTER can be used for mapping the gypsum and associated geological formations.     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.