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BACKGROUND Sepiolite is a very important non-metallic mineral, which is widely used in aviation, animal husbandry, the chemical industry, environmental protection and other fields. Sepiolite is in great demand and needs a lot of analysis and testing. However, the existing sepiolite reference materials are inadequate and do not satisfy the needs of sepiolite composition analysis. Furthermore, there are no sepiolite reference materials in China, making it necessary to develop one. OBJECTIVES To prepare a reference material for composition analysis of sepiolite whose certified value components cover as many elements as possible. METHODS Sepiolite samples were collected from Xiangtan, Hunan Province. The samples were subjected to primary crushing, coarse-grain sieving, inactivation, fine grinding and fine grain sieving. After passing the initial inspection, samples were bottled and numbered. Random samples were taken for homogeneity test, stability test. 24 components were selected for homogeneity and stability test. RESULTS The results showed that the RSD of 20 components were less than 3%, and the F value of the variance test was less than the critical value of the list[F0.05(29, 60)=1.65], indicating that the homogeneity of the reference material was good. During the investigation period, the contents of 24 components had no significant change, indicating that the standard material was stable. Nine laboratories cooperated with traditional chemical analysis methods and modern instrumental analysis methods to determine the value. The final values were 63 components, covering major, trace and all rare earth elements. The contents of characteristic components MgO and LOI were 18% and 8.55%, respectively. These two components form a certain ladder with the existing reference materials, which can better satisfy the requirements of sepiolite composition analysis. CONCLUSIONS The developed sepiolite reference material can be used as the quality control standards for geological prospecting, geochemical investigation and testing of geological and mineral products, as well as for other industries to analyze similar materials. Moreover, in the process of developing the reference material, improvements and developments to the new methods will provide technical support for the subsequent development of the sepiolite reference material.

BACKGROUND Tungsten molybdenum ores are strategic mineral resources. China is a large producer and consumer of tungsten and molybdenum ore. Accurate and efficient analysis of tungsten and molybdenum and its associated beneficial and harmful elements is of great significance for the evaluation and comprehensive utilization of tungsten and molybdenum ore deposits. Acid dissolution and alkali fusion are the general digestion methods in tungsten molybdenum ore analysis. However, the acid solution method cannot be used to overcome the hydrolysis problem when treating samples with high content of tungsten and molybdenum, whereas the alkali fusion method such as sodium peroxide and sodium hydroxide usually introduces a large content of alkali metals, so the determination of potassium and sodium cannot be finished. OBJECTIVES To find an efficient method for the determination of tungsten, molybdenum and 11 other elements in tungsten molybdenum ore. METHODS Lithium metaborate melting-tartaric acid ultrasonic leaching and inductively coupled plasma-optical emission spectrometry (ICP-OES) was used for the simultaneous determination of tungsten, molybdenum, copper, lead, zinc, aluminum, iron, calcium, magnesium, titanium, manganese, potassium and sodium in tungsten-molybdenum ore. The sample was completely digested by lithium metaborate fusion. No other elements were introduced except for B and Li. Tartaric acid was used to inhibit the hydrolysis of tungsten and molybdenum. Ultrasonic leaching speeds up the dissolution of the frit. RESULTS The experiment optimized the analysis spectrum and observation method of each element, compared the amount of flux and instrument conditions to obtain the best conditions, and used the matrix matching method to draw a standard curve to eliminate the influence of the matrix effect. The linear correlation coefficient of the standard curve of each element was greater than 0.9990, the detection limit of the method was 1.34-46.2μg/g, the relative error of measured results was 0.14%-8.7%, the relative standard deviation (RSD, n=10) of the measured results was 1.4%-7.6%. CONCLUSIONS This method can accurately and efficiently complete the simultaneous determination of multiple elements in tungsten and molybdenum ore samples.

BACKGROUND Sepiolite is a widely used fibrous magnesium-rich silicate clay mineral. Sepiolite is mainly composed of silicon and magnesium, with minor aluminum, potassium, sodium and other impurities. Determination of the major element of sepiolite usually adopts the classical chemical analytical method. After the alkali melting treatment, the sample is determined by volumetric method, photometry and atomic absorption spectrometry, which is inefficient and time-consuming. Moreover, potassium and sodium cannot be simultaneously determined. OBJECTIVES To find an efficient method for the determination of seven major elements in sepiolite. METHODS The samples were digested by hydrofluoric acid, nitric acid, and perchloric acid. Contents of major elements such as Al2O3 were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). The dosage of hydrofluoric acid was optimized. The analytical spectral lines were Al 396.153nm, Ti 334.940nm, K 766.490nm, Na 589.592nm, Ca 422.673nm, Mg 285.213nm and Fe 238.204nm, and elements were determined by axial observation. The content of magnesium in sepiolite was high, and there was a certain matrix effect during ICP-OES analysis. A series of high magnesium mixed standard solutions were prepared to match the matrix. RESULTS The linear correlation coefficient of the standard curve of each element was greater than 0.9990, the detection limits of the method were 0.53-3.25μg/g, the relative standard deviations (RSD, n=10) of the measured results were 0.66%-5.65%, and the recoveries of each element were 95.3%-108.5%. CONCLUSIONS Acid dissolution is easy to operate compared with the alkali fusion method. The results are consistent with those obtained by classical chemical analytical methods and thus meet the analytical requirements of sepiolite samples.

BACKGROUND The dissolution of antimony ore by aqua regia is often incomplete and antimony is easy to hydrolyze in the process of extraction, which leads to inaccurate results. Although atomic fluorescence spectrometry has been widely used in the determination of antimony, it is easy to introduce large dilution error for the determination of high-content antimony (>5%) due to the narrow linear range of the instrument. OBJECTIVES To solve the problem of incomplete dissolution of antimony ores and hydrolysis of antimony in the extraction process, and establish a new method with wider linear range for determination of antimony in antimony ores. METHODS Based on inductively coupled plasma-optical emission spectrometry (ICP-OES), the antimony ore was fully dissolved by hydrofluoric acid, nitric acid and hydrochloric acid, and the hydrolysis of antimony was fully inhibited by the complexation of tartaric acid and antimony. RESULTS The results showed that the solution of the mixed hydrofluoric acid, nitric acid and hydrochloric acid can effectively decompose the silicate components in antimony ores, which can make antimony ores dissolve more completely. The determination result of antimony was better than that of aqua regia, and the detection limit was lower (1.10μg/g). The determination result of antimony obtained by the mixed extraction method of tartaric acid and hydrochloric acid was better than that of aqua regia. The precision of the method was 0.11%-1.11%, which was more stable than that of hydrochloric acid or aqua regia. By using an inductively coupled plasma emission spectrometer, a wider linear range can be obtained by optimizing the spectrum of antimony element analysis, therefore realizing the accurate determination of high-content antimony. CONCLUSIONS This method can dissolve antimony ore quickly and effectively, and avoid the hydrolysis of antimony. The method is confirmed by national first grade standard materials, and the result is in agreement with the certified values. This method is suitable for the analysis of 0.7%-40% antimony in antimony ores.

BACKGROUND The sampling weight can be as low as milligram level when the contents of rare earth elements in rock and soil samples are determined by inductively coupled plasma-mass spectrometry (ICP-MS). However, the size of 200 mesh samples requires 100mg to ensure representativeness, which makes it difficult for ICP-MS to make full use of its advantages of high sensitivity and small sampling volume. OBJECTIVES To establish the method for the determination of rare earth elements in ultra-fine rock and soil samples by ICP-MS with microwave digestion. METHODS A method was developed for the determination of rare earth elements in ultra-fine rock and soil samples by ICP-MS with microwave digestion. The ultra-fine rock and soil samples were prepared by the planetary superfine pulverizing machine with wet grinding. Some parameters influencing the preparation of ultra-fine rock and soil samples, including grinding method, grinding time and the proportion of grinding balls were optimized. Microwave digestion of ultrafine-grained rock and soil samples in a nitric acid-hydrofluoric acid-hydrogen peroxide solution system, the sampling amount was reduced to 5mg, the total acid amount was reduced to 0.25mL and the digestion time was reduced to 25 minutes. RESULTS The results indicated that the samples were best refined when the wet-milling was adopted with ethanol as a dispersant and the milling time was 10 minutes and 15 minutes for 200 mesh soil and rock samples, respectively. The material ratios were 7g materials, 500 grinding balls, 45mL dispersants for the preparation of ultra-fine soil samples, whereas 5g materials, 500 grinding balls, 45mL dispersants for the preparation of ultra-fine rock samples. The particle size distribution D95 of soil standard substance GBW07404 and GBW07447 can be as low as 7.51μm and 7.05μm, and the D95 of rock standard substance GBW07104 and GBW07121 can be 8.42μm and 8.30μm under the optimized conditions. Microwave digestion of ultrafine-grained rock sample GBW07104 in a nitric acid-hydrofluoric acid-hydrogen peroxide solution system, the sampling amount was reduced to 5mg, the total acid amount was reduced to 0.25mL, the digestion time was reduced to 25 minutes, and the measured value of rare earth elements was consistent with the certified value with the relative standard deviation is between 1.64% and 5.21%. CONCLUSIONS This method was used for the detection of rare earth elements in other ultra-fine standard materials (GBW07404, GBW07447 and GBW07121), which yielded the relative standard deviation of 0.17%-6.60%, meeting the first criterion of Geology and Minerals Laboratory Testing Quality Management Standards.

BACKGROUND The fluorine content in lithium mica is very high (1.36% to 8.71%), and the leaching rate of lithium during roasting lithium mica minerals decreases gradually with the increase of fluorine content. With increased defluorination of lithium mica, the leaching rate of lithium is also increased accordingly. Therefore, accurate determination of fluorine in lithium mica and control of fluorine content can provide a basis for determining the process conditions, equipment parameters and cost of roasting process. At present, the most common used method for determination of fluorine is the ion selective electrode method. However, the process is complex, the analysis time is long and the blank value is high. X-ray Fluorescence Spectrometry (XRF) is a green and pollution-free method, which is simple, fast and accurate. OBJECTIVES To determine the fluorine content in lithium mica. METHODS The fluorine content in lithium mica was determined by XRF with pressed-powder pellets. The working curve was made from standard material lithium ore and manually prepared calibration material, and the experience coefficient was used to correct the matrix effect and spectral interference. RESULTS The method precision(RSD, n=10) is 1.03% and the detection limit of fluorine is 46±4μg/g. Analytical results of samples synthesized from standard samples acquired by this method are in good agreement with theoretical values. It is demonstrated by actual samples that the determination results are consistent with those of the ion selective electrode method. CONCLUSIONS This method is suitable for determining fluorine in lithium mica with contents ranging from 0.68% to 9.14%.

BACKGROUND Sepiolite is a fibrous hydrous magnesium rich silicate clay mineral with the content of rare earth elements between 1×10-7 and 1×10-5. There is no national standard method for the determination of rare earth elements in sepiolite. Determination of rare earth elements in rocks commonly uses ICP-MS. Sample pretreatments generally use closed digestion and alkaline fusion, but these two treatments are time consuming and inefficient. OBJECTIVES To find an efficient dissolution method for the determination of 15 rare earth elements in sepiolite. METHODS By comparing three sample pretreatment methods of nitrate hydrofluoric acid hydrogen peroxide, nitric acid-hydrofluoric acid and nitric-acid hydrogen peroxide, the nitric acid-hydrofluoric acid solution system was selected. Microwave digestion was carried out and the hydrofluoric acid was driven off to avoid the formation of insoluble fluorides from the hydrofluoric acid. The content of 15 rare earth elements was determined by ICP-MS. RESULTS Due to the high content of magnesium in sepiolite, two internal standards of 103Rh and 185Re are selected to compensate for the drift of analytical signals and to correct matrix effects. The recoveries of the method range from 91.2% to 110.9%. The detection limits are 0.002-0.011 μg/L, and the precisions are 0.81%-2.79%. CONCLUSIONS The result of this method is in good agreement with that of the closed acid-digestion ICP-MS method, and with a small amount of acid (7 mL), high digestion efficiency (1 h), and a lower detection limit.

BACKGROUND With advantages of small sample quantity, less acid, and low blank, high-pressure closed digestion-Inductively Coupled Plasma-Mass Spectrometry became the main method in the determination of rare earth elements. However, the composition of manganese ore is complex with varying manganese contents and different valence states of Mn, often with accompanying (co)producing metals and other impurities. The ore is difficult to digest completely using conventional acid-soluble systems, resulting in inaccurate ICP-MS analytical results. OBJECTIVES To optimize the acid-solution system condition of the high-pressure closed digestion method, in order to completely and effectively digest the manganese ore with complex components and improve the accuracy of the results. METHODS Three standards GBW07261, GBW07263, GBW07266 and an unknown sample of manganese ore were digested using three different acid-solution systems of high-pressure closed digestion:Hydrofluoric acid-nitric acid closed digestion, extracted with nitric acid (Method 1); Hydrofluoric acid-nitric acid-hydrogen peroxide closed digestion, redissolved with nitric acid-hydrogen peroxide, extracted with nitric acid (Method 2); Hydrofluoric acid-nitric acid closed digestion, redissolved with hydrochloric acid, extracted with nitric acid (Method 3). The contents of rare-earth elements were then determined by ICP-MS. RESULTS Methods 2 and Methods 3 can completely digest manganese ore samples. The results of rare-earth elements by ICP-MS were similar, and were consistent with the results of conventional sodium peroxide fusion. However, during the experimental process, for samples with high manganese content, Method 3 required repeated additions of hydrochloric acid before the samples were completely digested, whereas Method 2 need only one repeat. The precision of Method 2 was 0.96%-2.68%, and the recovery was 95.0%-107.0%. CONCLUSIONS For different manganese ore samples, Method 2 can completely digest the samples. The determination of rare earth elements was reliable by ICP-MS. Method 2 was the most suitable sample digestion method for the determination of rare earth elements in manganese ores.

Alpha dose matrix effect is the discrepancy of ablation rate and down-hole fractionation induced by the difference of crystal damage degree (alpha dose) between standard zircons and sample zircons. It has been proved to be the cause of systematic bias of zircon U-Pb dating by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Alpha dose is closely related to ablation rate and down-hole fractionation behaviour of zircon. The higher the alpha dose, the faster the ablation rate and more obvious is the down-hole fractionation. However, the correction of alpha dose matrix effect has received little attention thus far. In this study, Laser Raman Spectroscopy and LA-ICP-MS were used to analyze zircons from the Badaling Granitic Complex rocks. Results show that the metamictization degree is low when the actual retained alpha dose (DαP) is no more than 0.75×1018 g-1 and the matrix effect is negligible. However, when the actual retained alpha dose (DαP) is larger than 0.75×1018 g-1, metamictization degree is high and the dating results are obviously affected byalpha dose matrix effect. For this reason, U-Pb data of zircons need to be corrected using the'Age offset-DαP'empirical equation such as y=347.8×exp(0.260×10-15x). In conclusion, it was found that this is a feasible method to correct alpha dose matrix effect by using Laser Raman Spectroscopy and a full width at half maximum (FWHM)-DαP correction curve to obtain DαP values of analyzed zircons by using age deviations-DαP empiric formula to determine the systematic deviations of LA-ICP-MS.