Mineralogical effect correction in wavelength dispersive X-ray florescence analysis of pressed powder pellets

Two methods are utilized to correct the influence of the mineralogical effect on the calibration of elements in geological samples when the pressed powder pellet method is used in wavelength dispersive X-ray fluorescence analysis. The first method involves checking of the 2θ angle for the analyzed element in each sample to correct peak shift and the second method involves replacing the peak intensity with the peak area of the analytical line, so to correct for any shape distortion of the peak. The results were compared with those obtained from the normal method. Major elements in 27 Chinese Certified Reference Materials (CRMs) of rocks, soils and sediments were calibrated with a linear regression curve without theoretical or empirical coefficients. In view of the K values, the calibrations of all 8 elements were improved by the first method and those of 6 elements were improved by the second method. Sulfur calibrations with 4 iron ore CRMs were improved with the use of both methods. The methods have been successfully applied for the analysis of the major elements in limestone ores from different resources of a cement factory.     

Radioactivity of Phosphate Ores from Karatas-Mazidag Phosphate Deposit of Turkey

The specific activities of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K in the composite samples of phosphate ores of type 1 (grey-coloured ore, with high P₂O₅ (21–35%) and low calcite content) and of type II (grey coloured calcite ore, with low P₂O₅ content (5–17%)) of Karatas-Mazidag phosphate deposit, Turkey, have been determined by gamma spectrometry together with phosphatic animal feed ingredients. The concentrations of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K were found to be up to 557, 625, 26 and 297 Bq·kg^–1, respectively. Radium equivalent activities of samples examined were calculated and compared with those given in the literature. Uranium concentration of the individual phosphate samples, from which composite samples of ores of type I and II have been prepared, were found to show an increasing trend with increasing P₂O₅ and F concentrations.     

Analysis for the rare-earth elements by neutron activation and Ge(Li) spectrometry

A procedure for analysis of 12 of the rare-earths, tested on more than a hundred samples of rocks and minerals, is described. Carrier is added for each element to be determined. Samples are fused with Na₂O₂. The rare-earths are separated as a group, then precipitated and mounted as oxalates for Ge(Li) spectrometry. Following radioassay, chemical yields for the individual rare-earths are obtained by irradiation and counting of the carrier. About two months are needed to obtain complete data for a set of four samples, but many samples are analyzed concurrently. The precision and accuracy exceed ±5 per cent for 10 of the elements in 0.1 to 0.5 g samples of common rocks.     

Distribution pattern of REE and other elements in the host rocks of the Gubrunde uranium occurrence,NE Nigeria

Prospecting for high grade uranium deposits in NE Nigeria has over the years among other reasons been handicapped by lack of adequate understanding of the elemental primary dispersion pattern associated with known occurrences in this region. Thirty six samples from a low grade uranium occurrence at Gubrunde consisting of disseminated ores and hostrocks were therefore analyzed for 38 elements by NAA, DNAA, EDXRF and flame AAS techniques. The analytical data were evaluated using multivariate statistical techniques. The results show three element groupings (associations). The first group consists of Pb, Ba, Ce, Sm (LREE), that are enriched with increasing uranium concentration in the mineralized zone and are therefore capable of serving as pathfinder elements for uranium. The second group comprising of MgO, K₂O, CaO, Na₂O and the HREE are depleted in the mineralized zone due to action of hydrothermal fluids and are indicative of altered/mineralized rocks. The third group consists of the rest bulk of elements which feature little or no significant enrichment with increasing uranium but associate with ferruginization (haematite) and possibly refractory minerals.     

Analysis of ores by simple grinding and circular thin-layer chromatography and the nichrome wire ring chamber

Summary A method for the preparation of ore solutions by grinding the ore with distilled water is developed for the analysis of minerals and ores in the field by the circular thin-layer Chromatographic technique.

---

Zusammenfassung Die Herstellung von Erzlösungen durch Mahlen des Erzes mit dest. Wasser zur Feldanalyse von Mineralen und Erzen durch Ring-Dünnschichtchromatographie wird empfohlen.

     

电感耦合等离子体质谱(ICP-MS)法测定磷矿石中的8种痕量金属元素

建立了四酸(硝酸-氢氟酸-高氯酸-硫酸)敞口分解-电感耦合等离子质谱法同时测定磷矿样品中钨、钼、铊、镉、铋、铀、钍、铬等8种微量元素的方法,结果和经典碱熔法比对,准确度满意.经过对易挥发元素、难溶元素影响的研究,选取了合适的分析同位素及采用干扰校正方程以消除质谱干扰,利用103 Rh和186 Re为内标元素,有效校正了...     

MEKC determination of vanadium from mineral ore and crude petroleum oil samples using precapillary chelation with bis(salicylaldehyde)tetramethyl‐ethylenediimine

An analytical procedure has been developed for the separation of Cu(II), Ni(II), Co(II), Fe(II), Pd(II), Th(IV), V(IV), and determination of Fe(II), Co(II), Ni(II), and V(IV) by MEKC after chelation with bis(salicylaldehyde)tetramethylethylenediimine (H₂SA₂Ten). Uncoated fused silica capillary was used with an applied voltage of 30 kV with photo‐diode array detection at 228 nm. SDS was added as micellar medium at pH 8.2 with sodium tetraborate buffer (0.1 M). Linear calibrations were established within 0.015–1000 μg/mL of each element with LOD within 5–67 ng/mL. The method was applied for the determination of vanadium from crude oil and ore samples in the range 0.34–2.40 and 114.2–720.7 μg/g with RSD 1.7–3.8 and 0.98–2.30% (n = 3), respectively. Fe, Ni, and Co present in crude oil and ore samples were also determined with RSD 1.3–2.8, 1.1–4.1, and 1.2–3.5% (n = 3), respectively. The results were compared with that of supplier's specifications and atomic absorption spectrometry (AAS). Method was evaluated by standard addition technique.     

Using the activation radiography in geological and geochemical studies

To study the spatial distribution of gold and other elements in various specimens, a method of neutron activation radiography has been elaborated based on irradiating the sample studied with neutrons followed by photoregistration of the induced activity of the element under examination. The main factors, such as the resolution, detection limit, as well as the optimal conditions of irradiation, exposure and photoexposure for obtaining the selective radiographs have been evaluated. Radiographic methods with a resolution of 1–100 m for studying the distribution of more than 30 elements having local detection limits of 10^–3–10^–8 g·mm^–2 have also been developed. Representative data on the regularities of element distribution in minerals and samples of ores and holding rocks were obtained by applying these methods to the analysis of geological and geochemical specimens.     

Characterization and differentiation of iron ores using X-ray diffractometry,k0 instrumental neutron activation analysis and inductively coupled plasma optical emission spectrometry

This study was aimed at developing methodology for the characterization and differentiation of iron ores from different ore deposits. X-ray diffractometry (XRD) was used for the determination of major and minor chemical phases in the ores, k₀-instrumental neutron activation analysis (k₀-INAA) and inductively coupled plasma optical emission spectrometry (ICP-OES) were employed for the determination of elemental profiles of iron ores. The quality of the ores was evaluated to establish their suitability to serve as a raw material for iron production. Principal component analysis was performed on the elemental data for the classification of ores. It was also shown that ores can be differentiated on the basis of rare earth elemental profiles. In this paper a new indicator, based on four elements (Ca, S, Sb, Yb), was proposed for the classification.

     

A factor analysis study of phosphate beneficiation by calcination

Mineralogical changes during beneficiation of phosphate ore by calcination and washing were studied by factor analysis with oblique rotation, and by using factors of factors (obtained with a factor—factor correlation matrix as input). Several minerals and reactions are indicated, including the possibility of distinguishing between different contributions to the CO₂ variance. From the point of view of using the results as a guide for multiregression analysis and building a linear model for the process, the most important results are as follows. The parameters of the product grade (P₂O₅ and chloride) are influenced by factors measured by x-ray fluorescence (Al₂O₃, SiO₂ SO₃ and MgO). Factors measured by thermogravimetry (water of hydration, portlandite and carbonate) have only a small influence. Most of the variance for halite is determined by elements derived from clay, whereas most of the variance for CO₂ is correlated with MgO. Magnesium replacing calcium in the francolite indicates the CO₂ level and thus the decrease in P₂O₅ content. The MgO content in the francolite can be used to indicate the maximum P₂O₅ content in the product.     

Determination of Rare Earth Elements in Garnet Minerals,Geological Materials by Inductively Coupled Plasma–Atomic Emission Spectral and Mass Spectral Analysis

Abstract

The performance of inductively coupled plasma–atomic emission spectrometry (ICP‐AES) for the determination of 14 lanthanides and Yttrium was evaluated by comparison with inductively coupled plasma–mass spectral (ICP‐MS) analysis. The geochemical reference samples (GRS), DNC‐1(diabase), AGV‐1(andesite), Sy‐2(syenite), MRG‐1(gabbro), AN‐G(anorthosite), AC‐E(granite), and MAG‐1(marine mud) were chosen as test materials and analyzed for checking the precision and reproducibility of the methods. The mineral garnet is separated from the black sands of the southwest coast of India, and the combined cation exchange–ICP method of AES analysis and MS analysis were carried out for the determination of rare earth elements. Both techniques are within the requirements needed for garnet minerals. The determination of rare‐earth elements in these minerals, which contain other elements as major contribution and trace distribution of rare‐earth elements, shows that ICP applied under the proper working condition lives up to the expectations. Major element analysis gives the formula of garnet of Manavalakurichi (MK) as (FeCaMg)_2.79Al_2.07Si_3.05O₁₂ approximated to Fe₃Al₂Si₃O₁₂, hence of almandine-type garnet. The enrichment of heavy lanthanides compared to the light lanthanides indicates that these lanthanides occupy the coordinaton site of Fe²⁺ by replacement. Both techniques are excellent in determining the very low concentration of lanthanides in geological materials, specifically garnet.     

高分辨电感耦合等离子体质谱(ICP-MS)法测定铁锰氧化态中57种元素

元素活动态分析作为深穿透地球化学的新方法,得到了广泛的应用。将ELEMENT XR型高分辨率等离子体质谱(HR-ICP-MS)法引入元素活动态的分析中,具有动态线性范围宽(10-12~1012)和灵敏度高的特点,使可同时测定的元素拓展至57种,大大提高了工作效率。根据实验结果结合响应面分析法,对HR-ICP-MS的主要仪器条件辅助气流量、雾化气流量和采样深度等进行了优化,确定了仪器的最佳测定条件;对铁锰氧化态的提取条件进行了系统研究:分别考察了提取时间、液固比、离心转速、提取液放置时间对提取效果的影响,确定了最佳提取条件,提取时间为24 h,液固比为15∶1,离心转速4000 r/min;在最优的测定条件和提取条件下,建立了HR-ICP-MS对铁锰氧化物结合相中57种元素的分析方法,得到了各元素的方法检出限和方法精密度,微量和痕量元素的方法检出限达到了10-9(ng/g),主量元素的检出限为10-6(mg/kg)水平,精密度为2.3%~32.5%,完全满足当前元素活动态的分析测试需要。     

Geochemical and gamma spectrometric analysis of ores and hostrocks of the Kanawa uranium occurrence in NE Nigeria

The Kanawa mineralization is one of the numerous low grade U-occurrences in the Gubrunde horst, NE Nigeria. Eighty nine samples consisting of ore and host rocks have been analyzed for 12 elements and 3 isotopes by atomic absorption spectrometry, colorimetry and direct -spectrometric methods and the data described using multivariate statistical techniques. The results show an enhancement of U, Mn, P₂O₅, Fe₂O₃, CaO,²¹⁰Pb,²²⁶Ra and²³⁴Th in the ore zones. The element/isotopic associations (U–P₂O₅–²¹⁰Pb–²²⁶Ra–²³⁴Th), (Na₂O–K₂O–MgO), (Fe₂O₃–MnO–CaO–Cu) were established in the mineralized rhyolites, while (P₂O₅–²¹⁰Pb–²²⁶Ra–²³⁴Th), (Na₂O–K₂O–MgO–Zn) and Fe₂O₃–Mn–U) occur in the altered/unmineralized rocks. The variation in the pattern of association of Cu, U, Zn and CaO could be ascribed to their remobilization, depletion, enrichment or introduction in the ore zone by hydrothermal solutions. The elements/isotopes U, Zn, Cu, P₂O₅,²²⁶Ra,²¹⁰Pb,²³⁴Th or their ratios could in addition to Pb, Ba, Ce, Sm be used as pathfinder elements in prospecting concealed ores in NE Nigeria.     

Study on the effect of collector and inhibitor acid on the floatability of collophane and dolomite in acidic media by TOF-SIMS and XPS

Most of the phosphate ore in southern China is contained within siliceous dolomite phosphate rock, and more than 90% of it is medium and low-grade collophane. Reverse flotation of carbonate gangue minerals (dolomite) from phosphate in acidic media is still the most economical method for the reduction of carbonate in collophane concentrates. It has been recognized that the collophane and dolomite in acidic media affect the surface properties of minerals, thereby affecting their flotation properties. In this paper, HCl and H₃PO₄ were used as regulators or inhibitors to study the flotation behaviour of collophane and dolomite. The inhibition mechanism of collophane and dolomite in two acid media was studied by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) analyses. It was found that the addition of an inhibiting acid can partially depress the collophane and improve the flotation of dolomite, thus achieving their flotation separation, and the inhibition effect of H₃PO₄ on collophane is better than that of HCl. And it was found by TOF-SIMS analysis that the increase in acid concentration did not reduce the adsorption concentration of the collector, and the main reason for the inhibition was not the decrease in the adsorption concentration of the collector. The adsorption capacity of collector on dolomite surface with H₃PO₄ is greater than that with HCl. The XPS test indicated that metaphosphate (PO₃⁻¹) is the pivotal ion for depressing collophane under acid conditions.     

Determination of tungsten in ores by X-ray fluorescence technique and X-rays in neutron activation analysis

Two distinct analytical methods have been described for analysis of W in tungsten ores. For the proposed study, thick and thin samples were analyzed by using X-ray fluorescence technique with great accuracy. Standard comparison method is based on the measurement of K line for tungsten. Also, W has been determined in similar ore samples by neutron activation analysis followed by X-ray spectrometry employing a²³⁸Pu-Be neutron source. The measured Re K-X rays are emitted in internal conversion of¹³⁷W produced during thermal neutron activation.     

Laser-ablation ICP-MS analysis of siliceous rock glasses fused on an iridium strip heater using MgO dilution

Trace element determination in rocks by fusion on an iridium strip heater followed by LA-ICP-MS analysis of the glass beads is extended here to SiO₂-rich rocks; rapid fusion of samples with >55 wt% SiO₂ is facilitated by dilution by high purity MgO. The method developed here can rapidly and accurately determine numerous trace elements in a large range of rock compositions in a short time (about 50 samples/day). Systematic evaluation for a large range of rock compositions (natural rocks and reference materials AGV-2, GSP-2, JG-1a) with SiO₂ contents between 45 and 80 wt% shows that reproducibility and accuracy within 10% can be routinely achieved for most of the 28 trace elements investigated (Rb, Sr, Cs, Ba, Ti, Zr, Hf, Nb, Ta, Sc, V, Cr, Ni, Pb, Th, U, REE). The 40 mg sample size is smaller than for XRF, INAA or solution-ICP-MS, detection limits are lower, and trace element palettes more complete than XRF and INAA. This microchemical method is thus attractive for the analysis of all natural geological materials as well as for experimental applications with small samples. Samples with SiO₂-contents >55 wt% require hot and long melting to achieve homogeneous glasses and eliminate all residual minerals, particularly refractory accessory phases. Melting conditions of 1600 °C and 20 s for samples are recommended for SiO₂ contents between 55 and 70 wt%, whereas 1800 °C and 20–30 s are often required for samples with >70 wt% SiO₂. Problems are encountered for Pb and Cs due to volatilization on the Ir strip, for Sc due to interferences, and Zr and Hf due to their sequestration in refractory accessory minerals. Correspondence: Franziska Nehring, Department of Geosciences, University of Mainz, Becherweg 21, 55099 Mainz, Germany     

Uranium recovery from Uro area phosphate ore,Nuba Mountains,Sudan

This study was carried out in a laboratory scale to recover uranium from Uro area phosphate ore in the eastern part of Nuba Mountains in Sudan. Phosphate ore samples were collected, and analyzed for uranium abundance. The results showed that the samples contain a significant concentration of uranium with an average of 310.3 μg/g, which is 2.6 times higher than the world average of phosphate. The green phosphoric acid obtained from the samples was found to contain uranium in the range of 186–2049 μg/g, with an average of 603.3 μg/g, and about 98% of uranium content of the phosphate ore was rendered soluble in the phosphoric acid. An extraction process using 25% tributylphosphate, followed by stripping process using 0.5 M sodium carbonate reported that more than 98% of uranium in the green phosphoric acid exists as uranyl tricarbonate complex, moreover, sodic decomposition using 50% sodium hydroxide showed that about 98% of the uranium was precipitated as sodium diuranate concentrate that is known as the yellow cake (Na₂U₂O₇). Further purification and calcinations of the yellow cake led to the formation of the orange powder of uranium trioxide (UO₃). The chemical analysis of the obtained uranium concentrates; yellow cake and uranium trioxide proved their nuclear purity and that they meet the standard commercial specification. The obtained results proved that uranium from Uro phosphate ore was successfully recovered as uranium trioxide with an overall recovery percentage of 93%.     

External gamma radiation levels and natural radioactivity in soil around a phosphate fertilizer plant at Mumbai

Fertilizers containing phosphate have been used worldwide in increasing quantities in order to replenish natural nutrients, which are being continuously depleted from the soil by virtue of farming activities. Phosphate rocks together with potassium ores and nitrogenous compounds are the main raw materials used for industrial fertilizer production. Rock phosphate ore processing and disposal of phosphogypsum contribute to enhanced levels of natural radionuclides in the environment. The levels of naturally occurring radionuclides such as ²³⁸U, ²³²Th, ²²⁶Ra and ⁴⁰K in soil samples collected around a phosphate fertilizer plant were estimated. Radium equivalent activity, external hazard index and external dose rate due to natural gamma background at various locations around the plant were also measured.     

Phase and Element Contents of the cBN Based Composites as Estimated by XPS

X-ray photoelectron spectroscopy (XPS) is used to estimate phase and element contents of the composites based on cubic boron nitride. A composite is a mixture of several compounds and the use of traditional X-ray diffraction for phase analysis in many cases can be difficult. By using XPS, we were able to evaluate the atomic concentration of elements and the content of different compounds of each element. SEM and XPS showed that samples are heterogeneous. The TiB₂ phase, expecting from thermodynamic calculations, was formed in both investigated samples of cBN/Ti₃SiC₂/TiC but in different amount. The Ti₃SiC₂ additive was found more chemically active then TiC.     

Analytical applications of a differential technique in laser-induced fluorimetry: accurate and precise determination of uranium in concentrates and for designing microchemielectronic devices for on-line determination in processing industries

A novel instrumental technique for the direct, fast, accurate, and precise determination of uranium in concentrates and other U-rich materials (as well as to mineralized rocks) is presented. The proposed technique is an absolute methodology, based on the comparison of the fluorescence of the accurately known standard with a sample of similar but unknown concentration in the low operational range of the instrument (on same sample-dilution basis), by the use of H₃PO₄-NH₄H₂PO₄ as a fluorescence-enhancing reagent. The relative standard deviation of the proposed technique was 0.5-0.9% (n=9) at 18.1, 36.2, 61.2, and 99.6% U₃O₈. The proposed technique is suitable for the determination of uranium in samples arising from exploration projects, ores from mining operations, mill process samples, uranium ore concentrates leading to fuel fabrication as well as samples from environmental monitoring containing up to 100% uranium. The results are in good agreement with those obtained by titrimetric, gravimetric, and TBP extraction-H₂O₂ spectrophotometric methods. The precision of the technique is within the acceptable ‘pure geochemistry’ type of analysis (R.S.D. ∼ 1.0%) and is comparable even those obtained with titrimetric and gravimetric assay. The proposed differential technique coupled with flow injection may open up new advancement in instrumentation leading to design and development of microchemielectronic devices for direct on-line determination, more compatible with the tools of computer age as also to help in handling of radioactive solutions in chemical laboratories in uranium processing industries.