Potential Applications of X-ray Fluorescence Core Scanner in Elemental Analyses of the Muddy Sediments on the Coastal Shelves of China and in Ecological Study

Large areas of muddy sediments on the coastal shelves of China provide important samples for studying climate and ecological changes. Analysis of a large number of such samples, which is essential for systematic study on environmental information recorded in mud areas because of complicated sedimentary environment and variable sedimentary rate, requires a fast and economical method. In this study, we investigated the potential of X-ray fluorescence core scanner （XRFS）, a fast analytical instrument for measuring the elemental concentrations of muddy sediments, and observed a significant correlation between the element concentrations of muddy sediments determined by regular X-ray fluorescence spectrometer （XRF） and XRFS, respectively. The correlations are mainly determined by excitation energy of elements, but also influenced by solubility of element ions. Furthermore, we found a striking link between A1 concentrations and marine-originated organic carbon （MOC）, a proxy of marine primary productivity. This indicates that MOC is partly controlled by sedimentary characteristics. Therefore, XRFS method has a good potential in fast analysis of a large number of muddy sediment samples, and it can also be used to calibrate MOC in ecological study of coastal seas.

Effect of Mg^(2+) content in ion-exchanged Shengli lignite on its equilibrium adsorption water content and its mechanism

Mg ion-exchanged samples were prepared with acid-washed Shengli lignite.The chemical composition of the ash of the raw sample was determined by X-ray fluorescence.The equilibrium adsorption water contents of samples were determined in a range of relative humidity.The ion-exchange process was characterized by FT-IR,ash content,and p H value.A possible mechanism is proposed for equilibrium adsorption water of ion-exchanged samples at different humidities.The extent of ion-exchange reaction between Mg2+and lignite is controlled by the concentration of Mg2+in Mg SO4solution.The effect of Mg2+on equilibrium adsorption water content varies with relative humidity and content of Mg2+.The factor that controls equilibrium adsorption water content at low relative humidity is water interactions with sorption sites,which are Mg2+–carboxyl group complex.At middle relative humidity capillary force between Mg2+–water clusters Mg+(H2O)nand capillary is more important.At high relative humidity,free water–free water interactions are more significant.

Prediction of XRF analyzers error for elements on-line assaying using Kalman Filter

Determination of chemical elements assay plays an important role in mineral processing operations.This factor is used to control process accuracy,recovery calculation and plant profitability.The new assaying methods including chemical methods,X-ray fluorescence and atomic absorption spectrometry are advanced and accurate.However,in some applications,such as on-line assaying process,high accuracy is required.In this paper,an algorithm based on Kalman Filter is presented to predict on-line XRF errors.This research has been carried out on the basis of based the industrial real data collection for evaluating the performance of the presented algorithm.The measurements and analysis for this study were conducted at the Sarcheshmeh Copper Concentrator Plant located in Iran.The quality of the obtained results was very satisfied;so that the RMS errors of prediction obtained for Cu and Mo grade assaying errors in rougher feed were less than 0.039 and 0.002 and in final flotation concentration less than 0.58 and 0.074,respectively.The results indicate that the mentioned method is quite accurate to reduce the on-line XRF errors measurement.

Characterization and recycling of nickel- and chromium-contained pickling sludge generated in production of stainless steel

Pickling sludge generated during the neutralization of pickling wastewater with calcium hydroxide in stainless steel pickling process was characterized using X-ray fluorescence spectrometry, X-ray diffractometry, scanning electron microscopy, thermogravimetry and differential scanning calorimetry, etc. The major compositions of pickling sludge are CaF2, CaSO4, Me（OH）, （M： Fe, Cr, Ni）, and the content of CaF2 is high in the sludge. The melting point of pickling sludge is about 1350℃ and the viscosity is about 0.14 Pa.s at 1450 ℃, which are comparatively lower than those of normal refining slag. After heat treatment, the contents of sulfur and fluorine in the pickling sludge were reduced, confirming the thermal decomposition of sulfate in the sludge. Fluorine in the sludge is reduced by the gaseous SiF4 and A1F3 generated through the reactions of CaF2 with SiO2 and Al2O3. The preliminary results from the reduction test indicate that the sulfur content in the steel is not affected by the presence of sulfur in the sludge. The recovery of nickel is about 40%, and the chromium content changes marginally due to the protective atmosphere under the reduction condition of chromic oxide. The pickling sludge is a potential auxiliary material for the production of stainless steel.

Geochemical characteristics of illite clay rocks from the Shihezi Formation in the Hanxing mining area and its sedimentary environment

We studied the geochemical characteristics of illite clay rocks and their importance from the 5hihezi Formation of Late Permian in the Hanxing mining area by means of ICP-M5 and sequential X-ray fluorescence spectrometry. The results show that the amount of SiO2 is between 53.37% and 61.58% （by weight） and that of Al2O3 22.40% and 31.31% （by weight）. The ratio of SiO2/Al2O3 lies between 1.71 and 2.75. The amount of K2O ranges from 1.11% to 2.56% （by weight）. The amounts of Fe and Ti are higher than the theoretical values in illite clay rock would indicate. The amounts of some trace elements, such as Ga, As, Ba, Cu, Th and U are higher than their Clark values, while that of another 23 trace elements are found to be dose to their Clark values. The amounts of REE range from 22.59 to 570.54 μg/g, with an average of 163.23μg/g. The ratios of LREE/HREE range from 5.41 to 21.82, with an average of 8.87. These characteristics show that LREE are much richer in content than HREE. The REE distribution patterns of our samples were characterized by clearly negative Ce and Eu anomalies. We analyzed the sedimentary environment of the Hanxing mining area in Late Permian by the characteristic element ratio method. The ratios of Mn/Fe range from 0 to 0.0168, which are lower than those in a marine sedimentary environment. The ratios of Sr/Ba （0.20-0.41） are less than 1. These are all indications that the sediments of the Hanxing mining area in Late Permian form largely a continental sedimentary environment. The sedimentary water is freshwater, a conclusion reached on the basis of the ratios of Th/U （2.66-6.62） and of Ca/（Ca ＋ Fe） （0.01-0.059）; the average ratio of Fe2＋/Fe3＋ is 4.8. The sedimentary water condition is weakly acidic and weakly oxidative-weakly reductive, a conclusion reached on the basis of ratios of Fe2＋/Fe3＋ （4.8） and of Ceanom （-0.08）.

数理统计方法在仪器运行检查中的应用

本文以 Philips PW140 4型 X射线荧光光谱仪的使用为例 ,应用数理统计理论 ,提出了一种仪器运行状态检查的方法 ,该方法具有简便、快速的特点 ,非常适合生产要求。

Influence of Ice on Soil Elemental Characterization via Portable X-Ray Fluorescence Spectrometry

Field portable X-ray fluorescence （PXRF） spectrometry has become an increasingly popular technique for in-situ elemental characterization of soils. The technique is fast, portable, and accurate, requiring minimal sample preparation and no consumables. However, soil moisture 〉 20% has been known to cause fluorescence denudation and error in elemental reporting and few studies have evaluated the presence of soil moisture in solid form as ice. Gelisols （USDA Soil Taxonomy）, permafrost-affected soils, cover a large amount of the land surface in the northern and southern hemispheres. Thus, the applicability of PXRF in those areas requires further investigation. PXRF was used to scan the elemental composition （Ba, Ca, Cr, Fe, K, Mn, Pb, Rb, Sr, Ti, Zn, and Zr） of 13 pedons in central and northern Alaska, USA. Four types of scans were completed： 1） in-situ frozen soil, 2） re-frozen soil in the laboratory, 3） melted soil/water mixture in the laboratory, and 4） moisture-corrected soil. All were then compared to oven dry soil scans. Results showed that the majority of PXRF readings from in-situ, re-frozen, and melted samples were significantly underestimated, compared to the readings on oven dry samples, owing to the interference expected by moisture. However, when the moisture contents were divided into 〉 40% and 〈 40〈 groups, the PXRF readings under different scanning conditions performed better in the group with 〈 40% moisture contents. Most elements of the scans on the melted samples with 〈 40% moisture contents acceptably compared to those of the dry samples, with R2 values ranging from 0.446 （Mn） to 0.930 （St）. However, underestimation of the melted samples was still quite apparent. Moisture-corrected sample PXRF readings provided the best correlation to those of the dry, ground samples as indicated by higher R2 values, lower root mean square errors （RMSEs）, and slopes closer to 1 in linear regression equations. However, the in-situ （frozen） sample scans did not differ appreciably from the melted sample scans in their correlations to dry sample scans in terms of R2 values （0.81 vs. 0.88）, RMSEs （1.06 vs. 0.85）, and slopes （0.88 vs. 0.92）. Notably, all of those relationships improved for the group with moisture contents 〈 40%.

The distribution and variation of elements in sediments off the Huanghe (Yellow) River mouth

Surface sediment samples collected off the Huanghe （Yellow） River mouth during the period 2007-2009 were analyzed for major and trace element concentrations. Concentrations of 16 elements were measured using X-ray fluorescence spectrometry. Results demonstrate that sediment grain size is the dominant factor controlling the spatial variations of elemental concentrations. Correlation and cluster analyses allowed classification of the study area into four geochemical regions： Regions Ⅰ and Ⅲare characterized by high concentrations ofAl2O3, Fe2O3, MgO, Na2O, K2O, Cr, Cu, Mn, Ni, Pb, V, and Zn, and contain fine-grained sediments with mean grain size （Mz）〈22 μm; and; Regions Ⅱ and Ⅳcontain mostly coarse-grained sediments, and are characterized by high concentrations of SiO2, Na2O, and Zr. The sediment entering the sea from the Huanghe River and its tributaries is enriched in Ca. Thus, the Ca/Al ratio was used as an indicator of the proportion of sediments in the study area that originated from the Huanghe River. Ca/Al ratios decrease from Regions Ⅰ and Ⅱ（located in the nearshore zone of the Huanghe River delta） to Regions Ⅲand Ⅳ（distributed in the offshore zone of the northern Huanghe River delta, southern and southeastern Laizhou Bay area）.

Overview of Abandoned Mines in the Limpopo Province, South Africa： Rehabilitation Challenges

South Africa is facing enormous financial, environmental and social challenges posed by abandoned mines. This investigation focused on field verification of 850 abandoned mines and associated rehabilitation challenges in the Limpopo Province. The investigations included desktop studies, standardised field-based ranking system and sampling. The waste material samples were analysed using XRF （X-ray fluorescence spectrometry） at the Council for Geoscience Laboratory. Approximately 5% of 850 abandoned mines in the Limpopo Province require urgent rehabilitation either due to high concentrations of metals from mine dumps or presence of open shafts. For example, copper concentrations at Messina and Spoedwel were 9,719 ppm and 56,160 ppm, respectively. Birthday Gold Mine in Giyani area is characterised by un-safe open shafts and un-stable grounds which poses safety problems and limits the future land-use. Although these investigations have been conducted, it is not possible to rehabilitate all abandoned mines mainly due to limited financial resources. The abandoned mines close to human settlement are given priority due to their immediate threat to people. This study recommends that rehabilitation of abandoned mines should take cognisance of the sustainable future land use that will favour the creation of jobs and nature conservation.

Electron Beam Application for Regeneration of Catalysts Used in Refinery Cracking Units

A catalyst is a substance that alters the rate of a reaction. The process of catalysis is essential to the modem day manufacturing industry, mainly in FCC （Fluid Catalytic Cracking） process units. However, long-term exploitation of oil and gas processing catalysts leads to formation of carbon- and sulfur-containing structures of coke and dense products on the catalyst surface. They block reactive catalyst sites and reduce the catalytic activity. The main advantage of radiation processing by EB （electron beam） and gamma rays is chain cracking reaction in crude oil. Otherwise, under exposure to ionize radiation, considerable structure modification of equilibrium silica-alumina catalyst from FCC process may occur, in addition to the removal of impurities. The conditions applied in the irradiation range （20-150 kGy） of gamma rays and EB were not sufficient to alter the structure of the catalyst, whether for removal of the contaminant nickel, a major contaminant of the FCC catalyst, either to rupture of the crystalline structure either for the future reutilization of chemical elements. ATR-FTIR （Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and EDXRFS （Energy Dispersive X-Ray Fluorescence Spectrometry） analysis were used to characterize and evaluate effects of radiation processing on equilibrium catalysts purification. To evaluate and comprehend the reactive catalyst sites, SEM （Scanning Electron Microscopy） and particle size distribution analyses were carried out.