稀土冶炼废水中稀土总量的极谱法测定

一、引言钪、钇和镧系元素等称为“稀土元素”,简称为“稀土”。因为稀土金属及其化合物具有许多优异的性质,所以它们的应用迅速遍及各个科学技术领域;含稀土的食品和用品不断进入人类生活领域。但是,稀土不是人体所必需的元素,属于中等毒性物质。稀土易被人体某些组织吸收、富集,如长期食用含稀土的食物,将会产生危害。我国稀土资源极其丰富,约占世界总储量的80％。近年来,我国的稀土冶炼工业迅猛发展,其废水对环境的污染日益加剧。研究环境中稀土含量的测定,已成了毋庸忽视的课题。本研究在国内外文献资料的基础上,通过     

二维单体同位素分析在有机污染物转化研究中的运用进展

单体同位素分析(CSIA)作为一门新技术日渐应用于有机污染物的降解研究。降解过程中,同位素分馏受环境因素影响较大,导致CSIA技术应用存在一定的不足。多维同位素分析通过对不同元素同位素分馏的相关性分析,可消除有机污染物降解过程中环境因素变化对同位素分馏行为的影响,因而对有机污染物降解的评价更为准确。主要总结了二维单体同位素分析(2-D CSIA)技术在有机污染物降解、转化机制等领域的研究进展,并对未来的发展方向进行了展望。     

道南膜技术在重金属化学形态研究中的应用

重金属化学形态影响其反应活性、迁移特性、生物可利用性及生物毒性,因而备受关注。道南膜技术(DMT)因具有测定范围广、检测限低、对待测体系扰动小等优点,被广泛应用于多种环境介质重金属形态的研究。结合最新相关研究成果,概述了DMT原理、方法及改进过程,系统综述了DMT在不同环境介质和在重金属同位素分馏效应中的应用,并在此基础上针对装置的改进和应用环境的扩展展望了DMT的未来发展方向。     

CuMnO_x/γ-Al_2O_3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加人稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T_(99)(催化处理效率达到99%时的温度)比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

CuMnOx／γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu—Mn复合氧化物催化剂和加入不同稀土含量的Cu—Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加入稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T99（催化处理效率达到99％时的温度）比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

CuMnOx/γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加入稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T₉₉（催化处理效率达到99%时的温度）比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

利用木素-SiO2凝胶制备稀土催化剂及对蒽醌废水处理的研究

探讨利用木质素-二氧化硅凝胶制备高比表面稀土催化剂的方法、性能及其在非均相催化体系中稀土催化剂对双氧水的催化行为与效果.结果表明,负载型稀土对双氧水产生羟基自由基氧化染料中间体废水具有明显的增效行为,并对该行为的机理进行了探讨.     

一种从有机废水中获取甲酸的方法

探讨了从环己醇/环己酮生产装置产生的酸性有机废水中获取甲酸的方法.在实验基础上,确定了共沸-分馏组合法回收甲酸的工艺过程、适宜挟带剂及工艺条件.采用共沸-分馏组合法处理该有机废水,可获取质量分数为80%以上的甲酸水溶液,甲酸回收率可达70%以上.同时,经本法处理后,该有机废水的COD由1.0×105～1.6×105 mg/L降至5× 102 mg/L以下,COD去除率达98%以上.     

稀土荧光粉回收利用技术研究现状与发展趋势

中国是稀土资源最为丰富的国家之一,但随着稀土消费需求的增加、大量廉价出口和长期掠夺式开采等因素的影响,近年来中国的稀土储量锐减.因此,迫切需要对废旧稀土产品进行高效回收再利用.综述了直接萃取、CO2超临界萃取分离、离心分离、浮选分离、湿法浸取分离这几种主要的稀土荧光粉回收利用技术的研究现状,并对不同方法的优缺点进行了比较,最后指出了未来的发展方向.     

利用木素-SiO2凝胶制备稀土催化剂及对蒽醌废水处理的研究

探讨利用木质素-二氧化硅凝胶制备高比表面稀土催化剂的方法、性能及其在非均相催化体系中稀土催化剂对双氧水的催化行为与效果.结果表明,负载型稀土对双氧水产生羟基自由基氧化染料中间体废水具有明显的增效行为,并对该行为的机理进行了探讨.     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone

Environmental Science and Pollution Research - Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due...     

Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain)

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.     

Scandium,yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Go? soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

     

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation–proton exchange with HA (i.e., pK_MHA) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK_MHA values is more suitable for use in Model V for the simulation of REE complexation with HA.     

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.     

Effects of fulvic acid on the bioavailability of rare earth elements and GOT enzyme activity in wheat (Triticum aestivum)

Fulvic acid (FA) was extracted and purified from natural soil and the effects of such FA on the bioaccumulation of rare earth elements (REEs, La3+, Gd3+ and Y3+) in wheat seedling were investigated. The results indicated that low concentration of FA (<0.4 mg C/l to root, <0.7 mg C/l to tops (stem and leaves)) could increase the bioaccumulation values of REEs in wheat, but when the concentration of FA was high (>0.4 mg C/l to root, >1.5 mg C/l to tops) the bioaccumulation values were decreased. Kinetic experimental results suggested that bioaccumulation values of REEs in roots for 30 days were correlated with the kinetic linear growth equation, and correlation coefficients were higher than 0.861. The kinetic bioaccumulation pattern of REEs in tops was different from that in root. The bioaccumulation values of REEs in wheat root were much higher than in wheat tops. Variations of glutamic oxaloacetic transaminase (GOT) enzyme activities in wheat root and tops were determined. A good correlation existed between the bioaccumulation values of REEs and GOT enzyme activities, and the correlation coefficients were higher than 0.922. GOT is an important parameter influencing the bioavailability of REEs.     

Effects of rare earth elements on the distribution of mineral elements and heavy metals in horseradish

In order to investigate the effects of rare earth elements (REEs) on horseradish, the distribution of the mineral elements and heavy metals in different organs of horseradish have been studied by using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Meanwhile, three variable major parameters, namely the concentration of REEs, the type of REEs, and the growth stage of plant were chosen. The results indicated that the test REEs, Ce(III) and Tb(III), could be accumulated in leaves, stems and roots of horseradish. In addition, we found that the content of mineral elements was increased in horseradish treated with 20mgl(-1) of Ce(III), but not those with the 20mgl(-1) of Tb(III). Moreover, the content of mineral elements in horseradish was decreased with the increasing concentration of REEs (100, 300mgl(-1)). Furthermore, we found that there were the opposite effects on the content of the heavy metals in horseradish treated with REEs. Finally, we found that the effect of REEs on the accumulation of REEs, and the content of mineral elements or heavy metals of horseradish during vigorous growth stage, no matter positive or negative, was more obvious than that of the other growth stages. These results demonstrated that the distribution behaviors of mineral elements and heavy metals in horseradish can be affected by the type and concentration of REEs, and the growth period of plant.     

Rare earth elements (REEs) in naturally grown plants in relation to their variation in soils

The concentrations of rare earth elements (REEs) in plant leaves, soils in which they grow, and mother rocks were determined using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). Concentration levels of REEs in most plants were low. However, one of the herb species, pokeweed (Phytolacca americana) and two species of ferns (Dicranopteris dichotoma and Athyrium yokoscence) revealed relatively high concentrations of REEs. In the case of pokeweed, the REE distribution pattern reflected well that of its soils. On the whole, high concentrations of REEs in plants were related to REE concentrations in the soils in which they grow. These observations are promising to evaluate the possible contamination of environment by REEs resulting from their increased usage in modern industry.     

Effect of earthworms (Eisenia fetida) on the fractionation and bioavailability of rare earth elements in nine Chinese soils

The effect of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), fraction distribution pattern and bioavailability of rare earth elements (REEs) Y, La, Ce, Pr and Nd in nine Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community (Standards, Measurements and Testing Programme) was used to fractionate REEs in soils into water soluble, exchangeable and carbonate bound (B1), Fe- and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). Inoculated with earthworms, the soil pH, DOC and water-soluble rare earth elements fraction increased. A significant correlation was obtained between the increased DOC and the increased water-soluble REEs. REEs in fraction B1 increased after earthworm inoculation, while those in fraction B3 decreased. No significant differences were observed for REEs in fraction B2. The biomass and the concentrations of REEs in wheat shoots and roots increased after the treatment with earthworms. The results demonstrated that earthworm activity increased the mobility and bioavailability of REEs in soils.