铬(Ⅵ)在铁(Ⅲ)-丙酮酸盐体系中的紫外光还原研究

初步研究了含有Fe(Ⅲ)及丙酮酸盐的溶液在紫外灯照射下对铬(Ⅵ)的光还原反应．考察了溶液pH值、Fe(Ⅲ)浓度、丙酮酸钠浓度、Cr(Ⅵ)浓度对反应的影响;分析了光还原反应的动力学及反应机制．结果表明,铁．丙酮酸盐体系能够光还原Cr(Ⅵ);最佳pH为3．0;Cr(Ⅵ)光还原的初始速率随着加入的铁(Ⅲ)、丙酮酸盐、Cr(Ⅵ)初始浓度的增加而增加;表观动力学方程为-dCcr(Ⅵ)／dt=0．023[Cr(Ⅵ)]^0.25[Fe(Ⅲ)^0.96[CH3COCOONa]^0.66;Fe(Ⅲ)-丙酮酸盐配合物光解产生的Fe(Ⅱ)是Cr(Ⅵ)的主要还原剂．     

苏州河底泥中重金属的烧结无害化研究

采用有氧烧结法和还原烧结法处理苏州河底泥,研究了底泥中重金属的无害化效果.结果表明,有氧烧结温度900℃以上时,对Cu、Pb、Zn、Cd去除率达40%～65%;烧结温度为500～900℃时,尽管对Cu、Pb、Zn、Cd去除效果不明显,但能有效抑制其溶出.有氧烧结法不仅不能实现Cr的去除,而且会增加Cr的溶出,这是由于有氧烧结过程中Cr(III)被转化为Cr(VI),而底泥对Cr(VI)的吸附能力很有限.还原烧结法则能有效防止底泥中Cr(III)向Cr(VI)的转化,从而抑制包括Cr在内的重金属的溶出.     

Direct and indirect methods for chromium identification in industrial wastes

The examinations of selected wastes and stream sediments from the vicinity of a chemical plant by sequential extraction procedures and direct methods, SEM/EDX and XRD, were carried out in order to identify the different forms of chromium, particularly as they are released to potential mobility. The results show that the top and bottom waste samples contain 37,756 and 53,650 μg g¹ Cr, respectively, but about 7% and 2% of the total chromium type Cr(VI). The chemical extraction results show that the mobility of Cr in the upper part of the waste pile is significantly higher than in the bottom section; the exchangeable form of Cr accounts for 25% and < 1%, respectively, the last one irrespective of redox conditions. About 50% of Cr is associated with the reducible fraction of the top waste, and similar with the residual fraction in the bottom waste. Oxidation of the bottom waste shift some portion of Cr from residual to the moderately reducible fraction. The major Cr-forms in the river sediments are compounded with Fe-oxides. The < 2 μm size fraction of the selected sediment sample, particular enriched in chromium contained up to 73,000 μg g¹ Cr with about 95% of this in the moderately reducible fraction, predominantly bound with oxyhydroxides. SEM/EDX and XRD analysis of wastes and river sediment indicate that the main insoluble Cr-phase is ferroan — (Mg, Fe) (Cr, Al)²O⁴ which would be dissolved mainly in the residual fraction.     

陕西某地区地下水Cr(Ⅵ)异常的水化学特征及其富集因素分析

以42组水化学测试数据为基础,结合野外调查资料,分析研究区Cr(Ⅵ)异常地下水的分布规律和水化学特征,探讨Cr(Ⅵ)富集的影响因素.结果表明Cr(Ⅵ)异常地下水主要位于基岩含水层,水化学类型以HCO3-Na、HCO3-Na·Ca型为主,随地下水埋深的增加,Cr(Ⅵ)浓度、γNa+/γCl-系数逐渐增大,γCa2+/γHCO-3系数逐渐减小;与正常水相比,Cr(Ⅵ)异常地下水的p H、溶解氧、离子强度的平均值分别由7.2、4.3 mg·L-1、0.011 mol·L-1变为7.6、5.5 mg·L-1、0.028 mol·L-1,溶解氧增加有利于Cr(Ⅲ)的氧化,p H升高、离子强度降低可以促进Cr(Ⅵ)的活化,这些是促使含水介质中Cr(Ⅵ)的解吸、迁移和富集的主要水化学因素.     

Pomegranate husk as an adsorbent in the removal of toxic chromium from wastewater

The use of a new sorbent developed from the husk of pomegranate, a famous fruit in Egypt, for the removal of toxic chromium from aqueous solution has been investigated. The batch experiment was conducted to determine the adsorption capacity of the pomegranate husk. The effects of initial metal concentration (25 and 50 mg l^?1), pH, contact time, and sorbent concentration (2–6 g l^?1) have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increased as the pH decreased, and the optimum pH value was pH 1.0. Adsorption equilibrium and kinetics were studied with different sorbent and metal concentrations. The adsorption process was fast, and equilibrium was reached within 3 h. The maximum removal was 100% for 25 mg l^?1 of Cr⁶⁺ concentration on 5 g l^?1 pomegranate husk concentration, and the maximum adsorption capacity was 10.59 mg g^?1. The kinetic data were analysed using various kinetic models—pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion equations—and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Tempkin, Dubinin–Radushkevich, and Generalized isotherm equations. The Elovich and pseudo-second-order equations provided the greatest accuracy for the kinetic data, while Langmuir and Generalized isotherm models were the closest fit for the equilibrium data. The activation energy of sorption has also been evaluated as 0.236 and 0.707 kJ mol^?1 for 25 and 50 mg l^?1 chromium concentration, respectively.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Fluorescence studies of dye displacement from DNA by chromium(III) complexes: Evidence for cation induced DNA condensations

The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)₆]Cl₃.3H₂O, [Cr(1,10‐phenanthroline)₃](ClO₄)₃.2H₂O, [Cr(2,2'‐bipyridyl)₃] (ClO₄)₃.2H₂O, [Cr(ethylendiamine)₃]Cl₃.3.5H₂O and [Cr(NH₃)₆](NO₃)₃ displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)₂Cl₂]Cl.2H₂O, cis‐[Cr(2,2'‐bipyridyl)₂Cl₂]Cl.2H₂O, [Cr(glutathione)₂]Na₂, [Cr(cysteine)₂]Na.2H₂O and [Cr(glycine)₃] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.     

Comparative effects of trivalent and hexavalent chromium on spermatogenesis of the mouse

It has been repeatedly stressed that the biological effectiveness of chromium depends entirely on its oxidation state. The present work compares the histological effects of ingested trivalent and hexavalent chromium compounds on the mouse testes. The results showed comparable data of food consumption and gain in body weight. Both compounds produced ambiguous levels of degeneration in the outmost cellular layers of a number of seminiferous tubules, reduced the number of spermatogonia per tubule and the sperm count, and caused significant increases in the percentage of morphologically abnormal sperms. Generally, all these effects were more pronounced in animals which ingested the hexavalent chromium.     

磷酸盐对水稻土团聚体不同类型重金属镉、铬（Ⅵ）吸附的影响

利用低能量超声波分散、虹吸法沉降分离的方法分离不同粒径的水稻土团聚体颗粒,采用恒温振荡法研究不同浓度磷酸盐预处理的团聚体对Cd2+、Cr(Ⅵ)平衡吸附以及吸附动力学的影响。结果表明,砂粒级、粗粉砂级、粉砂级和粘粒级对P吸附量分别小于50、46、50和97 mg?kg-1,Cd2+吸附量低于未处理土样,P吸附量大于该数值,Cd2+吸附量高于未处理土样,团聚体吸附磷酸盐对Cd2+吸附量的影响,表现为低P吸附量抑制Cd2+的吸附,高P吸附量促进Cd2+的吸附,即随P吸附量增加Cd2+的吸附量呈波谷形变化;而团聚体吸附磷酸盐后对Cr(Ⅵ)的吸附则表现明显的抑制作用。磷酸盐预处理的团聚体对Cd2+、Cr(Ⅵ)吸附量大小顺序均为粘粒级>砂粒级>粗粉砂级>粉砂级,与有机质和游离氧化铁的含量顺序一致。团聚体对Cd2+的吸附过程分为快、慢两个阶段,快吸附阶段用一级动力学方程拟合最佳,而慢吸附时段用扩散方程和Elovich方程拟合最佳,表明吸附过程由不同的吸附因素控制。团聚体吸附磷酸盐后对Cd2+的吸附动力学常数增大。团聚体对Cr(Ⅵ)的吸附过程无明显快、慢阶段,对Cr(Ⅵ)吸附的整个过程用双常数速率方程和Elovich方程进行描述最佳,团聚体吸附磷酸盐后对Cr(Ⅵ)的吸附动力学常数减小。磷酸盐对土壤中重金属吸附的影响与金属离子类型以及磷吸附量有关,所以采用磷肥等含磷物质修复重金属污染土壤要注意金属离子的类型和磷肥的施用量。     

含铬废渣填埋场渗滤液污染地下水问题实例分析

结合工程实例叙述了含铬废渣填埋场地的选择．并建立针对填埋场地下水污染问题的数学预测模型,利用该模型对填埋场渗滤液污染地下水进行计算与分析。结果表明,选择合适的填埋场不仅工程措施简单,工程投资少,而且对地下水的污染甚微,能够更好地满足填埋要求。