EDTA与柠檬酸复配洗涤修复多重金属污染土壤效果研究

乙二胺四乙酸二钠(EDTA)和柠檬酸是土壤重金属污染洗涤修复中最常用的洗涤剂,现以某化工场多种重金属污染土壤为对象,开展室内搅拌实验考察EDTA与柠檬酸复配对As、Cd、Cu及Pb的洗脱效果和最佳洗涤条件下重金属形态变化.结果表明,在最佳复配比(EDTA与柠檬酸的摩尔比为1∶1)条件下,当混合液pH为3、洗涤时间为30 min、搅拌强度为150r·min-1和液固比为5∶1时,As、Cd、Cu及Pb去除率可达11.72%、43.39%、24.36%和27.17%.洗涤后,酸溶解态As、Cu浓度增加,相应提高了其有效态所占比例.铁锰氧化态Cu对浓度的削减贡献最大.Cd的酸溶解态、铁锰氧化态、氧化物结合态所占比例均有所降低.洗涤修复后重金属形态变化会带来一定环境风险,实际工程应用中应充分考虑.     

EDTA对波士顿蕨吸收Hg的影响及其光合响应

采用水培实验方法研究EDTA对波士顿蕨吸收和转移Hg的影响,以及波士顿蕨对Hg及Hg和EDTA胁迫下光合系统II(PSII)的响应.结果显示:波斯顿蕨的根部能富集Hg,加入EDTA可以提高Hg从其根部转移到地上部分.单独Hg处理略微抑制了叶绿素的合成,Hg或Hg与EDTA处理对叶绿素的合成没有明显的影响.Hg或Hg与EDTA对植物的光合作用产生一定程度的胁迫作用.Hg单独处理或Hg与EDTA一起处理都导致了植物光合效能指数下降,干扰光系统II中的能量转移,将部分反应中心被转化为能耗中心,在一定程度上抑制了光系统II中的电子传递.     

水溶液中二氧化氯及系列氧化物的测定

根据碘离子在不同pH值与ClO2、Cl2、ClO2-、ClO3-发生不同反应的原理,提出同时分析含氯系列氧化物的方法.相对标准偏差1.2%～6.5%,加标回收率可达92.6%～94.8%.该方法不仅可用于测定二氧化氯发生器产物各组分的浓度,还能用于测定给水和废水处理中的二氧化氯.     

Heavy-metal ion complexation by particulate matter in the leachate of solid waste: a multi-method approach

The metal ion binding characteristics of particulate matter obtained from column experiments on the anaerobic digestion of solid waste were studied using a titrimetric approach. The experimental set-up allowed us to study the dynamics of particle bound ligand concentrations during digestion processes typically found in landfills.We developed a continuous titration method by simultaneously using a Cd-sensitive and pH electrode and combining metal and acid/base titrations. This technique allows for a more precise determination of pK_a-log K_M pairs for each ligand than metal titrations alone. The results were compared with titration methods using differential pulse anodic stripping voltammetry (DPASV) and atomic absorption spectroscopy (AAS) with longer equilibration times in order to further characterize ligand properties such as reaction kinetics, the electrochemical lability of the respective complex during DPASV, the distinction between metal adsorption to particulate matter and metal complexation by soluble ligands adhered to particles, reversibility of the binding process by competition studies, and resistance against purging with nitrogen gas.The properties of seven major metal binding ligands were identified and assignments to the most likely functional groups were made. The most important ligand properties are for ligand A: pK_a ≈ 9.2, log K_cd ≈ 7.0 fast reaction kinetics (mercapto groups); ligand B: pK_a = 4.8, log K_Cd ≈ 6.0, slow reaction kinetics (chelates with 3 or 4 carboxylic groups); ligand C: pK_a ≈ 6.0, log K_Cd ≈ 13.0, irreversible metal binding at basic pH-values (uptake inside bacterial cells); ligand D: pK_a = 7.7, log K_Cd = 4.0, runs parallel to N content of particulate matter with digestion time (primary amines neighboring oxo groups); ligand E: pK_a ≈ 12.0, log K_Cd = 9.0, runs parallel to P content of particulate matter (phosphate); ligand F:pK_a > 9.0, log K_{Cdf = pKa + 0.4}, runs parallel to N content of particulate matter (primary amines neighboring SH groups); and ligand G: pK_a ≤ 4.8, log K_Pb ≈ 4.3, strong Pb²⁺ ligand, even at low pH-values.Metal ions were found to be irreversibly bound by ligand C at low heavy-metal concentratins, whereas at higher concentrations the binding is reversible and can be predicted using the mass of the digestion process (methanogenic phase). All other ligands have their concentration maximum in the transition phase between acetogenic and methanogenic phase.     

重金属离子在二氧化锰上竞争/络合吸附行为的模拟

通过实验考察了Cu2+、Co2+、Cd2+、Zn2+和Ni2+五种重金属离子共存时各自在二氧化锰上的吸附边以及EDTA存在时Cu2+在二氧化锰上的吸附边。在改良型金属匹配模型的基础上,发展了多种重金属离子共存的竞争吸附模型和EDTA存在时的重金属离子络合吸附模型,利用所建立的吸附模型可以较好地模拟重金属离子的吸附行为,且利用模拟所得的参数可以预测EDTA存在时Cu2+在二氧化锰上的吸附边。     

电位滴定法测定水中高锰酸盐指数

提出实验室用电位滴定测定水中高锰酸盐指数的方法。在国标法的基础上研究及优化了标定方法和实验方法,用电位滴定仪测定水中高锰酸盐指数,方法的检出限约为0.15mg/L,测定下限为0.60mg/L。实验证明,标准样品测量值均在推荐值范围内,对0.6mg/L,5.0mg/L,8.0mg/L浓度的NaC2O4标准溶液进行5次测定,得到的相对标准偏差分别为1.59%,0.97%,0.73%。在做低浓度的水样时,高锰酸钾溶液的浓度可以选择0.005mol/L。     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Analysis of polymeric quaternary ammonium salts as found in cosmetics by metachromatic polyelectrolyte titration

Metachromatic polyelectrolyte titration was investigated as a means of analyzing polymeric quaternary ammonium salts (polyquaterniums) of relatively low charge density used as ingredients in cosmetics. They are of possible toxicological concern, but little is known of their environmental fate and behavior. With o-toluidine blue as the indicator, determination of the concentration of a range of polyquaterniums of commercial importance and cosmetic origin was possible. Using a visual endpoint, normalities as low as 3 × 10^?5 N could be determined, while with a spectrophotometric endpoint, the technique was effective to approximately 3 × 10^?6 N. The concentrations (g L^?1) to which these normalities correspond depend on the charge density of the polymer. Polyquaterniums are frequently used in association with anionic surfactants in cosmetic formulations and the presence of an anionic surfactant even in excess did not affect results although the color change was less stable. Titration in the presence of prepared humic acid was also possible.     

重金属离子与典型离子型有机污染物的络合效应研究

采用自动电位滴定法,研究了水环境中4种常见的重金属离子Cu2+、Pb2+、Zn2+、Cd2+与环丙沙星、磺胺甲基嘧啶和全氟辛酸的络合效应.测定了3种有机物与4种金属离子的络合常数logK值,计算了各种络合物在不同pH值下的形态分布. 结果表明,Cu2+与环丙沙星能形成较为稳定的络合物Cu(cip±)2+、Cu(cip±)22+、Cu(cip-·cip±)+,其络合能力要远强于Pb2+、Zn2+、Cd2+,前者形成的络合常数要比后三者高出3个数量级.4种金属离子与磺胺甲基嘧啶均有一定的络合能力,但稳定常数差别不大.全氟辛酸分子中由于带有较多的电负性强的F,表现出强酸的性质,与4种金属离子未见明显的络合作用.