Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

液体高铁酸钠同时去除电镀废水中氰化物和重金属

采用自制的电化学装置在线制备液体高铁酸钠,然后将制得的高铁酸钠投加到电镀废水中进行处理,考察不同pH值和不同高铁酸钠投加量对废水中总氰化物、Cu2+、Ni2+去除率的影响;对比研究了高铁酸钠氧化法和次氯酸钠氧化法在处理低浓度含氰电镀废水的效果。结果表明,当pH为9~10,高铁酸钠的最佳投加量为0.024~0.048 mmol·L-1时,总氰化物、Cu2+和Ni2+的同时去除率均在90%以上;在处理低浓度含氰电镀废水时,高铁酸钠对总氰化物、Cu2+和Ni2+的同时去除率均明显高于次氯酸钠。这是因为高铁酸钠能够有效地氧化多种络合态的氰化物,包括Cu（CN）43-、Cu（CN）42-、Ni（CN）42-等,使废水中的重金属转变为离子态;然后在碱性条件下,在高铁酸盐还原产物-Fe（OH）3助凝和絮凝作用下,反应生成沉淀,达到同时去除氰化物和重金属的目的。     

Synergetic effects of anodic-cathodic electrocatalysis for phenol degradation in the presence of iron(II)

A novel electrocatalysis method for phenol degradation was described using a β-PbO₂ anode modified with fluorine resin and a Ni–Cr–Ti alloy cathode. In case of air sparging at the cathodic zone, the techniques of anodic–cathodic electrocatalysis (ACEC) and ferrous ion catalyzed anodic–cathodic electrocatalysis (FACEC) in the presence of iron(II) were developed. Both of ACEC and FACEC were more effective than anodic electrocatalysis (AEC). The percentage of phenol eliminated by FACEC could increase by nearly 30% compared with that of AEC, and the current efficiency could reach to 70%. Important operating factors such as ferrous ion concentration, air-sparging rate and applied current were investigated and it was found that such beneficial effects could be achieved at a suitable current and ratio of the concentration of ferrous ion to the air sparged. The mechanism of phenol degradation is proposed to be the generation of hydroxyl radicals concerned with the two electrodes. Results also indicated that the process provided an efficient way to regenerate ferrous ion compared with the conventional Fenton's system.     

Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu^2 +–Fe^3 + combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn^2 +–Fe^3 + combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn^2 +–Fe^3 +, while together with 0.2 mmol/L N,N′-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the F_OF₁-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe^3 + was added separately disappeared in both cases, which might be a result of competing processes between Fe^3 + and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.     

燃煤电厂排放细颗粒物的水溶性无机离子特征综述

当前我国面临严重的大气细颗粒物(PM2.5)污染,燃煤电厂是大气中PM2.5的重要来源之一.为了实现国家"十一五"和"十二五"规划对二氧化硫(SO2)和氮氧化物(NOx)的总量减排目标,燃煤电厂大规模安装烟气脱硫和脱硝设施,这虽然减少了气态污染物转化生成的二次PM2.5,但另一方面也会对烟气中PM2.5的物理化学特征产生影响,有可能增加一次PM2.5的排放.本文综述了燃煤电厂排放PM2.5及其水溶性离子的粒径分布特征,重点介绍了脱硫和脱硝这两种烟气处理设施对燃煤电厂排放PM2.5的影响原理及相关研究结果,特别是对细颗粒物中水溶性离子(如SO2-4、Ca2+和NH+4)的影响.在目前我国PM2.5污染十分严重和燃煤电厂大量安装脱硫和脱硝装置的背景下,定量研究脱硫和脱硝对PM2.5排放特征的影响具有十分重要的意义.     

Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu²⁺-Fe³⁺ combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn²⁺-Fe³⁺ combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn²⁺-Fe³⁺, while together with 0.2 mmol/L N,N'-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the FOF1-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe³⁺ was added separately disappeared in both cases, which might be a result of competing processes between Fe³⁺ and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.     

光照下铜离子对水中氢氧自由基生成量的影响

研究了水溶液中铜离子与抗坏血酸、柠檬酸盐及藻等配合体系在高压汞灯光照下产生氢氧自由基的情况,其中铜与抗坏血酸系统反应最强,高压汞灯光照增强了铜与抗坏血酸反应产生氢氧自由基的过程,高压汞灯光照时所产生的自由基量为不光照时的6～7倍。同时铜(或抗坏血酸)单一的水溶液在光照条件下也能产生氢氧自由基。铜离子与柠檬酸钠溶液混合在光照下能产生氢氧自由基;铜离子与藻液混合能加倍藻液中氢氧自由基的产生。     

Enhanced resistance of yeast mutants deficient in low-affinity iron and zinc transporters to stannous-induced toxicity

Tin or stannous (Sn²⁺) compounds are used as catalysts, stabilizers in plastic industries, wood preservatives, agricultural biocides and nuclear medicine. In order to verify the Sn²⁺ up-take and toxicity in yeast cells we utilized a multi-elemental analysis known as particle-induced X-ray emission (PIXE) along with cell survival assays and quantitative real-time PCR. The detection of Sn²⁺ by PIXE was possible only in yeast cells in stationary phase of growth (STAT cells) that survive at 25 mM Sn²⁺ concentration. Yeast cells in exponential phase of growth (LOG cells) tolerate only micro-molar Sn²⁺ concentrations that result in intracellular concentration below of the method detection limit. Our PIXE analysis showed that STAT XV185-14c yeast cells demonstrate a significant loss of intracellular elements such as Mg, Zn, S, Fe and an increase in P levels after 1 h exposure to SnCl₂. The survival assay showed enhanced tolerance of LOG yeast cells lacking the low-affinity iron and zinc transporters to stannous treatment, suggesting the possible involvement in Sn²⁺ uptake. Moreover, our qRT-PCR data showed that Sn²⁺ treatment could generate reactive oxygen species as it induces activation of many stress-response genes, including SOD1, YAP1, and APN1.     

百色市右江区大气PM10中水溶性无机离子的化学特征与来源

2010年10月至2011年9月采集百色市右江区大气PM10样品,分析PM10及其水溶性无机离子的化学特征与来源。结果表明:(1)百色市右江区大气PM10为13.89～319.44μg/m3,年均117.48μg/m3,年均值超过《环境空气质量标准》(GB 3095-2012)二级标准(100μg/m3)。百色市右江区大气可吸入颗粒物的污染主要出现在春冬季节。(2)水溶性无机离子浓度年均值依次为SO24->NO3->Cl->NH4+>K+>Na+>Mg2+>F-,SO24-、NO3-和Cl-浓度最高,分别占水溶性无机离子的57.7%、14.9%和14.5%。(3)百色市右江区大气PM10呈较强的酸性,高浓度的SO42-可能是导致百色市右江区大气PM10呈较强酸性的主要原因。(4)PM10的季节变化受气温和风速的影响极显著;气象因素对SO42-、NO3-、F-的影响不显著。(5)主因子分析表明,PM10中水溶性无机离子可能来自3个方面,Cl-和NO3-主要来自于当地低烟卤煤燃烧排放的烟气;Mg2+、K+和Na+主要来自于自然源;F-、SO24-和NH4+主要来自于混合源。     

自组装纳米金修饰玻碳电极检测亚硝酸根

将N-［3-(三甲氧硅基)丙基］-乙二胺与金溶胶通过自组装制备亚硝酸根的电化学传感器.原子力显微镜图(AFM) 显示纳米金自组装在氨基硅烷修饰的玻碳电极表面.由于质子化的氨基硅烷与带负电的亚硝酸根间的相互作用以及纳米金对亚硝酸根具有较好的催化作用,亚硝酸根在该修饰电极上的氧化电位与在玻碳电极上的氧化电位相比负移了140 mV.利用微分脉冲伏安法和微分脉冲安培法研究了亚硝酸根电流响应信号与浓度间的关系.在最优实验条件下,亚硝酸根的氧化峰电流与其浓度在5.0×10^-7～1.0×10^-3 mol·L^-1的浓度范围内呈良好的线性关系, 检测限可达到2.0×10^-7 mol·L^-1(信噪比为3). 用分光光度法及本研究提出的方法对实际样品中亚硝酸根的测定进行了比较,测定结果的差异很小.本研究所提出的测定亚硝酸根的方法具有较高的灵敏度和较好的重现性.