重金属离子在腐殖酸表面的吸附——类颗粒表面吸附模型

本实验用伏安质子滴定法获得重金属离子(Cu~(2+)、Pb~(2+)、Cd~(2+))在腐殖酸表面吸附的实验数据,并基于这些数据提出重金属离子在腐殖酸表面的络合模型。模型中引入两个实验常数:反应系数α和竞争反应常数K_H。实验结果表明,这两个常数的实验值在一相当宽的起始溶液条件下基本稳定。基于这两个常数而获得的pH相关吸附等温线和实验数据相当符合。模型中采用了由电位滴定得到的腐殖酸表面羧基浓度作为最大表面基团浓度,并对其质子解离常数进行了表面电荷影响的修正。     

Electrochemical study of sulfide solution in the presence of surfactants

ｌｅｃｔｒｏｃｈｅｍｉｃａｌｓｔｕｄｙｏｆｓｕｌｆｉｄｅｓｏｌｕｔｉｏｎｉｎｔｈｅｐｒｅｓｅｎｃｅｏｆｓｕｒｆａｃｔａｎｔｓＹｉＱｉｎｇｆｅｎｇＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｃａｌＥｎｇｉｎｅｒｉｎｇ，ＸｉａｎｇｔａｎＰｏｌｙｔｅｃｈｎｉｃＵ...     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

基于方波溶出伏安法的电化学传感器检测水体中痕量铅

基于方波溶出伏安法运用丝网印刷电极探索了一种利用电化学传感器检测水样中痕量铅的方法.得到了该检测方法的最佳参数:方波频率30 Hz,振幅80 mV,电位增量5 mV;0.5 mol/L的支持电解质(KCl);沉积电位-1.1 V,沉积时间400 s.在该优化条件下,在浓度为25 ～ 500μg/L范围内溶出峰电流与铅离子浓度呈良好的线性关系(R2=0.9945).对于几种其他金属离子的干扰实验结果表明,Mn2的存在严重抑制铅离子的峰电流.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D – first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

活性炭纤维对于离子的电吸附选择性能研究

通过循环伏安测试、交流阻抗测试、电吸附实验等方法研究了单组分和多组分溶液中不同离子在活性炭纤维电极表面的选择性电吸附性能。结果表明,电吸附选择性能与离子的水合半径、离子价态、离子浓度有关;增大初始浓度可以提高电吸附容量;并且,由于强烈的选择吸附作用,Ca2+离子可以吸附取代其它已经被吸附的离子。     

In-situ electrochemical measurements of total concentration and speciation of heavy metals in acid mine drainage (AMD): assessment of the use of anodic stripping voltammetry

We assessed the use of anodic stripping voltammetry (ASV) for in-situ determinations of both total concentration and speciation of dissolved heavy metals (Cd, Cu, Pb and Zn) in acid mine drainage (AMD). In the Kwangyang Au–Ag mine area of South Korea, different sites with varying water chemistry within an AMD were studied with a field portable anodic stripping voltammeter. Anodic stripping voltammetry after wet oxidation (acidification) was very sensitive enough to determine total concentration of dissolved Cd because Cd was dominantly present as ‘labile’ species, whilst the technique was not so effective for determining total Cu especially in the downstream sites from the retention pond, due to its complexation with organic matter. For dissolved Pb, the concentrations determined by ASV after wet oxidation generally agreed with those by ICP-AES. In the downstream samples (pH>5), however, ASV data after wet oxidation were lower than ICP-AES data because a significant fraction of dissolved Pb was present in those samples as ‘inert’ species associated with colloidal iron oxide particles. The determination of total dissolved Zn by ASV after wet oxidation appeared to be unsatisfactory for the samples with high Cu content, possibly due to the interference by the formation of Zn–Cu intermetallic compounds on the mercury coated electrode. In AMD samples with high dissolved iron, use of ultraviolet irradiation was not effective for determining total concentrations because humate destruction by UV irradiation possibly resulted in the removal of a part of dissolved heavy metals from waters through the precipitation of iron hydroxides.     

Analysis of chromium and copper by cathodic stripping voltammetry with mixed ligands

Cathodic adsorptive stripping voltammetry is one of the most sensitive analytical methods for ultratrace analysis. The detection limit is usually lower than 10⁻⁹ mol/L. Most adsorptive stripping procedures have been focused on the one ligand/one analyte approach. In order to reduce analysis time and sample volume, the possibility of simultaneously determining several metals by cathodic stripping voltammetry using a mixture of ligands was explored, e.g., by Colombo and van den Berg (1997). Here, we describe a new procedure for quantifying chromium and copper using 2,2′-bipyridine and 8-hydroxyquinoline (oxine). The effect of various operational parameters such as buffer type, ligand concentration, potential and time collection were assessed and optimized. Possible interferences by trace metals and organic matter were also investigated. Applicability for fresh water is illustrated. Electronic Publication     

高浓度苯酚在石墨电极上电解特性的研究

研制了数据在线采集记录系统对高浓度苯酚在石墨电极上电解过程的循环伏安行为进行了研究。采用连续循环伏安法考察了体系电解的特点,并考察了支持电解质、扫描速率、苯酚的浓度对反应体系的影响。结果表明:峰电流密度与扫描速率的平方根及苯酚浓度呈线性递增关系,支持电解质的添加量在苯酚电解过程存在最佳值,多次扫描过程中峰电流密度有下降趋势。实验推断电解效率下降是由于电极表面被聚合物污染导致,这一现象对电解处理有机物种的系统控制过程具有重要意义。