松花江水中23种有机污染物的迁移转化研究——应用野外实验池方法

应用野外实验池实测及模式模拟等实验与计算方法对松花江水中２３种有机污染物的迁移转化行为进行了模拟研究，应用３个小型野外池于江边现场，经７３ｈ，３个不同实验条件的同时测定，得到各池条件下，每一化合物表观总一级动力学常数，由之估算了挥发性有机物的挥发速率常数，硝基芳烃的光解速率常数，建立了适于实验池及河流的箱式模型，应用箱式模型及所得上述参数，数学模拟了污染物在实验池及江水中变化规律，得到现实际符合的     

氯代苯在鱼体内富集和释放行为的研究

运用快速测定ＢＣＦ的方法,研究了７种氯代苯在鲤鱼体内富集和释放的行为。实验结果表明,用脂肪含量标化的ＢＣＦＬ与辛醇分配系数Ｋｏｗ吻合较好,吸收速率常数（Ｋ１２）、释放速率常数（Ｋ２１）和生物富集系数的对数值与ｌｇＫｏｗ有较好的相关关系;对于高脂溶性氯代苯,由于其结构的庞大,影响富集过程,所以本文采用了分子表面积对拟合的线性方程进行了校正．改善了ｌｇｋ１２和ｌｇＫｏｗ之间的线性关系。     

氯化苯在鱼体内富集和释放行为的研究

运用快速测定ＢＣＦ的方法，研究了７种氯代苯在鲤鱼体内富集和释放的行为，实验结果表明，用脂肪含量标化的ＢＣＦＬ与辛醇分配系数Ｋｏｗ吻合较好；吸收速率常数（Ｋ１２）、释放速率常数（Ｋ２１）和生物富集系数的对数值与１ｇｋｏｗ有较好的相关关系，对于高脂溶性氯化苯，由于其结构的庞大，影响富集过程，所以本文采用了分子表面积对拟合的线性方程进行了校正，改善了１ｇＫ１２和１ｇＫｏｗ之间的线性关系。     

硝基芳烃对鲤鱼鱼鳃ATPase的活性抑制和QSARs

在离体实验条件下,测定了20种硝基芳烃化合物对鲤鱼鱼鳃ATPase活性的半抑制浓度－logIC₅₀值,以一阶价分子连接性指数¹X^V,取代基常数总和∑σ^－、指示变量Ｉ、分子分支指数¹Ka、分子最低空轨道能ELUMO及辛醇─水分配系数logP为参数,进行定量结构活性相关性（QSAR）研究。结果表明,硝基芳烃的毒性和∑σ^－、Ｉ、ELUMO3个参数密切相关。在上述基础上,成功地建立了20种硝基芳烃的QSAR方程,其相关系数为0.927。     

模拟实验测定江河中有机物的挥发速率

本文模拟生态体系,测定37种有机物的挥发速率常数,得出有机物的挥发符合一级动力学过程;并用改进的双膜理论模型预测挥发速率常数,结果表明预测值和实测值符合较好;同时介绍了几种参数的测定和佔算方法。     

酚类污染物解离态与非解离态光解特性及其速率常数的预测

以氙灯为光源模拟太阳光,通过研究不同pH条件下3种酚类污染物直接光解的过程,探讨了酚类污染物的解离对其光解规律的影响,并建立了解离态与非解离态酚类污染物光解速率常数的计算方法及预测模式.结果表明,随着pH从4.0增加到9.0,五氯酚的光解速率常数随之从25.30×10-4min-1增加到82.90×10-4min-1,而对硝基酚的光解速率常数相应从11.90×10-4min-1降低到了3.18×10-4min-1.苯酚的光解趋势与对硝基酚相似,当pH从4.0增加到11.0时,其光解速率常数依次从32.50×10-4min-1降低至13.40×10-4min-1.3种酚类化合物的光解总速率常数与解离度之间均满足幂函数变化规律.任意解离度条件下的解离态和非解离态光解速率常数,可根据幂函数的切线方程来确定.解离对酚类物质降解规律的影响主要是通过氧负离子的形成,改变苯环以及其他取代基团的活性而造成的.该研究结果为进一步了解天然水环境中酚类污染物的环境行为提供了理论参考.     

应用次最低空轨道能研究硝基芳烃的生物活性

采用半经验分子轨道ＡＭ１方法计算了１８种硝基芳烃化合物的分子轨道能ＥＨＯＭＯ、ＥＬＵＭＯ、ＥＵＬＵＭＯＥＮＨＯＭＯ,生成热△Ｈｂ,偶极矩μ等量化参数;结合一阶价分子连接性指数Ｘ和正辛醇／水分配系数ｌｏｇＫｏｗ与发光菌的３０ｍｉｎ－半数活性浓度（ＥＣ５０）,黑呆头鱼９６ｈ－急性毒性值建立了包括ＥＮＬＵＭＯ在内的ＱＳＡＲ模式,探讨了硝基芳烃化全物的毒性作用机制,研究表明,硝基芳烃化合物的生物活性不仅与     

应用ICE和PCA方法评价硝基芳烃的综合毒性

应用种间相关估算(ICE)方法预测50种硝基芳烃缺失的生物毒性数据,对通过ICE计算获得的各种生物毒性数据进行主成分分析(PCA),计算综合毒性因子(ITI),进行综合毒性评价.结果表明,除了黄瓜种子发芽抑制毒性以外,其他各种生物毒性都在1%的显著水平上呈显著的线性正相关.硝基芳烃的这些生物毒性机制基本相似,因此应用ICE方法预测其毒性数据是可行的.QSAR分析表明,ITI与分子最低未占轨道能E_lumo有显著的相关性,r=0.869,表明亲电反应性是硝基芳烃的各种生物毒性所综合反映的主要致毒机理.基于ICE和PCA方法计算得到的ITI与基于QSAR和PCA方法计算得到的ITI的大小趋势具有一致性,ICE与PCA方法的联合应用可以成功地评价和预测硝基芳烃的综合毒性.     

12种有机物在鲤鱼体内富集与释放行为的研究

本实验对第二松花江江水和鱼体中多次检出的12种化合物在鲤鱼(Cyprinus carpio L.)体内累积与释放行为进行了研究。提出了一个描述有机物在鱼体内富集行为的模式。给出了几种化合物生物富集因子(BCF)以及该因子与辛醇-水分配系数(K_(ow))之间的关系。研究结果表明,这些有机污染物在鱼体内的富集行为互不影响。含硝基化合物富集倍率低且易于释放,有机物是以一级动力学方式在鱼体内累积和释放。     

用片段常数法估算有机化合物在鱼体内的生物富集因子

根据337个有机化合物在鱼体内生物富集因子的实测数据建立了片段常数估算模型。涉及的有机物包括卤代苯、卤代联苯、氯代脂肪烃、多环芳烃、醇、醚、醛、酮、腈、苯酚、苯胺、硝基苯、呋喃、二误Yin、含氮氧硫的杂环混合和物、脲和有机磷农药等多种类别，logKow在0.39-8.60之间。模型可决系数0.982，标准差0.453，平均绝对误差0.322个对数单位。60种检验化合物的平均预测残差为0.320个对数单位。     

2,4-二硝基甲苯与共存硝基芳烃化合物对斜生栅列藻的联合毒性

为了客观地评价２,４－二硝基甲苯与其它硝基芳烃化合物共存时对藻类的生态毒理学效应,采用ＯＥＣＤ藻类生长抑制实验的国际标准方法,研究了２,４－二硝基甲苯与其它６种硝基芳烃化合物共存时,对斜生栅列藻的联合毒性,同时观察到细胞水平上的中毒症状,结果表明：２,４－二硝基甲苯加对硝基苯胺。２,４－二硝基甲苯加对二硝基苯;２,４－二硝基甲杠加对硝基苯甲醚均表现为协同作用。２,４－二硝基甲苯加对硝基苯酚,２,４     

Complex behaviour of trivalent rare earth elements by humic acids

The complexation behaviours of trivalent rare earth elements (La, Ce, Ho and Yb) by two types of humic acids were investigated under a specified set of conditions. Humic acids show quite different complexation capacities an conditional formation constants with the REEs. Apparently there are two types of binding sites in the functional groups of humic acid, in which the first binding sites have stronger ability than the second. Cerium shows the largest complexation capacities and highest formation constants among the four REEs with two humic acids, this anomaly may be relative to the distribution pattern of the REEs in seawater. The experimental results were comparable to the values of other metals reported and provided the basic data for the environmental geochemistry of rare earth elements.     

Complex behaviour of trivalent rare earth elements by humic acids

The complexation behaviours of trivalent rare earth elements (La, Ce, Ho and Yb) by two types of humic acids were investigated under a specified set of conditions. Humic acids show quite different complexation capacities an conditional formation constants with the REEs. Apparently there are two types of binding sites in the functional groups of humic acid, in which the first binding sites have stronger ability than the second. Cerium shows the largest complexation capacities and highest formation constants among the four REEs with two humic acids, this anomaly may be relative to the distribution pattern of the REEs in seawater. The experimental results were comparable to the values of other metals reported and provided the basic data for environmental geochemistry of rare earth elements.     

Complex behaviour of trivalent rare earth elements by humic acids

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微曝气垂直流湿地污染物去除动力学模型分析

通过对自主研发的微曝气垂直流湿地系统长期运行观测数据的统计分析,在参考填充塔模型基础上,利用质量衡算方程建立了微曝气垂直流湿地污染物去除动力学模型,并利用该模型对湿地在气水比分别为0.5:1、1:1、2:1和3:1时的污染物去除效果和去除动力学常数k值进行了计算和分析.结果表明,在处理水质稳定、水量恒定的情况下,微曝气垂直流湿地对各种污染物的去除过程动力学常数k值均随工艺参数气水比的增大而增大,即对污染物的去除能力随气水比的增大而增强;各水质指标的反应动力学常数变化曲线形状有所不同,动力学常数与气水比的关系主要有线性关系和对数关系.综合各个水质指标的曲线形式与变化规律可以得到微曝气垂直流湿地的最佳气水比设计值为2:1,对应BOD5和NH4+-N的k值分别为3.8d-1和4.1d-1.     

Predicting heavy metals’ adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics,edge, and isotherm data with one p H-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, K S-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, K S-Langmuir. The modified Langmuir kinetic model(MLK model) and modified Langmuir isotherm model(MLI model) incorporating p H factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on Mn O2 at p H 3.2 or 3.3 to get the values of K S-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model(MMP model), and the values of K S-Langmuir were obtained. The values of K S-kinetic and K S-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with K S-kinetic constants could predict the adsorption edges of heavy metals on Mn O2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on Mn O2 at various p H levels could be predicted reasonably well by the MLI model with the K S-kinetic constants.     

土壤胡敏酸的解离及其与Cu2+的络合特征

通过电位滴定法及恒定容量模式（CCM）研究了2种土壤胡敏酸的解离特性及其与Cu^2 的络合特征，结果证明在pH3－7范围内胡敏酸表现为2种一元酸组成的混合酸，实验数据适用于静电模式。胡敏酸的解离常数和Cu^2 的络合常数应用计算机程序FITEQL32表明，优化的解离常数pKHL1在3．50－4．89之间，pKHL2在6．17－8．38之间，2种形态一元胡敏酸解离常数之比小于10^5，与滴定曲线只有一个突跃区相一致。2种土壤胡敏酸与Cu^2 络合常数logK^intACu大小分别为Lou土HA1．346，黑垆土HA2．241，非静电模式的优化结果较好。     

Inactivated properties of activated carbon-supported TiO2 nanoparticles for bacteria and kinetic study

The activated carbon-supported TiO₂ nanoparticles (TiO₂/AC) were prepared by a properly controlled sol-gel method. The effects of activated carbons (AC) support on inactivated properties of TiO₂ nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli. The key factors affecting the inactivation efficiency were investigated, including electric power of lamp, temperature, and pH values. The results show that the TiO₂/AC composites have high inactivation properties of E. coli in comparison with pure TiO₂ powder. The kinetics of photocatalytic inactivation of E. coli was found to follow a pseudo-first order rate law for TiO₂/AC composites, and kinetic behavior could be described in terms of a modified Langmuir-Hinshelwood model. The values of the adsorption equilibrium constants for the bacteria, K_c, and for the rate constants, k_r, were certainly depended on TiO₂ content. At 47 wt.% TiO₂ coatings with the highest rate constant, the K_c and k_r were 1.17 × 10⁻⁸L/cfu and 1.43 × 10⁶ cfu/(L·min), respectively. The variety of parameters shows significant effects on inactivation rate. The outer layer of bacteria decomposed first resulting in inactivation of cell, and with further illumination, the cells nearly decomposed.     

Determination of the dissociation constants of polyepoxysuccinic acid

The dissociation constants of polyepoxysuccinic acid (PESA) were investigated in this study. Based on the potentiometric titration and the BEST program, the dissociation constants of PESA were determined. Considering the complexity of the dissociation of PESA in aqueous solution, several models were constructed to simulate the dissociation process of PESA. By comparison, the dissociation constants of PESA were obtained with model 4. The species distribution of PESA in aqueous solution as a function of pH was also presented according to the experimental and calculation results. It showed that the H₂L model with five basic structure units to describe the dissociation of PESA was reasonable, and the relevant constants had less error and better matching between the experimental and calculation data. The corresponding values of pK _ai were 4.68 and 4.92, respectively, for H₂L at 35°C with ionic strength of 0.1 mol/L.     

络合-超滤耦合工艺去除水中镍离子的研究

以聚丙烯酸钠(PAANa)和聚乙烯亚胺(PEI)作为络合剂,将其与镍离子络合后的溶液转移至超滤杯中,在0.1 MPa压力下通过聚醚砜超滤膜进行分离,研究pH值和络合剂/Ni2+装载质量比(L)对Ni2+去除率的影响,并根据朗缪尔等温模型拟合络合反应平衡常数.同时研究超滤时间对膜通量和Ni2+去除率的影响.结果表明,选用PAANa为络合剂,在pH值为8、L=5时,Ni2+的去除率达到最大值99.5%.PEI为络合剂时,Ni2+去除率在pH值为7、L为5时达到最大值93.0%.不同pH值条件下拟合得到的络合平衡常数表明,pH为7时最有利于络合反应.另外,单个络合剂单体所能结合的Ni2+个数随着pH值的升高而增大.研究结果还表明,在长达12 h的超滤时间内,PAANa为络合剂时,膜通量的衰减<10%;PEI为络合剂时,膜通量基本保持不变;Ni2+的去除率都基本保持恒定.因此,在合适条件下,络合-超滤耦合工艺能有效去除水中的镍离子.