阳极溶出法测定游离态金属过程中金属配合物解离动力学的计算机模拟

用计算机模拟了阳极溶出伏安法预电解过程中滞膜层中游离金属离子，游离配位体和配合物的转化及迁移过程。模拟结果证实，发生在滞膜层中的络和物解离过程是造成金属富集通量偏高的根本原因。测定偏差的大小与配合物解离常数，配位体浓度，物质迁移速率常数以及预电解时间等参数有关。     

F-SnO2/GAC粒子电极的制备及其电催化性能

以颗粒活性炭（GAC）为载体,通过溶胶-凝胶法制备了经F^-掺杂改性的F-SnO₂/GAC粒子电极.采用扫描电子显微镜（SEM）、X射线能谱（EDS）、X射线衍射（XRD）、X射线光电子能谱（XPS）、循环伏安曲线（CV）对粒子电极进行了表征.并以罗丹明B（RhB）为目标污染物,考察该粒子电极的电催化性能.结果表明：F-SnO₂纳米颗粒均匀分布在GAC的内外表面,且结晶完整;经F^-掺杂改性后的SnO₂活性组分能够增加反应体系中的转变电荷量,提高电催化活性.当RhB质量浓度为300mg/L、初始pH 3、槽电压为9V、处理30min时,在500℃下煅烧2h的10% F-SnO₂/GAC粒子电极对RhB的脱色率和COD去除率达到了97.6%和89.0%.运用电子自旋共振技术（ESR）确定了电催化过程主要是以羟基自由基（·OH）的间接氧化来实现对污染物的去除.     

LaCo0.5Cu0.5O3型钙钛矿活化过一硫酸盐降解AO7

采用溶胶-凝胶法制备LaCo_1-xM_xO₃（M=Cu、Fe、Mn）型钙钛矿并用来活化过一硫酸盐（PMS）降解偶氮染料AO7.选取效果最好的LaCo_0.5Cu_0.5O₃型钙钛矿为研究对象,考察了钙钛矿投加量、PMS浓度、pH和染料废水中常见Cl^-对LaCo_0.5Cu_0.5O₃/PMS体系降解AO7的影响,分析了体系的反应过程并考察了矿化能力.结果表明,LaCo_0.5Cu_0.5O₃可以有效活化PMS降解AO7,反应随着材料投加量和PMS浓度的增加而加快.在中性条件下反应速度最快,过酸过碱均会抑制反应的进行.在优化条件为LaCo_0.5Cu_0.5O₃投加量20mg/L、PMS浓度0.50mmol/L、AO7浓度0.05mmol/L时,AO7可在20min内完全降解.该反应主要发生在材料表面并且主要活性物种为·OH,对AO7具有优异的脱色能力和较好的矿化效果.     

优化SO4-·高级氧化技术修复PAHs复合污染土壤

采用硫酸根自由基高级氧化技术（SR-AOPs）修复南京某炼钢厂附近PAHs复合土壤,通过调整过硫酸钠（Na2S2O8）和亚铁离子（Fe²⁺）比例,结合添加不同种类和浓度的螯合剂和表面活性剂,获得修复的最佳条件,并比较分析不同类型PAHs的降解特征.结果表明：Na₂S₂O₈和Fe²⁺的配比显著影响土壤PAHs的降解效果,当Na₂S₂O₈用量为5mmol/g,Fe²⁺用量为0.5mmol/g,二者比例为10：1时,培养24h,PAHs总去除率最高,为29.32%;在此基础上添加螯合剂柠檬酸0.5mmol/g时,PAHs总去除率可提高至49.9%;继续添加0.27mg/g表面活性剂IGEPAL CA-720,PAHs总去除率最大,为80.8%.分析不同条件下SR-AOPs对PAHs的降解效果,得到总体上SR-AOPs对四环PAHs去除效果最好.添加柠檬酸和IGEPAL CA-720可以进一步强化对土壤中3环、6环PAHs的去除.柠檬酸和IGEPAL CA-720的添加可以更有效去除污染土壤中PAHs,尤其是针对高环PAHs.     

双酚A在河口水中的光解动力学

为研究双酚A（BPA）在河口水中的光解动力学及水中重要溶解性组分对其光解的影响,在广西钦州大榄江连接茅尾海的河口水域采取水样,通过模拟日光实验研究了河口水中BPA的光解动力学,及河口水中的重要溶解性组分Cl^-,Br^-,溶解性有机质（DOM）,NO₃^-和HCO₃^-对BPA光解的影响.结果表明,河口水中BPA的光解速率常数k值比纯水中大,且上游水样中BPA的k值是下游水样的2.5倍.稳态光解实验表明DOM及其与卤素离子作用显著影响BPA的光解,虽然NO₃^-也影响BPA光解,但与DOM共存时,NO₃^-的影响不明显.自由基淬灭和竞争反应动力学实验发现激发三重态DOM（³DOM^*）和卤素自由基（HRS）是决定河口水样中BPA光降解的主要活性物种,且³DOM^*与BPA的反应活性（二级反应速率常数k_3DOM*,BPA=4.42×10⁸L/（mol·s）要高于HRS与BPA的反应活性（k_BPA,Cl·=2.11×10⁸L/（mol·s）,k_BPA,Cl2·-=8.5×10⁶L/（mol·s）.下游水样中高含量的卤素离子（292mmol/L）易淬灭³DOM^*产生反应活性较低的HRS,致使下游水体中BPA的光解速率低于上游水体.     

醇类对UV-Fenton体系羟基自由基淬灭效率的影响

设计了醇类对UV-Fenton体系羟基自由基（·OH）淬灭的对比实验,考察了均相和多相UV-Fenton体系中醇的种类和浓度对·OH淬灭效率的影响,采用荧光光谱法定量测定了醇淬灭条件下多相UV-Fenton体系·OH浓度的变化规律.结果表明,一元醇对·OH淬灭能力为叔丁醇 > 异丙醇 > 乙醇 > 正丙醇 > 正丁醇 > 甲醇;多元醇对·OH的淬灭能力随链长和羟基数量的增加而增强.其中,丙三醇对Fe₃O₄多相UV-Fenton体系中·OH的1段淬灭效率为86.7%,2段为61.7%;其对均相UV-Fenton体系中·OH的1段淬灭效率为79.6%,2段为65.6%.丙三醇在均相和多相UV-Fenton体系均能高效稳定地淬灭·OH,是一种新型的高效·OH淬灭剂.     

A Review of the Fate and Effects of Silicones in the Environment

Silicones are well-known useful materials varying in structure, reactivity, and chemical and physical properties, but they all contain a covalent bond between the silicon atom and an organic group. Most common of these polymers are those based on polydimethylsiloxane (PDMS) having a siloxane (Si–O–Si) repeat unit and two methyl groups on each silicon atom. All these polymers are manmade, and the organosilicon linkage is not found in nature. It was therefore erroneously assumed that these polymers do not degrade naturally in the environment. It is the purpose of this review to refute this myth and to describe the degradation processes of PDMS in the environment and any potential ecological impact on the terrestrial, aquatic, and atmospheric compartments. Although it was found that minor degradation takes place by hydrolysis of PDMS to dimethylsilandiol followed by oxidation of the methyl group to aldehyde and ultimately to CO₂ by Arthobacter and Fusarium oxysporium schlechtendahl, the major degradation processes are abiotic. High molecular weight PDMS are initially depolymerized by soil hydrolysis of the siloxane bonds to yield organosilanol terminated oligomers. These organosilanols and low molecular weight linear PDMS and cyclics are evaporated into the atmosphere and are oxidized there by hydroxyl radicals to benign silica, water, and CO₂.     

加热与零价铁活化S2O8^2-氧化降解偶氮染料AO7的研究

以偶氮染料酸性橙AO7为目标污染物,研究了单独的热活化及零价铁（ZVI）活化S2O28-（PS）降解AO7过程温度、PS浓度及ZVI投加量对AO7降解率的影响,并将2种活化方式进行了对比,最终将其联合以期获得最好的降解效果.结果表明,热活化体系对AO7的降解符合一级动力学,其反应速率随温度（室温～90℃）升高而增加,随...     

河口水体中溶解CO_2及其稳定同位素在线同时测定的技术研究——吹扫-EA-IRMS联用法

稳定碳同位素比值(13 C/12 C)是指示碳生物地球化学行为的有效指标。本研究研制并优化了CO2及其稳定同位素测定的吹扫预处理系统,将该系统与EA-IRMS联用实现了溶解CO2、其它形式DIC及二者碳同位素比值的在线同时测定,测得河口水样中易逃逸CO2及其它形式DIC的相对标准偏差分别为3.7%和3.0%;二者的δ13 C值的标准偏差分别为0.30‰和0.15‰。运用此法对九龙江9个站位表层水中不同形态DIC的碳同位素进行测定,得出易逃逸CO2的δ13 C平均值为-12.90‰,其他形式DIC的δ13 C平均值为-5.63‰。该法为水体中无机碳及其稳定碳同位素的测定研究提供了新途径。     

Carbonaceous and nitrogenous disinfection by-product formation in the surface and ground water treatment plants using Yellow River as water source

This work investigated the formation of carbonaceous and nitrogenous disinfection by-products (C-DBPs, N-DBPs) upon chlorination of water samples collected from a surface water and a ground water treatment plant (SWTP and GWTP) where the conventional treatment processes, i.e., coagulation, sedimentation, and filtration were employed. Twenty DBPs, including four trihalomethanes, nine haloacetic acids, seven N-DBPs (dichloroacetamide, trichloroacetamide, dichloroacetonitrile, trichloroacetonitrile, bromochloroacetonitrile, dibromoacetonitrile and trichloronitromethane), and eight volatile chlorinated compounds (dichloromethane (DCM), 1,2-dichloroethane, tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene) were detected in the two WTPs. The concentrations of these contaminants were all below their corresponding maximum contamination levels (MCLs) regulated by the Standards for Drinking Water Quality of China (GB5749-2006) except for DCM (17.1 μg/L detected vs. 20 μg/L MCL). The SWTP had much higher concentrations of DBPs detected in the treated water as well as the DBP formation potentials tested in the filtered water than the GWTP, probably because more precursors (e.g., dissolved organic carbon, dissolved organic nitrogen) were present in the water source of the SWTP.