新污染物多环芳烃衍生物的来源、分布与光化学行为

环境中多环芳烃衍生物(SPAHs)来源广泛,具有“三致”效应,毒性与PAHs母体相当甚至高于母体,是一类具有较高风险的新型有机污染物.大气和表层水体等环境介质中,光化学降解是其重要的消减方式.在梳理文献的基础上,发现SPAHs在来源、分布、行为和风险研究方面与传统污染物PAHs相比有了新的突破.通过总结新污染物SPAHs的环境分布特征与光化学行为研究的最新进展,介绍了3类SPAHs的来源和形成机制,重点评述了不同环境介质中的存在状况与分布特征,讨论了水、冰等介质中SPAHs光化学转化动力学、反应路径以及影响因素,最后对SPAHs的环境行为和风险研究进行了展望.     

氯化铜催化二噁英生成实验及指纹特性分析

氯化铜被认为是对二■英(PCDD/F)生成促进作用最强的金属催化剂,温度和氧气含量是影响其催化二■英生成的关键因素.本文选取250～550℃间8个不同温度点及0～20%间4种不同氧气含量,系统性地研究了温度和氧气含量对含氯化铜模拟飞灰(MFA)生成二■英的影响,并通过分析指纹特性探讨二■英的生成路径和机理.结果发现,290～350℃之间二■英生成量较高,且在290℃时二■英总量达到最大值;氧气含量为10%时二■英生成量达到最高.研究二■英同分异构体分布可从分子层面为研究其生成路径和机理提供重要信息,因此,本文分析了四至八氯代PCDD/F的全部异构体的分布.结果表明,在本文所选取的温度和氧含量范围内,温度对二■英生成路径的影响高于氧气含量.最后,重点讨论了2,3,7,8位氯取代的17种有毒异构体的分布随温度和氧气的变化情况及生成路径.利用主成分分析法(PCA)证实了氯化铜催化二■英从头合成过程中存在经由氯酚路径生成的异构体,并讨论了不同工况下氯酚路径对二■英生成的影响.     

超滤膜负载UiO-66@Fe3O4@UiO-66强化PPCPs去除和膜污染控制

本研究通过聚偏氟乙烯（PVDF）膜内负载具有协同吸附和催化作用的金属有机骨架（MOFs）,吸附去除水中药品及个人护理品（PPCPs）,并且达到膜滤过程中多功能材料吸附能力再生和膜污染控制的双重目的.在膜吸附方面,共混基质膜（MMMs）内MOFs材料UiO-66@Fe₃O₄@UiO-66能够有效吸附以水杨酸（SA）和邻-苯二甲酸二甲酯（DMP）为模板化合物的两种常见PPCPs.在膜催化再生方面,UiO-66@Fe₃O₄@UiO-66中的Fe₃O₄能够催化H₂O₂生成强氧化性的羟基自由基（HO·）,实现对MOFs/PVDF膜吸附能力再生和膜内污染控制的耦合.结果表明,pH=7±0.1条件下,10% MOFs/PVDF膜对0.1 mmol·L^-1 SA和DMP吸附去除率最高,它们的去除率可分别达到64.2%和46.1%.除此之外,膜内UiO-66@Fe₃O₄@UiO-66催化5 mmol·L^-1 H₂O₂,能够使膜通量和膜吸附性能恢复率分别达到91.8%和94.2%.实验设计的这种负载多功能MOFs共混基质膜的特点是它对膜吸附能力再生和膜污染控制过程的耦合.这为生化尾水深度净化过程中PPCPs去除和膜抗污染性能改善提供了新的思路.     

晶面协同TiO2的制备及其可见光催化特性

以不同氟化物为晶面控制剂,采用超声辅助-溶胶凝胶法制备｛001｝和｛101｝晶面协同的F-TiO₂,借助XRD、TEM和EDS表征其物相结构、微观形貌和元素组成,通过改变氟化物种类和添加量确定F-TiO₂的最佳制备条件,并探讨其可见光催化过程中的主要活性物种及作用机理,研究关键反应参数对F-TiO₂光催化活性的影响.结果表明,引入NH₄F、NaF和HF可调控TiO₂沿｛001｝、｛101｝晶面生长,同时F^-掺杂能够增大材料的比表面积,制备所得材料的光催化性能均高于纯TiO₂.但在NaBF₄调控下合成的TiO₂为锐钛矿/金红石/Na₃TiF₆三相共存的半导体耦合结构,可见光催化活性显著下降.当NH₄F添加量为0.1 g时,材料显示出最强的光催化性能,可见光照射60 min后RhB的降解率为97.24%,矿化率达78.39%.降解反应符合一级反应动力学规律,速率常数为0.1321 min^-1.通过自由基捕获实验和ESR测试发现,h⁺、·OH均以关键活性因子参与F-TiO₂的可见光催化过程.F-TiO₂光催化活性增强主要归因于｛001｝和｛101｝晶面的协同作用和表面异质结的形成,其能有效提高光催化反应过程中光生电子空穴对的分离和迁移效率.在可见光照射下,适当增加催化剂投加量,降低RhB初始浓度,控制溶液为中性环境,可显著提高材料的降解速率.     

载银施氏矿物的制备及其对甲基橙的催化还原降解

采用硼氢化钠还原方法制备了不同载银量的银纳米粒子/施氏矿物复合催化剂（AgNPs/Sch）,利用扫描电镜（SEM）、X射线能谱（EDS）和X射线衍射（XRD）等测试方法对所制备催化剂的表面形貌、元素组成和物相组成进行了表征,证明了Ag成功负载于施氏矿物上.以甲基橙为目标污染物,硼氢化钠为还原剂,考察了不同载银量施氏矿物对甲基橙的催化降解性能,并探究了载银施氏矿物的投加量、硼氢化钠浓度、 甲基橙初始浓度、溶液初始pH等因素对甲基橙的催化还原降解效果的影响.结果表明,在甲基橙浓度为20 mg?L^-1、NaBH₄浓度为10 mmol?L^-1、初始pH=6条件下,反应90 min后,未载银的施氏矿物对甲基橙的降解率仅为7.5%,然而硝酸银添加量为0.10 g制备的AgNPs/Sch对甲基橙的降解率可达97.0%,该催化剂作为电子介质,能够将电子从还原剂（NaBH₄）转移到甲基橙中,进而加速甲基橙的降解.AgNPs/Sch在最佳的实验条件下5次循环性反应后,仍具有较高的催化稳定性.由此可见,载银施氏矿物作为一种新型的催化剂,在有机染料废水净化方面具有良好的应用前景.     

·OH自由基介导2,4-二氯酚光降解机理及产物毒性变化特征的理论研究

由于2,4-二氯酚(2,4-dichlorophenol,简称2,4-DCP)具有"三致"作用及潜在的生态风险,其光化学降解机理及产物的生态毒理效应目前成为人们关注的焦点。本研究采用理论化学计算手段,系统阐明了2,4-DCP在水环境中·OH介导的间接光化学转化机理、动力学和转化产物的生态毒性变化特征。结果表明2,4-DCP很容易被·OH氧化降解,其降解主要通过·OH-加成和H-迁移路径进行。在低温条件下·OH-加成路径将占主导,主要形成4,6-二氯苯-1,3-二酚;而当温度超过313 K时,·OH提取酚羟基上的氢原子为主要降解途径,主要形成2-氯苯-对苯醌。尤其在活性物种浓度较低的高温环境中,H-迁移路径有可能生成二噁英。计算毒理学结果表明:H-迁移产物的水生毒性超过·OH-加成产物,甚至超出母体2,4-DCP一个毒性等级。因此,我们建议在以后的环境监测以及风险评估过程中,关注2,4-DCP及其转化产物特别是H-迁移路径的转化产物的生态毒理学问题。     

Nitro polycyclic aromatic hydrocarbons in atmospheric particulate matter of Athens,Greece

Polycyclic aromatic hydrocarbons (PAHs) and nitro polycyclic aromatic hydrocarbons (N-PAHs) are chemical species of proven mutant and carcinogenic activity. In this study, the concentrations of seven different N-PAHs [2-nitronaphthalene (2N-NAP), 2-nitroflourene (2N-FLU), 2-nitroflouranthene (2N-FLA), 3-nitroflouranthene (3N-FLA), 1-nitropyrene (1N-PYR) and 2-nitropyrene (2N-PYR)] were determined in two fractions of atmospheric particulate matter from the atmosphere of Athens: coarse (2.4 μm?10 μm ) and fine (<2.4 μm ). 3N-FLA was not detected, whereas 1N-PYR, mostly originating from emissions from burning fuel, showed the maximum observed concentrations for both fractions and for the whole experimental period (especially during winter). In addition, 2N-FLA, a secondary nitro-PAH produced by photochemical reactions, showed relatively high values. Analysis of statistical data for N-PAH concentrations, using clustering technique, showed that: (1) 1N-NAP, 2N-FLU and 1N-PYR are mainly produced by direct burning; and (2) photochemical reactions are the dominant sources of 2N-NAP, 2N-PYR and 2N-FLA.     

Photo- and electro-catalysis for solar disinfection of Escherichia coli-contaminated water using Ag–TiO2/graphite

A titanium dioxide film on a graphite substrate was synthesized by chemical bath deposition from TiCl₄ as precursor and with the surfactant cetyl trimethyl ammonium bromide as a linking and assembling agent. Silver was loaded on the TiO₂ film by electrodeposition at 0.025?A. Water contaminated with Escherichia coli was disinfected under sunlight irradiation by photolysis (Lys), photocatalysis (PC), photoelectrocatalysis (PEC), and electrocatalysis (EC). The highest rate constant, k, was achieved with EC; k was 5.1?×?10^?2 colony forming units (CFU) mL^?1?min^?1. However, auto-oxidation of Ag occurred during EC and PEC. Meanwhile, the rate constant of disinfection by means of PC was lower than EC and PEC, and k was 3.82?×?10^?2 CFU?mL^?1?min^?1. Nevertheless, the auto-oxidation of Ag in the Ag–TiO₂/graphite tablet did not occur during the disinfection process.     

Behavior of aqueous stable colloidal nano-C60 aggregates exposed to TX100 micelles under different environmental conditions

C₆₀, as one of carbon nanomaterials widely used in various fields, could be released into the water environment thus exerting some potential health risks to human beings. This work examined the behavior of aqueous stable colloidal nano-C₆₀ (nC₆₀) aggregates under different environmental conditions including Polyethylene glycol octylphenol ether (TX100) micelles concentration, pH, and reaction time when exposed to TX100 micelles. Results show that the nC₆₀ aggregates became more dispersive and restored the capability of generating the singlet oxygen when exposed to TX100 micelles. With the increase of TX100 concentration, smaller average size of nC₆₀ aggregates was observed in dynamic light scattering (DLS) analysis, the fluorescence intensity of TX100 was more quenched by nC₆₀ aggregates, and the kinetic rate constant of generating the singlet oxygen for nC₆₀ aggregates was improved. The mean size of nC₆₀ aggregates in the presence of TX100 had no obvious variations when the pH ranged from 4 to 8. The longer reaction time between nC₆₀ aggregates and TX100 led to a higher kinetic rate constant of generating the singlet oxygen. Collective data suggest that variations in physicochemical properties of nC₆₀ aggregates are strongly dependent on the surrounding media under different environmental conditions and directly govern nC₆₀’s transport behavior and potential toxicity.     

Al(III)对糖浆溶液中有机还原物质还原六价铬的影响

通过批实验研究了Al(III)对糖浆溶液化学还原六价铬反应的影响,揭示了不同条件下Al(III)对六价铬还原反应动力学的影响.结果表明:Al(III)能够促进糖浆溶液还原六价铬反应进行;其作用机制是Al(III)与糖浆溶液中有机还原物质及Cr(VI)反应形成三者的络合物,降低糖浆中多酚等有机还原物质还原Cr(VI)的反应活化能,提高六价铬还原反应速率.Al(III)存在时,该六价铬还原反应符合准一级动力学反应; pH 2.0,2.5,3.0,3.5时,添加Al(III)的实验组中六价铬反应速率常数比对应的空白对照组中反应速率常数分别增加了0.0251,0.0139,0.0058, 0.0048h-1.添加Al(III)前后反应体系中六价铬还原的反应活化能(Eа)分别为66.38,62.80kJ/mol.当糖浆浓度不足时,Al(III)能够提高糖浆溶液还原六价铬的反应去除率.