OH自由基降解二噁英OCDD的反应机理及动力学研究

采用量子化学计算研究了OH自由基降解八氯代二苯并对-二噁英(OCDD)的微观反应机理,计算分析了微观反应进程,结果表明该反应存在两条途径:(1)α-氯取代:1,4,6,9位置氯取代,该路径反应活化能较高,反应难以进行,并以中间产物积聚,无法使OCDD的毒性消失;(2)β-氯取代:2,3,7,8位置氯取代,该路径的反应能相对较低,且能使OCDD的毒性消失,是有效降解OCDD的主要途径.结合过渡态理论,计算获得动力学参数:反应活化能为8.32 kJ·mol~(-1)(B3LYP/6-311G++(d,g)//B3LYP/6-31G(d)),阿仑尼乌斯表达式为k=1.29×10~(14)exp(-1049.6/T)(cm~3·mole~(-1)·s~(-1)).这与文献实验结果取得了很好的吻合,说明本文对OH自由基降解OCDD的反应机理及动力学研究是合理且可靠的.本文的计算结果可为催化氧化降解二噁英的进一步研究提供理论参考.     

热活化过硫酸盐降解三氯生

基于硫酸根自由基（SO₄^·-）的高级氧化技术被广泛应用于土壤和地下水污染修复.本研究系统地考察了三氯生在热活化过硫酸盐高级氧化过程中的动力学、中间产物和降解途径.结果表明,提高反应温度或增加过硫酸盐的浓度,可加快三氯生的降解.三氯生的降解符合假一级反应动力学规律,反应活化能（E_a）为142 kJ·mol^-1.水中的腐殖酸显著抑制了三氯生的降解,而氯离子（Cl^-）对三氯生降解的影响比较复杂.当Cl^-浓度为5 μmol·L^-1时,三氯生的降解受到了轻微的促进;但是当Cl^-的浓度增加至10 μmol·L^-1甚至更高时,三氯生的降解反而受到了抑制.通过质谱分析发现三氯生降解过程中生成了4-氯-邻苯二酚、2,4-二氯苯酚和2-氯-5-（2,4-二氯-6-羟基苯氧基）-1,4-苯醌等6种主要中间产物,并由此推测醚键的断裂和酚环羟基化是三氯生的可能降解途径.本研究为基于SO₄^·-的高级氧化技术去除水中三氯生的应用可行性提供了依据.     

紫外光活化亚硫酸盐降解水中卡马西平

研究了紫外光活化亚硫酸盐高级氧化工艺降解水中典型新污染物——卡马西平（CBZ）的效能和降解机制.探究了不同溶解氧浓度[ρ（DO）]对紫外光活化亚硫酸盐降解CBZ的影响,并在模拟自然水体环境控制初始ρ（DO）为（8.0±0.2） mg·L^-1条件下,考察了不同工艺参数（亚硫酸盐投加量、反应pH）与水环境要素（碳酸氢根离子、氯离子、腐殖酸）对CBZ降解效能的影响.结果表明,紫外光活化亚硫酸盐工艺可在30 min内降解85.3%的CBZ,降解过程遵循拟一级动力学,动力学常数为0.055 7 min^-1.并采用电子顺磁共振波谱技术、活性物质淬灭实验和竞争反应动力学实验发现,CBZ的降解主要来自紫外光活化亚硫酸盐工艺中硫酸根自由基（SO₄^-·）与羟基自由基（·OH）等活性物质,且降解贡献率分别为43.9%和56.1%.而且CBZ降解率随HCO₃^-浓度升高而降低,但Cl^-浓度变化对CBZ降解率影响不大,水中存在的腐殖酸可显著抑制CBZ的降解.反应过程中硫酸盐的积累量显著低于《生活饮用水卫生标准》（GB 5749-2022）限值,且亚硫酸盐消耗速率（0.004 4 min^-1）显著低于CBZ的降解速率,说明亚硫酸盐可被紫外光高效活化用于降解水中存在的CBZ.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

氯代乙烯的厌氧微生物还原脱氯特性

四氯乙烯（PCE）和三氯乙烯（TCE）是地下水中典型的卤代有机化合物,严重威胁生态环境与人体健康.为获得氯代乙烯高效厌氧降解菌剂并探究其在污染地下水中的应用潜能,利用某工业污染场地的地下水,通过投喂PCE或TCE进行长期富集培养,获得了可将PCE和TCE完全脱氯成无毒乙烯的厌氧菌剂W-1.菌剂W-1的PCE和TCE脱氯速率分别是（120.1 ±4.9） μmol·（L·d）^-1和（172.4 ±21.8） μmol·（L·d）^-1.16S rRNA基因扩增子测序和qPCR结果表明,98.3 μmol PCE还原脱氯至顺-1,2-二氯乙烯（cis-1,2-DCE）时,Dehalobacter丰度从1.9%增长至57.1%,基因拷贝数每释放1 μmol Cl^-增加1.7×10⁷ copies;cis-1,2-DCE完全还原脱氯至乙烯时,Dehalococcoides丰度从1.1%增长至53.8%;PCE完全还原脱氯至乙烯过程中Dehalococcoides基因拷贝数每释放1 μmol Cl^-增加1.7×10⁸ copies.以上结果说明Dehalobacter与Dehalococcoides协同互作实现PCE完全降解解毒.当菌群W-1以TCE为电子受体时,222.8 μmol TCE完全还原脱氯至乙烯时候,Dehalococcoides丰度从（29.1 ±2.4）%增长至（77.7 ±0.2）%,基因拷贝数每释放1 μmol Cl^-增加（1.9 ±0.4）×10⁸ copies.结合PCR和Sanger测序,获得了菌剂W-1中主要脱卤菌Dehalococcoides LWT1较完整的16S rRNA基因序列,其与D. mccartyi strain 195 16S rRNA基因序列相似度达100%.将菌群W-1添加至受TCE（418.7 μmol·L^-1）污染的地下水中,28 d内实现了（69.2 ±9.8）%的TCE被完全脱毒至乙烯,TCE脱氯速率为（10.3 ±1.5） μmol·（L·d）^-1.研究成果可为PCE或TCE污染地下水开展厌氧微生物修复提供菌剂资源和理论指导.     

ZnMnxCo2-xO4活化过一硫酸盐降解有机污染物

分别以Zn（CH₃COO）₂·2H₂O、Mn（CH₃COO）₃·2H₂O和Co（CH₃COO）₂·4H₂O为锌源、锰源和钴源,采用溶胶-凝胶自燃烧法成功制备了ZnMn_xCo_2-xO₄（x=0~2）复合物,并用X射线衍射和X射线光电子能谱对其进行表征.同时,还研究了Mn/Co物质的量比、催化剂用量及PMS用量对目标污染物降解的影响.结果表明,该复合物可催化活化过一硫酸钾（PMS）降解有机污染物,当催化剂中x=0.8,催化剂投加量为0.2 g·L^-1,PMS用量为0.4 mmol·L^-1（0.25 g·L^-1）时,20 μmol·L^-1（10 mg·L^-1）罗丹明B（RhB）可在15 min内完全降解.ZnMn_0.8Co_1.2O₄的高催化活性主要归功于Mn³⁺和Co²⁺的协同效应.将ZnMn_xCo_2-xO₄-PMS体系用于亚甲基蓝、结晶紫、金橙、双酚A、4-氯酚等其他污染物的降解,也取得了较好的效果.基于电子自旋共振ESR和自由基猝灭实验的结果,可以推测该反应体系中活性物种为硫酸根自由基和羟基自由基.     

紫外活化过硫酸盐降解磷酸氯喹

以抗新型冠状肺炎药物——磷酸氯喹（CQP）为研究对象,考察其在紫外活化过硫酸盐体系（UV/PS）中的降解效果.通过竞争动力学实验,确定了CQP与羟基自由基（HO·）和硫酸根自由基（SO₄^-·）的二级反应速率常数,同时考察了PS浓度、pH和常见无机阴离子对UV/PS体系中CQP降解的影响,并通过建立动力学模型预测CQP浓度和主要自由基浓度以探究其影响机制.结果表明,UV/PS体系对CQP的降解效果显著优于单一UV、单一太阳光或单一PS体系,在10 min内可降解91.3%的CQP;在pH为6.9的条件下,CQP与HO·和SO₄^-·的二级反应速率常数分别为8.9×10⁹ L·（mol·s）^-1和1.4×10¹⁰ L·（mol·s）^-1,其中SO₄^-·是主要活性物种;CQP的降解速率随PS浓度增加而增大,HCO₃^-和Cl^-的加入对UV/PS体系中CQP的去除起到抑制作用,碱性较强的条件不利于CQP的转化.经LC-MS分析,发现CQP在UV/PS体系中主要经过N-脱乙基化、C—N键断裂和抽氢等反应被逐步降解为其他有机中间产物.加大PS浓度和pH可提高其矿化率.此研究可为抗新冠肺炎医药废水的处理提供帮助.     

磁性生物炭负载α-MnO2活化过一硫酸盐降解2,2'',4,4''-四溴联苯醚

环境中的多溴联苯醚（PBDEs）对人类健康和生态环境存在潜在危害,开发高效、经济和环保的高级氧化体系对其进行有效降解具有重要意义.利用水热法合成的磁性生物炭负载二氧化锰复合材料（α-MnO₂/MWB）作为催化剂,有效活化过一硫酸盐（PMS）降解2,2'',4,4''-四溴联苯醚（BDE-47）,通过SEM、XRD、FT-IR和BET等手段对材料进行表征分析,同时探究了材料对PMS的催化活化能力.结果表明,α-MnO₂/MWB具有最佳的催化性能,在α-MnO₂/MWB负载质量比为1：2、催化剂投加量为0.05 g·L^-1、PMS浓度为5 mmol·L^-1的条件下,对1 mg·L^-1 BDE-47的降解率达到94%.溶液初始pH对体系的影响较小,氯离子（Cl^-）和腐殖酸（HA）对BDE-47的降解有抑制作用,随其浓度升高抑制作用增强,硝酸根离子（NO₃^-）和碳酸氢根离子（HCO₃^-）对降解几乎无影响.通过自由基淬灭实验证明SO₄^-·和·OH是该体系降解BDE-47的两种关键自由基,其中SO₄^-·占主导地位.反应前后材料的XPS表征分析表明,Mn和Fe元素的价态转化是活化PMS的主要原因.α-MnO₂/MWB经重复利用4次,仍保持着高效的催化性能.     

郑州市冬夏季污染过程中大气VOCs污染特征、来源解析及活性分析

为了研究挥发性有机物（VOCs）的污染特征,于2021年6月和12月在郑州市对两个污染过程中的VOCs进行了连续监测.结合气象条件,对比分析了VOCs冬夏季污染过程的污染特征、来源贡献和活性差异.结果显示,两个污染过程φ（VOCs）分别为（27.92±12.68）×10^-9和（24.30±5.93）×10^-9.冬季雾-霾污染过程相较于夏季O₃污染过程,VOCs体积分数变化范围更大.冬季污染过程源解析结果：工业源（27.0%）、机动车源（22.5%）、燃烧源（20.1%）、溶剂使用源（16.3%）和油气挥发源（14.1%）;夏季污染过程源解析结果：机动车源（24.8%）、工业源（24.1%）、溶剂使用源（17.4%）、油气挥发源（14.2%）、燃烧源（11.2%）和植物源（8.4%）.光化学烟雾产量模型结果显示,两个污染过程中夏季臭氧生成处于VOCs控制区的天数占比（66.7%）小于冬季（100.0%）.二次反应活性结果显示,冬季和夏季污染过程·OH自由基反应活性（L_·OH）均值分别为4.12 s^-1和4.76 s^-1.夏季污染过程臭氧生成潜势（OFP）均值108.36 μg·m^-3,L_·OH和OFP贡献率排名前10名物种夏季污染过程以烯烃为主.郑州市冬季污染过程的总二次有机气溶胶生成潜势（SOAFP）为54.38 μg·m^-3,冬季污染过程SOAFP贡献率前10名物种中芳香烃占9个.     

CDs-BOC复合催化剂可见光下活化过硫酸盐降解典型PPCPs

本研究通过简便的水热和煅烧两步法合成了一种新型光催化剂,该方法用碳量子点（CDs）修饰BiOCl纳米片.制备的纳米复合材料（CDs-BOC）通过X射线衍射（XRD）、扫描电子显微镜（SEM）、高分辨率透射电子显微镜（HRTEM）、紫外-可见漫反射吸收光谱（DRS）、X射线光电子能谱（XPS）和稳态荧光光谱（PL）等手段进行了表征.结果表明,此材料成功地引入了CDs.7% CDs-BOC纳米复合材料的光吸收边界被增强至可见光区域（424 nm）,并提高了光致电子-空穴对的分离效率.为了提高有机污染物降解的效果,过硫酸盐（PS）被引入了CDs-BOC光催化体系中.由于复合纳米催化剂具有出色的光催化能力,光生电子可以有效活化PS,产生更多的活性氧化物质.在可见光（λ>420 nm）照射下,20 min内可以完全去除5 mg·L^-1对-乙酰氨基酚（AAP）.通过自由基淬灭实验和电子顺磁共振波谱（EPR）,探明了此体系具有多种活性氧化物质：·OH、·SO₄^-、·O₂^-和h⁺,并提出了降解反应机制.以上结果体现出CDs-BOC/PS体系在光催化处理水污染方面具有广阔的应用前景.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.