三氯卡班环境暴露对斑马鱼神经行为的影响

为了探究三氯卡班(TCC)对脊椎生物神经行为的干扰及机制, 以脊椎模式生物斑马鱼为研究对象, 分别评判了TCC亚致死剂量急性暴露对幼鱼的神经发育毒性及慢性暴露对成鱼神经行为的影响.结果表明: TCC亚致死剂量急性暴露造成斑马鱼胚胎及幼鱼自主运动活力减少, 对声光刺激的敏感程度下降.吖啶橙凋亡染色表明, TCC诱导幼鱼头肾、脑部和眼睛等多部位发生细胞过度凋亡.通过扫描电镜观察, 侧线神经丘形态畸形, 发育受到抑制, 毛细胞团数量减少且排列紊乱.成鱼行为学试验结果显示, TCC长期暴露的成鱼过度焦虑及恐慌, 避险和警惕能力下降, 并表现出自闭, 不愿社交, 显著影响斑马鱼的记忆力、学习能力和辨别认知功能.     

大气臭氧损耗中双自由基反应机理的量子化学研究

用量子化学ＲＨＦ理论方法研究了单重态双自由基ＮＨ,ＣＨ２、ＣＣＬ２与大气臭氧Ｏ３的反应机理。在３－２１Ｇ水平上用梯度解析技术优化了上述瓜在的反应物、中间体和产物构型,６－３１Ｇ或６－２１Ｇ计算能量,得到了各构型的有关结构数据。计算表明：上述反应分２步进行,双自由基先与Ｏ３反应生成稳定的中间体,然后在光照条件下中间体分解为ＮＨＯ、Ｈ２Ｃ烽ＣＬ２ＣＯ等稳定分子。从动力学看,２步反应分别为「π４ｓ＋Ｗ２     

三元氧化体系中协同效应与羟基自由基产率关系的研究

本研究构建了VUV-US-O_3三元氧化体系,以水杨酸(SA)为分子探针,采用高效液相色谱和荧光检测器联用测定分析三元氧化体系的·OH产率.结果表明,各氧化体系的氧化能力排序为VUV/US/O_3VUV/O_3US/O_3VUV/USO_3VUVUS,120 min内对应的SA去除率分别为96.27%、83.57%、74.80%、68.88%、50.67%、36.06%、8.60%,组合体系显示出了明显的协同效应;VUV/O_3、VUV/US和US/O_3中检测出羟基化产物的最高浓度分别为12.32、7.51、4.47μmol·L~(-1),较VUV、US、O_3单独氧化产生的羟基化产物浓度(分别为5.22、0.34、3.61μmol·L~(-1))更高,推测各二元氧化体系中的协同效应主要是由·OH产率增加而引起;将US加入VUV/O_3体系中构成VUV/US/O_3三元氧化体系后,可加速O_3溶解并提高·OH最高产率至22.24μmol·L~(-1),使VUV/US/O_3氧化能力进一步提高.     

臭氧氧化水中2,4,6-三氯酚的反应机理研究

研究了臭氧氧化对2,4,6-三氯酚的去除效果,以及氧化过程中过氧化氢、氯离子、甲酸和乙二酸的变化情况,探讨了臭氧氧化2,4,6-三氯酚的反应机理和反应途径.实验结果表明,如果溶液中没有自由基清除剂,在臭氧投加量为24mg·L~(-1)时,0·1mmol·L~(-1)的2,4,6-三氯酚在6min内,去除率可达99%.臭氧分子氧化2,4,6-三氯酚的过程中产生过氧化氢,检测到的过氧化氢的最大摩尔浓度为初始2,4,6-三氯酚摩尔浓度的22·5%.中间产物过氧化氢随后和臭氧反应生成大量的羟基自由基,此时2,4,6-三氯酚是被臭氧和羟基自由基联合氧化,生成甲酸和乙二酸.当溶液中含有大量的自由基清除剂时,2,4,6-三氯酚首先被臭氧分子氧化成黄色的氯代对苯醌,然后氧化成甲酸和乙二酸.臭氧氧化2,4,6-三氯酚存在臭氧分子氧化以及O3/OH·联合氧化两种反应途径.     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

电化学氧化除氨氮过程中羟基自由基及中间产物定量分析

采用高效液相色谱对电化学氧化除氨氮过程,不同电流密度,Cl-浓度及初始pH值的·OH进行定量检测和分析,同时,对不同初始pH值和电流密度下,电化学氧化除氨氮的中间产物进行了定量分析,结果表明:·OH产生量与电流密度成正比,当有Cl-存在,且在碱性条件下会抑制·OH的产生;初始pH值为偏碱性时,NO2-和氯胺的产量均有所增加.建议电化学氧化脱氨氮过程,尽量保持溶液pH值在中性或酸性条件下;电流密度对氨氮电化学氧化过程中各中间产物的量有着较大影响,在电流密度为10mA/cm2时,活性物质产量最高,且有害中间产物产量最低.     

环境水体中自由基的检测技术研究进展

自由基化学性质高度活泼,极易发生得失电子的氧化还原反应,是环境水体中降解污染物的重要因素。自由基的环境鉴定和分析对揭示环境污染物降解转化机制具有重要意义。但由于自由基环境浓度极低、反应活性高、寿命短,再加上复杂环境基质的干扰效应,使其环境分析一直是研究的重点和难点。而且,目前的研究主要针对一些已知的自由基展开,对未知自由基的识别和鉴定研究较为匮乏。在系统总结典型自由基检测方法及其应用现状的基础上,阐述不同检测方法的优点和缺点,重点探讨适用于环境水体中羟基自由基等典型自由基的检测方法,并提出自旋捕获结合质谱分析技术具有特异性和高灵敏性的优点,可同时检测天然水体中多种自由基,并能够识别和鉴定未知自由基,是未来的研究方向。     

羟基自由基快速致死水华针杆藻的研究

库区、河流富营养化加剧,水华频繁爆发形成的高藻水已严重威胁饮用水的安全.本文利用大气压强电离放电高效生成的氧活性粒子(OASs),通过高压射流器将其注入到处理高藻水的主管路中,生成羟基自由基(·OH),同时·OH对引起水华的针杆藻(Synedra sp.)进行杀灭.采用荧光染色、测定光合能力等生物学方法,确定·OH致死针杆藻的阈值浓度及致死时间.结果显示,当初始藻细胞密度为10×104、50×104和100×104cells·m L-1,致死阈值浓度分别为0.25、0.71和1.18 mg·L-1,而最大光量子产率Fv/Fm的值在1 s内由0.50迅速减小为不能检出,表明可在运输高藻水的管路中完成·OH的处理过程.本研究表明,·OH快速致死的方法可高效地处理高藻水.     

丰枯水期鄱阳湖表层水中羟基自由基浓度及其抗生素净化作用研究

鄱阳湖位于我国农业大省江西省,表层湖水中羟基自由基(HO·)引发的水体光化学反应,可能对流域内的农业污染物—抗生素具有潜在的净化作用.因此,本研究以氙灯模拟太阳光测得鄱阳湖及周边河流羟基自由基表观光量子产率(ΦHO·),在丰水期为(0.57~10.33)×10~(-5),枯水期为(0.45~3.52)×10~(-5).丰水期溶解态有机物(DOM)对HO·形成的贡献率为85.8%~98.7%,枯水期为58.5%~97.6%,表明DOM是HO·形成的主导物质.可能由于水体混合均匀,丰水期除抚河水体可能有其特殊的化学组成外,其它湖泊与河流的水化学组成接近,表现出随溶解态有机碳含量升高,ΦHO·呈先增大后减小的现象.枯水期水体各化学组成含量显著高于丰水期,光屏蔽与淬灭可能起主要作用,只有当NO_2~-含量较高时才显示出对HO·形成的贡献.依据太阳光强可得鄱阳湖丰水期及枯水期表层水HO·的稳态浓度分别为9.51×10~(-16)与4.92×10~(-17)mol·L~(-1),湖水中5种抗生素在HO·作用下的半衰期分别为2.3~13.9 d与44.5~268.7 d,丰水期鄱阳湖表现出更高的光化学净化能力.     

NaClO、UV及UV/NaClO消毒过程中TCC的去除特性及遗传毒性

采用NaClO、UV和UV/NaClO复合消毒等方式研究了三氯卡班（TCC）在消毒过程中的去除特性,考察了3种消毒方式中TCC溶液的遗传毒性变化,鉴定了TCC的降解产物并探讨了其降解机制,以UV/NaClO复合消毒为研究对象,考察了NaClO投加量、TCC初始浓度、溶液pH值和腐殖酸（HA）等因素对TCC去除的影响.结果表明,3种消毒技术对TCC的去除效果依次为UV/NaClO、UV、NaClO.消毒处理不同程度增加了TCC溶液的遗传毒性.LC-MS鉴定出了8种TCC的降解产物,降解途径主要为脱氯、加氯以及·OH/O^·氧化.UV/NaClO复合消毒对TCC的去除率在97%以上;TCC的去除与其初始浓度呈负相关;TCC的去除率随pH值的增大先升高后降低;低浓度的腐殖酸（HA）对TCC的去除有促进作用,高浓度则相反.     

Theoretical insights into the degradation mechanisms, kinetics and eco-toxicity of oxcarbazepine initiated by OH radicals in aqueous environments

As an anticonvulsant, oxcarbazepine (OXC) has attracted considerable attention for its potential threat to aquatic organisms. Density functional theory has been used to study the mechanisms and kinetics of OXC degradation initiated by OH radicals in aqueous environment. A total of fourteen OH-addition pathways were investigated, and the addition to the C8 position of the right benzene ring was the most vulnerable pathway, resulting in the intermediate IM8. The H-abstraction reactions initiated by OH radicals were also explored, where the extraction site of the methylene group (C14) on the seven-member carbon heterocyclic ring was found to be the optimal path. The calculations show that the total rate constant of OXC with OH radicals is 9.47 × 10⁹ (mol/L)⁻¹sec⁻¹, and the half-life time is 7.32 s at 298 K with the [·OH] of 10⁻¹¹ mol/L. Moreover, the branch ratio values revealed that OH-addition (89.58%) shows more advantageous than H-abstraction (10.42%). To further understand the potential eco-toxicity of OXC and its transformation products to aquatic organisms, acute toxicity and chronic toxicity were evaluated using ECOSAR software. The toxicity assessment revealed that most degradation products such as OXC-2OH, OXC-4OH, OXC-1O-1OOH, and OXC-1OH' are innoxious to fish and daphnia. Conversely, green algae are more sensitive to these compounds. This study can provide an extensive investigation into the degradation of OXC by OH radicals and enrich the understanding of the aquatic oxidation processes of pharmaceuticals and personal care products (PPCPs).     

Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on superoxide radicals

Pentachlorophenol could be photocatalytically reduced with superoxide radicals in aqueous solution under simulated sunlight irradiation.     

OH自由基降解二英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：①α-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;②β-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=1.29×10¹⁴exp（-1049.6/T）（cm³·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英的进一步研究提供理论参考.     

辉光放电电解等离子体降解水体中的罗丹明B

用辉光放电电解等离子体(GDEP)对模拟染料废水罗丹明B(RhB)的降解过程进行了研究.通过发射光谱法测定了GDEP产生的活性粒子,采用紫外光谱分析了放电电压、溶液浓度、pH、Fe~(2+)等对RhB脱色率的影响,并用电导率仪和酸度计测定了降解过程中溶液的电导率和pH的变化,同时结合红外光谱粗略探讨了降解机理.结果表明,在最佳电压为600 V和放电60 min时,200 m L 20 mg·L~(-1)RhB的脱色率可达95.4%,降解过程符合动力学准一级反应;降解过程中溶液的电导率先增大后减小,溶液的pH呈现先减小后增大的趋势,说明在放电过程中产生了大量带电离子及酸性中间产物;加入0.03 mmol的Fe~(2+)对RhB的降解有催化作用,在pH=3.19条件下,放电5 min可使RhB的脱色率达到98.3%;羟基自由基(·OH)对RhB的降解起关键作用.     

Experimental study on oxidative decomposition of nitrobenzene in aqueous solution by honeycomb ceramic-catalyzed ozonation

The ozonation of nitrobenzene in aqueous solution was carried out in a semi-batch reactor to investigate the degradation efficiency, the effect factors, and the reaction mechanism, where honeycomb ceramic was used as a catalyst. The presence of honeycomb ceramic could improve the degradation rate of nitrobenzene by 15.46% compared to the results of ozonation alone. Under the conditions of this experiment, the degradation rate of honeycomb ceramic-catalyzed ozonation increased by 12.94% with the increase of the amount of catalyst from 1 to 5 blocks. The degradation rates all increased greatly with the increase of temperature and pH of the solution in the processes of honeycomb ceramiccatalyzed ozonation and ozonation alone. But, when the pH of the solution increased to 9.50, the advantage of the honeycomb ceramic-catalyzed ozonation process would be lost. The experimental findings indicated that in the processes of ozonation alone and honeycomb ceramic-catalyzed ozonation, nitrobenzene was primarily oxidized by ·OH free radical in aqueous solution. The adsorption of nitrobenzene was too limited to have an important influence on the degradation rate of nitrobenzene. With the same total dosage of applied ozone, the multiple step addition of ozone showed much higher removal efficiency than that obtained by one step in the two processes.     

裂解温度调控溶解性生物炭光敏化产生活性氧自由基

溶解性生物炭受紫外光辐射产生的活性氧自由基(Reactive oxygen species,ROS)易对环境造成影响,受到环境领域的持续关注.以玉米秸秆为原料,在不同裂解温度(200～600℃)下制备了5种生物炭,并通过水提得到溶解性生物炭(Dissolved biochar,DBC),系统考察了生物炭裂解温度对DBC结构和组分的影响,并利用化学分子探针定量研究了DBC在紫外光辐射下产生常见ROS的能力,如羟基自由基(Hydroxyl radical,?OH)、单线态氧(Singlet oxygen,¹O₂)和超氧自由基(Superoxide radical,O₂?^-).结果表明,DBC主要由有机酸、类蛋白质和纳米级生物炭构成,前两者皆会随生物炭裂解温度上升而减少,后者则会逐渐增多.高温DBC-(400～600℃)具有更强芳香性和疏水性,但荧光物质含量极低.对DBC产生的ROS进行定量研究发现,仅DBC-200℃和300℃产生少量?OH.DBC-300℃的¹O₂     

探究不同金属离子对电化学氧化去除水体中4-CP的影响

文章为探究金属离子(亚铁离子、铁离子、二价铜离子、二价锰离子)对电化学氧化降解废水中4-CP的影响。采用自制的圆形电化学反应器,通过添加不同含量的金属离子来探究对4-CP去除效果的影响。试验的研究表明,亚铁离子具有较好的催化强化效果,平均催化效率可达24%,且Fe(Ⅱ)最适宜投加量为1.5mmol/L,催化效率可提高31.5%。另外其他三种金属离子均存在不同程度的抑制,其中抑制效果由强到弱为Mn(Ⅱ)>Fe(Ⅲ)>Cu(Ⅱ),且当Mn(Ⅱ)投加量为3.0 mmol/L时,完全抑制4-CP的电化学氧化降解。     

Comparative study of degradation of toluene and methyl isobutyl ketone (MIBK) in aqueous solution by pulsed corona discharge plasma

Effectiveness of pulsed power plasma for the degradation of two toxic volatile organic compounds (VOCs), toluene and methyl isobutyl ketone (MIBK), in aqueous solution was evaluated. The plasma degradation of MIBK has been studied for the first time. The influence of initial concentration of target compound, solution pH and scavengers on percentage degradation was evaluated. 100% removal of 200 mg/L of toluene and MIBK was achieved both in liquid and gaseous phases after 12 and 16 min of plasma treatment, respectively. The first order rate constant of toluene and MIBK degradation (for 200 mg/L each) was 0.421 and 0.319 min^?1 respectively when they were treated individually, and these values decreased slightly during degradation of their mixture. MIBK degradation was slower than toluene and it might be due to semi volatile and hydrophilic nature of MIBK. The effect of initial concentration of toluene and MIBK showed different degradation patterns. Highest degradation of both the compounds was obtained in neutral pH and in absence of scavengers. ?OH radical was the major reactive species involved in their degradation. Their degradation in real environmental matrices showed that removal reduced significantly in secondary effluent due to scavenging of reactive species by various ions and organic matter. The total number of degradation intermediates identified in case of toluene and MIBK was 11 and 14 respectively and formate was the one recalcitrant byproduct generated. The degradation pathway of toluene and MIBK involving reactions of reactive oxygen and nitrogen species and reductive species is proposed.