光源和溶剂对十溴联苯醚光降解的影响

研究了不同光源和溶剂对十溴联苯醚(DecaBDE)光降解特性的影响,并对其降解产物进行了探讨.结果表明,在所试光源和溶剂条件下,DecaBDE均有一定程度的光降解,且都近似符合一级降解动力学.同一光源下,不同溶剂对DecaBDE降解表现出不同的影响.在太阳光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷>正己烷/丙酮>甲醇/水>乙醇/水;在模拟光源照射下,DecaBDE降解速率为甲苯>甲醇>甲醇/水>乙醇/水>正己烷>正己烷/丙酮;在紫外光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷/丙酮>正己烷>甲醇/水>乙醇/水.同一溶剂中,DecaBDE降解速率均为紫外光>太阳光>模拟光源.尽管光源和溶剂对DecaBDE降解速率产生了一定影响,但降解途径基本一致,均为DecaBDE经光解脱溴产生低溴联苯醚.     

腐殖酸和铁对阿特拉津光降解影响的研究

为考察除草剂在水体中的自净性能,对模拟太阳光(λ> 290 nm)下腐殖酸和铁元素对阿特拉津的光化学降解进行了研究。结果表明,单独辐照阿特拉津几乎不降解。在分别加入3、5和10 mg/L的腐殖酸时,阿特拉津的降解率分别为34.36 %、40.74%和15.66 %;在Fe(Ⅲ)投加量从0.01 mmol/L增加到0.2 mmol/L时,阿特拉津的降解率从24.36 %增加到34.97 %。而在当腐殖酸与铁共存时,阿特拉津降解率则进一步提高。紫外可见光谱和荧光光谱均表明,腐殖酸-铁络合物的形成及其光化学作用,促进了阿特拉津的降解。     

Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light

The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

铋修饰BiOBr/g-C3N4异质结光催化剂合成及其可见光催化性能研究

以尿素为氮化碳（g-C₃N₄）合成的前驱体,柠檬酸（CA）作为还原剂,以一步溶剂热法制备铋修饰BiOBr/g-C₃N₄异质结型复合光催化剂（简称Bi/BiOBr/g-C₃N₄）.通过调控CA的投加量,实现了对Bi/BiOBr/g-C₃N₄可见光催化的可控制备,并以RhB为目标污染物研究其光催化活性.结果表明：1被还原在BiOBr表面上的Bi金属含量随还原剂CA投加量增加而增加,CA最佳投加量为2 mmol,Bi/BiOBr/g-C₃N₄的光生载流子的分离效率最高、禁带宽度最窄（2.43 eV）.而未采用CA改性的BiOBr/g-C₃N₄,其禁带宽度为2.8 eV.2投加CA能调控BiOBr形貌（如结晶度、尺寸大小以及晶粒平均厚度）,进而调控其光催化活性.当CA投加量为2 mmol时,BiOBr纳米微球大小适中,结晶度最高,晶粒平均厚度最小.3Bi修饰BiOBr/g-C₃N₄光催化剂对RhB的可见光降解率高达99.8%,其光催化降解速率达到0.097 k·min^-1,是BiOBr/g-C₃N₄光催化速率（0.026 k·min^-1）的3.73倍.4Bi/BiOBr/g-C₃N₄异质结光降解机理是：在Bi金属等离子体效应、BiOBr表面氧空缺与异质结的协同作用下,提高了Bi/BiOBr/g-C₃N₄异质结对可见光吸收能力和光生载流子的分离效率,从而实现对RhB的高效降解.     

天然日光辐照下两江交汇处溶解性有机质(DOM)光漂白过程：以涪江-嘉陵江为例

利用三维荧光光谱手段,结合紫外-可见吸收光谱,分析了涪江(FJ)、嘉陵江(JLJ)及两江交汇处(FJ-JLJ)溶解性有机质(DOM)在太阳辐照下的光漂白过程.结果表明,在夏季短期太阳辐射作用下,所有样品的有色溶解性有机质(CDOM)浓度[a(280)]和荧光峰A、C、M、T均发生了较明显光漂白,降解程度大小顺序为JLJ>FJ-JLJ>FJ.3个采样河段DOM光漂白性质因采样水域周边土地利用类型不同、江水汇合的稀释作用等影响而存在一定差异.以森林系统为陆源输入的JLJ样本光漂白活性最高,城市输入占主导的FJ最低,两江汇合样本居中.DOM经日光辐照后,光谱斜率S和吸光度比值A250/A350增大,腐殖化指数HIX减小,它们可作为光漂白过程中DOM性质变化指标.光漂白过程中,几乎所有样本呈现出陆源特征向自生源特征转化的趋势,尤其IT/IC先降低后显著增加,因此光漂白过程可能会夸大DOM的内源贡献,同时对利用IT/IC评估水体人为影响程度时产生干扰.另外,吸收和荧光光谱参数在评估DOM光漂白过程中结构组分变化的一致性,进一步证明了采用两种互补的光谱手段对DOM地化特征进行辨析的可行性.     

不同形态无机氮对水中微量药物安替比林光降解效能影响

在300 W氙灯光照条件下,研究了消炎镇痛类药物安替比林(ANT)在纯水中的光降解效能与机制,重点考察了水中不同形态无机氮及pE值对ANT光降解效能的影响.结果表明,ANT在不同条件下的光降解均符合假一级反应动力学;ANT在纯水中的光降解包括直接光解以及由羟基自由基(.OH)和单线态氧(1O2)参与的自敏化光解,贡献率分别为55.27%、22.19%和22.54%.不同形态无机氮(NH4+、NO2-和NO3-)单独存在条件下对ANT光降解效能的影响差异较大.在pE值较低时,即无机氮主要以NH4+形式存在,对ANT的光降解几乎没有影响;随着pE值的升高(由4.82～6.85),NH4+向NO2-转化,由于NO2-不仅能与ANT竞争吸收光子,同时还对.OH具有较强的淬灭作用,使得其对ANT光降解的抑制作用逐渐增强,当pE值达到6.85,即无机氮主要以NO2-形式存在时,ANT光降解的抑制率达到最高为35.31%;随着pE值的继续升高(由6.85～8.15),NO2-向NO3-转化,对ANT光降解的抑制作用逐渐减弱.     

Effects of environmental factors on sulfamethoxazole photodegradation under simulated sunlight irradiation: Kinetics and mechanism

To advance the knowledge of the environmental fate of sulfamethoxazole (SMX), we systematically investigated the effects of natural water constituents and synthetic substances (i.e., TiO₂ nanoparticles (nTiO₂) and Ti-doped β-Bi₂O₃ (NTB)) on the photodegradation kinetics of SMX under xenon lamp irradiation. The photolysis of SMX in aqueous solution followed first-order kinetics. Our results showed that higher concentrations of SMX, fulvic acid, suspended sediments, NTB and higher pH value decreased the photodegradation rates of SMX, whereas H₂O₂ improved the SMX photodegradation. TiO₂ nanoparticles had a dual effect on photodegradation due to their photocatalytic activity and photoabsorption of photons. No intermediates more toxic toward Vibrio fischeri than SMX were produced after direct photolysis and photocatalytic degradation for 3 hr. The photolysis of SMX involved three pathways: hydroxylation, cleavage of the sulfonamide bond, and fragmentation of the isoxazole ring. This study lays the groundwork for a better understanding of the environmental fate of SMX.     

XAD-8树脂分组的富里酸组分对菲光降解的影响机制初探

采用XAD-8树脂分组方法,将富里酸分为:pH4.8、pH7.0、pH11.0、水和乙醇组分,初步探讨富里酸不同组分对菲光降解的影响.结果表明:实验浓度范围内,浓度越高的富里酸组分对菲的光降解影响越大;不同组分也具有不同表现,表现在pH4.8、pH7.0组分中菲的光降解速率比水与乙醇组分中菲的光降解速率大;进一步采用分子探针手段分析显示,各组分诱导产生的单线态氧(~1O_2)和羟基自由基(·OH)对菲光降解均起到作用.从富里酸各组分的紫外吸收光谱、元素分析和傅里叶红外光谱表征可以看出,pH4.8、pH7.0组分相对于其他组分含有更多的羧基成分,含氧量更高,这两个组分在光解时能够产生更多的·OH与~1O_2,而这两种物质能促进菲的光降解.     

二氧化钛催化下的氯代二苯并-对-二恶英光解反应

本文利用中压汞灯作光源,研究了氯代二苯并-对-二恶英(CDDs,包括CDD,DCDD,PeCDD和OCDD)在二氧化钛催化下的光解反应,并讨论了二氧化钛浓度、pH值、反应温度以及取代氯原子数目等对反应速率的影响.结果表明,二氧化钛能有效地催化CDDs的光降解,在室温下,4h内DCDD,PeCDD,OCDD分别降解了87.2%,84.6%,91.2%,反应温度和二氧化钛浓度是控制该反应的主要因素.