Photolysis of chlortetracycline in aqueous solution: Kinetics, toxicity and products

The aqueous photodegradation of the widely used antibiotic chlortetracycline (CTC) was investigated under simulated sunlight. The quantum yield of photodegradation increased from 3.3 × 10^-4 to 8.5 × 10^-3 within the pH range of 6.0 to 9.0. The presence of Ca²⁺, Fe³⁺, and NO₃^- enhanced the photodegradation of CTC, whereas Mg²⁺, Mn²⁺, and Zn²⁺ inhibited the degradation with the order Mn²⁺ > Zn²⁺ > Mg²⁺ at pH 7.3. The monovalent cations (Na⁺ and K⁺) had negligible effect on the photolysis of CTC. Fulvic acid (FA) decreased the photodegradation of CTC due to light screening effect. Hydrogen peroxide (H₂O₂) was formed concurrently with direct photodegradation of CTC. The generation rate of H₂O₂ increased from 0.027 to 0.086 μupmol/(L.min) when the pH ranged from 6.0 to 9.0. The CTC solution was about three-fold more toxic to the Photobacterium phosphoreum bacteria after irradiation, suggesting that the photoproducts and H₂O₂ formed in the CTC solution exhibited high risk on the bacteria. By LC-ESI(+)-MS, the photoproducts of CTC were identified. The direct photodegradation of CTC was involved in hydroxylation and N-demethyl/dedismethyl processes. The main photoproducts included the iso-CTC analog containing hydroxyl groups (m/z 511.4 and 495.4), and the N-demethyl/dedismethyl products of the photoproduct m/z 495.4 (m/z 481.3 and 467.4). In addition, the photochemical dechlorination of CTC led to tetracycline (m/z 445.5).     

Conversion characteristics and mechanism analysis of gaseous dichloromethane degraded by a VUV light in different reaction media

The photodegradation of gaseous dichloromethane (DCM) by a vacuum ultraviolet (VUV) light in a spiral reactor was investigated with different reaction media and initial concentrations. Through the combination of direct photolysis, O₃ oxidation and HO. oxidation, DCM was ultimately mineralized into inorganic compounds (such as HCl, CO₂, H₂O, etc.) in the air with relative humidity (RH) of 75%-85%. During the photodegradation process, some small organic acids (including formic acid, acetic acid) were also detected and the intermediates were more soluble than DCM, providing a possibility for its combination with subsequent biodegradation. Based on the detected intermediates and the confirmed radicals, a photodegradation pathway of DCM by VUV was proposed. With RH 75%-80% air as the reaction medium, the DCM removal followed the second-order kinetic model at inlet concentration of 100-1000 mg/m³. Kinetic analysis showed that the reaction media affected the kinetic constants of DCM conversion by a large extent, and RH 80% air could cause a much lower half-life for its conversion. Such results supported the possibility that VUV photodegradation could be used not only for the mineralization of DCM but also as a pretreatment before biodegradation.     

多势派氯代二噁在土壤表面的紫外光解研究

本文利用500W中压汞灯研究了二(口恶)(口英)在干燥土壤中的紫外光解.根据光解结果计算了土壤中二(口恶)(口英)的降解深度,并分析了五氯代二(口恶)(口英)(PeCDD)的光解产物.结果表明,二(口恶)(口英)在土壤表面发生了较快的光解反应,反应在2h内基本完成,降解深度为0.027mm.对PeCDD光解产物的分析结果显示,二(口恶)(口英)在土壤表面紫外光降解的主要途径为脱氯,而且脱氯优先发生在邻位上.     

UV-vis/草酸铁络合物/H2O2法处理垃圾渗滤液的研究

在紫外光照下,利用H2O2和草酸铁络合物对垃圾渗滤液进行了处理,探讨了紫外光照时间、pH值、fenton试剂、草酸铵对垃圾渗滤液中CODCr去除率的影响.结果表明:UV-vis/草酸铁络合物/H2O2法对垃圾渗滤液CODCr去除率有较好的效果,当操作条件是:pH取3,反应时间为1 h,H2O2投加量为1.4 mL,H2O2/FeSO4·7H2O投加比(摩尔比)为5∶1,草酸铵投加量为5.5 mL时,CODCr的去除率达到了78.8%.     

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.     

Fe_3O_4-xTiO_2复合光催化剂的制备及其对染料废水的处理效果

采用共沉淀法制备了复合光催化剂Fe_3O_4-xTiO_2。运用XRD、SEM、TEM和UV-Vis DRS等技术对光催化剂进行了表征,并考察了其在太阳光下对茜素红模拟染料废水的光催化降解活性。实验结果表明,当TiO_2与Fe_3O_4的质量比为0.75、初始溶液p H为3.0时,茜素红去除率最高,光催化反应120 min后,茜素红去除率为100%。表征结果显示,Fe_3O_4-0.75TiO_2复合光催化剂不是核壳结构,而是Fe_3O_4和TiO_2的聚集体。Fe_3O_4-0.75TiO_2复合光催化剂重复使用5次后茜素红去除率几乎没有下降,活性稳定性极佳。     

ZnIn2S4可见光催化降解水中的双氯芬酸

通过水热法制备了可见光下响应的光催化剂ZnIn2S4,研究了水中痕量医药类物质双氯芬酸的光解和光催化降解效果与降解途径,同时对催化剂进行了扫描电镜、X射线衍射、紫外可见漫反射、氮吸附和羟基自由基捕获的测试。结果表明,ZnIn2S4的比表面积为91.3 m2·g-1,且在可见光照射下具有良好光催化性能。以卤钨灯模拟太阳光,在双氯芬酸初始浓度100 μg·L-1,ZnIn2S4投加浓度10 mg·L-1条件下反应5 h可降解水中98%的双氯芬酸。卤钨灯直接光解5 h可降解91%的双氯芬酸。光解和光催化反应均符合假一级反应动力学,光催化反应速率是光解反应速率的1.5倍。双氯芬酸光解过程中主要发生光环化反应,生成了2-（1-氯-9H-咔吧唑-8-基）-乙酸;光催化过程则主要通过羟基自由基氧化降解双氯芬酸,中间产物主要有1-氯-8-甲基-9H-咔吧唑及2,6-二氯-N-邻甲苯基苯胺。     

新型可见光催化剂BiVO4降解中成药制药废水

以Bi（NO3）3.5H2O和NH4VO3为原料,采用水热法制备了新型可见光BiVO4催化剂,并用X-射线衍射（XRD）、扫描电子显微镜（SEM）、红外光谱（IR）和紫外-可见光漫反射光谱（UV-vis DRS）对产品进行了结构表征,并将其应用于光催化降解中成药制药废水降解反应中,通过正交实验和单因素分析,考察了催化剂用量、空气流量、溶液pH值和助氧化剂H2O2对制药废水COD去除率、脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.41 eV,并具有良好的可见光催化活性。对于经10倍稀释的制药废水,BiVO4添加量为2 g/L,通氧量为120 L/h,助氧化剂H2O2添加量为1 mL,不改变废水pH值,在400 W金属卤化物灯离液面11 cm照射反应180 min的条件下,制药废水的COD去除率为94.3%,脱色率为95.6%,得到了较好的降解。     

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.     

光诱导腐殖酸产生自由基对天然水中雌二醇光降解效能的影响

以腐殖酸（humic acid,HA）为光敏化剂,采用300 W氙灯模拟太阳光,研究雌二醇（E2）在HA溶液中的光降解动力学。结果表明：E2在HA溶液中的光解反应符合准一级动力学模型,HA对E2光解速率起促进作用,且随着HA浓度的增加（由0增至12 mg·L-1）对E2的促进作用增强;当HA继续升高至24 mg·L-1时,HA的光掩蔽作用增强,对E2光解的促进作用减弱。采用电子顺磁共振技术（EPR）直接证明了HA在E2的光解过程中会产生羟基自由基（·OH）。自由基淬灭实验表明·OH和单线态氧（1O2）对E2光解贡献率分别为62%和20%。TOC的去除率远低于E2的去除率,说明E2在光降解过程中并没有被完全矿化。