水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

抗菌剂三氯卡班在水溶液中的光降解

研究了抗菌剂三氯卡班(triclocarban,TCC)在水溶液中的光降解过程及其影响因素,考察了不同光源、溶液pH值、初始TCC浓度、添加光催化剂TiO2及自然界水体中常见阴离子(如Cl-、NO-3和SO2-4)存在的影响。结果表明,TCC在紫外光照射下能进行光降解,其反应符合假一级反应动力学。pH值对TCC在紫外光下的光解过程影响显著,且其降解速率随着pH值的升高而增大。适量添加TiO2能促进TCC的光解速率。无机阴离子Cl-、NO-3和SO2-4的存在阻碍了TCC的光解。此外,还对TCC的降解机理进行了初步推测。     

过氧化氢/草酸铁体系太阳光催化降解染料废水的研究

以过氧化氢 /草酸铁络合物作光氧化剂 ,利用太阳光对 10种水溶性染料模拟废水进行了光氧化降解试验研究 ,发现在日光照射下 ,过氧化氢 /草酸铁络合物能使染料溶液迅速降解。以活性艳蓝KN R为代表 ,研究各种因素对光降解的影响。结果表明 ,溶液pH为 2 0～ 4 0时 ,光降解速率快 ;溶液中Fe3 + 与草酸根的摩尔比为 1∶3时 ,光解效果最好 ;提高H2 O2 浓度可以提高光降解速率 ,但H2 O2 的利用率会降低。     

新型管状光催化反应器降解VOCs特性

以一种新型折流式管状光催化反应器为研究对象,选择甲醛、苯和甲苯为目标污染物,以紫外光源、催化剂负载量和反应器内循环流量为关键影响因素,利用非密闭型环境舱,分析了反应器降解室内VOCs特性。结果表明,在254 nm和365 nm紫外光源照射下,VOCs的总衰减系数随初始浓度的增加而增大,且254 nm紫外光源照射下的总衰减系数更大。365 nm紫外光源照射时,VOCs的反应有效度随催化剂负载量的增加而增大;254 nm紫外光源照射时,反应有效度受催化剂负载量变化的影响很小。VOCs的转化率随循环流量的增加而增大,而反应速率受循环流量的影响较小;相同的循环流量下,转化率和反应速率均随着VOCs初始浓度增加而增大。由于增设肋片,折流式管状反应器比传统无肋片管状反应器的洁净空气量提升60%,且反应有效度更接近0.5,说明前者的传质-反应速率更加匹配,降解性能明显更优。     

硝酸根紫外光降解对硝基苯甲酸的研究

以硝酸铝做光氧化剂,研究了紫外光照射下,NO-3对PNB(对硝基苯甲酸)的光降解作用.探索了NO-3投加量、模拟废水初始浓度和pH值、光照时间、溶解氧浓度对处理效果的影响.结果表明,NO-3对PNB具有良好的光氧化作用,在最佳处理条件下,NO-3光降解PNB 4 h后降解率达90.8%.廉价硝酸盐对于有机物能起到显著光...     

紫外光降解气态氯苯的影响因素及其动力学研究

紫外光降解挥发性有机物(VOCs)是一种新型的废气处理技术.采用主波长为365 nm的500 W高压汞灯为光源,重点考察了空塔停留时间、氯苯初始浓度、反应介质等对氯苯光降解效果的影响.结果表明,在氯苯初始浓度较低时.氯苯去除率随着空塔停留时间的延长而呈线性升高.最大去除率达87%;而氯苯初始浓度过高时会使单位分子接受的光子和活性基团数量下降,引起氯苯去除率降低,空气介质中的O2和H2O在光照下可转化为活性基团.进而增强了光降解效果;而在氮气介质下光降解氯苯的效率大大降低,最大去除率仅为61%.在氯苯为0.36～8.64 mg/L时,紫外光降解氯苯遵循二级反应动力学方程.     

光催化降解模拟室内挥发性有机污染物研究

用浸渍-提拉法制备玻璃弹簧负载型TiO2薄膜催化剂,在自制的反应器中进行光催化降解由丙酮、甲苯、对二甲苯组成的模拟室内挥发性有机污染物VOCs研究.研究发现:催化剂中掺杂金属离子能影响催化剂的降解效果,降解效果依次为掺铈TiO2＞纯TiO2＞掺银TiO2;气体流量显著影响降解效果,丙酮、甲苯和对二甲苯的最佳降解流量分别为3、5、7 L/min;混合气体中非对称性的极性分子的降解效率高于对称性分子,导致丙酮、对二甲苯组分降解率降低,甲苯降解率增高.     

紫外光照射与生物降解耦合用于PCBs降解的研究

介绍了PCBs紫外光降解的机理及研究进展 ,讨论了影响PCBs光降解的主要因素 ,即环上的氯原子数目、取代位置及所处的微环境均显著地影响PCBs的光降解速率。简述了PCBs生物降解的研究进展 ,重点概述了好氧降解、厌氧降解及好氧厌氧协同作用的机理及特点。最后 ,讨论了PCBs生物降解和光降解的互补性 ,介绍了最近的研究进展 ,指出光降解和生物降解耦合将加快PCBs的移走速率 ,提出了PCBs污染土壤原位修复需要进一步解决的问题。     

过氧化氢／草酸铁体系太阳光催化降解染料废水的研究

以过氧化氢／草酸铁络合物作光氧化剂，利用太阳光对10种水溶性染料模拟废水进行了光氧化降解试验研究，发现在日光照射下，过氧化氢／草酸铁络合物能使染料溶液迅速降解。以活性艳蓝KN-R为代表，研究各种因素对光降解的影响。结果表明，溶液pH为2．0～4．0时，光降解速率快；溶液中Fe^3 与草酸根的摩尔比为1：3时，光解效果最好；提高H2O2浓度可以提高光降解速率，但H2O2的利用率会降低。     

TiO_2膜光催化降解4,4’-二溴联苯的研究

研究了负载于玻璃上的同定化催化剂TiO2膜光催化降解水中4,4'-二溴联苯(4,4'-DBB)的效果,考察了溶液pH值和4,4'-DBB初始浓度等对TiO2膜光催化降解4,4'-DBB的影响,探讨了降解机理.结果表明.TiO2膜光催化降解水中4,4'-DBB的效果良好,紫外光照射8 b,初始浓度为4 mg/L的4,4'-DBB的降解率高达94%,降解速率随着4,4'-DBB初始浓度的增大而下降.在溶液pH=1时,4,4'-DBB的降解效率最高.超声的加入使降解反应的速率加快.经拟合发现4,4'-DBB的降解符合拟一级反应规律,并推导出动力学方程.     

Anaerobic degradation of brominated flame retardants in sewage sludge

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.     

Photodegradation of hexachlorobenzene and theoretical prediction of its degradation pathways using quantum chemical calculation

Experimentally determined photodegradation pathways of hexachlorobenzene (HCB), a chlorinated aromatic compound, in hexane, 2-propanol (IPA), and methanol were compared with those predicted by quantum chemical calculation based on density functional theory (DFT), and the adequacy of the prediction method was evaluated. The experimental main degradation pathways of HCB were virtually the same for the three solvents and also agreed with the predicted main degradation pathways. In the DFT method, the main degradation product was the dechlorinated benzene at the position where the C-Cl bond was predicted to have the lowest bond dissociation energy. This result suggested that the photodechlorination pathways of chlorinated aromatic compounds could be predicted by comparing the bond dissociation energies calculated with the DFT method.     

Study on the photodegradation of amidosulfuron in aqueous solutions by LC-MS/MS

Sulfonylurea herbicides are extensively widespread for the protection of a variety of crops and vegetables because of their low application rates, high selectivity and low persistency in the environment; unfortunately, their low persistence does not always correspond to a lower toxicity, since new species potentially more toxic and stable than the precursor herbicides can form, owing to natural degradation processes. Here, the photodegradation of amidosulfuron in aqueous solutions was studied by high-performance liquid chromatography with diode array detection and tandem mass spectrometry to identify the degradation products in order to outline the environmental fate of the molecules generating from the simulation of one of the natural processes that can occur, i.e., photoinduced degradation. The photodegradation process results in a first order kinetic reaction with a t _1/2 value of 276 h (11.5 days) and a kinetic constant of 0.0027 h^?1, and three possible degradation products were identified. The results obtained are then compared to those obtained in previous works carried out in comparable experimental conditions about nicosulfuron and tribenuron-methyl, two sulfonylurea herbicides belonging to different classes, and to literature data: hypotheses on the existence of preferential degradation pathways are then drawn, in consequence of the molecular structure of the sulfonylurea pesticide. In particular, the use of organic solvents to obtain complete solubilization of the sample plays a fundamental role and deeply influences the degradation processes that, therefore, not always fully adhere to the actual natural photodegradation pathways. Moreover, considerations about toxicity were driven since the complete mineralisation of the sample is not reached: even when the parent pesticides are totally degraded, they are, however, transformed into other organic compounds showing, if subject to ecotoxicological tests, at least the same toxicity of the precursor herbicides. The evidence here presented suggests that, at least for the class of sulfonylurea pesticides, their professed low persistence actually does not produce any real advantage.     

TiO2膜光催化降解4，4’-二溴联苯的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中4,4’-二溴联苯（4,4’-DBB）的效果,考察了溶液pH值和4,4’-DBB初始浓度等对TiO2膜光催化降解4,4’-DBB的影响,探讨了降解机理。结果表明,TiO2膜光催化降解水中4,4’-DBB的效果良好,紫外光照射8h,初始浓度为4mg／L的4,4’-DBB的降解率高达94％,降解速率随着4,4’-DBB初始浓度的增大而下降。在溶液pH：1时,4,4’-DBB的降解效率最高。超声的加入使降解反应的速率加快。经拟合发现4,4’-DBB的降解符合拟一级反应规律,并推导出动力学方程。     

TiO2光催化降解水中土霉素的动力学研究

环境中抗生素的出现及其引起的危害正受到越来越多的关注。以高压汞灯为光源,选用较为广泛的抗生素土霉素（OTC）为处理对象。考察了初始质量浓度、反应过程中光照、催化剂投加量、溶液起始pH、溶液中DOM和NO^-₃对光催化降解的影响,研究了其光降解动力学。结果表明,TiO₂光催化氧化法能够有效去除水中半微量的OTC,OTC的光降解过程符合一级反应动力学模型;UV/TiO₂联用工艺对TOC也有很好的去除效果,反应90 min,TOC去除率可达74%;OTC的初始浓度从30 mg/L增大到90 mg/L,反应速率从0.0619 min^-1降低到0.0130 min^-1;随着光催化剂投加量的增大,光降解速率常数先增大后减小;增加溶液的pH值,速率常数逐渐减小;溶液中的DOM和NO^-₃也可以影响光降解效率。     

负载型纳米复合半导体WO_3-TiO_2/AC光催化降解刚果红废水

采用溶胶-凝胶-浸渍-焙烧法制备了负载型纳米复合半导体WO3-TiO2/AC光催化剂,以偶氮染料刚果红为目标降解物,通过正交实验优化了刚果红废水的降解条件,并对其光催化动力学进行了探讨.结果表明,刚果红废水的最佳降解条件为:催化剂投加量10 g/L,pH=7,H2O2用量为3.5 mL/L.在最佳条件下,当刚果红废水起始浓度为40 mg/L时,反应120 min后,刚果红溶液的去除率可达95.21%,较相同条件下TiO2/AC对刚果红染料的降解率提高了19.57%.光催化剂对刚果红的光催化降解符合Langmuir-Hinshelwood(L-H)模型.     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

Photodegradation of Diquat and Paraquat in aqueous solutions by titanium dioxide: evolution of degradation reactions and characterisation of intermediates

The titanium dioxide assisted photodegradation of Diquat and Paraquat herbicides solutions has been the subject of the present investigation, considering its direct application in the treatment of contaminated waters and soils. To have a better understanding of the photodegradation process, different types of TiO2, commercial and 'home prepared' Ti(1-x)FexO2 (x = 0% and 4%), were used as catalysts, using an UV light as radiation source. The degradation reactions were followed by UV spectroscopy and the intermediates and reaction products were characterised by electrospray ionisation mass spectrometry (ESIMS) combined with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS). The present study shows that, for photocatalytic degradation of Diquat and Paraquat solutions, a basic pH can be determinant, as well as the type of catalyst. The type of catalyst can also strongly influence the degradation pattern of the herbicide. Regarding complete degradation, we were able to show that Diquat is more persistent than Paraquat. During the photocatalytic processes, several intermediate and reaction products are sequentially formed, to which structures are proposed.