Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

Long-term variation in surface ozone and its precursors in Athens,Greece

INTENTION, GOAL, SCOPE, BACKGROUND: Photochemical pollution is a very complex process involving meteorological, topographic, emission and chemical parameters. The most important chemical mechanisms involved in the atmospheric process have already been identified and studied. However, many unknown parameters still exist because of the large number of participating chemical reactions. OBJECTIVE: The present study investigates the processes involved in the photochemical pollution effect of an urban station located in the greater area of the Athens basin and gives a plausible explanation for the different seasonal ozone development between that station and another rural one. Furthermore, the distribution of the mean monthly surface ozone observed at the urban station during 1987-2001 is examined in order to create a relevant forecasting tool. METHODS: Averaged hourly data of O3 and NOx observations monitored at the above mentioned stations, during 1987-2001, have been used in order to derive the daytime (7:00-15:00) values. Trajectories calculated by using a 2D-trajectory code and meteorological data, during the period 1988-1996, have also been used. RESULTS AND DISCUSSION: At the urban station, the percentage negative trend of NO and NOx data in winter and summer is higher than that in spring and autumn, while the percentage ozone trend is maximum in the summer. On the contrary, the negative surface ozone trend at the rural station exhibits a minimum in summer and a maximum in autumn and winter. The mean seasonal wind-rose for the selected months shows that the northward wind flow dominates during June, the month of the lowest negative ozone trend in the rural station. Finally, the development of the forecasting tool shows that the mean monthly surface ozone data during the period (1987-2001) demonstrates a semi-log distribution. CONCLUSIONS: Air transport effect on the air pollution of the rural station (not blocked by mountains) is deduced as a possible reason for the different seasonal ozone development observed between the rural and the urban station. Finally, the discrepancies between the theoretical probabilities deduced by the model and the empirical ones appear to be very small, and the corresponding correlation coefficient is 0.99. RECOMMENDATION AND OUTLOOK: However, to interpret the aforementioned statistical results about the negative trends in ozone and its precursors, additional parameters can be taken into account. Changes in NOx concentrations, for instance, can result not only from changes in emissions or meteorological conditions. There might also be a contribution through changes in the atmospheric composition. A study of the contribution of changes in atmospheric composition to trends of observed NOx concentrations requires that a series of steps be taken (removal of meteorological influence in the time series, calculation of trends in OH concentrations, etc.).     

SG-Ⅰ型多功能光化学反应装置的研制

SG Ⅰ型多功能光化学反应装置是目前国内外处理容量较大、监测系统较为齐全 ,操作控制自动化程度较高的一种准工业化处理环境污染物的中间装置。它能有效地去除水、植物体及其果实中的环境污染物     

Photochemical behaviour of the systemic fungicide carboxin

Irradiation of carboxin (1) with a 500 W UV lamp (filter Pyrex) in CH3CN leads to the products 3, 5-8, 12-14 depending upon the reaction conditions. All photo-products were isolated and characterized. Photooxidation occurred even if unsensitized, while photoalteration was very slow in the absence of oxygen. The main oxygenated-products 3 and 13 were also recovered under biomimetic conditions by exposure of an aqueous solution of 1 to sunlight.     

TiO2诱导下左旋氧氟沙星的可见光降解及其机制

左旋氧氟沙星是一种新型污染物.单一的左旋氧氟沙星(LFV)和Ti O2无可见光响应,但二者共存下左旋氧氟沙星能发生显著的可见光降解.为此研究Ti O2用量、溶液p H以及左旋氧氟沙星浓度对Ti O2/Vis(可见光)降解左旋氧氟沙星的影响及机制.结果表明,左旋氧氟沙星能吸附在Ti O2表面,吸附服从准二级吸附动力学和Langmuir吸附等温线.吸附左旋氧氟沙星的Ti O2漫反射UV-Vis光谱进一步表明二者形成表面复合物.左旋氧氟沙星的Ti O2/Vis降解动力学符合LangmuirHinshelwood方程.合适的Ti O2浓度和中性p H有利于光解过程的进行.自由抑制实验、N2保护下左旋氧氟沙星的Ti O2/Vis降解实验揭示·O-2是该过程中的主要活性物种.同时,无氧左旋氧氟沙星-Ti O2悬浮液光照不同时间的UV-Vis光谱证明体系中存在电子向Ti O2导带的注入.依据实验结果提出吸附在Ti O2表面的左旋氧氟沙星与Ti O2形成表面复合物,在可见光照下发生电子迁移,从而引发左旋氧氟沙星降解.本研究表明利用污染与Ti O2形成表面复合物诱导其可见光降解可用来去除水中某些有机污染物.     

汞的环境光化学

作为一种全球污染物,汞在水体、底泥、土壤、大气等介质中以各种不同形态存在.各种汞形态具有不同的理化特性及毒性.汞形态的转化对于汞的迁移、毒性、食物链富集放大效应等具有重要影响.光照在汞的形态转化中起着重要作用,主要涉及光氧化、光还原、甲基汞的光降解以及无机汞的光化学甲基化等四个方面.本文对不同环境介质中汞的光化学转化过...     

上海市某化工区夏季典型光化学过程VOCs特征及活性研究

本研究基于夏季某化工区外5 km处观测点O_3及VOCs在线观测结果,分析了VOCs污染及光化学反应活性特征.结果显示,西南风向的VOCs平均体积分数为63.9×10~(-9)±28.6×10~(-9),高于其他风向42%(45.0×10~(-9)±28.0×10~(-9)),不同主导风向下的VOCs特征具有一定的相似性,均以烯烃、卤代烃和烷烃为主要组分,说明化工园区局地排放和累积对观测点VOCs影响较大.主要VOCs物种的日变化都具有夜间体积分数累积增多,白天逐步降低的特征;但是异戊二烯呈现日变化较小的特征,显示其受到人为源和天然源的双重影响.西南风向的臭氧生成潜势(Ozone Formation Potential,OFP)为242.1×10~(-9),远高于其他风向的OFP(174.1×10~(-9)),而平均MIR(Maximum Increment Reactivity)则较为接近;烯烃在VOCs总OFP中的贡献比例均在70%以上,其次是芳香烃.使用乙苯和间/对二甲苯的比值来表征气团光化学反应进程,计算得到观测点西南风向VOCs消耗量为(51.7×10~(-9)±38.8×10~(-9)),烯烃和卤代烃是最主要VOCs消耗组分.     

城市区域臭氧浓度变化的研究

通过中尺度气象模式和高分辨化学模式的耦合,研究广州地区O3的时空分布及其变化特征.结果表明,近地层上O3的分布与地面源排放的分布有非常好的对应关系,并且呈现出多中心分布;O3浓度随时间变化有很好的日变化周期,模拟结果与实测对比有较好的一致性;对单站O3浓度随高度的变化趋势的分析表明,对流层低层O3的日变化幅度较大.      

卤素离子对溶解性黑碳光化学活性的影响

溶解性黑碳(DBC)是天然有机质的重要组分,但其在河口水环境中的光化学活性尚不清楚.为解决这个问题,以大豆秸秆溶解性黑碳为目标物,使用山梨酸能量转移同分异构方法研究河口水卤素离子浓度条件下激发三重态DBC (³DBC^*)的生成速率(F_T)、淬灭速率(k_s')、稳态浓度([T]_ss)变化规律,并使用2,4,6-三甲基苯酚电子转移探针方法研究卤素离子对³DBC^*电子转移过程的影响.结果表明,卤素离子及其离子强度作用对F_T无显著影响,但k_s'因离子强度和Br^-重原子效应而减小,导致³DBC^*的[T]_ss增加.高浓度DBC光化学实验证实离子强度作用引起DBC分子聚集,导致³DBC^*的电荷转移过程减弱,从而抑制³DBC^*的淬灭.山梨酸探针实验表明,卤素离子及其离子强度作用对³DBC^*的能量转移无直接影响,主要是通过抑制³DBC^*的淬灭,增加[T]_ss.进一步研究发现卤素离子及其离子强度作用对低能态³DBC^*(E_T < 250kJ/mol)无显著影响,但抑制高能态³DBC^*(E_T > 250kJ/mol)的电子转移,且随卤素离子和离子强度的增加而愈发明显.     

臭氧对颗粒物中有机组分形成的关键作用

基于2019年10月广东省鹤山大气超级监测站的观测数据分析了臭氧浓度特征与单颗粒气溶胶中的有机物组分.结果表明,PM_2.5中OC的含量显著大于EC,OC/EC比值为0.7～10.4,其中,OC/EC>2的比例占91%,表明有机碳主要来自二次生成.高臭氧浓度下二次组分(Sec)单颗粒和老化有机无机碳(ECOC-aged)单颗粒的数浓度显著增加,Sec和ECOC-aged单颗粒中含乙酸根(⁵⁹CH₃CO₂^-)和乙醛酸(⁷³C₂HO₃^-)的单颗粒数浓度呈单峰分布,两种有机单颗粒的增加都发生在下午臭氧浓度升高光化学反应较强的时段,表明大气氧化性增强有利于含氧有机物的生成.此外,Sec单颗粒中两种有机单颗粒的峰值出现在16:00,而ECOC-aged单颗粒中两种有机单颗粒的峰值出现在18:00之后,这种差异产生的原因可能与含氧有机物氧化形成的过程有关,ECOC-aged粒子中的含氧有机物主要来自...