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...     

新污染物多环芳烃衍生物的来源、分布与光化学行为

环境中多环芳烃衍生物(SPAHs)来源广泛,具有“三致”效应,毒性与PAHs母体相当甚至高于母体,是一类具有较高风险的新型有机污染物.大气和表层水体等环境介质中,光化学降解是其重要的消减方式.在梳理文献的基础上,发现SPAHs在来源、分布、行为和风险研究方面与传统污染物PAHs相比有了新的突破.通过总结新污染物SPAHs的环境分布特征与光化学行为研究的最新进展,介绍了3类SPAHs的来源和形成机制,重点评述了不同环境介质中的存在状况与分布特征,讨论了水、冰等介质中SPAHs光化学转化动力学、反应路径以及影响因素,最后对SPAHs的环境行为和风险研究进行了展望.     

大气光化学反应高发季节NO、NO2和O3污染特征

文章通过对广州番禺大气成分站(GPACS)2010-2016年的历史观测数据进行分析,结果表明,2013年广州地区光化学高臭氧事件发生次数最多,且均发生在夏秋季。2013年日O_3最大均值和日均值在10月最大,分别为103.02×10~(-9)和53.81×10~(-9)。NO和NO_2浓度在7月最大,日均浓度分别为5.90×10~(-9)和16.03×10~(-9),7月NO对O_3化学滴定最明显。夏秋季O_3峰值出现时间较晚,在18:00左右。O_3浓度随着NO_2/NO比值升高而升高。选取夏季NO、NO_2、O_3与NO_x进行非线性拟合,发现当NO_x浓度19.35×10~(-9)或者87.71×10~(-9)时,O_3为光化学氧化剂O_x的主体;当NO_x浓度19.35×10~(-9)而87.71×10~(-9)时,NO_2为光化学氧化剂O_x的主体。秋季大量的气溶胶污染对辐射进行衰减,导致O_3生成在较低辐射范围内主要处于太阳辐射控制区。夏秋季的风速整体较小,有利于污染物的积累。     

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.     

基于碳同位素组成的大气NMHCs光化学寿命研究

利用热解析-气相色谱-同位素质谱联用仪测定了兰州市冬季和夏季昼夜大气非甲烷烃(NMHCs)的稳定碳同位素组成.结果表明,兰州市冬季大气NMHCs的δ13C值为-30.5‰～-24.3‰,夏季为-31.9‰～-24.2%,受燃煤烟气排放的影响,冬季大气NMHCs的δ13C值明显大于夏季;冬季大气NMHCs的δ13C值夜晚大于白天,夏季不同时间点C4、C5化合物的同位素值相差不大,正己烷和正庚烷的δ13C值白天比夜晚要高.利用"碳氢化合物同位素时钟"计算出正己烷和1-丁烯在兰州市夏季大气中的平均光化学寿命分别约为6d和25min.     

三唑酮在水体系中的光化学降解研究

系统研究了在天然日光和高压汞灯照射下三唑酮在蒸馏水、人工海水和天然海水中的光降解情况.结果表明,天然日光照射下,三唑酮在三种介质中降解较慢.高压汞灯较天然日光能够更有效地激发三唑酮的降解,且降解符合一级动力学规律.在300 W高压汞灯照射下,三唑酮在蒸馏水、人工海水和天然海水中的半寿期分别为54.14 min、144.38 min、177.69 min.三唑酮在蒸馏水中的光降解速率大于其在天然海水中的,这主要是由于天然海水中存在的阴、阳离子和其它特殊的物质所引起的.同蒸馏水中的光反应相比,人工海水中的离子抑制了三唑酮的光降解反应.在500 W高压汞灯照射下,三唑酮的反应速率明显提高.实验发现溶液中加入重金属离子(Cu2+、Pb2+、Cd2+)能够改变三唑酮的光降解速率.     

Effects of relative humidity on the characterization of a photochemical smog chamber

A linear relationship between k_NO2→HONO and relative humidity in smog chamber is found in this work.     

Life cycle assessment of mobile phone housing

The life cycle assessment of the mobile phone housing in Motorola(China) Electronics Ltd. was carried out, in which materials flows and environmental emissions based on a basic production scheme were analyzed and assessed. In the manufacturing stage, such primary processes as polycarbonate molding and surface painting are included, whereas different surface finishing technologies like normal painting, electroplate, IMD and VDM etc. were assessed. The results showed that housing decoration plays a significant role within the housing life cycle. The most significant environmental impact from housing production is the photochemical ozone formation potential.Environmental impacts of different decoration techniques varied widely, for example, the electroplating technique is more environmentally frieodly than VDM. VDM consumes much more energy and raw material. In addition, the results of two alternative scenarios of dematerialization showed that material flow analysis and assessment is very important and valuable in selecting an environmentally friendly process.     

Photochemistry of insecticide imidacloprid: direct and sensitized photolysis in aqueous medium

The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO2, CI^- and NO3^-. Complete photo-oxidation of nitrogen to NO3^- occurred very slowlyvia the intermediate formation of NH4^ and NO2^- .