Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

邻苯二甲酸二丁酯降解过程的单体同位素分析

研究对比了邻苯二甲酸二丁酯（DBP）在不同降解过程（水解、UV/H₂O₂光解、直接光解、过硫酸钾光氧化）中的碳、氢同位素组成变化、分馏特征及二维同位素（Δδ²H-Δδ¹³C）的相关性.水解反应中DBP分子产生了显著的碳同位素分馏,未发现氢同位素分馏,而且碳同位素富集因子ε_C为（-2.7±0.4）‰,表明DBP水解时发生C-O键断裂,氢原子不参与反应.而UV/H₂O₂光解和直接光解反应（pH值分别为2、7和10）中,DBP分子呈现了相似的二维同位素相关性Λ值[（9±2）~（11±2）],推测经历了相同的反应过程.过硫酸钾光氧化降解时,明显偏大的Λ值（31±3）说明反应可能发生C-H键断裂.结果表明：二维单体同位素分析（2D-CSIA）技术可以有效区分DBP的水解、光解、光氧化3种不同类型的降解过程,有助于分析其降解路径.     

新农药环境化学行为研究(V)-—三氟羧草醚(Acifluorfen)在土壤和水环境中的滞留、转化

从如下几方面研究了三氟羧草醚在土壤－水环境中的化学行为：一是土壤对该药的吸附，结果表明，吸附强度与土壤理化特性密切相关，Ｆｒｅｕｎｄｌｉｃｈ常数ｋｆ＝０．９４Ｗｏｍ＋０．６５Ｗｃｌａｙ－９．５９ｐＨ（ｒ＾２＝０．９４）；二是吸附机理研究，发现三氟羧草醚能与碱金属以外的许多金属离子形成配合物，并证实了与ＣＵ＾２＋形成的双核桥联合物的可能性；三是实验指出它在水中避光有一定的稳定性，不易水解；四是它在〈     

磺酰脲类除草剂在硅胶G表面的光解

应用高效薄层析方法研究了苄嘧磺隆，甲磺隆，氯磺隆，氯嘧磺隆4种磺酰脲类除草剂在氙灯与太阳光下的光解动力学，以及8种有机色素对苄嘧磺隆光降解的影响。结果表明4种除草剂在硅胶G表面的降解呈一级动力学反应；有机色素对除草剂的降解均表现显著的猝灭效应。其中以姜黄素的猝灭作用最强，色素剂量与光解中的猝灭效应存在着显著的相关性。色素剂量加大，猝灭效应加强。     

利用UVC去除低浓度苯的实验研究

探讨了不同实验参数对苯的UVC去除效果的影响，获得了苯的去除率与苯的初始浓度、气体流量、相对湿度和氧气含量等参数之间的关系。数据表明，在实验条件范围内，苯的去除率的倒数与苯初始浓度、气体流量之间为线性关系；苯的去除率随相对湿度的增加呈现先升高后缓慢降低的关系，最佳相对湿度值在30%～50%之间；苯的去除率随氧气量的增加而缓慢增加；波长为185+254 nm的UV与254 nm的UV相比净化效果更为理想。还分析了苯降解产生的中间产物，探讨了苯的降解机理。     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

几种天然矿物去除苯酚效果及日光光解效应评价

本文以四种天然矿物为受试矿物，评价了它们去除苯酚的效果，以及日光光解放应及温度，ＰＨ值，矿物浓度，苯酚初始浓度对去除效果的影响。     

Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

HNO_3在气相及SiO_2表面的紫外光解反应

利用紫外及红外吸收光谱等分析手段对365 nm光照下HNO3在气相与SiO2表面的光解反应进行了研究.考察了HNO3浓度、光照时间、相对湿度等条件对反应的影响.结果表明:随着HNO3浓度及光照时间的增加,光解产生的NO2和NO浓度均呈指数增加;无水汽情况下,400 Pa的HNO3光解45 min后,产生NO2及NO浓度比气相光解产生的分别高约3及1.7倍.HNO3光解产生的HONO的浓度随相对湿度的增加而呈线性增加,在SiO2颗粒物表面光解产生的NO2浓度随着相对湿度的增加而减少,而NO浓度则随之增大.400 Pa的HNO3光照45 min后,SiO2表面光解产生的HONO浓度是气相光解的3倍、SiO2表面暗反应的约30倍.     

氧氟沙星敏化光解磺胺甲恶唑

抗生素是环境中广泛存在的一类新兴污染物,因其可诱导细菌抗药性及产生抗性基因而备受关注.本研究发现氟喹诺酮类抗生素具有的光化学活性,可能影响共存的磺胺类抗生素（SAs）的转化.系统考察了一种典型的氟喹诺酮类抗生素—氧氟沙星（OFLO）对磺胺甲恶唑（SMX）的光化学转化.结果表明,在365 nm紫外光照条件下,OFLO可以有效敏化光解SMX.激发三重态（³OFLO^*）是促进SMX光解的主要活性物质.密度泛函理论（DFT）计算结合高分辨率质谱（HRMS）分析表明,³OFLO^*将SMX分子中的氨基氮氧化成一个自由基阳离子（R-NH₂^?+）.该自由基阳离子可水解生成羟胺衍生物,并进一步氧化生成亚硝化和硝化产物.此外,它们也可以二聚生成偶氮产物.光反应过程中,敏化剂OFLO也发生了降解.但OFLO的光解产物均保留了核心喹诺酮结构,因此也保留了OFLO分子的光敏活性.该研究有助于进一步了解抗生素复合污染情况下的环境行为,具有重要的环境意义.