单嘧磺隆的光化学降解研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
本论文以高压汞灯、紫外灯和太阳光为光源,研究了磺酰脲类除草剂单嘧磺隆在水中以及玻片表面的降解状况;并在高压汞灯的照射下,分别研究了不同水质和不同溶解氧量对单嘧磺隆在水中光解的影响。并利用GC-MS对单嘧磺隆在乙腈中的光解产物进行检测,推测出单嘧磺隆在乙腈中光解的可能反应途径。主要研究结果如下:
     1.建立了单嘧磺隆的残留分析方法,采用高效液相色谱可变波长紫外检测器检测,检测波长254nm,250mm×4.6mm不锈钢ODS 5μm球形硅胶填料色谱柱,甲醇/水(55∶45,V/V)为流动相,流速为0.8mL/min,此条件下单嘧磺隆的分离效果较好。
     2.在高压汞灯的照射下,玻片上的单嘧磺隆降解半衰期为147min,降解符合一级动力学方程。
     3.单嘧磺隆在不同光源、不同水质中降解速率存在着明显差异,在太阳光下,其在重蒸水中的半衰期为7.32d,在高压汞灯和紫外光灯下降解速率顺序相同,由大到小依次为重蒸水>自来水>河水>巢湖水。同时在紫外灯下的光解半衰期由高压汞灯下的3.05~4.86h延长到7.62~9.64h,表明不同光源、不同水质对单嘧磺隆光解产生重要影响。
     4.单嘧磺隆在高压汞灯下,同步通空气和同步通氮气的降解速率也存在着明显差异:降解半衰期分别为0.894h,15.07h。随着水溶液中溶解氧浓度的减少,降解半衰期相应延长。
     5.将单嘧磺隆在乙腈中光照后的试液在硅胶G板上点样,以三氯甲烷∶丙酮∶甲醇∶氨水=10∶2∶2∶0.5为配比的展开剂可以将光解产物1与原物质分离。其中单嘧磺隆比移值Rf为0.47,光解产物1的比移值Rf为0.95。
     6.通过GC—MS的检测光解产物1的分子量为:202,其分子结构式为:
The photochemical degradation of Monosulfuron irradiated by high pressure mercurylamp (HPML), ultraviolet light and sunlight was investigated. The effects of different typesof water, dissolved oxygen on the photodegradation of Monosulfuron in aqueous solutionwere studied. By GC-MS, photoproducts of Monosulforn in acetonitrile was detected. Thepathway of Monosulfron photodegradation in acetonitrile under HPML was proposed..
     1. The analytical method of monosulfuron by HPLC was established. A column ofstainless steel packed with ODS 5μm with 250mm×4.6mm was utilized.The operationparameters were optimized as: mobile phase, methanol/water=55/45(V/V) ,flow rate,0.8ml/min , a UV detection with wavelength of 254nm.
     2. The photodegradation rate of Monosulfuron in aqueous solution or on glass surfaceby HPML is not very quickly, the half-life was 147min on glass surface. And thephotolysis of Monosulfuron follows the first order kinetics.
     3. The results showed that Monosulfuron was very stable in water under sunlight, thehalf-lives of Monosulfuron under sunlight is 7.32d.But with the HPML and ultraviolet lightsources, the photolysis rates of Monosulfron ranged samely as:redistilled water > Tappedwater> river water(Dongpu reservoir) > lake water(Chaohu Lake). The half-lives ofmonosulfuron extended to7.62~9.64h under irradiation of ultraviolet light from 3.05~4.86h under HPML.
     4. Dissolved oxygen can greatly promote the photodegradation of Monosulfuron. UnderHPML irradiation, with the role of dissolved oxygen, the photolysis rates of monosulfuronwere improved about 3.411 times and the half-life shortened to 0.894 hour from 3.05 hour withoutaerifying O_2.
     5. Dissolve Monosulfron into acetonitrile then put this liquor under HPML. Spot the liquorwhich had been irradiated under HPML on surface of silica gel. Outspread the silica gelboard with the liquor that its compound is trichloromethane: methyl alcohol: acetone:ammonia=10:2:2:0.5 . And this liquor could separate monosulfuron with its product 1 ofphotodegradation. The Rf of Monosulfron is 0.47 while the product 1 is 0.95.
     6. The photoproduct of Monosulfron in acetonitrile were identified by GC-MS, obtainedone photoproduct of Monosulfron in aqueoussolution under HPML, its molecular weightsis 202, with molecularstructure as follows:
引文
[1].韩熹莱主编.农药概论[M].北京:北京农业大学出版社,1994,10-23
    
    [2].岳永德,花日茂,张承祥.茶叶农药残留与控制[M].北京:中国农业出版社,2001,12-15
    
    [3].华小梅,单正军.我国农药的生产、使用状况及其污染环境因子分析.环境科学进展.1996,4(2):33-45
    
    [4].韩熹莱主编.中国农业百科全书.农药卷.北京:农业出版社,1998,54-78
    
    [5].Durejs p,Casids J E,Ruzo L O.J.Agric food Chem.,1984,3 (32):24-27
    
    [6].徐晓白主编.典型化学污染物在环境中的变化及生态效应.北京:化学工业出版社.1998,81-92
    
    [7].蔡道基.农药与环境.安徽化工.2000,2(1):13-18
    
    [8].P.Cabras.,A.Angioni.Pesticide Residues in Grapes,Wine and their processing products.[J]Agric.Food Chem.2000,3(48):967-973.
    
    [9].A.Blair.,H.Malker et al.Cancer among Farmers:A Review Scand.[J] Work Environ.Health.1985,4(11):397-403
    
    [10].A.Blair.,M.Dosemeci.et al.Cancer and Other Causes of Death among Male and FemaleFanners from Twenty-three States.Am.J.Ind.Med.1993,3(23):729-732
    
    [11].R.W.Tanner,J.W.Laangston.Do Environmental Toxins Cause Parkinson's Disease:ACritical Review.Neurology.1990,5(40):17-21
    
    [12].B.Hileman.Environmental Cstrogens Linked to Reproduct Abnormalities and Cancer.Chem.News.1994,12(1):19-25
    
    [13].Anon.NRC Urges Pesticide Alternatives.Environ.Sci.Technol.2000,6(34):373-376
    
    [14].Anon.Very Little Known about Pesticide Usage in Schools.Environ.Sci.Technol 2000,7(34):169-175
    
    [15].周泽义,盖良京.中国食品的农药残留污染状况.资源生态环境网络研究动态,2001,12(1):24-28.
    
    [16].齐兆生,洪锡午.化学农药必将继续发展进步.农药,1995,6(2):33-34.
    
    [17].张秋芳,叶华仙,雷锦桂等.有机农药的微生物降解研究.福建环境,2000,17(3):34-37.
    
    [18-19].Toshinobu Mursi,曹如珍译.农药在环境中的光化学分解作用.农药译丛,1983,5(5):44-47,58-63.
    
    [20].王一茹,刘长武,蔡罗保等.光诱导下农药的化学转化及其环境意义[J].环境科学,1991,12(2):68-73.
    
    [21].王琴孙,刘玉鑫.有机磷农药的光分解.农药,1999,12(5):1-7
    
    [22].陈宗愚.国外农药环境副毒理学研究进展.农药,1999,8(2):45-46
    
    [23].蔡道基.化学农药环境安全评价试验准则,国家环保局
    
    [24].毕刚,田世忠.水环境中阴离子对表面活性剂光催化降解的影响分析科学学报,1995,11(4):15-18
    
    [25].宋文琦,刘文渊,石鸿昌等译.[英]J.巴尔特洛甫等著,J.科伊尔著;光化学原理第一版.北京:清华大学出版社.1983,145-167
    
    [26].蔡熹臣,韩镇辉,姚思德等.双光束激光光解方法的建立及应用.辐射研究与辐射工艺学报,2002,20(3):57-61.
    
    [27].方晓航,仇荣亮.农药在土壤环境中的行为研究.土壤与环境,2002,11(1):94-97.
    
    [28].Ruzo L.O.,HoLmstead R.L.and Casida J.E.Pyrethroid photochemistry:Decamethrin.J.AgricFood Chem.,1977,25(6):1385-1394.
    
    [29].Jirkocsky J.,Faure V.and BouLe.P.Photolysis of diuron.pestic.Sci.1997,50:42-52.
    
    [30].姚建仁,焦淑贞,钱盖新等.化学农药光解研究进展.农药译丛.1989,11(1):15-19.
    
    [31].Crosby D.G.,Moilanen K.W..Vapor-phase photo-decomposition of DDT.Chemosphere.1977,4:167-172
    
    [32].Soderquist C.J.,Crosby D.G.,Moilanen K.W.,et al.Occurrence of trifluralin and itsphotoproducts in air.J.Agri.Food Chem..1975,23(2):304-309
    
    [33].Monger K.,Miller GC..Vapor phase photolysis of trifluralin in an outdoor chamber.Chemosphere.1988,17(11):2183-2188.
    
    [34].Behymer T.D.,Hites R.A..Photolysis of polycyclic aromatic hydrocarbons adsorbedon simulated atmospheric particulates.Environ.Sci.Technol.1985,19(10):1004-1006.
    
    [35].Choudhry G G.,Webster G R.B..Protocol guidelines for the investigations ofphotochemical fate of pesticides in water,air,and soils.Residue Rev.1985,96:79-136
    
    [36].Burkhand N.et al.朱树秀译.有机磷农药在表土中的光解作用.原子能农业译丛.1980,4:49-52.
    
    [37].徐保才,岳永德.多菌灵的光化学降解研究。环境科学学报.2000,5(20):616-620
    
    [38].花日茂,樊德方.丁草胺在不同类型水中的光化学降解.应用生态学报.1999,1(10):57-59
    
    [39].于书琴.恶草酮在液相中的光化学降解研究.农药学学报.2002,2(4):71-74
    
    [40].P.N.Mozal,K.Hustert,S.pal et al,Photocatalytic decomposition of pendimethalin andalachlor.Chemosphere,Vol.25,No.11,pp1675-1682.
    
    [41].Burrows,H.D.,M.Canle L,Santaballa,J.A.,Steenken,S.Reaction pathways and mechanisms ofphotodegradation of pesticides[J].Journal of Photochemistry and PhotobiologyB:Biology,2002,67:71-108.
    
    [42].Mansour,M.,Feicht,E.A.,Behechti,A.,et al.Determination photostability of selectedagrochemicals in water and soil[J].Chemosphere,1999,39(4):575-585.
    
    [43].杨曦,孟庆宇.甲黄隆在有机溶剂中的光解.环境科学.1999,5(20):66-68
    
    [44].浦宇,杨曦.哒螨酮在甲醇中的光解.南京大学学报(自然科学)2002,2(38)211-215
    
    [45].Miller G.G.and Zepp R.G Residue Review.1983,(85):89-92
    
    [46].岳永德,花日茂,汤锋.土壤粒径对农药在土壤中的分布和光解的影响.安徽农业大学学报,1993,20(4):309-314
    
    [47].花日茂,程燕,杨晓凡等.3种农药对异菌脲的光解影响及相互作用.安徽农业大学学报,2003.30(4):353-357.
    
    [48].岳永德,花日茂,汤锋等.4种农药对3种拟菊酯杀虫剂在不同光源下的光解效应[J].中国环境科学,1997,17(1):72-75.
    
    [49].岳永德,花日茂.拟菊酯杀虫剂的光敏降解研究.环境科学学报,1992,12(4):466-472.
    
    [50].岳永德,花日茂,汤锋等.哒嗪硫磷对拟除虫菊酯杀虫剂植物表面降解的影响.安徽农业大学学报,1993,20(30):213-217.
    
    [51].岳永德,花日茂.混合农药对拟除虫菊酯杀虫剂在水中光解的敏化和猝灭效应研究[J].环境科学学报,1993,13(2):164-168.
    
    [52].岳永德、汤锋、花日茂.氟乐灵与混合农药的光化学相互作用研究.安徽农业大学学报,1995,22(4):346-350.
    
    [53].V.R.Hebert,G.C.Miller.Depth dependence of direct and indirect photolysis on soilsurfaces.J.Agric.Food.Chem.1990,2(38):913-918
    
    [54].Nilles G P,Zabik M J.Photochemistry of bioactive compounds,multiphase photodegradationand mass spectral analysis of basagran.J.Agric.Food Chem.1975,2(23):410-415
    
    [55].Pohlman A.,Miller T.,Peroxy radical interactions with soil constituents.SoilSci.Soc.Am.1983,8(31):1104-1108
    
    [56].Gohre K.,Miller GC.Photochemical generation of singlet oxygen on non-transition-metaloxide surfaces.J.Chem.Soc.Faraday Trans.1985,5(81):793-800
    
    [57].Paul ClementS,C.H.J.Wells.Soil sensitized generation of singlet oxygen in thephotodegradation of bioresmethrin.Pestic.Sci.1992,6(34):163-166
    
    [58].岳永德.高效薄层析进行农药吸附态光解的研究.环境科学.1995,16(4):16-18
    
    [59].岳永德.取代脲类和二苯基醚除草剂的表面光化学相互作用研究.安徽农业大学学报.1997,24(2):107-114.
    
    [60].司友斌,岳永德,汤锋等.磺酰脲类除草剂在硅胶G表面的光解.环境科学学报.2002,22(2):270-272
    
    [61].胡继业,范志金,钱传范.新磺酰脲除草剂单嘧磺隆的HPLC分析及其在土壤中吸附性能研究.农业环境保护,2001.20(1):12-14.
    
    [62].郭武棣,张瑞亭,李正名等.中国专利[51]IntC16,A01N47,CN114489A,1997.02.19.
    
    [63].范志金,钱传范,陈俊鹏等.1,8一萘二甲酸酐对高浓度单嘧磺隆协迫下玉米的解毒作用.农药学学报,2004.6(4):55-61.
    
    [64].王秀红,沈健英,陆贻通.单嘧磺隆对水华鱼腥藻生长的影响.安徽农业大学学报,2006,33(4):530-532.
    
    [65].王秀红,沈健英,陆贻通.单嘧磺隆在稻田中应用的安全性研究.云南农业大学学报,2006.12.Vol.21.No.6:60-65:733-736.
    
    [66].范志金,钱传范,陈俊鹏等.单嘧磺隆对小麦的安全性及在麦田除草效果的研究.中国农学通报,2003.6.Vol.19.No.3:4-8.
    
    [67].胡继业,钱传范,范志金.单嘧磺隆在土壤中的残留分析和消解动态研究.农药学学报,2000.12 Vol.2.No.4:60-65.
    
    [68].艾应伟,范志金,钱传范.磺酰脲类除草剂特点及其环境归趋.沈阳农业大学学报,1999.10.30(5):539-543.
    
    [69].Joshi M M,et al.Microbial transformations of prosulfuron.J.Agric.Food Chem.1997,45:1479-1485.
    
    [70].Schneiders G E,et al.Fate of rimusulfron in the environment.J.Agric.FoodChem.1993,41:2404-2410.
    
    [71].姚东瑞,磺酰脲类除草剂残留与降解研究进展.农药,1997,36(7):32-37.
    
    [72].Pantani O,et al.Adsorption and degradation of rimusulfuron on Al hectorite.J..Agric.FoodChem.1996,44:617-621.
    
    [73].Hemmamda S,Calmon M,Calmon J P.Kinetics and hydrolysis mechanism of chlorsulfuronand metsulfron-methyl.Weed Sci.1994,40:71-76.
    
    [74]Smith A E,Aubin A J.Degradation of (14)~C amidosulfron in aqueous buffles and in an acdic soil.J.Agric.Food Chem.1993,41:2400-2403.
    
    [75].花日茂,汤峰,岳永德.五种农药对三唑酮光降解的影响.环境化学学报,1995,14(1):21-24
    
    [76].花日茂,汤峰,岳永德.甲基对硫磷对三种拟除虫菊酯杀虫剂的光敏降解研究.环境化学学报,1995.11.14(6):508-512
    
    [77].严衍禄主编,现代仪器分析,北京:北京农业大学出版社,1995.10
    
    [78].皮光洁主编.农业资源利用与管理.中国林业出版社,2000,217-218
    
    [79].R.A.Larson,E.J.Weber,Reaction Mechanisms in EnvironmentaL Organic Chemistry,CRCPress,Boca Raton,FL,1994,8 (24):359-362
    
    [80].H.Gao,R.G.Zepp,Photo oxidative purifation of water remove organochLorine pecticide 2,4-dichLorophenoxyacetic acid.Environ.Sci.TechnoL.1998,9(32):2940-2945.
    
    [81].O.C.Zafiriou,J.Joussot-Dubien,R.G.Zepp,R.G.Zika,Photosensitized decomposition ofterbaciL in aqueous solutions.Environ.Sci.TechnoL.1984,9(18):358-395.
    
    [82].P.P.Vaughan,N.V.BLough,Photochemcal effects of humic substances on the degradationof organophosphorus pesticides.Environ.Sci.TechnoL.1998,7(32):2947-2952.
    
    [83].杨曦,王晓书,朱春媚等.磺酰脲类除草剂在环境中的光降解研究---水溶液中的光解动力学.环境科学,1998.19(6):29-32.
    
    [84].徐宝才.多菌灵在环境中的光化学转化研究:[硕士学位论文].合肥:安徽农业大学1999.
    
    [85].魏宏斌,彭海涛.有机分子结构与光催化氧化反应活性的关系.上海环境科学,1998,17(11):43-45.
    
    [86]Jirkocsky J.,Faure V.and Boule.P.Photolysis of diuron.Pestic.Sci.1997,11(50):42-52
    
    [87].傅献彩,沈文霞,姚天扬编.物理化学(上、下册)(第四版).北京:高等教育出版社,1991.65-66
    
    [88].王连生编.有机污染物化学(上册).北京:科学出版社(第一版),1990.89-92
    
    [89].王丹军.氯苯嘧啶醇的光化学降解研究:[硕士学位论文].合肥:安徽农业大学2004,7.
    
    [90].M.Mansour.EA Feicht.A.Beltechti and I.Scheunert*.Experimental approaches tostudyingthe photostability of selected pesticides in water and soil.Chemohpere.1997,3(35):39-50.
    
    [91].G.Durand,D.Barcelo,J.Albaiges and M.Mansour,Utilization of liquid chromatography inaquatic photodegradation studies of pesticides:a comparison between distilled water andseawater.Chromatographia.1990,5(29):120-124.
    
    [92].Sakkas V.A.,Lambropoulou D.A.,Albanis T.A..Study of chlorothalonilphotodegradtion in natural waters and in the presence of humic substances.Chemosphere.2002,5(48):939-945
    
    [93].孙亚杰,宋喜太,姜淑芳.氧分子三种自旋异构体及其反应活性理论分析.哈尔滨师范大学自然科学学报,1995,11(3):75-80.
    
    [94].彭姣凤,张磊.光氧化的成因及其削减机制.生命科学研究,2000,4(2):83-90.
    
    [95].J g Von EIb,Steven J Schwartz.食品化学(第三版).王璋译.北京:中国轻工业出版社,2003.544-549.
    
    [96].刘晓庚,光氧化及其对食品安全的影响,食品科学2006,27(11):579-583.