4种有机农药在水中的光降解对比研究
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摘要
为了解不同化学结构有机农药的光降解规律,以汞灯、氙灯为光源,在实验室中同时测定四种有机农药阿特拉津、异丙隆、灭草隆以及2,4-D丁酯,研究其在水体中的光解特性。结果表明,4种农药的光降解均符合一级降解动力学(r~2>0.9)。直接光解途径下,降解速率在两种光源下均遵循MN>ATZ>2,4-D>IPU(汞灯下半衰期7, 22, 4, 14 min,氙灯下半衰期16, 239, 8, 39 h);间接光解途径下,四种有机农药中IPU更容易受硝酸根诱导而加速降解(k_(indirect)/k_(direct)=8),ATZ降解速率几乎没有变化(k_(indirect)/k_(direct)=1),光解速率遵循MN>2,4-D>IPU>ATZ。从有机农药母体分子结构出发,提出芳环上取代基不同与光解机理对不同种农药光解动力学的影响。
In order to understand the photodegradation of organic pesticides with different chemical structures, four organic pesticides, atrazine, isoproturon, chlorpyrifos and 2,4-D, were simultaneously determined in the laboratory using mercury lamps and xenon lamps as light sources, to study its photolysis characteristics in water. The results showed that the photodegradation of the four pesticides accorded with the first-order degradation kinetics(r~2>0.9). Under the condition of direct photolysis, the degradation rate follows MN>ATZ>2,4-D>IPU under both light sources(the half-life of the mercury lamp is 7, 22, 4, 14 min, and the half-life of the xenon lamp is 16, 239, 8, 39 h). However, under the condition of indirect photolysis, IPU is more susceptible to nitrate-induced which accelerated degradation among the four organic pesticides(k_(indirect)/k_(direct)=8), while the ATZ degradation rate is stable(k_(indirect)/k_(direct)=1); the photolysis rate follows MN>2,4-D>IPU>ATZ. Based on the molecular structure of organic pesticides, the effects of different substituents on the aromatic ring and photolysis mechanism on the photolysis kinetics of different pesticides were proposed.
In order to understand the photodegradation of organic pesticides with different chemical structures, four organic pesticides, atrazine, isoproturon, chlorpyrifos and 2,4-D, were simultaneously determined in the laboratory using mercury lamps and xenon lamps as light sources, to study its photolysis characteristics in water. The results showed that the photodegradation of the four pesticides accorded with the first-order degradation kinetics(r~2>0.9). Under the condition of direct photolysis, the degradation rate follows MN>ATZ>2,4-D>IPU under both light sources(the half-life of the mercury lamp is 7, 22, 4, 14 min, and the half-life of the xenon lamp is 16, 239, 8, 39 h). However, under the condition of indirect photolysis, IPU is more susceptible to nitrate-induced which accelerated degradation among the four organic pesticides(k_(indirect)/k_(direct)=8), while the ATZ degradation rate is stable(k_(indirect)/k_(direct)=1); the photolysis rate follows MN>2,4-D>IPU>ATZ. Based on the molecular structure of organic pesticides, the effects of different substituents on the aromatic ring and photolysis mechanism on the photolysis kinetics of different pesticides were proposed.
引文
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[15] RUSSI H, KOTZIAS D, KORTE F.Photoinduzierte hydroxylierungsreaktionen organischer chemikalien in natürlichen Gew?ssern-Nitrate als potentielle OH-radikalquellen [J].Chemosphere, 1982, 11(10): 1041-1048.
[16] BREZONIK P L, FULKERSON-BREKKEN J.Nitrate-induced photolysis in natural waters: controls on concentrations of hydroxyl radical photo-intermediates by natural scavenging agents [J].Environmental Science & Technology, 1998, 32(19): 3004-3010.
[2] GILLIOM R J, BARBASH J E, CRAWFORD C G, et al.Pesticides in the nation's streams and ground water, 1992-2001 [M].US Geological Survey, 2006.
[3] 徐雄, 李春梅, 孙静, 等.我国重点流域地表水中 29 种农药污染及其生态风险评价 [J].生态毒理学报, 2016, 11(2): 347-354.
[4] FENNER K, CANONICA S, WACKETT L P, et al.Evaluating pesticide degradation in the environment: blind spots and emerging opportunities [J].science, 2013, 341(6147): 752-758.
[5] BURROWS H D, SANTABALLA J, STEENKEN S.Reaction pathways and mechanisms of photodegradation of pesticides [J].Journal of photochemistry and photobiology B: Biology, 2002, 67(2): 71-108.
[6] LAM M W, TANTUCO K, MABURY S A.PhotoFate: a new approach in accounting for the contribution of indirect photolysis of pesticides and pharmaceuticals in surface waters [J].Environmental Science & Technology, 2003, 37(5): 899-907.
[7] 张晓清, 单正军, 孔德洋, 等.4 种农药的光解动力学研究 [J].农业环境科学学报, 2008, 27(6): 2471-2474.
[8] 刘萱, 王华, 于春艳, 等.两种微藻胞外分泌物与 NO-2, NO-3 对 2, 4-D 光解的影响 [J].环境科学学报, 2014, 34(4): 944-949.
[9] 田芹, 周志强, 任丽萍, 等.农药在水体中光化学降解研究进展 [J].农药, 2005, 44(6): 247-250.
[10] 维屏.农药环境化学 [M].北京:化学工业出版社, 2006.
[11] TORRENTS A, ANDERSON B G, BILBOULIAN S, et al.Atrazine photolysis: mechanistic investigations of direct and nitrate-mediated hydroxy radical processes and the influence of dissolved organic carbon from the Chesapeake Bay [J].Environmental science & technology, 1997, 31(5): 1476-1482.
[12] ARKHIPOVA M, TERESHCHENKO L Y, ARKHIPOV Y M.Photooxidative purification of water to remove organochlorine pesticide 2, 4-D (2, 4-dichlorophenoxyacetic acid) [J].Russian journal of applied chemistry, 1997, 70(12): 1930-1935.
[13] AMINE-KHODJA A, BOULKAMH A, BOULE P.Photochemical behaviour of phenylurea herbicides [J].Photochemical & Photobiological Sciences, 2004, 3(2): 145-156.
[14] ORELLANA-GARCíA F, áLVAREZ M A, LóPEZ-RAMóN V, et al.Photodegradation of herbicides with different chemical natures in aqueous solution by ultraviolet radiation.Effects of operational variables and solution chemistry [J].Chemical Engineering Journal, 2014, 255:307-315.
[15] RUSSI H, KOTZIAS D, KORTE F.Photoinduzierte hydroxylierungsreaktionen organischer chemikalien in natürlichen Gew?ssern-Nitrate als potentielle OH-radikalquellen [J].Chemosphere, 1982, 11(10): 1041-1048.
[16] BREZONIK P L, FULKERSON-BREKKEN J.Nitrate-induced photolysis in natural waters: controls on concentrations of hydroxyl radical photo-intermediates by natural scavenging agents [J].Environmental Science & Technology, 1998, 32(19): 3004-3010.
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