2,4-滴异辛酯的水解及光解特性
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摘要
为明确2,4-滴异辛酯的环境行为规律,采用室内模拟试验方法,研究了2,4-滴异辛酯在不同温度、pH值、水体及初始浓度下的水解特性及其在不同pH值、水体、光源和初始浓度下的光解特性。结果表明:中性(pH=7)条件下,初始质量浓度为5 mg/L的2,4-滴异辛酯在15、25和35℃下的水解半衰期分别为346.6、231.0和173.3 h;25℃下,5 mg/L的2,4-滴异辛酯在pH值分别为4、7和9的缓冲溶液中的水解半衰期分别为77.0、231.0和138.6 h;2,4-滴异辛酯在稻田水、自来水和河水中的水解速率高于其在蒸馏水中的水解速率,4种条件下的半衰期分别为23.1、25.7、40.8和63.0 h;初始质量浓度分别为1、3和5 mg/L的2,4-滴异辛酯在pH值为7的缓冲溶液中的水解半衰期分别为231.0、173.3和138.6 h。300 W汞灯照射下,2,4-滴异辛酯在酸性条件下的光解速率大于其在中性和碱性条件下,半衰期分别为49.5、77.0和138.6 h;2,4-滴异辛酯在河水和稻田水中的光解速率高于其在自来水和蒸馏水中的光解速率,4种条件下的半衰期分别为6.7、7.6、43.3和46.2 h;2,4-滴异辛酯在不同光源下的光解速率依次为500 W汞灯> 300 W汞灯> 500 W氙灯;初始质量浓度分别为1、3和5 mg/L的2,4-滴异辛酯在pH值为7的缓冲溶液中的光解半衰期分别为63.0、43.3和40.8 h。2,4-滴异辛酯水解及光解的主要产物是2,4-滴,其降解机制主要是酯水解反应。研究结果可为2,4-滴异辛酯的合理使用及其环境风险评估提供参考。
In order to clarify the environmental behavior of 2,4-D isooctyl ester, the hydrolytic properties of 2,4-D isooctyl ester under different temperatures, pH values, types of water and initial concentrations, and its photolytic properties under different pH values, types of water, light sources and initial concentration were studied by the indoor simulation test method. The results showed that the hydrolysis half-lives of 2,4-D isooctyl ester with initial concentration of 5 mg/L were 346.6, 231.0 and173.3 h at 15, 25 and 35 ℃, respectively, under neutral(pH 7) conditions. The hydrolysis half-lives of2,4-D isooctyl ester in buffer solutions with pH values of 4, 7 and 9 were 77.0, 231.0 and 138.6 h, respectively,at 25 ℃. The hydrolysis rates of 2,4-D isooctyl ester in paddy water, tap water and river water were higher than that in the distilled water, the half-lives were 23.1, 25.7, 40.8 and 63.0 h, respectively. The hydrolysis half-lives of 2,4-D isooctyl ester with the initial concentration of 1, 3 and 5 mg/L in buffer solution with pH value of 7 were 231.0, 173.3 and 138.6 h, respectively. Under the irradiation of 300 W mercury lamp, the photolysis rates of 2,4-D isooctyl ester under the acidic condition was higher than that under the neutral and alkaline conditions, the half-lives were 49.5, 77.0 and 138.6 h, respectively.The photolysis rates of 2,4-D isooctyl ester in river water and paddy water were higher than that in tap water and distilled water, the half-lives were 6.7, 7.6, 43.3 and 46.2 h, respectively. The order of photolysis rates of 2,4-D isooctyl ester under different light sources were 500 W mercury lamp > 300 W mercury lamp > 500 W xenon lamp. The photolysis half-lives of 2,4-D isooctyl ester with initial concentration of 1, 3 and 5 mg/L in buffer solution with pH value of 7 were 63.0, 43.3 and 40.8 h,respectively. The main product of the hydrolysis and photolysis of 2,4-D isooctyl ester is 2,4-D. The main degradation mechanism is the hydrolysis of esters. The results can provide references for the rational use and environmental risk assessment of 2,4-D isooctyl ester.
In order to clarify the environmental behavior of 2,4-D isooctyl ester, the hydrolytic properties of 2,4-D isooctyl ester under different temperatures, pH values, types of water and initial concentrations, and its photolytic properties under different pH values, types of water, light sources and initial concentration were studied by the indoor simulation test method. The results showed that the hydrolysis half-lives of 2,4-D isooctyl ester with initial concentration of 5 mg/L were 346.6, 231.0 and173.3 h at 15, 25 and 35 ℃, respectively, under neutral(pH 7) conditions. The hydrolysis half-lives of2,4-D isooctyl ester in buffer solutions with pH values of 4, 7 and 9 were 77.0, 231.0 and 138.6 h, respectively,at 25 ℃. The hydrolysis rates of 2,4-D isooctyl ester in paddy water, tap water and river water were higher than that in the distilled water, the half-lives were 23.1, 25.7, 40.8 and 63.0 h, respectively. The hydrolysis half-lives of 2,4-D isooctyl ester with the initial concentration of 1, 3 and 5 mg/L in buffer solution with pH value of 7 were 231.0, 173.3 and 138.6 h, respectively. Under the irradiation of 300 W mercury lamp, the photolysis rates of 2,4-D isooctyl ester under the acidic condition was higher than that under the neutral and alkaline conditions, the half-lives were 49.5, 77.0 and 138.6 h, respectively.The photolysis rates of 2,4-D isooctyl ester in river water and paddy water were higher than that in tap water and distilled water, the half-lives were 6.7, 7.6, 43.3 and 46.2 h, respectively. The order of photolysis rates of 2,4-D isooctyl ester under different light sources were 500 W mercury lamp > 300 W mercury lamp > 500 W xenon lamp. The photolysis half-lives of 2,4-D isooctyl ester with initial concentration of 1, 3 and 5 mg/L in buffer solution with pH value of 7 were 63.0, 43.3 and 40.8 h,respectively. The main product of the hydrolysis and photolysis of 2,4-D isooctyl ester is 2,4-D. The main degradation mechanism is the hydrolysis of esters. The results can provide references for the rational use and environmental risk assessment of 2,4-D isooctyl ester.
引文
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[15]李芫慧.胺唑草酮的水解与光解特性研究[D].长春:吉林农业大学,2015.LI Y H.The Study of amicarazone hydrolysis and photolysis characteristics[D].Changchun:Jilin Agricultural University,2015.
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[18]食品安全国家标准食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2017.National food safety standard:maximum residue limits for pesticides in food:GB 2763-2016[S].Beijing:Standards Press of China,2017.
[19]吴星卫,单正军,薛韵涵.2,4-D的水解、光解及在土壤中的降解特性研究[J].安徽农业科学,2011,39(16):9711-9713.WU X W,SHAN Z J,XUE Y H.Photolysis,hydrolysis of 2,4-dicholrophenoxyacetic acid and its degradation characteristics in soils[J].J Anhui Agric Sci,2011,39(16):9711-9713.
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[22]EFSA.Conclusion on the peer review of the pesticide risk assessment of the active substance 2,4-D[EB/OL].(2017-03-21)[2018-11-29].http://www.efsa.europa.eu/en/efsajournal/pub/3812.
[23]JMPR.2017(R)report,evaluation[EB/OL].[2018-11-29].http://www.fao.org/agriculture/crops/core-themes/theme/pests/lpe/en/.
[24]SUNDA W,HUNTSMAN S.Effect of pH,light,and temperature on Fe-EDTA chelation and Fe hydrolysis in seawater[J].Mar Chem,2003,84(1-2):35-47.
[25]LOFTIN K A,ADAMS C D,MEYER M T,et al.Effects of ionic strength,temperature,and pH on degradation of selected antibiotics[J].J Environ Qual,2008,37(2):378-386.
[2]朱春杰.90%2,4-滴异辛酯乳油防除玉米田、大豆田阔叶类杂草效果评价[J].辽宁农业科学,2013(5):71-73.ZHU C J.90%2,4-D isooctyl ester EC for evaluation of control effect of broad-leaved weeds in corn and soybean fields[J].Liaoning Agric Sci,2013(5):71-73.
[3]张双,刘娜,程功,等.利用QuEChERS-GC-ECD法测定2,4-滴异辛酯在土壤中的残留及消解[J].农药,2018,57(4):290-293.ZHANG S,LIU N,CHENG G,et al.Determination of 2,4-D isooctyl ester residues in soil and dissipation process in soil by QuEChERS-GC-ECD[J].Agrochemicals,2018,57(4):290-293.
[4]PROSEN H,ZUPAN?I?-KRALJ L.Evaluation of photolysis and hydrolysis of atrazine and its first degradation products in the presence of humic acids[J].Environ Pollut,2005,133(3):517-529.
[5]ATKINSON S K,MARLATT V L,KIMPE L E,et al.Environmental factors affecting ultraviolet photodegradation rates and estrogenicity of estrone and ethinylestradiol in natural waters[J].Arch Environ Contam Toxicol,2011,60(1):1-7.
[6]化学农药环境安全评价试验准则第2部分:水解试验:GB/T31270.2-2014[S].北京:中国标准出版社,2015.Test guidelines on environmental safety assessment for chemical pesticides,part 2:hydrolysis:GB/T 31270.2-2014[S].Beijing:Standards Press of China,2015.
[7]化学农药环境安全评价试验准则第3部分:光解试验:GB/T31270.3-2014[S].北京:中国标准出版社,2015.Test guidelines on environmental safety assessment for chemical pesticides,part 3:phototransformation:GB/T 31270.3-2014[S].Beijing:Standards Press of China,2015.
[8]KWON J W,ARMBRUST K L,GREY T L.Hydrolysis and photolysis of flumioxazin in aqueous buffer solutions[J].Pest Manag Sci,2004,60(9):939-943.
[9]农药残留试验准则:NY/T 788-2004[S].北京:中国农业出版社,2004.Guideline on pesticide residue trials:NY/T 788-2004[S].Beijing:China Agriculture Press,2004.
[10]陈锡岭,徐新明,樊德方.温度和pH值对雷克拉水解速率的影响[J].农业环境保护,1999,18(6):275-277.CHEN X L,XU X M,FAN D F.The effect of temperature and pHvalue on carbetamide hydroysis rate[J].Agro-Environ Prot,1999,18(6):275-277.
[11]HONG F,PEHKONEN S O,BROOKS E.Pathways for the hydrolysis of phorate:product studies by 31P NMR and GC-MS[J].JAgric Food Chem,2000,48(7):3013-3017.
[12]刘晓旭.嘧菌酯的水解和光解特性研究[D].长春:吉林农业大学,2013.LIU X X.Study on the hydrolysis and photolytic characteristic of azoxystrobin[D].Changchun:Jilin Agricultural University,2013.
[13]欧晓明.农药在环境中的水解机理及其影响因子研究进展[J].生态环境,2006,15(6):1352-1359.OU X M.Hydrolysis and its influencing factors of pesticides in environment:a review[J].Ecol Environ,2006,15(6):1352-1359.
[14]梁菁,郭正元,冯丽萍,等.农药在环境中光化学降解的影响因素[J].农业环境科学学报,2007,26(增刊1):668-673.LIANG J,GUO Z Y,FENG L P,et al.The influence factors of pesticides photodegradation in the environment[J].J Agro-Environ Sci,2007,26(Suppl.1):668-673.
[15]李芫慧.胺唑草酮的水解与光解特性研究[D].长春:吉林农业大学,2015.LI Y H.The Study of amicarazone hydrolysis and photolysis characteristics[D].Changchun:Jilin Agricultural University,2015.
[16]殷花.联苯肼酯的水解及光解行为研究[D].重庆:西南大学,2015.YIN H.Study on the hydrolysis and the photodegradation of bifenazate[D].Chongqing:Southwestern University,2015.
[17]贾娜,施海燕,王鸣华.2,4-D丁酯的水解与光解特性研究[J].农业环境科学学报,2011,30(6):1082-1086.JIA N,SHI H Y,WANG M H.Hydrolysis and photolysis of 2,4-Dbutylate[J].J Agro-Environ Sci,2011,30(6):1082-1086.
[18]食品安全国家标准食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2017.National food safety standard:maximum residue limits for pesticides in food:GB 2763-2016[S].Beijing:Standards Press of China,2017.
[19]吴星卫,单正军,薛韵涵.2,4-D的水解、光解及在土壤中的降解特性研究[J].安徽农业科学,2011,39(16):9711-9713.WU X W,SHAN Z J,XUE Y H.Photolysis,hydrolysis of 2,4-dicholrophenoxyacetic acid and its degradation characteristics in soils[J].J Anhui Agric Sci,2011,39(16):9711-9713.
[20]VENKATESH R,HARRISON S K.Photolytic degradation of 2,4-Don Zea mays leaves[J].Weed Sci,1999,47(3):262-269.
[21]Pesticide Properties DataBase(PPDB).2,4-D.Key metabolites and other known metabolites for 2,4-D[EB/OL].(2018-08-23)[2018-11-28].http://sitem.herts.ac.uk/aeru/ppdb/en/Reports/4.htm.
[22]EFSA.Conclusion on the peer review of the pesticide risk assessment of the active substance 2,4-D[EB/OL].(2017-03-21)[2018-11-29].http://www.efsa.europa.eu/en/efsajournal/pub/3812.
[23]JMPR.2017(R)report,evaluation[EB/OL].[2018-11-29].http://www.fao.org/agriculture/crops/core-themes/theme/pests/lpe/en/.
[24]SUNDA W,HUNTSMAN S.Effect of pH,light,and temperature on Fe-EDTA chelation and Fe hydrolysis in seawater[J].Mar Chem,2003,84(1-2):35-47.
[25]LOFTIN K A,ADAMS C D,MEYER M T,et al.Effects of ionic strength,temperature,and pH on degradation of selected antibiotics[J].J Environ Qual,2008,37(2):378-386.