溴菌腈在香蕉和土壤中的残留及在土壤中吸附特性研究
摘要
溴菌腈(bromothalonil)是一种应用广泛的杀菌剂。本文以气相色谱(GC-ECD)为检测手段,研究了农药溴菌腈在香蕉和土壤中的残留分析方法、残留消解动态规律、最终残留量,溴菌腈在土壤中的吸附行为。为溴菌腈在香蕉上登记,最高残留量标准的制定,安全合理使用提供理论依据,为评价溴菌腈的环境安全性提供科学依据。研究结果如下：
1.建立了溴菌腈在香蕉和土壤中的气相色谱(GC-ECD)分析方法。
样品采用乙腈提取,弗罗里硅土柱净化,5：5的丙酮+正己烷洗脱液液洗脱,正己烷定容,气相色谱(GC-ECD)检测,气相色谱(GC-ECD)检测条件为：毛细管色谱柱：DB-1(30m×0.32 mm×1.0μm)；程序升温：起始温度80℃,保持0.3min,以25℃·min-1升温至240℃,保持0.5min,再以60℃·min-1升温至280℃,保持8min；检测器温度300℃；进样口温度250℃；载气：氮气,纯度≥99.999%；不分流进样；尾吹气流速：50mL·min-1;溴菌腈保留时间7.22min左右；溴菌腈的最小检测量(LOD)为8×10-12 mg,在香蕉中的最低检测浓度(LOQ)为0.02mg·kg-1。
添加回收率结果表明：在添加浓度为0.05～0.5 mg·L-1范围内,溴菌腈在土壤中的回收率为91%～105%,相对标准偏差为1.8%～4.4%；在香蕉中的回收率为80%～100%,相对标准偏差为1.8%～4.8%；方法简便、快速,灵敏度、精确度高、精密度良好,符合农药残留检测的要求。
2.研究了溴菌腈WP在香蕉和土壤中的残留消解动态。
按一次施药多次采样的方法对溴菌腈可湿性粉剂在香蕉和土壤中的残留消解动态进行研究。施药浓度为2250 g (a. i.)·hm-2,两年的结果表明：溴菌腈在香蕉和土壤中的消解动态曲线,降解过程均符合一级动力学模式。溴菌腈在香蕉中的消解动态方程为：2009年,C=0.4294e-0.3771t相关系数R2=0.9289；2010年,C=0.4974e-0.376t相关系数R2=0.9126；溴菌腈在土壤中的消解动态方程为：2009年,C=0.4914e-0.3611t,相关系数R2=0.91,2010年,C=0.122e-0.3735t,相关系数R2=0.9653；溴菌腈在香蕉中的半衰期为1.8d,药后14d消解达到90%以上,溴菌腈在土壤中的半衰期为1.9d,药后14 d消解达到90%以上,溴菌腈在香蕉和土壤中的消解都很快,属于易降解农药。
3.研究了澳菌腈WP在香蕉和土壤中的最终残留量。
施药时以登记时的最高推荐剂量作为残留试验的低剂量,低剂量的2倍剂量作为残留试验的高剂量,以1125 g (a. i.)·hm-2为低浓度,2250 g (a. i.)·hm-2为高浓度分别施药,低浓度很高浓度分别施药3次,4次,每次施药间隔7d,以最后一次施药后的7d、14d、21d分别采样测定结果,测定结果表明：溴菌腈在香蕉果中的最终残留量为0.03-0.066mg·kg-1之间,在土壤中的最终残留量为0.041-0.068mg·kg-1之间。香蕉上药后21d的残留量都比较低为0.03mg·kg-1,土壤中药后21d的残留量稍高为0.04mg·kg-1。根据实验结果,参照溴菌腈在其他作物上的最高残留限量0.1mg·kg-1,建议40%溴菌腈可湿性粉剂在香蕉和土壤中合理使用时施药剂量不要超过2250 g (a. i.)·hm-2,安全间隔期不少于7d,溴菌腈在香蕉上采收后食用是安全的。
4.研究了溴菌腈溴菌腈的土壤吸附行为。
本文还研究了溴菌腈在红土、泥土、沙土上的吸附特性,结果表明：溴菌腈的吸附主要跟土壤有机质含量有关,在相同条件下,有机质含量高的泥土对溴菌腈的吸附最强,随着有机质含量的减少,对溴菌腈的吸附也相对减弱。土壤对溴菌腈的吸附主要以物理吸附为主,溴菌腈易被土壤吸附,对环境影响相对比较小。
Bromothalonil is a widely used fungicide. In this paper, the residue dynamics and the final residues of bromothalonil in the banana and soil were determined by gas chromatography equipped with an electron-capture detector (GC-ECD), and residue detection method of bromothalonil was studied ang optimized with it, and adsorption in soil. The study provides reference for making the rules of MRL and using the pesticide properly in banana, and provides the scientific basis for evaluate environmental security of bromothalonil. The results were as follows:
1.The analysis method for determination of bromothalonil in banana and soil by GC-ECD was established.
The samples were extracted with acetonitrile and cleaned-up with florisil column, then eluted with acetone:hexane (5:5v/v), volume with hexane, and determined by gas chromatography equipped with an electron-capture detector (GC-ECD), GC-ECD test condition of bromothalonil:capillary column:DB-1 (30m×0.32 mm×1.0μm); temperature programming:initial temperature 80℃, hold time 0.3min, ramp 25℃·min-1 to 240℃, hold time 0.5min, ramp 60℃·min-1 to 280℃, hold time 8min; detector temperature 300℃; injector temperature 250℃; carrier gas:nitrogen, purity(?)99.999%; Splitless injection; makeup 50mL·min-1; retention time 7.22min; the minimum detectable amount of bromothalonil (LOD) for the 8×10-12 mg, the lowest detectable concentration of banana (LOQ) was 0.02 mg·kg-1
On the level of 0.05～0.5 mg·L-1,the results of recoveries showed that the recovery ratio of bromothalonil was 80% to 105% in the soil,the relative standard deviations was 1.8% to 4.8%, the recovery ratio in banana was 91% to 100%,relative standard deviation was 1.8% to 4.4%,. This method was simple, rapid, sensitive, high accuracy, good precision,in line with the requirements of pesticide residues.
2. The residue dynamics of bromothalonil WP in banana and soil.
The dosage 2250 g(a.i.)·hm-2 bromothalonil WP was applied in banana and soil, two years'field test showed that the degradation procedure of bromothalonil was correspond to the mathematic pattern,C=Coe-kt. In banana, the dynamic equations were C=0.4294e-0.3771t, R2=0.9289 (2009); C=0.4974e-0.376t, R2=0.9126 (2010); the dynamic equations in soil were C-0.4914e-03611t, R2=0.91 (2009); C=0.122e-0.3735t, R2=0.9653; The half-life of bromothalonil was 1.8 d in banana,1.9 d in soil in 2009 and in 2010, Bromothalonil decomposed more than 90% in banana and in soil after had been sprayed for 14 d. Bromothalonil was dissipated rapidly in banana and soil, bromothalonil is easy to degrade.
3. The final residue of bromothalonil in the banana and soil was studied.
The recommended maximum dose was the low dose,1125 g (a.i.)·hm-2. The double of The recommended maximum dose was high concentration,2250 g (a.i.)·hm-2. The pesticide was respectively sprayed three times and four times, the samples was collected at each seven days interval, after the last spraying 7d, 14d, 21d The results demonstrated that the final residue dose were 0.03-0.066mg·kg-1 in banana and 0.041-0.068mg·kg-1 in soil. The residues in 21 d after spraying were 0.03mg·kg-1 in banana and 0.04mg·kg-1 in soil, the maximum residue limit of bromothalonil with reference to that in other crops 0.1 mg·kg-1 was recommended. It was suggested that the drug dose of 40% bromothalonil WP should not exceed 2250 g (ai)·hm-2 when reasonably used, the safe internal time was no less than 7d. It was safe to eat after spraying bromothalonil to harvest banana.
4. The absorption of bromothalonil in clay, mud, sand were also studied in this paper that the absorption of bromothalonil mainly concerned with the soil organic matter content, under the same conditions, the soil with high organic matter behave the highest absorption of bromothalonil, the soil behave relatively less absorption of bromothalonil with the reduction in organic matter content. The adsorption of bromothalonil in soil mainly based on physical adsorption, which is susceptible to soil adsorption leading to relatively small impact on the environment.
1.建立了溴菌腈在香蕉和土壤中的气相色谱(GC-ECD)分析方法。
样品采用乙腈提取,弗罗里硅土柱净化,5：5的丙酮+正己烷洗脱液液洗脱,正己烷定容,气相色谱(GC-ECD)检测,气相色谱(GC-ECD)检测条件为：毛细管色谱柱：DB-1(30m×0.32 mm×1.0μm)；程序升温：起始温度80℃,保持0.3min,以25℃·min-1升温至240℃,保持0.5min,再以60℃·min-1升温至280℃,保持8min；检测器温度300℃；进样口温度250℃；载气：氮气,纯度≥99.999%；不分流进样；尾吹气流速：50mL·min-1;溴菌腈保留时间7.22min左右；溴菌腈的最小检测量(LOD)为8×10-12 mg,在香蕉中的最低检测浓度(LOQ)为0.02mg·kg-1。
添加回收率结果表明：在添加浓度为0.05～0.5 mg·L-1范围内,溴菌腈在土壤中的回收率为91%～105%,相对标准偏差为1.8%～4.4%；在香蕉中的回收率为80%～100%,相对标准偏差为1.8%～4.8%；方法简便、快速,灵敏度、精确度高、精密度良好,符合农药残留检测的要求。
2.研究了溴菌腈WP在香蕉和土壤中的残留消解动态。
按一次施药多次采样的方法对溴菌腈可湿性粉剂在香蕉和土壤中的残留消解动态进行研究。施药浓度为2250 g (a. i.)·hm-2,两年的结果表明：溴菌腈在香蕉和土壤中的消解动态曲线,降解过程均符合一级动力学模式。溴菌腈在香蕉中的消解动态方程为：2009年,C=0.4294e-0.3771t相关系数R2=0.9289；2010年,C=0.4974e-0.376t相关系数R2=0.9126；溴菌腈在土壤中的消解动态方程为：2009年,C=0.4914e-0.3611t,相关系数R2=0.91,2010年,C=0.122e-0.3735t,相关系数R2=0.9653；溴菌腈在香蕉中的半衰期为1.8d,药后14d消解达到90%以上,溴菌腈在土壤中的半衰期为1.9d,药后14 d消解达到90%以上,溴菌腈在香蕉和土壤中的消解都很快,属于易降解农药。
3.研究了澳菌腈WP在香蕉和土壤中的最终残留量。
施药时以登记时的最高推荐剂量作为残留试验的低剂量,低剂量的2倍剂量作为残留试验的高剂量,以1125 g (a. i.)·hm-2为低浓度,2250 g (a. i.)·hm-2为高浓度分别施药,低浓度很高浓度分别施药3次,4次,每次施药间隔7d,以最后一次施药后的7d、14d、21d分别采样测定结果,测定结果表明：溴菌腈在香蕉果中的最终残留量为0.03-0.066mg·kg-1之间,在土壤中的最终残留量为0.041-0.068mg·kg-1之间。香蕉上药后21d的残留量都比较低为0.03mg·kg-1,土壤中药后21d的残留量稍高为0.04mg·kg-1。根据实验结果,参照溴菌腈在其他作物上的最高残留限量0.1mg·kg-1,建议40%溴菌腈可湿性粉剂在香蕉和土壤中合理使用时施药剂量不要超过2250 g (a. i.)·hm-2,安全间隔期不少于7d,溴菌腈在香蕉上采收后食用是安全的。
4.研究了溴菌腈溴菌腈的土壤吸附行为。
本文还研究了溴菌腈在红土、泥土、沙土上的吸附特性,结果表明：溴菌腈的吸附主要跟土壤有机质含量有关,在相同条件下,有机质含量高的泥土对溴菌腈的吸附最强,随着有机质含量的减少,对溴菌腈的吸附也相对减弱。土壤对溴菌腈的吸附主要以物理吸附为主,溴菌腈易被土壤吸附,对环境影响相对比较小。
Bromothalonil is a widely used fungicide. In this paper, the residue dynamics and the final residues of bromothalonil in the banana and soil were determined by gas chromatography equipped with an electron-capture detector (GC-ECD), and residue detection method of bromothalonil was studied ang optimized with it, and adsorption in soil. The study provides reference for making the rules of MRL and using the pesticide properly in banana, and provides the scientific basis for evaluate environmental security of bromothalonil. The results were as follows:
1.The analysis method for determination of bromothalonil in banana and soil by GC-ECD was established.
The samples were extracted with acetonitrile and cleaned-up with florisil column, then eluted with acetone:hexane (5:5v/v), volume with hexane, and determined by gas chromatography equipped with an electron-capture detector (GC-ECD), GC-ECD test condition of bromothalonil:capillary column:DB-1 (30m×0.32 mm×1.0μm); temperature programming:initial temperature 80℃, hold time 0.3min, ramp 25℃·min-1 to 240℃, hold time 0.5min, ramp 60℃·min-1 to 280℃, hold time 8min; detector temperature 300℃; injector temperature 250℃; carrier gas:nitrogen, purity(?)99.999%; Splitless injection; makeup 50mL·min-1; retention time 7.22min; the minimum detectable amount of bromothalonil (LOD) for the 8×10-12 mg, the lowest detectable concentration of banana (LOQ) was 0.02 mg·kg-1
On the level of 0.05～0.5 mg·L-1,the results of recoveries showed that the recovery ratio of bromothalonil was 80% to 105% in the soil,the relative standard deviations was 1.8% to 4.8%, the recovery ratio in banana was 91% to 100%,relative standard deviation was 1.8% to 4.4%,. This method was simple, rapid, sensitive, high accuracy, good precision,in line with the requirements of pesticide residues.
2. The residue dynamics of bromothalonil WP in banana and soil.
The dosage 2250 g(a.i.)·hm-2 bromothalonil WP was applied in banana and soil, two years'field test showed that the degradation procedure of bromothalonil was correspond to the mathematic pattern,C=Coe-kt. In banana, the dynamic equations were C=0.4294e-0.3771t, R2=0.9289 (2009); C=0.4974e-0.376t, R2=0.9126 (2010); the dynamic equations in soil were C-0.4914e-03611t, R2=0.91 (2009); C=0.122e-0.3735t, R2=0.9653; The half-life of bromothalonil was 1.8 d in banana,1.9 d in soil in 2009 and in 2010, Bromothalonil decomposed more than 90% in banana and in soil after had been sprayed for 14 d. Bromothalonil was dissipated rapidly in banana and soil, bromothalonil is easy to degrade.
3. The final residue of bromothalonil in the banana and soil was studied.
The recommended maximum dose was the low dose,1125 g (a.i.)·hm-2. The double of The recommended maximum dose was high concentration,2250 g (a.i.)·hm-2. The pesticide was respectively sprayed three times and four times, the samples was collected at each seven days interval, after the last spraying 7d, 14d, 21d The results demonstrated that the final residue dose were 0.03-0.066mg·kg-1 in banana and 0.041-0.068mg·kg-1 in soil. The residues in 21 d after spraying were 0.03mg·kg-1 in banana and 0.04mg·kg-1 in soil, the maximum residue limit of bromothalonil with reference to that in other crops 0.1 mg·kg-1 was recommended. It was suggested that the drug dose of 40% bromothalonil WP should not exceed 2250 g (ai)·hm-2 when reasonably used, the safe internal time was no less than 7d. It was safe to eat after spraying bromothalonil to harvest banana.
4. The absorption of bromothalonil in clay, mud, sand were also studied in this paper that the absorption of bromothalonil mainly concerned with the soil organic matter content, under the same conditions, the soil with high organic matter behave the highest absorption of bromothalonil, the soil behave relatively less absorption of bromothalonil with the reduction in organic matter content. The adsorption of bromothalonil in soil mainly based on physical adsorption, which is susceptible to soil adsorption leading to relatively small impact on the environment.
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53. David T.R, Nanyan Zhang, Automating solid-phase extraction:current aspects and future prospects[J]. Journal of Chromatography A.2000,885(1-2):97～113.
54. C. Arthur, J. Pawliszyn. Solid phase microextraction with thermal desorption fused silica optical fibers[J]. Anal. Chem,1990,62:2145～2148.
55. A. L. Simplicio, L. V. Boas, J. Chromatogr. A[M].1999:833～835.
56. C.Z. Dong, Z.R.Zeng, X.J.Li, Talanta [J].2005,66(3):721.
57. G.Duflos,V.M. Coin, M.Cornu, J.F.Antinelli, P.Mallel, J.Sci [J]. Food Agric 2006,86(4):600
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59. J. X. Yu, C.Y. Wu,J.Xing, J.Chromatogr.A [J].2004,1036(2):101.
60. Zougagh M, Valcarcel M, Rios A. Supercritical fluid extraction:a critical review of its analytical usefulness[J]. Trends Anal Chem.2004,23(5):1～7.
61. Lehotay S J. Supercritical fluid extraction of pesticides in foods [J]. J Chromatography A,1997,785 (1-2):289～312
62. Tang Y L, Wang R C, Huang J F. Relations between red edge Characteristics and agronomic parameters of crops [J]. Pedosphere,2004,14(4):467～474.
63. Biggar J W, Cheung M W. Adsorption of picloram (4-amino-3,5,6-trichloropicolinic acid) on panoche, cphrata, and palouse soils thermo dynamic approach to the adsorption mechanism[J]. Soil Sci.Soc Am. Proc,1973,37:863～868.
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65. Burchil s et al[M]. Versiles,1973:70.
66. Pusino A, Liu W, Gessa C. J. [J]. Agric Food Chem.,1993,41(3):502.