Residue analysis of flucarbazone-sodium, mesosulfuron-methyl, clodinafop-propargyl and clodinafop in wheat
-
摘要: 以QuEChERS前处理方法为基础，采用高效液相色谱-串联质谱(HPLC-MS/MS)检测技术，建立了除草剂氟唑磺隆、甲基二磺隆、炔草酯及其代谢物炔草酸4种化合物在小麦中残留的分析方法。麦粒样品中加入5 mL体积分数为0.1%的甲酸水溶液后，以10 mL乙腈提取，用50 mg C18与100 mg 无水硫酸镁净化；麦秆样品中加入10 mL体积分数为2%的甲酸水溶液后，以10 mL乙腈提取，用100 mg C18与200 mg无水硫酸镁净化。结果表明：氟唑磺隆在0.005、0.01和0.1 mg/kg，甲基二磺隆在0.01、0.02和0.1 mg/kg，炔草酯和炔草酸在0.05、0.1和0.5 mg/kg添加水平下，4种化合物在麦粒中的回收率在76%~97%之间，在麦秆中的回收率在83%~102%之间，相对标准偏差均小于10%，r > 0.99。4种化合物在麦粒和麦秆中的定量限分别为：氟唑磺隆0.005 mg/kg，甲基二磺隆0.01 mg/kg，炔草酯和炔草酸均为0.05 mg/kg。该方法可满足小麦样品中4种化合物的残留分析要求。Abstract: A modified QuEChERS method was developed and validated for the determination of flucarbazone-sodium, mesosulfuron-methyl, clodinafop-propargyl and clodinafop in wheat kernel and straw by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The wheat kernel was extracted with 10 mL acetonitrile, after 5 mL 0.1% formic acid solution was added to improve the extraction efficiency. Samples were cleaned up by 50 mg C18 and 100 mg anhydrous MgSO4. After adding 10 mL 2% formic acid solution, the wheat straw was extracted with 10 mL acetonitrile. 100 mg C18 and 200 mg anhydrous MgSO4 were used to clean up the samples. The average recoveries of four compounds in wheat kernel and wheat straw were 76%-97% and 83%-102%, respectively, with the relative standard deviations (RSDs) for those four compounds less than 10%. Good linearity was achieved with determination coefficients higher than 0.99. The limit of quantity (LOQ) is 0.005 mg/kg for flucarbazone-sodium, 0.01 mg/kg for mesosulfuron-methyl, 0.05 mg/kg for clodinafop-propargyl and clodinafop. This method meets the requirements of pesticide residue analysis.
-
1 氟唑磺隆 (a)、甲基二磺隆 (b)、炔草酯 (c)和炔草酸 (d)的结构式
1. Structural formula of flucarbazone-sodium (a), mesosulfuron-methyl (b), clodinafop-propargyl (c) and clodinafop (d)
图 1 不同溶剂对麦粒和麦秆中4种化合物提取效果的影响
Figure 1. Extraction effect of four compounds in wheat kernel and wheat straw treated with different solvents
图 2 净化剂用量对麦粒和麦秆中4种化合物的净化效果
Figure 2. Cleanup effect of the amount of the cleanup absorbent for 4 compounds in wheat kernel and wheat straw matrix
图 3 无水硫酸镁用量对麦秆基质中4种化合物提取效果的影响
Figure 3. Extraction effect of the amount of MgSO4 for 4 compounds in wheat straw matrix
表 1 四种化合物已有残留分析方法
Table 1. Existing residue analysis methods for four compounds
化合物
Compound前处理方法
Extraction and cleanup仪器分析方法
Determination定量限
LOQ/(mg/kg)文献来源
Reference氟唑磺隆
flucarbazone-sodium50 mL乙腈振荡提取，ODS-C18固相萃取柱净化
Extracted with 50 mL acetonitrile and cleaned up with SPE高效液相色谱-紫外检测法
HPLC-UVD0.01 [6] 氟唑磺隆及其代谢物脱甲基氟唑磺隆
flucarbazone-sodium and its metabolite N-desmethyl20 mL乙腈超声提取，GCB分散固相萃取净化
Extracted with 20 mL acetonitrile on an ultrasonic bath and DSPE cleanup with GCB液相色谱-串联质谱法
LC-MS/MS0.02 [8] 甲基二磺隆
mesosulfuron-methyl120 mL提取剂浸提过夜(麦粒)，液-液萃取 + 固相萃取多重净化
Extracted with 120 mL solvent overnight (wheat kernel) and cleaned up with LLE and SPE液相色谱-紫外检测法
LC-UVD0.01 [10] 甲基二磺隆
mesosulfuron-methyl1%甲酸-乙腈浸渍提取，C18 + PSA + MgSO4分散固相萃取净化
Extracted with MeCN containing 1% formic acid and DSPE cleanup with C18 + PSA + MgSO4液相色谱-串联质谱法
LC-MS/MS0.005 [9] 炔草酯及其代谢物炔草酸
clodinafop-propargyl and its metabolite clodinafop80 mL丙酮浸泡过夜，振荡提取，检测炔草酯采用柱层析法净化，检测炔草酸采用固相萃取法净化
Coaked overnight and extracted with 80 mL acetone and column chromatography for clodinafop-propargyl and SPE for clodinafop高效液相色谱-紫外检测法
HPLC-UVD0.02(麦粒，炔草酯)，0.01(麦粒，炔草酸)
0.02 (wheat kernel,clodinafop-propargyl), 0.01 (wheat kernel, clodinafop)[7] 炔草酯及其代谢物炔草酸
clodinafop-propargyl and its metabolite clodinafop乙腈振荡提取，C18 + GCB分散固相萃取
Extracted with acetonitrile and DSPE cleanup with C18 + GCB高效液相色谱-串联质谱法
HPLC-MS/MS0.005(麦粒)，0.05(麦秆，炔草酯)，0.2(麦秆，炔草酸)
0.005 (wheat kernel), 0.05 (wheat straw, clodinafop-propargyl), 0.2 (wheat straw,clodinafop)[11] 
下载: 导出CSV
表 2 四种目标化合物的质谱检测参数
Table 2. MS parameters for the analysis of four target compounds
化合物
Compound离子对
Ion-pair, m/z驻留时间
Dwell time/msQ1 预四极偏置电压
Q1 Pre Bias/V碰撞能
CE/VQ3 预四极偏置电压
Q3 Pre Bias/V氟唑磺隆
flucarbazone-sodium419.1/152.05* 100 −19 −15 −30 419.1/337.10 100 −20 −11 −24 419.1/269.15 100 −21 −22 −28 甲基二磺隆
mesosulfuron-methyl502.10/267.10* 100 38 28 26 502.10/347.05 100 38 15 22 炔草酸
clodinafop310.1/238.05* 100 15 12 24 310.1/218.05 100 11 22 20 炔草酯
clodinafop-propargyl350.2/266.0* 100 −11 −15 −26 350.2/91.0 100 −10 −30 −16 注：*为定量离子对。Note: *Quantitative ion pair.
下载: 导出CSV
表 3 麦粒和麦秆中4种化合物的添加回收率和相对标准偏差
Table 3. Spiked recoveries and RSDs of four compounds in wheat kernel and wheat straw (n = 5)
基质
Matrix氟唑磺隆
flucarbazone-sodium甲基二磺隆
mesosulfuron-methyl炔草酯
clodinafop-propargyl炔草酸
clodinafop添加水平
Spiked level/
(mg/kg)平均回收率
Average recovery/%RSD/% 添加水平
Spiked level/
(mg/kg)平均回收率
Average recovery/%RSD/% 添加水平
Spiked level/
(mg/kg)平均回收率
Average recovery/%RSD/% 添加水平
Spiked level/
(mg/kg)平均回收率
Average recovery/%RSD/% 麦粒
Wheat kernel0.005 93 9.1 0.01 94 7.8 0.05 97 3.0 0.05 91 4.5 0.01 88 8.2 0.02 83 2.0 0.1 76 2.2 0.1 82 4.3 0.1 96 3.3 0.1 84 1.7 0.5 82 1.2 0.5 85 2.9 麦秆
Wheat straw0.005 91 2.9 0.01 96 6.6 0.05 92 1.7 0.05 83 2.8 0.01 98 1.5 0.02 100 4.8 0.1 97 3.9 0.1 101 3.2 0.1 92 8.5 0.1 102 3.7 0.5 99 3.9 0.5 100 4.9
下载: 导出CSV
表 4 麦粒和麦秆基质中4种化合物的线性范围和定量限
Table 4. Matrix standard curves of four compounds in wheat kernel and wheat straw
基质
Matrix化合物
Compound线性范围
Concentration range/(mg/L)回归方程
Regression equationR2 LOQ/(mg/kg) 麦粒
Wheat kernel氟唑磺隆 flucarbazone-sodium 0.001~0.075 y = 4 × 106x + 3 640.2 0.998 4 0.005 甲基二磺隆 mesosulfuron-methyl 0.002~0.15 y = 8 × 106x + 834.49 1.000 0 0.01 炔草酸 clodinafop 0.01~0.75 y = 2 × 107x – 23 618 0.999 8 0.05 炔草酯 clodinafop-propargyl 0.01~0.75 y = 8 × 106x + 86 342 0.998 5 0.05 麦秆
Wheat straw氟唑磺隆 flucarbazone-sodium 0.000 5~0.1 y = 5 × 106x – 4 900.7 0.996 0 0.005 甲基二磺隆 mesosulfuron-methyl 0.001~0.2 y = 1 × 107x – 886.01 0.999 9 0.01 炔草酸 clodinafop 0.005~1 y = 3 × 107x – 25 894 0.999 9 0.05 炔草酯 clodinafop-propargyl 0.005~1 y = 2 × 107x + 129 561 0.999 3 0.05
下载: 导出CSV
-
[1] 范添乐, 魏芩杰, 陈小军, 等. 氟唑磺隆在野燕麦中的内吸传导特性[J]. 农药学学报, 2018, 20(6): 1-5.FAN T L, WEI Q J, CHEN X J, et al. Uptake and translocation of flucarbazone-sodium in Avena fatua[J]. Chin J Pestic Sci, 2018, 20(6): 1-5. [2] ELIASON R, SCHOENAU J J, SZMIGIELSKI A M, et al. Phytotoxicity and persistence of flucarbazone-sodium in soil[J]. Weed Sci, 2004, 52(5): 857-862. doi: 10.1614/WS-03-047R2 [3] VAZAN S, OVEISI M, BAZIAR S. Efficiency of mesosulfuron-methyl and clodinafop-propargyl dose for the control of Lolium perenne in wheat[J]. Crop Prot, 2011, 30(6): 592-597. doi: 10.1016/j.cropro.2011.01.004 [4] GUI W J, DONG Q X, ZHOU S L, et al. Waterborne exposure to clodinafop-propargyl disrupts the posterior and ventral development of zebrafish embryos[J]. Environ Toxicol Chem, 2011, 30(7): 1576-1581. doi: 10.1002/etc.v30.7 [5] 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.Maximum residue limits for pesticides in food: GB 2763—2016[S]. Beijing: Standards Press of China, 2017. [6] 侯红敏, 乔琳, 刘惠敏, 等. 高效液相色谱法测定小麦中氟唑磺隆残留量[J]. 现代农药, 2015, 14(1): 35-36, 43. doi: 10.3969/j.issn.1671-5284.2015.01.011HOU H M, QIAO L, LIU H M, et al. Determination offlucarbazone-sodium residue in wheat by HPLC[J]. Mod Agrochem, 2015, 14(1): 35-36, 43. doi: 10.3969/j.issn.1671-5284.2015.01.011 [7] 段劲生, 王梅, 孙明娜, 等. 高效液相色谱法测定小麦和土壤中炔草酯及其代谢物炔草酸的残留量[J]. 农药学学报, 2013, 15(1): 121-124. doi: 10.3969/j.issn.1008-7303.2013.01.19DUAN J S, WANG M, SUN M N, et al. Determination of clodinafop-propargyl and its metabolite clodinafop in wheat and soil by high performance liquid chromatography[J]. Chin J Pestic Sci, 2013, 15(1): 121-124. doi: 10.3969/j.issn.1008-7303.2013.01.19 [8] XUE J, LI H, LIU F, et al. Determination and dissipation of flucarbazone-sodium and its metabolite in wheat and soils by LC-MS/MS[J]. Inter J Environ Anal Chem, 2014, 94(5): 479-492. doi: 10.1080/03067319.2013.841153 [9] NI Y X, YANG H, ZHANG H T, et al. Analysis of four sulfonylurea herbicides in cereals using modified Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method coupled with liquid chromatography-tandem mass spectrometry[J]. J Chromatogr A, 2018, 1537: 27-34. doi: 10.1016/j.chroma.2018.01.017 [10] 张少军, 杨更亮, 郑振山, 等. 甲基二磺隆在小麦和土壤中的残留动态研究[J]. 河北农业大学学报, 2009, 32(3): 12-16. doi: 10.3969/j.issn.1000-1573.2009.03.003ZHANG S J, YANG G L, ZHENG Z S, et al. Study on the residue dynamics of mesosulfuron-methyl in wheat and soil[J]. J Agric Univ Hebei, 2009, 32(3): 12-16. doi: 10.3969/j.issn.1000-1573.2009.03.003 [11] GUAN W B, MA Y Q, ZHANG H Y. Dissipation of clodinafop-propargyl and its metabolite in wheat field ecosystem[J]. Bull Environ Contam Toxicol, 2013, 90(6): 750-755. doi: 10.1007/s00128-013-0997-4 [12] ANASTASSIADES M, LEHOTAY S J, ŠTAJNBAHER D, et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce[J]. J AOAC Inter, 2003, 86(2): 412-431. [13] International Union of Pure and Applied Chemistry[DB/OL].[2018-09-13]. http://sitem.herts.ac.uk/aeru/iupac/Reports/441.htm. [14] 农作物中农药残留试验准则: NY/T 788—2018[S]. 北京: 中国农业出版社, 2018.Guideline for the testing of pesticide residues in crops: NY/T 788—2018[S]. Beijing: China Agriculture Press, 2018. -
点击查看大图
图(4) / 表(4)
计量
- 文章访问数: 1933
- HTML全文浏览量: 319
- PDF下载量: 144
- 被引次数: 0
