Acta Agriculturae Zhejiangensis ›› 2023, Vol. 35 ›› Issue (7): 1720-1728.DOI: 10.3969/j.issn.1004-1524.20220807
• Quality and Safety of Agricultural Products • Previous Articles Next Articles
YE Hui1,2(
), CHEN Yuting1, LUO Yuqin2, FAN Xuyan2, LEI Yuan2, LU Lanfei2, HAO Peipei3, CHENG Youpu1,*(
), ZHANG Changpeng2,*(
)
Received:2022-05-31
Online:2023-07-25
Published:2023-08-17
Contact:
CHENG Youpu,ZHANG Changpeng
CLC Number:
YE Hui, CHEN Yuting, LUO Yuqin, FAN Xuyan, LEI Yuan, LU Lanfei, HAO Peipei, CHENG Youpu, ZHANG Changpeng. Residue and dissipation dynamics of two formulations of pyraclostrobin in strawberry[J]. Acta Agriculturae Zhejiangensis, 2023, 35(7): 1720-1728.
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URL: http://www.zjnyxb.cn/EN/10.3969/j.issn.1004-1524.20220807
| 保留时间 Retention time/min | 母离子 Precursor ion(m/z) | 子离子 Product ion(m/z) | 滞留时间 Dwell time/s | 锥孔电压 Cone voltage/V | 碰撞能 Collision energy/eV |
|---|---|---|---|---|---|
| 1.51 | 388.01 | 197.03* | 0.061 | 18 | 28 |
| 388.01 | 163.05 | 0.061 | 18 | 12 |
Table 1 Mass spectrometric parameters of pyraclostrobin
| 保留时间 Retention time/min | 母离子 Precursor ion(m/z) | 子离子 Product ion(m/z) | 滞留时间 Dwell time/s | 锥孔电压 Cone voltage/V | 碰撞能 Collision energy/eV |
|---|---|---|---|---|---|
| 1.51 | 388.01 | 197.03* | 0.061 | 18 | 28 |
| 388.01 | 163.05 | 0.061 | 18 | 12 |
| 线性范围 Linear range/ (mg·L-1) | 基质 Matrix | 回归方程 Regression equation | 决定系数 Coefficient of determination | 基质效应 ME | 检出限 LOD/ (mg·L-1) | 定量限 LOQ/ (mg·kg-1) |
|---|---|---|---|---|---|---|
| 0.0005~0.1 | 乙腈Acetonitrile | y=1 938 010.57x+4 352.84 | 0.999 7 | — | — | — |
| 叶Leaf | y=2 804 465.99x+1 0761.20 | 0.998 9 | 0.87 | 0.000 5 | 0.005 0 | |
| 茎Stem | y=2 576 648.62x+3 515.89 | 1.000 0 | 0.85 | 0.000 5 | 0.005 0 | |
| 草莓Strawberry | y=1 992 976.51x+6 239.22 | 0.999 2 | 1.03 | 0.000 5 | 0.002 0 | |
| 根Root | y=2 081 043.87x+6 103.10 | 0.999 8 | 1.07 | 0.000 5 | 0.005 0 | |
| 土壤Soil | y=2 292 365.17x+7 089.11 | 0.999 8 | 1.21 | 0.000 5 | 0.002 0 |
Table 2 Regression equation, coefficient of determination (R2), limit of detection (LOD), limit of quantitation (LOQ) and matrix effect (ME) of pyraclostrobin in strawberry
| 线性范围 Linear range/ (mg·L-1) | 基质 Matrix | 回归方程 Regression equation | 决定系数 Coefficient of determination | 基质效应 ME | 检出限 LOD/ (mg·L-1) | 定量限 LOQ/ (mg·kg-1) |
|---|---|---|---|---|---|---|
| 0.0005~0.1 | 乙腈Acetonitrile | y=1 938 010.57x+4 352.84 | 0.999 7 | — | — | — |
| 叶Leaf | y=2 804 465.99x+1 0761.20 | 0.998 9 | 0.87 | 0.000 5 | 0.005 0 | |
| 茎Stem | y=2 576 648.62x+3 515.89 | 1.000 0 | 0.85 | 0.000 5 | 0.005 0 | |
| 草莓Strawberry | y=1 992 976.51x+6 239.22 | 0.999 2 | 1.03 | 0.000 5 | 0.002 0 | |
| 根Root | y=2 081 043.87x+6 103.10 | 0.999 8 | 1.07 | 0.000 5 | 0.005 0 | |
| 土壤Soil | y=2 292 365.17x+7 089.11 | 0.999 8 | 1.21 | 0.000 5 | 0.002 0 |
| 基质 Matrix | 加标水平 Spike level/ (mg·kg-1) | 日内精密度Intra-day (n=5)/% | 日间精密度Inter-day (n=15)/% | ||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 d | 2 d | 3 d | |||||||||
| Rec | RSD | Rec | RSD | Rec | RSD | Rec | RSD | ||||
| 叶Leaf | 0.005 | 89 | 8 | 89 | 4 | 87 | 5 | 89 | 8 | ||
| 0.01 | 78 | 4 | 79 | 3 | 74 | 3 | 76 | 3 | |||
| 2 | 83 | 5 | 80 | 6 | 79 | 5 | 81 | 3 | |||
| 茎Stem | 0.005 | 91 | 9 | 97 | 8 | 92 | 9 | 93 | 9 | ||
| 0.01 | 91 | 5 | 81 | 7 | 87 | 7 | 97 | 8 | |||
| 2 | 77 | 4 | 83 | 5 | 86 | 5 | 91 | 9 | |||
| 草莓 | 0.002 | 96 | 3 | 97 | 1 | 96 | 4 | 97 | 4 | ||
| Strawberry | 0.01 | 94 | 3 | 96 | 4 | 88 | 2 | 107 | 3 | ||
| 2 | 97 | 1 | 91 | 2 | 94 | 1 | 96 | 1 | |||
| 根Root | 0.005 | 106 | 2 | 108 | 6 | 101 | 4 | 107 | 4 | ||
| 0.01 | 96 | 6 | 94 | 6 | 101 | 5 | 105 | 5 | |||
| 2 | 93 | 2 | 92 | 3 | 92 | 3 | 94 | 2 | |||
| 土壤Soil | 0.002 | 110 | 9 | 105 | 6 | 101 | 6 | 104 | 7 | ||
| 0.01 | 99 | 7 | 103 | 6 | 104 | 7 | 102 | 6 | |||
| 2 | 99 | 4 | 95 | 3 | 97 | 4 | 94 | 4 | |||
Table 3 Average recoveries and relative standard deviations of pyraclostrobin in strawberry cultivation system
| 基质 Matrix | 加标水平 Spike level/ (mg·kg-1) | 日内精密度Intra-day (n=5)/% | 日间精密度Inter-day (n=15)/% | ||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 d | 2 d | 3 d | |||||||||
| Rec | RSD | Rec | RSD | Rec | RSD | Rec | RSD | ||||
| 叶Leaf | 0.005 | 89 | 8 | 89 | 4 | 87 | 5 | 89 | 8 | ||
| 0.01 | 78 | 4 | 79 | 3 | 74 | 3 | 76 | 3 | |||
| 2 | 83 | 5 | 80 | 6 | 79 | 5 | 81 | 3 | |||
| 茎Stem | 0.005 | 91 | 9 | 97 | 8 | 92 | 9 | 93 | 9 | ||
| 0.01 | 91 | 5 | 81 | 7 | 87 | 7 | 97 | 8 | |||
| 2 | 77 | 4 | 83 | 5 | 86 | 5 | 91 | 9 | |||
| 草莓 | 0.002 | 96 | 3 | 97 | 1 | 96 | 4 | 97 | 4 | ||
| Strawberry | 0.01 | 94 | 3 | 96 | 4 | 88 | 2 | 107 | 3 | ||
| 2 | 97 | 1 | 91 | 2 | 94 | 1 | 96 | 1 | |||
| 根Root | 0.005 | 106 | 2 | 108 | 6 | 101 | 4 | 107 | 4 | ||
| 0.01 | 96 | 6 | 94 | 6 | 101 | 5 | 105 | 5 | |||
| 2 | 93 | 2 | 92 | 3 | 92 | 3 | 94 | 2 | |||
| 土壤Soil | 0.002 | 110 | 9 | 105 | 6 | 101 | 6 | 104 | 7 | ||
| 0.01 | 99 | 7 | 103 | 6 | 104 | 7 | 102 | 6 | |||
| 2 | 99 | 4 | 95 | 3 | 97 | 4 | 94 | 4 | |||
| 剂型 Formulation | 剂量 Dose/ (g·hm-2) | 时间 Time | 草莓 Strawberry/ (mg·kg-1) | 叶 Leaf/ (mg·kg-1) | 茎 Stem/ (mg·kg-1) | 根 Root/ (mg·kg-1) | 土壤 Soil/ (mg·kg-1) |
|---|---|---|---|---|---|---|---|
| 乳油EC | 90 | 2 h | 0.25±0.01 | 7.83±0.12 | 1.64±0.04 | 0.11±0.01 | 0.02±0 |
| 1 d | 0.20±0.01 | 6.52±0.05 | 1.33±0.04 | 0.17±0.01 | 0.01±0 | ||
| 3 d | 0.14±0.01 | 5.53±0.01 | 1.27±0.02 | 0.07±0 | 0.01±0 | ||
| 5 d | 0.11±0 | 5.12±0.01 | 0.95±0.04 | 0.06±0 | 0.01±0 | ||
| 7 d | 0.10±0.01 | 4.69±0.30 | 0.87±0.66 | 0.04±0 | 0.01±0 | ||
| 10 d | 0.08±0.01 | 4.33±0.08 | 0.72±0.08 | 0.05±0 | 0.02±0 | ||
| 150 | 2 h | 0.27±0.01 | 9.75±0.05 | 2.12±0.07 | 0.22±0.01 | 0.02±0 | |
| 1 d | 0.28±0.01 | 8.80±0.10 | 2.28±0.08 | 0.16±0 | 0.01±0 | ||
| 3 d | 0.25±0.01 | 8.12±0.14 | 1.83±0.07 | 0.11±0 | 0.02±0 | ||
| 5 d | 0.19±0.01 | 8.03±0.16 | 1.56±0.09 | 0.10±0.01 | 0.02±0 | ||
| 7 d | 0.14±0 | 7.30±0.29 | 1.12±0.06 | 0.08±0 | 0.02±0 | ||
| 10 d | 0.11±0 | 6.42±0.19 | 1.07±0.09 | 0.05±0 | 0.02±0 | ||
| 微囊悬浮剂CS | 90 | 2 h | 0.16±0 | 5.94±0.10 | 1.09±0.03 | 0.07±0 | 0.02±0 |
| 1 d | 0.14±0.01 | 5.10±0.01 | 0.92±0.09 | 0.07±0 | 0.02±0 | ||
| 3 d | 0.10±0.01 | 4.97±0.06 | 0.76±0.03 | 0.09±0 | 0.01±0 | ||
| 5 d | 0.10±0.01 | 4.62±0.16 | 0.69±0.06 | 0.05±0 | 0.02±0 | ||
| 7 d | 0.09±0.01 | 4.56±0.01 | 0.65±0.05 | 0.07±0.01 | 0.01±0 | ||
| 10 d | 0.06±0.01 | 3.57±0.01 | 0.60±0.03 | 0.03±0 | 0.02±0 | ||
| 150 | 2 h | 0.21±0.01 | 8.90±0.17 | 1.68±0.03 | 0.10±0.01 | 0.02±0 | |
| 1 d | 0.20±0.01 | 8.53±0.14 | 1.62±0.06 | 0.14±0 | 0.03±0 | ||
| 3 d | 0.16±0.01 | 7.37±0.30 | 1.22±0.05 | 0.13±0.01 | 0.01±0 | ||
| 5 d | 0.16±0.01 | 7.25±0.22 | 1.16±0.01 | 0.07±0.01 | 0.02±0 | ||
| 7 d | 0.12±0.01 | 7.16±0.35 | 1.17±0.01 | 0.05±0.01 | 0.03±0 | ||
| 10 d | 0.10±0.01 | 6.48±0.35 | 0.94±0.06 | 0.04±0 | 0.03±0 |
Table 4 Residues of pyraclostrobin for different formulations and doses in strawberry cultivation system
| 剂型 Formulation | 剂量 Dose/ (g·hm-2) | 时间 Time | 草莓 Strawberry/ (mg·kg-1) | 叶 Leaf/ (mg·kg-1) | 茎 Stem/ (mg·kg-1) | 根 Root/ (mg·kg-1) | 土壤 Soil/ (mg·kg-1) |
|---|---|---|---|---|---|---|---|
| 乳油EC | 90 | 2 h | 0.25±0.01 | 7.83±0.12 | 1.64±0.04 | 0.11±0.01 | 0.02±0 |
| 1 d | 0.20±0.01 | 6.52±0.05 | 1.33±0.04 | 0.17±0.01 | 0.01±0 | ||
| 3 d | 0.14±0.01 | 5.53±0.01 | 1.27±0.02 | 0.07±0 | 0.01±0 | ||
| 5 d | 0.11±0 | 5.12±0.01 | 0.95±0.04 | 0.06±0 | 0.01±0 | ||
| 7 d | 0.10±0.01 | 4.69±0.30 | 0.87±0.66 | 0.04±0 | 0.01±0 | ||
| 10 d | 0.08±0.01 | 4.33±0.08 | 0.72±0.08 | 0.05±0 | 0.02±0 | ||
| 150 | 2 h | 0.27±0.01 | 9.75±0.05 | 2.12±0.07 | 0.22±0.01 | 0.02±0 | |
| 1 d | 0.28±0.01 | 8.80±0.10 | 2.28±0.08 | 0.16±0 | 0.01±0 | ||
| 3 d | 0.25±0.01 | 8.12±0.14 | 1.83±0.07 | 0.11±0 | 0.02±0 | ||
| 5 d | 0.19±0.01 | 8.03±0.16 | 1.56±0.09 | 0.10±0.01 | 0.02±0 | ||
| 7 d | 0.14±0 | 7.30±0.29 | 1.12±0.06 | 0.08±0 | 0.02±0 | ||
| 10 d | 0.11±0 | 6.42±0.19 | 1.07±0.09 | 0.05±0 | 0.02±0 | ||
| 微囊悬浮剂CS | 90 | 2 h | 0.16±0 | 5.94±0.10 | 1.09±0.03 | 0.07±0 | 0.02±0 |
| 1 d | 0.14±0.01 | 5.10±0.01 | 0.92±0.09 | 0.07±0 | 0.02±0 | ||
| 3 d | 0.10±0.01 | 4.97±0.06 | 0.76±0.03 | 0.09±0 | 0.01±0 | ||
| 5 d | 0.10±0.01 | 4.62±0.16 | 0.69±0.06 | 0.05±0 | 0.02±0 | ||
| 7 d | 0.09±0.01 | 4.56±0.01 | 0.65±0.05 | 0.07±0.01 | 0.01±0 | ||
| 10 d | 0.06±0.01 | 3.57±0.01 | 0.60±0.03 | 0.03±0 | 0.02±0 | ||
| 150 | 2 h | 0.21±0.01 | 8.90±0.17 | 1.68±0.03 | 0.10±0.01 | 0.02±0 | |
| 1 d | 0.20±0.01 | 8.53±0.14 | 1.62±0.06 | 0.14±0 | 0.03±0 | ||
| 3 d | 0.16±0.01 | 7.37±0.30 | 1.22±0.05 | 0.13±0.01 | 0.01±0 | ||
| 5 d | 0.16±0.01 | 7.25±0.22 | 1.16±0.01 | 0.07±0.01 | 0.02±0 | ||
| 7 d | 0.12±0.01 | 7.16±0.35 | 1.17±0.01 | 0.05±0.01 | 0.03±0 | ||
| 10 d | 0.10±0.01 | 6.48±0.35 | 0.94±0.06 | 0.04±0 | 0.03±0 |
Fig.1 Degradation dynamics of pyraclostrobin in strawberry, leaf and stem under different formulations and doses EC, Emulsifiable concentrate; CS, Microencapsule suspension; Recommended low dose 90 g·hm-2; Recommended high dose 150 g ·hm-2.
| 剂型 Formulation | 样品 Sample | 回归方程 Regression equation | 决定系数 Determination coefficient(R2) | 半衰期 Half-life/d | |||
|---|---|---|---|---|---|---|---|
| 90 g·hm-2 | 150 g·hm-2 | 90 g·hm-2 | 150 g ·hm-2 | 90 g ·hm-2 | 150 g ·hm-2 | ||
| 乳油EC | 草莓Strawberry | Ct=0.212 6e-0.1051t | Ct=0.301 8e-0.1015t | 0.923 5 | 0.925 6 | 6.6 | 6.8 |
| 茎Stem | Ct=1.581 2e-0.0814t | Ct=2.268 7e-0.0813t | 0.965 5 | 0.926 4 | 8.5 | 8.6 | |
| 叶Leaf | Ct=7.05 0e-0.0550t | Ct=9.419 3e-0.0380t | 0.890 3 | 0.951 1 | 12.6 | 18.2 | |
| 微囊悬浮剂 | 草莓Strawberry | Ct=0.148 7e-0.0895t | Ct=0.208 3e-0.0708t | 0.929 3 | 0.947 4 | 7.7 | 9.8 |
| CS | 茎Stem | Ct=0.978 1e-0.0558t | Ct=1.615 6e-0.0540t | 0.877 5 | 0.895 7 | 12.4 | 12.5 |
| 叶Leaf | Ct=5.690 2e-0.0423t | Ct=8.612 2e-0.0297t | 0.894 3 | 0.896 2 | 16.5 | 23.1 | |
Table 5 The half-life and degradation kinetic parameters of pyraclostrobin in strawberry, leaf and stem under different formulations and doses
| 剂型 Formulation | 样品 Sample | 回归方程 Regression equation | 决定系数 Determination coefficient(R2) | 半衰期 Half-life/d | |||
|---|---|---|---|---|---|---|---|
| 90 g·hm-2 | 150 g·hm-2 | 90 g·hm-2 | 150 g ·hm-2 | 90 g ·hm-2 | 150 g ·hm-2 | ||
| 乳油EC | 草莓Strawberry | Ct=0.212 6e-0.1051t | Ct=0.301 8e-0.1015t | 0.923 5 | 0.925 6 | 6.6 | 6.8 |
| 茎Stem | Ct=1.581 2e-0.0814t | Ct=2.268 7e-0.0813t | 0.965 5 | 0.926 4 | 8.5 | 8.6 | |
| 叶Leaf | Ct=7.05 0e-0.0550t | Ct=9.419 3e-0.0380t | 0.890 3 | 0.951 1 | 12.6 | 18.2 | |
| 微囊悬浮剂 | 草莓Strawberry | Ct=0.148 7e-0.0895t | Ct=0.208 3e-0.0708t | 0.929 3 | 0.947 4 | 7.7 | 9.8 |
| CS | 茎Stem | Ct=0.978 1e-0.0558t | Ct=1.615 6e-0.0540t | 0.877 5 | 0.895 7 | 12.4 | 12.5 |
| 叶Leaf | Ct=5.690 2e-0.0423t | Ct=8.612 2e-0.0297t | 0.894 3 | 0.896 2 | 16.5 | 23.1 | |
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