Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives
Abstract
:1. Introduction
2. Results and Discussion
2.1. Optimization of Sin-QuEChERS nano Cleanup Procedures
2.2. Method Validation and Comparison of Sin-QuEChERS nano and d-SPE Cleanup Methods
2.2.1. Linearity, Limits of Quantification (LOQs) and Limits of Detection (LODs)
2.2.2. Recovery and Precision
2.2.3. Cleanup Effect
2.2.4. Matrix Effect
2.3. Application to the Monitoring of Real Samples
3. Materials and Methods
3.1. Chemicals and Materials
3.2. Stock Solutions and Standards
3.3. GC–MS/MS Analytical Conditions
3.4. LC–MS/MS Analytical Conditions
3.5. Sample Preparation
3.6. Sin-QuEChERS nano and d-SPE Cleanup Procedures
3.7. Method Validation
3.8. Confirmation Criteria
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Abbreviations
CAC | Codex Alimentarius Commission |
d-SPE | dispersive solid phase extraction |
EU | European |
ESI | electrospray ionization |
GC | gas chromatography |
GCB | graphitized carbon black |
LC | liquid chromatography |
LOD | limit of detection |
LOQ | limit of quantification |
ME | matrix effect |
m-PFC | multiplug filtration cleanup |
MRL | maximum residue limit |
MS/MS | tandem mass spectrometry |
MWCNT | multi-walled carbon nanotube |
PSA | primary secondary amine |
QuEChERS | quick, easy, cheap, effective, rugged and safe |
RSD | relative standard deviation |
SRM | selective reaction monitoring |
TIC | total ion chromatograms |
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Sample Availability: Samples of the compounds are not available from the authors. |
Vegetable | Pesticide | Positive Samples | Samples Exceed MRL | Range of Residues (mg/kg) | LOQ (μg/kg) | MRL (China/CAC/EU) (mg/kg) | ||
---|---|---|---|---|---|---|---|---|
N | % | N | % | |||||
Lettuce | Difenoconazole | 3 | 16.7 | - | - | 0.041–0.87 | 1.2 | 2/2/4 |
Imidacloprid | 1 | 5.6 | - | - | 0.29 | 3.7 | 1/-/2 | |
Propiconazole | 4 | 22.2 | 3 EU | 16.7 | 0.010–0.30 | 1.2 | -/-/0.01 * | |
Hexaconazole | 1 | 5.6 | 1 EU | 5.6 | 0.013 | 2.3 | -/-/0.01 * | |
Myclobutanil | 1 | 5.6 | - | - | 0.020 | 0.3 | 0.05 a/0.05 a/0.05 | |
Cyhalothrin | 2 | 11.1 | - | - | 0.017–0.062 | 5.7 | 2/-/0.15 | |
Cypermethrin | 1 | 5.6 | - | - | 0.056 | 1.6 | 2/0.7 a/2 | |
Clothianidin | 1 | 5.6 | - | - | 0.015 | 8.4 | 2 a/2 a/0.1 | |
Thiametoxam | 1 | 5.6 | - | - | 0.19 | 1.5 | 3 a/-/- | |
Thifluzamide | 1 | 5.6 | - | - | 0.015 | 3.3 | -/-/- | |
Hexythiazox | 1 | 5.6 | - | - | 0.026 | 1.0 | -/-/0.5 | |
Buprofezin | 2 | 11.1 | 2 EU | 11.1 | 0.012–0.030 | 1.9 | -/-/0.01 * | |
Triadimefon | 1 | 5.6 | 1 EU | 5.6 | 0.035 | 1.0 | -/-/0.01 * | |
Cymoxanil | 1 | 5.6 | 1 EU | 5.6 | 0.12 | 7.4 | -/-/0.03 | |
Dimethomorph | 8 | 44.4 | - | - | 0.011–0.32 | 4.1 | -/9/15 | |
Chinese chives | Difenoconazole | 7 | 50.0 | - | - | 0.010–0.11 | 1.2 | -/-/- |
Pyridaben | 2 | 14.3 | 1 EU | 7.1 | 0.010–0.011 | 0.7 | -/-/0.01 * | |
Chlorpyrifos | 4 | 28.6 | 2 China | 14.3 | 0.011–1.4 | 10 | 0.1/-/- | |
Bifenthrin | 1 | 7.1 | 1 EU | 7.1 | 0.031 | 0.9 | - c/-/0.01 * | |
Cyhalothrin | 5 | 35.7 | 2 CAC | 14.3 | 0.017–0.50 | 6.0 | 0.5 c/0.2 b/0.2 | |
Cypermethrin | 4 | 28.6 | 1 China | 7.1 | 0.054–1.5 | 7.7 | 1 c/-/- | |
Kresoxim-methyl | 1 | 7.1 | - | - | 0.38 | 2.9 | -/-/- | |
Azoxystrobin | 2 | 14.3 | - | - | 0.012–0.021 | 0.8 | 1 b/10 b/10 b | |
Esfenvalerate | 1 | 7.1 | 1 EU | 7.1 | 0.020 | 7.0 | -/-/0.02 * | |
Clothianidin | 9 | 64.3 | 9 EU | 64.3 | 0.033–0.38 | 3.9 | - c/-/0.01 * | |
Thifluzamide | 1 | 7.1 | - | - | 0.035 | 3.3 | -/-/- | |
Triadimenol | 1 | 7.1 | 1 EU | 7.1 | 0.018 | 2.2 | -/-/0.01 * | |
Triazophos | 1 | 7.1 | 1 EU | 7.1 | 0.013 | 1.5 | -/-/0.01 * | |
Triadimefon | 1 | 7.1 | 1 EU | 7.1 | 0.017 | 5.0 | -/-/0.01 * | |
Trifloxystrobin | 1 | 7.1 | - | - | 0.41 | 1.7 | 0.7/-/- | |
Dimethomorph | 5 | 35.7 | - | - | 0.010–0.38 | 3.9 | -/-/- | |
Phosmet | 1 | 7.1 | 1 EU | 7.1 | 0.41 | 2.1 | -/-/0.05 * | |
Omethoate | 1 | 7.1 | 1 China | 7.1 | 0.32 | 3.1 | 0.02 b/-/- | |
Diethofencarb | 1 | 7.1 | 1 EU | 7.1 | 0.019 | 2.8 | -/-/0.01 * |
Reference | Samples | Pesticides | Extraction Method | Cleanup Method | Detection | Recovery | Detection Limits | Advantages | Disadvantages |
---|---|---|---|---|---|---|---|---|---|
Zhu et al. [32] | Garlic chives | 51 | Acetonitrile | d-SPE (GCB, PSA and MgSO4) | GC–MS/MS | 60.4%–111.5% (20.34%–36.7% for amitraz) | 0.8–25 μg/kg (LOD) | Economic; easy. | High detection limits; shaky purification and centrifugal separation. |
Ying et al. [33] | Chinese chives | 13 | Acetonitrile | none | GC–FPD | 78%–115% | 0.01–0.03 mg/kg (LOD) | Low operation fee; without centrifuge steps. | Reagents and time consuming; matrix effects; high detection limits. |
Han et al. [34] | Leaf lettuce | 70 | Acetonitrile | d-SPE (MWCNTs and MgSO4) | LC–MS/MS | 74%–119% | 0.3–6.2 μg/kg (LOQ) | Good cleanup performance; high sensitivity. | Shaky purification and centrifugal separation. |
Ribeiro Begnini Konatu et al. [35] | Lettuce | 16 | Acetonitrile, citrate buffer | d-SPE (GCB, PSA and MgSO4) | LC–MS/MS | 79%–115% | 5–3200 μg/kg (LOQ) | Economic; quick. | High detection limits; sorbents consuming, |
This study | Lettuce | 111 | Acetonitrile | Sin-QuEChERS nano cleanup method (MWCNTs, PSA, C18 and MgSO4) | GC–MS/MS and LC–MS/MS | 75%–136% (41%–45% for cyprodinil) | 0.3–10 μg/kg (LOQ) | Purification and separation in one step; easier and quicker. | Excess purified extracts. |
Leaf lettuce | 73%–119% (25%–28% for cyprodinil) | 0.4–10 μg/kg (LOQ) |
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Li, Y.; An, Q.; Zhang, C.; Pan, C.; Zhang, Z. Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives. Molecules 2020, 25, 3391. https://doi.org/10.3390/molecules25153391
Li Y, An Q, Zhang C, Pan C, Zhang Z. Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives. Molecules. 2020; 25(15):3391. https://doi.org/10.3390/molecules25153391
Chicago/Turabian StyleLi, Yanjie, Quanshun An, Changpeng Zhang, Canping Pan, and Zhiheng Zhang. 2020. "Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives" Molecules 25, no. 15: 3391. https://doi.org/10.3390/molecules25153391