Table 2.
Performance characteristics of the proposed LC–MS method depending on the evaluated sample treatments
| Compound | Dilute and shoot | QuEChERSa | SALLE (selected sample treatment)a | ||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| LOQs (µg/L) | Recoveries (%)b | LOQs (µg/L) | Recovery (%) | Intra-day/Inter-day precision (RSDs, %) | Matrix effect (%) | ||||||
| LOQs (µg/L) | 100 µg/L | 1 µg/L | 10 µg/L | 100 µg/L | 1 µg/L | 10 µg/L | 100 µg/L | ||||
| Pesticides | |||||||||||
| 5-hydroxycarbendazim | 10 | 0.25 | 92 ± 7 | 0.1 | 89 | 94 | 95 | 14/11 | 16/17 | 5/11 | − 42 |
| Acephate | 50 | 10 | 59 ± 15c | 10 | - | 59 | 63 | - | 3/7 | 1/10 | 299 |
| Acetamiprid | 1 | 0.5 | 81 ± 9 | 0.25 | 94 | 87 | 75 | 13/17 | 14/19 | 8/7 | − 58 |
| Acetamiprid-desmethyl | 25 | 5 | 92 ± 7 | 5 | - | 93 | 89 | - | 6/15 | 1/12 | − 58 |
| Azoxystrobin | 1 | 0.5 | 90 ± 11 | 0.25 | 91 | 94 | 91 | 10/18 | 7/15 | 5/11 | − 45 |
| Azoxystrobin acid | 2.5 | 0.5 | 94 ± 9 | 0.5 | 100 | 76 | 97 | 16/19 | 8/6 | 1/19 | − 51 |
| Carbendazim | 5 | 2.5 | 97 ± 1 | 0.5 | 111 | 97 | 96 | 14/16 | 8/16 | 4/16 | 17 |
| Chlorpyrifos | 1 | 2.5 | 56 ± 18 | 0.5 | 69 | 81 | 74 | 7/13 | 11/15 | 6/11 | − 21 |
| Chlorpyrifos methyl | 5 | 2.5 | 63 ± 17 | 2.5 | - | 85 | 93 | 8/11 | 8/14 | 5/16 | − 20 |
| Clothianidin | 10 | 10 | 90 ± 10 | 10 | - | 93 | 88 | 13/22 | 12/14 | 2/17 | 87 |
| Clothianidin desmethyl | 200 | 50 | 82 ± 8 | 100 | - | - | 78 | - | - | 5/16 | 50 |
| Cypermethrin | 100 | 100 | 51 ± 21 | 50 | - | - | 81 | - | - | 18/18 | 131 |
| DEAMPY | 5 | 2.5 | 85 ± 11 | 1 | 98 | 88 | 83 | 10/17 | 11/14 | 19/17 | − 63 |
| DEDTP | 200 | 50 | 44 ± 14 | 100 | - | - | 56 | - | - | 18/7 | − 72 |
| DEP | 100 | 25 | 43 ± 16 | 25 | - | - | 56 | - | - | 13/15 | − 57 |
| DETP | 200 | 50 | 40 ± 17 | 50 | - | - | 48 | - | - | 12/13 | − 63 |
| Desnitro-imidacloprid | 25 | 10 | 70 ± 6 | 10 | - | 61 | 69 | - | 13/14 | 6/10 | − 80 |
| Dimethoate | 2.5 | 0.5 | 79 ± 1 | 0.5 | 90 | 82 | 82 | 1/14 | 11/13 | 1/18 | − 44 |
| DMDTP | 100 | 50 | 40 ± 15 | 50 | - | - | 66 | - | - | 7/8 | − 94 |
| DMP | 200 | 50 | 42 ± 13 | 100 | - | - | 50 | - | - | 15/5 | − 88 |
| DMTP | 200 | 25 | 46 ± 18 | 10 | - | 58 | 62 | - | 6/19 | 10/11 | − 98 |
| Imidacloprid | 5 | 1 | 86 ± 3 | 1 | 85 | 96 | 85 | 15/13 | 3/16 | 4/17 | − 37 |
| Imidacloprid olefin | 100 | 25 | 93 ± 6 | 25 | - | - | 90 | - | - | 6/16 | − 43 |
| Hydroxy-imidacloprid | 10 | 2.5 | 92 ± 2 | 2.5 | - | 71 | 88 | - | 9/8 | 3/17 | 51 |
| PBA | 10 | 2.5 | 90 ± 7 | 1 | 72 | 80 | 89 | 8/19 | 16/14 | 3/15 | − 75 |
| DCCA | 25 | 2.5 | 89 ± 4 | 2.5 | - | 88 | 81 | - | 14/18 | 6/19 | − 19 |
| Pirimiphos methyl | 5 | 0.5 | 73 ± 8 | 0.1 | 73 | 62 | 66 | 17/14 | 6/14 | 4/19 | − 16 |
| TCPY | 10 | 2.5 | 86 ± 4 | 2.5 | - | 90 | 87 | - | 17/19 | 6/19 | 75 |
| Tebuconazole | 1 | 0.5 | 65 ± 15 | 0.1 | 83 | 76 | 92 | 13/13 | 6/15 | 7/16 | 1 |
| Tebuconazole hydroxy | 5 | 1 | 85 ± 12 | 0.5 | 87 | 82 | 99 | 6/14 | 7/14 | 4/7 | − 11 |
| Mycotoxins | |||||||||||
| 15-AcDON | 25 | 5 | 85 ± 9 | 5 | - | 86 | 87 | - | 16/18 | 10/14 | − 43 |
| 3-AcDON | 25 | 5 | 91 ± 7 | 2.5 | - | 97 | 92 | - | 6/17 | 18/11 | − 54 |
| Aflatoxin B1 | 1 | 0.25 | 86 ± 2 | 0.25 | 83 | 82 | 83 | 10/10 | 14/7 | 5/15 | − 67 |
| Aflatoxin B2 | 5 | 0.5 | 75 ± 4 | 0.5 | 92 | 77 | 73 | 11/11 | 1/8 | 2/9 | − 59 |
| Aflatoxin G1 | 2.5 | 0.5 | 79 ± 4 | 0.5 | 93 | 81 | 80 | 19/17 | 10/6 | 9/8 | − 61 |
| Aflatoxin G2 | 5 | 0.5 | 77 ± 3 | 0.5 | 101 | 85 | 72 | 18/6 | 7/7 | 7/6 | − 71 |
| Aflatoxin M1 | 1 | 0.25 | 79 ± 8 | 0.1 | 88 | 88 | 78 | 11/9 | 10/13 | 10/8 | − 55 |
| α-ZOL | 5 | 1 | 94 ± 10 | 1 | 63 | 84 | 96 | 9/14 | 7/5 | 5/19 | 22 |
| Beauvericin | 10 | 0.25 | 69 ± 16 | 0.1 | 85 | 88 | 74 | 12/17 | 13/16 | 9/14 | − 28 |
| β-ZOL | 5 | 2.5 | 95 ± 12 | 2.5 | - | 79 | 86 | - | 16/14 | 7/19 | 8 |
| DOM | 100 | 1 | 91 ± 5 | 1 | 72 | 85 | 90 | 12/17 | 13/14 | 4/16 | − 48 |
| DON | 50 | 5 | 89 ± 7 | 5 | - | 95 | 81 | - | 14/14 | 6/13 | 39 |
| Enniatin A | 1 | 0.25 | 61 ± 13 | 0.1 | 76 | 85 | 71 | 16/12 | 10/15 | 15/9 | − 22 |
| Enniatin A1 | 0.5 | 0.25 | 59 ± 17 | 0.1 | 77 | 79 | 73 | 7/14 | 12/11 | 17/4 | − 19 |
| Enniatin B | 0.5 | 0.25 | 65 ± 19 | 0.1 | 95 | 72 | 76 | 10/16 | 12/5 | 10/9 | − 23 |
| Enniatin B1 | 0.5 | 0.25 | 66 ± 18 | 0.1 | 78 | 84 | 71 | 13/17 | 13/11 | 5/8 | − 18 |
| HT2 toxin | 25 | 2.5 | 62 ± 16 | 5 | - | 58 | 55 | - | 10/13 | 6/19 | − 87 |
| Ochratoxin A | 2.5 | 0.5 | 83 ± 8 | 0.5 | 94 | 81 | 80 | 6/11 | 9/13 | 6/17 | − 30 |
| Ochratoxin α | 10 | 0.5 | 78 ± 4 | 1 | 64 | 90 | 74 | 8/12 | 7/14 | 1/8 | − 9 |
| Ochratoxin B | 0.5 | 0.25 | 88 ± 6 | 0.1 | 84 | 81 | 85 | 18/18 | 9/13 | 5/15 | − 35 |
| T2 toxin | 10 | 2.5 | 60 ± 18 | 2.5 | - | 58 | 56 | - | 14/10 | 7/11 | − 69 |
| ZAN | 10 | 2.5 | 88 ± 6 | 2.5 | - | 73 | 87 | - | 5/6 | 4/19 | 24 |
| ZEN | 1 | 1 | 96 ± 9 | 0.5 | 95 | 72 | 91 | 12/19 | 3/12 | 3/19 | − 15 |
a Number of replicates (n) = 5
b RSD with n = 5
c Validation parameters outranging adequate values (recoveries < 60% or RSD > 20%) are highlighted in red
Abbreviation: 15-AcDON 15-acetyldeoxinivalenol, 3-AcDON 3-acetyldeoxinivalenol, α-ZOL α-zearalenol, β-ZOL β-zearalenol, DCCA cis-permethrinic acid, DEAMPY 2-diethylamino-6-methyl-4-pyrimidinol, DEDTP diethyl dithiophosphate, DEP diethyl phosphate, DETP diethyl thiophosphate, DMDTP dimethyl dithiophosphate, DMP dimethyl phosphate, DMTP dimethyl thiophosphate, DOM deepoxy-deoxynivalenol, DON deoxinivalenol, PBA 3-phenoxybenzoic acid, TCPY 3,5,6-trichloro-2-pyridinol, ZAN zearalanone, ZEN zearalenone