Pesticide residues are a threat to the health of the global population, not only to farmers, applicators, and other pesticide professionals. Humans are exposed through various routes such as food, skin, and inhalation. Indirect approaches, also called “external exposure approaches”, estimate the exposure of a population through the measurements of pesticide residue levels in food and the environment. Environmental sampling involves water resources, soils, sediments, and air particles. Recent studies have also included indoor and road dust. In addition, indirect assessment models also include food, as fruits, vegetables, and cereals treated with pesticides have also been proven to be significant sources of pesticides. Furthermore, the pesticide residues in abiotic environmental samples also bioaccumulate in biota. Dietary intake of animal products, including meat and subproducts from farm animals, fish, and seafood, is considered an important route of exposure for population.
Sample | Nº Pesticides or Biomarkers | Sample Treatment | Separation and Detection Technique | Recovery % | LOD | Ref. | |||
---|---|---|---|---|---|---|---|---|---|
Matrix | Volume/Weight | Method | Extraction | Clean-up | |||||
Drinking water (TPW and tap) | 50 mL | 7 | LLE | 30 mL DCM | Purified passing sample through a chromatographic column | UPLC–QqQ-MS/MS: in MRM ESI + |
73–94% | 30–70 ng/L | [52] |
Drinking water (groundwater and tap) | 500 mL | 16 | SPE | Oasis HLB (6 cc/500 mg) eluted with 4 mL CAN + 4 mL methanol |
- | UPLC–MS/MS: in MRM ESI+ |
74–123% | 0.01–0.2 ng/L * | [53] |
Groundwater | 1000 mL | 56 | LLE | 20 mL DCM (×3): with three pH conditions (6.5–8.0, <2.0, and >10.0) | - | GC–MS: SIM and SCAN mode EI |
70–133% | 2.5–247 (ng/L) | [49] |
Tap water | 500 mL | 9 | LLE | 70 mL DCM | Silica gel column with anhydrous Na2SO4 (CNWBOND 10 cc/10 g) | GC–MS: in MRM mode EI | 76–94% | 0.0011–0.43 ng/L | [54] |
Surface water | 1000 mL | 65 | SPE | C18 (6 cc/1000 mg) | 5 mL ethyl acetate + 5 × 2 mL DCM | GC–MS/MS: in SRM EI |
- | - | [50] |
Sediment and soil | - | PLE | Acetone/DCM (1:1, v/v) | Florisil ® (6 cm3/1000 mg) eluted with 10 mL acetone/hexane (20/80 v/v) | |||||
Surface water | 1000 mL | 8 | LLE | Ethyl acetate + methylene | - | GC–MS: in SIM EI |
80–94% | 1.05–2.60 ppb | [55] |
Sediment | 5 g | QuEChERS | 15 mL ACN 1% AA + 6 g MgSO4 + 1.5 g NaOAc | d-SPE with 25 mg PSA + 25 mg C18 +7 mg GCB + 150 mg MgSO4 | |||||
Surface water | 10 mL | 224 | - | - | - | DAI to LC–MS/MS: in MRM ESI+/− |
34–135% | 1.0–106 ng/L | [51] |
Sediment | 10 g | 119 | PLE | DCM; purified in a Florisil® (6 cm3/1000 mg) |
Purification: 1º fraction: DCM + 50:50 DCM: ethyl acetate; 2º fraction: 20% DCM in hexane + 50% ethyl acetate in hexane | GC–MS/MS: in SIM EI |
75–102% | 0.6–3.4 μg/kg | |
Soil | 20 g | 21 | Soxhlet | Acetone/n-hexane (1:1, v/v) | Florisil cartridge (6 cc/1000 mg) eluted with 5 mL n-hexane/acetone (95:5, v/v) | GC–MS | 75.9–126.1% | - | [41] |
Soil | 5 g | 23 | QuEChERS | 10 mL ACN 1% AA + 1 g NaOAc + 4 g MgSO4 | dSPE with 50 mg PSA + 150 mg MgSO4 | Polar compounds: LC–MS/MS: Ionization in + and − |
70–120% | 1–10 μg/kg | [56] |
A-polar compounds: GC–MS/MS |
|||||||||
Soil | 1 g | 8 | SPE | 10 mL cartridge column packed with: Na2SO4 (0.5 g) | Florisil (1 g, 60–100 mesh), acidic silica gel (1 g) + copper powder (0.5 g) eluted with 15 mL DCM | GC–ECD: in SIM EI ionization |
80–96% | 0.001–0.025 ng/g | [39] |
Sediment | 4 g | 8 | PLE | Acetone/n-hexane (1:1, v/v); purified two times: (1) in an activated copper column (20% HCl); (2) ENVI-CARB/PSA cartridge (6 cc/500 mg) | 3 mL hexane (1st purification); 6 mL hexane-ethyl-acetate (7/3, v/v) (2nd purification) |
GC–MS: in SIM EI ionization |
89–118% | - | [40] |
Air particulates | 1344 m3 | 46 | Soxhlet | Hexane/acetone/MeOH (50:40:10 v/v/v) | - | UPLC–MS/MS: in MRM ESI+/− |
72–128% | 0.04–0.1 ng/m3 * | [63] |
GC–MS-QqQ: in MRM EI− |
|||||||||
Air particulates | - | 7 | SLE | 10 mL ethyl acetate/acetone (9:1, v/v) | - | LC–MS/MS: in MRM mode ESI+ |
- | - | [60] |
Air particulates | 30 m3 | 10 | Soxhlet | Acetone | Exchanged into hexane; purified in a silica gel column | GC–MS: EI ionization |
60–149% | 0.1–1 ng/m3 | [61] |
Air particulates | 432 m3 | 26 | PUF: Soxhlet | 150 mL n-hexane/acetone (v/v, 1:1) | Silica gel/alumina chromatographic column eluted with 70 mL DCM | GC–MS: in SIM mode Negative chemical ionization (NCI) | 65–120% | 0.1–25.0 pg/m3 | [62] |
GFF: SLE | 25 mL n-hexane/acetone (v/v, 1:1) | ||||||||
PM2.5 | 158.4 m3 | 4 | QuEChERS | 20 mL ACN | dSPE with 0.4 g PSA | LC–MS/MS-QqQ: in MRM ESI+ |
78–97% | 0.0005–0.355 ng/m3 | [59] |
PM2.6 and PM10 | 1627.2 m3 | 34 | SLE | 500 µL ethyl acetate/ACN (30:70) | - | GC–MS: in SIM EI |
90–144% | 0.14–0.44 ng/mL | [58] |
Dust (indoor) | 10 g | 26 | Soxhlet | DCM; purified in a silica–alumina column | - | GC–MS-QqQ: in SIM EI |
88–110% | 1.31–7.30 pg/g | [43] |
Dust (indoor) | 20 g | 24 | Soxhlet | 300 mL DCM; purified in a silica–alumina column | - | GC–MS-QqQ: in SIM EI |
88–110% | 1.31–7.30 pg/g | [44] |
Dust (road) | 2 g | 10 | SLE | 10 mL acetone + 10 mL acetone/hexane (1:1, v/v); purified in a silica gel column | DCM + hexane (purification) | GC–MS | 60–120% | 0.0010–0.010 μg/g | [34] |
Silicone wristband | - | 75 | SLE | 50 mL ethyl acetate; purified in a C18 silica column (500 mg) | 9 mL ACN (purification) |
GC–ECD | 11–142% (median 55%) | 0.44–20.9 pg/µL |
[64] |
Fish | 3 g | 8 | PLE | Acetone/n-hexane (1:1, v/v) | Twice: (1) with a copper column eluted with hexane (2) ENVI-CARB/PSA cartridge eluted with6 mL hexane/ethyl-acetate (7:3, v/v) |
GC–MS: in SIM EI |
89–118% | - | [40] |
Fish | 3 g | 18 | Soxhlet | 150 mL hexane/acetone (3:1, v/v) | Glass column (30 cm × 1 cm) [1 g neutral alumina + 1 g neutral silica + 8 g acidified silica + 4 g Na2SO4] eluted with 50 mL DCM and hexane (1:1, v/v) | GC–μECD | 61–136% | 0.0003–0.0054 ng/g | [68] |
Cow´s milk | 2 g | 18 | LLE | 3 mL n-hexane/DCM (1:1, v/v) | Glass column (30 cm × 1 cm) [1 g 5% deactivated silica + 1 g 5% deactivated Florisil + 1 g Na2SO4] eluted with 15 mL n-hexane + 10 mL DCM | GC–μECD | 70–109% | 0.003–0.63 ng/g | [69] |
Wax | 20 g | 1 | QuEChERS | 10 mL ACN; NaCl + MgSO4 + sodium citrate + sodium hydrogen citrate sesquihydrate | dSPE (150 mg MgSO4 + 25 mg C18 + 25 mg PSA) | LC–MS/MS: in MRM ESI− |
95% | 20 μg/kg * | [70] |
Wax | 1 g | More than 600 | QuEChERS | 10 mL water + 10 mL CAN + Supel™ QuE citrate/sodium bicarbonate | dSPE using Supel™ QuE PSA/C18 clean-up tube | LC–MS/MS: in MRM ESI+/− |
- | 0.0005–0.002 mg/kg | [67] |
Honey | 2 g | QuEChERS | 10 mL ACN + 4 g anhydrous MgSO4 + 1 g trisodium citrate dihydrate + 0.5 g disodium hydrogen citrate sesquihydrate + 1 g NaCl | dSPE clean-up with 900 mg anhydrous MgSO4 + 150 mg of PSA | GC–MS/MS: in SRM mode EI ionization |
- | 0.002 mg/kg | ||
Tomato | 10 g | 21 | QuEChERS | 10 mL ACN + 1 g NaCl + 1.5 g citrate | dSPE clean-up with 900 mg MgSO4 + 150 mg PSA 150 mg C18 | OPPs: GC–NPD | 72–116% | 0.5–10 μg/kg | [71] |
Halogenated: GC–ECD | |||||||||
Lettuce | Methyl-carbamates: HPLC–FLD | ||||||||
Imidacloprid and carbendazim: HPLC–DAD | |||||||||
96 types of vegetables | 50 g | 283 | SLE | 100 mL ACN; 10 g NaCl | For GC: Sep-Pak Florisil (6 cm3/1000 mg) eluted with 7 mL 20% acetone/hexane For LC: Sep-Pak NH2 (6 cm3/1000 mg) eluted with 5 mL 1% MeOH/DCM |
OPPs and nitrogen-containing compounds: GC–NPD | 82.5–103.1% | 0.0006–0.024 mg/kg | [65] |
OCPs, dicarboximide and PYR: GC–μECD | |||||||||
Carbamate pesticides: LC–FLD | |||||||||
UV-detected compounds: LC–DAD: APCI+ | |||||||||
Tomato | 10 g | 7 | QuEChERS | LC–MS/MS: ESI | 76.84–96.32% | 0.10 μg/kg | [72] | ||
French beans | 10 mL ACN + 150 mg MgSO4 | dSPE with 150 mg MgSO4 + 50 mg PSA + 50 mg GCB | |||||||
Kale | |||||||||
Tomato | 10 g | 2 | QuEChERS | 10 mL ethyl acetate + 4 g anhydrous MgSO4 + 1 g NaCl | dSPE 50 mg PSA + 150 mg anhydrous MgSO4 | GC–ECD | 83.1–102.2% | 0.01 mg/kg | [73] |
Water spinach | 5 g | 2 | SLE | 10 mL ACN; 1.5 g NaCl | - | LC–MS/MS: ESI | 91–101% | 0.02 mg/kg * | [74] |
Chlorothalonil: GC–MS: in SRM mode EI |
94–105% | 0.01 mg/kg * | |||||||
Kale | 10 g | 4 | SLE | 15 mL MeOH | Purified with 50 mg C18 | LC–MS/MS-QqQ: in MRM mode ESI+/− |
26.5–89.6% | 0.14–20.3 μg/kg | [75] |
Apple | 10 g | 3 | QuEChERS | 10 mL ACN + 1 g NaCl + 4 g MgSO4; | dSPE with 250 mg MgSO4 + 100 mg PSA + 15 mg GCB | Lambda-cyhalothrin: GC/MS: in SIM mode EI |
88–105% | 0.01 mg/kg * | [76] |
Thiamethoxam and clothianidin: RRLC–MS/MS-QqQ: in MRM EI+ | |||||||||
Peaches | 10 g | 2 | QuEChERS | 20 mL ACN + 3 g NaCl | dSPE with 100 mg C18, 100 mg PSA + 300 mg of MgSO4 | LC–MS/MS-QqQ ESI |
83–119% | 0.01 mg/kg | [77] |
Lettuce | 10 g | 18 | QuEChERS | 10 mL ACN/AA (99:1, v/v) + 6 g MgSO4 + 1.5 g NaOAc + 1.0 g sodium acetate trihydrate (CH3COONa·3H2O); | d-SPE clean-up with 1.2 g MgSO4, 0.4 g C-18, 0.4 g PSA + 0.4 g Florisil | GC × GC–TOF-MS | - | 0.5–0.9 ng/g | [78] |
Spinach | 74–106% | ||||||||
Spring onions | - | ||||||||
Peanuts | 5 g | 73–101% | |||||||
Lettuce | 2 g | 8 | SLE | 10 mL ACN + 4 g Na2SO4 +1 g NaCl; | Two SPE purification: (1) d-SPE clean-up with 75 mg of C18, 75 mg of PSA + 1350 mg of Na2SO4; (2) SPE cartridges of 6 cc/100 mg eluted with 4 mL ethyl acetate | GC–MS/MS-QqQ: in SRM mode EI |
- | 0.013–4.45 µg/kg | [79] |
Tomatoes | 69–96% | ||||||||
Cauliflower | 47–87% | ||||||||
Broad beans | 41–98% | ||||||||
Wheat grain | 5 g | 2 | QuEChERS | 10 mL ACN + 1 g NaCl + 4 g MgSO4; | d-SPE clean-up with 150 mg MgSO4 + 50 mg C18+ 10 mg GCB | HPLC–MS/MS: in MRM mode | 87–112% (epoxiconazole) and 85–102% (pyraclostrobin) | 0.01 mg/kg * | [80] |
Wheat straw | 1 g | ||||||||
Maize grain | 5 g | 2 | QuEChERS | 10 mL 5% AA/ACN + 1 g NaCl + 4 g MgSO4; | Two types of dSPE: Maize grain and straw: 50 mg PSA + 5 mg MWCNTs + 150 mg MgSO4; Corncob extract: 50 mg PSA + 150 mg MgSO4 | HPLC–MS/MS: in MRM mode ESI− |
98–107% (tembotrione) and 90–108% (M5) | 0.43–1.5 μg/L | [81] |
Maize corncob | 2 g | ||||||||
Maize straw | 1 g | ||||||||
Soybean | 5 g | 5 | QuEChERS | 10 mL 1% AA/ACN + 1 g NaCl + 3 g MgSO4; | Two types of dSPE: Soybean: 50 mg C18 + 150 mg MgSO4; Green soybean and straw: same + 5 mg MWCNTs |
UPLC–QqQ-MS/MS: ESI |
71–116% | 0.018–0.125 μg/kg | [82] |
Green soybean | 5 g | ||||||||
Soybean straw | 2.5 g | ||||||||
Common food (vegetables, fruit, cakes) | 10 g (non-cereal-based) 5 g (cereal-based) |
516 | Non-cereal-based: QuEChERS (vers. 1); Cereal-based: QuEChERS (vers. 2) |
Vers. 1: 10 mL ACN + 1 g NaCl + 4 g MgSO4 + 0.5 g disodium hydrogen citrate sesquihydrate + 1 g trisodium citrate dihydrate Vers. 2: 20 mL ACN + 1 g NaCl + 4 g MgSO4 + 0.5 g disodium hydrogen citrate sesquihydrate + 1 g trisodium citrate dihydrate; |
dSPE: 150 mg MgSO4 + 25 mg PSA | 221 analytes: LC–MS/MS-QqQ: ESI+/− |
70–120% | 0.1–10 µg/kg | [66] |
Baby food (prepared) | Non-cereal-based: QuEChERS (vers. 3); Cereal-based: QuEChERS (vers. 4) |
Vers. 3: 10 mL ethyl acetate + 1 g NaCl + 4 g MgSO4 + 0.5 g disodium hydrogen citrate sesquihydrate + 1 g trisodium citrate dihydrate;; Vers 4: 20 mL ethyl acetate/cyclohexane 81:1 + 1 g NaCl + 4 g MgSO4 + 0.5 g disodium hydrogen citrate sesquihydrate + 1 g trisodium citrate dihydrated |
Vers.3: Purified in HPGPC column Vers 4: dSPE with 25 mg PSA + 25 mg C18 + 5 mg carbon |
135 analytes: GC–MS/MS: in MRM mode EI |
This entry is adapted from the peer-reviewed paper 10.3390/molecules26123688