such as chlorothalonil and TPs (sulphonic acids and phenols) by LC-Orbitrap-MS [90]. However, sometimes these extraction procedures are avoided, and direct injection of water samples, after filtration, can be considered when using LC. In fact, its combination with tandem MS (MS/MS) has allowed for the determination of pesticides at ultra-trace levels in surface and groundwaters [25, 27, 91].
Table 1.1 Overview of analytical methods applied to monitor pesticides in environmental waters.a
| Pesticides | Matrix | Extraction technique | Determination technique | Recovery (%) | LOQ (µg l−1) | Reference |
| 4 OCP and 2 OPPs | Surface water | LLE (dichloromethane) | GC-FID | 80–90 | 0.002 | [68] |
| 296 pesticides + 156 pharmaceuticals, 18 consumer products, 10 industrial chemicals and 4 others | Coastal waters | SPE (Oasis HLB and SpePak cartridges) | LC-QTOF-MS | 70–130 | 0.00002–0.300b | [70] |
| 14 pesticides and TPs | Surface waterand drinking water | SPE (Oasis HLB cartridge) | UHPLC-QTrap-MS/MS | 85–105 | 0.01–0.1 | [71] |
| 19 acidic herbicides + metabolites | River water | SPE (Oasis HLB cartridge) | LC-QqQ-MS/MS | 64–111 | 0.004–0.022 | [72] |
| 6 neonicotinoids and metabolites | Drinking water | SPE (Oasis HLB cartridge) | LC-DAD-QqQ-MS/MS& QTOF-MS | 57–120 | 0.000057–0.000488b | [18] |
| ca. 500 pesticides and TPs | Surface water and groundwater | SPE (Oasis HLB cartridge) | UHPLC-QTOF-MS | — | — | [23] |
| 8 pesticides + TPs | Surface water | Mix mode SPE:(HLB: WAX: WCX, 2 : 1: 1) | LC-QqQ-MS/MS | 43–141 | 0.00002–0.0056b | [73] |
| 125 pesticides and metabolites + 130 pharmaceuticals and metabolites + 42 antibiotics and metabolites + 63 others | Surface and marine water | SPE (Strata-X and the mixture Strata-X-AW: Strata-X-CW: Isolute ENV + (1 : 1 : 1.5)) | LC-LTQ-Orbitrap-MS | 83–93 | — | [74] |
| 251 contaminants (pesticides, pharmaceuticals or industrial chemicals and their transformation products) | Surface water | Onsite integrative large-volume SPE (HR-X sorbent) | UHPLC-LTQ-Orbitrap MS | 60–123 | — | [75] |
| 96 including pesticides and TPs | Surface water,groundwater and drinking water | On-line SPE | UHPLC-QqQ-MS/MS | — | 0.005–0.025 | [24] |
| 51 pesticides | Surface water and groundwater | On-line SPE (Prospekt-2-system) | LC-QqQ-MS/MS | 80–125 | 0.010 | [78] |
| 8 pesticides | Surface water and groundwater | QuEChERS (Acetonitrile, MgSO4 and NaCl) | GC-Q-MS | 85–103 | 0.95–13.69 | [80] |
| Cyflumetofen + 2 metabolites | Surface water | QuEChERS (Acetonitrile, MgSO4 and NaCl) | UHPLC-QqQ-MS/MS | 79–118 | 0.7–9.8 | [21] |
| 102 pesticides | Surface water and groundwater | SBSE (PDMS) (GC)On-line SPE (LC) | GC-Q-MS (27)UHPLC-QqQ-MS/MS (75) | — | 0.015–0.025 (GC)0.005–0.025 (LC) | [77] |
| 10 pesticides | Surface water | HF-LPME | GC-Q-MS | 85–115 | 0.14–1.69 | [82] |
| 14 pesticides + 16 PAHs + 26 PCBs + 6 BDEs | Surface water | On-Line SPME (DI, PA fiber) | GC-DFS-HRMS | 87–116 | 0.0001–0.050 | [84] |
| 16 pesticides | Surface water, marine water and groundwater | Magnetic SPME with a magnetic DES-based polymeric hydrogel | GC-µECD | 61–120 | 0.006–0.399 | [86] |
| 24 pesticides | Surface water | SPME (Novel carbon nanomaterial sorbent) | GC-Q-MS | 70–123 | 0.0007–3.7320 | [87] |
| 18 chiral pesticides | Surface water and influent and effluent wastewater | Magnetic SPME (Amino modified multiwalled carbon nanotubes) | LC-QqQ-MS/MS | 83–105 | 0.00035–0.00204 | [88] |
| Pesticides | Matrix | Extraction technique | Determination technique | Recovery (%) | LOQ (µg l−1) | Reference |
| Chlorothalonil + 6 TPs | Surface water and groundwater | Vacuum-assisted evaporative concentration | LC-Orbitrap-MS | 85–110 | 0.0002–0.010 | [90] |
| 215 pesticides and TPs (Method SH2437)30 pesticides(Method LC9045)3 herbicides (glyphosate, AMPA and glufosinate)(Method GLYPH) | Groundwater | SH2437 &: LC9045: Direct injectionGLYPH: derivatization with FMOC prior to on-line SPE | LC-QqQ-MS/MS | 78–114 | 0.001–1.350b0.001–0.028b0.020b | [25] |
| 150 pesticide metabolites | Surface waterand groundwater | Direct injection | LC-QqQ-MS/MS | — | 0.003–2.000 | [27] |
| 16 polar pesticides + pharmaceuticals | Groundwater | Extraction from passive sampler (POCIS): acetone:methanol | UHPLC-QqQ-MS/MS | 42–116 | 0.00003–0.00135b | [59] |
aAbbreviations: BDEs: Brominated diphenyl ethers; DAD: Diode array detector; DES: Deep eutectic solvent; DFS-HRMS: Magnetic sector high resolution mass spectrometry: DI: Direct injection; FID: Flame ionization detection; FMOC: 9-florenylmethyl-chloroformate; GC: Gas chromatography; HF-LPME: Hollow fiber-liquid phase microextraction; HLB: Hydrophilic-lipophilic balanced; LC: Liquid chromatography; LLE: Liquid-liquid extraction; LOQ: Limit of quantification; LTQ: Linear ion trap; MS: Mass spectrometry; MS/MS: Tandem mass spectrometry; µECD: Micro electron capture detector; OCPs: Organochlorine pesticides; OPPs: Organophosphorus pesticides; PA: Polyacrilate; PAHs: Polycyclic aromatic hydrocarbons; PCBs: Polychlorinated biphenyls; PDMS: Polydimethylsiloxane; POCIS: Polar organic chemical integrative samples; Q: Single quadrupole; QqQ: Triple quadrupole; QTOF: Quadrupole time of flight; QTRAP: Hybrid triple quadrupole-linear ion trap; SBSE: Stir bar sorptive extraction; SPE: Solid phase extraction; SPME: Solid phase microextraction; TPs: Transformation products; UHPLC: Ultra-high-performance liquid chromatography; WAX: Weak anion exchange; WCX: Weak cation exchange.
bLimit of detection.
In relation to solid samples, such as soils, the most common methods were based on solid-liquid extraction (SLE), pressurized liquid extraction (PLE) and QuEChERS (see Table 1.2). In SLE methods, solvent mixtures such as acetonitrile and water have been widely used. For example, a mixture of water/acetonitrile (10 : 90, v/v) was utilized to monitor pesticide residues in soils from Argentina [62], or a mixture of water/acetonitrile (40 : 60, v/v) was used for the extraction of oxanilic and sulfonic acids metabolites [92]. Hu et al. employed methanol:water (50 : 50, v/v) instead of acetonitrile for the extraction of acetochlor and propisochlor in soils from Beijing (China) [63]. Colazzo et al. tested different solvents and mixtures, such as acetonitrile, methanol, water and methanol/water, choosing methanol as the best option (recoveries ranged from 45 to 90%) to determine pesticide residues in paddy fields and sugar cane from Uruguay [93].
Table 1.2 Overview of analytical methods applied to determine pesticides in soil matrices.a
| Pesticides | Extraction | Determination technique | Recovery (%) | LOQ (µg kg−1) | Reference |
|---|---|---|---|---|---|
|
Famoxadone
|