Applications of Hollow-Fiber and Related Microextraction Techniques for the Determination of Pesticides in Environmental and Food Samples—A Mini Review
Abstract
:1. Introduction
2. Membrane-Based Solvent Microextraction Techniques
3. Factors Influencing Membrane-Based Solvent Microextraction Techniques
4. Applications of HFME for Extraction of Pesticides
5. Applications of SBME for Extraction of Pesticides
6. Applications of EME for Extraction of Pesticides
7. Conclusions
Funding
Conflicts of Interest
References
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Property | Advantage | Adheres to GAC |
---|---|---|
Low amount of organic solvent | √ | yes |
Aqueous acceptor phase (3-phase HFME) | √ | yes |
High preconcentration factors | √ | NA |
No solvent evaporation needed | √ | yes |
No clean-up of extract needed | √ | yes |
No filtration of extract needed | √ | yes |
No filtration of sample needed | √/X | yes |
Compatibility of solvents with GC | √/X | NA |
Compatibility of solvents with LC | √/X | NA |
Disposable fiber | √/X | no |
Manual preparation of HF, SB, etc. | X | NA |
Long extraction time (HFME, SBME) | X | no |
Only for liquid samples | X | NA |
HFME | Sample | Analytes | Preliminary Sample Preparation | Extraction Conditions | Analytical Technique | Method Performance | Additional Features | Reference |
---|---|---|---|---|---|---|---|---|
Water samples | ||||||||
2-phase | Environmental waters | 29 pesticides | None | PP (non-specified) 10 cm; WS + AS 40 μL ethyl decanoate; T 30 °C; stirring 300 rpm; extraction time 30 min; passive sampling: as above except room T, 600 rpm, 250 mL sample, extraction time 8–10 days | GC–MS | LOQs 0.012–0.802 μg/L | In situ passive sampling device in disposable plastic bottle for monitoring and estimating time-weighted average of pesticides | [33] |
2-phase | Effluent wastewater, surface water | 27 emerging contaminants including 14 pesticides | Filtered | PP1, 5.5 cm; WS + AS 60 μL 1-octanol; 1000 mL sample + 3% NaCl + pH 7; T 24 °C; 100 rpm; 30 min | LC–MS/MS | LOQs 2.13–126.50 ng/L; EFs 6–4177; RSD 3–15% | Parameters optimized by two fractional factorial designs | [34] |
2-phase | Rain water, spring water, ground water | 9 pyrethroid insecticides | Filtered 0.45 μm | PP1, 1 cm; WS 1-octanol; air in the lumen; sample 10 mL; 1500 rpm, 6 h; desorbed in 50 μL i-octane (US 15 min) | GC–MS | LOQs 0.003–0.026 μg/L; RSD 1.1–14.8%; EFs 35–255 | Extractant solvent only in the pores and air in the lumen; fiber desorbed after extraction | [35] |
2-phase | Environmental waters: river, tap, agricultural Canal | 16 pesticides | None | PP2, 328 mm; WS + AS TOPO (10%) and TBP (10%) in DHE; sample 250 mL pH 8; 100 rpm, 4 h | LC–MS/MS | LOQs 0.087–0.269 μg/L; RSD 1.4–11.8% | Polar non-aqueous extracting solvents (not defined except by acronyms) | [36] |
2-phase | Tap water, Farm water | Hexaconazole, quinalphos, methidathion | None | PP1, 1.8 cm; WS + AS toluene 4 μL; 4 mL sample + 1.5% NaCl (w/v); 850 rpm, 20 min | GC–ECD | LODs 3–7 ng/L; RSD 4.6–7.9% | Accuracy (as η) 98.2–101.5% | [37] |
2-phase, continuous | Drinking water | Methidation, quinalphos, profenofos | None | PP1, 1.5 cm; WS + AS i-octane (3 μL) added continuously at 0.2 μL steps at 3-min intervals; sample 11 mL; 1260 rpm, 40 min | HPLC–UV | LODs 2.86–82.66 μg/L; RSD 0.10–0.29%; EFs 175.1–189.5 | Continuous replenishment of acceptor phase in the fiber lumen; accuracy (as η) 79.80–86.14% | [38] |
3-phase | Water | 4 N-carbamate pesticides | None | PP1, 4 cm; WS i-octane + 5% TOPO; AS 0.1 M HCl + KCl pH 1; sample pH 11; 300 rpm, 30 min | HPLC–DAD, LC–MS | EFs 1–9; η 0–96.57% | Compared to SPE | [39] |
3-phase | Environmental waters | 6 sulfonylurea herbicides | None | PP1, 10 cm; WS dihexyl ether; AS 0.5 mM phosphate buffer pH 11; sample 12 mL + 5 mM HCl + 5% NaCl (w/v); 1200 rpm, 1 h | HPLC–DAD | LOQs 0.3–5.7 μg/L; RSD 2.2–8.4% | / | [40] |
Soil samples | ||||||||
2-phase | Soil, water | 6 pesticides + 2 metabolites | 3 g s.s. + (2×) 20 mL MeOH + 2.5% (w/v) NaCl, US 10 min; centrifugated, filtered (0.45 μm); evaporated to dry, re-dissolved in 10 mL UPw | Soil: PP1, 2 cm; WS + AS 20 μL 1-octanol; 10 mL aqueous extract pH 9; 1440 rpm, 30 min; evap. to dry, re-dissolved in 50 μL mobile phase; water: as above, except 3 cm fiber, 20 mL sample pH 9 + 20% NaCl (w/v) | HPLC–FLD | Soil: LOQ 0.004–23.14 ng/g; accuracy (as η) 85–117% | / | [41] |
Fruit and vegetables, whole or juice | ||||||||
2-phase | Fruits (apple, peach, orange, kiwi), vegetable (parsley) | 3 pyrethroid insecticides | Homogenized s.s., filtered | PP1, 8.8 cm; WS + AS 1-octanol 24 μL; sample 5 mL + 5 mL buffer (acetic acid/acetate, 0.1 M, pH 5.5) + 3% (w/v) NaCl + 1 mL UPw; 480 rpm, 41 min | GC–MS | LOQs 0.08–0.10 ng/mL; RSD 3.4–5.9%; EFs 519–528 | Parameters optimized with rotatable-centered cube central composite design | [42] |
2-phase | Different environmental waters, grape juice | 4 triazole fungicides | Filtered; grape juice diluted with UPw (10×) | PP1, 1.5 cm; WS + AS 4 μL toluene; sample 5 mL; 720 rpm, 20 min | GC–MS | LOQs 1–2 μg/L; RSD 6.0–9.0%; EFs 134–239 | No matrix effect observed; relative recovery 83–119% in different samples | [43] |
2-phase | Fresh and commercial orange juice | 18 pesticides | Centrifuged | PP1, 1.5 cm; WS + AS none (dry); 9 mL sample pH 7 + 4 g (NH4)2SO4 + 400 μL toluene/EtAc (85:15, v/v); 35 min; desorbed in 50 μL MeOH/AC (50:50, v/v) by US, 2 min | LC–MS/MS | LOQs 0.01–1.11 mg/L; RSD 4.7–7.6%; relative recoveries given for different samples | Proposed hollow-fiber microporous membrane liquid–liquid extraction (HF-MMLLE); triangular surface mixture design for method optimization | [44] |
2-phase | Vegetables: tomato, cabbage, water convolvulus | Chlorpyrifos, profenofos | Homogenized s.s., 12 g + 20 mL AC, US 30 min, filtered | PP1, 1.5 cm; WS + AS 3 μL n-dodecane; 11 mL sample; 1360 rpm, 30 min | GC–ECD | LOQs 0.331–0.427 μg/mL; RSD 0.54–8.00% | Accuracy (as η) 60.8–88.0% | [45] |
3-phase | Environmental water, honey, tomato | 7 triazine herbicides | Water: filtered; honey: dissolved in UPw 1:10; tomato: juiced, juice centrifuged, supernatant diluted to 100 mL with UPw, filtered | PP1, 3 cm; WS decane, AS 10 μL 1 mol/L H3PO4; sample 6 mL with 15% NaCl (m/v); stirring 1200 rpm for 40 min; AS neutralized (NaOH) before analysis | Sweeping MEKC | LODs 0.07–0.69 μg/L; EFs 3100–10,000; RSD < 12% | Method validated by analyzing a CRM | [46] |
3-phase comb. with DLLME | Grape juice | Parathion-methyl, chlorpyrifos, difenoconazole | None | PP1, 2 cm on SS-wire; WS dodecanol; sample 9 mL + 0.5 mL buffer (pH 6) + 250 μL HX/AC (1:7.5 v/v); agitated 60 min; fiber desorbed with 100 μL ACN, 10 min (US) | HPLC–DAD | LOQs 58–107 μg/L; RSD 3.5–16.3% | 2-level factorial design for optimization; calibrated for each sample by SAD | [47] |
3-phase | Apple juice | Carbendazim, thiabendazole | None | PP1, 7.5 cm; WS 1-octanol; AS 20 μL 5 mM HCl pH 2.5; sample 4 mL pH 7.5; 800 rpm, 40 min | HPLC–FLD | LODs 0.8–1.5 μg/L; RSD 3.3–8.5%; EFs 106–114 | Accuracy (as η) 86.3–106.0% | [48] |
3-phase | Roots of Panax ginseng | 5 pesticides | Roots crushed; powder sieved (0.25 mm mesh) | PP1, 4 cm; WS 1-octanol; AS aqueous sol. pH 3; sample 500 mg + 5 mL 10% NaCl solution, US nebulized; 20 min; eluted (2×) with 200 μL MeOH 5 min; evaporated, re-dissolved in 10 μL MeOH | HPLC–UV | LODs 12.4–22.2 μg/kg; RSD 3.3–13.1% | Analytes extracted to 10% NaCl solution, nebulized and extracted by 3-phase HFME from headspace; accuracy (as η) 78.2–116.2% | [49] |
3-phase | Orange juice | Fungicides thiabendazole, carbendazim, imazalil | None | PP3, 2.2 cm; WS 2-octanone; AS 20 μL 10 mM HCl; sample 3 mL + 0.5 mL 0.84 M NaOH; 1000 rpm, 30 min | CE, LC–MS | LOQs 0.17–0.33 μg/L; RSDs 3.4–10.6%; η 17.0–33.7% | Fiber attached to pipette tip | [50] |
3-phase, online | Vegetables | 8 carbamate pesticides | 12.50 g s.s. + 25 mL buffer sol. (83.8 mM Na2HPO4 + 23.4 mM KH2PO4, pH 7.5), vortex 2 min, kept 3 min, filtered 0.22 μm | PP4, 10 cm; WS dodecanol; AS 10 μL 0.3 M NaOH sol.; sample 5 × 1 mL, F = 2 mL/min; 25–30 °C, 22 min | EFA–UV | LOD carbaryl 2 μg/kg; RSD 1.0–4.3%; EFs 300 | Wash cycle with 2 mL MeOH between extractions | [51] |
3-phase, online | Vegetables, fruit | 4 carbamate pesticides | 10 g s.s. + 10 mL buffer 83.8 mM Na2HPO4 + 23.4 mM KH2PO4 (pH 7.5) homogenized (2×), filtered | PP5, 7 mm; WS dodecanol; AS 0.20 μL buffer 30 mM methylamine hydrochloride (pH 11.6) + 0.5 mM tetradecyltrimethylammonium bromide; sample 15 mL; 25–30 °C; 800 rpm, 15 min | CZE | LODs 6–10 ng/g; RSD 4.5–5.5%; EFs 1100–1410; accuracy (as η) 90.3–92.7% | HFME followed by base-stacking prior to CZE | [52] |
Animal plasma and tissues | ||||||||
2-phase | Fish tissue (grass carp, tilapia, turbot) | 8 organophos-phorous pesticides | 8 g frozen tissue + 5 g activated anhydrous Na2SO4 + 2× 15 mL AC, US 25 min, centrifuge 5000 rpm 10 min; extracts evaporated under vacuum to near dry, re-dissolved in 8 mL of 5% (v/v) MeOH/UPw | PVDF1, 2 cm sealed at one end; WS + AS 30 μL o-xylene; 8 mL sample extract; 500 rpm, 30 min | GC–MS | LOQs 7.0–15.2 ng/g; RSD 4.8–18.1% | Compared to SE + gel permeation chromatography clean-up | [30] |
2-phase | Orange juice, tomato pulp, porcine plasma | 40 persistent organic pollutants incl. 20 organochlo-rine pesticides | None | PP1, 2.6 cm; WS + AS toluene; sample 4 mL; 1100 rpm, 37 min, 46 °C | GC–MS/MS | Orange juice: LODs 12–39 ng/L; EFs 38–60; tomato pulp: LODs 38–182 ng/L; EFs 53–170; porcine plasma: LODs 12–160 ng/L; EFs 1–146; only for some analytes: RSD 1–18% and accuracy (as η) 65–120% | Full second-order central composite design for parameter optimization; HF attached to micropipette tip | [53] |
Other types of food | ||||||||
2-phase | Cereal-based baby food, wheat flour | 13 organophos-phorous pesticides including metabolites | 1.5 g s.s. + 20 mL ACN + 1.25% (v/v) HCOOH shaken (2 min), US (5 min), centrifuged; supernatant filtered 0.45 μm (2× repeated); extracts combined, evaporated to dry under vacuum, re-dissolved in 10 mL UPw | PP1, 2 cm; WS + AS 1-octanol 20 μL; sample 10 mL pH 7 + 5% (w/v) NaCl; 960 rpm, 45 min; fiber desorbed in 350 μL ACN 10 min (US), evaporated, re-dissolved in 50 μL of CyHX | GC–NPD | LOQs 0.96–10.7 μg/kg | Fiber additionally desorbed in ACN after extraction | [54] |
Other samples | ||||||||
2-phase, dynamic | Human plasma | 5 nitrophenolic herbicides | 1 mL plasma + 0.5 mL UPw mixed 30 min, then added 0.9 mL UPw, 0.1 mL i-propanol, 2 drops H2SO4, US 1 min | PP2; WS dihexyl ether; AS aqueous pH 10, F = 7.5 μL/min; sample pH 2/6 + 10–400 mM NaCl, F = 30 μL/min | LC–MS | LOQs 0.05–0.1 μg/mL; RSD 1–4%; EFs 40–205 | Experimental design for parameter optimization; dynamic system with donor and acceptor phase flow by syringe pumps; wash cycle 30 min between extractions to prevent carry-over | [55] |
2-phase | Textiles (cotton, terylene, fur) | 10 organochlo-rine pesticides | Textile piece 5 mm × 5 mm extracted with 100 mL NaCl solution (0.5%) in US (40 min), 8 mL to HFME | PVDF1, 1.5 cm sealed at one end; WS + AS 30 μL n-octanol; 8 mL sample extract in 0.5% NaCl; 800 rpm, 50 min | GC–MS | LODs 0.07–2.30 ng/g; RSD 0.6–10.8% | Compared to SPME method (PDMS fiber) and to SE (AC, HX) | [56] |
2-phase microdia-lysis | Microbial cell culture | Alachlor and its metabolite | Dilution | Regenerated cellulose HF 20 cm; WS + AS hexane at F = 4 μL/min; 50 mL sample pH 7 | HPLC–UV | LODs 14–72 ng/mL; RSD < 5%; EFs 386–403 (for 40 cm HF and F 0.1 μL/min) | Microdialysis method using an HF as dialysis membrane | [57] |
SBME | Sample | Analytes | Preliminary Sample Preparation | Extraction Conditions | Analytical Technique | Method Performance | Additional Features | Reference |
---|---|---|---|---|---|---|---|---|
Water samples | ||||||||
2-phase | Environmental waters | 4 organophos-phorous pesticiees | None | PVDF3, 4 cm; WS + AS IL [C8mim] PF6; sample 25 mL; 30 °C; 600 rpm, 60 min; washed with 100 μL ACN | HPLC–UV | LOQs 0.050–0.087 μg/L; RSD 0.91–3.26%; | Accuracy (as η) 86.71–103.7% | [61] |
2-phase | River water | 6 acidic herbicides | None | PP1, 2 cm; WS + AS 1-octanol 10 μL; sample pH 1; 700 rpm, 30 min; diluted with MeOH (2×) | NACE–UV | LODs 0.08–0.14 ng/mL; RSD 6.09–10.8% | Comparison: single-drop microextraction and HFME, both with 1-octanol | [62] |
2-phase magnetic | Bottled, tap, ground, river water | 6 triazine pesticides | None | PP1, 2.2 cm + SS wire; WS IL [C4MIM] [PF6]; sample 10 mL pH 4 + 2.5 g NaCl + 10 μL [C8MIM] [BF4] + 0.1 g NH4PF6; 9 bars added to collect extract, 750 rpm, 15 min; eluted with 0.8 mL MeOH, 5 min, evaporated | HPLC–DAD | LOQs 0.46–1.59 μg/L; RSD 0.1–9.2% | Accuracy (as η) 73.4–118.5% | [63] |
2-phase | Environmental water including seawater | Lindane, aldrin, terbutylazine atrazine | Filtered: 0.7 μm pore size glass filter | PP6, 2 cm; WS + AS toluene; sample pH 6 + 35 g/L NaCl; 40 rpm, 60 min | GC–μECD | LODs 0.001–0.086 μg/L, RSD 2.8–9.6%, EFs 40–107; accuracy (as η) 79–113% | Sample salinity up to 35 g/L (real seawater) no effect | [64] |
3-phase | Seawater | 6 phenols including pentachloro-phenol | None | PP1, 2.2 cm; WS IL [BMIM] [PF6]; AS 4.8 μL 0.1 M NaOH solution; 10 mL sample + HCl to 0.1 M + 15% NaCl; 60 °C; 700 rpm, 20 min | HPLC–UV | PCP: LOD 0.05 μg/L; RSD 7.2%; EF 99 | comparison: conventional 3-phase SBME (AS 1-octanol) and 3-phase HFME with same IL as AS | [65] |
Soil and sediment samples | ||||||||
3-phase with MC | Water, soil, sediment | 4 phenylurea pesticides | Water: filtered 0.45 μm; soil and sediment: air-dried and sieved, washed with 19 mL UPw + 2× 1 mL ACN; liquids combined and diluted to 20 mL with UPw | PP1, 6 cm; WS 1-octanol; AS 15 μL 1-octanol + 1.5 mg/mL MC; 20 mL sample solution + 3 g NaCl; 800 rpm, 30 min; desorbed with 50 μL ACN 2 min (vortex) | HPLC–DAD | Water: LODs 0.05–0.1 ng/mL, RSD 4.6–6.2%; soil: LODs 0.5–1.0 ng/g, RSD 5.7–6.8% | MC particles dispersed in AS, but desorption with ACN needed to change solvent | [66] |
Fruit and vegetables, whole or juice | ||||||||
2-phase with gra- phene | Fruit (apple, pear) | 4 carbamate pesticides | Homogenized s.s., centrifuged (4000 rpm, 5 min), washed 2× 1 mL ACN; liquids combined and diluted to 15 mL with UPw | PP1, 6 cm; WS 1-octanol; AS 15 μL 1-octanol + 2 mg/mL graphene; 15 mL sample solution + 10 μL 1-octanol + 2.25 g NaCl; 800 rpm 30 min; desorbed with 50 μL MeOH 2 min (vortex) | HPLC–DAD | LODs 0.2–1.0 ng/g, RSD 6.2–7.8%, EFs 60–70 | / | [67] |
2-phase | Cucumbers | 7 pesticides: propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn, tebuconazole | 2 g of homogenized s.s. + 5 mL UPw; shaken + US; centrifugated | PVDF2, 8 cm; WS + AS: 32 μL CHCl3; 5 mL sample supernatant; 300 rpm, 20 min; desorbed 1 min; solvent exchange to MeOH/UPw (1:1) | UPLC–MS/MS | Method parameters for UPw only: LOQs 0.05–1.0 μg/kg; EFs 100–147 | Matrix effect as ratio of calibration slopes matrix/UPw 76.25–121.62% | [68] |
2-phase | Cucumbers | 7 pesticides: propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn, tebuconazole | 2 g of homogenized s.s. + 5 mL UPw; shaken + US; centrifugated | PVDF2, 8 cm; WS + AS: 32 μL CHCl3; 5 mL sample supernatant; 300 rpm, 20 min; desorbed 1 min; concentrated to 32 μL | IMS | LODs 0.02–0.1 mg/kg, RSDs 0.7–14.5%, matrix effect 79.87–98.77% | Accuracy as η from spiked samples: 60.92–88.48% | [69] |
2-phase magnetic | Fruit juice (lemon, orange, apple, peach) | 8 organophos-phorous pesticides | None | PP1 + SS wire 1.2 cm; WS + AS 1-octanol; 6 bars; sample 10 mL + 10% NaCl; 30 °C; 600 rpm, 25 min; elution 400 μL MeOH (US 3 min); evaporated to dry, re-dissolved in 100 μL HX, filtered | GC–MS | LOQs 0.06–0.32 μg/L; RSD 1.0–6.1% | Parameters optimized by three-factor, three-level Box–Behnken design; accuracy (as η) 81.3–104.6% | [70] |
2-phase magnetic | Pears | 4 sulfonylurea pesticides | Homogenized | PP1 + SS wire 1.2 cm; WS + AS CHCl3; 8 bars; sample 1 g + 5 mL UPw pH 3 + 10% NaCl; 30 °C; 700 rpm, 20 min; desorbed with 500 μL ACN (US 5 min); evap. to dry, re-dissolved in 100 μL ACN, filtered | HPLC–UV | LOQs 24.99–27.52 ng/g; RSD 1.3–6.8% | Accuracy (as η) 80.08–105.56% | [71] |
3-phase with NP | Vegetables (radish, rape) | 4 carbamate pesticides | Homogenized s.s.; centrifuged (4000 rpm, 5 min) and 2× washed with 1 mL AC; combined liquid phase diluted to 15 mL with UPw | PP1, 6 cm; WS 1-octanol; AS 15 μL 1-octanol + 2 mg/mL ODS-graphene; 15 mL sample solution + 10 μL 1-octanol + 2.25 g NaCl; 800 rpm 30 min; desorbed with 50 μL MeOH 2 min (vortex) | HPLC–UV | LOQs 0.6–1.8 ng/g; RSD 6.4–7.3% | ODS-graphene NPs dispersed in AS, but desorption to solvent (MeOH) needed | [72] |
3-phase with MW CNT | Tap and lake water, fruit | 5 carbamate pesticides | Water: filtered; fruit: homogenized, centrifuged | PP1, 9 cm; WS 1-octanol; AS 20 μL MWCNT (1 mg/mL) in 1-octanol; sample 15 mL + 10 μL 1-octanol + 3.75 g NaCl; 800 rpm, 30 min; desorbed with 50 μL MeOH 5 min (US) | HPLC–DAD | LODs 0.1–2 ng/g; RSD 3.1–9.2%; accuracy (as η) 77.5–103.7% | MWCNT particles dispersed in AS, but desorption with MeOH needed | [73] |
Other types of food | ||||||||
2-phase with gra- phene | Milk | 5 phenylurea pesticides | None | PP1, 7 cm; WS 1-octanol; AS 20 μL 1-octanol + 2 mg/mL graphene; 15 mL sample solution + 10 μL 1-octanol + 2.25 g NaCl; 800 rpm, 30 min; desorbed with 75 μL ACN 1 min (vortex) | HPLC–UV | LOQs 4.6–6.0 μg/L, RSD 5.2–7.3% | Graphene particles dispersed in AS, but desorption with ACN needed to exchange solvent | [74] |
2-phase | Peanuts, soybeans | 5 triazine herbicides | Crushing of s.s.; MSPD 1 g sample + 1.75 g diatomite; eluted with 7 mL ACN, evaporated & reconstructed in 0.1 mL ACN + 4 mL UPw | PP1, 2 cm; 15 μL of IL [C4mim] [PF6]; extract (4.1 mL) + 1.2 g NaCl + pH 8; stirred with 4 SBME bars, 800 rpm, 40 min; cut and IL dissolved in 100 μL ACN | HPLC–UV | LOQs 1.68–5.71 μg/kg; RSD <8.5%; extraction η 89.3–112.8% | Method compared to HFME only and to MSPD only with superior performance | [75] |
Other types of samples | ||||||||
2-phase | Hemolymph lipoproteins in hemipteran Triatoma infestans | Insecticide deltamethrin (DLM) | Insect hemolymph obtained by centrifugation; added phenylmethylsulfonyl fluoride to concentration 2 mM; added DLM in AC; 1 h at 30 °C vortex at 10-min intervals; centrifuged; lipoproteins fractionated by ultra-centrifugation | PP1, 1.2 cm; WS + AS 1-octanol; sample 90 μL lipoprotein fraction + 150 μL AC + UPw to 3 mL; 65 °C; 800 rpm, 20 min | GC–μECD | LOD 0.05 ng | Purpose: to determine DLM binding in vitro to hemolymph lipoproteins in Triatoma infestans | [76] |
3-phase | Environmental waters, human urine | Atrazine and 4 metabolites | Water: filtered; urine: left to sediment and filtered | PP2, 20 cm; WS di-n-hexylether; AS 1 M HCl 10–12 μL; 200 mL sample pH 7 (5 mM phosphate buffer) + 20% NaCl; 150 rpm, 5 h; AS neutralized with 7 M NaOH | HPLC–DAD | Water: LOQs 0.1–2.8 μg/L, RSD 5.2–11.1%, EFs 10–2351; urine: LOQs 0.17–3.73 μg/L, RSD 6.1–13.5%, EFs 103–2351 | Humic acid addition to water at 0–50% (w/v) no impact on EFs | [77] |
EME | Sample | Analytes | Preliminary Sample Preparation | Extraction Conditions | Analytical Technique | Method Performance | Additional Features | Reference |
---|---|---|---|---|---|---|---|---|
Water samples | ||||||||
3-phase | Tap and river water | Fungicides thiabendazole, carbendazim | Filtered; tap water: ascorbic acid added (10 mg/L) to remove chlorine | PP7, 2.8 cm; WS ENB; AS 20 μL 10 mM HCl solution + Pt wire d = 0.2 mm; sample + HCl to 1 mM, counter-electrode Pt wire d = 0.3 mm; 300 V, 1300 rpm, 15 min | CE–UV | LODs 1.1–2.3 μg/L; RSD 2.5–2.8%; EFs 26–50 | Face-centered central composition design for parameter optimization | [78] |
3-phase | Drain water | 6 chlorophenols incl. pentachlorophenol | None | PP8, bag 3.0 cm × 1.5 cm; WS 1-octanol; AS 1 mL pH 12 + electrode; sample 100 mL pH 12 + electrode; 50 V, 1000 rpm, 10 min | GC–MS | LOQs 0.030–0.070 μg/L; RSD 5.1–9.7%; EFs 1450–2198; accuracy (as η) 78–105% | Followed by low-density solvent-based US-assisted emulsification microextraction + derivatization | [79] |
3-phase | Seawater | Chlorophenols including pentachlorophenol (PCP) | None | PP8, bag 2.2 cm × 0.6 cm; WS 1-octanol; AS 20 μL pH 12; sample 1 mL, pH 12; 10 V, 1250 rpm, 10 min | HPLC–UV | PCP: LOQ 0.4 ng/mL; RSD 6.8%; EF 23; Accuracy (as η) 74% | Compared to HFME at same conditions except electric current | [80] |
Fruit juice samples | ||||||||
3-phase | Fruit juice (lemon) | Thiabendazole | Centrifuged | PP1, 6 cm; WS silica nanoporous material SBA-15 (3 mg/mL) in NPOE; AS 20 μL 0.1 M HCl solution + Pt wire; sample pH 2 + Pt wire; 175 V, 100 rpm, 30 min | CD–IMS | LOD 0.9 ng/mL; EF 167; η 83% | Compared to conventional EME | [81] |
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Prosen, H. Applications of Hollow-Fiber and Related Microextraction Techniques for the Determination of Pesticides in Environmental and Food Samples—A Mini Review. Separations 2019, 6, 57. https://doi.org/10.3390/separations6040057
Prosen H. Applications of Hollow-Fiber and Related Microextraction Techniques for the Determination of Pesticides in Environmental and Food Samples—A Mini Review. Separations. 2019; 6(4):57. https://doi.org/10.3390/separations6040057
Chicago/Turabian StyleProsen, Helena. 2019. "Applications of Hollow-Fiber and Related Microextraction Techniques for the Determination of Pesticides in Environmental and Food Samples—A Mini Review" Separations 6, no. 4: 57. https://doi.org/10.3390/separations6040057
APA StyleProsen, H. (2019). Applications of Hollow-Fiber and Related Microextraction Techniques for the Determination of Pesticides in Environmental and Food Samples—A Mini Review. Separations, 6(4), 57. https://doi.org/10.3390/separations6040057