Table 3.
Applications of LPME on solid sample extracts obtained by environmentally-friendly extraction.
| LPME | Analytical techn. | Sample | Analytes | Extraction procedure for solid sample | Optimized extraction conditions for s.s. | LPME procedure | Method performance | Ref. |
|---|---|---|---|---|---|---|---|---|
| US-DLLME | GC-ECD | soil | 3 pyrethroids | MSPD: 0.1 g s.s. + 0.3 g SiO2 (d 38 µm) blended in mortar; transf. to cartridge with 0.1 g Na2SO4(anhyd); eluted with 3 mL AC; evaporated to 0.5 mL | sorbent, sample/sorb. ratio, eluting solv. type and V, | AC extract (DS) + 50 µL TtCEt (ES) inj. into 5 mL w.; US 2 min; centrif.; sedim. phase evaporated, rediss. in 20 µL n-hexane | η 83.6%–98.5%; RSD < 7.3%; LOD 0.45–1.13 ng/g |
[77] |
| DLLME | HPLC-FLD | soil | carbendazime thiabendazole | 20 g s.s. + 40 mL 0.1 mol/L HCl; mech. shaking 30 min; filtered, pH adj. to 7.0 | not given | 0.75 mL THF (DS) + 80 µL CHCl3 (ES) inj. into 5.0 mL solution + 0.5 g NaCl; centrif.; sedim. phase evaporated, rediss. in 15 µL MeOH | η 82.0%–93.4% (2 levels); RSD < 7.3%; LOD 1.0–1.6 ng/g |
[78] |
| DLLME | GC-FID | sediment | PAHs | SFE: 1.2 g s.s. + 50 µL MeOH (PM); SFE at T 313 K, p 253.2 bar, static textr 10 min, dynamic textr 30 min, CO2 F = 0.5 mL/min; collected in 1 mL ACN in ice bath | pressure, temperature, static & dynamic extraction time | 1.0 mL extract (DS) + 16 µL ClBz (ES) inj. into 5 mL w.; centrif.; direct injection | η 67.8%–98.9%; RSD < 10.3%; LOD 200 ng/g |
[79] |
| DLLME | GC-FID | soil sediment |
7 organo-phosphor. pesticides |
SFE: 1.2 g s.s. . + 50 µL MeOH (PM); SFE at T 60 °C, p 150 bar, static textr 10 min, dynamic textr 30 min, CO2 F = 0.5 mL/min; collected in 1 mL ACN in ice bath | pressure, temperature, static & dynamic extraction time | 1.0 mL extract (DS) + 17 µL CCl4 (ES) inj. into 5 mL w.; centrif.; direct injection | η 80%–100%; RSD < 75%; LOD 1–9 ng/g |
[80] |
| DLLME | GC-FID | soil | 2 nitrotoluenes | SFE: 2 g s.s. + 150 µL MeOH (PM); SFE at T 35 °C, p 350 atm, static textr 10 min, dynamic textr 30 min, CO2 F = 0.4 mL/min; collected in 1 mL MeOH in ice bath | central composite design to optimize SFE parameters: T, pressure, VPM, dynamic textr |
1.0 mL extract (DS) + 20 µL CCl4 (ES) inj. into 5.0 mL w. (3% NaCl); centrif.; direct injection | η 80%–84%; RSD < 6.5%; LOD 0.12 µg/g |
[81] |
| DLLME | GC-MS | sediment | hydroxylated PAHs | SWE: 10 g s.s. + 2 g diatomaceous earth; PLE with w. pH 3.0 + 20% ACN (OM) 10 min at 150 °C & 1500 psi; purged with N2, collected 11 mL extract | type and V of organic modifier for SWE, pH, T, pressure, extr. time | 100 µL ClBz (ES) inj. into 11 mL extract (20% ACN as DS); VA 30 s; centrif.; sedim. phase evaporated, added 50 µL MTBSTFA to derivatize, evaporated, rediss. in 100 µL AC | η 57.63%–91.07%; RSD < 11.07%; LOD 0.0139–0.2334 ng/g; comparison with SWE-SPE - all parameters better for SWE-DLLME |
[82] |
| DLLME | GC-MS | pyrolysis solid residue | 15 aromatic volatiles | extracted s.s. (extr. with CH2Cl2) and raw s.s. leached with 0.001 M CaCl2 sol. (leach test ISO/TS 21268-2) |
not given | 0.5 mL AC (DS) + 50 µL CCl4 (ES) inj. into 5.0 mL leachate; centrif.; direct injection | LOD 1.02–24.6 ng/L a; compared with static HS and HS-SPME (both lower LODs) |
[83] |
| DLLME | GC-MS | pyrolysis solid residue | 11 alkylphenols | extracted s.s. (extr. with CH2Cl2) and raw s.s. leached with 0.001 M CaCl2 sol. (leach test ISO/TS 21268-2) |
not given | 1.0 mL AC (DS) + 15 µL TtCEt (ES) inj. into 4.0 mL leachate + NaCl (15%); centrif.; direct injection | η 61.9%–101.4%; RSD < 8.0%; LOD 0.07–0.17 µg/L b |
[84] |
| DLLME | GC-MS | particul. matter in seawater | 8 UV filters | unfiltered seawater, US 15 min; pH adj. to 2.5 with acetic a.; filtered | US time | 250 µL AC (DS) + 50 µL CHCl3 (ES) inj. into 5.0 mL sample; centrif.; direct injection | η 88%–117% (2 levels); RSD < 14%; LOD 10–30 ng/L a |
[85] |
| DLLME & in-syringe back-extract. |
HPLC-UV | soil sediment |
5 chlorophenols | MWE: 1.2 g s.s. + 2 mL w. (pH 10.0); MWE 90 s, cooling, diluted to 5 mL with w., pH adj. to 6.0; centrif., filtered | Vsolv, pHsolv, MWE time | 1.0 mL AC (DS) + 37 µL ClBz (ES) inj. into 5.0 mL extract; centrif.; 20 µL sedim. phase in syringe, then 20 µL w. (pH 12.0), plunger moving 5 min; w. phase injected | η 66.1%–82.0%; RSD < 7.6%; LOD 0.5–2.0 ng/g; chromatograms free of interferences |
[86] |
| USA-EME | HPLC-DAD | soil | triazine herbicides | 10 g s.s. + 10 mL w.; mech. shaking 40 min; filtered, diluted to 10.0 mL with w. | not given | 5.0 mL extract + 100 µL ClBz,; US 3 min at 25 °C; centrif.; sedim. phase evaporated, rediss. in 20 µL MeOH | η 82.6%–92% (2 levels); RSD < 4.3%; LOD 0.1–0.5 ng/g |
[87] |
| ATPS | HPLC-UV | soil | 2 phytohormones | 10 g s.s. + 30 mL MeOH/w. (80:20); US 20 min; centrif.; repeat; filtered, evaporated, rediss. in 10 mL MeOH/w. (80:20, pH 3) | not given | 1.0 mL solution + 0.6 g [BMIM]Br + 0.75 g K2HPO4; stirred 10 min at 30 °C; centrif.; upper phase collected, direct injection | η 86%–102%; RSD < 5.3%; LOD 2–10 ng/g; compared to direct HF-LPME |
[88] |
| CAE-ME | HPLC-DAD | sediment | PAHs, alkyl-phenols, paraben | MWE: 0.1 g s.s. + 3 mL 40 mM CTAB solution; MWE for 6 min at 90 °C and 140 W, cooled; centrif., filtered | T, MW power, CTAB solution V and concentration | 2 mL solution + 200 µL ACN + 46 µL Li-NTf2 0.5 g/mL; VA 3 min; heated 2 min at 65 °C; centrif.; sedimented droplet dil. to 100 µL with ACN, VA | η 92.8%–95.7% (2 levels); RSD < 19.3%; LOQ 0.02–0.36 µg/g; several interferences from the sample co-extracted |
[89] |
| in-situ LPME with IL-based surfactant | HPLC-DAD | sediment | PAHs, alkyl-phenols, paraben | MWE: 0.1 g s.s. + 3–5 mL 40 mM C16MIm-Br sol.; MWE for 6 min at 90 °C and 140 W, cooled; centrif., filtered | T, type of ILS, ILS solution V and concentration | 4 mL solution + 800 µL ACN + 92 µL Li-NTf2 0.5 g/mL; heated 5 min at 65 °C; VA 3 min; centrif.; sedimented droplet (≈90 µL) dil. to 200 µL with ACN, VA | η (2 levels) 91.1%–127%; RSD < 19%; LOQ 0.04–1.0 µg/g |
[90] |
| HF-LPME; DLLME |
GC-FPD | soil | 6 organosulfur pesticides |
5 g s.s. + 10 mL w.; US 40 min; centrif.; used for HF-LPME or filtered (2×), diluted 25× with w. for DLLME | not given | HF-LPME: 5.0 mL extract, 5 µL o-xylene (ES) in 1-cm HF; stirring 35 min at 1200 rpm; direct injectionDLLME: 0.8 mL MeOH (DS) + 10 µL CCl4 (ES) inj. into 5.0 mL solution; centrif.; direct injection | HF-LPME: η 81.7%–109.2%; RSD < 9.6%; DLLME: η 87.8%–100.6%; RSD < 9.0%; LOD not given for soil samples Comparison: DLLME faster & higher capacity, HF-LPME more robust & simple for complex samples |
[91] |
| HF-LPME | GC-MS | sediment | 12 OCPs 8 PCBs |
MWE: 1 g s.s. + 10 mL w.; MWE at 600 W for 20 min at 80 °C; supernatant diluted to 10 mL | T, extraction time | 10 mL extract, 5 µL toluene (ES) in 1.3-cm HF; stirring 20 min at 700 rpm; direct injection | η 73%–111% (OCP) 86–110 % (PCB); RSD < 20%; LOD 0.07–0.70 ng/g | [92] |
| HF-LLLME | LC-ESI-MS | dried sewage sludge | NSAIDs | PHWE: 0.5 g s.s. + 20 g sea sand, PLE with 0.01 M NaOH 5 min (5 cyc.) at 120 °C & 100 bar, flush V 60 %; purged with N2, collected 90 mL extract adj. pH to 1.5 and diluted to 100 mL | pH of solvent, T, number of cycles, flush volume | 100 mL extract, DHE in 10-cm HF wall (ES) & 25 µL 0.1 M (NH4)2CO3 (AS) in HF lumen; stirring 120 min at 600 rpm; direct injection | η (PHWE) 101%–109% (spike), 38.9%–90.3%(native); η (HF-LPME) 23.6%–30.3%; RSD < 20%; LOD 0.4–3.7 ng/g; only small matrix effect in ESI | [93] |
| HF-LLLME | LC-ESI-MS | dried sewage sludge | SSRIs | PHWE: 0.5 g s.s. + 20 g sea sand; PLE with 0.05 M H3PO4 pH 2 for 5 min (5 cyc.) at 120 °C & 100 bar, flush V 90%; purged with N2, collected 90 mL extract adj. pH to 12.4 and diluted to 100 mL | pH of solvent, T, number of cycles, flush volume | 100 mL extract, DHE in 10-cm HF wall (ES) & 0.1 M (NH4)H2PO4 pH 2.1 (AS) in HF lumen; stirring 8 h; direct injection | η (PHWE) 67%–83%(spike) 72.2%–85.8%(native); η (HF-LPME) 29%–47%; RSD < 20.8 %; LOD 6 ng/g; comparison to direct HF-LLLME method (without PHWE) | [94] |
| HF-LLLME | LC-MS/MS | sewage sludge | SSRIs and metabolites | 1 g s.s. + 1.1 L w. + 20 µL HCOOH; stirred 16 h at 900 rpm; filtered, diluted 1:100 or 1:20 | not given | solution + IS + 10 mL 5 M NaOH, DHE in 28-cm HF wall (ES) & 20 µL w.+HCOOH pH 2 (AS) in HF lumen; stirring 2 h at 800 rpm; direct injection | η 26.2%–71.4%; RSD < 24.6%(SSRI), < 51% (metab.); LOD not given |
[95] |
| DI-SDME | AP-MALDI-MS | soil | antibiotic monensin | 5 g s.s. + 15 mL w. (10% NaCl); shaking 5 min, US 5 min; centrif., repeat; supernatants collected | not given | 20.0 mL solution + 10% NaCl, 1.5 µL CHCl3/toluene (1:1) drop immersed for 10 min at 240 rpm; direct injection | η 74.5%–82.8% (3 levels); RSD < 6.5%; LOD 12.4 ng/mL b |
[96] |
| HS-SDME | GC-FID | fire debris | fire accelerants | 20x20 cm piece of textile soaked with accelerant, ignited; debris + 100 mL w., mixed 3 min; centrif., filtered | sample volume | 10 mL filtrate stirred at 1500 rpm, 2.5 µL benzyl alcohol drop exposed to HS for 20 min; direct injection | LOD 0.15 mg/L a | [97] |
| ESy | GC-ECD GC-MS |
soil | OCPs | 1 g s.s. + 10 mL w./ACN (8:2); US 15 min; centrif.; supernatant + 70 µL conc. H3PO4 + 100 mg Cu granules; US 15 min; filtered | ACN addition to extr. solvent | 3 mL filtrate flushed through donor side ESy at 100 µL/min; acceptor phase: n-undecane; direct injection | compared with SE and PLE: comparable results, less solvent (~4 mL vs. 420 mL-SE or 18 mL-PLE) and time (1.5 h vs. 4 h-SE or 0.85 h-PLE), less s.s. | [98] |
a given in liquid sample/leachate/filtrate; b LOD for soil given in ng/mL. Abbreviations: ES—extraction solvent; DS—disperser solvent in DLLME; AS—acceptor solvent in HF-LLLME; PM—polar modifier in SFE; OM—organic modifier in PLE; ATPS—aqueous two-phase system; ESy—extracting syringe; MSPD—matrix solid phase dispersion; s.s.—solid sample. Solvents: AC—acetone; ACN—acetonitrile; ClBz—chlorobenzene; DHE—di-n-hexyl ether; ILS—ionic liquid-based surfactant, MeOH—methanol; THF—tetrahydrofuran; TtCEt—tetrachloroethylene; w.—water (ultrapure/double deionized/MilliQ). Reagents: CTAB—cetyltrimethylammonium bromide; Li-NTf2—lithium bis[(trifluoromethane)sulfonyl]imide; MTBSTFA—N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide; [BMIm]Br—1-butyl-3-methylimidazolium bromide; C16MIm-Br—1-hexadecyl-3-methylimidazolium bromide.