Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples

Abstract

Dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFO) is one of the most interesting sample preparation techniques developed in recent years. Although several applications have been reported, the potentiality and limitations of this simple and rapid extraction technique have not been made sufficiently explicit. In this work, the extraction efficiency of DLLME-SFO for pollutants from different chemical families was determined. Studied compounds include: 10 polycyclic aromatic hydrocarbons, 5 pesticides (chlorophenoxy herbicides and DDT), 8 phenols and 6 sulfonamides, thus, covering a large range of polarity and hydrophobicity (LogKow 0-7, overall). After optimization of extraction conditions using 1-dodecanol as extractant, the procedure was applied for extraction of each family from 10-mL spiked water samples, only adjusting sample pH as required. Absolute recoveries for pollutants with LogKow 3-7 were >70% and recovery values within this group (18 compounds) were independent of structure or hydrophobicity; the precision of recovery was very acceptable (RSD<12%) and linear behavior was observed in the studied concentration range (r(2)>0.995). Extraction recoveries for pollutants with LogKow 1.46-2.8 were in the range 13-62%, directly depending on individual LogKow values; however, good linearity (r(2)>0.993) and precision (RSD<6.5%) were also demonstrated for these polar solutes, despite recovery level. DLLME-SFO with 1-dodecanol completely failed for extraction of compounds with LogKow≤1 (sulfa drugs), other more polar extraction solvents (ionic liquids) should be explored for highly hydrophilic pollutants.

Keywords: %R; 2,4,5-T; 2,4,5-trichlorophenoxy acetic acid; 2,4,6-trichlorophenol; 2,4,6TCP; 2,4-D; 2,4-DB; 2,4-dichlorophenol; 2,4-dichlorophenoxyacetic acid; 2,4-dichlorophenoxybutiric acid; 2,4-dimethylphenol; 2,4DCP; 2,4DMP; 2-chlorophenol; 2CP; 4,4′-dichlorodiphenyltrichloroethane; 4,6-dinitro-o-cresol; 4,6DNC; 4-chloro-3-methylphenol; 4C3MP; ACE; ACN; ACY; BaA; BaP; C(ext); C(sample); CHR; D(ow); DBahA; DDT; DLLME; DLLME-SFO; Dispersive liquid–liquid microextraction; Extraction efficiency; FLU; HFME; Hydrophobicity.; IcdP; K(a); K(ow); LLE; LPME; LPME-SFO; M.P.; MeOH; NAP; Organic pollutants; PCP; PHE; Q(add); Q(rec); SBSE; SDM; SDME; SDZ; SFX; SMR; SMX; STZ; Solidification of floating organic drop; USAEME; V(ext); V(sample); acenaphthene; acenaphthylene; acetonitrile; acidity constant; added analyte amount; benz[a]anthracene; benzo[a]pyrene; chrysene; correlation coefficient; determination coefficient; dibenz[a,h]anthracene; dispersive liquid–liquid microextraction; dispersive liquid–liquid microextraction with solidification of organic drop; fluorene; hollow fiber microextraction; indeno[1,2,3-cd]pyrene; liquid-phase microextraction; liquid-phase microextraction with solidification of organic drop; liquid–liquid extraction; melting point; methanol; naphthalene; octanol-water distribution coefficient at given pH; octanol-water partition coefficient; pentachlorophenol; percent absolute recovery; phenanthrene; r; r(2); recovered analyte amount; sample volume; single drop microextraction; solute concentration in extract; solute concentration in sample; stir bar sorptive extraction; sulfadiazine; sulfadimethoxine; sulfamerazine; sulfamethoxazole; sulfathiazole; sulfisoxazole; ultrasound assisted emulsification microextraction; volume of extract.