title: Generation of volatile copper species after in situ ionic liquid formation dispersive liquid-liquid microextraction prior to atomic absorption spectrometric detection.
abstract: The new procedure using in situ synthesis of ionic liquid extractant for dispersive liquid-liquid microextraction (in situ IL DLLME) combined with generation of volatile species prior to electrothermal atomic absorption spectrometry (ET AAS) for the determination of copper in soil samples was developed. Analytical signals were obtained without the back-extraction of copper from the IL phase prior to its determination. Under optimal conditions, the extraction in 10 mL of sample solution employing 8 μL of 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (HmimNTf2) (as the extraction solvent) was conducted. The ionic liquid served as two-task reagent: the efficient extractant and enhancement substance for generation step. The chemical generation of volatile species was performed by reduction of acidified copper solution (HCl 0.8 mol L(-1)) with NaBH4 (1.5%). Some essential parameters of the chemical generation such as NaBH4 and HCl concentrations, the kind and concentration of ionic liquid, carrier gas (Ar) flow rate, reaction and trapping time as well as pyrolysis and atomization temperatures were studied. For photogeneration the effect of the parameters such as the kind and concentration of low molecular weight organic acids and ionic liquid, carrier gas (Ar) flow rate, UV irradiation and ultrasonication time on the analytical signals were studied. The detection limit was found as 1.8 ng mL(-1) and the relative standard deviation (RSD) for seven replicate measurements of 100 µg mL(-1) in sample solution was 7%. The accuracy of the proposed method was evaluated by analysis of the certified reference materials. The measured copper contents in the reference materials were in satisfactory agreement with the certified values. The method was successfully applied to analysis of the soil and sediment samples.
authors.affiliation: Poznan University of Technology, Faculty of Chemical Technology, Piotrowo 3, 60-965 Poznań, Poland. Electronic address: ewa.stanisz@put.poznan.pl.
authors.forename: Ewa
authors.initials: E
authors.lastname: Stanisz
authors.affiliation: Poznan University of Technology, Faculty of Chemical Technology, Piotrowo 3, 60-965 Poznań, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Zgoła-Grześkowiak
authors.affiliation: Poznan University of Technology, Faculty of Chemical Technology, Piotrowo 3, 60-965 Poznań, Poland.
authors.forename: Henryk
authors.initials: H
authors.lastname: Matusiewicz
mesh_terms: D002138:Calibration; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry; D019015:Geologic Sediments / Q000737:chemistry; D052578:Ionic Liquids / Q000737:chemistry*; D059627:Liquid Phase Microextraction / Q000379:methods*; D010777:Photochemistry / Q000379:methods; D012016:Reference Values; D015203:Reproducibility of Results; D012987:Soil / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013054:Spectrophotometry, Atomic / Q000379:methods*; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013696:Temperature
chemical_list: D052578:Ionic Liquids; D012987:Soil; D012997:Solvents; D003300:Copper
keywords: Enhancement effect; In situ solvent formation; Ionic liquids; Photo-induced generation; Soil; Volatile copper species generation