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  • Ionic liquid-based dispersive liquidliquid microextractionfor the determination of formaldehyde in wastewatersand detergents

    Majid Arvand & Elahe Bozorgzadeh &Shahab Shariati & Mohammad Ali Zanjanchi

    Received: 12 August 2011 /Accepted: 2 January 2012# Springer Science+Business Media B.V. 2012

    Abstract Spectrophotometry in combination withionic liquid-based dispersive liquidliquid microex-traction (DLLME) was applied for the extraction anddetermination of formaldehyde in real samples. Themethod is based on the reaction of formaldehyde withmethyl acetoacetate in the presence of ammonia. Thevariation in the absorbance of the reaction product wasmeasured at 375 nm. An appropriate mixture of etha-nol (disperser solvent) and ionic liquid, 1-hexyl-3-methylimidazoliumhexafluoro-phosphate [C6MIM][PF6] (extraction solvent) was rapidly injected into awater sample containing formaldehyde. After extrac-tion, sedimented phase was analyzed by spectropho-tometry. Under the optimum conditions, thecalibration graph was linear in the range of 0.120 ng mL1 with the detection limit of 0.02 ng mL1

    and limit of quantification of 0.08 ng mL1 for form-aldehyde. The relative standard deviation (RSD%, n05)for the extraction and determination of 0.8 ng mL1 offormaldehyde in the aqueous samples was 2.5%. Theresults showed that DLLME is a very simple, rapid,

    sensitive, and efficient analytical method for the deter-mination of trace amounts of formaldehyde in waste-waters and detergents, and suitable results wereobtained.

    Keywords Formaldehyde . Ionic liquid . Dispersiveliquidliquid microextraction .Wastewaters .

    Spectrophotometry

    Introduction

    The most commonly used aldehyde is formaldehydeknown as oxymethylene or formalin. It is a cheappreservative, more easily soluble in water than in oiland fat, used in watery concoctions like shampoo,conditioner, shower gel, liquid hand wash, and bubblebath (Salvador and Chisvert 2007). Formaldehyde isunfavorable for our health because at low concentra-tions, it can cause irritation of eyes, nose, throat, andskin. Furthermore, people with asthma may be moresensitive to the effects of inhaled formaldehyde (Li etal. 2007; Kiba et al. 1999). Textiles are often finishedwith formaldehyde-containing chemicals which canprovide crease resistance, flame retardance, anddimensional stability (Priha 1995).

    Thus, there is a need to develop a simple, specific,and sensitive sample preparation and analytical tech-nique for the detection of trace quantities of this com-pound. In order to determine trace or ultra-traceamounts of formaldehyde, a chemical separation and

    Environ Monit AssessDOI 10.1007/s10661-012-2521-4

    M. Arvand (*) : E. Bozorgzadeh :M. A. ZanjanchiDepartment of Chemistry, Faculty of Science,University of Guilan,Namjoo Street, P.O. Box 1914, Rasht, Irane-mail: arvand@guilan.ac.ir

    S. ShariatiDepartment of Chemistry, Science and Research Branch,Islamic Azad University,Guilan, Iran

  • preconcentration step is often necessary prior to anal-ysis. Some analytical procedures including gas chro-matography (Hopkins et al. 2003; Pierotti 1990), solidphase microextraction (SPME) (Rivero and Topiwala2004), fluorometry (Li et al. 2007), spectrophotometry(Toda et al. 2005; Kawamura et al. 2005; Gmiz-Gracia and Luque de Castro 1999), and biosensor(Horstkotte et al. 2006) have been reported for thedetermination of formaldehyde.

    Dispersive liquidliquid microextraction (DLLME)is a very effective separation technique, finding nu-merous applications in analytical chemistry. Simplici-ty of the operation, speed, low sample volume, lowcost, high recovery, and high enhancement factor aresome advantages of DLLME (Rezaee et al. 2006). Theperformance of DLLME was illustrated by extractionof different organic and inorganic compounds (Jiang etal. 2008; Liang et al. 2008; Shamsipur and Ramezani2008; Garca-Lpez et al. 2007; Rezaee et al. 2009;Nagaraju and Huang 2007; Shariati et al. 2011) fromwater samples.

    Ionic liquids (ILs) have been considered as greensolvent and have been applied in many fields. Room-temperature ionic liquids (RTILs) can be used as theextraction solvent instead of organic solvents due to theirunique physicochemical properties, such as negligiblevapor pressure, good solubility for organic and inorganiccompounds, high thermal stability, and environmentalbenignity (Pandey 2006; Zhang and Shi 2010).

    The purpose of the present study is to develop aninexpensive, selective, and sensitive method for thedetermination of ultra-trace of formaldehyde in compli-cated matrices. The detection is based on the derivatiza-tion of formaldehyde using Hantzsch reaction, whichinvolves the cyclization between methyl acetoacetateand formaldehyde in the presence of ammonium acetate.

    Experimental

    Reagents and solutions

    All reagents were of analytical reagent grade and usedwithout further purification. Triply distilled water wasused throughout the study. A stock solution(1,000 g mL1) of formaldehyde was prepared byappropriate dilution of a 37% (v/v) formaldehyde so-lution (Merck, Darmstadt, Germany). A 0.2 mol L1

    methyl acetoacetate stock solution was prepared by

    diluting 2.15 mL of commercially available methylacetoacetate solution (Aldrich, Milwaukee, WI,USA) to 100 mL with purified water. An ammoniumacetate stock solution was prepared by dissolving7.71 g of ammonium acetate (Aldrich) in the purifiedwater and diluting it to 250 mL. 1-Hexyl-3-methyli-midazolium hexafluorophosphate [C6MIM][PF6] and1-butyl-3-methylimidazolium hexafluoro-phosphate[C4MIM][PF6] were obtained from Merck (Darmstadt,Germany). The ammonium acetate buffer was pre-pared in the range of pH 5.07.5: the pH was adjustedby adding acetic acid or NaOH to the ammoniumacetate solution.

    Apparatus

    UVVis absorbance digitized spectra were collectedon a Shimadzu UV-2100 ultravioletvisible spectro-photometer, using a quartz microcuvette (45 mm high,internal width 2 mm, and path length 10 mm). Meas-urements of pH were made with a Metrohm 744 pHmeter using a combined glass electrode. A centrifuge(Superior, Germany) with 10-mL calibrated tubes wasused to accelerate the phase separation process. AHaake Model FK2 circulation water bath (Hamburg,Germany) with a good temperature control within 1Cwas used.

    Analytical procedure

    For DLLME under optimum conditions, 10 mL ofsample solution containing the formaldehyde,0.05 mol L1 of methyl acetoacetate as derivatizingagent, and 20% (w/v) of NaCl was adjusted to pH 6.4in a glass test tube with conic bottom. The mixedsolution was left to react for 10 min at 60C in a waterbath, and then cooled down in water for 5 min. Thenthe injection of 1.0 mL ethanol (dispersive solvent)containing 75 L ionic liquid [C6MIM][PF6] wasperformed by using 1.0 mL syringe, rapidly. A cloudysolution (water, ethanol, and [C6MIM][PF6]) wasformed in the test tube. The produced cloudy solutionwas centrifuged for 5 min at 3,000 rpm to acceleratephase separation. After this process, 10 L of sedi-mented phase was removed using a 100-L syringeand diluted with 100 L ethanol and injected into amicro-cell. Subsequently, the micro-cell was located inspectrophotometer to obtain related spectra.

    Environ Monit Assess

  • Results and discussion

    The detection reaction is based on the Hantzsch reac-tion, which was first explained by Nash (1953). Thereaction is characterized by a cyclization of methylacetoacetate and formaldehyde in the presence of am-monia at 60C to form a color product, 2,6-dimethyl-1,4-dihydropyridine-3,5-di(methylcarboxylate)(Scheme 1). Methyl acetoacetate is one of the mostsoluble reagents in water. It is most reactive, selective,and sensitive for formaldehyde, and its product has alarge molar absorptivity (7.8103 dm3 mol1 cm1 at60C) (Li, Ma et al. 2008).

    In the proposed procedure, to achieve maximumextraction efficiency, various parameters affecting theDLLME of formaldehyde were studied and optimized.

    Preconcentration factor (PF) and percent extractionrecovery (ER%) as analytical responses were calculatedbased on the following equations:

    PF Csed=C0 1

    ER% Csed Vsed=C0 Vaq 100 2

    where Csed and C0 are the concentration of the analytein the sedimented phase and initial concentration ofthe analyte in the aqueous sample, respectively. Vsedand Vaq are the volume of the sedimented phase andvolume of the aqueous sample, respectively. Csed iscalculated from a calibration curve which wasobtained by direct injection of formaldehyde with theconcentrations in the range of 0.056 g mL1.

    On the other hand, the relative recovery (RR%) wasobtained from the following equation:

    RR% Cfound Creal=Cadded 100 3where Cfound, Creal, and Cadded are the concentrationsof analyte after addition of known amount of standardin the real sample, the concentration of analyte in realsample, and the concentration of known amount ofstandard which was spiked to the real sample,respectively.

    Selection of extractant solvent

    The extraction solvent has tomeet three requirements: (1)to extract analytes well, (2) to have higher density thanwater to sediment at the bottom of the extraction tube,and (3) to form a cloudy solution containing tiny dropletsin the presence of dispersive solvent when injected intoaqueous solution (Shariati et al. 2001). In this study, twohydrophobic ionic liquids, including [C4MIM][PF6] and[C6MIM][PF6], were investigated. By comparing themas extraction solvent, it was observed that formaldehydeexhibited a better affinity for [C6MIM][PF6] (Fig. 1).Therefore, [C6MIM][PF6] was selected as extractionsolvent in the subsequent experiments.

    Selection of dispersive solvent

    Dispersive solvent should be miscible in both extrac-tion solvent and aqueous sample. For this purpose,different solvents such as acetonitrile (AC

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