Journal of Trace Analysis in Food and Drugs (2013) 1: 1-13 doi:10.7726/jtafd.2013.

1001

Research Article

A New Separation and Preconcentration System Based on Dispersive Liquid-Liquid Microextraction for Spectrophotometric Determination of Trace Amounts of Boron in Water Samples
Ali Reza Zarei*, Sonia Nobakht, and Mohammad Ali Zaree
Received 15 July 2012; Published online 3 November 2012 The author(s) 2012. Published with open access at uscip.org

Abstract
A simple and sensitive method based on the dispersive liquid-liquid microextraction (DLLME) technique combined with UV-Vis spectrophotometry analysis has been developed for the determination of boron concentration in water samples. The method is based on ion-association formation of boron as boron tetraflouride (BF4-) with methylene blue (MB+) and extraction of the hydrophobic complex (BF4-:MB+) using the DLLME technique. Some important parameters, such as reaction conditions and the kind and volume of extraction solvent and disperser solvent were studied and optimized. Under the optimized experimental conditions, Beers law was obeyed over the concentration ranges of 0.50-50 ng mL-1. The apparent molar absorptivity and Sandells sensitivity of ion-pairing product were 3.39105 L mol-1 cm-1 and 0.032 ng cm-2, respectively. Also, the enrichment factor and extraction recovery obtained were 24.68% and 98.74%, respectively. The proposed method was successfully applied for determination of boron concentration in water samples. In addition, excellent agreement was observed between this proposed method and the reference method. Keywords: Boron; Dispersive liquidliquid microextraction; Spectrophotometry; Preconcentration

1. Introduction
Boron is an important micronutrient for plants, animals and humans and its presence has been demonstrated to affect the function or composition of several body compartments (such as the brain, the skeleton and the immune system) in humans and animals (Power and Woods, 1997; Nielsen, 1997). Too high an amount of boron can limit plant growth and even lead to plant death, and for humans an excessive amount may result in nausea, vomiting, diarrhea, dermatitis and
______________________________________________________________________________________________________________________________ *Corresponding e-mail: zarei1349@gmail.com Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, 1 15875-1774, Iran

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lethargy (Nielsen, 1993). Therefore, the consumption of food and water with high boron content can be potentially hazardous to health. As a consequence, the World Health Organization (WHO) has suggested that a safe range of boron intake for adult human beings is 1-13 mg per day (WHO, 1998). Boron is usually present in nutrients (water and milk samples) at the ug L-1 level (Hunt et al., 2004; Nielsen, 1992). Thus, the control of boron levels in samples related to animal and human nutrition is needed. However, the reliable determination of boron at these levels is not a simple analytical task, so the development of new microextraction techniques and low cost instrumental methods could be very interesting for the determination of trace amounts of boron. Different methods have been reported for the determination of boron, including electrothermal atomic absorption spectrometry (ETAAS) (Nowka et al., 2000; Burguera et al., 2001; Resano et al., 2007; Lopez-Garcia et al, 2009), inductively coupled plasma-atomic emission spectrometry (ICPAES) (Tamat and Moore, 1987; Krejcova and Cernohorsky, 2003; Simsek et al., 2003; Ozcan and Yilmaz, 2005; Kataoka et al., 2008), voltammetry (Thunus, 1996; Domenech-Carbo et al., 2004; Sahin and Nakiboglu, 2006), and liquid chromatography (Katagiri et al., 2006; Raol and Aggarwal, 2008) and spectrophotometry (Sanchez-Ramos et al., 1998; Thangavel et al., 2004; Carrero, et al., 2005; Zaijun et al., 2006; Li and Zhang, 2007; Rusnakova et al., 2011). Spectrophotometric determination of boron with curcumin as complexing agent is widely used for routine analysis because of simplicity and high sensitivity. But the interference of water in the reaction between boron and curcumin is a serious problem and it is necessary to remove water from samples. To overcome this problem, boron has to be selectively separated from the matrix either by solvent extraction with diols (such as 2-ethyl hexane 1,3-diol (EHD) (Dyrssen and Uppstrom, 1969) or by isothermal distillation of borate ester (Thangavel et al., 2004). Therefore, sample preparation for the determination of ultra-trace amounts of boron (ng mL-1) using these methods will be time consuming and suffer from lack of good sensitivity. Sample preparation has a direct impact on accuracy, precision, and quantitation limits and is often the rate-determining step of an analytical process, especially when trace determination is the purpose (Nerin, 2007). Liquid-liquid extraction (LLE) is a versatile classical sample preparation technique prescribed in many standard analytical methods. However, conventional LLE uses large amounts of potentially toxic organic solvents, which are often hazardous and explosive (EPA, 1986). To overcome these drawbacks, some techniques such as liquid-phase microextraction (LPME) and solid-phase microextraction (SPME) have been developed. Recent research trends involve miniaturization of the traditional liquid-liquid extraction principle. Dispersive liquid-liquid microextraction (DLLME) is a new liquid phase microextraction (LPME) technique based on a ternary component solvent system that is similar to the homogeneous liquid liquid extraction method (HLLE) (Rezaee et al., 2006; Anthemidis and Loannou, 2009; Hassan et al., 2011) and cloud point extraction (CPE) (Zarei, 2007). This method consists of two steps: (1) the injection of an appropriate mixture of extraction and disperser solvent into an aqueous sample containing analytes. In this step, extraction solvent is dispersed into the aqueous sample as very ne droplets and analytes are enriched into it. Because of the innitely large surface area between extraction solvent and aqueous sample, the equilibrium state is achieved quickly and extraction is independent of time. This is the most important advantage of this method. (2) The centrifugation of the cloudy solution. After centrifugation, the determination of analytes in the sedimented phase can be performed by instrumental analysis. Rapidity, high enrichment factor, simplicity of operation
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and low cost are some of the advantages of this method. Recently, Rusnakova et al. (2011) have reported a method for determination of boron based on dispersive liquid-liquid microextraction that was applicable for determination of boron in the range of 0.22-18.7 mg L-1. This method was applied for spiked waters (Rusnakova et al., 2011). This work is mainly focused on the suitability of DLLME combined with UV-Vis spectrophotometry for the determination of ultra-trace amounts of boron in the ranges of 0.50-50 ng mL-1. The influence of the different experimental parameters on the yield of the sample preparation step is described and discussed. To evaluate the applicability of the proposed method, it was then applied for the determination of boron in water samples and compared with results obtained by ICP-AES as a reference method.

2. Experimental
2.1 Apparatus A Hitachi model 3310 UV-Vis spectrophotometer with 1-cm quartz micro cells was used for recording absorbance spectra. All spectral measurements were performed using the blank solution as a reference. A Hettich centrifuge (EBA 20) with 10 mL calibrated centrifuge tubes was used to accelerate the phase separation process. 2.2 Reagents All reagents used were of analytical grade and all solutions were prepared with distilled water. All solutions were prepared in polypropylene volumetric flasks. Stock boron solution (1000 g mL-1) was prepared by dissolving 0.5636 g boric acid (Merck) in water and diluting to 100 mL in a volumetric flask. A 5.0 (w/v %) NaF was prepared by dissolving 5.0 g sodium fluoride in water and diluting to 100 mL in a volumetric flask. A 1.50 mM methylene blue solution (Merck) was prepared by dissolving 0.0480 g methylene blue in water and diluting to 100 mL in a volumetric flask. A 2 mol L-1 sulfuric acid solution was prepared by dissolving an appropriate amount of concentrated acid (Merck) in distilled water. 2.3 Dispersive Liquid-Liquid Microextraction Procedure An aliquot of the solution containing 5.0-500 ng of boron, 1.0 mL of 5.0 (w/v %) NaF, 1.0 mL of 1.50 mM methylene blue solution and 1.0 mL of 2 mol L-1 sulfuric acid solution was transferred into a 10 mL centrifuge tube and the contents were mixed well. The contents were diluted with water and then 400 L of acetonitrile (as disperser solvent) containing 100 L of 1,2-dichloroethane (as extraction solvent) was injected rapidly into a sample solution using a 2 mL syringe. A cloudy solution was formed in the test tube. In this step the ion-pair product was extracted into the fine droplets of 1,2-dichloroethane. The mixture was centrifuged at 3800 rpm for 2 min and the dispersed fine droplets of 1,2-dichloroethane were settled. The supernatant aqueous phase was readily decanted with a Pasteur pipette. The remaining organic phase was diluted to 400 L with acetonitrile and the absorbance measured at 657 nm against blank. The blank solution was prepared as for the sample solution except that distilled water was used instead of boron solution. 2.4 Reference Method (ICP-AES Method) The measurements were carried out with an ICP atomic emission spectrometer (ICP-AES) Perkin Elmer model 5300 DV. The operation conditions for ICP-OES were as follows: emission line: B (I)
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249.773 nm (other lines, 208.893, 208.959, 249.678 nm were also used to confirm the results in analyses), plasma power supply: 1.0 kW, observation height: 6 mm, plasma gas flow: 10.0 L min-1, auxiliary gas flow: 0.5 L min-1, nebuliser gas flow: 0.6 L min-1, photomultiplier voltage: 600 V, sample uptake rate: 1.7 mL min-1, integration time: 1 s and replicates: 3.

3. Results and Discussion

In acidic media, after conversion of boron to tetrafluoroborate anion, it reacts with methylene blue to form an ion-pair complex that can be extracted into 1,2-dichloroethane. Therefore, it can be a suitable method for separation and preconcentration of boron by DLLME. Fig. 1 shows the visible absorption spectra of the ion pair complex of tetrafluoroborate with methylene blue after DLLME, which exhibits a maximum absorbance at 657 nm. Therefore, all absorbance measurements were performed at this wavelength. To obtain high sensitivity, it is necessary to investigate the effect of all parameters that could influence the ion-association formation reaction and the performance of DLLME.
2
657 nm

1.5 Absorbance

(7)

0.5 (1) 0 550

600

650 Wavelength /nm

700

750

Fig 1. Absorption spectra of the ion pairing product of boron with methylene blue after DLLME, Conditions: Boron, (1) 1.0 (2) 5.0 (3)10 (4) 20 (5) 30 (6) 40 (7) 50 ng mL-1; Methylene blue, 150 M; NaF, 0.5 (w/v %); Sulfuric acid, 0.20 M. 3.1 Parameters Affecting the Ion-Association Formation Reaction 3.1.1 Effect of the Sodium Fluoride Concentration For the extraction of boron via ion pair, boric acid converts to boron tetrafluorate anion. The effect of sodium fluoride concentration on the absorbance of the system was investigated within the range 0.05-2.0 (w/v %) NaF. The results revealed that the absorbance increased by increasing reagent concentration up to 0.5 (w/v%) NaF and remained nearly constant at higher concentrations (Fig. 2). Therefore, a concentration of 0.5 (w/v %) NaF was applied in the proposed method.

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3.1.2 Effect of the Methylene Blue Concentration The effect of methylene blue concentration on the absorbance of the system was investigated within the range 50-300 M. As can be seen in Fig. 3, the maximum absorbance was achieved at 150 M, and remained nearly constant at higher concentrations. Therefore, a concentration of 150 M methylene blue was applied in the proposed method.
0.4

0.3 Absorbance

0.2

0.1

0 0 0.3 0.6 0.9 1.2 Concentration of sodium fluoride/ (w/v%)

Fig 2. Effect of sodium fluoride concentration on the analytical signals, Conditions: Boron, 10 ng mL-1; Methylene blue, 150 M; Sulfuric acid, 0.20 M.
0.4

0.3 Absorbance

0.2

0.1

0 0 50 100 150 200 250 Concentration of Methylene blue/M

Fig 3. Effect of methylene blue concentration on the absorbance of the system, Conditions: Boron, 10 ng mL-1; NaF, 0.5 (w/v %); Sulfuric acid, 0.20 M. 3.1.3 Effect of Sulfuric Acid Concentration The boron tetrafluorate anion that forms in acidic medium is extractable by DLLME. It is best to use sulfuric acid, because sulfate anions, unlike the anions of other strong acids, do not form extractable ion pairs with the methylene blue. The effect of sulfuric acid concentration on the absorbance of the system was investigated within the range 0.05-1.0 M. The results revealed that the absorbance increased by increasing reagent concentration up to 0.20 M, and decreased at higher concentrations (Fig. 4). Therefore, a concentration of 0.20 M sulfuric acid was applied in the proposed method.
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0.4

0.3 Absorbance

0.2

0.1

0 0 0.2 0.4 0.6 0.8 1 Concentration of sulfuric acid/ M

Fig 4. Effect of sulfuric acid concentration on the analytical signals, Conditions: Boron, 10 ng mL-1; Methylene blue, 150 M; NaF, 0.5 (w/v %). 3.2 Parameters Affecting the Extraction Efficiency of DLLME 3.2.1 Selection of the Extraction and Disperser Solvent Type In DLLME, the extraction solvent has to meet three requirements. It should demonstrate (i) higher density than water, which makes it possible to separate the extraction solvent from the aqueous phase by centrifugation; (ii) extraction capability for the relevant compounds and (iii) low solubility in water (Hashemi, 2010). Halogenated hydrocarbons are usually selected as an extraction solvent because of their high density. In this work, chloroform (CHCl3), carbon tetrachloride (CCl4), 1,2-dichloroethane (C2H4Cl2), dichloromethane (CH2Cl2) and 1,2dichloroethylene (C2H2Cl2) were examined in order to find the most suitable solvent for DLLME. For this purpose, a series of sample solutions were treated with 400 L of disperser solvents (methanol, ethanol, acetonitrile and acetone) containing 100 L of the extraction solvents. The results obtained are shown in Fig. 5. As seen, 1,2-dichloroethane has high extraction efficiency among the tested solvents, so it was selected as the extraction solvent in further experiments.
0.4 0.3 Absorbance 0.2 0.1 0
Chloroform Carbon tetrachloride 1,2-Dichloroethane Acetonitrile Methanol

1,2-Dichloroethylene

Dichlroromethane

Fig 5. Effect of the type of extraction and dispersant solvent on the analytical signals, Conditions: Boron, 10 ng mL-1; NaF, 0.5 (w/v %); Sulfuric acid, 0.20 M.
6

Acetone

Ethanol

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The main criteria for choosing the disperser solvent in DLLME is its miscibility in the organic phase (extraction solvent) and also in the aqueous phase (sample solution), which enables the extraction solvent to be dispersed as fine particles in the aqueous phase to form a cloudy solution (water/disperser solvent/extraction solvent). The commonly used disperser solvents that illustrate this ability include methanol, ethanol, acetonitrile and acetone. In this study, all combinations of 1,2-dichloroethane (100 L) as extraction solvents and methanol, ethanol, acetonitrile and acetone (400 L) as disperser solvents were examined. In the case of 1,2-dichloroethane with acetonitrile, a stable two-phase system and higher signal was observed (Fig. 5). We selected 1,2-dichloroethaneacetonitrile as a suitable set for microextraction of boron. 3.2.2 Effect of the Extraction Solvent Volume The extraction solvent volume has great effects on the enrichment factor. In order to evaluate on the extraction efficiency, additional experiments were performed using 400 L acetonitrile containing different volumes of 1,2-dichloroethane (Fig. 6).
0.4

0.3 Absorbance

0.2

0.1

0 0 50 100 150 200 250 Extraction solvent volume/ L

Fig 6. Effect of the extraction solvent (1,2-dichloroethane) volume on the analytical responses after DLLME, Conditions: Boron, 10 ng mL-1; NaF, 0.5 (w/v %); Sulfuric acid, 0.20 M. As can be seen, by increasing the extraction solvent volumes from 20 to 200 L, the absorbance increased by increasing the volume of the 1,2-dichloroethane to 100 L and then remained approximately constant with further increasing of its volume. Therefore, 100 L of extraction solvent was selected as volume optimum. 3.2.3 Effect of the Disperser Solvent Volume The disperser solvent volume directly affects the formation of the cloudy solution (water/disperser/extraction solvent), the degree of the dispersion of the extraction solvent in aqueous phase, and subsequently, the extraction efficiency. To study the effect of disperser solvent volume on the extraction efficiency, all experimental conditions were fixed except the volume of acetonitrile, which varied from 100-800 L. The results are shown in Fig. 7. According to the obtained results, the absorbance reached to its maximum value at 400 L acetonitrile and then
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gradually decreased by further increasing of its volume. It is noted that at low volumes of acetonitrile, the cloudy state is not formed well; in the high volumes of acetonitrile, solubility of the extraction solvent in water increases, therefore, the extraction efficiency decreases because of distribution coefficient decreasing. A 400 L volume was chosen as an optimum volume for disperser solvent.
0.4

0.3 Absorbance

0.2

0.1

0 0 200 400 600 800 Dispersive solvent volume /L

Fig 7. Effect of the dispersant solvent (acetonitrile) volume on the analytical responses after DLLME, Conditions: Boron, 10 ng mL-1; NaF, 0.5 (w/v %); Sulfuric acid, 0.20 M. 3.3 Method Validation Under the optimized experimental conditions for boron determination, the standard calibration curves were constructed by plotting absorbance versus concentration. The linear regression, the Beers law range, molar absorptivity, Sandells sensitivity, correlation coefficient, limits of detection, enrichment factor and extraction recovery are summarized in Table 1. Beers law is obeyed over the concentration range of 0.50-50 ng mL-1 of boron at 657 nm. The limit of detection (LOD) defined as CL=3SB/m where CL, SB, and m are the limit of detection, standard deviation of the blank, and slope of the calibration graph (Miller and Miller, 2000). The enrichment factor (EF) was defined as the ratio between the analyte concentration in the sedimented phase (Csed) and the initial concentration of the analyte (C0) in the aqueous sample (Yazdi et al., 2008; Caldas et al., 2010) EF= Csed/ C0 The extraction recovery (R%) was defined as the percentage of the total analyte which was extracted in the sedimented phase. R%= EF(Vsed/Vaq) 100 (2) (1)

Where R%, Vsed, and Vaq are the extraction recovery, the volume of the sedimented phase, and the volume of the aqueous sample, respectively. In order to examine the enrichment factor, three replicate extractions were performed at optimal conditions from aqueous solutions containing 10 ng mL-1 of boron. The enrichment factor was calculated as the ratio of final concentration of analyte
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in sedimented phase (Csed) and its concentration in the original solution (C0). Csed was calculated from the calibration graph obtained by the conventional LLE with 5 mL 1,2-dichloroethane. Based on Eqs. (1) and (2), the enrichment factor and extraction recovery (R%) obtained were 24.52% and 98.08%, respectively. 3.4 Selectivity To study the common ion effect or selectivity of the proposed method, the effect of various species on the determination of 10 ng mL-1 of boron was tested under the optimum conditions. The tolerance limit was defined as the concentration of added species caused less than 5% relative error. It was found that most of the investigated species did not interfere (Table 2). Therefore, the results presented in this table show the good selectivity of the procedure. Table 1 Regression and analytical parameters. max (nm) Regression equation using DLLME (n=10) Regression equation (n=10) using conventional LLE Molar absorptivity (Lit mol-1 cm-1) Sandells sensitivity (ngcm-2) Linear range (ng mL-1) Limit of detection (ng mL-1) Reproducibility (R.S.D., %) Enrichment factor (EF) Extraction recovery (R%) a For conventional LLE. 657 A= 0.0308C + 0.026, R2 = 0.998 A= 0.00125C + 0.0097, R2 = 0.999 3.39105 (3.97103)a 0.032 (2.8) 0.50-50 (50-1000)a 0.30 (30)a 1.86 24.52 98.08

Table 2 Tolerance limit of diverse ions on the determination of 10 ng mL-1 of boron. Species Na+, K+, Mg2+, NH4+, Ba2+, Zn2+, Cd2+, Ni2+, Ca2+, SO42-, NO3-, ClFe3+, NO2-, Br-, F-, CO32-, PO43Fe2+, SCN-, CNTolerance ratio (wion/wboron) 5000:1 2000:1 500:1

3.5 Applications In order to the test reliability of the proposed method, it was applied to the determination of boron in several water samples. The results are presented in Table 3. The results are in good agreement with those obtained by ICP-AES. The results indicated that the proposed method is helpful for the determination of boron in the natural water samples.

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Table 3 Determination of boron in water samples by the proposed method Boron (ng mL-1) Recovery a (%) Added Found Potable water 41.1 2.1 5.0 45.9 1.9 96.0 10.0 51.6 2.1 105 Well water 280.3 2.1 5.0 285.5 1.4 104 10.0 289.8 1.8 95.0 Mineral water 33.0 1.4 5.0 37.87 1.3 97.4 10.0 42.8 2.6 98.0 aAverage of three determination standard deviation Sample ICP-AES (ng mL-1) 40.0 1.2

267 2.5

31.5 1.7

4. Conclusion
This study proposes the use of DLLME as a method for extraction and preconcentration of boron as a prior step to its determination by spectrophotometry. The DLLME is versatile and simple and provides good enrichment factors and efficient separation. In comparison to solvent extraction methods, it is much safer, since only a small amount of the solvent is used. The results of this study clearly show the potential and versatility of this method, which could be applied to monitoring of boron in water samples. Finally, the coupling of DLLME with UV-Vis spectrophotometry gave a fast and low-cost procedure for determination of boron without requiring sophisticated instruments such as electrophoresis, AAS and ICP-AES.

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