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Determination of very low amounts of chromium(III) and (VI) using dispersive liquidliquid microextraction by in situ formation of an ionic liquid followed by electrothermal atomic absorption spectrometry
Ignacio L opez-Garc a, Yesica Vicente-Mart nez and Manuel Hern andez-C ordoba*
Received 19th December 2011, Accepted 27th February 2012 DOI: 10.1039/c2ja10378h A new procedure for the determination of very low levels of Cr(III) and Cr(VI) using ionic liquid dispersive liquidliquid microextraction (IL-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS) is presented. The ionic liquid, 1-octyl-3-methylimidazolium bis(triuoromethanesulfonyl)imide ([C8MIm][NTf2]), is formed in situ by mixing 1-octyl-3methylimidazolium chloride ([C8MIm]Cl) and lithium bis(triuoromethanesulfonyl)imide ([NTf2]Li) aqueous solutions, and is used to extract complexes originating from Cr(III) and Cr(VI) with ammonium pyrrolidinedithiocarbamate (APDC). No organic solvents are required, the dispersion being due to the very ne droplets of ([C8MIm][NTf2]) originated in the aqueous solution. After centrifugation, the concentration of chromium in the sedimented phase is determined by ETAAS. The total content of chromium is measured using 0.01 mol L1 APDC at pH 1. In the presence of 0.001 mol L1 ethylenediaminetetraacetate, Cr(III) is not extracted, and the analytical signal corresponds to Cr(VI). The level of Cr(III) is obtained by difference. The enrichment factor of the procedure is 300 and a detection limit of 2 ng L1 is achieved. The relative standard deviation for 10 replicates at the 0.05 mg L1 level is close to 8%. The recoveries of spiked samples are in the 95104% range. The method is applied to the analysis of water samples as well as lixiviates obtained from toys made of plastic materials.

Introduction
In the environment, chromium is mainly present in two different oxidation states, Cr(III) and Cr(VI), which have very different effects on living things.1,2 In its trivalent form, chromium is considered as an essential element, necessary for several metabolic processes, but the hexavalent species is a highly toxic chemical. Consequently, the determination and speciation of the element are subjects of considerable interest.35 There are a large number of analytical techniques that have been suggested for this purpose2,610 but most of them are not capable of determining the analyte at the very low levels in which it may be present,9,10 especially when speciation is required, and so a preconcentration stage is often needed. Conventional liquidliquid extraction, which has been used for decades in the laboratory to improve both sensitivity and selectivity of analytical procedures, has been surpassed by miniaturized approaches that involve low amounts of organic solvents, or even none, resulting in environmentally friendly procedures.1114 The recent literature reports a multitude of new ideas that permit separation by extraction at the microscale with considerable advantages. Dispersive liquidliquid microextraction (DLLME) is one interesting way in this respect,
Department of Analytical Chemistry, Faculty of Chemistry, University of Murcia, E-30071-Murcia, Spain. E-mail: hcordoba@um.es

since the partition equilibrium is attained almost instantaneously and, at the same time, the high aqueous/organic volume ratio means that a high enrichment factor can be achieved. The usual way to carry out a DLLME process involves the injection of an appropriate mixture of extraction and disperser solvents into the aqueous sample containing the analytes, followed by centrifugation of the turbid solution and measurement of the sedimented phase by means of a suitable instrumental technique.12,1520 The replacement of volatile organic solvents by ionic liquids (ILs) has aroused considerable interest in recent years because ILs, in addition to possessing many of the advantageous properties of classic organic solvents, have very low vapour pressures and a high thermal stability.2128 These characteristics have led several authors to suggest the substitution of conventional organic solvents by ILs for microextraction purposes, including DLLME analytical procedures. In this latter case, the most common strategies for IL dispersion have been based on controlling the temperature,29 ultrasounds,30 mechanical shaking31 or even mixing with a disperser solvent.32 However, it should be noted that the use of ILs for miniaturized analytical methodologies is not exempt of problems and, when dealing with small volumes, difculties caused by viscosity may arise in handling the IL fraction and its introduction into the instrument for the nal measurement.
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In this paper, an IL-DLLME procedure followed by ETAAS measurement is used for the determination and speciation of chromium. The procedure is based on an interesting idea reported by Yao and Anderson33 for the preconcentration of aromatic compounds from water. As discussed elsewhere,33 two water-soluble reagents can be mixed so that an insoluble IL, useful for extraction purposes, is formed in situ by a simple and immediate ion-exchange (metathesis) reaction. It should be noted that this is in fact a DLLME procedure although neither a conventional organic extractant nor an additional disperser solvent is required. Dispersion in this case is due to the formation of ne droplets of the water-immiscible IL generated in situ. All the advantages of DLLME are obtained while organic solvents or other ways to produce dispersion are not needed. Such a simple way of operation permits the determination and speciation of very low amounts of chromium through the formation and extraction of complexes with ammonium pyrrolidinedithiocarbamate (APDC). Both water samples and lixiviates, obtained from toys made of painted plastic materials under suspicion of containing chromium, are used as a testing ground to assess the practical usefulness of the procedure.

Table 1 Instrumental parameters for chromium determination Parameter Lamp current/mA Wavelength/nm Spectral resolution/nm Atomizer type Injected volume/mL Chemical modier Background correction Furnace heating program Step Temperature/ C Ramp/s Hold/s 30 30 20 5 5 30 (HCl) 357.9 0.7 Pyrolytic tube with LVov platform 30 NH4H2PO4 1% m/v Zeeman

1: Dry 110 10 2: Dry 300 5 3: Pyrolysis 1100 10 2400 0 4: Atomizeab 5: Clean 2450 1 Sequence Step A: pipette the modier and run step 1 Step B: inject sample or standard and run the entire program
a

Internal argon ow stopped. b Reading step.

Experimental
Instrumentation A model 800 atomic absorption spectrometer (Perkin-Elmer, Shelton, USA) equipped with a Zeeman-effect background correction device, a transversely heated graphite tube atomizer and an AS-800 autosampler were used. For the nal recommended procedure, the autosampler was not used, and the organic aliquots were introduced into the atomizer by manual injection using a chromatographic syringe. Pyrolytic graphite platforms inserted into pyrolytically coated tubes were obtained from the same manufacturer (part number B050-4033). Argon was the inert gas, the ow rate being 250 mL min1 during all the stages except atomization, when the ow was stopped. Measurements were carried out using a chromium hollow cathode lamp (Perkin-Elmer) as the radiation source. The transient absorbance signals were acquired in the peak area mode. The instrumental parameters are summarized in Table 1. Reagents and samples All the solutions were prepared with pure water (18 MU cm) obtained with a Milli-Q academic system (Millipore, Bedford, MA, USA). To decrease the risk of contamination, no glassware was used for storing solutions, and plastic (polypropylene) vessels were used instead. The plasticware was washed with 1% (v/v) nitric acid solution, and then rinsed with water before use. However, 15 mL glass tubes were used for the DLLME procedure, since the IL formed in situ adhered on the walls of the glass to a lesser extent than on the walls of the plasticware. Chromium(III) and (VI) standard solutions (1000 mg mL1) were prepared from Cr(NO3)3$9H2O and K2Cr2O7 (Fluka, Buchs SG, Switzerland), respectively, in pure water. Working standard solutions were obtained by appropriate dilution of the stock standard solutions. A 0.5 mol L1 ammonium pyrrolidinedithiocarbamate (APDC) solution was prepared by dissolving the compound (Sigma-Aldrich Chemie GmbH, Germany) in
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high purity methanol. A 0.1 mol L1 disodium dihydrogen ethylenediaminetetraacetate (EDTA) solution was prepared in water. Solutions (1 mol L1) of 1-octyl-3-methylimidazolium chloride ([C8MIm]Cl) and lithium bis(triuoromethanesulfonyl) imide ([NTf2]Li), obtained from IOLITEC (Heilbronn, Germany), were prepared by dissolving 1.15 and 1.43 g, respectively, in 5.0 mL of ultrapure water. 1-Octyl-3-methylimidazolium bis((triuoromethyl)sulfonyl)imide ([C8MIm] [NTf2]) was also obtained from IOLITEC and used for comparison purposes. A 0.2 mol L1 aqueous solution of (1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-114) obtained from Sigma was used as sticking agent. Other chemicals used were obtained from Fluka. Bottled water samples were purchased in a supermarket, and tap water was collected from the mains supply of the University of Murcia. Seawater samples were obtained from near the shore close to a harbour in southeastern Spain. The samples were ltered and maintained in plastic containers at 4  C until they were analyzed (less than 48 h). Ten toys made of plastic materials and of different shapes and colours were purchased in low-priced markets. None of the samples analyzed was marketed as made in the EU. The toys were thoroughly washed with water and dried at room temperature. Then, depending on their physical characteristics, they were broken into small pieces, or the supercial paint was scraped off, to be submitted to lixiviation with diluted hydrochloric acid. General procedure To 10 mL of sample solution containing chromium in the 0.005 0.1 mg L1 range, placed in a 15 mL glass tube, 1 mL of a 1 mol L1 nitric acid solution and 200 mL of a 0.5 mol L1 APDC solution were added. Then 100 mL of the [C8MIm]Cl solution and 100 mL of 0.2 mol L1 Triton X-114 solution were added, and the mixture homogenized by gently shaking. Next, 100 mL of the [NTf2]Li solution were incorporated, providing a turbid solution resulting from the dispersion of the IL formed. After
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centrifugation at 3000 rpm for 5 min, a low volume (33 1 mL) of the IL was recovered in the bottom of the tube. Using a chromatographic-type syringe provided with a polytetrauoroethylene tube in its tip to avoid physical contact between the plunger of the syringe and the IL, 30 mL were taken, injected into the electrothermal atomizer, and the program given in Table 1 was run. The analytical signal obtained corresponded to the total chromium content (Cr(III) + Cr(VI)). To determine Cr(VI), the procedure was repeated, again using a 10 mL sample aliquot but incorporating, in addition, 100 mL of a 0.1 mol L1 EDTA solution immediately before adding the acid and APDC solutions. The Cr(III) content was calculated from the difference between the result obtained for the total chromium content (rst measurement) and that for the Cr(VI) content (second measurement). Calibration was carried out using aqueous standard solutions of Cr(III) and Cr(VI) submitted to the above DLLME procedure. Procedure for water samples and for lixiviates of plastic toys The water samples were directly submitted to the general procedure without any additional treatment. To obtain lixiviates from the toy samples, portions of 300 mg were treated with 15 mL of a 0.1 mol L1 hydrochloric acid solution using magnetic stirring for 2 h at 37  C. The resulting suspensions were ltered through a 0.45 mm membrane lter before submitting a 10 mL aliquot to the general analytical procedure.

counterpart. When both water-soluble reagents are mixed, a turbidity due to the formation of insoluble 1-octyl-3-methylimidazolium bis((triuoromethane)sulfonyl)imide ([C8MIm] [NTf2]) is observed. The metathesis reaction was then: [C8MIm]Cl + [NTf2]Li / [C8MIm][NTf2] + LiCl The idea was originally used for preconcentrating aromatic compounds from water followed by a liquid chromatographic separation.33 In the case presented here, the generation of the microdroplets cloud is used to preconcentrate the complexes that APDC forms with chromium ions. Some relevant properties of the chemicals used are summarized in Table 2. It should be noted that the viscosity of the IL formed, which remains liquid at room temperature, allows for convenient manipulation. It was experimentally found that mixing 100 mL of 1 mol L1 [C8MIm]Cl with 100 mL of 1 mol L1 [NTf2]Li and 5 mL aqueous phase, followed by centrifugation, resulted in approximately 33 mL of IL in the bottom of the tube, which agrees35 with the theoretical prediction, taking into account the [C8MIm][NTf2] density. The preliminary experiments showed that, after centrifuging the turbid solution, some IL droplets remained on the walls of the centrifuge tube, and reproducibility was affected. To overcome this drawback, several anti-sticking agents,36 namely Triton X-100, Triton X-114, Tween 20 and Span 20, were assayed. Maximum and reproducible volumes for the recovered IL were obtained when the metathesis reaction was carried out in the presence of 0.004 mol L1 Triton X-114. For chromium extraction, ammonium pyrrolidinedithiocarbamate (APDC) was used. This chemical37 leads to neutral compounds with both Cr(III) and Cr(VI),38 and the literature reports that modication of the experimental conditions allows the selective complexation of these species, in such a way that speciation can be achieved.10,3945 The excellent complexing properties of APDC have already been used for several recent microextraction processes.13,4648 A number of experiments were devoted to studying the effect of pH and APDC concentration on the extraction of both Cr(III) and Cr(VI) in [C8MIm][NTf2] in a search for experimental conditions that would allow speciation without the need for heating or any other additional treatment. As can be seen in Fig. 1A, Cr(VI) is completely extracted in an acidic medium (pH 1), even when using very low APDC concentrations. In contrast, maximum extraction of Cr(III) requires the APDC concentration to be raised to 0.01 mol L1. Taking into account the data shown, it is clear that the total level of chromium can be determined provided that the APDC concentration is 0.01 mol L1 or higher and that the pH is unity. Such a degree of acidity is easily obtained by incorporating 0.1 mol L1 nitric acid into the sample without the need for a buffer solution. Although from the data given in Fig. 1 and in accordance with previous reports46 it

Results and discussion

Optimization of the DLLME conditions The use of ILs instead of organic solvents for microextraction purposes is greatly facilitated if the ILs in question have low solubility in water, as well as low viscosity, a double condition which is not easily met. An interesting way to overcome this, while at the same time providing additional advantages, has recently been reported by Yao and Anderson,33 who suggested mixing a water-soluble precursor with an ion-exchange reagent, in such a way that an in situ metathesis reaction immediately gives rise to a water-immiscible IL. This produces microdroplets with a large surface in contact with the aqueous phase, so that a DLLME process results. All the advantages of DLLME are obtained without the need for a specic disperser solvent, heating/cooling cycles or ultrasound treatment. With this in mind, several precursors were assayed to obtain turbid solutions that could be used to extract very small amounts of chromium from aqueous solutions. Excellent results were found when 1-octyl-3-methylimidazolium chloride ([C8MIm]Cl)34 was used to provide a voluminous cation, and mixed with lithium bis(triuoromethanesulfonyl)imide ([NTf2]Li) as the anionic
Table 2 Ionic liquids used in this work Substance 1-Octyl-3-methylimidazolium chloride Lithium bis(triuoromethylsulfonil)imide 1-Octyl-3-methylimidazolium bis((triuoromethyl)sulfonyl)imide Abbreviation ([C8MIm]Cl [NTf2]Li [C8MIm][NTf2]

Molecular formula C12H23ClN2 C2F6LiNO4S2 C14H23F6N3O4S2

Molecular mass/g 230.78 287.08 475.47

r/g cm3 1.01 1.33 1.33

h/cp 337 119

Melting point/ C 12.4 234

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calibration lines obtained from solutions that were not extracted. The results were very similar for Cr(III) and Cr(VI). When 5 and 10 mL were used for the aqueous phase, the experimental enrichment factors calculated were 152 and 301, respectively. It should be noted that these values are practically identical to the ratio of the volumes of the aqueous sample used and the IL recovered, conrming the DLLME was complete. Additional experiments were devoted to checking the effect of the extraction time, dened as the interval of time elapsed from the mixing of reagents until the beginning of the centrifugation stage. Maximum analytical signals for chromium were obtained even with an extraction time as short as 15 s. The extraction is practically instantaneous, conrming the efciency of the dispersion process. On the other hand, it was experimentally found that the incorporation of up to 1 mol L1 sodium chloride into the aqueous sample did not affect the analytical signal, which suggests that the procedure could be suitable for seawater samples. Optimization of the furnace heating program The presence of the IL used as acceptor affected the atomization prole of chromium in ETAAS, and so the conditions used for the heating program in the electrothermal atomizer were optimized in order to obtain maximum analytical signals. As can be seen in Fig. 2, which shows several atomization proles obtained using 2500  C as the atomization temperature, the signal obtained in the presence of the IL (curve b) was about 40% lower than that obtained in its absence (curve a). This decrease could not be overcome when the atomization temperature was varied within a wide range, and so several chemical modiers, added as solutions or used as impregnations of the pyrolytic atomizers, were assayed. The use of 15 mL of 1% (m/v) ammonium dihydrogen phosphate proved effective (curve c), leading to a considerable improvement in sensitivity. This simple, nonexpensive chemical is consequently recommended for chemical modication. The results for the pyrolysisatomization curves obtained for chromium solutions submitted to the extraction procedure are given in Fig. 3. Maximum signals were obtained when 1100 and

Fig. 1 Effect of APDC concentration on the extraction of Cr(VI)APDC (A) and Cr(III)APDC (B) complexes at different pH values (1, 4 and 6, curves a, b and c, respectively). Chromium concentration was 0.05 mg L1 in all cases.

should be possible to extract Cr(VI) selectively, a small proportion of the trivalent form is also extracted. To achieve complete separation, the addition of EDTA to the sample was assayed. Note that both APDC and EDTA compete for Cr(III), and the kinetics of the formation of the Cr(III)EDTA complex is slow. However, when the EDTA concentration was raised to 0.001 mol L1, the complex formed rapidly, with no interference on the part of APDC, and speciation could be achieved. The volume of both the aqueous phase and the nal IL recovered must be taken into account in order to obtain a high preconcentration. Since the volume of the IL sedimented after the centrifugation stage cannot be very low if a suitable aliquot is to be taken and injected into the electrothermal atomizer, the volumes of both [C8MIm]Cl and [NTf2]Li were always kept at 100 mL. On the other hand, because of the very low solubility of the nal IL in water, the volume of the sedimented phase was checked to be 33 1 mL, irrespectively of the variation in volume (210 mL) of the aqueous phase. The experimental results showed that the concentration of chromium in the nal IL was directly related to the chromium concentration in the initial aqueous sample, indicating that extraction was practically complete. Several experiments were carried out to calculate the extraction efciency by means of two successive extractions of the same sample. The calculations give 99 4 and 98 5% for Cr(III) and Cr(VI), respectively. The enrichment factors were calculated using the ratios between the slopes of calibration lines obtained from aqueous solutions submitted to the DLLME procedure and the slopes of
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Fig. 2 Atomization prole of chromium (1.5 pg) in 0.1 mol L1 nitric acid solution (curve a). Curve b corresponds to the same solution in the presence of IL. Curve c as b but using 0.1% m/v ammonium dihydrogen phosphate solution as a chemical modier.

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Analytical gures of merit Using the conditions described in the Experimental section, a linear relationship between the analytical signal and the chromium concentration in the aqueous phase was veried in the 0.0050.1 mg L1 range (linear equation: Y 5.412x + 0.037). The detection limit, calculated on the basis of three times the standard deviation of y-residuals from the calibration graph (sy/x) was 0.002 mg L1. The repeatability was estimated from ten consecutive experiments at the 0.05 mg L1 level, and the relative standard deviations (RSDs) were 7.2 and 8.1% for Cr(VI) and Cr(III), respectively. The reproducibility was calculated from ten measurements obtained on ve consecutive days, and the RSDs were 10.5 and 11.1% for Cr(VI) and Cr(III), respectively. These values slightly improved when the volume of the aqueous sample was decreased from 10 mL to 5 mL. In such a case, the RSDs were 5.2 and 6.1% for repeatability and 8.3 and 8.6% for reproducibility, for Cr(VI) and Cr(III), respectively. Additional experiments were made using very different proportions of both trivalent and hexavalent chromium, and the recoveries are given in Table 3. A comparison of the main characteristics of the procedure here studied with others reported in the recent literature for the determination of chromium using microextraction techniques is given in Table 4. Since the nal measurement involves ETAAS, the selectivity was excellent. It was experimentally veried that, as expected, the ions commonly present in water samples did not affect the results. However, the analytical signals decreased when relatively high concentrations of ions that can react with APDC were present. Mn(II), As(III) and (V), Sb(III) and (V) and Se at

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Fig. 3 Pyrolysis (a and a0 ) and atomization (b and b0 ) plots obtained in [C8MIm][NTf2] after extracting the APDC complex from a 0.07 mg L1 chromium solution. Ammonium dihydrogen phosphate solution was used as a chemical modier in plots a and b. Plots labelled as a0 and b0 were obtained in the absence of the modier.

2400  C were used as the calcination and atomization temperatures, respectively, and these are the values recommended. The heating program nally optimized is given in Table 1. It should be noted that the program uses two drying stages. Firstly a 15 mL aliquot of the modier solution is injected and dried. Then, after cooling the atomizer, the IL aliquot is injected and the entire program is run. This way of operation proved effective to bring about chemical modication by the phosphate solution and to completely remove any residue of aqueous solution before the calcination temperature was reached.

Table 3 Results (mean s, n 5) for the determination of Cr(VI) and Cr(III) in aqueous solutions Cr(VI)/Cr(III) ratio 0.1 1 10 Cr(VI)/mg L1 Added 0.01 0.1 0.1 Found 0.011 0.002 0.101 0.006 0.095 0.005 Recovery (%) 110 101 95 Cr(III)/mg L1 Added 0.1 0.1 0.01 Found 0.098 0.003 0.106 0.005 0.009 0.002 Recovery (%) 98 106 99

Table 4 Characteristics of similar microextraction procedures for the determination of chromium Preconcentration/ separation technique SDME + SIA DLLME CPEb USA-DLLMEc CMEd SPME DLLME SFO-DLLMEg SFO-DLLME DLLME DLLME
a

Species Cr(VI) Cr(III), Cr(III), Cr(VI) Cr(III) Cr(III) Cr(VI) Cr(III) Cr(III), Cr(VI) Cr(III),
a

Chelating agent APDC None APDC APDC APDC None Na-DDTC PADAPf None APDC APDC

Acceptor phase Toluene Cl4C Aliquat 336 + Triton X-114 [Hmin][PF6] ZrP SWCNTse Cl4C 1-Undecanol TTAi Cl4C [C8MIm][NTf2]

Detection technique ETAAS FAAS ICP-MS ETAAS ETAAS FAAS ICP-OES ETAAS ETAAS LA-ICP-MSj ETAAS

Linear range/ mg L1 0.56 0.320 0.110, 0.35 0.58 0.042100 50010 000 1750 0.21.3h 0.030.13 0250 0.0050.1

EF 20 270 10 300 10 30 8 800 327 154 300

LOD/ mg L1 0.02 0.08 0.01, 0.025 0.07 0.042 4.08 0.27 0.2h 0.006 0.1 0.002

Ref. 13 46 47 48 49 50 51 52 53 54 This work

Cr(VI) Cr(VI)

Cr(VI) Cr(VI)

Single drop microextraction and sequential injection analysis. b Cloud point extraction. c Ultrasonic probe-assisted dispersive liquidliquid microextraction. d Capillary microextraction with ZrP-coated capillary. e Single-walled carbon nanotubes. f 2-(5-Bromo-2-pyridylazo)-5(diethylamino)phenol. g Solidication of oating organic drop dispersive liquidliquid microextraction. h ng L1. i 1-Undecanol containing 2thenoyltriuoroacetone. j Dried-droplet laser ablation ICP-MS; EF enrichment factor.

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Table 5 Determination of Cr(VI) and Cr(III) in water samples Cr(VI)a/mg L1 Sample TW
b

Cr(III)a/mg L1 Found 0.098 0.003 0.150 0.004 0.197 0.005 0.022 0.003 0.071 0.004 0.121 0.005 0.025 0.003 0.074 0.004 0.125 0.005 0.032 0.004 0.083 0.004 0.131 0.005 0.026 0.003 0.075 0.003 0.125 0.004 0.008 0.004 0.054 0.004 0.106 0.005 0.033 0.003 0.084 0.004 0.135 0.004 0.038 0.003 0.086 0.004 0.137 0.005 0.141 0.003 0.190 0.004 0.243 0.004 Recovery (%) 104 99.5 98 99 98 100.5 103 95 97 99 92 98.5 102 102.5 97 99 99 102 Added 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1
d

Added 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1 0 0.05 0.01 0 0.05 0.1 0 0.05 0.1 0 0.05 0.1

Found <LOD 0.049 0.003 0.101 0.004 0.014 0.003 0.063 0.004 0.115 0.005 <LOD 0.049 0.004 0.100 0.004 <LOD 0.051 0.004 0.099 0.005 0.012 0.003 0.060 0.003 0.110 0.004 <LOD 0.051 0.003 0.098 0.004 0.029 0.003 0.078 0.004 0.129 0.005 0.059 0.004 0.108 0.004 0.159 0.005 0.043 0.003 0.094 0.004 0.142 0.005

Recovery (%) 98 100.5 98 100.5 99 100.5 101 99 101 98.5 102 98.5 99 100.5 99 100.5 102 99.5

BMWc 1

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BMWc 2 TW + ORSd BMCWe 1 BMCWe 2 SWf 1 SWf 2 SWf 3

a e

Mean value standard deviation (n 3). b TW: tap water. c BMW: bottled mineral water. BMCW: bottled mineral carbonated water. f SW: seawater.

TW + ORS: tap water with reverse osmosis system.

concentrations below 1 g L1 did not interfere. Hg(II) and Fe(III) were tolerated up to 0.5 g L1, Cu(II), Co(II) and Zn(II) up to 0.1 g L1, while the level of tolerance for Pb(II), Cd(II) and Ni(II) was 0.05 g L1. Note that these results mean high interferent/ analyte ratios and, due to the sensitivity of the procedure, most of them could be overcome by simply diluting the sample solution. Analysis of real samples The optimized procedure was applied to water samples of different origins. Because of the very low concentrations involved, the direct comparison of the results with those found by an alternative procedure was considered unreliable, and standard additions were used instead. As can be seen in Table 5, where the results are summarized, the levels of total chromium were in all cases below 0.2 mg L1, a concentration so low that does not represent a risk. The high recoveries found in all the experiments again conrm the reliability of the procedure. On the other hand, a study was made as regards the possible release of small amounts of chromium from toys used by children. The hand-to-mouth activity developed by children could imply a risk to health due to the presence of chromium in the toys, especially in those painted with brilliant colors. To this effect, the samples were submitted to a treatment regulated by the European Union,55 and recently modied,56 which assesses lixiviation from this type of samples. The maximum migration limits accepted by the normative are given in Table 6, while the values found by application of the procedure studied to several toys purchased in low-cost markets are shown in Table 7. All the
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results were clearly below the permitted limits, although two toys painted yellow gave rise to much more concentrated lixiviates of Cr(III) than the rest.
Table 6 Migration limits from toys or components of toys that should not be exceeded Childrens toys Cr(III)/mg g1 Cr(VI)/mg g1 0.02 0.005 0.2

Brittle, powder-like or pliable toy material 37.5 Liquid or sticky toy material 9.4 Scraped-off toy material 460

Table 7 Leaching of chromium from toy samples Content founda/ng g1 Sample Pink cat Blue kitchen set Yellow kitchen set Pink kitchen set Violet kitchen set Brown kitchen set Green kitchen set Blue ball Yellow ball Pink ball
a

Cr(III) 4.9 0.5 1.9 0.5 42.5 0.5 4.8 0.5 2.6 0.5 3.7 0.5 7.5 0.5 3.3 0.5 22.1 0.5 2.6 0.5

Cr(VI) 2.9 2.1 2.9 2.3 2.8 1.9 2.8 2.1 3.5 2.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Mean value standard deviation (n 3).

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Conclusion
The procedure here described is easy to carry out, involves minimal amounts of organic compounds and permits very high sensitivity for chromium determination and speciation. However, due to the characteristics of the detector used (ETAAS) and to the viscosity of the ionic liquid, which hinders the use of an autosampler, the degree of automation is low.
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Acknowledgements
The authors are grateful to the Spanish MICINN (Project noma de la CTQ2009-08267/BQU) and to Comunidad Auto n de Murcia (CARM, Fundacio n S Regio eneca Project 11796/PI/ 09) for nancial support. YVM also acknowledges a fellowship of MICINN.

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This journal is The Royal Society of Chemistry 2012