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Use of silica gel chemically modied with zirconium phosphate for preconcentration and determination of lead and copper by ame atomic absorption spectrometry
E. Matoso, L.T. Kubota, S. Cadore *
Departamento de Quimica Analitica, Instituto de Qu mica, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, SP, Brazil Received 6 August 2002; received in revised form 24 February 2003; accepted 26 February 2003

Abstract An analytical method using silica gel chemically modified with zirconium (IV) phosphate for preconcentration of lead and copper, in a column system, and their sequential determination by flame atomic absorption spectrometry (FAAS), was developed. Sample solutions are passed through a glass column packed with 100 mg of the sorbent material, at pH 4.5, and lead and copper are eluted with 1.0 mol l  1 HNO3 at a flow rate of 2.0 ml min  1. The extraction of copper is affected by Fe(II), Mn(II), Zn(II), Ni(II) and Co(II) while only Fe(II) interferes in the lead determination. These interferences may be overcome with an appropriate addition of a KI or NaF solution. An enrichment factor of 30 was obtained for both metals. While the limits of detection (3s) were 6.1 and 1.1 mg l 1, for Pb and Cu, respectively, the limits of determination were 16.7 and 3.3 mg l 1. The precision expressed as relative standard deviation (R.S.D.) obtained for 3.3 mg l  1 of Cu and 16.7 mg l 1 of Pb were 4.3 and 4.7%, respectively, calculated from ten measurements. The proposed method was evaluated with reference material and was applied for the determination of lead and copper in industrial and river waters. # 2003 Elsevier B.V. All rights reserved.
Keywords: Lead; Copper; Preconcentration; Atomic absorption spectrometry

1. Introduction Metals at trace levels are components of the natural biosphere. Some of them are considered essential but at high concentrations they are toxic and the range between essentiality and toxicity is

* Corresponding author. Fax: /55-19-3788-3023. E-mail address: cadore@iqm.unicamp.br (S. Cadore).

often very small [1,2]. In this aspect, reliable and sensitive analytical methods have an important role to evaluate the environmental impact of metal pollutants [2]. Copper occurs in nature as mineral compounds like CuS, CuS2, CuFeS2, CuSO4 /5H2O and others. More than 75% of copper that is mined is used in the electrical industries. Other applications include household, metallic blends and pigments [3]. It is an essential element for enzymes, but over a

0039-9140/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0039-9140(03)00215-7

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healthy limit it accumulates in the liver, causing dizziness, vomiting, diarrhea, transpiration and, depending on its concentration, can lead to the death [1]. Lead occurs naturally mainly as PbS and it is widely distributed all over the world. It is used in accumulators, to produce tetraethyl lead, guns, solders and X-ray equipment, among other uses [4]. This metal inhibits biosynthesis and affects the kidneys, brain cells and liver membrane permeability, reducing some of their functions [2]. It can be accumulated in the body and can promote disturbances such as nausea, vomiting, diarrhea, sweating and, in some cases, convulsions, coma and death [3]. For the quantification of low concentrations of metals it is necessary to utilize either very sensitive instrumental techniques or preconcentration methods, in order to achieve detection limits within the range of the available equipment [2]. An initial preconcentration step in samples such as seawater, natural waters and rainwater allows lower limits of detection, as well as the separation of the target metal from its matrix, which may interfere in AAS measurements [5]. This procedure is attractive when flame atomic absorption spectrometry (FAAS), a relatively simple and available technique in many laboratories, is used. Many methods, either on-line or batch systems, have been developed for the preconcentration of trace metals from various samples, including coprecipitation, electrodeposition, liquid /liquid extraction, liquid /solid extraction, cloud point extraction and the use of filter paper impregnated with a complexing agent [6]. Liquid /liquid extraction, consisting of the complexation of metals with reagents such as ammonium pyrrolidine dithiocarbamate, followed by extraction of the complex into an organic solvent like isobutyl methyl ketone [7], has been widely used but sometimes shows problems associated with the time required, reagent consumption and the formation of emulsions. By using liquid /solid extraction, the selective retention of metal ions can be carried out in two ways: (i) a complexing agent can first interact with the metal under study, present in the sample, and afterwards the resulting complex is adsorbed on a solid material with adsorbent

properties; (ii) the solid material is first modified by an adequate complexing reagent, which reacts with the metals that will be passed through the retained solid [8]. An example for the first type is the use of 1-(2-pyridylazo)-2-naphthol (PAN) as a chelating agent for metals, followed by adsorption of the resulting complex on microcrystalline naphthalene, which is then dissolved in organic solvents like dimethylformamide (DMF) for determination [9]. Some methods belonging to the second type of procedure have been proposed using polymeric resins [10] or solid materials such as activated alumina [11] or silica gel modified by a ligand or complexing reagent [12 /15]. Silica gel is one of the most used solid materials due to its well-established particle size and well-defined porosity, high surface area and high mechanical, chemical and thermal stability. Kubota et al. [16] have studied the modification of silica gel with four different groups: aminopropyl-benzenesulfonate, niobium oxide, zirconium oxide and zirconium phosphate, in batch experiments, in order to verify the adsorption behavior of amino acids. Nagata et al. [17] have observed that silica modified with zirconium (IV) phosphate increases the adsorption capacity for positive ions and can be used for the determination of some metals by X-ray fluorescence. Silica gel modified with zirconium phosphate is largely used in electrochemical procedures but its potentiality as a preconcentration material for metal ions in atomic spectrometry has not been yet explored. In order to evaluate the applicability of this material for atomic absorption determination of metals, this paper describes an analytical procedure for preconcentration of lead and copper in water samples using silica gel modified with zirconium(IV) phosphate, in a column system, and their determination by FAAS.

2. Experimental 2.1. Apparatus The absorption measurements were made with a Perkin /Elmer model 5100 atomic absorption spectrometer, equipped with hollow cathode lamps

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for lead and copper as well as a deuterium lamp for background correction, under the conditions described in Table 1. The pH measurements were made by a Hanna Instruments pH-meter equipped with a combined electrode. The preconcentration system consisted of glass columns (200 mm height /4 mm internal diameter) equipped with a Teflon tap, packed with zirconium (IV) phosphate modified silica gel, through which the solution containing the metals is passed. 2.2. Reagents All the reagents used were of analytical reagent grade. Deionized water was used throughout. Laboratory glassware was kept overnight in a 10% v/v HNO3 solution and then rinsed with deionized water (Milli-Q Water Purification System-Millipore, Bedford, USA). Standard solutions were prepared from Titrisol Lead and Copper Standard Solutions (Merck, 1000 mg l 1) and appropriate dilutions were made from these solutions, whenever necessary, with deionized water. Acetate buffer solution (pH 4.5) was prepared by mixing 60 ml of 0.2 mol l1 acetic acid and 40 ml of 0.2 mol l 1 sodium acetate solution. 2.3. Preparation of silica gel modied with zirconium (IV) phosphate , Silica gel (Fluka, average pore diameter of 60 A and particle size 0.2 /0.7 mm) was chemically modified in two steps, as described by Kubota et
Table 1 Operating parameters for ame atomic absorption spectrometer Parameter Wavelength Lamp current Slit width Acetylene flow Air flow Aspiration rate Copper 324.8 nm 15 mA 0.7 nm 1.8 l min  1 8.8 l min  1 7 ml min  1 Lead 217.0 nm 10 mA 0.7 nm 1.8 l min 1 8.8 l min 1 7 ml min  1

al. [16]: 50 g of activated silica gel were added to 11.6 g of zirconium tetrachloride, previously dissolved in 300 ml of dry ethanol. The mixture was maintained at reflux for 8 h with stirring. The resulting material was washed by decantation, dried at 150 8C for 4 h and hydrolyzed by immersing the solid in deionized water. After removing all chloride ions with deionized water, the material, called SZ, was dried at 120 8C for 5 h. In order to introduce phosphate groups onto the SZ surface, 25 g of this material were added to 200 ml of 0.1 mol l1 phosphoric acid. The mixture was kept under stirring for 10 h, at 90 8C. The resulting material, denominated SZP, was filtered and washed with deionized water and then dried in an oven at 100 8C for 4 h. The surface of SZP was characterized by XRF and BET surface analysis. The material presented 0.57 mmol g1 of zirconium and 0.45 mmol g1 of phosphate and a specific surface area of 513 m2 g  1.

2.4. General procedure The columns were packed with 100 mg of silica modified with zirconium (IV) phosphate and conditioned with a buffer solution at pH 4.5. An aliquot of the sample solution containing 50 mg of lead and 50 mg of copper was taken into a 500 ml beaker, the pH was adjusted to 4.5 and the solution diluted to 300 ml with deionized water. It was then passed through the column at a flowrate of 2.0 ml min 1. The metal adsorbed on the silica was eluted with 10.0 ml of 1.0 mol l1 HNO3. The final solution was aspirated into an air /acetylene flame and the absorbance for both the studied elements was measured against a blank prepared in a similar way. To confirm the efficiency of retention on modified silica, the solution, which passed through the column, was also analyzed by FAAS. After adequate treatment with concentrated HNO3 and heating until almost dryness the final solution was transferred to a 10.0 ml volumetric flask and aspirated into an air / acetylene flame in order to measure its absorbance.

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2.5. Regeneration of the column The modified silica gel used in the column for copper and lead preconcentration may be regenerated by using water, an NH3 solution (pH 8) and a HNO3 solution (pH 4.5), that neutralizes the effect of the eluent, reconditioning the column and allowing its re-utilization.

According to a systematic study realized by Nagata et al. [17] the ionic exchange process may be represented by the following reaction: 2SiZrP(H)  M 2 0 2SiZrP(M )  2H Using this sorption material for lead and copper preconcentration, the optimum conditions for metal extraction are associated with some parameters that are described as follows. 3.1. Effect of pH One of the most important factors in a liquid / solid adsorption procedure is the pH of the aqueous phase. The reaction between Pb or Cu and the complexing agent can be influenced by changes of pH value. In order to determine this parameter, the effect of the pH on Pb and Cu sorption onto SZP was investigated over the range from 2 to 9. Fig. 1 shows that lead and copper were effectively adsorbed in pH range 4 /5, which is in agreement with Nagata et al. [17] for the determination of lead in batch systems. At pH 4.5 it was possible to carry out the determination of both lead and copper. In order to control the pH during the analytical procedure, it was adjusted to 4.59/0.3 with a buffer solution of acetic acid/ sodium acetate. Under these conditions the determination of lead and copper yields quantitative recoveries. At pH higher than 6.0 the extraction decreases, probably due to hydrolysis with formation of lead and copper hydroxides. 3.2. Effect of ow rate for sorption

2.6. Determination of lead and copper The accuracy of the proposed method was determined using 0.1 g of certified reference material (Ounce Metal 124d-NBS), which was treated with 5 ml of concentrated HCl/HNO3 (1/3 v/v). After evaporation, 1 ml of H2O2 was added and the solution was heated. The sample was diluted to 100.0 ml with deionized water. Adequate volumes were used to determine the copper and lead content according to the general procedure. Samples of industrial waste waters from a chemical industry located near Campinas, SP, Brazil, were analyzed after filtration through a 0.45 mm membrane, using the preconcentration procedure. Samples of Atibaia River (SP, Brazil) and Capivari River (SP, Brazil) were also analyzed and the concentrations of copper and lead were determined.

3. Results and discussion Zirconium (IV) phosphate has been studied for a long time as a cationic exchange material, due to its strong acid character. Taking into account EDXRF studies, the silica gel modification can be represented as [17]:

The adsorption efficiency of ions on SZP depends on the interaction between the analyte and the reagent (phosphate). The sample flow rate during its passage through the solid material may

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Fig. 1. Effect of pH on the adsorption of 50 mg of Cu and 50 mg of Pb in a silica gel /zirconium (IV) phosphate system.

affect the effectiveness of the reaction. In this study different flow rates (1.5, 2.0, 3.0 and 5.0 ml min 1) were investigated and quantitative recoveries of both metals were obtained with 1.5 and 2.0 ml min1. Higher flow rates reduce the efficiency of the extraction, suggesting a less effective metalreagent interaction. Using 0.10 g of SZP as the solid material and considering the analytical frequency, a flow rate of 2.0 ml min 1 was selected for retention of the metals.

3.4. Study of the column capacity The column capacity for lead and copper was evaluated considering both the aqueous phase volume which passes through the column and the amount of the metals that are retained in this process. Sometimes it may be necessary to use a large volume of sample in order to reach the detection limit of the technique, mainly if the concentration of the analyte is very low. Considering a column of 110 mm length and 4.5 mm i.d. filled with 0.10 g of silica gel modified with zirconium phosphate, the effect of sample volume on lead and copper extraction was studied by passing 50 mg of Pb(II) and 50 mg of Cu(II) in increasing volumes, in a range from 50 to 500 ml. Recoveries of 99% were obtained with volumes up to 400 ml (corresponding to a preconcentration factor of 16, when 25.0 ml of eluent was utilized) and of 95% with 500 ml (preconcentration factor of 20) for both elements. The preconcentration factor may be enhanced to 30 if metal ions are eluted with 10.0 ml of 1.0 mol l1 HNO3. To determine the amount of analyte retained on the column, that is, the maximum quantity of the elements, which can be sorbed by SZP, increasing quantities of Cu and Pb were introduced into the column. It was possible to obtain quantitative recovery by using 0.1 mg of modified silica and up

3.3. Conditions for elution Several preconcentration papers employing modified silica gel use nitric acid as eluent, in concentrations varying from 0.1 to 4.5 mol l 1 [18 /20], as well as hydrochloric acid [12]. Preliminary studies showed that hydrochloric acid affects this kind of sorption material, leaching the phosphate and leading to the formation of chlorocomplexes [21]. Due to this and also considering the determination by FAAS, nitric acid was evaluated in this work at three different concentrations, 0.25, 0.5 and 1.0 mol l1 and quantitative recoveries of both metals were obtained with 1.0 mol l1 HNO3. Concerning the flow rate for the elution, a study carried out with 1.5, 2.0, 3.0 and 5.0 ml min 1 showed that 2.0 ml min 1 was the most adequate for the elution of the metal ions.

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to 0.5 mg of Cu(II) and 2.0 mg of Pb(II), that means that the column capacity was 175.2 mmol g1 of modified silica (78.7 mmol g1 for Cu and 96.5 mmol g1 for Pb). Concerning the regeneration of the column, metal recovery was evaluated and quantitative extraction was observed after using the same solid material five times for Pb(II) and Cu(II). After this, the packing of the column has been sufficiently modified to prejudice the successive passages of the sample and eluent solutions, mainly considering the time spent for the preconcentration step. 3.5. Interference studies The complexing reagent used for the modification of silica gel may interact with other metals, according to the experimental conditions. In order to verify the selectivity of the proposed method, solutions containing 50 mg Cu(II) and 50 mg Pb(II) in the presence of Al (III), Fe(II), Cd(II), Co(II), Ni(II), Zn(II) and Mn(II) were prepared and the recovery of copper and lead were established. Results showed that the extraction of Pb(II) was affected only by the presence of Al(III) and Fe(II) in amounts higher than 0.15 mg. For Cu(II), it was observed that the presence of 0.15 mg of Al(III), Fe(II), Co(II), Ni(II), Zn(II) and Mn(II) decreased the analytical signals. No effect of nitrate, chloride, phosphate or sulfate was observed at a proportion of 1:200 (metals:anions). There was no evidence of interference of Cu(II) and Pb(II) in the determination of lead and copper, respectively, even in the presence of a great amount of one analyte with relation to the other. The use of anions to eliminate metal interference was evaluated, considering either their capacity for complex formation with the interferent species or their precipitation with the foreign metal. Good results were obtained when a 0.1 mol l 1 solution of NaF was used [22]. It allows a recovery higher than 93% for Cu(II) and 99% for Pb(II) in the presence of 0.15 mg of each Fe(II), Co(II), Ni(II), Zn(II) and Mn(II) ions. Probably, the interaction between F ions and the interferent species leads to the formation of species, which interact less with SZP than it does copper and lead.

3.6. Figures of merit Considering that it is possible to retain 1 mg of copper and 4 mg of lead from 300 ml of solution passing through a column (110 /4.5 mm) filled with 0.10 g of SZP, the elution of the resulting complexes with 10.0 ml of 1.0 mol l 1 HNO3, at a flow rate of 2.0 ml min 1, gives a limit of determination of 3.3 mg l1 for copper and 16.7 mg l1 for lead, and an enrichment factor of 30. The precision, expressed as a relative standard deviation (R.S.D., n /10) is 4.3% for a copper solution containing 3.3 mg l 1 and 4.7% for a lead solution having 16.7 mg l 1. The limits of detection, calculated as three times the blank standard deviation were 1.1 mg l 1 for Cu and 6.1 mg l1 for Pb. The accuracy of the proposed preconcentration methodology was evaluated by means of copper and lead determination in certified sample material (NBS-Ounce metal 124d). The results obtained (82.79/2.8% for Cu and 5.229/0.39% for Pb) were in good agreement with the certified values (85 and 5% for Cu and Pb, respectively). 3.7. Determination of copper and lead in waters The proposed method was applied to samples of industrial waste water from a chemical industry, after the addition of known amounts of copper and lead, and the results for the recovery of both metals are presented in Table 2. The samples of water from two rivers of State of Sao Paulo, Brazil, were analyzed using the analyte addition procedure and the results (Table 3) showed the presence of low amounts of copper and lead, that is in agreement with the permissible values of Brazilian Legislation.

4. Conclusions Silica gel modified with zirconium (IV) phosphate showed to be a good system for metal preconcentration with atomic absorption determination. The proposed methodology was simple and of low cost, mainly if more sophisticated techniques such as GF AAS or ICP OES are not

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Table 2 Recovery of copper and lead in industrial waste waters Sample Industrial waste 1 Industrial waste 2 Industrial waste 3
a

Analyte added (mg l  1) 0.30 0.50 0.80 1.20

Pb found (mg l  1)a / 0.539/0.03 0.919/0.02 1.279/0.02

Recovery (%) / 106 113 106

Cu found (mg l  1)a 0.359/0.02 / 0.769/0.02 1.219/0.05

Recovery (%) 116 / 95 101

Average of three determinations. [4] R.E. Kirk, D.F. Othmer, Encyclopaedia of Chemical Technology, vol. 14, third ed., John Wiley and Sons, New York, 1979. [5] A.M. Lopez, A. Camean, M. Repetto, At. Spectrosc. 17 (1996) 83. [6] D.E. Leyden, W. Wegscheider, Anal. Chem. 53 (1981) 1059A. [7] Standard Methods for the Examination of Wastes and Waste Water, 3-55, American Public Health Association, Washington, 1998. [8] V. Porta, C. Sarzanini, O. Abollino, E. Mentasti, E. Carlini, J. Anal. At. Spectrom. 7 (1992) 19. [9] A.T. Mohammad, P. Swati, R.K. Bansal, B.K. Puri, Talanta 45 (1997) 411. [10] S.L.C. Ferreira, J.R. Ferreira, A.F. Dantas, V.A. Lemos, N.M.L. Arau jo, A.C. Spinola Costa, Talanta 50 (2000) 1253. [11] S. Karthikeyan, T. Prasada Rao, C.S.P. Iyer, Talanta 49 (1999) 523. [12] P. Lessi, N.L. Dias Filho, J.C. Moreira, J.T.S. Campos, Anal. Chim. Acta 327 (1996) 183. [13] N.L. Dias Filho, Y. Gushikem, W.L. Polito, J.C. Moreira, E.O. Ehirim, Talanta 42 (1995) 1625. [14] O. Zaporozhets, N. Petruniock, O. Bessarabova, V. Sukhan, Talanta 49 (1999) 899. [15] E. Hosten, B. Welz, Anal. Chim. Acta 392 (1999) 55. [16] L.T. Kubota, A. Gambero, A.S. Santos, J.M. Granjeiro, J. Colloid Interf. Sci. 183 (1999) 453. [17] N. Nagata, L.T. Kubota, M.I.M.S. Bueno, P.G. PeraltaZamora, J. Colloid Interf. Sci. 200 (1998) 121. [18] E. Morosanova, A. Velikorodny, Y. Zolotov, Fresenius J. Anal. Chem. 361 (1998) 305. [19] L. Roman, E. Florean, R. Sandulescu, S. Mirel, J. Pharm. Biomed. Anal. 14 (1996) 1003. [20] H. Ji, Z. Liao, J. Sun, Z. Jiang, Fresenius J. Anal. Chem. 360 (1998) 721. [21] L.T. Kubota, Y. Gushikem, J.C. Moreira, Analyst 116 (1991) 281. [22] N. Baccan, L.M. Aleixo, E. Stein, O.E.S. Godinho, Introduc ` Semimicroana lise Qualitativa, third ed., a o a Unicamp, Campinas, 1990.

Table 3 Determination of copper and lead in river waters Sample Atibaia River Capivari River
a

Pb (mg l  1)a 0.0289/0.001 0.0119/0.001

Cu (mg l  1)a 0.0439/0.002 0.0519/0.002

Average of three determinations.

available. The simultaneous preconcentration of copper and lead showed the versatility of the system, increasing the analytical frequency. The use of 100 mg of the modified silica allows the enrichment of Pb(II) and Cu(II) by a factor of 20, at least, and the modified material can be reused five times, for Pb and Cu. The determination of Pb and Cu in certified reference material showed good accuracy. The proposed procedure can be successfully applied for the determination of Pb(II) and Cu(II) in industrial and river water samples.

Acknowledgements The authors thank Carol H. Collins for assistance with the English manuscript.

References
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