Spectrochimica Acta Part B 57 (2002) 21752180

Technical note

Determination of lead in seawater by inductively coupled plasma optical emission spectrometry after separation and preconcentration with cocrystallized naphthalene alizarin
Marcia Sousa Bispoa, Maria das Gracas Andrade Korna,*, Elane Santos da Boa Mortea, Leonardo Sena Gomes Teixeiraa,b
a

Salvador, Bahia 40170-290, Brazil Universidade Federal da Bahia, Instituto de Qumica, Campus Universitario da Federacao, b Departamento de Engenharia e Arquitetura, Universidade Salvador Unifacs, Av. Cardeal da Silva 132, Salvador, Bahia 40220-141, Brazil Received 17 May 2002; accepted 20 August 2002

Abstract An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 89, and the metal was eluted using 5.0 ml of 2 mol ly1 nitric acid. The effect of NaCl, KCl, BaCl2 , CaCl2 , Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% myv) with Pb (50 mg) was prepared and the recommended procedure applied. The Na3PO4 was found to interfere; the other electrolytes did not interfere up to 5% myv. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 mg ly1, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.84.6%, and the recovery of lead added to seawater samples was 9597%. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Lead; Naphthalene; Alizarin; ICP OES; Saline samples

1. Introduction Determination of trace metals in environmental

This paper was presented at the 7th Rio Symposium on Atomic Spectrometry, held in Florianopolis, Brazil, April 2002 and is published in the Special Issue of Spectrochimica Acta Part B, dedicated to that conference *Corresponding author. Fax: q55-71-2374117. E-mail address: korn@ufba.br (M.G.A. Korn).

samples is a subject of considerable interest because trace metals play important roles in biological processes both as essential components and toxins w1x. Among these, lead, even at very low concentrations, is a well-known element with toxic effects for animals and humans. Cumulative poisoning effects of lead are serious hematological damage, anemia, kidney malfunctioning and brain damage w2,3x. For humans, the main lead sources

0584-8547/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 5 8 4 - 8 5 4 7 0 2 . 0 0 1 7 9 - 9

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are water and food, and therefore rapid and sensitive methods must be accessible for its determination in these samples w4x. Inductively coupled plasma optical emission spectrometry (ICP OES) can be used to determinate lead at low concentration levels in saline matrices, but previous separation and pre-concentration steps are usually required. There are several pre-concentration methods for Pb(II) described in the literature, such as liquidliquid extraction, ion exchange and solid phase extraction (SPE). SPE has a number of attractive features compared with traditional extraction techniques. It is fairly simple, inexpensive, can be used in the field, needs relatively little toxic solvents, and can be easily automated w2,5,6x. As an effective technique for separation and pre-concentration of trace elements, SPE with naphthalene has received great attention in recent years. Due to its simple procedure, rapid phase separation and high extraction capacity, SPE with naphthalene has great prospect in trace and ultratrace analysis w6x. Alizarin (1,2-dihydroxyanthraquinone) is an ochre-yellow powder that melts at 290 8C and sublimes above 110 8C. Alizarin is soluble in 300 parts of water, it is moderately soluble in alcohol, but is quite soluble in hot methanol, benzene, ether, glacial acetic acid, acetone, carbon disulfide, and pyridine. Due to its structure, alizarin reacts with many metallic ions to form stable complexes. Other elements that may be detected or determined with the aid of alizarin are copper, indium, uranium, platinum, bismuth, chromium, scandium, mercury and titanium w7x. The complexation reaction between alizarin complexan and Pb(II) has been studied by spectrophotometric method w8x and preconcentration methods with the association between alizarin and different solid supports have been investigated w9,10x. The association of complexing agents and naphthalene has been applied to the extraction of metal complexes. In these systems the metal ions react with the chelating agent to form a complex, which is extracted with naphthalene. In this way, a method for the determination of lanthanum, europium and ytterbium after solidliquid extraction

with microcrystalline naphthalene was developed w11x. Zinc, cadmium and lead were determined by a spectrophotometric method after extraction of their morpholine-4-carbodithioates into molten naphthalene w12x. Another procedure describes atomic absorption spectrometric determination of zinc after pre-concentration with the ion pair of 2(5-bromo-2-pyridylazo)-5-diethylaminophenol and ammonium tetraphenylborate on naphthalene w13x. In this work, a new pre-concentration and separation method has been developed using alizarin red (1,2-dihydroxyanthraquinone) as lead chelating agent and naphthalene as the solid phase extractor. The developed method was applied for the determination of lead in seawater samples by ICP OES. 2. Experimental 2.1. Apparatus An Applied Research Laboratories model 3410 minitorch sequential inductively coupled plasma spectrometer (Valencia, CA), equipped with an IBM PC-AT computer (Armonk, NY) was used for lead determination. The emission intensity measurements were made under the conditions shown in Table 1. A DIGIMED DM-20 digital pH meter (Sao Paulo, Brazil) was used to measure the pH values. 2.2. Reagents and solutions All reagents were of analytical grade unless otherwise stated. Ultrapure water from Milli-Q water purification system (Millipore, Bedford, MA) was used to prepare all solutions. The laboratory glassware was kept overnight in a 10% nitric acid solution. Before use, the glassware was washed with deionized water and dried in a dustfree environment. The lead stock solution was prepared from Titrisol concentrates (Merck, Darmstadt, Germany) to a final concentration of 1000 mg mly1. The working solutions were obtained by dilution of the stock solution with deionized water.

M.S. Bispo et al. / Spectrochimica Acta Part B 57 (2002) 21752180 Table 1 Operating parameters for the inductively coupled plasma spectrometer Incident output power Reflected power Nebulizer Plasma gas flow rate Auxiliary gas flow rate Aerosol carrier gas flow rate Solution uptake rate Wavelength Signal integration time Integration for determination

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650 W -5 W Glass (Meinhard Associates, Santa Ana, CA) 7.5 l miny1 0.8 l miny1 0.8 l miny1 2.5 ml miny1 220.353 nm 5s 3

The pH of the working solution was adjusted to pH values of 3, 6 and 810 using buffer solutions of glycine, Tris(hydroxymethyl)aminomethane and ammonium, respectively. The glycine buffer was prepared by diluting 50 ml of 0.2 mol ly1 glycine solution and 1.14 ml of 2 mol ly1 HCl to 1 l with deionized water. The Tris buffer was prepared by diluting 50 ml of 0.2 mol ly1 Tris solution to 200 ml. The ammonium buffer was prepared using 53.5 g of NH4Cl and 500 ml of 2 mol ly1 NH3 solution diluted to 1 l with deionized water. Sulfuric acid, nitric acid and hydrochloric acid were of suprapure quality (Merck). The alizarin red (Merck) was used as received. The samples analyzed were collected from seawater in Salvador, Bahia and filtered through 0.45 mm Millipore membrane and acidified with 1% v y v HNO3. 2.3. Preparation of alizarin red-naphthalene solid phase Naphthalene (80 g) was impregnated with alizarin red (0.8 g) in the presence of 1 l of acetone (Merck) for 30 min by using a magnetic stirrer. The mixture was transferred to a beaker with deionized water in order to initiate the naphthalenealizarin red cocrystallization process. The solid phase was vacuum filtered, dried and stored for further use. 2.4. Procedure for the sorption of lead in the solid phase Ten to two hundred milliliters of sample containing up to 20 mg of lead were placed in conical

flasks, and 10 ml of ammonium buffer solution pH 8.1 was added, followed by 0.5 g of the solid phase. The flask was closed with a stopper and mechanically shaken for 5 min. The Pb(II) was quantitatively retained, and the solid mass, consisting of naphthalene and metal complex, was separated by filtration on filter paper and washed with 5 ml of 2 mol ly1 HNO3 to desorb the lead from the phase. The resulting solution was analyzed by ICP OES at a wavelength of 220.353 nm. 3. Results and discussion Several parameters were studied to determine the optimum conditions for quantitative recovery of lead by using naphthalenealizarin red as solid phase: pH, reaction time, mass of solid phase, eluent type, sample volume, and sorption capacity. 3.1. Effect of pH on lead sorption Extraction was carried out by the general procedure at different pH values, keeping other conditions constant. The effect of pH on the recovery of Pb(II) was examined and the experimental results indicated that lead recovery is maximum and quantitative ()95%) within a pH range from 8.1 to 9.1. A pH value of 8.1, controlled with ammonium buffer, was selected for subsequent experiments. 3.2. Effect of mass of solid phase The mass of solid phase was varied between 0.1

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and 1.0 g under optimum conditions. Results demonstrated that 0.5 g of solid phase was sufficient for quantitative retention of Pb(II). 3.3. Effect of shaking time The effect of extraction time between lead and solid phase was studied by varying the shaking time from 1 to 30 min. It was observed that quantitative lead recovery ()95%) was obtained after a shaking time of 5 min. This shaking time was therefore chosen in all future experiments. 3.4. Effect of volume of aqueous phase As the volume of solid phase is small compared with that of the aqueous phase, it was important to study the effect of the latter on the extraction of Pb(II). The volume of the aqueous phase was varied from 10 to 1000 ml, and the extraction was found to be quantitative when the volume of the aqueous phase did not exceed 200 ml. 3.5. Retention capacity of the solid phase The sorption capacity of the naphthalenealizarin solid phase for lead was determined using 50 ml of deionized water, 10 ml of ammonium buffer (pH 8.1), 0.5 g of solid phase and a set of solutions containing varying amounts of lead in the range of 51000 mg. Results demonstrated that 0.5 g of solid phase had a capacity to retain up to 200 mg of Pb(II), hence, the phase had a sorption capacity of 1.93 mmolPb gy1 of solid phase. 3.6. Choice of eluent Sulfuric acid, nitric acid and hydrochloric acid in different concentrations (2.0; 3.0; 4.0 and 6.0 mol ly1) and volumes (18 ml) were tried to desorb the lead from the solid phase. It was essential to select an eluent that could also be used for ICP OES measurements without problems. Hence, organic solvents could not be used for that purpose. The best results for recovery of lead were obtained using nitric acid as eluent. It was found

that 5 ml of 2.0 mol ly1 HNO3 was sufficient to desorb quantitatively the metal. 3.7. Effect of electrolytes The effect of NaCl, KCl, BaCl2, CaCl2, Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amount of electrolyte (0.5; 1.0; 3.0 and 5.0%) with Pb (50 mg) was taken and the recommended procedure applied. Phosphate interferes in the sorption of lead in all proportions; the other electrolytes did not interfere up to 5% m y v. The effect of phosphate is due to precipitation losses of lead. 3.8. Procedural blanks and detection limit The accurate determination of lead at low concentration levels in seawater after pre-concentration requires low and reproducible blanks. Absolute blanks, based on the analysis of separate concentrates from different volumes of ultrapure water were submitted to the pre-concentration procedure. The limit of detection (3s of 30 measures of blank, where s is the S.D. of blank) for the determination of Pb was 53 mg ly1, and the limit of quantification (10s of 30 measures of blank) was 176 mg ly1. This limit remained unchanged varying the volume of blank solution between 20 and 200 ml. 3.9. Applications The experimental procedure was applied for lead determination in seawater samples (saline level ;3.5%) collected from different places of Salvador city, Bahia, Brazil. The samples were collected in urban beaches near to wastewater effluents. The results, as means of three determinations on each of four samples, are shown in Table 2 and exhibit a good precision (R.S.D. 1.84.6%). The method validation was made through spike recovery tests with the addition of 20 mg of lead, and the recovery was between 95 and 97%.

M.S. Bispo et al. / Spectrochimica Acta Part B 57 (2002) 21752180 Table 2 Determination of lead in seawater samples Sample Ondina seawater Rio Vermelho seawater Barra seawater Ipitanga seawater
a

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Added lead (mg mly1) 0 0.100 0 0.100 0 0.100 0 0.100

Found leada (mg mly1) 0.014"0.002 0.109"0.002 0.011"0.002 0.108"0.005 0.012"0.002 0.106"0.002 0.007"0.001 0.102"0.002

Recovery (%) 96 97 95 95

At 95% confidence level. and soil samples using 2,5-dimercapto-1,3,4-thiadiazole, Talanta 55 (2001) 4354. P.K. Tewari, A.K. Singh, Preconcentration of lead with Amberlite XAD-2 and Amberlite XAD-7 based chelating resins for its determination by flame atomic absorption spectrometry, Talanta 56 (2002) 735744. R. Lima, K.C. Leandro, R.E. Santelli, Lead preconcentration onto C-18 minicolumn in continuous flow and its determination in biological and vegetable samples by flame atomic absorption spectrometry, Talanta 43 (1996) 977983. Z. Zhang, M.J. Yang, J. Pawliszyn, Solid-phase microextraction, Anal. Chem. 66 (1994) 844A853A. M.C. Yebra, N. Carro, A.M. Cid, L. Pulg, Minicolumn field sampling and flow-injectionatomic absorption spectrometric determination of lead in seawater, Field Anal. Chem. Technol. 5 (2001) 239243. F.J. Welcher, Organic Analytical Reagents, vol. 4, third ed., USA, 1947, p. 409. W. Xing, F. Ingman, A photometric study of the complexation reaction between alizarin complexan and zinc(II), nickel(II), lead(II), cobalt(II) and copper(II), Talanta 29 (1982) 707711. R. Saxena, A.K. Singh, S.S. Sambi, Synthesis of a chelating polymer matrix by immobilizing Alizarin RedS on Amberlite XAD-2 and its application to the preconcentration of lead(II), cadmium(II), zinc(II) and nickel(II), Anal. Chim. Acta 295 (1994) 199204. T. Nagahiro, G.F. Wang, M. Satake, Column preconcentration of aluminium and copper(II) in alloys, biological samples, and environmental samples with Alizarin Red S and cetyltrimethylammonium-perchlorate adsorbent supported on naphthalene using spectrometry, Microchem. J. 52 (1995) 247256. B. Cai, B. Hu, H. Xiong, Z. Liao, L. Mao, Z. Jiang, Preconcentration of lanthanum, europium and ytterbium with tribromoarsenazo-cetylpyridinium bromide sup-

4. Conclusion This study demonstrated that the use of solid phase naphthalenealizarin red for the extraction of lead from seawater presents some advantages due to rapid kinetic, low consumption of reagents and eluent, good stability and a good enrichment factor (40=). The naphthalene used to prepare the solid phase was of commercial grade and the low cost of this phase is an additional advantage. Furthermore, the elution step does not involve the use of organic solvents as other procedures do. The spike recovery showed that the proposed procedure had good accuracy. The proposed method is simple and suitable for the separation and determination of lead in saline water samples. Acknowledgments The authors acknowledge the grants from CTPETRO y CNPq, SEPLANTEC y CADCT-BAHIA, PIBIC y CNPq, CNPq, FINEP and CAPES. References
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