ANALYTICAL LETTERS Vol. 37, No. 9, pp.

19091924, 2004

ATOMIC SPECTROMETRY

Determination of Trace Metals in Fuel Alcohol by FAAS Using Nb2O5 SiO2 as Sorbent Material in a Flow Injection On-Line Preconcentration System
Edson Luiz da Silva, Dilma Budziak, and Eduardo Carasek*
mica, Universidade Federal de Santa Catarina, Departamento de Qu polis, Santa Catarina, Brazil Floriano

ABSTRACT
This paper describes an on-line preconcentration system for the determination of copper(II), cadmium(II), cobalt(II), and zinc(II) in samples of fuel alcohol. The analytes were enriched in a minicolumn containing with silica gel chemically modied with niobium(V) oxide (Nb2O5 SiO2). The metals were desorbed from the minicolumn with a solution of nitric acid and determined on-line by ame atomic absorption spectrometry (FAAS). Enrichment factors for copper(II), cadmium(II), cobalt(II), and zinc(II) were 21.3, 23.1, 16.6, and 27.5, respectively, using a preconcentration time of 2 min. Detection limits for copper(II), cadmium(II), cobalt(II), and zinc(II) were 1.4, 0.2, 1.4, and 1.0 mg L21,

*Correspondence: Eduardo Carasek, Departamento de Qu mica, Universidade Federal polis, SC, Brazil; Fax: 55-48-3319711; de Santa Catarina, 88040-900 Floriano E-mail: carasek@qmc.ufsc.br. 1909
DOI: 10.1081/AL-120039435 Copyright # 2004 by Marcel Dekker, Inc. 0003-2719 (Print); 1532-236X (Online) www.dekker.com

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da Silva, Budziak, and Carasek respectively. Method precision was evaluated by analyzing an alcoholic solution containing 30 mg L21 of Cu(II), 15 mg L21 of Cd(II), 45 mg L21 of Co(II), and 15 mg L21 of Zn(II), and their respective relative standard deviation (RSD) were 1.3%, 4.2%, 1.7%, and 1.7% (n 7). The accuracy of the method was assessed by testing analyte recovery in the fuel alcohol samples. Key Words: FAAS; On-line preconcentration; Fuel alcohol; Nb2O5 SiO2.

1.

INTRODUCTION

The development of analytical methods to determine trace metals has been an aspect of interest in the research on ethanol as a fuel, because it is extensively used as automotive fuel in some countries such as Brazil, where a government program (Proalcool) was once able to replace a signicant part of the automotive eet from gasoline to alcohol propelled engines. The presence of some metal ions in ethanol fuel is generally not desirable because it may induce corrosion in the vehicle components in contact with the liquid, it promotes poor fuel performance due to oxidative decomposition reactions, and generates environmental pollution.[1 3] The conventional procedure to determine trace metals in fuel alcohol is generally tedious and involves steps such as evaporating the solvent until dryness prior to analysis, which makes it a very time-consuming method.[3] Alternative methods using organically functionalized silica gel for the column preconcentration of metal ions from alcoholic matrix have been proposed. Moreira and Gushikem[2] have preconcentrated metal ions in a glass column (40 cm high and 0.7 cm i.d.) containing 2 g of silica gel functionalized with 3(imidazolyl)propyl groups. The adsorption method was used to determine the metals in commercial ethanol by passing between 0.1 and 5.9 L of sample through the column. Lessi et al.[3] have used silica gel modied with 2,5-dimercapto-1,3,4thiadiazole to adsorb Cu(II), Zn(II), Cd(II), Ni(II), Pb(II), Co(II), and Fe(III) by column techniques. The metals in ethanol fuel were determined by AAS, after passing 0.17.0 L of sample through column with a ow rate of 5 mL min21. Dias Filho et al.[4] have investigated the preconcentration and determination of Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Fe(III) in commercial ethanol by ame atomic absorption spectrometry (FAAS), using a glass column of 20 cm height and 0.8 cm i.d. packed with 2 g of silica gel modied with benzimidazole. Between 0.2 and 6.5 L of the sample percolated through the column with ow rate of 0.51.0 mL min21. Kubota et al.[5] have described the application of immobilized silica gel with iminosalicyl for the adsorption of metal ions from ethanol and its determination by complexometric titration

Determination of Trace Metals in Fuel Alcohol by FAAS

1911

with EDTA. In this study, 100 mL of sample was percolated through a 13 0.6 cm i.d. glass column containing 1 g of sorbent with a ow rate of 2 mL min21. Prado et al.[6] have employed a 2.0-cm length glass column with 0.5 cm i.d. packed with 0.2 g of silica gel modied with 2,4-dichlorophenoxyacetic acid for the preconcentration and quantication of Cu(II), Ni(II), Zn(II), and Cd(II) from aqueous and ethanolic solutions by ICP-AES. Gomes et al.[7] have described the synthesis of silica modied with 5-amino-1,3,4-thiadiazole2-thiol groups, which was used for the preconcentration and determination of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II), and Zn(II) in fuel ethanol by FAAS, using a 15 0.6 cm i.d. glass column packed with 2 g of sorbent and 50 mL of sample with a ow rate of 2 mL min21. For inorganic functionalized silica, few studies of metal ion adsorption properties have been described in the literature. Besides, existing studies with inorganically functionalized silica gel have been carried out in aqueous matrices. Nagata et al.[8] have investigated adsorption properties of Cd(II), Pb(II), and Hg(II) on silica chemically modied with zirconium(IV) phosphate, using batch systems. Vassileva and Furuta[9] developed an on-line multi-element method for the simultaneous preconcentration and determination of many metals using a minicolumn of ZrO2 and detection by ICP-AES. Matoso et al.[10] have described the application of silica gel chemically modied with zirconium(IV) phosphate for preconcentration of lead and copper by column technique, and their determination by FAAS. Denofre et al.[11] have studied adsorption isotherms for Co(II), Ni(II), and Cu(II) by the bath technique, using Nb2O5 SiO2 as extractor material. This sorbent (Nb2O5 SiO2) has high capability of ion exchange and has been used in our laboratory to develop analytical methods, using ow injection preconcentration systems for the enrichment of copper and cadmium from aqueous samples and its determination off-line[12] and on-line[13] by FAAS. These authors do not know studies on sample preparation for enrichment of metals in fuel alcohol, using Nb2O5 SiO2 in on-line ow systems coupled to FAAS. This study is a proposal for a new method to determine traces of copper, cadmium, cobalt, and zinc in fuel alcohol. The analytes were previously enriched in a minicolumn containing Nb2O5 SiO2, and subsequently eluted with a nitric acid solution. Metals were determined on-line by FAAS.

2. 2.1.

EXPERIMENTAL Instrumentation

A Varian SpectrAA 50 (Varian, Victoria, Australia) atomic absorption spectrometer, equipped with ame atomizer and a Hitachi HLA-4S hollow

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da Silva, Budziak, and Carasek

cathode lamp, was used to determine the analytes. The integrated absorbance readings were carried out according to the operational conditions suggested by the manufacturer and with an aspiration rate of 6 mL min21. An Ismatec-IPC peristaltic pump equipped with eight channels and Tygon and Viton tubes was used to pump all the solutions through the minicolumn in the on-line preconcentration system shown in Fig. 1. Three-way solenoid valves were used to select adsorption and desorption steps of the analytes in the minicolumn. The connector of the preconcentration systems was made of Teon in a Y-shape. Polyethylene tubes of 0.8 mm were used in the ow system.

Figure 1. The on-line preconcentration system. (A): Preconcentration stage and (B): elution stage. V: valve, L: open way, D: close way, MC: minicolumn fullled with the absorbent, R: return of sample or eluent, hatched circle: valve on, and white circle: valve off.

Determination of Trace Metals in Fuel Alcohol by FAAS

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2.2.

Reagents and Solutions

All reagents used were of analytical degree. All laboratory glassware was washed with neutral detergent and kept in a 10% (v/v) nitric acid solution overnight. Afterwards it was then rinsed with water and ethanol. Working standard solutions of Cu(II), Cd(II), Co(II), and Zn(II) were prepared daily by appropriate dilution from 1000 mg L21 stock solution of the respective analytes (standard for atomic absorption from Carlo Erba) with ethanol (Merk, Darmstadt, Germany). Nitric acid solutions used as eluent in the on-line preconcentration system were prepared by diluting concentrated nitric acid (Carlo Erba, Milan, Italy) with water. Fuel alcohol samples were polis, SC, Brazil, ltered and obtained from gas stations in the area of Floriano enriched with adequate volumes of aqueous standard of the analyte in question.

2.3.

Preparation of the Solid Sorbent

About 22 g of sublimed NbCl5 was suspended in 300 mL of carbon tetrachloride and 40 mL of dry ethanol was slowly added. The mixture was stirred at room temperature for 30 min in a dry nitrogen atmosphere, until complete dissolution of the solid. When the evolution of gaseous HCl ceased, 75 g of activated silica gel (specic surface area, SBET 322 m2 g21, average pore diameter of 6 nm) was added to the solution and the mixture was reuxed for 52 hr under nitrogen atmosphere. The resulting silica was then ltered in a Schlenk apparatus, washed with anhydrous ethanol, and dried for 4 hr under vacuum at 413 K. The dry material was immersed in bidistilled water and allowed to stand for 5 days with occasional replacement of the water. The product was then ltered, washed, and dried in an oven at 373 K.

2.4.

On-Line Preconcentration System

Enrichment of the analyte was carried out in an automated ow preconcentration system similar to the one developed by Ferreira et al.[14]. The analysis module employed is composed of a peristaltic pump, four three-way solenoid valves, and a Teon minicolumn lled with 100 mg of Nb2O5 SiO2, which was coupled to the ame atomic absorption spectrometer (as shown in Fig. 1). The minicolumn with 55 mm of length and i.d. 3 mm was sealed on both ends with small glass wool beds in order to avoid loss of sorbent material. The performance of the minicolumn was stable during all experiments. The four three-way solenoid valves (Fig. 1) are represented by V1 4 and were activated by a computer program written in Quick BASIC 4.5.

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da Silva, Budziak, and Carasek

Chemical and ow parameters of the on-line preconcentration system were optimized by the uniavariate method. A volume of 10 mL of each standard alcoholic solution containing 100, 50, 100, and 50 mg L21 of Cu, Cd, Co, and Zn, respectively, was introduced into the ow system through a peristaltic pump. All assays were performed in triplicate and the optimization of the metals was carried out separately. In the adsorption stage of the analyte by active sites of the adsorbent material contained in the minicolumn (Fig. 1A), V1 was activated and the others remained turned off. A sample or standard solution was injected in the ow system through the minicolumn where ion exchange takes place. This solution owed through V1, the minicolumn, and V2, respectively, and the efuent was discarded. At this stage, a solution of nitric acid was pumped into its own container through the return line. The preconcentrated volume of the sample solution was proportional to the sample ow rate and to the time of V1 deployment. In the desorption stage, [Fig. 1(B)], V1 was turned off and V2, V3, and V4 were activated by the computer. The eluent, a nitric acid solution, passed through V2, V3, and the minicolumn, respectively. The eluate, which is the eluent plus the analyte, was introduced directly into the nebulizer combustor system of the spectrometer when it passed through V4. Eluent ow then passed through the minicolumn in reverse direction than that of the sample. Readings of the analytical signals were carried out as the peak area. As baseline of the instrument increased with time, blank reading was carried out after each replicate to be analyzed.

2.5.

Procedure to Calculate Enrichment Factor

The calibration curves without analyte pre-concentration were obtained according to the procedures described below. The on-line pre-concentration system was utilized, in which the minicolumn was substituted by a manual injector-commutator with a sampling loop, as shown in Fig. 2. The sampling loop was constructed with a polyethylene tube with 0.8 mm internal diameter. The sampling loop was lled with a concentrated solution of the analyte. At this stage [Fig. 2(A)], the V1 valve was activated for a 15-sec period, in order to insure total lling of the sampling loop. The concentrated solution excess was discarded. The volume of this sampling loop was calculated taking into consideration the elution ow rate and the time for which the transient signal was produced by the on-line pre-concentration system shown in Fig. 1. To introduce the concentrated solution into the nebulizercombustor of the spectrometer [Fig. 2(B)], the V1 valve was turned off and the injector was switched to the elution position. The V2 4 valves were then activated and a

Determination of Trace Metals in Fuel Alcohol by FAAS

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Figure 2. On-line ow system used to calculate enrichment factor. (A) injector in the ll position of the sampling loop and (B) injector in the elution position. V1 4: threeway solenoid valves, R: sample and eluent back stream.

nitric acid solution at the same concentration optimized by the proposed on-line pre-concentration system, was pumped through the sampling loop, carrying the concentrated analyte solution to the ame.

3. 3.1.

RESULTS AND DISCUSSION

Study of Chemical and Flow Variables

The effect of the sample loading ow rate on the preconcentration of the analytes was studied aiming at assessing whether the interaction between the analyte and the Nb2O5 SiO2 was fast enough for its on-line collection. Flow

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da Silva, Budziak, and Carasek

rates from 2.2 to 8.5 mL min21 were studied. The analytical signals did not vary meaningfully until ow rate of 7.5 mL min21, thus indicating a fast adsorption kinetic for the system under study. Bearing in mind that greater sample ow rates lead to higher analytical frequency, a 7.5 mL min21 sample ow rate was chosen for further work. The condition of desorption of the analytes from the minicolumn was tested with nitric acid solutions at concentrations of 0.025 3 mol L21. As shown in Fig. 3, the concentration range that showed maximal analytical signal for Cu, Cd, Co, and Zn was 0.025 1, 0.025 0.1, 0.01 0.025, and 0.025 3 mol L21, respectively. The analytical signals for Cu and Cd practically did not vary within the studied concentration range, whereas the signals for Cd and Co showed signicant decrease in higher eluent concentrations. The concentrations selected for Cu, Cd, Zn, and Co elution were 0.5, 0.1, 0.025, and 0.1 mol L21, respectively. Passage of the eluent through the minicolumn during the stage of analyte elution was kept for 45 sec in order to guarantee regeneration. The inuence of eluent ow rate on analyte desorption from the minicolumn was investigated. Figure 4 shows that analytical signals decrease slowly as eluent ow rate increases, except for Cd, whose effect was more outstanding. For eluent ow rate lower than 5.0 mL min21, the transient signal was broadened and deformed. This effect of eluent ow rate on the peak

Figure 3. Effect of nitric acid concentration on desorption of the analytes. Sorbent: 0.1 g; Cu: 100 mg L21; Cd: 50 mg L21; Co: 100 mg L21; Zn: 50 mg L21; sample ow rate: 7.5 mL min21; eluent ow rate: 5.0 mL min21.

Determination of Trace Metals in Fuel Alcohol by FAAS

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Figure 4. Inuence of eluent ow rate on analyte desorption in the minicolumn. Sorbent: 0.1 g; Cu: 100 mg L21; Cd: 50 mg L21; Co: 100 mg L21; Zn: 50 mg L21; sample ow rate: 7.5 mL min21; eluent concentration: depends on the concentration chosen above.

form obtained was also considered. Therefore, a 5.0 mL min21 ow rate was chosen for all analytes.

3.2.

Merit Analytical Parameters

Table 1 contains information about the merit analytical parameters obtained by the on-line preconcentration system shown in Fig. 1. In order to obtain these data was used a preconcentration time of 2 min. The RSD values were obtained from a solution at concentrations of 30, 15, 45, and 15 mg L21 for Cu(II), Cd(II), Co(II), and Zn(II), respectively (n 7). The detection limit was calculated as three times the RSD of the blank (n 11) divided by angular coefcient of the calibration curve. Table 2 shows the equations for the calibration curves obtained with and without the preconcentration procedure for all metals studied. Calibration curves without the preconcentration procedure were obtained by the on-line ow system depicted in Fig. 2. We used the slope ratio of these curves to calculate the enrichment factors (EF) of the proposed procedure.

1918 Table 1. Ion Cu(II) Cd(II) Co(II) Zn(II)

a b

da Silva, Budziak, and Carasek The main merit analytical parameters obtained by the proposed method. Range (mg L21) 100 200 10 100 20 100 10 200 Linearitya (R) 0.9998 0.9967 0.9969 0.9974 RSDb (%) 1.3 4.2 1.7 1.7 LODc (mg L21) 1.4 0.2 1.4 1.0 EF
d

RFe (%) 69 59 74 95

21.3 23.1 16.6 27.5

Linear correlation coefcient. Relative standard deviation. c Detection limit. d Enrichment factor. e Recovery factor.

3.3.

Fuel Alcohol Samples

The method proposed was applied to determine Cu, Cd, Co, and Zn in fuel alcohol. Samples were collected from ve gas stations within the area of Florianopolis, SC, Brazil. For Cu, Cd, and Co analytes, metal concentration in the samples submitted to analysis were below the methods quantication limits (dened as three times the detection limit). Thus, the recovery test was carried out aiming at assessing the accuracy of the on-line preconcentration procedure due to the inexistence of certied material. The samples were previously ltered and analyses were performed in triplicate, using parameters optimized in the ow system and a 1 min of preconcentration time. Initially, recovery of the analytes from the alcohol samples was not appropriate. A test was conducted with copper and cadmium at 100 and 50 mg L21, respectively, adding 0.5 10% deionized water to the samples and alcohol standards. Analytical signals of both the standard and the sample solution were subtracted from their respective blanks. The behavior of analytical signals from copper and cadmium is shown on Fig. 5. One can therefore conclude that adding 6 10% water to the samples and alcohol standards caused meaningful reduction in the difference between signal of the samples and standards for copper. In this study, the copper standard solution was prepared with ethanol from Merck. For cadmium, this difference was a more signicant effect, and standard solutions were prepared with ethanol of two different brands. According to Fig. 5, cadmium signals for calibration solutions mica increased with a growing addition of water to 8% for the brand Dina and to 6% for Merck. From these values, the signals remained practically constant until 10% water was added to the ethanol solutions, and that was

Table 2. The equations for the calibration curves obtained with and without the preconcentration procedure for all metals studied. Calibration curve without preconcentration 0.01865 0.00445x 0.04372 0.00147x 0.02499 0.000509x 0.0579 0.000982x

Ion 10 50 10 30 60 140 10 30

Calibration curve with preconcentration

Range (mg L21)

Range (mg L21) 309 1548 387 1162 671 2013 288 865

Determination of Trace Metals in Fuel Alcohol by FAAS

Cu(II) Cd(II) Co(II) Zn(II)

0.00641 0.00948x 2 0.06444 0.0339x 2 0.15175 0.00847x 2 0.13318 0.02704x

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da Silva, Budziak, and Carasek

Figure 5. The behavior of the analytical signal when water was added to the samples and alcohol standards. Sorbent: 0.1 g; Cu: 100 mg L21; Cd: 50 mg L21; sample ow rate: 7.5 mL min21; eluent ow rate: 5.0 mL min21.

enough to reduce this difference. So, an 8% addition of water was chosen for all analytes. After this study, the quantication of Zn(II) (Table 3) and recovery tests (Tables 4 and 5) in samples of fuel alcohol collected in the Florianopolis area were carried out. For the recovery tests, samples were previously enriched with a small quantity of copper, cadmium, and cobalt (shown in Tables 4 and 5 as an addition of 0 mg L21). Concentration of zinc was relatively high in all samples, which had to be diluted by a factor of two. Results of the recovery studies show satisfactory accuracy and that the method proposed is free from interference.
Table 3. Concentration of zinc in commercial fuel alcohol. Sample Vendor Vendor Vendor Vendor Vendor A1 A2 A3 A4 A5 Concentration (mg L21) 48.84 + 1.14 35.24 + 1.02 22.10 + 0.06 49.10 + 0.72 30.06 + 0.28

Table 4. Recovery (%) Cd2 added (mg L21) Cd2 found (mg L21)

Recovery of copper and cadmium in fuel alcohol samples. Recovery (%)

Sample

Cu added (mg L21)

Cu2 found (mg L21)

Vendor A1

Vendor A2

Vendor A3

Determination of Trace Metals in Fuel Alcohol by FAAS

Vendor A4

Vendor A5

0 15 30 0 15 30 0 15 30 0 15 30 0 15 30

48.40 + 0.48 64.54 + 0.44 75.85 + 0.56 49.09 + 0.37 65.45 + 0.14 76.58 + 0.44 44.19 + 0.28 58.92 + 0.39 69.88 + 0.32 47.16 + 0.43 62.89 + 0.54 74.46 + 0.34 45.92 + 0.40 61.23 + 0.47 72.77 + 0.42 101.8 96.7 102.1 96.8 99.5 94.2 101.2 96.5 100.5 95.8 0 10 30 0 10 30 0 10 30 0 10 30 0 10 30

21.80 + 0.25 32.72 + 0.55 51.77 + 0.18 20.86 + 0.15 30.40 + 0.28 50.40 + 0.40 20.15 + 0.18 29.61 + 0.10 49.94 + 0.41 20.52 + 0.11 30.19 + 0.14 50.30 + 0.63 20.36 + 0.17 30.06 + 0.34 49.46 + 0.24

102.9 99.9 98.5 99.1 98.2 99.6 98.9 99.6 99.0 98.2

1921

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Table 5. Recovery of zinc and cobalt in fuel alcohol samples. Recovery (%) Co2 added (mg L21) Co2 found (mg L21)

Sample

Zn2 added (mg L21)

Zn2 found (mg L21)

Recovery (%)

Vendor A1

Vendor A2

Vendor A3

Vendor A4

da Silva, Budziak, and Carasek

Vendor A5

0 10 20 0 10 20 0 10 20 0 10 20 0 10 20

24.42 + 0.57 35.89 + 0.62 48.40 + 0.92 17.62 + 0.51 27.93 + 0.12 37.65 + 0.46 11.05 + 0.03 20.65 + 0.05 28.46 + 0.25 24.55 + 0.36 34.49 + 0.33 44.58 + 1.02 15.03 + 0.14 25.97 + 0.55 38.20 + 0.52 104.3 108.9 101.1 100.1 98.1 91.6 99.8 100.1 103.7 109.0 0 50 75 0 50 75 0 50 75 0 50 75 0 50 75

51.15 + 0.98 99.36 + 1.21 123.86 + 1.00 51.76 + 1.26 98.25 + 1.30 124.48 + 1.52 50.96 + 1.14 96.44 + 1.44 122.05 + 1.12 49.87 + 1.43 94.88 + 1.09 118.15 + 0.56 50.05 + 0.87 96.93 + 1.62 123.03 + 0.74

98.2 98.2 96.6 98.2 95.5 96.9 95.0 94.6 96.9 98.4

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4.

CONCLUSION

The use of Nb2O5 SiO2 was successfully applied to the on-line preconcentration and determination of copper, cadmium, cobalt, and zinc in fuel ethanol by FAAS. The minicolumn packed with Nb2O5 SiO2 in ow system did not show any overpressure or swelling. It is effective, stable, and reproducible with an unlimited lifetime. The sample preparation is simple and fast, and the elution step does not involve use of organic solvent. This solid phase extraction system shows fast metal ion-exchange kinetics, permitting the use of high sample loading ow rates in order to achieve better enhancement factors. Therefore, the proposed procedure improved signicantly the performance of off-line column methods. Besides the enhanced sensitivity and analytical frequency, FI on-line preconcentration procedure with a mini-column has proved to be a suitable method and has been widely used in trace element analysis owing to its simple automated operation and high reproducibility.

ACKNOWLEDGMENTS The authors thank Agencia Nacional de Petroleo (ANP) and Conselho Nacional de Desenvolvimento Cientico e Tecnologico (CNPq, Project 460368/01-0) for the nancial support. Edson Luiz da Silva and Dilma Budziak have a research scholarship from CNPq.

REFERENCES lio, R.Q.; Curtius, A.J. Trace elemental determi1. SaintPierre, T.; Auce nation in alcohol automotive fuel by electrothermal atomic spectrometry. Microchem. J. 2003, 75, 59 67. 2. Moreira, J.C.; Gushikem, Y. Preconcentration of metal ions on silica gel modied with 3(imidazolyl)propryl groups. Anal. Chim. Acta 1985, 176, 263 267. 3. Lessi, P.; Dias Filho, N.L.; Moreira, J.C.; Campos, J.T.S. Sorption and preconcentration of metal ions on silica gel modied with 2,5-dimercapto1,3,4-thiadiazole. Anal. Chim. Acta 1996, 327, 183190. 4. Dias Filho, N.L.; Gushiken, Y.; Polito, W.L.; Moreira, J.C.; Ehirim, E.O. Sorption and preconcentration of metal ions in ethanol solution with a silica gel surface chemically modied with benzimidazole. Talanta 1995, 42, 1625 1630.

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5. Kubota, L.T.; Jose, C.M.; Gushikem, Y. Adsorption of metal ions from ethanol on an iminosalicyl-modied silica gel. Analyst 1989, 114, 1385 1388. 6. Prado, A.G.S.; Airoldi, C. Adsorption, preconcentration and separation of cations on silica gel chemically modied with the herbicide 2,4-dichlorophenoxyacetic acid. Anal. Chim. Acta 2001, 432, 201 211. 7. Gomes, L.A.M.; Padilha, P.M.; Moreira, J.C.; Dias Filho, N.L.; Gushikem, Y. Dermination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modied silica gel. J. Brazil. Chem. Soc. 1998, 9 (5), 494 498. 8. Nagata, N.; Kubota, L.T.; Bueno, M.I.M.S.; Peralta-Zamora, P.G. Adsorption parameters of Cd(II), Pb(II) and Hg(II) on zirconium(IV) phosphate chemically grafted onto silica gel surface. J. Colloid Interf. Sci. 1998, 200, 121 125. 9. Vassileva, E.; Furuta, N. Application of high-surface area ZrO2 in preconcentration and determination of 18 elements by on-line ow injection with inductively coupled plasma atomic emission spectrometry. Fresenius J. Anal. Chem. 2001, 370, 52 59. 10. Matoso, E.; Kubota, L.T.; Cadore, S. Use of silica gel chemically modied with zirconium phosphate for preconcentration and determination of lead and copper by ame atomic spectrometry. Talanta 2003, 60, 1105 1111. 11. Denofre, S.; Gushikem, Y.; Castro, S.C.; Kawano, Y. Stability and surface acidity of niobium(V) oxide grafted on a silica gel surface. J. Chem. Soc. Farad. Trans. 1993, 89 (7), 1057 1061. 12. Budziak, D.; da Silva, E.L.; de Campos, S.D.; Carasek, E. Application of Nb2O5 SiO2 in pre-concentration and determination of copper and cadmium by ow system with ame atomic absorption spectrometry. Microchim. Acta 2003, 141, 169 174. 13. da Silva, E.L.; Ganzarolli, E.M.; Carasek, E. Use of Nb2O5 SiO2 in an automated on-line preconcentration system for determination of copper and cadmium by FAAS. Talanta 2004, 62 (4), 727 733. 14. Ferreira, S.L.C.; Lemos, V.A.; Santelli, R.E.; Ganzarolli, E.; Curtius, A.J. An automated on-line ow system for the pre-concentration and determination of lead by ame atomic absorption spectrometry. Microchem. J. 2001, 68, 41 46.

Received January 16, 2004 Accepted March 25, 2004