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Analytica Chimica Acta 494 (2003) 87–95 Amberlite XAD-2 functionalized with Nitroso R salt: synthesis and
Analytica Chimica Acta 494 (2003) 87–95 Amberlite XAD-2 functionalized with Nitroso R salt: synthesis and

Analytica Chimica Acta 494 (2003) 87–95

Analytica Chimica Acta 494 (2003) 87–95 Amberlite XAD-2 functionalized with Nitroso R salt: synthesis and application

Amberlite XAD-2 functionalized with Nitroso R salt: synthesis and application in an online system for preconcentration of cobalt

Valfredo Azevedo Lemos , Juracir Silva Santos, Luana Sena Nunes, Marcilio Bezerra de Carvalho, Patr´ıcia Xavier Baliza, Regina Terumi Yamaki

Departamento Qu´ımica e Exatas, Laboratório de Qu´ımica Anal´ıtica (LQA), Campus de Jequié, Universidade Estadual do Sudoeste da Bahia, Jequié Bahia 45200-000, Brazil

Received 10 June 2003; received in revised form 30 June 2003; accepted 1 August 2003

Abstract

The synthesis and characterization of the resin Amberlite XAD-2 functionalized with Nitroso R salt and its application in an online system for preconcentration of cobalt and determination by flame atomic absorption spectrometry (FAAS) is proposed. Cobalt(II) ions are sorbed in a minicolumn packed with the synthesized solid phase. Thereafter, these ions are eluted by acid solution to the nebulizer of a flame atomic absorption spectrometer. Sample throughput is 51 h 1 or 18 h 1 , depending on preconcentration time, 60 s or 180 s, respectively. Cobalt was determined at pH 6.5–8.0, using a sample flow rate of 9.5 ml min 1 . Elution was performed with 30 l of 1.0 mol l 1 hydrochloric acid. The enrichment factors obtained were 79 and 223, with 3σ detection limits of 1.25 and 0.39 g l 1 , for respective preconcentration periods of 60 and 180 s. The accuracy of the procedure was evaluated by analysis of biological certified material. The method was successfully applied for cobalt determination in natural water samples. © 2003 Elsevier B.V. All rights reserved.

Keywords: Preconcentration; Cobalt; Amberlite XAD-2; Nitroso R salt; Online; Flame atomic absorption spectrometry

1. Introduction

Cobalt is an essential micronutrient for life. De- termination of low levels of cobalt by flame atomic absorption spectrometry (FAAS) often demands separation and preconcentration steps because of insufficient sensitivity or matrix interference. Sev- eral procedures of enrichment have been developed for cobalt determination involving different ana- lytical techniques, such as coprecipitation [1], or liquid–liquid [2], cloud point [3] or solid-phase [4] extraction. Processes involving solid-phase extraction

Corresponding author. Tel.: +55-73-5268621; fax: +55-71-2355166/55-73-5256683. E-mail address: vlemos@ufba.br (V.A. Lemos).

[5] show several advantages, like availability and easy recovery of sorbent, attainability of high preconcen- tration factors, and facility of handling. Therefore, these procedures avoid or minimize the use of organic solvents that are generally toxic. Online preconcentration systems using solid-phase extraction are opportune for metal determination, due to their flexibility, simplicity, high sample throughput and versatility. These characteristics permit the use of online systems coupled with different detectors. Many online procedures using solid-phase extrac- tion can be found in the literature. The materials generally used are ion-exchangers [6,7], silica [8,9], activated alumina [10,11], carbon [12], fullerene [13], polyurethane foam [14,15] and chelating resins

[16].

0003-2670/$ – see front matter © 2003 Elsevier B.V. All rights reserved.

doi:10.1016/j.aca.2003.08.002

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There is continued interest in development of chelating sorbents for use in metal preconcentration systems. To produce these matrices, chelating ligands can be loaded on solid supports [17–20], or can be co- valently bonded to a polymeric matrix through an azo [21,22] or methylene group [23]. Coupling by covalent bond reduces problems of leaching of the ligand from the column. When multielemental determinations are required, such as systems that use inductively coupled plasma-atomic emission spectrometry (ICP-AES) as the detection technique, the use of unselective ligands is convenient. However, in some determinations in which the goal is reduction of interference problems, the use of selective reagents is more suitable. Disodium 1-nitroso-2-hydroxynaphthalene-3,6-di- sulfonate (Nitroso R salt) is an 1-nitroso-2-naphthol derivative that is highly selective for cobalt(II), and it is the most used substance for spectrophotometric determination of this metal [24]. Amberlite XAD-2 (styrene-divinylbenzene copolymer) is a support wi- dely used to develop several chelating resins for pre- concentration procedures due to its good physical and chemical properties such as porosity, surface area, durability and purity. This support has been mo- dified with 2-(2-benzothiazolylazo)-p-cresol (BTAC) [25], o-vanillin thiosemicarbazone [18], 1-(2-pyridyl- azo)-2-naphthol (PAN) [26], 2-(2 -thiazolylazo)-5- dimethylaminophenol (TAM) [27], calmagite [28], chromotropic acid [29], tiron [30], catechol violet [31], salicylic acid [32], catechol [33] and thiosali- cylic acid [34].

In this study, an online preconcentration method

has been developed for determination of cobalt using a minicolumn packed with Amberlite XAD-2 support functionalized with Nitroso R salt (NRS-XAD). The synthesis and characterization of the chelating resin was followed by the study of its chemical and hydro- dynamic parameters. The developed method has been applied to the trace determination of cobalt in natural water samples.

2. Experimental

2.1. Instrumentation

A Varian model SpectrAA 220 (Mulgrave, Vic.,

Australia) flame atomic absorption spectrometer

equipped with a deuterium arc lamp was used for co- balt measurements. A cobalt hollow cathode lamp was used according to the manufacturer’s recommen- dations (current 4.0 mA, wavelength 240.7 nm, slit bandwidth 0.5 nm and burner height 13.5 mm). The flame composition was acetylene (2.0 l min 1 ) and air (13.5 l min 1 ). The nebulizer flow rate was 4.0 ml min 1 . Infrared spectra were recorded in an ABB Bomen MB series model MB100 Fourier transform IR spectrometer. A Thermo Finnigan Flash elemental analyzer 1112 series was used for elemental analysis. The diagram of the online preconcentration system is shown in Fig. 1. The manifold was adapted to the nebulizer system of the flame atomic absorption spec- trometer. The flow system was made up of a peristaltic pump (Alitea C-6 XV, Stockholm, Sweden) furnished with Tygon tubes to deliver all solutions, two Rheo- dyne 5041 (Cotati, CA) six-port valves to select elution and preconcentration steps, and a NRS-XAD packed minicolumn for the online preconcentration of cobalt. The manifold was built up with PTFE tubing of 0.5 mm bore. To minimize dispersion, the length of the PTFE capillary tube between the end of mini- column and the nebulizer was as short as possible (about 5 cm). A Digimed DM 20 (Santo Amaro, Brazil) pH meter was used for pH monitoring.

(Santo Amaro, Brazil) pH meter was used for pH monitoring. Fig. 1. Schematic diagram of the

Fig. 1. Schematic diagram of the online system used for cobalt de- termination and preconcentration by FAAS. S: sample; E: eluent; CR: carrier; P: peristaltic pump; C: minicolumn of NRS-XAD; V 1 and V 2 : six-port valves; L: eluent loop; FAAS: flame atomic absorption spectrometer; W: waste. (1) six-port valves in precon- centration position, (2) six-port valves in elution position.

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89

The laboratory-made cylindrical minicolumn of 3.5 cm length and internal diameter of 4.0 mm con- tains about 100 mg of NRS-XAD. A syringe was used to put the sorbent in the column. Plastic foam was placed at both ends of the minicolumn to keep the packing material in place. Afterwards, the col- umn was washed with ethanol, 5% (v/v) nitric acid and deionized water at 2.50 ml min 1 . Washing with nitric acid and ethanol was necessary in order to remove any metal or organic contamination, respec- tively. All columns prepared in this way shown good reproducibility.

2.2. Reagents

Ultrapure water from an Easypure RF water purifi- cation system (Barnstead, Dubuque, IA, USA) was used to prepare all solutions. All reagents were of

analytical reagent grade. Cobalt(II) working solutions

at the g l 1 level were prepared daily by diluting

a 1000 g ml 1 cobalt(II) solution (Merck). Hy- drochloric acid, 1.0 mol l 1 , was prepared by direct dilution with ultrapure water from the concentrated Suprapur solution (Merck). The laboratory glassware was kept overnight in 5% v/v nitric acid. After- wards, it was rinsed thoroughly with ultrapure water and dried in a dust-free environment. Tris–acetate (tris-(hydroxymethyl)aminomethane), borate and am- moniacal buffers conveniently prepared [35] were used to adjust the sample pH in the range 4.8–6.0, 7.0–10.0, 8.0–9.0 and 9.0–10.0, respectively. Amberlite XAD-2 (Sigma, 20–60 mesh), Nitroso R salt (Sigma), nitric and sulfuric acids (Merck) and sodium hydroxide and nitrite (Reagen) were used for synthesis of the sorbent.

2.3. Synthesis of resin

A modified version of a procedure described in

the literature for similar reagents [29,36] was used

to synthesize NRS-XAD. Amberlite XAD-2 (5 g) was

treated with 10 ml of concentrated HNO 3 and 25 ml of concentrated H 2 SO 4 and the mixture stirred at 60 C for 1 h on a water bath. Thereafter, the reaction mixture was poured into an ice–water mixture. The nitrated resin was filtered, washed repeatedly with water until free from acid and thereafter, treated with a reducing mixture of tin(II) chloride, concentrated hydrochloric acid and ethanol. The system was refluxed for 12 h at

90 C. The precipitate was filtered off and washed with water and 2 mol l 1 NaOH. The amino resin was first washed with 2 mol l 1 HCl and finally with ultrapure water to remove the excess of HCl. It was suspended

in an ice–water mixture (150 ml) of 1 mol l 1 HCl and

1 mol l 1 NaNO 2 . The diazotized resin was filtered, washed with ice-cold water and reacted with Nitroso

R salt (3.0 g in 250 ml of 5% (w/v) NaOH solution) at

0–5 C for 24 h. The resulting dark-brown resin was filtered, washed with water and dried in air.

2.4. Sample preparation

The certified reference material (CRM) Spinach Leaves NIST 1570a, obtained from the National In- stitute of Standards and Technology (Gaithersburg, MD) was analyzed for accuracy studies. For decom- position of this material [37], about 0.4 g was treated with 4.0 ml of 1:1 (v/v) nitric acid solution and kept overnight in a PTFE vessel. Afterwards, the vessel was closed and put into a pressurized digestion sys- tem. The thermal heating was carried out in a stove at 130 C for 12 h. After cooling to room temperature, the pH of this solution was adjusted to a convenient value with a 10% (w/v) sodium hydroxide solution and appropriate buffer solution. After this step, the solution was transferred to a 100 ml volumetric flask and the volume was completed with ultrapure water. Natural waters were sampled in the coastal region

of Salvador City, BA, Brazil. For these samples, the only pre-treatment was acidification to pH 2.0 with nitric acid, which was performed immediately after collection, in order to prevent adsorption of the Co(II) ions on the flask walls. Samples were filtered and 80 ml

of the filtrate was added to a 100 ml volumetric flask;

the pH was adjusted by addition of 5 ml of appropriate buffer solution. Co(II) addition was carried out, and the flask volume was completed with ultrapure water. At least one blank solution was run for each sample in order to evaluate cobalt contamination by the reagents used.

2.5. Online preconcentration system

The system operated on a time-based mode for sample introduction. A solution containing cobalt(II) ions (S) was kept at a convenient pH with a buffer solution and was percolated through a minicolumn

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packed with the sorbent NRS-XAD. Cobalt(II) ions were retained on the minicolumn and the remaining solution was discharged (W). Carrier (CR) was taken directly to the nebulizer of the flame atomic absorp- tion spectrometer while the eluent is filling loop (L) and flowing to waste (W). Turning two valves simul- taneously, the carrier transports the eluent through the column, displacing cobalt ions, because sorption does not occur at low pH values. This eluate is taken to the spectrometer. Signals were measured as peak height by using FAAS software. It was measured four times (four preconcentration steps) and averaged. Precision was measured as relative standard deviation for 10 readings by peak height and peak area. Peak height was eventually used because it resulted in better pre- cision than peak area. The achieved sampling rate was 51 h 1 , when a preconcentration time of 60 s and an elution time of 10 s were used.

3. Results and discussion

To determine the chemical and hydrodynamic vari- ables that provide the higher analytical signals, a 50.0 g l 1 cobalt(II) solution was employed.

3.1. Resin characterization

Elemental analysis (found: C, 47.9%; H, 3.1%; N, 8.5%; calculated for C 18 H 13 N 3 O 8 S 2 : C, 46.6%; H, 2.8%; N, 9.1%) shown that on an average one Nitroso

R

salt molecule is present in the resin per repeat unit

of

the polymer. A structure according with elemental

analysis is shown in Fig. 2. The infrared spectrum of

NRS-XAD resin is compared with that of free Amber- lite XAD-2. There are additional bands at 3460, 1540, 1440, 1400 and 1335 cm 1 , which appear to origi-

( HC-CH 2 ) n NO OH N=N HO SO 3 H 3 S
( HC-CH 2
)
n
NO
OH
N=N
HO
SO 3 H
3 S

Fig. 2. Proposed structure for NRS-XAD.

nate due to modification of resin by the ligand and are characteristic of O–H, –N=N–, C–N, N=O and C–OH vibrations, respectively.

3.2. Chemical variables

The effect of sample pH was studied in the range 4.8–10.2. Buffer solutions acetate, borate and ammo- niacal were used to adjust the sample pH to appropri- ate values. The analytical signal reached its maximum value in the narrow range of pH 6.5–8.0, as can be seen in Fig. 3. This result is in accord with the favor- able range to formation of the complex Co(II)–NRS [38]. At pH values >8.0, if an ammoniacal buffer solution is used, there is a depression in the analyt- ical signal. It can be attributed to the formation of ammonia–cobalt complexes, which allow that part of analyte do not be sorbed in the minicolum. So, for all subsequent experiments, a borate buffer solution, pH 7.5 was used to adjust the sample pH. Elution of cobalt from the minicolumn was studied using hydrochloric acid solutions of several concen- trations. Elution with acid is fast, because it very rapidly changes the appropriate pH. Hydrochloric acid of concentrations varying from 0.0 to 2.00 mol l 1 were used. The results demonstrated that, for concen- trations of acid >0.50 mol l 1 , the analytical signal is maximal. So 1.00 mol l 1 hydrochloric acid was selected as the eluent for further studies. The influ- ence of the volume of the eluent loop (L) was also studied, because it determines the quantity of acid that passes through the column. It was found that for an eluent loop >25 l the signal is constant. So, a volume of 30 l was chosen for subsequent experi- ments in order to pass a minimum quantity of acid through the column, reducing the risk of losses of cobalt in the preconcentration step due inadequate pH during sorption. The lifetime of the column packed with NRS reagent immobilized on Amberlite XAD-2 resin was monitored. It was made by measuring the signal of a 50.0 g l 1 cobalt solution at the end of each day of work. Results demonstrated that the column shown good performance for at least 500 daily cycles. An- choring of the reagent in the support is the principal

reason for the long lifetime of the column, because leaching of the reagent from column is reduced. Another parameter that can contribute to the long

V.A. Lemos et al. / Analytica Chimica Acta 494 (2003) 87–95

91

25 20 15 10 5 0 4685 7 9 10 11 height absorbance xPeak 10
25
20
15
10
5
0
4685 7
9
10
11
height absorbance xPeak
10 -2

Sample pH

Fig. 3. Influence of sample pH in online cobalt preconcentration using a NRS-XAD minicolumn.

lifetime is system design, that permits washing with water before each preconcentration step.

3.3. Hydrodynamic variables

The influence of flow rate of the cobalt solution in the proposed system was studied. A volume of 3.00 ml of a 50 g l 1 cobalt solution was pumped through the column at various flow rates from 1.8 to 17.3 ml min 1 . Analytical signals decreased slightly at high flow rates, above 10.0 ml min 1 . These results in- dicate that the sorption is decreased at high flow rates because cobalt(II) ions passes through the column too quickly, and contact time between the phases is not sufficient for complete retention of cobalt. Moreover, high flow rates increase back-pressure and this could cause leakage. However, working with high flow rates provides large amounts of cobalt passing through the column, in time-based systems, assuring good sensi- tivity. A flow rate of 9.50 ml min 1 was chosen for subsequent experiments as a compromise between ef- ficiency and stability. The transfer phase factor is a parameter defined as the ratio between analyte mass in the original sam- ple solution and in the concentrate after elution [7].

It is influenced by each specific solid-phase. For this experiment, 10.0 ml of a 50.0 g l 1 cobalt solution was percolated through the column. So, the elution was performed and 1.00 ml of the concentrate con- taining the analyte was collected; the cobalt in this solution was directly determined by FAAS. Working with a sample flow rate of 9.50 ml min 1 , a trans- fer phase factor obtained for the system was 0.97. The result indicates that retention is complete in these conditions. The influence of carrier flow rate in the elution step was also studied, because it establishes the velocity of the eluent through the minicolumn. Results obtained shown that the analytical signal is maximum at car- rier flow rates within the range 3.5–6.0 ml min 1 . At flow rates <3.5 ml min 1 , the analytical signal con- siderably decreased, resulting in broader peaks. Prob- ably, it is due to incompatibility between the elution and nebulization flow rates, which cause significant dispersion when the carrier flow rate is much smaller than the nebulizer flow rate. Thus, a carrier flow rate of 4.0 ml min 1 was selected in subsequent studies, in order to match elution and aspiration flow rates. However, this experiment was repeated but the trans- fer phase factor of cobalt at each carrier flow rate

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was measured to evaluate this effect independently of the detection system. All the results obtained did not show significant differences, which demonstrates that the cobalt desorption is fast and independent of the elution flow rate. Preconcentration time in the online system was studied in the range 30–300 s. The analytical signal increased proportionally with the preconcentration time up to 240 s. This indicates that the transfer phase factor is constant within this time interval. If precon- centration times >180 s are used, analytical signals decreased, probably because partial leaching of the ions Co(II) from the column occurs, due to lability of the Co(II)–NRS complex. So, a preconcentration time of 60 s was chosen to combine sensitivity and efficiency. When more sensitive determinations were required, a preconcentration time of 180 s was used.

3.4. Analytical features

Using characteristic data under the optimum chem- ical and hydrodynamic conditions of the manifold de- picted in Fig. 1, some parameters of the online sys- tem were determined. The analytical performance of the method is described in Table 1. The solid-phase flow system allowed the determination of cobalt in the range 1.25–220 g l 1 for 60 s preconcentration time. The calibration graph in the time interval considered was given as A = 0.0119 + 0.00328C, where A is the analytical absorbance signal, measured as peak height and C is the cobalt concentration in solution ( g l 1 ). For 180 s of preconcentration time, the linear range

Table 1 Analytical performance of the procedure for online cobalt precon- centration

Loading time (s)

60

180

Sampling frequency (h 1 )

51

18

Sample volume (ml)

9.50

28.5

Linear range ( g l 1 )

1.25–220

0.39–80

Enrichment factor

79

223

Concentration

67

67

efficiency (h 1 ) Comsumptive index (ml)

0.12

0.13

Transfer phase factor

0.97

0.97

Detection limit ( g l 1 )

1.25

0.39

Regression equation

A = 0.01187 + 0.00328C

A = 0.02483 + 0.00925C

A: peak height absorbance; C: cobalt concentration.

was 0.39–80 g l 1 , and the corresponding equation is A = 0.02483+0.00925C. When cobalt is measured by direct aspiration by FAAS, the calibration line is A = 0.007 + 4.14 × 10 5 C, for the concentration range of 72–12 000 g l 1 . The experimental enrichment factor [7,39] of the proposed system, calculated as the ratio of the slopes of the calibration graphs with and without preconcen- tration was 79, for 60 s preconcentration time, and 223, for 180 s preconcentration time. The detection limit (DL), calculated as 3s b /b, where s b is the standard deviation for the blank (n = 11) and b is the regression coefficient of the linear section of the calibration graph, was found to be 1.25 g l 1 for 60 s preconcentration and 0.39 g l 1 for 180 s preconcentration. The precision of measurements was evaluated as the relative standard deviation (R.S.D.) corresponding to each concentration value in the cal- ibration graph, and was calculated as (s/X) × 100, where s in standard deviation for seven measurements and X is the mean of these measurements. R.S.D. val- ues varying between 6.1 and 1.5%, were obtained for cobalt concentrations of 5.0–100 g l 1 , respectively. Other important analytical parameters for online systems (concentration efficiency (CE) and comsup- tive index (CI)) were also calculated [7]. The figures of merit of this work and other selected online methods, which use FAAS, ICP-AES or elec- trothermal AAS for measurement, are summarized in Table 2. The enrichment factor of the proposed method is higher than those obtained using other sorbent materials. Comparing the detection limit (DL) of the proposed method with another that uses FAAS, this pa- rameter can be decreased by using alumina as sorbent [45]. However, this method has a very low sampling frequency. In the methods that use electrothermal AAS or ICP-AES, the detection limits obtained are lower than the proposed procedure, but the sampling frequency is very low in all these methods. Therefore, the proposed method using XAD-NRS as sorbent con- sists of simpler apparatus with easier manipulation of the system, and much lower equipment and running costs.

3.5. Selectivity of the sorbent

Solutions containing cobalt (50.0 g l 1 ) and other ions were prepared and the developed procedure was

 

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93

Table 2 Comparison of procedures for online cobalt preconcentration

 

Sorbent

Sample

EF

CE (min 1 )

CI (ml)

f (h 1 )

DL ( g l 1 )

Detection

Reference

NRS-XAD

Natural water and biological reference material Seawater Biological reference material Synthetic samples Natural water and reference material Potable water Steel Natural water and medicaments

79

67

0.12

51

1.25

FAAS

This work

223

67

0.13

18

0.39

S´ılica C 18 Polygosil C 18

80

80

0.09

30

1.0

FAAS

[9]

40

30

0.18

45

3.0

FAAS

[40]

Chelex-100

48

48

60

0.2

FAAS

[41]

TAC-XAD

87

29

0.17

20

0.13

FAAS

[42]

Chromosorb 105

50

2.5

FAAS

[43]

C 18

17

26

0.19

90

3.2

FAAS

[44]

Alumina

125

8

0.20

4

0.02

FAAS

[45]

TAC-PUF

Natural water

37

14

0.27

24

3.2

FAAS

[46]

 

51

14

0.29

17

2.4

IDAEC PTFE Silica C 18 Muromac A-1

Natural water Natural water and biological material Biological matrices, seawater and steel Reference material: seawater

47

9

0.16

12

0.06

ICP-AES

[47]

87

29

0.13

20

0.004

ETAAS

[4]

210

21

6

0.0017

ETAAS

[48]

40

10

0.04

15

0.007

ETAAS

[49]

DL: detection limit; f: sample throughput; CI: comsumptive index. EF: enrichment factor; CE: concentration efficiency; TAC:

2-(2-thiazolylazo)-p-cresol; PUF: polyurethane foam; IDAEC: iminodiacetic ethylcellulose acid; PTFE: polytetrafluoroethylene; FAAS:

flame atomic absorption spectrometry; ICP-AES: inductively coupled plasma-atomic emission spectrometry; ETAAS: electrothermal atomic absorption spectrometry.

applied in order to determine the selectivity of the sorbent. The effect of each species was considered an interference when the signal in the presence of the species resulted in a deviation of the peak height by >±5%. Considered substances and their maximum amounts studied are shown in Table 3. The results demonstrate that ions tolerated only in minor quanti- ties are Ni(II), Cu(II) and Fe(III), probably because these ions react with NRS, forming stable complexes, and occupying sites in the sorbent, thus reducing cobalt sorption. However, these quantities of foreign ions are relatively high if compared to quantities present in most samples.

Table 3 Maximum tolerable ratios of other ions for the online system using NRS-XAD minicolumn (Co concentration = 50 g l 1 )

Substance

Weight ratio substance: Co(II)

Na(I), Cl(I) K(I), NO 3 Ba(II), Ca(II), Mg(II) Zn(II), Pb(II), Cd(II), SO 4 2 Cu(II), Fe(III) Ni(II)

600000

20000

15000

1000

100

10

a

a

a

a Maximum ratio studied.

3.6. Accuracy of the method

In order to evaluate the accuracy of the developed procedure, the following certified reference material was analyzed: NIST 1570a Spinach Leaves. The result found by proposed methodology is 0.41±0.08 g g 1 , for n = 3 and confidence interval at 95% level. So, it was found that there is no significant difference be- tween achieved result by the proposed method and the certified value (0.39 ± 0.05 g g 1 ).

3.7. Determination of cobalt in or added to water

samples

The analytical system was used for cobalt determi- nation of cobalt in or added to natural water samples. The results are described in Table 4. Recoveries (R) of spike additions were calculated as follows:

R(%) = {(C m C o )/m} × 100, where C m is the concentration of cobalt in a spiked sample, C o is the value for cobalt in a sample and m is the amount of copper spiked. For determination of cobalt in or added to natural water samples, 180 s preconcentra- tion time was used, because a more sensitive system is required.The results demonstrate the applicability

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Table 4 Results obtained for cobalt determination in natural waters (n = 3)

Sample

Cobalt added ( g l 1 )

Cobalt found

Recovery(%)

(

g l 1 )

Lagoon water 1

0.0

<DL

1.0

1.05 ± 0.08

105

2.0

1.93 ± 0.11

96

Lagoon water 2

0.0

0.96 ± 0.05

1.0

1.90 ± 0.12

94

2.0

2.01 ± 0.03

105

Seawater

0.0

<DL

1.0

0.94 ± 0.09

94

2.0

1.89 ± 0.14

94

Confidence interval at 95% level. DL: detection limit.

of the procedure for cobalt determination in natural waters.

4. Conclusion

Nitroso R salt bound to an Amberlite XAD-2 sup- port, gave a chelating system used successfully in on- line preconcentration of cobalt. The online manifold improved significantly FAAS performance, reaching a enrichment factor (EF) comparable to many other pro- cedures described in the literature, including some pro- cedures using detection by electrothermal AAS. The low detection limits obtained are also very convenient for application to cobalt determination at g l 1 level in a variety of samples. Moreover, selectivity in the sorption due to high selectivity of the reagent, and selectivity of FAAS, allows cobalt determinations in the presence of signif- icant amounts of foreign substances generally present in real samples. The system also shows simplicity, because it involves only two steps, elution and precon- centration, and rapidity (sample throughput 51 h 1 ), for 60 s preconcentration. These characteristics are very important in laboratories for routine analysis, equipped only for metal determination by FAAS.

Acknowledgements

The authors acknowledge the financial support of the Conselho Nacional de Desenvolvimento Cient´ıfico e Tecnológico (CNPq) and Fundação de Amparo à Pesquisa do Estado da Bahia (FAPESB).

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