ААС

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650 Narin et al.

Reuse of Chelating Resin

The stability and regeneration of the XAD-16-PAN resin were

and is relatively stable up to 40 runs without appreciable loss of sorption capacity.

E ect of Sample Volume on the Recoveries

In order to explore the possibility of enriching low concentrations of the analyte ions from the large sample volume, the influences of the sample volume on the recovery of the metal ions were also investigated. The metal amounts were 10–20 mg and in the model solution, the metal amounts were held constant while increasing the sample volume. The e ect of sample volume on the sorption of metal ions was also investigated by passing 50–1200 mL volumes through the XAD-16-PAN column. The results are depicted in Fig. 4. The adsorption of the metal ions with 600 mg resin was not a ected by sample volume till 1000 mL. The highest preconcentration factor was 200 for analyte ions when final volume was 5.0 mL.

Figure 4. Influences of sample volume on the recoveries of analyte ions (N ¼ 4, eluent: 2 M HCl in acetone).

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Flow Rates of Sample and Eluent Solutions

Sample and eluent flow rates are important parameters to obtain quantitative retention and elution of analyte ions, respectively. The

were virtually quantitative for sample flow rates up to 4 mL/min. Variation of the elution flow rate in the range of 1.0–4.0 mL/min has no e ect on the elution e ciency. In consequence, 4 mL/min was selected as flow rate for sample loading and sample elution from the XAD-16-PAN resin.

Capacity of XAD-16-PAN Resin

In order to study the adsorptive capacity of XAD-16-PAN resin, the batch method was used. To 1.0 g resin was added 50 mL of solution containing 10 mg of analyte ion at pH 9. After shaking for 1 h, the mixture was filtered. 10 mL of the supernatant solution was diluted to 100 mL and determined by flame atomic absorption spectrometry. This procedure was repeated for each analyte ions. The capacity of sorbent for Ni(II), Cd(II), Co(II), Cu(II), Pb(II), and Cr(III) was found 4.7, 4.9, 4.7, 5.0, 4.8, and 5.0 mg metal/g XAD-16-PAN.

E ects of Some Cations and Anions

In order to evaluate the possibility of selective recovery of Ni(II), Cd(II), Co(II), Cu(II), Pb(II), and Cr(III) on XAD-16-PAN resin in the presence of some cations and anions in the natural water samples, the procedure has been performed with 100 mL solutions containing these ions. The results are given in Table 2. Quantitative recoveries were obtained for analyte ions, while lower values were found for Ca, Mg, K and Na. It can be mentioned that the low ion recoveries for these ions are helpful in the determination of heavy metals at trace levels in natural waters. These results are desired in view of applications to natural water samples.

The recoveries of Ca, Mg, K, and Na were determined by flame AAS and approximately found to be less than 1%. The salt contents in the eluent solutions were found to be significantly lower and suitable for flame atomic absorption spectrometric determination.

Table 2. Eects of matrix ions (N ¼ 5).

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Detection Limits

The detection limits of the investigated metal ions based on three times the standard deviations of the blank (k ¼ 3, N ¼ 21) on a sample volume 100 mL for Ni, Cd, Co, Cu, Pb, and Cr were 0.161, 0.056, 0.072, 0.079, 0.121, and 0.268 mg/L, respectively. The detection limits of the analyte ions can be decreased by one order of magnitude by increasing the sample volume.

Accuracy of the Results

In order to estimate the accuracy of the procedure, di erent amounts of investigated ions were added to 500 mL of drinking water samples collected from Nigde University and Erciyes University and the resulting solutions were submitted to the preconcentration procedure given in Experimental. The results are shown in Table 3. A good agreement was obtained between the added and measured analyte amounts. The recovery values calculated for the added standards were always

Table 3. Recovery of Cu, Cd, Ni and Pb from tap water samples (N ¼ 6, sample volume: 500 mL, final volume: 5 mL).

N.D.: Not Detected.

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Table 4. The concentration of analyte ions in the tap water samples from Nigde city (n ¼ 4).

BDL: Below the detection limit. aUncertainty at 95% confidence limit.

higher than 95%, thus confirming the accuracy of the procedure and its independence from the matrix e ects. These results confirm the validity of the proposed method.

Application to Natural Water Samples

The Amberlite XAD-16-PAN method has been employed for the separation/preconcentration of Ni(II), Cd(II), Co(II), Cu(II), Pb(II) and Cr(III) in natural water samples. For that purpose, the procedure given in Experimental was applied. The results, which are shown in Table 4, have been calculated on the assumption of 100% recovery of working elements.

CONCLUSION

Based on these results found in the present study, it can be concluded that XAD-16-PAN resin is an e ective material for the separation and preconcentration of traces metal ions in the natural water samples. The method gives a better preconcentration factor. The new resin can be used at least 40 times. Future works will be focused on the usage of the resin on-line solid phase extraction of the metal ions and on the application of

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the method to other samples containing high salinity such as dialysis solution and urine etc.

ACKNOWLEDGMENT

Ibrahim Narin is grateful for the financial support of Research Foundation of Nigde University (Nigde-Turkey). The authors thank Mr. E. Sahmetlioglu for his help on the IR evaluations.

REFERENCES

1.Minczevski, J.; Chwastowska, J.; Dybczynski, D. Separation and Preconcentration Methods in Inorganic Analysis; Ellis Horwood: Chichester, 1982.

2.Hansen, E.H.; Nielsen, S. Flow Injection and Atomic Absorption Spectrometry, An E ective and Attractive Analytical Chemical Combination, Laboratory Robotics Automation 1998, 10, 347–354.

3.Soylak, M.; Elci, L.; Dogan, M. Solid phase extraction of trace metal ions with amberlite XAD resins prior to atomic absorption spectrometric analysis. J. Trace Microprobe Techn. 2001, 19, 329–344.

4.Cai, Y.; Jiang, G.; Liu, J. Preconcentration of trace amounts of cadmium in aqueous samples on mini columns packed with chromosorb series gas chromatographic stationary phases and its determination by electrothermal atomic absorption spectrometry. Analyst 2001, 126, 1678–1682.

5.Fang, Z.; Sperling, M.; Welz, B. Flame atomic absorption

spectrometric determination of lead in biological samples using a flow injection system with on-line preconcentration by coprecipitation without filtration. J. Anal. At. Spectrom. 1991, 6, 301–306.

6.Yebra, M.C.; Garcı´a, A.; Carro, N.; Moreno-Cid, A.; Puig, L. Design of a field flow preconcentration system for cadmium determination in seawater by flow-injection-atomic absorption spectrometry. Talanta 2002, 56, 777–785.

7.Giokas, D.L.; Paleologos, E.K.; Prodromidis, M.I.; Karayannis, M.I. Development of 1-(2-pyridylazo)-2-naphthol-modified polymeric membranes for the e ective batch pre-concentration and determination of zinc traces with flame atomic absorption spectrometry. Talanta 2002, 56, 491–498.

Downloaded by [Mount Royal University] at 07:03 23 May 2013

8.Soylak, M. Determination of trace amounts of copper in metallic aluminium samples after separation and preconcentration on an activated carbon column. Fresen. Environ. Bull. 1998, 7, 383–387.

9.Cesur, H.; Bati, B. Determination of cadmium by FAAS after solid-phase extraction of its 1-benzyl-piperazinedithiocarbamate complex on microcrystalline naphthalene. Turk J. Chem. 2002, 26, 29–35.

10.Garg, B.S.; Sharma, R.K.; Bist, J.S.; Bhojak, N. Column chro-

matographic preconcentration of cobalt and zinc with 3-hydroxy- 4-imino-(n-20-pyridyl)-2-methylnaphthalen-1-one adsorbed on naphthalene and their estimation in vitamin and milk samples. Indian J. Chem. 2002, 39A, 564 –566.

11.Quina´ia, S.P.; da Silva, J.B.B.; Rollemberg, M.C.E.; Curtius, A.J. Preconcentration of lead complexed with O,O-diethyldithiopho- sphate by column solid-phase extraction using di erent sorbents in a flow injection system coupled to a flame atomic absorption spectrometer. Talanta 2001, 54, 687–696.

12.Bilba, D.; Bejan, D.; Tofan, L. Chelating sorbents in inorganic chemical analysis. Croat. Chem. Acta 1987, 71, 155–178.

13.Garg, B.S.; Sharma, R.K.; Bhojak, N.; Mittal, S. Chelating resins and their applications in the analysis of trace metal ions, microchem. J. 1999, 61, 94–114.

14.Bogachiova, L.V.; Kovaliov, I.A.; Tsizin, G.I.; Formanovskii, A.A.; Zolotov, Y.A. On-line sorption preconcentration and atomic absorption determination of palladium in solutions. Vestn. Mosk. Univ. Khim. 1999, 40, 110–114.

15.Dev, K.; Pathak, R.; Rao, G.N. Sorption behavior of lanthanum(III), neodymium(III), terbium(III), thorium(IV) and uranium(VI) on amberlite XAD-4 resin functionalized with bicine Lligands. Talanta 1999, 48, 579–584.

16.Tewari, P.K.; Singh, A.K. Amberlite XAD-7 impregnated with xylenol orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS. Fresen. J. Anal. Chem. 2000, 367, 562–567.

17.Pathak, R.; Rao, G.N. Preparation and analytical properties of a chelating resin functionalized with 1-hydrazinophthalazine ligand. Talanta 1997, 44, 1447–1453.

18.Pathak, R.; Rao, G.N. Synthesis and metal sorption studies of P-tert-butylcalix[8]ayrene chemically bound to polymeric support. Anal. Chim. Acta 1996, 335, 283–290.

19.Saxena, R.; Singh, A.K.; Sambi, S.S. Synthesis of a chelating polymer matrix by immobilizing alizarin red-S on amberlite XAD-2 and

Downloaded by [Mount Royal University] at 07:03 23 May 2013

its application to the preconcentration of lead(II), cadmium(II), zinc(II) and nickel(II). Anal. Chim. Acta 1994, 295, 199–204.

20.Saxena, R.; Singh, A.K. Pyrocatechol violet immobilized amberlite XAD-2: synthesis and metal-ion uptake properties suitable for analytical applications. Anal. Chim. Acta 1997, 340, 285–290.

21.Jain, V.K.; Sait, S.S.; Shrivastav, P.; Agrawal, Y.K. Application of chelate forming resin amberlite XAD-2-o-vanillinthiosemicarbazone to the separation and preconcentration of copper(II), zinc(II) and lead(II). Talanta 1997, 45, 397–404.

22.Kumar, M.; Rathore, D.P.S.; Singh, A.K. Amberlite XAD-2 functionalized with o-aminophenol: synthesis and applications as extractant for copper(II), cobalt(II), cadmium(II), nickel(II), zinc(II) and lead(II). Talanta 2000, 51, 1187–1196.

23.Kumar, M.; Rathore, D.P.S.; Singh, A.K. Quinalizarin anchored on amberlite XAD-2. A new matrix for solid-phase extraction of metal ions for flame atomic absorption spectrometric determination. Fresen. J. Anal. Chem. 2001, 370, 377–382.

24.Tewari, P.K.; Singh, A.K. Synthesis, characterization and applications of pyrocatechol modified amberlite XAD-2 resin for preconcentration and determination of metal ions in water samples by flame atomic absorption spectrometry (FAAS). Talanta 2001, 53, 823–833.

25.Soylak, M.; Elci, L. Preconcentration and separation of trace metal ions from sea water samples by use of amberlite XAD-16 after complexation with sodium diethyldithiocarbamate. Int. J. Envir. Anal. Chem. 1997, 66, 51–59.

26.Soylak, M.; Dogan, M. Separation and enrichment of zinc, iron, copper, cadmium, cobalt and nickel from urine with amberlite XAD-16 resin. Trace Elem. Electroly. 1996, 13, 130–132.

27.Soylak, M.; Elci, L.; Dogan, M. Determination of trace amounts of cobalt in natural water samples as 4-(2-thiazolylazo) recorcinol complex after adsorptive preconcentration. Anal. Lett. 1997, 30, 623–631.

28.Soylak, M.; Divrikli, U.; Dogan, M. Column separation and enrichment of trace amounts of Cu, Ni and Fe on XAD-16 resin in industrial fertilisers after complexation with 4-(2-thiazolylazo) resorcinol. J. Trace Microprobe Techn. 1997, 15, 197–204.

29.Soylak, M.; Divrikli, U.; Elci, L.; Dogan, M. Column chromatographic preconcentration of copper, nickel and iron in ammonium salts by graphite furnace atomic absorption spectrometry. Kuwait J. Science Eng. 1998, 25, 389–396.

Downloaded by [Mount Royal University] at 07:03 23 May 2013

30.Elci, L.; Soylak, M.; Uzun, A.; Buyukpatir, E.; Dogan, M. Determination of trace impurities in some nickel compounds by flame atomic absorption spectrometry after solid phase extraction using amberlite XAD-16 resin. Fresen. J. Anal. Chem. 2000, 368, 358–361.

31.Lee, C.H.; Suh, M.Y.; Kih, S.J.; Tae, Y.E.; Won, L. A chelating resin containing 4-(2-thiazolylazo) resorcinol as the functional group. Chromatographic application to the preconcentration and separation of some trace metal ions including uranium. Anal. Chim. Acta 1997, 351, 57–63.

32.Lee, C.H.; Kim, J.S.; Suh, M.Y.; Lee, W. A chelating resin containing 4-(2-thiazolylazo) resorcinol as the functional group synthesis and sorption behavior for trace metal ions. Anal. Chim. Acta 1997, 339, 303–312.

33.Lee, C.H.; Suh, M.Y.; Kim, J.S.; Kim, D.Y.; Kim W.H., Eom, T.Y. Separation and preconcentration of uranium from geological materials with chelating resin containing 4-(2-thiazolylazo) resorcinol functional groups, Anal. Chim. Acta 1999, 382, 199–203.

34.Lee, W.; Lee, S.E.; Lee, C.H.; Kim, Y.S.; Lee, Y.I. A chelating resin containing 1-(2-thiazolylazo)-2-naphthol as the functional group; synthesis and sorption behavior for trace metal ions. Microchem. J. 2001, 70, 195–203.

35.Marczenko, Z. Separation and Spectrophotometric Determination of Elements; Wiley: Chichester, 1986.

36.Cheng, K.L.; Ueno, K.; Imamura, T. Handbook of Organic Analytical Reagents; CRC Press: Inc., Florida, 1982.

37.Soylak, M.; Dogan, M. Physical and chemical properties of the mineral spring waters from central region of Anatolia, Turkiye. Fresen. Envir. Bull. 1995, 4, 35–40.

38.Narin, I.; Soylak, M.; Kayakirilmaz, K.; Elci, L.; Dogan, M. Speciation of Cr(III) and Cr(VI) in tannery wastewater and sediment samples on ambersorb 563 resin. Anal. Lett. 2002, 35, 1437–1452.

Received August 20, 2002

Accepted October 24, 2002