Journal of Analytical Chemistry, Vol. 58, No. 6, 2003, pp. 528532. Translated from Zhurnal Analiticheskoi Khimii, Vol.

58, No. 6, 2003, pp. 590594. Original Russian Text Copyright 2003 by Shvoeva, Dedkova, Savvin.

ARTICLES

Determination of Mercury(II) with Dithizone by Diffuse Reflectance Spectrometry on a Fibrous Anion Exchanger
O. P. Shvoeva, V. P. Dedkova, and S. B. Savvin
Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul. Kosygina 19, Moscow, 119991 Russia
Received May 6, 2002; in nal form, September 30, 2002

AbstractThe possibility of the determination of mercury(II) with dithizone on the solid phase of a brous ion-exchange material lled with the AV-17 anion exchanger was studied. Mercury is adsorbed as an anionic complex. The sorption of mercury as chloride, iodide, sulfate, thiosulfate, nitrate, and EDTA complexes was studied. A procedure was proposed for the sorptionspectrometric determination of mercury with dithizone on a solid phase after sorption as the chloride complex. For improving the selectivity of the method, EDTA is added to the solution. The determination is affected only by Pd(II). The time of analysis is 15 min. The procedure was tested in the analysis of tap and river water and a solution modeling natural water.

The Environmental Protection Agency specied mercury and some other heavy metals as priority pollutants. Mercury, along with cadmium and beryllium, is among the most toxic inorganic pollutants [1] with extremely low maximum permissible concentrations (MPC) in water. In recent years, procedures have been developed for the determination of mercury using instrumental methods: atomic-absorption, atomicemission, and X-ray uorescence spectrometry and stripping voltammetry. Because of the low MPC of mercury (0.0005 mg/L), in the most cases samples are preconcentrated by evaporation, adsorption, and other techniques. Different methods were proposed for the sorption spectrometric and test determination of mercury [210]. However, the sensitivity of determination of all of these methods does not reach the MPC level. The determination limit of copper is in the range of 0.0010.1 mg/L. Only the enzymatic test method for the determination of mercury and organomercury compounds provides the determination of 150 ng/mL mercury depending on the solid phase in use [810]. The development of simple and highly sensitive procedures for the determination of mercury remains a topical problem. The aim of this work was to study possibilities of the use of brous lled materials in the determination of mercury. Sorbents of this type are polyacrylonitrile ber in which the required ion exchanger is introduced in the process of ber formation. As a result, a colorless or weakly colored brous material lled with the ion exchanger is obtained. The degree of lling can be varied and is usually 5080%. Fibrous sorbents exhibit good kinetic and ion-exchange characteristics. They are ne brous materials stable in the range from strongly acidic to weakly alkaline solutions. These sorbents can

be conveniently used in sorptionspectrometric and test methods, in ow analysis, and in the batch mode. They exhibit a rather high exchange capacity and serve simultaneously for the preconcentration and determination of the adsorbed element on the solid phase. EXPERIMENTAL Reagents. Chemically pure or analytical-grade reagents were used. Solutions of metal salts (0.01 M) were prepared according to known procedures by the dissolution of corresponding nitrates or chlorides; working solutions were prepared by the dilution of more concentrated solutions. A stock 0.01 M mercury solution was prepared by the dissolution of a weighed portion of Hg(NO3)2 in 0.01 M HNO3; a working solution with a concentration of mercury of 50 g/mL was prepared by the dilution of the stock solution with 0.01 M HNO3. A stock 0.05% solution of dithizone was prepared by the dissolution of 0.05 g of the compound in 100 mL of acetone; the solution was stored in a refrigerator. A working solution of dithizone was prepared by mixing 5 mL of the stock solution, 5 mL of a 2.5% NH3 solution, and 1 or 5 mL of a 0.05 M EDTA solution and diluting to 50 mL with water. This working solution containing 0.005% dithizone, 10% acetone, 0.25% NH3, and 1 103 or 5 103 M EDTA was used for 2 days and stored in a refrigerator. Solutions of KI, KCl, NaCl, NaNO3, Na2SO4, Na2S2O3, and EDTA (0.1 and 0.01 M) were prepared by the dissolution of weighed portions of compounds in water or from commercial volumetric samples. The required acidity of the solutions was adjusted using 0.1 and 0.01 M solutions of HNO3 and NaOH.

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As a support, we used a brous material lled with the strongly alkaline AV-17 anion exchanger; the degree of lling was ~50%. The support was previously washed of cations with 1 M HCl until the negative reaction for iron(III) with thiocyanate ions and then with water until the negative reaction with silver(I) for chloride ions. The sorbent was used in the form of disks with a diameter of 20 mm and a mass of 2530 mg in the swollen state; for this purpose, the disks were held for a day and then stored in distilled water. Instruments. The acidity of the test solutions was measured with a glass electrode using a pH-673 potentiometer. Support disks were placed in glass ow cells, and solutions were pumped though the disks using a PP-2-15 peristaltic pump at a ow rate of 10 mL/min. Diffuse reectance spectra were recorded on a Spectroton colorimeter (Chirchik Experimental Design Bureau of Automatic Equipment, Tashkent, Uzbekistan). The difference between the diffuse reection coefcients of disks after passing the reference and test solutions at the optimal wavelength (R) was taken as the analytical signal. The reference solution contained all the components of the reaction except the determined ion. It was passed through all of the operations along with the test solution. Procedure. A support disk was placed in a ow cell, and a test solution was pumped through the disk at a ow rate of 10 mL/min using a peristaltic pump. Next, 1 mL of a reagent solution was pumped through this disk, the disk was transferred into the measuring chamber of a Spectroton colorimeter, and the diffuse reection coefcient was measured at the optimal wavelength. RESULTS AND DISCUSSION Mercury(II) forms stable complexes with many inorganic and organic substances. Complex compounds of mercury with halide ions are widely used in their sorption with anion exchangers. The stability of halide complexes in aqueous solutions increases in the order F < Cl < Br < I [11]. Mercury forms complexes with oxygen-containing ligands. Among organic reagents for the photometric determination of mercury, dithizone and 4-(2-pyridylazo)resorcinol (PAR) are widely used. We studied the color reactions of Cd(II), Pb(II), and Hg(II) with dithizone and PAR on the solid phase after their sorption in the form of anionic complexes [12]. It was demonstrated that the maximum analytical signal is observed at 590 nm. Mercury is partially adsorbed on the anion exchanger even in the absence of the additional anion. The analytical signal is detected in the presence of 2 105 M NO 3 (introduced together with the mercury solution). The effect of the acidity of the solution at the stage of sorption in the absence of the

R 0.4

0.2

0 1

11 pH

Fig. 1. Dependence of the analytical signal of the mercury complex of dithizone on the AV-17 brous anion exchanger on the pH of the solution at the stage sorption; 0.2 g/mL Hg(II), V = 25 mL, 590 nm.

R 0.4 1 4 0.3 3 5 0.2 6 2

0.1

5 pcANn

Fig. 2. Dependences of the analytical signals of the mercury complex of dithizone on the concentration of (1) KI, (2) Na2S2O3, (3) KCl, (4) EDTA, (5) Na2SO4, and (6) NaNO3 in the solution; 0.2 g/mL Hg(II), V = 25 mL, 590 nm, and pH 4.85.2.

additional anion is presented in Fig. 1. As seen in the gure, nearly the same analytical signal is observed at pH 310. It was demonstrated previously that the largest difference in the reactivity of mercury, lead, and cadmium is observed at pH 45; therefore, subsequent studies were performed at pH 4.85.2. In the sorption from a 104 M KI solution in the presence of equimolar amounts of cadmium and lead, mercury exhibits an individual analytical signal; cadmium and lead do not interfere with the determination of mercury. The effect of different anions on the sorption of mercury and the subsequent determination with dithizone on the AV-17 brous anion exchanger is presented in Fig. 2. It is seen that the largest analytical signals of the mercury complex of dithizone are observed
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SHVOEVA et al.

0.2

0.1

3 pcEDTA

Fig. 3. Dependence of the analytical signal of the mercury complex of dithizone on the concentration of EDTA in the reagent solution; 0.2 g/mL Hg(II), V = 25 mL, pH 4.85.2, and 590 nm; the reagent is 1 mL of a solution containing 0.005% dithizone, 10% acetone, and 0.25% NH3.

of one of the components of the reaction. In the sorption of the anionic complex on the anion exchanger, some correspondence must exist between the stability of the complex and the strength of the binding of this complex with the anion exchanger. This condition is fullled at the plateaus of the curves. For the most stable anionic complexes, the masking of the cation with this anion is observed, and these complexes are not adsorbed on the anion exchanger. On the other hand, the adsorbed complex can be so stable that it does not react with dithizone. Finally, the saturation of the anion exchanger, on which sorption occurs, can be attained at a high concentration of anions in the solution. Generally, note that complex competitive interactions occur between the introduced anion and the metal cation, between the anionic complex and the anion exchanger, and between the adsorbed anionic complex and the reagent. This issue was not studied in this work. In the sorption of chloride complexes (Fig. 2, curve 3), the analytical signals are nearly independent of the concentration of the ligand in a wide range of concentrations 102105 M. To approximate the conditions of analysis of real water, in further studies we used the sorption of mercury from chloride solutions in spite of some loss in sensitivity. It was important that the analytical signal was maximum in 104105 M EDTA solutions. Dithizone is a group reagent and reacts with many elements, which, in turn, are readily masked with EDTA. The signicant dependence of the analytical signal on the concentration of EDTA precludes its use in the sorption of mercury because it is difcult to provide a certain excess of EDTA in a rather mineralized solution, such as natural water. This will lead to nonreproducible results. Therefore, in the sorption of mercury we used a 0.01 M NaCl solution, and EDTA was introduced at the stage of determination. EDTA was added to the solution of the reagent providing the masking of the concomitant cations that were adsorbed together with mercury ions. The effect of the amount of EDTA in the solution of dithizone on the analytical signal is presented in Fig. 3. For the subsequent studies, we used a solution containing 1 103 M dithizone and 5 103 M EDTA.

on the sorption of mercury from solutions of KI, Na2S2O3, and EDTA. Sorption can be performed in the concentration ranges of 103105 M KI, 104105 M EDTA, and 105 M Na2S2O3. The smallest analytical signals are observed in the sorption of mercury from nitrate solutions. These dependences of the analytical signals on the nature of the anion are consistent with the stability of mercury complexes of these anions. For the least stable nitrate complexes of mercury, the analytical signal is two times lower than for iodide, thiosulfate, or EDTA complexes. The curves in Fig. 2 demonstrate the signicant decrease in the analytical signal upon increasing the concentration of anions in the solution. At concentrations above 105 M S2 O 3 , 104 M EDTA, and 103 M SO 4 and NO 3 , the analytical signal drastically decreases. For KI solutions (Fig. 2, curve 1), this relationship is less pronounced. The decrease in the analytical signal upon increasing the concentration of anions in the solution can be explained by an increase in the stability of the anionic complex or a change in its composition because of the shift of the equilibrium of complex formation upon increasing the concentration
2 2

Table 1. Selectivity factors in the determination of mercury with dithizone on a fibrous anion exchanger filled with AV-17 Foreign ion Pd(II) Au(III) Cu(II) Ag(I), Fe(II, III) Sn(II) Selectivity factor <1* 4* 10, 40* 20* 20 Foreign ion Bi(III) Ni(II) Cd(II), Co(II) Pb(II), Zn(II), Mn(II) Selectivity factor 40 200 500 >1000

* The reagent contains 5 103 M EDTA; in the other cases, the reagent contains 1 103 M EDTA. JOURNAL OF ANALYTICAL CHEMISTRY Vol. 58 No. 6 2003

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Dithizone forms colored complexes with Mn(II), Fe(II), Co, Ni, Cu, Zn, Pb, Ag, In, Sn, Te, Pt, Au, Hg, Bi, etc. [13]. We studied the selectivity of the determination of mercury with respect to these elements. Table 1 presents the selectivity factors, i.e., the mass ratios of the foreign and analyte ions at which the error in the determination of mercury is within 10%. The selectivity factors were determined for an adsorbed solution with a Hg(II) concentration of 0.1 g/mL, a NaCl concentration of 0.01 M, pH 4.85.2, and a variable concentration of the studied concomitant cation. For the determination, we used 1 mL of a reagent solution containing 0.005% dithizone, 10% acetone, 0.25% NH3, and 1 103 M EDTA. In the study of the interfering effect of Au(III), Cu(II), Ag, and Fe(III), the selectivity factors were determined with a reagent solution containing 5 103 M EDTA. As is seen in Table 1, a high selectivity is observed for Mn(II), Zn, Pb, Co, Cd, and Ni; Pd(II) and fourfold amounts of Au(III) interfere with the determination of mercury. For the other elements, the selectivity is satisfactory, which makes it possible to use the proposed procedure for the determination of mercury in natural water. To expand the analytical range of mercury, we studied the possibility of sorption of 05 g of mercury from 20, 100, and 500 mL of a 0.01 M NaCl solution with pH 4.85.2. A dithizone solution containing 1 103 M EDTA was used as the reagent. For 500, 100, and 20 mL of the solution, the obtained calibration plots are linear in mercury concentration ranges of 0.0020.008, 0.0080.04, and 0.0250.2 g/mL, respectively, and are described by the equations R = 25.84c + 0.13, R = 7.69c + 0.06, and R = 1.48c + 0.06, respectively, where c is the concentration of mercury, g/mL, and R is the analytical signal. At a volume of the test solution of 500 mL, the detection limit of mercury calculated by the 3s value is 1 ng/mL. In the case when the concentration of EDTA in the reagent solution is ve times higher and the volume of the test solution is 100 mL, the equation of the calibration plot is R = 4.37c + 0.07. This equation was used in the development of a procedure for the determination of mercury in natural water. The procedure for the sorptionspectrometric determination of mercury was tested with a solution modeling natural water and in the analysis of river water (Moskva river) and tap water. The accuracy of the results was estimated by the addedfound method. Determination procedure. One milliliter of a 1 M NaCl solution and 1.52.5 mL of 1.0 M HNO3 (to pH 4.85.2) are added to 100 mL of a sample, and the mixture is pumped at a ow rate of 10 mL/min through a support disk with AV-17 placed in a glass cell. Next, 1 mL of a reagent solution containing 0.005% dithizone, 10% acetone, 0.25% NH3, and 5 103 M EDTA is pumped through the disk (in the analysis of distilled water or a solution modeling natural water, the
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Table 2. Results of the determination of mercury(II) in water (n = 3, P = 0.95) Water Distilled water Solution modeling natural water* Tap water* Added Hg, mg/L 0.025 0.020 0.015 0.025 0.015 0.030 Found Hg, mg/L 0.025 0.002 0.020 0.003 <0.005 0.015 0.003 0.025 0.003 <0.005 0.012 0.004 0.031 0.005 RSD, % 5 6

8 5

River water (Moskva river)**

20 8

*Solution modeling natural water: 0.02 M NaCl, 0.002 M MgSO4 , and 0.004 M CaCl2 and KCl. **The reagent is 5 103 M EDTA.

reagent solution contained 1 103 M EDTA), and within 12 min the diffuse reection coefcient is measured at 590 nm. Analogously, the diffuse reection coefcient is measured for a blank sample containing distilled water instead of the test solution. The concentration of mercury is calculated by the equation c (g/mL) = (R 0.07)/4.37 and, when the reagent solution contains 1 103 M EDTA, by the equation c (g/mL) = (R 0.06)/7.69. Results of the analysis of water are presented in Table 2. The data in the table suggest that the procedure for the sorptionspectrometric determination of mercury with dithizone on the solid phase of a brous material lled with the AV-17 anion exchanger can be used for the analysis of natural waters. The relative standard deviation is no higher than 20%. The time of analysis is 15 min. Thus, this study makes it possible to recommend the new sorptionspectrometric method for the determination of mercury, which consists in the sorption preconcentration of anionic mercury complexes on a brous anion exchanger lled with AV-17 and the determination of mercury with dithizone on the solid phase. The use of the sorption preconcentration of mercury in the form of anionic complexes and the determination directly on the brous anion exchanger can signicantly decrease the detection limit, signicantly improve the selectivity of the determination, simplify the procedure, and decrease the time of analysis. REFERENCES
1. Fresenius, W. and Dylick, C.E., Fresenius J. Anal. Chem., 2000, vol. 366, no. 5, p. 417. 2. Savvin, S.B., Trutneva, L.M., Shvoeva, O.P., and Effendieva, K.A., Zh. Anal. Khim., 1991, vol. 46, no. 4, p. 709.
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SHVOEVA et al. 9. Shekhovtsova, T.N., Muginova, S.V., and Bagirova, N.A., Anal. Chim. Acta, 1997, vol. 344, p. 145. 10. Shekhovtsova, T.N. and Chernetskaya, S.V., Anal. Lett., 1994, vol. 27, p. 2883. 11. Gladyshev, V.P., Levitskaya, S.A., and Filippova, L.M., Analiticheskaya khimiya rtuti (The Analytical Chemistry of Mercury), Moscow: Nauka, 1974. 12. Dedkova, V.P., Shvoeva, O.P., and Savvin, S.B., Zh. Anal. Khim., 2002, vol. 57, no. 4, p. 355. 13. Iwantscheff, G., Das Dithizon und seine Anwendung in der Mikro- und Spurenanalyse, Weinheim: Chemie, 1972. Translated under the title Ditizon i ego primenenie, Moscow: Inostrannaya Literatura, 1961.

3. Ostrovskaya, V.M., Aksenova, M.S., Osyka, V.F., et al., Vysokochist. Veshchestva, 1992, no. 3, p. 152. 4. Gureva, R.F. and Savvin, S.B., Zh. Anal. Khim., 1997, vol. 52, no. 3, p. 247. 5. Zaporozhets, O., Petruniock, N., and Sukhan, V., Talanta, 1999, vol. 50, no. 4, p. 865. 6. Amelin, V.G., Zh. Anal. Khim., 1999, vol. 54, no. 6, p. 651; no. 7, p. 753. 7. Ivanov, V.M. and Kochelaeva, G.A., Vestn. Mosk. Univ., Ser. 2: Khim., 2001, vol. 42, no. 1, p. 17. 8. Shekhovtsova, T.N., Chernetskaya, S.V., Belkova, N.V., and Dolmanova, I.F., Zh. Anal. Khim., 1995, vol. 50, no. 5, p. 538.

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