ELECTROCHEMICAL DETERMINATION OF HEAVY METALS IN RAINWATER Petr MAJZLÍK1, David HYNEK1, Rene KIZEK1,2* 1 Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University in Brno, Zemedelska 1, 613 00 Brno, Czech Republic 2 Central European Institute of Technology, Brno University of Technology, Technicka 3058/10, 616 00 Brno, Czech Republic *kizek@sci.muni.cz Abstract Electrochemical determination of heavy metals in rain water is the aim of this paper. Determination of heavy metals in rainwater from weather-station Bořitov in course of one year was carried out. For electrochemical determination measuring system Metrohm (Autosampler 813 Compact and measuring unit VA Computrace 797) was employed. 1. INTRODUCTION Electrochemical determination of heavy metals in rain water is simple, practic and useful way how to check the amount of heavy metals in environment [1]. Zinc, cadmium, lead and copper belong to the group of heavy metals [2]. There are two insights into pollution of living environment by heavy metals [3]. First represents occurrence of these metals in rocks, from which can be gradually released and entry the plants, respectively food chain. Second possibility of occurrence of heavy metals in living environment represents human itself due to anthropogenic activity (mining and processing of ore, chemical industry). Heavy metals represent significant problem, especially because of their toxicity, which may cause acute as well as chronic intoxication and lead to origination of malignant tumour disease [4 - 6]. Due to these facts, improving of methods of their qualification and quantification using various measuring procedures is very advisable. 2. MATERIAL AND METHODS Electrochemical determination Measuring system Metrohm was employed for the determination of heavy metals – Autosampler 813 Compact and measuring unit VA Computrace 797. Samples were prepared in this manner: 15μl of sample were mixed with 985μl of acetic buffer (pH = 5). Diferential pulse voltametry was used for the measurement with these parameters: potencial of deposition -1,3V, time of deposition 240s, range of potencial from -1,3V to 0,15V, pulse amplitude 0,025V, pulse time 0,04s, unit step 0,005035V, time of unit step 0,3s. A standard cell with three electrodes was used for the measurment. A hanging mercury drop electrode (HMDE) with a drop area of 0.4 mm2 was employed as the working electrode. An Ag/AgCl/3M KCl electrode served as the reference electrode. Pt electrode was used as the auxiliary electrode. 3. RESULTS AND DISCUSSION Measurement of heavy metals by DPV technique has been described many times over in literature; therefore, it is not necessary to represent accomplishments and negatives of this technique. Main aim of our work consisted in proposing and realization of automated measuring procedure for analysis of defined small volume of sample for determination of above mentioned heavy metals in rainwater. Preparation of sample proceeded in accordance with following procedure: volume of 15μl of sample for measurement of heavy metals (Zn, Cd, and Cu) was placed into Eppendorf micro test tube together with 985μl of acetate buffer (pH 5.00). Samples were subsequently placed into Autosampler 813; in enclosed software, list of measured samples was created. Dependence of buffer pH and concentration of heavy metals illustrates Fig. 1. It is obvious that the best detection of heavy metals is by pH 5.00. That is the reason for use of acetic buffer pH 5.00 for other measurements. Figure 1.: Dependence of buffer pH and system response Rainwater samples were measured for present of heavy metals. Furthermore conductivity and pH were measured. Average characteristic values for each season in one year are presented in Table 1. Concentration of pollutants which are presented in table is increasing in summer months. Opposite in winter the concentration of pollutants is higher. Probably it is due to human activity, especially heating and pollutants emitted into air). Dependence of pH in one year is increasing from spring to winter as well as conductivity. Table 1: Comparison of various characterictic values in course of one year. pH conductivity (µS/cm) conc. Zn (µM) conc. Cd (µM) conc. Pb (µM) conc. Cu (µM) 1. spring (6,53) spring (56,12) spring (28,05) spring (0,54) spring (1,29) spring (21,58) 2. summer (6,37) summer (63,38) summer (29,32) summer (0,12) summer (1,44) summer (19,91) 3. autumn (6,90) autumn (71,74) autumn (90,41) autumn (5,66) autumn (4,55) autumn (37,27) 4. winter (7,15) winter (88,47) winter (98,80) winter (6.00) winter (7,06) winter (51,06) 4. CONCLUSION Monitoring of amount of heavy metals in rainwater is presented in this paper. Electrochemical detection of heavy metals represents analytical method with good reproducibility, effortless service and relatively rapid determination. It seems to be good analytical tool for periodic determination of heavy metals in rainwater. Monitoring of pollutants in rainwater is very useful tool for environment control. 5. ACKNOWLEDGEMENT The work has been supported by NANIMEL GA ČR 102/08/1546. 6. REFERENCES [1] Vacek J, Petrek J, Kizek R, et all.: Bioelectrochemistry, 63 (2004), 1-2, 347-351 [1] Strouhal M, Kizek R, Vacek J, et all.: Bioelectrochemistry, 60 (2003), 1-2, 29-36 [2] Adam V, Petrlova J, Potesil D, et all.: Electroanalysis, 17 (2005), 18, 1649-1657 [3] Kovarova J, Kizek R, Adam V, et all.: Sensors, 9 (2009), 6, 4789-4803 [4] Adam V, Sileny J, Hubalek J, et all.: Toxicology Letters, 180 (2008), Suppl.1, S227-S228 [5] Adam V, Fabrik I, Kohoutkova V, et all.: International Journal of Electrochemical Science, 5 (2010), 429-447 [6] Krystofova O, Trnkova L, Adam V, et all.: Sensors, 10, 6, 5308-5328