Annals of West University of Timisoara

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1 Annals of West University of Timisoara Series Chemistry 19 (1) (2010) 9-16 PRELIMINARY STUDY REGARDING THE HEAVY METAL CONCENTRATION IN SOME SURFACE WATERS FROM THE OCNA DE FIER MINING AREA, BANAT Stela Uruioc a, Smaranda Mâşu b, Mariana Albulescu c, Maria Popa d a West University of Timişoara, Faculty of Chemistry, Biology, Geography, Department of Biology, Pestalozzi, 16, Timişoara, , ROMANIA b National Research and Development Institute for Industrial Ecology ECOIND, Victoriei Square,.2, PO Box 254, Timişoara, ROMANIA c West University of Timişoara, Faculty of Chemistry, Biology, Geography, Department of Chemistry, Pestalozzi, 16, Timişoara, , ROMANIA d 1 Decembrie 1918 University, Science Faculty, Nicolae Iorga, 11-13, Alba Iulia, , ROMANIA Received: 10 January 2010 Modified: 20 January 2010 Accepted : 30 January 2010 SUMMARY This article presents the results of an environmental study at the Ocna de Fier mining area, Banat. The study presents the preliminary assessment of the heavy metal concentration in Moravita stream and its tributary - Ursoanea, which flows through the refuse dump of the Ursoanea mine from Ocna de Fier. Concentration in heavy metal was determined for total Fe, total Mn, total Cr, Cu, Cd, Pb, Zn and Ni using an atomic absorption spectrophotometer of the AAS Varian type. Iron was the abundant heavy metal and the relative abundance of metal varied in the following order: Fe>Mn>Zn>Pb>Cu>Cd. The total Fe concentrations ranged between and mg/l, the total Mn between and mg/l, Zn between and mg/l, Pb between and mg/l, Cu between and mg/l. In only one sample cadmium was found in low concentration (0.001 mg/l). The total Cr and Ni were below the analytical detection limits. The analyzed samples do not contain nitrates, nitrites and ammonium and have a ph around 6.75 value. Keywords: refuse dump, heavy metals, surface water, Ocna de Fier, Romania 9

2 U RUIOC S., M Â Ş U S., A LBULESCU M., P OPA M. INTRODUCTION It is well known today that any mine, quarry, cocsochemical factory or siderurgical factory produces a local or regional pollution of the environment. As these activities are concentrated on smaller areas, as the local pollution is more intense and diverse [1]. Thus, it is well known the influence of exploitation and use of mineral resource on the environment in countries such as France, Germany, Holland, Belgium, Great Britain, USA, Russia etc. In our country, the quantitative and qualitative effects upon the environment of mineral resource exploitation and industrial use, are locally felt, especially in the vicinity of the main mining centres among which we mention: Baia Mare area, Zlatna, and in Banat Moldova Noua, Sasca Montana, Ruschita, Oravita, Ciclova, Bocsa, Dognecea, Ocna de Fier. The unfitted placement of the mining dumps and thus the migration of the toxic elements through the action of water and wind, implicitly led to the contamination of extended areas [2, 3]. In addition there is a very low recovery of the usable, as well contributing to the increase of the pollutant potential [2]. Mineral resource exploitation and industrial use influence, often unpredictably, the entire ecosystem [1]. The contamination of aquatic and terrestrial ecosystems with heavy metals is a major environmental problem [4-6]. In this paper, we proposed a study regarding the preliminary assessment of the heavy metal concentration from the Moravita stream and its tributary - Ursoanea, which flows through the refuse dump of the Ursoanea mine from the Ocna de Fier city. MATERIALS AND METHODS Water samples were collected in plastic bottles with a 500 ml capacity, from Ursoanea stream, in three points placed as follows: before flowing through the refuse dump (sample A1), from the middle of the dump (sample A2) and after the exiting dump (sample A3). Because this is a tributary stream to Moravita, we considered it interesting to sample water from this stream, as well, as follows (Figure 1): - 2 m before it receives Ursoanea as tributary (A4) and - 2 m after Ursoanea flows into Moravita (sample A5) All samples were taken in October

3 HEAVY METAL CONCENTRATION IN SOME SURFACE WATERS FROM THE OCNA DE FIER Figure 1. Areal distribution of collected points of water samples named A1, A2, A3, A4, and A5. Water samples were processed and analyzed according to the standards and normatives in consensus with the Romanian Association for Standardization (A.S.R.O.), at the INCD-ECOIND laboratories, Timisoara Branch. Heavy metal concentration was determined as total Fe, total Mn, Cu, total Cr, Cd, Pb, Zn and Ni using an atomic absorption spectrophotometer of the AAS Varian type. The obtained data are presented as graphics and were compared with the reference values for chemical elements norms, in accordance with the five classes of quality for the surface waters, annexed to the Waters Law from 2006, published in the O.M. of Romania, part I, no. 511bis from June 16 th, 2006 [7] and International standard ISO : 1994 (E) [8]. Usually for trace analysis the bottle for samples should be filed with nitric acid 1M or hydrochloric acid and left to soak for at least one day, followed by washing with distilled water. Samples are the filtered and acidyfied with HCl to ph lower than 2. In the case of Pb analysis, nitric acid was used. All the acidified samples were read using atomic absorption spectrophotometer of the AAS Varian type with detection limit mg /L. 11

4 U RUIOC S., M Â Ş U S., A LBULESCU M., P OPA M. RESULTS The metals determined in the water samples taken from the Ursoanea and Moravita streams are: total Fe, total Mn, Cu, Cr, Cd, Pb, Zn and Ni. Cr and Ni were under the detection limit or absent. There were also performed determinations for ph, nitrates, nitrites and ammonium. The total Fe content in water samples is presented in the following figure: Figure 2. The total Fe content (mg/l) in A1, A2, A3 water samples - Ursoanea stream and A4, A5 water samples - Moravita stream The Figures 3 and 4 represent the Mn and Cu content (mg/l) of A1, A2, A3 water samples from Ursoanea stream and A4, A5 water samples from Moravita stream. Figure 3. The Mn content (mg/l) in A1, A2, A3 water samples Ursoanea stream and A4, A5 water samples Moravita stream 12

5 HEAVY METAL CONCENTRATION IN SOME SURFACE WATERS FROM THE OCNA DE FIER Figure 4. The Cu content (mg/l) in A1, A2, A3 water samples Ursoanea stream and A4, A5 water samples Moravita stream The Figures 5 to 7 represent the Cd, Pb and Zn content (mg/l) respectively of A1, A2, A3 water samples from Ursoanea stream and A4, A5 water samples from Moravita stream. Figure 5. The Cd content(mg/l) in A1, A2, A3 water samples Ursoanea stream and A4, A5 water samples Moravita stream 13

6 U RUIOC S., M Â Ş U S., A LBULESCU M., P OPA M. Figure 6. The Pb content in mg/l from A1, A2, A3 water samples Ursoanea stream and A4, A5water samples Moravita stream Figure 7. The Zn content in mg/l from A1, A2, A3 water samples Ursoanea stream and A4, A5 water samples Moravita stream The analyzed samples do not contain nitrates, nitrites and ammonium and have a ph around DISCUSSION The chemical analysis results reveal the following situation: Considering the total Fe quantity (between and mg/l) from all the analyzed samples (A1, A2, A3 Ursoanea stream and A4, A5 Moravita stream) these waters rank in the first class of quality (maximum 0.3 mg/l) (Figure 2) Total Mn content (between and mg/l) ranks waters in the same first class of quality (max mg Mn/L) (Figure 3). For Cu, the situation is different; sample A1 (0.032 mg/l) from Ursoanea ranks in the second class of quality (max mg of Cu/L), and the other samples in the first class 14

7 HEAVY METAL CONCENTRATION IN SOME SURFACE WATERS FROM THE OCNA DE FIER of quality (max mg of Cu/L) (Figure 4). Cd was tracked down only in the A1 sample taken from Ursoanea before flowing through the dump, ranking this water in the second class of quality (max mg of Cd/L) (Figure 5) Pb shows variability in the samples taken from Ursoanea: A1 (0.036 mg/l) rank the water in the 4 th class of quality (max mg/l); A2 (0.008 mg/l) in the second class of quality (max mg/l); A3 (0.013 mg/l) in the 3 rd class of quality (max mg/l); A4 (0.003 mg/l) and A5 (0.001 mg/l), even though they come from the Moravita stream which flows through Ocna de Fier and receives as tributary Ursoanea, self-purifies, ranking the waters in the first class of quality (max mg/l) (Figure 6) Zn is present in all the samples in very low concentrations, under 0.1 mg/l, the respective waters ranking in the first class of quality (max. 0.1 mg/l) (Figure 7). Chemical analyses done on the water samples show that the waters are not contaminated. Comparing the analysis bulletin data with the reference values of chemical elements, for the surface water quality classes, annexed to the Waters Law from 2006, the chemical elements are within normal limits. CONCLUSION Processing data regarding the heavy metal content of surface water from Ocna de Fier area we can conclude the following: - Chemical analyses performed over water samples to find the heavy metal content show up that they are not contaminated; - Determined heavy metals in water, respectively total Fe, total Mn, Cu, Cd, Pb, Zn are in normal limits; - Considering the total Fe, Mn and Zn quantity in all the analyzed samples (A1, A2, A3 Ursoanea stream and A4, A5 Moravita stream) can be concluded that the waters rank in the first class of quality; - Regarding the Cu content of waters, the situation is different; sample A1 from Ursoanea ranks in the second class of quality, and the other samples in the first class of quality; - Cd was found in higher quantity only in A1 sample from Ursoanea so this water ranks in the second class of quality; - Surprisingly the water sample taken from Ursoanea before flowing through the refuse dump content more total Fe, Cu, Cd, Pb and Zn than other samples; - Pb shows variability in the samples taken from Ursoanea and rank in different classes of quality; 15

8 U RUIOC S., M Â Ş U S., A LBULESCU M., P OPA M. - Analyzed samples do not contain nitrates, nitrites and ammonium; - ph s water is around 6.75 values. REFERENCES 1. Albu M., Popa I., Management şi marketing în geologie, Ed. Universităţii Bucureşti, 1996, p Popescu Gh.C., Marinescu M., Predeţeanu D., Potenţialul metalogenetic al Munţilor Apuseni actual şi viitor potenţial poluant!?, in (Popescu Gh. Ed.) Munţii Apuseni, profil geoecologic, Ed. Bucureşti, 1995, p Uruioc, S., Elemente de geologie, Ed. Eurobit, Timişoara, 2010, p Andráš P., Lichý A., Rusková J.,Matúšková, L. Heavy metal contamination of the landscape at the Ľubietová deposit (Slovakia). Proceedings of World Academy of Science, Engineering and Technology, 34, Venice, Italy, 2008, p Andráš P., Lich A., Kušnierová, M., Križáni I., Ladomerský J., Rusková J., and Hroncová E., Heavy metal distribution at dump-field Ľubietová-Podlipa and possibilities of clay fraction natural sorbeant utilisation. Acta Montanistica Slovaca, Ročnic 14(2) (2009) Khan R., Israili S., H., Ahmad H., and Mohan A., Heavy Metal Pollution Assessment in surface Water Bodies and its Suitability for Irrigation around the Neyevli Lignite Mines and Associated Industrial Complex, Tamil Nadu, India, Mine Water and the Environment, 24 (2005) *** Legea apelor nr. 107 din 25 septembrie 1996, 8. International standard ISO : 1994 (E), 16