Annals of the „Constantin Brâncuşi” University of Târgu Jiu, Economy Series, Special Issue/2014- Information society and sustainable development RESEARCH ON HEAVY METAL POLLUTION OF THE RIVER MUREŞ IN HUNEDOARA COUNTY DUE TRIBUTARIES AFFECTED BY HUMAN ACTIVITIES, INDUSTRIAL AND MINING

SZOLLOSI-MOŢA ANDREI, drd.chim. SÂRBU ROMULUS PROF.UNIV.DR.ING., UNIVERSITATEA PETROŞANI

ABSTRACT: Mureş crosses over a length of 105 km, a broad tectonic corridor between mountains Şureanu, Poiana Rusca Mountains and the Apuseni Mountains in the north. Hunedoara County has significant quantities of mineral resources, mining specific activities effectively represents one of the main economic sectors. Ore processing gave rise to significant amounts of mining waste. Tailings dams and waste dumps obtained from ore processing in preparation plants are large and have led to changes in the morphology of the area. The purpose of this study is to examine the degree of pollution of the river Mures in Hunedoara county, with heavy metals due to various human activities. For monitoring and evaluation in terms of water quality of the river Mures and studying the degree and effects of pollution were collected and analyzed water samples from Mures River and tributaries from the main mining areas, such Certej. Samples were analyzed by emission spectrometry with inductively coupled plasma and the results of measurements allowed us to assess the degree of pollution of the aquatic environment and sediments . The effects of mining waste on the environment persists for a long time , even after the operation closed. Rehabilitation mining areas and those adjacent to improve the quality of life, as a prerequisite for sustainable development.

1. Introduction Mureş River crossing over a length of 105 km, a broad tectonic corridor between mountains Şureanu and Poiana Rusca Mountains and the Western Mountains in the North.When entering the county town of Aurel Vlaicu upstream , the river has a 20100 km2 basin and outlet downstream from Zam, of 25315 km2.The major tributaries such as Strei, Cerna Geoagiu and other reduse sized rivers . Annual average flow of the river Mures, over the last 30 years ranging from 120 m3 / s in the input section in the county to 165m3 / s in the output .

2.Polution of surface waters

Pollution is the circumstance where the natural components in the environment are damaged or replaced by hazardous chemical substances or energy which can create a imbalance in the system and number of health hazards to nature and humans.

2.1. Polution due to human activities

Such components are known as pollutants and may be gases (causes air pollution); solids/liquids (can cause water and soil pollution). All these components cause imbalance to the natural environment either directly or indirectly. Water pollution is altering the physical, chemical and biological water produced directly or indirectly, natural or anthropogenic . Polluted water becomes unfit normal use .

2.2.Polution surface water with mining water and industrial activity

Minerals in Hunedoara county is characterized by complex mining conditions and also the physical, mechanical and mineralurgical difficult. It works directly through technological water treatment before being discharged into the river .Dumps contain metal ions (Zn , Cu, Cd, Cr , Pb, etc.). [1 ] , residues from preparation plants impregnated with reagents that are transported by surface water groundwater and soil . Storage ponds tailings resulting from the processing of ores in preparation plants are relatively large , and fundamentally changes the morphology of the zone , and the content of pollutants are factors and sources of pollution and water - the suspension by metal ions and reagents use. Past floods on the rivers Certej ( the Mures River Basin ) and their tributaries have led to large amounts of tailings sands flotation tailings and coarse material that have been deposited on agricultural land resulting in

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162 Annals of the „Constantin Brâncuşi” University of Târgu Jiu, Economy Series, Special Issue/2014- Information society and sustainable development contamination of the area . It takes water Storage ponds tailings resulting from the processing of ores in preparation plants are relatively large , and fundamentally changes the morphology of the zone , and the content of pollutants are factors and sources of air pollution - the dust - and water - through suspension by metal ions and reagents. 2.3. Caracterization of mine wastewater

Mining water infiltrates through the rock formations which occur in the mineralized complex dissolution processes [2 ] , decomposition and deposition of chemicals or components resulting from mineral components , which gives groundwater specific physico-chemical characteristics of which the most important are: The pH - value is variable within wide limits, expressed acidic or alkaline water according to the concentration of hydrogen ions 2- 4 - - The mine water are dissolved various substances , such as can be grouped into anions ( SO4 , PO3 , Cl ) and cations (Ca2 + , Cu 2 + , Zn 2 + ,) [3 ] . The acidity of water is one of the most important issues affecting the fauna and flora acidification

3.Material and methods used in the research

To characterize the pollution of water samples were collected from the Mureş River water and sediment samples from the river Certej and the confluence of the Mures River and the main tributaries of the river Mures county of Hunedoara . For analyzes sediment samples collected were subjected to the processes of drying, crushing , grinding , sieving , weighing and bringing the solution . For mineralization was used to microwawe digestion sistem and to perform the optical emission spectrometer .

Figure no.1 Sediment samples

Figure No. 2. Optical emission spectrometer with inductively coupled plasma .

Figure no.3 Image overlay spectra for cadmium .

„ACADEMICA BRÂNCUŞI” PUBLISHER, ISSN 2344 – 3685/ISSN-L 1844 - 7007

163 Annals of the „Constantin Brâncuşi” University of Târgu Jiu, Economy Series, Special Issue/2014- Information society and sustainable development In the optical emission spectrometry , the sample is subjected to temperatures high enough to promote the dissociation of atoms for ionization thereof and the emission of electrons. The optical emission spectrometry inductively coupled plasma electromagnets intensity of the radiation emitted at the specific wavelength is measured and used to determine concentrations of components of interest. [5]. To calibrate the optical emission spectrometer with inductively coupled plasma were used certified reference materials. In an earlier stage analyzes were performed on samples from the main tributaries of the river Mures, Hunedoara County and Strei, Cerna, Geoagiu. Following the analysis of samples we concluded that water samples analyzed from main tributaries has a lower pollution level compared to rivers that cross a major mining area and Certej.

Figure no.4 - The test results of water samples downstream of the confluence of river Mures and River Geogiu , and represented in graphics. Element Sample 1 Sample 2 Permissible values µg/l mg/l mg/l Cu 0,022 0,008 20 Cr 0,013 0,012 25 Zn 0,097 0,072 100 Fe 0,076 0,032 300

Figure No.5 outcome analyzes of water samples taken in January and March , harvested in the town of upper Certeju de Sus. [4 ] .

Name of Sample Sample Permisibble Exceending Exceending nr.1 nr.2 value or or nr.1 nr.2 metal µg/l µg/l µg/l

Lead 64 48 5 12,8 9,6 Copper 547 424 20 27,35 21,2 Zinc 16290 13990 100 162,9 139,9 Cadmium 107 90 0,5 214 180 Nickel 272 225 10 27,2 22,5 Cobalt 79 45 10 7,9 4,5

Figure No.6 metal concentration in sediment samples that we collected from the village of upper Certeju de Sus[4 ] .

Maximum Exceeding or The concentration of concentration [mg/kg] Element determined mg/kg] Cd 10,04 0,8 12,55 Cu 188,9 40 4,72 Fe 44910 - - Mn 415,2 - - Pb 538,8 85 6,33

Figure No.6 Diagram of metal concentrations in sediments

Pb

Mn

Fe

Cu

Cd

0 10000 20000 30000 40000 50000 Concentratia mg/kg

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164 Annals of the „Constantin Brâncuşi” University of Târgu Jiu, Economy Series, Special Issue/2014- Information society and sustainable development

Figure No.7 Concentration of heavy metals in sediments collected downstream of the confluence of river Mures River Certej

The concentration of Maximum Exceeding or Element determined [mg/kg] concentration [mg/kg] Cd 34 0,8 42,5 Cu 189,20 40 4,72 Fe 594,8 - - Mn 13,64 - - Pb 31,245 85 -

4. Conclusion

Watercourses that drain mine water flowing from the research subject , lead us to the consideration that ecosystem Certej riverr ( a tributary of the river Mures ) is partially destroyed due to mining activities. Samples with the highest concentrations of heavy metals in the river were collected and analyzed Certej area representing areas affected by mining activities. After determining the concentrations of these heavy metals can we characterized the current state of courses water main that feeds the river Mures in Hunedoara county, so water samples collected were significant exceedances dozen times to certain metals : lead, copper, cadmium, nickel cobalt up to hundreds of times (the maximum value allowed for zinc). Water samples collected and analyzed by optical emission spectrometry with inductively coupled plasma of the main tributaries of Hunedoara and Strei, Cerna shown significant concentrations exceeded . Sample analyzes showed main tributaries showed a much lower degree of pollution compared to surface waters from mining areas . Analyzing sediments and Mureş rivers Certej observed exceedances for cadmium, copper and lead. The balance of an ecosystem can be easily destroyed by modifying any biotic or abiotic characteristics , the effect of heavy metals can occur through bioaccumulation term. The mining activity has a strong impact on the environment and the Environment have been Accumulated problems in time. Its necessary to monitor the acid drainage and to mitigation this phenomen.

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