Biomonitoring Air Pollution in Chelyabinsk Region (Ural Mountains, Russia) Through Trace-Elements and Radionuclides: Temporal and Spatial Trends
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BIOMONITORING AIR POLLUTION IN CHELYABINSK REGION (URAL MOUNTAINS, RUSSIA) THROUGH TRACE-ELEMENTS AND RADIONUCLIDES: TEMPORAL AND SPATIAL TRENDS V.D. CHERCHINTSEV, M.V. FRONTASYEVA*, S.M. LYAPUNOV*, L.I. SMIRNOV* Magnitogorsk State Academy of Mining and Metallurgy, Lenin Prospect, 38, 455000 Magnitogorsk, Russia, *Joint Institute for Nuclear Research, 141980 Dubna, Moscow Region, Russia, ** Geological Institute of RAS, Pyizhevskij per., 7, 109017 Moscow, Russia Abstract: XA0102868 This report contains the results on the analysis of the moss species Hylocomium splendens and Pleurozium schreberi -which were used to study heavy metal atmospheric deposition, as -well as other toxic elements, in the Chelyabinsk Region (the South Ural Mountains) characterized by intense anthropogenic impact from various industries including plutonium production - the source of radionuclides of great potential hazard. A two years summer field work followed by the applying two most appropriate analytical techniques to the analyses of the collected moss•— NAA and AAS— allowed us to determine the atmospheric deposition of about 40 elements over the examined areas. One on them is considered to be the most polluted place in the world, the copper mining and reprocessing centre of the Russian Federation in Karabash, and the other adjacent area is of no less ecological stress, the area to the north of the Mayak complex for plutonium production, next to the city of Ozersk. The element concentrations in moss samples from the Urals are compared with those available for the Copper Basin in Poland, Tula Region (Russia), Germany and Norway, obtained by the same moss biomonitoring technique. Information on radionuclides in soils collected during the same fieldwork in the northern part of the Chelyabinsk region in July, 1998 is given. Plans for moss and soil -survey-2000 are reported. 1. SCIENTIFIC BACKGROUND AND SCOPE OF THE PROJECT The South Ural Mountains are among of the most polluted areas in the world where human impact in the environment is practically irreversible. These areas include several industrial cities such as Karabash, Chelyabinsk, Ozersk and many others, where the clustering of heavy industry has produced extremely high levels of air and water pollution. In addition, substantial emissions of radioactive substances have occurred in the Ural region as the result of full-scale activities of the radiochemical "Mayak" Production Association (PA), from liquid radioactive waste disposal into the river Techa and lake Karachay, the Kyshtym accident in 1957, and the Karachay wind dispersion in 1967. The latter is reviewed in a report "Behind the Nuclear Curtain. Radioactive Waste Management in this Former Soviet Union" of Battelle Memorial Institute, USA, 1997 [1]. Thus two the most important groups of pollutants emitted into the atmosphere in this region are heavy metals and long-lived radionuclides. Studies of atmospheric emissions of heavy metals from metal mining and processing and other industries have so far been limited to pollution within and in the near vicinity of the factories. The impact of these emissions on a regional scale is not known, as well as their influence on the natural environment and their possible impact on human health. Monitoring efforts of the present study will help to elucidate these problems. 197 This project originated at a NATO Advanced Research Workshop "Air Pollution in the Ural Mountains" (May 25-29, 1997, Magnitogorsk, Russia) organized by Harvard University (USA) and Magnitogorsk Academy of Mining and Metallurgy. It was hosted by the Chief Scientific Investigator, Prof. V.D. Cherchintsev, a Co-Chairman of the ARW. The present CRP's expert, Prof. E. Steinnes (Norway), who participated in that Workshop, suggested a Prospectus "Monitoring of Heavy Metals and Radionuclides in the Ural Region: Temporal and Spatial Trends". It was emphasized, discussed and adopted at the Round Table by a distinguished group of the international experts from 16 countries. During that Workshop Dr. M.V. Frontasyeva initiated fieldwork that has been done on a small geographical scale, in the vicinity of Lake Bannoe, situated 30 km from the Joint-Stock Company «Magnitogorsk Iron and Steel Works», South Ural Mountains. The results of this pilot study has been published as a reprint of JINR, Dubna [2] (in English) and in the collection of papers "Ecology of Industrial Regions at the Boarder of the XXI Century", Ural, 1999 [3] (in Russian). It was also accepted by the Journal of Radioanalytical and Nuclear Chemistry. 2. METHODS A combination of epithermal neutron activation analysis (ENAA) and atomic absorption spectrometry (AAS) provides data for concentration of about 45 chemical elements (Al, As, Ba, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Dy, Eu, Fe, Hf, I, In, La, Lu, Mg, Mn, Na, Nd, Ni, Pb, Rb, Sb, Sc, Se, Sm, Ta, Th, V, W, Yb, Zn). Not all of the above trace elements are strictly relevant as air pollutants, but they come additionally from the multi-element analyses with insignificant extra cost, and most of them can be used as air mass tracers. GREENVEIW with raster and vector graphics will be used to generate colored raster- based pollution contour maps of the chemical elements and radionuclides of interest for the entire studied area. The GIS integrated system analysis of different level information will be provided with the interfaces for all international standard GIS systems: ARC-Info, MAP-Info, GIS-INTEGRO, etc. 2.1. Sampling Sampling sites are shown in maps in Annex 1. Sampling strategy and procedure followed those adopted by the Atmospheric Heavy Metal Deposition in Europe Project [4]. All sampling sites are placed at least 300 m away from main roads, villages and at least 100 m away from smaller roads and houses. The sampling was carried out according to the standard procedure described in detail in [5]. For each sampling site around 10 subsamples were taken within 50x50 sq. m area and combined to one collective sample. The unwashed samples were air-dried at 30 °C and extraneous plant material was removed. The three fully developed segments of each Hylocomium plant or green part of Pleurosium were taken for analysis. No further homogenization of samples was performed. Disposable polyethylene gloves were used during all handling of samples. 2.2. Analysis Moss samples of about 0.3 g were heat-sealed in polyethylene foil bags for short-term irradiation and packed in aluminum cups for long-term irradiation. Neutron flux density characteristics and the temperature in the channels equipped with a pneumatic system are given in Table I. 198 TABLE I. CHARACTERISTICS OF THE IRRADIATION CHANNELS [6] 12 u Temp Oth 10" 3>epi 10 Ofast 10 <Efast> Mev Irradiation (n/cm2 s) (n/cm2 s) (n/cm2 s) e- site E =0- 0.55 eV E=0.55- 105 eV E=0.1-25MeV E=0.1-25MeV rature, °C Chi Cdcoat 0.023 3.31 4.32 0.88 70 Ch2 1.23 2.96 4.10 0.92 60 Long-lived isotopes of Sc, Cr, Fe, Co, Ni, Zn, As, Se, Br, Rb, Ag, Sb, Cs, Ba, La, Ce, Sm, Tb, Yb, Hf, Ta, W, Au, Th and U, were determined using channel 1 (Chi). Samples were irradiated for 4 d, repacked and then measured twice after 4-5 d of decay, Respectively. Measuring time varied from 1 to 5 h. To determine the short-lived isotopes Na, Mg, Al, Cl, V, Mn, Cu, Al, In, and I, channel 2 (Ch2) was used. Samples were irradiated for 5 min and measured twice after 3-5 min and 20 min of decay for 5-8 and 20 min, respectively. To determine Cu, K, Na the same samples were irradiated for an additional 30 min, and after 12- 15 h of decay measured for 30 min. Gamma spectra were measured using Ge(Li) detectors with a resolution of 2.5 keV for the 60Co 1332.5 keV line, with an efficiency of about 6% relative to a 3D3" Nal detector for the same line. Radionuclides and y-energies used are given in Table II. Table II. Radionuclides and energies of y-lines used for calculations Element Radionuclide Ey measured Element Radionuclide Ey measured used (keV) used (keV) Na ^Na 2753.6 Rb 0DRb 1876.6 Mg z'Mg 1014.4 Ag liumAg 657.7 Al Z8A1 1778.9 In llomIn 1097.1 Cl 38C1 2166.8 Sb lz"Sb 1691.0 K «K 1524.7 I 442.7 Ca "Ca 3084.4 Cs 13Ts 795.8 Sc 40Sc 889.2 Ba 1J1Ba 496.8 V 1434.1 La lwLa 1596.5 J1~v 1HO Cr Cr 310.1 Ce Ce 145.4 Mn JOMn 1810.7 Sm JMSm 103.2 Fe 3yFe 1291.6 Tb iOTb 879.4 Co ouCo 1332.4 Yb 1DyYb 198.0 Ni "8Co 810.8 Hf i01Hf 482.0 Cu °°Cu 1039.2 Ta lszTa 1221.4 Zn raZn 1116.0 W JO'W 685.7 As /oAs 559.1 Au 'y6Au 411.8 Se "Se 264.7 Th '"Pa 312.0 Br 8ZBr 776.5 U "jyNp 228.2 Data processing and element concentration determination was performed using software developed in FLNP JINR [7]. For long-term irradiation in Chi single comparators of Au (1 Hg) and Zr (10 ug) were used. For short-term irradiation in Ch2 a comparator of Au (10 ug) was used. Concentrations of elements yielding above mentioned isotopes were determined using certified reference materials: SDM (International Atomic Energy Agency, Vienna) and Nordic moss DK-1 [8]). Lead, cadmium and copper were determined by flame AAS at the Geological Institute of RAS, Moscow. 199 3. RESULTS The results obtained for the moss samples collected along Lake Bannoe are presented in Table in. A total of 38 elements were determined, including most of the heavy metals.