Biomonitoring Air Pollution in Chelyabinsk Region (Ural Mountains, Russia) Through Trace-Elements and Radionuclides: Temporal and Spatial Trends
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
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. The data for the Ural moss samples were compared with those obtained by one of the authors of the present project, Dr. M.V. Frontasyeva, for Copper Basin (Poland) [9], Tula Region (Central Russia) [10], around iron smelter in northern Norway [11], as well as for Germany [12] and typical background concentrations of the elements observed in Hylocomium splendens in areas little affected by air pollution from previous studies in Norway (background levels in moss) [13,14].
It appeared that the concentration of Sb has the highest ever published for mosses level in atmospheric deposition: 2,63 ppm, showing maximum value of 29 (!) ppm (near "town of steel" Magnitogarsk). High values for antimony clearly indicate strong pollution with this element in the Chelyabinsk Region. In this connection it may be noted that in a study of trace elements in human cancer mammae carried out in Magnitogorsk [15], the reported tissue concentrations of Sb were about 5 times higher than the normal level. Patients suffering from cancer had significantly higher level of antimony than healthy persons. Our data for copper allowed us to examine the gradient of its concentration from the pollution source. It is clearly seen from Fig.l that pollution pattern is quite local, and covers area of 40 km in radius (if to consider background value to be equal to 10 ppm, as recommended in [12]).
0 20 40 60 80 100 120 km
Fig.l. Karabash, Chelyabinsk Region, South Ural Mountains
In order to better distinguish between contribution from air pollution and a crustal component from windblown soil particles enrichment factors (EF = (X/Sc)moSs/(X/Sc)crUst) were calculated and plotted in Fig. 2. Typical crustal components, such as Al, REE, Th, etc. show EF values near unity, whereas values appreciably above that level indicate that the element in question is either enriched in the moss by active biological processes (K, Ca) or stems from atmospheric deposition.
200 1000
o # An # CO 100 r HI i- .... ID 1 J_ 0) $^ o 10 % 1 CO i>- : ^fa:::: -JJ-- i—< • • "IT (F u_ - —SE: it1 : m 3SEEB -1— ' =«:"" Hna In 0.1 II i i . ——L-.. 0.0001 0.001 0.01 0.1 10 100 1000 10000
(X/Sc)crust
Fig. 2. Enrichment factors for elements
It may be noted that V and Fe, in spite of there high concentrations in the moss, are enriched only a factor 2-3 over the expected crustal contribution, whereas other heavy metals such as Cr, Zn, As, Se, Ag, Cd, Sb, and Au enriched 10 times or more, clearly indicating that these elements represent a regional problem. High correlation coefficient for such elements as Cu and Ag, Fe and Cr reflect the type industry responsible for contamination of the environment in the areas where moss samples were collected (Fig.3). Examples of GIS maps are given in Figs.4 and 5.
7000
6000
5000 HI&MEM- •I
O 4000 S ft
LL 3000
2000 Fi:=0.78 1000
0 50 100 150 200 Cr/Sc
201 TABLE EL Element concentration (ppm) in moss from Ural and in some other relevant areas used for comparison
Element Ural (Russia) Copper Basin Poland [9] Tula (Russia) [10] Mo (Norway) [11] Germany [12] Norway [13,14] background levels Mean Range Mean Range Mean Range Mean Range Mean Range Mean Na 394 174-1051 152 74-302 403 147-882 294 93-635 200 Mg 5003 1353- 15400 1694 800-6480 2878 1160-4982 1861 556-4230 1200 Al 2819 810-7000 815 237-2590 2486 402-6015 1244 243-3100 350 Cl 314 44-1114 226 113-537 859 232-2521 294 50-1110 200 K 6842 2642 - 13260 5005 515-8708 19628 8910-42230 3845 1930-7160 3000 Ca 5093 2030 - 13800 2229 1190-12800 7260 3290-12380 2871 1450-6740 1500 Sc 0.60 0.10-1.45 0.15 0.03-0.63 0.39 0.09-1.19 0.41 0.06-1.41 0.06 V 8.50 2.0-22.4 2.60 1.14-8.13 11.2 1.38-62 5.72 1.05-31.0 3.11 1.7-17.0 2 Cr 18.6 2.2- 194 1.43 0.80-3.16 2.95 0.88-9.6 11.7 0.5-50 2.11 0.97-7.98 1.5 Mn 344 88-1402 287 65-847 391 100-817 384 89-1460 200 Fe 1888 335 - 7438 520 219-1405 3030 471-19670 12280 700-72100 720 386-6830 400 Co 0.64 0.14-1.95 0.32 0.11-1.96 0.13 0.05-0.29 0.61 0.06-2.2 0.3 Ni 8.4 0.96-94 2.49 0.21-38 0.53 0.21-1.21 1.69 <0.5-6.96 2.61 1.03-6.29 1.6 Cu* 34 5-200 73 3.11-2040 Zn 72 14.8-304 41 21-83 69 27.15-105 99 31-397 55 33-463 36 As 2.17 0.63 - 9.7 0.73 0.12-6.04 0.51 0.11-1.47 0.62 0.06-2.20 0.39 0.3 Se 0.34 0.02-1.1 0.32 0.10-0.77 0.13 0.05-0.20 0.47 0.21-1.17 0.25 Br 6.20 1.52-25 1.38 0.89-2.85 4.05 1.44-12.7 6.94 3.6-12.2 5 Rb 10.3 2.8-39 21 1.95-45.51 19 6.2-32 17.2 6.7-46.2 10 Sr 18 1.96-65 12.4 0.69-339 Mo 0.29 0.041-0.71 0.29 0.05-2.42 Ag 0.124 0.011-0.47 0.12 0.02-1.74 0.06 0.02-0.15 0.059 <0.03-0.16 0.04 Cd* 0.63 0.16-2.86 0.30 0.03-1.07 SI. 2.63 0.08-29 0.26 0.12-0.79 0.13 0.05-0.7 0.25 <0.05-0.76 0.09 I 1.35 0.51-3.41 1.14 0.35-2.68 1.58 0.51-4.3 2.26 <1.0-4.3 2 Cs 0.22 0.04-0.61 0.43 0.08-1.29 0.20 0.06-0.48 0.37 <0.05-1.03 0.18 Ba 44 6.3- 125 13.6 5.47-79 65 10-145 33.1 12.0-83.0 24 La 2.43 0.47- 13 0.52 0.14-1.61 2.40 0.42-6,75 0.69 <0.10-2.87 0.3 Ce 3.24 0.53-11.7 1.27 0.24-3.74 3.45 0.64-10.9 - Sm 0.29 0.07-1.05 0.13 0.06-0.63 0.40 0.08-1.05 0.33 0.05-1.34 0.06 Tb 0.035 0.004-0.17 0.01 0.003-0.09 0.04 0.008-0.126 0.019 <0.005-0.067 0.015 Yb 0.107 0.005-0.55 0.04 0.01-0.18 0.13 0.028-0.38 0.069 <0.010-0.230 0.03 Hf 0.276 0.023- 1.78 0.13 0.01-0.58 0.45 0.08-1.51 0.179 <0.04-0.71 0.05 Ta 0.045 0.004 - 0.48 0.02 0.004-0.13 0.04 0.01-0.13 0.043 <0.003-0.180 0.005 W 0.34 0.06-1.27 0.17 0.02-0.62 0.14 0.05-0.40 1.71 <0.6-6.4 - Au 0.011 0.002 - 0.086 0.005 0.0004-0.02 0.02 0.005-0.067 0.0002 <0.0001-0.010 - Pb* 8.18 2.30-24 32 5.63-411 14.6 8-269 3 Th 0.36 0.054-1.72 0.13 0.05-0.45 0.47 0.095-1.46 0.267 0.04-1.10 0.08 V 0.15 0.057-0.73 0.10 0.02-0.99 0.18 0.052-0.59 0.143 <0.03-0.51 0.05 *- results obtained by AAS 202 u < 0.9 i [J 0.9-1.2 i 1.2 - 1.5
2 - 2.5
F] 2.5-3
izhno-Uralsk I > 10
dneu ra Isk < O.9
U 0.9 - 1.2
1.2 - 1.5 1 n i-5-;
2 -2.5
4 2.5 - 3
3-5
5-10
> 10 .as.
FIG. 4. DEPOSITION PATTERNS OF U AND TH (Relative units, normalized to the Norwegian background)
203 r < 0.9 0.9- 1.2
1.2-1.5 • 1.5-2
2-2.5
n 2.5 - 3
3-5
5-10
iJuzhno-Uralsk =» 10 Jfcl
-L :S redneura lsk < 0.9 iTERINB
O.9 - 1.2
ralska 1.2-1.5
1.5-2
n2-5-
3-5
5-10
> 10
FIG. 5. DEPOSITION PATTERNS OF CS AND CU (Relative units, normalized to the Norwegian background)
204 4. PLANS FOR FUTURE WORK The detailed working plan is as follows: Months 1-3 • Sample preparation for short- and long-term irradiation at IBR-2 reactor, Dubna • Multi-elemental analysis of moss and soil samples collected during summer, 1999 by epithermal NAA in Dubna and by AAS in Moscow • Measurements of radionuclides in soil samples at the Institute of Biophysics («Mayak»), and at JINR, Dubna Months 4-6 • Data processing of the results obtained for moss and soil samples by epithermal NAA in Dubna and AAS in Moscow. • Developments of GIS technology for the examined territory of the Chelyabinsk Region at the University of «Dubna» Months 7-8 • Field work: sampling of mosses and soils in the Central part of the Chelyabinsk Region (to the South of enterprise "Mayak"), according to a detailed plan approved by the expert consultant of the Project, Prof. E. Steinnes (Norway). A sampling grid of 30 x 30 km will be applied, giving a total of about 50 sampling sites Months 9-12 • Statistical analysis of the results obtained for the samples collected during summer, 1997- 1999, including principal component analysis. • Preparation of maps of heavy metal distributions in Chelyabinsk Region on the basis of the developed GIS. • Preparation of interim (third year) report. Since the same moss species may not be found at all sites, extension of the sampling to include additional moss species or lichens as well as some species intercalibration work will be necessary. We expect that some peat cores will be analyzed during autumn 2000. To succeed with fieldwork in summer 2000, we requested UDS 8,000 from the IAEA having in mind difficult conditions of sampling in the mountains lacking transport roads, distant location of the areas of investigation from the central Russia where the project analytical studies are carried out. The most important results expected after completion of the project are as follows: • establishment of a regional sampling network for future monitoring programmes; • identification of areas with high contamination levels not previously considered to be of environmental risk; • creation of a database for continued studies at regular intervals; • comparison of environmental contamination levels in the Ural region with other strongly polluted areas in Europe, such as the "Black Triangle'7, Copper Basin in Poland and the Romanian Carpathians. Altogether, the results from the project will form an excellent basis for local authorities to implement the necessary measures to reduce emissions to environmentally acceptable levels. Moreover, the responsible public health authorities will have a significantly improved basis for assessing possible risk to the population from previous and current emissions.
205 REFERENCES
[I] BRADLEY, Don J., Behind the Nuclear Curtain. Radioactive Waste Management in the Former Soviet Union. Edited by David R. Payson, Battelle Press, Columbus Richland, 1977, p. 371-450. [2] FRONTASYEVA, M.F., STEINNES, E., LYAPUNOV, S.V., CHERCHINTSEV, V.D., SMIRNOV. L.I., Biomonitoring of Heavy Metal Deposition in the South Ural Region: Some Preliminary Results obtained by Nuclear and Related TechniqueSyPreprint of JINR, El4-99-257, Dubna (in English); [3] FRONTASYEVA, M.F., STEINNES, E., LYAPUNOV, S.V., CHERCHINTSEV, V.D., SMIRNOV, L.I., Biomonitoring of Heavy Metal Deposition in the South Ural Region:"Ecology of Industrial Regions at the Boarder of the XXI Century", Ural, 1999, p. 7-13. (in Russian). [4] RUEHLING, A., Survey of Atmospheric Heavy Metal Deposition in Europe: Organization of the Project. In the Book of Abstracts Workshop Monitoring of Natural and Man-Made Radionuclides and Heavy Metal Waste in Environment. E-14-99-290, Dubna, 1999, p. 20-21. [5] RUEHLING, A. and TYLER, G., Sorption and Retention of Heavy Metals in the Woodland Moss Hylocomium splendens, Oikos. 21 (1970) 92-97. [6] PERESEDOV, V.F., ROGOV, A.D., Simulation and Analysis of Neutron Energy Spectra from Irradiation Channels of the Reactor IBR-2. JINR Rapid Communications. No. l[75]-96 (1996) 69-74 (in Russian). [7] OSTROVNAYA, T.M., NEFEDYEVA, L.S., NAZAROV, V.M., BORZAKOV, SB., STRELKOVA, L.P. "Software for INAA on the Basis of Relative and Absolute Methods Using Nuclear Data Base". Activation Analysis in Environment Protection, D-14-93-325, Dubna, 1993, p. 319-326. [8] FRONTASYEVA, M.V., NAZAROV, V.M., and STEINNES, E., Moss as Monitor of Heavy Metal Deposition: Comparison of Different Multi-Element Analytical Techniques, J.RadioanalNucl.Chem. 181 (1994) 363-371. [9] FRONTASYEVA M.V., GRODZINSKA K., STEINNES E.. Atmospheric Deposition of Heavy Metals in Two of The Most Polluted Areas in The World: The Copper Basin in Poland and the South Ural Mountains in Russia. In Proceedings, Int. Conf. Modern Trends in Activation Analysis, MTAA-10, 19-23 April, 1999, Bethesda, Maryland, USA, p. 117. [10] YERMAKOVA, Ye. V., FRONTASYEVA M.V., STEINNES E., Reliability of Mosses {Hylocomium Splendens, Pleurozium Schreberi and Calliergon Geganteum) as Biomonitors of Heavy Metal Atmospheric Deposition in Central Russia. IV Conference of Young Scientists and Specialists of JINR, (31 January - 4 February, 2000, Dubna, Russia) [II] FRONTASYEVA M.V., STEINNES E., Epithermal Neutron Activation Analysis of Mosses Used to Monitor Heavy Metal Deposition Around an Iron Smelter Complex, The Analyst, May 1995, Vol.120, p. 1437-1440. [12] RUEHLING, A., Atmospheric Heavy Metal Deposition in Europe - Estimation Based on Moss Analysis, Nordic Council of Ministers, Nord 1994, 9. [13] STEINNES, E., RAMBAEK, J.P., HASSEN, J.E., Large Scale Multi-Element Survey of Atmospheric Deposition Using Naturally Growing Moss as Biomonitor, Chemosphere, 25, 1992, p.735-752. [14] BERG, T, ROYSET, O., STEINNES, E.,. VADSET, M., Atmospheric Trace Element Deposition: Principal Component Analysis of ICP-MS Data from Moss Samples, Environ. Pollut.,%% 1995, p. 67-77. [15] KOSHKINA, V.S., KOTLYAR, N.N., A Cancer Mammae Under Technogenic Impact on Population of the Town of Magnitogorsk, Environment and Health, Magnitogorsk, 1998, p.33- 39.
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