Integrative Journal of Environmental & Earth Science [IJES] Volume 2020 Issue 01 Research Article
Comparative Analysis of Chemical Composition of Snow Melt Water and River Water from Areas with Aluminum Production (Russia, Baikal region) Valentina I. Grebenshchikova* and M.I. Kuzmin A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences
Received: February 28, 2020; Accepted: March 09, 2020; Published: March 13, 2020 R-Infotext Citation: Grebenshchikova VI, Kuzmin MI (2020) Comparative Analysis of Chemical Composition of Snow Melt Water and River Water from Areas with Aluminum Production (Russia, Baikal region). Integrative J of Envi & Ear Sci 01 (01): 1–15.
Abstract
This paper is focused on the comparative analysis of the chemical composition of snow melt water and surface water in two areas holding aluminum production (Baikal region): both under operation (Shelekhov town) and under construction (Tayshet town). It appears that the levels of contamination of the studied environmental components (snow melt water, snow solid phase, river water) with Al and its satellite elements (F, Be, Li) in the towns hosting aluminum production are from 2 to 5 times higher than the regional background values. The monitoring studies in areas with aluminum production are still going on.
Keywords: aluminum production, chemical composition, pollution, snow melt water, snow solid phase, surface water.
Introduction They are able to accumulate in the human body for a long time and exceed the concentration (dose) necessary for life Aluminum production has been continuously growing (Martin, Larivière 2014). Thus, aluminum widely occurs worldwide as this element is actually of great importance in technogenic processes, but it is poorly studied, though in different industries: aircraft construction, motor and its chemistry is closely related to medicine and biology. food industries, electronics, etc. Aluminum is derived from The elements, satellites of aluminum production such as bauxite. Bauxite is a breed with a complex composition. F, Be, Li, B, etc. are related to certain diseases and turn alumina (Al O ) is obtained from bauxite. Then from First, 2 3 out to be highly toxic. Many of water- soluble inorganic alumina as a result of electrolysis in the melt of fluoride salts aluminum compounds are long-preserved and they might at a temperature of about 950 ºC, the main component cause harmful effect on humans and warm-blooded animals of the melt, cryolite, is obtained. Cryolite is Na AlF salt 3 6 through drinking water, food, soil and even dishware, that (Anshits et al 1991). In the process of electrolysis, aluminum is confirmed by medical and sanitary observations in urban is deposited in special electrolysis baths. In its pure form, systems [3–8]. aluminum is used much less frequently than in the form of alloys. The alloys additionally contain various elements The snow cover is known to be an informative and that increase their hardness, density, thermal conductivity, depositing medium capable of accumulating pollutants etc. For this purpose, Be, B, Li, Fe, Si, Mg, Mn, Zr, Ag, entering the environment. It influences the hydrological Pb, Cu, Ni and other elements are used (Table 1, 2). All of regime of rivers and has an effect on soil chemical the above elements, which exceed the regional background composition. In the Eastern Siberia, the snowpack content [1] or the city clarke [2] (Table 1), are to some generally accumulates over a longer period of time extent toxic to humans, as shown by numerous publications. (generally 5 months) and thus is considered to be a natural
March 13, 2020 Integrative J of Envi & Ear Sci, Volume 01(01): 1–15, 2020 Comparative Analysis of Chemical Composition concentrator of many chemical elements including toxic specific diseases. The maximum permissible concentrations ones. The elemental composition of snow cover can give the (MPC) do not exist for different elements, including those information concerning geochemistry and geology of an considered in this article (Al, Be, Li, F and some others) area under study and therefore can provide the information both for liquid and solid phases of snow cover. The standard on industries available there. It is known, that the snow concentrations of different elements in drinking water for cover chemical composition influences the composition domestic purposes are: of other environmental components (soil, plants, water). Al – 500 μg/ L, Be- 1 μg/L, Li – 30 μg/ L, F- 1.5 mg/ L The pollutants accumulated in the snow cover can cause (GN 2.1.5.1315–03.., 2003; Control.., 1998).
Table 1. Contents of components (mg/L), pH and the sum of major components in the city’s snow water and in the background areas of the Baikal region
Component Shelekhov Shelekhov (2012) Tayshet Biryusinsk District of Regional background (2008-2012) (2014) (2014) factories under (Grebenshchikova et construction in al., 2008) Taychet region (2014 ) pH 5.7-6.9 6.3-6.9 5.4-6.5 6.2-8.1 3.8-6.3 5.8-6.9 6.65 6.0 7.0 4.9 6.5 – HCO3 1.34-11.10 3.05-10.25 4.5-20.4 6.0-29.5 3.8-12.3 1.59-8.42 5.22 9.5 12.2 6.9 5.12 Cl– 0.39-2.97 0.39-1.65 0.72-2.08 0.92-1.26 0.77-1.25 0.38-0.65 0.66 0.97 1.0 0.94 0.5 2– SO4 0.09-15.0 0.18-2.90 1.10-4.30 1.2-2.0 0.74-2.56 0.7-3.9 0.48 1.70 1.6 1.43 1.5 F– 0.3-26.0 0.30-10.75 0.0005-0.03 0.003-0.05 0.01-0.03 0.04-0.09 3.62 0.02 0.02 0.02 0.08 – NO3 0.22-1.2 0.22-0.44 0.20-0.52 0.28-0.60 0.17-0.58 0.47-2.28 0.33 0.35 0.46 0.36 1.04 – NO2 0.007-0.187 0.007-0.187 0.006-0.072 0.008-0.039 0.003-0.023 0.01-0.03 0.03 0.014 0.03 0.009 0.02 + NH4 0.006-1.071 0.004-0.277 0.002-0.19 0.02-0.11 0.001-0.039 0.027-0.103 0.12 0.02 0.03 0.004 0.06 K+ 0.09-1.87 0.09-1.06 0.02-0.12 0.07-0.09 0.05-0.17 0.15-0.29 0.38 0.07 0.08 0.09 0.18 Na+ 0.26-25.3 0.26-9.17 0.04-0.12 0.05-0.20 0.04-0.08 0.28-0.90 2.68 0.07 0.07 0.05 0.3 Ca2+ 0.17-6.09 0.17-6.09 0.7-3.9 2.0-8.0 0.5-1.5 1.8-3.1 1.53 1.6 4.4 0.7 2.0 Mg2+ 0.05-1.99 0.05-0.51 0.1-0.7 0.2-0.8 0.06-0.73 0.24-0.49 0.17 0.3 0.5 0.3 0.3 TDS 11.4-94.6 5.91-27.32 8.5-28.1 11,7-41,5 7.3-18.0 10.1-18.7 14.55 18.0 21.0 10.9 15.1 Number of 45 25 11 4 14 4 samples The maximum concentrations is highlighted in bold.
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Table 2. Concentrations of trace elements in snow melt water (μg/L) of cities with aluminum production and the background area of the Baikal region
Element Shelekhov Shelekhov Tayshet Biryusinsk District of factories under Baikal natural (2009-2012) (2012 ) (2014) (2014) construction background (mean in Taychet region (2014 ) value) (2012) Be 0.02-3.73 0.02-1.12 0.003-0.014 0.0029-0.0033 0.002-0.01 0.01 0.37 0,01 0.003 0.005 Al 63-7730 63-7730 10.8-343 13.1-354 5.5-170 28 2020 72 145 38 B 2.5- 51.12 2.5-25.6 0.53-8.0 1.2-9.4 0.3-1.9 0.71 8.2 3.0 4.6 0.8 Li 0.52-60.1 0.52-13.0 0.04-0.29 0.15-0.20 0.02-0.18 0.57 3.86 0.12 0.18 0,06 As 0.1-3.38 0.03-0.59 0.06-0.30 0.06-0.14 0.04-0.18 0.24 0.24 0.16 0.09 0.09 Cd 0.013-0.28 0.01-0.20 0.006-0.033 0.005-0.02 0.005-0.03 0.04 0.09 0.01 0.01 0.01 Ni 1.22-19.13 0.90-12.9 0.12-0.58 0.15-0.36 0.07-0.36 0.4 5.03 0.24 0.22 0.17 Pb 0.056-0.81 0.019-0.35 0.16-0.51 0.27-0.39 0.08-0.56 0.3 0.16 0.32 0.33 0.29 Sb 0.10-0.71 0.10-0.35 0.14-0.34 0.03-0.05 0.09-0.16 0.06 0.15 0.19 0.04 0.13 Zn 8.7-202 10.3-35 5.67-17.9 6.24-26.9 4.5-11.1 15 20 10.6 12.4 7.3 Co 0.12-0.93 0.12-0.93 0.04-0.18 0.03-0.08 0.02-0.11 0.12 0.34 0.08 0.05 0.05 Cu 0.20-8.4 0.20-5.62 0.27-1.04 0.28-0.57 0.12-0.58 1.0 1.07 0.51 0.42 0.27 V 0.06-2.1 0.06-1.18 0.05-0.92 0.09-0.95 0.05-0.62 0.30 0.63 0.41 0.39 0.15 Cr 0.02-0.76 0.04-0.58 0.05-0.67 0.09-0.23 0.04-0.41 0.1 0.16 0.20 0.14 0.14 Mo 0.034-1.3 0.034-0.82 0.03-0.12 0.04-0.11 0.02-0.06 0.09 0.19 0.06 0.08 0.03 S 268-4502 311-2960 84-688 233-648 64-336 939 1236 349 493 192 Hg 0.0005-0.13 0.0005-0.0053 0.0005- 0.0005-0.0018 0.0005-0.001 0.001 0.001 0.0017 0.002 0.001 0.001 Number of 45 25 11 4 14 8 samples In the numerator – minimum-maximum, in the denominator – average; the maximum content of the elements is shown in boldface.
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The background values of these elements were earlier sector and production of construction materials. The flat obtained for the snow melt water of the Baikal Region lands of the suburbs are basically occupied by agriculture (1991–1993; 2006, 2008) [1,7,9] and these values were and collective vegetable gardens. Virgin gardens still grow later confirmed for the ecologically clean area with no within the town itself. industrial enterprises [10] 28 μg/L for Al; 0.01 μg/L for The aluminum is produced from raw alumina obtained Be; 0.57 μg/L for Li. This is a local nature background from other Russian regions. The plant produces primary of chemical elements concentration (Baikal region). The aluminum ingots, aluminum alloys, and other products. chemical compositions of snow melt and surface water of The capacity of the smelter is almost 2 times higher urban areas used by the population for different purposes than international standards for the environmental have been constantly studied both by Russian [11–22 ]and management [12]. The operating aluminum smelter and foreign [23–25] scientists in assessing the ecological and its environs have for a long time been under monitoring, geochemical state of the environment. thus extensive information has been collected about the This work aims at: chemical compositions of different environmental media including the snow cover [10,12,19] We conducted • conducting specialized ecological and geochemical annual monitoring of snow cover (Shelekhov town) in studies of the composition of snowy water, solid order to track the changes in its composition over time. precipitation of snow, surface and groundwater in In addition, we studied the compositions of urban soil cities with existing and under construction aluminum and water. Recently together with the East-Siberian smelters; Institute of Medical and Ecological Research, Angarsk, • identification of the possibility of long-term we are conducting a risk assessment to public health in accumulation of many toxic elements and heavy metals Shelekhov town [1,8]. The author’s data are presented in (Table 1–4) in the conditions of cities with aluminum Tables 1–4. Tayshet town is located in the northwest of production; Irkutsk Region, 675 km from the Irkutsk regional center, • identify changes in the environment after three years of on the right side of the Birjusa River, in the interfluve of the aluminum production (Tayshet town); its tributaries Tayshetka and Akulshetka Rivers (Fig. 1, • Determination of possible additional negative impact 3). Approximately 10 km north-west off Tayshet, there is on the environment of thermal power plants serving a small town called Birjusinsk. In the north-east (~10 km) aluminum smelters. the territory between Akulshetka and Baironovka Rivers was chosen for constructing a new aluminum smelter and Objects and methods anode-producing plant. The basic enterprises in Tayshet town are railway engine-house, sleeper factory, printing, The study objects are urban ecological systems of the construction and forestry industries. Baikal Region with long-operating aluminum plant and a plant under construction (in the towns of Shelekhov and As a result of long-term comprehensive studies in Tayshet) (Fig.1). The aluminum production in Bratsk town Shelekhov and Tayshet towns, the concentrations of major and its impact on the environment was earlier considered in and trace elements have been obtained for the snow melt, [10] but it has been considered in more detail with regard river and ground water, snow solid phase; the statistical to the fluoride release into the atmosphere in a number parameters were calculated and the maps of chemical of publications by N.I. Yanchenko et al. [22]. Shelekhov element distributions compiled (Fig. 2, 3). Tables 1–4 town, a small industrial town in the Baikal region was present the number of analyzed samples and obtained founded back in 1956 with the construction of the Irkutsk data. In this study, the snow samples were collected Aluminum Plant (Fig. 1, 2). It is located 18 km south-west from selected points (from 30 by 30 cm to 70 by 70 cm) of the Irkutsk regional center in the interfluve of the Irkut depending on a snow cover depth. In our case, specific and Olkha Rivers (Fig. 2). The main industries of this town attention was given to surface snow samples in order to are nonferrous metallurgy, e.g. Irkutsk Aluminum Smelter prevent the migration of harmful substances from the (IrkAZ), Cable-producing Plant, heat power engineering soil and vegetation. Therefore, the lower layers of snow
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(5–10 cm) were not selected. Samples of snow were technogenic dust (solid precipitation of snow), solid phase collected around the aluminum plant on an irregular survey was immediately separated (filtered) from the liquid one. grid in connection with the development of the territory of For filtration of snow water, an impure, dense filter of the the city (Fig. 3). The collected samples were stored at room ‘‘blue tape’’ type with a pore diameter of 1–2.5 microns was temperature below 0 ºC. For snow melting, the samples used. Since the filtration of snow water occurred quickly, were put in polyethylene baskets which were then placed the solid material did not have time to dissolve or dissolve in warm conditions. To minimize the dissolving of the in a very small amount.
Table 3. Concentrations of elements in the hard sediment of the snow cover in the regions aluminum production and the background area of the Baikal region
Number of Element Be Li B Cr V Ni Co Pb Zn Cu F samples
Shelekhov 6-20 20-100 30-300 50-800 80-300 100-600 8-40 60-200 70-200 70-400 500-15000 25 (2012)
Mean value 12 52 150 180 150 275 22 120 124 190 1900 (95% confidence), mg/kg
SPM, 0.0004 0.0039 0.0082 0.0002 0.0006 0.005 0.003 0.0002 0.02 0.0011 0.0036 mg/L
Tayshet 2-5 14-50 34-100 23-130 37-120 21-68 8-23 12-140 34-490 64-190 110-460 11 (2014)
Mean value (95% confidence), 3 29 58 49 66 39 15 40 140 116 230 mg/kg
Biryusinsk 1,5-1,9 20-36 26-78 32-68 40-150 28-42 7-24 17-46 23-200 48-170 110-310 4 (2014) Mean value (95% confidence), 1.7 29 54 46 78 32 13 31 103 94 208 mg/kg
The area around 1,8-3,1 6-86 15-110 30-200 35-170 15-130 7-27 23-400 36-630 58-210 150-11000 14 the Tayshet plant (2014)
Mean value 2.1 56 54 78 101 49 14 127 217 116 1660 (95% confidence), mg/kg
Baikal natural 2 17 40 80 100 60 30 40 100 80 470 8 background (mean value), mg/kg
SPM – the snow water by suspended particles (see the text).
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Table 4. Concentrations of elements in the surface and groundwater of the Shelekhov and Tayshet regions and source of Angara river
Place and time of water sampling Al, μg/L Li, μg/L Be, μg/L F, μg/L
SOURCE OF THE ANGARA
The runoff of Lake Baikal, mean value 0.56-60 0.13-2.5 0.0001-0.014 0.11-0.30 (Grebenshchikova et al., 2018)
SHELEKHOV REGION
Irkut river
Mar. 2008, in front of IrkAZ 1.95 3.8 0.0002 0.13
Mar. 2008, downstream, 1 km 9.9 4.6 0.0005 0.22
May 2008, downstream, 1 km 35.6 3.6 0.016 0.15
Jun. 2015, downstream, 1 km 44.0 2.3 0.0051 0.13
Olha river
Mar. 2008, in front of IrkAZ 37.3 60 0.0011 0.30
Aug. 2009, before IrkAZ 21.0 2.25 0.01 0.22
Mar.2008, downstream, 1 km 12.1 28.6 0.016 0.73
May 2008, opposite IrkAZ 22.3 2.33 0.0045 -
Aug. 2015, well, 9 m, riverbank before 1.18 4.0 0.0008 0.40 IrkAZ
Aug. 2009, well, mineral water 2.40 92 0.0095 1.18 “Irkutsk”, riverbank up to IrkAZ
Aug. 2009, self-pumping well in river, 2.63 180 0.018 1.95 before IrkAZ
Tayshet region
Biryusa river
Sep. 2012 (I) 31.6 1.06 0.0078 0.15
Sep. 2012 (II) 32.7 1.07 0.0066 0.13
Akul’shetka river
Sep. 2012, above the factory, 10 km 3.2 3.69 0.0021 0.29
Sep. 2012, below factory, 5 km 5.2 10.75 0.0015 0.32
Bayronovka river,
Sep 2012, above the factory, 10 km 164.9 3.21 0.0158 0.19
Sep. 2012, below the factory, 10 km 153.1 3.74 0.0121 0.20
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Figure 1. Overview map layout of the cities of the Baikal region with aluminum production (asterisk - selection of snow on Baikal, natural background).
Figure 2. Map-scheme of the distribution of aluminum concentrations in snow water (a) and in the solid sediment of snow (b) in Shelekhov in its suburbs (Baikal region).
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Figure 3. Map-scheme of the distribution of aluminum content in snow water in Tayshet, Biryusinsk and their surroundings (Baikal region). TAS is the site of an aluminum plant under construction and an anode factory.
Chemical analyses were accomplished using the scientific graphite electrode. Fluorine in powders of snow solid phase equipment of the certified analytical center of the collective was analyzed with arc atomic emission spectroscopy using use ‘‘Isotopic-geochemical investigations’’. The Institute of the method of blowing-waking in the content range from Geochemistry, SB RAS (IGC, SB RAS), where the authors 0.0050 to 3.5 wt/% with an error being 20.5% relative, of the article work, is licensed by Rosgidromet giving the developed and certified at the IGC SB RAS. The accuracy of right to sample various environmental data. This means results was verified by the analysis of the reference material that the authors of the publication are licensed specialists (ash of coals and soils) [27]. in sampling. ICP-MS (Finnigan MAT Element 2) was used to analyze snow water and river water (K, Na, Ca Mg, Al, Results and discussion Be, Li, F, Zn, Pb, Cu, Ni, Co, Cr, V, etc. total 55 elements). The following techniques were selected to analyze other The dust level in the snow cover of Shelekhov town varies in ions: mercury metric for chlorine, turbidimetric for a wide range and can reach as high as 71 g/m2. Lower dust sulfate, titrimetric for hydrocarbonate and potentiometric levels were found in the town’s environs. For comparison, for fluorine. Mercury was analyzed by atomic-absorption the dust level on Lake Baikal makes up only 1 g/m2 and via RA- 915+ device with the attachment RP-91 and a even lower. The hydrochemical analysis shows that the computer registration. The snow solid phase (dust, remnants pH of the snow melt water of Shelekhov samples changes of unburned coal and other particles precipitated) insoluble from 5.7 to 6.9. The mean pH value in 2012 (6.65) was in water and mineral acids was analyzed with arc atomic- slightly different from the values of local background on emission spectroscopy with photoelectric registration and the western shore of Lake Baikal (5.8–6.9) (Table 1, Fig. 4). computer spectra interpretation [26]. Major and trace Major element concentrations lie in the range from 11 to elements including Al and Be in the snow solid phase 95 mg/L. The samples collected within 2008–2012 nearby were determined using the method of complete substance the aluminum plant exhibit a concentration of F-ion up evaporation (subsample of 5–20 mg) from the channel of a to 23–26 mg/L, which is almost 600 times higher than
March 13, 2020 Integrative J of Envi & Ear Sci, Volume 01(01): 8–15, 2020 Comparative Analysis of Chemical Composition a local natural background on Lake Baikal (0.05–0.09) their increased contents. The shading shows the minimum [10]. In addition to fluorine, the increased ion contents in and maximum contents of macrocomponents (A - 2008– snow melt water have been recorded for other ions: Cl–, 2012) and microelements (B - 2009–2012) in the snow 2– – + + SO4 NO2 , NH4 и Na (Table 1). However, maximum water of Shelekhov during the monitoring period. The concentrations of a number of ions were found in samples trend shows a decrease in the average content of elements collected in 2008. The Shelekhov snow melt water samples in the snow water of the Baikal natural territory. Fluorine exhibit markedly increased (100 times higher) abundances is a toxic element and can be brought into the atmosphere of F, Al as well as higher (over 10 times) contents of nearby the aluminum production as F ion, perfluorocarbons, other elements (Be, Li, B, Ni (Table 1, 2, Fig. 1, 4). In in compounds with sulfur and as a mineral state (fluorite, Figure 4, the elements are arranged in order of priority of fluorapatite, etc.) 13[ , 18, 19, 23].
Figure 4. Interannual dynamics (2008–2012) of the distribution of maximum contents of the elementsin the snow water of Shelekhov: A) macrocomponents (minimum-maximum content - shadowed area); B) microcomponents (minimum-maximum content - shadowed area); the background area on Lake Baikal (solid line).
The concentrations of other toxic elements (Co, Cd, The weight of the solid snow sediment in 14–15 liters Mo, As, Sb, V, Cu, Zn, Pb, Cr и S) are recorded as from of snow water varied in different years from 0.2 to 11 g 2 to 10 times exceeding background values for the Baikal in Shelekhov and town’s environs. At the same time, the region (Table 2). At the same time, the annual variations of weight of the snow cover on the western shore of Lake the maximum contents of different elements are significant. Baikal is significantly lower (lower than < 0.1 g). The dust However, the analysis shows that starting from 2008–2009, content varies from 13 (mg/m2)/day at a distance of 15 km the technogenic load on the snow cover decreased for a from the plant to 358 (mg/m2)/day nearby the aluminum number of toxic elements that is most likely related to a smelter [19] The maximum snow cover contamination better technology of emission cleaning at the Shelekhov is found close to the plant. Considering the fact that the aluminum smelter [28]. The concentration of Be (μg/L) in population is concentrated in 500–1000 m from the the snow melt water reached values up to 3.73 (Table 2) plant, the solid snow phase pollutes the town’s area as with the background values as 0.01 μg/L. The maximum well. The mineral composition of the solid phase is diverse Al content makes up 7730 μg/L; background values and contains minerals of natural and technogenic origin: constitute 28 μg/L. At the same time, the higher aluminum quartz, albite, mullite (aluminum-containing mineral), concentrations in the snow melt water are recorded for the fluorite, etc. The phase also contains the products of coal major part of the town (Fig. 2) and even in its environs. The combustion from thermal power plants and boilers (quartz, samples also demonstrate increased concentrations of Li (to magnetite, aluminum oxide, mullite, etc.). 60.1 μg/L) and other elements Zn, Ni, As, S (Table 2). The latter is most likely related to the operation of the cable- The solid show phase, as well as snow melt water exhibit producing plant as well as heat power station emissions. higher contents of toxic elements typical of aluminum Higher concentrations of the same elements were found in production (Al, Be, B, Li, as well as Cr, V, Ni, Pb, Zn and the soil cover nearby the plants as well [12]. Cu) (Table 3) (influence from the cable-producing plant,
March 13, 2020 Integrative J of Envi & Ear Sci, Volume 01(01): 9–15, 2020 Comparative Analysis of Chemical Composition thermal power plant, motor transport). The concentrations significant distance from the Irkut River (about 15–20 km) of a number of toxic elements in the solid snow phase are but close to the Olkha River (500–700 m) (Fig. 2). The one order higher than on Lake Baikal (Table 3). Early Olkha River water cannot be polluted as a result of a direct comparison of metals in the solid snow residue and in the waste contact; however the snow melt water from the site snow water by suspended particles (SPM) in town Svirsk of aluminum production can enter the underground water (Baikal region) showed a significant difference: in snow and Olkha River [15, 20]. melt water, the content of toxicants is much less than 1 The concentrations of some elements (Hg, Be, Se, mg/L; in the solid precipitate, it is hundreds of mg/kg [29]. F) in the water of other rivers in the Baikal region are This situation is typical for snow in this case in the city given in [16]. Several large rivers flow in the studied area of Shelekhov (Table 3). Other researchers (Shevchenko et such as Irkut and Olkha are similar in composition and al., 2009) [30] have already noted that the typical SPM belong to HCO 2– hydrogeochemical type, pH values concentration in the White Sea is only about 1 mg/L. 3 range from 6.1 to 7.7 in the Irkut River and from 6.4 to The snow melt water and solid snow phase within 8.4 in the Olkha River depending on a season. The total the city and its environs (3–5 km) show similarities in mineralization (mg/L) varies as well: 169–186 in the Irkut the composition of toxic elements: either the decrease or River and 187-213 in the Olkha River [11] or from 43.0 increase of a certain element is found both in the snow to 156.1 [20]. The analysis of water from Olkha River melt water and solid snow phase. This tendency is observed collected in different seasons and from different sampling for major pollutants: such a correlation is observed for Al sites showed the following results: 12.1-37.3 μg/L for Al; contents from the same sampling site both in snow melt 0.0011-0.016 μg/L for Be; 2.3-60 μg/L for Li, 0.22-0.73 water and solid snow phase (Fig. 4). The obtained data mg/L for F (Table 4). The increased contents of these indicate that despite the nature-protection measures the elements are recorded for the Olkha samples collected situation with snow cover pollution in Shelekhov town nearby the aluminum smelter: F – 0.73 mg/L, Al (μg/L) – remains unchanged. As the industrial enterprises are 37.3, Li – 2.3, Be – 0.01. It should be noted that some of located close to the city, the residential areas are also subject these concentrations (F, Be) lie within or higher than the to technogenic pollution (Fig. 2, 3). However, despite maximum permissible limits set for water bodies used for the improvements in technology procedure and nature a fishery. In close proximity to the aluminum smelter (6-7 conservation measures the contents of chemical elements km) upstream the Olkha River in the Olkha settlement in the snow melt water didn’t change significantly during there is a mineral spring (2 holes with the depth of over the period of monitoring (2008–2012). The technogenic 300 m) holding the mineral water which is used by the pollution influences the biosubstrata (hair) of people living citizens of the Irkutsk Region for health resorts. The water there and intensifies the aggregated (inhalation and peroral type is chloride-sulfate magnesium-calcium-sodium with risk) risk to the population health, which was established by the mineralization of 1000-5000 mg/L (Alieva, Zagorul’ko us earlier [3,8]. The medical- ecological situation in another 2013; Shpayzer 2010). The mineral water demonstrates city with the aluminum production (Bratsk) is the same. higher concentrations of the following elements (μg/L): Be (~ 0,018), Li (~ 180), B (~ 214), Rb (~ 11), Sr (~ 5000), The chemical composition of the river water is not Cs (~ 0,036), Ag (~ 0,0014) and F (mg/L) ~ 1.18-1.95. stable and changes rapidly over time. This depends on a Moreover, Al concentrations are lower than in the Olkha number of factors: geologic structure, hydrological regime, River and lie within ~ 2.4-2.6 μg/L, lower concentrations climate, season, current’s speed, changing anthropogenous are recorded for Co, Ni, Cu, Zn and some other elements. load, self-purification, as confirmed by many researchers. The sampling of river water nearby Shelekhov and Tayshet The analysis of water from the surface hole with the depth aluminum production was done in different seasons of 9 m, drilled in the Olkha settlement shows the following (Table 4). The River samples were collected upstream up water characteristics: Al – 1.18 μg/L, Li – 4.0 μg/L, Be – to the site with the aluminum production; opposite the 0.0008 μg/ L, F – 0.4 mg/L and total mineralization of aluminum plant and at a distance from it (downstream). 528 mg/L mainly due to higher content of bicarbonate The aluminum production in Shelekhov town is placed at a (Table 4). It means that the concentrations of elements
March 13, 2020 Integrative J of Envi & Ear Sci, Volume 01(01): 10–15, 2020 Comparative Analysis of Chemical Composition specific of emissions from aluminum production placed factories under construction are markedly lower than in downstream are relatively low. The concentrations of the surrounding cities. In terms of major elements, their elements in the Irkut River at different places are lower concentrations in the snow melt water on the west shore of than in the Olkha River and make up (Table 4 ): ): Al Lake Baikal are similar to those in samples collected nearby – 1.95-44.0 μg/L, Be – 0.0002-0.016 μg/L, Li – 2.3- the plants under construction, thus indicating a relatively 4.6 μg/L, F – 0.13-0.22 mg/L thus indicating a possible low pollution level of this area at present (Table 1). The atmosphere transfer of toxicants resulting from the impact trace element composition (Table 2) in the snow melt water of the aluminum smelter in Shelekhov town only. At the from Tayshet town and its environs is also similar to that same time, the samples collected from the Angara River of the Baikal background site. Moreover, both in terms of source (Fig.1, Runoff from Lake Baikal) with no industries major and trace element concentrations the Tayshet snow show much lower contents of considered toxic elements, melt water samples show higher concentrations of trace specific of the aluminum production: Al – 1,16-3,54 μg/L, elements (Al, Bi, B, etc) as compared with the composition Be – 0,0004-0,0017 μg/L, Li – 2,0-2,41 μg/L. However, F of the snow melt water collected around plants under concentrations are rare up to 0.30 mg/L. It may be pointed construction and in the background area on Lake Baikal. As a result, higher Al contents are found only in Tayshet out that pollutants can be transferred from the aluminum and Birjusinsk towns (Fig. 2). The situation is the same for smelter towards Lake Baikal by wind over a larger distance other trace elements as well. Mercury and uranium levels (about 60 km). At the same time the water from Lake are slightly higher in these towns, that can be explained by Baikal and the Angara River remain clean and is considered emissions from numerous coal-fired boilers that use local to be best for drinking [31]. coal (Cheremkhovo coal basin) [32]. The concentrations of In addition to the above inorganic elements the water other toxic metals in the snow melt water samples collected and sediment samples of the Olkha River contain higher in Tayshet and Birjusinsk and their environs are low and are concentrations of polyaromatic compounds (benzo(a) at level in the snow melt water samples from the west shore pyrene, fluoranthene and others) [20], however, their of Lake Baikal. content is lower than the MPC for natural and drinking The distribution of Al, Be, Li, F i.e. elements typical of water established in European countries. In Tayshet town aluminum production in the snow melt water and snow and its environs, the pH of the show melt water changes solid phase around the plants under construction is regular from neutral to acid (from 6.3 to 3.8). The snow melt and their concentrations do not exceed the background water in Birjusinsk town is alkaline (6.2-8.1) (Table 1), values (Table 3) with the exceptions of two sites located at which may be due to the long-term wood processing distances of 300 m and 4 km to the west from the plants plant there. At present, the industrial trends of this town under construction (Fig. 3). They show relatively high Al are determined by railway transport, wood processing and contents in the snow melt water (163 μg/L and 170 μg/L, heat power system. As compared with Tayshet town, the correspondingly, with an average value for the Tayshet area major element concentrations of the snow melt water of as 16 μg/L. Moreover, Al, Be Li demonstrate a simultaneous Birjusinsk samples indicate that they show higher total increase or decrease of contents (correlation of contents is mineralization (to до 41.5 mg/l), increased concentration established) (Fig. 6). Snow melt water samples from Tayshet of major ions in particular hydrocarbonate, Na+ and Ca2+. and Birjusinsk show higher levels of Al (in some places up Nitrogen dioxide content is higher in Tayshet town, thus to 354 μg/L) as well as Be (to 0.014 μg/L). Higher levels of reaching the level found in Irkutsk city (Grebenshchikova these elements and their correlation can be explained by a 2013) [10] that may be explained by the sleeper factory and wind transfer from the places of the supply of raw material printing industry. for Al production. If we compare the concentrations of all major elements Snow solid phase. The weight of Tayshet snow solid in the Birjusinsk and Tayshet snow water samples with phase samples is insignificant (0.07-2.4 g) and the solid those in samples collected in the town’s environs it is snow phase is found only in the area intended for building. significant noting that the concentrations of these elements During the snow solid phase the contents of toxic elements in samples collected around the anode and aluminum are low: 1-7.0% for Al, 1.5-5.0 mg/kg for Be; 6.0-86 mg/
March 13, 2020 Integrative J of Envi & Ear Sci, Volume 01(01): 11–15, 2020 Comparative Analysis of Chemical Composition kg for Li; 150- 11000 mg/kg for F (Table 3). The element the rivers of the studied area (Tayshetka, Akulshetka and correlation between snow melt water and snow solid phase Baironovka) differs in the chemical composition. The is common to Al and Be while such a correlation is lacking most abundant cations present in the water of Akulshetka for F and Al. The comparative analysis of element (F, Al, Be River are chloride (Cl–), bicarbonate (HCO–), calcium etc.) concentrations in the snow melt water and snow solid (Ca2+), magnesium (Mg2+) and sodium (Na+); other ions phase in samples collected in the areas holding aluminum are in low concentrations. The water in the Tayshetka production (Shelekhov and Bratsk towns, Irkutsk Region) River is bicarbonate-magnesium-calcium-type water. The and in the area where the aluminum plant is under concentrations of trace elements in the studied rivers are construction (Tayshet) reveals significant differences in at the Clarke value or even lower except for Al, Cr and Pb, the concentrations of toxic elements. Surface water in whose dissolved form concentrations are markedly higher.
Figure 5. Distribution of Al content in snow water and in solid snow residue in the territory of Shelekhov and its outskirts (the value of numbers on the X-axis is shown in the figure).
Figure 6. Correlation of the contents of Al, Li, Be in snow water in the area of plants under construction near Tayshet (Baikal region).
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Sampling and analysis of surface water collected close F, Li, B; to a lesser extent, Ni, Co, Cd, Mo, As, V, Cu, S. to the plant under construction (Fig. 3) was done in 2012 However, the levels of toxic elements doesn’t always reach when the pilot shop of aluminum production was operating. the MPC values, but their long-term entry results in the The results of the analysis show higher concentrations of contamination of the atmosphere, water, soil, plants of the Al and Be in the Baironovka River (Table 4) as compared areas thus making them inappropriate for living. with Akulshetka, Tayshetka and other Rivers of the Baikal The analysis of the snow melt water coupled with the Region [16]. Thus, it can be suggested that the increased Al study of river water indicates that the general level of the and Be concentrations in the Baironovka River (both in its environmental pollution in Tayshet and Birjusinsk towns upper part and close to the mouth (Fig. 3, Table 4) are due and their environs is relatively low and is similar to that of to the discharge of ground mineralized water saturated with the Baikal Region with no industrial enterprises. Moreover, these elements. The shoreline of this river has a series of self- the amount of pollution in the towns is less as compared pumping boreholes with the mineralized water. However, with that in their environs, including the construction sites the application of this mineralized water for drinking of the aluminum smelter and the anode plant. It can be and medical purposes has not been studied. The Li and explained by the presence of boilers that use coal, sewage Al contents are however higher in the Akulshetka River and wastewater treatment facilities, motor transport and located nearby the plant. The Al level in the Birjusa River is other industries in the towns. The study of the snow melt similar to that in the Olkha River opposite the Shelekhov and surface water quality in the vicinity of aluminum aluminum smelter. The distance to the sampling site here is over 10 km (Fig. 3). From this, it follows that the increase smelters (Bratsk and Shelekhov towns) provides background in the content of elements associated with aluminum information on how the environmental status can change production, which affects the chemical composition of the during the aluminum smelting process. water in the Akulshetka and Baironovka Rivers. Thus, the obtained data show that the environment in The studies of river water in Russia indicate 17[ ] that the Baikal Region experiences the pollution induced both the contamination of rivers leads to the disturbance of by aluminum smelting process (anthropogenic factor) and self-purification process. In most cases, pollution is either thermal power that uses local coal (natural pollution). due to disposal of sewage occurring from time to time or This work was executed in terms of research projects№ melting of the snow cover and therefore higher element 0350-2019-0005 АААА-А17- 117041910034-5 and was concentrations are rarely found in the river water. In most supported by RFBR ofi_m №( 17-29-05022). cases, the concentrations of toxic elements are lower than maximum permissible concentrations for water reservoirs Acknowledgement intended for industrial, domestic and drinking use. Thus, rivers can preserve natural ecosystems long and have a faster The authors are grateful to the staff of the Institute of recovery. Major toxic elements of aluminum production Geochemistry, Siberian Branch of the Russian Academy of such as Al and Be show an evident correlation in the river Sciences, Irkutsk, who took part in the research. water both in the Shelekhov and Tayshet regions.
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28. Golovnykh NV, Bychinsky VA, Filimonova LM, Chudnenko KV (2016) Modeling and reduction of losses of fluorine-containing components in aluminum production. Chemical technology 17: 65–73. 29. Grebenshchikova VI, Efimova NV, Doroshkov AA (2017) Chemical composition of snow and soil in Svirsk city (Irkutsk Region, Pribaikal’e). Environmental Earth Sciences 76. 30. Shevchenko VP, Gordeev VV, Demina LL (2009) Geochemistry of snow-ice cover of Chupa inlet, Kandalaksha Bay of the White Sea at the end of winter. In: Geology of the Seas and Oceans: proceedings of the XVIII international Scientific Conference (School) on Marine Geology. V.III. GEOS, Moscow 114–119 (in Russian). 31. Grebenshchikova VI, Kuzmin MI, Proydakova OA, Zarubina OV (2018) Long-Term Geochemical Monitoring of the Source of the Angara River (Runoff from Lake Baikal). ISSN 1028- 334X, Doklady Earth Sciences 480: 735–740. 32. Grebenshchikova VI, Gritsko PP, Kuznetsov PV, Doroshkov AA (2017) a. Uranium and thorium in the soil cover of the Irkutsk-Angarsk industrial zone (Baikal region). Bulletin of the Tomsk Polytechnic University. Geo Assets Engineering 328: 93–104.
Corresponding author: Valentina I. Grebenshchikova, A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, 664033, Russia; Email: [email protected];
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