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Snowpack As Indicators of Atmospheric Pollution: the Valday Upland

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Snowpack As Indicators of Atmospheric Pollution: the Valday Upland atmosphere Article Snowpack as Indicators of Atmospheric Pollution: The Valday Upland Marina Dinu *, Tatyana Moiseenko * and Dmitry Baranov * Vernadsky Institute of Geochemistry and Analytical Chemistry, 119334 Moscow, Russia * Correspondence: [email protected] (M.D.); [email protected] (T.M.); [email protected] (D.B.) Received: 23 March 2020; Accepted: 1 May 2020; Published: 3 May 2020 Abstract: Snowpack is a unique indicator in assessing both local and transboundary contaminants. We considered the features of the snow chemical composition of the Valday Upland, Russia, as a location without a direct influence of smelters (conditional background) in 2016–2019. We identified the influence of a number of geochemical (landscape), biological (trees of the forest zone, vegetation), and anthropogenic factors (technogenic elements—lead, nickel) on the formation of snow composition. We found increases in the content of metals of technogenic origin in city snowfall in the snowpack: cadmium, lead, and nickel in comparison with snowfall in the forest. Methods of sequential and parallel membrane filtration (in situ) were used along with ion-exchange separation to determine metal speciation (labile, unlabile, inorganic speciation with low molecular weight, connection with organic ligands) and explain their migration ability. We found that forest snow samples contain metal compounds (Cu, Pb, and Ni) with different molecular weights due to the different contributions of organic substances. According to the results of filtration, the predominant speciation of metals in the urban snow samples is suspension emission (especially more 8 mkm). The buffer abilities of snowfall in the forest (in various landscapes) and in the city of Valday were assessed. Based on statistical analysis, a significant difference in the chemical composition of snow in the forest and in the city, as well as taking into account the landscape, was shown. Snow on an open landscape on a hill is most susceptible to airborne pollution (sulfates, copper, nickel), city snow is most affected by local pollutants (turbidity, lead). Keywords: snowfall; background area; heavy metals; local input and transboundary migration 1. Introduction The contents of various pollutants in the snowpack (copper, nickel, lead, sulfates, nutrients, etc.) are objective indicators of air quality in winter [1]. A number of properties of the snowpack (high ability to absorb, store pollution) make it convenient for understanding the migration of airborne pollutants [2]. If the snow was not subjected to intensive melting, all atmosphere pollutants (heavy metals, nitrogen oxides, sulfates) would be actively accumulated and saved in various concentrations depending on the weather conditions. Snowpack contains two to three orders more pollutants than other atmospheric precipitation [1–3]. 2 Technogenic components—metal (Cu, Ni, and Cd) ions and anions (SO4 − and NO3−)—are of significant interest for atmospheric pollution assessment. Pollutants are characterized by different sources—located within the same place and as transboundary transfers from other locations [3]. The research on snow in background areas has allowed us to assess the migration of the most active components. The snowpack in Greenland and the Arctic, which reflect the pollutants’ transboundary flows, is an area of background research. Based on chemical and isotopic analysis, a 2 number of authors [4–6] showed that SO4 − in winter and early spring snowpack may come from both Atmosphere 2020, 11, 462; doi:10.3390/atmos11050462 www.mdpi.com/journal/atmosphere Atmosphere 2020, 11, 462 2 of 14 anthropogenic and natural sources, respectively, covering long distances due to migration. A number of articles also considered the trends in snow chemical composition changes at certain points at a distance from industrial plants [5–7]. These articles indicated the highest possible metal contents, mainly associated with technogenic impacts. The authors attributed especially high contents of Pb and Cu to the effect of urban infrastructure. However, research on unpolluted areas is especially important in protected areas [8]. Along with the distribution of heavy metals, the acidic neutralizing capacity (ANC) indicator is used to determine the buffer capacity of snowfall (i.e., system stability) with respect to pollutants. The balance between cations and anions allows the assessment of acidic or basic domination in the chemical composition and the determination of the main sources of the chemical migration [3,4,8]. Depending on the locations of the sampling sites, many authors have considered both a strong technogenic impact close to the pollution source and at a considerable distance from the source of pollutions [4,5,9]. Background conditions reflecting global and regional flows of pollutants are of interest. The example of small lakes not subjected to direct anthropogenic impacts has proven that air pollution leads to acidification (in acid-vulnerable regions) and increases in heavy metals in water [10]. To assess the impact of air pollution, a conditional reference area, the Valday National Park in Russia, was chosen. Valday National Park is one of the largest specially protected natural sites of European Russia and was formed to preserve the lake–forest complex of the Valday Upland. The territory of the Valday district is located in the taiga zone, composed of a powerful complex of sedimentary rocks that ubiquitously cover the crystalline basement. It is located far from direct sources of pollution; therefore, the chemical composition of the snowpack reflects the natural and region-wide pattern of elements distribution over and precipitation on the underlying surface. The objectives of the research were to (1) identify the temperature fluctuations in the studied winter period for air and snow cover; (2) study the physicochemical parameters of snow samples in situ and melted snow samples, and the features of the element speciation migration with respect to the landscape; and (3) assess the snowpack pollution as an indicator of the impact of air pollutions in background areas. 2. Materials and Methods 2.1. Sampling Sites The selected area is the lack of local sources of pollution (it is a protected area of the Russian Federation). The city of Valday, located more than 100 km away from large industrial centers, does not have any developed industry [8–11]. Local urban impacts and transboundary transfers may influence the formation of the snow’s chemical composition [5]. The studies were conducted from 2016–2018. Two sites were selected for sampling (Figure1). The first is located 20 km away from the city of Valday near the small Lake Gusinoye; the second is close to the city of Valday. In the first studied area, the landscape is characterized by a slightly sloping terrain with weak podzols (Albic Retisols); the vegetation is represented by coniferous and broad-leaved trees (spruce, birch, pine, alder etc.). We selected 4 sampling points corresponding to various types of elementary landscapes [11]. Sampling point No. 1 was located on a characteristic eluvial landscape with sufficient atmospheric feed and proximity to coniferous trees; no sloping terrain was observed. Sampling point No. 2 was located on the transeluvial landscape with a surface slope angle of 10◦–15◦; the territory is characterized by sparse vegetation and the proximity of coniferous trees. Sampling point No. 3 was located on a superaqual landscape with a low terrain. This superaqual landscape represents a geomorphological structure (marshes). In the summer, this type of landscape is heavily flooded, water-sick in some places, and vegetation is represented by mosses that are common in water-sick areas. This point is closest to Lake Gusinoye. Point No. 4 represents the subaquatic landscape. The subaquatic landscape is a water body, Lake Gusinoye (210,000 m2), predominantly of atmospheric feeding (the snow Atmosphere 2020, 11, x FOR PEER REVIEW 3 of 14 The terrain of the studied area near Lake Gusinoye formed as a result of the interaction between various processes of prolonged continental denudation and glacial deposition, being glacial-deposit terrain with a predominance of hilly outwash valleys. AtmosphereSamples2020, 11No., 462 5 and No. 6 of the second site were located within the territory of the city of Valday3 of 14 at different distances from Lake Valday. Sampling point No. 5 was located on a slightly sloping hill (upland) with sparse vegetation; the soils are highly differentiated compared to soils of the forest sampleterritory, was which taken indicates from the different lake’s frozen rock-forming surface). mi Thenerals. terrain The of thelandscape studied is area predominantly near Lake Gusinoye eluvial. formedSampling as point a result No. of 6 the represents interaction a flat between lake plain various close processes to Lake Valday, of prolonged with sparse continental vegetation denudation and a andsuperaquatic glacial deposition, landscape. being glacial-deposit terrain with a predominance of hilly outwash valleys. Figure 1. Sampling points and filtering filtering equipment. 2.2. SampleSamples Collection No. 5 and and No. Preparation 6 of the second site were located within the territory of the city of Valday at different distances from Lake Valday. Sampling point No. 5 was located on a slightly sloping hill (upland)2.2.1. Chemical with sparse Analysis vegetation; of Samples the soils are highly differentiated compared to soils of the forest territory,Snow which samples indicates
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