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Publicly Available Published by De Gruyter October 12, 2021

Results of AAS-measurements of atmospheric deposition of copper and lead in the snow cover of Almaty agglomeration

  • Аzamat Madibekov ORCID logo EMAIL logo , Laura Ismukhanova ORCID logo , Ainur Mussakulkyzy ORCID logo , Roza Kulbekova ORCID logo and Askhat Zhadi ORCID logo

Abstract

The article presents the results of the study conducted on the territory of the Almaty agglomeration (AA) in the first half of 2019. During the expeditionary studies, sampling was carried out at 30 permanent points established taking into account the degree of anthropogenic load and sources of technogenic pollution. The content of trace elements (TE) in the snow was determined by a flame atomic absorption spectrometric method using an AA-7000 spectrophotometer with a hollow cathode lamp and with a nozzle burner operating on an acetylene-air mixture. The paper considers the amount of content of copper and lead in the snow, as well as the nature of their distribution over the study area. Calculations were carried out on the number of depositions of the TE in question per unit area over the territory of the agglomeration, with the allocation of zones experiencing the highest technogenic load.

The increasing urbanization of megacities poses a real threat to the ecosystem surrounding natural complexes, creating unsafe conditions for human health. The most effective method to evaluate the impact of technogenic stress on urban environment and population health is to monitor a pollution of precipitation.

The object of the study is the snow cover (SC) of the territory of the Almaty agglomeration (AA). SC has high sorption ability and it is the most informative in the study of technogenic air pollution. The amount of solid precipitation falling with the snow characterizes the dustiness of the territory, the filtrate of melt snow (snow water) reflects the degree of air basin pollution with well-soluble forms of elements, which are the most toxic to plants and living organisms.

As a result of economic activity, various pollutants, in particular, toxic trace elements (TE), are emitted into the atmosphere. Anthropogenic flow of TE into the atmosphere is many times greater than the flow caused by natural cycles, i.e., dissipated in the atmosphere due to wind flows, etc., falling on the underlying surface due to dry and wet excretion processes [1, 2]. Data on pollutant concentrations in precipitation volume unit, certainly the most important characteristic of precipitation. However, they do not provide enough information to estimate how much pollutants fell per unit area, because the amount of pollutants falling per unit area is determined not only by the concentrations of these substances, but also by the amount of falling precipitation [3]. According to the chemical composition of snow it is possible to establish the distribution area and quantitative characteristics of substances precipitating in winter from the atmosphere, thereby it is possible to identify the sources of pollution and their ranges of influence, to get an approximate estimate of the number of toxic substances carrying from cities and industrial sites by meltwater and migration into soils and groundwater [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13].

The paper presents the results of the study conducted on the territory of AA in the first half of 2019. To study the physicochemical parameters and the level of HM accumulation, snow sampling was carried out at constant points (Fig. 1). Sampling points are located by the degree of anthropogenic stress and conditionally divided into five zones: mountainous territories; territory of Almaty city; small towns; small settlements; coast of the Kapshagay reservoir.

Fig. 1: 
Scheme of sampling points of snow cover (SC).
Fig. 1:

Scheme of sampling points of snow cover (SC).

During the field research, snow samples were taken according to the generally accepted method [14]. To study the level of accumulation of heavy metals in snow, sampling was carried out in an open flat area, 100 m away from local sources of pollution during the period of maximum accumulation of water content in the snow. Snow sampling was carried out by the pit method for the entire thickness of SC, with the exception of a 5 cm layer above the soil, with measuring the sides and depth of the pit, depending on the height of the SC on an area of 1 × 1 m2; the samples were placed in polyethylene bags (Fig. 2).

Fig. 2: 
Sampling.
Fig. 2:

Sampling.

When sampling according to the method, the ingress of foreign substances into the samples was excluded, both at the time of sampling and during their storage and transportation to the laboratory. The samples delivered to the laboratory were stored at a temperature of −5 … –15 °С. To melt snow, the sample was placed in pre-prepared containers. The sedimented samples were filtered through a paper filter with a white tape for further toxicological analysis.

As is known, the various high-precision equipment is used to determine toxic compounds, for example, mass spectrometers, gas chromatographs [15] and GF-AAS [16], which allow the detection of organic complexes rarely found in the environment. In our studies, to determine metals in snow, we used the results of AAS-measurements by the flame atomic absorption spectrometric method with preliminary processing of samples using AA-7000 atomic absorption spectrophotometer (Shimadzu, Japan). Atomic absorption spectrophotometer with a hollow copper-lead cathode lamp for correcting the non-specific absorption coefficient and with a nozzle burner operated using acetylene-air mixture. When analyzing snow samples, the State standard samples (standard sample of the composition of aqueous solution of copper ions (3K-1) SSS 7998-93 and a standard sample of the composition of aqueous solution of lead ions (2K-1) SSS 7012-93) were used to build a calibration graph with standard samples for copper: 0.0125; 0.025; 0.05; 0.1 mg/dm3, for lead: 0.05; 0.1; 0.15; 0.2 mg/dm3 with correlation coefficients r = 0.99. The test report of snow samples for the content of copper and lead are shown in Fig. 3. To assess the level of pollution of the SC, the current regulatory documents were used [17], [18], [19].

Fig. 3: 
Test report of snow samples for the content of copper and lead.
Fig. 3:

Test report of snow samples for the content of copper and lead.

To estimate the flow of copper and lead to the underlying surface of the territory of AA, a methodical recommendation was used [20], where data on the mass concentration of each component in snow per unit area were used. It should be noted that for the territory of AA, the evaluation of TE in the SC is performed for the first time. The receipt of chemical elements on the underlying surface was calculated including the reserves of SC.

The results of the toxicological analysis of metals are provided in Table 1, the copper content in the snow of mountainous areas, small towns and small settlements is slightly lower (2.5 μg/dm3) than in the territory of Almaty city and the coast of the Kapshagai reservoir (3.6 and 4.7 μg/dm3, respectively).

Table 1:

Average values of concentration of trace elements in snow cover of Almaty agglomeration (AA), µg/dm3.

Zone Mountainous territories Territory of Almaty city Small towns Small settlements Coast of the Kapshagay reservoir
Content of trace elements
Cu 2.4 3.6 2.4 2.5 4.7
Pd 17.8 23.5 27.5 25.4 20.9

Lead content in the snow is different, in mountainous territories up to 17.8 μg/dm3, whereas in the rest of the territory of agglomeration ranged from 20.9 to 27.5 μg/dm3, with elevated values in small towns and small settlements.

First of all, lead is taken into attention when considering the impact of transport on the ecological condition. This fact is due to the widespread use of tetraethyl lead as an additive to gasoline [21], i.e., emissions of motor vehicles, the use of low-quality gasoline, emissions of Thermal power stations (ThPS), as well as the high cumulative capacity of these compounds in the snow. In studies of urban areas of the city of Ulan-Bator [22], excesses were also observed for standards for lead, the soluble forms of which are contained in snow and are characterized by the highest degree of danger of urban pollution.

There are no excesses of regulations for household-drinking and cultural domestic water use throughout the territory of AA, except for fisheries MPC, where content of copper exceed by 3.1 times and content of lead exceed by 2.3 times.

To illustrate the quantity of copper and lead to the underlying surface of the territory of AA, maps were built using the ArcGIS 10.1 software product, which are presented in Fig. 4.

Fig. 4: 
The quantity of receipt of trace elements per unit area of the territory of the Almaty Agglomeration (AA).
а) copper; b) lead.
Fig. 4:

The quantity of receipt of trace elements per unit area of the territory of the Almaty Agglomeration (AA).

а) copper; b) lead.

In the distribution of TE fallout across the territory of AA as the absolute mark increases, there are changes from mountainous areas to plains, and there is a relation between the water reserves in the SC and the absolute mark (r = 0.85). A mountain-valley circulation, where pollutants with convective streams are carried along the gorges upwards, reaching the heights of the location of the ski base, the Big Almaty Lake and et al. has the importance in the fallout of toxic compounds on the mountainous territory.

At the snow sampling areas along motorways (Eastern and Northern belt highways) amount of precipitating TE per unit area also is high, due to the heavy technogenic stress caused by vehicle exhaust and ThPS. This fact proves that, SC plays the role of a natural accumulator of atmospheric dust for several winter months, and shows that a significant part of the accumulation in snow is formed by dry precipitation from the lower layer of the atmosphere and is predominantly anthropogenic.

Thus, as the result of dry and wet washing processes, the concentration of pollutants is usually 2–3 times higher than in the atmosphere. Therefore, the ongoing studies of the territory of AA in order to evaluate the spatial distribution of pollutants, makes it possible to determine the geochemical background and to contour areas with abnormal values of the investigating parameters.

In addition to this dependence, as an objective measure of the similarity of behavior of chemical elements in the processes of dispersal and accumulation during the observation period, a statistical and mathematical analysis was done [23] – the pair correlation ratio between metals was determined. Analysis of the pair correlation revealed a high positive correlation between copper and lead, the level r = 0.62.

The obtained results expand the idea of the nature of pollution of the SC of the territory of AA, as well as precipitation on a unit area. Identified abnormal concentrations of pollutants are environmentally hazardous to human health and the environment. These pollution data for the aforementioned natural environments serve as a starting point for eliminating localized elevated concentrations, as well as for monitoring.


Article note:

Snow cover, atmospheric precipitation, aerosols: chemistry and climate: reports of the III Baikal international scientific conference endorsed by IUPAC (March 23-27, 2020).



Corresponding author: Аzamat Madibekov, Institute of Geography and Water Security, Ministry of Education and Science of the Republic of Kazakhstan, Almaty, Kazakhstan, E-mail:

Funding source: Committee of Sciences of the MES

Award Identifier / Grant number: AP09260361

  1. Research funding: The work was funded by the Science and Education Committee under the Ministry of Education and Science of the Republic of Kazakhstan within the framework of grant funding for scientific and/or scientific and technical projects for 2021–2023. Grant No. AP09260361 «Geoecological monitoring of the deposit environment of Ile river delta and “Ile-Balkash” State Natural Reserve».

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Published Online: 2021-10-12
Published in Print: 2022-03-28

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