Scientific registration no : 771 Symposium no : 28 Presentation : poster

Heavy Metals in Urban Soils in Russia Mtaux lourds dans les sols urbains en Russie
KASIMOV Nikolay , LYCHAGIN Michail Faculty of Geography, Moscow State University, Vorobevy gory, 119899 Moscow, Russia

Introduction Nowadays ecological situation in many towns of Russia and other countries is close to the level of high risk. The mostly pronounced technogenic geochemical impact on the environment and population is observed in large industrial towns, which present geochemical provinces according to levels of pollution and area of anomalies. Towns serve as powerful sources of technogenic substances for the regional migration cycles. Fate of pollutants in the urban environment depends on internal (chemical, toxicological) and external (geochemical conditions of migration, geochemical barriers, landscape conditions) factors. So that the landscape geochemical research appears to be the important block of the ecological assessment of the urban environment. The environmental geochemical situation in 20 studied Russian towns derives from the natural and technogenic agents ratio. Hence, all kinds of environmental assessments made for urban soils presume the analysis of the nature-dependent ingredients of the landscape-geochemical environment, such as geochemical conditions for pollutants migrations, location of urban soils in the cascade transfer system, pollution and selfpurification capacities of natural media, etc. Technogenic agents as criteria for assessments should be accepted as well; these are: geochemical speciation of pollution sources, chemical properties of toxicants, etc. Both groups of approaches have been applied for the geochemical systematic of towns and urban soils. Materials and methods The paper is based on materials obtained by researchers of the Department of Landscape Geochemistry and Soil Geography (Faculty of Geography, MSU) with the involvement of other institutions in 1985-1995 [1]. The research of the urban environment has been done in different towns of Russia (Moscow, Togliatti, Bratsk, Yaroslavl, Cherepovets, etc.). Methods of the research are based on the landscape-geochemical approach, which presuppose a study of levels and pathways of migration of chemical elements in different components of landscapes: soils, plants, snow cover, water, bottom sediments, etc. The most attention here is paid to the contamination of soils with heavy metals.

Results and discussion As a rule, technogenic anomalies in soils record pollution of the last 20-50 years. The minimum time of the formation of distinct geochemical anomalies in soils varies due to type of influence. Usually it is about 5-10 years, but for some pollutants (As, Zn) it is lower down to 1-2 years. Soils accumulate contaminants during all the period of a technogenic impact, hence anomalies in soils are more stable than the ones in air, snow cover or plant cover. So that soil-geochemical research and mapping serve as the basic method for ecological assessment of the urban environment. Heavy metals in soils. High levels of pollution by industrial, heat energetics, transport and municipal sources in towns lead to a formation of technogenic anomalies of heavy metals and other contaminants in urban soils. Anomalous zones of heavy metals in soils present areas of the most hard impact on the urban environment, which are dangerous for plants, animals and people, especially children. There are different approaches for the evaluation of heavy metal pollution in soils. The first one consists in a comparison of contaminated soils with their natural analogues. For instance, anomality coefficient Kc (ratio of the elements content within a technogenic anomaly to its background concentration) is used. This coefficient is quite useful to determine a level of pollution, but it doesnt reflects clearly the danger of pollution. The other way is to compare heavy metal levels with permissible limits found experimentally. Elaboration of such limits is troubled by high variability of the natural background levels for soils of different geochemical provinces and natural zones. Soil vulnerability to pollution depends on organic matter and clay content, pH and Red-Ox conditions. Hence, permissible limits have to be different depending on soil properties. In case of a poly-element contamination a toxicity of various chemical elements can be summarized with a synergetic influence for the living nature. One of the simple ways to evaluate complex technogenic anomalies is to use so-called summarizing pollution index (Zc), which is widely applied in Russia [2]. It is calculated as Zc = Kc - (n-1), where Kc - anomality coefficient, n - number of anomalous elements quantified. As a generalized coefficient, Zc is not free of shortcomings, it gives, however, possibility to compare pollution levels of different towns. Besides, this index is used for standardization purposes, as close correlation have been revealed between its values for soils and risks of threatens to human health. Thus, if it is below 16, pollution is not harmful for people, whereas if it exceeds 100-120, the human health is in a great danger. A method to determine geochemical anomalies have been elaborated in our country for the geochemical search of economic minerals, i.e. continuous grid or vector sampling of topsoils. In large towns rather regular grid sampling is usually done. The optimal grid size for large and medium towns is 500x500 m, if necessary a more detailed sampling is applied. Thus, such data base for Togliatti comprises 800-1000 samples. Geochemical sampling of towns enables to distinguish heavy metal anomalies of various contrast. Heavy contaminated areas are located in the vicinity of industrial plants and 2

other technogenic sources. Hence, the next stage of the research includes evaluation of anomalies and identification of pollution sources. Analysis of geochemical conditions, ways of pollutant migration, technogenic transformation of soils allows to distinguish in the town area soil-geochemical zones with different natural features, levels and associations of contaminants. Soil-geochemical mapping is a main method of the data analysis. As a result, number of maps are compiled, both mono-element and summarized. The highest summarized levels of heavy metal pollution (Zc > 120, up to 500-1000) are determined for towns with ferrous and non-ferrous metallurgy. In centers of anomalies concentrations of heavy metals are dozens times higher than permissible levels. High pollution is observed in towns - centers of machinery construction and instrumentmaking (Zc= n*10). Towns of chemical industry are characterized by strong pollution with specific gases and lower levels of heavy metals. Of the especial contrast are technogenic anomalies of heavy metal mobile forms. Kc of these forms in anomalies are 5-10 times higher than the ones of bulk values. Spatial distribution of mobile forms distinctly depends on the landscape-geochemical conditions. Anomalies of them are highly pronounced in autonomous landscapes, windward to the pollution sources slopes, flood-lands and coasts of rivers, lakes, water reservoirs. Technogenic transformation of soil properties and geochemical conditions. Substances of the technogenic origin can influence on geochemical conditions of chemical element migration in soils, such as pH and Red-Ox values. It concerns mainly to the macroelements (Fe, Ca, Mg), mineral acids, etc., which themselves usually are not toxic for flora and fauna. High input of dust in towns leads to enrichment of soils by Fe and CaCO3. Ferrugination weakly influence to pH and Eh values of soils. On the contrary, input of carbonates results in alkalization and base saturation of soils, precipitation of heavy metals in weakly dissolved forms. In case of the long and considerable influence acid soils can be transformed to neutral or even alkaline soils. Anthropogenic factors affect the localization or destabilization of anomalies in urban soils. To comprehend the destabilization processes and mechanisms it is worth to bear in mind that chemical elements behave quite differently, so that the same anthropogenic agent may be a mobilizer in some cases and a stabilizer in the other ones. For example, in some geochemical classifications all the elements are subdivided into three groups according to their migration capacity in various natural media. The first one received a conventional name of cationogenic elements - elements that usually migrate in the cationic form (Na, K, Ca, Sr, Ba); in acid soils heavy metals behave in the same way. The second group, or association, comprises the complex-forming elements (hydrolysates); they migrate mainly as intricate complex compounds and have two solubility maxima: in strongly acid and strongly alkaline media. The third group is composed by anionogenic elements migrating mainly as ingredients of various complexes. These elements are very mobile in alkalization media and less mobile in acid ones.

Consequently, it is possible to outline the probable trends in their behavior due to the impact of two basic urban transformation processes. The first one is acidification (caused by release of sulfur, nitrogen and some other elements), which has mobilizing effect for cationogenic elements, heavy metals first of all. For the other group of elements, that are mobile in alkaline conditions, acidification acts as a stabilizing agent fixating them in soils. If we apply the terminology of geochemical barriers concept, we can say that the alkaline barriers are more characteristic of the cationogenic elements, whereas the acid barriers are proper to the anionogenic ones. The second process, more typical for the majority of towns than acidification, is alkalization caused by precipitation of carbonate-containing dust. Towns serve as sources of dust for themselves and surrounding areas. So that in areas with stable snow cover pH values of snow in the vicinity of towns (8.0-8.5) are distinctly higher than background values (5.5-6.0). Hence, topsoils of towns often show higher pH values than background ones. Effect of some branches of industry (heat energetics, cement production) consists in strong alkalization of the snow cover and soils. Thus, the cement plant in Togliatti is responsible for a technogenic pH anomaly in the snow cover with a difference in pH values up to 5 gradations. Background snow pH values of the area are about 6.0-6.5, while near the plant they rise to 11.0. Constant alkalization transforms the pH conditions of topsoils, although the shift in the mean anomaly indices is only 2-3 pH gradations. Natural pH values of grey forest soils (about 5.5) change in the area of a cement plant impact to values of 8.0-8.5. It leads to a transformation of basic soil properties and development of an alkaline (carbonate) geochemical barrier in the topsoils. This barrier is important for many heavy metals as hindering their mobilization. Hence, migration pathways of chemical elements change: more alkaline soils are usually enriched in cationogenic, while the more acid ones - in anionogenic elements. The alkalization process is more conspicuous in acid taiga soils (Moscow, Yaroslavl, Novgorod, etc.), whereas the technogenic alkalization is hardly discernible in steppe and desert zones with their natural neutral or alkaline soils. There are two types of pollutants behavior in the urban soils. The first type may be defined as conjugated. It is peculiar by the existence of a certain ratio between the atmotechnogenic input and contamination of soils, plants, bottom sediments; this idea of a ratio, or balance, was basic for the concept of media - deponents applied for the environmental geochemical assessment of towns. The second, dissonance, type is characterized by shifts in this conjugated ratio. We proposed a notion of a technogenic geochemical dissonance for the phenomenon of such shifting. Two variants of geochemical dissonance may exist. An accumulative geochemical dissonance evolves in cases when natural and natural-technogenic agents intensify a rather small atmotechnogenic pollution. A good example of such dissonance is Novgorod, where the pollutants from the atmosphere become concentrated in the city, which is situated in the Ilmen lacustrine depression - final member of the local surface and underground runoff discharge. 4

An obliterating geochemical dissonance may be proper to towns with heavy atmospheric targets, that are strongly reduced by leaching of metals from light-textured taiga soils with very low natural background (Cherepovets). That is why the technogenic anomalies of metals being formed in soils, even highly contrasting, display low absolute concentrations of heavy metals, they are even far from reaching permissible concentration levels. High values of the coefficient Zc do not indicate the dangerous level of soil pollution in this case. Conclusions 1. Pollution of towns by heavy metals reached a level of high risk. The majority of towns under study approximate technogenic geochemical anomalies or nets of anomalies in soils and other natural components. Most unfavorable is the environmental-geochemical status in towns-centers of ferrous and non-ferrous metallurgy, engineering and metalworking industries. 2. The environmental geochemical situation in towns derives from the natural and technogenic agents ratio. Hence, all kinds of environmental assessments made for urban soils presume the analysis of the nature-dependent ingredients of the landscapegeochemical environment (geochemical conditions for pollutant migration, location of urban soils in the cascade transfer system, pollution and self-purification capacities of natural media, etc.) and technogenic agents (geochemical speciation of pollution sources, chemical properties of toxicants, etc.). 3. A peculiar phenomenon has been reported as a widely spread one in many towns: a pH shift to alkalinity in urban soils with a subsequent development of an alkaline (carbonate) geochemical barrier in the topsoils. This barrier is important for many heavy metals as hindering their mobilization. 4. There are two types of pollutant behavior in the urban soils. The first type may be defined as conjugated. It is peculiar by the existence of a certain ratio between the atmotechnogenic input and contamination of soils. The second, dissonance, type is characterized by shifts in this conjugated ratio. Two variants of geochemical dissonance may exist. An accumulative geochemical dissonance evolves in cases when natural and natural-technogenic agents intensify a rather small atmotechnogenic pollution. An obliterating geochemical dissonance may be proper to towns with heavy atmospheric targets, that are strongly reduced by leaching of metals from light textured soils with very low natural background. References
1. Ecogeochemistry of Urban Landscapes // MSU Publ., Moscow,1995. 333 pp. (In Russian). 2. Geochemistry of the Environment // Nedra Publ., Moscow, 1990. 335 pp. (In Russian).

Keywords: pollutants, heavy metals, urban soils, geochemical barriers, Russia Mots cls : poluants, mtaux lourds, sols urbains, barrire gochimique, Russie