Contamination of Soils with Heavy Metals and Metalloids and Its ...

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At present, the stress is made on the investigation of heavy metals/metalloids in agricultural soils ... heavy metal/metalloid vary depending on the techno.
ISSN 10642293, Eurasian Soil Science, 2013, Vol. 46, No. 7, pp. 793–801. © Pleiades Publishing, Ltd., 2013. Original Russian Text © Yu.N. Vodyanitskii, 2013, published in Pochvovedenie, 2013, No. 7, pp. 872–881.

DEGRADATION, REHABILITATION, AND CONSERVATION OF SOILS

Contamination of Soils with Heavy Metals and Metalloids and Its Ecological Hazard (Analytic Review) Yu. N. Vodyanitskii Faculty of Soil Science, Lomonosov Moscow State University, Moscow, 119991 Russia Email: [email protected] Received January 17, 2011

Abstract—According to the presentday ecotoxicologic data, hazardous heavy metals/metalloids form the following sequence in the soil: Se > Tl > Sb > Cd > V > Hg > Ni > Cu > Cr > As > Ba. This sequence differs from the wellknown series of the hazardous heavy elements, in which the danger of Pb and Zn is exaggerated, whereas that of V, Sb, and Ba, is underestimated. Tl also should be included in the list of hazardous elements in the soil. At present, the stress is made on the investigation of heavy metals/metalloids in agricultural soils rather than in urban soils, as the former produce contaminated products poisoning both animals and humans. The main sources of soil contamination with heavy metals are the following: aerial deposition from stationary and moving sources; hydrogenic contamination from the industrial sewage discharging into water bodies; sewage sediments; organic and mineral fertilizers and chemicals for plant protection, tailing dumps of ash, slag, ores, and sludge. In addition to the impact on plants and groundwater, heavy metals/metalloids exert a negative effect on the soil proper. Soil microorganisms appear to be very sensitive to the influence of heavy elements. Keywords: heavy elements, aerial fallout, hydrogenic contamination, sewage, tailings DOI: 10.1134/S1064229313050153

INTRODUCTION At present, the following main tasks are distin guished within the problem “Heavy metals in soils”: (1) to study the input of metals to agricultural soils; (2) to study the biological availability of metals in sew age mud used for plant nutrition, with phosphorus, above all; (3) to study the chemical aspects of metal behavior in soils, i.e., fixation, redistribution, and release [65]. Thus, the tasks are aimed at the investiga tion and control of agricultural rather than urban soils. This is explainable, as it is agricultural soils where the contaminated products poisoning animals and humans come from. It is also no surprise that in those countries where the standard content of heavy met als/metalloids is differentiated depending on the land use, the maximal permissible content for the arable soils is much lower than for the urban soils either at office or recreational plots. A researcher inevitably faces the question about the study of the most hazardous pollutants. A total of 57 heavy metals/metalloids are known [12, 13], with their hazard degree varying substantially; and no answer can be given to this question. The aim of this work is to revise the list of the most hazardous heavy metals/metalloids in the soil, to reveal their principal sources, and to characterize the influence of pollutants on soils, agricultural soils, in particular.

Determination of the hazard degree of heavy metals and metalloids in soils. Only three heavy metals (Pb, Cd, and Hg) were mentioned in the Global Monitor ing Program adopted by UNO in 1973 (cited after [23]). Later, in the report by the Executive Director of UN Environment Program (UNEP), seven heavy metals (Cu, Sn, V, Cr, Mo, Co, Ni) and three metal loids (Sb, As, and Se) were added to the list of the most hazardous elements [55]. Monitoring of heavy elements in the soil is still based on these recommendations [18]. The Ministry of Natural Resources and Ecology of the Russian Fed eration controls a total content of nine heavy metals in the soils [19]. The maximum permissible concentra tions (MPCs) are adopted for one group of them (V, Mn, and Pb); the provisional permissible concentra tions (PPCs) are adopted for another group (Cd, Cu, Ni, Zn); and for the third group of elements with no adopted standards, the contamination degree is esti mated according to an empirical criterion, i.e., by the excess of four background values. Sometimes, the absence of standards for heavy metals in soils is con sidered to point to their inactivity; Ba and Sr are clas sified as low toxic metals; whereas Ga, Sc, and Ag are regarded to be conventionally toxic [48]. Note a serious drawback of the MPC/PPC: the fixed concentrations of heavy metals and metalloids without distinguishing natural and technogenic shares in them are used for the assessment of soil contamina

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tion (cited after [10]). This leads to the overestimation of pollution hazard within the territory of positive geochemical anomaly and to underestimation of the hazard within the negative natural anomaly. As is seen, the fixed standard values do not take into account the natural climatic and geochemical specifics of regions [9, 44]. These specifics may be very contrasting. The background content of As varies from 0.1 mg/kg in podzols of the Kola Peninsula to 100–150 mg/kg in chernozems of Altai foothills (Russia) [42]. A high content of heavy metal in the soil (exceeding MPC/PPC) does not obligatorily mean the soil con tamination. Finally, standards do not take into account such important factor as the contamination age; however, the pollutant mobility and, hence, its hazard, decreases with time [26]. The prerequisites to a more adequate approach were created as long ago as 1987, when Sanitary Rules and Norms (SanPiN) 42128443387 were adopted by the Ministry of Public Health of the USSR for sev eral heavy metals using “flexible” MPC and applying an equation: MPC = background + MPS, where the second summand was later designated as MPS, i.e., the maximal permissible supplement of heavy metal as a pollutant (cited after [58]). The MPC value charac terizes the hazard degree of the given heavy metal. This principle of MPC expression based on distin guishing between the variable natural and technogenic permissible shares of metals/metalloids, permits us to determine the local MPC values and to avoid disad vantages of standards caused by the application of fixed figures. The flexible approach to standardization was later developed in the Netherlands [63, 78]. In this country, new MPS values were obtained from numerous and diverse ecotoxicological studies: a large work was per formed in determining MPS values for 17 heavy met als and metalloids. The influence of water extracts from soils contaminated with these elements on differ ent types of organisms (no less than four) was investi gated: plants, bacteria and other microorganisms; i.e., the toxic influence on soil biota was taken into account rather than the direct impact of heavy metals/metal loids on the human health upon dust inhalation and drinking potable water. Afterwards, the harmonization of obtained MPS values was performed [63]. The obtained MPS values for metals/metalloids form the following succession in the soil: Se > Tl > Sb > Cd > V > Hg > Ni > Cu >Cr > As > Ba > Zn > Co > Sn > Ce > Pb > Mo. This succession shows the hazard degree of chemical elements in soils as regards biota. Unfortu nately, the list of 17 elements enumerated in the table is not broad enough, taking into consideration a total of 57 heavy metals. The lacking MPS for uranium is noticeable, as the technogenic share of this undoubt edly toxic element rose swiftly after the World War II [14]. Thus, a very useful investigation in MPS should be spread over the other heavy metals /metalloids in soils.

The Dutch values of MPS are given for the soil containing 25% clay particles ( Tl > Sb > Cd > Hg > Ni > Cu > Cr > As > Ba. Tl should be included in the list of hazardous elements in the soil. At present, the attention worldwide is focused on the studies of heavy metals/metalloids in agricultural rather than urban soils. This is explainable since it is agricultural soils, where the polluted products poison ous to animals and humans come from. In the coun tries, where the allowed content of heavy metals/met alloids varies depending on the land use, the lower MPC values are adopted for arable soils as compared to the urban soils. 2. A number of elements with low clarkes are poorly studied, which is explained by the difficulty in their identification. The bulk of hazardous heavy met als/metalloids are identified using an expensive method of atomic emission spectroscopy. Many heavy elements are also determined by the expensive method of neutron activation. An easy and cheap method of Xray fluorescence is applicable not to all hazardous heavy elements. 3. The main sources of soil contamination with hazardous heavy elements are the following: aerial fallout from stationary and mobile sources; hydro genic contamination by the discharge of industrial sewage to the water bodies; sewage sediments; organic and mineral fertilizers and chemicals for plant protec tion; tailing dumps of ash, slag, ores, and sludge. 4. Heavy metals/metalloids adversely influence not only plants and groundwater, but also the soil proper. Soil microorganisms are the most susceptible to the impact of heavy elements. Worsening of phosphate regime and humus loss are possible. REFERENCES 1. E. Yu. Altukhova, Extended abstract of Candidate’s dissertation in Biology (Moscow, 2010). 2. V. S. Arzhanova, V. P. Elpat’evskaya, and P. V. Elpat’evskii, “Soil transformation under the impact of mining industry: methodological aspects and results,” in Mod ern Problems of Soil Pollution, Vol. 1, 11–16 (Moscow, 2004) [in Russian]. 3. S. Yu. Artamonova, “Permafrost soils of the Aldan goldmining region (Yakutia),” in Modern Problems of Soil Pollution, Vol. 1, 167–169 (Moscow, 2004) [in Rus sian]. 4. I. A. Arkhipov, A. S. Sakladov, Yu. V. Robertus, and A. V. Puzanov, “The impact of technogenic exhausts of oresmelting industry and the soilgeochemical fea tures of mercury distribution in highland soils (the Aktashski ore smelter),” in Modern Problems of Soil Pollution, Vol. 1, 54–57 (Moscow, 2004) [in Russian]. 5. Zh. U. Akhanov and T. K. Tomina, “Problems of tech nogenic pollution of soils in Kazakhstan,” in Modern EURASIAN SOIL SCIENCE

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