ISSN 1064-2293, Eurasian Soil Science, 2017, Vol. 50, No. 3, pp. 359–372. © Pleiades Publishing, Ltd., 2017. Original Russian Text © I.V. Zamotaev, I.V. Ivanov, P.V. Mikheev, V.P. Belobrov, 2017, published in Pochvovedenie, 2017, No. 3, pp. 370–384.

DEGRADATION, REHABILITATION, AND CONSERVATION OF SOILS

Transformation and Contamination of Soils in Iron Ore Mining Areas (a Review) I. V. Zamotaeva, *, I. V. Ivanovb, P. V. Mikheevc, and V. P. Belobrovd a

Institute of Geography, Russian Academy of Sciences, Moscow, 119017 Russia Institute of Physicochemical and Biological Problems of Soil Science, Russian Academy of Sciences, Pushchino, 142290, Russia c Erisman Federal Scientific Centre of Hygiene, Federal Service for Supervision of Consumer Rights Protection and Human Welfare, Moscow, 141014 Russia d Dokuchaev Soil Science Institute, Moscow, 119017 Russia *e-mail: [email protected] b

Received February 11, 2016

Abstract⎯Current concepts of soil transformation and contamination in iron ore mining areas have been reviewed. Changes of soils and ecosystems in the mining areas are among the largest-scale impacts of economic activity on the nature. Regularities in the radial differentiation, spatial distribution, and accumulation of heavy metals in soils of different natural zones are analyzed. The effects of mining technogenesis and gas– dust emissions from enterprises on soil microbial communities and fauna are considered. In zones of longterm atmotechnogenic impact of mining and processing plants, the stable state of ecosystems is lost and/or a new technoecosystem different from the natural one, with own microbial cenosis, is formed, where communities of soil organisms are in the stress state. In the ore mining regions, embriozems are formed, which pass through specific stages of technogenically-determined development, as well as technosols, chemozems, and technogenic surface formations with variable material compositions and properties. Technogenic soils and soil-like bodies form a soil cover differing from the initial one, whose complexity and contrast are not related to the natural factors of differentiation. Keywords: iron ores, heavy metals, mining technogenesis, atmotechnogenic impact, soil contamination, microbial communities, embriozems, chemozems, technogenic surface formations, remediation DOI: 10.1134/S1064229317030127

INTRODUCTION The mining and processing of iron ores containing Pb, Zn, Ni, Co, Cd, Cu, Mn, and some other chemical elements as companions for the production of steel, cast iron, and alloys with polymetals are among the largest-scale technogenic impacts on the natural environment and soils. The global production of iron is about 5 × 109 tons [47]. A similar amount of the metal is in use by humans at present and has been dispersed over the Earth surface during the last 200 years. The extraction of iron from the earth and its input to the surface and in soils because of losses during the mining and smelting operations and in the course of ironware corrosion result in an increase in the iron content in the surface layer of the planet (ferrugination) [17, 42]. Iron is the second element after carbon in terms of production (1010 tons, including coal, petroleum, gas, and construction materials: limestone, chalk, etc.). Significant amounts of contaminant elements, whose high concentrations are toxic and hazardous for living organisms, are simultaneously involved in technogenic migration [12, 89, 90].

In this paper, on the basis of the review of main publications and some own data, we describe characteristic features of the transformation of heavy metals (HMs) and the contamination of soils with HMs in the regions of iron ore production and refining, as well as the nomenclature of technogenic soils and soil-like formations, and assess the effect of mining industry on soil biota. REASONS OF SOIL TRANSFORMATION AND THE SOURCES OF CONTAMINATION Scale and features of technogenic impacts. The reasons of soil transformation and the sources of soil contamination are of complex character. The main of them are the mechanical transformation of relief surface and the translocation of large rock masses with alteration of their chemical composition. New hydrogeological conditions are created, which result in the degradation and transformation of natural ecosystems. An important factor of ecosystem formation is the fallout of significant amounts of atmospheric dust con-

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taminated with HMs, which act as climatic and geochemical factors. The mining of iron ores (iron quartzites, rich hematite-martite and hydroxide ores, stratal sedimentary siderite-chlorite-hydrogoethite, magnetite, goethitehydrogoethite ores with siderite cement, etc.) results in the development of new technogenic relief forms— quarries, cavities, dumps, and tailings with stored overburden rocks and rock refuses—on vast areas. The largest dumps of 60 to 100 m in height and quarries of more than 350 m in depth and 7–10 km2 in area are located in the iron ore region of the Kursk Magnetic Anomaly (KMA) [91]. The mean weighted depth of large iron ore quarries (Olenegorsk, Kovdor, Kostomuksha, Mikhailovsk, Lebedinoe, Stoilensk, Kachkanar, and Korshunov mining and processing plants (MPPs)), where 87.5% of total iron ore in Russia is produced, is 259 m [113]. The dominance of sloped surfaces (12°–30°) and water-permeable filled overburdens in quarry–dump complexes favors the gravity sorting, sliding, suffusion, and other processes [52, 57, 58, 81, 89, 91]. Benches, scarps, slide mounds and sinks, and local alluvial cones are thus formed. Open-pit mining operations result in the discharge of highly mineralized water and the flooding of neighboring areas, as was observed in the basins of Oskolets and Chufichka rivers in Belgorod oblast and Chern’ and Pesochnaya rivers in Kursk oblast, which occur in the affected areas of the Lebedinoe and Mikhailovsk MPPs [125]. Mechanical disturbances of the soil and plant cover, up to complete elimination, are most significant on the areas of direct production within the quarries and ore refining. They are less intensive and local in the zones adjacent to MPPs [8, 19, 89, 90, 92]. The burial of soils under refuse piles and tailing sites is widely used. For example, the area of the direct disturbance of soils by quarries and mines in the KMA basin is about 170 km2; dumps and tailings occupy an area of 85 km2 [91]. The comparison of satellite-based and aerial images made in different times is the best method for assessing the scales of mechanical disturbances of soil cover and the distribution of technogenic relief forms and sediments [2, 91, 93, 132]. The ore mining is characterized by subsidence of rocks, industrial karst, sliding of sediments, and changes in surface runoff. Hydraulic borehole mining is less hazardous for the natural environment. However, its use is also accompanied by the appearance of large artificial cavities in the iron ore massifs, the deformation of overlaying rocks, surface subsidence, the disturbance of groundwater regime, and the formation of slurry-like fine pulp containing iron oxide pigments (iron minium and ochre) [53, 56, 81, 91, 111, 127].

Like other mining operations, mechanical transformations in iron ore areas result in the displacement of soils by sediments and technogenic surface formations (TSFs), the appearance of weakly developed soils and those covered by technogenic and/or natural materials (technosols) under lower loads [16, 49]. Along with mechanical disturbances, differently manifested chemical contamination by toxic elements and their compounds is also recorded in most soils and TSFs. Main pollutants of soils. The contamination of landscapes and soils is related to dusting from quarries, tailings, dumps, and storages of final products (aerial technogenesis); wastes from ore mining and processing; discharges from refining plants (mining technogenesis); etc. [6, 27, 37, 57, 58, 69, 81, 83, 85, 87, 91, 98, 106, 117, 118, 120, 127, 128, 131, 136, 141, 145, 150, 151]. For example, the KMA enterprises annually mine about 170 million tons of iron ore and wallrocks containing Рb, Zn, Ni, Cu, Cо, Cr, Cd, V, Мn, and sometimes Gе, В, Вi, Sb, Sе, and Нg. The amount of waste from ore mining is about 60% [91]. During the 40 years of mining activity in the basin, almost 5 billion tons of overburden rocks and more than 2 billion tons of mine refuse were accumulated in the basin. These technogenic lithomorphological objects together with their affected zones are technogenic geochemical anomalies, where many microelements are concentrated, including rare earths and radioactive elements (Y, Ce, La, U, Th, etc. [46, 69, 103]. Enrichment rejects resulting from the processing of iron ores (grinding and pulverization, subsequent washing, magnetic separation, flotation, etc.) are hydrotransported to tailing sites using drainage waters. Flotation reagents (xanthogenates, cyanides, phenols) and acid-forming sulfide materials (fahl ores, cinnabar, pyrite, pyrrhotine, arsenopyrite, etc.) negatively affect the environment and its components. Sulfides from tailings and dumps coming to the hypergenesis zone are oxidized intensively, which results in the formation of technogenic flows of acid sulfate waters with high contents of Fe, As, and chalcophilic and lithophilic elements (Zn, Cd, Cu, Pb, Al, etc.). These outflows are the main reason for the transformation of soils in transient sloped and superaqual landscapes coupled to dumps. The main sources of emissions in iron ore areas are blasts in quarries and dry beaches of tailings occupying up to 25% of their area. During the blasts, 80 to 300 g dust aerosol with particle size <20 μm per 1 kg of explosive arrives to the atmosphere [27]. According to some estimates [98, 120], tailings in the KMA basin deliver up to 50% of total technogenic emissions to the atmosphere. The total annual emissions from tailings of the KMA MPPs exceed 8319 t/year, despite different methods (mechanical, hydrotechnical, biological, etc.) for the fixation of surface of these technogenic objects [13, 25, 98]. The zone of the atmotechnogenic impact of tailing beaches can reach tens of kilometers EURASIAN SOIL SCIENCE

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even at insignificant wind velocities. To compare, the spreading of dust from open ore storages is observed within a radius of 1 km. In the close vicinity of tailing beaches, the concentration of dust in the air exceeds the permissible levels in hundreds of times [126]. In dust arriving from the Mikhailovsk MPP tailing, Fe prevails (168500 mg/kg), and a wide range of microelements is present, whose concentrations exceed the background levels for zonal soils. Their contents in dust are as follows (mg/kg): Cu, 70; Mn, 750; Pb, 60; Ni, 60; Cr, 110; Co, 20; and Zn, 350. From 1000 to 1200 t of the silt fraction is removed annually from 1 ha of a technogenic tailing composed of lighttextured rocks [88, 97, 98]. Under these conditions, the soil and plants serve as a sufficiently efficient landscape-geochemical barrier, which fixes the major part of metals coming by the aerial way and decreases the opportunity for their input to river water. The processing of ores results in even higher contents of metals in the atmospheric air and soils. The structure of discharges from the refining plants varies depending on their capacity and processing technology. The Olenegorsk MPP (Kola Peninsula) releases inorganic dust (36.1%), sulfur dioxide (29.7%), carbon dioxide (22.4%), nitrogen oxides (8.8%), and hydrocarbons (3%) into the environment [15]. The mineralogical analysis of dust deposits on filters showed the presence of quartz, feldspar, biotite, and protobase. Atmospheric fallouts are also enriched with Ca (in 3 times) and Mg (in 8 times) compared to the background areas. In discharges from the Lebedinoe and Stoilensk MPPs (MKA), whose mean values are estimated at about 30 000 t/year, the share of solid pollutants (dust) is 75.5%, and those of sulfur dioxide, carbon dioxide, nitrogen oxide, and hydrocarbons are 11.65, 7.4, 4.9, and 2.0%, respectively [27, 91]. Crushing-and-preparation plants are additional contamination sources of the environment, including soils. Dust from the crushing-and-preparation and jaspilite-pelletizing plants of the Mikhailovsk MPP contains large amounts of toxic elements (mg/kg): 0.7–1.7 (Cd), 12.2–20.3 (Pb), 12.5–26.6 (Co), 3.8– 17.9 (Ni), 0.5–1.1 (Mo), 9.4–11.9 (Cu), 2.6–9.9 (Sb), and 10.6–16.1 (Cr) [20]. The concentration of Fe in dust is very high and varies from 1100 to 4400 mg/kg. Co and Sb are apparently the most environmentally hazardous elements, whose contents in iron ore raw materials and their processing products exceed the background levels for soils in several times and, in some cases, in 10–14 times. Elevated concentrations of some toxic heavy meals (Mn, Ni, Co, Cr, V, Tl, Ba, and Sr, as well as As and Ag) are found in the dust deposits on electrofilters in the pelletizing shop (Kostomuksha MPP) [85, 86]. The imperfection and wear of drainage systems affect the regimes and levels of groundwater; soils and surface waters are contaminated with dust and waste to tens kilometers from the boundaries of the allocated EURASIAN SOIL SCIENCE

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area [6, 97]. For example, the water migration of pollutants in the affected zone of the Mikhailovsk MPP tailing results in the formation of a hydrogeochemical contamination halo about 3000 ha in area with contrast (against MPC) for Fe (concentration factor (CF) 691), Pb (72), Co (63), Mn (33.6), S (10.2), and Ni (1.9). The total contamination coefficient of water (integrated parameter of water transformation) on the studied area varies from 922 to 21 [97]. The impact on surface and soil waters can be continuous during a specific period (filtration through dams, regular discharge of wastewater) or discrete (discharge of water from dumps because of rainfalls or snow melting). After the cessation of deposit exploitation, tailings, abandoned mines, and other technogenic objects become uncontrolled delayed-action chemical bombs and can present potential hazard of secondary environmental contamination by the accumulated pollutants [90, 133, 138]. CONTAMINATION OF SOILS IN ORE MINING AREAS WITH HEAVY METALS The revelation of the contamination level of soils and TSFs in mining areas with toxic elements, primarily HMs, is an essential problem in the assessment of their environmental status. In the last decades, a large body of data has been accumulated on this topic; theoretical principles of the theory of HMs were developed, and the role of some soil components in the fixation of HMs was determined [7, 10, 11, 29, 30, 61, 79, 107, 108]. Scientifically substantiated maximum permissible levels in soils contaminated from different technogenic sources were determined for some HMs. In a collective monograph [130], some limitations for the development of norms were revealed on the basis of analysis of Russian and foreign works. These limitations are related to the geographical differentiation (soil types/subtypes, texture, humus content, cation exchange capacity, acid–base and redox properties, etc.); the character, level, and duration of technogenic loads on the soil; and procedures for the acquisition and analysis of factual data. It is noted that the revelation of contamination levels and the estimation of the negative effect of technogenic objects are frequently complicated because of their location within industrial regions and sites under stressed environmental and sanitary-hygienic conditions [34, 91, 95, 117]. The impact of enterprises extracting and processing iron ores on the environment and soils, as in other mining areas, is estimated using methods of landscape geochemistry, which not only reveal anomalous contents of elements in soils, but also determine the nature of natural and technogenic geochemical anomalies. These estimations are based on the landscape-geochemical background of the area considered. Technogenic anomalies formed in the iron ore mining areas usually result from the joint impact of

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several contamination sources. For example, the increased concentrations of HMs in bottom sediments observed in some rivers down the town of Zheleznogorsk (Kursk oblast) are due to the effect of mining plants and the input of wastewater from the town territory and surrounding agricultural lands [19, 20, 60]. Most authors used the following criteria for revealing the input of pollutants into soils (including low contents): (a) the presence of geochemical anomalies of total and mobile forms of Fe, Cr, Ni, and some other metals; (b) the radial redistributions of elements in the soil profile and, more rarely, lateral distributions depending on the contamination source, wind direction, and transient or accumulative landscape features; and (c) the composition of pollutant association. The standard list of geochemical (coefficients of accumulation and distribution relative to the lithosphere clarks, coefficients of technogenic concentrations of elements compared to the background (Kc), the total contamination coefficient Zc characterizing the degree of contamination by the association of elements, etc.) and sanitary-hygienic parameters (MPC and PPC) is considered. Several landscape-functional zones of the technogenic transformation of natural complexes and the contamination of soils with HMs are distinguished in iron ore mining areas [89, 90, 110]. For example, two landscape-functional zones of topsoil contamination are formed in the taiga-forest zone around the Kostomuksha plant (OAO Karel’skii Okatysh). The former is the zone of hazardous contamination located within a radius of 1–2 km; the latter is the zone of moderate contamination with a radius of 7–8 km [119]. The boundaries of the zones are traced by the content of total metal forms in the upper horizons of soils, where their concentrations are maximum. The long-term (27-year-long) impact of atmotechnogenic discharges resulted in the contamination of soils with Fe > Ni > Cr [63, 86, 119]. In the first zone near the iron ore quarry, the central pelletizing plant, and the industrial water settler of the Kostomuksha plant, increased total iron concentrations are universally observed in the organic horizons of iron-illuvial podzols. The content of iron varies in a wide range, its mean value being 30 401 mg/kg in organic horizons and 27738 mg/kg in mineral horizons. According to Panteleeva [86], the mean content of iron in soils of the Kostomuksha Reserve is 150.77 mg/kg. An increase in background values in 39–59 times is noted in the upper soil horizons at some points. Litters accumulate heavy metals of hazard classes II and III: Cr (Kc = 6.0–6.7), Ni (Kc = 6.1–17.1), Co (Kc = 4.6–6.3), and Mn (Kc = 2.2–4.3). The contents of pollutants of hazard class I (Pb and Zn, Kc = 1.4–1.6) are usually within the background range. Most metals are removed from organic horizons and fixed in illuvial horizons; insignificant amounts come to groundwater [55, 78]. This is confirmed by some increase in its content of HMs.

The total content of sulfur and its organic compounds in forest litters always exceeds the background values (Kc = 3.3–20.0); it usually increases with reducing distance to the pelleting plant and reaches 0.25–0.30% [119]. Along with metal accumulation, alkalization of litters occurs, which is related to the input of alkaline and alkaline-earth metals with aerotechnogenic emissions from the plant [63, 67, 85, 86, 119, 129]. In separate samples taken on the embankment of the pulp storage, quarry, and settler, pH values higher than 5.5 are noted, which negatively affect the growth and development of trees [63]. In the embankment sediments, alkalinity increases with depth to pH 7–8, which results in the fixation of many metals as hardly soluble forms. In litters, an increase in the ash content in 2.0–2.5 times compared to the background is also observed. More contrast and extended anomalies form environmentally more hazardous mobile HM forms [36]. Coefficients of technogenic concentration of mobile metal forms in organic horizons are several times higher than for total metals. Because of aerial migration, the contamination of soils with mobile Fe, Cr, Cu, Zn, Co, and Mn, as well as S, is recorded within a radius of 20–30 km. Many works deal with the effect of atmotechnogenic emissions in the KMA basin on soils in the forest-steppe and steppe areas. According to Lisetskii et al. [66], the zone of the maximum impact on agrolandscapes (3–5 km in radius) in the Staryi Oskol–Gubkin region is characterized by the high dust contamination of humus horizons in typical and leached chernozems (1000–1500 kg/ha per year). Studies performed on the assigned mountain area of the Stoilensk MPP [56] showed a high (hazardous) contamination level of chernozemic soils with polyelement association of HMs (Zc > 32). The highest Kc values are noted for Cr, Zn, Pb, Mo, and Cu. In isolated cases, As, Cd, and Hg accumulated in soils compared to the background. A stable polyelement association of HMs (Zn, Pb, Be, Cu, Mo, Cr, Sb, Ni; Zc = 64–128, very high level) is typical for technogenic soils and TSFs of the Stoilensk quarry dumps. Near the Lebedinoe deposit and MPP, a zone of strong soil contamination is formed, which includes surrounding landscapes within a radius of 10 km [27]. The contents of some HMs of hazard class II (Cr, Ni, and Cu) in the surface horizons of soils exceed their MPCs in two times, while the contents of metals of hazard class I (Cd, Pb, and Zn) are within the background range. Geochemical studies of snow cover in the affected zone of quarries and MPPs [2, 83] give an idea of HM input into landscapes and soils in winter. A universal alkalization and an increase in the electrical conductivity of melt water compared to the background in 3–5 times is revealed in the close vicinity of the Lebedinoe MPP [2]. HMs sink with snow water into melt water and arrive to depressions and riverbeds. EURASIAN SOIL SCIENCE

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The dispersion halo of Fe (its area is more than 100 km2) in the iron ore mining area of Belgorod oblast (Lebedinoe, Korobkovo, and Gostishchevo deposits) spreads to 7–15 km from the contamination sources [66, 91, 125]. These data well agree with analogous studies in the affected zone of the quarry and tailing of Mikhailovsk MPP in Kursk oblast [20, 88]. High concentrations of HMs in surface horizons of soils were noted in the mining landscapes of Urals, Siberia, Kola Peninsula, Kazakhstan (Sokolov, Sarbai, Kachar, and Lisakov deposits), and Ukraine (Krivoi Rog deposit) [15, 22, 23, 54, 127, 128]. Contamination of the environment and soils in iron ore areas can also be due to emergencies. The formation and functioning of hydraulic-mine dumps and tailings frequently results in the contamination of air, soil and surface waters, and soil cover on vast areas [13, 14]. For example, the accident on the Olenegorsk MPP tailing in the southern Kolozero bay resulted in the spill of construction material and water to an area of more than 320.4 ha [14]. Emergencies also occurred in the KMA basin. The Grachev Log tailing of the KMAruda plant was not deactivated for several years, which resulted in the contamination of soils on the adjacent area of 17 km2 [81]. The transformation of soils in subordinated landscapes under the effect of infiltration waters coming from dumps and tailings of MPPs is least studied. It was noted [37, 90] that ferruginous sulfuric landscapes form under the effect of technogenic fluxes and at the mining of polymetal ores; in these landscapes, metals are leached from rocks and soils and migrate with acid waters to significant distances. Under these conditions, the original (mineral and organic) soils are displaced by technogenically conditioned modifications, e.g., surface-ferruginized peat mucky gley soils in superaqual positions. During the interaction of hydrochemical flows (sulfuric filtration waters) generated by dumps with soils of transit and superaqual landscapes, some elements (Fe, P, As, Pb, Cu, Zn, and Cd) are fixed on geochemical barriers. CHANGES IN THE MICROBIOLOGICAL AND BIOCHEMICAL PARAMETERS OF SOILS IN THE AFFECTED ZONES OF MINING AND PROCESSING PLANTS Studies of soil bacterial communities and mesofauna in different technogenic landscapes and special model experiments [23, 24, 28, 41, 64, 68, 96, 109, 122, 140, 143, 144, 155, 157, 159, 161] showed that the input of high concentrations of HMs into soils significantly affects the bacterial diversity; inhibits the activity of most soil enzymes; and reduces the abundance of bacteria, actinomycetes, soil micromycetes, and microorganisms from other physiological groups. The mechanism of the toxic effect of HMs depends on the compound nature, the localization of the induced EURASIAN SOIL SCIENCE

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damage, the growth phase of microorganism, lowmolecular-weight substances (complexones) of different nature synthesized by many microorganisms, the content of organic matter, and the physicochemical properties of soils [39, 41, 68]. The increased input of iron into soils is undoubted, but the geochemical impact of iron on soil processes and the biosphere is still insufficiently understood. The high clark of Fe made it low toxic for biota, and the variable valence ensued its participation in many geochemical situations and niches. Numerous works give evidence of iron activation in biogeochemical processes and an increase in the role of oxidogenesis [9–11, 17, 31, 42, 51, 59, 123, 135, 139, 154, 156, 158]. The toxicity of some metals can also be related to their biosorption on the surface of microbial cells, which is one of their accumulation mechanisms [64]. Toxic concentrations were determined for some compounds containing HMs and metalloids (As and Sb). Cd has the most negative effect on soil biota in iron ore regions; the effect of Cu is lower, and those of Zn and Pb are still lower [39, 64, 147, 153]. Information is available about the long-term side effects of HMs on soil microorganisms and plants [152]. Despite the large number of works on the microbiology of soils contaminated with HMs, insufficient data are still available on the sensitivity and resistance of different groups of soil microorganisms in the zone of mining and aerial technogenesis types in different natural zones. Effect of gas–dust emissions from enterprises on soil microbial communities. The analysis of intensities of soil-biological processes and microbial community structure in the affected zone of the Kostomuksha MPP [74] showed that an increased general biological activity of almost all microbial groups is typical for disturbed soils compared to background iron-illuvial podzols. An increase in the abundance of ammonifying microorganisms is revealed in soils in the close vicinity of the plant, which suggests an increase in the hydrolytic splitting of nitrogen-containing compounds in the soil, as well as the abundance and functional activity of cellulosolytics. The revealed tendencies are confirmed by model field experiments, which showed an increase in the decomposition rate of spruce and pine waste in more contaminated soils. On one hand, the high activity of some ecological-trophic microbial groups in soils in the zone of long-term atmotechnogenic impact of the plant indicates the loss of the stable ecosystem state and/or the formation of a new technoecosystem different from the natural one, with own technobiocenosis, where communities of soil organisms are in the stress state. On the other hand, the enhanced activity of microbiological processes favors the self-purification of soils. The effect of plant emissions on the biological activity of soils is also manifested on the biochemical level. An increase in the content of carbohydrates and

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changes in the content and composition of free amino acids occur in soils under the direct effect of the MPP on the background of atmotechnogenic contamination [75]. Many enzymes, e.g., protease, are specifically activated by metal ions, which arrive into the soil with aeropollutants and affect living organisms. This results in the input of nutrients into microbial cells and the enhancement of metabolic processes. Microorganisms begin to develop intensively and synthesize different exogenic compounds, including amino acids, whose pool differs from those in undisturbed background soils. In addition, an increase in the contents of asparagic and glutaminic amino acids and their amides is traced in soils on the plots adjacent to the plant, which can be indicative of changes in the rate and depth of mineralization, as well as an active decomposition of carbon- and nitrogen-containing compounds in the soil. Microbiological parameters of soils on tailings and quarry dumps. According to Pigareva et al. [94], the HM contamination of soils and TSFs on the Mikhailovsk MPP tailing leads to a considerable (in several times) rise of the microbial metabolic quotient (the respiration-to-biomass ratio) in comparison with that of uncontaminated background gray forest soils. Even the short-term (for 15–35 years) development of pedogenesis on naturally overgrown dumps results in a significant transformation of rock properties, which affects the features of vegetation and the abundance, composition, and biological activity of microorganisms and fauna [8, 18, 40, 65, 72, 76, 112, 116]. The study of algal communities on different-aged dumps of iron ore deposits in the Southern Urals [44] showed that the formation of algal groups begins from the settlement of unicellular green algae. The species diversity increases during overgrowth, and algal communities similar to the zonal communities are already formed on 50-year-old dumps. According to Stifeev [112], when 5-year-old dumps of loess-like loam and Callovian clay in the Mikhailovsk iron ore quarry of the KMA are colonized by vegetation, microbial groups adapted to extreme environmental conditions appear first. They have oligotrophic nutrition and low biochemical activity, sometimes at a relatively high abundance of microbial communities, which is indicative of an r ecological strategy. Nonsporulating heterotrophic bacteria utilizing organic nitrogen are of deciding importance. In addition, abundant fungi and rare bacilli and actinomycetes utilizing mineral nitrogen forms are detected at this stage. Studies performed on 15-year-old dumps composed of loess-like loams showed that a more stable microbiocenosis is already formed and r-strategy changed to K-strategy. A decrease in the abundance of oligotrophs and fungi is also noted on the background of increasing amounts of bacilli and actinomycetes participating in the mineralization of nitrogen compounds.

STATES OF SOILS, SOIL COVER, AND VEGETATION IN IRON ORE MINING AREAS Generalization of literature data [3, 16, 18, 38, 66, 72, 82, 104, 107, 115, 125, 160] and our studies allowed distinguishing embriozems, technogenic surface formations (TSFs), technosols, and chemozems within the ore mining regions. Technogenic soils and soil-like bodies are usually combined with nonsoil formations: mixed loose and dense surface formations and filled and inwashed technogenic (artificial) sediments [14, 69, 83]. These sediments compose rock dumps and are also found in quarries. Young technogenic soils. In literature, main attention is given to embriozems (young weakly developed accumulative soils) formed on mixtures of overburden and inclosing rocks (poor and out-of-balance ores) of dumps. These parent rocks vary in genesis, physicochemical properties, mineralogy, chemistry, texture, and proportions of fine-earth and skeletal components. They can mainly consist of cover loams, chalk-marl rocks, and poor ores (KMA); gravelites, sandstones, aleurites, and clays (Bakchar ore cluster, Western Siberia); and loams, loamy sands, and Quaternary siltyclayey sands (Sokolov–Sarbai deposit, Kazakhstan). Rocks vary in the resistance to weathering and the degree of toxicity, which is determined by the increased content of some microelements and sulfides. Technogenic sediments are usually characterized by high contents of total and nonsilicate iron. For example, according to Makhonina [72], the content of total iron in dump sediments of 27 Ural deposits varies from 16 to 60% (ore). The diversity of properties and composition of mixed rocks in dumps also determines their capacity to the natural (successional) self-restoration of plant cover and soils [26, 43, 54, 72, 76, 115], as well as the suitability (potentially fertile, low-suitable, and unsuitable) for remediation [8, 13, 35, 39, 40, 45, 70, 73, 77, 80, 84, 100, 112, 124, 133, 134, 137, 142, 146, 148, 149, 151]. In any physicogeographical situations, embriozems pass specific stages (successions) of technogenically determined development [18, 21, 43, 72, 76, 114, 115]. The duration of soil self-development stages and the formation rate of their local profiles (humus, textural, acid-base, and others) are determined by the character of technogenic relief (dumping technology), parent rock composition, hydrothermal conditions, species diversity, and plant cover productivity. The composition of pioneer plant communities and the features of the initial pedogenesis stage largely depend on the properties and material composition of substrates used for cultivation. Because of the heterogeneity of texture, mineralogy, and physicochemical properties and the phytotoxicity of ground mixtures, different dump zones are characterized by dissimilar intensities of pedogenesis processes (structuration; humus accuEURASIAN SOIL SCIENCE

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mulation and illuviation; biogenic accumulation of Ca, Mg, and P; sodding; etc.). The forming soils significantly differ from the original substrates of quarry–dump complexes in waterphysical properties, acidity, exchangeable bases, occurrence forms of metals, their differentiation, and other parameters. Under favorable bioclimatic and lithological–geomorphological conditions, e.g., on subhorizontal surfaces of the KMA dumps under herb-grass vegetation, soils with a manifested humusaccumulative horizon about 7.5 cm thick are formed during 35 years; these soils contain up to 5% humus and up to 0.5% nitrogen [18]. The newly formed soils on low and nontoxic parent rocks of dumps acquire some traits similar to those of zonal varieties with time (100–200 years) [72, 115]. However, the total content of amorphous and organic matter-bound iron in these soils yet does not reach the background values. On phytotoxic substrates, e.g., those containing sulfides, the complete approach of embriozem properties to those of background natural soils is unlikely or impossible in the foreseeable feature. Technogenic surface formations. Among the TSFs, one distinguishes artiindustrates (nontoxic material of tailings), lithostrates (filled mineral sediments, including dumps of overburden and inclosing rocks of MPPs), toxilithostrates, toxiindustrates (toxic material of the dumps of overburden rocks, slime storages, and tailings, on which the growth of cultural or natural plants is impossible without using special deactivating materials), and technozems. Technozems are soil-like bodies from the group of quasizems, which consist of filled layers, including a filled humus-enriched layer; they are created purposefully at the biological remediation of dumps, slime storages, and tailings [3]. Their physicochemical and biological properties in the iron ore regions of the KMA were studied by many researchers during the last years [32, 82, 88, 91, 119]. In most cases, the major part of soil mesofauna (more than 60%) is concentrated in the 20–40-cm-thick filled fertile chernozem layer, as typical for soil-like formations of remediated lands [3, 116]. Technosols (technochernozems, technogray soils, etc.) occur on the areas where soil profile disturbances are manifested within the upper 5- to 50-cm-thick layer. The upper horizons are formed due to the deposition of filled technogenic waste of iron ore production, the mixing of technogenic material with the initial genetic horizons, the accumulation of technogenic solid-phase material coming from the atmosphere, the accumulation of colluvium, the hydromechanical translocation of overburden and inclosing rocks, and the shielding by different coatings (asphaltic, concrete, etc.). For example, southern technochernozems mechanically disturbed in the upper part, with significant inclusions of fragmentary material and the very EURASIAN SOIL SCIENCE

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low content of humus, are formed within the Sokolov–Sarbai deposit (Kazakhstan) [22]. Chemically modified soils. Discharges from MPPs and auxiliary facilities; large-scale blasting operations in quarries; and deflation from dumps, tailings, and open storages of final products result in the contamination of surface horizons of technosols and technozems with HMs. In some cases, their contamination is estimated as hazardous according to the established norms. By this parameter, soils and TSFs are close to anthropogenically modified soils from the order of chemozems [49]. The technogenic contamination with HMs causes no visible changes in their morphological profile but disturbs the natural functioning of soils; it primarily affects the structure and functioning of microorganisms and fauna in technogenic soils and can affect the state of soil cover. The biotesting of rocks from dump complexes, slime settler, and tailings of the Teya iron ore mine (Khakassia) using Drosophila melanogaster as a test organism for the presence of mutagenic compounds showed that all samples have a toxic effect [1]. The authors attribute the main negative effect to the presence of As, Ni, V, and U in increased concentrations, as well as mobile Cr and Cu. Soil nematodes are bioindicators of the atmotechnogenic contamination of taiga ecosystems [62, 71]. Within the radius of 0.5 km from the Kostomuksha MPP, industrial contamination results in a decrease in the degree of maturity of nematode community, disappearance of species from the tropic group of polytrophs, and an increase in the abundance of phytotrophic species. The dominant position is occupied by Paratylenchus nanus, a parasite of meadow grasses. The cause for decreasing abundance or disappearance of different species under the effect of industrial discharges can be the direct impact of toxicant, as well as their indirect effect through the deterioration of habitat conditions. Accumulation of heavy metals by plants. Higher plants in the close vicinity of the quarry–dump complexes and the areas of refining factories and auxiliary facilities frequently accumulate HMs in amounts exceeding the regional background values in several times. For example, the steppe communities of most quarry–dump complexes of KMA are characterized by a high level of HM accumulation, misbalance of biophilic and toxic elements, necrosis of leaf canopy, inhibition of plants, and an increase in the share of more xerophytic ruderal species in edifiers [125]. The study of the effect of the Kostomuksha MPP on herbaceous plants [62] showed that when the distance from the contamination source decreases, the total number of vascular species, especially herbaceous species, appreciably decreases, and the productivity of aboveground phytomass is reduced, but the projective cover of some Poaceae and Fabaceae species increases.

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Several authors [48, 65, 88, 120] revealed the accumulation of total iron in grass species (Роа pratensis, Dactylis glomerata, Arrhenatherum elatius) and some toxic microelements (Pb, Cu, and Zn) in agricultural crops at 5–10 km from the Mikhailovsk, Stoilensk, and Lebedinoe MPPs. From literature data [65], the highest concentrations of metals were recorded for Cu in oat plants (10.1 mg/kg); Zn in sunflower (35.7 mg/kg), soybean (29.9 mg/kg), and buckwheat (28.2 mg/kg); and Pb in barley (17.1 mg/kg) and sunflower (16.3 mg/kg). Leaves of Chinese elm (Ulmus parvifolia) contain increased amounts of Pb (1.59 mg/kg) and Cu (4.91 mg/kg) in the affected zone of the Sokolov–Sarbai deposit (Kazakhstan) [22]. Mosses are among the most sensitive bioindicators of environmental contamination with HMs. Panteleeva [86] showed that mosses around the working site and tailing of the Kostomuksha MPP accumulate metals compared to the background level for Karelia: Fe (4296 mg/kg), Pb (up to 20 mg/kg), and Zn (up to 55 mg/kg). Soil cover changes. In ore deposit areas, a wide range of technogenic soils are formed, where mechanical, chemical, bioremediation, and other transformations prevail, which are untypical for the natural background soils surrounding the production area. These newly formed soils have direct or indirect effects on the surrounding landscape, including natural and agrogenic soils; they form complex anthropogenic combinations with strongly contrast soil cover in many soil properties, including the content of HMs. The KMA, including the Lebedinoe MPP, is one of the typical objects of iron ore production, complex and contrast in soil and ecological terms. The current quarry size (more than 5 km in diameter and more than 350 m in depth in 2009) has been formed during half-century, which resulted in the capture of surrounding chernozems on a vast area and moved the technogenic sediments very closely to the standard chernozems of Russia (the Yamskaya Steppe virgin plot in the Belogor’e Reserve). The detailed study of soil cover in the Yamskaya Steppe plot in the 1970s [5, 99, 121] by mapping the entire area and key plots characterizing different relief conditions revealed a high diversity of soils with the dominance of typical chernozems on watersheds and the well-developed gully erosion network of calcareous residual deep calcareous or residual calcareous chernozems on slopes [50]. Typical soil cover structures of the Yamskaya Steppe consist of simple microcombinations (complexes, spottiness, and mosaics). The number of soil cover components significantly increases, as well as the complexity and contrast of soil cover, when going from watersheds to ravines. No obvious gleying signs were revealed in soil profiles; groundwater occurred at a depth of more than 7 m. Later studies [2, 4, 33, 101, 102, 104, 105] revealed some features in landscapes and soil properties related

to the effect of the MPP water-settling tank located not far from the Yamskaya Steppe (closer than 1 km): (1) increase in the total base runoff of hydrogeological basin within the northern part, which resulted in an increase in the wetting of adjacent slopes; (2) gleying signs at a depth of about 1 m in the profile of typical chernozems on binary sediments of watersheds and near-watershed slopes of northern and northwestern exposures [33]; (3) sporadic distribution of humusaccumulative gleyic soils as a possible result of the local groundwater rise [104]; and (4) increased content of mobile cadmium in the humus horizon of grayhumus stratozems and in almost entire profile of a migration-micellar chernozem [104]. Despite the local character of hydromorphism signs in the Yamskaya Steppe soils and the transformation of the whole soil cover, the obvious general trend of increasing wetting on the reserve area under the effect of the Lebedinoe MPP should be taken into consideration. The fields adjacent to water settlers and tailings of iron ore plants, where a complex polygenetic soil cover with the dominance of technogenic soils of different genesis forms, are significantly more affected. CONCLUSIONS Iron ore mining is one of the largest-scale technogenic impacts on the environment affecting the distribution and transformation of soils and ecosystems. At the construction of deep pits (deeper than 350 m), high dumps (up to 100 m), and vast tailings, the soil cover is mechanically destroyed on large areas. The construction of MPPs and their operations increase the aerosol contamination of the surrounding areas to tens of kilometers. Hydrogeological conditions change radically, from excessive drainage to soil flooding with contaminated waters from tailings and dumps. An important factor of technogenic impact on soils is the fallout of atmospheric aerosols because of the formation of immense amounts of dust and the dispersion of translocated material during overburden operations and ore mining and milling. Dust affects soils as a dispersed material and mainly as a source of HMs, accessory elements of iron ores (Zn, Pb, Be, Cu, Mo, Cr, Sb, Ni). The sources of soil contamination also include flotation reagents used for ore processing (xanthogenates, cyanides, and phenols) and toxic ore components (sulfides). The role of the ferrugination of the earth surface in the formation of soils and the life of biota is still unclear. In the first approximation, it can be considered positive or neutral. The most attention in the literature is given to the contamination of soils and TSFs with HMs. Some norms are found for the permissible concentrations of HMs in terms of their effect on biota. Important and mobile parameters of soils (exchangeable ions, pH, etc.) are actively studied for predicting the behavior of soils and ecosystems under contamination. It is noted that in the study of soil conEURASIAN SOIL SCIENCE

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tamination with HMs, of extreme importance is the analysis of ore mining and processing technologies and emergency probabilities, as well as scientific approaches to general geochemistry and landscape geochemistry. The latter involve the composition of maps of chemical element concentrations and evaluation and prediction ecological-geochemical maps and the delineation of zones of background and anomalous values exceeding the MPCs, as well as the analysis of the genesis of these zones, conditions of element migration, and the location of geochemical barriers. The concentrations of elements in the surface layer of soils in autonomous landscapes are best understood; their concentrations in subordinated positions and soil profiles are significantly less studied. It was shown that embriozems, TSFs, technosols, and chemozems are widely distributed, along with natural soils and ecosystems, in the iron ore mining regions. Major attention is given to embriozems, young weakly developed accumulative soils on mixed rocks of different texture and mineralogy. Among them, dumps on calcareous loess-like loams are most rapidly remediated. Their succession changes, the formation rates of humus-enriched and other horizons, and the alternation of microbial and plant groups with different ecological strategies for periods up to 200 years were studied. Technogenic soils and TSFs with different material composition are usually combined with nonsoil formations: mixed loose and dense surface formations and filled and inwashed technogenic sediments. The diversity of overburden rocks, their physicochemical composition, and mineralogy determine the capacity of plant cover and soils to natural self-restoration. Therefore, remediation and restoration measures on the disturbed areas are strongly differentiated. These measures maximally use the most fertile local substrates and plants adapted to soilecological conditions. However, the remediation of dumps and tailings occupying hundreds of hectares is a sufficiently complex problem. The permanent tridimensional increase of dumps related to some restrictions for the use of lands surrounding the ore mining areas presents obvious difficulties for the current and permanent remediation of different types and forms proposed in numerous publications on this topic. More than one generation should obviously wait for the self-restoration of contaminated soils in the zones of iron ore mining. Therefore, the remediation of dumps should not go behind of ore mining, but it should correspond to the current high level of soil contamination. ACKNOWLEDGMENTS The work was supported in part by the Russian Science Foundation, project no. 14-27-00133. EURASIAN SOIL SCIENCE

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Translated by K. Pankratova

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