Yu. N. Vodyanitskii

Iron hydroxides in soils: A review of publications

Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe3+ (as ferrihydrite) or Fe2+ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The structure of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by manganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron-manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with light-weight 54Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite.

Contamination of soils with heavy metals and metalloids and its ecological hazard (analytic review)

According to the present-day 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 well-known 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.

The role of iron in the fixation of heavy metals and metalloids in soils: a review of publications

Iron’s contribution to fixing heavy metals and metalloids in soils is very important. Iron compounds participating in redox processes control the behavior of siderophilic elements with variable oxidation degrees (Cr, As, and Sb). The behavior of heavy elements with permanent oxidation (Zn, Co, and Ni) indirectly depends on iron compounds. In organic soils, iron competes with heavy metals for active places in the functional groups of organic substances. Organic pollutants intensify the reduction of iron (hydr)oxides in an anaerobic environment, which influences the release of arsenic. Iron compounds are used as ameliorating agents and geochemical barriers for fixing heavy elements.

Mineralogy and geochemistry of manganese: A review of publications

The relatively low hydrolyzing capacity of Mn(II) leads to the formation of oxides rather than hydroxides of this element in soils. The formation of vernadite, birnessite, todorokite, and lithiophorite was recently proved in soils. Vernadite with an Fe admixture and Mn-containing iron minerals, i.e., ferroxyhyte, ferrihydrite, and magnetite, were also found. Fe-vernadite and Mn-ferroxyhyte are the most abundant in soils. Manganese oxidogenesis is the most intensely pronounced in the soils of steppe and forest-steppe zones, in which the assemblage of Mn-containing minerals is wider than in taiga soils. Carbonates are able to inhibit the development of Mn oxidogenesis. The bulk of Mn compounds are confined to the silt rather than to the clay fraction, since manganese oxides are negatively charged in the pH interval typical of the bulk of soils. Manganese oxides are able to retain heavy metals, i.e., Co, Ni, Zn, and others. The active participation of Mn oxides in Cr(III) oxidation raises its mobility and toxicity. Manganese oxides may favor humus formation by taking part in phenol oxidation.

Effect of reduced iron on the degradation of chlorinated hydrocarbons in contaminated soil and ground water: A review of publications

Chlorinated hydrocarbons are among the most hazardous organic pollutants. The traditional remediation technologies, i.e., pumping of contaminated soil- and groundwater and its purification appear to be costly and not very efficient as applied to these pollutants. In the last years, a cheaper method of destroying chlorine-replaced hydrocarbons has been used based on the construction of an artificial permeable barrier, where the process develops with the participation of in situ bacteria activated by zerovalent iron. The forced significant decrease in the redox potential (Eh) down to −750 mV provides the concentration of electrons necessary for the reduction of chlorinated hydrocarbons. A rise in the pH drastically accelerates the dechlorination process. In addition to chlorine-organic compounds, ground water is often contaminated with heavy metals. The influence of the latter on the effect of zerovalent iron may be different: both accelerating its degradation (Cu) and inhibiting it (Cr). Most of the products of zerovalent iron corrosion, i.e., green rust, magnetite, ferrihydrite, hematite, and goethite, weaken the efficiency of the Fe0 barrier by mitigating the dechlorination and complicating the water filtration. However, pyrrhotite FeS, on the contrary, accelerates the dechlorination of chlorine hydrocarbons.

Soil contamination with emissions of non-ferrous metallurgical plants

The upper soil horizons are strongly contaminated in the area influenced by the Mid-Urals copper smelter. In the technogenic desert and impact zones, the contents of a number of elements (Cu, Zn, As, Pb, P, and S) by many times exceed their clarke values and the maximum permissible concentrations (or provisional permissible concentrations). The degree of technogeneity (Tg) for these elements is very high in these zones. In the far buffer zone, Tg is about zero for many elements and increases up to Tg = 27–42% for four heavy elements (Cu, Zn, Pb, and As) and up to 81–98% for P and S. The buffer capacity of the humus horizon depends on the soil’s location within the technogeochemical anomaly and also on the particular pollutant. In the impact zone, it is equal to 70–77% for lead and arsenic, although other technogenic elements (Zn, Cr, S, and P) are poorly retained and readily migrate into the deeper horizons (the buffer capacity is equal to 14–25%). Nearly all the heavy metals enter the soil in the form of sulfides. The soils in the area affected by the Noril’sk mining and smelting metallurgical enterprise are subdivided into two groups according to the degree of their contamination, i.e., the soils within Noril’sk proper and the soils in its suburbs to a distance of 4–15 km. The strongest soil contamination is recorded in the city: the clarke values are exceeded by 287, 78, 16, 4.1, and 3.5 times for Cu, Ni, Cr, Fe, and S, respectively. The major pollutants enter the soil from the ferruginous slag. The soil’s contamination degree is lower in the suburbs, where heavy metal sulfides reach the soils with the aerial emission from the enterprise.

Chromium and arsenic in contaminated soils (review of publications).

In the last decades, the chromium clarke in the world’s soils has been revised and reduced; at present, it is equal to 70 mg/kg. No maximal permissible concentration is accepted for the total chromium content in the soils of Russia; it appears reasonable to use the Western European and North American standards in Russia and to take the average value of the maximal permissible concentration equal to 200 mg Cr/kg. Chromium toxicity depends on its oxidizing status. The hazardous effect decreases with the reduction of Cr(VI) to Cr(III). There are various chemical reducers of Cr(VI), including sulfides, dissolved organic substance, aqueous Fe(II) and minerals enriched in Fe(II), and Fe(0).As-containing ore tailings represent a powerful source of technogenic arsenic. Significant environment contamination with natural As is registered in a number of Asian countries. The maximal permissible concentration of total arsenic is equal to 2 mg/kg in Russian soils; it is probably underestimated, because it is lower than the As clarke in soil (5 mg/kg). The approximately permissible concentration (APC) values for As look more reasonable. Arsenic toxicity depends on its oxidation degree: As(III) is 2–3 times more toxic than As(V).

Geochemical fractionation of lanthanides in soils and rocks: A review of publications

In recent years, lanthanides (Ln) have become an object of active studies by soil scientists and geologists, which is favored by the development of instrumental equipment. It has become possible to obtain reliable soil clarkes of lanthanides. The study of lanthanides in soils is important not only from the theoretical and pedogenetic viewpoints but also because of its applied value, as Ln-containing substances and wastes are used as microfertilizers. The established fact of the geochemical fractionation of lanthanides in soils and rocks appears to be one of the latest significant achievements. The tetrad-effect in lanthanides was revealed and theoretically substantiated. Strong positive anomalies of the Ce content and weak anomalies of the Eu content were found in soils (unlike many rocks). Ferromanganese soil concretions are depleted in Y as compared with light-weight lanthanides. The type of lanthanide fractionation in the course of soil formation in different zones depends on the content of Ln-minerals in the parent rock. In the zone of supergenesis, Mn oxides are among the most important Ln-bearing phases, many of which (Ce, in particular) are classified as manganophilic. In calcite, Ca2+ may be replaced by lanthanides, including Y. Humus acids stabilize Ce3+ and prevent positive cerium anomalies in the newly formed bodies. Microorganisms favor Ln accumulation in biogenic bodies, such as Fe-Mn nodules and Fe-ocher.

Standards for the Contents of Heavy Metals and Metalloids in Soils

In line with the present-day ecological and toxicological data obtained by Dutch ecologists, heavy metals/metalloids form the following succession according to their hazard degree in soils: Se > Tl > Sb > Cd > V > Hg > Ni > Cu > Cr > As > Ba. This sequence substantially differs from the succession of heavy elements presented in the general toxicological GOST (State Norms and Standards) 17.4.1.02-8, which considers As, Cd, Hg, Se, Pb, and Zn to be strongly hazardous elements, whereas Co, Ni, Mo, Sb, and Cr to be moderately hazardous. As compared to the general toxicological approach, the hazard of lead, zinc, and cobalt is lower in soils, and that of vanadium, antimony, and barium is higher. The new sequence also differs from that of the metal hazard in soils according to the Russian standard on the maximal permissible concentration of mobile metal forms (MPCmob): Cu > Ni > Co > Cr > Zn. Neither an MPCmob nor an APCmob has been adopted for strongly hazardous thallium, selenium, and vanadium in Russia. The content of heavy metals in contaminated soils is very unevenly studied: 11 of them, i.e., Cu, Zn, Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se, are better known, while the rest, much worse, although there are dangerous elements (Ba, V, Tl) among them.

Chemical aspects of uranium behavior in soils: A review

Uranium has varying degrees of oxidation (+4 and +6) and is responsive to changes in the redox potential of the environment. It is deposited at the reduction barrier with the participation of biota and at the sorption barrier under oxidative conditions. Iron (hydr)oxides are the strongest sorbents of uranium. Uranium, being an element of medium biological absorption, can accumulate (relative to thorium) in the humus horizons of some soils. The high content of uranium in uncontaminated soils is most frequently inherited from the parent rocks in the regions of positive U anomalies: in the soils developed on oil shales and in the marginal zone of bogs at the reduction barrier. The development of nuclear and coal-fired power engineering resulted in the environmental contamination with uranium. The immobilization of anthropogenic uranium at artificial geochemical barriers is based on two preconditions: the stimulation of on-site metal-reducing bacteria or the introduction of strong mineral reducers, e.g., Fe at low degrees of oxidation.