Sequential Extraction of Potentially Toxic Metals: Alteration of Method for Cu-Ni Polluted Peat Soil of Industrial Barren

An evaluation of fraction composition and transformation of metal compounds emitted by metal ore processing enterprises and accumulated in soils is crucial for assessing the environmental risks of pollution and ecosystem benefit of remediation. The aim of this study was to develop a suitable sequential fractional procedure for metal pollutants for the peat soils matrix in the impact zone of a Cu-Ni smelter. Three experiment series were performed: (a) the study of the effect of ammonium acetate buffer pH in the range of 3.7–7.8 on the soil metal extraction; (b) the study of the effect of additional volume and frequency of soil treatment with solutions on the content of water-soluble, ammonium acetate extractable, and 0.1 N HNO3 extractable fractions; and, (c) the determination of the metal fraction composition in the modified technique. Soil treatment with ammonium acetate buffer with a pH range of 4.5–5.5 was the most appropriate for the determination of mobile compounds of Cu and other metals in highly polluted peat soil. Triple soil treatment with water and ammonium acetate is necessary for the complete extraction of the water-soluble and exchangeable fractions, respectively. Additionally, we propose a procedure of full extraction of the exchangeable metal fraction from peat soils while using single treatment with 0.1 N HNO3. This scheme allows evaluating geochemical mobility of metals and current environmental harm of polluted soils with a high content of organic matter

Magnesium Silicate Binding Materials Formed from Heat-Treated Serpentine-Group Minerals and Aqueous Solutions: Structural Features, Acid-Neutralizing Capacity, and Strength Properties

The influence of structural features of three serpentine-group minerals (antigorite, chrysotile, and lizardite) on the hydration of heat-treated materials and the formation of magnesium silicate binder has been studied. Initial serpentine samples have been fired in the interval 550–800 °C with a step of 50 °C; acid neutralization capacity (ANC) values have been determined for all samples. Antigorite samples (SAP) have exhibited a maximum reactivity at a temperature of 700 °C (ANC 7.7 meq/g). We have established that the acid-neutralizing capacity of chrysotile and lizardite samples in the temperature range of 650–700 °C differ slightly; the capacity varied in the interval of 19.6–19.7 meq/g and 19.6–19.7 meq/g, respectively. The samples obtained at optimal temperatures (antigorite—700 °C, lizardite, and chrysotile—650 °C) have been studied. Heat-treated serpentines have interacted with water vapor for a year; serpentine hydration has been investigated. The strength characteristics of the resulting binder agents were studied after 7, 28, 180, and 360 days. Upon hardening within 7 days, the strengths of the SAP and SCH samples have been almost the same (2.2 MPa), whereas this indicator for the SLH and SLK samples has been significantly lower (0.5 MPa). After hardening for over a year, the chrysotile sample SCH had the highest strength (about 8 MPa), whereas the strength of antigorite SAP was 3 MPa. The samples of initial, heat-treated, and hydrated heat-treated serpentines have been studied using XRD, differential scanning calorimetry, and surface texture analysis. The serpentine structure is crucial in destroying the mineral crystal lattice during heat treatment. In contrast to heat-treated chrysotile and lizardite, antigorite did not adsorb water. Structural features of chrysotile provided the highest compressive strength of the binding agent compared with antigorite and lizardite. The acid-neutralizing ability of lizardite was noticeably higher than antigorite, whereas its compressive strength was lower due to the layered mineral structure and impurities. We have established that the minerals’ structural features are crucial for the hydration of heat-treated serpentines; the structure determines material utilization in various environmental technologies

Technosols on mining wastes in the subarctic: Efficiency of remediation under Cu-Ni atmospheric pollution

The copper-nickel factory's emissions in the Murmansk region, Russia, led to the degradation of plant cover and topsoil with the subsequent formation of industrial barrens. In this study, the industrial barrens were remediated by means of Technosol engineering, when grasses were sown on the two different types of mining wastes (carbonatite and serpentinite-magnesite) covered by hydroponic vermiculite. The serpentinite-magnesite waste was significantly different from the carbonatite waste in the content of silicon (Si) and manganese (Mn), pH, and texture. Both wastes had an alkaline pH level and high content of calcium (Ca) and magnesium (Mg). The vegetation and Technosol properties at the remediated sites were analyzed in 2017 and compared to the initial state (2010 year) to assess the efficiency of the long-term remediation. The quality and sustainability of Technosols based on the serpentinite-magnesite wastes were substantially higher compared to the carbonatite-based Technosol. Biomass and a projective cover of the grass community depended on Si content in the original mining waste and were found to be higher in the serpentinite-magnesite Technosol. The content of organic carbon and its fractions, microbial biomass and basal respiration after seven years of Technosol evolution was comparable to natural values. These parameters were directly related to plant cover state and were inversely proportional to copper (Cu) content in Technosol. The Technosol development led to the reduction of nickel (Ni) and Cu migration in soil-plant ecosystems due to neutralization and adsorption properties of mining wastes and phytostabilization by underground parts of grass communities. The Technosol development in its early stage of pedogenesis indicates the efficiency of applied remediation technology to the degraded acidic soil under the conditions of industrial atmospheric pollution

Organic matter accumulation by alkaline-constructed soils in heavily metal-polluted area of Subarctic zone

Purpose: The research aimed to investigate properties and functions of soils constructed from alkaline mining wastes of different origin to remediate the industrial barren resulted from long-term emissions of the copper-nickel factory in the Subarctic region (Kola Peninsula, Russia). Conventional indicators of the remediation effectiveness (pH and metal content in geochemical fractions) were related to the indicators of soil functions such as biomass production, accumulation of organic carbon, microbial activity, and soil respiration. Materials and methods: The experimental area included two sites with polluted and degraded Podzol and Histosol soils located in 1.5 and 0.7 km from the nonferrous (Cu-Ni) smelter, respectively. At the sites, artificial soil constructions were made from mining wastes or quarry sand covered by the vermiculite layer with lawn grasses planted on top. Plant biomass was collected every year starting from the experiment set-up. In 5 to 8 years, soil samples were collected on the layer basis, and chemical, biological, and morphological properties were analyzed. Sequential fractionation of metals was conducted using a modified Tessier’s scheme. The microbial biomass and its respiration activity were determined. Micromorphological studies were conducted using an optical microscope. Soil respiration was measured on-site by IRGA with simultaneous observations of soil moisture and temperature. Results: The plant growth and residues' deposition at both experimental sites triggered carbon accumulation and resulted in 2–3 times higher content of organic carbon in the upper constructed soil layer compared to the initial content in mining wastes. Carbon accumulation was a key driver for the development of soil microbial communities and had a positive effect on the metal immobilization. This effect was strengthened by high pH inherited from the alkaline wastes and resulted in the performance of constructed soils as geochemical barriers. In their upper layers, where the root biomass was the highest, about 30–60% of Cu and Ni were bound by organic matter. In the underlying polluted soil, the most toxic water-soluble metal fraction was completely neutralized; and the metal concentrations in exchangeable fraction decreased by a factor of four improving the habitat conditions of the microbiome. Organic matter accumulation by clay material with the formation of organo-mineral films was found in the vermiculite-lizardite variant. Conclusion: Soil constructions made from alkaline mining wastes in the Subarctic supported the development of plant and microbial communities, organic matter accumulation, and metal immobilization. This technology allows protecting the environment from further pollution under the continuous emissions of the copper-nickel factory