Accumulation and migration of heavy metals in soils of the Rostov region,south of Russia

Purpose

The main aim of the study performed during 6 years was to determine the specific features of heavy metal contamination of soil cover in the city of Rostov-on-Don and its agglomeration. It was supposed to answer the question: Does soil inherit heavy metals mainly from the parent rocks, or they enter the soil mainly as a result of anthropogenes in the city condition.

Materials and methods

Seventeen soil profiles were established in different parts of the Rostov agglomeration, within the city and in the urbanized agricultural region. The following objects were studied: (1) calcareous ordinary chernozem under steppe vegetation (fallow) and under trees (parks): soils of natural structure insignificantly affected by urbanization processes; (2) urbostratozems: soils of natural structure overlain by loose anthropogenic deposits; (3) screened urbostratozems (or ecranozems): soils of natural structure overlain by asphalt and/or another impermeable surface. The contents of heavy metals were determined by X-ray fluorescence. The degree of soil contamination with heavy metals was assessed by comparing their content with the MPC values (danger coefficient method) or using the total contamination factor Zc.

Results and discussion

The comparison of chernozems under different plant covers shows that the woody plants capable of retaining moisture in the soil and more deeply wetting the soil layer decrease the accumulation of vanadium, chromium, cobalt, nickel, and copper in the surface layer. The accumulation coefficients of these metals in urbostratozems are still lower for some reason. At the same time, an increase in the accumulation of zinc and lead is observed in the surface layer of soils under the forest canopy, as well as in the urbostratozems. In the Urbostratozems, screened by dense surfaces, a high variation is observed, which is related to the different times of soil sealing with asphalt.

Conclusions

The results showed that the concentrations of most elements in the parent rock of Rostov-on-Don exceed the background values, and those of some elements exceed the MPC levels. The main source of accumulation of these elements in the soil profile is the parent rock. Additional input from anthropogenic sources is contributed by the accumulation of such elements as chromium, nickel, zinc, and lead.

     

New alternative method of benzo[a]pyrene extractionfrom soils and its approbation in soil under technogenic pressure

Purpose

The optimization of benzo[a]pyrene extraction conditions by subcritical water extraction method from soils is the purpose of the research. The optimal conditions for benzo[a]pyrene recovery are 30-min extraction by water in a special steel cartridge at 250 °C and 100 atm.

Materials and methods

Studies were conducted on the soils of monitoring plots subjected to Novocherkassk Power Station emissions. Monitoring plots were established at different distances from the Novocherkassk Power Station (NPS; 1.0–20.0 km).

Results and discussion

It was shown that the use of water in subcritical state as a solvent for benzo[a]pyrene extraction from soil allows to avoid large volumes of organic solvents and to decrease the time of sample preparation. It is shown that the maximum benzo[a]pyrene maintenance was observed in soils of the monitoring plots located most close (to 5 km) to a pollution source in the area of the prevailing direction of a wind rose. Dynamics of pollutant accumulation in soils depend on number of Novocherkassk state district power station emissions.

Conclusions

The method of benzo[a]pyrene subcritical water extraction from soil was developed and approbated during long-term monitoring researches of technogenic polluted territories. The optimum conditions for benzo[a]pyrene extraction from soil have been determined: the soil is treating by subcritical water at 250 °C and 100 atm of pressure for 30 min. Trends in the accumulation of benzo[a]pyrene in soil zones of the thermal power plant influence have been researched over a 5-year period of monitoring observations by subcritical water extraction method. Benzo[a]pyrene accumulation in soils depends on the technogenic emissions to the atmosphere from Novocherkassk power station and on the soil physical and chemical properties.

     

Nucleophilic radical substitution reaction of triazine herbicides with polysulfides

Triazine herbicides are among the most widely used herbicides in the United States. Many triazine compounds are relatively stable under natural conditions and have become prominent contaminants in hydrologic systems. It was previously reported that chloro-s-triazine compounds were rapidly dechlorinated in water by polysulfides, and the reaction was assumed to be aromatic nucleophilic substitution (SNAr). In this study, we evaluated the effect of free radical inhibitors on the reaction rate of polysulfides with herbicides atrazine, simazine, and cyanazine. The reaction was significantly inhibited by radical scavengers oxygen and 1,4-benzoquinone, suggesting involvement of free radicals in the reaction. Spectral analysis of the reaction mixture using electron spin resonance showed that after the reaction, the free radical concentration in polysulfide solution substantially decreased. These evidences indicate that radical sulfur anions may also be involved in the reaction, likely via a free radical substitution reaction (SRN1) mechanism. Amendment of sodium tetrasulfide significantly reduced the leaching of atrazine or simazine from packed sand columns. Therefore, polysulfide salts may be potentially used to remove residues of triazine herbicides in environmental media.     

Characterization of an aspartic proteinase activity in buckwheat (Fagopyrum esculentum Moench) seeds

The pepstatin A sensitive acidic proteolytic activity of total protein extracts of buckwheat seeds has been analyzed in developing, mature, and germinating seeds by activity measurements as well as by electrophoretic and immunochemical techniques. Immunoblot analysis using cross-reactive antibodies raised against barley phytepsin suggested that specific proteolytic activity could be attributed to a 47 kDa heterodimeric polypeptide, composed of two subunits: 31 and 16 kDa polypeptides. The analysis of time course expression revealed that the 47 kDa heterodimer accumulated during seed maturation starting from 12 days after pollination and was also present at the beginning of germination. Milk-clotting activity of this proteinase was also indicated.     

Sonication-assisted extraction of chitin from shells of fresh water prawns (Macrobrachium rosenbergii)

The effect of sonication during chitin extraction from freshwater prawn shells on yield, purity, and crystallinity of chitin was investigated. Dry prawn shells were suspended for 4 h in 0.25 M HCl at 40 degrees C while they were sonicated for 0, 1, and 4 h. Demineralized shells were lyophilized, resuspended in 0.25 M NaOH, and sonicated again for 0, 1, and 4 h for protein removal. The yield of chitin decreased from 8.28 to 5.02% for nonsonicated and sonicated samples, respectively, which was attributed to losses of depolymerized materials in the wash water. The application of ultrasound enhanced the removal of proteins. In nontreated shells, the amount of protein was 44.01% and was reduced to 12.55, 10.59, and 7.45% after 0, 1, and 4 h of sonication treatments. The glucosamine content slightly decreased with sonication probably because of losses due to depolymerization. The crystallinity indices of chitins decreased as the time of sonication increased. The degree of acetylation of chitins was unaffected by sonication, but the degree of acetylation of chitosans produced from sonicated chitin decreased from 70.0 to 68.7 and 61.4% for 1 and 4 h sonicated samples, respectively.     

Sonication-assisted extraction of chitin from North Atlantic shrimps (Pandalus borealis)

The influence of sonication during extraction of chitin from North Atlantic shrimp (NAS) shells (Pandalus borealis) on chitin yield, purity, and crystallinity was investigated. Shells were peeled, washed, lyophilized, ground, and suspended for 4 h in 0.25 M HCl (1:40) at 40 degrees C followed by ultrasonication at 41 W/cm(2) for 0, 1, and 4 h, respectively. Demineralized shells were lyophilized, resuspended in 0.25 M NaOH (1:40), and ultrasonicated at 41 W/cm(2) for 0, 1, and 4 h to remove proteins. The yield and mineral and protein contents were determined after each processing step. The purity of extracted chitin was determined from the total amount of glucosamine. The crystallinity index and size of crystals were calculated from wide-angle X-ray scattering measurements. Scanning electron microscope images were recorded to evaluate morphological changes in samples. The yield of chitin from NAS decreased from 16.5 to 11.4% for 0 and 1 h sonicated samples, respectively, which was attributed to increased concentrations of depolymerized materials in the wash water. Sonication did not enhance the removal of minerals. The application of ultrasound enhanced the removal of proteins from 39.8 to 10.6, 8.3, and 7.3% after 0, 1, and 4 h of sonication treatments. The crystallinity index of chitin decreased from 87.6 to 79.1 and 78.5% after 1 and 4 h of sonication, yielding chitosans with crystallinity indices of 76.7, 79.5, and 74.8% after deacetylation, respectively. Fourier transform infrared spectroscopy scans indicated that the degree of acetylation of chitins was unaffected by sonication. Comparison of the extraction results of NAS with that from freshwater prawns indicated that more impurities were left in NAS chitin, suggesting that composition and structural arrangement of chitin in shells influence the efficiency of ultrasound-assisted extraction.     

Ex situ evaluation of cultivation potential in wild populations of large-flowered vetch (Vicia grandiflora)

Large-flowered vetch (Vicia grandiflora Scop.) is widely present in many Eurasian wild floras, where it has significance in improving grassland communities and environment-friendly uses as a cover crop and green manure. The main goal of this study was to assess the possibility of transforming large-flowered vetch into a field crop and assess the basics for its breeding. A small-plot trial was carried out in three consecutive growing seasons 2005–2008 in Novi Sad, including twelve large-flowered wild populations collected at various sites in Serbia and France from 2002 to 2004 and multiplied ex situ during subsequent years. The population MM 02/01 of Serbian origin had the highest three-year average proportion of plants surviving winter (0.96). The smallest average number of days from sowing to first flower was in the population MM 03/10 (199 days). The population MM 03/08 produced the highest forage dry matter (8.0 Mg ha^?1) yield stage between full flowering and forming first pods. The highest seed yield was in the population MM 03/10 (2,084 kg ha^?1). Forage dry matter yield was significantly correlated to main stem length (r = 0.932), number of fertile nodes (r = 0.710), number of internodes (r = 0.640) and number of leaves (r = 0.604). Seed yield was significantly correlated to number of pods (r = 0.930), number of seeds (r = 0.883), number of stems (r = 0.882) and number of fertile nodes (r = 0.768). Our study confirmed that large-flowered vetch may represent a stable and quality source of forage in temperate regions such as the Balkans, as well as that it may have its place in various crop rotations and farming systems. At the same time, the existing phenotypic variability offers a solid basis for further improvement of this species.     

Analysis of oil composition in cultivars and wild species of oat (Avena sp.)

Oil quality and content were analyzed in 33 accessions from 13 wild species and 10 accessions of cultivated oat. Wild oat species tended to have higher oil and 18:1 fatty acid (FA) contents and lower amounts of 18:2 and 18:3 FAs as compared to cultivated oats. In addition to common FAs, minor amounts of several hydroxy and epoxy FAs were also present in the oat oil and mainly confined to specific lipid classes. These unusual FAs included the previously reported 15-hydroxy 18:2 (Delta9,12) (avenoleic acid) mostly found among polar lipids and a novel 7-hydroxyhexadecanoic acid located to 1,2-diacylglycerol. The present study highlights the potential of making use of the existing germplasm, consisting of wild oat species, in breeding programs for achieving new oat varieties that produce a range of oils with different FA compositions as well as having high oil contents. However, in one matter, oats apparently lack genetic diversity and that is for oil qualities that are highly enriched in the omega 3 (omega-3) FA 18:3. Consequently, developing oat cultivars with highly unsaturated oils will need involvement of other techniques such as biotechnology.     

Specificity of soil functioning and formation on gas-bearing areas

Background, aim, and scope  Exploited gas fields and underground gasholders are specific sources of increasing methane concentration. Methane migrates into the soils by diffusion and convection through natural and technogenic cracks in geological structures and influences the function of the soils. Soil cover of gas-bearing area functions as a specific, bilateral, periodically penetrating, geomembrane. Soils shield, transform, and differentiate migrating fluxes of technogenic-allochthonous methane, preventing its emission to the atmosphere. Problems of methane’s emission are rather current at the present, as methane is the second in importance after CO₂ greenhouse gas, since its concentration in the atmosphere annually grows by approximately 1%. By global estimations, methane emissions in the gas industry make about 8% of annual receipt to the atmosphere, equal on the average to 500 Тg per a year (Cicerone and Oremland, Global Biogeochem Cy 2:299–327, 1988). But these calculations are based on the account of the technological losses making 3–12% from the mining of natural gas. The contribution of migratory methane fluxes to the atmosphere, as a rule, is not considered. The need for research of soil cover functioning on gas-bearing areas is explained by the fact that processes of methane oxidation, its transformation in soils, and emission to the atmosphere at these objects are now practically not being studied. The aim of our study was to reveal specific processes of soil function and formation on gas-bearing areas by an example of underground gasholder. Materials and methods  The material was sampled in 1998–2003 at the territory of underground gasholder located in Albeluvisol’s zone in Russia. According to the comparative-geographical method, 51 soil profiles have been studied in similar litologically geomorphological conditions in various geochemical zones: in the industrial zone, in the zone of gas dissipation, and at the regional background. The total square of investigated territory is about 60 km². Six soil profiles were investigated in seasonal dynamics. Samples of soils for physical, chemical, and microbiological analyses were taken from each horizon of soil profiles (202 samples). Samples of soil air for a definition of methane concentration were taken from depths of 20, 40, and 60 cm. Methane emission to the atmosphere was measured near soil’s cuts and, in addition, on all area of the investigated territory at knots of squares network through 700–1,000 m, in total at 32–42 points in May, July, and November. Years of investigation have been split by technological and hydrothermal conditions. The periods with the normal and lowered compression of gas in gasholder, dry and warm, and damp and cool years have been allocated. It has influenced the soil function processes and considered an interpretation of the data received. Results  The changes of functional parameters of soils at a gas-bearing area influenced by methane fluxes migrating from gas deposits, in comparison with background soils, are revealed. Such functional parameters are methane concentration in the soils, activity of its bacterial oxidation, methane emission to the atmosphere, and oxidation–reduction potential. Spatial and temporary dynamics of these parameters at gas-bearing and background territory are investigated. Discussion  Methane interaction with soil’s air is in its ascending (descending) and lateral diffusion and convection in soils. Methane fluxes dissipate in porous space of soils forming gas anomalies. The technogenic-allochthonous methane concentration strongly varies in soil’s air on gas-bearing area (1–10,500 ppm) and, on average, exceeds the autochthonous, microbiologically produced methane at background territories. Migratory methane is deposited on diffusion and sorption barriers. The capacity of diffusion barrier depends on effective coefficient of diffusion, the attitude of air and general porosity, and granulometric composition and sharply differs in auto-, semi-hydro-, and hydromorphic soils reaching maximum in hydromorphicity and among the soils with identical water content—in heavy soils. The capacity of the sorption barrier is defined by abiotic methane absorption and a specific surface of soils and grows with their increasing intensity in soils to a heavier granulometric composition or into soils with peat and gleyic horizons. The low sorption capacity leads to an increase of methane concentration in the soil’s air and decreases its utilization by microorganisms, in which its quantity depends on sorption properties. The central component of functioning that promotes a number of essential transformations in soils on gas-bearing areas is methane interaction with the biotic phase. The periods of methane deposition by diffusion and sorption barriers are used for biological methane oxidation and formation of biogeochemical barriers in soils. The activity of bacterial methane oxidation is characterized by spatial variability and depends on the entrance of methane, defined by granulometric composition, soil moisture, the attitude of air and general porosity, Eh, organic matter content, and salinization. During interaction between technogenic-allochthonous methane and soil on diffusion, sorption, and biogeochemical barriers, its transformation occurs, accompanied by a strengthening of variability of oxidation–reduction potential and formation of pedogenic, bacteriomorphic, and nanodispersic magnetic oxides of iron. Conclusions and perspectives  Specificity of soil functioning on a gas-bearing area is in interaction of technogenic-allochtonous methane with solid, liquid, gaseous, and living substance of the soil system. Spatial laws of soils functioning on gas-bearing area in the Albeluvisol’s zone are revealed. Distinctions of soil functions depending on litologically geomorphological conditions are shown. The greatest changes of parameters of functioning under the influence of technogenic-allochthonous methane occur in automorphic soils, and it is less in semi-hydromorphic soils. Activity of bacterial methane oxidation in soils, emission, and consumption from the atmosphere and their spatial laws are characterized by the time dynamics depending on hydrothermal and technological conditions of seasons and years. During oxidation in soils of gas-bearing areas, carbon of methane is concentrated on a biogeochemical barrier that is shown in the increase of methylotrophic microorganisms’ biomass and leads to a high variability and decrease of Eh and to the formation of magnetic oxides of iron. Recommendations  Results of research can be used for carrying out ecological monitoring and an estimation of tightness of objects of the gas industry. Activity of bacterial methane oxidation, Eh, and magnetic oxides of iron can be used as diagnostic parameters of soils on gas-bearing areas. This paper has been developed from a presentation at the conference SUITMA-4 (Soils in Urban, Industrial, Traffic, Mining and Military Areas) Nanjing, China, 2007