Alkanes as Components of Soil Hydrocarbon Status: Behavior and Indication Significance

Studies of soils on three key plots with different climatic conditions and technogenic impacts in Volgograd, Moscow, and Arkhangelsk oblasts have showed that alkanes in the soil exchange complex have some indication potential for the identification of soil processes. The following combinations of soil-forming factors and processes have been studied: (a) self-purification of soil after oil pollution; (b) accumulation of hydrocarbons coming from the atmosphere to soils of different land use patterns; and (c) changes in the soil hydrocarbon complex beyond the zone of technogenic impact due to the input of free hydrocarbon-containing gases. At the injection input of hydrocarbon pollutants, changes in the composition and proportions of alkanes allow tracing the degradation trend of pollutants in the soil from their initial content to the final stage of soil self-purification, when the background concentrations of hydrocarbons are reached. Upon atmospheric deposition of hydrocarbons onto the soil, from the composition and mass distribution of alkanes, conclusions can be drawn about the effect of toxicants on biogeochemical processes in the soil, including their manifestation under different land uses. Composition analysis of soil alkanes in natural landscapes can reveal signs of hydrocarbon emanation fluxes in soils. The indication potentials of alkanes in combination with polycyclic aromatic hydrocarbons and other components of soil hydrocarbon complex can also be used for the solution of other soil-geochemical problems.     

Hydrocarbon status of soils in an oil-producing region with karst relief

Features and factors of the hydrocarbon status of soils developed in oil-producing karst regions were considered using an oilfield as an example. The notion of the hydrocarbon status of soils involves the proportions of the gas, bitumen, and polyarene components of the total hydrocarbons and their radial and lateral variations. The following types of soil hydrocarbon status were identified: (1) the background (reference) type; (2) the first kind of emanation type related to soil degassing (most probably, in an oilfield); (3) the technogenic type developed in the areas of oil spills, contaminated surface runoff, and industrial waste storage; and (4) the emanation type of the second kind related to the degassing and evaporation of spilled oil and other substances in underground karst caves. It was shown that the data on the hydrocarbon status of the soils can be used for the identification of hydrocarbon areas in the soil cover and the indication of the sources of pollutants deteriorating the environmental conditions in the landscape.     

Hydrocarbon status of soils under different ages of oil contamination

Modifications of the hydrocarbon status (HCS) of soils at the stages of the injection input of oil pollutants and the subsequent self-purification of the soil layer from technogenesis products have been revealed in studies conducted on an oil field. Comparison with the HCS of background soils has been performed. Changes in the composition and concentration of bitumoids, polycyclic aromatic hydrocarbons (PAHs), and hydrocarbon gases have been established. The HCS of a freshly contaminated soil is characterized by the predominance of butane (the highest component) in the gaseous phase, an abrupt increase in the concentration of second-kind bitumoids, and a 100-fold increase in the content of PAHs compared to the background soil. In the old contaminated soil, free and fixed methane becomes the predominant gas; the content of bitumoids in the upper soil horizons is lower than in the freshly contaminated soils by two orders of magnitude but higher than in the background soil by an order of magnitude; the PAH composition in the soil with old residual contamination remains slightly more diverse than in the background soil.     

Volatilisation of aromatic hydrocarbons from soil: Part I,fluxes from coal tar contaminated surface soils

The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar. Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 µg/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch — by a factor of 8 to 25 — than expected for natural organic matter. The fluxes were also estimated using an analytical solution of the Fick's diffusion equation and assuming that the compounds diffused independently of each other and that instant equilibrium existed between the air, water and sorbed phases. A relatively good agreement was found between the predicted and the measured flux. The predicted fluxes were between 0.11 and 7.5 time the measured fluxes. The fluxes were overestimated for the monocyclic aromatic hydrocarbons and underestimated for 3-rings-PAHs.     

Laboratory analytical methods for the determination of the hydrocarbon status of soils (a review)

Laboratory analytical methods suitable for the determination of the hydrocarbon status of soils (a specific soil characteristic involving information on the total content and qualitative features of soluble (bitumoid) carbonaceous substances and individual hydrocarbons (polycyclic aromatic hydrocarbons, alkanes, etc.) in bitumoid, as well as the composition and content of hydrocarbon gases) have been considered. Among different physicochemical methods of study, attention is focused on the methods suitable for the wide use. Luminescence-bituminological analysis, low-temperature spectrofluorimetry (Shpolskii spectroscopy), infrared (IR) spectroscopy, gas chromatography, chromatography–mass spectrometry, and some other methods have been characterized, as well as sample preparation features. Advantages and limitations of each of these methods are described; their efficiency, instrumental complexity, analysis duration, and accuracy are assessed.     

土壤有机和无机组分对多环芳烃环境行为影响的研究进展

土壤中多环芳烃(PAHs)的环境行为取决于它们与土壤不同组分之间的相互作用。本文综述了土壤有机质、黏土矿物以及有机矿质复合体对PAHs土壤环境行为影响的研究进展,期望从土壤基本组成和性质上对PAHs的土壤环境行为有一个本质的了解。     

Hydrocarbon status of soils in the asphalt deposit area (Samara Bend)

The composition and distribution features of the main components of soil hydrocarbon complex― organic (noncarbonate) carbon, hexane bitumoids, and individual polycyclic aromatic hydrocarbons (PAHs)―in the area of depleted Bakhilovo asphalt deposit (Samara oblast) have been studied. According to their proportions, three genetic types of soil hydrocarbon status are distinguished: (a) emanation–injection type prevailing within the limits of the former production field and characterized by anomalous contents of heavy resinous bitumoids (5000–7000 mg/kg on the average) throughout the soil profile and a high content of PAHs (4–9 mg/kg on the average, 29 mg/kg as the maximum, with the dominance of naphthalene homologues); (b) emanation–biogeochemical type confined to mechanogenically undisturbed soils within and beyond the deposit area, where the emanation component is manifested in soils with heavy texture and higher concentrations and very light composition of bitumoids in the lower parts of the soil profile; and (c) atmosedimentation–biogeochemical type characteristic of conventionally background soils with light texture; benzo[a]pyrene traces are detected among PAHs in the upper soil horizon, which indicates the input of this hydrocarbon with aerosols from the atmosphere; the concentrations of bitumoids and PAHs in parent rocks are lower than in the soils.     

Accumulation of Polycyclic Aromatic Hydrocarbons in Soils and Mosses of Southern Tundra at Different Distances from the Thermal Power Plant

A number of polycyclic aromatic hydrocarbon (PAH) structures have been identified in organic horizons of surface-gley tundra soils (Stagnic Cambisols) and the moss Pleurozium schreberi. The total content of polyarenes in soils and P. schreberi exceeds the background values in 3.5–5 times. A tendency of increasing content of polyarenes with the distance from the source to 1 km has been revealed. High coefficients of variation have been found between the contents of PAHs in snow cover, organic soil horizons, and mosses. Light hydrocarbons dominate in the composition of PAHs from the snow and ground covers and mosses. Naphthalene dominates on the surface of mosses in all of the studied plots, which is largely related to its intensive uptake by mosses under pollution conditions. It has been found that when the input of polyarenes onto the surface of tundra phytocenoses increases, the bioaccumulation of PAHs by P. schreberi is intensified, and PAHs begin to penetrate into moss. The increase in the concentration of high-molecularweight polyarenes in the environment plays the key role in the activation of PAH bioaccumulation by moss. It has been shown that P. schreberi can be used as an indicator species for monitoring the contamination of tundra phytocenoses by polyarenes. Both living and dead parts of P. schreberi are suitable for the environmental monitoring of PAH contamination.     

江西省土壤典型有机污染物的水平和来源及其健康风险

筛选有机氯农药(六六六和滴滴涕)和多环芳烃作为典型土壤有机污染物,以江西省为例,开展了污染评价、源识别以及健康风险评价研究。结果表明:(1)所有样品中总六六六均未超过我国土壤环境质量二级标准,有8个样品中总滴滴涕超过该标准,另外,7.9%的样品中总多环芳烃超过荷兰土壤环境质量标准中最高允许浓度阈值;(2)接近29%的样品中六六六来自于当前林丹的使用,滴滴涕主要来源于近期输入,而对于多环芳烃而言,其中66%的样品中多环芳烃来源于石油源,34%的样品来源于燃料燃烧;(3)有机氯农药和多环芳烃对人体健康的风险都在可接受的范围内。     

The maps of soil tolerance toward pollution with oil products and polycyclic aromatic hydrocarbons: Methodological aspects

Natural factors ensuring soil tolerance toward pollution with technogenic hydrocarbons, particularly, oil products and polycyclic aromatic hydrocarbons, are considered. The maps of the self-purification capacity of the soils of Russia and its particular humid and arid regions with respect to their contamination with technogenic hydrocarbons are analyzed. The principles lying in the basis of these maps are discussed. It is argued that the cartographic assessment of soil tolerance toward pollution with technogenic hydrocarbons is necessary for setting the values of maximum permissible concentrations of hydrocarbons in soils, for the choice of adequate soil rehabilitation procedures, and for the organization of soil monitoring.     

Hydrocarbon Status of Alluvial Soils in the Istra Morphostructural Node (Moscow Oblast)

The effect of the current block structure of the earth’s crust and its most active sites (morphostructural nodes) on the natural hydrocarbon status of alluvial soils has been considered. Studies have been performed in the Istra district of Moscow oblast within the Istra morphostructural node. The node represents an area of increased geodynamic activity of the earth’s crust located at the convergence or intersection of block boundaries: mobile linear zones following large river valleys with alluvial soils. Soil cover mainly consists of alluvial humic-gley soils (Eutric Gleyic Fluvisols) of different depths and alluvial mucky-gley soils (Eutric Gleyic Histic Fluvisols). Some soils manifest stratification. Two factors forming the hydrocarbon status of soils are considered: soil processes and the effect of geodynamic activity, which is manifested within the morphostructural node. The contents of bitumoids and retained methane and butanes in alluvial soils appreciably increase at the entry of river valley into the node. The occurrence frequency of 5–6-ring polycyclic aromatic hydrocarbons (perylene and benzo[ghi]perylene) in mineral horizons increases. It has been concluded that alluvial soils within the Istra morphostructural node are characterized by the biogeochemical type of hydrocarbon status with signs of emanation type at sites with the highest geodynamic activity.     

不同掺混比例生物柴油的非常规污染物排放特性

为了实现柴油机的清洁燃烧,需要系统研究非常规污染物的生成机理与排放特性。根据羰基类、芳香烃类物质的理化性质特点,提出了柴油机非常规污染物高效快速的测量方法,采用不同掺混比例的生物柴油进行了柴油机台架试验,探讨了不同燃料、不同工况下柴油机非常规污染物的排放特性。结果表明,二硝基苯腙采样结合高效液相色谱技术,可以实现柴油机排气中15种羰基类污染物的快速准确测定,活性炭吸附结合气相色谱-质谱联用技术可以实现芳香烃污染物的定性定量分析;中、低负荷时,生物柴油掺混比例对柴油机总羰基排放的影响不大,随着负荷的增加,BD50（生物柴油和市售0#柴油按体积比1:1配制的调合油）和BD0（纯柴油）的总羰基排放呈升高趋势,BD100（以地沟油为原料的生物柴油）的总羰基排放有所降低;BD0的单环芳香烃最大排放浓度最高,3种燃料的气相多环芳香烃排放在低负荷和高负荷工况点存在"双峰"特征,三环菲约占所有环数多环芳香烃总量的44%,燃用生物柴油可降低柴油机约32%的多环芳香烃排放。该研究为柴油机非常规污染物的排放控制提供了参考。     

Concentrations and composition of polycyclic aromatic hydrocarbons in the granulodensimetric fractions of soils in Moscow parks

A comprehensive study of the contents and composition of 15 compounds from the group of polycyclic aromatic hydrocarbons in granulodensimetric fractions of soddy-podzolic soils was performed. The specificity of the accumulation of these substances in the clay (heavy-weight) and light-weight soil fractions was investigated. The levels of the soil contamination in Moscow parks with polyarenes were determined, and the assessment of changes in the degree of the soil contamination over a long period of time was made.     

Formation of polycyclic aromatic hydrocarbons in northern and middle taiga soils

An integrated study of the qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric precipitation-soil-lysimetric water system was performed using high performance liquid chromatography. It was shown that the accumulation of low-molecular PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, and chrysene) in soils is due to the transformation of organic matter and the regional transport and deposition of PAHs with atmospheric precipitation on the underlying surface. High-molecular polyarenes (benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene) mainly result from the decomposition of soil organic matter.     

Hydrocarbon contamination of arctic tundra soils of the Bol’shoi Lyakhovskii Island (the Novosibirskie Islands)

Data on the distribution of the components of oil products that have accumulated in the arctic tundra soils of the Bol’shoi Lyakhovskii Island (the Novosibirskie Islands) under the impact of technogenic loads are analyzed. The examined soils differ in the vertical and lateral distribution patterns of the methanenaphthenic and naphthenic hydrocarbons and in the degree of their transformation. This is determined by the position of particular soils in the catenas and by the sorption of particular hydrocarbon compounds in the soils. The portion of light molecular-weight hydrocarbons in the upper horizons decreases by two-ten times in comparison with the deeper soil layers. In the lateral direction, the twofold difference in the contents of the methane-naphthenic and naphthenic hydrocarbons in the upper horizons is seen. The degree of transformation of the hydrocarbons under the impact of microbiological processes depends on the aeration conditions, the depth of permafrost table, the composition of oil products, and the soil organic matter content.     

堆肥化过程中有机污染物生物降解的研究进展

简介了卤代烃、多环芳烃、农药类及石油烃类等几种有机污染物在堆肥过程中的生物降解及其机理研究进展,并指出今后应重点加强高效降解微生物的分离培养、基因工程菌的开发、表面活性剂对生物降解的强化作用以及适合有机污染物降解的堆肥条件和有机污染物在堆制过程中降解的中间产物及终产物等方面研究。     

Soil properties in the Tol’yatti pine forest after the 2010 catastrophic wildfires

The results of the studies of soil changes after the 2010 fires in the forest outliers of the city of Tolyatti have been reviewed. The morphological analysis of postpyrogenic soils has showed that the fire touched only the upper part of their profiles. It has been revealed that the surface fires favor the more intense loss of organic carbon than the crown fires (2.85 and 2.37%, respectively). However, the crown fires are more destructive for soils, because, first, they are a continuation of the surface fires and, second, sheet and linear water erosion of soils develops because of the complete denudation of the soil cover. It has been found that forest fires result in the dehumification of soils, which is related to the destruction of the organic horizons, the mineralization of root residues, and the almost complete absence of fresh plant waste on the postfire areas. The pyrogenic impact increases the portion of humic acids in the organic matter. Along with the transfer of the clay fraction, the translocation of polycyclic aromatic hydrocarbons resulting from the fires to the accumulative geochemical positions is also possible.     

Procedure to measure the level of polycyclic aromatic hydrocarbons in wood ashes used as fertilizer in agroforestry soils and their transfer from ashes to water

Before wood ash can be safely used as a fertilizer in soils, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to optimize and characterize extraction methods to isolate and quantitatively measure polycyclic aromatic hydrocarbons (PAHs) concentrations in wood ash that can be used as amendment of soils. It will be then possible to examine the effects of wood ash application on PAHs concentrations in the washing waters with the aim of evaluating their distribution by storage in the different compartments and what influences their stability and persistence. Simple, rapid and inexpensive methods have been set up for the determination of seven polycyclic aromatic hydrocarbons (PAHs) in wood ashes and ash aqueous extracts without interferences from other chemical contaminants using organic solvent extraction and/or SPE techniques and analyzed by an optimized RP-HPLC-FLD method. The feasibility of extraction for the determination of PAHs in wood ashes has been evaluated because PAHs are strongly sorbed to such a matrix, which explains why the PAHs content in ash was seldom studied. The method resulted to be of recoveries ranging from 81 to 97% for the different PAHs, with repeatabilities (RSDs%) better than 6%. Detection levels were from 0.2 to 2.2 microg/kg, while quantification limits were from 0.7 to 5.6 microg/kg, low enough to evaluate the presence of PAHs in wood ashes.     

Polycyclic aromatic hydrocarbons in pyrogenic soils of swampy landscapes of the Meshchera lowland

The composition and distribution of polycyclic aromatic hydrocarbons (PAHs) were studied in organomineral and organic soils of the Meshchera National Park. It was found that the background oligotrophic peat soils unaffected by fires in central parts of the bogs are characterized by the increased PAH concentrations due to their high sorption capacity. The fires of 2007 and 2010 resulted in the transformation of the plant cover and soil morphology, the formation of new horizons, and the change in the PAHs content and composition. Significant burn-off of organic matter was found in oligotrophic-eutrophic soils and resulted in the decrease of PAHs content after fire. Only partial burn-off of organic horizons and intense formation of PAHs were recorded in the soil with initially great thickness of peat horizons. Pyrogenic accumulation of PAHs was identified in organomineral soils of the marginal parts of bogs and of forest sites.     

Polycyclic aromatic hydrocarbons in tundra soils of the Komi Republic

The qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in tundra soils has been studied by gradient high-performance liquid chromatography. The differentiation of the PAHs in the soil profile is of clear accumulative character. The pool of polyarenes in the soils is determined by the cryogenesis processes and mainly consists of low-molecular-weight bi- to tetranuclear PAHs, the high-molecular-weight PAHs in the organic horizons make up no more than 20% of the total polyarenes in the soil, and penta- and hexanuclear structures are almost absent in the mineral layer.