Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions

Purpose

Combined pollution by polycyclic aromatic hydrocarbons (PAHs) and heavy metals are commonly found in industrial soils. This study aims to investigate the effect of the coexistence of heavy metals on the sorption of PAHs to soils. We focused specifically on the relationship of the sorption capacity with the estimation of the binding energy between PAHs and heavy metals.

Materials and methods

The sorption of typical PAHs (naphthalene, phenanthrene, and pyrene) to soils coexisting with heavy metals (Cu(II), Pb(II), and Cr(III)) was characterized in batch sorption experiments. The binding energy between PAHs and heavy metals in aqueous solution was estimated by quantum mechanical (QM) method using density functional theory (DFT) at the M06-2x/def2svp level of theory.

Results and discussion

Sorption capacity and nonlinearity of the PAHs to the soils were enhanced by the coexisting heavy metals. The extent of increment was positively associated with the hydrophobicity of the PAHs and the electronegativity and radius of the metal cations: Cr(III)?>?Pb(II)?>?Cu(II). The cation-π interaction was revealed as an important noncovalent binding force. There was a high correlation between the binding energies of the PAHs and K _f ′ (K _f adjusted after normalizing the equilibrium concentration (C _e) by the aqueous solubility (C _s)) (R ²?>?0.906), indicating the significant role of the cation-π interactions to the improved PAH sorption to soils.

Conclusions

In the presence of heavy metals, the sorption capacities of naphthalene, phenanthrene, and pyrene to soils were enhanced by 21.1–107 %. The improved sorption capacity was largely contributed from the potent interactions between PAHs and heavy metals.

     

Extractable heavy metals in Atlantic coast soils

Abstract

The analysis of soils, using 0.1 N HC1 as an extractant for the heavy metals, Cd, Cr, Ni and Pb on “fine”; textured North Shore and “coarse”; textured Annapolis Valley soils was completed. Results show ranges of 0.012 to 0.469 parts per million Cd; 0.102 to 2.90 parts per million Cr; 0.16 to 29.25 parts per million Ni and 0.12 to 244.8 parts per million Pb. Correlation studies indicate that the heavy metal content of fine textured soils is less influenced by changes in clay content and organic matter than are coarse textured soils. Generally the surface layers (0–15 cms) are higher in extractable heavy metal content than the lower layers (15–30 cms).     

Accumulation of heavy metals in oil-contaminated peat soils

X-ray fluorescence and X-ray radiometry represent easy and simple methods to determine concentrations of heavy metals in the ash of peat soils contaminated with oil and can be applied for soil monitoring purposes. Oil spills on peat bogs produce two contamination zones differing in the composition of heavy metals. In the zone of primary contamination, the peat surface is covered by a bitumen crust with V, Ni, Sr, Ba, Ce, and La accumulating there. This zone adjoins the zone of secondary peat contamination, where heavy alkaline-earth metals (Sr, Ba) and lanthanides (Ce and La) are accumulated to a lesser extent. Biological preparations recommended for remediation of oil-contaminated peat soils should be tolerant to high concentrations of heavy metals, particularly, V, Ni, and Ba that are present in the oil contaminated soils in relatively high amounts.     

Streptomyces communities in soils polluted with heavy metals

The contents of differently mobile heavy metal compounds and their influence on the formation of microbial cenoses (particularly, streptomyces communities) in technogenically disturbed soils are considered. Elevated concentrations of mobile Cu, Zn, Ni, Cd, and Fe compounds are shown to determine structural-functional changes in microbial cenoses that are displayed in a decreasing number of microorganisms and a narrower spectrum of the streptomyces species. Some specific features of the formation of streptomyces communities in technogenic soils were revealed on the basis of the analysis of their species structure with the use of the Margalef, Berger-Parker, and Sorensen indices of biodiversity.     

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.

     

Assessment of the migration of heavy metals in soils

Qualitative and quantitative studies of the kinetics and dynamics of technogenic migration of heavy metals (HMs) have been performed in laboratory experiments. It is shown that the redistribution of HMs applied into soils in neutral form has an impulsive pattern. Soil texture does not have a decisive influence on the migration capacity of metals. An important feature of the technogenic migration of HMs is the effect of the polymetallic contamination, upon which the migration capacity of a set of heavy metals is higher than that of separate metal compounds. An index characterizing the ratio of absolute values of migration rates of ionic forms of metals estimated from electrical conductivity values to the rate of infiltration of the soil solution (v_m/v_f) is suggested to estimate the kinetics of HM migration in soils.     

重金属和有机污染物在修饰土中的吸附

Sorption characteristics of both an organic pollutant （phenol） and a heavy metal （cadmium ion） on the clay layer of a Lou soil （Eum-orthic Anthrosol in Chinese Soil Taxonomy） along with the sorption mechanism were investigated using three soil treatments： modification with a cationic surfactant cetyltrimethylammonium bromide added at an amount equivalent to 50% and 100% of the soil CEC （50? and 100?）, modification with an amphoteric surface-modifying agent dodecyldimethylbetaine （commercially known as BS-12） added at an amount equivalent to 50% and 100% of the soil CEC （50% BS and 100%BS）, and an unmodified control （CK）. Results showed that the BS soil treatments increased sorption of both the heavy metal Cd^2＋ and the organic pollutant phenol. The equilibrium sorption amount of Cd^2＋ decreased in the order： 50%BS 〉 100%BS 〉 CK 〉 50? 〉 100?, with the BS soil treatments being about 1.3 to 1.8 times higher and the CB soil treatments about 23% to 41% lower than CK. Both the single-site and two-site Langmuir models could be applied to describe the sorption of Cd^2＋ in each soil treatment. The equilibrium sorption amount of phenol on the soil samples decreased in the order： 100? 〉 50? 〉 100%BS 〉 50%BS 〉 CK, with the CB soil treatments being 41.0 to 79.6 times higher and the BS soil treatments 4.0 to 8.3 times higher than CK. The Freundlich equation could also be used to describe the sorption characteristics of phenol. In the BS soil treatments, both an organophobic long carbon chain and hydrophilic charged groups resulted in a relatively strong sorption ability for both heavy metals and organic pollutants. In addition, the sorption ratio K, the ratio of phenol sorption amount of the modified soil to that of CK, increased initially and decreased later with the amount of phenol added, and the critical sorption ratio Kc, the peak value of the sorption ratio curve plotted against the added phenol concentration, was a good index for evaluating the sorption ability of phenol in the soil.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

典型设施栽培土壤重金属含量变化及其风险评价

采用野外调查采样和室内分析相结合的方法,对典型设施栽培地山东寿光的部分土壤重金属含量进行测定,并根据温室蔬菜产地环境质量评价标准,选取单项污染指数法和尼梅罗综合指数法对土壤的重金属污染状况进行了环境质量评价。结果表明,重金属Cu、C r、Pb在设施栽培土壤耕层(0—20 cm)的含量达最大值,显著高于露地土壤;而设施栽培土壤中Zn和Cd的含量分别在20—40 cm和40—60 cm的土层达到最大值,其中Zn含量在0—20 cm和60—80 cm的土层显著高于露地土壤,Cd含量在0—20 cm,40—60 cm,60—80 cm和80—100 cm的土层显著高于露地土壤。从不同使用年限设施栽培土壤中重金属含量变化看出,重金属在设施栽培24~年的土壤中含量最高。对研究区设施栽培土壤重金属含量进行风险评估及分级发现,山东寿光设施土壤耕层主要受到重金属Cd的污染。     

Natural and technogenic compounds of heavy metals in soils

The existing geological classification of heavy metals (HMs) is not suitable for their characterization in soils. The carriers of HMs in soils differ from those in the lithosphere. These are clay minerals; iron oxides, whose composition varies between the background and urban soils; various manganese oxides; and different groups of organic substances. The mineral composition of HM carriers can vary significantly. The main iron oxides are ferrihydrite, goethite, feroxyhyte, and lepidocrocite in the background soils and technogenic magnetite in the urban soils. The different structures of manganese oxides determine their affinity for specific HMs. Metallic iron and green rust are very efficient in artificial geochemical barriers, although they act as strong reducers there. HM compounds strongly vary in soils because of the unstable conditions.     

Sorption of dimethylselenide by soils

Air-dry and moist soils were shown to possess the capacity to sorb substantial amounts of (⁷⁵Se)dimethylselenide produced by the yeast Candida humicola in culture, or by soil supplied with (⁷⁵Se)selenite, depending largely upon the organic matter content and selenium concentration of the soils. The sorption capacities of individual soil constituents followed the order; organic matter > clay minerals > manganese oxides > iron oxides > acid-washed sand.A chemical fractionation procedure applied to soils fumigated with (⁷⁵Se)dimethylselenide revealed that the majority of the selenium sorbed was converted after 1 month to other forms, extractable mainly with strong acid solutions. Experiments with sterilized (autoclaved and γ-irradiated) soils indicated that soil microorganisms played little, if any, part in the sorption process.The work reported here indicates that soil is an important natural “sink” for atmospheric dimethylselenide.     

贵阳市主要土壤重金属状况研究

通过对2000～2003年贵阳市的白云区、修文县、开阳县、清镇市、息烽县、乌当区、小河区以及花溪区的多个旱地的表土和底土（53个样品）中重金属元素（汞、砷、铅、镉、铬）含量进行检测，以GB／T18407．1—2001《农产品安全质量无公害蔬菜产地环境要求》为标准，采用单因子指数法及N．L．Nemerow综合指数法进行评价，分析结果表明：贵阳市无公害蔬菜生产基地的大部分土壤中的5种重金属元素的含量基本在GB／T18407．1—2001规定的范围内，但也有个别区域内土样中砷、镉含量达到了警戒线的含量范围，如白云区底土中砷的单因子综合污染指数达到0．7968、乌当区表土中镉的单因子综合污染指数达到0．7542，两者都属于0．7～1．0污染警戒线范围内。总体土壤的表土、底土重金属综合污染指数分别为0．3785、0．4204，小于0．7，污染等级属于安全，污染水平为清洁，土壤环境质量为1级。     

Mobility of heavy metals in pine forest soils as influenced by experimental acidification

The mobility of Pb, Zn, Cd and Cu was examined at two adjacent experimental plots at åmli, southern Norway, B-1 and B-2. Both experiments were established on the same glacifluvial deposits, with forest consisting of uniform stands of Pinus sylvestris L. The forest in B-1 was planted between 1968 and 1970, while B-2 consisted of naturally regenerated trees. The experiments included plots supplied with artificial rain of varying acidity over a period of seven and eight years for B-1 and B-2, respectively, in addition to control plots. In experiment B-1, experimental acidification was carried out both in unlimed plots and in plots applied with three different levels of lime. The two experiments showed distinct differences with respect to effects of the acidification on mobilization of heavy metals from the O horizon. In experiment B-1, the amount of Zn and Cd decreased with decreasing pH in artificial rain, while Pb and Cu were not appreciably affected. The reduction in Zn and Cd concentrations ceased after termination of the acidification experiment. Liming reduced the leachability of Zn, but still appreciable amounts of Zn were obviously leached from the O horizon during the experiment. In experiment B-2 a high retention even of Zn and Cd was observed in the O horizon, probably due to microbial uptake and accumulation.     

Myriapod and isopod communities in soils contaminated by heavy metals in northern France

Soil invertebrates suffer from contamination of the soil by heavy metals. We have studied the effects of contamination by cadmium, zinc and lead on their communities in soils in northern France by comparing polluted land with non‐contaminated sites. We have followed the seasonal variations and effects of soil properties. Saprophagous invertebrates (Diplopoda, Isopoda) and Chilopoda were sampled by pitfall‐trapping from February to November in fairly contaminated areas. In addition, a Berlese extraction of the litter in two very highly contaminated sites was conducted during autumn; animals were also trapped during June in the same locations. The most active period for myriapods was spring (April and May), whereas isopods were abundant from April to the end of summer. No clear relation was found relating dominant species or number of myriapods or isopods to concentration of heavy metal in the little‐contaminated soils. The dominant species seemed not to be related to pollution but to vegetation or soil characteristics. In the most contaminated sites, with metalliferous grassland and a thick undecomposed litter layer, a threshold in contamination values seemed to be reached: no isopods or millipedes were found, but only Chilopoda and Symphyla.     

Mutagenic activity of heavy metals in soils of wayside slopes

The genotoxic properties of soils polluted with heavy metals were studied on two wayside slopes covered with trees in the city of Voronezh. The nucleolar test in cells of the apical meristem of Zebrina pendula Schnizl. roots was used. The genotoxic effect of the soils was revealed according to the increased number of 2-and 3-nucleolar cells (from 41 to 54% and from 19 to 23% in the upper part of the first and second slopes, respectively; in the control, their number was 18 and 7%). The mean number of nucleoli per cell increased from 1.7 to 1.95 in the experiment and 1.31 in the control. The increased vehicle emissions, especially when cars go up the slopes (mainly in the upper and middle parts), correlated with the elevated heavy metal (Pb, Cu, Cd, and Zn) contents in the soil. The mutagenic substances may be removed to the Voronezh Reservoir, where they may be accumulated in some living organisms.     

中国原油污染区重金属空间分布模式及其潜在来源研究

Twenty-two soil samples were collected at the subregional scale （50 km2） around Gudao Town, a typical oil-producing region of the Shengli Oilfield in the Yellow River Delta, China to determine the spatial distribution patterns and potential sources of heavy metals in soils of crude oil-polluted regions. The concentrations of total petroleum hydrocaxbons （TPHs） and heavy metals as well as other soil properties were determined and the enrichment factor values were calculated for the heavy metals measured. Principal component analysis （PCA） and cluster analysis （CA） were used to estimate potential sources contributing to the concentrations of heavy metals in the soils. The results revealed that the soils were slightly alkaline （pH = 7.33-8.05） and high in salinity （1.43-41.30 g kg-1）, TPHs （0.51 28.40 g kg-1） and organic matter （1.74-31.50 g kg-1）. The mean concentrations of the measured heavy metals Cu, Zn, Pb, Cd, Cr, Ni and V were 18.4, 78.2, 20.8, 0.19, 56.6, 26.3 and 62.1 mg kg-1, respectively. Although the concentrations of all the metals measured in this study were not high enough to exceed the national control standards, there was a significant enrichment of Cd in the study area and Zn and Ni were in the category of deficiency to minimal enrichment. The spatial distribution patterns of Cu, Cr, Ni and V were similar and partially affected by oil exploitation and petroleum hydrocarbon spills. Potential sources of Cr, Ni, V and Cu in the soils were both natural sources and petroleum hydrocarbon spills, while Zn, Pb and Cd were probably from anthropogenic sources such as farming activities and traffic.     

复垦土壤重金属污染潜在生态风险评价

为揭示矿区复垦土壤中重金属元素潜在的污染特征,采用Hakanson 潜在生态风险指数（The Potential Ecological Risk Index）,对安太堡露天煤矿复垦土壤中Cd,Cr,Cu,Pb,Hg,As等6种污染元素进行了分析,研究了露天煤矿复垦土壤重金属污染程度及潜在的生态危害性。结果表明：安太堡露天煤矿不同复垦时间和复垦模式下不同层次的复垦土壤的综合污染程度范围为8.29～16.90,平均值为10.72,处于中等的污染程度。重金属潜在风险指数在131.43～331.03之间,平均191.68,生态风险达到了中等程度,特别是复垦13年的南排1?420退化平台,综合潜在生态风险指数为331.03,达到了较高程度。0～40 cm土层的潜在生态风险综合评价属于中度的潜在生态风险。Hg是主要的污染因子,其对潜在的生态风险指数所贡献的比例达到了72.5%～84.62%。其余重金属的生态风险较低。因此,在安太堡露天煤矿复垦土壤中,Hg是最主要的潜在污染因子,应采取一定的措施,防止Hg的污染。应用该体系对复垦土壤重金属污染生态风险评价所得的结论同其它研究结果互为补充和借鉴。     

Mobility of heavy metals in polluted soils near zinc smelters

The distribution and the availability of Cd, Zn, Cu, and Pb along the entire profile of two highly polluted soils located near Zn smelters have been related to the chemical and mineralogical composition of the soil. Lead and Cu deposits always remain in the surface layers and their availability measured by neutral ammonium acetate extraction was very weak. The behavior of Cd and Zn appears different in sandy acidic podzolic soils and in neutral loamy soils. These metals are associated with the organic matter migration in podzolic soils, while they remain in the upper layers in loamy soils provided that the pH is higher than 6. When the pH drops below 6, the mobility of Cd increases while that of Zn increases only below pH 5. The availability of heavy metals is lower in neutral loamy soils than in sandy acidic soils due to precipitation of carbonates and phosphates. With increasing depth, Cd and Zn are more available if the soil is acid; but, if the soil is neutral and loamy the availability is kept low by adsorption on clays and free oxides. The results of the complex trace metals interactions with the soil components show a higher accumulation capacity for loamy soils than for sandy soils notwithstanding the fact that their CEC is similar.     

北京耕作土壤重金属多尺度空间结构

为了有效揭示土壤重金属的空间分布特征,为土壤环境质量评价提供科学依据,该研究以北京市耕作土壤中重金属为例,通过地统计学方法分析了重金属空间结构的尺度效应。研究结果表明：土壤重金属Cr、Ni、Zn和Hg的空间结构性对空间尺度有明显的依赖,理论半方差函数的最优性检验进一步表明多尺度套合模型能充分地挖掘和利用土壤重金属Cr、Ni、Zn和Hg的空间变异结构,并且采用多尺度套合模型法对重金属Cr、Ni、Zn和Hg进行克里格插值,其插值效果明显优于单一尺度下的普通克里格插值。因此,多尺度套合模型法能有效地揭示耕作土壤中重金属的空间分布特征。     

土壤中重金属离子竞争吸附的研究进展

本文主要对土壤中重金属离子竞争吸附的研究现状进行了综述。讨论了影响重金属离子竞争吸附能力的一些主要因子、吸附平衡模型及吸附反应的动力学过程。重金属离子的一级水解常数、离子半径、电负性等性质及其外界环境条件,如pH值、离子强度、有机质含量等因素影响着离子选择性吸附的强弱。竞争的Langmuir方程和扩展的Freundlich方程被用来对竞争吸附过程进行描述,同时指出竞争吸附过程中存在着一个"过饱和点"。最后,对竞争吸附的发展方向进行了展望,指出应加强理论模型和多因子综合作用影响的研究。