Heavy metal contamination of roadside soils in the Greater Athens area

The airborne contamination of roadside soils with Pb, Cd, Zn and Ni was evaluated for the Greater Athens Area of Greece. High levels of lead enrichment were found in the upper 0-5 cm soil layer along roads with heavy traffic loads. The central section of the study area appeared to have soils with the highest levels of lead enrichment. The contamination decreased exponentially with the distance from the road edge and dropped to a background level at about 50 m. Most of the lead was concentrated in the upper 5 cm of the soil and was associated with carbonates and crystalline oxides. The main source of contamination was automobile exhausts. Roadside soils were also enriched with airborne Cd and Zn, but to a lesser degree than with Pb. The enrichment of the soil with these two elements fell rapidly and exponentially with distance. No evidence of Ni contamination of roadside soils was obtained.     

Fate and behaviour of phenanthrene in the natural and artificial soils

For the assessment of contaminated soils ecotoxicological tests are used to estimate the bioavailability of contaminants in soil samples. Terrestrial tests reveal the habitat function of soils, and parameters applied in tests involving microorganisms include respiration activity and potential ammonium oxidation. For such tests, the threshold values needed to assess the results have already been established in guidelines ISO 17155 and ISO 15685. In this paper, we discuss about the respiration activity and potential ammonium oxidation results obtained from a wide variety of soils with different physico-chemical properties and levels of contamination. These results show that microbial respiration and potential ammonium oxidation have different sensitivities to various classes of contaminants. We demonstrated that both organic and inorganic contaminants influence potential ammonium oxidation, whereas microbial respiration is predominantly affected by biodegradable organic contaminants. These differences might be useful for more detailed assessments of soil contamination, leading to different recommended actions depending on which parameter is affected.     

Total mercury concentrations in an industrialized catchment,the Thur River basin (north-eastern France): geochemical background level and contamination factors

River bottom sediments and soils were collected from the industrialized Thur River basin (north-eastern France) to assess mercury contamination. The regional geochemical background level of total mercury was evaluated to calculate mercury contamination factors (Fc) in soils and river bottom sediments. Our estimate of the mean background mercury levels in river sediments and soils, not affected by human activities, was 232 ng x g(-1) (range: 27-406 ng x g(-1)). Sediments contaminated by the effluent from a chlor-alkali plant yielded the highest contamination factors (Fc=1784). Contamination factors of surficial soils within 1 km of the industrial site range from 6.3 to 43.6. This contamination is attributed to diffuse atmospheric deposition from this local plant. However, even upstream from this industrial area elevated contamination factors were recorded for river bottom sediments (Fc=3.2 to 26.4) and for one alluvial soil profile (Fc=10). This is possibly due to past pollution resulting from waste water discharges. Mercury contamination in the different horizons of alluvial soils is not correlated with soil organic carbon content, but may be the result of occasional accidental pollution arising from the introduction of contaminated suspended particulate matter by the Thur River during periods of flooding.     

The organic contamination level based on the total soil mass is not a proper index of the soil contamination intensity

Concentrations of organic contaminants in common productive soils based on the total soil mass give a misleading account of actual contamination effects. This is attributed to the fact that productive soils are essentially water-saturated, with the result that the soil uptake of organic compounds occurs principally by partition into the soil organic matter (SOM). This report illustrates that the soil contamination intensity of a compound is governed by the concentration in the SOM (C_om) rather than by the concentration in whole soil (C_s). Supporting data consist of the measured levels and toxicities of many pesticides in soils of widely differing SOM contents and the related levels in in-situ crops that defy explanation by the C_s values. This SOM-based index is timely needed for evaluating the contamination effects of food crops grown in different soils and for establishing a dependable priority ranking for intended remediation of numerous contamination sites.     

Arsenic residue in residential area after cleanup of pesticide illegal dumping sources in Thanh Hoa province,Central Vietnam

In Vietnam, Nicotex's site is perhaps the most infamous case of illegal disposal of toxic pesticides near residential areas. In 2013, affected villagers discovered illegal burials of around 1,000 tons of expired pesticides in the Nicotex factory. Organic pesticides were detected in illegal burial areas (IBAs) around 60 times greater than acceptable levels, but no attention was paid to contamination of metals, metalloids, and other classes of organic contaminants, which could be co-contaminants in pesticide formulation. This study assessed the contaminants remaining in the IBAs and surrounding residential areas two years after the source removal conducted in 2014. Additionally, a preliminary health risk assessment from residual contaminants was performed. Nine classes of chemicals including parental pesticides, inorganic and organic degradation byproducts, and metals and metalloids, comprising 123 chemicals were quantified in soil, sediment, and water samples from Nicotex and surrounding residential areas. Although concentrations of organic pesticides were below acceptable levels, arsenic contamination in the soil in a Nicotex IBA named NCT5 and Nap village (NV) exceeded the acceptable level. The enrichment factor and log-probability plot indicate that arsenic enrichment at NV is not from natural sources but is associated with arsenic contamination in NCT5. Arsenic may be a co-contaminant in pesticide manufacturing or an arsenical pesticide, such as monosodium methanearsonate. Arsenic found in NV was toxic arsenate for which the preliminary risk assessment yielded an unacceptable excess carcinogenic risk (1 × 10^?4). While all attention was paid to investigate and treat contamination of organic pesticides, it turns out that arsenic is the major existing threat which poses an unacceptable cancer risk in good agreement with the high cancer rate claimed by villagers near Nicotex. This justifies the need for further investigation of the extent of the arsenic contamination and restoration of the contaminated land.     

Contribution of heavy metals and As-loaded lupin root mineralization to the availability of the pollutants in multi-contaminated soils

White lupin (Lupinus albus L.) is an annual crop that has been used for phytostabilization of acidified multi-contaminated soils. Once the culture cycle is over, after shoot harvesting, a progressive transference of contaminants from roots to soil may take place as decomposition of roots occurs. An incubation experiment with Cu, Zn, Cd, and As-loaded roots of white lupin and soils with different pH values and concentrations of these contaminants from the area affected by a mine spill at Aznalcóllar (near Seville, Spain) was performed in order to assess the effect of the decomposition of the roots to the pH and (NH4)2SO4-extractable levels of these pollutants in the soils. Pollutants loaded-roots were mineralized (56 d) at a ratio similar to animal manures (15.8-19.4% of total organic carbon) in soil. The estimated root inputs of contaminants in comparison to their extractable concentrations in soil were high, especially in the control, non-contaminated and neutral contaminated soils. However, the extractable concentrations of the toxic elements in the soil were mainly governed by soil pH. Hence, the correction and maintenance of the soil pH within the range 5-6 after lupin culture is essential for long-time phytostabilization of acidified multi-contaminated soils.     

Multivariate statistical and GIS-based approach to identify heavy metal sources in soils

The knowledge of the regional variability, the background values and the anthropic vs. natural origin for potentially harmful elements in soils is of critical importance to assess human impact and to fix guide values and quality standards. The present study was undertaken as a preliminary survey on soil contamination on a regional scale in Piemonte (NW Italy). The aims of the study were: (1) to determine average regional concentrations of some heavy metals (Cr, Co, Ni, Cu, Zn, Pb); (2) to find out their large-scale variability; (3) to define their natural or artificial origin; and (4) to identify possible non-point sources of contamination. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of three main factors controlling the heavy metal variability in cultivated soils. Geostatistics were used to construct regional distribution maps, to be compared with the geographical, geologic and land use regional database using GIS software. This approach, evidencing spatial relationships, proved very useful to the confirmation and refinement of geochemical interpretations of the statistical output. Cr, Co and Ni were associated with and controlled by parent rocks, whereas Cu together with Zn, and Pb alone were controlled by anthropic activities. The study indicates that background values and realistic mandatory guidelines are impossible to fix without an extensive data collection and without a correct geochemical interpretation of the data.     

Soil remediation: humic acids as natural surfactants in the washings of highly contaminated soils

The remediation of the highly contaminated site around the former chemical plant of ACNA (near Savona) in Northern Italy is a top priority in Italy. The aim of the present work was to contribute in finding innovative and environmental-friendly technology to remediate soils from the ACNA contaminated site. Two soils sampled from the ACNA site (A and B), differing in texture and amount and type of organic contaminants, were subjected to soil washings by comparing the removal efficiency of water, two synthetic surfactants, sodium dodecylsulphate (SDS) and Triton X-100 (TX100), and a solution of a natural surfactant, a humic acid (HA) at its critical micelle concentration (CMC). The extraction of pollutants by sonication and soxhlet was conducted before and after the soil washings. Soil A was richer in polycyclic aromatic hydrocarbons, whereas soil B had a larger content of thiophenes. Sonication resulted more analytically efficient in the fine-textured soil B. The coarse-textured soil A was extracted with a general equal efficiency also by soxhlet. Clean-up by water was unable to exhaustively remove contaminants from the two soils, whereas all the organic surfactants revealed very similar efficiencies (up to 90%) in the removal of the contaminants from the soils. Hence, the use of solutions of natural HAs appears as a better choice for soil washings of highly polluted soils due to their additional capacity to promote microbial activity, in contrast to synthetic surfactants, for a further natural attenuation in washed soils.     

Chemical and mineralogical forms of Cu and Ni in contaminated soils from the Sudbury mining and smelting region, Canada

Available information on soil contamination by trace elements in the Sudbury Cu/Ni mining and smelting region consists largely of total elemental concentration data. Little is known about the mode of occurrence and behaviour of Cu and Ni (the main metallic contaminants) in the soils of the region. In this study, sequential extraction and Scanning Electron Microscopy and Energy Dispersive X-ray Analysis (SEM/EDX) observations were complementarily used to define Cu and Ni forms in the Sudbury soils, so as to assess metal mobility. Most Cu (on average 75%) was associated with 'non-residual' soil forms, whereas Ni was mainly (on average 60%) associated with inorganic 'residual' forms of a sulphide and oxide nature. Therefore, Cu occurs in the soils in more mobile forms than Ni. Consequently, Cu should be removed from these soils at a faster rate than Ni. This is an unusual finding, because generally Ni is known to be more mobile in soils than Cu. SEM/EDX analysis confirmed the greater Cu mobility by showing that the metal was strongly associated with organic matter and was homogeneously distributed on the clay fraction surfaces. Nickel occurred alone or was associated with Fe oxides in various size fractions. Both elements were found as sulphides but Ni was often included in the silicate matrices of spherical particles in associations with Fe. SEM/EDX observations have shown that Cu and Ni are associated with soil forms which would not have been predicted by the sequential extraction alone, such as carbonaceous material, silicate spheres and carbonate particles, supporting complementary use of the two techniques.     

Electrokinetic remediation of organochlorines in soil: enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.     

Contaminant-induced irreversible changes in properties of the soil-vadose-aquifer zone: an overview

Most studies on contaminant interactions with the subsurface environment focus on contaminant transport, retention and persistence, and on potential remediation of polluted soils, vadose zones and aquifers. Changes in the soil-vadose-aquifer zone (SVAZ) matrix and properties, caused by human activities, are thus usually considered to be deviations from a normal geochemical environment, which will disappear by natural processes or by specific remediation procedures. However, contaminants may also cause, under specific conditions, irreversible changes in SVAZ properties. In this critical overview, we discuss a different aspect of contaminant-SVAZ interactions: irreversible changes in natural SVAZ properties as a result of anthropogenically-induced chemical contamination. We survey selected research results that illustrate various aspects of such phenomena, in soils, aquifers and the vadose zone. Grouping contaminants according to major and trace elements, we observe that major elements can irreversibly affect water transmission and other physical and chemical properties of the SVAZ, mainly in the liquid phase, while trace elements affect mostly the solid phase matrix.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Assessment of Human and Ecosystem Risk Due to Agricultural Waste Compost Application on Soils: A Review

Agricultural wastes (AW) are often characterized by varying pH and substantial contamination potential, which are mainly related to their high organic load, thus affecting—when improperly disposed of—soils, living organisms, and water bodies. Composting of AW is the most commonly used management option and results in the production of soil improver that enhances crop growth and contributes to agricultural sustainability. This study aims to present the framework for assessing human and ecosystem risk when compost produced from AW is applied on soil. In order to develop this framework, issues such as origin, composition and pre-treatment of AW, application rates on soils, bioavailability and mobility of contaminants present in compost, exposure routes and rates as well as determination of the fate of contaminants in soil, air, and water, should be taken into consideration.     

Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy

The concentration trends and chemical fractionation of Pb was studied in eight tilled and forest soil profiles heavily polluted by Pb metallurgy in the Pribram district, Czech Republic. The highest Pb concentrations were observed in surface and subsurface horizons attaining 35,300 mg kg-1 in forest soils and 1233 mg kg-1 in tilled soils. Total Pb concentrations were one order of magnitude lower in tilled soil due to intensive ploughing and annual crop off-take. The results of the Tessier sequential extraction procedure showed the preferential binding of Pb in forest soils to operationally-defined exchangeable positions and soil organic matter (oxidisable fraction). The Pb exchangeable fraction is thought to correspond to weak electrostatic binding on the functional groups of organic matter. In tilled soil, Pb is predominantly bound to operationally-defined Fe and Mn oxides (reducible fraction). A comparison with the background Pb concentration values showed a strong contamination even in mineral horizons IIC and confirmed a strong vertical mobility of Pb within the soil profiles. The calculated mobility factors (MF) showed that up to 72% of Pb is mobile and bioavailable in forest soils. In contrast, the bioavailability of Pb in tilled soils was significantly lower as the MF accounted for up to 30%. In the most polluted horizon of forest soil profile, the X-ray powder diffraction (XRPD) analysis confirmed the presence of anglesite (PbSO4), derived likely from the smelter emissions.     

Occurrence of Eleven Metals in Airborne Participates and in Surficial Materials

The amounts of eleven metals in urban airborne particulate matter samples collected in the United States from 1965 to 1974 (urban and nonurban) are described in two frames of reference: 1) concentration per unit volume of air; and 2) relative abundance in the collected particulate matter compared with surficial materials (subsurface soils) of the continental U. S. If it may be assumed that airborne particulates of solely natural origin would contain these metals in proportions similar to those in uncontaminated subsurface soils, then instances of metals whose proportions in actual particulate samples exceed soil sample proportions may reasonably be ascribed to the influence of human activity. Lead and, tentatively, cadmium exhibit general and significant enrichment in airborne particulate matter above their natural abundances in U. S. soils. Vanadium exhibits enrichment primarily in the northeastern U. S. The enrichment of copper has been traced to contamination from the sampler's own motor. Beryllium, chromium, cobalt, iron, manganese, nickel, and titanium appear to occur in airborne particulates in proportions comparable with those to be expected in natural aeolian dusts.     

Assessing anthropogenic sources of mercury in soil in Wanshan Hg mining area, Guizhou, China

Long-term mining and smelting activities brought a series of environmental issues into soils in Wanshan mercury (Hg) mining area (WMMA), Guizhou, China. Several studies have been published on the concentrations of Hg in local soils, but a comprehensive assessment of the mass of Hg in soil induced by anthropogenic activities, as presented in this paper, has not been previously conducted. Three districts of WMMA were chosen as the study areas. We summarized previous published data and sampled 14 typical soil profiles to analyze the spatial and vertical distributions of Hg in soil in the study areas. The regional geologic background, direct and indirect Hg deposition, and Hg-polluted irrigation water were considered as the main sources of Hg contaminations in local soils. Furthermore, the enrichment factor (EF) method was applied to assess the extent of anthropogenic input of Hg to soil. Titanium (Ti) was chosen to be the reference element to calculate the EF. Generally, the elevated values of EF were observed in the upper soil layers and close to mine wastes. The total budget of Hg in soil contributed from anthropogenic sources was estimated to be 1,227 t in arable soil and 75 t in natural soil. Our data showed that arable soil was the major sink of anthropogenic Hg in the study area.     

A comparison of indigenous mosses and topsoils for use in monitoring atmospheric heavy metal deposition in Galicia (northwest Spain)

Samples of moss (Scleropodium purum or, in its absence, Hypnum cupressiforme) and of topsoil (0-5 cm) were collected in the spring of 1995, from 75 sites distributed throughout Galicia (northwest Spain) in order to compare the potential usefulness of each in evaluating the atmospheric deposition of contaminants. Analysis was made of the total content of various metals in the moss and of different soil metal fractions (including total metal content, labile metals and metals bound to organic material). We found that the labile fraction most closely resembled the metal content of the moss. Calculation of enrichment factors allowed us to show that the soil was not, except in the case of Cr, the main source of contamination in the moss. By comparing contamination factors of metals in moss and soil fraction samples we found that moss samples were more useful for evaluating the degree of contamination at different sites.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Impact of river overflowing on trace element contamination of volcanic soils in south Italy: part I. Trace element speciation in relation to soil properties

Volcanic soils affected by different numbers of polluted river flooding events were investigated. Chromium and Cu were the major soil contaminants. Nickel, Fe, Zn and Mn total content never exceeded the Italian mandatory limits. The distribution of Cr and Cu total contents among studied soils indicated that only Cr contamination was related to overflowing events. In polluted soils, sequential chemical extractions revealed a preferential association of Cr and Cu with organic forms. A progressive Cr insolubilization with ageing was observed. Significant amounts of Cr and Cu were extracted by NH(4)-oxalate, suggesting metals association with short-range-order aluminosilicates and organo-mineral complexes. Possible methodological drawbacks in the use of the EU-BCR chemical speciation protocol on volcanic soils are discussed. Micromorphology and SEM/WDS analyses revealed Cr and Cu enriched silt and clay coatings in surface and subsurface soil horizons, suggesting a transfer of metal-rich sediments along the soil pore network with water movement.     

Combining a finite mixture distribution model with indicator kriging to delineate and map the spatial patterns of soil heavy metal pollution in Chunghua County, central Taiwan

This study identifies the natural background, anthropogenic background and distribution of contamination caused by heavy metal pollutants in soil in Chunghua County of central Taiwan by using a finite mixture distribution model (FMDM). The probabilities of contaminated area distribution are mapped using single-variable indicator kriging and multiple-variable indicator kriging (MVIK) with the FMDM cut-off values and regulation thresholds for heavy metals. FMDM results indicate that Cr, Cu, Ni and Zn can be individually fitted by a mixture model representing the background and contamination distributions of the four metals in soil. The FMDM cut-off values for contamination caused by the metals are close to the regulation thresholds, except for the cut-off value of Zn. The receiver operating characteristic (ROC) curve validates that indicator kriging and MVIK with FMDM cut-off values can reliably delineate heavy metals contamination, particularly for areas lacking background information and high heavy metal concentrations in soil.