Petroleum contaminated soil in Oman: Evaluation of bioremediation treatment and potential for reuse in hot asphalt mix concrete

This paper presents a study that aims at evaluating the leaching characteristics of petroleum contaminated soils as well as their application in hot mix asphalt concrete. Soil samples are environmentally characterized in terms of their total heavy metals and hydrocarbon compounds and leachability. The total petroleum hydrocarbon (TPH) present in the PCS before and after treatment was determined to be 6.8% and 5.3% by dry weight, indicating a reduction of 1% in the TPH of PCS due to the current treatment employed. Results of the total heavy metal analysis on soils indicate that the concentrations of heavy metals are lower when extraction of the soil samples is carried out using hexane in comparison to TCE. The results show that the clean soils present in the vicinity of contaminated sites contain heavy metals in the following decreasing order: nickel (Ni), followed by chromium (Cr), zinc (Zn), copper (Cu), lead (Pb), and vanadium (V). The current treatment practice employed for remediation of the contaminated soil reduces the concentrations of nickel and chromium, but increases the concentrations of all remaining heavy metals.     

Effects of lead and zinc mining contamination on bacterial community diversity and enzyme activities of vicinal cropland

In the process of mining activity, many kinds of heavy metals enter into soils with dust, causing serious contamination to the environment. In this study, six soils were sampled from cropland at different distances from a lead/zinc mine in Heilongjiang Province, China. The total contents of lead and zinc in the vicinal cropland exceeded the third level of environmental quality standard for soil in China, which indicated that soils in this area were moderately contaminated. Bacterial community diversity and population were greatly decreased when the concentrations of lead and zinc were beyond 1,500 and 995 mg kg(-1), respectively, as analyzed by plate counting and polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). The bands of DGGE patterns varied with the degree of contamination. The activities of soil urease, phosphatase, and dehydrogenase were negatively correlated with the concentrations of lead and zinc. The highest inhibitory effect of heavy metals on soil enzyme activities was observed in urease. It was noted that PCR-DGGE patterns combined with soil enzyme activity analysis can be indices for the soil quality assessment by heavy metal contamination.     

Copper and Zinc in a paddy field and their potential ecological impacts affected by wastewater from a lead/zinc mine, P. R. China

As well known, at normal levels, copper and zinc are essential micronutrients for plants, animals, and humans. However, excessive Cu and Zn are toxic and disturb a wide range of biochemical and physiological processes. Using Atomic Absorption Spectrophotometer (AAS; Perkin-Elmer 3030, USA), soil and rice plant (Oryza sativa L.) samples collected from a paddy field in Lechang lead-zinc mine area, Guangdong Province, China were analyzed and their potential ecological impacts to local human and livestock were evaluated. The results showed that the paddy soils were contaminated with Cu and Zn. Both metals in soils had low bio-available fractions for paddy plants, animal and human by three chemically analytical techniques. Generally, were concentrations of copper and zinc root > straw > stalk > grain with hull > grain without hull (i.e. unpolished rice) and in the normal ranges indicating no ecological risk for local livestock and residents. All positive correlation coefficients, however, between heavy metals in rice plant and total, exchangeable (step 1 in Tessier's method established in 1979) and DTPA-extractable fractions in soils were found in this study indicating that elevated heavy metal in soils would increase long-term exposition and possible consequence of ecological hazard through food chains.     

Total concentrations and speciation of heavy metals in soils of the Shenyang Zhangshi Irrigation Area, China

The Shenyang Zhangshi Irrigation Area (SZIA) was used for the spreading of municipal and industrial waste water, which is an economic way of irrigating crops, recycling nutrients and water treatment. Long-term irrigation resulted in a severe metal contamination of soils. To identify the soil phases implicated in retaining the metals, sequential extractions were performed. The most predominant metal was cadmium which was mainly associated with mobile, easily soluble and easily reducible fractions. Copper was mainly associated with the residual, EDTA extractable and moderately reducible fractions. Lead was bound to organic matter and poorly crystalline Fe-oxides. Nickel and zinc were mainly associated with the residual and strongly reducible fractions. Although copper, lead, nickel and zinc concentrations were of minor importance mobile metal concentrations of these metals as well as of cadmium exceeded German trigger values for plant production and plant growth.     

Environmental risk assessment of heavy metal extractability in a biosludge from the biological wastewater treatment plant of a pulp and paper mill

A five-stage sequential extraction procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V and Ba) in a biosludge from the biological wastewater treatment plant of Stora Enso Oyj Veitsiluoto Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction, (2) exchangeable fraction, (3) easily reduced fraction, (4) oxidizable fraction, and (5) residual fraction. The biosludge investigated in this study is a combination of sludge from the primary and secondary clarifiers at the biological wastewater treatment plant. Extraction stages (2)–(4) follow the protocol proposed by the Measurements and Testing Program (formerly BCR Programme) of the European Commission, which is based on acetic acid extraction (stage 2), hydroxylamine hydrochloride extraction (stage 3), and hydrogen peroxide digestion following the ammonium acetate extraction (stage 4). The residual fraction (stage 5) was based on digestion of the residue from stage 4 in a mixture of HF + HNO₃ + HCl. Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, it was notable that the total heavy metal concentrations in the biosludge did not exceed the maximal allowable heavy metal concentrations for sewage sludge used in agriculture, set on the basis of environmental protection of soil by European Union Directive 86/278/EEC, and by the Finnish legislation. The Ca (98.6 g kg⁻¹; dry weight) and Mg (2.2 g kg⁻¹; dry weight) concentrations in the biosludge were 62 and 11 times higher than the typical values of 1.6 and of 0.2 g kg⁻¹ (dry weight), respectively, in arable land in Central Finland. The biosludge had a slightly alkaline pH (∼8.30), a high loss-on-ignition value (∼78%) and a liming effect of 10.3% expressed as Ca equivalents (dry weight). This indicates its potential as a soil conditioner and improvement agent, as well as a pH buffer.     

Heavy metal risk assessment for potatoes grown in overused phosphate-fertilized soils

The long-term application of phosphate fertilizers on vegetable production fields has raised concerns about the potential health risks of heavy metal contamination of crops grown on contaminated soils in the Hamadan province, western Iran. This study found that long-term fertilizer use led to a growing accumulation of heavy metals in soils. High concentrations of elemental As, Cd, Cr, Cu, Pb, and Zn were found in potatoes sampled from overused phosphate-fertilized soils, which increased the daily intake of metals in food. However, the ingestion of potatoes from soils affected by phosphate fertilizers posed a low health risk when compared with the health risk index of <1 for heavy metals. Nevertheless, heavy metal concentrations should be periodically monitored in vegetables grown in these soils. It would also be beneficial to implement effective remediation technologies to minimize possible impacts on human health.     

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or soil type. In most cases an increase in more mobile forms of metals in soils was observed as the final effect.     

Use of zeolite to neutralise nickel in a soil environment

Nickel is a heavy metal which is a stable soil pollutant which is difficult to remediate. An attempt to reduce its impact on the environment can be made by changing its solubility. The right level of hydrogen ions and the content of mineral and organic colloids are crucial in this regard. Therefore, methods to neutralise heavy metals in soil are sought. There are no reports in the literature on the possibility of using minerals in the detoxication of a soil environment contaminated with metals. It is important to fill the gap in research on the effect of zeolites on the microbiological, biochemical and physicochemical properties of soils under pressure from heavy metals. Therefore, a pot experiment was conducted on two soils which examined the effect of various levels of contamination of soil with nickel on the activity of soil enzymes, physical and chemical properties and growth and development of plants. An alleviating effect of zeolite Bio.Zeo.S.01 on the negative impact of nickel on the soil and a plant (oats) was examined. The enzyme activity and the oat yield were found to be significantly and negatively affected by an excess of nickel in the soil, regardless of the soil type. The metal was accumulated more in the oat roots than in the above-ground parts. An addition of zeolite decreased the level of accumulation of nickel in oats grown only on sandy-silty loam. Zeolite Bio.Zeo.S.01 used in the study only slightly alleviated the negative effect of nickel on the biochemical properties of soil. Therefore, its usability in the remediation of soil contaminated with nickel is small.     

Restoration of fly ash dump through biological interventions

Field experiment on 10 ha area of fly ash dump was conducted to restore and revegetate it using biological interventions, which involves use of organic amendment, selection of suitable plant species along with specialized nitrogen fixing strains of biofertilizer. The results of the study indicated that amendment with farm yard manure at 50 t/ha improved the physical properties of fly ash such as maximum water holding capacity from 40.0 to 62.42% while porosity improved from 56.78 to 58.45%. The nitrogen content was increased by 4.5 times due to addition of nitrogen fixing strains of Bradyrhizobium and Azotobacter species, while phosphate content was increased by 10.0 times due to addition of VAM, which helps in phosphate immobilization. Due to biofertilizer inoculation different microbial groups such as Rhizobium, Azotobacter and VAM spores, which were practically absent in fly ash improved to 7.1 × 10⁷, 9.2 × 10⁷ CFU/g and 35 VAM spores/10 g of fly ash, respectively. Inoculation of biofertilizer and application of FYM helped in reducing the toxicity of heavy metals such as cadmium, copper, nickel and lead which were reduced by 25, 46, 48 and 47%, respectively, due to the increased organic matter content in the fly ash which complexes the heavy metals thereby decreasing the toxicity of metals. Amendment of fly ash with FYM and biofertilizer helped in profuse root development showing 15 times higher growth in Dendrocalamus strictus plant as compared to the control. Thus amendment and biofertilizer application provided better supportive material for anchorage and growth of the plant.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

Impact of overland traffic on heavy metal levels in highway dust and soils of Istanbul, Turkey

The purpose of this study was to investigate the impact of overland traffic on the spatial distribution of heavy metals in urban soils (Istanbul, Turkey). Road dust, surface, and subsurface soil samples were collected from a total of 41 locations along highways with dense traffic and secondary roads with lower traffic and analyzed for lead (Pb), zinc (Zn), and copper (Cu) concentrations. Statistical evaluation of the heavy metal concentrations observed along highways and along the secondary roads showed that the data were bimodally distributed. The maximum observed Pb, Zn, and Cu concentrations were 1,573, 522 and 136 mg/kg, respectively, in surface soils along highways and 99.3, 156, and 38.1 mg/kg along secondary roads. Correlation analysis of the metal concentrations in road dust, surface and 20-cm depth soils suggests the presence of a common pollution source. However, metal concentrations in the deeper soils were substantially lower than those observed at the surface, indicating low mobility of heavy metals, especially for Pb and Zn. A modified kriging approach that honors the bimodality of the data was used to estimate the spatial distribution of the surface concentrations of metals, and to identify hotspots. Results indicate that despite the presence of some industrial zones within the study area, traffic is the main heavy metal pollution source.     

Impacts of epigeic, anecic and endogeic earthworms on metal and metalloid mobility and availability

The introduction of earthworms into soils contaminated with metals and metalloids has been suggested to aid restoration practices. Eisenia veneta (epigeic), Lumbricus terrestris (anecic) and Allolobophora chlorotica (endogeic) earthworms were cultivated in columns containing 900 g soil with 1130, 345, 113 and 131 mg kg(-1) of As, Cu, Pb and Zn, respectively, for up to 112 days, in parallel with earthworm-free columns. Leachate was produced by pouring water on the soil surface to saturate the soil and generate downflow. Ryegrass was grown on the top of columns to assess metal uptake into biota. Different ecological groups affected metals in the same way by increasing concentrations and free ion activities in leachate, but anecic L. terrestris had the greatest effect by increasing leachate concentrations of As by 267%, Cu by 393%, Pb by 190%, and Zn by 429% compared to earthworm-free columns. Ryegrass grown in earthworm-bearing soil accumulated more metal and the soil microbial community exhibited greater stress. Results are consistent with earthworm enhanced degradation of organic matter leading to release of organically bound elements. The degradation of organic matter also releases organic acids which decrease the soil pH. The earthworms do not appear to carry out a unique process, but increase the rate of a process that is already occurring. The impact of earthworms on metal mobility and availability should therefore be considered when inoculating earthworms into contaminated soils as new pathways to receptors may be created or the flow of metals and metalloids to receptors may be elevated.     

Heavy metal contamination in a vulnerable mangrove swamp in South China

Concentrations of six heavy metals (Cu, Ni, Zn, Cd, Cr, and Pb) in sediments and fine roots, thick roots, branches, and leaves of six mangrove plant species collected from the Futian mangrove forest, South China were measured. The results show that both the sediments and plants in Futian mangrove ecosystem are moderately contaminated by heavy metals, with the main contaminants being Zn and Cu. All investigated metals showed very similar distribution patterns in the sediments, implying that they had the same anthropogenic source(s). High accumulations of the heavy metals were observed in the root tissues, especially the fine roots, and much lower concentrations in the other organs. This indicates that the roots strongly immobilize the heavy metals and (hence) that mangrove plants possess mechanisms that limit the upward transport of heavy metals and exclude them from sensitive tissues. The growth performance of propagules and 6-month-old seedlings of Bruguiera gymnorhiza in the presence of contaminating Cu and Cd was also examined. The results show that this plant is not sufficiently sensitive to heavy metals after its propagule stage for its regeneration and growth to be significantly affected by heavy metal contamination in the Futian mangrove ecosystem. However, older mangrove seedlings appeared to be more metal-tolerant than the younger seedlings due to their more efficient exclusion mechanism. Thus, the effects of metal contamination on young seedlings should be assessed when evaluating the risks posed by heavy metals in an ecosystem.     

Variability in concentrations of potentially toxic elements in urban parks from six European cities

Use of a harmonised sampling regime has allowed comparison of concentrations of copper, chromium, nickel, lead and zinc in six urban parks located in different European cities differing markedly in their climate and industrial history. Wide concentrations ranges were found for copper, lead and zinc at most sites, but for chromium and nickel a wide range was only seen in the Italian park, where levels were also considerably greater than in other soils. As might be expected, the soils from older cities with a legacy of heavy manufacturing industry (Glasgow, Torino) were richest in potentially toxic elements (PTEs); soils from Ljubljana, Sevilla and Uppsala had intermediate metal contents, and soils from the most recently established park, in the least industrialised city (Aveiro), displayed lowest concentrations. When principal component analysis was applied to the data, associations were revealed between pH and organic carbon content; and between all five PTEs. When pH and organic carbon content were excluded from the PCA, a distinction became clear between copper, lead and zinc (the "urban" metals) on the one hand, and chromium and nickel on the other. Similar results were obtained for the surface (0-10 cm depth) and sub-surface (10-20 cm depth) samples. Comparisons with target or limit concentrations were limited by the existence of different legislation in different countries and the fact that few guidelines deal specifically with public-access urban soils intended for recreational use.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Heavy metal phytoextraction—natural and EDTA-assisted remediation of contaminated calcareous soils by sorghum and oat

The abilities of sorghum (Sorghum bicolor L.) and oat (Avena sativa L.) to take up heavy metals from soils amended with ethylenediaminetetraacetic acid (EDTA) were assessed under greenhouse conditions. Both plants were grown in two soils contaminated with heavy metals (Gujranwala—silty loam and Pacca—clay loam). The soils were treated with 0, 0.625, 1.25, and 2.5 mM EDTA kg^?1 soil applied at both 45 and 60 days after sowing (DAS); the experiment was terminated at 75 DAS. Addition of EDTA significantly increased concentrations of Cd, Cr, and Pb in roots and shoots, and bio-concentration factors and phytoextraction rates were also increased. Post-harvest soil analysis showed that soluble fractions of metals were also increased significantly. The increase in Cd was ≈ 3-fold and Pb was ≈ 15-fold at the highest addition of EDTA in Gujranwala soil; in the Pacca soil, the increase was less. Similarly, other phytoremediation factors, such as metal translocation, bio-concentration factor, and phytoextraction, efficiency were also maximum when soils were treated with 2.5 mM EDTA kg^?1 soil. The study demonstrated that sorghum was better than oat for phytoremediation.     

Distribution of heavy metals in agricultural soils near a petrochemical complex in Guangzhou, China

The aim of the study was to investigate influence of an industrialized environment on the accumulation of heavy metals in agricultural soils. Seventy soil samples collected from surface layers (0-20 cm) and horizons of five selected pedons in the vicinity area of petrochemical complex in Guangzhou, China were analyzed for Zn, Cu, Pb, Cd, Hg and As concentrations, the horizontal and vertical variation of these metals were studied and geographic information system (GIS)-based mapping techniques were applied to generate spatial distribution maps. The mean concentrations of these heavy metals in the topsoils did not exceed the maximum allowable concentrations in agricultural soil of China with the exception of Hg. Significant differences between land-use types showed that Cu, Pb, Cd, Hg and As concentrations in topsoils were strongly influenced by agricultural practices and soil management. Within a radius of 1,300 m there were no marked decreasing trends for these element concentrations (except for Zn) with the increase of distance from the complex boundary, which reflected little influence of petroleum air emission on soil heavy metal accumulation. Concentrations of Zn, Cu, Pb, Cd, Hg and As in the five pedons, particularly in cultivated vegetable field and orchard, decreased with soil depth, indicating these elements mainly originated from anthropogenic sources. GIS mapping was a useful tool for evaluating spatial variability of heavy metals in the affected soil. The spatial distribution maps allowed the identification of hot-spot areas with high metal concentration. Effective measures should be taken to avoid or minimize heavy metal further contamination of soils and to remediate the contaminated areas in order to prevent pollutants affecting human health through agricultural products.     

Effect of fertilizer application on soil heavy metal concentration

A large amount of chemicals is annually applied at the agricultural soils as fertilizers and pesticides. Such applications may result in the increase of heavy metals particularly Cd, Pb, and As. The objective of this study was to investigate the variability of chemical applications on Cd, Pb, and As concentrations of wheat-cultivated soils. Consequently, a study area was designed and was divided into four subareas (A, B, C, and D). The soil sampling was carried out in 40 points of cultivated durum wheat during the 2006–2007 periods. The samples were taken to the laboratory to measure their heavy metal concentration, soil texture, pH, electrical conductivity, cationic exchange capacity, organic matter, and carbonate contents. The result indicated that Cd, Pb, and As concentrations were increased in the cultivated soils due to fertilizer application. Although the statistical analysis indicates that these heavy metals increased significantly (P value < 0.05), the lead and arsenic concentrations were increased dramatically compared to Cd concentration. This can be related to overapplication of fertilizers as well as the pesticides that are used to replant plant pests, herbs, and rats.     

Characterization and validation of a Portuguese natural reference soil to be used as substrate for ecotoxicological purposes

This study describes the first attempt to validate a Portuguese natural soil (PTRS1) to be used as reference soil for ecotoxicological purposes, aimed to both: (i) obtain ecotoxicological data for the derivation of Soil Screening Values (SSVs) with regional relevance, acting as a substrate to be spiked with ranges of concentrations of the chemicals under evaluation and (ii) act as control and as substrate for the dilution of contaminated soils in ecotoxicological assays performed to evaluate the ecotoxicity of contaminated soils, in tier 2 of risk assessment frameworks, applied to contaminated lands. The PTRS1 is a cambisol from a granitic area integrated in the Central Iberian Zone. After chemical characterization of the soil in terms of pseudo-total metals, PAHs, PCBs and pesticide contents, it was possible to perceive that some metals (Ba, Be, Co, Cr and V) surpass the Dutch Target Values (Dtvs) corrected for the percentage of organic matter and clay of the PTRS1. Nevertheless, these metals displayed total concentrations below the background total concentrations described for Portuguese soils in general. The same was observed for aldrin, endosulfan I, endosulfan II, heptachlor epoxide, and heptachlor; however the Dtvs corrected become negligible. The performance of invertebrate and plant species, commonly used in standard ecotoxicological assays, was not compromised by both soil properties and soil metal contents. The results obtained suggest that the PTRS1 can be used as a natural reference soil in ecotoxicological assays carried out under the scope of ecological risk assessment.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.