Remediation of contaminated agricultural soils near a former Pb/Zn smelter in Austria: batch, pot and field experiments

Metal contaminated crops from contaminated soils are possible hazards for the food chain. The aim of this study was to find practical and cost-effective measures to reduce metal uptake in crops grown on metal contaminated soils near a former metal smelter in Austria. Metal-inefficient cultivars of crop plants commonly grown in the area were investigated in combination with in-situ soil amendments. A laboratory batch experiment using 15 potential amendments was used to select 5 amendments to treat contaminated soil in a pot study using two Barley (Hordeum vulgare L.) cultivars that differed in their ability to accumulate cadmium. Results from this experiment identified 3 of these amendments for use in a field trial. In the pot experiment a reduction in ammonium nitrate extractable Cd (<41%) and Pb (<49%) compared to the controls was measured, with a concurrent reduction of uptake into barley grain (Cd<62%, Pb<68%). In the field extractable fractions of Cd, Pb, and Zn were reduced by up to 96%, 99%, and 99%, respectively in amended soils.     

Assessment of trace metal distribution and contamination in surface soils of Hong Kong

An intensive investigation was conducted to study the distribution of trace metals in surface soils of Hong Kong and to assess the soil environmental quality. From results of cluster analysis, and comparisons among soil types and areas, it is clearly shown that increases in trace metal concentrations in the soils were generally extensive and obvious in urban and orchard soils, less so in vegetable soils, whilst rural and forest soils were subjected to the least impact of anthropogenic sources of trace metals. However, some of the forest soils also contained elevated levels of As, Cu, and Pb. Urban soils in Hong Kong were heavily polluted by Pb from gasoline combustion. Agricultural soils, both orchard and vegetable soils, usually accumulated As, Cd, Cu, and Zn originating from applications of pesticides, animal manures, and fertilizers. In general, trace metal pollution in soils of the industrial areas and Pb pollution in the soils of the commercial and residential areas were obvious.     

Airborne Pb,Cd, Zn and Cu concentration by particle size near a Pb smelter

A study of airborne Pb, Cd, Zn and Cu was conducted on 2 farms: a test farm exposed to a lead smelter and associated sources of lead contamination in the New Lead Belt of southeast Missouri, and a control farm outside the lead production area. An Andersen eight-stage impactor sampler was used on both farms to collect air samples during winter, spring and summer seasons. The trace element concentrations were measured by atomic absorption spectrophotometry. The concentrations of all four elements were higher on the test farm than on the control farm in all of the three seasons. Approximately 66% of the Pb. 88% of the Cd. 73% of the Zn and 54% of the Cu was composed of particles smaller than 4.7 μm the upper practical limit of respirable size.     

Vertical distribution of Cd, Pb and Zn in soils near smelters in the North of France

The analysis of the horizons of 12 soil profiles confirm occasionally significant levels of Cd, Pb and Zn contamination in the areas surrounding two lead and zinc smelters in the North of France. A pedological approach enabled the original Cd, Pb and Zn content of the horizons to be estimated, based on physico-chemical characteristics of soil unaffected by contamination. The main contamination was found in the upper 20-30 cm. Traces of Cd and Zn contamination were found at a depth of around 2 m. The mobility of the metals may be classified in the following order: Cd>Pb> or =Zn. The concentration profile of a metal seems insufficient to evaluate its movement as the metal could have been leached beyond the contaminated horizons. The depth reached by the metals increases with their concentration in the surface horizon; a decrease in pH and an increase in sand content seem to facilitate their movement. The depth reached by Zn increases with the organic carbon content in the surface horizon. Earthworm galleries act as paths via which metals migrate downwards     

Growth and trace metal accumulation of two Salix clones on sediment-derived soils with increasing contamination levels

The growth and metal uptake of two willow clones (Salix fragilis 'Belgisch Rood' and Salix viminalis 'Aage') was evaluated in a greenhouse pot experiment with six sediment-derived soils with increasing field Cd levels (0.9-41.4 mg kg-1). Metal concentrations of eight elements were measured in roots, stems and leaves and correlated to total and soil water metal concentrations. Dry weight root biomass, number of leaves and shoot length were measured to identify eventual negative responses of the trees. No growth inhibition was observed for both clones for any of the treatments (max. 41.4 mg kg-1 Cd, 1914 mg kg-1 Cr, 2422 mg kg-1 Zn, 655 mg kg-1 Pb), allowing their use for phytoextraction on a broad range of contaminated sediments. However, dry weight root biomass and total shoot length were significantly lower for S. viminalis compared to S. fragilis for all treatments. Willow foliar Cd concentrations were strongly correlated with soil and soil water Cd concentrations. Both clones exhibited high accumulation levels of Cd and Zn in aboveground plant parts, making them suitable subjects for phytoextraction research. Cu, Cr, Pb, Fe, Mn and Ni were found mainly in the roots. Bioconcentration factors of Cd and Zn in the leaves were highest for the treatments with the lowest soil Cd and Zn concentration.     

Modelling trace metal partitioning in forest floors of northern soils near metal smelters

Trace metal (TM) mobility and toxicity varies with changing soil conditions. Geochemical models can account for the influence of soil characteristics on TM behaviour. We tested the effectiveness of the Stockholm humic model (SHM), and the NICA-Donnan model (NDM) to estimate partitioning coefficients (logKd) in 26 forest floor horizons of podzolic soils enriched in trace metals from deposition by metal smelters. We wanted to know if a consistent approach could be applied to model metal partitioning in forest floors without optimizing each individual soil. When optimized, the SHM reproduced the partitioning of Cd, Cu and Zn but not Pb. It was necessary to revise the affinity constants for the NDM to simultaneously simulate the partitioning of the four metals. Revised affinity constants for the NDM model based on a fixed definition of soil organic carbon, i.e., a fixed ratio of fulvic and humic acids per unit carbon, reproduced metal partitioning more effectively in an independent data set of 16 soils than the use of generic affinity constants available for these models. From the perspective of the applicability of these models to risk assessment, this result suggests geochemical models using affinity constants that have been verified and/or modified against multiple soils from a region can provide good estimates of metal partitioning on a regional scale.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.     

Potentially toxic metal contamination of urban soils and roadside dust in Shanghai, China

A detailed investigation was conducted to understand the contamination characteristics of a selected set of potentially toxic metals in Shanghai. The amount of Pb, Zn, Cu, Cr, Cd and Ni were determined from 273 soil/dust samples collected within urban area. The results indicated that concentration of all metals except Ni in soils was significant, and metal pollution was even severer in roadside dust. A series of metal spatial distribution maps were created through geostatistical analysis, and the pollution hotspots tended to associate with city core area, major road junctions, and the regions close to industrial zones. In attempt of identifying the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Pb, Zn and Cu mainly originated from traffic contaminants; soil Ni was associated with natural concentration; Cd largely came from point-sourced industrial pollution; and Cr, Ni in dust were mainly related to atmospheric deposition.     

Simultaneous immobilization of metals and arsenic in acidic polluted soils near a copper smelter in central Chile

Introduction  

Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined.     

Human PCDD/PCDF levels near a pentachlorophenol contamination site in Tainan, Taiwan

A pentachlorophenol (PCP) manufacturing plant in southern Taiwan discontinued production in 1989. The site of the abandoned plant was heavily contaminated by PCDD/PCDFs, impurities formed in the PCP production process. Serum samples collected from 27 residents living near the deserted plant were evaluated to determine whether this contamination had associated serum levels of PCDD/PCDFs in local residents. The average level of 17 tested congeners ranged from 556 to 5240 pg/g lipid (mean, 1670 pg/g lipid). The corresponding 2,3,7,8-TCDD toxicity equivalent quotient values calculated by international toxicity equivalent factors (I-TEFs) and those recommended by WHO (WHO-TEFs) were 47.2 pg I-TEQ/g lipid and 53.4 pg WHO-TEQ/g lipid, respectively. Levels in other parts of Taiwan typically range from 15 to 20 pg WHO-TEQ/g lipid; therefore, it is likely that the heavily contaminated plant site caused these unusually high serum levels. The average PCDD/PCDF levels of 29 fish-tissue and nine soil samples collected from the sea reservoir surrounding the abandoned PCP plant were also abnormally high: 8630 pg/g lipid (985 pg WHO-TEQ/g lipid) and 606000 pg/g-sample (922 pg WHO-TEQ/g-sample), respectively. Factor analysis indicated that the congener pattern of human serum samples collected from residents living near the abandoned PCP plant different from samples collected from other areas in Taiwan without known PCDD/PCDF pollution. Similar results were observed for the fish tissue and soil samples. The current study may have discovered a "hot spot" for elevated dioxin human exposure in Taiwan. The preliminary finding has raised a public health concern in the inspected area and requires further investigations to clarify the nature of the contamination and potential impact on the local environment and human health.     

Micro-spatial variation of soil metal pollution and plant recruitment near a copper smelter in Central Chile

Soil chemical changes produced by metal smelters have mainly been studied on a large scale. In terms of plant survival, determination of small scale variability may be more important because less toxic microhabitats may represent safe sites for successful recruitment and thus for plant survival. Three dominant microhabitats (open spaces and areas below the canopy of Sphaeralcea obtusiloba and Baccharis linearis shrubs) were defined in a heavily polluted area near a copper smelter and characterised in terms of microclimate, general soil chemistry, total and extractable metal concentrations in the soil profile (A0 horizon, 0-5 and 15-20 cm depth), and seedling densities. Results indicated a strong variability in microclimate and soil chemistry not only in the soil profile but also among microhabitats. Air/soil temperatures, radiation and wind speed were much lower under the canopy of shrubs, particularly during the plant growth season. Soil acidification was detected on top layers (0-5 cm depth) of all microhabitats while higher concentrations of N, Cu and Cd were detected on litter and top soil layers below shrubs when compared to open spaces; however, high organic matter content below shrubs decreased bioavailability of metals. Plant recruitment was concentrated under shrub canopies; this may be explained as a result of the nursery effect exerted by shrubs in terms of providing a more favourable microclimate, along with better soil conditions in terms of macronutrients and metal bioavailability.     

Heavy metal (Cu, Zn, Cd and Pb) contamination of vegetables in urban India: a case study in Varanasi

The contributions of heavy metals in selected vegetables through atmospheric deposition were quantified in an urban area of India. Deposition rate of Zn was recorded maximum followed by Cu, Cd and Pb. The concentrations of Zn and Cu were highest in Brassica oleracea, Cd in Abelmoschus esculentus and B. oleracea, while Pb was highest in Beta vulgaris. Heavy metal pollution index showed that B. oleracea was maximally contaminated with heavy metals followed by A. esculentus and then B. vulgaris. The results of washing showed that atmospheric deposition has contributed to the increased levels of heavy metals in vegetables. Both Cu and Cd posed health risk to local population via test vegetables consumption, whereas Pb posed the same only through B. oleracea. The study concludes that atmospheric depositions can elevate the levels of heavy metals in vegetables during marketing having potential health hazards to consumers.     

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.     

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.     

Heavy metal contamination in the vicinity of an industrial area near Bucharest

Background, aim, and scope  

Heavy metals such as lead are well known to cause harmful health effects. Especially children are particularly susceptible to increased levels of lead in their blood. It is also a fact that lead concentration is increasing in the environment due to increased anthropogenic activity. The risk of heavy metal contamination is pronounced in the environment adjacent to large industrial complexes. In a combined case study, the environmental pollution by heavy metals was related to children’s health in the vicinity of an industrial area located 4 km south-east from Bucharest about 2 km east from the nearest town—Pantelimon. This site includes companies processing different, nonferrous solid wastes for recovery of heavy metals and producing different nonferrous alloys and lead batteries. In this paper, mainly the results of environmental sampling and analyses are summarized.     

Heavy metal contamination in the vicinity of an industrial area near Bucharest

BACKGROUND, AIMS AND SCOPE: Chromium enters into the aquatic environment as a result of effluent discharge from steel works, electroplating, leather tanning industries and chemical industries. As the Cr(VI) is very harmful to living organisms, it should be quickly removed from the environment when it happens to be contaminated. Therefore, the aim of this laboratory research was to develop a rapid, simple and adaptable solvent extraction system to quantitatively remove Cr(VI) from polluted waters. METHODS: Aqueous salt-solutions containing Cr(VI) as CrO4(2-) at ppm level (4-6 ppm) were prepared. Equal volumes (5 ml) of aqueous and organic (2-PrOH) phases were mixed in a 10 ml centrifuge tube for 15 min, centrifuged and separated. Concentrations of Cr(VI), in both the aqueous and organic phases, were determined by atomic absorption spectrometry. The effects of salt and acid concentrations, and phase-contact time on the extraction of Cr(VI) were investigated. In addition, the extraction of Cr(VI) was assessed in the presence of tetramethylammonium chloride (TMAC) in 2-PrOH phase. Effects of some other metals, (Cd(II), Co(II), Cu(II), Ni(II) and Zn(II)), on the extraction of Cr(VI) were also investigated. RESULTS AND DISCUSSION: The Cr(VI) at ppm level was extracted quantitatively by salting-out the homogeneous system of water and 2-propanol(2-PrOH) using chloride salts, namely CaCl2 or NaCl, under acidic chloride media. The extracted chemical species of Cr(VI) was confirmed to be the CrO3Cl-. The ion-pair complex extracted into the organic phase was rationalized as the solvated ion-pair complex of [2-PrOH2+, CrO3Cl-]. The complex was no longer stable. It implied the reaction between extracted species. Studies revealed that salts and acid directly participated in the formation of the above complex. Use of extracting agents (TMAC) didn't show any significant effect on the extraction of Cr(VI) under high salting-out conditions. There is no significant interference effect on the extraction of Cr(VI) by the presence of other metals. The Cr(VI) in the organic phase was back-extracted using an aqueous ammonia solution (1.6 mol dm(-3)) containing 3 mol dm(-3) NaCl. The extraction mechanism of Cr(VI) is also discussed. CONCLUSIONS: Salting-out of homogeneous mixed solvent of 2-propanol can be employed to extract Cr(VI) quantitatively, as an ion-pair of [2-PrOH2+ * CrO3Cl-] solvated by 2-PrOH molecules. Then, the complex becomes 'solvent-like' and is readily separated into the organic phase. The increase of Cl- ion concentration in the aqueous phase favors the extraction. The 2-PrOH, salts and acid play important roles in the extraction process. There is no need to use an extracting agent at a high salting-out condition. RECOMMENDATIONS AND PERSPECTIVES: Chromium(VI) must be quickly removed before it enters into the natural cycle. As the 2-PrOH is water-miscible in any proportion, ion-pairing between 2-PrOH2+ and CrO3Cl- becomes very fast. As a result, Cr(VI) can easily be extracted. Therefore, the method is recommended as a simple, rapid and adaptable method to quickly separate Cr(VI) from aqueous samples.     

Heavy metal contamination in the vicinity of an industrial area near Bucharest

Background, aim, and scope

Heavy metals such as lead are well known to cause harmful health effects. Especially children are particularly susceptible to increased levels of lead in their blood. It is also a fact that lead concentration is increasing in the environment due to increased anthropogenic activity. The risk of heavy metal contamination is pronounced in the environment adjacent to large industrial complexes. In a combined case study, the environmental pollution by heavy metals was related to children’s health in the vicinity of an industrial area located 4 km south-east from Bucharest about 2 km east from the nearest town—Pantelimon. This site includes companies processing different, nonferrous solid wastes for recovery of heavy metals and producing different nonferrous alloys and lead batteries. In this paper, mainly the results of environmental sampling and analyses are summarized.

Materials and methods

Water, soil, and atmospheric deposition samples were collected from different locations within 3 km from the industrial area. For comparison, samples were also taken from Bucharest. Water samples were filtered (<0.45 μm), extracted by salpetric acid, and quantified by ICP-OES and ICP-MS. Soil samples were dried, sieved (<2 mm), extracted by aqua regia and analyzed by AAS. In order to quantify the atmospheric deposition, three kinds of permanently open collecting pots were used on nine different sites between August and November 2006.

Results

At most sampling locations, the heavy metal concentrations in soil decrease with increasing distance to the presumably major source of pollution. Highest heavy metal concentrations were found in 10–20 cm soil depths. There were also decreasing heavy metal concentrations for atmospheric deposition with increasing distance to the industrial site. In surface and groundwater samples, traces of zinc, copper and lead were detected.

Discussion

The heavy metal concentrations in soil were increased in the study area, mostly under legal action limits in low-concern areas (e.g., 1,000 mg Pb/kg dry soil), but often above action limits for high-concern areas (100 mg Pb/kg dry soil) such as populated areas. The soluble lead concentrations in water samples indicate a need for monitoring and assessing water quality in more detail. The results for atmospheric deposition showed increased dust precipitation and heavy metal loads in the study area compared to Bucharest. However, based on mass flow balance calculations, the actual atmospheric deposition of heavy metals must be much lower than it was in the past decades.

Conclusions

It was shown that highest lead values in water, soil and atmospheric deposition are rather to be found near the investigated industrial site than at the control sites in Bucharest. Our results correspond very well with results that show that children from Pantelimon have significantly increased lead concentrations in their blood compared to children in Bucharest. The increased lead contamination around the investigated industrial area is likely to have caused the increased exposure for children living in Pantelimon.

Recommendations and perspectives

In high-concern areas, such as found in populated areas, further measures have to be taken to avoid health risks for people living in these areas. The measures already taken to reduce emissions from the industrial site will help to avoid further increases in heavy metal concentrations. In areas with exceeded action limits, measures have to be taken as required by law. Detailed risk assessments could help to take necessary actions to protect public health in this area. The public should be informed about the potential hazards of eating plants grown in that area. Educational programs for schools, informing children about the contamination, should lead to a better understanding of environmental problems and a more sustainable behavior in the future.

     

某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况,对该矿区东河流域附近重金属污染源进行了调查,同时,对地下水和土壤样品进行了采样分析,结果表明：（1）该矿区东河流域附近的主要污染源有18个,其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源;（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995）,综合污染指数P综〉1,该矿区主要的重金属污染元素为Cd、As和Hg,且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系;（3）重金属元素在土壤中的纵向迁移不明显,该矿区附近20个采样点的地下水并未受到污染,综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Measurements of Cd, Cu, Pb and Zn in the lower reaches of major Eurasian arctic rivers using trace metal clean techniques

Concentrations of dissolved and particulate Cd, Cu, Pb and Zn were determined in samples collected in summer 1998 from the lower reaches of six major Eurasian arctic rivers: the Onega, Severnaya Dvina, Mezen, Pechora, Ob and Yenisey. These data comprise some of the earliest measurements of trace metals in Eurasian arctic rivers above the estuaries using recognized clean techniques. Significant (α = 0.05) differences were observed among mean concentrations of particulate metals in the individual rivers (F ≤ 0.006), with highest levels overall observed in the Severnaya Dvina and Yenisey. No significant differences were observed among mean concentrations of dissolved metals in the individual rivers (F = 0.10-0.84). Contributions from anthropogenic sources are suggested by comparison of trace metal ratios in the samples to crustal abundances. These results establish a baseline for assessing future responses of Eurasian arctic river systems to climate-related environmental changes and shifting patterns of pollutant discharge.     

Using stable lead isotopes to trace heavy metal contamination sources in sediments of Xiangjiang and Lishui Rivers in China

Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower ²⁰⁶Pb/²⁰⁷Pb and higher ²⁰⁸Pb/²⁰⁶Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), indicated a significant input of non-indigenous Pb with low ²⁰⁶Pb/²⁰⁷Pb and high ²⁰⁸Pb/²⁰⁶Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.