Bioresource Technology 99 (2008) 85788584

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Bioresource Technology
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Soil contamination by heavy metals: Measurements from a closed unlined landll

A. Kasassi a, P. Rakimbei b, A. Karagiannidis b, A. Zabaniotou a,*, K. Tsiouvaras c, A. Nastis c, K. Tzafeiropoulou c
a

Department of Chemical Engineering, U. Box 455, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece Department of Mechanical Engineering, U. Box 483, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece c Department of Forestry and Natural Environment, U. Box 236, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
b

a r t i c l e

i n f o

a b s t r a c t
The aim of the present study was the characterization of soil samples of a closed unlined landll located northwest of Thessaloniki, North Greece, in relation to heavy metals values. Samples were obtained by drilling in different depths (2.517.5 m). Then they were analyzed by atomic absorption spectrophotometry for Cd, Cr, Cu, Ni, Pb and Zn investigation. The chemical analysis showed that the metal values varied over a wide range: from 0.50 to 18.75 mg/kg for Cd, 3.88171.88 mg/kg for Cr, 8.13356.25 mg/kg for Cu, 5.6363.75 mg/kg for Ni, 2.5092.50 mg/kg for Pb and 6.38343.75 mg/kg for Zn. The highest values found in three of the six drillings, in depths over 2.5 m. Although the area is heavily industrialized, the presented results indicated that local industries have not constituted an extensive metal pollution source for the site. Finally, after all necessary preparatory operations of site cleaning and attening, surface planting selected and applied as a phytoremediation rehabilitation method of the site. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 12 December 2007 Received in revised form 27 March 2008 Accepted 3 April 2008 Available online 27 May 2008 Keywords: Heavy metals Soil contamination Regulatory limits Unlined landlls Industrial waste

1. Introduction Modern civilization is completely dependent on a large range of metals for all aspects of daily life. There is a long history of association between metals and human development. However, due to mining, mineral, smelting and tannery industry, heavy metal pollution has become serious. Heavy metal pollution not only affects the production and quality of crops, but also inuences the quality of the atmosphere and water bodies, and threatens the health and life of animals and human being (Kumar, 2008). Several researchers have clearly identied the inuence of human activity as a major cause for metal contamination of the ecosystem (Charlesworth et al., 2003; Tzen, 2003; Al-Khashman, 2004; Banat et al., 2005; Chen et al., 2005). Metals are considering among the most dangerous environmental pollutants, because they do not disintegrate with physical processes and therefore remain for longtime period. They affect biogeochemical cycles and accumulate within living organisms, eventually making their way to humans through the food chain, where they can cause perturbation to biological reactions, longlasting harm to vital organs or even death (Tiller, 1989). Ingestion,
* Corresponding author. Tel.: +30 2310 996274; fax: +30 2310 996209. E-mail address: sonia@cheng.auth.gr (A. Zabaniotou). 0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2008.04.010

inhalation and skin contact are the main routes of human exposure to soil metals. Since soil is the major sink for airborne metals, the measurement of their levels in this media is useful to establish trends in abundance and their consequences because of natural and anthropogenic changes (Nadal et al., 2004). Hazardous metals like Pb, Zn and Cd take part in the biogeochemical cycles and their mobility depends strongly on their chemical forms rather than total element concentration (Garcia et al., 2005). Metal speciation can help to assess how strongly they are retained in soil and how easily they may be released into soil solution (Kaasalainen and Yli-Halla, 2003). The main objective of this study was the characterization of soil samples issued from a closed unlined landll located near Thessaloniki, in northern Greece, in relation to their content of heavy metals. The soil samples collected from the under study area, one of the largest industrial areas where metal-processing, chemical, cement, food and wood industries are located. In the studied disposal site, during the period 19901997, both industries and the community dumped their wastes. In order to assess the situation of the site and to decide for its rehabilitation for both esthetic and ecological purposes, a wide survey performed, focusing on the evaluation of heavy metal pollution and their associated risk. This risk assessed by comparing results to guidelines developed in Europe for heavy metals in soils.

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Nomenclature D L/S drilling liquid/solid

Table 1 Characteristics of the soil samples Samples 4 Drilling D1 Mean sample depth (m) 0.45 1.00 1.55 2.25 0.25 0.75 1.75 3.00 3.75 0.90 3.50 1.10 2.00 2.75 5.15 1.00 4.50 5.75 6.25 6.75 7.70 8.65 9.95 12.75 14.4 0.90 2.60 5.75 6.20 7.90 9.25 10.50 11.50 12.85 13.25 13.75 14.75 15.15 15.45 15.80 Description Brown-reddish sandy potters clay earth Green schist vitiated with calcite concretions Grit, clays

D2

Grit, timbers, braces, bricks Grit, clays Peridotites, green schist Grit, pieces of schist Peridotites, green schist Grit, clays Waste

2 4

D3 D4

10

D5

Peridotites, green schist Grit, clays Waste

15

D6

Peridotites, green schist Total

40

2. Methods 2.1. Site description The closed unlined landll of Efkarpia, is located in the northwestern part of Thessaloniki (longitude: 22970 , latitude: 40500 ). The community of Efkarpia is the second largest industrial area in the greater Thessaloniki area, after Sindos. Its population according to inventory of 2001 is 6.645. A large number of metal-processing, furniture and wood, textiles and clothing, food, chemical and cement industries are located there. The related produced wastes are 240, 220, 200, 150, 110 and 40 t/y, respectively. The closed landll site located in a gully, covers 3 hectares and it is 5 km far from the nearest residential area of the village of Efkarpia. Nearby, there are also many sheepfold units, the nearest of which is 200 m far from the site. Local

industries and the community of Efkarpia have dumped their waste in this disposal site during the period 19901997. The most intensive deposition of urban waste took place between 1993 and 1995, while between 1995 and 1997 the landll received mainly waste from local industries. An average of amount of 16 t of waste was estimated as the daily dumped quantity during 19901997. For the purpose of the present investigation, six wells (termed D1 D6) were drilled at the disposal site for sampling purposes, in December 2003. Drilling depth was extended up to nding the maternal rock and wells depth varied between 2.5 and 17.5 m, because the thickness of waste in the old landll varied. Soil sampling was performed on a dry basis via a barrier sampler. In this way, 40 soil samples collected from the six drillings. Initially, all samples were stored in a covered place and left to dry out. Then, they were pulverized and sorted with a 2-mm sieve (Nastis et al., 2005) and analyzed for the estimation of Cd, Cr, Cu, Ni, Pb and Zn values. A short description of the samples is given in Table 1. The physical properties (soil prole) of the in situ soil for each of the six drillings (D1D6) are as follows: D1: Only natural ground was found, since this drilling was relatively near the ofcial landll border. Down to 1 m, brown-reddish sandy potters clay earth was found and, then, down to the nal depth of 2.5 m, green schist vitiated with calcite concretions. D2: It reached a nal depth of 4.5 m, after which natural ground was found; disposed excavation wastes (consisting primarily of rubble grit and clays) were found down to a depth of 2.5 m, followed by disposed wood, bricks and generally inert construction wastes which were found next and until the nal drilling depth. D3: With a nal depth of 4 m, disposed excavation wastes (i.e. rubble, grit and clays) were (again) found down to 2.5 m, whereas natural soil (consisting of peridotites and smashed green schist) was located next and down to the nal drilling depth. D4: With a total depth of 6 m, primarily excavation waste (grit, pieces of limestone, etc) and secondarily industrial wastes (mainly rugs) were found down to a 4 m-depth. Then (and down to the nal drilling depth), natural soil was found, consisting of peridotites and schist. D5: It had a nal depth of 14.8 m. Excavation waste was found here also and down to the rst 5 m, whereas then and down to a 14 m-depth, mainly municipal and industrial wastes of miscellaneous nature were observed. Finally, down to the nal depth of 14.8 m, the above-mentioned peridotites and green schist were found again. D6: This was the deepest drilling, as it reached 17.5 m down. Rubbles from the landll were found again down to 4 m and, further down, wastes were found up to a depth of 16 m. Then, natural soil was found consisting of peridotites and smashed green schist. In general, the type of discovered waste was related mainly to the type of regions industries, as it consisted mainly of by-products from cement, metal-processing and clothing industries. However, a relatively high amount of plastic bags was also found, these were probably used for packing the waste. At the same time, significant quantities of debris and timber by-products were dug out. 2.2. Sample processing Several chemical and fractionation methods for heavy metal analysis in soils and sediments have been and are still being

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Table 2 Average values, standard limits and ranges for the measured metal content (mg/kg) of the 40 soil samples Drilling 1 Metals Cd Cr Cu Ni Pb Zn Cd Cr Cu Ni Pb Zn Cd Cr Cu Ni Pb Zn Cd Cr Cu Ni Pb Zn Cd Cr Cu Ni Pb Zn Cd Cr Cu Ni Pb Zn Mean values 2.50 74.69 18.75 40.00 10.62 24.84 2.33 18.83 27.88 30.50 9.38 38.38 1.19 39.69 27.81 35.63 7.50 25.94 6.84 15.88 18.28 34.38 10.00 29.69 2.66 43.52 26.31 40.27 13.67 49.63 3.15 49.43 68.58 23.05 29.43 78.72 Std. dev. 1.50 55.30 5.30 16.04 5.25 3.83 1.31 12.41 12.82 11.93 5.18 6.13 0.80 11.05 6.63 29.17 1.77 3.09 8.09 10.85 5.98 29.07 6.96 12.08 1.85 17.28 8.62 17.81 6.04 30.21 2.59 48.24 97.39 13.94 25.99 108.12 Range 0.753.88 37.50156.25 15.0026.25 20.0058.75 3.7516.25 20.0029.38 0.634.00 6.2538.13 17.5042.50 18.1345.00 3.7514.38 30.0046.88 0.631.75 31.8847.50 23.1332.50 15.0056.25 6.258.75 23.7528.13 0.7518.75 3.8825.00 10.0023.75 5.6363.75 2.5016.25 14.3841.88 0.507.50 24.3873.13 14.3840.63 13.1359.38 7.5026.25 23.13100.00 0.759.38 10.00171.88 8.13356.25 6.0046.88 11.2592.50 6.38343.75

stirring system. Stirring took place for 24 0.5 h at 30 rpm and the container was then left to equilibrate; next, the mixture was introduced to vacuum ltering. Finally, acidication of ltrates followed (pH  2.53) and the samples were refrigerated (4 C). This method was applied to all 40 taken samples. For the extraction with HNO3, 2 g of each pulverized sample were weighed and placed in conical bottles of 100 or 200 mL. After the addition of 25 mL of HNO3 4 M, the bottle was placed in a sand bath; funnels with lters were placed in the neck of the bottle, in order for the digestion to take place under constant volume. The solution was heated in 7080 C for 16 h. After heating, the sample was ltered in a volumetric bottle of 50 mL. Finally, the bottle was lled up to the slit with deionized water. The samples were refrigerated for maintenance (4 C). This method was applied to all 40 samples as well. 2.3. Sample analysis After the preparation of the samples with both methods, leaching values of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) estimated using a PerkinElmer 403 furnace spectrometer (atomic absorption spectrophotometric analysis). The calibration of the spectrometer for each metal was performed according to its wavelength and standard solutions. For Cu, a 5-ppm standard solution was prepared, for Ni two standard solutions (5 and 25 ppm), for Pb a 10ppm solution, for Cd and Cr two solutions (1 and 2 ppm, 2 and 5 ppm, respectively) and for Zn a 0.5 ppm standard solution. The spectrometer re-calibrated after each group of 10 successive measurements. The initial dilution of samples was 1:5, while samples with high metal leaching values were further diluted to 1:25, in order to t within the linear region of the calibration curve.

3. Results and discussion The European method EN 12457-2 did not give traceable leaching values for heavy metals. On the contrary, the leaching values of heavy metals, which were extracted with 4 M HNO3; measured in certain cases higher than the allowable limit values. Figs. 16 depict the distributions of the leaching values for the six metals in all depths of all drillings. Quality control of the soil in the studied area was performed according to the limit values published by the European community. In addition, the respective values of a Mediterranean country, a new EU member and three older members were used for comparison. Limits issued by EU sometimes are less strict than the corresponding national ones; one example is Poland with stricter values for Cd (13 mg/kg), Cu (2575 mg/kg), Ni (2050 mg/kg), Pb (40 80 mg/kg) and Zn (80180 mg/kg), than EU due to the local historical extensive coal mining and use. From the other side, some countries, like Germany and the UK, have established lower acceptable values for some metals (e.g. Cr), than other countries because they face less severe pollution problems (e.g. Austria). Comparing the values found in the present work with the aforementioned European countries (Poland, Germany, UK, Austria) it is obvious that at the landll of Efkarpia, the average Cd, Cr, Cu, Ni, Pb and Zn leaching values were in most of the cases (with a few exceptions though) lower than the European ones. From the chemical analysis of solid samples with atomic absorption, the leaching values of metals varied over a wide range as follows: 0.5018.75 mg/kg for Cd, 3.88171.88 mg/kg for Cr, 8.13356.25 mg/kg for Cu, 5.6363.75 mg/kg for Ni, 2.50 92.50 mg/kg for Pb and 6.38343.75 mg/kg for Zn. The average metal leaching values found in this study (Table 2) were also compared with values reported from other studies. Generally, Cd value was found to be lower in concentration compared

developed and applied. They are primarily intended for understanding the particular environmental behavior of metals, which are present in a variety of forms and matrices (Tack and Verloo, 1995). The studied samples were extracted according to the European standard EN 12457-2 (batch leaching test, part 2: liquid/solid (L/S) = 10 L/kg, particle size < 4 mm), as well as with nitric acid (4 M HNO3 Council Decision, Ofcial Publications of the European Communities, 2002). According to EN 12457-2, deionized water was used as extractor for attributing the soluble fraction of the heavy metals forms, which includes immediately soluble metals in the form of free cations or soluble complexes (Garcia et al., 2005). As an alternative, many researchers suggest the use of 4 M HNO3 in order to extract the total values of heavy metals, in various soil matrices and mainly at sewage sludge or wastewateramended soil samples (Chuan et al., 1995; Richards et al., 1998). Linde (2005) determines the trace-metal content of soils through digestion with boiling (120 C) 7 M HNO3; he reports that the difference between the HNO3 and the aqua-regia-extractable values are relatively small (015% of aqua-regia-extractable) for most metals. Garcia et al. (2005) cited that the exchangeable metals could be determined using 1 M HNO3. Metals extracted include those fractions complexed by or co-precipitated with hydrous oxides, carbonates and suldes. The following procedure was applied which is in accordance with the European Standard EN12457-2. Sufciently pulverized sample (100 g) were weighed and initially placed in a 1 L container made of polypropylene. The container was lled with 1 L of deionized water and placed in a

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Fig. 1. Distribution of Cd leaching values according to the drillings depth.

Fig. 2. Distribution of Cr leaching values according to the drillings depth.

to other metals in the investigated area (in this study, Cd range was 0.519 mg/kg). In most drillings, the average Cd values were lower than the limit value dened by other countries, but higher than the value of 1.2 mg/kg reported by Jain et al. (2005), measured in soil reclaimed from a municipal solid waste landll. Concerning Cd emissions into the atmosphere, this is due to both natural and anthropogenic sources. In particular, 1015% of total emissions come from natural sources (e.g. volcanoes), whereas metal production is the largest source of anthropogenic atmospheric Cd emissions, followed by emissions from waste incineration, production

of batteries, fossil fuel combustion and industrial processes, such as cement manufacturing and fertilizers production. Cr leaching values varies from 4 to 172 mg/kg. The highest values of Cr was recorded at D6 well. Compared to measurements of other researchers (Schuhmacher et al., 2002; Jain et al., 2005; AlKhashman and Shawabkeh, 2006), increased Cr values were found in our soil samples. This is due to local existed metal-processing and -production industries, which produce scrap iron and mineral wastes and used to dispose their waste in the Efkarpia landll. A cement industry located near to the Efkarpia landll used to dis-

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Fig. 3. Distribution of Cu leaching values according to the drillings depth.

Fig. 4. Distribution of Ni leaching values according to the drillings depth.

pose the linings for the rotaries containing Cr in the landll. These waste might caused the Cr emissions due to their wear and friction. The highest Cu leaching value (356.25 mg/kg) was also observed at D6 well. D6 well was dominated by waste rich in Cu. These wastes issued from clothing or wood industries (Cu is used as timber preservative) or old pipeline sections are the reason for high concentration of Cu. Another study made AlKhashman and Shawabkeh (2006), in Jordan for a site near to a cement factory reported values lower that those of the present study.

The highest average Ni leaching value was measured in D4 well, which varies between 5.63 and 63.75 mg/kg. The average value of 11.3 mg/kg measured by Schuhmacher et al. (2002) is much lower than the values of our study in the six drillings. A possible reason of the high Ni values might be contributed to metal-processing waste and/or municipal wastes including batteries and electric and electronic equipment waste. Despite the signicant difference observed between the values measured, no Ni-contamination problem is determined for the study area, as the European limit value is 75 mg/kg.

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Fig. 5. Distribution of Pb leaching values according to the drillings depth.

Fig. 6. Distribution of Zn leaching values according to the drillings depth.

Pb leaching values in soil samples varied between 2.50 and 93 mg/kg and were generally high compared to the 9.0 mg/kg measured by Jain et al. (2005) in California. This could be attributed to the different type of wastes deposited at the two areas. In Efkarpias site, 23.3% of wastes came from metal-processing industries, whereas in California site only 5.7% of the reclaimed material was metal. On the contrary, measured leaching values in Efkarpia were below regulatory thresholds of the EC (300 mg/kg). Zn was found to have the highest leaching values of all other metals. However, it is still below the limit value set by the EC

(300 mg/kg). The existence of Zn in the soil was associated mainly to emissions from metal-processing, clothing and cement industries as well as to the near-by signicant trafc emissions from the aforementioned Egnatia highway. By comparing average leaching values of Zn measured in Catalonia/Spain (Schuhmacher et al., 2002) and Qadissiya/Jordan (Al-Khashman and Shawabkeh, 2006) with the respective in Efkarpia, the Efkarpias D6 well values were higher than the Spanish and Jordanian ones. Surface planting was selected for the rehabilitation of the closed landll. All necessary eld operations were designed and imple-

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mented, in order for the area of the disposal site to be attened and prepared for seeding. Fencing was mounted, an irrigation system was installed and herbaceous plants were seeded. For the rehabilitation of the site, as mentioned above, surface planting was selected and seeding of herbaceous species (Cynodon dactylon, Lolium perenne, Festuca arundinacea and Koeleria macrantha) at the appropriately prepared ground, as part of the cover layer for the landll. Other researchers have also studied the behavior of the above-mentioned plants in relation to heavy metal environment (Taylor et al., 1993; Pichtel and Salt, 1998) and, eventually, buried wastes had not affected the plant growth and heavy metal values of their tissues. The site was successfully plant-covered, esthetically restored and found to have become a sanctuary for the gray partridge Perdixperdix. For enhanced risk assessment of the closed landll, measurements of biogas and leachate were also performed in this work. The quantity of biogas was found to be very low; furthermore, no obvious leakage of leachate out of the site was observed, although no bottom liner system is in place. It is possible that leakage transfer has taken place in the interior of the landll, regarding that the biggest leachate values were measured at the lowest layers. However, continuous monitoring and control of biogas and leachate is required, in order for future spills and leakages and even accidents to be avoided. The effect of heavy metals on the plants is currently under investigation, together with the effects of emitted biogas and leachates. The site could be used as a park or entertainment area, but without any heavy construction on top, due to the potential for differential settlements and potential future biogas pockets. The latter, it can only be denitely dealt with the application of stabilization techniques like landll aeration, followed eventually by excavation and complete restoration; this was, however, beyond the scope and the resources of the present work, although it was emphatically suggested as a future priority. Generally, remediation of heavy-metal polluted soils can be achieved by using various suitable methods. The choice of the proper technology depends on a variety of factors like the concentration of metals, the form in which these are found in the soil, their mobility, the type of soil and the depth up to which intense pollution is observed, whereas cost considerations are always important. 4. Conclusions In spite of extensive industrialization in the area of Efkarpia site, the results of this work which emphasized on heavy metals in the landll suggest that the long-existing and -operating metal-processing, wood and chemical industries did not prove to be a significant metal pollution source by their deposited wastes to the near-by closed unlined landll. The highest values of heavy metals were found in depths over 2.5 m for three of the six performed drillings. Soil content in heavy metals within the landll was found to be heavily dependant on the deposition patterns of municipal and industrial waste, whereas less heavy metal contents were measured in samples that were assessed to include debris and inert excavation waste, issued from near-by construction worksites.

Acknowledgements The Hellenic Secretariat funded the present work for Research and Technology (GSRT) in the frame of a PENED project (Contract Nr 2001/01ED626). The authors would like to thank the municipal authority of the Efkarpia Community in Thessaloniki, for the valuable and contractive collaboration and support of this work. References
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