Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Heavy metal contamination from mining sites in South Morocco: 1. Use of a biotest to assess metal toxicity of tailings and soils

Our work was conducted to investigate the heavy metal toxicity of tailings and soils collected from five metal mines located in the south of Morocco. We used the MetPAD biotest Kit which detects the toxicity specifically due to the heavy metals in environmental samples. This biotest initially developed to assess the toxicity of aquatic samples was adapted to the heterogeneous physico-chemical conditions of anthropogenic soils. Contrasted industrial soils were collected from four abandoned mines (A, B, C and E) and one mine (D) still active. The toxicity test was run concurrently with chemical analyses on the aqueous extracts of tailings materials and soils in order to assess the potential availability of heavy metals. Soil pH was variable, ranging from very acidic (pH 2.6) to alkaline values (pH 8.0-8.8). The tailings from polymetallic mines (B and D) contained very high concentrations of Zn (38,000-108,000 mg kg(-1)), Pb (20,412-30,100 mg kg(-1)), Cu (2,019-8,635 mg kg(-1)) and Cd (148-228 mg kg(-1)). Water-extractable metal concentrations (i.e., soil extracts) were much lower but were highly toxic as shown by the MetPAD test, except for soils from mines A, E and site C3 from mine C. The soil extracts from mine D were the most toxic amongst all the soils tested. On this site, the toxicity of soil water extracts was mainly due to high concentrations of Zn (785-1,753 mg l(-1)), Cu (1.8-82 mg l(-1)) and Cd (2.0-2.7 mg l(-1)). The general trend observed was an increase in metal toxicity measured by the biotest with increasing available metal contents in tailings materials and soils. Therefore, the MetPAD test can be used as a rapid and sensitive predictive tool to assess the heavy metal availability in soils highly contaminated by mining activities.     

Retention and distribution of heavy metals in mangrove soils receiving wastewater

The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.     

Heavy metal accumulation in wheat plant grown in soil amended with industrial sludge

The concentrations of different forms of Zn, Cu, Mn, Ni, Cd, Cr, Pb and Fe metals were determined for the roadside sludge collected from pickling-rolling and electroplating industrial area. In sludge the relative abundance of total heavy metals were Fe>Mn>Cr>Ni>Cu>Pb>Zn>Cd and DTPA-extractable metals were in the order--Fe>Ni>Mn>Cr>Cu>Zn>Pb>Cd. Pot-culture experiment was conducted in soils amended with sludge (0%, 10%, 20%, 30%), pretreated with lime (0%, 0.5% and 1%). The soils were alkaline in nature (pH>8.3) with organic carbon contents were 0.34% and 0.72%. The most abundant total and bio-available metal was Fe. Two wheat seedlings were grown in each pot containing 3kg sludge-amended or control soil and the experiment was conducted till harvesting. Application of sludge increased both total and bio-available forms of metals in the soils, while lime application decreased the bioavailability of heavy metals in sludge-amended soils. The content of organic carbon showed positive correlation with all metals except Zn, Cr and Pb. CEC also showed a strong positive correlation (R2>0.7) with Fe, Mn, Cu, Ni and Cd. Though wheat plants are not accumulators, the translocation efficiency was appreciably high. The translocation factor from shoot to grain was found smaller than that of root to shoot of wheat plants. This makes an implication that the heavy metal accumulation was proportionally lesser in grain than in shoot. In, 10% sludge with 0.5% lime-amended soils; each of these toxic heavy metals was found to be within permissible range (USEPA). Hence, on the basis of present study, the best possible treatment may be recommended.     

Health risk assessment of heavy metals in soil-plant system amended with biogas slurry in Taihu basin,China

Biogas slurry is a product of anaerobic digestion of manure that has been widely used as a soil fertilizer. Although the use for soil fertilizer is a cost-effective solution, it has been found that repeated use of biogas slurry that contains high heavy metal contents can cause pollution to the soil-plant system and risk to human health. The objective of this study was to investigate effects of biogas slurry on the soil-plant system and the human health. We analyzed the heavy metal concentrations (including As, Pb, Cu, Zn, Cr and Cd) in 106 soil samples and 58 plant samples in a farmland amended with biogas slurry in Taihu basin, China. Based on the test results, we assessed the potential human health risk when biogas slurry containing heavy metals was used as a soil fertilizer. The test results indicated that the Cd and Pb concentrations in soils exceeded the contamination limits and Cd exhibited the highest soil-to-root migration potential. Among the 11 plants analyzed, Kalimeris indica had the highest heavy metal absorption capacity. The leafy vegetables showed higher uptake of heavy metals than non-leafy vegetables. The non-carcinogenic risks mainly resulted from As, Pb, Cd, Cu and Zn through plant ingestion exposure. The integrated carcinogenic risks were associated with Cr, As and Cd in which Cr showed the highest risk while Cd showed the lowest risk. Among all the heavy metals analyzed, As and Cd appeared to have a lifetime health threat, which thus should be attenuated during production of biogas slurry to mitigate the heavy metal contamination.     

Monometal and competitive adsorption of heavy metals by sewage sludge-amended soil

Sewage sludge-amended soils may alter their ability to adsorb heavy metals over time, due to the decomposition of sludge-borne organic matter. Thus, we studied Cd, Ni, and Zn adsorption by a sewage sludge-amended soil (Typic Xerofluvent) before and after one-year incubation in both monometal and competitive systems. In the monometal system, the order of decreasing sorption was Zn>Cd>Ni. Competition significantly reduced metal K(d), especially that of Cd which decreased by nearly 50%. Over the course of the incubation there was a 31% reduction of soil organic matter content. At the same time, in competitive systems Cd K(d) significantly decreased, while Zn K(d) significantly increased, and Ni K(d) remained unaffected. This study shows that sewage sludge-amended soils may change in their ability to sorb heavy metals over time at high metal concentrations. The data suggest that Cd is likely to be of most environmental significance in such soils, since it exhibited decreased sorption under competitive conditions and as the organic matter content of the soil was reduced. The potential for long-term release of metals should be considered in the risk assessment associated with sewage sludge addition to soils, particularly in climates where degradation of organic matter is likely to be enhanced.     

Heavy Metals in Urban Soils of East St. Louis,IL, Part I: Total Concentration of Heavy Metals in Soils

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produce organic and inorganic chemicals, and petroleum refineries. A protocol for soil analysis was developed to produce sufficient information on the extent of heavy metal contamination in East St. Louis soils. Soil cores representing every borough of East St. Louis were analyzed for heavy metals—As, Cd, Cu, Cr, Hg, Ni, Pb, Sb, Sn, and Zn. The topsoil contained heavy metal concentrations as high as 12.5 ppm Cd, 14,400 ppm Cu, ppm quantities of Hg, 1860 ppm Pb, 40 ppm Sb, 1130 ppm Sn, and 10,360 ppm Zn. Concentrations of Sb, Cu, and Cd were well correlated with Zn concentrations, suggesting a similar primary industrial source. In a sandy loam soil from a vacated rail depot near the bank of the Mississippi River, the metals were evenly distributed down to a 38-cm depth. The clay soils within a half-mile downwind of the Zn smelter and Cu products company contained elevated Cd (81 ppm), Cu (340 ppm), Pb (700 ppm), and Zn (6000 ppm) and displayed a systematic drop in concentration of these metals with depth. This study demonstrates the often high concentration of heavy metals heterogeneously distributed in the soil and provides baseline data for continuing studies of heavy metal soil leachability.     

Heavy metals in urban soils of East St. Louis, IL, Part I: Total concentration of heavy metals in soils

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produce organic and inorganic chemicals, and petroleum refineries. A protocol for soil analysis was developed to produce sufficient information on the extent of heavy metal contamination in East St. Louis soils. Soil cores representing every borough of East St. Louis were analyzed for heavy metals--As, Cd, Cu, Cr, Hg, Ni, Pb, Sb, Sn, and Zn. The topsoil contained heavy metal concentrations as high as 12.5 ppm Cd, 14,400 ppm Cu, ppm quantities of Hg, 1860 ppm Pb, 40 ppm Sb, 1130 ppm Sn, and 10,360 ppm Zn. Concentrations of Sb, Cu, and Cd were well correlated with Zn concentrations, suggesting a similar primary industrial source. In a sandy loam soil from a vacated rail depot near the bank of the Mississippi River, the metals were evenly distributed down to a 38-cm depth. The clay soils within a half-mile downwind of the Zn smelter and Cu products company contained elevated Cd (81 ppm), Cu (340 ppm), Pb (700 ppm), and Zn (6000 ppm) and displayed a systematic drop in concentration of these metals with depth. This study demonstrates the often high concentration of heavy metals heterogeneously distributed in the soil and provides baseline data for continuing studies of heavy metal soil leachability.     

Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth

The effects of chemical amendments (zeolite, compost and calcium hydroxide) on the solubility of Pb, Cd and Zn in a contaminated soil were determined. The polluted soil was from the Southwest Sardinia, Italy. It showed very high total concentrations of Pb (19663 mgkg(-1) d.m.), Cd (196 mgkg(-1) d.m.) and Zn (14667 mgkg(-1) d.m.). The growth and uptake of heavy metals by white lupin (Lupinus albus L., cv. Multitalia) in amended soils were also studied in a pot experiment under greenhouse conditions. Results showed that the amendments increased the residual fraction of heavy metals in the soils, and decreased the heavy metals uptake by white lupin compared with the unamended control. Among the three amendments, compost and Ca(OH)2 were the most efficient at reducing Pb and Zn uptake, while zeolite was the most efficient at reducing Cd uptake by the plants. White lupin growth was better in amended soils than in unamended control. The above ground biomass increased with a factor 1.8 (soil amended with zeolite), 3.6 (soil amended with compost) and 3.1 (soil amended with Ca(OH)2) with respect to unamended soil. The roots biomass increased with a factor 1.4 (soil amended with zeolite), 5.6 (soil amended with compost) and 4.8 (soil amended with Ca(OH)2). Results obtained suggest that the soil chemical treatment improved the performance of crops by reducing bioavailability of metals in the soils. However it would be therefore interesting to find a suitable mixture of these amendments to contemporarily immobilize the three main pollutants in the polluted soils.     

Growth and metal accumulation in vetiver and two Sesbania species on lead/zinc mine tailings

The lead (Pb)/zinc (Zn) tailings contained high concentrations of heavy metals (total Pb, Zn, Cu and Cd concentrations 4164, 4377, 35 and 32 mg kg(-1), respectively), and low contents of major nutrient elements (N, P, and K) and organic matter. A field trial was conducted to compare growth performance, metal accumulation of Vetiver (Vetiveria zizanioides) and two legume species (Sesbania rostrata and Sesbania sesban) grown on the tailings amended with domestic refuse and/or fertilizer. It was revealed that domestic refuse alone and the combination of domestic refuse and artificial fertilizer significantly improved the survival rates and growth of V. zizanioides and two Sesbania species, especially the combination. However, artificial fertilizer alone did not improve both the survival rate and growth performance of the plants grown on tailings. Roots of these species accumulated similar levels of heavy metals, but the shoots of two Sesbania species accumulated higher (3-4 folds) concentrations of Pb, Zn, Cu and Cd than shoots of V. zizanioides. Most of the heavy metals in V. zizanioides were accumulated in roots, and the translocation of metals from roots to shoots was restricted. Intercropping of V. zizanioides and S. rostrata did not show any beneficial effect on individual plant species, in terms of height, biomass, survival rate, and metal accumulation, possibly due to the rather short experimental period of 5 months.     

Determination of chemical availability of cadmium and zinc in soils using inert soil moisture samplers

A rapid method for extracting soil solutions using porous plastic soil-moisture samplers was combined with a cation resin equilibration based speciation technique to look at the chemical availability of metals in soil. Industrially polluted, metal sulphate amended and sewage sludge treated soils were used in our study. Cadmium sulphate amended and industrially contaminated soils all had > 65% of the total soil solution Cd present as free Cd2+. However, increasing total soil Cd concentrations by adding CdSO4 resulted in smaller total soil solution Cd. Consequently, the free Cd2+ concentrations in soil solutions extracted from these soils were smaller than in the same soil contaminated by sewage sludge addition. Amendment with ZnSO4 gave much greater concentrations of free Zn2+ in soil solutions compared with the same soil after long-term Zn contamination via sewage sludge additions. Our results demonstrate the difficulty in comparing total soil solution and free metal ion concentrations for soils from different areas with different physiochemical properties and sources of contamination. However, when comparing the same Woburn soil, Cd was much less available as Cd2+ in soil solution from the CdSO4 amended soils compared with soil contaminated by about 36 years of sewage sludge additions. In contrast, much more Zn was available in soil solution as free Zn2+ in the ZnSO4 amended soils compared with the sewage sludge treated soils.     

Chemical speciation and extractability of Zn,Cu and Cd in two contrasting biosolids-amended clay soils

An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.     

Heavy metals in agricultural soils of the Pearl River Delta,South China

There is a growing public concern over the potential accumulation of heavy metals in agricultural soils in China owing to rapid urban and industrial development and increasing reliance on agrochemicals in the last several decades. Excessive accumulation of heavy metals in agricultural soils may not only result in environmental contamination, but elevated heavy metal uptake by crops may also affect food quality and safety. The present study is aimed at studying heavy metal concentrations of crop, paddy and natural soils in the Pearl River Delta, one of the most developed regions in China. In addition, some selected soil samples were analyzed for chemical partitioning of Co, Cu, Pb and Zn. The Pb isotopic composition of the extracted solutions was also determined. The analytical results indicated that the crop, paddy and natural soils in many sampling sites were enriched with Cd and Pb. Furthermore, heavy metal enrichment was most significant in the crop soils, which might be attributed to the use of agrochemicals. Flooding of the paddy soils and subsequent dissolution of Mn oxides may cause the loss of Cd and Co through leaching and percolation, resulting in low Cd and Co concentrations of the paddy soils. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the Fe-Mn oxide and residual fractions, while Zn was predominantly found in the residual phase. A significant percent fraction of Cu was bound in the organic/sulphide and residual phases. Based on the 206Pb/207Pb ratios of the five fractions, it was evident that some of the soils were enriched with anthropogenic Pb, such as industrial and automobile Pb. The strong associations between anthropogenic Pb and the Fe-Mn oxide and organic/sulphide phases suggested that anthropogenic Pb was relatively stable after deposition in soils.     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Implications of rhizospheric heavy metals and nutrients for the growth of alfalfa in sludge amended soil

Rhizospheric distribution of nutrients and heavy metals in sludge amended soil was investigated using the rhizobag technique to give an indication of the release of metals from wastewater sludge. DTPA-extractable Zn, Cd, Ni and Mn, and available P, K and NH4+-N in the rhizosphere were markedly depleted when soil was amended with sludge. There was no conspicuous depletion or accumulation of DTPA-extractable Cu in the rhizosphere when the soil was amended with sewage sludge but DTPA-extractable Fe accumulated in the rhizosphere when the soil was amended with increasing amounts of sludge. The pH value in the rhizosphere increased with distance from the roots when soil was amended with larger amounts of sludge. The exchangeable fraction of Cu in the rhizosphere was depleted whether or not the soil was treated with sludge. Carbonate, oxide, organic and residual fractions of Cu and Zn were depleted in the rhizosphere at a distance of 0-2 mm from the roots when soil was amended with 50% sludge. Application of sewage sludge had a positive effect on alfalfa growth. With an increase in sludge amounts, the concentrations of Fe, Cu and Zn in alfalfa shoots did not change. Soil amendments with less than 25% sludge did not increase the availability or mobility of heavy metals. The depletion in rhizospheric DTPA-extractable Zn, Cd and Ni indicates that with the sole exception of Cu, release of metals from sludge amended soil was very limited.     

Heavy metals incidence in the application of inorganic fertilizers and pesticides to rice farming soils

The concentrations of Cd, Co, Cu, Ni, Pb, Zn, Fe and Mn in different inorganic fertilizers (urea, calcium superphosphate, iron sulphate and copper sulphate) and in pesticides (two herbicides and one fungicide) are evaluated together with the contribution of these metals in soils from their use. The study was made in rice farming areas to the north of Albufera Natural Park (Valencia, Spain). The results obtained show that superphosphate is the fertilizer that contains the highest concentrations of Cd, Co, Cu and Zn as impurities. Copper sulphate and iron sulphate have the most significant concentrations of Pb, and are the only fertilizers in which Ni was detected. The three pesticides analysed show similar Cd contents and the highest levels of Fe, Mn, Zn, Pb and Ni are found in the herbicides. The most significant additions of heavy metals as impurities that soil receives from agricultural practices, are Mn, Zn, Co and Pb. Three contamination indexes have been applied to provide a basis for comparison of potential heavy metal toxicity. These results denote the potential toxicity of heavy metals in the studied soils.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.