Effects of sewage sludge biochar on plant metal availability after application to a Mediterranean soil

Pyrolytic conversion of sewage sludge into biochar could be a sustainable management option for Mediterranean agricultural soils. The aim of this work is to evaluate the effects of biochar from sewage sludge pyrolysis on soil properties; heavy metals solubility and bioavailability in a Mediterranean agricultural soil and compared with those of raw sewage sludge. Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500 °C. The pyrolysis process decreased the plant-available of Cu, Ni, Zn and Pb, the mobile forms of Cu, Ni, Zn, Cd and Pb and also the risk of leaching of Cu, Ni, Zn and Cd. A selected Mediterranean soil was amended with SL and B at two different rates in mass: 4% and 8%. The incubation experiment (200 d) was conducted in order to study carbon mineralization and trace metal solubility and bioavailability of these treatments. Both types of amendments increased soil respiration with respect to the control soil. The increase was lower in the case of B than when SL was directly added. Metals mobility was studied in soil after the incubation and it can be established that the risk of leaching of Cu, Ni and Zn were lower in the soil treated with biochar that in sewage sludge treatment. Biochar amended samples also reduced plant availability of Ni, Zn, Cd and Pb when compared to sewage sludge amended samples.     

Effects of sewage sludge biochar on plant metal availability after application to a Mediterranean soil

Pyrolytic conversion of sewage sludge into biochar could be a sustainable management option for Mediterranean agricultural soils. The aim of this work is to evaluate the effects of biochar from sewage sludge pyrolysis on soil properties; heavy metals solubility and bioavailability in a Mediterranean agricultural soil and compared with those of raw sewage sludge. Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500 °C. The pyrolysis process decreased the plant-available of Cu, Ni, Zn and Pb, the mobile forms of Cu, Ni, Zn, Cd and Pb and also the risk of leaching of Cu, Ni, Zn and Cd. A selected Mediterranean soil was amended with SL and B at two different rates in mass: 4% and 8%. The incubation experiment (200 d) was conducted in order to study carbon mineralization and trace metal solubility and bioavailability of these treatments. Both types of amendments increased soil respiration with respect to the control soil. The increase was lower in the case of B than when SL was directly added. Metals mobility was studied in soil after the incubation and it can be established that the risk of leaching of Cu, Ni and Zn were lower in the soil treated with biochar that in sewage sludge treatment. Biochar amended samples also reduced plant availability of Ni, Zn, Cd and Pb when compared to sewage sludge amended samples.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

Remediation of metal contaminated soil with mineral-amended composts

This study examined the use of two composts derived from green waste and sewage sludge, amended with minerals (clinoptilolite or bentonite), for the remediation of metal-contaminated brownfield sites to transform them into greenspace. Soils contaminated with high or low levels of metals were mixed with the mineral-enhanced composts at different ratios and assessed by leaching tests, biomass production and metal accumulation of ryegrass (Lolium perenne L.). The results showed that the green waste compost reduced the leaching of Cd and Zn up to 48% whereas the composted sewage sludge doubled the leachate concentration of Zn. However, the same soil amended with composted sewage sludge showed an efficient reduction in plant concentrations of Cd, Cu, Pb or Zn by up to 80%. The results suggest that metal immobilisation and bioavailability are governed by the formation of complexes between the metals and organic matter. The amendment with minerals had only limited effects.     

Impact of sewage sludge spreading on heavy metal speciation in tropical soils (Réunion, Indian Ocean)

This study was designed to evaluate the impact of sewage sludge spreading on tropical soilborne heavy metal speciation. Sludgeborne heavy metal speciation was also assessed, and the potential mobility of the elements was classified as follows: Zn>Ni>Cu approximately Cr. Two sequential extraction procedures were applied to study Cr, Cu, Ni and Zn speciation in control soils and sludge-amended soils. We demonstrated that sewage sludge spreading over a 2-year period did not have an impact on soilborne heavy metal concentrations but affected speciation of the most mobile fractions of Ni and Zn. Both protocols were consistent for the organic matter fractions, with an increase in Cu, Zn and Cr concentrations in the amended soil as compared to the control soil. In addition, we highlighted that the two protocols characterized different pools of organic matter and that organic compounds remained in the solid matrix after extraction. With respect to the reducible fraction, completely opposite results were obtained with the two protocols and the solid residue study revealed that the two schemes were ineffective in characterizing iron and manganese fractions.     

Contrasting effects of manure and compost on soil pH, heavy metal availability and growth of Chenopodium album L. in a soil contaminated by pyritic mine waste

Chenopodium album L. was found to be one of the initial plant species colonising a heavy metal-contaminated site, polluted by pyritic (sulphide-rich) waste from the Aznalcóllar mine spill (South-western Spain). This indicates its importance in the re-vegetation of this soil. In a pot experiment, C. album was sown in soil collected from the contaminated site, either non-amended or amended with cow manure or compost produced from olive leaves and olive mill wastewater, in order to study the effect on heavy metal bioavailability and soil pH. In non-amended and compost-amended soils, soil acidification, probably resulting from oxidation and hydrolysis of sulphide, led to increases in the concentrations of soluble sulphate and plant-available Cu, Zn and Mn in the soil (extractable with 0.1 M CaCl(2)). Under these conditions, shoot growth of C. album was negligible and shoot concentrations of Zn (2,420-5,585 microg g(-1)) and Mn (5,513-8,994 microg g(-1)) were phytotoxic. Manure application greatly increased shoot growth and reduced the shoot concentrations of Cu, Zn, and Mn, and their plant-available concentrations in the soil. These effects appeared to be related to an increase of soil pH, due to an inhibition of sulphide oxidation/hydrolysis, relative to the non-amended soil. For metal sulphides-contaminated soil, liable to acidification, manure application appears to be able to enhance the initial stages of re-vegetation, by species such as C. album.     

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.     

Effects of past sewage sludge additions on heavy metal availability in light textured soils: implications for crop yields and metal uptakes

The effect of heavy metal additions in past sewage sludge applications on soil metal availability and the growth and yield of crops was evaluated at two sites in the UK. At Gleadthorpe, sewage sludges enriched with salts of zinc (Zn), copper (Cu) and nickel (Ni) had been applied to a loamy sand in 1982 and additionally naturally contaminated Zn and Cu sludge cakes in 1986. At Rosemaund, sewage sludges naturally contaminated with Zn, Cu, Ni and chromium (Cr) had been applied in 1968-1971 to a sandy loam. From 1994 to 1997, the yields of both cereals and legumes at Gleadthorpe were up to 3 t/ha lower than the no-sludge control where total topsoil Zn and Cu concentrations exceeded 200 and 120 mg/kg, respectively, but only when topsoil ammonium nitrate extractable metal levels also exceeded 40 mg/kg Zn and 0.9 mg/kg Cu. At Rosemaund, yields were only decreased where total topsoil Cu concentrations exceeded 220 mg/kg or 0.7 mg/kg ammonium nitrate extractable Cu. These results demonstrate the importance of measuring extractable as well as total heavy metal concentrations in topsoils when assessing likely effects on plant yields and metal uptakes, and setting soil quality criteria.     

Effects of sewage sludge amendment on heavy metal accumulation and consequent responses of Beta vulgaris plants

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for palak (Beta vulgaris var. Allgreen H-1), a leafy vegetable and consequent heavy metal contamination, a pot experiment was conducted by mixing sewage sludge at 20% and 40% (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductance, organic carbon, total N, available P and exchangeable Na, K and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Cr, Cd, Cu, Zn and Ni concentrations of soil. Cd concentration in soil was found above the Indian permissible limit in soil at both the amendment ratios.

The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in heavy metal uptake and shoot and root concentrations of Ni, Cd, Cu, Cr, Pb and Zn in plants as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Concentrations of Cd, Ni and Zn were more than the permissible limits of Indian standard in the edible portion of palak grown on different sewage sludge amendments ratios. Sewage sludge amendment in soil decreased root length, leaf area and root biomass of palak at both the amendment ratios, whereas shoot biomass and yield decreased significantly at 40% sludge amendment. Rate of photosynthesis, stomatal conductance and chlorophyll content decreased whereas lipid peroxidation, peroxidase activity and protein and proline contents, increased in plants grown in sewage sludge-amended soil as compared to those grown in unamended soil.

The study clearly shows that increase in heavy metal concentration in foliage of plants grown in sewage sludge-amended soil caused unfavorable changes in physiological and biochemical characteristics of plants leading to reductions in morphological characteristics, biomass accumulation and yield. The study concludes that sewage sludge amendment in soil for growing palak may not be a good option due to risk of contamination of Cd, Ni and Zn and also due to lowering of yield at higher mixing ratio.     

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.     

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation,growth and biomass of cucumbers (Cucumis sativus L.)

When sewage sludge is incorrectly applied, it may adversely impact agro-system productivity. Thus, this study addresses the reaction of Cucumis sativus L. (cucumber) to different amendment rates (0, 10, 20, 30, 40 and 50 g kg^?1) of sewage sludge in a greenhouse pot experiment, in which the plant growth, heavy metal uptake and biomass were evaluated. A randomized complete block design with six treatments and six replications was used as the experimental design. The soil electrical conductivity, organic matter and Cr, Fe, Zn and Ni concentrations increased, but the soil pH decreased in response to the sewage sludge applications. As approved by the Council of European Communities, all of the heavy metal concentrations in the sewage sludge were less than the permitted limit for applying sewage sludge to land. Generally, applications of sewage sludge of up to 40 g kg^?1 resulted in a considerable increase in all of the morphometric parameters and biomass of cucumbers in contrast to plants grown on the control soil. Nevertheless, the cucumber shoot height; root length; number of leaves, internodes and fruits; leaf area; absolute growth rate and biomass decreased in response to 50 g kg^?1 of sewage sludge. All of the heavy metal concentrations (except the Cu, Zn and Ni in the roots, Mn in the fruits and Pb in the stems) in different cucumber tissues increased with increasing sewage sludge application rates. However, all of the heavy metal concentrations (except the Cr and Fe in the roots, Fe in the leaves and Cu in the fruits) were within the normal range and did not reach phytotoxic levels. A characteristic of these cucumbers was that all of the heavy metals had a bioaccumulation factor <1.0. All of the heavy metals (except Cd, Cu and Zn) had translocation factors that were <1.0. As a result, the sewage sludge used in this study could be considered for use as a fertilizer in cucumber production systems in Saudi Arabia and can also serve as a substitute method of sewage sludge disposal.

The effects of different sewage sludge amendment rates on the heavy metal bioaccumulation, growth and biomass of cucumbers

     

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 metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 × 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre^?1, six plots were mixed with sewage sludge (SS) at 15 t acre^?1, and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO₃, NH₄, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO₃-N and NH₄-N) in runoff water than SS treatments. Total marketable yield (lbs acre^?1) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Metal mobility at an old, heavily loaded sludge application site

This study was undertaken to determine the present distribution and mobility of sludge-applied metals at an old land application site. Trace metals concentrations were determined for soils (using 4 M HNO3 extracts), soil leachates (collected with passive wick lysimeters over a 2.5-year period), and plant tissue from a field site which received a heavy loading of wastewater sludge in 1978 and an adjacent control plot. Blue dye was used to indicate preferential percolate flowpaths in the sludge plot soil for sampling and comparison with bulk soil metals concentrations. After nearly 20 years, metals in the sludge plot leachate were found at significantly greater concentrations than in the control plot, exceeding drinking water standards for Cd, Ni, Zn, and B. Annual metals fluxes were only a fraction of the current soil metal contents, and do not account for the apparent substantial past metals losses determined in a related study. Elevated Cd, Cu, and Ni levels were found in grass growing on the sludge plot. Despite heavy loadings, fine soil texture (silty clay loam) and evidence of past and ongoing metals leaching, examination of the bulk subsoil indicated no statistically significant increases in metals concentrations (even in a calcareous subsoil horizon with elevated pH) when comparing pooled sludge plot soil profiles with controls. Sampling of dyed preferential flow paths in the sludge plot detected only slight increases in several metals. Preferential flow and metal complexation with soluble organics apparently allow leaching without easily detectable readsorption in the subsoil. The lack of significant metal deposition in subsoil may not be reliable evidence for immobility of sludge-applied metals.     

Effect of sludge-processing mode, soil texture and soil pH on metal mobility in undisturbed soil columns under accelerated loading

The effect of sludge processing (digested dewatered, pelletized, alkaline-stabilized, composted, and incinerated), soil type and initial soil pH on trace metal mobility was examined using undisturbed soil columns. Soils tested were Hudson silt loam (Glossaquic Hapludalf) and Arkport fine sandy loam (Lamellic Hapludalf), at initial pH levels of 5 and 7. Sludges were applied during four accelerated cropping cycles (215 tons/ha cumulative application for dewatered sludge; equivalent rates for other sludges), followed by four post-application cycles. Also examined (with no sludge applications) were Hudson soil columns from a field site that received a heavy loading of sludge in 1978. Romaine (Lactuca sativa) and oats (Avena sativa) were planted in alternate cycles, with oats later replaced by red clover (Trifolium pratense). Soil columns were watered with synthetic acid rainwater, and percolates were analyzed for trace metals (ICP spectroscopy), electrical conductivity and pH. Percolate metal concentrations varied with sludge and soil treatments. Composted sludge and ash had the lowest overall metal mobilities. Dewatered and pelletized sludge had notable leaching of Ni, Cd and Zn in Arkport soils, especially at low pH. Alkaline-stabilized sludge had the widest range of percolate metals (relatively insensitive to soils) including Cu, Ni, B and Mo. Old site column percolate concentrations showed good agreement with previous field data. Little leaching of P was observed in all cases. Cumulative percolate metal losses for all treatments were low relative to total applied metals. Leachate and soil pH were substantially depressed in dewatered and pelletized sludge soil columns and increased for alkaline-stabilized and ash treatments.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Extractability and bioavailability of zinc over time in three tropical soils incubated with biosolids

Phytotoxicity of heavy metal is the primary concern in applying biosolids (sewage sludge) to agricultural land. This study evaluates the changes in chemical speciation of Zn in three tropical soils of Taiwan measured with sequential extraction over a one-year period. Biosolids were applied to the soils at application rates of 10, 50 and 100 Mg ha(-1), and correlated diethylene triamine pentaacetic acid (DTPA) and sequential extraction as extract for prediction of Zn bioavailability to Chinese cabbage (Brassica chinensis L.). Experimental results indicated that the exchangeable (F1) and Fe-Mn oxide (F3) fractions in the sequential extractions increased with application rate of biosolids in the soils over time. Large amounts of Zn in the soils following the cessation of biosolids application were identified as soluble and were adsorbed by Fe-Mn oxides. The organically bound Zn, which is associated with readily decomposable carbon, is in limited amounts in the biosolid-treated soils. The DTPA-extractable concentrations of Zn in all biosolid-treated soils decreased over the time. A positive and significant correlation (r(2) = 0.96) was found between the Zn concentrations extracted with DTPA and sum of F1 and carbonate-bound (F2) fractions in the sequential extractions. Additionally, the concentrations of Zn extracted with DTPA were strongly correlated with the concentrations of Zn in the shoots of Chinese cabbages, indicating that F1+F2 in the sequential extractions was reliable for predicting Zn bioavailability to Chinese cabbage in the biosolid-treated soils.     

The influence of past metallurgical activity on the concentration of heavy metals in the soil/grass system in Sibenik (Croatia)

Degree of heavy metal pollution in soil caused by a former Ferromanganese Plant (FMP) and aluminium factory was investigated and the potential of metal mobility and bioavailability was estimated. Elemental concentrations in soil, vegetation and soil extracts were determined by EDXRF. In the nearest vicinity of the factory, soil concentrations ranged as follows: Mn 12,700-342,000 ppm, Zn 200-1090, Cu 50-440, Ni 60-330, V 60-410 and Pb 24-320 ppm. Significantly higher concentrations of V, Ni, Cu, Zn and Pb compared with control samples were also found in the soil samples taken in the vicinity of aluminium plant.     

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.