Adsorption and desorption of Cu at high equilibrium concentrations by soil and clay samples from Bulgaria

Studies were carried out on the adsorption and desorption of added copper (from 100 to 600 microg g(-1)) to whole soils with contrasting properties: a Podzol (Godech A and Godech B) and a Chernozem (Gramada). Adsorption resulted in high Cu concentrations for the Podzol. The adsorbed copper, especially that in the B-horizon, is also potentially mobile, as judged by its ease of desorption on treatment with 0.01 m CaCl(2). A higher proportion of the added adsorbed copper is retained in Godech A soil (4% clay), than in Godech B soil (41% clay). Clay minerals are the principal adsorbent in the Podzol (Godech B), because of the high desorption observed at a low site coverage (7% CEC). The Godech B clay fraction (<0.001 mm) simulates the behaviour of the whole soil. The clay fraction from the Chernozem (Gramada) shows contrasting behaviour, as compared to the whole soil. Copper in the Chernozem is specifically (non-exchangeably) adsorbed, even at pH 2.7. A Langmuir model is appropriate for describing Cu-adsorption for the systems investigated at the acid pH values.     

Effect of the cationic composition of sorption solution on the quantification of sorption-desorption parameters of heavy metals in soils

We obtained the sorption isotherms of Cd, Cu, Pb and Zn in clay, clay saline and organic soils. The distribution coefficients (K(d)) were determined in 0.02 eq l(-1) CaCl(2) and in a solution that simulated the soil solution cationic composition. The K(d) values greatly varied with the composition of the sorption solution and the initial metal concentration. The sorption experiments were complemented with the quantification of the extractable metal, to estimate the reversibility of metal sorption. The extraction yields depended on the metal-soil combination, and the initial metal concentration, showing no correlation with previous K(d) values. The effect of the solution composition in mobility predictions was estimated through a Retention Factor, defined as the ratio of the K(d) versus the extraction yield. Results showed that risk was over- or underestimated using the CaCl(2) medium in soils with a markedly different soil solution composition.     

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.     

Zinc-copper interaction affecting plant growth on a metal-contaminated soil

In order to assess the effects of metal interactions on plant growth, a greenhouse experiment was conducted, in which spring barley was grown for 48 days in a soil to which cadmium, copper, lead and zinc were added singly and in combination. Plant growth was measured as shoot and root dry matter production. At the end of the experiment the plant material was analysed for metal uptake and the soil was extracted with CaCl(2) solution, to measure the plant-available metal content. The most consistent effect on plant growth was an interaction between copper and zinc, which was also important in determining uptake of these metals and the amounts extractable with CaCl(2) solution. An analysis of the underlying mechanism led to the conclusion that the growth of barley was controlled principally by the amount of plant-available zinc, which depended on the amounts of both added zinc and added copper. The effect of the added copper was to increase the toxicity of the added zinc.     

Effect of soil on microbial responses to metal contamination

An experiment was conducted to investigate microbial responses to metal inputs in five soils with varying clay and organic contents; one soil had also a higher pH. These soils were treated with a low metal, sewage sludge control or with this sludge contaminated to achieve Cu=112, Ni=58 and Zn=220 mg kg(-1) in medium and Cu=182, Ni=98 and Zn=325 mg kg(-1) in high metal soils. CO(2) evolution rates were measured at 1 week and at 4-5-day intervals thereafter until the end of the incubation (7 weeks). Extractable metals (CaCl(2) and water), biomass C, metabolic quotient, ergosterol, bacterial-fungal phospholipid fatty acid (PLFA-3 weeks only) ratio and mineral N were measured at 3 and 7 weeks. Metal inputs caused a marked increase in metal availability in the slightly acidic sandy loams, a smaller increase in slightly acidic clays and had little effect in the alkaline loam. After an initial increase in CO(2) evolution with metal inputs in all soils, the high metal treatment alone caused a significant decrease at later stages, mainly in sandy loams. Although biomass C and metabolic quotient decreased in all soils with higher metal inputs, the effect was more pronounced in the sandy loams. Metal inputs increased ergosterol and decreased bacterial-fungal PLFA ratios in most soils. Larger mineral N contents were found in all high metal soils at 3 weeks but, after 7 weeks, metals caused a significant decrease in sandy loams. CaCl(2) and water-extractable Cu, Ni and Zn contents were closely correlated with microbial indices in sandy loam but not in clay soils. Overall, the effect of treatments on microbial and extractable metal indices was greater in loams. Within a single series, higher organic soils showed less pronounced responses to metal inputs, although this trend was not always consistent.     

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.     

The role of dissolved organic carbon in the mobility of Cd, Ni and Zn in sewage sludge-amended soils

A pot experiment was conducted to investigate the effect of application of naturally derived dissolved organic compounds (DOC) on the uptake of Cd, Ni and Zn by Lolium perenne L. from mixtures of soil and sewage sludge and on their extractability with CaCl2. DOC was applied at concentrations of 0, 285 and 470 mg l(-1) to a loamy sand (LS) and a sandy clay loam (SCL) soil mixed with sewage sludge at rates equivalent to 0, 10 and 50 t ha(-1). DOC applications significantly increased the extractability of metals and also their uptake by ryegrass, but the increase was greater where sludge was applied at 50 t ha(-1). It is suggested that DOC in soils significantly increased the availability of the metals to plants. This was especially the case in the LS soil, where DOC had less competition with surface sorption than in the SCL soil.     

Plant accumulation of potentially toxic elements in sewage sludge as affected by soil organic matter level and mycorrhizal fungi.

Leek (Allium ameloprasum) was grown in pot trials in two clay loams of contrasting organic contents, with and without indigenous mycorrhizal propagules. Sewage sludges containing varying levels of Cd, Cu and Zn were added. Extractable soil metals, plant growth, major nutrient content and accumulation of metals, and soil microbial indices were investigated. The aim was to establish whether soil organic content and mycorrhizal status affected plant and microbial exposure to these metals. Extractable metals were higher and responses to inputs more pronounced in the arable, lower organic matter soil, although only Cd showed a soil difference in the CaCl2 fraction. There were no metal toxic effects on plants and some evidence to suggest that they promoted growth. Uptake of each metal was higher in the larger plants of the grassland, higher organic matter soil. Inoculation with arbuscular mycorrhizal fungi increased root Cd and Zn concentrations. With the exception of Cd (roots) and Zn (shoots), higher inputs of sludge metals did not increase plant metals. Zn and Cu, but not Cd, concentrations were higher in roots than in shoots.     

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.     

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.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg(-1)) and DEHP (100 mg kg(-1)) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1-0.45 μm to 500-2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

Soil pH and anion abundance affects on copper adsorption

Copper (Cu) input to agricultural soils results from Cu containing pesticides and or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2-9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0-100 mg L(-1) in the equilibration solution, 95-99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl2 or Ca(NO3)2 as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500-2000 mg L(-1), the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2-7.9. In a high pH soil (pH=9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

The effects of pH and soil type on concentrations of zinc, copper and nickel extracted by calcium chloride from sewage sludge-treated soils

The effects of pH on concentrations of zinc, copper and nickel extracted by calcium chloride from a clay loam and two sandy loam soils that had been treated with sewage sludge were studied. Concentrations of all the metals increased rapidly as pH decreased below a threshold value ranging from 6.2 to 7.0 for Zn, 6.2 to 7.2 for Ni and 4.7 to 5.7 for Cu. Both the total concentrations and the threshold pH values were influenced by differences in soil texture and (between the two light-textured soils) by differences in soil cation exchange capacity. The amount of zinc and copper extracted from the mixtures was considerably less than that extracted from the same quantity of sludge alone.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

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.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg^?1) and DEHP (100 mg kg^?1) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1–0.45 μm to 500–2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

The influence of organic amendment and nickel pollution on tomato fruit yield and quality

The effects of organic fertilization (sludge application) and/or different levels of Ni pollution on tomato fruit yield, quality, nutrition, and Ni accumulation were investigated. The mass loading of sewage sludge solids used in this study for the amendment of a calcareous soil with low organic matter content was 2% (w/w). A control with no sewage sludge amendment was also included (S). Nickel was added to the sludge amended soil at 0, 60, 120 and 240 mg kg-1 concentrations. Sewage sludge addition to the calcareous soil significantly increased fruit yield but did not adversely affect the quality and nutritional status of the tomato fruit. The results demonstrated that sewage sludge could be successfully used as a horticultural fertilizer. Only the highest addition rate of Ni (240 mg kg-1) to an organic amended calcareous soil had negative effects on fruit yield and quality, and caused a Ni accumulation in fruit that could be considered as a hazard for human health. Thus, no toxic problems will be encountered in tomato fruit due to Ni pollution provided the total Ni (soil Ni plus Ni incorporated with sludge amendment) concentration is kept below the maximum concentration of Ni allowed for agricultural alkaline soils in Spain (112 mg Ni kg-1).     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.