Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

A review and experimental verification of using chitosan and its derivatives as adsorbents for selected heavy metals

A literature survey on liquid-phase adsorption of selected heavy metals including Cu(II), Zn(II), Ni(II), Cd(II), Pb(II), Hg(II), and Cr(VI) on chitosan (CTS) and its derivatives was made from the viewpoint of adsorption capacity. This parameter was obtained from the Langmuir fit of isotherm data. The magnitude of adsorption capacity of heavy metals on pristine CTS was also used to discuss the mechanism of adsorption; that is, how many amino groups in CTS chains would coordinate with one heavy metal ion. Furthermore, a newly defined parameter, the approaching equilibrium factor R_L, was proposed to quantitatively indicate the favorability of the related adsorption process and to judge the correctness of adsorption capacity determined by the Langmuir equation.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Binding of heavy metal contaminants onto chitosans--an evaluation for remediation of metal contaminated soil and water

The binding efficiency of chitosan samples for Ag(+), Cd(2+), Cu(2+), Pb(2+) and Zn(2+) has been evaluated in order to consider their application to remediate metal contaminated soil and water. The sorption behaviour of metal ions was assessed using a batch technique at different contact time and initial metal concentration with different background electrolytes. The kinetics followed a pseudo-second-order model, while the equilibrium data correlated well with the Freundlich and Langmuir isotherm models. For example, the maximum sorption capacity (Q) for chitosan was estimated as 1.93 mmol/g for Ag(+), 1.61 mmol/g for Cu(2+), 0.94 mmol/g for Zn(2+), 0.72 mmol/g for Cd(2+) and 0.64 mmol/g for Pb(2+). Covalent interaction between metal ions and functional groups (amino and hydroxyl) of the chitosans was the main binding mechanism. Ion exchange is not an important process. Chitosan and cross-linked chitosans were able to bind metal ions in the presence of K(+), Cl(-) and NO(3)(-). The nature of Cl(-) and NO(3)(-) ions did not affect Zn(2+) binding by the chitosans. Even at 11x dilution, the chitosans were able to retain metal ions on their surfaces.     

Removal of Pb(II) from wastewater using wheat bran

The adsorption of Pb(II) ions from aqueous solutions on wheat bran (WB) has been investigated as a function of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time and pH of solution. The equilibrium process was described well by the Langmuir isotherm model with maximum sorption capacities of 69.0, 80.7 and 87.0 mgg(-1) of Pb(II) on wheat bran at 20, 40 and 60 degrees C, respectively. Thermodynamic parameters, i.e. DeltaG(0), DeltaH(0) and DeltaS(0) have also been calculated for the system and the sorption process was found to be endothermic. Good correlation coefficients were obtained for the pseudo second-order kinetic model. The metal ion could be stripped by addition of 0.5M HCl, making the adsorbent regeneration and its reutilization possible.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.     

Sorption and desorption of Cd, Cu and Pb using biomass from an eutrophized habitat in monometallic and bimetallic systems

This work examines the sorption capacity of a natural biomass collected from an irrigation pond. The biomass mainly consisted of a mixture of chlorophyte algae with caducipholic plants. Biosorption experiments were performed in monometallic and bimetallic solutions containing different metals commonly found in industrial effluents (Cd, Cu and Pb). The biosorption process was slightly slower in the binary system comparing with monometallic system which was related to competition phenomena between metal cations in solution. The biosorbent behaviour was quantified by the sorption isotherms fitting the experimental data to mathematical models. In monometallic systems, the Langmuir model showed a better fit with the following sorption order: Cu ~ Pb > Cd; and biomass-metal affinity order: Pb > Cd ~ Cu. In bimetallic systems, the binary-type Langmuir model was used and the sorption order obtained was: Pb ~ Cu > Cd. In addition, the effectiveness of the biomass was investigated in several sorption-desorption cycles using HCl and NaHCO(3). The recovery of metal was higher with HCl than with NaHCO(3), though the sorption uptake of the biomass was sensitively affected by the former desorption agent in subsequent sorption cycles.     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

超声波去除农用污泥中重金属的试验研究

污水处理厂污泥中的重金属浓度高是污泥农用的主要障碍。为了降低农用污泥中的重金属含量,以Cu、Zn、Ni、Pb为对象,研究了超声波对其的影响。结果表明:超声对污泥中重金属有一定的溶出作用。当超声时间为30min时,溶解状态Cu、Zn、Ni、Pb的析出率分别为42.1%、37.5%、12.7%、14.7%;总的析出率分别为52.7%、44.7%、23.6%、71%。其中析出的Pb大部分以胶体状态存在,而溶解状态只占很少一部分。其他几种金属则以溶解状态为主。     

Comparison of biosorbents with inorganic sorbents for removing copper(II) from aqueous solutions

In comparison with several other reported inorganic sorbents, Camellia tree leaf and primary sludge obtained from a settling tank as a pretreatment to the activated sludge system in a Hong Kong sewage treatment plant were evaluated for removing Cu(II) from aqueous solutions. Experimental data were modeled by the Langmuir isotherm equation to estimate the maximum sorption capacity (q_max). Results show that, at pH 5.6, biosorbents, Camellia tree leaf and primary sludge in particular, exert higher sorption capacities (q_max > 40 mg g⁻¹) than inorganic sorbents, Na-montmorillonite (q_max = 33.3 mg g⁻¹), fly ash (q_max = 18.8 mg g⁻¹), and goethite powder (10.3 mg g⁻¹). Furthermore, a pseudo second-order kinetic model was found to properly describe the experimental data for both bio- and inorganic sorbents. Sorption of Cu(II) on the Camellia tree leaf and primary sludge were much faster than that on the inorganic sorbents. In addition, desorption tests revealed that the desorption capacities of the two biomaterials are higher than the other selected materials; and much more Cu(II) can be retrieved from the Cu(II)-loaded biosorbents. Finally, increasing solution pH was found to greatly increase q_max and accelerate sorption processes.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Biosorption of lead by maize (Zea mays) stalk sponge

This study investigated the removal of Pb(II) from aqueous solutions by a maize (Zea mays) stalk sponge. Equilibrium and kinetic models for Pb(II) sorption were developed by considering the effect of the contact time and concentration at the optimum pH of 6 ± 0.2. The Freundlich model was found to describe the sorption energetics of Pb(II) by Z. mays stalk sponge, and a maximum Pb(II) loading capacity of 80 mg g^?1 was determined. The kinetic parameters were obtained by fitting data from experiments measuring the effect of contact time on adsorption capacity into pseudo-first and second-order equations. The kinetics of Pb(II) sorption onto Z. mays biosorbent were well defined using linearity coefficients (R²) by the pseudo-second-order equation (0.9998). The results obtained showed that Zea may stalk sponge was a useful biomaterial for Pb(II) sorption and that pH has an important effect on metal biosorption capacity.     

Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

Heavy metal content and distribution in surface sediments of the Seyhan River, Turkey

Chemical fractionation of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) was studied using a modified three-step sequential procedure to assess their impacts in the sediments of the Seyhan River, Turkey. Samples were collected from six representative stations in two campaigns in October 2009 and June 2010, which correspond to the wet and dry seasons, respectively. The total metal concentrations in the sediments demonstrated different distribution patterns at the various stations. Cadmium was the only metal that was below detection at all stations during both sampling periods. Metal fractionation showed that, except for Mn and Pb, the majority of metals were found in the residual fraction regardless of sampling time, indicating that these metals were strongly bound to the sediments. The potential mobility of the metals (non-residual fractions) is reflected in the following ranking: Pb > Mn > Zn > Cu > Ni > Cr in October 2009 and Mn > Pb > Zn > Cu > Ni > Cr in June 2010. The second highest proportion of metals was bound to organic matter/sulfides, originating primarily from anthropogenic activities. Non-residual metal fractions for all stations were highest in June 2010, which may be linked to higher organic matter concentrations in the sediment samples with 1.40% and 15.1% in October 2009 and June 2010, respectively. Potential sediment toxicity was evaluated using the Risk Assessment Code (RAC). Based on RAC classification, Cd and Cr pose no risk, Cu and Ni pose low risk, Pb and Zn were classified as medium risk metals, while the environmental risk from Mn was high. In addition, based on the sediment quality guidelines (SQG), the Seyhan River can be classified as a river with no, to moderate, toxicological risks, based on total metal concentrations.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).     

Assessment of heavy metal pollutants accumulation in the Tisza river sediments

In this study we have worked on the evaluation of heavy metal contamination in the sediments taken from the Tisza River and its tributaries, and thereby used the sequential extraction method, geochemical normalization, the calculation of the enrichment factor (EF), and the methods of statistical analysis. The chemical fractionation of Ni, Cu, Zn, Cr, Pb, Fe, and Mn, carried out by using the modified Tessier method, points to different substrates and binding mechanisms of Cu, Zn and Pb in sediments of the tributaries and sediments of the Tisza River. The similarities in the distributions of Fe and Ni in all types of sediments are the result of geochemical similarity as well as of the fact that natural sources mainly affect the concentration levels of these elements. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that metal contamination (Cu, Pb, Zn and Cr) was recorded in the sediments of the Tisza River, while no indications of pollution were detected in the tributaries of the Tisza River and the surrounding pools. The maximum values of the EF were close to 6 for Cu and Pb (moderately severe enrichment) and close to 4.5 for Zn (indicating moderate enrichment). It can be said that the Tisza River is slightly to moderately severely polluted with Cu, Zn, and Pb, and minorly polluted with Cr. It is concluded that sediments of the Tisza serve as a repository for heavy metal accumulation from adjacent urban and industrial areas.     

Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Single-element and competitive metal mobility measured with column infiltration and batch tests

The distribution coefficient, Kd, is often used to quantify heavy metal mobility in soils. Batch sorption or column infiltration tests may be used to measure Kd. The latter are closer to natural soil conditions, but are difficult to conduct in clays. This difficulty can be overcome by using a laboratory centrifuge. An acceleration of 2600 gravities was applied to columns of London Clay, an Eocene clay sub-stratum, and Cu, Ni, and Zn mobility was measured in centrifuge infiltration tests, both as single elements and in dual competition. Single-element Kd values were also obtained from batch sorption tests, and the results from the two techniques were compared. It was found that Kd values obtained by batch tests vary considerably depending on the metal concentration, while infiltration tests provided a single Kd value for each metal. This was typically in the lower end of the range of the batch test Kd values. For both tests, the order of mobility was Ni>Zn>Cu. Metals became more mobile in competition than when in single-element systems: Ni Kd decreased 3.3 times and Zn Kd 3.4 times when they competed with Cu, while Cu decreased only 1.2 times when in competition with either Ni or Zn. Our study showed that competitive sorption between metals increases the mobility of those metals less strongly bound more than it increases the mobility of more strongly bound metals.     

Distribution and movement of sludge-derived trace metals in selected Nigerian soils

Use of metal-rich sewage sludge as soil fertilizer may result in trace- metal contamination of soils. This study was conducted to evaluate the effects of long-term sludge application on trace-metal (Zn, Cu, Pb, and Ni) distribution and potential bioavailability in Nigerian soils under a tropical wet-dry climate. Total metal analyses, sequential chemical fractionation, and DTPA extractions were carried out on samples of control and sludge-amended pedons in Nigeria (a Rhodic Kandiustult and two Rhodic Kandiustalfs from Nigeria, respectively). The sewage sludge applied to the soils contained higher levels of Zn and Cu than Pb and Ni. The control pedon contained low levels of all four metals. Soil enrichment factors (EF) were calculated for each metal in the sludge-amended pedons. Compared with the control soil, the sludge-amended pedons showed elevated levels of Zn and Cu, reflecting the trace-metal composition of the sewage sludge. Zinc and Cu in the sludge-amended soils were strongly enriched at all depths in the profile, indicating that they had moved below the zone of sludge application. The sequential extraction and DTPA analyses indicated that the sludge-amended soils contained more readily extractable and bioavailable metal ions than the unamended soil.