Heavy metal removal from sediments by biosurfactants.

Batch washing experiments were used to evaluate the feasibility of using biosurfactants for the removal of heavy metals from sediments. Surfactin from Bacillus subtilis, rhamnolipids from Pseudomonas aeruginosa and sophorolipid from Torulopsis bombicola were evaluated using a metal-contaminated sediment (110mg/kg copper and 3300mg/kg zinc). A single washing with 0.5% rhamnolipid removed 65% of the copper and 18% of the zinc, whereas 4% sophorolipid removed 25% of the copper and 60% of the zinc. Surfactin was less effective, removing 15% of the copper and 6% of the zinc. The technique of ultrafiltration and zeta potential measurements were used to determine the mechanism of metal removal by the surfactants. It was then postulated that metal removal by the biosurfactants occurs through sorption of the surfactant on to the soil surface and complexation with the metal, detachment of the metal from the soil into the soil solution and hence association with surfactant micelles. Sequential extraction procedures were used on the sediment to determine the speciation of the heavy metals before and after surfactant washing. The carbonate and oxide fractions accounted for over 90% of the zinc present in the sediments. The organic fraction constituted over 70% of the copper. Sequential extraction of the sediments after washing with the various surfactants indicated that the biosurfactants, rhamnolipid and surfactin could remove the organically-bound copper and that the sophorolipid could remove the carbonate and oxide-bound zinc. Therefore, heavy metal removal from sediments is feasible and further research will be conducted.     

Heavy metal removal from waste waters by ion flotation

Flotation studies were carried out to investigate the removal of heavy metals such as copper (II), zinc (II), chromium (III) and silver (I) from waste waters. Various parameters such as pH, collector and frother concentrations and airflow rate were tested to determine the optimum flotation conditions. Sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide were used as collectors. Ethanol and methyl isobutyl carbinol (MIBC) were used as frothers. Metal removal reached about 74% under optimum conditions at low pH. At basic pH it became as high as 90%, probably due to the contribution from the flotation of metal precipitates.     

Heavy metal removal from aqueous solutions by activated phosphate rock

The use of natural adsorbent such as phosphate rock to replace expensive imported synthetic adsorbent is particularly appropriate for developing countries such as Tunisia. In this study, the removal characteristics of lead, cadmium, copper and zinc ions from aqueous solution by activated phosphate rock were investigated under various operating variables like contact time, solution pH, initial metal concentration and temperature. The kinetic and the sorption process of these metal ions were compared for phosphate rock (PR) and activated phosphate rock (APR). To accomplish this objective we have: (a) characterized both (PR) and (APR) using different techniques (XRD, IR) and analyses (EDAX, BET-N(2)); and, (b) qualified and quantified the interaction of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) with these sorbents through batch experiments. Initial uptake of these metal ions increases with time up to 1h for (PR) and 2h for (APR), after then, it reaches equilibrium. The maximum sorption obtained for (PR) and (APR) is between pH 2 and 3 for Pb(2+) and 4 and 6 for Cd(2+), Cu(2+) and Zn(2+). The effect of temperature has been carried out at 10, 20 and 40 degrees C. The data obtained from sorption isotherms of metal ions at different temperatures fit to linear form of Langmuir sorption equation. The heat of sorption (DeltaH degrees), free energy (DeltaG degrees) and change in entropy (DeltaS degrees) were calculated. They show that sorption of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) on (PR) and (APR) an endothermic process. These findings are significant for future using of (APR) for the removal of heavy metal ions from wastewater under realistic competitive conditions in terms of initial heavy metals, concentrations and pH.     

Heavy metal removal from water by sorption using surfactant-modified montmorillonite

Removal of Cu2+ and Zn2+ from aqueous solutions by sorption on the montmorillonite modified with sodium dodecylsulfate (SDS) was investigated. Experiments were carried out as a function of solution pH, solute concentration, and temperature (25-55 degrees C). The Dubinin-Kaganer-Radushkevick model was adopted to describe the single-solute sorption isotherms. Also, the binary-solute sorption equilibria could be reasonably predicted by the competitive Langmuir model, in which the Langmuir parameters were directly taken from those obtained in single-solute systems. The thermodynamic parameters (DeltaH(o) and DeltaS(o)) for Cu2+ and Zn2+ sorption on the modified clay were also determined from the temperature dependence. The kinetics of metal ions sorption was examined and the pseudo-first-order rate constant was finally evaluated.     

Heavy metal sorption and desorption capacity of soils containing endogenous contaminants

Soils on serpentinites in some regions of northwestern Spain have been the subject of agricultural management practices involving the use of fertilizers and various types of organic waste containing heavy metals. Although such practices have facilitated crop growth, they have also raised the natural contents in heavy metals of the soils. In this work, three ferralic Cambisols and another three mollic Leptosols with high Cr and Ni contents were used to study competitive sorption and desorption of six heavy metals via K(d100), which was employed as a measure of the ability of the soils to adsorb and retain each metal. Lead was found to be the metal sorbed and retained to the greatest extent, and Cd, Ni and Zn those sorbed and retained in the smallest amounts. Although the ferralic Cambisols were found to contain greater amounts of natural heavy metals, they exhibited an increased ability to adsorb and retain the body of metals relative to the mollic Leptosols by effect of their increased contents in clay and Fe, Mn and Al oxides, in addition to their higher ion-exchange capacity. Based on the results, Pb and Cu are strongly bound, and Zn, Cd and Ni weakly bound, to the soils. The ferralic Cambisols exhibited an increased capacity to adsorb and retain Cd, Ni, Zn and--especially--Cr than the mollic Leptosols; the latter, however, proved more effective in adsorbing and retaining Cu and Pb by virtue of their increased organic matter contents. Copper sorption and retention, and Pb retention, were found to be correlated with the content in organic matter and that in vermiculite--which was only present in the mollic Leptosols--in the clay fraction.     

Remediation of heavy metal contaminated soil washing residues with amino polycarboxylic acids

Removal of Cu, Pb, and Zn by the action of the two biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS) and methylglycinediacetic acid (MGDA), as well as citric acid, was tested. Three soil samples, which had previously been treated by conventional soil washing (water), were utilized in the leaching tests. Experiments were performed in batches (0.3 kg-scale) and with a WTC-mixer system (Water Treatment Construction, 10 kg-scale). EDDS and MGDA were most often equally efficient in removing Cu, Pb, and Zn after 10–60 min. Nonetheless, after 10 d, there were occasionally significant differences in extraction efficiencies. Extraction with citric acid was generally less efficient, however equal for Zn (mainly) after 10 d. Metal removal was similar in batch and WTC-mixer systems, which indicates that a dynamic mixer system could be used in full-scale. Use of biodegradable amino polycarboxylic acids for metal removal, as a second step after soil washing, would release most remaining metals (Cu, Pb and Zn) from the present soils, however only after long leaching time. Thus, a full-scale procedure, based on enhanced metal leaching by amino polycarboxylic acids from soil of the present kind, would require a pre-leaching step lasting several days in order to be efficient.     

Heavy metal ions and organic dyes removal from water by cellulose modified with maleic anhydride

A novel type of adsorbent (CM) was synthesized by cellulose modified with maleic anhydride to remove heavy metal ions and organic dyes in this work. The synthesized adsorbent was characterized by FTIR, SEM, TGA and XRD. The degree of carboxyl group of CM was found to be 2.7 mmol g⁻¹ by the titration method. The adsorption of Hg(II) ions as heavy metal ions while basic fuchsine, methylene blue and crystal violet as organic dyes by CM was investigated. The influence of different experimental parameters such as pH, contact time, temperature on removal process was evaluated. The results indicated that the CM has a good adsorption capacity for Hg(II). The maximum adsorption capacity of Hg(II) was found to be 172.5 mg g⁻¹, and the adsorption process was described by Freundlich isotherm model of adsorption well. The process of basic fuchsine, methylene blue and crystal violet adsorbed by CM was also studied and the adsorption removal rate of those organic dyes was 88.10, 98.47 and 92.85 % under the optimum conditions, respectively. The adsorption process was depicted by the Langmuir isotherm model more correctly.     

Heavy metal removal from copper smelting effluent using electrochemical cylindrical flow reactor

The purpose of this study is mainly to evaluate the performance of the continuous recirculation flow cell at low current density and pH (the pH at which the effluents are available) in removing heavy metals from copper smelting effluent by cathodic reduction. During the electrolysis at different pH, % removal of heavy metals removal, energy consumption and heterogeneous reaction rate constants were investigated at given flow rate and current density on the selected industrial effluent. The overall specific energy consumption at the pH 0.64 was observed to be lowest, which is 10.99kWh/kg of heavy metal removal.     

Soil washing for metal removal: a review of physical/chemical technologies and field applications

Soil washing is one of the few permanent treatment alternatives to remove metal contaminants from soils. This paper reviews the various technology types and pilot/full-scale field applications of soil washing applicable to soils highly contaminated with heavy metals. The physical separation technologies, the chemical extraction processes and the integrated processes that combine both physical and chemical methods are discussed separately. This paper reviews basic principles, applicability, advantages and limitations, methods of predicting and improving performance of each physical/chemical technology. The discussion is based on a review of 30 recent laboratory investigations and 37 field applications of soil washing systems which have been undertaken, mostly in the US, for the period 1990-2007. This paper also examines and compares the status of soil washing technology for remediation of soils contaminated with metals in the US, in Canada and in Europe.     

Impact of carbonate on the efficiency of heavy metal removal from kaolinite soil by the electrokinetic soil remediation method

While the feasibility of using electrokinetics to decontaminate soils has been studied by several authors, the effects of soil composition on the efficiency of this method of decontamination has yet to be fully studied. This study focuses its attention on the effect of “calcite or carbonate” (CaCO₃) on removal efficiency in electrokinetic soil remediation. Bench scale experiments were conducted on two soils: kaolinite and natural-soil of a landfill in Hamedan, Iran. Prescribed quantities of carbonates were mixed with these soils which were subsequently contaminated with zinc nitrate. After that, electrokinetic experiments were conducted to determine the efficiency of electrokinetic remediation. The results showed that an increase in the quantity of carbonate caused a noticeable increase on the contaminant retention of soil and on the resistance of soil to the contaminant removal by electrokinetic method. Because the presence of carbonates in the soil increases its buffering capacity, acidification is reduced, resulting in a decrease in the rate of heavy metal removed from the contaminant soil. This conclusion was validated by the evaluation of efficiency of electrokinetic method on a soil sample from the liner of a waste disposal site, with 28% carbonates.     

Plasma-assisted removal of organic contaminants inside cavities

Parametric studies have been carried out to determine the cleaning efficiency of a low-pressure microwave discharge at 2.45 GHz in Ar and O₂. The prototypical problem of reduced cleaning efficiency inside deep bore holes is studied with modular 3D test substrates containing bore holes of different depths. The design of the substrates allows for a simplified access of surface diagnostic techniques to measure the mass removal depending on the aspect ratio of cavities.The cleaning effect is verified by the reduction of thin oil films or polypropylene samples situated at the bottom or sidewall of the substrate. Gravimetric and profilometric measurements are presented and the effect of process parameters (power, pressure, pulse duration, and gas mixture) on the removal rate of organic material from the surface is illuminated.Within the conditions under investigation pressures between 10 and 20 Pa lead to optimum results for an aspect ratio of 16.7 and absolute depths of 100 mm. While higher pressures lead to better cleaning at the surface, the removal diminishes greatly in deeper trenches, however, the cleaning efficiency in depth regions below 30 mm can be enhanced by choosing proper treatment parameters.The results suggest that the cleaning process under these conditions is dominated by chemical surface reactions and the transport of reactive species in the holes is strongly influenced by losses due to wall reactions.     

Full-scale and pilot-scale soil washing.

The purpose of this paper is to describe soil washing and to present results obtained from pilot-scale and full-scale projects. The soil washing system to be described is a water-based physical separation process which relies on traditional physical and chemical extraction and separation processes for removing a broad range of organic, inorganic, and radioactive contaminants from soil. Although soil washing is becoming more accepted as a treatment technology in the United States, limited experience in field application still appears to be a barrier to more widespread implementation. This paper will attempt to overcome some of those barriers by describing the system and its applications, and providing case histories of successful experiences in full-scale and pilot-scale field operations. Both levels of operations have been very successful, and confirm the viability of soil washing for treating contaminated soils.     

Integrated treatment of PAH contaminated soil by soil washing, ozonation and biological treatment

The aim of the study was to optimise three different treatment methods and to find out if the integration of soil washing, ozonation and biological treatment could be a feasible method for the remediation of aged oil contaminated with PAHs. Three different ozone doses and soil washing were studied in different pHs in order to assess their effect to the degradation and enhancement of biodegradability of PAH in the soil and water phase. Main target of the study was to find out a method with which the PAH concentrations could be decreased below the Finnish guideline level for total PAHs. In this case, the initial concentration of PAHs was 1200 mg kg(-1) and therefore almost 85% degradation of PAHs was required. Any of the methods studied was not able to reach this target level alone, but by several combinations of the methods studied achieved 90% reduction of PAHs. The consumption of ozone was 5-10 times lower in the integrated treatments of soil washing, ozonation and biological treatment than without prewashing.     

Simultaneous removal of organic contaminants and heavy metals from kaolin using an upward electrokinetic soil remediation process

Kaolins contaminated with heavy metals, Cu and Pb, and organic compounds, p-xylene and phenanthrene, were treated with an upward electrokinetic soil remediation (UESR) process. The effects of current density, cathode chamber flushing fluid, treatment duration, reactor size, and the type of contaminants under the vertical non-uniform electric field of UESR on the simultaneous removal of the heavy metals and organic contaminants were studied. The removal efficiencies of p-xylene and phenanthrene were higher in the experiments with cells of smaller diameter or larger height, and with distilled water flow in the cathode chamber. The removal efficiency of Cu and Pb were higher in the experiments with smaller diameter or shorter height cells and 0.01M HNO(3) solution as cathode chamber flow. In spite of different conditions for removal of heavy metals and organics, it is possible to use the upward electrokinetic soil remediation process for their simultaneous removal. Thus, in the experiments with duration of 6 days removal efficiencies of phenanthrene, p-xylene, Cu and Pb were 67%, 93%, 62% and 35%, respectively. The experiment demonstrated the feasibility of simultaneous removal of organic contaminants and heavy metals from kaolin using the upward electrokinetic soil remediation process.     

Heavy metal recovery from electroplating effluent using adsorption by jute waste-derived biochar for soil amendment and plant micro-fertilizer

Clean Technologies and Environmental Policy - Effluent from electroplating industries contains various toxic heavy metal ions such as chromium, nickel, lead, cadmium, copper and zinc. Recovery of...     

Heavy metal adsorption by a formulated zeolite-Portland cement mixture

Large amounts of fine zeolite by-product were produced when natural zeolite was processed into a powder with a specific particle size. In Korea, large piles of this by-product exist with no disposal options. We conducted studies to determine whether mixtures of this by-product with other materials could be used as a substitute to activated carbon for wastewater treatment. A granular material was formulated by mixing zeolite by-product with Portland cement (ZeoAds), and this material was tested for its efficiency for heavy metal removal from aqueous solutions. The ZeoAds removed Pb and Cu in an aqueous solution up to 27.03 and 23.25 mg g(-1), respectively. Adsorption kinetics of the ZeoAds for heavy metals was first-order, and the ZeoAds removed about 90% of the Cu within 30 min. At solution pH lower than five, the adsorption specificity of the ZeoAds for metals was Pb>Cu>Cd>or=Zn. Langmuir isotherms adequately described the adsorption, and adsorption capacity increased as the particle size decreased to 2 mm in diameter. The maximum adsorption capacities of the metals for the ZeoAds were, irrespective of the kinds of metals, about two times greater than those of activated carbon. Column experiments demonstrated that the ZeoAds was more efficient and had a higher sorptive capacity than activated carbon for removing metals from industrial wastewater.     

Effect of different extraction agents on metal and organic contaminant removal from a field soil

This paper presents an evaluation of different extracting solutions for the removal of phenanthrene, lead and zinc from a contaminated soil obtained from a former manufactured gas plant site. The field soil contained 50%-88% sand, 11%-35% fines, 2.7%-3.7% organic matter and high concentrations of phenanthrene (260 mg/kg), lead (50.6 mg/kg) and zinc (84.4 mg/kg). A series of batch extraction experiments were conducted using the field soil with different extracting solutions at various concentrations to investigate the removal efficiency and to optimize the concentration of each extractant. The results showed that removal efficiencies of different flushing systems were significantly influenced by their affinity and selectivity for the contaminants in the soil matrix. Non-ionic surfactants (Igepal CA720 and Tween 80) were found to be effective in removing phenanthrene, but they were ineffective in removing lead and zinc. Chelating agents (ethylenediamine tetra acetic acid, EDTA and diethylene triamine penta acetic acid, DTPA) and selected acids were effective in removing lead and zinc, but they were ineffective for the phenanthrene removal. Co-solvents and cyclodextrins were not effective for removal of any of the contaminants. A sequential use of the 0.2 M EDTA followed by 5% Tween 80 or 5% Tween 80 followed by 1 M citric acid was found to be effective for the removal of lead, zinc, and phenanthrene. Overall, it can be concluded that sequential use of different extracting solutions is required for the removal of both heavy metals and organics from field contaminated silty sand soils.     

Heavy metal sorption by calcium alginate beads from Laminaria digitata

Alginate with a high M/G ratio, extracted from Laminaria digitata, was evaluated for Cu(2+), Cd(2+) and Pb(2+) sorption in acidic solutions, in the form of calcium cross-linked beads. The high M/G ratio of alginate extracted from this algal species is most likely the determining factor for the increased adsorption capacity of the investigated metals, indicating that the mannuronic acid is responsible for the ion exchange mechanism. The data obtained from the batch experiments have been interpreted with Langmuir, Freundlich and Sips models. The Sips equation provided the best fit with the experimental results, indicating sorption sites heterogeneity for the material. The pH was found to have a significant effect on the process, with sorption capacity reaching a maximum at pH 4.5, indicating a competition mechanism between H(+) and metal ions. Kinetic experiments were performed at the optimum pH. For the interpretation of the kinetic experiments the Linear Adsorption Model was employed and diffusion coefficients were determined. The model fits the experimental data at higher concentrations, where the adsorbed quantity remains almost constant. Finally, a simplified expression of the batch kinetic adsorption model was employed. The model, predicts adequately, not only the diffusivity values, but also the concentration profiles inside the spherical particles.     

Physico-chemical treatments for removal of recalcitrant contaminants from landfill leachate

In this paper, the technical applicability and treatment performance of physico-chemical techniques (individual and/or combined) for landfill leachate are reviewed. A particular focus is given to coagulation-flocculation, chemical precipitation, ammonium stripping, membrane filtration and adsorption. The advantages and limitations of various techniques are evaluated. Their operating conditions such as pH, dose required, characteristics of leachate in terms of chemical oxygen demand (COD) and NH3-N concentration and treatment efficiency are compared. It is evident from the survey of 118 papers (1983-2005) that none of the individual physico-chemical techniques is universally applicable or highly effective for the removal of recalcitrant compounds from stabilized leachate. Among the treatments reviewed in this article, adsorption, membrane filtration and chemical precipitation are the most frequently applied and studied worldwide. Both activated carbon adsorption and nanofiltration are effective for over 95% COD removal with COD concentrations ranging from 5690 to 17,000 mg/L. About 98% removal of NH3-N with an initial concentration ranging from 3260 to 5618 mg/L has been achieved using struvite precipitation. A combination of physico-chemical and biological treatments has demonstrated its effectiveness for the treatment of stabilized leachate. Almost complete removal of COD and NH3-N has been accomplished by a combination of reverse osmosis (RO) and an upflow anaerobic sludge blanket (UASB) with an initial COD concentration of 35,000 mg/L and NH3-N concentration of 1600 mg/L and/or RO and activated sludge with an initial COD concentration of 6440 mg/L and NH3-N concentration of 1153 mg/L. It is important to note that the selection of the most suitable treatment method for landfill leachate depends on the characteristics of landfill leachate, technical applicability and constraints, effluent discharge alternatives, cost-effectiveness, regulatory requirements and environmental impact.     

Abiotic oxidation of catechol by soil metal oxides

The mechanism of catechol oxidation by soil metal oxides is investigated in a slurry reactor. This abiotic transformation is shown to consist in a three-step process. The first step is a heterogeneous reaction. Catechol undergoes fast, partial oxidation at the expenses of Fe and Mn oxides contained in the soil. In the second step, reduced Fe and Mn are released into the aqueous solution and immediately complexed by catechol. Metal-catecholate complexes are stable at the very low dissolved-oxygen concentration levels attained under nitrogen sparging. The third step is a homogenous reaction. The highly reactive intermediate produced by catechol partial oxidation initiates catechol polymerisation. Under nitrogen sparging, the polymerisation process ends rather rapidly, thus yielding only partial conversion of the phenol and producing low-molecular weight, water-soluble polymers. Further oxidation of the metal-catecholate complexes formed in the second step only occurs under air sparging. Thus, reactive intermediates are formed at much higher concentration levels than those attained when nearly no oxygen is present in solution. The polymerisation proceeds at a much faster rate until, under the experimental conditions adopted, complete catechol conversion is attained and high-molecular-weight, insoluble polymers are produced.