Improvement in electrokinetic remediation of heavy metal spiked kaolin with the polarity exchange technique.

In the electrokinetic treatment of heavy metal polluted soil, an alkaline environment is generated at the cathode side. It provokes the precipitation of metal ions as hydroxides into the soil and diminishes the capability of the electroremediation to clean the polluted site. In this work the "polarity exchange" technique is presented as a simple way to avoid the negative effect of OH(-) on metal transportation. This technique lies in the operation during short time intervals at inverted polarity, so that the generation of H+ ions from the oxidation of water neutralize in the alkaline zone where the metal is precipitated, favouring its dissolution. Once the metals are redissolved, the polarity is set to the original position to transport them to the desired direction. Kaolin clay contaminated with Mn was used to test the feasibility of the polarity exchange technique. The application of the "conventional technique" dealt with a removal of 14% of the initial Mn in 7.6d. For a similar treatment time the polarity exchange technique resulted in 72% of removed Mn. Successive polarity exchanges will yield with a complete decontamination of the soil with a moderate increment in the electric power consumption.

Selection of an electrolyte to enhance the electrochemical decolourisation of indigo. Optimisation and scale-up.

The investigation presented here focussed on the electrochemical decolourisation of a commercial, textile indigo dye, in an undivided electrochemical cell using graphite electrodes. The decolourisation values obtained employing halide salts--sodium chloride, potassium bromide and potassium iodide--and a reductive agent--sodium meta-bisulphite--as electrolytes are higher than those attained when no electrolyte was used. The highest decolourisation value at a low level of electric power consumption was obtained with sodium chloride. Besides, this electrolyte is usually found in the coloured wastewaters of textile industry. Thus, a detailed study was carried out to determine the influence of electrolyte--sodium chloride--and dye concentration on the efficiency of the process expressed in terms of energy consumption and extension of the decolourisation reaction. The scale-up of the treatment with sodium chloride was satisfactorily tested in a 20 l cell.

Study of the degradation of dyes by MnP of Phanerochaete chrysosporium produced in a fixed-bed bioreactor.

The production of ligninolytic enzymes by the fungus Phanerochaete chrysosporium in a fixed-bed tubular bioreactor, filled with cubes of nylon sponge, operating in semi-solid-state conditions, was studied. Maximum individual manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of 1293 and 225 U/l were detected. The in vitro decolourisation of two structurally different dyes (Poly R-478, crystal violet) by the extracellular liquid obtained in the above-mentioned bioreactor was monitored in order to determine its degrading capability. The concentration of some compounds (sodium malonate, manganese sulphate) from the reaction mixture was optimised in order to maximise the decolourisation levels. A percentage of Poly R-478 decolourisation of 24% after 15 min of dye incubation was achieved. On the other hand, a methodology for a long treatment of these dyes based on the continuous addition of MnP enzyme and H(2)O(2) was developed. Moreover, this enzymatic treatment was compared with a photochemical decolourisation process. The former allowed to maintain the degradation rate almost constant for a long time, resulting in a decolourisation percentage of 70% and 30% for crystal violet and Poly R-478, respectively, after 2 h of treatment. As for the latter, it was not able to degrade Poly R-478, whereas crystal violet reached a degradation of 40% in 2 h.

Electrochemical decolourisation of structurally different dyes.

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.

Electrochemical remediation of phenanthrene from contaminated kaolinite.

In this work a two-stage process combining soil electrokinetic remediation and liquid electrochemical oxidation for the remediation of polluted soil with organic compounds has been developed and evaluated using phenanthrene-spiked kaolinite. Application of an unenhanced electrokinetic process resulted in negligible removal of phenanthrene from the kaolinite sample. Addition of co-solvents and electrolyte to the processing fluid used in the electrode chambers enhanced phenanthrene desorption from the kaolinite matrix and favoured electro-osmotic flow. Near-complete removal of phenanthrene was achieved using Na2SO4 and ethanol in the processing fluid. Phenanthrene was transported towards the cathode chamber where it was collected. The cathodic solution containing the pollutant was treated by electrochemical oxidation; complete degradation of phenanthrene occurred after 9 h using Na2SO4 as electrolyte.

Electromigration of Mn, Fe, Cu and Zn with citric acid in contaminated clay.

Metal reactivity, speciation and solubility have an important influence in its transportation through a porous matrix by electrokinetics and, therefore, they dramatically affect the removal efficiency. This work deals with the effect of solubility and transport competition among several metals (Mn, Fe, Cu and Zn) during their transport through polluted clay. The unenhancement electrokinetic treatment results in a limited removal of the tested metals because they were retained into the kaolinite sample by the penetration of the alkaline front. Metals showed a removal degree in accordance with the solubility of the corresponding hydroxide and its formation pH. In 7 days of treatment, the removal results were: 75.6% of Mn; 68.5% of Zn, 40.6% of Cu and 14.8% of Fe. In order to avoid the negative effects of the basic front generated at the cathode, two different techniques were proposed and tested: the addition of citric acid as complexing agent to the polluted kaolinite sample and the use of citric acid to control de pH on the cathode chamber. Both techniques are based on the capability of citric acid to act as a complexing and neutralizing agent. Almost complete removal of Mn, Cu and Zn was achieved when citric acid was used (as neutralizing or complexing agent). But Fe only reached 33% of removal because it formed a negatively charged complex with citrate that retarded its transportation to the cathode.

Remediation of phenanthrene from contaminated kaolinite by electroremediation-Fenton technology.

Polycyclic aromatic hydrocarbons (PAHs) cause a high environmental impact when released into the environment. The objective of this study was to evaluate the capacity to decontaminate polluted soils with phenanthrene as a model PAH using a combination of two technologies: electrokinetic remediation and Fenton process. Kaolinite was used as a model sample that was artificially polluted at the laboratory at an initial concentration of phenanthrene of 500 mg kg(-1) of dried kaolinite. The standard electrokinetic process resulted in negligible removal of phenanthrene from the kaolinite sample. Faster and more efficient degradation of this compound can be promoted by introduction of a strong oxidant into the soil such as hydroxyl radicals. For this reason, the Fenton reactions have been induced in several experiments in which H(2)O(2) (10%) was used as flushing solution, and kaolinite polluted with iron was used. When anode and cathode chambers were filled with H(2)O(2) (10%), the kaolinite pH is maintained at an acid value around 3.5 without pH control and an overall removal and destruction efficiency of phenanthrene of 99% was obtained in 14 days by applying a voltage gradient of 3 V cm(-1). Therefore, it is evident that a combined technology of electrokinetic remediation and Fenton reaction is capable of simultaneously removing and degrading of PAHs in polluted model samples with kaolinite.

Removal of organic pollutants and heavy metals in soils by electrokinetic remediation.

In this work, the feasibility of electrokinetic remediation for the restoration of polluted soil with organic and inorganic compounds had been development and evaluated using a model soil sample. The model soil was prepared with kaolinite clay artificially polluted in the laboratory with chromium and an azo dye: Reactive Black 5 (RB5). The electromigration of Cr in a spiked kaolinite sample was studied in alkaline conditions. Despite of the high pH registered in the kaolinite sample (around pH 9.5), Cr migrated towards the cathode and it was accumulated in the cathode chamber forming a white precipitate. The removal was not complete, and 23% of the initial Cr was retained into the kaolinite sample close to the cathode side. The azo dye RB5 could be effectively removed from kaolinite by electrokinetics and the complete cleanup of the kaolinite could be achieved in alkaline environment. In this condition, RB5 formed an anion that migrated towards the anode where it was accumulated and quickly degraded upon the electrode surface. The electrokinetic treatment of a kaolinite sample polluted with both Cr and RB5 yielded very good results. The removal of Cr was improved compared to the experiment where Cr was the only pollutant, and RB5 reached a removal as high as 95%. RB5 was removed by electromigration towards the anode, where the dye was degraded upon the surface of the electrode by electrochemical oxidation. Cr was transported towards the cathode by electromigration and electroosmosis. It is supposed that the interaction among RB5 and Cr into the kaolinite sample prevented premature precipitation and allow Cr to migrate and concentrate in the cathode chamber.

Enhanced decolourisation ability of laccase towards various synthetic dyes by an electrocatalysis technology.

Laccase in culture filtrates of Trametes versicolor degraded a number of structurally different dyes by about 30% after 30 min though only 5% of Azure B was degraded in 1 h and Poly R-478 and fuchsin were not degraded at all even after 24 h. However, by using enzymatic electrocatalysis technology all dyes were decolourised in about 30 to 135 min.