Removal of heavy metals from mine tailings by in-situ bioleaching coupled to electrokinetics.

This work utilizes a combined biological-electrochemical technique for the in-situ removal of metals from polluted mine tailings. As the main novelty point it is proposed to use electrokinetics (EK) for the in-situ activation of a bioleaching mechanism into the tailings, in order to promote biological dissolution of metal sulphides (Step 1), and for the subsequent removal of leached metals by EK transport out of the tailings (Step 2). Mine tailings were collected from an abandoned Pb/Zn mine located in central-southern Spain. EK-bioleaching experiments were performed under batch mode using a lab scale EK cell. A mixed microbial culture of autochthonous acidophilic bacteria grown from the tailings was used. Direct current with polarity reversal vs alternate current was evaluated in Step 1. In turn, different biological strategies were used: biostimulation, bioaugmentation and the abiotic reference test (EK alone). It was observed that bioleaching activation was very low during Step 1, because it was difficult to maintain acidic pH in the whole soil, but then it worked correctly during Step 2. It was confirmed that microorganisms successfully contributed to the in-situ solubilization of the metal sulphides as final metal removal rates were improved compared to the conventional abiotic EK (best increases of around 40% for Cu, 162% for Pb, 18% for Zn, 13% for Mn, 40% for Ni and 15% for Cr). Alternate current seemed to be the best option. The tailings concentrations of Fe, Al, Cu, Mn, Ni and Pb after treatment comply with regulations, but Pb, Cd and Zn concentrations exceed the maximum values. From the data obtained in this work it has been observed that EK-bioleaching could be feasible, but some upgrades and future work must be done in order to optimize experimental conditions, especially the control of soil pH in acidic values.

Coupling the electrocatalytic dechlorination of 2,4-D with electroactive microbial anodes.

This work proves the feasibility of dechlorinating 2,4-D, a customary commercial herbicide, using cathodic electrocatalysis driven by the anodic microbial electrooxidation of sodium acetate. A set of microbial electrochemical systems (MES) were run under two different operating modes, namely microbial fuel cell (MFC) mode, with an external resistance of 120 Ω, or microbial electrolysis cell (MEC) mode, by supplying external voltage (0.6 V) for promoting the (bio)electrochemical reactions taking place. When operating the MES as an MFC, 32% dechlorination was obtained after 72 h of treatment, which was further enhanced by working under MEC mode and achieving a 79% dechlorination. In addition, the biodegradability (expressed as the ratio BOD/COD) of the synthetic polluted wastewater was tested prior and after the MES treatment, which was improved from negative values (corresponding to toxic effluents) up to 0.135 in the MFC and 0.453 in the MEC. Our MES approach proves to be a favourable option from the point of view of energy consumption. Running the system under MFC mode allowed to co-generate energy along the dechlorination process (-0.0120 kWh mol-1 ), even though low removal rates were attained. The energy input under MEC operation was 1.03 kWh mol-1 -a competitive value compared to previous works reported in the literature for (non-biological) electrochemical reactors for 2,4-D electrodechlorination.

Modelling the cathodic reduction of 2,4-dichlorophenol in a microbial fuel cell.

This work presents a simplified mathematical model able to predict the performance of a microbial fuel cell (MFC) for the cathodic dechlorination of 2,4-dichlorophenol (2,4-DCP) operating at different cathode pH values (7.0 and 5.0). Experimental data from previous work were utilized for the fitting of the model. The MFC modelled consisted of two chambers (bioanode and abiotic cathode), wherein the catholyte contained 300 mg L-1 of 2,4-DCP and the anolyte 1000 mg L-1 of sodium acetate. The model considered two mixed microbial populations in the anode compartment using sodium acetate as the carbon source for growth and maintenance: electrogenic and non-electrogenic biomass. 2,4-DCP, its intermediates of the reductive process (2-chlorophenol, 2-CP and 4-chlorophenol, 4-CP) and protons were considered in the model as electron acceptors in the electrogenic mechanism. The global process rate was assumed to be controlled by the biological mechanisms and modelled using multiplicative Monod-type equations. The formulation of a set of differential equations allowed to describe the simultaneous evolution of every component: concentration of sodium acetate in the anodic compartment; and concentration of 2,4-DCP, 2-CP, 4-CP, phenol and chloride in the cathode chamber. Current production and coulombic efficiencies were also estimated from the fitting. It was observed that most of the organic substrate was used by non-electrogenic mechanism. The influence of the Monod parameters was more important than the influence of the biomass yield coefficients. Finally, the model was employed to simulate different scenarios under distinct experimental conditions.

Biodegradability improvement and toxicity reduction of soil washing effluents polluted with atrazine by means of electrochemical pre-treatment: Influence of the anode material.

This work focuses on the partial anodic electro-oxidation of atrazine-polluted soil washing effluents (SWE) in order to reduce its toxicity and to improve its biodegradability. Concretely it has been evaluated the influence of the anodic material used. It is hypothesized that such partial oxidation step could be considered as a pre-treatment for a subsequent biological treatment. At first, atrazine was extracted from a polluted soil by means of a surfactant-aided soil-washing process. Then, four different anodic materials were studied in partial electro-oxidation pre-treatment batch experiments at different electric charges applied: Boron Doped Diamond (BDD), Carbon Felt (CF), and Mixed Metal Oxides Anodes with Iridium and Ruthenium. Atrazine, TOC, surfactant and sulphate species concentrations, as well as changes in toxicity and biodegradability, were monitored during electrochemical experiments, showing important differences in their evolution during the treatment. It was observed that BDD was the most powerful anodic material to completely degrade atrazine. The other materials achieve an atrazine degradation rate about 75%. Regarding mineralization of the organics in SWE, BDD overtakes clearly the rest of anodes tested. CF obtains good atrazine removal but low mineralization results. All the anodes tested slightly reduced the ecotoxicity of the water effluents. About the biodegradability, only the effluent obtained after the pre-treatment with BDD presented a high biodegradability. In this sense, it must be highlighted the mineralization obtained during the BDD pre-treatment was very strong. These results globally indicate that it is necessary to find a compromise between reaching efficient atrazine removal and biodegradability improvement, while also simultaneously avoiding strong mineralization. Additional efforts should be made to find the most adequate working conditions.

Analysis of a photobioreactor scaling up for tertiary wastewater treatment: denitrification, phosphorus removal, and microalgae production.

The present work studies the removal of nutrients (nitrate and phosphate) from a synthetic wastewater simulating a secondary treatment effluent using the microalgae Chlorella vulgaris in autotrophic photobioreactors, together with an analysis of the critical points affecting the scaling-up process from laboratory to pilot scale. Laboratory experiments were done in open agitated 1-L photobioreactors under batch operation mode, while pilot-scale experiments were done using a 150-L closed tubular photobioreactor under continuous operation mode. In both scales, nitrate was the limiting substrate and the effect of its concentration on microalgae performance was studied. From laboratory experiments, an average microalgae productivity of 85 mgVSS L-1 day-1 and approximate maximum N-NO3- and P-PO43- removal rates of 8 mg N gVSS-1 day-1, and 2.6 mg P gVSS-1 day-1 were found. Regarding pilot scale, the average microalgae productivity slightly decreased (76 mgVSS L-1 day-1) while the approximate maximum N-NO3- and P-PO43- removal rates slightly were increased (11.7 mg N gVSS-1 day-1 and 3.04 mg P gVSS-1 day-1) with respect to the laboratory-scale results. The pilot-scale operation worked under lower levels of turbulence and higher dissolved oxygen concentration and light intensity than laboratory experiments; those parameters were difficult to control and they can be identified as the critical points in the differences found on both nutrient removal and microalgae production.

Combination of bioremediation and electrokinetics for the in-situ treatment of diesel polluted soil: A comparison of strategies.

The aim of this work is to compare different strategies based on electrokinetic soil flushing and bioremediation for the remediation of diesel-polluted soil. Four options were tested at the laboratory scale: single bioremediation (Bio), performed as a control test; a direct combination of electrokinetic soil flushing and biological technologies (EKSF-Bio); EKSF-Bio with daily polarity reversal of the electric field (PR-EKSF-Bio); and a combination of electrokinetic soil flushing and a permeable reactive biological barrier (EKSF-BioPRB). Four batch experiments of 14 days duration were carried out for comparing technologies at room temperature with an electric field of 1.0 V cm(-1) (in EKSF). A diesel degrading microbial consortium was used. The experimental procedure and some specific details, such as the flushing fluids used, varied depending on the strategy. When using the EKSF-Bio option, a high buffer concentration was required to control the pH, causing soil heating, which negatively affected the biological growth and thus the diesel removal. The PR-EKSF-Bio and the EKSF-BioPRB options attained suitable operating conditions and improved the transport processes for biological growth. Polarity reversal was an efficient option for pH, moisture and temperature control. Homogeneous microbial growth was observed, and approximately 20% of the diesel was removed. The BioPRB option was not as efficient as PR-EKSF-Bio in controlling the operating conditions, but the central biobarrier protected the biological activity. Microbial growth was observed not only in the biobarrier but also in a large portion of the soil, and 29% of the diesel was removed in the short remediation test.