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.

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.

A classical modelling of abandoned mine tailings' bioleaching by an autochthonous microbial culture.

The aim of this study was to study and model the bioleaching of abandoned mine tailings at different pulp densities 1-20% w/v by using an autochthonous mesophilic microbial culture. Because of the importance of the ferrous-iron oxidation as sub-process on the bioleaching of sulphide mineral ores, the ferrous-iron oxidation process by the autochthonous microbial culture was studied at different ferrous-iron concentrations. A mathematical model fitted to the experimental results and the main kinetic and stoichiometric parameters were determined, being the most relevant the maximum ferrous-iron oxidation rate 5.1 (mmol Fe2+/mmol C·h) and the biomass yield, 0.01 mmol C/mmol Fe2+, values very similar to that of mixed cultured dominated by Leptospirillum strains. This autochthonous culture was used in the bioleaching experiment carried out at different pulp densities, obtaining a maximum metal recovery in the tests carried out at 1% w/v, recovering a 90% of Cd, 60% of Zn, 30% of Cu, 25% Fe and 6% of Pb. Finally, the different leaching mechanisms were modelled by using the pyrite as ore model obtaining a bioleaching rate of 0.316 mmol Fe2+/(L·h) for the direct mechanisms and a bioleaching rate for the indirect and cooperative leaching mechanisms of 0.055 Fe2+/(L·h).

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.

Model based evaluation of plant improvement at a large wastewater treatment plant (WWTP).

In this work, the effect of the improvement carried out at a large-scale wastewater treatment plant (WWTP) was evaluated, by means of modelling works, with the aim to determine the influence of the modernization over the process performance. After modernization, the energy consumption due to the aeration decreased about a 20% maintaining the effluent quality. In order to double-check the good effluent quality, modelling works were carried out at the full-scale plant. After calibration, the model was applied to the upgraded full-scale plant obtaining deviations lower than 10%. Then, the performance of the main biochemical processes was evaluated in terms of oxygen uptake rate (OUR), ammonia uptake rate (AUR), and chemical oxygen demand (COD) consumption. The rate of the main processes depending on the aeration, that is OUR and AUR, were about 22 gO2/(kg VSS·h) and 2.9 gN/(kg VSS·h), respectively.

A new hyperaccumulator plant (Spergularia rubra) for the decontamination of mine tailings through electrokinetic-assisted phytoextraction.

The screening of new effective metal hyperaccumulators is essential for the development of profitable phytoremediation projects in highly degraded environments such as mining areas. The goal of this research was to analyze the phytoextraction potential of the native plant Spergularia rubra to decontaminate and eventually recover metals (phytomining) from the mine tailings (belonging to an abandoned Pb/Zn Spanish mine) in which it grows spontaneously. To do so, the ability of this plant species to accumulate metals was evaluated both under natural conditions and through simple and electrokinetically assisted phytoextraction tests using alternating current and different combinations of voltage gradient (1/2 V cm-1) and application time (6/12 h per day). The complete duration of the greenhouse trial was 64 days, although alternating current was applied only during the last 14 days. The results obtained demonstrated the exceptional effectiveness of S. rubra for metal hyperaccumulation and growth without affecting toxicity in highly contaminated mining waste. Zn was the metal accumulated to a higher extent in the shoots, reaching concentrations up to 17,800 mg kg-1; Pb was mainly accumulated in the roots reaching a maximum concentration of 8709 mg kg-1. Cu and Cd were accumulated to a lesser extent but the bioconcentration factors were much >1. It has been proved that S. rubra is a hyperaccumulator species for Zn and Cd both in natural and greenhouse conditions and, very probably, Pb in wild conditions. The application of AC current did not significantly increase metal concentrations in plant tissues but it was able to increase the aerial biomass of S. rubra by 49.8 %. As a result, the phytoextraction yields of all metals were significantly improved as compared to wild conditions (up to 86 % for Zn). It could open new expectations about the economic viability of recovering high-value metals from mine tailings.

Effect of hydrochar-doping on the performance of carbon felt as anodic electrode in microbial fuel cells.

In this study, the feasibility of using hydrochars as anodic doping materials in microbial fuel cells (MFCs) was investigated. The feedstock used for hydrochar synthesis was metal-polluted plant biomass from an abandoned mining site. The hydrochar obtained was activated by pyrolysis at 500 °C in N2 atmosphere. Under steady state conditions, the current exerted by the MFCs, as well as the cyclic voltammetry and polarization curves, showed that the activated hydrochar-doped anodes exhibited the best performance in terms of power and current density generation, 0.055 mW/cm2 and 0.15 mA/cm2, respectively. These values were approximately 30% higher than those achieved with non-doped or doped with non-activated hydrochar anodes which can be explained by the highly graphitic carbonaceous structures obtained during the hydrochar activation that reduced the internal resistance of the system. These results suggest that the activated hydrochar materials could significantly enhance the electrochemical performance of bioelectrochemical systems. Moreover, this integration will not only enhance the energy generated by MFCs, but also valorize metal polluted plant biomass within the frame of the circular economy.

Can rare earth elements be recovered from abandoned mine tailings by means of electrokinetic-assisted phytoextraction?

Given the high impact of traditional mining, the recovery of rare earth elements (REEs) from hazardous waste materials could become an option for the future in accordance with the principles of the circular economy. In this work, the technical feasibility of REEs recovery from metal mine tailings has been explored using electrokinetic-assisted phytoremediation with ryegrass (Lolium perenne L.). Phytoextraction combined with both AC current and DC current with reversal polarity was applied (1 V cm-1, 8 h day-1) to real mine tailings containing a total concentration of REEs (Sc, Y, La, Ce, Pr, and Nd) of around 146 mg kg-1. Changes in REEs geochemical fractionation and their concentrations in the soil pore water showed the mobilization of REEs caused by plants and electric current; REE availability was increased to a higher extent for combined electrokinetic-assisted phytoextraction treatments showing the relevant role of plants in the process. Our results demonstrated the initial hypothesis that it is feasible to recover REEs from real metal mining waste by phytoextraction and that the performance of this technology can be significantly improved by applying electric current, especially of the AC type, which increased REE accumulation in ryegrass in the range 57-68% as compared to that of the treatment without electric field application.

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.

Electro Fenton removal of clopyralid in soil washing effluents.

The removal of a commercial herbicide, based on clopyralid, by means of Electro-Fenton (EF) was studied using a soil washing effluent obtained using synthetic ground water as washing fluid. From the results, it was observed that the degradation and mineralization yields of clopyralid were high, even without the addition of supporting electrolyte. The groundwater could be then used as a sustainable supporting electrolyte. The influence of the minerals constituents, the current and the ferrous ions regeneration was evaluated. The highest hydrogen peroxide production was achieved working at 200 mA but regeneration of ferrous ions was not efficient at this current. Iodide ions were one of the main responsible in the EF efficiency decrease due to their reaction with the produced hydrogen peroxide. Electrochemical study proved that clopyralid was not electroactive and that its degradation was mainly due to radical oxidation. Long duration electrolysis carried out at 200 mA in groundwater provided an improvement of the solution biodegradability after 480 min that can be linked to a significant increase in the carboxylic acids production. These results support the feasibility of applying an EF process in order to carry out a subsequent biological mineralization.

A Critical View of Microbial Fuel Cells: What Is the Next Stage?

Microbial fuel cells (MFCs) have garnered interest from the scientific community since the beginning of this century and this has caused a considerable increase in the scientific production of MFCs. However, the ability of MFCs to generate power has not increased considerably within this timeframe. In recent years, the power generated by MFCs has remained at an almost contact level owing to difficulties in the scale-up of the technology and thus the application of MFCs for powering systems with high energy demands will not be fully developed, at least within a short temporal horizon. Scale-up by increasing the size of the electrodes has failed, because of the wrong assumption that a linear function describes the relationship between the amount of power generated by a MFC and its size. However, more efficient energy generation upon working with small MFCs has been described. This has led to a new approach for scaling up on the basis of miniaturization and replication. Then, MFCs can be connected electrically in series to increase the overall potential and in parallel to increase the overall current. However, cell-voltage reversal and ionic short-circuit issues must be solved for this approach to be successful. Nowadays, the applicability of MFC technology in wastewater treatment does not make any sense in light of the power levels reached, despite the fact that MFCs were seen as a paramount opportunity less than a decade ago. However, MFCs can be used for wastewater treatment with coupled energy generation, as well as for other technologies such as biosensors and biologically inspired robots.

Modelization of Nutrient Removal Processes at a Large WWTP Using a Modified ASM2d Model.

The biodegradation of particulate substrates starts by a hydrolytic stage. Hydrolysis is a slow reaction and usually becomes the rate limiting step of the organic substrates biodegradation. The objective of this work was to evaluate a novel hydrolysis concept based on a modification of the activated sludge model (ASM2d) and to compare it with the original ASM2d model. The hydrolysis concept was developed in order to accurately predict the use of internal carbon sources in enhanced biological nutrient removal (BNR) processes at a full scale facility located in northern Poland. Both hydrolysis concepts were compared based on the accuracy of their predictions for the main processes taking place at a full-scale facility. From the comparison, it was observed that the modified ASM2d model presented similar predictions to those of the original ASM2d model on the behavior of chemical oxygen demand (COD), NH4-N, NO3-N, and PO4-P. However, the modified model proposed in this work yield better predictions of the oxygen uptake rate (OUR) (up to 5.6 and 5.7%) as well as in the phosphate release and uptake rates.

Driving force behind electrochemical performance of microbial fuel cells fed with different substrates.

The performance of miniaturized microbial fuel cells operating with five different substrates (acetate, lactate, glucose and octanoate) were studied with the aim to identify the reason for its different performance. In all cases, the COD removal rate was about 650 mg COD L-1 d-1. However, the bio-electrochemical performance of the MFC was very different, showing the MFC fed with acetate the best performance: 20 A m-2 as maximum current density, 2 W m-2 of maximum power density, 0.376 V of OCV and 12.6% of CE. In addition, the acetate showed the best bio-electrochemical performance in the polarization curves and cyclic voltammetries. These polarization curves were modelled and the key to explain the better electrical performance of acetate was its lower ohmic losses. When working with acetate, its ohmic losses were one log-unit below those attained by the other substrates. These lower ohmic losses were not associated to the electrolyte conductivity of the fuel but to the lower ohmic loses of the biofilm generated.

Biological treatment of wastewater polluted with an oxyfluorfen-based commercial herbicide.

Fluoxil-24 is a commercial herbicide based on oxyfluorfen (a hazardous non-soluble organochlorinated compound) and additional compounds used as solvents. The aim of this work is to study the biotreatability of this commercial herbicide in water through batch experiments performed at different temperatures (15, 20, 25 and 30 °C) and initial concentrations (85, 150, 300 and 500 mg L-1 of oxyfluorfen). Activated sludge from an oil refinery wastewater treatment plant was acclimated and used for biodegradation experiments. Two main mechanisms, volatilization and biodegradation, were observed to be responsible of the herbicide removal. Fluoxil-24 removal efficiencies between approximately 40% and 80% were reached after 70 h, depending on the conditions used, and oxyfluorfen was not completely removed. Regarding the influence of the temperature, thermal inhibition problems appeared at 30 °C, and the volatilization rate of solvents increased, causing oxyfluorfen to become unavailable for microorganisms. An increase of herbicide initial concentration did not clearly affect the herbicide removal efficiency, whereas it negatively affected the biological mechanism. The experimental results were fitted to a mathematical model that included both simultaneous mechanisms of volatilization and Monod biodegradation kinetics. The model was able to predict the experimental results, and the calculated model parameters confirmed the effect of the variables under study.

Improving biodegradability of soil washing effluents using anodic oxidation.

In this work, a combination of electrochemical and biological technologies is proposed to remove clopyralid from Soil Washing Effluents (SWE). Firstly, soil washing was carried out to extract clopyralid from soil. After that, four different anodes-Ir-MMO, Ru-MMO, pSi-BDD and Carbon Felt (CF)-were evaluated in order to increase the biodegradability of the SWE. CF was selected because was the only one able to transform the pesticide to a more biodegradable compounds without completely mineralizing it. Finally, biological oxidation tests were performed to determine the aerobic biodegradability of the SWE generated. From the obtained results, it was observed that at the beginning of the electrolysis the toxicity slightly increased and the biodegradability decreases. However, for electric current charges over 2.5 A·h dm-3 the toxicity drastically decreased, showing an EC50 of 143 mg L-1, and the BOD5/COD ratio increased from 0.02 to 0.23.

Modelling aerobic biodegradation of atrazine and 2,4-dichlorophenoxy acetic acid by mixed-cultures.

The aim of this work was to study and to model the biodegradation of atrazine and 2,4-dichlorophenoxy acetic acid by aerobic mixed cultures. Slow removal rates were observed when biodegrading atrazine, in spite of the initial concentrations. However, high removal rates were obtained when biodegrading 2,4-D, removing up to 100mg/L in about 2months. Regarding the 2,4-D it must be highlighted that a lag phase appears, being its length proportional to the initial 2,4-D concentration. The biodegradation trends were fitted to a Monod based model and the value of the main parameters determined. In the case of atrazine they were µmax: 0.011 1/d and Y: 0.53g/g and in the case of 2,4-D µmax: 0.071 1/d and Y: 0.44g/g, indicating the higher persistence of atrazine. Once finished the experiments the microbial population was characterized being the major genus Pseudomonas when treating atrazine and Rhodococcus when treating 2,4-D.

Oxygen availability effect on the performance of air-breathing cathode microbial fuel cell.

The effect of the oxygen availability over the performance of an air-breathing microbial fuel cell (MFC) was studied by limiting the oxygen supply to the cathode. It was found that anodic reaction was the limiting stage in the performance of the MFC while oxygen was fully available at cathode. As the cathode was depleted of oxygen, the current density becomes limited by oxygen transport to the electrode surface. The exerted current density was maintained when oxygen mole fraction was higher than 10% due to the very good performance of the cathodic catalysts. However, the current density drastically falls when working at lower concentrations because of mass transfer limitations. In this sense it must be highlighted that the maximum exerted power, when oxygen mole fraction was higher than 10%, was almost three times higher than that obtained when oxygen mole fraction was 5%. Regarding to the wastewater treatment, a significant decrease in the COD removal was obtained when the MFC performance was reduced due to the limited availability of oxygen, which indicates the significant role of the electrogenic microorganisms in the COD removal in MFC. In addition, the low availability of oxygen at the cathode leads to a lower presence of oxygen at the anode, resulting in an increase in the coulombic efficiency.