Simultaneous degradation of contaminants of emerging concern and disinfection by solar photoelectro-Fenton process at circumneutral pH in a solar electrochemical raceway pond reactor.

Simultaneous contaminants of emerging concern (CECs) removal and wild microorganisms' inactivation was evaluated by applying solar photoelectro-Fenton (SPEF) process in actual secondary effluent collected from a real municipal wastewater treatment plant (MWWTP). 20 L of a mixture of four CECs was used as model pollutants (200 µg/L of acetaminophen, caffeine, sulfamethazine, and sulfamethoxazole each one). The SPEF process was carried out on fully sunny days, at circumneutral pH using the complex Fe3+-EDDS, in a solar electrochemical - raceway pond reactor (SEC-RPR). Initially, the optimal conditions for CECs degradation were determined using a response surface model based on current density, iron complex concentration and Fe3+-EDDS addition time (to allow previous accumulation of H2O2) as model inputs. A current density of 24.6 mA/cm2, a Fe3+-EDDS complex concentration of 0.089 mM and 3.8 min of previous H2O2 accumulation were the resulting optimum conditions that were afterwards applied for the simultaneous degradation of the CECs synthetic mixture and wild microorganisms inactivation in actual secondary effluent. About 85% CECs removal and complete E. coli inactivation were achieved in 30 min, approximately, while E. faecalis and total coliforms could be inactivated under detection limit in 60 min and 75 min, respectively.

New development of a solar electrochemical raceway pond reactor for industrial wastewater treatment.

In this work, a solar electrochemical-raceway pond reactor (SEC-RPR) is used to treat textile industrial wastewater by solar photoelectron-Fenton (SPEF) at pilot plant scale for the first time. The SEC-RPR is composed of an electrochemical filter press-cell coupled to RPR, where H2O2 is electro-generated. A complete study about experimental variables such as current, catalyst concentration, pollutant load or liquid depth is conducted based on methyl orange removal, mineralization and decolorization. Validation of the SPEF process using SEC-RPR reached more than 80% of mineralization, as well as the complete decolorization of the solution. The good performance of the SPEF treatment in the new SEC-RPR led to quick degradation kinetics, mainly due to the synergetic action of solar radiation and good distribution of H2O2 electrogenerated in the photoreactor. 100% Methyl Orange degradation was achieved after 150, 60, 45, 30 and 20 min of reaction time applying current density equal to 5, 10, 20, 40 and 60 mA cm-2, respectively. However, the increase of current density decreased the mineralization current efficiency. Up to 10 aromatics intermediates and 5 short-chain carboxylic acids were identified by LC-MS and HPLC analysis and a reaction pathway for MO mineralization by SPEF is proposed. This study represents an essential preliminary step towards the development of the first SEC-RPR at demo scale.

Towards an Efficient Generalization of the Online Dosage of Hydrogen Peroxide in Photo-Fenton Process to Treat Industrial Wastewater.

This work addresses the dosage of H2O2 in photo-Fenton processes and the monitoring of Dissolved oxygen (DO) that can be used to drive the dosage of H2O2. The objective of this work is to show that a smarter monitoring of a process variable such as DO (for which on-line measurement can be inexpensively obtained) enables the proposal and implementation of efficient dosage strategies. The work explores the application of a recent proposed strategy consisting of: (i) initial H2O2 addition, (ii) continuous H2O2 addition until a DO set up is reached, and (iii) automatic H2O2 addition by an on-off control system based on DO slope monitoring, and applies it to the treatment of different individual contaminants and their mixtures (paracetamol and sulfamethazine). The assays performed following this dosage strategy showed improved values of TOC removed per H2O2 consumed. For the case of sulfamethazine, this improvement increased up to 25-35% with respect to the efficiency obtained without dosage. Furthermore, a deeper analysis of the results allowed detecting and assessing the opportunity to redesign the dosage scheme and reduce its complexity and the number of control parameters. The promising results obtained are discussed in regard of future research into further increasing the simplicity and robustness of this generalized control strategy that improves the applicability of the photo-Fenton process by reducing its operating costs and increasing automation.

A Rational Analysis on Key Parameters Ruling Zerovalent Iron-Based Treatment Trains: Towards the Separation of Reductive from Oxidative Phases.

The development of treatment trains for pollutant degradation employing zerovalent iron has been attracting a lot of interest in the last few years. This approach consists of pre-treatment only with zerovalent iron, followed by a Fenton oxidation taking advantage of the iron ions released in the first step. In this work, the advantages/disadvantages of this strategy were studied employing commercial zerovalent iron microparticles (mZVI). The effect of the initial amount of mZVI, H2O2, pH, conductivity, anions and dissolved oxygen were analysed using p-nitrobenzoic acid (PNBA) as model pollutant. 83% reduction of PNBA 6 µM into p-aminobenzoic acid (PABA) was achieved in natural water at an initial pH 3.0 and 1.4 g/L of mZVI, under aerobic conditions, in 2 h. An evaluation of the convenience of removing mZVI after the reductive phase before the Fenton oxidation was investigated together with mZVI reusability. The Fenton step against the more reactive PABA required 50 mg/L of H2O2 to achieve more than 96% removal in 15 min at pH 7.5 (final pH from the reductive step). At least one complete reuse cycle (reduction/oxidation) was achieved with the separated mZVI. This approach might be interesting to treat wastewater containing pollutants initially resistant to hydroxyl radicals.

Fe3+-NTA as iron source for solar photo-Fenton at neutral pH in raceway pond reactors.

This work presents, for the first time, a kinetic study of the solar photo-Fenton process at neutral pH mediated by the Fe3+-NTA complex (molar ratio 1: 1) applied to remove contaminants of emerging concern (CECs). To this end, wastewater treatment plant (WWTP) secondary effluents were treated in a raceway pond reactor (RPR) at pilot plant scale with 0.1 mM Fe3+-NTA and 0.88 mM H2O2 under average solar UVA irradiance of 35 W/m2. Sulfamethoxazole and imidacloprid, at 50 µg/L of initial concentration each, were selected as model CECs. Up to 40% of the sum of both model CECs was removed from simulated WWTP effluent by the Fe3+-NTA Fenton-like process, and >80% was removed by solar photo-Fenton. The effect of liquid depth in the reactor was evaluated, showing an increase of the treatment capacity from 12 mg CEC/m2·h to 18 mg CEC/m2·h when liquid depth increased from 5 to 15 cm. Afterwards, these results were validated with real WWTP effluents and compared with the results obtained with the Fe3+-EDDS complex under the same operating conditions. The same CEC removal rates were obtained with Fe3+-NTA and Fe3+-EDDS at 5 cm of liquid depth (kinetic constants of 0.110 min-1 and 0.046 min-1 for sulfamethoxazole and imidacloprid, respectively). Conversely, at 15 cm of liquid depth, the degradation rates were lower with Fe3+-NTA (kinetic constants of 0.034 min-1 for sulfamethoxazole and 0.017 min-1 for imidacloprid), whereas with Fe3+-EDDS the values were 0.076 min-1 and 0.047 min-1 for sulfamethoxazole and imidacloprid, respectively. Regarding process cost estimation, the use of NTA as iron chelate for solar photo-Fenton at neutral pH at pilot plant scale resulted very cost-effective (0.13-0.14 €/m3) in comparison with the use of EDDS (0.46-0.48 €/m3) at the two liquid depths tested.

Effect of liquid depth on microcontaminant removal by solar photo-Fenton with Fe(III):EDDS at neutral pH in high salinity wastewater.

In arid Mediterranean countries, such as Tunisia, wastewater often has high salinity, being an obstacle to the elimination of microcontaminants for the reuse of water in agriculture. In this paper, the photo-Fenton process in raceway pond reactors (RPRs) has been successfully applied to a simulated secondary effluent from a Tunisian urban wastewater treatment plant (WWTP), with high chloride load. A mixture of three contaminants of emerging concern (CECs) was used as model pollutants at 50 µg/L each (one antibiotic, sulfamethoxazole and two pesticides, pyrimicarb and imidacloprid). All the assays were conducted at neutral pH with 0.1 mM Fe(III):EDDS at 1:1 molar ratio. The effect of hydrogen peroxide initial concentration (20, 30, and 90 mg/L) on microcontaminant removal was studied. Different liquid depths (5 and 15 cm) were selected to assess the relationship between the microcontaminant removal and the volumetric rate of photon absorption (VRPA). Although the reaction rate was initially photo-limited, after a short reaction time of 15 min, the final yield (≈ 80% of CEC removal) was limited by the photo-degradation of the Fe(III):EDDS complex and excess H2O2 was found at all concentrations used. Therefore, treatment times below 15 min should be used. The treatment capacity was three times higher when the liquid depth was increased from 5 to 15 cm. For the first time, these results show that the operation of a 15 cm-deep RPR in continuous flow mode would be suitable for large-scale implementation of the solar photo-Fenton process.

Environmental assessment of solar photo-Fenton processes in combination with nanofiltration for the removal of micro-contaminants from real wastewaters.

Scarcity of water and concerns about the ecotoxicity of micro-contaminants are driving an interest in the use of advanced tertiary processes in wastewater treatment plants. However, the life cycle environmental implications of these treatments remain uncertain. To address this knowledge gap, this study evaluates through life cycle assessment the following four advanced process options for removal of micro-contaminants from real effluents: i) solar photo-Fenton (SPF) operating at acidic pH; ii) acidic SPF coupled with nanofiltration (NF); iii) SPF operating at neutral pH; and iv) neutral SPF coupled with NF. The results show that acidic SPF coupled with NF is the best option for all 15 impacts considered. For example, its climate change potential is almost three times lower than that of the neutral SPF process (311 vs 928 kg CO2 eq./1000 m3 of treated effluent). The latter is the worst option for 12 impact categories. For the remaining three impacts (acidification, depletion of metals and particulate matter formation), acidic SPF without NF is least sustainable; it is also the second worst option for seven other impacts. Neutral SPF with NF is the second worst technology for climate change, ozone and fossil fuel depletion as well as marine eutrophication. In summary, both types of SPF perform better environmentally with than without NF and the acidic SPF treatment is more sustainable than the neutral version. Thus, the results of this work suggest that ongoing efforts on developing neutral SPF should instead be focused on further improvements of its acidic equivalent coupled with NF. These results can also be used to inform future development of policy related to the removal of micro-contaminants from wastewater.

Inactivation of E. coli and E. faecalis by solar photo-Fenton with EDDS complex at neutral pH in municipal wastewater effluents.

Photo-Fenton is a solar disinfection technology widely demonstrated to be effective to inactivate microorganisms in water by the combined effect of photoactivated iron species and the direct action of solar photons. Nevertheless, the precipitation of iron as ferric hydroxide at basic pH is the main disadvantage of this process. Thus, challenge in photo-Fenton is looking for alternatives to iron salts. Polycarboxylic acids, such as Ethylendiamine-N',N'-disuccinic acid (EDDS), can form strong complex with Fe3+ and enhance the dissolution of iron in natural water through photochemical process. The aim of this study was to evaluate the disinfection effectiveness of solar photo-Fenton with and without EDDS in water. Several reagent concentrations were assessed, best bacterial (Escherichia coli and Enterococcus faecalis) inactivation was obtained with 0.1:0.2:0.3 mM (Fe3+:EDDS:H2O2) in isotonic water. The benefit of using EDDS complexes to increase the efficiency of kept dissolved iron in water at basic pH was proven. Solar disinfection and H2O2/solar with and without EDDS, and Fe3+:EDDS complexes were also investigated. Bacterial inactivation results in municipal wastewater effluents (MWWE) demonstrated that the competitive role of organic matter and inorganic compounds strongly affect the efficacy of Fe3+:EDDS at all concentrations tested, obtaining the fastest inactivation kinetics with H2O2/solar (0.3 mM).

Pilot-plant evaluation of TiO2 and TiO2-based hybrid photocatalysts for solar treatment of polluted water.

Materials with photocatalytic and adsorption properties for advanced wastewater treatment targeting reuse were studied. Making use of TiO2 as a well-known photocatalyst, Cu2S as a Vis-active semiconductor, and fly ash as a good adsorbent, dispersed mixtures/composites were prepared to remove pollutants from wastewater. X-ray diffraction, scanning electron microscopy, energy-dispersive X-Ray spectroscopy, atomic force microscopy, band gap energy, point of zero charge (pHpzc) and BET porosity were used to characterize the substrates. Phenol, imidacloprid and dichloroacetic acid were used as pollutants for photocatalytic activity of the new photocatalysts. Experiments using the new dispersed powders were carried out at laboratory scale in two solar simulators and under natural solar irradiation at the Plataforma Solar de Almería, in a Compound Parabolic Collector (CPC) for a comparative analysis of pollutants removal and mineralization efficiencies, and to identify features that could facilitate photocatalyst separation and reuse. The results show that radiation intensity significantly affects the phenol degradation rate. The composite mixture of TiO2 and fly ash is 2-3 times less active than sol-gel TiO2. Photodegradation kinetic data on the highly active TiO2 are compared for pollutants elimination. Photodegradation of dichloroacetic acid was fast and complete after 90min in the CPC, while after 150min imidacloprid and phenol removal was 90% and 56% respectively.

Coupling between high-frequency ultrasound and solar photo-Fenton at pilot scale for the treatment of organic contaminants: an initial approach.

This study aims to evaluate the performance of a novel pilot-scale coupled system consisting of a high frequency ultrasonic reactor (400kHz) and a compound parabolic collector (CPC). The benefits of the concurrent application of ultrasound and the photo-Fenton process were studied in regard to the degradation behavior of a series of organic pollutants. Three compounds (phenol, bisphenol A and diuron) with different physicochemical properties have been chosen in order to identify possible synergistic effects and to obtain a better estimate of the general feasibility of such a system at field scale (10L). Bisphenol A and diuron were specifically chosen due to their high hydrophobicity, and thus their assumed higher affinity towards the cavitation bubble. Experiments were conducted under ultrasonic, photo-Fenton and combined treatments. Enhanced degradation kinetics were observed during the coupled treatment and synergy factors clearly in excess of 1 have been calculated for phenol as well as for saturated solutions of bisphenol A and diuron. Although the relatively high cost of ultrasound compared to photo-Fenton still presents a significant challenge towards mainstream industrial application, the observed behavior suggests that its prudent use has the potential to significantly benefit the photo-Fenton process, via the decrease of both treatment time and H2O2 consumption.