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.

Individual and combined effect of ions species and organic matter on the removal of microcontaminants by Fe3+-EDDS/solar-light activated persulfate.

This work is focused on improving the understanding of the complex water matrix interactions occurring during the removal of a microcontaminants mixture (acetamiprid, carbamazepine and caffeine) by solar/Fe3+-EDDS/persulfate process. The individual and combined effects of sulfates (100-500 mg/L), nitrates (20-160 mg/L), bicarbonates (77-770 mg/L) and chlorides (300-1500 mg/L) were assessed by comparing the outcomes obtained in different synthetic and actual water matrices. In general, the results showed negligible effects of the different anions on Fe3+-EDDS concentration and PS consumption profiles, while the combination of bicarbonates and chlorides seemed to be the key for the MC removal efficiency decrease found when working with complex matrixes. Finally, the influence of dissolved organic matter on process performance was evaluated. It was concluded that there is neither any influence of this variable on Fe3+-EDDS concentration and PS consumption profiles. In contrast, there was a general negative effect on MC removal efficiency, which strongly depended on both the concentration and composition of the dissolved organic matter.

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.

TiO2 photocatalysis under natural solar radiation for the degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions at pilot plant scale.

This paper deals with the removal of two last-resort antibiotics, namely imipenem and meropenem, in aqueous solutions employing heterogeneous photocatalysis with TiO2 under natural solar radiation at pilot plant scale. It was found that TiO2 photocatalysis is a very efficient technique for the degradation of both compounds in aqueous solutions, albeit it's relatively low quantum efficiency. At the experimental conditions employed in the present work (compound parabolic collectors photoreactor) the optimal TiO2 concentration was about 50 mg L-1. Experiments conducted in various aqueous matrices lead to the conclusion that the method can be applied to real aqueous matrices, such as natural waters and wastewaters. The comparison of TiO2 photocatalysis and natural photolysis showed an important decrease of the accumulated energy required to achieve the complete removal of both antibiotics which, in terms of normalized illumination time (t30W), represented a reduction of 50 min for imipenem and 60 min for meropenem.

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.

Economic evaluation of a combined photo-Fenton/MBR process using pesticides as model pollutant. Factors affecting costs.

The aim of this paper is to carry out an economic assessment on a solar photo-Fenton/MBR combined process to treat industrial ecotoxic wastewater. This study focuses on the impact of the contamination present in wastewater, the photochemical oxidation, the use of an MBR as biological process and the plant size on operating and amortization costs. As example of ecotoxic pollutant, a mixture of five commercial pesticides commonly used in the Mediterranean area has been used, ranging from 500 mg/L to 50mg/L, expressed as dissolved organic carbon concentration. The economic evaluation shows that (i) the increase in pollution load does not always involve an increase in photo-Fenton costs because they also depend on organic matter mineralization; (ii) the use of an MBR process permits lower photochemical oxidation requirements than other biological treatments, resulting in approximately 20% photo-Fenton cost reduction for highly polluted wastewater; (iii) when pollution load decreases, the contribution of reactant consumption to the photo-Fenton process costs increase with regard to amortization costs; (iv) 30% total cost reduction can be gained treating higher daily volumes, obtaining competitive costs that vary from 1.1-1.9 €/m(3), depending on the pollution load.