Systematic analysis of the scientific-technological production on the use of the UV, H2O2, and/or Cl2 systems in the elimination of bacteria and associated antibiotic resistance genes.

This study presents a systematic review of the scientific and technological production related to the use of systems based on UV, H2O2, and Cl2 for the elimination of antibiotic-resistant bacteria (ARB) and genes associated with antibiotic resistance (ARGs). Using the Pro Know-C (Knowledge Development Process-Constructivist) methodology, a portfolio was created and analyzed that includes 19 articles and 18 patents published between 2011 and 2022. The results show a greater scientific-technological production in UV irradiation systems (8 articles and 5 patents) and the binary combination UV/H2O2 (9 articles and 4 patents). It was emphasized that UV irradiation alone focuses mainly on the removal of ARB, while the addition of H2O2 or Cl2, either individually or in binary combinations with UV, enhances the removal of ARB and ARG. The need for further research on the UV/H2O2/Cl2 system is emphasized, as gaps in the scientific-technological production of this system (0 articles and 2 patents), especially in its electrochemically assisted implementation, have been identified. Despite the gaps identified, there are promising prospects for the use of combined electrochemically assisted UV/H2O2/Cl2 disinfection systems. This is demonstrated by the effective removal of a wide range of contaminants, including ARB, fungi, and viruses, as well as microorganisms resistant to conventional disinfectants, while reducing the formation of toxic by-products.

An efficient simultaneous degradation of sulfamethoxazole and trimethoprim by photoelectro-Fenton process under non-modified pH using a natural citric acid source: study of biodegradability, ecotoxicity, and antibacterial activity.

In this work, the use of natural organic wastes (orange and lemon peels) as sources of citric acid was evaluated along with the application of the photoelectro-Fenton (PEF) system under non-modified pH as a novel alternative to degrade a complex mixture of pharmaceuticals: sulfamethoxazole (SMX-7.90 × 10-5 mol/L) and trimethoprim (TMP-6.89 × 10-5 mol/L). The system was equipped with a carbon felt air diffusion cathode (GDE) and a Ti/IrO2 anode doped with SnO2 (DSA). A 3.6 × 10-5 mol/L solution of commercial citric acid was used as a reference. The pharmaceuticals' evolution in the mixture was followed by high-performance liquid chromatography (HPLC). The addition of natural products showed an efficient simultaneous degradation of the antibiotics (100% of SMX and TMP at 45 min and 90 min, respectively) similar to the performance produced by adding the commercial citric acid to the PEF system. Moreover, the addition of natural products allowed for an increment of biodegradability (100% removal of TOC by a modified Zahn Wellens test) and a decrease in ecotoxicity (0% in the bioassay with D. Magna) of the treated solutions. The antibacterial activity was eliminated after only 45 min of treatment, suggesting that the degradation by-products do not represent a significant risk to human health or the environment in general. Results suggest that, because of the efficient formation of Fe-citrate complexes, the PEF could be enhanced by the addition of natural organic wastes as a sustainable alternative ecological system for water contaminated pharmaceuticals. Additionally, the potential of reusing natural organic wastes has been exposed, contributing to an improved low-cost PEF by decreasing the environmental contamination produced by this type of waste.

Treatment of wastewater effluents from Bogotá - Colombia by the photo-electro-Fenton process: Elimination of bacteria and pharmaceutical.

In this work, the occurrences of bacteria families and relevant pharmaceuticals in municipal wastewater effluents from Bogotá (Colombia), and their treatment by the photo-electro-Fenton process were studied. Twenty-five representative pharmaceuticals (azithromycin, carbamazepine, ciprofloxacin, clarithromycin, diclofenac, enalapril, gabapentin, iopromide, metoprolol, sulfamethoxazole, trimethoprim, valsartan, clindamycin, erythromycin, levamisole, lincomycin, norfloxacin, oxolinic acid, phenazone, primidone, salbutamol, sulfadiazine, tetracycline, tramadol, and venlafaxine) were quantified in the effluent by LC-MS/MS analysis. Four of these target compounds (azithromycin, diclofenac, trimethoprim, norfloxacin) were found at concentrations that represent an environmental risk. In addition, several bacteria families related to water and foodborne diseases were identified in such effluents (e.g., Pseudomonadaceae, Campylobacteraceae, Aeromonadaceae, Enterobacteriaceae, and Bacteroidaceae), via shotgun-metagenomic technique. Then, a bench-scale photo-electro-Fenton (PEF) system equipped with a DSA anode (Ti/IrO2-SnO2) and a GDE cathode was applied to treat such effluents. After 60 min, this treatment led to a decrease in the ratio of the bacterial content in the original samples, ~150 thousand times, and a pondered removal of 66.12% for the pharmaceuticals. The study of the process pathways indicated that the bacteria and pharmaceuticals elimination mainly occurred through attacks of hydroxyl and chlorine radicals. Interestingly, in the case of pharmaceuticals, their environmental risk quotients were diminished after the PEF application. Furthermore, the prolonged action of this electrochemical process induced ~15% of mineralization and a significant reduction of the total DNA (removal >85%). Hence, the photo-electro-Fenton process showed to be a promising alternative to deal with municipal effluents for limiting the waterborne diseases, pollution by pharmaceuticals, and mobility/availability of genetic material coming from microorganisms.

Treatment of two sartan antihypertensives in water by photo-electro-Fenton using BDD anodes: Degradation kinetics, theoretical analyses, primary transformations and matrix effects.

Degradation of two representative antihypertensives, losartan (LOS) and valsartan (VAL) in water by photo-electro-Fenton (PEF), using a BDD anode in presence of sulfate anion was evaluated. PEF showed a fast elimination of these pollutants (>95% at 30 and 60 min of treatment for LOS and VAL, respectively). The main elimination route was the attacks of radicals produced in the system, having pseudo-first-order rate constants of 0.154 and 0.054 min-1 for LOS and VAL, correspondingly. Theoretical analyses of atomic charges were performed to rationalize the antihypertensives reactivity toward the electrogenerated degrading agents. Afterwards, the primary transformation products were assessed. The transformation products revealed that the degrading species attack the biphenyl-tetrazole, imidazole, and alcohol moieties on LOS. Meanwhile, carboxylic and amide groups, plus the central nucleus, were modified on VAL. These moieties corresponded well with the electron-rich sites indicated by the theoretical calculations. Also, the PEF process removed between 33 and 38% of total organic carbon after 5 h of electrolysis. Finally, it was considered LOS treatment in presence of oxalic acid (a typical organic waste of pharmaceutical industry), in addition to the pollutant degradation in effluents from municipal sewage treatment plants by PEF at pH ∼5. Oxalic acid accelerated LOS degradation. Meanwhile, in the effluent, the process led to 64% of LOS removal after 120 min of treatment, indicating the high potentiality of PEF to degrade antihypertensives in water containing organic and inorganic substances.

Using computer tools for the evaluation of biodegradability, toxicity, and activity on the AT1 receptor of degradation products identified in the removal of valsartan by using photo-electro-Fenton process.

This work deals with the theoretical approach of biodegradability, lipophilicity, and physiological activity of VAL and four degradation products (DPs) detected after 20 min of the photo-electro-Fenton (PEF) process. The biodegradability calculation, taking into account the change in the theoretical oxygen demand, showed that the four DPs had a more negative value than VAL, indicating that they are more susceptible to oxidation. However, these results do not imply more accessible biotransformation pathways than VAL, as observed using the EAWAG-BBD program, through which neutral biotransformation pathway prediction for VAL and DPs was made. Subsequently, by calculating the theoretical lipophilicity of the molecules (log P), the theoretical toxicity of the DPs was proposed, where the DPs had log P values between 1 and 3, lower values than those of VAL (log P = 4), indicating that DPs could be less toxic than the original compound (VAL). Both results suggest that VAL degradation (by photo-electro-Fenton process proposed) yields a positive effect on the environment. Finally, when molecular dynamic simulations were carried out, it was observed that DP1, DP2, and DP3 maintained similar interactions to those of VAL with the binding site of the AT1R. DP4 did not show any interaction. These results indicated that, despite the presence of DPs, generated after 20 min of the treatment, they could not exert a physiological activity in any organism the same way that does VAL.

Degradation of seventeen contaminants of emerging concern in municipal wastewater effluents by sonochemical advanced oxidation processes.

The simultaneous degradation of seventeen emerging concern pollutants in effluent from the municipal wastewater treatment plant (MWTP) of Bogotá-Colombia was studied using high frequency ultrasound (375 kHz). The considered compounds in the effluent corresponded to pharmaceuticals (diclofenac, carbamazepine, venlafaxine, ciprofloxacin, norfloxacin, valsartan, losartan, irbesartan, sulfamethoxazole, clarithromycin, azithromycin, erythromycin, metronidazole, trimethoprim and clindamycin); cocaine and its major metabolite benzoylecgonine. Due to limitation of the MWTP for the pollutants elimination, ultrasound was applied to remove these compounds. Interestingly, ultrasonic physical action led to releasing of ciprofloxacin, norfloxacin, diclofenac and sulfamethoxazole from suspended solids, whereas the chemical effects induced degradation of the rest of compounds. For the latter ones, an interesting correlation between the sonodegradation and arithmetic multiplication between hydrophobicity and concentration of pollutants was established. Afterwards, the sonochemical process was complemented with ferrous ions (sono-Fenton), ferrous ions plus light (sono-photo-Fenton) or ferrous ions plus light in presence of oxalic acid (sono-photo-Fenton/oxalic acid). Additionally, to clarify fundamental aspects of the different systems, individual treatments in distilled water of a model pollutant (valsartan) were performed. The complemented processes significantly enhanced all compounds degradation, following the order: sono-photo-Fenton/oxalic acid > sono-photo-Fenton ∼ sono-Fenton > sonochemistry. The Fe2+ addition improved the pollutants elimination by generation of more hydroxyl radicals in the solution bulk. Meanwhile, oxalic acid avoided Fe3+ precipitation favoring the iron catalytic cycle. Thus, the work demonstrates the high potentiality of the sono-photo-Fenton/oxalic acid system for the pollutants elimination in real-world wastewater matrices.

Advanced oxidation of antihypertensives losartan and valsartan by photo-electro-Fenton at near-neutral pH using natural organic acids and a dimensional stable anode-gas diffusion electrode (DSA-GDE) system under light emission diode (LED) lighting.

In this work photo-electro-Fenton (PEF) processes using a dimensionally stable anode-gas diffusion electrode (DSA-GDE) system under light emission diodes (LED)-type radiation were used in the degradation of the angiotensin-II-receptor antagonists (ARA II), valsartan (VAL), and losartan (LOS), which are used in the treatment of hypertension diseases, and are considered among the emerging contaminants (ECs). Organic acids as citric, tartaric, and oxalic acids were used as complexing agents of iron ions in order to maintain the performance of the Fenton reaction at near-neutral pH value. The results show that at 3.42 mA/cm2 after 90 min of electro-Fenton (EF) treatment, degradation of 70% of VAL and 100% of LOS were observed. Total degradation of VAL and LOS was reached with a PEF process at the same time with mineralization of 30%. When citric and tartaric acids were used instead of oxalic acid, similar results were obtained, i.e., total degradation of both compounds, LOS and VAL, after 90 min of treatment. The degradation performance can be attributed to the increase of the initial dissolved iron in the system, facilitating the Fe3+/Fe2+ turnover in the catalytic photo-Fenton reaction and consequently, hydroxyl radical (•OH) production. In addition, the increased photo-activity of the complexes can be associated with their high capability to complex Fe3+ and to promote ligand-to-metal charge transfer, which is of key importance to feed Fe2+ to the Fenton process. The results show that the system evaluated was more efficient to eliminate sartan family compounds using LED lighting in comparison with traditional UV-A lamps used in this kind of work. Moreover, three transformation products of VAL degradation and two transformation products of LOS degradation were identified by high-resolution mass spectrometry (HRMS) using hybrid quadrupole-time-of-flight (QTOF) MS and, at the end of the PEF system, the several organic compounds accumulated and no mineralized were effectively treated in a subsequent aerobic biological system.