Influence of water matrix components and peroxide sources on the transformation products and toxicity of tebuthiuron under UVC-based advanced oxidation processes.

Coupling of UV-C irradiation to different peroxides (H2O2, S2O82- and HSO5-) has great potential to degrade persistent organic compounds due to the formation of HO• or SO4•- species. However, an in-depth comparison between the performance of different UV-C/peroxide processes as a function of (i) target compound degradation, (ii) generated transformation products and (iii) lethal/sub lethal toxicity effects has not yet been performed. To this end a comparison study was carried out to evaluate the effectiveness of different UV-C/peroxide processes using the herbicide tebuthiuron (100 or 500 µg L-1) as a model pollutant. TBH degradation experiments were performed at lab-scale in real municipal wastewater treatment plant effluent and distilled water. Faster degradation occurred by increasing peroxide concentration from 735 to 2206 µmol L-1 in the municipal wastewater treatment plant effluent, mainly for S2O82-. Experiments performed in the presence of peroxide trapping agents - HO• and SO4•- (methoxibenzene) or HO• (2-propanol) - revealed that oxidation in the UV-C/S2O82- system occurs mainly through SO4•-. Lower toxicity for the MWWTP effluent was obtained after oxidative treatments using hydrogen peroxide or monopersulfate as oxidants which react mainly through HO• radicals. Two mechanistic pathways were proposed for tebuthiuron degradation: (i) hydrogen abstraction by HO• (H2O2 and HSO5-) and (ii) electron transfer by SO4•- (S2O82-). In addition, one unprecedented transformation product was identified. In conclusion, results emphasize the relevance of comparing the degradation of toxic compounds in the presence of different peroxide sources and matrices and simultaneouly evaluating responses chemical and biological endpoints.

A review toward contaminants of emerging concern in Brazil: Occurrence, impact and their degradation by advanced oxidation process in aquatic matrices.

This work presents data regarding the occurrence and treatment of Contaminants of Emerging Concern (CECs) in Brazil in the past decade. The literature review (2011-2021) revealed the detection of 87 pharmaceutical drugs and personal care products, 58 pesticides, 8 hormones, 2 illicit drugs, caffeine and bisphenol A in distinct matrices (i.e.: wastewater, groundwater, sea water, rainwater, surface water, drinking water and hospital effluent). Concentrations of CECs varied from ng-µg L-1 depending on the location, compound and matrix. The inefficiency of conventional wastewater treatment methods on the removal of CECs and lack of basic sanitation in some regions in the country aggravates contamination of Brazilian aquatic environments and poses potential environmental and health risks. Advanced oxidation processes (AOPs) are pointed out as viable and efficient alternatives to degrade CECs and prevent environmental contamination. A total of 375 studies involving the use of AOPs in Brazilian aqueous matrices were published in the last decade. Fenton and photo-Fenton processes, photo-peroxidation, ozonation, electrochemical advanced oxidation and heterogeneous photocatalysis are some of the AOPs applied by Brazilian research groups. Although many works discuss the importance of applying these technologies for CECs removal in real treatment plants, most of these studies assess the treatment of distilled water or simulated effluent. Therefore, the conduction of studies applying AOPs in real matrices are critical to drive the implementation of these processes coupled to conventional water and wastewater treatment in real plants in order to prevent the contamination of environmental matrices by CECs in Brazil.

Reducing toxicity and antimicrobial activity of a pesticide mixture via photo-Fenton in different aqueous matrices using iron complexes.

This is the first study to investigate ethylenediamine-N,N'-disuccinic acid (EDDS)/photo-Fenton process to polish real wastewater containing pesticides for possible water reuse. To this end, simultaneous degradation of pesticides ametrine, atrazine, imidacloprid and tebuthiuron was evaluated in distilled water (DW) and in sewage treatment plant (STP) effluent at initial pH 6.0. Several operational parameters (Fe3+-EDDS concentration, Fe3+-EDDS molar ratio, EDDS addition patterns and radiation source) were evaluated. 80-98% removal of target pesticides were obtained in DW using 30 µmol L-1 of Fe3+-EDDS with a molar ratio of 1:2 (300 µmol L-1 of H2O2). In addition, the proposed Fe3+-EDDS photo-Fenton at pH 6 was more efficient than classic photo-Fenton at pH 2.7 (30-84% removal). Experiments conducted in the presence of radical trapping agents (2-propanol or chloroform) revealed that HO• was the most active radical during treatment. Matrix composition strongly affected the degradation of target pesticides as a six-fold higher concentration of reagents (180 µmol L-1 of Fe3+-EDDS and 1800 µmol L-1 of H2O2) was needed to reach the same efficiency in STP compared to DW. Even so, first order rate constants corresponding to the degradation of pesticides in DW (k = 0.098-0.85 min-1) were nearly two-fold higher than in STP (k = 0.079-0.49 min-1) under the same radiation source (black-light or solar radiation). Finally, acute toxicity towards Vibrio fischeri and Drosophila melanogaster flies, and antibacterial activity assessed for Escherichia coli were eliminated after the application of the proposed treatment, thus indicating environmental safety for either discharge or reuse of treated wastewater for crop irrigation in agriculture.

Degradation of Direct Red 81 mediated by Fenton reactions: multivariate optimization, effect of chloride and sulfate, and acute ecotoxicity assessment.

The role of different operational parameters related to Fenton reactions (pH, concentration of Fe2+ and H2O2, and reaction time) and of Cl- and SO 4- was investigated in the degradation of the azo dye Direct Red 81, expressed in terms of its decolorization. The factorial design and Pareto's charts showed that only Fe2+ concentration and pH influence the decolorization under the conditions evaluated. So, only these parameters were optimized using the response surface model. Under the best experimental conditions (initial pH 2.5, 11 mg L-1 Fe2+, 78 mg L-1 H2O2, and 20 min of reaction), 94 % of decolorization was achieved. However, even under the these conditions, but in the presence of Cl- and SO 4- , a striking loss of efficiency was observed as the concentration of these ions was increased, due the formation of chloride- and sulfate-iron complexes and less reactive inorganic radicals (Cl2•- and SO4•-). The results show that the presence of Cl- is more deleterious, since sulfate-iron complexes are more reactive towards H2O2, and the SO4•- turns out to favor the degradation. On the other hand, the  negative effect of Cl- can be compensated by increasing the chloride concentration up to 300 mmol L-1. In addition, although a high degradation level has been obtained by monitoring the dye absorbance and by HPLC-UV, a low mineralization occurred, being generated degradation products of higher ecotoxicity to Vibrio fischeri, showing the need of subsequent studies to identify these compounds as well as the application of additional treatments aiming the complete mineralization of the dye.