Search

Coupling of UV-C irradiation to different peroxides (H 2 O 2 , S 2 O 8 2- and HSO 5 - ) has great potential to degrade persistent organic compounds due to the formation of HO • or SO 4 •- 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 S 2 O 8 2- . Experiments performed in the presence of peroxide trapping agents - HO • and SO 4 •- (methoxibenzene) or HO • (2-propanol) - revealed that oxidation in the UV-C/S 2 O 8 2- system occurs mainly through SO 4 •- . 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 • (H 2 O 2 and HSO 5 - ) and (ii) electron transfer by SO 4 •- (S 2 O 8 2- ). 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., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Benzophenone-3, fipronil and propylparaben are micropollutants that are potential threats to ecosystems and have been detected in aquatic environments. However, studies involving the investigation of new technologies aiming at their elimination from these matrices, such as advanced oxidation processes, remain scarce. In this study, different iron complexes (FeCit, FeEDTA, FeEDDS and FeNTA) were evaluated for the degradation of a mixture of these micropollutants (100 µg L−1 each) spiked in municipal wastewater treatment plant (MWWTP) effluent at pH 6.9 by solar photo-Fenton. Operational parameters (iron and H2O2 concentration and Fe/L molar ratio) were optimized for each complex. Degradation efficiencies improved significantly by increasing the concentration of iron complexes (1:1 Fe/L) from 12.5 to 100 µmol L−1 for FeEDDS, FeEDTA and FeNTA. The maximum degradation reached with FeCit for all iron concentrations was limited to 30%. Different Fe/L molar ratios were required to maximize the degradation efficiency for each ligand: 1:1 for FeNTA and FeEDTA, 1:3 for FeEDDS and 1:5 for FeCit. Considering the best Fe/L molar ratios, higher degradation rates were reached using 5.9 mmol L−1 H2O2 for FeNTA and FeEDTA compared to 1.5 and 2.9 mmol L−1 H2O2 for FeEDDS and FeCit, respectively. Acute toxicity to Canton S. strain D. melanogaster flies reduced significantly after treatment for all iron complexes, indicating the formation of low-toxicity by-products. FeNTA was considered the best iron complex source in terms of the kinetic constant (0.10 > 0.063 > 0.051 > 0.036 min−1 for FeCit, FeNTA, FeEDTA and FeEDDS, respectively), organic carbon input and cost-benefit (USD 327 m−3 > USD 20 m−3 > USD 16 m−3 > USD 13 m−3 for FeEDDS, FeCit, FeEDTA and FeNTA, respectively) when compared to the other tested complexes.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

As the presence of antibiotics in environmental waters enhances antimicrobial resistance, photolysis and heterogeneous photocatalysis of chloramphenicol (CAP) were evaluated in deionized water (DW) and in sewage treatment plant (STP) effluent under black light and solar irradiation. Processes were compared in terms of CAP degradation, reaction kinetics, and electrical energy per order, as well as regarding theoretical toxicity, biodegradability, carcinogenicity, and mutagenicity of transformation products (TPs). Rate constants obtained under photolysis (0.008 min -1 ) and heterogeneous photocatalysis (0.18 min -1 ) only differed in DW. This is due to the generation of photo-active reactive oxygen species (HO · and HO 2 ·- /O 2 ·- ) under photolysis in STP effluent, as verified by experiments in the presence of 2-propanol and chloroform. Natural organic matter and HCO 3 - were the main responsible for reducing CAP degradation in STP effluent. Fifteen TPs were identified during both processes in DW, 13 of which are unprecedented. TPs were formed mainly via HO · preferential attack on the aromatic ring and on the α-carbon, and some of them were classified as persistent and toxic, genotoxic, or carcinogenic by Toxtree software. Results confirm that solar photocatalysis is less costly than to photocatalysis under black light for wastewater treatment.

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 (Fe 3+ -EDDS concentration, Fe 3+ -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 Fe 3+ -EDDS with a molar ratio of 1:2 (300 μmol L -1 of H 2 O 2 ). In addition, the proposed Fe 3+ -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 Fe 3+ -EDDS and 1800 μmol L -1 of H 2 O 2 ) 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This study presents the degradation of fipronil in sewage treatment plant (STP) effluent by photo-Fenton at near neutral pH (pH 6.0) using Fe 3+ /Citrate complex. 83% of fipronil degradation was reached using a molar iron/citrate ratio of 1:3 (192 μmol L -1 of Fe 3+ /576 μmol L -1 of citrate). Photo-Fenton reduced the toxicity of treated solutions as according to the survival of Drosophila melanogaster exposed to non-treated and treated samples. Control experiments performed in distilled water using 32 μmol L -1 of Fe 3+ /96 μmol L -1 of citrate achieved 98% of fipronil degradation within 100 kJ m -2 (UV-A radiation, k = 30 × 10 -3  kJ -1  m 2 and t 1/2  = 23 kJ m -2 ), thus indicating that fipronil degradation is impaired by natural organic matter and inorganic ions present in STP effluent. Degradation was faster under solar radiation, as the same efficiency (98%) was obtained after 75 kJ m -2 (k = 63 × 10 -3  kJ -1  m 2 and t 1/2  = 11 kJ m -2 ). In addition, pathways of fipronil degradation using Fe 3+ /Citrate under solar and UV-A radiation were investigated and transformation products proposed. Results revealed that the HO • attack occurred preferentially in the pyrazole ring. Eight transformation products were identified by UHPLC-Q-TOF-MS and four are unprecedented in the literature. Control experiments in distilled water demonstrated that toxicity reduction is related to fipronil degradation and that transformation products are less toxic than fipronil. Furthermore, toxicity of STP fortified with fipronil was reduced after photo-Fenton. These results demonstrate the feasibility of applying this process using Fe 3+ /Citrate complex for fipronil degradation in a real matrix., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe 2+ , Fe 3+ and Fe 3+ -citrate and Fe 3+ -oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C 17 H 19 FN 3 O 4 , m/z 348; C 17 H 21 FN 3 O 5 , m/z 366; and C 13 H 12 FN 2 O 3 , m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C 17 H 21 FN 3 O 5 , m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The degradation of caffeine in different kind of effluents, via photo-Fenton process, was investigated in lab-scale and in a solar pilot plant. The treatment conditions (caffeine, Fe(2+) and H(2)O(2) concentrations) were defined by experimental design. The optimized conditions for each variable, obtained using the response factor (% mineralization), were: 52.0 mg L(-1)caffeine, 10.0 mg L(-1)Fe(2+) and 42.0 mg L(-1)H(2)O(2) (replaced in kinetic experiments). Under these conditions, in ultrapure water (UW), the caffeine concentration reached the quantitation limit (0.76 mg L(-1)) after 20 min, and 78% of mineralization was obtained respectively after 120 min of reaction. Using the same conditions, the matrix influence (surface water - SW and sewage treatment plant effluent - STP) on caffeine degradation was also evaluated. The total removal of caffeine in SW was reached at the same time in UW (after 20 min), while 40 min were necessary in STP. Although lower mineralization rates were verified for high organic load, under the same operational conditions, less H(2)O(2) was necessary to mineralize the dissolved organic carbon as the initial organic load increases. A high efficiency of the photo-Fenton process was also observed in caffeine degradation by solar photocatalysis using a CPC reactor, as well as intermediates of low toxicity, demonstrating that photo-Fenton process can be a viable alternative for caffeine removal in wastewater., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The photo-Fenton degradation of paracetamol (PCT) was evaluated using FeSO(4) and the iron complex potassium ferrioxalate (FeOx) as iron source under simulated solar light. The efficiency of the degradation process was evaluated considering the decay of PCT and total organic carbon concentration and the generation of carboxylic acids, ammonium and nitrate, expressed as total nitrogen. The results showed that the degradation was favored in the presence of FeSO(4) in relation to FeOx. The higher concentration of hydroxylated intermediates generated in the presence of FeSO(4) in relation to FeOx probably enhanced the reduction of Fe(III) to Fe(II) improving the degradation efficiency. The degradation products were determined using liquid chromatography electrospray time-of-flight mass spectrometry. Although at different concentrations, the same intermediates were generated using either FeSO(4) or FeOx, which were mainly products of hydroxylation reactions and acetamide. The toxicity of the sample for Vibrio fischeri and Daphnia magna decreased from 100% to less than 40% during photo-Fenton treatment in the presence of both iron species, except for D. magna in the presence of FeOx due to the toxicity of oxalate to this organism. The considerable decrease of the sample toxicity during photo-Fenton treatment using FeSO(4) indicates a safe application of the process for the removal of this pharmaceutical., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The influence of iron species on amoxicillin (AMX) degradation, intermediate products generated and toxicity during the photo-Fenton process using a solar simulator were evaluated in this work. The AMX degradation was favored in the presence of the potassium ferrioxalate complex (FeOx) when compared to FeSO(4). Total oxidation of AMX in the presence of FeOx was obtained after 5 min, while 15 min were necessary using FeSO(4). The results obtained with Daphnia magna biossays showed that the toxicity decreased from 65 to 5% after 90 min of irradiation in the presence of FeSO(4). However, it increased again to a maximum of 100% after 150 min, what indicates the generation of more toxic intermediates than AMX, reaching 45% after 240 min. However, using FeOx, the inhibition of mobility varied between 100 and 70% during treatment, probably due to the presence of oxalate, which is toxic to the neonates. After 240 min, between 73 and 81% TOC removal was observed. Different pathways of AMX degradation were suggested including the opening of the four-membered β-lactamic ring and further oxidations of the methyl group to aldehyde and/or hydroxylation of the benzoic ring, generating other intermediates after bound cleavage between different atoms and further oxidation to carboxylates such acetate, oxalate and propionate, besides the generation of nitrate and ammonium., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The photochemical transformation of sulfamethoxazole (SMX) was investigated in different water matrices: distilled water (DW), distilled water+nitrate (10 and 20 mg L(-1)) and seawater (SW) to evaluate its persistence, toxicity and degradation pathway. A solar simulator Suntest CPS+ was used for the irradiation experiments. Identification of transformation products was performed in DW by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Acute toxicity of irradiated solutions was monitored by Vibrio fischeri and Daphnia magna bioassays in DW. Differences in the degradation rates were observed between DW and SW, being slower in SW. Presence of nitrate (indirect photolysis) in distilled water did not affect SMX degradation rate. No dissolved organic carbon (DOC) removal was observed in any case, thus indicating the formation of abundant transformation products (TPs). Analysis by LC-TOF-MS allowed the identification of up to nine transformation products during photolysis in DW. Only three of them had been previously reported in the literature, detected with other techniques. The cleavage of the sulfonamide bond and the photoisomerization by rearrangement of the isoxazole ring represent the main pathways, at the time that generate the most abundant and persistent intermediates. The acute toxicity of SMX solution varied according to test organisms. Daphnia magna was the most sensitive showing an increase from 60% to 100% immobilization after 30 h of irradiation when depletion of SMX was achieved, thus indicating the higher toxicity of the phototransformation products generated.

In this work, the photocatalytic degradation of the antibiotic sulfamethoxazole (SMX) by solar photo-Fenton at pilot plant scale was evaluated in distilled water (DW) and in seawater (SW). Degradation and mineralization of SMX were strongly hindered in SW compared to DW. The influence of H(2)O(2) and iron concentration on the efficiency of the photocatalytic process was evaluated. An increase in iron concentration from 2.6 to 10.4 mg L(-1) showed only a slight improvement in SMX degradation and mineralization. However, an increase in H(2)O(2) concentration up to 120 mg L(-1) during photo-Fenton in DW decreased SMX solution toxicity from 85% to 20%, according to results of Daphnia magna bioassays. The same behaviour was not observed after photo-Fenton treatment in SW. Despite 45% mineralization in SW, toxicity increased from 16% to 86% as shown by Vibrio fischeri bioassays, which suggests that the intermediates generated in SW are different from those in DW. A SMX degradation pathway during the photo-Fenton treatment in DW is proposed.