Occurrence and potential ecological risks of PFAS in Pampulha Lake, Brazil, a UNESCO world heritage site.

Per- and polyfluoroalkyl substances (PFAS) comprise >4000 synthetic substances used in industrial applications and consumer products. PFAS used daily in households and manufacturing plants end up in domestic sewage, and industrial effluents can be discharged to surface water. Urban watersheds located in low and middle-income countries (LMIC), which lack sanitation infrastructure, are potential recipients of waste containing PFAS. Yet, only a few studies report PFAS occurrence in urban reservoirs and lakes, especially those located in the Global South due to resource limitations. This is the first study aimed to assess PFAS occurrence and ecological risks in Pampulha Lake, Brazil, a site which represents the reality of many other urban watersheds in LMIC as it is surrounded by densely populated areas and manufacturing plants. Surface water samples were collected monthly for 1 year from four sampling points at Pampulha Lake. Sample analysis was based on US Environmental Protection Agency Method 1633, which employs solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Species sensitivity distribution (SSD) curves were built to identify potentially susceptible species based on detected water concentrations. Bioaccumulation was estimated for fish tissue. Short-chain (perfluorobutanesulfonic acid, PFBS and perfluorohexanoic acid, PFHxA) and long-chain PFAS (perfluorodecanoic acid, PFDA; perfluorooctanoic acid, PFOA; perfluorododecanoic acid, PFDoA; and perfluorooctanesulfonic acid, PFOS) were detected at the µg L-1 range. Total PFAS concentrations in the wet season were generally higher than in the dry season, likely due to limited capacity of the treatment plant processing water from tributaries which receive raw sewage. More than 5 % of aquatic species are potentially susceptible to chronic effects of PFOS at detected concentrations (0.2-2.2 µg L-1). Predicted bioaccumulation of PFOS in fish was above advisory diet intake levels for humans. Results emphasize the need for studies related to PFAS occurrence in watersheds located in LMIC.

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.

Challenges on solar oxidation as post-treatment of municipal wastewater from UASB systems: Treatment efficiency, disinfection and toxicity.

The application of solar photo-Fenton as post-treatment of municipal secondary effluents (MSE) in developing tropical countries is the main topic of this review. Alternative technologies such as stabilization ponds and upflow anaerobic sludge blanket (UASB) are vastly applied in these countries. However, data related to the application of solar photo-Fenton to improve the quality of effluents from UASB systems are scarce. This review gathered main achievements and limitations associated to the application of solar photo-Fenton at neutral pH and at pilot scale to analyze possible challenges associated to its application as post-treatment of MSE generated by alternative treatments. To this end, the literature review considered studies published in the last decade focusing on CECs removal, toxicity reduction and disinfection via solar photo-Fenton. Physicochemical characteristics of effluents originated after UASB systems alone and followed by a biological post-treatment show significant difference when compared with effluents from conventional activated sludge (CAS) systems. Results obtained for solar photo-Fenton as post-treatment of MSE in developed countries indicate that remaining organic matter and alkalinity present in UASB effluents may pose challenges to the performance of solar advanced oxidation processes (AOPs). This drawback could result in a more toxic effluent. The use of chelating agents such as Fe3+-EDDS to perform solar photo-Fenton at neutral pH was compared to the application of intermittent additions of Fe2+ and both of these strategies were reported as effective to remove CECs from MSE. The latter strategy may be of greater interest in developing countries due to costs associated to complexing agents. In addition, more studies are needed to confirm the efficiency of solar photo-Fenton on the disinfection of effluent from UASB systems to verify reuse possibilities. Finally, future research urges to evaluate the efficiency of solar photo-Fenton at natural pH for the treatment of effluents from UASB systems.

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.

Combat of antimicrobial resistance in municipal wastewater treatment plant effluent via solar advanced oxidation processes: Achievements and perspectives.

This review aims to gather main achievements and limitations associated to the application of solar photocatalytic processes with regard to the removal of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) from municipal wastewater treatment plant effluent (MWWTPE). Solar photocatalytic processes were chosen considering the context of developing tropical countries. Among these processes, solar photo-Fenton has been proved effective for the elimination of ARB from MWWTPE at neutral pH in bench and pilot scale and also under continuous flow. Yet, ARG removal varies as according to the gene. Irradiation intensity and matrix composition play a key role on treatment efficiency for this purpose. The use of sulfate radical in modified solar photo-Fenton is still incipient for ARB and ARG removal. Also, investigations related to ARB resistance profile and horizontal gene transfer rates after solar photo-Fenton treatment must be further analyzed. Regarding solar heterogeneous photocatalysis, TiO2 and TiO2-composites applied in suspension are the most commonly investigated for the removal of ARB and ARGs. Irradiation intensity, temperature and catalyst dosage affect treatment efficiency. However, most studies were performed in synthetic solutions using reduced sample volumes. Extended exposition times and addition of H2O2 to the system (solar/TiO2/H2O2) are required to prevent bacteria regrowth and ensure ARG abatement. In addition, enhancement of TiO2 with graphene or (semi)metals improved ARB elimination. Differences concerning irradiation intensity, matrix composition, catalyst dosage, and model ARB and ARGs used in studies analyzed in this review hinder the comparison of photocatalysts synthesized by various research groups. Finally, future research should aim at evaluating the efficiency of solar photocatalytic processes in real matrices originated from sewage treatment systems applied in developing countries; determining indicators of antimicrobial resistance in MWWTPE; and investigating ARB mutation rate as well as the removal of cell-free ARGs present in suspension in MWWTPE.

Persulfate mediated solar photo-Fenton aiming at wastewater treatment plant effluent improvement at neutral PH: emerging contaminant removal, disinfection, and elimination of antibiotic-resistant bacteria.

This work investigated an innovative alternative to improve municipal wastewater treatment plant effluent (MWWTP effluent) quality aiming at the removal of contaminants of emerging concern (caffeine, carbendazim, and losartan potassium), and antibiotic-resistant bacteria (ARB), as well as disinfection (E. coli). Persulfate was used as an alternative oxidant in the solar photo-Fenton process (solar/Fe/S2O82-) due to its greater stability in the presence of matrix components. The efficiency of solar/Fe/S2O82- at neutral pH using intermittent iron additions is unprecedented in the literature. At first, solar/Fe/S2O82- was performed in a solar simulator (30 W m-2) leading to more than 60% removal of CECs, and the intermittent iron addition strategy was proved effective. Then, solar/Fe/S2O82- and solar/Fe/H2O2 were compared in semi-pilot scale in a raceway pond reactor (RPR) and a cost analysis was performed. Solar/Fe/S2O82- showed higher efficiencies of removal of target CECs (55%), E. coli (3 log units), and ARB (3 to 4 log units) within 1.9 kJ L-1 of accumulated irradiation compared to solar/Fe/H2O2 (CECs, 49%; E. coli, 2 log units; ARB, 1 to 3 log units in 2.5 kJ L-1). None of the treatments generated acute toxicity upon Allivibrio fischeri. Lower total cost was obtained using S2O82- (0.6 € m-3) compared to H2O2 (1.2 € m-3). Therefore, the iron intermittent addition aligned to the use of persulfate is suitable for MWWTP effluent quality improvement at neutral pH.