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Contamination of natural water (NW) by emerging contaminants has been widely pointed out as one of the main challenges to ensure high-quality drinking water. Thus, the effectiveness of a solar-driven free chlorine advanced oxidation process simultaneously investigating the elimination of six organic microcontaminants (OMCs) and three bacteria from NW at a pilot-scale was evaluated in this study. Firstly, the solar/free chlorine process was studied at lab-scale using a solar simulator to evaluate the effect of free chlorine concentration (0.5-10 mg L-1) on OMC degradation and generation of toxic oxyanions (e.g., ClO3- ions). Thus, the best free chlorine concentration observed was applied for the simultaneous removal of OMCs and pathogens under natural solar light at pilot scale. At lab-scale, the solar/free chlorine (2.5 mg L-1) process achieved 80% of total degradation in 5 min (1.4 kJ L-1 of accumulative UV energy) with an oxidant consumption of 0.3 mg L-1 and without ClO3- generation. Similar results were attained under natural solar irradiation at a pilot-scale. For all bacteria strains, the legally required detection limit (DL = 1 CFU 100 mL-1) for reclaimed water reuse was attained in a short contact time. Still, more importantly, the solar/free chlorine (2.5 mg L-1) process effectively avoided the possible bacterial regrowth in the post-treated sample after six days. Finally, the combination of free chlorine with solar irradiation provided a simple and energy-efficient process for OMC and bacteria removal in NW at a pilot-scale.

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Extracts of copoazu (Theobroma gramdiflorum), canangucha (Maurita Flexuosa), and coffee (Coffea arabica) were explored as enhancers of the solar photo-Fenton process to eliminate acetaminophen, sulfamethoxazole, carbamazepine, and diclofenac in raw municipal wastewater. The process, at pH 6.2 and 5 mg L-1 of iron without the presence of extracts, had a very limited action (~35% of the pollutants degradation at 90 min of treatment) due to the iron precipitation. Interestingly, the extract addition increased the soluble iron forms, but only copoazu extract improved the pollutant degradation (~95% of elimination at 20 min of the process action). The copoazu extract components acted as natural complexing agents, maintaining the soluble iron up to 2 mg L-1 even after 90 min and, consequently, enhancing the pollutant degradation. The effect of copoazu extract dose on the process performance was also assessed, finding that an iron:polyphenols (from the copoazu extract) at a molar ratio equal to 1:0.16 was the most favorable condition. Then, the process improved by copoazu extract was applied to raw municipal wastewater. Remarkably, the process led to ~90% of total pharmaceuticals degradation at 20 min of treatment. This work evidenced the feasibility of amazonian fruit extracts to improve the solar photo-Fenton process to degrade pharmaceuticals in aqueous matrices at near-neutral pH.

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RESUMO O presente estudo teve por objetivo investigar a presença dos fármacos Cafeína, Genfibrozila, Bezafibrato, Metformina, Prometazina e Loratadina em manancial superficial e em água para consumo. Para determinar a ocorrência desses fármacos, foram realizadas seis campanhas amostrais durante o período chuvoso e seis durante o período seco, em três pontos de coleta localizados no Complexo Bolonha, cidade de Belém, região Norte do Brasil: reservatório Bolonha (captação) e estação de tratamento de água Bolonha (câmara de água filtrada e reservatório de água tratada). Para a avaliação das remoções dos fármacos nas etapas de filtração e desinfecção (com gás cloro) foram calculadas as eficiências de cada um desses processos e foi avaliada a remoção ao fim do tratamento. Como esperado, a água bruta apresentou maiores concentrações de fármacos do que a água tratada. As concentrações dos reguladores lipídicos Bezafibrato e Genfibrozila variaram de 11,4 a 1364,9 ng·L-1 na água bruta e de 15,7 a 435,9 ng·L-1 na água tratada. Já o antialérgico Loratadina foi o fármaco com maior frequência de ocorrência, e sua concentração variou de 15,7 a 45,0 ng·L-1 na água bruta e de 15,2 a 24,3 ng·L-1 na água tratada. Os resultados indicam a influência antrópica que o reservatório e a estação de tratamento de água vêm sofrendo e mostram que o tratamento de ciclo completo utilizado na estação de tratamento de água Bolonha não foi eficiente para a remoção completa dos compostos de preocupação emergente investigados. As remoções médias anuais foram de 5% para Genfibrozila, 26% para Loratadina e 52% para Bezafibrato, sendo a cloração particularmente importante para a remoção de Genfibrozila e Cafeína.

ABSTRACT The present study aimed to investigate the occurrence of the drugs Caffeine, Gemfibrozil, Bezafibrate, Metformin, Promethazine, and Loratadine in water supply and water for human consumption. To determine the occurrence of drugs, six sampling campaigns were carried out during the rainy season and six during the dry season, at three collection points located in the Bolonha Complex, Belém city, Northern Brazil: Bolonha reservoir (catchment) and Bolonha filtered water chamber and treated water reservoir. To evaluate the removal of drugs in the filtration and disinfection stages, the efficiencies of each of these processes were calculated, in addition to the removal evaluation at the end of the treatment. The raw water was the one with the highest concentrations of drugs, while the treated water had lower concentrations. The concentrations of lipid regulators Bezafibrate and Gemfibrozil ranged from 11.4 to 1,364.9 ng·L-1 in raw water and from 15.7 to 435.9 ng·L-1 in treated water. The antiallergic Loratadine was the drug with the highest frequency of occurrence whose concentration ranged from 15.7 to 45.0 ng·L-1 in raw water and from 15.2 to 24.3 ng·L-1 in treated water. The results indicate the anthropic influence that the reservoir and the filtered water chamber and treated water reservoir have been suffering and show that the full cycle treatment used in Bolonha filtered water chamber and treated water reservoir was not efficient for the complete removal of the compounds of emerging concern investigated. The average annual removals were, respectively, 5% for Gemfibrozil, 26% for Loratadine, and 52% for Bezafibrate. The chlorination step seemed to be particularly important for the removal of Gemfibrozil and Caffeine.

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This study aimed to investigate the occurrence of drugs and endocrine disrupters in water supplies and in water for human consumption. Twelve sampling campaigns were carried out during the rainy and dry season at four sampling points in the Bolonha Complex, in the city of Belém, northern region of Brazil: Bolonha reservoir (catchment) and Water Treatment Plant (WTP) Bolonha (filtered water chamber, treated water tank, and washing water from the filters). The determination of the compounds was performed by solid phase extraction followed by gas and liquid chromatography coupled to mass spectrometry. The results confirmed the anthropic influence that the reservoir and WTP-Bolonha have been suffering, as consequence of the discharge of domestic sewage in natura. Among 25 microcontaminants analyzed, 12 were quantified in raw water and 10 in treated water. The antiallergic Loratadine (LRT) was the contaminant that occurred most frequently in all sample points, having been poorly removed (median 12%) in the conventional treatment used. Losartana (LST), 4-octylphenol (4-OP), and Bisphenol A (BPA) also occurred very frequently in raw water with concentrations ranging from 3.7 to 194 ng L-1. Although such contaminants occurred in treated water in concentrations varying from 4.0 to 135 ng L-1, the estimated margin of exposure ranged from 55 to 3333 times which indicates low risk of human exposure to such contaminants through ingestion of treated water.

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In this work, the activated persulfate oxidation of ciprofloxacin (CIP) using a low-grade titanium ore under sunlight or simulated sunlight were conducted to analyze the CIP degradation efficiency and to identify the transformation products (TPs) generated during oxidation under both types of irradiation sources by using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). All advance oxidation process experiments were performed in a 2700-mL raceway reactor at a pH value of ~ 6.5 and an initial CIP concentration of 1 mg/L, during 90 min of reaction time. The control experiments carried out under simulated sunlight achieved a 97.7 ± 0.6% degradation efficiency, using 385 W/m2 of irradiation with an average temperature increase of 11.7 ± 0.6 °C. While, the experiments under sunlight reached a 91.2 ± 1.3% degradation efficiency, under an average irradiation value of 19.2 ± 0.3 W/m2 in October-November 2019 at hours between 11:00 am and 3:00 pm with an average temperature increase of 1.4 ± 0.8 °C. Mass spectrometry results indicated that 14 of the 108 possible TPs reported in the literature were detected. The calculated exact mass, measured accurate mass, and its characteristic diagnostic fragment ions were listed, and two new TPs were tentative identified. The TP generation analysis showed that some specific compounds were detected in different time intervals with kinetic variations depending on the irradiation used. Consequently, two CIP degradation pathways were proposed, since the type of irradiation determines the CIP degradation mechanism. Graphical abstract.

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An evaluation of the environmental risk assessment (ERA) proposed by European Medicines Agency (EMA) and its applicability in Brazil was performed on ten of Belo Horizonte's most pharmaceuticals by the Brazilian National Health Service (SUS). The predicted environmental concentrations (PECs) was proposed, with some refinements to a better representation of the city of study. All PECs obtained were compared only to measured environmental concentrations around the world, due to the lack available data in the city of study and in Brazil. During the performance of EMA's guideline, the risk quotient (RQ) of impact was established through the ratio of PECs and predicted no-effect concentrations (PNECs). The PECs obtained in more refined phases show the initial evaluation of EMA's guideline, possible subdimensions, and the potential risks. The RQ for all studied pharmaceuticals ranges from clonazepam (1.26) to losartan (5457.45). These results indicate potential risks to the aquatic life present in the streams that receive the wastewater treatment plant's effluent. This risk can be spread since the streams carry these contaminants to other water bodies that undergo to multiple cities of Brazil, and even after dilutions, it can still be potentially toxic to the biotic life. ERA shows that it can be a useful tool for a better understanding and modeling of pharmaceuticals fate in the environment, specifically in water bodies. In addition, the usage of this model shows to be a useful tool that determines which contaminant should follow a more thorough study since the detection and analysis of pharmaceuticals in environmental samples are costly and technically challenging.

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Organic matter (OM) in aquatic system is originated from autochthonous and allochthonous natural sources as well as anthropogenic inputs, and can be found in dissolved, particulate or colloidal form. According to the type/composition, OM can be divided in non-humic substances (NHS) or humic substances (HS). The present review focuses on the main groups that constitute the NHS (carbohydrates, proteins, lipids, and lignin) and their role as chemical biomarkers, as well as the main characteristics of HS are presented. HS functions, properties and mechanisms are discussed, in addition to their association to the fate, bioavailability, and toxicity of organic microcontaminants in the aquatic systems. Despite the growing diversity and potential impacts of organic microcontaminants to the aquatic environment, limited information is available about their association with OM. A protective effect is, however, normally seen since the presence of OM (HS mainly) may reduce bioavailability and, consequently, the concentration of organic microcontaminants within the organism. It may also affect the toxicity by either absorbing ultraviolet radiation incidence and, then, reducing the formation of phototoxic compounds, or by increasing the oxygen reactive species and, thus, affecting the decomposition of natural and anthropogenic organic compounds. In addition, the outcome data is hard to compare since each study follows unique experimental protocols. The often use of commercial humic acid (Aldrich) as a generic source of OM in studies can also hinder comparisons since differences in composition makes this type of OM not representative of any aquatic environment. Thus, the current challenge is find out how this clear fragmentation can be overcome.

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RESUMO Fármacos e desreguladores endócrinos são encontrados em águas naturais brasileiras, incluindo alguns mananciais de abastecimento, também em função da baixa cobertura de coleta e tratamento de esgotos no Brasil. Nesse cenário, o presente trabalho intentou avaliar a remoção de três fármacos - sulfametoxazol (SMX), diclofenaco (DCF) e 17β-estradiol (E2) - em água destilada por meio da oxidação com cloro (hipoclorito de sódio), variando-se a dose de cloro e o tempo de contato em ensaios de batelada. As soluções cloradas foram analisadas, ainda, por cromatografia acoplada à espectrometria de massas para identificação de eventuais subprodutos de oxidação. Para tempo de contato de 10 min e dose de cloro de 1,5 mg.L-1, foi observada remoção média de 61% para DCF, 36% para E2 e 33% para SMX. Apenas para o DCF verificou-se diferença estatisticamente significativa (α=0,05) para dose de cloro de 3,0 mg.L-1. A oxidação seguiu modelo cinético de pseudossegunda ordem, com valores de k2 de 0,0168 L.µg.min-1 para SMX (para ambas doses testadas), de 0,0133 e 0,0798 L.µg.min-1 para DCF, e de 0,0326 e 0,0289 L.µg.min-1 para E2, para doses de cloro de 1,5 e 3,0 mg.L-1, respectivamente. Por fim, verificou-se que o aumento do tempo de contato favoreceu a oxidação dos fármacos, ainda que com a perspectiva de formação de subprodutos para SMX e E2.

ABSTRACT Pharmaceuticals and endocrine disrupting compounds are found in Brazilian natural waters, including some water sources for public supply, also due to the low coverage of sewage collection and treatment in Brazil. This study investigated the removal of three pharmaceutical compounds - sulfamethoxazole (SMX), diclofenac (DCF) and 17β-estradiol (E2) - from aqueous solutions by means of chlorine oxidation (sodium hypochlorite) by varying the dose of chlorine and contact time in batch tests. The chlorine solutions were examined by chromatography attached to the mass spectrometry in order to identify the oxidation by-products. For 10 min contact time, mean removal values of 61% were observed for DCF; 36% for E2; and 33% for SMX, when the chlorine dose was 1.5 mg L-1. Just for DCF there was a statistically significant difference (α=0.05) in the removal efficiency when increasing the chlorine dose to 3.0 mg.L-1. The oxidation followed the kinetic model of pseudo-second order, with k2 values of 0.0168 L.µg.min-1 for SMX (at both chlorine doses tested); 0.0133 and 0.0798 L.µg.min-1 to DCF; and 0.0326 and 0.0289 L.µg.min-1 to the E2 at chlorine doses of 1.5 and 3.0 mg L-1, respectively. Finally, it was verified that an increase of the contact time favored the oxidation of all pharmaceuticals tested, although with the perspective of by-products formation for SMX and E2.