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This study evaluates both the occurrence and removal of 24 compounds, including drugs and endocrine disruptors, in 8 water treatment plants (WTP) located in the metropolitan region of Belo Horizonte (Minas Gerais State, Brazil). The compounds 4-nonylphenol, 4-octylphenol, 17α-ethinylestradiol, 17ß-estradiol, acyclovir, bisphenol A, bezafibrate, caffeine, dexamethasone, diclofenac sodium, diltiazem, estrone, estriol, gemfibrozil, ibuprofen, linezolid, loratadine, losartan, metformin, naproxen, paracetamol, promethazine, propranolol and sulfamethoxazole were monitored at 3 sampling points (raw water, filtered water, treated water) over 10 or 12 collection campaigns for each WTP. The results showed that bisphenol A occurred at higher concentrations during the dry period with a maximum concentration of 3257.1 ng L-1, while the compounds 4-nonylphenol and losartan exhibited higher concentrations in the rainy period with maximum concentrations of 8577.2 ng L-1 and 705.8 ng L-1, respectively. Regarding the removal of compounds in the monitored WTPs, the clarification step demonstrated better removals for 4-nonylphenol, bisphenol-A, paracetamol, and sulfamethoxazole, whereas the disinfection step mainly removed the compounds 4-octylphenol and estrone. Margin of exposure (ME) assessment results indicated that only dexamethasone, ethinyl estradiol, diclofenac, estradiol, and estrone were classified as imminent risk or alert considering the 95th percentile concentration found in the samples of treated water.

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Sugars released by thermochemical pretreatment of lignocellulosic biomass are possible substrate for hydrogen production. However, the major drawback for bacterial fermentation is the toxicity of weak acids and furan derivatives normally present in such substrate. This study aimed to investigate the metabolism involved in hydrogen production by the isolate Enterobacter LBTM2 using 10, 20 and 30-fold diluted synthetic (SH) and sugarcane bagasse hemicellulose (SBH) hydrolysates. In addition, the effects of acetic acid, formic acid and furfural on the bacterial metabolism, as well as detoxification of SBH with activated carbon and molecularly imprinted polymers on the hydrogen production were assessed. The results showed the best hydrogen yield was 0.46 mmol H2/mmol sugar for 20-times diluted SH, which was 2.3-times higher than obtained in SBH experiments. Bacterial growth and hydrogen production were negatively affected by 0.8 g/L of acetic acid when added alone, but were totally inhibited when formic acid (0.4 g/L) and furfural (0.3 g/L) were also supplied. However the maximum hydrogen production of SBH20 has duplicated when 3% of powdered activated carbon was added to the SBH experiment. The results presented herein can be helpful in understanding the bottlenecks in biohydrogen production and could contribute towards development of lignocellulosic biorefinery.

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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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This study describes the application of gas chromatography coupled to mass spectrometry (GC-MS) to evaluate the occurrence of 12 CECs-contaminants of emerging concern (bisphenol A, diclofenac, 17ß-estradiol, estriol, estrone, 17α-ethinylestradiol, gemfibrozil, ibuprofen, naproxen, 4-nonylphenol, 4-octylphenol, and acetaminophen) in surface waters from Paraopeba River Basin, Minas Gerais State, Brazil. The analytical procedure was validated and applied to 60 surface water samples collected across four sampling campaigns along the upper and middle watershed. Methods for CECs determination involved sample filtration, and solid-phase extraction (SPE) with subsequent derivatization of the target compounds prior to their analysis by GC-MS. The LOQ varied from 3.6 to 14.4 ng/L and extraction recoveries ranged from 46.1 to 107.1% for the lowest spiked concentration level (10 ng/L). The results showed a profile of spatial distribution of compounds, as well as the influence of rainfall. Ibuprofen (1683.9 ng/L), bisphenol (1587.7 ng/L), and naproxen (938.4 ng/L) occurred in higher concentrations during the rainy season, whereas during the dry season, the concentrations of bisphenol (1057.7 ng/L), estriol (991.0 ng/L), and estrone (978.4 ng/L) were highlighted. The risk assessment of human exposure shows that for most contaminants, the concentration is well below the estimated thresholds for chronic toxicity from water intake. However, estradiol and 17α-ethinylestradiol showed concentrations in the same order of magnitude as the guide values estimated for babies.

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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.

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The study presented here aims at identifying the source of redox mediators (riboflavin), electron carriers nicotinamide adenine dinucleotide (NAD) and carbon to perform decolorization of azo dye under anaerobic conditions after osmotic shock pretreatment of residual yeast from industrial fermentation. Pretreatment conditions were optimized by Doehlert experiment, varying NaCl concentration, temperature, yeast density and time. After the optimization, the riboflavin concentration in the residual yeast lysate (RYL) was 46% higher than the one present in commercial yeast extract. Moreover, similar NAD concentration was observed in both extracts. Subsequently, two decolorization experiments were performed, that is, a batch experiment (48 h) and a kinetic experiment (102 h). The results of the batch experiment showed that the use of the RYL produced by the optimized method increased decolorization rates and led to color removal efficiencies similar to those found when using the commercial extract (∼80%) and from 23% to 50% higher when compared to the control (without redox mediators). Kinetics analysis showed that methane production was also higher in the presence of yeast extract and RYL, and biogas was mostly generated after stabilization of color removal. In all kinetics experiments the azo dye degradation followed the pseudo-second-order model, which suggested that there was a concomitant adsorption/degradation of the dye on the biomass cell surface. Therefore, results showed the possibility of applying the pretreated residual yeast to improve color removal under anaerobic conditions, which is a sustainable process.

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The aim of this study was to evaluate the performance of two forms of basic granular activated carbon (GAC), mineral (pH = 10.5) and vegetal (pH = 9), for the removal of three pharmaceuticals, as sulphamethoxazole (SMX), diclofenac (DCF) and 17ß-estradiol (E2), from two different matrices: fortified distilled (2.4-3.0 mg L(-1) and pH from 5.5 to 6.5) and natural (∼1.0 mg L(-1) and pH from 7.1 to 7.2) water in a bench scale. The Rapid Small-Scale Column Test used to assess the ability of mineral and vegetal GAC on removal of such pharmaceuticals led to removal capacities varying from 14.9 to 23.5 mg g(-1) for E2, from 23.7 to 24.2 mg g(-1) for DCF and from 20.5 to 20.6 mg g(-1) for SMX. Removal efficiencies of 71%, 88% and 74% for DCF, SMX and E2, respectively, were obtained at breakthrough point when using mineral GAC, whereas for the vegetal GAC the figures were 76%, 77% and 65%, respectively. The carbon usage rate at the breakthrough point varied from 11.9 to 14.5 L g(-1) for mineral GAC and from 8.8 to 14.8 L g(-1) for vegetal GAC. Mineral CAG also exhibited the best performance when treating fortified natural water, since nearly complete removal was observed for all contaminants in the column operated for 22 h at a carbon usage rate of 2.9 L g(-1).

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RATIONALE: Environmental bisphenol A (BPA) contamination is currently a matter of concern. This compound can disrupt the endocrine system by mimicking natural hormones and cause adverse effects on different organisms. In addition, it has been suggested that BPA can impair brain development, especially in fetuses and children. To efficiently remove BPA from contaminated water and wastewaters, several emerging technologies have been developed. Most are based on photodegradation. However, by-products resulting from the application of such methods have not been properly characterized. METHODS: The photodegradation of BPA was conducted using two different methods: photocatalysis (TiO2/UV-A and TiO2/UV-C systems) and direct photolysis (UV-A and UV-C radiation). The degradation process was continuously monitored to identify and observe the by-products formed under these conditions. Direct infusion electrospray ionization coupled to high-resolution mass spectrometry in negative ion mode [ESI(-)-HRMS] and liquid chromatography coupled to high-resolution mass spectrometry (HPLC/HRMS) were employed to monitor these by-products. RESULTS: The results revealed that the TiO2/UV-C system was the most efficient in causing both BPA depletion and mineralization of the organic matter in solution. Moreover, accurate mass data allowed for the assignment of molecular formulae for seven by-products, many of them unprecedented, formed under these conditions. Thus, a route for the photodegradation of BPA in aqueous medium could be proposed based on these results. Finally, additional tests revealed that the by-products showed a higher toxicity against Artemia salina than the primary precursor. CONCLUSIONS: All of these findings indicate that the identification of by-products arising from oxidative treatments is of primary importance because such compounds can be more hazardous than their precursors.

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This work assessed the behaviour of nine pharmaceuticals and/or endocrine disrupting chemicals (EDCs) in demo-scale upflow anaerobic sludge blanket reactors (UASB reactors) coupled to distinct simplified post-treatment units (submerged bed, polishing ponds, and trickling filters) fed on raw sewage taken from a municipality in Brazil. The dissolved concentration of the studied micropollutants in the raw and treated sewage was obtained using solid phase extraction (SPE) followed by analysis in a liquid chromatography system coupled to a hybrid high resolution mass spectrometer consisting of an ion-trap and time of flight (LC-MS-IT-TOF). The UASB reactors demonstrated that they were not appropriate for efficiently removing the assessed compounds from the sewage. Furthermore, this study demonstrated that the hydraulic retention time (HRT) was an important parameter for the removal of the hydrophilic and less biodegradable compounds, such as trimethoprim and sulfamethoxazole. The post-treatment units substantially increased the removal of most target micropollutants present in the anaerobic effluents, with a greater removal of micropollutants in simplified systems that require a large construction area, such as the submerged bed and polishing ponds, probably because of the higher HRT employed. Alternatively, compact post-treatment systems, such as trickling filters, tended to be less effective at removing most of the micropollutants studied, and the type of packing proved to be crucial for determining the fate of such compounds using trickling filters.

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Volatile fatty acid (VFA) profile is an important parameter in anaerobic reactors because it enables the assessment of metabolic pathways. Volatile fatty acids were monitored during sulfate reduction in a UASB (upflow anaerobic sludge blanket) reactor treating 2g/L sulfate concentration and with the organic loading increasing from 3.5 kg COD/m(3)d to 5.9 kg COD/m(3)d, for a 1-day residence time. In the absence of recirculation, the best outcome (65% reduction) was noticed with the lowest organic loading (3.55 kg/m(3)d). When recirculation was applied, sulfate reduction yields increased to 89%, corresponding to a sulfate removal rate of 1.94 kg SO(4)(2-)/m(3)d. The reactor performance was discussed in relation to microbial diversity and metabolic pathways. At high organic loading, two metabolic pathways account for lactate degradation: (i) lactate is oxidized to acetate and carbon dioxide by the incomplete-oxidizer SRB (sulfate-reducing bacteria) Desulfomonas, Desulfovibrio, Desulfolobus, Desulfobulbus and Desulfotomaculum spp.; (ii) lactate is converted to acetate by fermenting bacteria such as Clostridium sp. High propionate concentrations imply that there are low sulfate reduction efficiencies.

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