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Using the Response Surface Methodology (RSM) and Rotational Central Composite Design (RCCD), this study evaluated the removal of DCF under denitrifying conditions, with ethanol as cosubstrate, in batch reactors, being 1 L Erlenmeyer flasks (330 mL of reactional volume) containing Dofing medium and kept under agitation at 130 rpm and incubated at mesophilic temperature (30 °C). It considered the individual and multiple effects of the variables: nitrate (130 - 230 mg NO 3 - L -1 ), DCF (60-100 µg DCF L -1 ) and ethanol (130 - 230 mg EtOH L -1 ). The highest drug removal efficiency (17.5%) and total nitrate removal were obtained at 176.6 ± 4.3 mg NO 3 - L -1 , 76.8 ± 3.7 µg DCF L -1 , and 180.0 ± 2.5 mg EtOH L -1 . Under such conditions, the addition of ethanol and nitrate was significant for the additional removal of diclofenac ( p  > 0.05). The prevalence of Rhodanobacter , Haliangium and Terrimonas in the inoculum biomass (activated sludge systems) was identified through the 16S rRNA gene sequencing. The potential of these genera to remove nitrate and degrade diclofenac was inferred, and the main enzymes potentially involved in this process were α-methylacyl-CoA racemase, long-chain fatty acid-CoA ligase, catalases and pseudoperoxidases.

The present study reports the development of a bioassay using Artemia spp. to analyse the preliminary ecotoxicity of atmospheric aerosols (PM), which can affect the environment and human health. Herein, PM samples were collected in the city of Goiânia (Brazil) in 2016, extracted with ultrapure water and subsequently filtered through membranes with different pore sizes (100, 0.8, and 0.22 μm), and the extracts employed in the bioassays. The mortality rates (endpoint analysed) declined to membranes with smaller pore sizes (15 ± 4%, 47 ± 10% and 43 ± 9% for pore sizes of 100 μm, 0.8 μm and 0.22 μm, respectively). In general, the toxicity of the extract depended on its concentration, except for the sample with a higher negative particle surface charge, which presents a lower affinity for the negatively charged surfaces of cellular membranes. Moreover, although the PM concentration was higher for the sample collected during the dry season (September), the mortality rate was not significantly different to that determined for a sample with similar physical and chemical characteristics collected in the rainy season (December). This result demonstrates the importance of monitoring PM toxicities and their chemical and physical characteristics, in addition to their concentrations. Therefore, the new protocol to provide a preliminary analysis of the toxicity of the extracts of aerosol emerges as a useful, accessible, and fast tool for monitoring possible environmental hazards, and can simplify fieldwork., 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 © 2023 Elsevier Ltd. All rights reserved.)

In this study, positive matrix factorization method was used for source apportionment of PM 10 in the city of São Carlos from 2015 to 2018. The annual mean concentrations of PM 10 , 15 PAHs, 4 oxy-PAHs, 6 nitro-PAHs, 21 saccharides, and 17 ions in these samples were in the ranges 18.1 ± 6.99 to 25.0 ± 11.3 μg m -3 for PM 10 , 9.80 × 10 -1 ± 2.06 to 2.03 ± 8.54 × 10 -1  ng m -3 for ΣPAHs, 83.9 ± 35.7 to 683 ± 521 pg m -3 for Σoxy-PAHs, 1.79 × 10 -2 ± 1.23 × 10 -1 to 7.12 ± 4.90 ng m -3 for Σnitro-PAHs, 83.3 ± 44.7 to 142 ± 85.9 ng m -3 for Σsaccharides, and 3.80 ± 1.54 to 5.66 ± 4.52 μg m -3 for Σions. For most species, the concentrations were higher in the dry season than in the rainy. This was related not only to the low rainfall and relative humidity characteristic of the dry season but also to an increase in fire spots recorded in the region between April and September every year from 2015 to 2018. A 4-factor solution provided the best description of the dataset, with the four identified sources of PM 10 being soil resuspension (28%), biogenic emissions (27%), biomass burning (27%), and vehicle exhaust together with secondary PM (18%). Although the PM 10 concentrations were not above the limit established by local legislation, the epidemiological study showed that by reducing PM 2.5 concentrations to the level recommended by the WHO, approximately 35 premature deaths per 100,000 population could be avoided annually. The results revealed that biomass burning continues to be one of the main anthropic sources of emissions to the atmosphere in the region, so it needs to be incorporated into the existing guidelines and policies to reduce the concentration of particulate matter to within the limits recommended by the WHO, in order to avoid premature deaths., 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 © 2023 Elsevier Ltd. All rights reserved.)

Diclofenac (DCF), ibuprofen (IBU), propranolol (PRO), triclosan (TCS) and linear alkylbenzene sulfonate (LAS) can be recalcitrant in Wastewater Treatment Plants (WWTP). The removal of these compounds was investigated in scale-up (69 L) Expanded Granular Sludge Bed (EGSB) reactor, fed with sanitary sewage from the São Carlos-SP (Brazil) WWTP and 200 mg L -1 of ethanol. The EGSB was operated in three phases: (I) hydraulic retention time (HRT) of 36±4 h; (II) HRT of 20±2 h and (III) HRT of 20±2 h with ethanol. Phases I and II showed no significant difference in the removal of LAS (63 ± 11-65 ± 12 %), DCF (37 ± 18-35 ± 11 %), IBU (43 ± 18-44 ± 16 %) and PRO (46 ± 25-51 ± 23 %) for 13±2-15 ± 2 mg L -1 , 106 ± 32-462 ± 294 μg L -1 , 166 ± 55-462 ± 213 μg L -1 and 201 ± 113-250 ± 141 μg L -1 influent, respectively. Higher TCS removal was obtained in phase I (72 ± 17 % for 127 ± 120 μg L -1 influent) when compared to phase II (51 ± 13 % for 135 ± 119 μg L -1 influent). This was due to its greater adsorption (40 %) in the initial phase. Phase III had higher removal of DCF (42 ± 10 % for 107 ± 26 μg L -1 influent), IBU (50 ± 15 % for 164 ± 47 μg L -1 influent) and TCS (85 ± 15 % for 185 ± 148 μg L -1 influent) and lower removal of LAS (35 ± 14 % for 12 ± 3 mg L -1 influent) and PRO (-142 ± 177 % for 188 ± 88 μg L -1 influent). Bacteria similar to Syntrophobacter, Smithella, Macellibacteroides, Syntrophus, Blvii28_wastewater-sludge_group and Bacteroides were identified in phase I with relative abundance of 3.1 %-4.7 %. Syntrophobacter was more abundant (15.4 %) in phase II, while in phase III, it was Smithella (12.7 %) and Caldisericum (15.1 %). Regarding the Archaea Domain, Methanosaeta was more abundant in phases I (84 %) and II (67 %), while in phase III it was Methanobacterium (86 %)., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Triclosan (TCS) and propranolol (PRO) are emerging micropollutants that are difficult to remove in wastewater treatment plants. In this study, methanogenic potential (P) of anaerobic sludge submitted to TCS (3.6 ± 0.1 to 15.5 ± 0.1 mg L -1 ) and PRO (6.1 ± 0.1 to 55.9 ± 1.2 mg L -1 ) in sanitary sewage, was investigated in batch reactors. The use of cosubstrates (200 mg L -1 of organic matter) ethanol, methanol:ethanol and fumarate was evaluated for micropollutant degradation. Without cosubstrates, P values for 5.0 ± 0.1 mgTCS L -1 , 15.5 ± 0.1 mgTCS L -1 and 55.0 ± 1.3 mgPRO L -1 were 50.53%, 98.24% and 17.66% lower in relation to Control assay (855 ± 5 μmolCH4) with sanitary sewage, without micropollutants and cosubstrates, respectively. The use of fumarate, ethanol and methanol:ethanol favored greater methane production, with P values of 2144 ± 45 μmolCH 4 , 2960 ± 185 μmolCH 4 and 2239 ± 171 μmolCH 4 for 5.1 ± 0.1 mgTCS L -1 , respectively; and of 10,827 ± 185 μmolCH 4 , 10,946 ± 108 μmolCH 4 and 10,809 ± 210 μmolCH 4 for 55.0 ± 1.3 mgPRO L -1 , respectively. Greater degradation of TCS (77.1 ± 0.1% for 5.1 ± 0.1 mg L -1 ) and PRO (24.1 ± 0.1% for 55.9 ± 1.2 mg L -1 ) was obtained with ethanol. However, with 28.5 ± 0.5 mg PRO L -1 , greater degradation (88.4 ± 0.9%) was obtained without cosubstrates. With TCS, via sequencing of rRNA 16S gene, for Bacteria Domain, greater abundance of phylum Chloroflexi and of the genera Longilinea, Arcobacter, Mesotoga and Sulfuricurvum were identified. With PRO, the genus VadinBC27 was the most abundant. Methanosaeta was dominant in TCS with ethanol, while in PRO without cosubstrates, Methanobacterium and Methanosaeta were the most abundant. The use of metabolic cosubstrates is a favorable strategy to obtain greater methanogenic potential and degradation of TCS and PRO., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Diclofenac (DCF) and ibuprofen (IBU) are widely used anti-inflammatory drugs and are frequently detected in wastewater from Wastewater Treatment Plants and in aquatic environments. In this study, the methanogenic potential (P) of anaerobic sludge subjected to DCF (7.11 ± 0.02 to 44.41 ± 0.05 mg L -1 ) and IBU (6.11 ± 0.01 to 42.61 ± 0.05 mg L -1 ), in sanitary sewage, was investigated in batch reactors. Cosubstrates (200 mg L -1 of organic matter) in the form of ethanol, methanol:ethanol and fumarate were tested separately for the removal of drugs. In the DCF assays, P was 6943 ± 121 μmolCH 4 , 9379 ± 259 μmolCH 4, 9897 ± 212 μmolCH 4 and 11,530 ± 368 μmolCH 4 for control, fumarate, methanol:ethanol and ethanol conditions, respectively. In the IBU assays, under the same conditions, P was 6145 ± 101 μmolCH 4 , 6947 ± 66 μmolCH 4 , 8141 ± 191 μmolCH 4 and 10,583 ± 512 μmolCH 4 , respectively. Without cosubstrates, drug removal was below 18% for 43.10 ± 0.01 mgDCF L -1 and 43.12 ± 0.03 mgIBU L -1 , respectively. Higher P and removal of DCF (28.24 ± 1.10%) and IBU (18.72 ± 1.60%) with ethanol was observed for 43.20 ± 0.01 mgDCF L -1 and 43.42 ± 0.03 mgIBU L -1 , respectively. This aspect was better evidenced with DCF due to its molecular structure, a condition that resulted in a higher diversity of bacterial populations. Through the 16S rRNA sequencing, bacteria genera capable of performing aromatic ring cleavage, β-oxidation and oxidation of ethanol and fatty acids were identified. Higher relative abundance (>0.6%) was observed for Smithella, Sulfuricurvum and Synthophus for the Bacteria Domain and Methanosaeta (>79%) for the Archaea Domain. The use of ethanol favored greater mineralization of organic matter and greater methane production, which can directly assist in the metabolic pathways of microorganisms., 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.)

A simple and reproducible method was developed and validated for simultaneous quantification of the pesticide fipronil and its intermediates fipronil desulfinyl, fipronil sulfone and fipronil sulfide, in soil. The analytes were extracted by ultrasonic bath and the ratio of solvents (hexane/acetone), number and time of cycles were optimized by Box-Behnken design with a triplicate central point. The optimal extraction conditions were achieved through a response surface analysis. The clean-up step was conducted by cartridges of solid phase extraction (SPE) containing silica (Florisil®) and aluminum oxide. Gas chromatography with electron capture detection (GC-ECD) was employed for separating fipronil and its intermediates with a suitable resolution and runtime of 20 minutes. The best quantification was achieved with 1 : 1 (v/v) acetone/hexane and 2 ultrasound cycles of 15 minutes each. The recovery values were between 81 to 108%, with relative standard deviation (RSD) lower than 6%, with no effect of the used matrix. Analytical curves presented regression coefficients values above 0.9908 for a concentration range from 0.005 to 0.6 μg g-1. Limits of detection (LOD) from 0.002 to 0.006 μg g-1 and limits of quantification (LOQ) from 0.006 to 0.020 μg g-1 were reached for all analytes. This method can be used to monitor and quantify fipronil and its intermediates in soil.

Freshwater resources are increasingly scarce due to human activities, and the understanding of water quality variations at different spatial and temporal scales is necessary for adequate management. Here, we analyze the hypotheses that (1) the presence of a wastewater treatment plant (WWTP) and (2) a polluted tributary that drains downstream from the WWTP change the spatial patterns of physicochemical variables (pH, turbidity, dissolved oxygen, and electrical conductivity) and nutrient concentrations (reactive soluble phosphorus, total phosphorus, nitrogen series, total nitrogen, and total dissolved carbon) along a mid-order river in SE Brazil and that these effects depend on rainfall regime. Six study sites were sampled along almost 4 years to evaluate the impacts of human activities, including sites upstream (1-3) and downstream (5-6) from the WWTP. The impacts were observed presenting an increasing trend from the source (site 1) towards Água Quente stream (site 4, the polluted tributary), with signs of attenuation at site 5 (downstream from both WWTP and site 4) and the river mouth (site 6). Input of nutrients by rural and urban runoff was observed mainly at sites 2 and 3, respectively. At sites 4 and 5, the inputs of both untreated and treated wastewaters increased nutrient concentrations and changed physicochemical variables, with significant impacts to Monjolinho River. Seasonal variations in the measured values were also observed, in agreement with the pluviometric indexes of the region. Univariate analyses suggested no effect of the WWTP for most variables, with continued impacts at sites downstream, but non-parametric multivariate analysis indicated that these sites were recovering to chemical characteristics similar to upstream sites, apparently due to autodepuration. Therefore, multivariate methods that allow rigorous tests of multifactor hypotheses can greatly contribute to determine effects of both point and non-point sources in river systems, thus contributing to freshwater monitoring and management.

Sediments are the fate of several emerging organic contaminants, such as pharmaceuticals, personal care products and hormones, and therefore an important subject in environmental monitoring studies. In the present work, a simple and sensitive method was developed, validated and applied for the simultaneous extraction of atenolol, caffeine, carbamazepine, diclofenac, ibuprofen, naproxen, propranolol, triclosan, estrone, 17-β-estradiol and 17-α-ethinylestradiol using ultrasound-assisted extraction from freshwater sediment samples followed by solid-phase extraction clean-up and liquid chromatography with tandem mass spectrometry detection. The solvent type and extraction pH were evaluated to obtain the highest recoveries of the compounds. The best method shows absolute recoveries between 54.0 and 94.4% at 50 ng/g concentration. The method exhibits good precision with relative standard deviation ranging from 1.0-16%. The detection and quantification limits ranged from 0.006-0.067 and 0.016-0.336 ng/g, respectively. The developed method was successfully applied to freshwater sediment samples collected from different sites in Jundiaí River basin of São Paulo State, Brazil. The compounds atenolol, caffeine, propranolol and triclosan were detected in all the sampling sites with concentrations of 13.8, 41.0, 28.5 and 176 ng/g, respectively., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This manuscript reports a 3-year study on occurrence of pharmaceuticals, hormones, and triclosan in surface waters of a central urban region of São Paulo State of Southeast Brazil (the Monjolinho River in São Carlos). Water samples collected once at every 2 months were pre-concentrated by solid-phase extraction (SPE) and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The most frequently detected compounds in higher concentrations were caffeine, paracetamol, and atenolol (maximum concentrations 129,585, 30,421, and 8199 ng L(-1), respectively), while hormones estrone and 17-β-estradiol were the least detected, in levels up to 14.8 ng L(-1). There was an increasing trend in concentrations of most of the compounds along the river course, especially downstream of the river where there is discharge of both wastewater treatment plant effluent and raw sewage from a particular region of São Carlos city. Concentrations of contaminants were higher during dry periods as a result of decline in the water levels. Decrease in concentrations near the river mouth occurred to different extents for each compound. It was high for caffeine and atenolol, but was very low for carbamazepine and diclofenac. The present study reports the first data about the occurrence of some major emerging contaminants in the Monjolinho River. Besides its regional significance, this work may assist in composing a dataset for water contamination diagnosis focusing on emerging contaminants, both in the Brazilian as well as in the Global studies related to aquatic ecosystems. Such datasets can be helpful for making future public policies on water quality, since these compounds are not yet legally regulated.