Removal of acephate and methamidophos from water: Coagulation and adsorptive treatment approaches.

Pesticides has transformed the agricultural industry, primarily by enhancing productivity. However, the indiscriminate use of such compounds can adversely affect human health and disrupt ecosystem balance. Limited knowledge exists regarding the removal of these compounds from water, particularly for organophosphate pesticides when employing conventional treatment technologies. Therefore, this study aimed to assess the removal of acephate (ACE) and methamidophos (MET) - considered priority pesticides in Brazil - from waters with high and low turbidity during the clarification process carried out with aluminum sulfate (AS) and ferric chloride (FC), either alone or combined with powdered activated carbon (PAC) adsorption. All water samples were submitted to solid phase extraction (SPE C18 cartridges) prior to acephate and methamidophos analysis by HPLC MS/MS. The clarification process with either AS or FC coagulant did not efficiently remove acephate or methamidophos and maximum average removal (27 %) was observed with waters of high turbidity when using ferric chloride as coagulant. Addition of mineral PAC was also ineffective for removing both pesticides. However, the use of vegetable PAC (10 mg/L) resulted in better removal percentages, up to 80%, but only for methamidophos. The limited removal rates were attributed to the high hydrophilicity of acephate and methamidophos, along with their neutral charge at coagulation pH. These factors hinder the interaction of such organophosphorus pesticides with the flocs formed during coagulation as well as with PAC surface.

Effect of inoculum composition on the microbial community involved in the anaerobic digestion of sugarcane bagasse.

In anaerobic digestion (AD), the choice of inoculum type seems to be relevant for methane production for complex substrates, such as lignocellulosic material. Previous work demonstrated that the addition of fresh manure and ruminal fluid to anaerobic sludge improved methane productivity and kinetics of AD of crude sugarcane bagasse (CSB). Considering that the improvement of methane production could be a result of a more adapted microbial community, the present study performed the Next Generation Sequencing analysis to identify changes in the microbiome of anaerobic sludge inoculum, resulting from fresh manure and ruminal fluid addition. In comparison with AD performed only with anaerobic sludge inoculum (50:50, U), accumulated methane production was 15% higher with anaerobic sludge plus ruminal fluid inoculum (50:50, UR) and even higher (68%) with anaerobic sludge with fresh bovine manure inoculum (50:50, UFM), reaching the value of 143 NmLCH4.gVS-1. Clostridium species were highly abundant in all inocula, playing an important role during the hydrolysis and fermentation of CSB, and detoxifying potential inhibitors. Microbial composition also revealed the occurrence of Pseudomonas and Anaerobaculum at UFM inoculum that seem to have contributed to the higher methane production rate, mainly due to their hydrolytic and fermentative ability on lignocellulosic substrates. On the other hand, the presence of Alcaligenes might have had a negative effect on methane production due to their ability to perform methane oxidation.

Identification of metabolites generated in the biotransformation process by the Danio rerio (zebrafish) exposed to the fungicide tebuconazole.

Tebuconazole is a triazole fungicide widely used in agricultural crops for control of multiple fungal, mainly foliar and soil-borne diseases. Due to its intense use, this pesticide has been detected on aquatic matrices in different countries, which makes it necessary to identify metabolites capable to be used in its exposure monitoring. The aim of this work was to evaluate tebuconazole metabolites in zebrafish water tanks using liquid chromatography coupled to a high-resolution mass spectrometer (LCHRMS) to highlight analytical targets to monitor tebuconazole exposure in aquatic environments. Two Phase I metabolites, TEB-OH and TEB-COOH, and one Phase II metabolite, TEB-S, were identified. Target metabolomics pointed TEB-S as the most important metabolite for discrimination between treatment and negative control group and potential surrogate for detection and monitoring of tebuconazole exposure in aquatic environments. To the best of our knowledge, this is the first study to suggest the sulphation of tebuconazole (TEB-S) by zebrafish metabolism. Moreover, the use of water samples proved to be a promising approach when compared to the usual biological matrices (e.g. plasma) for evaluating the exposure of aquatic animals to tebuconazole because it is a clean and easy to obtain matrix. Water samples presented a higher concentration of metabolites when compared to plasma samples. The results suggest the applicability of this assay model for the identification of potential biomarkers for monitoring the presence of xenobiotics in water.

Role of a typical swine liquid manure treatment plant in reducing elements of antibiotic resistance.

Biological treatment of swine liquid manure may be a favorable environment for the enrichment of bacteria carrying antibiotic resistance genes (ARGs), raising the alert about this public health problem. The present work sought to investigate the performance of a swine wastewater treatment plant (SWWTP), composed of a covered lagoon biodigester (CLB) followed by three facultative ponds, in the removal of usual pollutants, antibiotics, ARGs (blaTEM, ermB, qnrB, sul1, and tetA), and intI1. The SWWTP promoted a 70% of organic matter removal, mainly by the digester unit. The facultative ponds stood out in the solids' retention carried from the anaerobic stage and contributed to ammonia volatilization. The detected antibiotic in the raw wastewater was norfloxacin (< 0.79 to 60.55 µg L-1), and the SWWTP seems to equalize peaks of norfloxacin variation probably due to sludge adsorption. CLB reduced the absolute abundance of ARGs by up to 2.5 log, while the facultative stage does not seem to improve the quality of the final effluent in terms of resistance elements. Considering the relative abundances, the reduction rates of total and ARG-carrying bacteria appear to be similar. Finally, correlation tests also revealed that organic matter and solids control in liquid manure treatment systems could help reduce the spread of ARGs after the waste final disposal.

Occurrence and environmental risk assessment of 22 pesticides in Brazilian freshwaters.

Pesticide contamination in water resources is a global threat. Although usually found at low concentrations, pesticides raise considerable toxicological concerns, mainly when mixtures are considered. The occurrence of 22 pesticides (2,4 D, alachlor, aldicarb, aldrin, atrazine, carbendazim, carbofuran, chlordane, chlorpyrifos, DDT, diuron, glyphosate, lindane, mancozeb, methamidophos, metolachlor, molinate, profenofos, simazine, tebuconazole, terbufos, and trifluralin) was investigated, through consolidated database information, in surface freshwaters of Brazil. Moreover, scenarios of environmental risk assessment considering isolated compounds and mixtures were performed, as well as a meta-analytic approach for toxicity purposes. Pesticides in freshwater have been reported from 719 cities (12.9% of Brazilian cities), where 179 (3.2%) showed pesticide occurrence above the limit of detection or quantification. Considering cities with more than five quantified, 16 cities were prone to environmental risks considering individual risks. However, the number increased to 117 cities when the pesticide mixture was considered. The mixture risk was driven by atrazine, chlorpyrifos, and DDT. The national maximum acceptable concentrations (MAC) for nearly all pesticides are higher than the predicted no-effect concentration (PNEC) for the species evaluated, except aldrin. Our results show the need to consider mixtures in the environmental risk assessment to avoid underestimation and review MAC to protect aquatic ecosystems. The results presented here may guide the revision of the national environmental legislation to ensure the protection of Brazilian aquatic ecosystems.

Hydrothermal pre-treatment followed by anaerobic digestion for the removal of tylosin and antibiotic resistance agents from poultry litter.

Hydrothermal pretreatment (HPT) followed by anaerobic digestion (AD) is an alternative for harvesting energy and removing organic contaminants from sewage sludge and animal manure. This study investigated the use, in an energetically sustainable way, of HPT and AD, alone or combined, to produce methane and remove tylosin and antimicrobial resistance genes (ARG) from poultry litter (PL). The results showed that HPT at 80 °C (HPT80), followed by single-stage AD (AD-1S), led to the production of 517.9 ± 4.7 NL CH4 kg VS-1, resulting in 0.11 kWh kg PL-1 of electrical energy and 0.75 MJ kg PL-1 of thermal energy, thus supplying 33.6% of the energy spent on burning firewood at a typical farm. In this best-case scenario, the use of HPT alone reduced tylosin concentration from PL by 23.6%, while the process involving HPT followed by AD-1S led to the removal of 91.6% of such antibiotic. The combined process (HPT80 + AD-1S), in addition to contributing to reduce the absolute and relative abundances of ARG ermB (2.13 logs), intI1 (0.39 logs), sul1 (0.63 logs), and tetA (0.74 logs), led to a significant removal in the relative abundance of tylosin-resistant bacteria present in the poultry litter.

Aerobic post-treatment of effluent from anaerobic reactors fed with residues from 1G and 2G sugarcane biorefineries.

This study aimed to evaluate an activated sludge system as a post-treatment step of anaerobic effluents from the co-digestion of sugarcane vinasse and hemicelluloses hydrolysate. The system consisted, initially, of a two-stage anaerobic system followed by a continuously fed activated sludge, all in bench scale. After adaptation of aerobic microorganisms to effluent conditions, the anaerobic digestion was conducted in a single-stage anaerobic reactor, increasing the influent organic loading rate (OLR) of activated sludge from 0.73 to an average of 2.36 gCOD/L·day. Under optimal conditions (12-h hydraulic retention time [HRT]), a 62 ± 9% efficiency was observed on the aerobic post-treatment, resulting in effluent chemical oxygen demand (COD) of 414.3 ± 95 mg/L. Overall efficiency of the combined system (anaerobic + aerobic) averaged 88 ± 3%. Influent and effluent characteristics were then analyzed by Folin-Ciocalteau method, UV-Vis spectrophotometry, and gas chromatography-mass spectrometry (GC-MS) for identification of potentially toxic and recalcitrant compounds. Compounds that absorb light within the visible spectra were well removed by the combined treatment system. Most compounds identified by GC-MS in the influent were completely removed by aerobic microorganisms. Saturated fatty acids such as adipic acid, hexadecanoic acid, and octadecanoic acid were observed in the final effluent, as well as other potentially toxic compounds such as stigmasterol, di-isobutyl phthalate, and benzene. Activated sludge proved to be an efficient post-treatment for anaerobic co-digestion, able to cope with changes of anaerobic effluent quality and providing a final effluent of stable organic load. However, phenol removal was not efficient and further studies could be performed to optimize its degradation. PRACTITIONER POINTS: Conventional activated sludge with a 12-h HRT was capable of handling significant OLR variation, providing a final effluent with lower and stable COD concentration. Glucose addition for carbon supplementation was necessary during the start-up of activated sludge. Compounds that absorb light within the visible spectra were mostly removed by the combined (anaerobic-aerobic) treatment system. Most potentially toxic compounds were well removed in the post-treatment system. Saturated fatty acids, VFA, phenols, and low molecular weight aromatic compounds remained in the final effluent.

Occurrence and removal of drugs and endocrine disruptors in water supply systems in the metropolitan region of Belo Horizonte (Minas Gerais State, Brazil).

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.

Tylosin in anaerobic reactors: degradation kinetics, effects on methane production and on the microbial community.

Tylosin eliminated in animal waste, during therapeutic treatment, can be efficiently removed in anaerobic systems. The present study investigated the influence of tylosin concentration and assessed its degradation kinetics and the microorganisms involved in each stage of its anaerobic digestion (hydrolysis/acidogenesis; acetogenesis; methanogenesis). The results showed a stimulating effect on methane production with increasing tylosin concentration in the poultry litter up to 80 mg kg-1 tylosin (232.9 NL CH4 kg SV-1). As for tylosin degradation, greater removal of antibiotics was observed in the methanogenic phase (88%), followed by acetogenic (84%) and hydrolytic/acidogenic (76%) phases. The higher rate of tylosin degradation obtained in the methanogenic step, is mainly related to the co-metabolic effect exerted by the presence of acetate and its degradation by acetoclastic methanogens. Indeed, metagenomic analyses suggested a syntrophic action between archaea of ​​the genus Methanobacterium, and bacteria such as Clostridium and Flexilinea, which seemed decisive for tylosin degradation.

Biogas production by anaerobic co-digestion of sugarcane biorefinery byproducts: Comparative analyses of performance and microbial community in novel single-and two-stage systems.

Anaerobic co-digestion (AcD) of sugarcane biorefinery byproducts (hemicelluloses hydrolysate (HH), vinasse, yeast extract and sugarcane bagasse fly ashes was evaluated using new anaerobic reactors fed with organic loading rates (OLR) from 0.9 to 10.8 gCODL-1d-1. The best results were obtained in a two-stage system when the OLR was 5.65 gCODL-1d-1, leading to a total chemical oxygen demand (COD) removal of 87.6 % and methane yield of 243NmLCH4gCODr-1. Microbial community analyses of sludge from both systems (one and two-stages) revealed structural changes and relationship among the main genus found (Clostridium (62.8%), Bacteroides(11.3 %), Desulfovibrio (19.1 %), Lactobacillus(67.7 %), Lactococcus (22.5%), Longilinea (78%), Methanosaeta (19.2 %) and Syntrophus (18.9 %)) with processes performance, kinetic and hydrodynamic parameters. Moreover, biomass granulation was observed in the novel structured anaerobic reactor operated at single stage due to sugarcane bagasse fly ash addition.

Investigação de cafeína, Genfibrozila, Bezafibrato, Metformina, Prometazina e Loratadina em águas de sistema de abastecimento público / Investigation of caffeine, Gemfibrozil, Bezafibrate, Metformine, Prometazine, and Loratadine in waters of public supply systems

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.

Occurrence of Pharmaceuticals and Endocrine Disrupting Compounds in Brazilian Water and the Risks They May Represent to Human Health.

The risks of pharmaceuticals and endocrine disrupting compounds (P&EDC) to the environment and human health are a current topic of interest. Hundreds of P&EDC may reach the environment, hence, there is a need to rank the level of concern of human exposure to these compounds. Thus, this work aimed at setting a priority list of P&EDC in Brazil, by studying their occurrence in raw and drinking water, calculating health guideline values (GV), and estimating the risks of population exposure to water intake. Data on the Brazilian pharmaceutical market as well as published data of the monitoring of Brazilian natural and drinking water have been collected by means of an exhaustive literature review. Furthermore, many foreign data were also collected to enable a comparison of the values found in Brazilian studies. A list of 55 P&EDC that have the potential to be found in Brazilian water is proposed, and for 41 of these a risk assessment was performed by estimating their margin of exposure (ME), by considering their occurrence in drinking water, and guideline values estimated from reported acceptable daily intake (ADI) data. For seven compounds the risk was deemed high (three estrogens and four anti-inflammatories), whereas for another seven compounds, it was regarded as an 'alert' situation. Although such risk analysis is conservative, since it has been calculated based on the highest reported P&EDC concentration in drinking water, it highlights the need to enhance their monitoring in Brazil to strengthen the database and support decision makers. An analysis of the occurrence of antimicrobial resistance agents (antibiotics, resistant bacteria, and resistance genes) in surface waters was also carried out and confirmed that such agents are present in water sources throughout Brazil, which deserves the attention of policy makers and health agents to prevent dissemination of antimicrobial resistance through water use.

Hydrogen production by Enterobacter sp. LBTM 2 using sugarcane bagasse hemicellulose hydrolysate and a synthetic substrate: understanding and controlling toxicity.

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.

Occurrence and removal of drugs and endocrine disruptors in the Bolonha Water Treatment Plant in Belém/PA (Brazil).

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.

Distribution of genetic elements associated with antibiotic resistance in treated and untreated animal husbandry waste and wastewater.

Animal breeding for meat production based on swine, cattle, poultry, and aquaculture is an activity that generates several impacts on the environment, among them the spread of antibiotic resistance. There is a worldwide concern related to the massive use of antibiotics, which causes selective pressure on the microbial community, triggering bacteria that contain "antibiotic resistance genes." According to the survey here presented, antibiotic resistance-related genes such as tetracyclines (tet), erythromycin (erm), and sulfonamides (sul), as well as the genetic mobile element interferon (int), are the most reported genetic elements in qualitative and quantitative studies of swine, cattle, poultry, and aquaculture manure/wastewater. It has been observed that biological treatments based on waste composting and anaerobic digestion are effective in ARG removal, particularly for tet, bla, erm, and qnr (quinolone) genes. On the other hand, sul and intI genes were more persistent in such treatments. Tertiary treatments, such advanced oxidative processes, are suitable strategies to improve ARG reduction. In general temperature, hydraulic retention time, and penetration of sunlight are the main operational parameters for ARG reduction in treatments applied to animal waste, and therefore attention should be addressed to optimize their efficacy regarding ARG removal. Despite being reduced, the presence of ARG in treated effluents and in biosolids indicates that there is a potential risk of antibiotic resistance spread in nature, especially through the release of treated livestock waste into the environment.

Occurrence of contaminants of emerging concern in surface waters from Paraopeba River Basin in Brazil: seasonal changes and risk assessment.

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.

Preliminary assessment of antimicrobial activity and acute toxicity of norfloxacin chlorination by-product mixture.

Among drugs and personal care products, antibiotics arouse interest since they are widely used in human and veterinary medicine and can lead to the development of bacterial resistance. Usually, sewage treatment does not remove most of these compounds. So, these drugs can reach water treatment plants (WTP), where disinfection with chlorine compounds is common. This work aimed to evaluate the antimicrobial activity and preliminary toxicity of the mix of by-products forming due to the chlorination of norfloxacin. This is a fluoroquinolone antibiotic indicated for the treatment of urinary infection and gonorrhea, with sodium hypochlorite (NaClO). The drug was subjected to chlorination tests, on a bench scale, with several reaction times (from 5 min to 24 h). Analyses of high-resolution mass spectrometry (MS) were performed for the characterization of the by-products. The MS results showed five peaks attributed to the by-products' formation, of which four were identified. The antibiogram results indicated that the solution that contained the mixture of the by-products lost antibacterial activity against the E. coli strain studied. The acute toxicity tests for the Artemia salina microcrustacean showed that the blend of the by-products exhibited higher toxicity than pure norfloxacin.

Ensaios toxicológicos aplicados à análise de águas contaminadas por fármacos / Toxicological tests applied to the analysis of water contaminated by drugs

RESUMO Fármacos de diversas classes têm sido detectados no ambiente aquático nos últimos anos. A presença desses compostos químicos deve-se, sobretudo, ao lançamento de esgoto in natura ou à remoção incompleta durante as etapas do tratamento de esgoto. Embora tais materiais sejam detectados em baixas concentrações (ng.L-1 - µg.L-1), os impactos de alguns fármacos à biota aquática já são conhecidos, sendo os efeitos na saúde humana, especialmente aqueles relacionados à exposição crônica, ainda pouco conhecidos e/ou controversos. Ensaios biológicos são ferramentas valiosas para avaliar a toxicidade de fármacos aos organismos expostos, e a sua adoção conjunta aos ensaios de tratabilidade da água e efluentes permitiria preencher lacunas de conhecimento e a construção de consenso na literatura científica sobre os seus efeitos toxicológicos. Pelo exposto, este artigo de revisão apresenta uma visão geral da ocorrência de fármacos em amostras ambientais do país e a toxicidade observada por meio de diferentes ensaios biológicos.

ABSTRACT Drugs of several classes have been detected in the aquatic environment in recent years. The presence of these chemicals is mainly due to the discharge of raw sewage or to their incomplete removal in sewage treatment plants. Although they have been detected at low concentrations (ng.L-1 - µg.L-1), the effects of pharmaceutical compounds on the aquatic biota are already acknowledged, being the effects on human health, especially those related to chronic exposure, still unknown and/or controversial. Biological assays are valuable tools for assessing drug toxicity to exposed organisms and their joint adoption in water and effluent treatability trials would fill up knowledge gaps and build consensus in the scientific literature on their toxicological effects. This review paper presents an overview of the occurrence of drugs in several Brazilian environmental samples and compiles the toxicity observed by means of different biological assays.

Can high rate algal ponds be used as post-treatment of UASB reactors to remove micropollutants?

The present study evaluated the removal capacity of a UASB-HRAP treatment system, combining anaerobic and microalgae-based, aerobic treatment, for eleven organic micropollutants present in raw sewage, including pharmaceuticals, estrogens and xenoestrogens. The UASB reactor and the HRAP were operated at a hydraulic retention time (HRT) of 7 h and 8 days, respectively. Influent and effluent samples from the UASB and HRAP were collected periodically. All the target compounds were detected in raw sewage, with an occurrence ranging from 70 to 100%. Removal rates in the UASB reactor were generally incomplete, ranging from no removal (-25.12% for the hormone EE2-ethinylestradiol) to 84.91% (E2 - estradiol). However, the overall performance of the UASB + HRAP system was highly efficient for the majority of the compounds, with removal rates ranging from 64.8% (ibuprofen) to 95% (estrone). Gemfibrozil and bisphenol A were the only exceptions, with overall removal rates of 39% and 43%, respectively. Hormones were the compounds with the highest removal rates in the system.

Methane production by co-digestion of poultry manure and lignocellulosic biomass: Kinetic and energy assessment.

Six typical Brazilian lignocellulosic biomasses (rice straw, corn cob, peanut shell, sawdust, coffee husk and sugarcane bagasse) were evaluated for methane production by solid-state anaerobic co-digestion with poultry manure. The results showed the highest methane production was obtained with corn cob and poultry manure (126.02 Nm3 CH4. ton residue-1) using a food to inoculum ratio of 0.5, which lowered volatile fatty acids accumulation. In this condition, the thermal energy production (1.73 MJ.kg live chicken-1) would be able to replace 53.2% of the energy with firewood in poultry farming. The high hemicellulose and low lignin content in corn cob seem to explain the biomethanation of such biomass, and this agrees with the microbial analysis which revealed the predominance of bacteria related to plant polysaccharides hydrolysis and carbohydrate conversion in the inoculum. The methane production was best modelled by Groot's multi-stage model, and the microbial adaptation to lignin might explain this.