Ecotoxicological study of seven pharmaceutically active compounds: Mixture effects and environmental risk assessment.

Pharmaceutically active compounds (PhACs) have been detected in several aquatic compartments, which has been of environmental concern since PhACs can cause adverse effects on the aquatic ecosystem at low concentrations. Despite the variety of PhACs detected in surface water, ecotoxicological studies are non-existent for many of them, mainly regarding their mixture. In addition, water bodies can continuously receive the discharge of raw or treated wastewater with micropollutants. Thus, PhACs are subject to mixture and interactions, potentiating or reducing their toxicity. Therefore, the present study evaluated the toxicity on Aliivibrio fischeri of seven PhACs, which still needs to be explored in the literature. The effects were evaluated for the PhACs individually and for their binary and tertiary mixture. Also, the experimental effects were compared with the concentration addition (CA) and independent action (IA) models. Finally, an environmental risk assessment was carried out. Fenofibrate (FEN), loratadine (LOR), and ketoprofen (KET) were the most toxic, with EC50 of 0.32 mg L-1, 6.15 mg L-1 and 36.8 mg L-1, respectively. Synergistic effects were observed for FEN + LOR, KET + LOR, and KET + FEN + LOR, showing that the CA and IA may underestimate the toxicity. Environmental risks for KET concerning algae, and LOR e 17α-ethynylestradiol (EE2) for crustaceans and fish were high for several locations. Besides, high removals by wastewater treatment technologies are required to achieve the concentrations necessary for reducing KET and LOR risk quotients. Thus, this study contributed to a better understanding of the toxic interactions and environmental risks of PhACs.

Successful application of photocatalytic recycled TiO2-GO membranes for the removal of trace organic compounds from tertiary effluent.

Photocatalytic membranes are a promising technology for water and wastewater treatment. Towards circular economy, extending the lifetime of reverse osmosis (RO) membranes for as long as possible is extremely important, due to the great amount of RO modules discarded every year around the world. Therefore, in the present study, photocatalytic membranes made of recycled post-lifespan RO membrane (polyamide thin-film composite), TiO2 nanoparticles and graphene oxide are used in the treatment tertiary-treated domestic wastewater to remove trace organic compounds (TrOCs). The inclusion of dopamine throughout the surface modification process enhanced the stability of the membranes to be used as long as 10 months of operation. We investigated TrOCs removal by the membrane itself and in combination with UV-C and visible light by LED. The best results were obtained with integrated membrane UV-C system at pH 9, with considerable reductions of diclofenac (92%) and antipyrine (87%). Changes in effluent pH demonstrated an improvement in the attenuation of TrOCs concentration at higher pHs. By modifying membranes with nanocomposites, an increase in membrane hydrophilicity (4° contact angle reduction) was demonstrated. The effect of the lamp position on the light fluence that reaches the membrane was assessed, and greater values were found in the middle of the membrane, providing parameters for process optimization (0.29 ± 0.10 mW cm-2 at the center of the membrane and 0.07 ± 0.03 mW cm-2 at the right and left extremities). Photocatalytic recycled TiO2-GO membranes have shown great performance to remove TrOCs and extend membrane lifespan, as sustainable technology to treat wastewater.

Integrating reverse osmosis to a conventional river water treatment plant as a strategy to produce drinking water after mining dam rupture events: a case study.

Incidents of mining dam failure have compromised the water quality, threatening the water supply. Different strategies are sought to restore the impacted area and to guarantee the water supply. One example is water treatment plants that treat high-polluted waters within the required limits for their multiple usages. The current study assesses the integration of reverse osmosis (RO) to a river water treatment plant (RWTP) installed in Brumadinho (Minas Gerais, Brazil) to treat the water from the Ferro-Carvão stream impacted by the B1 dam rupture in 2019. The RWTP started eleven months after the mining dam rupture and is equipped with eight coagulation-flocculation tanks followed by eight pressurised filters. A pilot RO plant was installed to polish the water treated by the RWTP. Water samples were collected at different points of the water treatment plant and were characterised by their physical, chemical, and biological parameters (160 in total). The results were compared with the historical data (1997-2022) to reveal the alterations in the water quality after the rupture event. The compliance with both parameters was only achieved after the RO treatment, which acted as an additional barrier to 30 contaminants. The water quality indexes (WQI) suggested that the raw surface water, even eleven months after the incident, was unfit for consumption (WQI: 133.9) whereas the reverse osmosis permeate was ranked as excellent in the rating grid (WQI: 23.7).

Converting recycled membranes into photocatalytic membranes using greener TiO2-GRAPHENE oxide nanomaterials.

Despite the widespread use of membrane separation processes for water treatment, operation costs and fouling still restrict their application. Costs can be overcome by recycled membranes whereas fouling can be mitigated by membrane modification. In this work, the performance of recycled reverse osmosis membranes modified by greener titanium dioxide (TiO2) and graphene oxide (GO) in different modification routes were investigated and compared. The use of recycled membranes as a support acted more than a strategy for costs reduction, but also as an alternative for solid waste reduction. Low adhesion of nanoparticulate materials to the membrane surfaces were verified in depositions by self-assembly, whereas filtration and modification with dopamine generated membranes with well adhered and homogeneous layers. Considering the stability, permeability, and rejection efficiency of dyes as model substrates, the membranes modified with the aid of dopamine-TiO2-GO were the most promising. The nanomaterials increased the membrane hydrophilicity and formed a hydrated layer that repels the organic contaminants and reduces fouling. Besides membrane rejection, adsorption (contribution: ∼10%) and photocatalysis (contribution: ∼20%) were additional mechanisms for pollutants removal by the modified membranes. The photocatalytic membrane modified with dopamine-TiO2-GO was furthermore evaluated for the removal of six different pharmaceutical active compounds (PhACs), noticing gains in terms of removal efficiency (up to 95.7%) and fouling mitigation for the modified membrane compared to the original membranes. The photocatalytic activity still contributed to a simultaneous degradation of PhACs avoiding the generation of a concentrated stream for further disposal.

Effects of pharmaceuticals compounds and calcium on granulation, microbiology, and performance of anaerobic granular sludge systems.

Granular sludge is a promising biotechnology to treat sewage contaminated with pharmaceuticals due to its increased toxicity resistance. In this context, this study evaluated the potential of Ca2+ as a granulation precursor and how pharmaceutical compounds (loratadine, prednisone, fluconazole, fenofibrate, betamethasone, 17α-ethinyl estradiol, and ketoprofen) affect granulation. Continuous and intermittent dosages of Ca2+ in the presence and absence of pharmaceuticals were evaluated. The results showed that intermittent addition of Ca2+ reduces the time for anaerobic sludge granulation, and pharmaceuticals presence did not impair granulation. 10% of the granules presented mean diameters greater than 2.11 mm within 93 days with intermittent Ca2+ dosage in the pharmaceuticals' presence. In contrast, no granules higher than 2.0 mm were observed with no precursor addition. The pharmaceuticals' toxicity may have created a stress condition for the microbial community, contributing to more EPS production and a greater potential for granulation. It was also verified that pharmaceuticals' presence did not decrease organic matter, total alkalinity, and volatile fatty acids removals. The 16S rRNA gene analysis revealed taxa resistance to recalcitrant compounds when pharmaceuticals were added. Besides, the efficiency of a granular sludge bioreactor (EGSB) was evaluated for pharmaceuticals removal, and betamethasone, fenofibrate, and prednisone were effectively removed.

Biodegradability, environmental risk assessment and ecological footprint in wastewater technologies for pharmaceutically active compounds removal.

Several studies have investigated the removal of pharmaceutically active compounds (PhACs) by wastewater treatment technologies due to the risk that these compounds pose to the environment. In this sense, advanced biological processes have been developed for micropollutants removal, such as membrane bioreactors and moving bed biofilm reactors. Thus, this review holistically evaluated the biodegradation of 18 environmentally hazardous PhACs. Biological processes were assessed including removal efficiencies, environmental risk, and ecological footprint (consumption of resources and energy, atmospheric emissions, and waste generation). The maximum concentration of PhACs for a low or negligible risk scenario in treated wastewater and the potential of biological processes to meet this goal were assessed. Among the evaluated PhACs, the most biodegradable was paracetamol, while the most recalcitrant was diclofenac. Combination of conventional processes and advanced biological processes proved to be the most efficient way to remove several PhACs, mainly the osmotic membrane bioreactor.

Phenolic compounds in surface water: methodology and occurrence in Doce River, Brazil.

Phenolic compounds are widely spread in surface water, mainly in developing countries, where sewage and wastewater treatment are still reduced. Thus, this work quantified these pollutants in the Doce River analyzing the associated risk for the environment and human health. This river is in the state of Minas Gerais in Brazil and was recently impacted by the collapse of a mining dam that compromised the resilience of the entire watershed. For that purpose, a methodology for simultaneous identification and quantification of 17 different phenols was developed. It was possible to verify phenolic compounds' occurrence with concentration ranging from 0.13 to 24.16 µg·L-1. 2-Nitrophenol and bisphenol A appeared in all samples analyzed. The analytical method was processed using solid-phase extraction (SPE) (C18 cartridge), gas chromatography with FID, and mass spectrometry to define the analytes' retention time. For case validation, the selectivity, linearity, detection and quantification limits, sensitivity, precision, accuracy, resolution, matrix effect, and peak quality were assessed. Four different solvents were tested in the recovery-grade trials, which were dichloromethane, methanol, acetonitrile, and ethyl acetate. Among them, methanol had a better performance and was used throughout all analyses. The phenolic compounds had a recovery degree higher than 50% after SPE, regardless of the matrices.

Aquatic concentration and risk assessment of pharmaceutically active compounds in the environment.

Pharmaceutically active compounds are increasingly detected in raw and treated wastewater, surface water, and drinking water worldwide. These compounds can cause adverse effects to the ecosystem even at low concentrations and, to assess these impacts, toxicity tests are essential. However, the toxicity data are scarce for many PhACs, and when available, they are dispersed in the literature. The values of pharmaceuticals concentration in the environment and toxicity data are essential for measuring their environmental and human health risks. Thus this review verified the concentrations of pharmaceuticals in the aquatic environment and the toxicity related to them. The risk assessment was also carried out. Diclofenac, naproxen, erythromycin, roxithromycin, and 17ß-estradiol presented a high environment risk and 17α-ethinylestradiol presented a high human health risk. This shows the potential of these pharmaceuticals to cause adverse effects to the ecosystem and humans and establishes the necessity of their removal through advanced technologies.

The viralization of online education: Learning beyond the time of the coronavirus.

In response to the global crisis resulted from the spread of the coronavirus in Brazil, many schools and universities suspended face-to-face classes and began to offer remote classes using digital resources. In this unprecedented crisis, educators, managers and families had to deal with unpredictability and look for new ways of learning and teaching. Based on the paradigm of transmission of mass distribution, remotely teaching has gained strength, with the teacher as the protagonist of the education process. Instead of interactivity, content is emphasized to the detriment of more participatory, dialogic, and collaborative methodologies. It is necessary to prepare teachers and students for the online education modality to face this critical moment. Thus, this article suggests online pedagogical actions supported by the multireferential research-formation and everyday school methodologies, which promote the teachers' and students' participation in an interactive and collaborative way.

A survey on experiences in leachate treatment: Common practices, differences worldwide and future perspectives.

The necessity for landfill leachate treatment is a requisite to reduce the environmental impact related to municipal solid waste landfills and different aspects must be considered while deciding for an appropriate treatment process. For example, it was demonstrated that the landfill leachate stabilization in tropical regions is achieved right after its first year of operation, requiring technologies capable of treating leachates of a higher recalcitrant character if compared to those leachates from temperate regions and same landfill age. In view of its complexity and variability, stand-alone processes (either biological or physicochemical) are often ineffective in attaining the threshold values for its discharge in receiving bodies. Due to that fact, full-scale facilities have adopted integrated routes, harvesting the benefits of both biological and physicochemical processes. The implementation of membrane bioreactors followed by polishing membrane separation process (nanofiltration and reverse osmosis) seems to be a trend in leachate treatment by full-scale treatment plants. This technology is widely employed in China, European countries, and tropical countries as Brazil, generally with a treatment cost lower than the costs related to its disposal in domestic effluent collection systems. From the technologies already employed by full-scale facilities, four integrated routes were proposed for a sensitive analysis considering the treatment of a landfill leachate of different physicochemical characteristics. From all routes, those employing the membrane separation process as a polishing step had a better efficacy in attaining the threshold values for leachate disposal, being that an interesting alternative for leachate polishing by full-scale facilities.

Integration of ozonation and an anaerobic expanded granular sludge bed reactor for micropollutant removal from sewage.

Conventional sewage treatment systems are generally not designed to remove micropollutants, requiring the development of new technologies, such as the combination of biological processes with advanced oxidative processes. The configuration of an anaerobic expanded granular sludge bed (EGSB) reactor stands out for its use of granular biomass and high sludge bed expansion. Ozonation is an advanced oxidative process that stands out as one of the most promising technologies for the degradation of micropollutants. Thus, the present work aimed to evaluate the removal of drugs through the application of ozonation as a polishing process for the effluent of an EGSB reactor that was fed with synthetic sewage. Ozonation was shown to be efficient in the degradation of these compounds, reaching removals above 90%. It was found that the degradation profile of each drug varied according to its chemical structure since some drugs are more susceptible to oxidation than others and since the concentrations of pharmaceuticals are also related to their removal. Moreover, the assessment of risks to the environment and human health confirmed the need to assess the best scenario for risk reduction considering all drugs, since even with almost complete removal of some compounds, the effluents still showed toxicity. Thus, the high removal efficiencies found for the evaluated micropollutants showed that this technique has the potential to be used to improve the quality of biological reactor effluents or even to be combined in effluent reuse systems.

Phenolic compounds seasonal occurrence and risk assessment in surface and treated waters in Minas Gerais-Brazil.

This study provided a monitoring of phenolic compounds occurrence in a river and in its treated water by a conventional water treatment plant (WTP) throughout a year-period, in Minas Gerais - Brazil. Furthermore, the environmental risk (hazard quotient - HQ), the human health risk (margin of exposure - MOE), and the cancer risk were calculated for the compounds. The results indicated that sixteen out of the seventeen investigated phenolic compounds were detected at some point during the sampling campaign. The most frequent compounds in the raw surface water were 2,3,4-trichlorophenol (234TCP), 2,4-dimethylphenol (24DMP), and 4-nitrophenol (4NP), whereas in treated water were 4NP and bisphenol A (BPA). In addition, the highest total concentration values were corelated to the months in which there was less precipitation, demonstrating that the presence of this micropollutants may be subject to seasonality. From the treated water results, it was not possible to state the efficiency of the conventional WTP in eliminating the phenols, since in some samples the phenolic compounds were totally removed and in others their increase or formation occurred. Regarding to the risk assessments, most of the evaluated compounds were considered highly toxic to some trophic level and posed a significant human health risk. Additionally, the risk reduction of phenolics using conventional WTP was low. The sixteen phenols contamination in surface and drinking waters appears to be subject to seasonality. Besides that, an alarming risk for environment and human health was identified.

Occurrence and risk assessment of pharmaceutically active compounds in water supply systems in Brazil.

The presence of pharmaceutically active compounds (PhACs) in water supply systems has been generating great concern about their effects on the environment and human health. Twenty-eight PhACs were monitored during one year in four Brazilian water sources, aiming to understand the factors that influence their occurrence and removal in conventional drinking water treatment plants (DWTPs) and to assess the environmental and human health risks. Trace levels of PhACs were detected in surface and drinking water in all assessed water sources. Effects of seasonality and socioeconomic aspects were observed in PhACs occurrence, like their higher concentrations during winter and in locales with higher values of gross domestic product per capita and human development index. Betamethasone, prednisone, and fluconazole were the most commonly detected PhACs, and also presented the highest concentrations. However, they were not related to toxicological risks. Nonetheless, all surface waters were subject to toxicological risk owing to at least one PhAC. PhACs related to the highest toxicological risks were loratadine, atorvastatin, norfloxacin, caffeine, and ranitidine, however, all these PhACs presented low quantification frequency. DWTPs capacity to remove PhACs was only partial, so treated water was still contaminated with these compounds. Furthermore, atorvastatin presented a margin of exposure below 100, indicating possible risk for public health. Thus, additional advanced treatment steps should be considered to improve PhACs removal during drinking water treatment.

Estudo da biodegradabilidade de fluoroquinolona por meio da utilização de biomassas aeróbias e anaeróbias / Study of fluoroquinolone biodegradability by using aerobic and anaerobic biomass

RESUMO Os antibióticos como o norfloxacino constituem os fármacos mais utilizados na Medicina, com consumos expressivos no mundo todo. Por ser quimicamente estável, após sua administração a maior parte do fármaco é excretada de forma inalterada e, geralmente, é removida apenas parcialmente nas estações de tratamento de esgoto (ETEs). Assim, o presente trabalho buscou avaliar a eficiência dos processos biológicos na remediação de norfloxacino investigando os mecanismos de remoção envolvidos. O objetivo foi verificar a biodegradabilidade do fármaco e sua toxicidade. Para realização dos ensaios de biodegradabilidade, coletaram-se lodos na ETE Arrudas (Sabará, Minas Gerais) dos processos de tratamento com lodos ativados, reatores upflow anaerobic sludge blanket (UASB) e biodigestor anaeróbio. Reatores em escala de bancada foram montados com lodo aclimatado e não aclimatado. Amostras tiveram a biodegradabilidade acompanhada por meio da determinação do carbono orgânico total e da absortividade molar do norfloxacino por espectrofotometria de UV/Vis. Determinou-se a toxicidade por intermédio de ensaios com a bactéria Aliivibrio fischeri. Entre as biomassas utilizadas, a mais eficiente na remoção do norfloxacino foi advinda dos reatores UASB (23%), seguida do biodigestor anaeróbio (18%) e, então, dos lodos ativados (13%). Quanto à ecotoxicidade, a degradação anaeróbia promoveu a eliminação da toxicidade do antibiótico, enquanto com relação à degradação aeróbia os efluentes gerados permanecem tóxicos.

ABSTRACT Antibiotics, such as norfloxacin, are the most widely used drugs in medicine, with significant consumption in the world. By being chemically stable, most of the drug is excreted unchanged after administration, and is generally only partially removed in the sewage treatment plants (STPs). Thus, the efficiency of biological processes in the remediation of norfloxacin was investigated by the present work, verifying the removal mechanisms involved. Its objective was to verify the drug's biodegradability and toxicity. In order to perform biodegradability tests, sludges were collected in Arrudas STP (Sabara, Minas Gerais) from the treatment processes with activated sludge, upflow anaerobic sludge blanket (UASB) reactors and anaerobic biodigester. Bench-scale reactors were assembled with acclimatized and non-acclimatized sludge. Samples had their biodegradability monitored by determination of total organic carbon and norfloxacin molar absorptivity by UV/Vis spectrophotometry. The toxicity was determined by tests with Aliivibrio fischeri. Among the used biomass, UASB reactors was the most efficient in removing norfloxacin (23%), followed by anaerobic biodigester (18%), and activated sludge (13%). Regarding ecotoxicity, the anaerobic degradation promoted the elimination of antibiotic toxicity, while with aerobic degradation, the effluents generated remained toxic.

Bench and pilot scale performance assessment of recycled membrane converted from old nanofiltration membranes.

Recycling of end-of-life polyamide-based thin film composite (TFC) membranes is gaining interest in academic and industrial contexts. The effects of chlorine exposure on the performance of polyamide membranes result in an increase in membrane permeability, whereas the solute rejection decreases. Therefore, the controlled chemical conversion of old reverse osmosis (RO) membranes has been reported by some previous papers. The objectives of this study were to assess recycling of old nanofiltration (NF) membrane, to assess the performance of the recycled membranes for a river water treatment application, and to conduct preliminary cost evaluations. Recycling technique consisted of exposing the membrane to a sodium hypochlorite solution in order to remove its polyamide layer and conversion to a low-pressure membrane. The work conducted bench scale and long-time pilot tests, and the recycled membranes showed a low fouling tendency. The difference between some results in bench- and pilot scale underscores the importance of evaluating design parameters using pilot scale units. Based on the cost analysis, the total cost of chemical recycling end-of-line NF membranes for a river water treatment is approximately 1.1% of the cost of using a new UF membrane. There is a great potential in using recycled membranes for rivers water treatments.

Improving knowledge about permeability in membrane bioreactors through sensitivity analysis using artificial neural networks.

Membrane bioreactor (MBR) has been widely employed for industrial effluent treatment, as its higher efficiency in removing pollutants makes effluent reuse more feasible. However, membrane fouling remains as a limiting factor for its greater diffusion. This work performed a sensitivity analysis study to investigate the effects of analytical and operating variables on membrane permeability. The case study is a MBR treating oil refinery effluents. After the identification and validation of a predictive neural model for permeability, sensitivity analysis methods based on both connection weights and variable disturbances were used to quantify and rank the variables influence. A comprehensive analysis showed that Suspended solids and Days between cleanings exerted greater effects on permeability, whereas sludge filterability and sludge temperature were less significant. In sequence, a specific analysis revealed distinct dynamics in MBR operation given different solids concentrations. For instance, from higher solids concentrations, among all the evaluated parameters, only COD presented low significance to the permeability. This evidence suggests that permeability is more susceptible to variations when operating with higher concentrations of Suspended solids. The global result of this study contributes to more efficient MBR operations since distinct relations with permeability imply different effects on membrane fouling.

Occurrence, removal and seasonal variation of pharmaceuticals in Brasilian drinking water treatment plants.

The presence of pharmaceuticals in aquatic environments has become a major issue of concern for scientific community, since there is a lack of information about risks and impacts to the environment and public health. In the context of Brazil, many cities do not have Wastewater Treatment Plants (WWTPs) and domestic sewage is dumped directly into the water bodies, aggravating the problem. Thus, the present study aimed to evaluate the presence of 28 prescribed pharmaceuticals from different therapeutic classes in six full-scale Drinking Water Treatment Plants (DWTPs) in Minas Gerais state. Samples were collected in twelve field campaigns from August 2016 to August 2017 and water quality were monitored. Analytical methodology was based on solid phase extraction (C18 cartridge) followed by High Performance Liquid Chromatography (Prominence DGU/20A3 - Shimadzu) coupled to Mass Spectrometry (micrOTOF-QII - Bruker). Considering the 28 pharmaceuticals analyzed, 18 were detected in the surface water source at concentrations ranging from Method Quantification Limit (MQL) to 11,960 ng/L. In drinking water, the concentration of the 11 pharmaceuticals detected ranged from

Long-term evaluation of membrane bioreactor inoculated with commercial baker's yeast treating landfill leachate: pollutant removal, microorganism dynamic and membrane fouling.

In this study, commercial baker's yeast (Saccharomyces cerevisiae) was employed as a novel inoculum for a membrane bioreactor (MBRy). It was applied to landfill leachate (LFL) treatment to remove recalcitrant organic compounds as well as for the assimilation of recalcitrant compounds, since yeasts have a high ability to break such compounds down. The MBR was inoculated with 10 g L-1 of commercial baker's yeast and was operated at a hydraulic retention time of 48 h and pH of 3.5. The specific air demand based on the membrane area (SADm) was maintained at 0.6 m3 h-1 m-2. The MBRy achieved chemical oxygen demand (COD), color, NH3, and humic substances removal of 68, 79, 68, and 50%, respectively. Furthermore, the MBRy showed lower fouling potential, which can be attributed to the low extracellular polymeric substances production, as the formation of a cake layer was the major mechanism of membrane fouling. The work demonstrated that novel MBR is a promising technology for treating recalcitrant landfill leachate.