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.

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.

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.

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.

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.

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.

Determination of nine pharmaceutical active compounds in surface waters from Paraopeba River Basin in Brazil by LTPE-HPLC-ESI-MS/MS.

A simple, inexpensive, versatile, and environment-friendly extraction method, using low-temperature partitioning extraction (LTPE), was validated to quantify pharmaceutical-active compounds (PhACs) in surface water samples by high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The PhACs analyzed were acetaminophen, bezafibrate, diclofenac, diltiazem, fluconazole, linezolid, miconazole, ondansetron hydrochloride, and trimethoprim. The detection and quantification limits ranged from 0.15 to 12.30 ng L-1 and 0.43 to 40.60 ng L-1, respectively. Recovery rates ranged from 46 to 135%, and relative standard deviation (RSD%) varied between 0.49 and 6.13%. This method was applied to monitor water contamination by PhACs in the Paraopeba River Basin (PRB), Minas Gerais state, Brazil. All PhACs, except linezolid which was not detected, were found in PRB water samples in concentrations that ranged from 2.6 ng L-1 to 2.62 µg L-1.

Anaerobic co-digestion of coffee husks and microalgal biomass after thermal hydrolysis.

Residual coffee husks after seed processing may be better profited if bioconverted into energy through anaerobic digestion. This process may be improved by implementing a pretreatment step and by co-digesting the coffee husks with a more liquid biomass. In this context, this study aimed at evaluating the anaerobic co-digestion of coffee husks with microalgal biomass. For this, both substrates were pretreated separately and in a mixture for attaining 15% of total solids (TS), which was demonstrated to be the minimum solid content for pretreatment of coffee husks. The results showed that the anaerobic co-digestion presented a synergistic effect, leading to 17% higher methane yield compared to the theoretical value of both substrates biodegraded separately. Furthermore, thermal hydrolysis pretreatment increased coffee husks anaerobic biodegradability. For co-digestion trials, the highest values were reached for pretreatment at 120 °C for 60 min, which led to 196 mLCH4/gVS and maximum methane production rate of 0.38 d-1.

Steam explosion pretreatment improved the biomethanization of coffee husks.

This study evaluated the potential of energy generation using a combined heat and power co-generation system (CHP) from biogas produced during the anaerobic digestion of coffee husks (CH) pretreated with steam explosion. Pretreatment conditions assessed were time (1, 5, 15 and 60min) and temperature (120, 180 and 210°C). Polysaccharides solubilisation and biogas production were not correlated. While pretreatment with severities higher than 4 resulted in a highest solubilisation of cellulose, hemicelluloses and lignin; however, furans concentration in those cases hindered biomass biodegradation. Considering a CHP, all pretreatment conditions were worthwhile when compared to non-pretreated CH. The best condition was 120°C for 60min, in which a 2.37 severity showed the highest methane yield (144.96NmLCH4gCOD-1) and electricity production (0.59kWhkgCH-1). However, even better results could be achieved using 120°C for only 5min, which would lead to a larger amount of CH daily processed.

Use of aqueous two-phase PEG-salt systems for the removal of anionic surfactant from effluents.

Linear alkylbenzene sulfonates (LAS) are synthetic anionic surfactants that are extensively used in many industries. As a result, large volumes of effluents containing high levels of these compounds are discharged into water bodies, causing risks to aquatic flora and fauna. Then, there is a need for environmentally safe and economically viable technologies for the removal of LAS from aqueous matrices. The present work evaluates the use of aqueous two-phase systems (ATPS) composed of PEG and sulfate salts for this purpose, considering the effects of tie line length (TLL), molar mass of polymer, and type of cation-forming salt on the partitioning behavior of LAS. All the LAS partition coefficient (KLAS) values were greater than unity, and the LAS extraction efficiencies (%ELAS) were higher than 97%. The system consisting of PEG 1500 + (NH4)2SO4 + H2O provided the highest KLAS (1083.34) and %ELAS (99.9%), indicating that the method provided good extraction of LAS to the top phase. This system was applied using a real effluent sample in laboratory-scale experiments as well as in bench-scale batch trials. The results obtained at the laboratory scale showed %ELAS values greater than 98%, while the best KLAS value obtained in the batch experiments was 8.50 (±1.75) (%ELAS = 78.17%). These values demonstrated the potential of ATPS for the removal of LAS from industrial effluents.

Anaerobic digestion of hemicellulose hydrolysate produced after hydrothermal pretreatment of sugarcane bagasse in UASB reactor.

In the context of a sugarcane biorefinery, sugarcane bagasse produced may be pretreated generating a solid and liquid fraction. The solid fraction may be used for 2G bioethanol production, while the liquid fraction may be used to produce biogas through anaerobic digestion. The aim of this study consisted in evaluating the anaerobic digestion performance of hemicellulose hydrolysate produced after hydrothermal pretreatment of sugarcane bagasse. For this, hydrothermal pretreatment was assessed in a continuous upflow anaerobic sludge blanket (UASB) reactor operated at a hydraulic retention time (HRT) of 18.4h. Process performance was investigated by varying the dilution of sugarcane bagasse hydrolysate with a solution containing xylose and the inlet organic loading rate (OLR). Experimental data showed that an increase in the proportion of hydrolysate in the feed resulted in better process performance for steps using 50% and 100% of real substrate. The best performance condition was achieved when increasing the organic loading rate (OLR) from 1.2 to 2.4gCOD/L·d, with an organic matter removal of 85.7%. During this period, the methane yield estimated by the COD removal would be 270LCH4/kg COD. Nonetheless, when further increasing the OLR to 4.8gCOD/L·d, the COD removal decreased to 74%, together with an increase in effluent concentrations of VFA (0.80gCOD/L) and furans (115.3mg/L), which might have inhibited the process performance. On the whole, the results showed that anaerobic digestion of sugarcane bagasse hydrolysate was feasible and may improve the net energy generation in a bioethanol plant, while enabling utilization of the surplus sugarcane bagasse in a sustainable manner.