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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.

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A widely used herbicide, metribuzin, was evaluated for degradation, mineralization and disinfection by-products (DBPs) formation during aqueous chlorination. In addition, to assess the toxicity effects of chlorination on metribuzin solution the following tests were performed: acute toxicity using Artemia salina nauplii; cell viability using MTT assay; estrogenicity using a re-engineered Bioluminescent Yeast Estrogen Screen (BLYES) and a constitutively bioluminescent strain (BLYR); mutagenicity and developmental toxicity using Q(SAR) methodology. Metribuzin at 10 mg·L-1 was degraded by chlorination, achieving 93% of removal at 30 min of reaction. TOC analysis showed that the herbicide does not suffer complete mineralization, even after 24 h of contact with free chlorine. Seventeen DBPs were detected and their structural formulae were elucidated by high resolution mass spectrometry. Toxicity effects for chlorinated solutions increased when compared to the unreacted metribuzin solution. DBPs were more toxic to Artemia salina nauplii, increasing around 20% on nauplii mortality. It was also observed high estrogenicity to human receptors in BLYES assays and mutagenic and developmental toxicant effects to animals and humans in Q(SAR) methodology, suggesting that DBPs are potentially more toxic than the precursor metribuzin. Metribuzin solutions at 10 mg·L-1 showed equivalent 17-ß-estradiol values ranged from 0.061 to 6.71 µg·L-1 after to be chlorinated at different reaction times.

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During this research, chemometric approaches were applied for optimization of the low-temperature partitioning extraction (LTPE) for the simultaneous analysis of the pesticides: acephate, difenoconazole, fenamidone, fluazifop, fluazinam, methamidophos, and thiamethoxam from surface water samples and determination by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry. It was used the 23 full factorial and the Doehlert experimental designs. The extraction technique was optimized by evaluating the effects of the three variables: sample pH, ionic strength (addition of Na2HPO4), and organic solvent volume. Considering the interest to find an optimal condition for all analytes simultaneously, the best extraction parameters found were as follows: pH = 5.33, concentration of Na2HPO4 = 0.0088 mol L-1 and organic phase volume = 4.5 mL. The optimized methodology showed LOD and LOQ levels from 0.33 to 8.13 ng L-1 and from 1.09 to 26.84 ng L-1, respectively. The recovery values ranged from 38.37 and 99.83% and the RSD values varied from 2.33 to 18.92%. The method was applied to surface water analysis sampled in areas with intensive agricultural practices in Ouro Branco City, Minas Gerais, Brazil. The difenoconazole was detected in concentrations between 12.53 and 94.76 ng L-1.

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RESUMO Os compostos de preocupação emergente (contaminants of emerging concern - CECs) atingem constantemente os corpos d'água via lançamento de esgoto sanitário, efluentes industriais e lixiviados de aterro, disposição inadequada de resíduos sólidos e escoamento superficial, ocasionando a poluição dos cursos d'água. Geralmente estes se encontram em concentrações da ordem de nanograma por litro ou micrograma por litro, dificultando sua análise ou onerando esse processo, demandando, assim, o desenvolvimento de técnicas de preparo e extração. Nesse contexto, destaca-se a Partição a Baixa Temperatura (EPBT), que se baseia na partição do analito de interesse entre fase aquosa e fase orgânica. Face ao exposto e à relevância do tema, o presente trabalho teve como objetivo avaliar, pelo uso da EPBT e cromatografia gasosa acoplada à espectrometria de massas, a ocorrência de 16 CECs no esgoto bruto e no tratado de Belo Horizonte (MG).

ABSTRACT Contaminants of Emerging Concern (CECs) constantly reach water bodies through the discharge of sanitary sewage, industrial effluents and landfill leachate, inadequate disposal of solid waste and surface runoff, causing the pollution of watercourses. In general, these are in concentrations of the order of mg / L or ng / L, making it difficult to analyze or burden this process, thus requiring the development of preparation and extraction techniques. In this context, it stands out the Low Temperature Patitioning Extraction (LTPE), which is based on the partition of the analyte of interest between aqueous phase and organic phase. Bearing this and the relevance of the subject in mind, the present work had the objective of evaluating the occurrence of 16 CECs in the crude and treated sewage of Belo Horizonte / MG, by using LTPE and gas chromatography coupled to mass spectrometry.

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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.

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This work has assessed the seasonal changes and the dynamics in the concentration of six pharmaceutical compounds during photolysis as a tertiary treatment of sewage previously treated by an anaerobic/aerobic system comprising a UASB (Upflow Anaerobic Sludge Blanket) reactor and a trickling filter (TF). The target compounds were four antibiotics (ciprofloxacin (CPF), clindamycin (CLM), sulfamethoxazole (SMX), and trimetoprim), one ß-blocker (atenolol), and one anti-inflammatory (diclofenac (DCF)). Six hydraulic retention times (HRTs) were evaluated (5, 10, 20, 40, 80, and 160 min) with the intent of varying the ultraviolet C (UVC) radiation doses applied to the effluent from biological treatment containing the target contaminants. The concentrations of pharmaceutical compounds in the effluent of the UASB/TF system were in agreement with the concentration levels reported in the literature. Aside from DCF, the seasonality seems to be a preponderant characteristic regarding the pharmaceutical concentration found in the effluent of biological treatment systems. The radiation dose of 117 mJ cm-2 seemed to be most suited for the photolysis application to tertiary treatment of domestic effluents. It was observed that lower UVC doses led to deconjugation of pharmaceuticals, which can result in increased concentrations of target pollutants in the photoreactor effluent.

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A new highly sensitive and environmentally friendly analytical method, using low-temperature partition extraction and ultra-high-performance liquid chromatography with tandem mass spectrometry, without the use of a labeled analyte, was developed and validated to determine and quantify urinary S-phenylmercapturic acid in urine samples. The World Health Organization, in its guidelines for air quality in Europe, recognizes that benzene is carcinogenic to humans and there is no safe level of exposure. Urinary S-phenylmercapturic acid is a sensitive and specific biological marker of exposure to benzene. The new analytical method, extraction, and analysis, were linear in the working range between 0.1 and 200.0 µg/L, precise (relative standard deviation lower than 6.0%), accurate (97.0-105.0%), and sensitive. The method's limits of detection and quantification were 0.02 and 0.084 µg/L, respectively. The recovery with the low-temperature partition extraction was 96.1%, with relative standard deviation less than 3.8%. The method is simple, accurate, and reproducible, and has been successfully applied in the evaluation of nonoccupational exposure to benzene, by urinary S-phenylmercapturic acid in urine samples.

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RESUMOEste trabalho avaliou a remoção de diclofenaco (DCF), bezafibrato (BZF) e etinilestradiol (EE2) de efluentes de sistema UASB-FBP (reator anaeróbio de manta de lodo seguido de filtro biológico percolador) em fotorreatores UV de lâmpadas imersas (FRI) e emersas (FRE). Os resultados mostram que baixa eficiência de remoção de tais compostos foi obtida em ambos fotorreatores quando se utilizou baixo tempo de contato (~10 min) e baixa concentração inicial de fármacos (0,5 µg.L-1 para EE2, e 21 µg.L-1 para DCF e BZF). O aumento da concentração inicial de DCF (para 20 mg.L-1) e do tempo de contato (para 20 min) resultaram em aumento da eficiência de remoção (de 31 para 83% no FRI e de 36 para 86% no FRE), indicando que compostos dissolvidos presentes no efluente biológico afetaram adversamente a remoção de fármacos nos fotorreatores devido a competição pela radiação UV incidente.

ABSTRACTThis paper evaluated the removal of diclophenac (DCF), bezafibrate (BZF) and ethynylestradiol (EE2) from effluent of an anaerobic reactor coupled to a trickling filter (UASB-TF) in two types of UV photoreactors (immerse UV lamps - FRI and emmersed UV lamps - FRE). The results showed low removal efficiencies in both photoreactors when low contact times (10 min) and low initial concentration of such compounds was used (0.5 µg.L-1 for EE2 and 21 µg.L-1 for DCF and BZF). An increase in the initial concentration of DCF (to 20 mg.L-1) and of the contact time (to 20 min) led to an increase in the removal efficiency (from 31 to 83% in FRI and from 36 to 86% in FRE), suggesting that dissolved compounds present in the biological effluent adversely affected the removal of the pharmaceutical tested due to competition for the incident UV radiation.

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This study identified phenotypic traits appropriate for biotechnological applications of 118 yeasts isolated from cachaça distilleries. Different properties were verified: capacity to use alternative carbon sources; ability to tolerate high concentrations of sucrose, ethanol, methanol, aluminum and zinc as well as different pH values and foam production. Pichia guilliermondii and Pichia anomala strains were identified as the most promising ones for application in the second-generation biofuel industry, showing ability to grow on high glycerol concentrations. Other isolates, identified as Saccharomyces cerevisiae, produced bioethanol comparable to the industrial strains, and were therefore ideal for use in the first-generation ethanol industry. Some of these strains also showed high resistance to aluminum, as observed in sugarcane juice, and to inter-cycle washings with diluted sulphuric acid, as performed in the industrial bioethanol production process. In summary, yeast isolates from cachaça distilleries displayed robustness and phenotypic plasticity, which makes them interesting for biotechnological applications.

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