Navegando por Autor "Silva, Júlio César Cardoso da"

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Characterisation of captopril photolysis and photocatalysis by-products in water by direct infusion, electrospray ionisation, high-resolution mass spectrometry and the assessment of their toxicities.
(2017) Freitas, Julia Raquel Lino e; Quintão, Frederico Jehár Oliveira; Silva, Júlio César Cardoso da; Silva, Silvana de Queiroz; Aquino, Sergio Francisco de; Afonso, Robson José de Cássia Franco
Pharmaceuticals of different therapeutic classes are found in the environment. Captopril is used worldwide as an antihypertensive drug, and it has been found in the influent, effluent and secondary sludge of wastewater treatment plants. Advanced oxidation processes, such as direct photolysis (UV-C) and heterogeneous photocatalysis (TiO2/UV-C), are alternatives to enhance mineralisation of pharmaceuticals and their removal during water treatment. In this article, it was evaluated the degradation of captopril in aqueous solution induced by UV-C and TiO2/UV-C systems. The process focused on the identification and monitoring of the by-products formed under these conditions by applying direct-infusion electrospray ionisation high-resolution mass spectrometry in the negative ion mode (ESI(-)-HRMS) and high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC/HRMS). To evaluate the by-products toxicity, acute ecotoxicity tests were performed with the crustacean Artemia salina, and the cytotoxicity was evaluated with (4,5-dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide (MTT) assay using HepG2 cells. It was observed by ESI(-)-HRMS that after 120 min of light exposure, there was almost complete removal of captopril, with 93.5% removal efficiency during photolysis and 99.9% during photocatalysis. At these conditions, the rate of mineralisation, by total organic carbon (TOC), was only 2.92% for photolysis and 9.09% for photocatalysis, evidencing the formation of degradation byproducts. Nine by-products of captopril photodegradation were identified, and their respective chemical structure elucidations were proposed. The treated samples were nontoxic to A. salina and HepG2 cells, indicating that both oxidative treatments (photocatalytic or photolytic processes) can be conveniently employed to remove captopril from aqueous media.
Desenvolvimento de metodologia analítica para determinação de microcistina-LR e agrotóxicos em águas superficiais, utilizando as técnicas de cromatografia líquida e cromatografia gasosa acopladas a espectrometria de massas.
(Programa de Pós-Graduação em Engenharia Ambiental. PROÁGUA, Pró-Reitoria de Pesquisa e Pós Graduação, Universidade Federal de Ouro Preto., 2010) Silva, Júlio César Cardoso da; Afonso, Robson José de Cássia Franco
Alguns compostos orgânicos têm causado preocupações às autoridades sanitárias no que diz respeito à quão tóxicos podem ser a organismos humanos e se os tratamentos convencionais utilizados nas estações de tratamento de água são eficientes em suas remoções. Dentre os microcontaminantes atualmente presentes no ambiente destacam-se microcistina-LR (MC-LR) e alguns agrotóxicos (organoclorados, organofosforados, carbamatos, etc). Os baixos níveis de concentração desses contaminantes encontrados no ambiente exigem etapas de tratamento e concentração das amostras para determinação analítica, que normalmente demandam tempo e custo. Essa dissertação teve como objetivo desenvolver metodologia analítica para quantificação de MC-LR e trinta e sete agrotóxicos multirresíduo em amostras de água superficial, utilizando apenas uma única etapa de preparo e concentração das amostras. A quantificação de MC-LR nas amostras de água foi feita por cromatografia líquida acoplada a espectrometria de massas (CLAE/EM), e o método multiressíduo para determinação de agrotóxicos em água foi feito por cromatografia gasosa acoplada à espectrometria de massas. A concentração e o clean-up das amostras foram obtidos usando extração em fase sólida, cartucho C18. A recuperação de MC-LR para o método variou entre 93,6% a 96,9%, e os limites de detecção e de quantificação analítico foram 0,03 e 0,1ng/L, respectivamente. A recuperação para agrotóxicos de diferentes classes (organoclorados, carbamatos, organofosforados, clorotriazinas, diarboximidas), variou de 90% a 117% exceto para clorpirifós etílico (72% a 80%), e os limites de detecção e de quantificação do método analítico variaram entre 0,3 a 19,9ng/L e 0,9 a 66,2ng/L, respectivamente. As metodologias foram aplicadas em amostras de água, coletadas mensalmente, em 44 pontos durante 11 meses, em mananciais e estações de tratamento de água de Viçosa-MG e apresentaram resultados abaixo LD, tanto para os agrotóxicos como para MC-LR. O método também foi aplicado a amostras de água de uma lagoa, em Ouro Preto, MG, coletada em triplicata, onde foi detectada a presença de MC-LR na concentração de 5,8ng/L.
Determination of endocrine disrupters and pharmaceuticals in sewage samples by tandem solid phase clean up/extraction and high performance liquid chromatography-negative and positive electrospray high-resolution mass spectrometry.
(2014) Queiroz, Fernanda Barbosa de; Silva, Júlio César Cardoso da; Aquino, Sergio Francisco de; Coutrim, Maurício Xavier; Afonso, Robson José de Cássia Franco
Foi desenvolvido e validado um método para determinação de três perturbadores endócrinos (estradiol, etinilestradiol e bisfenol A) e cinco produtos farmacêuticos (sulfametoxazol, trimetoprima, diclofenaco, bezafibrato e miconazol) em amostras de esgoto bruto, utilizando extração em fase sólida (SPE) e cromatografia líquida à espectrometria de massas em alta resolução (HPLC-HRMS) com ionização por eletrospray, nos modos positivo e negativo. Foi utilizado na extração em fase sólida um cartucho de troca iônica forte (Strata SAX) e um cartucho contendo divinilbenzeno-pirrolidona, para reduzir os níveis dos alquilbenzeno-sulfonados de cadeia linear (LAS) e para concentrar os analitos de interesse das amostras de esgoto. A influência do efeito matriz na eficiência da ionização, a recuperação da EFS e a sensibilidade do método foi identificada e quantificada. O método foi aplicado com sucesso na determinação dos analitos em amostras de esgoto coletadas na entrada da estação de tratamento de efluentes (ETE) do Arrudas em Belo Horizonte, MG, Brasil.
Fast determination of benzodiazepines in human urine via liquid-liquid extraction with low temperature partitioning and LC-HRMS.
(2012) Magalhães, Elisângela Jaqueline; Nascentes, Clésia Cristina; Augusti, Rodinei; Queiroz, Maria Eliana Lopes Ribeiro de; Silva, Júlio César Cardoso da; Afonso, Robson José de Cássia Franco
A simple and high-throughput method to simultaneously determine selected benzodiazepines (i.e., diazepam, lorazepam, clonazepam, and bromazepam) in urine was developed and validated. The entire methodology consisted of the applica-tion of an innovative extraction/cleanup procedure, namely liquid-liquid extraction with low-temperature partitioning (LLE-LTP), and analysis by liquid chromatography combined with high-resolution mass spectrometry (LC-HRMS). The LLE-LTP procedure was optimized via factorial design and by evaluating crucial variables, specifically the freez-ing mode (either slow or fast), the urine/acetonitrile volume ratio, and the sample ionic strength. The benzodiazepines were quantified using matrix-matched calibration curves where the following parameters were assessed by validation protocol: in general, linearity range of 17 - 200 μg•L–1 (r > 0.9957); limits of detection lower than 5 μg•L–1; relative standard deviations (RSD) lower than 12.5%; and accuracy ranging from 72.3% to 117%. To test this procedure’s per-formance, the method was applied to determine the content of diazepam in actual urine samples. The validation results obtained for the method demonstrated that the present methodology could be potentially applied in proficient laborato-ries as a routine approach for determining benzodiazepines compounds content in urine.
Nickel, manganese and copper removal by a mixed consortium of sulfate reducing bacteria at a high COD/sulfate ratio.
(2014) Barbosa, Leonardo de Paiva; Costa, Patrícia Freitas; Bertolino, Sueli Moura; Silva, Júlio César Cardoso da; Cota, Renata Guerra de Sá; Leão, Versiane Albis; Teixeira, Mônica Cristina
The use of sulfate-reducing bacteria (SRB) in passive treatments of acidic effluents containing heavy metals has become an attractive alternative biotechnology. Treatment efficiency may be linked with the effluent conditions (pH and metal concentration) and also to the amount and nature of the organic substrate. Variations on organic substrate and sulfate ratios clearly interfere with the biological removal of this ion by mixed cultures of SRB. This study aimed to cultivate a mixed culture of SRB using different lactate concentrations at pH 7.0 in the presence of Ni, Mn and Cu. The highest sulfate removal efficiency obtained was 98 %, at a COD/sulfate ratio of 2.0. The organic acid analyses indicated an acetate accumulation as a consequence of lactate degradation. Different concentrations of metals were added to the system at neutral pH conditions. Cell proliferation and sulfate consumption in the presence of nickel (4, 20 and 50 mg l-1), manganese (1.5, 10 and 25 mg l-1) and copper (1.5, 10 and 25 mg l-1) were measured. The presence of metals interfered in the sulfate biological removal however the concentration of sulfide produced was high enough to remove over 90 % of the metals in the environment. The molecular characterization of the bacterial consortium based on dsrB gene sequencing indicated the presence of Desulfovibrio desulfuricans, Desulfomonas pigra and Desulfobulbus sp. The results here presented indicate that this SRB culture may be employed for mine effluent bioremediation due to its potential for removing sulfate and metals, simultaneously.
Ozonation of the food dye Brilliant Blue in aqueous medium : monitoring and characterization of products by direct infusion electrospray ionization coupled to high-resolution mass spectrometry.
(2012) Silva, Júlio César Cardoso da; Bispo, Glayson Leonardo; Pavanelli, Sérgio Pinton; Afonso, Robson José de Cássia Franco; Augusti, Rodinei
Dyes have been widely used to accentuate or to provide different colors to foods. However, the high concentrations of dyes in effluents from the food industries can cause serious and unpredictable damages to aquatic life in general. Furthermore, since conventional biological treatments have been shown to be ineffective, the use of advanced oxidation processes to promote the depletion of such dyes in water bodies has turned out to be mandatory.
Photodegradation of bisphenol A in aqueous medium : monitoring and identification of by-products by liquid chromatography coupled to high-resolution mass spectrometry.
(2014) Silva, Júlio César Cardoso da; Teodoro, Janaina Aparecida Reis; Afonso, Robson José de Cássia Franco; Aquino, Sergio Francisco de; Augusti, Rodinei
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.
Photolysis and photocatalysis of ibuprofen in aqueous medium : characterization of byproducts via liquid chromatography coupled to high-resolution mass spectrometry and assessment of their toxicities against Artemia Salina.
(2014) Silva, Júlio César Cardoso da; Teodoro, Janaina Aparecida Reis; Afonso, Robson José de Cássia Franco; Aquino, Sergio Francisco de; Augusti, Rodinei
The degradation of the pharmaceutical compound ibuprofen (IBP) in aqueous solution induced by direct photolysis (UV-A and UV-C radiation) and photocatalysis (TiO2/UV-A and TiO2/UV-C systems) was evaluated. Initially, we observed that whereas photocatalysis (both systems) and direct photolysis with UV-C radiation were able to cause an almost complete removal of IBP, the mineralization rates achieved for all the photodegradation processes were much smaller (the highest value being obtained for the TiO2/UV-C system: 37.7%), even after an exposure time as long as 120 min. Chemical structures for the byproducts formed under these oxidative conditions (11 of them were detected) were proposed based on the data from liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) analyses. Taking into account these results, an unprecedented route for the photodegradation of IBP could thus be proposed. Moreover, a fortunate result was achieved herein: tests against Artemia salina showed that the degradation products had no higher ecotoxicities than IBP, which possibly indicates that the photocatalytic (TiO2/UV-A and TiO2/UV-C systems) and photolytic (UV-C radiation) processes can be conveniently employed to deplete IBP in aqueous media.
Soluble Microbial Product (SMP) characterization in bench-scale aerobic and anaerobic CSTRS under different operational conditions.
(2010) Mesquita, Patrícia da Luz; Aquino, Sergio Francisco de; Xavier, Amália Luísa Pedrosa; Silva, Júlio César Cardoso da; Afonso, Robson José de Cássia Franco
This work presents results on the production and characterization (by both mass spectrometry and conventional chemical analyses) of Soluble Microbial Products (SMP) that accumulated in aerobic and anaerobic bench scale completely stirred tank reactors (CSTRs) fed with glucose or acetate under different hydraulic retention times (HRT) and temperatures. SMP accumulation varied from 2 to 68% of the influent COD in the aerobic reactor and from 9 to 27% in the anaerobic reactor and increased with the decrease in temperature and with the HRT reduction in the aerobic reactor. On the other hand, in the anaerobic reactor, the organic loading rate and the temperature had little impact on SMP production, implying that the SMP originated from different mechanisms in each system. For both reactors, a higher accumulation of SMPs was observed as the substrate was acetate when compared to glucose, and the chemical analysis showed that the majority of the SMP did not seem to be proteins or carbohydrates. Principal component analysis (PCA) of the mass spectra from positive and negative mode electron-spray ionization (LC-IT-TOF-MS) and results from matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS) confirmed the chemical analyses and showed the absence of proteins in the effluents and the predominance of low molecular weight SMP. The PCA analysis also showed that the majority of the SMP from aerobic and anaerobic reactors did not seem to originate from soluble extracellular polymeric substances (EPS) or cell lysis products. Keywords: Biological wastewater treatment; Soluble microbial products; Residual COD; Volatile fatty acids; mass spectrometry