DLLME-SFO-GC-MS procedure for the determination of 10 organochlorine pesticides in water and remediation using magnetite nanoparticles.

There exists a high demand for fast, simple, and reliable methodologies for determining the presence of organochlorine pesticides (OCPs) on environmental samples. Moreover, the toxicity and accumulation of potential OCPs in several environments have led to the development of technologies that achieve their removal from contaminated waters. In this study, a novel method combining a dispersive liquid-liquid microextraction procedure based on the solidification of floating organic drop is developed and validated for the extraction, preconcentration, and determination of 10 OCPs: α-BHC, p,p'-DDE, δ-BHC, dieldrin, p,p'-DDT, endosulfan I, endosulfan sulfate, heptachlor, heptachlor epoxide (isomer B), and methoxychlor in water samples. The results show that the calibration curves were linear for all the studied compounds, and the coefficients of correlation higher than 0.99. The variation coefficient for precision and accuracy was lower than 10%, and the accuracy ranged from 93 to 105%. Low limit of detection and limit of quantification values ranging from 0.06-3.00 ng mL-1 and 0.20-10 ng mL-1 were obtained, respectively. The capability of the proposed method was confirmed using an analysis of the water samples before and after the degradation process; this was achieved by employing nanomaterials, while performing an analysis of 160 real samples that were sourced from a Brazilian river. A cobalt-doped magnetite was applied for the environmental remediation of the studied compounds, and it was verified that the novel material has the potential to be used in environmental remediation with a degradation efficiency exceeding 80% for the majority of the studied compounds.

Validação de método analítico por ELL-CG-EM para detecção de trialometanos decorrentes da cloração de águas contendo Microcystis / Analytical method and trihalomethanes formation by Microcystis

RESUMO Estudos demonstram que a utilização do cloro em estações de tratamento de água (ETA) pode contribuir para a formação de subprodutos orgânicos halogenados indesejados, tais como os trialometanos (TAM), quando há presença de matéria orgânica algogênica, composta de algas e cianobactérias. A Microcystis aeruginosa é uma espécie de cianobactéria com frequentes registros em eventos de florações no país e é relacionada com a formação de TAM durante a cloração da água. Desse modo, este estudo teve como objetivo o desenvolvimento e a validação do método analítico por extração líquido-líquido para detecção e quantificação de TAM por cromatografia gasosa acoplada à espectrometria de massas (ELL-CG-EM), bem como a aplicação deste para avaliar a formação de TAM em ensaios de cloração de células de Microcystis aeruginosa, simulando situações em ETA. O método obteve baixo tempo de análise (< 12 minutos), excelente seletividade, precisão, repetitividade e sensibilidade, com possibilidade de aplicação para análises de rotina em detrimento de outras técnicas consideradas mais automatizadas. Foram observadas alta demanda de cloro durante os ensaios e elevada concentração dos subprodutos quando submetida à dose de cloro gasoso (Cl2) de 2,5 e 5 mg.L-1, com destaque para o triclorometano, sendo outras espécies de monitoramento obrigatório não detectadas ou não formadas, o que pode ser justificado pela ausência de bromo.

ABSTRACT Studies have shown that the use of chlorine in water treatment plants (WTPs) can contribute to formation of undesirable halogenated organic by-products, such as trihalomethanes (THMs), when algae and cyanobacteria are present. Microcystis aeruginosa is a cyanobacteria specie with frequent recordings of flowering events in the country and is related to the formation of THMs during water chlorination. Thus, the objective of this study was to develop and validate Liquid-Liquid Extraction the analytical method for detection and quantification of THMs by gas chromatography coupled to mass spectrometry (LLE-GC-MS), as well as the application of the method to evaluate the formation of TAMs from Microcystis aeruginosa cells chlorination tests, simulating situations in WTPs. The method obtained low time of analysis (< 12 minutes), excellent selectivity, precision, repeatability and sensitivity, with possibility of application for routine analysis to the detriment of other techniques considered more automated. High chlorine demand was observed during the tests and high concentration of by-products when submitted to the chlorine gas (Cl2) dose of 2.5 and 5 mg.L-1, with emphasis on trichloromethane. Other species of mandatory monitoring were not detected or not formed, justified by the absence of bromine.

Degradation of haloacetic acids with the Fenton-like and analysis by GC-MS: use of bioassays for monitoring of genotoxic, mutagenic and cytotoxic effects.

In this study, a method was developed to evaluate the degradation of haloacetic acids (HAAs) in water by a heterogenous Fenton-like process catalyzed by cobalt-doped magnetite nanoparticles (Fe3 - xCoxO4), extraction of the contaminants by liquid-liquid extraction (LLE), and analysis by gas chromatography-mass spectrometry (GC-MS). The developed method was efficient in the degradation of HAAs, with the following degradation values: 63%, 62%, 30%, 39%, 37%, 50%, 84%, 41%, and 79% for monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, trichloroacetic acid, bromochloroacetic acid, dibromoacetic acid, bromodichloroacetic acid, dibromochloroacetic acid, and tribromoacetic acid compounds, respectively. Through the application of the Allium cepa test, the cytotoxicity, genotoxicity, and mutagenicity of HAAs were evaluated. The results confirm its genotoxic and mutagenic effects on Allium cepa meristematic cells. Through this study, it was possible to verify the effectiveness of the developed method and its potential as a proposal for environmental remediation.