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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-β-estradiol values ranged from 0.061 to 6.71 µg·L-1 after to be chlorinated at different reaction times. Copyright © 2020 Elsevier Ltd. All rights reserved.


André Luis Corrêa de Barros, Daniel Aparecido da Silva Rodrigues, Camila Cristina Rodrigues Ferreira da Cunha, Igor Aparecido Santana das Chagas, Daiana Rocha do Espirito Santo, Silvana de Queiroz Silva, Robson José de Cássia Franco Afonso. Aqueous chlorination of herbicide metribuzin: Identification and elucidation of "new" disinfection by-products, degradation pathway and toxicity evaluation. Water research. 2021 Feb 01;189:116545

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PMID: 33160237

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