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Master's Dissertation
DOI
https://doi.org/10.11606/D.3.2021.tde-17012022-125223
Document
Author
Full name
Carolina Mendes Rocha
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2021
Supervisor
Committee
Teixeira, Antonio Carlos Silva Costa (President)
Amaral, Camila Costa de Amorim
Dantas, Renato Falcão
Title in Portuguese
Persistência ambiental fotoquímica de pesticidas em águas superficiais.
Keywords in Portuguese
Fotodegradação
Modelo cinético
Persistência ambiental fotoquímica
Pesticidas
Simulações matemáticas
Abstract in Portuguese
Conhecer a persistência fotoquímica de pesticidas no meio ambiente se faz necessário para avaliação dos impactos que podem ser causados, uma vez que têm sido utilizadas quantidades expressivas desses compostos, sendo preciso garantir a preservação dos recursos hídricos por meio do entendimento dos processos que podem impactar a permanência no meio natural. Neste trabalho, foi investigado o comportamento fotoquímico de dois pesticidas, imidacloprido (IMD) e ametrina (AMT). Além de estudos da fotólise direta, também foram obtidas as constantes de taxa de reação de segunda ordem dos pesticidas com espécies reativas foto-induzidas-RPS (radicais hidroxila, HO; oxigênio singlete, 1O2; e estados excitados triplete da matéria orgânica cromofórica dissolvida,3CDOM* ) por meio do método de competição cinética, em pH 7. Os resultados mostraram que o rendimento quântico da fotólise direta sob luz solar dos pesticidas foram IMD = 1,23 × 10-2 mol Einstein-1 e AMT = 7,99 × 10-3 mol Einstein-1, valores baixos, justificando a degradação lenta dos pesticidas na ausência das RPS. As constantes de taxa de reação de segunda ordem entre IMD com radicais HO, 1O2 e 3CDOM* foram kIMD,HO, kIMD,1O2 e kIMD,3CDOM* foram (3,51 ± 0,06) × 109, (2,86 ± 0,65) × 105 e (3,17 ± 0,14) × 108 L mol-1s-1, respectivamente. Já para AMT, kAMT,HO, kAMT,1O2 e kAMT, 3CDOM* foram (4,97 ± 0,37) × 109, (3,43 ± 0,58) × 104 e (7,75 ± 0,80) × 108 L mol-1s-1, respectivamente. Simulações matemáticas realizadas utilizando o modelo cinético APEX, com base em concentrações típicas dos constituintes da água (NO3-, NO2-, CO32-, TOC) do rio Paranapanema (São Paulo, Brasil), indicaram que os tempos de meia-vida dos pesticidas devem variar entre 24,1 e 19,2 dias. Estudos da toxicidade com Daphnia similis mostraram a capacidade do poluente de atingir organismos não-alvo quando em água no rio. Já os testes de genotoxicidade com Allium cepa revelaram anomalias e aberrações cromossômicos causadas pelos pesticidas aos bulbos de cebola.
Title in English
Photochemical environmental persistence of pesticides in surface water.
Keywords in English
Kinetic model
Mathematical simulations
Pesticides
Photochemical environmental persistence
Photodegradation
Abstract in English
Knowing the photochemical persistence of pesticides in the environment is necessary to assess the impacts that may be caused, since significant quantities of these compounds have been used, and it is necessary to ensure the preservation of water resources by understanding the processes that can impact environmental persistence as well as the transport of contaminants in the aquatic environment. In this work, the photochemical behavior of two pesticides, imidacloprid (IMD) and ametryn (AMT) was investigated. In addition to direct photolysis studies, the second-order rate constants of the reactions between the pesticides and hydroxyl radicals (HO), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were obtained by the kinetic competition method at pH 7. The results showed that the quantum yields of direct photolysis of IMD and AMT under sunlight were IMD = 1.23 × 10-2 mol Einstein-1 and AMT = 7.99 × 10-3 mol Einstein-1, respectively; these low values justify the slow degradation of the pesticidesin the absence of the reactive photo-induced species (RPS). The second order reaction rate constants of IMD with the RPS, kIMD, HO, kIMD,1O2 and kIMD,3CDOM* were (3.51 ± 0.06) × 109, (2.86 ± 0.65) × 105 and (3.17 ± 0.14) × 108 L mol-1s-1, respectively. For AMT, the values kAMT,HO, kAMT,1O2 and kAMT,3CDOM* were (4.97 ± 0.37) × 109, (3.43 ± 0.58) × 104 and (7.75 ± 0.80) × 108 L mol-1s-1, respectively. Mathematical simulations carried out using the APEX kinetic model, based on the typical concentrations of water constituents (NO3-, NO2-, CO32-, TOC) of the Paranapanema River (São Paulo, Brazil), indicated that the half-lives of these pesticides range between 24.1 and 19.2 days. Finally, toxicity studies with Daphnia similis demonstrated the ability of the pollutant to reach nontarget organisms when in river water. In addition, genotoxicity tests with Allium cepa confirmed chromosomal abnormalities and aberrations caused by pesticides in onion bulbs.
 
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Publishing Date
2022-01-17
 
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