Micotoxinas estrogênicas em águas superficiais da microbacia hidrográfica do Córrego Rico (SP): desenvolvimento de método analítico verde, ocorrência e persistência ambiental

• Ano de defesa: 2016
• Autor(a) principal: Emídio, Elissandro Soares [UNESP]
• Tipo de documento: Tese
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Estadual Paulista (Unesp)
• Palavras-chave em Português: Estrogenic mycotoxins; DLLME; HPLC; Natural waters; Photodegradation; Micotoxinas estrogênicas; Águas naturais; Fotodegradação
• Link de acesso: http://hdl.handle.net/11449/138323

Estrogenic mycotoxins (EM) are estrogens produced as secondary metabolites of fungi. The well known EM are zearalenone (ZEN) and its metabolites primarily produced by the mold Fusarium growing on a variety of crops. The influence of exposure to EM on human/mammalian health via food has been extensively studied. In contrast, studies focus on EM in surface waters and their possible impacts in aquatic environment are negligible. The current work presents the most recent developments concerning estrogenic mycotoxins, in regard to the analytic methodologies utilized in their determination and the behavior assessment in surface waters. The study was developed in two steps: (1) analytical study - Green analytical method development for determination of estrogenic mycotoxin employing microextraction liquid-liquid dispersive (DLLME) using bromosolvent and ionic liquid (IL) followed by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) or mass spectrometry (MS); (2) Environmental study - evaluation of the presence of analytes in Rico stream watershed with spatial-temporal distribution and the persistence of zearalenone mycotoxin in aquatic environments by simulated sunlight. Several important parameters influencing the extraction efficiency of DLLME were optimized. Under optimal conditions, extraction recovery for ZEN and its metabolites by DLLME and IL-DLLME were within the range of 81-118 % e 76-81 % respectively; the relative standard deviations (RSDs) for intra-day and inter-day precision were lower than 13% by DLLME, and lower than 5.7 % (intra-day) by ILDLLME. The method limits of detection (LOD) and quantification (LOQ) were from 4– 20 ng L−1 and 8–40 ng L−1, for DLLME and from 0.2 ng L−1 and 0.5 ng L−1 for ILDLLME, respectively. Determination of estrogenic mycotoxins in water samples from Rico Stream watershed reached levels of up to 59.3 ng L-1 and their corresponding calculated estrogenic equivalents (cEEQ) values were <0.06 and 1.42 ng L-1. These concentrations are related to adverse effects on growth and reproduction of some fish species. In phototransformation study ZEN degraded quickly in natural waters, with half-lives (t1/2) of 28.3 min (estuarine water) and 135.9 min (river water). The results indicated that after 1 h irradiation time, the degradation percentage of ZEN were 69.4% (river water) and 90.8% (estuarine water). From an environmental point of view, the rapid degradation observed, under laboratory conditions, should not be interpreted "a priori" as indicative of low environmental risk for ZEN, should be investigated environmental behavior and toxicology of degradation products, beyond it is necessary to considering the constant introduction into surface water of microcontaminants associated with sewage, such as this mycotoxin.