Control analítico de fungicidas triazólicos y sus metabolitos en productos agrícolas y fitosanitarios
- Autores: María Elena Hergueta‐Castillo
- Directores de la Tesis: Roberto Romero González (dir. tes.), Rosalía López Ruiz (codir. tes.), Antonia Garrido Frenich (tut. tes.)
- Lectura: En la Universidad de Almería ( España ) en 2026
- Idioma: español
- Número de páginas: 309
- Títulos paralelos:
- Analytical control of triazole fungicides and their metabolites in agricultural and plant protection products
- Tribunal Calificador de la Tesis: Antonio Ruiz Medina (presid.), F. J. Egea González (secret.), Laura Gámiz-Gracia (voc.)
- Programa de doctorado: Programa de Doctorado en Química Avanzada por la Universidad de Almería
- Materias:
- Enlaces
- Tesis en acceso abierto en: TESEO
- Resumen
- español
La Tesis Doctoral titulada “Control analítico de fungicidas triazólicos y sus metabolitos en productos agrícolas y fitosanitarios” aborda un tema de gran relevancia científica y aplicada, centrándose en el control de la familia de fungicidas triazólicos y sus metabolitos. De esta forma, aporta información relacionada con el comportamiento de dichos plaguicidas en muestras del sector agroalimentario. Para ello, se aborda el problema relativo al control de fungicidas triazólicos y sus metabolitos desde una perspectiva integral, considerando su estudio no sólo en muestras de diferentes matrices hortofrutícolas, de especial relevancia en Andalucía, sino también en los productos fitosanitarios que se aplican en la producción agroalimentaria.
Para tal fin, se han empleado tres métodos de tratamiento de muestra: diluir y pinchar, para los productos fitosanitarios, y la extracción sólido-líquido (Solid-Liquid Extraction, SLE) y el método QuEChERS (acrónimo por sus siglas en inglés: Quick, Easy, Cheap, Effective, Rugged y Safe) para la determinación de fungicidas triazólicos en productos agrícolas. Posteriormente se ha realizado el análisis mediante dos técnicas cromatográficas ampliamente utilizadas, como son la cromatografía de líquidos de ultra alta resolución (Ultra-High Performance Liquid Chromatography, UHPLC) y la cromatografía de gases (Gas Chromatography, GC), ambas acopladas a analizadores de espectrometría de masas de alta resolución (High Resolution Mass Spectrometry, HRMS). Se han usado dos enfoques de análisis: dirigido y no dirigido, aplicándose este último tanto en el modo de trabajo de análisis de sospechosos (suspect screening) y el de análisis de desconocidos (unknown analysis), posibilitando un análisis integral de los problemas abordados en esta Tesis Doctoral.
Los trabajos desarrollados se han dividido en dos bloques. El primero se ha focalizado en el análisis de la composición de los productos fitosanitarios que contienen fungicidas triazólicos, concretamente a la detección e identificación de coformulantes. Se ha realizado un estudio mediante el desarrollo y validación de un método basado en UHPLC-Q-Orbitrap-MS y otro en GC-Q-Orbitrap-MS.
En definitiva, la Tesis presenta un enfoque innovador en la identificación, cuantificación y control de compuestos con impacto directo en la seguridad alimentaria y en el medio ambiente. Para ello, ha sido necesario realizar la optimización de diferentes tratamientos de muestra y la validación de métodos analíticos. Por otro lado, se plantean estudios de toxicidad de coformulantes detectados en los productos fitosanitarios que contienen fungicidas triazólicos, así como de los metabolitos de flutriafol y penconazol. El trabajo aporta avances metodológicos y resultados que contribuyen significativamente al conocimiento actual en el ámbito del análisis químico.
- English
This current Thesis, entitled “Analytical control of triazole fungicides and their metabolites in agricultural and plant protection products”, provides new knowledge related to the behaviour of these pesticides in samples from the agri-food sector. Therefore, the problem of the control of triazole fungicides and their metabolites is addressed from a comprehensive perspective, considering their study in different horticultural samples, of special relevance in Andalusia, and in plant protection products that are applied in agri-food production.
For this purpose, three extraction techniques as “dilute and shoot” for plant protection products, and solid-liquid extraction (SLE) and QuEChERS method (Quick, Easy, Cheap, Effective, Rugged and Safe) were applied for the determination of triazole fungicides in agricultural products. After that, the determination was carried out using two chromatographic techniques widely applied, as ultra-high performance liquid chromatography (UHPLC) and gas chromatography (GC), both coupled to high resolution mass spectrometry analyzers (HRMS). Two working modes, targeted and non-targeted, were employed using the last one to perform suspect screening and unknown analysis.
This Thesis was divided in two sections. The first one was focused on the analysis of the composition of plant protection products containing triazole fungicides, specifically on the detection and identification of co-formulants. A study has been carried out through the development and validation of a method based on UHPLC-Q-Orbitrap-MS and another on GC-Q-Orbitrap-MS. The developed studies included in this section were:
• Optimization of a sample extraction of plant protection products based on “dilute and shoot”. This method was applied to 6 plant protection products with different type of formulation and composition of active substance (triazole fungicide).
• Development and validation of an analytical procedure based on UHPLC-Q-Orbitrap-MS for the identification of potential co-formulants in plant protection products. This procedure was applied to six plant protection products with different type of formulation and composition of triazole fungicide.
• Development and validation of an analytical procedure based on GC-Q-Orbitrap-MS using two complementary injection modes (direct injection and headspace) for the identification of potential co-formulants in plant protection products. This procedure was applied to 6 plant protection products with different type of formulation and composition of triazole fungicide.
The second part was focused on the determination of triazole fungicides and their metabolites in horticultural samples using UHPLC-Q-Orbitrap-MS. The developed studies were:
• Optimization of two extraction methods focused on solid-liquid extraction (SLE) and QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) for the determination of triazole fungicides and their metabolites in horticultural matrices.
• Development and validation of an analytical procedure using UHPLC-Q-Orbitrap-MS for the determination of 21 triazole fungicides and 5 metabolites in horticultural samples.
• Analysis of horticultural samples to evaluate the applicability of the developed method for the determination of triazole fungicides. This method was applied in 30 samples (6 courgettes, 6 oranges, 6 grapes and 12 strawberries).
• A suspect screening (from a homemade database containing more than 2,000 contaminants) was carried out in order to identify pesticides not included in the former study. This method has been applied in 30 samples of courgettes, oranges, strawberries and grapes.
• Study of the behaviour and dissipation under laboratory and field conditions of two triazole fungicides (flutriafol and penconazole) in courgette and tomato samples, respectively, using UHPLC-Q-Orbitrap-MS. Their metabolites were also monitored.
• Study of the potential toxicity of the co-formulants detected in the plant protection products, and of the metabolites detected in courgette or tomato samples of the two triazole fungicides (flutriafol and penconazole) in laboratory and field studies.
- español
