Multi-residue methods for the analysis of pesticides in airborne particulate matter by LC_MS/ and GC-MS/MS. Monitoring levels in the atmosphere

Zusammenfassung

Currently used pesticides (CUPs) appear in the atmosphere as a consequence of its massive use in the agricultural areas during the application periods. More than 300 active substances are nowadays authorised by the European Union for their application on different crops according to Directive 91/414/CEE. The total use of plant protection products in the European Union (EU-27) during 2008 was of about 310.011 tons of active ingredients, with France (25.3%), Spain (12.9%) and Italy (13.3%) as the three main consumer countries. The emissions of pesticides during application, volatilization from soil and plants after application and wind erosion of soil particles containing sorbed pesticides are the key processes driving to their presence in the ambient air. Once in the air pesticides can suffer different mechanisms such as transportation, degradation and deposition. The research aim of this thesis was to develop different analytical methods for the determination of currently used pesticides in airborne particulate matter and to provide information about the levels of these pesticides in two Europeans regions (France and Spain). This thesis is composed of one review study and four experimental chapters. The scope of the review study is focuse on currently collecting and analytical methods for determination of CUPs in ambient air. Additional considerations about the occurrence of pesticides in ambient air are included. In the first chapter an analytical method was developed in order to determinate nine CUPs in PM 2.5. Pesticides were extracted by PLE and analyzed by LC-MS/MS. PLE conditions as well as parameters in the ESI source ionization were optimized using a statistical design of experiments. In the second chapter an analytical method for analyze 30 CUPs in PM 2.5 were developed. Pesticides were extracted by MAE and analyzed by LC-MS/MS. MAE conditions were also optimized using a statistical design of experiments. In the third chapter an analytical methodology in order to analyze 40 CUPs in PM 10 by CG-MS/MS triple Q was developed. A GPC clean-up was introduce in this study. The analytical methods developed in chapters 1, 2 and 3 were applied to analyze real samples in Valencia region (Spain) during 2007-2010 in order to evaluate the presence of pesticides in ambient air. Valencia region has an intensive agricultural production mainly in citrics. Samples were collected in different sampling sites focuse on rural, urban and remote stations. Chapter 4 describes a study about the presence of CUPs in Centre Region (France). Centre region is one of the country's largest regions with many agricultural activities focused mainly in arable crops. Some spatial and temporal studies were carried out. The influence of the metereological conditions, such as humidity or wind direction were also evaluated. Rural and urban stations were sampled from 2006 to 2008 in Centre region. The analytical methods developed and the concentrations levels of CUPs provided by this thesis could be very useful in order to establish a monitoring and surveillance network of pesticides in the ambient air around different countries of the European Union.