This thesis contains three published papers: [1] B. Desharnais, F. Camirand-Lemyre, P. Mireault, C. D. Skinner, Procedure for the selection and validation of a calibration model I — Description and application, Journal of Analytical Toxicology 41 (4) (2017) 261–268. doi:10.1093/jat/bkx001. [2] B. Desharnais, F. Camirand-Lemyre, P. Mireault, C. D. Skinner, Procedure for the selection and validation of a calibration model II — Theoretical basis, Journal of Analytical Toxicology 41 (4) (2017) 269–276. doi:10.1093/jat/bkx002. [3] B. Desharnais, M.-J. Lajoie, J. Laquerre, S. Savard, P. Mireault, C. D. Skinner, A tool for automatic correction of endogenous concentrations: application to BHB analysis by LC–MS-MS and GC-MS, Journal of Analytical Toxicology 43 (7) (2019) 512–519. doi:10.1093/jat/bkz024. This thesis contains two papers accepted for publication with modifications: [4] F. Camirand Lemyre, B. Desharnais, J. Laquerre, M.-A. Morel, C. Côté, P. Mireault, C. D. Skinner, Qualitative method validation and uncertainty evaluation via the binary output I — Validation guidelines and theoretical foundations, Journal of Analytical Toxicology (2019) submission number JAT–19–2881. [5] B. Desharnais, M.-J. Lajoie, J. Laquerre, P. Mireault, C. D. Skinner, Qualitative method validation and uncertainty estimation via the binary output II — Application to a multi-analyte LC-MS/MS method for oral fluid, Journal of Analytical Toxicology (2019) submission number JAT–19–2882.