This paper presents our latest findings regarding the structure and reactivity of the nitroaromatics, TNT and selected derivatives, within their environmental context. We also demonstrate the useful and proactive role of combined computational chemistry and spectroscopy tools in studying competing transformation mechanisms, particularly those with toxic potential. TNT and selected derivatives were reacted via alkaline hydrolysis as well as via free radical initiators through monochromatic irradiation and through Fenton reactions in complex competing transformation mechanisms. Only alkaline hydrolysis produced consistent and effective transformation intermediate and final products in this research. However, irradiation of the product generated by alkaline hydrolysis at 450 nm (wavelength of maximum absorption) caused complete disappearance of the spectra.