Forced and long-term degradation assays of tenoxicam, piroxicam and meloxicam in river water. Degradation products and adsorption to sediment.

The fate of the pharmaceutical drugs tenoxicam, piroxicam and meloxicam in river water is evaluated here for first time. So, biological, photochemical and thermal degradation assays have been conducted to estimate their degradation rates and know their degradation products. Results indicated that the direct sunlight irradiation, without any protection, promoted a fast degradation of the oxicams while the chemical reactions in solution were less important. The biological degradation in water was negligible except for tenoxicam in whose case its influence was scarce. When the exposition of river water to sunlight was partially limited and kept under the natural day-night cycle, as occurs inside a body of water, tenoxicam, piroxicam and meloxicam (at 2 μg L-1 ) were detected during a period of 15, 27 and 45 days, respectively. Residues were monitored by ultra-pressure liquid chromatography/quadrupole time-of-flight/mass spectrometry after solid-phase extraction and several degradation products were found (10 for tenoxicam, 9 for piroxicam and 7 for meloxicam) and monitored over time. Their structures were proposed from the molecular formulae and fragmentation observed in high-resolution tandem mass spectra; the nature of the transformation products found in the long-term resulted to be very variable for each oxicam. Furthermore, the degradation in presence of river sediment was also monitored over time, with some differences being noted; the adsorption coefficients of the compounds on sediment were calculated, meloxicam exhibited a higher sorption capacity. The ecotoxicity of the different compounds in aquatic ecosystems was predicted, too.