Degradation studies of UV filter hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]-benzoate (DHHB) in aqueous solution.

High performance liquid chromatography coupled with ultra-violet, diode array detection (HPLC-UV-DAD), was used to study the degradation reactions of ultraviolet (UV) filter hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]-benzoate (DHHB). Degradation by-products were detected and identified by means of liquid chromatography coupled with diode array detection and mass spectrometry (LC-DAD-MS). Environmentally-relevant characteristics, such as water pH, chlorine levels, water temperature and dissolved organic matter (DOM) concentration, were modulated and studied in order to determine their influence on the degradation reactions. Results show that DHHB degrades quite rapidly in typical drinking water disinfection conditions, displaying a kinetic rate constant of kobs = 0.0060 ± 0.0002 s-1 and a half-life period of merely t1/2 = 116 ± 4 s. As far as the non-volatile disinfection by-products (DBPs) are concerned, only the mono and dichlorinated forms of DHHB were detected in the degradation reactions. Regarding influential variables on DHHB degradation, the presence or absence of DOM in solution did not alter the trends that were found (degradation of DHHB is more significant at lower pH values and higher levels of active chlorine in solution). Chlorinated DBPs have also been found to predominate under higher pH values and lower levels of chlorine, whereas they were found to be unstable and further degradable, quite likely into smaller and more volatile compounds, when in lower pH and higher chlorine concentrations. As for the photo-degradation studies, DHHB was found to be extremely photo-stable, with only about 15% degradation rate detected during artificial irradiation periods of 6 h.

Fate and behaviour of acetaminophen, 17α-ethynylestradiol and carbamazepine in aqueous solution.

Pharmaceuticals are invaluable tools for the prevention and treatment of human and animal diseases. Human evolution led to the increase of life expectancy, which promoted the increase of consumption of pharmaceuticals. These compounds are consistently detected in superficial waters, and whilst degradation processes are expected to mitigate their levels, they also induce the formation of potentially harmful by-products. The compounds studied in this work were acetaminophen, 17α-ethynylestradiol and carbamazepine. High-performance liquid chromatography coupled with ultraviolet diode-array detection was used to follow the degradation reactions, whilst liquid chromatography associated with ultraviolet diode-array detection and mass spectrometry was applied in the determination of by-products. Ethynylestradiol proved to be the most reactive (t1/2 = 38.6 ± 1.9 seconds) and carbamazepine the least reactive (t1/2 = 481.4 ± 16.7 minutes) when exposed to active chlorine. In relation to disinfection by-products, two monochlorinated analogues were detected for acetaminophen, one monochlorinated for carbamazepine, and one mono- and one trichlorinated for ethynylestradiol. Chlorine levels and water pH proved to be the most influential variables on the degradation of the compounds, with and without dissolved organic matter in solution. All pharmaceuticals displayed significant photostability towards artificial solar radiation, with acetaminophen being slightly more stable.