Direct Photolysis of Sulfamethoxazole Using Various Irradiation Sources and Wavelength Ranges-Insights from Degradation Product Analysis and Compound-Specific Stable Isotope Analysis.

The environmental micropollutant sulfamethoxazole (SMX) is susceptible to phototransformation by sunlight and UV-C light which is used for water disinfection. Depending on the environmental pH conditions SMX may be present as neutral or anionic species. This study systematically investigates the phototransformation of these two relevant SMX species using four different irradiation scenarios, i.e., a low, medium, and high pressure Hg lamp and simulated sunlight. The observed phototransformation kinetics are complemented by data from compound-specific stable isotope and transformation product analysis using isotope-ratio and high-resolution mass spectrometry (HRMS). Observed phototransformation kinetics were faster for the neutral than for the anionic SMX species (from 3.4 (LP lamp) up to 6.6 (HP lamp) times). Furthermore, four phototransformation products (with m/z 189, 202, 242, and 260) were detected by HRMS that have not yet been described for direct photolysis of SMX. Isotopic fractionation occurred only if UV-B and UV-A wavelengths prevailed in the emitted irradiation and was most pronounced for the neutral species with simulated sunlight (εC = -4.8 ± 0.1 ‰). Phototransformation of SMX with UV-C light did not cause significant isotopic fractionation. Consequently, it was possible to differentiate sunlight and UV-C light induced phototransformation of SMX. Thus, CSIA might be implemented to trace back wastewater point sources or to assess natural attenuation of SMX by sunlight photolysis. In contrast to the wavelength range, pH-dependent speciation of SMX hardly impacted isotopic fractionation.

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation.

A New Reaction Pathway for Bromite to Bromate in the Ozonation of Bromide.

Ozone is often used in the treatment of drinking water. This may cause problems if the water to be treated contains bromide as its reaction with ozone leads to the formation of bromate, which is considered to be carcinogenic. Bromate formation is a multistep process resulting from the reaction of ozone with bromite. Although this process seemed to be established, it has been shown that ozone reacts with bromite not by the previously assumed mechanism via O transfer but via electron transfer. Besides bromate, the electron-transfer reaction also yields O3(•-), the precursor of OH radicals. The experiments were set up in such a way that OH radicals are not produced from ozone self-decomposition but solely by the electron-transfer reaction. This study shows that hydroxyl radicals are indeed generated by using tBuOH as the OH radical scavenger and measuring its product, formaldehyde. HOBr and bromate yields were measured in systems with and without tBuOH. As OH radicals contribute to bromate formation, higher bromate and HOBr yields were observed in the absence of tBuOH than in its presence, where all OH radicals are scavenged. On the basis of the results presented here, a pathway from bromide to bromate, revised in the last step, was suggested.