Origin of Xylitol in Chewing Gum: A Compound-Specific Isotope Technique for the Differentiation of Corn- and Wood-Based Xylitol by LC-IRMS.

The sugar replacement compound xylitol has gained increasing attention because of its use in many commercial food products, dental-hygiene articles, and pharmaceuticals. It can be classified by the origin of the raw material used for its production. The traditional "birch xylitol" is considered a premium product, in contrast to xylitol produced from agriculture byproducts such as corn husks or sugar-cane straw. Bulk stable-isotope analysis (BSIA) and compound-specific stable-isotope analysis (CSIA) by liquid-chromatography isotope-ratio mass spectrometry (LC-IRMS) of chewing-gum extracts were used to determine the δ13C isotope signatures for xylitol. These were applied to elucidate the original plant type the xylitol was produced from on the basis of differences in isotope-fractionation processes of photosynthetic CO2 fixation. For the LC-IRMS analysis, an organic-solvent-free extraction protocol and HPLC method for the separation of xylitol from different artificial sweeteners and sugar-replacement compounds was successfully developed and applied to the analysis of 21 samples of chewing gum, from which 18 could be clearly related to the raw-material plant class.

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.