Carbon Isotope Fractionation of Substituted Benzene Analogs during Oxidation with Ozone and Hydroxyl Radicals: How Should Experimental Data Be Interpreted?

Oxidative processes frequently contribute to organic pollutant degradation in natural and engineered systems, such as during the remediation of contaminated sites and in water treatment processes. Because a systematic characterization of abiotic reactions of organic pollutants with oxidants such as ozone or hydroxyl radicals by compound-specific stable isotope analysis (CSIA) is lacking, stable isotope-based approaches have rarely been applied for the elucidation of mechanisms of such transformations. Here, we investigated the carbon isotope fractionation associated with the oxidation of benzene and several methylated and methoxylated analogs, namely, toluene, three xylene isomers, mesitylene, and anisole, and determined their carbon isotope enrichments factors (εC) for reactions with ozone (εC = -3.6 to -4.6 ‰) and hydroxyl radicals (εC = 0.0 to -1.2‰). The differences in isotope fractionation can be used to elucidate the contribution of the reactions with ozone or hydroxyl radicals to overall transformation. Derivation of apparent kinetic isotope effects (AKIEs) for the reaction with ozone, however, was nontrivial due to challenges in assigning reactive positions in the probe compounds for the monodentate attack leading to an ozone adduct. We present several options for this step and compare the outcome to quantum chemical characterizations of ozone adducts. Our data show that a general assignment of reactive positions for reactions of ozone with aromatic carbons in ortho-, meta-, or para-positions is not feasible and that AKIEs of this reaction should be derived on a compound-by-compound basis.

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 Polymeric Brominated Flame Retardants: Development of an Analytical Approach Using PolyFR and UV Irradiation.

Many well-established methods for studying the degradation of brominated flame retardants are not useful when working with polymeric and water insoluble species. An example for this specific class of flame retardants is PolyFR (polymeric flame retardant; CAS No 1195978-93-8), which is used as a substituent for hexabromocyclododecane. Although it has been on the market for two years now, almost no information is available about its long time behavior in the environment. Within this study, we focus on how to determine a possible degradation of both pure PolyFR as well as PolyFR in the final insulation product, expanded polystyrene foam. Therefore, we chose UV radiation followed by analyses of the total bromine content at different time points via ICP-MS and identified possible degradation products such as 2,4,6-tribromophenol through LC-MS. These results were then linked with measurements of the adsorbable organically bound bromine and total organic carbon in order to estimate their concentrations. With respect to the obtained 1H NMR, GPC, and contact angle results, the possibility for further degradation was discussed, as UV irradiation can influence the decomposition of molecules in combination with other environmental factors like biodegradation.

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.

Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater.

Due to the lack of analytical standards the application of surrogate parameters for organofluorine detection in the aquatic environment is a complementary approach to single compound target analysis of perfluoroalkyl and polyfluoroalkyl chemicals (PFASs). The recently developed method adsorbable organically bound fluorine (AOF) is based on adsorption of organofluorine chemicals to activated carbon followed by combustion ion chromatography. This AOF method was further simplified to enable measurement of larger series of environmental samples. The limit of quantification (LOQ) was 0.77 µg/L F. The modified protocol was applied to 22 samples from German rivers, a municipal wastewater treatment plant (WWTP) effluent, and four groundwater samples from a fire-fighting training site. The WWTP effluent (AOF = 1.98 µg/L F) and only three river water samples (AOF between 0.88 µg/L F and 1.47 µg/L F) exceeded the LOQ. The AOF levels in a PFASs plume at a heavily contaminated site were in the range of 162 ± 3 µg/L F to 782 ± 43 µg/L F. In addition to AOF 17 PFASs were analyzed by high performance liquid chromatography-tandem mass spectrometry. 32-51% of AOF in the contaminated groundwater samples were explained by individual PFASs wheras in the surface waters more than 95% remained unknown. Organofluorine of two fluorinated pesticides, one pesticide metabolite and three fluorinated pharmaceuticals was recovered as AOF by >50% from all four tested water matrices. It is suggested that in the diffusely contaminated water bodies such fluorinated chemicals and not monitored PFASs contribute significantly to AOF.

Particles in swimming pool filters--does pH determine the DBP formation?

The formation was investigated for different groups of disinfection byproducts (DBPs) during chlorination of filter particles from swimming pools at different pH-values and the toxicity was estimated. Specifically, the formation of the DBP group trihalomethanes (THMs), which is regulated in many countries, and the non-regulated haloacetic acids (HAAs) and haloacetonitriles (HANs) were investigated at 6.0≤pH≤8.0, under controlled chlorination conditions. The investigated particles were collected from a hot tub with a drum micro filter. In two series of experiments with either constant initial active or initial free chlorine concentrations the particles were chlorinated at different pH-values in the relevant range for swimming pools. THM and HAA formations were reduced by decreasing pH while HAN formation increased with decreasing pH. Based on the organic content the relative DBP formation from the particles was higher than previously reported for body fluid analogue and filling water. The genotoxicity and cytotoxicity estimated from formation of DBPs from the treated particle suspension increased with decreasing pH. Among the quantified DBP groups the HANs were responsible for the majority of the toxicity from the measured DBPs.

Effect of pH on the formation of disinfection byproducts in swimming pool water--is less THM better?

This study investigated the formation and predicted toxicity of different groups of disinfection byproducts (DBPs) from human exudates in relation to chlorination of pool water at different pH values. Specifically, the formation of the DBP groups trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs) and trichloramine (NCl(3)), resulting from the chlorination of body fluid analog, were investigated at 6.0 ≤ pH ≤ 8.0. Either the initial concentration of active chorine or free chlorine was kept constant in the tested pH range. THM formation was reduced by decreasing pH but HAN, and NCl(3) formation increased at decreasing pH whereas the formation of HAAs remained constant. Under our experimental conditions, the formation of NCl(3) (suspected asthma inducing compound) at pH = 6.0 was an order of magnitude higher than at pH = 7.5. Furthermore, the effect of the presence of bromide on DBP formation was investigated and found to follow the same pH dependency as without bromide present, with the overall DBP formation increasing, except for HAAs. Estimation of genotoxicity and cytotoxicity of the chlorinated human exudates showed that among the quantified DBP groups, HAN formation were responsible for the majority of the toxicity from the measured DBPs in both absence and presence of bromide.