Auswahl der wissenschaftlichen Literatur zum Thema „UV-C photolysis“

Methotrexate (MTX) is a folic acid analog and has been used to treat a wide variety of malignant and non-malignant diseases. The wide use of these substances has led to the continuous discharge of the parent compound and its metabolites in wastewater. In conventional wastewater treatment plants, the removal or degradation of drugs is not complete. In order to study the MTX degradation by photolysis and photocatalysis processes, two reactors were used with TiO2 as a catalyst and UV-C lamps as a radiation source. H2O2 addition was also studied (absence and 3 mM/L), and different initial pHs (3.5, 7, and 9.5) were tested to define the best degradation parameters. Results were analyzed by means of ANOVA and the Tukey test. Results show that photolysis in acidic conditions with 3 mM of H2O2 added is the best condition for MTX degradation in these reactors, with a kinetic constant of 0.028 min−1. According to the ANOVA test, all considered factors (process, pH, H2O2 addition, and experimentation time) caused statistically significant differences in the MTX degradation results.

Methotrexate (MTX) is an anti-cancer drug that can be excreted up to 90% after administration due to its low biodegradability. Advanced Oxidation Processes (AOPs) are a feasible alternative for the elimination of MTX in the environment. In this research, AOPs were performed in specialized patented reactors (UBE Photocatalytic systems and BrightWater Titanium Advanced Oxidation Process) under experimental pilot conditions. Photolysis and heterogeneous photocatalysis (UV and UV/TiO2) experiments were performed with and without addition of H2O2 and at different initial pHs. Best degradation percentage was achieved by photolysis when initial pH was 3.5 and added H2O2 was 3 mM, reaching a MTX degradation of 82% after 120 min of reaction. HPLC-MS analysis of the resulting samples showed four possible byproducts of MTX degradation, which presented a higher ecotoxicity than the starting compound.

6-Mercaptopurine (6-MP) is a commonly used cytostatic agent, which represents a particular hazard for the environment because of its low biodegradability. In order to degrade 6-MP, four processes were applied: Photolysis (UV-C), photocatalysis (UV-C/TiO2), and their combination with H2O2, by adding 3 mM H2O2/L (UV-C/H2O2 and UV-C/TiO2/H2O2 processes). Each process was performed with variable initial pH (3.5, 7.0, and 9.5). Pilot scale reactors were used, using UV-C lamps as radiation source. Kinetic calculations for the first 20 min of reaction show that H2O2 addition is of great importance: in UV-C experiments, highest k was reached under pH 3.5, k = 0.0094 min−1, while under UV-C/H2O2, k = 0.1071 min−1 was reached under the same initial pH; similar behavior was observed for photocatalysis, as k values of 0.0335 and 0.1387 min−1 were calculated for UV-C/TiO2 and UV-C/TiO2/H2O2 processes, respectively, also under acidic conditions. Degradation percentages here reported for UV-C/H2O2 and UV-C/TiO2/H2O2 processes are above 90% for all tested pH values. Ecotoxicity analysis of samples taken at 60 min in the photolysis and photocatalysis processes, suggests that contaminant degradation by-products present higher toxicity than the original compound.

Paracetamol is generally used as analgesic and antipyretic drugs. Contamination paracetamol in the environment can occur because of waste material disposal from production site and immediate disposal of household that cause water pollution. Paracetamol is degraded by photolysis method under irradiation 10 watt UV-light (λ=365 nm), visible-light (Philips LED 13 watt 1400 lux) and solar-light with and without addition C-N-codoped TiO2catalyst. The solution is analyzed by UV-Vis spectrophotometer at λ 200-400 nm. Optimum weight of C-N-codoped TiO2 catalyst obtained is 20 mg under UV-light photolysis. Paracetamol 4 mg/L is degraded 45.48% after 120 minutes under UV-light irradiation without catalyst, and increases to be 69.31% by using 20 mg catalyst. While degradation percentage of paracetamol is 16.96 % without catalyst, the percentage increases to be 34.29% after using 20 mg catalyst for 120 minutes photolysis under visible-light. Degradation of paracetamol by solar light achieves only 12.27% in absance of catalyst for 120 minutes irradiation, but it increases significantly until 70.39% in presence of 20 mg catalyst.

Abstract Acetaminophen (N-acetyl-p-aminophenol, APAP) is one of the most common antipyretic analgesics used to treat common ailments throughout the world. Recently, APAP has been frequently detected in wastewater effluent and groundwater, resulting in potential risks to the environment. Current methods for eliminating APAP are complicated and cost-prohibitive. This study examined APAP degradation by ultraviolet-C (UV-C) and UV-C irradiation combined with activated sludge (UV/AS) to evaluate potential applications in wastewater treatment. The results of this study indicate that UV-C irradiation reached an APAP degradation efficiency of more than 52% and a degradation rate of 0.0012–0.0013 min−1 during 720 min of exposure, while the initial APAP concentration exhibited only a nominal effect on the degradation rate. However, the UV/AS treatment demonstrated an APAP degradation rate that was 9.6 times the rate of the UV-C-only treatment, with a degradation efficiency of 99% over the same UV irradiation period. The results further indicated that APAP photolysis efficiency was more effective when applied to sterilized AS than when applied to unsterilized AS. Finally, excessive dosage of both AS and humic acid inhibited APAP photolysis efficiency.

Pharmaceuticals are present in an aquatic environment usually in low (ng/L) concentrations. Their continuous release can lead to unwanted effects on the nontarget organisms. The main points of their collection and release into the environment are wastewater treatment plants. The wastewater treatment plants should be upgraded by new technologies, like advanced oxidation processes (AOPs), to be able to degrade these new pollutants. In this study, the degradation of albendazole (ALB), a drug against parasitic helminths, was investigated using four UV-based AOPs: UV photolysis, UV photocatalysis (over TiO2 film), UV + O3, and UV + H2O2. The ranking of the degradation process degree of the ALB and its degradation products for studied processes is as follows: UV photolysis < UV photocatalysis with TiO2 < UV + O3 < UV + H2O2. The fastest degradation of ALB and its degradation products was obtained by UV-C + H2O2 process with a degradation efficiency of 99.95%, achieved in 15 minutes.

Abstract. Stable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleoatmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotope ratios at Dome C, Antarctica, during the austral summer of 2011/2012. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10-day frequency. At the end of the season, a comparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm) attributed to mixing with the surrounding snow. After excluding samples impacted by the mixing process, we derived an average apparent nitrogen isotopic fractionation (15&amp;varepsilon;app) of −67.8 ± 12 ‰ for the snow nitrate exposed to solar UV using the nitrate stable isotope ratios and concentration measurements. For the control samples in which solar UV was blocked, an apparent average 15&amp;varepsilon;app value of −12.0 ± 1.7 ‰ was derived. This difference strongly suggests that solar UV photolysis plays a dominant role in driving the isotopic fractionation of nitrate in snow. We have estimated a purely photolytic nitrogen isotopic fractionation (15&amp;varepsilon;photo) of −55.8 ± 12.0 ‰ from the difference in the derived apparent isotopic fractionations of the two experimental fields, as both pits were exposed to similar physical processes except exposure to solar UV. This value is in close agreement with the 15&amp;varepsilon;photo value of −47.9 ± 6.8 ‰ derived in a laboratory experiment simulated for Dome C conditions (Berhanu et al., 2014). We have also observed an insensitivity of 15&amp;varepsilon; with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15&amp;varepsilon; is strongly dependent on the spectral distribution of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the stable isotope ratios of snow nitrate at low-accumulation sites, where many deep ice cores are drilled. Nevertheless, modeling the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided.

Aims. We investigate the possible role of polycyclic aromatic hydrocarbons (PAHs) as a sink for deuterium in the interstellar medium (ISM) and study UV photolysis as a potential underlying chemical process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologs of deuterium-enriched, protonated anthracene and phenanthrene ions (both C14H10 isomers) was recorded in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Infrared multiple photon dissociation spectroscopy using the Free-Electron Laser for Infrared eXperiments was applied to provide IR spectra. Infrared spectra calculated using density functional theory were compared to the experimental data to identify the isomers present in the experiment. Transition-state energies and reaction rates were also calculated and related to the experimentally observed fragmentation product abundances. Results. The photofragmentation mass spectra for both UV and IRMPD photolysis only show the loss of atomic hydrogen from [D − C14H10]+, whereas [H − C14D10]+ shows a strong preference for the elimination of deuterium. Transition state calculations reveal facile 1,2-H and -D shift reactions, with associated energy barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes of the two different PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The ∼0.1 eV difference in zero-point energy between C–H and C–D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D atom loss. Conclusions. We conclude that scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to a strongly bound aromatic site, protecting it from elimination. We speculate that this could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C–HD group on solo sites might be responsible for the majority of aliphatic C–D stretching bands seen in astronomical spectra. An accurate photochemical model of PAHs that considers deuterium scrambling is needed to study this further.

Photolysis of 3-azidoquinoline 6 in an Ar matrix generates 3-quinolylnitrene 7, which is characterized by its electron spin resonance (ESR), UV, and IR spectra in Ar matrices. Nitrene 7 undergoes ring opening to a nitrile ylide 19, also characterized by its UV and IR spectra. A subsequent 1,7-hydrogen shift in the ylide 19 affords 3-(2-isocyanophenyl)ketenimine 20. Matrix photolysis of 1,2,3-triazolo[1,5-c]quinoxaline 26 generates 4-diazomethylquinazoline 27, followed by 4-quinazolylcarbene 28, which is characterized by ESR and IR spectroscopy. Further photolysis of carbene 28 slowly generates ketenimine 20, thus suggesting that ylide 19 is formed initially. Flash vacuum thermolysis (FVT) of both 6 and 26 affords 3-cyanoindole 22 in high yield, thereby indicating that carbene 28 and nitrene 7 enter the same energy surface. Matrix photolysis of 3-quinolyldiazomethane 30 generates 3-quinolylcarbene 31, which on photolysis at >500 nm reacts with N2 to regenerate diazo compound 30. Photolysis of 30 in the presence of CO generates a ketene (34). 3-Quinolylcarbene 31 cyclizes on photolysis at >500 nm to 5-aza-2,3-benzobicyclo[4.1.0]hepta-2,4,7-triene 32. Both 31 and 32 are characterized by their IR and UV spectra. FVT of 30 yields a mixture of 2- and 3-cyanoindenes via a carbene–carbene–nitrene rearrangement 31 → 2-quinolylcarbene 39 → 1-naphthylnitrene 43. The reaction mechanisms are supported by density functional theory calculations of the energies and spectra of all relevant ground and transition state structures at the B3LYP/6–31G* level.

Cette thèse s'inscrit dans la phase 5 du programme « OPUR : Observatoire des Polluants Urbains » et a pour objectif d'améliorer la compréhension et l’élimination des micropolluants pharmaceutiques (résidus de médicaments) le long des filières de traitement des eaux résiduaires urbaines. La présence de micropolluants pharmaceutiques dans les eaux résiduaires urbaines est principalement due à la consommation répandue de médicaments dans les zones urbaines, en particulier par le biais de l'excrétion humaine. L’élimination insuffisante de ces micropolluants pharmaceutiques par les stations d'épuration est la principale raison de leur présence dans les milieux aquatiques. Afin de réduire les risques liés à la présence de ces micropolluants pour la faune et la flore aquatiques, l'ajout d'un traitement tertiaire (avancé) aux stations d'épuration conventionnelles est l'une des solutions possibles et permettrait de diminuer la concentration de ces polluants émergents dans le rejet des stations d’épuration. L'importance de cette étude réside dans l'utilisation de l'acide performique, un désinfectant employé pour améliorer la qualité des effluents rejetés par les stations d'épuration dans la Seine en préparation des Jeux olympiques et paralympiques de 2024 qui se tiendront à Paris. Ainsi, cette étude vise à optimiser les conditions d'utilisation de ce désinfectant, que ce soit en utilisation individuelle ou en couplage avec d’autres oxydants sous forme de procédé d’oxydation avancée, en vue de l'élimination des micropolluants pharmaceutiques. Les diverses expérimentations menées, d'abord en utilisant de l'eau ultrapure, ont révélé la réactivité marquée mais sélective de l'acide performique envers les composés organiques contenant du soufre réduit ou les amines tertiaires déprotonées, le mécanisme d’oxydation principal étant le transfert d'un atome d'oxygène. Dans les eaux résiduaires urbaines, l'acide performique est relativement réactif avec les micropolluants pharmaceutiques étudiés et leur élimination dépend fortement des différents constituants présents dans les effluents, certains pouvant activer l'acide performique et engendrer des espèces réactives capables de réduire un nombre plus important de micropolluants pharmaceutiques. Les résultats ont également montré que l’acide performique est efficace pour éliminer les micropolluants organiques polaires souvent moins bien éliminés par les procédés classiques. Le couplage de l'acide performique avec la photolyse UV-C ou l'ozone a significativement amélioré l'élimination des micropolluants pharmaceutiques résistants à l'acide performique
This thesis is part of phase 5 of the "OPUR: Urban Pollutants Observatory" program and aims to enhance the understanding and elimination of pharmaceuticals (pharmaceutical residues) in the context of urban wastewater treatment processes. The presence of pharmaceuticals in urban wastewater is primarily attributed to widespread drug use in urban areas, particularly through human excretion. The insufficient removal of these pharmaceuticals by wastewater treatment plants is the main cause of their presence in aquatic environments.To mitigate the risks associated with these micropollutants for aquatic flora and fauna, the addition of an advanced (tertiary) treatment to conventional wastewater treatment plants is one of the possible solutions. This approach would result in the reduction of the concentration of these emerging micropollutants in wastewater plant effluents.The significance of this study lies in the use of performic acid, a disinfectant employed to improve the quality of effluent discharged in the Seine River by the wastewater treatment plants in preparation for the 2024 Olympic and Paralympic Games to be held in Paris. Thus, this study aims to optimize the conditions for using this disinfectant, either individually or in conjunction with other oxidants in tertiary (advanced) oxidation processes, for the removal of pharmaceuticals.Various experiments, initially conducted using deionized water, revealed the pronounced yet selective reactivity of performic acid towards organic compounds containing reduced sulfur or deprotonated tertiary amines, with the primary oxidation mechanism involving the transfer of an oxygen atom.In urban wastewater, performic acid exhibits relatively high reactivity with the pharmaceuticals under investigation, and their removal is significantly influenced by the diverse constituents present in the effluent. Some of these constituents could activate performic acid, thereby generating reactive species that can effectively reduce a greater number of pharmaceuticals. Furthermore, the results demonstrate the efficacy of performic acid in eliminating polar organic micropollutants, a task often challenging for conventional treatment processes. The combination of performic acid with UV-C photolysis or ozone significantly improved the removal of pharmaceuticals resistant to performic acid alone

Abstract As with alkanes, reaction with OH is the dominant loss mechanism for haloalkanes. However, unlike the case for alkanes, photolysis can be an important loss mechanism for brominated and iodinated alkanes in the troposphere, chlorinated alkanes in the stratosphere, and fluorinated alkanes in the mesosphere. UV spectra and photolysis lifetimes for haloalkanes are discussed in chapter VII. In this chapter we first review the available kinetic data for reactions of OH radicals with haloalkanes (section VI-A). Reactions with Cl, O(3P), NO3, and O3 are then considered in section VI-B. Rules for the empirical estimation of rate coefficients of OH radicals with the haloalkanes are presented in section VI-C. The atmospheric chemistry of haloalkylperoxy and haloalkoxy radicals is described in sections VI-D and VI-E, respectively. Finally, the major products of the OH-initiated oxidation of haloalkanes are discussed in section VI-F.

Organic acids, particularly formic and acetic acid, are ubiquitous components of the troposphere (Chebbi and Carlier, 1996); see table I-D-1. However, the atmospheric budget of these species is at present poorly constrained, and global models often underestimate their abundance (von Kuhlmann et al., 2003). The presence of organic acids in the atmosphere can be attributed to two distinct mechanisms: direct emission from anthropogenic and natural sources; and in situ production via gas-phase or condensed-phase chemistry. Direct emissions result from biomass burning (e.g., Christian et al., 2007), from motor vehicle use (Kawamura et al., 2000) and other anthropogenic activities (see chapter I), and from biogenic sources (e.g., Seco et al., 2007). Production in the gas phase can occur via the reactions of acylperoxy radicals with HO2: . . . CH3C(O)O2 + HO2 → CH3C(O)OOH + O2 . . . . . . CH3C(O)O2 + HO2 → CH3C(O)O + OH + O2 . . . . . . CH3C(O)O2 + HO2 → CH3C(O)OH + O3 . . . or via the ozonolysis of unsaturated species (Orzechowska and Paulson, 2005a, b). Additional in situ acid production (particularly with multi-functional species and diacids) likely occurs in the condensed phase as well, via the oxidation of carbonyl and other oxygen-containing and multi-functional organics (e.g., Ervens et al., 2004). In general, the organic acid moiety, —C(O)OH, is rather unreactive in the gas phase. This is in large part due to the strength of the O—H bond, ∼460 kJ mole−1 versus 400–420 kJ mole−1 for typical C—H bonds (Sander et al., 2006). The organic acid moiety also acts to inhibit somewhat the reactivity of neighboring sites (Kwok and Atkinson, 1995), further decreasing the reactivity of small saturated acids. UV spectra for unsubstituted acids are located at relatively short wavelengths, [e.g., λmax< 210 nm for acetic acid, Orlando and Tyndall (2003); see figure IX-A-1], so tropospheric photolysis is of negligible importance. Thus, the gas-phase lifetime for small saturated organic acids (e.g., formic and acetic acid) can be quite long, about 1 month.

Esters are emitted directly into the atmosphere from both natural and anthropogenic sources and are produced during the atmospheric oxidation of ethers. Methyl acetate and ethyl acetate have found widespread use as solvents. Vegetable oils and animal fats are esters. Transesterification of vegetable oils and animal fats with methanol gives fatty acid methyl esters (FAMEs) which are used in biodiesel. Many esters have pleasant odors and are present in essential oils, fruits, and pheromones, and are often added to fragrances and consumer products to provide a pleasant odor. Table VII-A-1 provides a list of common esters and their odors. It is surprising to note that despite their ubiquitous nature, volatility, and fragrance, it is only very recently that quantitative measurements of esters in ambient air have been reported (Niedojadlo et al., 2007; Legreid et al., 2007). The atmospheric oxidation of saturated esters is largely initiated by OH radical attack. Reaction with O3 and NO3 radicals contributes to the atmospheric oxidation of unsaturated esters. As discussed in chapter IX, UV absorption by esters is only important for wavelengths below approximately 240 nm and, hence, photolysis is not a significant tropospheric loss mechanism. When compared to the ethers from which they can be derived, the esters are substantially less reactive towards OH radicals. The ester functionality —C(O)O— in R1C(O)OR2 deactivates the alkyl groups to which it is attached with the deactivation being most pronounced for the R1 group attached to the carbonyl group. The atmospheric oxidation mechanisms of the esters are reviewed in the present chapter. The reaction of OH with methyl formate has been studied by Wallington et al. (1988b) and Le Calvé et al. (1997a) over the temperature range 233–372 K. Data are summarized in table VII-B-1 and are plotted in figure VII-B-1. The room temperature determination of k(OH + CH3OCHO) by Wallington et al. is in agreement with that by Le Calvé et al. (1997) within the experimental uncertainties. Significant curvature is evident in the Arrhenius plot in figure VII-B-1.

A thin film ZnO nanostructured catalyst exhibited a significantly greater superiority for the photodegradation of 2, 4, 6-TCP in water over photolysis via irradiation with UV of 254 nm wavelength. This ZnO photocatalyst was prepared via Zn metal evaporation and deposition on a glass sheet followed by calcination ature from 350 to 500 °C and the calcination time from 1 to 2h shows via SEM photography a decrease of ZnO nanoparticales sizes sheet followed by calcination (oxidation). Increasing the calcination temperature from 350 to 500 °C and the calcination time from 1 to 2h shows via SEM photography a decrease of ZnO nanoparticales sizes as well as the shape of their crystals finer needles, for which the crystallinity enhances as revealed by XRD. 2, 4, 6-Trichlorophenol was used as a model pollutant in water. Its photolysis using UV only or photocatalysis using UV irradiation in presence of the ZnO thin film catalyst indicated aromatic intermediates, which suffered of Cl by OH, addition of OH in a bare carbon in the aromatic ring, whereas in Photocatalysis deeper oxidation products, e.g., quinones and hydroquinones were also formed.