VUV absorption spectra of water and nitrous oxide by a double-duty differentially pumped gas filter.

The differentially pumped rare-gas filter at the end of the VUV beamline of the Swiss Light Source has been adapted to house a windowless absorption cell for gases. Absorption spectra can be recorded from 7 eV to up to 21 eV photon energies routinely, as shown by a new water and nitrous oxide absorption spectrum. By and large, the spectra agree with previously published ones both in terms of resonance energies and absorption cross sections, but that of N2O exhibits a small shift in the {\tilde{\bf D}} band and tentative fine structures that have not yet been fully described. This setup will facilitate the measurement of absorption spectra in the VUV above the absorption edge of LiF and MgF2 windows. It will also allow us to carry out condensed-phase measurements on thin liquid sheets and solid films. Further development options are discussed, including the recording of temperature-dependent absorption spectra, a stationary gas cell for calibration measurements, and the improvement of the photon energy resolution.

Dimeric product formation in the self-reaction of small peroxy radicals using synchrotron radiation vacuum ultraviolet photoionization mass spectrometry.

Peroxy radicals (RO2) are key reactive intermediates in atmospheric oxidation processes and yet their chemistry is not fully unraveled. Little is known about their structures and the structures of the dimeric products (ROOR) in the self-reaction of small RO2, which are among the most abundant RO2 in the atmosphere. The product branching ratios of ROOR and their atmospheric roles are still in controversy. Here, the self-reaction of propyl peroxy radicals (C3H7O2), a typical small RO2 radical in the atmosphere, has been studied using synchrotron radiation vacuum ultraviolet photoionization mass spectrometry. Both radical (C3H7O) and closed-shell molecular (C3H6O, C3H7OH, C3H7OOC3H7) products in the self-reaction are observed in photoionization mass spectra and their elusive isomers are definitely identified in mass-selected photoionization spectra. Three isomers of the C3H7OOC3H7 dimeric products, R1OOR1, R1OOR2, and R2OOR2 (R1 and R2 represent 1-C3H7 and 2-C3H7, respectively), as well as their complex structures have been determined for the first time. Kinetic experiments are performed and compared with chemical simulations to reveal the sources of specific products. The branching ratio of the C3H7OOC3H7 dimeric channel is measured at 10 ± 5%. This work demonstrates that the dimeric product formation in the self-reaction of small RO2 radicals is non-negligible and should provide valuable new insight into atmospheric modelling.

Vacuum-ultraviolet based advanced oxidation and reduction processes for water treatment.

The use of vacuum-ultraviolet (VUV) photolysis in water treatment has been gaining significant interest due to its efficacy in degrading refractory organic contaminants and eliminating oxyanions. In recent years, the reactive species driving pollutant decomposition in VUV-based advanced oxidation and reduction processes (VUV-AOPs and VUV-ARPs) have been identified. This review aims to provide a concise overview of VUV photolysis and its advancements in water treatment. We begin with an introduction to VUV irradiation, followed by a summary of the primary reactive species in both VUV-AOPs and VUV-ARPs. We then explore the factors influencing VUV-photolysis in water treatment, including VUV irradiation dose, catalysts or activators, dissolved gases, water matrix components (e.g., DOM and inorganic anions), and solution pH. In VUV-AOPs, the predominant reactive species are hydroxyl radicals (˙OH), hydrogen peroxide (H2O2), and ozone (O3). Conversely, in VUV-ARPs, the main reactive species are the hydrated electron (eaq-) and hydrogen atom (˙H). It is worth noting that VUV-based advanced oxidation/reduction processes (VUV-AORPs) can transit between VUV-AOPs and VUV-ARPs based on the externally added chemicals and dissolved gases in the solution. Increase of the VUV irradiation dose and the concentration of catalysts/activators enhances the degradation of contaminants, whereas DOM and inorganic anions inhibit the reaction. The pH influences the redox potential of ˙OH, the speciation of contaminants and activators, and thus the overall performance of the VUV-AOPs. Conversely, an alkaline pH is favored in VUV-ARPs because eaq- predominates at higher pH.

Polyethylene, whose surface has been modified by UV irradiation, induces cytotoxicity: A comparison with microplastics found in beaches.

Microplastics, plastic particles 5 mm or less in size, are abundant in the environment; hence, the exposure of humans to microplastics is a great concern. Usually, the surface of microplastics found in the environment has undergone degradation by external factors such as ultraviolet rays and water waves. One of the characteristics of changes caused by surface degradation of microplastics is the introduction of oxygen-containing functional groups. Surface degradation alters the physicochemical properties of plastics, suggesting that the biological effects of environmentally degraded plastics may differ from those of pure plastics. However, the biological effects of plastics introduced with oxygen-containing functional groups through degradation are poorly elucidated owing to the lack of a plastic sample that imitates the degradation state of plastics found in the environment. In this study, we investigated the degradation state of microplastics collected from a beach. Next, we degraded a commercially available polyethylene (PE) particles via vacuum ultraviolet (VUV) irradiation and showed that chemical surface state of PE imitates that of microplastics in the environment. We evaluated the cytotoxic effects of degraded PE samples on immune and epithelial cell lines. We found that VUV irradiation was effective in degrading PE within a short period, and concentration-dependent cytotoxicity was induced by degraded PE in all cell lines. Our results indicate that the cytotoxic effect of PE on different cell types depends on the degree of microplastic degradation, which contributes to our understanding of the effects of PE microplastics on humans.

Changes in the fatty acid profiles and health indexes of bovine colostrum during the first days of lactation and their impact on human health.

Our objective was to analyze the changes in fatty acid (FA) profiles of bovine colostrum and immature milk during the first four days of lactation and assess their potential impact on human health. Colostrum and immature milk samples were collected from Czech Fleckvieh cows during their first to third lactation and the FA profiles were analyzed using multidimensional gas chromatography with a vacuum ultraviolet detector (GC×GC-VUV). The colostrum of primiparous cows contained lower levels of medium-chain and saturated fatty acids, and higher levels of mono- and unsaturated fatty acids compared to that of multiparous cows. The atherogenic and thrombogenicity indexes, as well as the hypocholesterolemic-to-hypercholesterolemic fatty acid ratio, were more favourable in primiparous cows. This makes colostrum fat an attractive product for human nutrition. To obtain the maximum health benefits, we recommend collecting and processing the colostrum of primiparous cows and immature milk at the end of the milk transition separately.

Insights into the efficient mineralization of antibiotic trimethoprim in aqueous media by Fe2+ catalytically enhanced vacuum-UV irradiation: Kinetics, mechanisms, and toxicity evaluation.

The widespread existence of antibiotics in the environment has attracted growing concerns regarding the potential adverse effects on aquatic organisms, ecosystems, and human health even at low concentrations. Extensive efforts have been devoted to developing new methods for effective elimination of antibiotics from wastewater. Herein, a novel process of Fe2+ catalytically enhanced vacuum ultraviolet (VUV) irradiation was proposed as a promising approach for the removal of antibiotic trimethoprim (TMP) in water. Compared with UVC photolysis, VUV photolysis, and UVC/Fe2+, VUV/Fe2+ could increase the pseudo-first-order reaction rate constant of TMP removal by 6.6-38.4 times and the mineralization rate by 36.5%-59.9%. The excellent performance might originate from the synergistic effect of VUV and Fe2+, i.e., VUV irradiation could effectively split water and largely accelerate the Fe3+/Fe2+ cycle to generate more reactive oxygen species (ROS). EPR results indicated that •OH and O2•- were identified as the main ROS in the UVC/Fe2+ and VUV/Fe2+ processes, while •OH, O2•-, and 1O2 were involved in the VUV process. The operating parameters, such as Fe2+ dosage and initial TMP contents, were evaluated and optimized. Up to 8 aromatic intermediates derived from hydroxylation, demethylation, carbonylation, and methylene group cleavage were identified by UPLC-QTOF-MS/MS technique, the possible pathways of TMP degradation were proposed. Finally, the acute and chronic toxicity of intermediates formed during TMP degradation in the VUV/Fe2+ process were also evaluated.

Exhaled breath is found to be better than blood samples for determining propofol concentrations in the brain tissues of rats.

The correlation between propofol concentration in exhaled breath (CE) and plasma (CP) has been well-established, but its applicability for estimating the concentration in brain tissues (CB) remains unknown. Given the impracticality of directly sampling human brain tissues, rats are commonly used as a pharmacokinetic model due to their similar drug-metabolizing processes to humans. In this study, we measuredCE,CP, andCBin mechanically ventilated rats injected with propofol. Exhaled breath samples from the rats were collected every 20 s and analyzed using our team's developed vacuum ultraviolet time-of-flight mass spectrometry. Additionally, femoral artery blood samples and brain tissue samples at different time points were collected and measured using high-performance liquid chromatography mass spectrometry. The results demonstrated that propofol concentration in exhaled breath exhibited stronger correlations with that in brain tissues compared to plasma levels, suggesting its potential suitability for reflecting anesthetic action sites' concentrations and anesthesia titration. Our study provides valuable animal data supporting future clinical applications.

Chemical-free vacuum ultraviolet irradiation as ultrafiltration membrane pretreatment technique: Performance, mechanisms and DBPs formation.

Membrane fouling induced by natural organic matter (NOM) has seriously affected the further extensive application of ultrafiltration (UF). Herein, a simple, green and robust vacuum ultraviolet (VUV) technology was adopted as pretreatment before UF and ultraviolet (UV) technology was used for comparison. The results showed that control effect of VUV pretreatment on membrane fouling was better than that of UV pretreatment, as evidenced by the increase of normalized flux from 0.27 to 0.38 and 0.73 after 30 min UV or VUV pretreatment, respectively. This is related to the fact that VUV pretreatment exhibited stronger NOM degradation ability than UV pretreatment owing to the formation of HO•. The steady-state concentration of HO• was calculated as 3.04 × 10-13 M and the cumulative exposure of HO• reached 5.52 × 10-10 M s after 30 min of VUV irradiation. And the second-order rate constant between NOM and HO• was determined as 1.36 × 104 L mg-1 s-1. Furthermore, fluorescence EEM could be applied to predict membrane fouling induced by humic-enriched water. Standard blocking and cake filtration were major fouling mechanisms. Moreover, extension of UV pretreatment time increased the disinfection by-products (DBPs) formation, the DBPs concentration was enhanced from 322.36 to 1187.80 µg/L after 210 min pretreatment. However, VUV pretreatment for 150 min reduced DBPs content to 282.57 µg/L, and DBPs content continued to decrease with the extension of pretreatment time, revealing that VUV pretreatment achieved effective control of DBPs. The variation trend of cytotoxicity and health risk of DBPs was similar to that of DBPs concentration. In summary, VUV pretreatment exhibited excellent effect on membrane fouling alleviation, NOM degradation and DBPs control under a certain pretreatment time.

Vacuum ultraviolet irradiation for reduction of the toxicity of wastewater towards mammalian cells: Removal mechanism, changes in organic compounds, and toxicity alternatives.

Vacuum ultraviolet (VUV, 185 + 254 nm) irradiation performs well for oxidation of model pollutants. However, oxidation of pollutants does not necessarily lead to a reduction in toxicity. Currently, a comprehensive understanding of the effect of VUV irradiation on the toxicity of real wastewater is still lacking. In this study, the influence of VUV irradiation on the toxicity of secondary effluents to Chinese hamster ovary (CHO) cells was investigated. The induction units of endogenous reactive oxygen species (ROS) and 8-hydroxyguanosine (8-OHdG) in cells continuously decreased with prolonged irradiation time. After 36 min of irradiation, the cytotoxicity and the genotoxicity of the secondary effluents were reduced by 57%-63% and 56%-61%, respectively. The UV (254 nm), •OH, and other substances generated during the VUV irradiation directly drive toxicity changes of wastewater. The contribution of •OH generated during VUV irradiation to the reductions in cytotoxicity and genotoxicity of the secondary effluents reached 72%-78% and 77%-84%, respectively. Hydroxyl radicals generated during VUV irradiation played an important role in the detoxification. The relative signal intensity of dissolved organic carbon (DOC) > 500 Da was partially removed, whereas that of DOC < 500 Da was small changed. Since the content of DOC > 500 Da in the samples was much lower than that of DOC < 500 Da, the removal of total DOC was only 15.8%-20.0% after 36 min of irradiation. The UV254 values and the fluorescence intensity values for different molecular weights (MWs) were all reduced effectively by VUV irradiation. Electron-rich organic compounds of all MWs were all sensitive to VUV irradiation. There were mono-linear relationships between changes in chemical indexes and changes in cytotoxicity or genotoxicity. The total fluorescence intensity (Ex: 220-420 nm, Em: 280-560 nm) was identified as the best indicator of the reduction in toxicity.

UV-Induced Synthesis of Hybrid HMDSO/SiO2 Thin Films with Compositional Gradients for High-Performance Atomic Oxygen Resistance.

A flexible, dense, defect-free, highly adhesive, and highly dissociation energy-rich protective coating is essential to enhance the atomic oxygen (AO) resistance of polymeric materials in a low Earth orbit (LEO). In this work, a dense, defect-free hybrid HMDSO/SiO2 thin film coating with compositional gradients on the surface of polyimide was synthesized using vacuum-ultraviolet (VUV) irradiation. The effects of VUV irradiation on the morphology, optical transmittance, and chemical components of plasma-polymerized HMDSO (pp-HMDSO) thin-film coatings deposited on the polyimide surface were investigated in depth. There were no defects such as cracks and holes in the surface morphology of pp-HMDSO films after VUV irradiation, but the surface roughness increased slightly, and the corresponding optical transmittance decreased slightly. The chemical components of pp-HMDSO films were changed in the depth direction starting from the top of the surface, forming hybrid HMDSO/SiO2 thin films with compositional gradients. The component gradient HMDSO/SiO2 composite coating further enhanced the atomic oxygen resistance of the polyimide due to the surface layer of the UV-modified coating enriched with high dissociation energy SiOx material. Therefore, this work provides a facile UV-induced synthesis method to prepare dense, defect-free, and highly dissociation energy-rich protective gradient coatings, which are promising not only for excellent AO protection in LEO but also for potential application in water-oxygen barrier films.

Accelerated oxidation of VOCs via vacuum ultraviolet photolysis coupled with wet scrubbing process.

Vacuum ultraviolet (VUV) photolysis is a facile method for volatile organic compounds (VOCs) elimination, but is greatly limited by the relatively low removal efficiency and the possible secondary pollution. To overcome above drawbacks, we developed an efficient method for VOCs elimination via VUV photolysis coupled with wet scrubbing process. In this coupled process, volatile toluene, a representative of VOCs, was oxidized by the gas-phase VUV photolysis, and then scrubbed into water for further oxidation by the liquid-phase VUV photolysis. More than 96% of toluene was efficiently removed by this coupled process, which was 2 times higher than that in the gas-phase VUV photolysis. This improvement was attributed to the synergistic effect between gas-phase and liquid-phase VUV photolysis. O3 and HO• are the predomination reactive species for the toluene degradation in this coupled process, and the generation of O3 in gas-phase VUV photolysis can efficiently enhance the HO• production in liquid-phase VUV photolysis. The result from in-situ proton transfer reaction ionization with mass analyzer (PTR-MS) further suggested that most intermediates were trapped by the wet scrubbing process and efficiently oxidized by the liquid-phase VUV photolysis, showing a high performance for controlling the secondary pollution. Furthermore, the result of stability test and the reuse of solution demonstrated that this coupled process has a highly stable and sustainable performance for toluene degradation. This study presents an environmentally benign and highly efficient VUV photolysis for gaseous VOCs removal in the wet scrubbing process.

Exploring the vacuum ultraviolet photochemistry of astrochemically important triatomic molecules.

The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely detailed information about the photofragmentation dynamics of many small gas-phase molecules. This Review focuses particular attention on five triatomic molecules-H2O, H2S, CO2, OCS and CS2. Each shows excitation wavelength-dependent dissociation dynamics, yielding photofragments that populate a range of electronic and (in the case of diatomic fragments) vibrational and rotational quantum states, which can be characterized by different translational spectroscopy methods. The photodissociation of an isolated molecule from a well-defined initial quantum state provides a lens through which one can investigate how and why chemical reactions occur, and provides numerous opportunities for fruitful, synergistic collaborations with high-level ab initio quantum chemists. The chosen molecules, their photofragments and the subsequent chemical reaction networks to which they can contribute are all crucial in planetary atmospheres and in interstellar and circumstellar environments. The aims of this Review are 3-fold: to highlight new photochemical insights enabled by the VUV-FEL at the DCLS, notably the recently recognized central atom elimination process that is shown to contribute in all of these triatomic molecules; to highlight some of the potential implications of this rich photochemistry to our understanding of interstellar chemistry and molecular evolution within the universe; and to highlight other and future research directions in areas related to chemical reaction dynamics and astrochemistry that will be enabled by increased access to VUV-FEL sources.

Efficient removal of electroneutral carbonyls by combined vacuum-UV oxidation and anion-exchange resin adsorption: mechanism, model simulation, and optimization.

Electroneutral carbonyls (ENCs) with low molecular weights (e.g., aldehydes and ketones) are recalcitrant to single water treatment process to achieve ultralow concentration. Residual ENCs are present in reverse osmosis permeate and pose risks to human health during potable use or industrial application in manufacturing processes. Herein, a combined vacuum-UV (VUV) oxidation and anion-exchange resin (AER) adsorption method was developed to treat the ENCs and reduce total organic carbon (TOC) to an ultralow concentration (< 5 µg/L) with high efficiency and at low cost. VUV-AER was 2.1-2.4 times more efficient than VUV alone for the removal of TOC. VUV oxidized the ENCs to electronegative carboxylic acids, which were adsorbed by the AER through electrostatic interactions and hydrogen bonding. When the VUV fluence was lower than 643 mJ cm-2, the AER could not achieve ultralow TOC removal of ENCs. The treat capacity of 1500-2900 valid bed volume (BVs) was achieved after increasing the VUV fluence to 1929 mJ cm-2. The AER could more efficiently adsorb carboxylic acids that contained more carboxylic groups or shorter carbon chain. Acetate was identified as the primary breakthrough product at relatively low VUV fluence, and oxalate was the main byproduct at relatively high VUV fluence. A mathematical model to predict TOC breakthrough was developed considering the VUV-oxidation kinetics and the AER breakthrough curve. The model was used to optimize the method to maximize TOC removal and minimize energy consumption. These results imply that VUV-AER is technically feasible and economically applicable to eliminate recalcitrant ENCs to ultralow concentration for the production of water requires high quality (e.g., potable water or electronic-grade ultrapure water).

Degradation characteristics of refractory organic matter in naproxen pharmaceutical secondary effluent using vacuum ultraviolet-ozone treatment.

Vacuum ultraviolet-ozone (VUV-O3) treatment was found to be superior to ultraviolet-ozone (UV-O3) treatment in terms of ozone utilization and hydroxyl radicals (·OH) generation when used to treat the secondary effluent (SE) from a naproxen pharmaceutical plant. VUV-O3 treatment was beneficial in terms of decolorization (100%), chemical oxygen demand removal (43.29%), and total organic carbon removal (54.81%). The VUV-O3 process was applicable over a wide pH range, and the presence of various anions had no significant influence on the oxidation efficiency. After treatment, the genotoxicity, unsaturation degree, and polarity of the SE decreased. In addition, the oxidation sensitivities of the fluorescent organic compounds were ranked as follows: humic acid-like > tyrosine-like > fulvic acid-like > tryptophan-like Moreover, the VUV-O3 process effectively converted refractory organic matter (molecular weights, MW > 2000 Da) into short-chain molecules with low MWs. The removal efficiency of dissolved organic matter (DOM) was 63.27%, and 77.27% of the DOM was found to be reactive to VUV-O3 oxidation. The unsaturation, polarity, and compositional complexity of the DOM decreased after VUV-O3 treatment. Finally, it was deduced that the direct O3 oxidation,·OH, O2·- and 1O2 played a role in the VUV-O3 oxidation process.

VUV to IR Emission Spectroscopy and Interferometry Diagnostics for the European Shock Tube for High-Enthalpy Research.

The European Shock Tube for High-Enthalpy Research is a new state-of-the-art facility, tailored for the reproduction of spacecraft planetary entries in support of future European exploration missions, developed by an international consortium led by Instituto de Plasmas e Fusão Nuclear and funded by the European Space Agency. Deployed state-of-the-art diagnostics include vacuum-ultraviolet to ultraviolet, visible, and mid-infrared optical spectroscopy setups, and a microwave interferometry setup. This work examines the specifications and requirements for high-speed flow measurements, and discusses the design choices for the main diagnostics. The spectroscopy setup covers a spectral window between 120 and 5000 nm, and the microwave interferometer can measure electron densities up to 1.5 × 1020 electrons/m3. The main design drivers and technological choices derived from the requirements are discussed in detail herein.

Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)7 and TM(CO)8 (TM=Y, La).

Spectroscopic characterization of neutral highly-coordinated compounds is essential in fundamental and applied research, but has been proven to be a challenging experimental target because of the difficulty in mass selection. Here, we report the preparation and size-specific infrared-vacuum ultraviolet (IR-VUV) spectroscopic identification of group-3 transition metal carbonyls Sc(CO)7 and TM(CO)8 (TM=Y, La) in the gas phase, which are the first confinement-free neutral heptacarbonyl and octacarbonyl complexes. The results indicate that Sc(CO)7 has a C2v structure and TM(CO)8 (TM=Y, La) have a D4h structure. Theoretical calculations predict that the formation of Sc(CO)7 and TM(CO)8 (TM=Y, La) is both thermodynamically exothermic and kinetically facile in the gas phase. These highly-coordinated carbonyls are 17-electron complexes when only those valence electrons that occupy metal-CO bonding orbitals are considered, in which the ligand-only 4b1u molecular orbital is ignored. This work opens new avenues toward the design and chemical control of a large variety of compounds with unique structures and properties.

Enhanced permeation performance of biofiltration-facilitated gravity-driven membrane (GDM) systems by in-situ application of UV and VUV: Comprehensive insights from thermodynamic and multi-omics perspectives.

Biofouling is a major challenge limiting the practical application of biofiltration-facilitated gravity-driven membrane (GDM) systems in drinking water treatment. In this study, ultraviolet irradiation, including ultraviolet (UV) and vacuum ultraviolet (VUV) irradiation, was used for in-situ purification of membrane tanks to control membrane biofouling. After using UV and VUV, the permeate flux increased significantly by 26.1% and 78.3%, respectively, which was mainly due to the decreased cake layer resistance (Rc). The permeability of the biofouling layer improved after UV and VUV application, as evidenced by the increased surface porosity and decreased thickness. The contents of loosely bound extracellular proteins (LB-PN) and tightly bound extracellular proteins (TB-PN) in the biofouling layer were reduced after UV and VUV irradiation. The decreased LB-PN and TB-PN improved the interfacial free energy between the fouling itself and between the fouling and the membrane, which contributed to the reduction of interfacial cohesion and adhesion, resulting in a looser and thinner biofouling layer and a cleaner membrane. The concentration of protein-like material in the membrane tank decreased after UV and VUV irradiation, significantly altering the bacterial community structure on the membrane surface (Mantel's r > 0.7, p < 0.05). The changes in the metabolic state were responsible for the differences in the LB-PN and TB-PN contents. The inhibition of "Alanine, aspartate and glutamate metabolism" and "Glycine, serine and threonine metabolism" reduced amino acid biosynthesis, which restricted the secretion of LB-PN and TB-PN. Critical genera in the Proteobacteria phylum, such as Hirschia, Rhodobacter, Nordella, Candidatus_Berkiella, and Limnohabitans, were involved in metabolite transformation. Overall, the in-situ application of UV and VUV can be an effective alternative strategy to mitigate membrane biofouling, which would facilitate the practical application of biofiltration-facilitated GDM systems in drinking water treatment.

Remediation of Surfactants Used by VUV/O3 Techniques: Degradation Efficiency, Pathway and Toxicological Analysis.

Surfactants are increasingly used in systems that come into contact with the human body, such as food, pharmaceuticals, cosmetics and personal hygiene products. Increasing attention is being devoted to the toxic effects of surfactants in various human contact formulations, as well as the removal of residual surfactants. In the presence of ozone (O3), anion surfactants-a characteristic micro-pollutant-such as sodium dodecylbenzene sulfonate (SDBS) in greywater, can be removed using radical advanced oxidation. Herein, we report a systematic study of the SDBS degradation effect of O3 activated by vacuum ultraviolet (VUV) irradiation and the influence of water composition on VUV/O3, and determined the contribution of radical species. We show a synergistic effect of VUV and O3, while VUV/O3 reached a higher mineralization (50.37%) than that of VUV (10.63%) and O3 (29.60%) alone. The main reactive radicals of VUV/O3 were HO•. VUV/O3 had an optimal pH of 9. The addition of SO42- had almost no effect on the degradation of SDBS by VUV/O3, Cl- and HCO3- slightly reduced the reaction rate, and NO3- had a significant inhibition on the degradation. In total, SDBS had three isomers, with which the three degradation pathways were very comparable. Compared with SDBS, the toxicity and harmfulness of the degradation by-products of the VUV/O3 process decreased. Additionally, VUV/O3 could degrade synthetic anion surfactants from laundry greywater effectively. Overall, the results show the potential of VUV/O3 in safeguarding humans from residual surfactant hazards.

Limits of identification using VUV spectroscopy applied to C8H18 isomers isolated by GC×GC.

The vacuum ultraviolet detector for gas chromatography can be used to identify structural differences between isomers with similar chromatographic elution times, which adds detail to characterization, valuable for prescreening of sustainable aviation fuel candidates. Although this capability has been introduced elsewhere, vacuum ultraviolet spectroscopy for saturated hydrocarbons has been examined minimally, as the similarities between their spectra are much less significant than their aromatic counterparts. The fidelity with which structural differences can be identified has been unclear. In this work, all possible structural isomers of C8H18 are measured and determined to have unambiguously unique vacuum ultraviolet spectra. Using a statistically based residual comparison approach, the concentration limits at which the spectral differences are interpretable are tested in both a controlled study and a real fuel application. The concentration limit at which the spectral differences between C8H18 isomers are unambiguous is below 0.40% by mass and less than 0.20% with human discretion in our experimental configuration.

Roles of radical species in vacuum-UV/UV/peroxydisulfate advanced oxidation processes and contributions of the species to contaminant degradation at different water depths.

Vacuum-UV (VUV) (wavelength 185 nm)/ UV (wavelength 254 nm) are applied to improve performances of UV-based advanced oxidation processes. However, the improvements were strongly affected by water depth because of poor VUV transmittance in water. In this study, VUV/UV and peroxydisulfate (PDS) were used to degrade carbamazepine. More SO4•- oxidation occurred in VUV/UV/PDS than VUV/UV with similar •OH oxidation occurring. The additional SO4•- oxidation could be caused by VUV/PDS in superficial water or UV/PDS in deeper water. The synergistic factor for VUV/UV/PDS processes relative to VUV/UV and UV/PDS processes was 1.32. VUV/UV/PDS performances were affected by competition for photon absorption by dissolved organic matter (32-58 % inhibition), radical quenching by CO32-/HCO3- and NO3-, and conversion of •OH and SO4•- into reactive chlorine species by Cl-. Radical probe experiments and steady-state kinetic modeling simulations indicated that 34 %, 25 %, and 40 % of carbamazepine degradation occurring in 2-cm-deep bulk solution was due to •OH oxidation through VUV/H2O, SO4•- oxidation through VUV/PDS, and SO4•- oxidation through UV/PDS, respectively. Contribution of VUV-driven processes decreased with increasing water depth and became equivalent to contribution of 3.5-cm-deep UV-driven processes, which indicated the importance of optimizing water depth in VUV/UV-advanced oxidation process reactors.