Vacuum Ultraviolet System Research Articles

Efficient degradation of ciprofloxacin by innovative VUV/BN system: Kinetics, mechanism and toxicity assessment

Given the increasing emergence of widespread fluoroquinolones (FQs) in natural water environments and the limitations of traditional vacuum ultraviolet (VUV) systems for water decontamination, an innovative VUV/BN system was developed for the degradation and detoxification of ciprofloxacin (CIP) in this work. Unlike the VUV system, which primarily relies on hydroxyl radicals (·OH), the VUV/BN system significantly enhances the concentration of singlet molecular oxygen (1O2) to target the piperazine ring of CIP, achieving a defluorination efficiency of 98.88 % within 60 min. The degradation rate constant for CIP was found to be 2.76 times greater than that of the traditional VUV system. Additionally, varying concentrations of reactive species (RSs) in the VUV and VUV/BN systems resulted in distinct CIP degradation pathways. Due to the high selective oxidation capacity and environmental compatibility of 1O2, the VUV/BN system demonstrated excellent adaptability to environmental factors, maintaining stable operation in complex water matrices. Furthermore, the system exhibited high degradation capacity for CIP even in the fifth cycle, confirming its exceptional stability and reusability. The economic feasibility of the VUV/BN system was confirmed by its low electrical energy per order (EEO). This study underscores the potential of VUV/BN systems and enhances the understanding of CIP photodegradation.

The synergistic effect of radical and non-radical processes on the dephosphorization of dimethoate by vacuum ultraviolet: The overlooked roles of singlet oxygen atom and high-energy excited state

Organophosphorus pesticides are extensively utilized worldwide, but their incomplete dephosphorization poses significant environmental risks. This study investigates the dephosphorization of dimethoate (DMT), a representative organophosphorus pesticide, using a vacuum ultraviolet system. Surprisingly, in addition to hydroxyl radicals (•OH), non-radical processes such as photoexcitation and singlet oxygen atoms (O(1D)) exert more significant effects on DMT dephosphorization. The degradation kinetics of DMT demonstrate a perfect linear correlation with the radical yield in both UV-based and VUV-based advanced oxidation processes (AOPs), with greater efficacy of radical attack observed in the VUV system. This heightened efficiency is attributed to the excitation of DMT to a high-energy excited state induced by UV185 radiation. Additionally, •OH alone is inadequate for achieving complete dephosphorization of DMT. The Fukui index and singly occupied orbital (SOMO) analysis reveal that the O(1D) generated by UV185-induced photolysis of O2 exhibits exceptional selectivity towards P=S bonds, thereby playing an indispensable role in the dephosphorization process of DMT. This study highlights the significant contribution of non-radical pathways in DMT dephosphorization by VUV, which holds great implications for the advancement of photochemical-based AOPs.

Photodegradation of xylene isomers: Kinetics, mechanism, secondary pollutant formation potential and health risk evaluation

Photodegradation technology has been widely applied in the purification of industrial aromatic hydrocarbons. However, whether this technology efficiently removes the pollutants to prevent secondary pollution and health risk is still unclear. Here, the photodegradation processes of three xylenes were compared under designed reaction atmospheres and light sources. Xe lamp showed poor photodegradation ability toward xylenes, no matter in N2 or N2+O2 system, while much higher photodegradation performance of xylenes were obtained under ultraviolet (UV) and vacuum ultraviolet (VUV) irradiation, especially in N2+O2+VUV system, where 97.9% of m-xylene, 99.0% of o-xylene or 87.5% of p-xylene with the initial concentration of 860 mg/m3 was removed within 240 min. The xylenes underwent three processes of photo-isomerization, photodecomposition and photo-oxidation to produce intermediates of aromatics, alkanes and carbonyls. Among them, the photo-isomerization products showed the highest concentration percentage (e.g., ≥50% in o-xylene system), confirming that photo-isomerization reaction was the dominated photodegradation process of xylenes. Moreover, these isomerized products not only contributed about 97% and 91% to the formation potential of O3 (OFP) and secondary organic aerosols (SOAFP), but also displayed obvious non-carcinogenic risk, although one of photodecomposition product—benzene showed the highest occupational exposure risk. Therefore, the secondary pollution and health risks of photodegradation products of xylenes were non-ignorable, although the OFP, SOAFP and health risks of the generated products reduced at least 4.5 times in comparison with that of the degraded xylenes. The findings are helpful for the appropriate application of this technology in the purification of industrial organic waste gas.

Vacuum ultraviolet nonlinear metalens

Vacuum ultraviolet (VUV) light plays an essential role across science and technology, from molecular spectroscopy to nanolithography and biomedical procedures. Realizing nanoscale devices for VUV light generation and control is critical for next-generation VUV sources and systems, but the scarcity of low-loss VUV materials creates a substantial challenge. We demonstrate a metalens that both generates—by second-harmonic generation—and simultaneously focuses the generated VUV light. The metalens consists of 150-nm-thick zinc oxide (ZnO) nanoresonators that convert 394 nm (~3.15 eV) light into focused 197-nm (~6.29 eV) radiation, producing a spot 1.7 μm in diameter with a 21-fold power density enhancement as compared to the wavefront at the metalens surface. The reported metalens is ultracompact and phase-matching free, allowing substantial streamlining of VUV system design and facilitating more advanced applications. This work provides a useful platform for developing low-loss VUV components and increasing the accessibility of the VUV regime.

Reactivity and mechanism between [rad]OH and phenolic pollutants: Efficiency and DFT calculation

Phenolic pollutants (PPs) are regarded as hazardous pollutants, posing severe threats to humans. In this study, a vacuum ultraviolet (VUV) lamp was used to decay PPs with different functional groups, including phenol, paradioxybenzene (PDB), and p-nitrophenol (PNP). Results showed the removal rate for phenol, PDB, and PNP reached 99.78 %, 97.78 %, and 80.73 % within 60 min. Density functional theory (DFT) involving in quantum chemical descriptors (QCD), frontier molecular orbitals (FMO), thermochemical properties, and the Gibbs free energy was applied to reveal the reactivity and mechanism between ·OH and PPs with various functional groups. Results confirmed that PDB and phenol with the electron-donating group exhibited favorable reactivity, while PNP with an electron-withdrawing group presented a lower one. Furthermore, the oxidation mechanism between PPs and ·OH in the VUV system was also deeply investigated, mainly following four steps: photo-excitation, ·OH substitution, molecular rearrangement, and finally ring-opening. Among them, the required energy for the ring-opening was about 145 and 787-fold higher than that of ·OH substitution and molecular rearrangement. Results suggested that the formation of micro-fatty acids were the primary rate-controlling step.

The defluorination of perfluorooctanoic acid by different vacuum ultraviolet systems in the solution.

Perfluorooctanoic acid (PFOA) is one kind of persistent organic pollutants that is often detected in water. In recent years, the effective degradation technologies of PFOA have attracted widespread attentions. Thus, in this study, the defluorination efficiency of PFOA in different systems (i.e., ultraviolet (UV), vacuum ultraviolet (VUV), vacuum ultraviolet/persulfate (VUV/PS) and vacuum ultraviolet/residual chlorine (VUV/RC)) was evaluated. Moreover, the different impact factors (i.e., the initial concentrations of persulfate and PFOA, temperature, anions, and initial pH values) on PFOA degradation by VUV/PS system were investigated. The results showed that VUV system was more effective than UV system for PFOA defluorination. VUV system combined with persulfate would further enhance the defluorination efficiency while residual chlorine would decrease it. In VUV/PS system, the defluorination efficiency of PFOA was the best as the molar ratio of PFOA and persulfate at 1:60. Moreover, higher temperature, lower initial PFOA concentration, and acid condition were favorable for the defluorination of PFOA. Under the different influence factors, the defluorination efficiency of PFOA fitted well to the first-order reaction kinetic model. When the temperature was range from 20°C to 40°C, the value of activation energy was 8.73kJ/mol. Besides, the inhibition effect of three kinds of anions on PFOA defluorination followed the order: >Cl- > . PRACTITIONER POINTS: The defluorination efficiency of perfluorooctanoic acid (PFOA) in water by different VUV systems was compared. VUV system is more effective than UV system for PFOA defluorination. Persulfate will enhance the defluorination efficiency by VUV system. Hypochlorite will decrease the defluorination efficiency by VUV system.

Efficient removal of halogenated phenols by vacuum-UV system through combined photolysis and OH oxidation: Efficiency, mechanism and economic analysis

In this study, efficient simultaneous degradation and dechlorination of the photo-recalcitrant emerging disinfection byproduct, 2-chlorophenol (2-CP), was achieved by vacuum-ultraviolet (VUV) system for the first time. Different from the conventional UV system, the combined action of direct photolysis and OH oxidation in VUV system led to a significantly higher removal efficiency for 2-CP. In UV system, 2-CP degradation rate constants was independent of the initial 2-CP concentration, and was increased with enhancing pH. To the contrary, in VUV system, higher initial concentration of 2-CP resulted in lower rate constant, and the degradation rates of 2-CP under both acidic and alkaline conditions were higher than that at the neutral pH. Moreover, humic acid could inhibit 2-CP degradation more prominently in VUV system than in UV system, owing to the scavenging effect of OH by it. The degradation pathways of 2-CP were proposed based on the identified main degradation products by GC–MS/MS. Furthermore, degradation of the other seven typical halogenated phenols by VUV irradiation in tap water, ultrafiltrated water and Mill-Q water were investigated to verify the feasibility of the system. Based on the systematic economic analysis, VUV process is economically feasible for the advanced treatment of tap water to remove halogenated phenols.

Stagnation-point heating of Fire II with a non-Boltzmann radiation model

The present work analyzes the stagnation-point radiative heating in the Fire II flight experiment by devising a collisional-radiative model with non-local absorption. In the stagnation-line flow-field calculations, a viscous shock layer method with a thermochemical nonequilibrium model is utilized. In the radiation calculations, a line-by-line method with the non-Boltzmann electronic populations is employed by adopting the quasi-steady state approach of the electronic master equation calculations. In constructing the electronic master equation, the best set of the electron and heavy-particle impact excitation rates is proposed to achieve better agreement with the measured radiative heating flight data. In the flow-radiation coupling procedure, the effect of the non-local absorption is modeled by devising an iterative process between the quasi-steady state electronic master equation and the radiative transfer equation calculations. Escape factors of the strongest atomic lines and the diatomic nitrogen vacuum ultraviolet systems with the non-local absorption effect are also proposed to more efficiently consider the non-local nature of the radiative transition. When compared with the experimental data from the Fire II trajectories, it is found that the present collisional-radiative model with the non-local absorption improves the ability to predict non-Boltzmann radiative heating.

Degradation of imipramine by vacuum ultraviolet (VUV) system: Influencing parameters, mechanisms, and variation of acute toxicity

Degradation of imipramine (IMI) in the VUV system (VUV185 + UV254) was firstly evaluated in this study. Both HO• oxidation and UV254 direct photolysis accounted for IMI degradation. The quantum yields of UV254 direct photolysis of deprotonated and protonated IMI were 1.31×10−2 and 3.31×10−3, respectively, resulting in the higher degradation efficiency of IMI at basic condition. Increasing the initial IMI concentration lowered the degradation efficiency of IMI. While elevating reaction temperature significantly improved IMI degradation efficiency through the promotion of both the quantum yields of HO• and the UV254 direct photolysis rate. The apparent activation energy was calculated to be about 26.6 kJ mol−1. Negative-linear relationships between the kobs of IMI degradation and the concentrations of HCO3−/CO32−, NOM and Cl− were obtained. The degradation pathways were proposed that cleavage of side chain and hydroxylation of iminodibenzyl and methyl groups were considered as the initial steps for IMI degradation in the VUV system. Although some high toxic intermediate products would be produced, they can be further transformed to other lower toxic products. The good degradation efficiency of IMI under realistic water matrices further suggests that the VUV system would be a good method to degrade IMI in aquatic environment.

Deoxyribonucleic-acid-sensitive Polycrystalline Diamond Solution-gate Field-effect Transistor with a Carboxyl-terminated Boron-doped Channel.

This paper describes a deoxyribonucleic-acid-sensitive electrolyte solution-gate field-effect transistor (SGFET) sensor utilizing a partial carboxyl-terminated boron-doped polycrystalline diamond surface as a linker to connect a deoxyribonucleic acid (DNA) probe. A high density of carboxyl termination on the polycrystalline diamond surface that was employed as a FET channel was achieved using a vacuum ultraviolet system with oxygen gas. A single-stranded DNA probe was immobilized on the polycrystalline diamond channel via amino coupling. The current-voltage characteristics of the polycrystalline diamond SGFET sensor was examined with bias voltages within its potential voltage window. The characteristics of the drain-source current verses the drain-source voltage showed a pinch-off, a shift voltage of up to 40 mV with a coefficient of variation of 4 - 11% was obtained between hybridization and denaturation. In addition, a single nucleotide mutation of DNA sequence was selectively recognized by the shift voltage up to ca. 10 mV.

Degradation of organic pollutants by Vacuum-Ultraviolet (VUV): Kinetic model and efficiency

Vacuum-Ultraviolet (VUV), an efficient and green method to produce hydroxyl radical (•OH), is effective in degrading numerous organic contaminants in aqueous solution. Here, we proposed an effective and simple kinetic model to describe the degradation of organic pollutants in VUV system, by taking the •OH scavenging effects of formed organic intermediates as co-existing organic matter in whole. Using benzoic acid (BA) as a •OH probe, •OH was regarded vital for pollutant degradation in VUV system, and the thus developed model successfully predicted its degradation kinetics under different conditions. Effects of typical influencing factors such as BA concentrations and UV intensity were investigated quantitatively by the model. Temperature was found to be an important influencing factor in the VUV system, and the quantum yield of •OH showed a positive linear dependence on temperature. Impacts of humic acid (HA), alkalinity, chloride, and water matrices (realistic waters) on the oxidation efficiency were also examined. BA degradation was significantly inhibited by HA due to its scavenging of •OH, but was influenced much less by the alkalinity and chloride; high oxidation efficiency was still obtained in the realistic water. The degradation kinetics of three other typical micropollutants including bisphenol A (BPA), nitrobenzene (NB) and dimethyl phthalate (DMP), and the mixture of co-existing BA, BPA and DMP were further studied, and the developed model predicted the experimental data well, especially in realistic water. It is expected that this study will provide an effective approach to predict the degradation of organic micropollutants by the promising VUV system, and broaden the application of VUV system in water treatment.

Development of two-channel prototype ITER vacuum ultraviolet spectrometer with back-illuminated charge-coupled device and microchannel plate detectors

A vacuum ultraviolet (VUV) spectrometer of a five-channel spectral system is designed for ITER main plasma impurity measurement. To develop and verify the system design, a two-channel prototype system is fabricated with No. 3 (14.4-31.8 nm) and No. 4 (29.0-60.0 nm) among the five channels. The optical system consists of a collimating mirror to collect the light from source to slit, two holographic diffraction gratings with toroidal geometry, and two different electronic detectors. For the test of the prototype system, a hollow cathode lamp is used as a light source. To find the appropriate detector for ITER VUV system, two kinds of detectors of the back-illuminated charge-coupled device and the microchannel plate electron multiplier are tested, and their performance has been investigated.

Continuous calibration of a vacuum ultraviolet system from 65 to 125 nm by a cascade arc and comparison with the calibrated line radiation of a hollow cathode

A high-power stationary helium cascade arc has been developed as a standard source for continuum radiation in the VUV spectral range from 65 to 125 nm. The calibration of the VUV system response was based on the calculated and measured continuum radiation of a 2-mmphi pure He arc. Diagnostics of the arc plasma in partial thermal equilibrium yielded the electron density and the temperature that were inserted in the calculations of the continuous radiation. The results were compared with the helium, argon, and krypton radiation lines of a high-current hollow cathode lamp. This lamp was built according to the construction drawings of a hollow cathode, which was calibrated by means of the electron synchrotron radiation at the Physikalisch Technische Bundesanstalt Berlin.

Intensity calibration of a VUV system by branching line pairs of low ionized light atoms

A method for determining the relative sensitivity of a vacuum ultraviolet (VUV) monochromator is described for the wavelength region from 200 to 1200 A. Eleven VUV line pairs of low ionized atoms of nitrogen and oxygen are selected for which recent data of transition probabilities or branching ratios are available. Calibration is made by measuring the intensity ratios of these line pairs emitted from a stationary helium plasma into which a nitrogen or an oxygen gas is introduced. The results are in good agreement with those obtained using the usual atomic branching ratio method for hydrogen and helium.

Absolute cross sections for excited Ba iii states produced by single-electron impact from Ba i

Absolute cross sections for simultaneous double ionization and excitation of Ba by electron impact have been measured in a crossed-beam experiment. The lines investigated are at 74.3, 58.7, and 55.5 nm. The vacuum-ultraviolet system was calibrated using a single-ionization chamber. Absolute cross sections were derived by comparison with the known excitation function of the Ba I resonance line at 553.5 nm.

Ultraviolet and Vacuum Ultraviolet Systems

Ultraviolet and Vacuum Ultraviolet Systems