Vacuum Ultraviolet Research Articles

Efficient photo-dissociation-induced production of hydrogen radicals using vacuum ultraviolet light from a laser-produced plasma

One of the critical issues in lithography using extreme ultraviolet (EUV) light is tin contamination of the EUV collector mirrors in the tin-based LPP-EUV light source. The contamination can be removed by the reaction of tin atoms with hydrogen radicals producing stannane (SnH4), which is gaseous at the normal temperature. Hydrogen radicals can be produced from hydrogen molecules through photo-dissociation and photo-ionization induced by broadband radiation emitted from the EUV light source. In this work, an efficient production of hydrogen radical using vacuum ultraviolet (VUV) light emitted from laser-produced high-Z plasma is experimentally demonstrated. A two-dimensional radiation hydrodynamic simulation, coupled with photoionization and photo-dissociation cross sections, also shows the efficient hydrogen radical production by increased VUV light emission, as observed in the experiment.

Self-aspiration sampling design for rapid analyses of volatile organic compounds based on atmospheric pressure chemical ionization/photoionization combined ionization source mass spectrometry.

Development of combined mass spectrometry ionization sources has enabled expansion of the application and scope of mass spectrometry. A novel hybrid ionization system combining vacuum ultraviolet (VUV) and atmospheric pressure chemical ionization (APCI) was constructed. Gaseous samples were self-aspirated into an ionization zone through a capillary by negative pressure, generated by high-speed airflow based on the Venturi effect. Compared with APCI mode alone, the signal-to-noise ratio (S/N) in APCI/VUV mode was increased by about 276-times. To increase the ionization efficiency further, correlated experimental conditions were optimized. Four types of volatile organic compounds (VOCs) were tested to evaluate the performance of the APCI/VUV ion source. Excellent linearity and limit of detection were achieved for compounds in mixed solutions. Quantitative analyses of four VOCs (toluene, cyclohexanone, styrene and ethylbenzene) using APCI/VUV-MS were done, and the relative standard deviations (RSDs) were 1.57%, 6.30%, 4.49% and 8.21%, respectively, indicating that the APCI/VUV ionization source had excellent reproducibility. Our results demonstrated that the developed method was promising for analyzing VOCs as well as being rapid, simple, and easy to operate.

Mechanisms of controlled stabilizer-free synthesis of gold nanoparticles in liquid aerosol containing plasma.

The interaction between low-temperature plasma and liquid enables highly reactive solution phase chemistry and fast reaction kinetics. In this work, we demonstrate the rapid synthesis of stabilizer-free, spherical and crystalline gold nanoparticles (AuNP). More than 70% of gold ion complex (AuCl- 4) conversion is achieved within a droplet residence time in the plasma of ∼10 ms. The average size of the AuNPs increases with an increase in the droplet residence time and the particle synthesis showed a power threshold effect suggesting the applicability of the classical nucleation theory. Leveraging UV-vis absorption and emission spectroscopy, and nanoparticle size distributions obtained from TEM measurements, we showed that the AuCl- 4 conversion exceeded by 250 times the maximum faradaic efficiency. We identified important roles of both short-lived reducing species including solvated electrons and possibly vacuum ultraviolet (VUV) photons, and long-lived species, H2O2, in the reduction of AuCl- 4. A quantitative investigation was performed by a 1-D reaction-diffusion model which includes transport, plasma-enabled interfacial reduction of AuCl- 4, classical nucleation, monomer absorption and autocatalytic surface growth enabled by H2O2. The model shows good agreement with the experimental results. The timescale analysis of the simulation revealed that nucleation is enabled by fast reduction of gold ions, and autocatalytic growth mainly determines the particle size and is responsible for the majority of the ion precursor conversion while also explaining the excessively large faradaic efficiency found experimentally.

Two-photon chemistry of tetrahydrofuran in clathrate hydrates.

High-lying electronic states hold the potential for new and unusual photochemical reactions. However, for conventional single-photon excitation in the condensed phase, reaching these states is often not possible because the vacuum-ultraviolet (VUV) light required is competitively absorbed by the surrounding matrix rather than the molecule of interest. Here, this hurdle is overcome by leveraging nonresonant two-photon absorption (2PA) at 265 nm to achieve preferential photolysis of tetrahydrofuran (THF) trapped within a clathrate hydrate network at 77 K. Electron spin resonance (ESR) spectroscopy enables direct observation and identification of otherwise short-lived organic radicals stabilized by the clathrate cages, providing clues into the rapid dynamics that immediately follow photoexcitation. 2PA induces extensive fragmentation of enclathrated THF yielding 1-alkyl, acyl, allyl and methyl radicals-a stark departure from the reactive motifs commonly reported in γ-irradiated hydrates. We speculate on the undetected transient dynamics and explore the potential role of trapped electrons generated from water and THF. This demonstration of nonresonant two-photon chemistry presents an alternative approach to targeted condensed phase photochemistry in the VUV energy range.

Flux and fluence effects on the vacuum-UV photodesorption and photoprocessing of CO2 ices.

CO2 is a major component of the icy mantles surrounding dust grains in planet and star formation regions. Understanding its photodesorption is crucial for explaining gas phase abundances in the coldest environments of the interstellar medium irradiated by vacuum-UV (VUV) photons. Photodesorption yields determined experimentally from CO2 samples grown at low temperatures (T = 15 K) have been found to be very sensitive to experimental methods and conditions. Several mechanisms have been suggested for explaining the desorption of CO2, O2 and CO from CO2 ices. In the present study, the cross-sections characterizing the dynamics of photodesorption as a function of photon fluence (determined from released molecules in the gas phase) and of ice composition modification (determined in situ in the solid phase) are compared for the first time for different photon flux conditions (from 7.3 × 1012 photon per s cm-2 to 2.2× 1014 photon per s cm-2) using monochromatic synchrotron radiation in the VUV range (on the DESIRS beamline at SOLEIL). This approach reveals that CO and O2 desorptions are decorrelated from that of CO2. CO and O2 photodesorption yields depend on photon flux conditions and can be linked to surface chemistry. In contrast, the photodesorption yield of CO2 is independent of the photon flux conditions and can be linked to bulk ice chemical modification, consistently with indirect desorption induced by an electronic transition (DIET) process.

Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde.

The reaction of unsaturated compounds with ozone (O3) is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs with different functionality, i.e. acetaldehyde oxide (CH3CHOO) and glyoxal oxide (CHOCHOO) formed in the ozone-assisted oxidation reaction of crotanaldehyde (CA), is investigated over a temperature range between 390 K and 840 K in an atmospheric pressure jet-stirred reactor (JSR) at a residence time of 1.3 s, stoichiometry of 0.5 with a mixture of 1% crotonaldehyde, 10% O2, at an fixed ozone concentration of 1000 ppm and 89% Ar dilution. Molecular-beam mass spectrometry in conjunction with single photon tunable synchrotron vacuum-ultraviolet (VUV) radiation is used to identify elusive intermediates by means of experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, which is below the temperature where the oxidation reaction of CA was observed in the absence of ozone. The observed CA + O3 product, C4H6O4, is found to be linked to a ketohydroperoxide (2-hydroperoxy-3-oxobutanal) resulting from the isomerization of the primary ozonide. Products corresponding to the CIs uni- and bi-molecular reactions were observed and identified. A network of CI reactions is identified in the temperature region below 600 K, characterized by CIs bimolecular reactions with species like aldehydes, i.e., formaldehyde, acetaldehyde, and crotonaldehyde and alkenes, i.e., ethene and propene. The region below 600 K is also characterized by the formation of important amounts of typical low-temperature oxidation products, such as hydrogen peroxide (H2O2), methyl hydroperoxide (CH3OOH), and ethyl hydroperoxide (C2H5OOH). Detection of additional oxygenated species such as alcohols, ketene, and aldehydes are indicative of multiple active oxidation routes. This study provides important information about the initial step involved in the CIs assisted oligomerization reactions in complex reactive environments where CIs with different functionalities are reacting simultaneously. It provides new mechanistic insights into ozone-assisted oxidation reactions of unsaturated aldehydes, which is critical for the development of improved atmospheric and combustion kinetics models.

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry.

The signal levels observed from mass spectrometers coupled by molecular beam sampling to shock tubes are impacted by dynamic pressures in the spectrometer due to rapid pressure changes in the shock tube. Accounting for the impact of the pressure changes is essential if absolute concentrations of species are to be measured. Obtaining such a correction for spectrometers operated with vacuum ultra violet photoionization has been challenging. We present here a new external calibration method which uses VUV-photoionization of CO2 to develop time-dependent corrections to species concentration/time profiles from which kinetic data can be extracted. The experiments were performed with the ICARE-HRRST (high repetition rate shock tube) at the DESIRS beamline of synchrotron SOLEIL. The calibration experiments were performed at temperatures and pressures behind reflected shock waves of 1376 ± 12 K and 6.6 ± 0.1 bar, respectively. Pyrolytic experiments with two aromatic species, toluene (T5 = 1362 ± 22 K, P5 = 6.6 ± 0.2 bar) and ethylbenzene (T5 = 1327 ± 18 K, P5 = 6.7 ± 0.2 bar), are analyzed to test the method. Time dependent concentrations for molecular and radical species were corrected with the new method. The resulting signals were compared with chemical kinetic simulations using a recent mechanism for pyrolytic formation of polycyclic aromatic hydrocarbons. Excellent agreement was obtained between the experimental data and simulations, without adjustment of the model, demonstrating the validity of the external calibration method.

Method development and evaluation of product gas mixture from a semi-industrial scale fluidized bed steam cracker with GC-VUV

Steam cracking in fluidized beds offers an alternative to conventional steam cracking for sustainable hydrocarbon production. This approach has gained interest, particularly in the context of recycling plastics to generate valuable hydrocarbons. Integrating this process into existing petrochemical clusters necessitates a thorough characterization of the products derived from this new feedstock. This work focuses on addressing the challenges associated with species quantification and characterization time for assessing the product mixture resulting from a steam cracking process. The experiments were conducted in a semi-industrial scale dual fluidized bed steam cracker, utilizing polyethylene as the feedstock. To sample species spanning from C1 to C18, cooling, scrubbing, and adsorption were introduced. These steps were integrated with GC-VUV (Gas Chromatography with Vacuum Ultraviolet Spectroscopy) and other widely recognized analytical methods to quantify the sampled species. The primary focus was on GC-VUV analysis as a suitable characterization method for identifying and quantifying C4 to C18 species, which can constitute up to 35% of the product mixture obtained from polyethylene steam cracking (750 °C to 850 °C). Quantifying C6 to C18 hydrocarbons becomes the time-critical step, with GC-VUV potentially achieving this in 1/6th of the analysis time and with relatively optimal quantification compared to the traditional characterization methods.

Electronic energy transfer ionization in naphthalene-CO2 clusters reveals excited states of dry ice.

Electronic energy relaxation and transfer shapes the photochemistry in molecules and materials that are exposed to UV radiation in areas ranging from astrochemistry to biology. The interaction between CO2 and polycyclic aromatic hydrocarbons (PAHs) specifically, is of paramount interest in astrochemically relevant ices, the transition to renewable energy and the development of green chemistry. We investigate the vacuum UV excitation of the naphthalene-CO2 complex and observe excited states of CO2 through a newly identified molecular electronic energy transfer ionization mechanism. We evaluate the spectral development upon cluster growth with time-dependent density functional theory and show that the photoionization spectrum of naphthalene-CO2 closely resembles the photon-stimulated desorption spectrum of CO2 ice. The molecular electronic energy transfer ionization mechanism may affect the energy redistribution and charge balance in the interstellar medium significantly and therefore we discuss its implications for astrochemical models.

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 Photolysis of Condensed Methyl Chloride in Interstellar Model Conditions and Trapping of Intermediates at Intergrain Interfaces

Vacuum Ultraviolet Photolysis of Condensed Methyl Chloride in Interstellar Model Conditions and Trapping of Intermediates at Intergrain Interfaces

Highly efficient reduction of bromate by vacuum UV/sulfite system

Bromate (BrO3-), a worldwide regulated by-product after ozone disinfection, is often detected in bromide-containing water, and has a strict limit of 10 μg L−1 in potable water. BrO3- degradation by advanced reduction processes (ARPs) has gained much attention because of efficient removal and easy integration with ultraviolet disinfection (UV at 254 nm). In the vacuum UV (VUV, 185/254 nm)/sulfite system, the elimination kinetics of BrO3− increased by 9-fold and 15-fold comparing with VUV alone and UV/sulfite system. This study further demonstrated the hydrated electron (eaq-) works as the dominant species in BrO3- degradation in alkaline solution, while in the acidic solution the H• became a secondary reactive species besides eaq−. Hence, the influences of pH, sulfite concentration, dissolved gas and water matrix on effectiveness of degradation kinetics of BrO3- was explored in details. With increasing pH, the proportion of SO32− species increased and even became the major ones, which also correlated well with the kobs (min−1) of BrO3− degradation. The stability of eaq− also climbs with increasing pH, while that of H• drops significantly. Higher sulfite dosage favored a more rapid degradation of BrO3−. The presence of dissolved oxygen inhibited BrO3- removal due to the scavenging effect of O2 toward eaq− and transformed VUV/sulfite-based ARP to an advanced oxidation process (AOP), which was ineffective for BrO3- removal. BrO3- removal was inhibited to varying degrees after anions (e.g., bicarbonate (HCO3−), chloride (Cl−), nitrate (NO3−)) and humic acid (HA) being added.

Identification of electronic dimensionality reduction in semiconductor quantum well structures

Two-dimensional (2D) systems, such as high-temperature superconductors, surface states of topological insulators, and layered materials, have been intensively studied using vacuum-ultraviolet (VUV) angle-resolved photoemission spectroscopy (ARPES). In semiconductor films (heterostructures), quantum well (QW) states arise due to electron/hole accumulations at the surface (interface). The quantized states due to quantum confinement can be observed by VUV-ARPES, while the periodic intensity modulations along the surface normal (kz) direction of these quantized states are also observable by varying incident photon energy, resembling three-dimensional (3D) band dispersion. We have conducted soft X-ray (SX) ARPES measurements on thick and ultrathin III-V semiconductor InSb(001) films to investigate the electronic dimensionality reduction in semiconductor QWs. In addition to the dissipation of the kz dispersion, the SX-ARPES observations demonstrate the changes of the symmetry and periodicity of the Brillouin zone in the ultrathin film as 2D QW compared with these of the 3D bulk one, indicating the electronic dimensionality reduction of the 3D bulk band dispersion caused by the quantum confinement. The results provide a critical diagnosis using SX-ARPES for the dimensionality reduction in semiconductor QW structures.

A solar-blind vacuum-ultraviolet photodetector based on free-standing lamellar aluminum nitride single crystal

High-quality aluminum nitride (AlN) crystals are the key material for the development of high-performance solid-state solar-blind vacuum-ultraviolet (VUV) photodetectors. However, the commonly used epitaxial method to grow AlN crystals would limit this development due to the existence of indispensable substrates. This study addresses this issue using free-standing lamellar AlN single crystals that are grown using the physical vapor transport method. The large lateral dimension of the crystal enables the construction of an Au-AlN-graphene van der Waals heterojunction, which can function as a vertical VUV photodetector with the graphene serving as the light window. The asymmetric junctions formed on the two sides of the crystal and the limited penetration of the VUV endow the device with a bias polarity-dependent photoresponse feature arising from different photoelectric processes. Furthermore, the device demonstrates a high responsivity of 5.77 A W−1 and a high specific detectivity of 1.71 × 1013 cm Hz1/2 W−1 under the illumination of a 193 nm laser. The high crystallinity of the AlN guarantees a high spectral selectivity of responsivity with a 193 nm/280 nm rejection ratio of 3 × 102. This work would inspire the development of wide-bandgap-semiconductor-based VUV photodetectors in terms of methodology and mechanism.

Observation of Continuum State Dissociation Enables the Determination of N2 Bond Dissociation Energy to Spectroscopic Accuracy.

Nitrogen (N) is one of the most fundamental elements of life. Precise determination of the bond dissociation energy (BDE) of the corresponding homonuclear diatomic molecule N2 is not only important for calculating the enthalpies of formation for any N-containing molecules but also provides the best benchmark for evaluating theoretical computational methods. Thus, it has attracted many experimental and theoretical studies, while controversies still exist. Here, we report the observation of continuum state dissociation of N2 into the channel N(2D5/2,3/2)+N(2D5/2,3/2) for the first time by using the vacuum ultraviolet (VUV)-pump-VUV-probe time-sliced velocity-mapped imaging setup. The quantum-state-resolved images enable the direct visualization of the dissociation onsets corresponding to each of the correlated spin-orbit fine-structure channels within a few tenths of wavenumber. The BDEs of 14N2 and 15N2 are directly determined to be 78691.8 ± 0.3 cm-1 and 78731.5 ± 0.3 cm-1, respectively, which should represent the most accurate BDE of N2 thus far.

Reductive degradation mechanism of perfluorooctanoic acid (PFOA) during vacuum ultraviolet (VUV) reactions combining with sulfite and iodide

In this study, PFOA removal and defluorination were examined during vacuum ultraviolet (VUV) photolysis in the presence of sulfite and sulfite/iodide conditions. PFOA (24 μM) degradation rate constant (kobs) and defluorination amount in VUV photolysis, and VUV/sulfite, and VUV/sulfite/iodide reactions under nitrogen-purging condition were 5.50 × 10−3, 7.26 × 10−2, 1.60 × 10−1 min−1, and 34.6, 72.7, 73.9% in 6 h, respectively. When tert-butanol (t-BuOH), NO2−, and NO3− ions were added as radical scavengers, hydrated electrons (eaq−) was confirmed as the main species responsible for degrading PFOA and mediating defluorination in VUV-based reactions. While, during VUV photolysis, short-chain perfluoroalkyl carboxylic acids (PFCAs), such as PFHpA, PFHxA, PFPeA, and PFBA, were mainly produced as transformation products (TPs) by the chain-shortening mechanism, additional 14 and 15 TPs were identified in the VUV/sulfite and VUV/sulfite/iodide reactions by LC-QTOF/MS, respectively. The main degradation mechanisms in these reactions are H–F exchange (e.g., TP395 (m/z = 394.9739) and TP377 (m/z = 376.9838)), •SO3−–F exchange (TP474, m/z = 474.9323), carbon double bond formation by defluorination (e.g., TP392 (m/z = 392.9455), TP410 (m/z = 410.9355), and TP436 (m/z = 436.9347)), and H–F exchange followed by hydration reaction (TP393, m/z = 392.9773), respectively. PFOA degradation pathways were proposed for these VUV-based reactions based on the identified TPs, their time profiles, and the density functional theory (DFT). Finally, the toxicity of PFOA and its TPs produced during three reactions were assessed using ECOSAR simulation.

Impact of vacuum ultraviolet (VUV) intensity on the performance of VUV irradiation for the mineralization of trimethoprim in neutral media: Kinetics, mechanisms, and by-products formation.

A comparative study on the mineralization of antibiotic trimethoprim (TMP) in neutral medium was investigated by applying irradiation with five types of ultraviolet lamps. Among these lamps, the whole envelope of one lamp contained ordinary quartz, which could only transmit ultraviolet-C (UVC) light. For the other four lamps, approximately one tenth, a quarter, a half, and full of envelopes were comprised of high-purity synthetic quartz, which can transmit both vacuum ultraviolet (VUV) and UVC light. TMP decay was well fitted to pseudo-first-order reaction kinetics and occurred more quickly as the VUV intensity increased. Poor mineralization was achieved in the absence of VUV light, whereas the mineralization efficiency was also enhanced with increasing VUV intensity. The presence of hydroxyl radicals (•OH), superoxide radicals (O2•-) and singlet oxygen (1O2) during VUV photolysis of water was confirmed by electron paramagnetic resonance (EPR) analysis. Appropriate radical quenching experiments and fluorescent molecular probe detection provided the evidence that •OH played a significant role in TMP mineralization. Higher VUV intensity favored the generation of H2O2 and •OH. The evolution of NH4+ and NO3- as well as carboxylic acids (formic, acetic, oxalic, and oxamic acids) released in the treated solution were quantified. Ten aromatic intermediates were also identified by UPLC-QTOF-MS. Thereby, a plausible reaction sequence for TMP mineralization in VUV/UVC photolysis was finally proposed.

Photo-anammox by vacuum ultraviolet tandem chlorine

Excessive ammonia (NH4+) discharge can lead to algal blooms and disrupt water sustainability, so its control is imperative. Although microbiology-triggered anammox process is promising, its application is limited due to time-consuming cultivation of specific microorganisms and need for skilled operation. To bypass these barriers, this study proposed and verified a photo-induced anammox technology that removes NH4+ and total nitrogen (TN) from water by ultraviolet (UV)/vacuum UV (VUV)/chlorine under anoxic conditions. Under the Cl/N mass ratio of 5:1, the anoxic VUV/UV/chlorine process achieved 66.8% removal of 10 mg-N/L NH4+ within 10 min along with 57.8% reduction in TN. Besides the evidence from TN loss, this study confirmed nitrogen gas (N2) as the primary degradation product at low dissolved oxygen (DO) concentration of 2.0 mg/L. The selective conversion of NH4+ into N2 was mainly attributed to reactive nitrogen species (RNS, 42.5%) and reactive chlorine species (RCS, 57.5%). The TN removal efficiency was insensitive to certain variations of pH (7.0–9.0), NH4+ concentration (1–30 mg-N/L), chloride (50–125 mg/L), and sulfate (25–100 mg/L), but sensitive to DO and bicarbonate (25–100 mg/L). Given its robustness and high efficiency, the anoxic VUV/UV/chlorine technology may serve as a potentially promising alternative for NH4+ and TN alleviation in wastewater.

Novel vacuum UV/ozone/peroxymonosulfate process for efficient degradation of levofloxacin: Performance evaluation and mechanism insight

Vacuum UV (VUV) irradiation has advantage in coupling oxidants for organics removal because VUV can dissociate water to produce reactive oxygen species (ROS) in situ and decompose oxidants rapidly. In this study, the synergistic activation of peroxymonosulfate (PMS) by VUV and ozone (O3) was explored via developing a novel integrated VUV/O3/PMS process, and the performance and mechanisms of VUV/O3/PMS for levofloxacin (LEV) degradation were investigated systematically. Results indicated that VUV/O3/PMS could effectively degrade LEV, and the degradation rate was 1.67–18.79 times of its sub-processes. Effects of PMS dosage, O3 dosage, solution pH, anions, and natural organic matter on LEV removal by VUV/O3/PMS were also studied. Besides, hydroxyl radical and sulfate radical were main ROS with contributions of 49.7% and 17.4%, respectively. Moreover, the degradation pathways of LEV in VUV/O3/PMS process were speculated based on density functional theory calculation and by-products detection. Furthermore, synergistic reaction mechanisms in VUV/O3/PMS process were proposed. The energy consumption of VUV/O3/PMS decreased by 22.6%− 88.1% compared to its sub-processes. Finally, the integrated VUV/O3/PMS process showed satisfactory results in removing LEV in actual waters, manifesting VUV/O3/PMS had great application potential and feasibility in removing organics in wastewater reuse.

Ecotoxicity and rapid degradation of quaternary ammonium compounds (QACs) subjected to combined vacuum UV and UV-C treatment

Quaternary ammonium compounds (QACs) are active ingredients in a palette of commercially available disinfectants, sanitizers, and biocides. QACs are widely used because of their broad-spectrum antimicrobial properties but the ubiquitous uses have resulted in frequent detection in aquatic and terrestrial matrices including domestic wastewater, surface waters, urban soils and sediments. An increased domestic QACs consumption has increased the environmental occurrence, and investigation of mitigation methods and effects on non-target organisms are in demand. In this study, we examined the potential ecotoxicity of six QACs and investigated the effect of combined vacuum UV (185 nm) and UV-C (254 nm) irradiation (VUV/UVC) on degradation and mitigation of ecotoxicity of QACs. The study showed that combined VUV/UVC irradiation facilitated rapid degradation of benzalkonium chloride, benzethonium chloride, didecyldimethylammonium chloride, dodecyltrimethylammonium chloride, and hexadecyltrimethylammonium chloride. The estimated half-lives varied between 2 and 7 min, and degradation was affected by the initial QAC concentrations, the UV fluence, and the water matrix. The potential ecotoxicity of QACs and VUV/UVC treated QACs was examined using a battery of test organisms that included the luminescent bacterium Aliivibrio fischeri, the gram-negative and gram-positive bacteria Escherichiacoli and Enterococcus faecalis, the freshwater microalga Raphidocelis subcapitata, and the crustacean Daphia magna. The potential for trophic transfer of QACs was investigated in a simplified aquatic food web. Test organisms from different trophic levels were included to assess adverse effects of bioactive compounds in VUV/UVC treated samples including transformation products. The study showed that several QACs were highly toxic to aquatic test organisms with EC50 and/or EC20 values < 1 μM. VUV/UVC treatment of QACs resulted in substantial photolysis of the parent compounds and comprehensive mitigation of the ecotoxicity potential. VUV/UVC represent an attractive oxidation technology for abatement QACs in contaminated water because the process does not require addition of catalysts or precursors.