UV-based Advanced Oxidation Processes Research Articles

Unveiling the optical and molecular characteristics of aging microplastics derived dissolved organic matter transformed by UV/chlor(am)ine oxidation and its potential for disinfection byproducts formation

The investigations into the existence and behavior of microplastics (MPs) in water environment were widely conducted, while the characteristics of dissolved organic matter derived from MPs (MPs-DOM) during advanced oxidation have garnered comparatively little attention. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was employed along with multiple statistical analyses to gain a deeper understanding of the conversion of MPs-DOM in UV/chlor(am)ine advanced oxidation processes (AOPs). The diverse treatments exhibited varying degrees of augmentation in both aging and fragmentation of MPs with the order of UV/Cl2 > UV > UV/NH2Cl. The fragmentation degree of MPs upon two UV-based AOPs (UV-AOPs) was dependent on their monomer chemical structure. The highest TOC values of three MPs-DOM were observed after UV/Cl2 AOP and the lowest after UV/NH2Cl AOP. Polyvinyl chloride (PVC) displayed a greater release of MPs-DOM under varying leaching conditions. UV/Cl₂ AOP favored the reaction with saturated MPs-DOM, while UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating disinfection byproducts (DBPs) formation after chlorination. The precursors generated by UV/Cl₂ AOP owned lower H/C, higher modified aromatic index (AImod), and lower molecular weight (MW) products after chlorination. PVC-DOM with fewer CH₂ groups was more reactive. -H₂O, +O and -CH₂ reactions dominated in PVC-DOM (CHO compounds), while -2H, +O, -CH₂ did in PVC-DOM (CHON compounds). The dominant chlorine addition/substitution reactions occurred in PVC-DOM treated by UV/Cl₂ AOP, identifying 195 Cl-DBPs with 220 precursor-product pairs. Mass difference analyses showed that +2H and +O reactions were the most frequent of the 24 reaction types. Environmental ImplicationMicroplastics derived dissolved organic matters (MPs-DOM) transformed into disinfection byproducts (DBPs) under advanced oxidation processes (AOPs), heightening environmental risks. In this study, Fourier transform ion cyclotron resonance mass spectrometry was employed to gain a deeper understanding of MPs-DOM conversion in UV/chlor(am)ine AOPs. MPs fragmentation and fluorescent components varied with monomer chemistry and polymers. UV/Cl₂ AOP reacted with saturated MPs-DOM. UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating DBPs formation. DBPs precursors generated by UV/Cl₂ AOP owned higher modified aromatic index, lower H/C and molecular weight. Unveiling the MPs-DOM transformation during AOPs can mitigate the negative environmental impacts of MPs and their derivatives.

Transformation of dissolved organic matter leached from biodegradable and conventional microplastics under UV/chlorine treatment and the subsequent effect on contaminant removal

The ultraviolet (UV)/chlorine process has been widely applied for water treatment. However, the transformation of microplastic-leached dissolved organic matter (MP-DOM) in advanced treatment of real wastewater remains unclear. Here, we investigated alterations in the photoproperties of MP-DOM leached from biodegradable and conventional microplastics (MPs) and their subsequent effects on the degradation of sulfamethazine (SMT) by the UV/chlorine process. Spectroscopy was used to assess photophysical properties, focusing on changes in light absorption capacity, functional groups, and fluorescence components, while photochemical properties were determined by calculating the apparent quantum yields of reactive intermediates (ΦRIs). For photophysical properties, our findings revealed that the degree of molecular structure modification, functional group changes, and fluorescence characteristics during UV/chlorine treatment are closely linked to the type of MPs. For photochemical properties, the ΦRIs increased with higher chlorine dosages due to the formation of new functionalities. Both singlet oxygen (1O2) and hydroxyl radicals (•OH) formation were strongly correlated with excited triplet state of DOM (3DOM*) in the UV/chlorine treatment. Additionally, we found that the four types of MP-DOM inhibit the degradation of SMT and elucidated the mechanisms behind this inhibition. We also proposed degradation pathways for SMT and assessed the ecotoxicity of the resulting intermediates. This study provides important insights into how the characteristics and transformation of MP-DOM affect contaminant degradation, which is critical for evaluating the practical application of UV-based advanced oxidation processes (UV-AOPs).

Assessing excimer far-UVC (222 nm) irradiation for advanced oxidation processes: Oxidants photochemistry and micropollutants degradation

The KrCl* excimer lamp (UV222) is a promising alternative of low-pressure mercury lamp (UV254) for UV-based advanced oxidation processes (UV-AOPs), because it is mercury-free and has high photon energy. But there lacks a comprehensive assessment of UV222-AOPs based on different radicals. Herein, the properties (e.g., oxidant decay and innate radical quantum yield), and micropollutant degradation, were comprehensively studied for representative oxidants (i.e., hydrogen peroxide, persulfate (PDS), monochloramine, and free active chlorine (FAC)) under UV222 irradiation. UV222 outperformed UV254 for the activation of oxidants with 2.6–14.4 times fluence-based kinetic constant (kF). The main reason of enhanced activation varied with oxidants: higher UV absorbance for H2O2, higher innate quantum yield for monochloramine and FAC, and both reasons for PDS. Overall, PDS was the optimum oxidant under UV222 for the degradation of 8 representative micropollutants because of effective promotion of radical formation, as confirmed by radical competitive kinetics and modeling simulations. In real water, UV222/PDS still show advantages than UV254/PDS in terms of micropollutant elimination efficacy (3.2–5.3 times) and energy consumption (33.9 %-57.6 % lower) though it was more inhibited by water constituents via competing for UV222 photons. This study fills gaps in photochemistry knowledge and will facilitate engineering practice of UV222-AOPs.

The degradation of 8 PPCPs in UV/chlorine: Effect of chloride and sulfate ions and the role of radicals

The degradation of 8 structurally diverse pharmaceuticals and personal care products (PPCPs) by UV/chlorine and the effects of Cl- and SO42- were systematically investigated. The 8 PPCPs are divided into 2 groups based on their stability under UV light. This is the first time the kinetic degradation of the 8 PPCPs in the presence of Cl- and SO42- have been intensively evaluated. The results showed that the high degradation rate of the PPCPs is attributed to their second-order rate constants towards radicals (i.e., •OH, and reactive chlorine species (RCS)). 0–500 mM Cl- enhanced kPPCPs, while this range of SO42- inhibited most of them (except in the case of ciprofloxacin (CIP)). An overview of the effect of 0–200 mM Cl-/SO42- on the degradation of micropollutants by different UV-based advanced oxidation processes (UV-AOPs) in previous studies indicates that Cl-/SO42- can cause varying effects on the degradation rate of pollutants (i.e., “increase”, “decrease”, or “no effect”), depending on the type of pollutant and the process. Cl-/SO42- did not change the trend of pH influence on the PPCPs degradation rates by UV/chlorine. Acidic and neutral conditions were favorable to the degradation of the PPCPs in all cases. Under three operating conditions (i.e., the control process, 500 mM Cl- and SO42-), [•OH]ss decreased considerably, but [Cl•]ss or ([Cl•]ss + [SO4•-]ss) slightly fluctuated when the pH was increased from 2.5 to 10.5. The synergistic effect of seawater and Cl-/SO42- significantly improved some kPPCPs, thereby, decreasing energy consumption.

Degradation of Atrazine by Flow-Through UV-Based Advanced Oxidation Processes: Roles of Light Source and Chlorine Addition

Understanding the degradation kinetics and mechanisms of trace organic contaminants (TrOCs) by UV-based advanced oxidation processes (UV-AOPs) are pivotal in realizing their efficient application in water treatment. However, the relevant knowledge in practical flow-through reactors remains a void, compared with that of commonly used batch reactors. To fill the knowledge gaps, the current work investigated the degradation of atrazine (ATZ) in flow-through UV-AOP systems with different light sources and chlorine additions. The results showed that UV/Cl2 in the reactors (with a diameter of 50 mm) was not very efficient in ATZ degradation while the pseudo-first order degradation rate constant was elevated by over 2.7 times with vacuum UV (VUV)/UV. In contrast to observations in the batch reactors, the addition of chlorine to the flow-through VUV/UV system unexpectedly decreased the rate constant by about 39%. The analysis of the relative contributions of different degradation pathways revealed that the inhibitory effect of the chlorine addition arose from the transformation of HO• to reactive chlorine species (e.g., ClO•) which had low reaction rate constants with ATZ. The baffle implementation promoted the ATZ degradation by 12–58%, mainly due to an enhanced mixing that facilitated the radical oxidation. The energy costs of the UV-AOPs in ATZ removal ranged within 0.40–1.11 kWh m−3 order−1. The findings of this work are helpful in guiding efficient VUV/UV and VUV/UV/Cl2 processes in drinking water treatment.

Molecular-level transformations of dissolved black carbon in UV-based advanced oxidation processes

Dissolved black carbon (DBC) released from biochar, is an essential group in the dissolved organic matter (DOM) pool and is widely distributed in aquatic environments. In various advanced oxidation processes (AOPs), DBC exhibits enhanced free radical scavenging compared to typical DOM, attributed to its smaller molecular weight and more compacted aromatic structure; however, the molecular-level transformations of DBC in different AOPs, such as UV/H2O2, UV/PDS, and UV/Chlorine, remain unclear. This study employed a DBC derived from wheat biochar for experimentation. Characterization involved ultraviolet-visible (UV–Vis) spectroscopy and fluorescence excitation-emission-matrix (EEM) spectroscopy, revealing the transformation of DBC through diminished SUVA254 values and reduced intensity of three-dimensional fluorescence peaks. Further insights into the transformation were gained through Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). After each UV-AOP treatment, a conspicuous augmentation in the oxygen content of DBC was observed. The detailed oxygenation processes were elucidated through mass difference analysis, based on 23 types of typical reactions. Results indicated that oxygenation reactions were most frequently detected in all three UV-AOP treatments. Specifically, the hydroxylation (+O) predominated in UV/H2O2, while the di-hydroxylation (+2O) prevailed in UV/PDS. UV/Chlorine treatments commonly exhibited tri-hydroxylation (+3O), with the identification of 1194 Cl-BPs of unknown structures. This study contributes to a comprehensive understanding of the molecular transformations of DBC induced by various free radicals in different UV-AOP processes, leading to a better understanding of the different fates of DBC in UV-AOP processes. In addition, the identification of DBC as a precursor of by-products will also contribute to the understanding of how to inhibit the generation of by-products.

Far-UVC Photolysis of Peroxydisulfate for Micropollutant Degradation in Water.

Increasing radical yields to reduce UV fluence requirement for achieving targeted removal of micropollutants in water would make UV-based advanced oxidation processes (AOPs) less energy demanding in the context of United Nations' Sustainable Development Goals and carbon neutrality. We herein demonstrate that, by switching the UV radiation source from conventional low-pressure UV at 254 nm (UV254) to emerging Far-UVC at 222 nm (UV222), the fluence-based concentration of HO• in the UV/peroxydisulfate (UV/PDS) AOP increases by 6.40, 2.89, and 6.00 times in deionized water, tap water, and surface water, respectively, with increases in the fluence-based concentration of SO4•- also by 5.06, 5.81, and 55.47 times, respectively. The enhancement to radical generation is confirmed using a kinetic model. The pseudo-first-order degradation rate constants of 16 micropollutants by the UV222/PDS AOP in surface water are predicted to be 1.94-13.71 times higher than those by the UV254/PDS AOP. Among the tested water matrix components, chloride and nitrate decrease SO4•- but increase HO• concentration in the UV222/PDS AOP. Compared to the UV254/PDS AOP, the UV222/PDS AOP decreases the formation potentials of carbonaceous disinfection byproducts (DBPs) but increases the formation potentials of nitrogenous DBPs.

Development of dissolved organic matter-based indicators to understand the degradation of organic contaminants in reverse osmosis concentrate from potable reuse systems

Reverse osmosis (RO)-based treatment of municipal wastewater effluent allows for potable reuse, but this process generates reverse osmosis concentrate (ROC) that needs further treatment before disposal. This study investigated the application of UV-based advanced oxidation processes (AOPs) to degrade nine contaminants of emerging concern (CECs) from real ROC waste streams, using UV-only and UV-AOPs with hydrogen peroxide, free chlorine, and persulfate. Dissolved organic matter (DOM) in ROC was characterized using fluorescence excitation emission matrix data and analyzed by a four-component parallel factor (PARAFAC) analysis model. UV-only treatment showed considerable removal of CECs that displayed high values of quantum yields and molar absorption coefficients. UV-AOP treatment of ROC exhibited heavy scavenging of reactive species during CEC degradation. A probe-based approach established that hydroxyl radical was the dominant reactive species in all UV-AOPs. A kinetic analysis of PARAFAC components of DOM showed that the visible humic-like and protein-like components exhibited the higher reaction kinetics compared to UV humic-like and nutrient-like components. The strong linear correlation of protein-like component and seven of the nine CECs across multiple AOPs indicated that they have similar reactivity, enabling the establishment of chemical-reactivity based surrogates for prediction CEC fate in ROC wastes.

Nitrogen-reliant degradation behaviors of characteristic NHCs by UV-based advanced oxidation processes: Kinetics, pathways and toxicity assessment

In recent decades, nitrogen-containing heterocyclic compounds (NHCs) have been widely synthesized and applied due to their excellent coordination capability of heterocyclic N atoms. However, their high toxicity and poor biodegradability pose significant hazards to aquatic ecosystems. Three characteristic NHCs (cNHCs) with similar molecular structures but minor differences in the number and position of N atoms, namely benzotriazole (BTA), benzimidazole (BMZ), and indazole (IDZ), were selected to evaluate impacts of these differences on their degradation behaviors during UV/H2O2 treatments. It was found that the key mechanism for the removal of BTA, BMZ, and IDZ in the UV/H2O2 processes was the generation of ∙OH through UV-excited H2O2 decomposition. Density functional theory (DFT) calculations revealed that the variation in the number and position of heterocyclic ring N atoms significantly affected the electron cloud distribution of the cNHCs, thereby resulting in different reactivities. Mineralization results and N evolution experiments indicated that N elements were initially released in the form of ammonia nitrogen during UV/H2O2 treatments, which then underwent oxidation to form nitrite and nitrate. The two ortho-N atoms were most easily mineralized and release inorganic nitrogen, followed by the two meta-N atoms. However, the BTA compound containing three N atoms, exhibited inertness towards radicals after hydroxylation, thereby hindering mineralization. A dual-directional transformation products (TPs) identification protocol was employed to identify 30 TPs of the cNHCs and propose recommended degradation pathways. Furthermore, Vibrio fischeri bioluminescence inhibition bioassay and QSAR prediction models were used to preliminarily screen and identify 13 toxic TPs with potential ecological risks.

Elucidating the performance of UV-based photochemical processes for the removal of trace organic contaminants: Degradation and toxicity evaluation

In this study, the performance of standalone ultraviolet (UV) photolysis and UV-based advanced oxidation processes (AOPs), namely, UV/hydrogen peroxide, UV/chlorine, UV/persulphate, and UV/permonosulphate, were investigated for the degradation of 31 trace organic contaminants (TrOCs). Under the tested conditions, standalone UV photolysis did not achieve effective removal of TrOCs. To improve the degradation efficiency of UV photolysis, four different oxidants were added individually to the test solution. The effect of these oxidants in the absence of UV irradiation was also explored and only chlorine showed promising degradation of some contaminants. During the chlorination of 31 investigated TrOCs, only six demonstrated greater than 50% degradation. The combined UV-based AOPs demonstrated much improved degradation (ranging from 65 to 100%) depending on TrOC-structure and oxidant concentration. The UV/hydrogen peroxide process showed similar degradation of TrOCs, irrespective of the functional groups (i.e., electron withdrawing groups, EWGs and electron donating groups, EDGs) present in their structures. Conversely, the UV/sulphate and UV/chlorine based processes achieved better degradation of the TrOCs with EDGs in their structures. TrOCs degradation improved up to 40% when oxidants concentrations were increased from 0.1 to 1 mM, and further increasing the concentration to 2 mM did not improve degradation. Toxicity evaluation using bioluminescence test (BLT assay) demonstrated that except for UV/hydrogen peroxide, all UV-based AOPs increased the toxicity of the treated effluent, indicating generation of toxic by-products. This study elucidates the performance of four different UV-based AOPs for the removal of commonly detected diverse TrOCs for the first time.

The various effects of hydrogen phosphate and bicarbonate in the degradation of some pollutants in the UV/chlorine and the UV/H2O2 processes

In this study, the degradation kinetics of three target pollutants (i.e., levofloxacin (LEV), P-nitrosodimethylaniline (RNO), and basic fuchsin (BF) in four UV-based Advanced Oxidation Processes (UV/AOPs) (i.e., UV/NaOCl/HPO42−, UV/NaOCl/HCO3−, UV/H2O2/HPO42−, and UV/H2O2/HCO3−) were comprehensively investigated. The results showed that LEV and RNO were resistant to UV irradiation, chlorination, and H2O2 when applied separately, but significantly degraded in UV/AOPs. The chlorination process and alkaline conditions were beneficial to the degradation of BF. In UV/AOPs, the degradation rates of the pollutants were enhanced remarkably with different rate constants which were dependent on the dosage of oxidants, and the presence of HPO42− and HCO3−. This enhancement is due to the generation of reactive species (i.e., •OH, RCS, and secondary reactive radicals like PO42•-, and CO3•-). The study also investigated the role and contribution of the reactive species to the degradation of the pollutants in UV/AOPs. The study demonstrated the difference in the degradation kinetics of the pollutants in UV/H2O2/(HPO42− or HCO3−) and UV/NaOCl/(HPO42− or HCO3−) in which the contribution of each oxidizing factor was determined. Acidic conditions were beneficial to the degradation rate of the pollutants in all UV/AOPs, except BF in UV/NaOCl. Seawater and river water were demonstrated to significantly promote the degradation rate of pollutants in UV/NaOCl/(HPO42− or HCO3−) but depressed it in UV/H2O2/(HPO42− or HCO3−). In addition, a typical PPCP (pharmaceutical and personal care product) (here LEV) was selected for further LC-MS analysis to determine its degradation pathway. The results provide a novel alternative strategy in the use of HPO42− and HCO3− in UV/NaOCl and UV/H2O2 to increase the removal efficiency of organic pollutants.

Spectroscopic analysis on effluent organic matter (EfOM) evolution in different UV-based advanced oxidation processes

The effluent organic matter (EfOM) removal performance of the advanced wastewater treatment process has drawn great attention owing to the potential ecological risk of EfOM in the receiving aquatic environments. However, the EfOM evolution process is still unclear in the various advanced wastewater treatment processes. In this study, the EfOM evolution process in terms of components, structures, and functional groups was investigated in four kinds of UV-based advanced oxidation processes (AOPs). The overall EfOM removal performances were in the order: UV/NaClO > UV/PMS > UV/H2O2 > UV. According to the spectroscopic analysis results, simple aliphatics/aromatic/acetylenes compounds with C–O, =C–H, amides, or amino structures deriving from protein-like substances, are easily destroyed under UV irradiation. Apart from these structures, microbial metabolic was strongly sensitive to a reactive chlorine species (RCS)-dominated system, especially nutrients, amino acids, and small peptides with ester. Total of 22 species of halogen by-products with high biotoxicity (acetonitrile-based chlorinated EfOM, chlorinated acetate, chlorinated methane) were detected in the UV/NaClO group. In contrast, the reactive oxygen species (ROS)-dominated systems exhibited strong structure selectivity for ester (UV/H2O2) and carbonyl (UV/PMS) in all of the EfOM components, exhibiting strong reaction activity with EfOM at different stages. The results reveal the EfOM evolution in different UV-based AOPs, providing a strategy for selecting suitable UV-based AOPs in the advanced wastewater treatment process in terms of high-efficiency removal of EfOM.

Promoting multiple reactive oxygen species generation for deep oxidation of VOCs by UV/persulfate/permanganate

Advanced oxidation processes (AOPs) could effectively remove volatile organic compounds (VOCs) when coupled with wet scrubbing process. However, it still faces challenges in achieving deep oxidation of VOCs due to the limited production of reactive oxygen species (ROS). Herein, we present the utilization of permanganate (KMnO4) as a co-oxidant to enhance VOCs oxidation in UV/persulfate (PDS)/KMnO4 system. The removal efficiency of a targeted VOC, toluene, kept high at above 90% throughout the entire long-term reaction of 4 h, which was much higher than that of UV/PDS and UV/KMnO4. Notably, the in-situ formed manganese oxide (MnOx) acts as a catalyst in UV/MnOx and UV/MnOx/PDS, facilitating the generation of various ROS and thereby enhancing VOCs degradation. Electron paramagnetic resonance (EPR) and quenching experiments indicated that sulfate radical (SO4−), hydroxyl radical (HO), superoxide radical (O2−) and singlet oxygen (1O2) were the main ROS generated in the UV/PDS/KMnO4 system. The overall oxidation process can be divided into three stages: the UV/KMnO4-dominated stage, the UV/MnOx/PDS-dominated stage, and the UV/MnOx-dominated stage. Correspondingly, HO played a major role in toluene oxidation in the UV/KMnO4-dominated and UV/MnOx-dominated stages, with the contributions of 48% and 52%, respectively. Meanwhile, SO4− played a more significant role in the UV/MnOx/PDS-dominated stage, with a contribution of 59%. Three main reaction pathways involving electron abstraction, HO addition and benzene ring opening were proposed based on the intermediates identified by proton-transfer-reaction mass spectrometry (PTR-MS). This study provided a deep understanding of KMnO4 in improving the oxidation capacity of UV-based AOPs for VOCs degradation, emphasizing the importance of in-situ formed MnOx for promoting multiple ROS generation.

UV-based advanced oxidation processes in photoreactors with reflective sleeves

UV-based advanced oxidation processes (UV-based AOPs) via photolysis of radical precursor chemicals (RPCs) are among the most effective technologies for eliminating trace organic contaminants in water treatment facilities. However, mathematical discussions on the kinetics and energy consumption for the engineering photoreactor set-up of UV-based AOPs, especially the newly proposed UV-based AOPs (e.g., UV/persulfate, UV/chlorine and UV/chloramine), are scarce. In this study, a photoreactor with reflective sleeves was mathematically characterized and validated using clean and complex water matrices, and approaches for measuring effective light absorbance by RPC (IRPC) and the reflectance of the photoreactor wall (η) were proposed. By applying IRPC and η, and employing geosmin as a model compound, energy optimization of the UV-based AOPs was conducted based on an updated kinetic model. A new equation was derived for UV/H2O2 to obtain the most cost-effective RPC dose regarding EE/O (electric energy required for one order of contaminant removal) (Copt-EE/O). This equation was then successfully extended to other UV-based AOPs (including UV/persulfate, UV/chlorine, and UV/chloramine). The balance between the treatment goals and operational costs was also discussed. Overall, the new concepts and approaches proposed in this study may aid in the energy optimization and reduce RPC consumption of various UV-based AOPs for engineering applications.

Degradation of 75 organic micropollutants in fresh human urine and water by UV advanced oxidation process

In household wastewater, a large proportion of organic micropollutants (OMPs) load is attributed to human urine. OMPs could pose a risk to human and environmental health when urine collected in source-separating sanitation systems is recycled as crop fertiliser. This study evaluated degradation of 75 OMPs in human urine treated by a UV-based advanced oxidation process. Fresh urine and water samples were spiked with a broad range of OMPs and fed into a photoreactor equipped with a UV lamp (185 and 254nm) that generated free radicals in situ. Degradation rate constant and the energy required to degrade 90% of all the OMPs in both matrices were determined. At a UV dose of 2060J m-2, average ΣOMP degradation of 99% (±4%) in water and 55% (±36%) in fresh urine was achieved. The energy demand for removal of OMPs in water was <1500J m-2, but for removal of OMPs in urine at least 10-fold more energy was needed. A combination of photolysis and photo-oxidation can explain the degradation of OMPs during UV treatment. Organic substances (e.g. urea, creatinine) likely inhibited degradation of OMPs in urine by competitively absorbing UV-light and scavenging free radicals. There was no reduction in the nitrogen content of urine during treatment. In summary, UV treatment can reduce the load of OMPs to urine recycling sanitation systems.

Combination of H2O2-producing microbial desalination cells and UV/H2O2 advanced oxidation process: Water salinity reduction and microbial inactivation

Microbial desalination cells (MDCs) are bioelectrochemical devices that can recover usable energy and chemicals from organic wastes and concurrently desalinate saltwater. MDCs can also produce the green oxidant, H2O2, through a two-electron oxygen reduction reaction occurring on the cathode electrode. If MDCs producing H2O2 are used in the pretreatment of brackish water or seawater for reverse osmosis (RO) processes, the salinity of feed water can be reduced in MDCs and the MDC-produced H2O2 can be utilized onsite to oxidize organic contaminants or disinfect microorganisms in the feed water. This strategy of using MDC pretreatment may substantially alleviate the energy requirements and biofouling tendency of downstream RO units. Herein, we assessed the applicability of a combination of H2O2-producing MDCs and ultraviolet (UV) or UV254nn -based advanced oxidation process (AOP) (i.e., UV/H2O2) as pretreatment for RO processes. We first examined the effect of catholyte conditions, which is one of the most crucial factors directly affecting the H2O2 composition and decomposition, on the performance of MDCs. Then, we evaluated the microorganism disinfection efficiencies of advanced photo-oxidation processes using H2O2 obtained from MDCs. The MDC investigated herein achieved 93.1% desalination efficiency and > 5.0 mM H2O2 concentration. In addition, UV-based AOP with the produced H2O2 demonstrated up to 15-fold higher inactivation kinetics than that by UV254 nm disinfection alone.

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.

A novel approach to interpret quasi-collimated beam results to support design and scale-up of vacuum UV based AOPs

UV-C at 254 nm and vacuum UV (VUV) at 185 nm are the two major emission lines of a low-pressure mercury lamp. Upon absorption of VUV photons, water molecules and selected inorganic anions generate hydroxyl (HO.) and other redox radicals, both capable of degrading organic micropollutants (OMPs), thereby offering the opportunity to reduce H2O2 and energy consumption in UV-based advanced oxidation process (AOP). To be successfully scaled-up, the dual-wavelength VUV+UV/H2O2 AOP requires laboratory-scale experiments to establish design criteria. The figures of merit typically used for reporting and interpreting quasi-collimated beam results for UV-based AOPs (time, dose, absorbed energy and EEO) are insufficient and inaccurate when employed for dual-wavelength AOP such as the VUV+UV/H2O2 AOP, and do not support system scale-up. In this study, we introduce a novel figure of merit, useful absorbed energy (uAE), defined as fraction of absorbed energy that results in the generation of oxidative radicals. Here, results of quasi-collimated beam VUV+UV/H2O2 AOP experiments on four different water matrices are used to introduce 2D plots that employ both uAEUV and uAEVUV as a novel method to represent laboratory-scale experiments of VUV+UV/H2O2 AOP and demonstrate how the 2D plots sufficiently support scale-up of the AOP.

Degradation of Antibiotics via UV-Activated Peroxodisulfate or Peroxymonosulfate: A Review

The ultraviolet (UV)/H2O2, UV/O3, UV/peroxodisulfate (PDS) and UV/peroxymonosulfate (PMS) methods are called UV-based advanced oxidation processes. In the UV/H2O2 and UV/O3 processes, the free radicals generated are hydroxyl radicals (•OH), while in the UV/PDS and UV/PMS processes, sulfate radicals (SO4•−) predominate, accompanied by •OH. SO4•− are considered to be more advantageous than •OH in degrading organic substances, so the researches on activation of PDS and PMS have become a hot spot in recent years. Especially the utilization of UV-activated PDS and PMS in removing antibiotics in water has received much attention. Some influencing factors and mechanisms are constantly investigated and discussed in the UV/PDS and UV/PMS systems toward antibiotics degradation. However, a systematic review about UV/PDS and UV/PMS in eliminating antibiotics is lacking up to now. Therefore, this review is intended to present the properties of UV sources, antibiotics, and PDS (PMS), to discuss the application of UV/PDS (PMS) in degrading antibiotics from the aspects of effect, influencing factors and mechanism, and to analyze and propose future research directions.

Comparative evaluation of MSW incineration leachate treatment by heterogeneous catalytic O3 and UV/O3: The unexpected contribution of high salinity and overlooked role of excited state

The efficiency and mechanism of heterogeneous catalytic O3 and UV/O3 for municipal solid waste (MSW) incineration leachate advanced treatment was systematically compared. Prior to comparison, catalyst used in heterogenous catalytic O3 and operation parameters for each technology were optimized. The COD removal of CuO@Al2O3/O3 under its optimal parameters was 57.2%, which failed to meet the standard (≥75%). In contrast, the COD removal by UV/O3 could be 82.3%. The superior efficiency of UV/O3 over CuO@Al2O3/O3 could be summarized into three aspects: (I) Cu bounded ·OH (≡Cu–O·) preferentially attacked hydrophilic groups, while free hydroxyl radical (·OH) was non-selective, thus UV/O3 exhibited a unique three-stage mechanism; (II) The oxidation potential of ≡Cu–O· was higher than that of ·OH, therefore was more vulnerable to the negative effect of radical self-quenching; (III) The existence of UV-induced excited states made organics in UV/O3 more active than in CuO@Al2O3/O3 system, thus high concentration of anions enhanced COD removal in UV/O3 but affected that in CuO@Al2O3/O3. The study further revealed the characteristics of heterogeneous catalytic O3 and UV/O3, and UV induced excited state should be considered in UV-based advanced oxidation processes (AOPs).