Electrical Energy Consumption of Multiscale UV-AOP Reactors for Micropollutant Removal in Drinking Water: Facilitated Prediction by Reaction Rate Constants Measured on a Mini-Fluidic Photoreaction System.

Electrical energy consumption per order (EEO) is an important figure-of-merit for the selection and optimization of ultraviolet (UV)-based advanced oxidation processes (UV-AOPs). However, EEO applications are limited by the lack of an accurate and facilitative evaluation method because EEO presents reactor property dependence. In this study, we developed an EEO prediction method for multiscale UV-AOP reactors for micropollutant removal in water. The method utilized the reaction rate constants determined in a reference reactor (e.g., mini-fluidic photoreaction system), complemented by a scale-up method that clarified the dependence of EEO on reactor properties. The predicted results of various UV-AOPs were verified experimentally in four bench/pilot-scale reactors in laboratory and a full-scale flow-through reactor (FFR) in field using sulfamethazine as a model micropollutant. For example, EEO values of 0.105 and 0.058 kWh m-3 order-1 were predicted in the FFR at H2O2 doses of 5 and 10 mg L-1, respectively, which generally agreed with verification results. Additionally, the developed method could assist the identification of appropriate reactors in the laboratory for EEO measurements, providing a valuable supplement for the EEO prediction in practice. The developed method presents acceptable accuracy, convenience, and low cost, which would significantly facilitate EEO evaluations for practical UV-AOP applications.

Protocol for UVC uridine actinometry.

Uridine contains the chromophore uracil, a base forming part of RNA. In the range 240-290 nm, the absorption spectra of uridine and DNA are very similar and correspond to the spectral inactivation sensitivity of almost all microorganisms. This makes the uridine (absorption maximum 262 nm) an ideal actinometer for determining the germicidal photon flux in the range of 240 to 290 nm. Uridine actinometry is a simple, environmental-friendly, and easy-to-operate actinometry. Thanks to the uridine absorbance spectrum, it was found to be a perfect fit for the photon flux validation of UVC systems. Conventional UV disinfection systems are generally based on low-pressure (LP) mercury lamps which emit at 254 nm. On the other hand, UV light-emitting diodes (UV-LEDs) are a relatively new source of UV light for water treatment, emitting at various wavelengths. This protocol suggests an accurate, simple, easy to operate and straightforward way to determine the photon flux of UVC systems. Contain between 1 and 3 bullet points highlighting the customization rather than the steps of the procedure.•Because of the uridine absorbance spectrum, it is an ideal actinometer for photon flux validation of UVC systems.•Initial uridine concentration and photoproduct absorbance impact the kinetic order and quantum yield.•The protocol for UVC uridine actinometry is appropriate for UV-LP and UV-LED sources for water disinfection.

Revealing photon transmission in an ultraviolet reactor: Advanced approaches for measuring fluence rate distribution in water for model validation.

Fluence rate (FR) distribution (optical field) is of great significance in the optimal design of ultraviolet (UV) reactors for disinfection or oxidation processes in water treatment. Since the 1970s, various simulation models have been developed, which can be combined with computational fluidic dynamic software to calculate the fluence delivered in a UV reactor. These models strive for experimental validation and further improvement, which is a major challenge for UV technology in water treatment. Herein, a review of the simulation models of the FR distribution in a UV reactor and the applications of the current main experimental measurement approaches including conventional flat-type UV detector, spherical actinometer, and micro-fluorescent silica detector (MFSD), is presented. Moreover, FR distributions in a UV reactor are compared between various simulation models and MFSD measurements. In addition, the main influential factors on the FR distribution, including inner-wall reflection, refraction and shadowing effects of adjacent lamps, and turbidity effect are discussed, which is helpful for improving the accuracy of the simulation models and avoiding dark regions in the reactor design. This paper provides an overview on the simulation models and measurement approaches for the FR distribution, which is helpful for the model selection in fluence calculations and gives high confidence on the optimal design of UV reactors in regard to present methods.

Practical Chemical Actinometry-A Review.

Actinometers are physical or chemical systems that can be employed to determine photon fluxes. Chemical actinometers are photochemical systems with known quantum yields that can be employed to determine accurate photon fluxes for specific photochemical reactions. This review explores in detail several practical chemical actinometers (ferrioxalate, iodide-iodate, uranyl oxalate, nitrate, uridine, hydrogen peroxide and several actinometers for the vacuum ultraviolet). Each actinometer is described with recommended conditions for its use.

A Master Equation for Photochemical Rates.

Traditionally, the general photochemical rate equation could be integrated only at two limits (high concentration and low concentration). In this paper, the general photochemical equation has been integrated to yield a master equation that is valid for any chromophore concentration. Hence, in future, data for all concentrations can be utilized in deriving the incident photon flux and/or the quantum yield for a photochemical reaction. Unfortunately, the master equation can only be used for monochromatic light sources.

Disinfection by-product formation during UV/Chlorine treatment of pesticides in a novel UV-LED reactor at 285 nm and the mitigation impact of GAC treatment.

The UV/Chlorine process has gained attention in recent years due to the high quantum yield and absorbance of the chlorine species. However, there are still many unknowns around its application as a treatment for drinking water. The potential for the formation of disinfection by-products (DBPs) is one of them. There are no studies reporting on the formation of trihalomethanes (THMs) or haloacetic acids (HAAs) in complex matrices, such as real source waters, at UV wavelengths tailored to the UV/Chlorine process, which has been possible thanks to the development of light emitting diodes (LEDs). In addition, consideration of mitigation measures that might be needed after UV/Chlorine treatment for full scale application have not been previously reported. Specifically, the novelty of this work resides in the use of an innovative reactor using UV-LEDs emitting at 285 nm for the removal of three pesticides (metaldehyde, carbetamide and mecoprop), the evaluation of THM, HAA and bromate formation in real water sources by UV/Chlorine treatment and the mitigation effect of subsequent GAC treatment. A new parameter, the applied optical dose (AOD), has been defined for UV reactors, such as the one in the present study, where the irradiated volume is non-uniform. The results showed the feasibility of using the UV/Chlorine process with LEDs, although a compromise is needed between pH and chlorine concentration to remove pesticides while minimising DBP formation. Overall, the UV/Chlorine process did not significantly increase THM or HAA formation at pH 7.9-8.2 at the studied wavelength. At acidic pH, however, THM formation potential increased up to 30% after UV/Chlorine treatment with concentrations up to 60 µg/L. HAA formation potential increased between 100 and 180%, although concentrations never exceeded 35 µg/L. In all cases, GAC treatment mitigated DBP formation, reducing THM formation potential to concentrations between 3 and 16 µg/L, and HAA formation potential between 4 and 30 µg/L.

Micropollutant Degradation by the UV/H2O2 Process: Kinetic Comparison among Various Radiation Sources.

Kinetic comparisons of micropollutant degradation by ultraviolet (UV) based advanced oxidation processes among various radiation sources are an important issue, yet this is still a challenge at present. This study investigated comparatively the kinetics of sulfamethazine (SMN) degradation by the UV/H2O2 process among three representative radiation sources, including low-pressure mercury UV (LPUV, monochromatic), medium-pressure mercury UV (MPUV, polychromatic), and vacuum UV(VUV)/UV (dual wavelengths causing different reaction mechanisms) lamps. Experiments were conducted with a newly developed mini-fluidic MPUV photoreaction system and a previously developed mini-fluidic VUV/UV photoreaction system. Measured and modeled results both indicate that the photon fluence-based SMN degradation rate constant ( kp') followed a descending order of VUV/UV/H2O2 > MPUV/H2O2 (200-300 nm) > LPUV/H2O2, and the kp' of the MPUV lamp was dependent on the wavelength range selected for photon fluence calculation. Analysis of potential errors revealed that a shorter effective path-length could have a lower error, and the maximum errors for the MPUV/H2O2 and LPUV/H2O2 processes in this study were 7.7% and 18.2%, respectively. This study has developed a new method for kinetic comparisons of micropollutant degradation by UV-AOPs among various radiation sources at bench-scale, which provides useful reference to practical applications.

Organic Pollutant Degradation in Water by the Vacuum-Ultraviolet/Ultraviolet/H2O2 Process: Inhibition and Enhancement Roles of H2O2.

A vacuum-ultraviolet/ultraviolet (VUV/UV) mercury lamp was found to be a highly efficient radiation source for UV-based advanced oxidation processes (AOPs). If this lamp could enhance the UV/H2O2 process, it would be very attractive. Hence, we have investigated sulfamethazine (SMN) degradation by the VUV/UV/H2O2 process based on a bench-scale mini-fluidic VUV/UV photoreaction system (MVPS), a pilot reactor, and a model analysis. At high [SMN]0 in the MVPS, the apparent SMN degradation rate constant ( k'app) increased with increasing H2O2 dose, while at low [SMN]0, k'app decreased with increasing H2O2 dose; this behavior was unexpected. Meanwhile, at low [SMN]0 in a pilot reactor, H2O2 induced just a slight enhancement in the VUV/UV/H2O process. A numerical simulation of the process suggested that for an integrated AOP (i.e., VUV/UV/H2O2) consisting of various component AOPs, H2O2 could inhibit the component AOPs with HO* that did not originate from H2O2 (e.g., VUV photolysis of water). The apparent H2O2 role in the integrated AOPs was dependent on the contribution comparison between component AOPs that involved HO* that did or did not originate from H2O2. These results revealed important information regarding the application of the VUV/UV/H2O2 process in water treatment.

Trace Organic Pollutant Removal by VUV/UV/chlorine Process: Feasibility Investigation for Drinking Water Treatment on a Mini-Fluidic VUV/UV Photoreaction System and a Pilot Photoreactor.

The vacuum-ultraviolet/ultraviolet/chlorine (VUV/UV/chlorine) process, with a VUV/UV mercury lamp used as the light source, was found to be a highly efficient advanced oxidation process (AOP) in a previous study. Hence, its application feasibility for trace organic pollutant removal from drinking water becomes attractive. In this work, a bench-scale mini-fluidic VUV/UV photoreaction system was used to determine the degradation kinetics of sulfamethazine (SMN), a model sulfonamide antibiotic frequently detected with trace levels in aquatic environments. Results indicated that SMN (0.1 mg L-1) could be degraded rapidly by VUV/UV/chlorine, and a synergism was observed between the VUV/UV and UV/chlorine processes. Photon-fluence based rate constants of SMN degradation were determined to be 6.76 × 103 and 8.51 × 103 m2 einstein-1 at chlorine doses of 0.05 and 0.5 mg L-1, respectively. The presence of natural organic matter in real waters significantly inhibited SMN degradation. In addition, pilot tests were conducted to explore the practical performance of the VUV/UV/chlorine process, thereby allowing electrical energy per order to be calculated for cost evaluation. The effect of flow pattern on photoreactor efficiency was also analyzed by computational fluid dynamics simulations. Both bench- and pilot-scale tests have demonstrated that the VUV/UV/chlorine process, as a new AOP, has potential applications to trace organic pollutant removal in small-scale water treatment.

Monochloramine loss mechanisms and dissolved organic matter characterization in stormwater.

Monochloramine (NH2Cl) is widely used for secondary disinfection by water utilities. However, Edmonton field stormwater sampling results have shown that NH2Cl, because of its long-lasting property, can cause stormwater contamination through outdoor potable water uses during the summer season. To protect water sources, it is important to understand NH2Cl dissipation mechanisms in stormwater. Natural organic matter (NOM) is the dominant species that contributes to NH2Cl decay in stormwater. In this research, it is proposed that NOM reacted with both NH2Cl and free chlorine through rapid and long-term reactions during NH2Cl dissipation. Based on this assumption, a kinetic model was developed and applied to estimate the NH2Cl decay in real stormwater samples, and the modeling results matched experimental data well under all the conditions. Further, the stormwater dissolved organic matter (SWDOM) collected from different neighborhoods was analyzed by Fourier transform infrared (FTIR) and fluorescence excitation-emission matrix (EEM) techniques. Humic substances were found to be dominant in SWDOM, and the samples from different neighborhoods had similar organic constituents. After reaction with excess NH2Cl, 25%-41% SWDOM fluorophores converted to inorganic components, while most of DOM remained in organic form. Humic substances as the major components in SWDON, are the dominant precursors of disinfection by-products in chloramination. Therefore, the potential reaction products of stormwater humic substances with NH2Cl should also be of concern. This research provided a useful method to estimate the NH2Cl dissipation in stormwater, and the methodology can also be applied for stormwater NH2Cl decay studies in other cities. Further, it is believed the SWDOM analysis in this research will contribute to future studies of NH2Cl NOM reaction mechanisms in both storm sewers and drinking water distribution systems.

A Green Method to Determine VUV (185 nm) Fluence Rate Based on Hydrogen Peroxide Production in Aqueous Solution.

A mini-fluidic vacuum ultraviolet/ultraviolet (VUV/UV) photoreaction system (MVPS) was developed in our previous study. Based on the MVPS, a green method to determine VUV fluence rate has been developed using the production rate of H2 O2 when water is exposed to 185 nm VUV. The H2 O2 production followed pseudo-zero-order reaction kinetics well over the first 10 min of VUV/UV exposure. This new method was well calibrated with a standard cis-cyclooctene cis-trans photoisomerization actinometer as recommended by the International Union of Pure and Applied Chemistry. The apparent quantum yield for H2 O2 production by 185 nm VUV irradiation of water was determined to be 0.024 ± 0.002. As the solution pH increased from 5.0 to 8.0, the H2 O2 production rate decreased from 0.83 to 0.40 µm min-1 . Dissolved oxygen had a negligible influence on the H2 O2 production. This study proposes a novel VUV fluence rate determination method with advantages of nontoxicity, low detection limits, low costs and convenience, and it can be used as a good alternative to traditional actinometers.

Field data analysis of active chlorine-containing stormwater samples.

Many municipalities in Canada and all over the world use chloramination for drinking water secondary disinfection to avoid DBPs formation from conventional chlorination. However, the long-lasting monochloramine (NH2Cl) disinfectant can pose a significant risk to aquatic life through its introduction into municipal storm sewer systems and thus fresh water sources by residential, commercial, and industrial water uses. To establish general total active chlorine (TAC) concentrations in discharges from storm sewers, the TAC concentration was measured in stormwater samples in Edmonton, Alberta, Canada, during the summers of 2015 and 2016 under both dry and wet weather conditions. The field-sampling results showed TAC concentration variations from 0.02 to 0.77 mg/L in summer 2015, which exceeds the discharge effluent limit of 0.02 mg/L. As compared to 2015, the TAC concentrations were significantly lower during the summer 2016 (0-0.24 mg/L), for which it is believed that the higher precipitation during summer 2016 reduced outdoor tap water uses. Since many other cities also use chloramines as disinfectants for drinking water disinfection, the TAC analysis from Edmonton may prove useful for other regions as well. Other physicochemical and biological characteristics of stormwater and storm sewer biofilm samples were also analyzed, and no significant difference was found during these two years. Higher density of AOB and NOB detected in the storm sewer biofilm of residential areas - as compared with other areas - generally correlated to high concentrations of ammonium and nitrite in this region in both of the two years, and they may have contributed to the TAC decay in the storm sewers. The NH2Cl decay laboratory experiments illustrate that dissolved organic carbon (DOC) concentration is the dominant factor in determining the NH2Cl decay rate in stormwater samples. The high DOC concentrations detected from a downstream industrial sampling location may contribute to a high stormwater NH2Cl decay rate in this area.

Monochloramine dissipation in storm sewer systems: field testing and model development.

Monochloramine (NH2Cl), as the dominant disinfectant in drinking water chloramination, can provide long-term disinfection in distribution systems. However, NH2Cl can also be discharged into storm sewer systems and cause stormwater contamination through outdoor tap water uses. In storm sewer systems, NH2Cl dissipation can occur by three pathways: (i) auto-decomposition, (ii) chemical reaction with stormwater components, and (iii) biological dissipation. In this research, a field NH2Cl dissipation test was conducted with continuous tap water discharge into a storm sewer. The results showed a fast decrease of NH2Cl concentration from the discharge point to the sampling point at the beginning of the discharge period, while the rate of decrease decreased as time passed. Based on the various pathways involved in NH2Cl decay and the field testing results, a kinetic model was developed. To describe the variation of the NH2Cl dissipation rates during the field testing, a time coefficient fT was introduced, and the relationship between fT and time was determined. After calibration through the fT coefficient, the kinetic model described the field NH2Cl dissipation process well. The model developed in this research can assist in the regulation of tap water outdoor discharge and contribute to the protection of the aquatic environment.

Experimental Assessment of Photon Fluence Rate Distributions in a Medium-Pressure UV Photoreactor.

The performance of a medium-pressure (MP) mercury lamp photoreactor is strongly influenced by the spatial photon fluence rate (PFR) distributions which are wavelength-dependent. To address this issue, PFR distributions in an MP lamp photoreactor were measured using a 360-degree response microfluorescent silica detector (MFSD). To accurately express the optical behavior in an MP photoreactor, PFR, MFSD response PFR (PFRMFSD), and effective germicidal PFR (PFRGER) were defined and compared. The measured axial and radial PFRMFSD values agreed well with the corresponding results from a simulation model (UVCalc). The PFR and PFRGER were obtained from the measured PFRMFSD by using correction factors calculated by the UVCalc. Under identical UV transmittance (254 nm) conditions (75% and 85%), the weighted average PFRGER values were 13.3-18.7% lower than the corresponding PFR values, indicating that PFRGER, rather than PFR should be used in MP photoreactor design to meet disinfection standards. Based on measured lamp output, medium absorption spectrum, MFSD response, and microbial DNA response spectrum, the detailed relationships between the PFR, PFRMFSD, and PFRGER were elucidated. This work proposes a new method for the accurate description of wavelength-dependent PFR distributions in MP photoreactors, thus providing an important tool for the optimal design of these systems.

Impact of environmental conditions on bacterial photoreactivation in wastewater effluents.

Photoreactivation is a process where ultraviolet (UV)-induced damage to the DNA of microorganisms can be reversed by exposure to near UV and visible light. To date, most photoreactivation experiments have been carried out under laboratory conditions using standard microorganisms that do not reflect the natural conditions of municipal wastewater effluents. Photoreactivation could increase the concentration of pathogens released into natural systems, leading to negative impacts on fish, shellfish, and clams. In addition, pathogen release can increase health risks of downstream activities, such as swimming. This study focused on the photoreactivation of total coliforms in municipal wastewater effluents under natural sunlight conditions. The concept of 'effective reactivation fluence' (ERF) is used to evaluate and normalize the results from various light sources for a direct comparison. ERF values higher than 30 J cm-2, in conjunction with lowered nutrient concentrations (dilution of effluents with river water), decreased the photoreactivation of total coliforms. In contrast, higher temperatures (up to 25 °C) and blocking the UV-B portion of natural sunlight using a polyethylene terephthalate (PET) bottle increased their photoreactivation. The results of this research will provide guidance to wastewater plant operators on the potential need to minimize the level of photoreactivation in effluents before the effluents were released into receiving water bodies.

Impact of inner-wall reflection on UV reactor performance as evaluated by using computational fluid dynamics: The role of diffuse reflection.

Making use of the reflected ultraviolet (UV) radiation with a reflective inner wall is a promising way to improve UV reactor performance. In this study, the impact of inner-wall reflection on UV reactor performance was evaluated in annular single-lamp UV reactors by using computational fluid dynamics, with an emphasis on the role of diffuse reflection. The UV radiation inside the reactor chamber was simulated using a calibrated discrete ordinates radiation model, which has been proven to be a reliable tool for modeling fluence rate (FR) distributions in UV reactors with a reflective inner wall. The results show that UV reactors with a highly reflective inner wall (Reflectivity = 0.80) had obviously higher FRs and reduction equivalent fluences (REFs) than those with an ordinary inner wall (Reflectivity = 0.26). The inner-wall diffuse reflection further increased the reactor REF, as a result of the elevated volume-averaged FR. The FR distribution uniformity had conditioned contributions to UV reactor performance. Specifically, in UV reactors with a plug-like flow the FR distribution uniformity contributed to the REF to some extent, while in UV reactors with a mixed flow it had little influence on the REF. This study has evaluated, for the first time, the impact of inner-wall diffuse reflection on UV reactor performance and has renewed the understanding about the contribution of FR distribution uniformity to UV reactor performance.

Sulfamethazine degradation in water by the VUV/UV process: Kinetics, mechanism and antibacterial activity determination based on a mini-fluidic VUV/UV photoreaction system.

A mini-fluidic VUV/UV photoreaction system (MVPS) was developed in our previous study, and it was demonstrated as a powerful tool for studies on pollutant degradation by the VUV/UV process. In this study, we investigated the VUV/UV photodegradation of sulfamethazine (SMN), one of the most frequently detected antibiotics in the environment. The determination methods of photochemical kinetic parameters (e.g., photon fluence-based rate constant and quantum yield) were developed based on the MVPS. The photon fluence-based reaction rate constants for SMN degradation by UV alone and VUV/UV processes were determined as 0.07 × 103 and 4.11 × 103 m2 einstein-1, respectively, while their quantum yields were calculated as 0.019 and 0.369, respectively. The second-order reaction rate constant between hydroxyl radical (HO•) and SMN was determined to be 8.9 × 109 M-1 s-1 in VUV/UV irradiation experiments, which were conducted without addition of any other chemical. The pH effect on the SMN degradation by the VUV/UV process arose principally from SMN and HO speciation. In addition, six byproducts were identified and the potential degradation pathways of SMN including hydroxylation and SO2 elimination were proposed. The antibacterial activity of the SMN solution, assessed by the growth inhibition tests of Escherichia coli, decreased by about 80% after VUV/UV treatment up to a photon fluence of 3.58 × 10-3 einstein m-2. This study has developed methods for the determination of photochemical kinetic parameters using the newly developed MVPS and has demonstrated that the VUV/UV process is an effective technology to remove sulfonamide antibiotics in water.

Pilot-scale UV/H2O2 advanced oxidation process for municipal reuse water: Assessing micropollutant degradation and estrogenic impacts on goldfish (Carassius auratus L.).

Low concentrations (ng/L-µg/L) of emerging micropollutant contaminants in municipal wastewater treatment plant effluents affect the possibility to reuse these waters. Many of those micropollutants elicit endocrine disrupting effects in aquatic organisms resulting in an alteration of the endocrine system. A potential candidate for tertiary municipal wastewater treatment of these micropollutants is ultraviolet (UV)/hydrogen peroxide (H2O2) as an advanced oxidation process (AOP) which was currently applied to treat the secondary effluent of the Gold Bar Wastewater Treatment Plant (GBWWTP) in Edmonton, AB, Canada. A new approach is presented to predict the fluence-based degradation rate constants (kf') of environmentally occurring micropollutants including carbamazepine [(0.87-1.39) × 10(-3) cm(2)/mJ] and 2,4-Dichlorophenoxyacetic acid (2,4-D) [(0.60-0.91) × 10(-3) cm(2)/mJ for 2,4-D] in a medium pressure (MP) UV/H2O2 system based on a previous bench-scale investigation. Rather than using removal rates, this approach can be used to estimate the performance of the MP UV/H2O2 process for degrading trace contaminants of concern found in municipal wastewater. In addition to the ability to track contaminant removal/degradation, evaluation of the MP UV/H2O2 process was also accomplished by identifying critical ecotoxicological endpoints (i.e., estrogenicity) of the treated wastewater. Using quantitative PCR, mRNA levels of estrogen-responsive (ER) genes ERα1, ERα2, ERß1, ERß2 and NPR as well as two aromatase encoding genes (CYP19a and CYP19b) in goldfish (Carassius auratus L.) were measured during exposure to the GBWWTP effluent before and after MP UV/H2O2 treatment (a fluence of 1000 mJ/cm(2) and 20 mg/L of H2O2) in spring, summer and fall. Elevated expression of estrogen-responsive genes in goldfish exposed to UV/H2O2 treated effluent (a 7-day exposure) suggested that the UV/H2O2 process may induce acute estrogenic disruption to goldfish principally because of the possible formation of various oxidation by-products. However, prolonged exposure of goldfish (60 days) in UV/H2O2 treated effluent showed a restoration trend of ER gene expressions, especially in the summer. Collectively, our findings provide valuable indications regarding the long-term in vivo assessment of the MP UV/H2O2 process for removing/degrading endocrine disrupting compounds detected in the municipal wastewater effluents.

VUV/UV/Chlorine as an Enhanced Advanced Oxidation Process for Organic Pollutant Removal from Water: Assessment with a Novel Mini-Fluidic VUV/UV Photoreaction System (MVPS).

Vacuum ultraviolet (VUV) and ultraviolet (UV)/chlorine processes are regarded as two of many advanced oxidation processes (AOPs). Because of the similar cost of VUV/UV and UV lamps, a combination of VUV and UV/chlorine (i.e., VUV/UV/chlorine) may enhance the removal of organic pollutants in water but without any additional power input. In this paper, a mini-fluidic VUV/UV photoreaction system (MVPS) was developed for bench-scale experiments, which could emit both VUV (185 nm) and UV (254 nm) or solely UV beams with a nearly identical UV photon fluence. The photon fluence rates of UV and VUV output by the MVPS were determined to be 8.88 × 10(-4) and 4.93 × 10(-5) einstein m(-2) s(-1), respectively. The VUV/UV/chlorine process exhibited a strong enhancement concerning the degradation of methylene blue (MB, a model organic pollutant) as compared to the total performance of the VUV/UV and UV/chlorine processes, although the photon fluence of the VUV only accounted for 5.6% of that of the UV. An acidic pH favored MB degradation by the VUV/UV/chlorine process. The synergistic mechanism of the VUV/UV/chlorine process was mainly ascribed to the effective use of (•)OH for pollutant removal through formation of longer-lived secondary radicals (e.g., (•)OCl). This study demonstrates that the new VUV/UV/chlorine process, as an enhanced AOP, can be applied as a highly effective and energy-saving technology for small-scale water and wastewater treatment.

Application of Engineered Si Nanoparticles in Light-Induced Advanced Oxidation Remediation of a Water-Borne Model Contaminant.

Surface-engineered amphiphilic polymer-coated silicon nanoparticles (SiNPs) were employed as photocatalysts to capture and degrade a model organic contaminant (methanol) in water. This study represents the first time SiNPs have been employed in the initiation of advanced oxidation processes that are commonly used to degrade organic constituents in industrial wastewaters. The quantum yield of photocatalytic methanol oxidation and the corresponding yield factor for the generation of active OH radicals are reported. The size and surface defect dependent photocatalytic activity of SiNPs was investigated. The yield factors (η) decreased with increasing particle size and reached impressive values that exceeded that of equivalent TiO2 nanoparticle systems by 3-4 times and are comparable to the robust UV/Cl2 and UV/H2O2 systems. The higher photocatalytic efficiency of SiNPs is attributed to the combined effects of quantum confinement, effective band gap, and surface states, among which surface states play a dominant role. SiNPs provide a potentially tunable, biologically inert, and robust nanoparticle system for photocatalytic oxidation of wastewater contaminants.