Facilely tuning the intrinsic catalytic sites of the spinel oxide for peroxymonosulfate activation: From fundamental investigation to pilot-scale demonstration.

Heterogeneous peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) have shown a great potential for pollutant degradation, but their feasibility for large-scale water treatment application has not been demonstrated. Herein, we develop a facile coprecipitation method for the scalable production (∼10 kg) of the Cu-Fe-Mn spinel oxide (CuFeMnO). Such a catalyst has rich oxygen vacancies and symmetry-breaking sites, which endorse it with a superior PMS-catalytic capacity. We find that the working reactive species and their contributions are highly dependent on the properties of target organic pollutants. For the organics with electron-donating group (e.g., -OH), high-valent metal species are mainly responsible for the pollutant degradation, whereas for the organics with electron-withdrawing group (e.g., -COOH and -NO2), hydroxyl radical (•OH) as the secondary oxidant also plays an important role. We demonstrate that the CuFeMnO-PMS system is able to achieve efficient and stable removal of the pollutants in the secondary effluent from a municipal wastewater plant at both bench and pilot scales. Moreover, we explore the application prospect of this PMS-based AOP process for large-scale wastewater treatment. This work describes an opportunity to scalably prepare robust spinel oxide catalysts for water purification and is beneficial to the practical applications of the heterogeneous PMS-AOPs.

Recombinant human adenovirus type 5 promotes anti-tumor immunity via inducing pyroptosis in tumor endothelial cells.

Recombinant human type 5 adenovirus (H101) is an oncolytic virus used to treat nasopharyngeal carcinoma. Owing to the deletion of the E1B-55kD and E3 regions, H101 is believed to selectively inhibit nasopharyngeal carcinoma. Whether H101 inhibits other type of tumors via different mechanisms remains unclear. In this study we investigated the effects of H101 on melanomas. We established B16F10 melanoma xenograft mouse model, and treated the mice with H101 (1 × 108 TCID50) via intratumoral injection for five consecutive days. We found that H101 treatment significantly inhibited B16F10 melanoma growth in the mice. H101 treatment significantly increased the infiltration of CD8+ T cells and reduced the proportion of M2-type macrophages. We demonstrated that H101 exhibited low cytotoxicity against B16F10 cells, but the endothelial cells were more sensitive to H101 treatment. H101 induced endothelial cell pyroptosis in a caspase-1/GSDMD-dependent manner. Furthermore, we showed that the combination of H101 with the immune checkpoint inhibitor PD-L1 antibody (10 mg/kg, i.p., every three days for three times) exerted synergic suppression on B16F10 tumor growth in the mice. This study demonstrates that, in addition to oncolysis, H101 inhibits melanoma growth by promoting anti-tumor immunity and inducing pyroptosis of vascular endothelial cells.

IL-36α inhibits melanoma by inducing pro-inflammatory polarization of macrophages.

Interleukin-36α (IL-36α) is essential for various inflammatory conditions, such as psoriasis and rheumatoid arthritis, whereas its role in tumor immunity is unclear. In this study, it was demonstrated that IL-36α could activate the NF-κB and MAPK signaling pathways in macrophages, leading to the expression of IL-1ß, IL-6, TNF-α, CXCL1, CXCL2, CXCL3, CXCL5 and iNOS. Importantly, IL-36α has significant antitumor effects, altering the tumor microenvironment and promoting the infiltration of MHC IIhigh macrophages and CD8+ T cells while decreasing the levels of monocyte myeloid-derived suppressor cells, CD4+ T cells and regulatory T cells. This ultimately results in the inhibition of tumor growth and migration. Furthermore, IL-36α synergized with the PD-L1 antibody increased the immune cells infiltration and enhanced the anti-tumor effect of the PD-L1 antibody on melanoma. Collectively, this study reveals a new role for IL-36α in promoting anti-tumor immune responses in macrophages and suggests its potential for cancer immunotherapy.

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.

Overcoming the Ambient Manufacturability-Performance Bottleneck in Perovskite Nanocrystal Emitters for Efficient Light-Emitting Diodes.

Colloidal perovskite nanocrystals (NCs) have risen rapidly in luminescence efficiency and color purity. However, their high performance requires careful and complex pre-treatment of precursors and precise regulation of the reaction atmosphere; otherwise, their emission will be weak and broad. To overcome these limitations, we develop a facile ligand exchange method using a new type of bidentate ligand, which is obtained by reacting cheap sulfur with tributylphosphine (S-TBP). During ligand exchange, the double bond between P and S atoms breaks and a single bond is formed between them, after which S-TBP switches into a bidentate ligand and binds to a perovskite NC at two points. With short-chain S-TBP ligands that have high spatial position resistance, both NC spacing and surface ligand density can be reduced, thereby improving carrier injection and transport. On the NC surface after ligand exchange, halogen vacancies were substantially filled, leading to a PbSP (Pb, S, and P elements) component-dominated shell that greatly decreases trap density and enhances material stability. The resulting perovskite NCs are stable and bright with a photoluminescence quantum yield of ≈96 %, and an external quantum efficiency of 22 %. Note that our ligand-exchange strategy remains effective even when scaling up, which should accelerate commercialization.

BEXCIS: Bayesian methods for estimating the degree of the skewness of X chromosome inactivation.

BACKGROUND: X chromosome inactivation (XCI) is an epigenetic phenomenon that one of two X chromosomes in females is transcriptionally silenced during early embryonic development. Skewed XCI has been reported to be associated with some X-linked diseases. There have been several methods measuring the degree of the skewness of XCI. However, these methods may still have several limitations. RESULTS: We propose a Bayesian method to obtain the point estimate and the credible interval of the degree of XCI skewing by incorporating its prior information of being between 0 and 2. We consider a normal prior and a uniform prior for it (respectively denoted by BN and BU). We also propose a penalized point estimate based on the penalized Fieller's method and derive the corresponding confidence interval. Simulation results demonstrate that the BN and BU methods can solve the problems of extreme point estimates, noninformative intervals, empty sets and discontinuous intervals. The BN method generally outperforms other methods with the lowest mean squared error in the point estimation, and well controls the coverage probability with the smallest median and the least variation of the interval width in the interval estimation. We apply all the methods to the Graves' disease data and the Minnesota Center for Twin and Family Research data, and find that SNP rs3827440 in the Graves' disease data may undergo skewed XCI towards the allele C. CONCLUSIONS: We recommend the BN method for measuring the degree of the skewness of XCI in practice. The R package BEXCIS is publicly available at https://github.com/Wen-YiYu/BEXCIS .

Association of cerebrospinal fluid advanced oxidation protein products levels with early brain injury and prognosis of aneurysmal subarachnoid hemorrhage: A preliminary prospective study.

OBJECTIVES: In this study, we investigated the time course in the cerebrospinal fluid (CSF) advanced oxidation protein products (AOPPs) levels in patients with aneurysmal subarachnoid hemorrhage (aSAH), and ascertained the relationship between the levels of AOPPs and early brain injury (EBI), hydrocephalus and prognosis of patients with aSAH. METHODS: We measured the CSF AOPPs levels in 50 patients with aSAH at 1-3 d, 4-6 d, 7-9 d, and 10-12 d after hemorrhage. The modified Fisher grades, Hunt-Hess grades, CSF IL-6 levels, peripheral blood count of white blood cells, cerebral edema scores and hydrocephalus were used to assess the severity of brain injury. Modified Rankin Scale (mRS) scores were used to assess the prognosis. Patients with mRS scores greater than 2 were considered to have a poor outcome. RESULTS: CSF AOPPs levels were significantly higher in patients with aSAH with poor prognosis, compared to patients with good prognosis and peaked in the early stage. Among patients with aSAH, the levels of CSF AOPPs on days 1-3 were significantly correlated with modified Fisher grades, Hunt-Hess grades, CSF IL-6 levels, peripheral blood count of white blood cells, and cerebral edema scores. Also, in patients with hydrocephalus, early CSF AOPPs levels were significantly elevated. Levels of CSF AOPPs in aSAH patients on days 1-3, 4-6, and 7-9 were independently associated with poor prognosis at the 90-day follow-up, and the optimal area under the curve (AUC) values for CSF AOPPs levels were found on days 1-3. CONCLUSIONS: AOPPs may serve as the potential biomarker to assess the severity of EBI and prognosis in patients with aSAH.

Tetraethylthiuram disulphide alleviates pulmonary fibrosis through modulating transforming growth factor-ß signalling.

Idiopathic pulmonary fibrosis (IPF) induces significant morbidity and mortality, for which there are limited therapeutic options available. Here, we found that tetraethylthiuram disulphide (disulfiram, DSF), a derivative of thiuram, used in the treatment of alcohol abuse, has an inhibitory effect on bleomycin (BLM)-induced pulmonary fibrosis via the attenuation of the fibroblast-to-myofibroblast transition, migration, and proliferation of fibroblasts. Furthermore, DSF inhibited the activation of primary pulmonary fibroblasts and fibroblast cell line under transforming growth factor-ß 1 (TGF-ß1) challenge. Mechanistically, the anti-fibrotic effect of DSF on fibroblasts depends on the inhibition of TGF-ß signalling. We further determined that DSF interrupts the interaction between SMAD3 and TGF-ß receptor Ι (TBR Ι), and identified that DSF directly binds with SMAD3, in which Trp326, Thr330, and Cys332 of SMAD3 are critical binding sites for DSF. Collectively, our results reveal a powerful anti-fibrotic function of DSF in pulmonary fibrosis through the inhibition of TGF-ß/SMAD signalling in pulmonary fibroblasts, indicating that DSF is a promising therapeutic candidate for IPF.

Degradation of micropolluants in flow-through VUV/UV/H2O2 reactors: Effects of H2O2 dosage and reactor internal diameter.

The degradation of atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET) in flow-through VUV/UV/H2O2 reactors was investigated with a focus on the effects of H2O2 dosage and reactor internal diameter (ID). Results showed that the micropollutants were degraded efficiently in the flow-through VUV/UV/H2O2 reactors following the pseudo first-order kinetics (R2 > 0.92). However, the steady-state assumption (SSA) kinetic model being vital in batch reactors was found invalid in flow-through reactors where fluid mixing was less sufficient. With the increase of H2O2 dosage, the ATZ removal efficiency remained almost constant while the SMX and MET removal was enhanced to different extents, which could be explained by the different reactivities of the pollutants towards HO•. A larger reactor ID resulted in lower degradation rate constants for all the three pollutants on account of the lower average fluence rate, but the change in energy efficiency was much more complicated. In reality, the electrical energy per order (EEO) of the investigated VUV/UV/H2O2 treatments ranged between 0.14-0.20, 0.07-0.14 and 0.09-0.26 kWh/m3/order for ATZ, SMX and MET, respectively, with the lowest EEO for each pollutant obtained under varied H2O2 dosages and reactor IDs. This study has demonstrated the efficiency of VUV/UV/H2O2 process for micropollutant removal and the inadequacy of the SSA model in flow-through reactors, and elaborated the influential mechanisms of H2O2 dosage and reactor ID on the reactor performances.

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.

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.

Ray Tracing for Fluence Rate Simulations in Ultraviolet Photoreactors.

The performance of photochemical reactors is governed by the spatial distribution of radiant energy within the irradiated region of the reactor. Ray tracing has been widely used for simulation of lighting systems. The central hypothesis of this work was that ray tracing can provide accurate simulations of fluence rate fields within ultraviolet (UV) photoreactors by accounting for the physical and optical phenomena that will govern fluence rate fields in UV photoreactors. Ray tracing works by simulating the behavior of a large population of rays emanating from a radiation source to describe the spatial distribution of radiant energy (i.e., fluence rate) within a system. In this study, fluence rate calculations were performed using commercial ray tracing software for three basic UV reactors, each with a single low-pressure Hg lamp. Fluence rate calculations in the ray tracing program were based on the formal definition of fluence rate, calculated as the incident radiant power from all directions on a small spherical receptor, divided by the cross-sectional area of that sphere. The results of this study demonstrate that ray tracing can provide predictions of fluence rate in UV radiative systems that are close to experimental measurements and the predictions of other numerical methods.

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.

On-Site Determination and Monitoring of Real-Time Fluence Delivery for an Operating UV Reactor Based on a True Fluence Rate Detector.

At present, on-site fluence (distribution) determination and monitoring of an operating UV system represent a considerable challenge. The recently developed microfluorescent silica detector (MFSD) is able to measure the approximate true fluence rate (FR) at a fixed position in a UV reactor that can be compared with a FR model directly. Hence it has provided a connection between model calculation and real-time fluence determination. In this study, an on-site determination and monitoring method of fluence delivery for an operating UV reactor was developed. True FR detectors, a UV transmittance (UVT) meter, and a flow rate meter were used for fundamental measurements. The fluence distribution, as well as reduction equivalent fluence (REF), 10th percentile dose in the UV fluence distribution (F10), minimum fluence (Fmin), and mean fluence (Fmean) of a test reactor, was calculated in advance by the combined use of computational fluid dynamics and FR field modeling. A field test was carried out on the test reactor for disinfection of a secondary water supply. The estimated real-time REF, F10, Fmin, and Fmean decreased 73.6%, 71.4%, 69.6%, and 72.9%, respectively, during a 6-month period, which was attributable to lamp output attenuation and sleeve fouling. The results were analyzed with synchronous data from a previously developed triparameter UV monitoring system and water temperature sensor. This study allowed demonstration of an accurate method for on-site, real-time fluence determination which could be used to enhance the security and public confidence of UV-based water treatment processes.

Experimental Evaluation of Turbidity Impact on the Fluence Rate Distribution in a UV Reactor Using a Microfluorescent Silica Detector.

Turbidity is a common parameter used to assess particle concentration in water using visible light. However, the fact that particles play multiple roles (e.g., scattering, refraction, and reflection) in influencing the optical properties of aqueous suspensions complicates examinations of their effects on ultraviolet (UV) photoreactor performance. To address this issue, UV fluence rate (FR) distributions in a photoreactor containing various particle suspensions (SiO2, MgO, and TiO2) were measured using a microfluorescent silica detector (MFSD). Reflectance of solid particles, as well as transmittance and scattering properties of the suspensions were characterized at UV, visible, and infrared (IR) wavelengths. The results of these measurements indicated that the optical properties of all three particle types were similar at visible and IR wavelengths, but obvious differences were evident in the UV range. The FR results indicated that for turbidity associated with SiO2 and MgO suspensions, the weighted average FR (WAFR) increased relative to deionized water. These increases were attributed to low particle photon absorption and strong scattering. In contrast, the WAFR values decreased with increasing turbidity for TiO2 suspensions because of their high particle photon absorption and low scattering potential. The findings also indicate that measurements of scattering and transmittance at UV wavelengths can be used to quantify the effects of turbidity on UV FR distributions.

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.

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 high-dose UV irradiation as nanofiltration pretreatment for drinking water production: Organic fouling mitigation and micropollutant removal.

Nanofiltration (NF) is being increasingly applied to produce high-quality drinking water; however, its cost-effective operation remains challenging due to the perennial membrane fouling. On account of the low tolerance of common NF membranes to chemical oxidants, this study proposed high-dose UV irradiation as a pretreatment strategy for organic fouling mitigation. Results showed that the permeate flux decline of the membrane with UV-treated feedwater (with a dose of 750 mJ cm-2) was less drastic than that with raw feedwater, but slightly faster as compared to that with UV/Cl2 pretreatment. The final normalized fluxes were 0.69, 0.79, and 0.82, respectively, after 10 h of operation with raw, UV- and UV/Cl2-treated feedwaters. With the characterization of feedwaters and membranes, the fouling was found to be initiated by the adsorption of hydrophilic biopolymers onto the membrane, followed by the deposition of hydrophobic humic substances. Reduction of the "glue" biopolymers was crucial to membrane fouling mitigation. The applicability of UV pretreatment in practice was testified with a pilot-scale UV-NF system where permeate flux of the NF module decreased by 37% after six-week continuous operation. Moreover, UV pretreatment could remove most of the identified pesticides in the feedwater with a removal efficiency over 80% for metolachlor and imidacloprid, but had no or even a negative effect on perfluorinated compounds. This work discloses the efficacy and mechanism of high-dose UV irradiation for NF membrane fouling control, which facilitates future research and application of NF technology.

Potential of solar photodegradation of antibiotics in shallow ditches: Kinetics, the role of dissolved organic matter and prediction models.

Shallow ditches, which generally receive livestock or domestic sewage, are widely distributed in rural and suburban areas, making them important sites for antibiotic exposure. Because of the easy penetration of solar irradiation, the photochemical reactions of antibiotics tend to be active in shallow ditches. This study investigated the photodegradation potential of 21 commonly used antibiotics belonging to five categories in a typical shallow ditch by conducting simulated solar irradiation experiments. The influence of dissolved organic matter (DOM) in ditch water on the photodegradation of antibiotics was analyzed, and a model based on DOM changes was established to predict the degradation behavior of antibiotics. The results indicated that the degradation rates of different varieties of antibiotics in ultrapure water and ditch water followed the trend of fluoroquinolones > tetracyclines > sulfonamides > macrolides > lincosamides. In ditch water, direct photodegradation and photooxidation mediated by 3DOM∗ played predominant roles in the antibiotic photodegradation, whereas the contributions of singlet oxygen (1O2) and hydroxyl radicals (·OH) varied significantly depending on the reactivity of the antibiotics. A simple and effective model was proposed for predicting the photodegradation process of antibiotics in ditch water based on the degree of DOM photobleaching determined by excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis. The prediction model was simplified by considering the similarity in photochemical properties within the same category of antibiotics and was validated by field tests. This study fills a critical research gap by evaluating the photodegradation of antibiotics in shallow ditches, thereby providing valuable insights into their fate and transport in shallow ditch water.