Performance analysis of a stormwater green infrastructure model for flow and water quality predictions.

Nature-based solutions or Green infrastructure (GI) used for managing stormwater pollution are growing in popularity across the globe. Stormwater GI models are important tools to inform the planning of these systems (type, design, size), in the most efficient and cost-effective manner. MUSIC, an example of such a tool, uses regression and first order decay models. Studies validating MUSIC model performance are, however, scarce, hindering future model development and transferability of the model for systems operating under different design and climatic conditions. To close this gap, this paper evaluates MUSIC for a field scale bioretention system, stormwater wetland and vegetated swale operating under Singapore tropical climate. The treatment modules were able to simulate outflows and effluent pollutant concentrations reasonably well for cumulative event volumes (mostly within ±25%) and cumulative TP and TN loads (within ±30%). Outflow TSS loads were significantly under-estimated as a result of greater variability in measured TSS concentrations across events. The findings indicate that simple empirical models such as MUSIC can be transferred to different regions provided that management decisions are based on long-term modelling efforts. The modules generally simulated the outflow hydrographs and pollutographs of the different inflow and drying/wetting conditions relatively poorly.

Degradation of carbamazepine by UVA/WO3/hypochlorite process: Kinetic modelling, water matrix effects, and density functional theory calculations.

The rapid recombination of electron/hole pairs is a major setback in the application of WO3-based photocatalysis in water treatment. In this study, hypochlorite (ClO-) was used as an electron acceptor to enhance the photocatalytic degradation of carbamazepine (CBZ) using UVA-excited WO3. The results showed that CBZ degradation in the UVA/WO3/ClO- system followed a pseudo-first order reaction kinetic model. The addition of 0.1 mM ClO- to the UVA/WO3 system at pH values of 8.2 and 6.2 increased the rate constant (kobs) of the degradation process 5.3- and 11.5-fold, respectively. Further, increasing the WO3 dosage or decreasing the initial CBZ concentration resulted in an increase in kobs. However, at high concentrations, ClO- inhibited CBZ degradation. Based on the kinetic model, it could be suggested that ClO played a dominant role in the degradation process. Furthermore, the water matrix effects were as follows: the optimal pH was 6.2; humic acid, chloride, bicarbonate, and ammonium exhibited inhibitory effects on CBZ degradation; and sulfate ion significantly enhanced the degradation. Density functional theory (DFT) calculations indicated a strong affinity between ClO- and the WO3 surface. Specifically, the electrical energy per order that was associated with the use of ClO- varied in the range of 0.100-1.617 kWh/m3. In summary, this study shows that ClO- is an excellent electron acceptor for excited WO3, while clarifying the CBZ degradation-enhancing effect of ClO- as well as the kinetic model and DFT calculations. These findings can be employed in the degradation of recalcitrant contaminants in a cost-effective manner, while being significant for the development of more effective catalysts of UV-assisted advanced oxidation processes.

Water treatment residual: A critical review of its applications on pollutant removal from stormwater runoff and future perspectives.

In recent years, many studies have been conducted on using different filter media in bioretention systems for stormwater runoff treatment. This critical review paper provides a comprehensive review on the current state of water treatment residual (WTR), a recycled material that can be used as bioretention filter media for removals of key stormwater runoff pollutants (especially phosphorus) and future perspectives with innovative modification on WTR applied for pathogen removal from stormwater runoff. This review paper comprised (i) a brief summary of the reported WTR characteristics, (ii) a thorough evaluation of WTR performance on major pollutants removal from stormwater runoff (iii) a discussion on phosphorus removal mechanisms by WTR applied in the stormwater runoff treatment, and (iv) a review of the future perspectives of WTR for pathogen removal and other potential practical application in the field of stormwater treatment. As outlined in this review, WTR in stormwater runoff treatment has yet to be fully explored. The possible enhancements, especially metal surface modification on WTR are reviewed to bring about the widespread use of WTR in stormwater reuse practices.

Sorption and biodegradation characteristics of the selected pharmaceuticals and personal care products onto tropical soil.

In the present study, the sorption and biodegradation characteristics of five pharmaceutical and personal care products (PPCPs), including acetaminophen (ACT), carbamazepine (CBZ), crotamiton (CTMT), diethyltoluamide (DEET) and salicylic acid (SA), were studied in laboratory-batch experiments. Sorption kinetics experimental data showed that sorption systems under this study were more appropriately described by the pseudo second-order kinetics with a correlation coefficient (R2)>0.98. Sorption equilibrium data of almost all target compounds onto soil could be better described by the Freundlich sorption isotherm model. The adsorption results showed higher soil affinity for SA, following by ACT. Results also indicated a slight effect of pH on PPCP adsorption with lower pH causing lower adsorption of compounds onto the soil except for SA at pH 12. Moreover, adsorption of PPCPs onto the soil was influenced by natural organic matter (NOM) since the higher amount of NOM caused lower adsorption to the soil. Biodegradation studies of selected PPCPs by indigenous microbial community present in soil appeared that the removal rates of ACT, SA and DEET increased with time while no effect had been observed for the rest. This study suggests that the CBZ and CTMT can be considered as suitable chemical sewage indicators based on their low sorption affinity and high resistance to biodegradation.

Impact of elevated Ca(2+)/Mg(2+) concentrations of reverse osmosis membrane desalinated seawater on the stability of water pipe materials.

Hardness and alkalinity are known factors influencing the chemical stability of desalinated water. This study was carried out to investigate the effect of Ca(2+) and Mg(2+) on corrosion and/or scale formation on the surface of different water distribution pipe materials under tropical conditions. The corrosion rates of ductile iron, cast iron and cement-lined ductile iron coupons were examined in reverse osmosis (RO) membrane desalinated seawater which was remineralised using different concentrations of Ca(2+) and Mg(2+). The changes in water characteristics and the coupon corrosion rates were studied before and after the post-treatment. The corrosion mechanisms and corrosion products were examined using scanning electron microscope and X-ray diffraction, respectively. We found that the combination of Ca(2+) and Mg(2+) (60/40 mg/L as CaCO3) resulted in lower corrosion rates than all other treatments for the three types of pipe materials, suggesting that Ca(2+)/Mg(2+) combination improves the chemical stability of desalinated seawater rather than Ca(2+) only.

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process.

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon (BAC) (Process A) and ceramic membrane-BAC (Process B) were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm (UV254, a parameter indicating organic matter with aromatic structure) were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.

Mineralization characteristics and behavior of polyethylene microplastics through ozone-based treatment.

The elimination of microplastics (MPs) has become an urgent issue due to their large quantities and imperfect treatment technologies. In this work, polyethylene (PE), which is ubiquitous in the environment, was selected to study its removal by ozone-based treatment. Catalysts including α-MnO2 and α-FeOOH were synthesized for catalytic ozonation to improve efficiency. The study focused on simulating the conversion of CO2 in the off-gas via the detection of inorganic carbon produced. The morphology and structure of the remaining PE MPs were characterized using scanning electron microscope and Fourier-transform infrared spectroscopy-attenuated total reflection. Our results confirmed that fragmentation and oxidation occurred in the remaining PE MPs, which enhanced the adsorption capacity of ofloxacin (OF). Besides, the 20 mM α-FeOOH could better improve the mineralization efficiency by 3.27 folds with more production of •OH (1.09*10-12 M). Moreover, possible products identified by liquid chromatography-time-of-flight mass spectrometer confirmed the decomposition of main chains of MPs into low-molecular-weight organic compounds with functional groups such as C-OH, C-O-C, and CO. The finding that photoaged PE MPs could be efficiently mineralized under the attack of O3/•OH provides a solid foundation for the removal of natural MPs in the environment.

Ferromanganese oxide-functionalized TiO2 for rapid catalytic ozonation of PPCPs through a coordinated oxidation process with adjusted composition and strengthened generation of reactive oxygen species.

Ferromanganese oxide (MFOx) was first utilized to functionalize TiO2 and an MFOx@TiO2 catalyst was developed for catalytic ozonation for rapid attack of pharmaceutical and personal care products (PPCPs) with adjusted reactive oxygen species (ROSs) composition and strengthened ROSs generation. Unlike Al2O3, which strongly relied on adsorption and was significantly influenced by MFOx loading, synergistic catalytical effects of MFOx and TiO2 were observed, and optimal MFOx doping of 2 wt% and MFOx@TiO2 dosage of 500 ppm were obtained for catalyzing ozonation. In ibuprofen (IBP) degradation, MFOx@TiO2-catalyzed ozonation (MFOx@TiO2/O3) obtained 2.0-, 4.7- and 6.9-folds the kobs of TiO2/O3, MFOx/O3 and bare ozonation (B/O3). Stronger O3 decomposition was observed by MFOx@TiO2 over bare TiO2 with the participation of redox pairs Fe(II)/Fe(III) and Mn(II)/Mn(III)/Mn(IV) and increased surface oxygen vacancies (SOVs) from 9.8 % to 33.7 % was detected. The results revealed that Fe(II), Mn(II) and Mn(III) with low valance accelerated Ti(III) generation from Ti(VI), obtaining an unprecedented high Ti(III) composition occupying 35.3 % of the total Ti atoms. Ti(III) catalyzed the direct reduction of SOVs-O2 to •O2-, and it accelerated the formation of Ti(VI)-OH and Ti(VI)-O which catalyzed O3 decomposition into •O2-. •O2- was found to primarily initiate IBP degradation with nucleophilic addition and dominated over 66 % IBP removal. The enhanced •O2- generation further strengthened •OH and 1O2 production. MFOx@TiO2/O3 obtained 17 %, 21 % and 30 % higher TOC removal over TiO2/O3, MFOx/O3 and B/O3, respectively. Acute toxicity tests confirmed the effective toxicity control of organics by MFOx@TiO2/O3 process (inhibition rate: 10.9 %). Degradation test of atenolol and sulfamethoxazole confirmed the catalytic effects of MFOx@TiO2. MFOx@TiO2 performed strong resistance to water matrix in application test and showed good stability and reusability. The study proposed an effective catalyst for strengthening the ozonation process on PPCPs degradation and provided an in-depth understanding of the mechanisms and characteristics of the MFOx@TiO2 catalyst and MFOx@TiO2/O3 process.

Application of UV LEDs to inactivate antibiotic resistant bacteria: Kinetics, efficiencies, and reactivations.

Unregulated antibiotic use has led to the proliferation of antibiotic-resistant bacteria (ARB) in aquatic environments. Ultraviolet light-emitting diodes (UV LEDs) have evolved as an innovative technology for inactivating microorganisms offering several advantages over traditional mercury lamps. This research concentrated on utilizing UV LEDs with three distinct wavelengths (265 nm, 275 nm, and 285 nm) to inactivate E. coli DH10ß encoding the ampicillin-resistant blaTEM-1 gene in its plasmid. Non-linear models, such as Geeraerd's and Weibull, provided more accurate characterization of the inactivation profiles than the traditional log-linear model due to the incorporation of both biological mechanisms and a deterministic approach within non-linear models. The inactivation rates of ARB were higher than antibiotic-sensitive bacteria (ASB) when subjected to UV LEDs. The highest inactivation rates were observed when all microorganisms were exposed to 265 nm. Photoreactivation emerged as the primary mechanism responsible for repairing DNA damage induced by UV LEDs. 285 nm showed the highest reactivation efficiencies for ARB under different fluences. At higher fluences, both 265 and 275 nm displayed similar effectiveness in suppressing reactivation, while at lower fluences, 275 nm exhibited better efficacies in controlling the reactivation. Therefore, the inhibition of reactivation was influenced by the extent of damage incurred to both DNA and enzymes. In nutrient-poor media (0.9 % NaCl), ASB did not exhibit any reactivation potential. However, the addition of Luria-Bertani (LB) broth promoted the reactivation of ASB. Lower fluence rate was more beneficial at 265 nm whereas higher fluence rates were more effective for longer wavelengths. The inactivation of ARB was enhanced by dissolved organic carbon (DOC) at low fluences. However, the removal of ARB was reduced due to the presence of DOC at higher fluences. The highest energy demand for ARB inactivation was reported at 285 nm. ENVIRONMENTAL IMPLICATION: The excessive and unregulated utilization of antibiotics has emerged as a significant issue for public health. This paper presents a comprehensive analysis of the effectiveness of UV LEDs, an emerging technology, in the inactivation of antibiotic-resistant bacteria (ARB). This research paper explores the kinetics of UV LEDs with different wavelengths to inactivate ARB along with the reactivation efficiencies. This research work also explores the impact and relevant mechanisms of the impact of dissolved organic carbon (DOC) on the inactivation of ARB by UV LEDs.

Microplastics and PAHs mixed contamination: An in-depth review on the sources, co-occurrence, and fate in marine ecosystems.

Microplastics (MPs) and polycyclic aromatic hydrocarbons (PAHs) are toxic contaminants that have been found in marine ecosystems. This review aims to explore the sources and mechanisms of PAHs and MPs mixed contamination in marine environments. Understanding the released sources of PAHs and MPs is crucial for proposing appropriate regulations on the release of these contaminants. Additionally, the mechanisms of co-occurrence and the role of MPs in distributing PAHs in marine ecosystems were investigated in detail. Moreover, the chemical affinity between PAHs and MPs was proposed, highlighting the potential mechanisms that lead to their persistence in marine ecosystems. Moreover, we delve into the various factors influencing the co-occurrence, chemical affinity, and distribution of mixed contaminants in marine ecosystems. These factors, including environmental characteristics, MPs properties, PAHs molecular weight and hydrophobicity, and microbial interactions, were critically examined. The co-contamination raises concerns about the potential synergistic effects on their degradation and toxicity. Interesting, few studies have reported the enhanced photodegradation and biodegradation of contaminants under mixed contamination compared to their individual remediation. However, currently, the remediation strategies reported for PAHs and MPs mixed contamination are scarce and limited. While there have been some initiatives to remove PAHs and MPs individually, there is a lack of research specifically targeting the removal of mixed contaminants. This deficiency highlights the need for further investigation and the development of effective remediation approaches for the efficient remediation of PAHs and MPs from marine ecosystems.

Peroxydisulfate-based Non-radical Oxidation of Rhodamine B by Fe-Mn Doped Granular Activated Carbon: Kinetics and Mechanism Study.

While numerous persulfate-based advanced oxidation processes (AOPs) have been studied based on fancy catalysts, the practical combination of Fe or Mn modified granular activated carbon (GAC) has seldom been investigated. The present study focused on a green and readily synthesized Fe-Mn bimetallic oxide doped GAC (Fe-Mn@GAC), to uncover its catalytic kinetics and mechanism when used in the peroxydisulfate (PDS)-based oxidation process for degrading Rhodamine B (RhB), a representative xenobiotic dye. The synthesized Fe-Mn@GAC was characterized by SEM-EDS, XRD, ICP-OES and XPS analyses to confirm its physicochemical properties. The catalytic kinetics of Fe-Mn@GAC+PDS system were evaluated under varying conditions, including PDS and catalyst dosages, solution pH, and the presence of anions. It was found Fe-Mn@GAC exhibited robust catalytic performance, being insensitive to a wide pH range from 3 to 11, and the presence of anions such as Cl-, SO4 2-, NO3 - and CO3 2-. The catalytic mechanism was investigated by EPR and quenching experiments. The results indicated the catalytic system processed a non-radical oxidation pathway, dominated by direct electron transfer between RhB and Fe-Mn@GAC, with singlet oxygen (1O2) playing a secondary role. The catalytic system also managed to maintain a RhB removal above 81 % in successive 10 cycles, and recover to 89.5 % after simple DI water rinse, showing great reusability. The catalytic system was further challenged by real dye-containing wastewater, achieving a decolorization rate of 84.5 %. This work not only provides fresh insight into the kinetics and mechanism of the Fe-Mn@GAC+PDS catalytic system, but also demonstrates its potential in the practical application in real dye-containing wastewater treatment.

Disinfection by-products control in wastewater effluents treated with ozone and biological activated carbon followed by UV/Chlor(am)ine processes.

Sequential utilization of ozone (O3) and biological activated carbon (BAC) followed by UV/chlor(am)ine advanced oxidation process (AOP) has drawn attention in water reuse. However, the formation of disinfection by-products (DBPs) in this process is less evaluated. This study investigated the DBP formation and the relevant toxicity during the O3-BAC-UV/chlor(am)ine treatment of sand-filtered municipal secondary effluent. DBP formation in UV/chlorine and UV/dichloramine (NHCl2) processes were compared, where the impact of key operational parameters (e.g., UV wavelength, pH) on DBP formation were comprehensively evaluated. O3-BAC significantly reduced DBP formation potential (DBPFP) (58.2 %). Compared to UV/chlorine AOP, UV/NHCl2 AOP reduced DBP formation by 29.7 % in short-time treatment, while insignificantly impacting on DBPFP (p > 0.05). UV/NHCl2 AOP also led to lower calculated cytotoxicity (67.7 %) and genotoxicity (55.9 %) of DBPs compared to UV/chlorine AOP. Compared to 254 nm UV light, the utilization of 285 nm UV light decreased the formation of DBPs in wastewater treated with the UV/chlorine AOP and UV/NHCl2 AOP by 31.3 % and 19.2 %, respectively. However, the cytotoxicity and genotoxicity in UV/NHCl2 AOP using 285 nm UV light increased by 83.4 % and 58.5 %, respectively, compared to 254 nm. The concentration of DBPs formed in the UV/NHCl2 AOP at pH 8 was 54.3 % lower than that at pH 7, suggesting a better control of DBPs at alkaline condition. In the presence of bromide, UV/NHCl2 AOP tended to generate more brominated DBPs than UV/chlorine AOP. Overall, UV/NHCl2 AOP resulted in lower concentration and toxicity of DBPs compared to UV/chlorine AOP.

Ozonation facilitates the aging and mineralization of polyethylene microplastics from water: Behavior, mechanisms, and pathways.

Microplastics (MPs) are ubiquitous in the environment, of which 94 % undergo the aging process. Accelerated aging induced by advanced oxidation processes (AOPs) is significant in explaining the formation pathway of secondary MPs and enables possible mineralization. In this study, ozonation coupled with hydrogen peroxide (O3/H2O2), a type of AOPs, was applied for the aging of MPs (polyethylene, PE). Physiochemical properties of aged PE MPs were analyzed through scanning electron microscope, Fourier-transform infrared spectroscopy-attenuated total reflection, and X-ray photoelectron spectroscopy. The mechanism regarding the contribution of reactive oxygen species (•OH) was determined using chemical probe (p-chlorobenzoic acid) and quencher (tert-butanol). Possible transformation pathways were modeled via two-dimensional correlation spectroscopy. Mineralization of MPs, associated with aging was also studied, with the percentage of PE degradation determined by mass loss. Our results confirmed that ozonation promoted fragmentation of PE, with 20 mM H2O2 facilitating the production of •OH. The growth of oxygen-containing functional groups on the surface of PE was consistent with the alteration of the oxygen-to­carbon atom ratio, revealing the formation of CO, CO, and C-O-C. The enhanced adsorption property of aged PE for triclosan was due to the increased specific surface area and negative charges on the surface. Moreover, the percentage of PE degradation was higher at lower concentrations, and the mass loss reached 32.56 % at a PE concentration of 0.05 g/L after 8-h ozonation. These results contribute to revealing the long-term aging behavior of MPs and providing significant guidance for employing AOPs to achieve efficient removal.

Analyzing disinfection by-products yield and mechanisms in UV/Cl2 using response surface methodology and quantitative structure-activity relationship models.

The study aimed to investigate the formation of halogenated disinfection byproducts (DBPs) during applying UV/chlorine (UV/Cl2) and unravel the interactive impacts of critical operational parameters and the mechanisms behind DBPs formation. Response surface methodology and quantitative structure-activity relationship models were developed to evaluate the contribution of electrophilic, nucleophilic, and free radical reactions to the formation of DBPs in UV/Cl2. The study found that Cl2 and its interactions dominated the total DBPs and non-Br-DBPs formation, while Br- and the Cl2-Br- interaction played a decisive role in the Br-DBPs formation. The study also observed significant interactions of Br, Cl2, and pH on chloroform, bromodichloromethane, dichloroacetonitrile, 1,1-dichloro-2-propanone, trichloroactic acid, and chlorodibromoacetic acid formations, while no evident interaction on chloral hydrate, dibromochloromethane, trichloroacetone, dibromoacetic acid, and bromodichloroacetic acid formations. The electrophilic substitution of HOBr mainly controlled the formation of trihalomethanes, and the contribution of nucleophilic, electrophilic, and free radical (•OH, Cl•, Cl2•- and ClO•) reactions depended on the molar ratio of Cl2 to Br, and pH-determined hydrolysis rate constants of DBPs and the types of free radicals. Overall, the response surface methodology and quantitative structure-activity relationship models provided a reference for revealing DBPs formation mechanisms in other disinfection processes.

Characteristics and behaviors of microplastics undergoing photoaging and Advanced Oxidation Processes (AOPs) initiated aging.

The fact that 94% of microplastics (MPs) ubiquitous in the environment are subject to natural weathering makes the aging study currently a research hotspot. This review summarized the physicochemical characteristics of MPs undergoing natural and artificial aging and evaluated current analytical methods used in aging studies. Besides, the differences in photoaging and aging induced by advanced oxidation processes (AOPs) were discussed, leading to a conclusion that AOPs composed of oxidant and ultraviolet (UV) irradiation can better facilitate the alteration of MPs compared to UV irradiation alone. In addition, the environmental behavior of aged MPs was outlined and their adsorption properties for organics and metals were highlighted as a result of combined effects of hydrophobic, π-π, diffusion, and hydrogen bond interaction. Furthermore, the mechanisms of photoaging and AOPs-initiated aging were analyzed, mainly the role of reactive oxygen species (ROS) and environmentally persistent free radicals (EPFRs). Finally, the applications of two-dimensional correlation spectroscopy (2D-COS) and three-dimensional fluorescence spectra using excitation emission matrix-parallel factor analysis (EEM-PARAFAC) were discussed for the aging process analysis. This overview plays an important role in explaining the aging characteristics of MPs and provides a theoretical foundation for further investigations into their toxicity and removal.

Cu(II) assisted peroxymonosulfate for antibiotic resistant bacteria inactivation: A potential disinfection technology in swimming pool.

Alternative disinfection technology to chlorination is required to control the risk of antibiotic resistance in swimming pools. In this study, copper ions (Cu(II)), which often exist in swimming pools as algicides, were used to activate peroxymonosulfate (PMS) for the inactivation of ampicillin-resistant E. coli. Cu(II) and PMS showed synergistic effects on E. coli inactivation in weak alkaline conditions, obtaining 3.4 log inactivation in 20 min with 10 µM Cu(II) and 100 µM PMS at pH 8.0. Quenching experiments indicated that radicals (i.e., OH and SO4-) were not the main disinfectors for E. coli inactivation. Based on the structure of Cu(II) and density functional theory calculations, the Cu(II)-PMS complex (Cu(H2O)5SO5) was recommended as the active species for E. coli inactivation. Under the experimental conditions, the PMS concentration had a greater influence on E. coli inactivation than the Cu(II) concentration, possibly because increasing PMS concentration accelerates ligand exchange reaction and facilitates active species generation. By forming hypohalous acids, halogen ions could improve the disinfection efficiency of Cu(II)/PMS. The addition of HCO3- concentration (from 0 to 1.0 mM) and humic acid (0.5 and 1.5 mg/l) did not significantly inhibit the E. coli inactivation. The feasibility of adding PMS to waters containing Cu(II) for the inactivation of antibiotic-resistant bacteria was validated in actual swimming pool waters, where 4.7 log inactivation of E. coli was achieved in 60 min.

Degradation of organics and formation of DBPs in the combined LED-UV and chlorine processes: Effects of water matrix and fluorescence analysis.

Combined processes of light-emitting diodes ultraviolet (LED UV) and chlorination (Cl2) are alternative disinfection technologies in drinking water, while the formation of disinfection by-products (DBPs) needs to be evaluated. This study investigated the impacts of critical water matrix factors on the DBP formation in the combined processes. Moreover, the correlation between the degraded natural organic matter (NOM) and the formed DBP was studied. Simultaneous UV/Cl2 outperformed single Cl2 and sequential combined processes in degrading humic acids (HA) and resulted in the highest DBP yield. Iodide at 5-20 µg/L and bromide at 0.05-0.2 mg/L slightly affected the degradation of organics, while increased the formation of brominated DBPs up to 36.6 µg/L. pH 6 was regarded as the optimum pH, achieving high efficiency of HA degradation and a lower level of total DBP formation than pH 7 and 8 by 11 % and 24 %, respectively. Compared to HA samples (46.8-103.9 µg/L per mg/L DOC), NOM in canal water were less aromatic and yielded fewer DBPs (19.6 and 21.2 µg/L per mg/L DOC). However, the extremely high bromide in site 1 samples (18.6 mg/L) shifted the chlorinated DBPs to their brominated analogues, posting around 1 order of magnitude higher levels of toxicities than HA samples. The reduction of absorbance at 254 nm (UV254) correlated with all DBP categories in HA samples, while the correlation coefficients were compromised when included in the canal samples. For the first time, this study found that parallel factor analysis (PARAFAC) would neglect the fluorescence change caused by iodide/bromide in UV/Cl2, while the changes could be captured by self-organising map (SOM) trained with full fluorescence spectra. Fluorescence Ex/Em pairs were proposed to predict DBP formation, suggesting a potential method to develop an online monitoring system for DBPs.

Investigation of the efficacy of the UV/Chlorine process for the removal of trimethoprim: Effects of operational parameters and artificial neural networks modelling.

The UV/Cl2 process (also known as chlorine photolysis, which is the combination of chlorine and simultaneous irradiation of UV light) is conventionally applied at acidic mediums for drinking water treatment and further treatment of wastewater effluents for secondary reuse. This is because the quantum yield of HO• from HOCl (ϕHO•, 254 = 1.4) is greater than the one from OCl- (ϕHO•, 254 = 0.278) by approximately 5 times. Moreover, chlorine photolysis in acidic mediums also tends to have lower radical quenching rates than that of their alkaline counterparts by up to 1000 times. The aim of this research is to investigate the applicability of the UV/Cl2 process by assessing its efficacy on the removal of trimethoprim (TMP) at not only acidic to neutral conditions (pH 6-7), but also alkaline mediums (pH 8-9). At alkaline pH, free chlorine exists as OCl- and since OCl- has a higher molar absorption coefficient as compared to HOCl at higher wavelengths, there would be higher reactive chlorine species (RCS) formation and contribution. TMP removal followed pseudo-first order kinetics and depicted that a maximum fluence based constant (kf' = 0.275 cm2/mJ) was obtained using 42.25 µM (3 mg/L) of chlorine at pH 9, with an irradiation of 275 nm. At alkaline conditions, chlorine photolysis performance followed the trend of UV (275)/Cl2 > UV (265)/Cl2 > UV (310)/Cl2 > UV (254)/Cl2. RCS like Cl•, Cl2-• and ClO• contributed to the degradation of TMP. When the pH was increased from 6 to 8, contribution from hydroxyl radicals (HO• ) was decreased whilst that of RCS was increased. Application of UV (310)/Cl2 had the highest HO• generation, contributing to TMP removals up to 13% to 48% as compared to 5% to 27% in UV (254, 265, 275)/Cl2 systems at pH 6-9. Artificial neural networks modelling was found to be able to verify and predict the contribution of HO• and RCS conventionally calculated via the general kinetic equations in the UV/Cl2 system at 254, 265, 275 and 310 nm.

Enhancing the degradation of carbamazepine by UVA-LED/WO3 process with peroxydisulfate: Effects of light wavelength and water matrix.

In this study, peroxydisulfate (PDS) was used as electron acceptor to improve the photocatalytic activity of WO3. The results indicated that the degradation of carbamazepine by UVA-LED/WO3/PDS process followed pseudo-first order and PDS addition significantly enhanced the degradation rate by inhibiting the recombination of electrons and holes. The observed pseudo-first order rate constant (kobs) was in linear relationship with the dosage of WO3, while inversely proportional to the initial concentration of CBZ. PDS decreased the kobs slightly when its concentration exceeded 0.5 mM. The 365 nm UVA-LED performed much better than 385 nm or 405 nm even though its energy efficiency was the lowest. Based on the steady-state kinetic model, sulfate radical was the dominant radical. The effects of water matrix were complex: bicarbonate ion and humic acid showed strong inhibitory effect; increasing the pH above 7 led to significant drop in CBZ removal; sulfate ion slightly decreased the kobs while 5 mM chloride ion more than doubled the kobs. The interactions between anions and WO3 surface were theoretically analysed to explain the effects of anions. The electrical energy per order values suggest that UVA-LED/WO3/PDS process is suitable for water with low organic carbon.

The optimal method for peroxydisulfate quenching: A comparison of commonly used reductants.

Peroxydisulfate-based advanced oxidation process has drawn increasing interest recently. Quenching the residual peroxydisulfate is essential for the accurate measurement of the concentration of target pollutants. However, it was rarely discussed which reductant is best for peroxydisulfate quenching. In this study, how the quenching of peroxydisulfate by four commonly used quenchers (methanol, ascorbic acid, sodium thiosulfate and sodium sulfite) affected the concentration of carbamazepine was investigated. Sodium sulfite reacted with carbamazepine directly, with the highest removal rate up to 39%. Higher carbamazepine removal rate was achieved by peroxydisulfate/sodium sulfite than by sodium sulfite alone. SO3•- and SO5•- rather than SO4•- played the major role in carbamazepine removal by sodium sulfite or peroxydisulfate/sodium sulfite. Methanol was found unable to reduce peroxydisulfate. Ascorbic acid, when used with a concentration more than three times higher than that of peroxydisulfate, was the best quencher with the lowest carbamazepine removal rate observed at a pH range of 3.5-10.0. Sodium thiosulfate was unfit for peroxydisulfate quenching at pH 3.5 as it was decomposed and formed bisulfite under strong acidic condition. The results of this study provided valuable guidance to the selection of proper quenchers for peroxydisulfate-related advanced oxidation processes.