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.

Simple and Sensitive Method for Synchronous Quantification of Regulated and Unregulated Priority Disinfection Byproducts in Drinking Water.

Due to their elevated concentrations in drinking water, compared to other emerging environmental contaminants, disinfection byproducts (DBPs) have become a global concern. To address this, we have created a simple and sensitive method for simultaneously measuring 9 classes of DBPs. Haloacetic acids (HAAs) and iodo-acetic acids (IAAs) are determined using silylation derivatization, replacing diazomethane or acidic methanol derivatization with a more environmentally friendly and simpler treatment process that also offers greater sensitivity. Mono-/di-haloacetaldehydes (mono-/di-HALs) are directly analyzed without derivatization, along with trihalomethanes (THMs), iodo-THMs, haloketones, haloacetonitriles, haloacetamides, and halonitromethanes. Of the 50 DBPs studied, recoveries for most were 70-130%, LOQs for most were 0.01-0.05 µg/L, and relative standard deviations were <30%. We subsequently applied this method to 13 home tap water samples. Total concentrations of 9 classes of DBPs were 39.6-79.2 µg/L, in which unregulated priority DBPs contributed 42% of total DBP concentrations and 97% of total calculated cytotoxicity, highlighting the importance of monitoring their presence in drinking water. Br-DBPs were the dominant contributors to total DBPs (54%) and total calculated cytotoxicity (92%). Nitrogenous DBPs contributed 25% of total DBPs while inducing 57% of total calculated cytotoxicity. HALs were the most important toxicity drivers (40%), particularly four mono-/di-HALs, which induced 28% of total calculated cytotoxicity. This simple and sensitive method allows the synchronous analysis of 9 classes of regulated and unregulated priority DBPs and overcomes the weaknesses of some other methods especially for HAAs/IAAs and mono-/di-HALs, providing a useful tool for research on regulated and unregulated priority DBPs.

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.

Interactions between H2O2 and dissolved organic matter during granular activated carbon-based residual H2O2 quenching from the upstream UV/H2O2 process.

Granular activated carbon (GAC) filtration can be employed to synchronously quench residual H2O2 from the upstream UV/H2O2 process and further degrade dissolved organic matter (DOM). In this study, rapid small-scale column tests (RSSCTs) were performed to clarify the mechanisms underlying the interactions between H2O2 and DOM during the GAC-based H2O2 quenching process. It was observed that GAC can catalytically decompose H2O2, with a long-lasting high efficiency (>80% for approximately 50,000 empty-bed volumes). DOM inhibited GAC-based H2O2 quenching via a pore-blocking effect, especially at high concentrations (10 mg/L), with the adsorbed DOM molecules being oxidized by the continuously generated ·OH; this further deteriorated the H2O2 quenching efficiency. In batch experiments, H2O2 could enhance DOM adsorption by GAC; however, in RSSCTs, it deteriorated DOM removal. This observation could be attributed to the different ·OH exposure in these two systems. It was also observed that aging with H2O2 and DOM altered the morphology, specific surface area, pore volume, and the surface functional groups of GAC, owing to the oxidation effect of H2O2 and ·OH on the GAC surface as well as the effect of DOM. Additionally, the changes in the content of persistent free radicals in the GAC samples were insignificant following different aging processes. This work contributes to enhancing understanding regarding the UV/H2O2-GAC filtration scheme, and promoting the application in drinking water treatment.

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O3) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br-). Considering the risk of bromate (BrO3-) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H2O2) and ammonia (NH3) on BrO3- formation during ozonation process were compared. The addition of H2O2 effectively inhibited BrO3- formation at an initial Br- concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H2O2/O3 was 0.25 and > 0.5, respectively. The UV254 and total organic carbon (TOC) also decreased after adding H2O2, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H2O2. To control the formation of both BrO3- and THMs, a relatively large dose of O3 and a high ratio of H2O2/O3were generally needed. NH3 addition inhibited BrO3- formation when the background ammonia nitrogen (NH3N) concentration was low. There was no significant correlation between BrO3- inhibition efficiency and NH3 dose, and a small amount of NH3N (0.2 mg/L) could obviously inhibit BrO3- formation. The oxidation of NOM seemed unaffected by NH3 addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH3. Considering the formation of BrO3- and THMs, the optimal dose of NH3 was suggested to be 0.5 mg/L.

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.

Modeling iron release from cast iron pipes in an urban water distribution system caused by source water switch.

Significant iron release from cast iron pipes in water distribution systems (WDSs), which usually occurs during the source water switch period, is a great concern of water utilities because of the potential occurrence of "red water" and customer complaints. This study developed a new method which combined in-situ water stagnation experiments with mathematical models and numerical simulations to predict the iron release caused by source water switch. In-situ water stagnation experiments were conducted to determine the total iron accumulation in nine cast iron pipes in-service in Beijing when switching the local water to treated Danjiangkou Reservior water. Results showed that the difference in the concentration increment of total iron in 24 hr (ΔCITI,24), i.e. short-term iron release, caused by source water switch was mainly dependent on the difference in the key quality parameters (pH, hardness, nitrate, Larson Ratio and dissolved oxygen (DO)) between the two source waters. The iron release rate (RFe) after switch, i.e. long-term iron release, was closely related to the pipe properties as well as the DO and total residual chlorine (TRC) concentrations. Mathematical models of ΔCITI,24 and RFe were developed to quantitatively reveal the relationship between iron release and the key quality parameters. The RFe model could successfully combine with EPANET-MSX, a numerical simulator of water quality for WDSs to extend the iron release modeling from pipe level to network level. The new method is applicable to predicting iron release during source water switch, thus facilitating water utilities to take preventive actions to avoid "red water".

Disinfection by-product (DBP) research in China: Are we on the track?

Disinfection by-products (DBPs) formed during water disinfection has drawn significant public concern due to its toxicity. Since the first discovery of the trihalomethanes in 1974, continued effort has been devoted on DBPs worldwide to investigate the formation mechanism, levels, toxicity and control measures in drinking water. This review summarizes the main achievements on DBP research in China, which included: (1) the investigation of known DBP occurrence in drinking water of China; (2) the enhanced removal of DBP precursor by water treatment process; (3) the disinfection optimization to minimize DBP formation; and (4) the identification of unknown DBPs in drinking water. Although the research of DBPs in China cover the whole formation process of DBPs, there is still a challenge in effectively controlling the drinking water quality risk induced by DBPs, an integrated research framework including chemistry, toxicology, engineering, and epidemiology is especially crucial.

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.

Formation of Iodinated Disinfection Byproducts (I-DBPs) in Drinking Water: Emerging Concerns and Current Issues.

Formation of iodinated disinfection byproducts (I-DBPs) in drinking water has become an emerging concern. Compared to chlorine- and bromine-containing DBPs, I-DBPs are more toxic, have different precursors and formation mechanisms, and are unregulated. In this Account, we focus on recent research in the formation of known and unknown I-DBPs in drinking water. We present the state-of-the-art understanding of known I-DBPs for the six groups reported to date, including iodinated methanes, acids, acetamides, acetonitriles, acetaldehyde, and phenols. I-DBP concentrations in drinking water generally range from ng L-1 to low-µg L-1. The toxicological effects of I-DBPs are summarized and compared with those of chlorinated and brominated DBPs. I-DBPs are almost always more cytotoxic and genotoxic than their chlorinated and brominated analogues. Iodoacetic acid is the most genotoxic of all DBPs studied to date, and diiodoacetamide and iodoacetamide are the most cytotoxic. We discuss I-DBP formation mechanisms during oxidation, disinfection, and distribution of drinking water, focusing on inorganic and organic iodine sources, oxidation kinetics of iodide, and formation pathways. Naturally occurring iodide, iodate, and iodinated organic compounds are regarded as important sources of I-DBPs. The apparent second-order rate constant and half-lives for oxidation of iodide or hypoiodous acid by various oxidants are highly variable, which is a key factor governing the iodine fate during drinking water treatment. In distribution systems, residual iodide and disinfectants can participate in reactions involving heterogeneous chemical oxidation, reduction, adsorption, and catalysis, which may eventually affect I-DBP levels in finished drinking water. The identification of unknown I-DBPs and total organic iodine analysis is also summarized in this Account, which provides a more complete picture of I-DBP formation in drinking water. As organic DBP precursors are difficult to completely remove during the drinking water treatment process, the removal of iodide provides a cost-effective solution for the control of I-DBP formation. This Account not only serves as a reference for future epidemiological studies to better assess human health risks due to exposure to I-DBPs in drinking water but also helps drinking water utilities, researchers, regulators, and the general public understand the formed species, levels, and formation mechanisms of I-DBPs in drinking water.

Organic Amines Enhance the Formation of Iodinated Trihalomethanes during Chlorination of Iodide-Containing Waters.

The effects of organic amines (OAs) including glycine (Gly), sarcosine (Sar), and triethanolamine (Tea), representing primary, secondary, and tertiary amines, respectively, on iodinated trihalomethanes (I-THMs) formation during chlorination of iodide (I-)-containing waters were investigated. The total concentration of I-THMs formed in the co-presence of an OA and natural organic matter (NOM) was more than 3 times the sum of those formed in the presence of an OA alone and NOM alone, as OAs competed for free chlorine (FC) to form organic chloramines. Taking Gly as an example, the transformation of I- was determined. In the absence of NOM, the yields of iodate (IO3-) were 89%, 60%, and nearly 0 at [Gly]o/[FC]o = 0:1, 3:4, and 1:1, but 0, 2%, and 43% for hypoiodous acid (HOI), respectively. In the presence of NOM, as [Gly]o/[FC]o increased from 0:1 to 1:1, the yield of IO3- decreased from 66% to 0, while that of I-THMs increased from 2.9% to 16.1%. The competition of FC by OAs inhibited the oxidation of HOI to IO3-, and the formed organic chloramines can oxidize I- to HOI, thus promoting I-DBPs formation. Finally, the enhanced I-THMs formation was verified in real waters.

Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability.

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants. However, few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound. Herein, we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups. The second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants, yielding kTC0 = 11.7 (mol/L)-1 sec-1, kTC- = 35.7 (mol/L)-1 sec-1, kTC2- = 43.1 (mol/L)-1 sec-1 for individual reaction channels. Degradation products were then identified as the hydroxylated and demethylated compounds. The result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties, while the demethylation should be caused by the unavoidably formed manganese oxide via single electron oxidation. This is supported by the DFT calculation, indicating the primary oxidation of phenolic group of TC0 with activation barrier of 44.5 kcal/mol and of alkene group of TC- and TC2- with activation barriers of 44.0 and 43.4 kcal/mol, respectively. This is in agreement with the experimental results, implying the alternation of regioselectivity associated with the deprotonation process. The result was further supported by performing the Fukui function and electrostatic potential analysis, reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.

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.

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.

An insight into the removal of fluoroquinolones in activated sludge process: Sorption and biodegradation characteristics.

The detailed sorption steps and biodegradation characteristics of fluoroquinolones (FQs) including ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin were investigated through batch experiments. The results indicate that FQs at a total concentration of 500µg/L caused little inhibition of sludge bioactivity. Sorption was the primary removal pathway of FQs in the activated sludge process, followed by biodegradation, while hydrolysis and volatilization were negligible. FQ sorption on activated sludge was a reversible process governed by surface reaction. Henry and Freundlich models could describe the FQ sorption isotherms well in the concentration range of 100-300µg/L. Thermodynamic parameters revealed that FQ sorption on activated sludge is spontaneous, exothermic, and enthalpy-driven. Hydrophobicity-independent mechanisms determined the FQ sorption affinity with activated sludge. The zwitterion of FQs had the strongest sorption affinity, followed by cation and anion, and aerobic condition facilitated FQ sorption. FQs were slowly biodegradable, with long half-lives (>100hr). FQ biodegradation was enhanced with increasing temperature and under aerobic condition, and thus was possibly achieved through co-metabolism during nitrification. This study provides an insight into the removal kinetics and mechanism of FQs in the activated sludge process, but also helps assess the environmental risks of FQs resulting from sludge disposal.

Adsorptive removal of antibiotics from water using magnetic ion exchange resin.

The occurrence of antibiotics in the environment has recently raised serious concern regarding their potential threat to aquatic ecosystem and human health. In this study, the magnetic ion exchange (MIEX) resin was applied for removing three commonly-used antibiotics, sulfamethoxazole (SMX), tetracycline (TCN) and amoxicillin (AMX) from water. The results of batch experiments show that the maximum adsorption capacities on the MIEX resin for SMX, TCN and AMX were 789.32, 443.18 and 155.15µg/mL at 25°C, respectively, which were 2-7 times that for the powdered activated carbon. The adsorption kinetics of antibiotics on the MIEX resin could be simulated by the pseudo-second-order model (R2=0.99), and the adsorption isotherm data were well described by the Langmuir model (R2=0.97). Solution pH exhibited a remarkable impact on the adsorption process and the absorbed concentrations of the tested antibiotics were obtained around the neutral pH. The MIEX resin could be easily regenerated by 2mol/L NaCl solution and maintained high adsorption removal for the tested antibiotics after regeneration. Anion exchange mechanism mainly controlled the adsorption of antibiotic and the formation of hydrogen binding between the antibiotic and resin can also result in the increase of adsorption capacity. The high adsorption capacity, fast adsorption rate and prominent reusability make the MIEX resin a potential adsorbent in the application for removing antibiotics from water.