Optimization of Electron Transport Pathway: A Novel Strategy to Solve the Photocorrosion of Ag-Based Photocatalysts.

Although Ag-containing photocatalysts exhibit excellent photocatalytic ability, they present great challenges owing to their photocorrosion and ease of reduction. Herein, an electron acceptor platform of Ag2O/La(OH)3/polyacrylonitrile (PAN) fiber was constructed using a heterojunction strategy and electrospinning technology to develop a novel photocatalytic membrane with a redesigned electron transport pathway. Computational and experimental results demonstrate that the optimized electron transport pathway included intercrystal electron transfer induced by the La-O bond between Ag2O and La(OH)3 as well as electron transfer between the catalyst crystal and electrophilic PAN membrane interface. In addition, the photocatalytic performance of the Ag2O/La(OH)3 membrane for tetracycline (TC) removal was still above 97% after five photocatalytic reaction cycles. Furthermore, the carrier life was greatly extended. Mechanistic study revealed that photogenerated holes on the Ag2O/La(OH)3 membrane were the main reactive species in TC degradation. Overall, this study proposes a novel electron transport pathway strategy that effectively solves the problems of photocatalyst photocorrosion and structural instability.

Unveiling the Mechanism of Urine Source Separation-Derived Pretreatment on Enhancing Short-Chain Fatty Acid Yields from Anaerobic Fermentation of Waste Activated Sludge.

A novel strategy employing urine wastewater derived from source separation technology, to pretreat waste activated sludge (WAS) for promoting yields of short-chain fatty acids (SCFAs), has been proposed in this study. It was found experimentally that SCFA production could ascend up to 305.4 mg COD/g VSS (volatile suspended solids) with a urine volumetric proportion of 1:2 to the whole reaction system, being 8.8 times that produced in the control. Exploration of the mechanism indicated that WAS disintegration was significantly enhanced due to the synergistic effect of urea and free ammonia (FA). Degradation rates of model organic substrates and measurements of critical enzymatic activities demonstrated that hydrolysis and acidogenesis were inhibited under high urine content (urine proportion of 1:2), while not significantly affected under low urine content (i.e., 1:4), which might be attributed to metal ions existing in urine wastes alleviating the inhibition induced by FA. In contrast, methanogenesis was negatively suppressed by any urine concentration owing to its higher sensitivity to the environmental variations. Shift of microbial population further elucidated the abundance of hydrolytic and acidogenic microbes were enriched in the fermenters with urine addition. The findings provide a new thought for recovering resources from wastes, potentially reducing the pressure of sewage and sludge treatment in wastewater treatment plants.

Estimation of Unintended Treated Wastewater Contributions to Streams in the Yangtze River Basin and the Potential Human Health and Ecological Risk Analysis.

"Clean water and sanitation" is one of the United Nations Sustainable Development Goals. One primary objective of wastewater treatment is to remove contaminants such as pathogens, nutrient, and organic matter from wastewater, while not all contaminants could be removed effectively. Wastewater treatment plants would inevitably represent concentrated point sources of residual contaminant loadings into surface waters. This study focuses on the populated Yangtze River Basin where emerging contaminants are frequently detected in the rivers in the recent years. A python-based ArcGIS model is developed to estimate the contributions of effluent discharges in water supply sources and quantify fate and environmental risks of human-derived contaminants in the river network. We find that one-third of the river networks are potentially influenced by the effluents through local or upstream inputs. Average fraction of unintended wastewater reuse in water supply intakes is estimated to be lower than 3% under the average flow scenario with an average traveling time of 0.05 day from the nearest effluent input site to water supply intakes. However, under low flow scenario, the percentage of effluent discharge would increase largely, leading to substantial increases in human health and ecological risks. This study provides a systematic investigation to understand extents of impacts of effluent inputs in river networks as well as identify the opportunities to improve the water management in the densely populated regions.

An emerging unrated mobile reservoir for antibiotic resistant genes: Does transportation matter to the spread.

The regional distribution of antibiotic resistance genes has been caused by the use and preference of antibiotics. Not only environmental factors, but also the population movement associated with transportation development might have had a great impact, but yet less is known regarding this issue. This research study has investigated and reported that the high-speed railway train was a possible mobile reservoir of bacteria with antibiotic resistance, based on the occurrence, diversity, and abundance of antibiotic resistant bacteria (ARB), antibiotic resistance genes (ARGs), and mobile gene elements (MGEs) in untreated train wastewater. High-throughput 16S rRNA sequencing analyses have indicated that opportunistic pathogens like Pseudomonas and Enterococcuss were the predominant bacteria in all samples, especially in cultivable multi-antibiotic resistant bacteria. The further isolated Enterococcus faecalis and Enterococcus faecium exhibited multi-antibiotic resistance ability, potentially being an indicator for disinfection proficiency. Positive correlations amongst ARGs and MGEs were observed, such as between intI1 and tetW, tetA, blaTEM, among Tn916/154 and mefA/F, qnrS, implying a broad dissemination of multi-ARGs during transportation. The study findings suggested that the high-speed railway train wastewater encompassed highly abundant antibiotic-resistant pathogens, and the wastewater discharge without effective treatment may pose severe hazards to human health and ecosystem safety.

Performance and mechanism of sodium percarbonate (SPC) enhancing short-chain fatty acids production from anaerobic waste activated sludge fermentation.

A novel pretreatment technique (i.e., using Sodium percarbonate, SPC) to improve the short-chain fatty acids (SCFA) production waste activated sludge (WAS) was proposed in this study. Results indicated that the maximum SCFA production of 1605.7 mg COD/L and acetic acid of 52.9% were attained at 0.2 g SPC/g TSS, being 8.4 and 2.8 times of the control (191.3 mg COD/L and 19%), respectively. Meanwhile, the optimal time for SCFA accumulation was decreased from 6d (control) to 4d (0.2 g/g TSS). Mechanism explorations unraveled that SPC largely accelerated WAS solubilization and enhanced the bioavailability of organics released from WAS. It improved enzymatic activities related to hydrolysis and acidogenesis, while suppressed the Coenzyme F420 responsible for SCFA consumption. Illumina MiSeq sequencing analysis showed that SPC substantially enhanced the relative abundances of hydrolytic and/or acid-forming microbes. Furthermore, CO3- and O2- were the key factors to production enhancement in SPC-involved sludge fermentation.

Remediation of trichloroethylene contaminated soil by unactivated peroxymonosulfate: Implication on selected soil characteristics.

The advanced oxidation process (AOP) based on activated Peroxymonosulfate (PMS) has been attracting many people in the field of soil and water remediation in many ways while ignoring the shortcomings. The high cost of activators, and energy input, as well as the expense to separate the catalyst and transition metal reducing agent from the treated soil, were some disadvantages of using activated PMS. Based on the above rationales of problems related to the use of activated PMS, this study aimed to study the performance of using unactivated peroxymonosulfate for the advanced oxidation process to remediate soil contaminated by trichloroethylene (TCE), and to evaluate the synergistic effect on selected soil properties after treatment. The results showed that within 45 min, a single injection of 5 mM PMS at its initial pH value can degrade 86.90% of the total TCE in the soil. However, when PMS was continuously injected, the removal rate was increased to 95.25%. The direct reaction of TCE and PMS was the main cause of degradation. PMS can degrade TCE in a wide pH range (pH 3-11), but the maximum degradation was at pH = 2.9 (the initial pH of PMS). After the treatment, the soil organic matter (SOM) was degraded significantly. In contrast, FTIR, SEM, and hydrometer tests conducted on the soil showed that the treatment had no significant effect on the functional groups and particle size distribution of the treated soil. The study on the effect of the treatment on the concentration of bioavailable heavy metals in the treated soil showed that only manganese and copper metals were significantly increased after the treatment. According to the results obtained in this study, it is more beneficial and feasible to use unactivated peroxymonosulfate in the advanced oxidation process when remediating soil contaminated by chlorinated organic matter.

Significant Effect of Evaporation Process on the Reaction of Sulfamethoxazole with Manganese Oxide.

Soil in the vadose zone is an important sink for antibiotics. However, previous studies have examined only the degradation of antibiotics in soil slurry systems, which were largely different from real-world unsaturated soil environments. Whether the same transformation mechanisms apply to unsaturated soil systems has been a question. Here, the degradation of sulfamethoxazole (SMX) by manganese dioxide (γ-MnO2) in both suspension systems and evaporation processes were examined. Results show that the slow degradation of SMX in the suspension system can be significantly promoted as the water gradually evaporates. SMX degraded differently in evaporation as compared to suspension systems because of the quenching effect of generated Mn2+. Transformation products of SMX in both systems also showed different toxicity toward Escherichia coli because of different evolutions of intermediates. This study has strong implications for the assessment and prediction of the transformation and fate of antibiotics in natural soil environments.

Complexation Enhances Cu(II)-Activated Peroxydisulfate: A Novel Activation Mechanism and Cu(III) Contribution.

While aqueous free Cu(II) ion is known to be ineffective to activate peroxydisulfate (PDS), here we report for the first time that Cu(II) complexes are potentially effective activators for PDS when the coordination involves suitable ligands. Using cefalexin (CFX) as a representative, studies show that the complex of Cu(II) with CFX can efficiently activate PDS to induce rapid degradation of CFX. Transformation products of CFX by PDS/Cu(II) differ substantially from those generated from the typical radical oxidation process, for example, PDS/Ag(I), but quite resemble the products from oxidation of CFX by Cu(III). Complexation with CFX increases the electron density of Cu(II), favoring electron transfer from Cu(II) to PDS to generate radicals and Cu(III). The produced Cu(III), rather than radicals, plays the primary role in the overall CFX degradation and regenerates Cu(II) in a catalytic cycle. This novel activation process can occur for a wide range of contaminants (cephalosporin, penicillin, and tetracycline antibiotics) and ligands when coordinated with Cu(II), and N-containing functional groups (e.g. amines) were found to form effective Cu(II) complexes for PDS activation. The new findings of this study further broaden the knowledge on PDS activation by aqueous Cu(II), and verify the contribution of Cu(III) to contaminant elimination.

Degradation of Organic Micropollutants in UV/NH2Cl Advanced Oxidation Process.

Monochloramine (NH2Cl) can be irradiated by UV to create an advanced oxidation condition (i.e., UV/NH2Cl) for the elimination of organic micropollutants (OMPs) from source water. However, information in retrospective studies was scarce on how UV/NH2Cl performance would be affected by the water matrix and OMP molecular structures. In this study, the degradation of five representative OMPs, including triclosan, carbamazepine, sulfamethoxazole, estradiol (E2), and ethinylestradiol (EE2), was examined in different water matrices. All OMPs were rapidly removed by UV/NH2Cl but exhibited different degradation mechanisms. Although •OH, •Cl, and direct photolysis mainly contributed to the overall degradation of OMPs in buffered nanopure water, the contribution of reactive nitrogen species (RNS) generated from the photolysis of NH2Cl was not negligible in the degradation of E2 and EE2. A phenolic group was identified as the moiety reactive toward RNS. Based on quantitative analysis of the impact on OMP degradation from cosolutes (including Cl-, HCO3-, NOM) as well as pH and NH2Cl doses, we developed a kinetic model for the prediction of OMP degradation in complex water matrices. In environmental water matrices, the performance and radical contributions in UV/NH2Cl and UV/H2O2 systems were taken into comparison, which showed faster degradation of OMPs and a more significant contribution of CO3•- in the UV/NH2Cl process.

Reactive Nitrogen Species Mediated Degradation of Estrogenic Disrupting Chemicals by Biochar/Monochloramine in Buffered Water and Synthetic Hydrolyzed Urine.

There is increasing concern about the severe endocrine-related health problems because of the discharge of estrogenic disrupting chemicals (EDCs) into the natural environment. In this study, we investigated the activation of monochloramine (NH2Cl) by biochar [pyrolyzed by cotton straw at 350 °C (Cot350), wheat straw at 350 and 700 °C (WS350 and WS700), and corn straw at 350 and 700 °C (CS350 and CS700)] for the degradation of estradiol (E2) and ethinylestradiol (EE2). Approximately 95% of parent E2 and EE2 was removed by Cot350/NH2Cl in buffered solution, and 87% of E2 and 75% of EE2 were removed in urine within 24 h. Electronic paramagnetic resonance analysis and radical-quenching experiments showed that biochar activated NH2Cl and primarily generated •NO radicals for the degradation of the EDCs. The nitrogen and silicon elements of Cot350 served as primary catalytic sites for NH2Cl activation, whereas the sp2-hybridized carbon on WS700 and CS700 played a major role. The effect of major urine components (i.e., ammonia species, chloride, and bicarbonate) on the reaction pathways of biochar/NH2Cl was also elucidated. This study provides new insights into the reaction pathways of NH2Cl activation by biochar and suggests potential applications for other carbonaceous materials for NH2Cl activation.

Seasonal Pattern of Nutrient Limitation in a Eutrophic Lake and Quantitative Analysis of the Impacts from Internal Nutrient Cycling.

Nutrient dynamics in lakes are determined by the external anthropogenic discharges and unobserved internal cycling processes. In this work, a decadal nutrient data set from the eutrophic Lake Taihu, China, revealed a strong seasonal pattern of nutrient concentration and limitation. A nutrient-driven dynamic eutrophication model based on a Bayesian hierarchical framework was established to quantify the relative contributions to temporal variations from external discharges and internal processes. Results showed that after years of efforts on nutrient reduction, external discharges were relatively small and fluctuated less between seasons compared to the internal processes. A quantitative relationship between monthly nutrient concentration and corresponding internal loading was observed. Lake sediment could transform from a source of phosphorus in overlying water in summer and autumn to a sink in winter and spring. Together with temporal variations in nitrification and denitrification, seasonal transformation from the limitation of phosphorus induced colimitation of nitrogen and phosphorus. Understanding the potential impact of internal nutrient cycling on a seasonal pattern of nutrient concentration and limitation, the growth of phytoplankton, and, possibly, phytoplankton community composition should be emphasized, given the change in the relative importance of external discharges and internal loading in the process of lake restoration.

PPCP Degradation by Chlorine-UV Processes in Ammoniacal Water: New Reaction Insights, Kinetic Modeling, and DBP Formation.

The combination of chlorine and UV (i.e., chlorine-UV process) has been attracting more attention in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of the chlorine-UV process (i.e., chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO- and ONOOH/ONOO-, along with •OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH2Cl conditions. •OH and •Cl were the major reactive species to degrade DEET and CAF under UV/NH2Cl conditions, whereas •OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under the chlorine-UV process in ammoniacal water.

UV/Peracetic Acid for Degradation of Pharmaceuticals and Reactive Species Evaluation.

Peracetic acid (PAA) is a widely used disinfectant, and combined UV light with PAA (i.e., UV/PAA) can be a novel advanced oxidation process for elimination of water contaminants. This study is among the first to evaluate the photolysis of PAA under UV irradiation (254 nm) and degradation of pharmaceuticals by UV/PAA. PAA exhibited high quantum yields (Φ254 nm = 1.20 and 2.09 mol·Einstein-1 for the neutral (PAA0) and anionic (PAA-) species, respectively) and also showed scavenging effects on hydroxyl radicals (k•OH/PAA0 = (9.33 ± 0.3) × 108 M-1·s-1 and k•OH/PAA- = (9.97 ± 2.3) × 109 M-1·s-1). The pharmaceuticals were persistent with PAA alone but degraded rapidly by UV/PAA. The contributions of direct photolysis, hydroxyl radicals, and other radicals to pharmaceutical degradation under UV/PAA were systematically evaluated. Results revealed that •OH was the primary radical responsible for the degradation of carbamazepine and ibuprofen by UV/PAA, whereas CH3C(═O)O• and/or CH3C(═O)O2• contributed significantly to the degradation of naproxen and 2-naphthoxyacetic acid by UV/PAA in addition to •OH. The carbon-centered radicals generated from UV/PAA showed strong reactivity to oxidize certain naphthyl compounds. The new knowledge obtained in this study will facilitate further research and development of UV/PAA as a new degradation strategy for water contaminants.

Inactivation of Escherichia coli, Bacteriophage MS2, and Bacillus Spores under UV/H2O2 and UV/Peroxydisulfate Advanced Disinfection Conditions.

Ultraviolet light (UV) combined with peroxy chemicals, such as H2O2 and peroxydisulfate (PDS), have been considered potentially highly effective disinfection processes. This study investigated the inactivation of Escherichia coli, bacteriophage MS2, and Bacillus subtilis spores as surrogates for pathogens under UV/H2O2 and UV/PDS conditions, with the aim to provide further understanding of UV-based advanced disinfection processes (ADPs). Results showed that one additional log of inactivation of E. coli was achieved with 0.3 mM H2O2 or PDS at 5.2 × 10(-5) Einstein·L(-1) photo fluence (at 254 nm) compared with UV irradiation alone. Addition of H2O2 and PDS greatly enhanced the inactivation rate of MS2 by around 15 folds and 3 folds, respectively, whereas the inactivation of B. subtilis spores was slightly enhanced. Reactive species responsible for the inactivation were identified to be •OH, SO4(·-), and CO3(·-) based on manipulation of solution conditions. The CT value of each reactive species was calculated with respect to each microbial surrogate, which showed that the disinfection efficacy ranked as •OH > SO4(·-) > CO3(·-) ≫ O2(·-)/HO2(·). A comprehensive dynamic model was developed and successfully predicted the inactivation of the microbial surrogates in surface water and wastewater matrices. The concepts of UV-efficiency and EE/O were employed to provide a cost-effective evaluation for UV-based ADPs. Overall, the present study suggests that it will be beneficial to upgrade UV disinfection to UV/H2O2 ADP for the inactivation of viral pathogens.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br- and Cl- may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Multiple Roles of Cu(II) in Catalyzing Hydrolysis and Oxidation of ß-Lactam Antibiotics.

The widely used ß-lactam antibiotics such as penicillins and cephalosporins are known to be susceptible to CuII-catalyzed hydrolysis at their four-membered ß-lactam ring. However, this study elucidates that CuII can in fact play multiple roles in promoting the hydrolysis and/or oxidation of ß-lactam antibiotics under environmental aquatic conditions (pH 5.0-9.0 and 22 °C), depending on ß-lactams' structural characteristics and solution pH. Most significantly, the ß-lactam antibiotics that contain a phenylglycine primary amine group on the side chain can undergo direct oxidation by CuII via this functional group. On the other hand, the ß-lactam ring of penicillins is susceptible to CuII-catalyzed hydrolysis, followed by oxidation of the hydrolysis product by CuII. In contrast, the ß-lactam ring of cephalosporins is susceptible to CuII-catalyzed hydrolysis only. Solution pH influences the CuII-promoted transformation by affecting the ß-lactam and CuII complexation through protonation/deprotonation of critical organic functional groups. When CuII acts as an oxidant to promote the transformation of ß-lactam antibiotics to yield CuI, the overall role of CuII appears catalytic if the reaction occurs under ambient atmospheric condition, due to quick oxidation of CuI by oxygen to regenerate CuII. Compared to earlier literature that largely assumed only the hydrolytic catalyst role of CuII in promoting degradation of ß-lactam antibiotics, the oxidative roles of CuII identified by this study mark important contributions to a more accurate mechanistic understanding.

Transformation of Tetracycline Antibiotics and Fe(II) and Fe(III) Species Induced by Their Complexation.

Tetracycline antibiotics (TCs) are frequently detected micropollutants and are known to have a strong tendency to complex with metal ions such as Fe(II) and Fe(III) in aquatic environments. Experiments with Fe(II) and TCs showed that the complexation of Fe(II) with tetracycline (TTC), oxytetracycline (OTC), or chlorotetracycline (CTC) could lead to the accelerated oxidation of Fe(II) and the promoted degradation of TCs simultaneously. The reaction started with complexation of Fe(II) with TC followed by oxidation of the Fe(II)-TC complex by dissolved oxygen to generate a Fe(III)-TC complex and reactive oxygen species (ROS). The ROS (primarily ·OH) then degraded TC. The oxidation rate constants of Fe(II) in the Fe(II)-H2L and Fe(II)-HL complexes were 0.269 and 1.511 min(-1), respectively, at ambient conditions (pH 7, 22 °C, and PO2 of 0.21 atm), which were about 60 and 350 times of the oxidation rate of uncomplexed Fe(II). Humic acids (HA) compete with TCs for Fe(II), but the effect was negligible at moderate HA concentrations (≤10 mg·L(-1)). Experiments with Fe(III) and TCs showed that the complexation of Fe(III) with TC could generate oxidized TC and Fe(II) without the need of oxygen at a relatively slower rate compared to the reaction involving Fe(II), O2, and TCs. These findings indicate the mutually influenced environmental transformation of TCs and Fe(II) and Fe(III) induced by their complexation. These newly identified reactions could play an important role in affecting the environmental fate of TCs and cycling of Fe(II) and Fe(III) in TCs-contaminated water and soil systems.

UV/H2O2 and UV/PDS Treatment of Trimethoprim and Sulfamethoxazole in Synthetic Human Urine: Transformation Products and Toxicity.

Elimination of pharmaceuticals in source-separated human urine is a promising approach to minimize the pharmaceuticals in the environment. Although the degradation kinetics of pharmaceuticals by UV/H2O2 and UV/peroxydisulfate (PDS) processes has been investigated in synthetic fresh and hydrolyzed urine, comprehensive evaluation of the advanced oxidation processes (AOPs), such as product identification and toxicity testing, has not yet been performed. This study identified the transformation products of two commonly used antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), by UV/H2O2 and UV/PDS in synthetic urine matrices. The effects of reactive species, including •OH, SO4(•-), CO3(•-), and reactive nitrogen species, on product generation were investigated. Multiple isomeric transformation products of TMP and SMX were observed, especially in the reaction with hydroxyl radical. SO4(•-) and CO3(•-) reacted with pharmaceuticals by electron transfer, thus producing similar major products. The main reactive species deduced on the basis of product generation are in good agreement with kinetic simulation of the advanced oxidation processes. A strain identified as a polyphosphate-accumulating organism was used to investigate the antimicrobial activity of the pharmaceuticals and their products. No antimicrobial property was detected for the transformation products of either TMP or SMX. Acute toxicity employing luminescent bacterium Vibrio qinghaiensis indicated 20-40% higher inhibitory effect of TMP and SMX after treatment. Ecotoxicity was estimated by quantitative structure-activity relationship analysis using ECOSAR.

Perfluorooctanoic Acid Degradation Using UV-Persulfate Process: Modeling of the Degradation and Chlorate Formation.

In this study, we investigated the destruction and by-product formation of perfluorooctanoic acid (PFOA) using ultraviolet light and persulfate (UV-PS). Additionally, we developed a first-principles kinetic model to simulate both PFOA destruction and by-product and chlorate (ClO3(-)) formation in ultrapure water (UW), surface water (SW), and wastewater (WW). PFOA degradation was significantly suppressed in the presence of chloride and carbonate species and did not occur until all the chloride was converted to ClO3(-) in UW and for low DOC concentrations in SW. The model was able to simulate the PS decay, pH changes, radical concentrations, and ClO3(-) formation for UW and SW. However, our model was unable to simulate PFOA degradation well in WW, possibly from PS activation by NOM, which in turn produced sulfate radicals.