Effects of wavelength on the treatment of contaminants of emerging concern by UV-assisted homogeneous advanced oxidation/reduction processes.

Pollutants of emerging concern in aqueous environments present a significant threat to both the aquatic ecosystem and human health due to their rapid transfer. Among the various treatment approaches to remove those pollutants, UV-assisted advanced oxidation/reduction processes are considered competent and cost-effective. The treatment effectiveness is highly dependent on the wavelength of the UV irradiation used. This article systematically discusses the wavelength dependency of direct photolysis, UV/peroxides, UV/chlor(am)ine, UV/ClO2, UV/natural organic matter, UV/nitrate, and UV/sulfite on the transformation of contaminants. Altering wavelengths affects the photolysis of target pollutants, photo-decay of the oxidant/reductant, and quantum yields of reactive species generated in the processes, which significantly impact the degradation rates and formation of disinfection byproducts. In general, the degradation of contaminants is most efficient when using wavelengths that closely match the highest molar absorption coefficients of the target pollutants or the oxidizing/reducing agents, and the contribution of pollutant absorption is generally more significant. By matching the wavelength with the peak absorbance of target compounds and oxidants/reductants, researchers and engineers have the potential to optimize the UV wavelengths used in UV-AO/RPs to effectively remove pollutants and control the formation of disinfection byproducts.

UV/Sodium percarbonate for bisphenol A treatment in water: Impact of water quality parameters on the formation of reactive radicals.

Reported herein is an investigation of the impact of water quality parameters on the formation of carbonate radical anion (CO3•-) and hydroxyl radical (HO•) in UV/sodium percarbonate (UV/SPC) system versus in UV/hydrogen peroxide (UV/H2O2) system for bisphenol A (BPA) degradation in water. Pathways of CO3•- oxidation of BPA were proposed in this study based on the evolution of direct transformation products of BPA. Observed in this study, the degradation of BPA in the UV/SPC system was slower than that in the UV/H2O2 system in the secondary effluents collected from a local wastewater treatment plant due to the significant impact of coexisting constituents in the matrices on the former system. Single water quality parameter (e.g., solution pH, common anion, or natural organic matter) affected radical formations and BPA degradation in the UV/SPC system in a way similar to that in the UV/H2O2 system. Namely, the rise of solution pH decreased the steady state concentration of HO• resulting in a decrease in the observed pseudo first-order rate constant of BPA (kobs). Chloride anion and sulfate anion played a negligible role over the examined concentrations; nitrate anion slightly suppressed the reaction at the concentration of 20 mM; bicarbonate anion decreased the steady state concentrations of both CO3•- and HO• exerting significant inhibition on BPA degradation. Different extents of HO• scavenging were observed for different types of natural organic matter in the order of fulvic acid > mixed NOM > humic acid. However, the impact was generally less pronounced on BPA degradation in the UV/SPC system than that in the UV/H2O2 system due to the existence of CO3•-. The results of this study provide new insights into the mechanism of CO3•- based oxidation and new scientific information regarding the impact of water quality parameters on BPA degradation in the sytems of UV/SPC and UV/H2O2 from the aspect of reactive radical formation, which have reference value for UV/SPC application in wastewater treatment.

Cyanotoxin-encoding genes as powerful predictors of cyanotoxin production during harmful cyanobacterial blooms in an inland freshwater lake: Evaluating a novel early-warning system.

Freshwater harmful cyanobacterial blooms (HCBs) potentially produce excessive cyanotoxins, mainly microcystins (MCs), significantly threatening aquatic ecosystems and public health. Accurately predicting HCBs is thus essential to developing effective HCB mitigation and prevention strategies. We previously developed a novel early-warning system that uses cyanotoxin-encoding genes to predict cyanotoxin production in Harsha Lake, Ohio, USA, in 2015. In this study, we evaluated the efficacy of the early-warning system in forecasting the 2016 HCB in the same lake. We also examined potential HCB drivers and cyanobacterial community composition. Our results revealed that the cyanobacterial community was stable at the phylum level but changed dynamically at the genus level over time. Microcystis and Planktothrix were the major MC-producing genera that thrived in June and July and produced high concentrations of MCs (peak level 10.22 µg·L-1). The abundances of the MC-encoding gene cluster mcy and its transcript levels significantly correlated with total MC concentrations (before the MC concentrations peaked) and accurately predicted MC production as revealed by logistic equations. When the Microcystis-specific gene mcyG reached approximately 1.5 × 103 copies·mL-1 or when its transcript level reached approximately 2.4 copies·mL-1, total MC level exceeded 0.3 µg L-1 (a health advisory limit) approximately one week later (weekly sampling scheme). This study suggested that cyanotoxin-encoding genes are promising predictors of MC production in inland freshwater lakes, such as Harsha Lake. The evaluated early-warning system can be a useful tool to assist lake managers in predicting, mitigating, and/or preventing HCBs.

Molybdenum disulfide nanosheets vertically grown on self-supported titanium dioxide/nitrogen-doped carbon nanofiber film for effective hydrogen peroxide decomposition and "memory catalysis".

A self-supporting catalyst consisting of 1D/2D vertical molybdenum disulfide@titanium dioxide/nitrogen-doped carbon nanofiber (MoS2@TiO2/NCNFs) was prepared and tested. It showed efficient hydrogen peroxide (H2O2) decomposition to generate hydroxyl radical (OH) and degradation of various pollutants under solar irradiation. The contribution of the increase in MoS2 edges for decomposing H2O2 was 0.0698 min-1. That is 9.83 times the rate of the original MoS2 edges resulting from the vertical structure. Specially, the catalyst degraded various aromatic pollutants even in the dark by releasing electrons stored in its graphite component to realize "memory catalysis". Also, it exhibited high degradation efficiency under outdoor solar irradiation. The catalyst was easily separated from the treated water, avoiding complex separation processes. All these features suggest this catalyst has great potential in practical water and sewage treatment applications.

Efficient degradation of clofibric acid by heterogeneous catalytic ozonation using CoFe2O4 catalyst in water.

CoFe2O4 (Cobalt ferrite, CF) nanoparticles were prepared, well characterized and applied as efficient solid catalyst in catalytic ozonation, named CF/O3 process, for the removal of emerging organic contaminants (EOCs). The degradation and mineralization of clofibric acid (CA) in CF/O3 process were dramatically enhanced in comparison with those under the O3 system. Surface hydroxyl groups (HGs) were considered as an important factor for ozone decomposition and the reactive oxygen species (ROS) on the catalyst surface were mainly responsible for CA elimination. The contribution and formation of ROS, including hydroxyl radicals (•OH), especially superoxide radicals (O2•-), singlet oxygen (1O2), and hydrogen peroxide (H2O2) were evaluated, and a rational mechanism was elucidated accordingly. Probable degradation pathway of CA was proposed according to the organic intermediates identified. The acute toxicity of the treated solution increased during the first 15 min and then declined rapidly and nearly disappeared as the reaction proceeded. In addition, acceptable catalytic performance of CF/O3 can be obtained for the treatment of other EOCs and the treatment of natural surface water spiked with CA. This work presents an efficient and promising catalytic ozonation technique for the elimination of EOCs in complex water matrices.

Comparative toxicity reduction potential of UV/sodium percarbonate and UV/hydrogen peroxide treatments for bisphenol A in water: An integrated analysis using chemical, computational, biological, and metabolomic approaches.

Bisphenol A (BPA) is a common industrial chemical with significant adverse impacts on biological systems as an environmental contaminant. UV/hydrogen peroxide (UV/H2O2) is a well-established technology for BPA treatment in water while UV/sodium percarbonate (UV/SPC) is an emerging technology with unclear biological impacts of treated effluent. Therefore, in this study, the toxicity evaluation of BPA solution treated with UV/H2O2 and UV/SPC was preformed and compared based on transformation products (TPs) profile, quantitative structure-activity relationship (QSAR), Escherichia coli (E. coli) toxicity assays, and metabolomic analysis. TPs with hydroxylation, double-ring split, and single-ring cleavage were generated from BPA during the treatments with both technologies, but TPs with quinonation were specifically detected in UV/H2O2 treated solution at the UV dose of 1470 mJ cm-2. QSAR prediction based on TPs profile (excluding benzoquinone TPs) suggested that UV/H2O2 and UV/SPC treatments of BPA may increase matrix toxicity due to the formation of multi-hydroxylated TPs; however decreased bioaccumulation potential of all TPs may mitigate the increase of toxicity by reducing the chance of TPs to reach the concentration of toxicity threshold. In vivo assays with E. coli showed inhibited cell growth, arrested cell cycle, and increased cell death in BPA solution treated with UV/H2O2 at the UV dose of 1470 mJ cm-2. Metabolomic analysis indicated that BPA solution treated with UV/H2O2 at UV dose of 1470 mJ cm-2 impacted E. coli metabolism differently than other solutions with unique inhibition on glycerolipid metabolism. Moreover, BPA interfered in various metabolic pathways including alanine, aspartate and glutamate metabolism, starch and sucrose metabolism, pentose phosphate pathway, and lysine degradation, which were mitigated after the treatments. UV/SPC showed advantage over UV/H2O2 of attenuated impact on butanoate metabolism with UV irradiation. This study has generated valuable data for better understanding of biological impacts of BPA and its solutions treated with UV/H2O2 or UV/SPC, thus providing insights for their application prospect for water and wastewater treatment.

Efficient degradation of bisphenol A in water by heterogeneous activation of peroxymonosulfate using highly active cobalt ferrite nanoparticles.

Cobalt ferrite CoFe2O4 catalyst was fabricated and systematically investigated as an efficient peroxymonosulfate (PMS, HSO5-) activator for the degradation of recalcitrant organic contaminants (ROCs) in water treatment. Both SO4- and OH on the surface of catalyst were unveiled to be primarily responsible for bisphenol A (BPA) degradation by a comprehensive study using electron paramagnetic resonance (EPR), radical scavengers and quantification of SO4-, and the negligible contribution of singlet oxygen (1O2) was also observed. BPA degradation was accelerated in the presence of humic acid, and it increased first but then decreased with the further addition of fulvic acid. Moreover, the presence of chloride and bicarbonate ions can enhance both BPA and TOC removal. The toxicity of the target aqueous solution ascended slowly at the early stage but then declined dramatically and almost vanished as the reaction proceeded. The removal efficiencies of other typical ROCs (clofibric acid, 2,4-dichlorophenol, etc.) and the decontamination of natural surface water spiked with BPA were also evaluated. This CoFe2O4/PMS process could be well applied as a safe, efficient, and sustainable approach for ROCs remediation in complex wastewater matrix.

Mitogenomic Perspectives on the Adaptation to Extreme Alkaline Environment of Amur ide (Leuciscus waleckii).

Amur ide (Leuciscus waleckii, Family Cyprinidae) is widely distributed in Northeast Asia. L. waleckii usually inhabits freshwater environments but can also survive in the Lake Dali Nur, one of the most extreme aquatic environments on the earth, with an alkalinity up to 50 mmol/L (pH 9.6). To investigate mechanisms of mitogenomic evolution underlying adaptation to extreme environments, we determined 30 complete mitogenomes that included Lake Dali Nur (alkaline environment, AL) population and Amur basin (freshwater environment, FW) population. Through phylogenetic and divergence time analysis, we found that AL and FW populations forming distinct two groups which were consistent with geographic divergence (the formation of Lake Dali Nur). In addition, we found that almost of the windows exhibited higher nucleotide diversity in FW population (avg 0.0046) than AL population (avg 0.0012). This result indicated that severe environment selection had remarkably reduced the genetic diversity of mitogenome in AL population and suggested that severe environment selection had remarkably reduced the genetic diversity of mitogenome in the AL population. Compared with the FW population (ω = 0.064), the AL population (ω = 0.092) had a larger mean ω (dN/dS ratios) value for the 13 concatenated mitochondrial protein-coding genes, indicating that the high alkaline tolerated group had accumulated more nonsynonymous mutations. These nonsynonymous mutations had resulted in slightly beneficial amino acid changes that allowed adaption to the severe conditions. This study provides an additional view to decipher the adaptive mitogenome evolution of L. waleckii of the high alkaline environment.

Non-negligible risk of chloropicrin formation during chlorination with the UV/persulfate pretreatment process in the presence of low concentrations of nitrite.

The UV/persulfate (PS) process is a promising water treatment technology, and it can not only effectively degrade contaminants of emerging concern, but also control formation of disinfection byproducts (DBPs). In this study, we investigated the potential and mechanisms of chloropicrin (i.e. trichloronitromethane, TCNM) formation during chlorination that followed UV/PS pretreatment in the presence of low concentrations of nitrite. We found that when nitrite was present in the UV/PS system, unexpected high concentrations of TCNM were formed. The formation potential of TCNM was impacted by operational conditions and water matrix components: (1) high pH enhanced TCNM formation; (2) high UV fluence inhibited TCNM formation; and (3) organic compounds containing phenolic groups enhanced TCNM formation. We discovered that electrophilic substitutions by reactive nitrogen species were favored for phenolic groups, and thus more nitrite-N was transformed to organic nitrogen. We also found that more TCNM was generated from natural organic matter than algal organic matter during chlorination following pretreatment using UV/PS. Accordingly, more attention needs to be paid to TCNM formation, if nitrite is present and the water is pretreated using UV/PS (when applied at upstream of chlorination). For example, we found that if monochloramine was used as a disinfectant downstream of the UV/PS process, the formation of TCNM was reduced.

Susceptibility of atrazine photo-degradation in the presence of nitrate: Impact of wavelengths and significant role of reactive nitrogen species.

The role of reactive nitrogen species (RNS) formed from nitrate photolysis has aroused interests in transformation of contaminants of emerging concern. This study investigated the influence of UV wavelengths (255, 285 and 365 nm) on photolysis of nitrate for degradation of atrazine (ATZ). The UV285/nitrate system showed the fastest rate constant for degradation of ATZ with kobs of 0.0022 cm2 mJ-1. UV photolysis, RNS, and hydroxyl radical (HO) were identified as main contributors to ATZ degradation in UV/nitrate system. Among the contributors, RNS made the major contribution to degradation of ATZ in UV285/nitrate system, while HO is the predominant specie in UV255/nitrate system. Variance decomposition analysis showed that degradation of ATZ was slightly impacted by natural organic matter and carbonate/bicarbonate in UV285/nitrate system but was dramatically affected in UV255/nitrate system. Main transformation products of ATZ in UV285/nitrate system were identified and possible pathways were proposed. RNS were confirmed to be favorable for acceleration of ATZ photolysis through further reaction of RNS with hydroxyatrazine (with electron-rich moieties). Our study provides deep insights on the influence of UV wavelength on nitrate photolysis and ATZ degradation, and provides a novel method for remediation of water co-contaminated by nitrate and organic contaminants.

Degradation and transformation of bisphenol A in UV/Sodium percarbonate: Dual role of carbonate radical anion.

The bicarbonate and carbonate ions (HCO3- &CO32-) will consume hydroxyl radical (HO•) to generate carbonate radical anion (CO3•-) in hydroxyl radical based advanced oxidation processes (HO•-AOPs) resulting in reduced oxidation efficiencies of the systems. However, despite the HO• quenching effect of carbonate species, the contribution of CO3•- to the degradation of bisphenol A (BPA) was observed in UV/sodium percarbonate (UV/SPC). In order to study the performance of UV/SPC for BPA degradation and the role of CO3•- in this process, the degradation kinetics and mechanisms of BPA in UV/SPC and in UV/hydrogen peroxide (UV/H2O2) were compared at equivalent concentration of H2O2. In this study, the observed degradation rates of BPA by UV/SPC and by UV/H2O2 in Milli-Q water were similar. Variation of the BPA degradation rates in the presence of radical quenchers, tert-butanol and phenol, suggested that both CO3•- and HO• contributed to the degradation of BPA in UV/SPC. Second order rate constant of CO3•- towards BPA ( [Formula: see text]  = 2.23 × 108 M-1 s-1) and steady state concentrations of CO3•- ( [Formula: see text]  = 2.3 × 10-12 M) and HO• ( [Formula: see text]  = 1.82 × 10-14 M) in UV/SPC were determined with competition kinetics at 1 mM SPC and pH 8.5. The high [Formula: see text] observed in UV/SPC compensated for the smaller [Formula: see text] compared to [Formula: see text] and the consumption of HO• making the degradation rate of BPA in UV/SPC comparable to that in UV/H2O2. Detailed studies on identification of transformation products (TPs) of BPA in UV/SPC revealed that phenol ring and isopropylidene bridge were the main reactive sites of BPA. Degradation pathways were proposed accordingly. The results of kinetic and mechanistic studies provide better fundamental understanding of the degradation of BPA in UV/SPC and HCO3-&CO32- impact on BPA degradation by HO•-AOPs. This also demonstrates potential for CO3•- based water purification technologies.

Effects of dietary supplementation of three strains of Lactococcus lactis on HIFs genes family expression of the common carp following Aeromonas hydrophila infection.

HIFs (Hypoxia inducible factors) are the main regulators of the expression change of oxygen-dependent genes, in addition, they also play important roles in immune regulation. HIFs participate in infectious diseases and inflammatory responses, providing us a new therapeutic target for the treatment of diseases. In this study, 16 HIFs were identified in common carp genome database. Comparative genomics analysis showed large expansion of HIF gene family and approved the four round whole genome duplication (WGD) event in common carp. To further understand the function of HIFs, the domain architectures were predicted. All HIF proteins had the conserved HLH-PAS domain, which were essential for them to form dimer and bind to the downstream targets. The differences in domain of HIFα and HIFß might result in their different functions. Phylogenetic analysis revealed that all HIFs were divided into two subfamilies and the HIFs in common carp were clustered with their teleost counterparts indicating they are highly conservative during evolution. In addition, the tissue distribution was examined by RT-PCR showed that most of HIF genes had a wide range of tissue distribution but exhibited tissue-specific expression patterns. The expression divergences were observed between the copy genes, for example, HIF1A-1, HIF2A-1, ARNT-2 had wide tissue distribution while their copies had limited tissue distribution, proving the function divergence of copies post the WGD event. In order to find an effective activation of HIFs and apply to treatment of aquatic diseases, we investigate the dietary supplementation effects of different strains of Lactococcus lactis on the expression of HIFα subfamily members in kidney of common carp infected with A. hydrophila. In addition, all of the HIF genes have a high expression in the early stages of infection, and decreased in the treatment time point of 48 h in common carp. This phenomenon confirms that as a switch, the main function of HIFs is to regulate the production of immune response factors in early infection. So activation of the switch may be an effective method for infectious disease treatment. As expected, the treatment groups improved the expression of HIFs compared with the control group, and the effects of the three strains are different. The strain1 of L. lactis had a stronger induction on HIF genes than strain2 and strain3, and it might be applied as a potential activation of HIF genes for disease treatment. So, adding befitting L. lactis maybe a well method to activate the HIF genes to protect them from mycobacterial infection.

Distribution of organic phosphorus species in sediment profiles of shallow lakes and its effect on photo-release of phosphate during sediment resuspension.

In this work, the distribution of organic phosphorus (Po) species in sediment profiles of five shallow lakes was analyzed and its effect on the photo-release of dissolved phosphate (Pi) was investigated during sediment resuspension under simulated sunlight irradiation. The results show that Po was highly enriched in the surface sediment and gradually decreased as sediment depths increased: 33.10 ±â€¯2.55-96.71 ±â€¯7.60 mg/kg, 33.55 ±â€¯2.34-142.86 ±â€¯5.73 mg/kg, 57.50 ±â€¯3.46-149.68 ±â€¯7.67 mg/kg, 55.18 ±â€¯4.67-168.73 ±â€¯8.31 mg/kg, 98.75 ±â€¯7.56-275.74 ±â€¯10.70 mg/kg for Lake Hou, Lake Tuan, Lake Tangling, Lake Guozheng and Lake Miao, respectively. The photo-release amount of dissolved Pi in the resuspension composed of surface sediments was also higher than that of deep sediment during sediment resuspension under the simulated sunlight irradiation for 9 h. The potential reasons for these results are: (1) difference in morphology and composition of sediments at different depths: the mean particle size of sediment decreased first and then increased as sediment depths increased; (2) difference in composition of Po species with depths in the sediment profiles: more photolytic Po species existed in surface sediments confirmed by sequential extraction and 31P NMR analysis; and (3) more OH production in the resuspension composed of surface sediment under simulated sunlight irradiation, which directly influence the photo-release of dissolved Pi from photodegradation of organic phosphorus. All of these results indicate that the distribution of organic phosphorus species in the sediment profiles plays an important role in P cycle and its photodegradation during sediment resuspension may be one of the potential pathways for phosphate supplement in shallow lakes.

Contamination Profiles of Perfluoroalkyl Substances (PFAS) in Groundwater in the Alluvial-Pluvial Plain of Hutuo River, China.

Over the past decade, concerns about perfluoroalkyl substances (PFAS) have increased rapidly among the scientific community due to their global distribution and persistence in various environmental matrices. The occurrences of 10 PFAS in groundwater in the alluvial-pluvial plain of Hutuo River (APPHR) in the North China Plain (NCP) were analyzed via UPLC-MS/MS and solid phase extraction. Total PFAS concentrations ranged from 0.56 ng/L to 13.34 ng/L, with an average value of 2.35 ng/L. Perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were dominant PFAS contaminants with high detection rates of 98.39% and 95.16%, respectively, and PFOA was the main pollutant with a mean concentration of 0.65 ng/L. The hydrogeological conditions have an important influence on the concentrations of PFAS in groundwater. Comparatively, the concentration of PFAS in groundwater in the study area is not very high, but it reflects that the groundwater in this region is affected by industrial sources to some extent. Local government should pay more attention on industrial pollution control and groundwater protection in this area.

Insight into carbamazepine degradation by UV/monochloramine: Reaction mechanism, oxidation products, and DBPs formation.

UV/monochloramine (NH2Cl) process has attracted some attention for the elimination of contaminants of emerging concern as a novel advanced oxidation process. However, there is still much uncertainty on the performance and mechanisms of UV/NH2Cl process because of its complexity and generation of various species of radicals, including NH2•, HO•, Cl• and other reactive chlorine species (RCS). The mechanism and influence factors of degradation of carbamazepine (CBZ) in the UV/NH2Cl process were investigated, and a synergistic effect was observed. Degradation of CBZ under all investigated conditions followed pseudo-first order kinetics. The corresponding rate constant increased along with the dosage of NH2Cl, and was affected significantly by the presence of bicarbonate and natural organic matter. The process has little pH-dependency, while the specific contribution of RCS and HO• changed with solution pH, and RCS always act as a major contributor to the degradation of CBZ. Eleven byproducts of CBZ were identified and their respective evolution profiles were determined. The participation of UV in chloramination can reduce the formation of nitrogenous DBPs, but promote the formation of carbonaceous DBPs. Furthermore, when influent, sand filtered, and granular activated carbon filtered water was respectively used as background, degradation of CBZ was inhibited to different degree and more disinfection byproducts (DBPs) were generated, compared to deionized water. The electrical energy per order for degradation of CBZ in the UV/NH2Cl process was also calculated to obtain some preliminary cost information.

Susceptibility of the Algal Toxin Microcystin-LR to UV/Chlorine Process: Comparison with Chlorination.

Microcystin-LR (MC-LR), an algal toxin (cyanotoxin) common in sources of drinking water, poses a major human health hazard due to its high toxicity. In this study, UV/chlorine was evaluated as a potentially practical and effective process for the degradation of MC-LR. Via mass spectrometry analysis, fewer chlorinated-MC-LR products were detected with UV/chlorine treatment than with chlorination, and a transformation pathway for MC-LR by UV/chlorine was proposed. Different degrees of rapid degradation of MC-LR were observed with varying pH (6-10.4), oxidant dosage (0.5-3 mg L-1), natural organic matter (0-7 mg L-1), and natural water sources. In contrast to the formation of primarily chloroform and dichloroacetic acid in deionized water where MC-LR serves as the only carbon source, additional chlorinated disinfection byproducts were produced when sand filtered natural water was used as a background matrix. The UV/chlorine treated samples also showed quantitatively less cytotoxicity in vitro in HepaRG human liver cell line tests than chlorination treated samples. Following 16 min (96 mJ cm-2) of UV irradiation combined with 1.5 mg L-1 chlorine treatment, the cell viability of the samples increased from 80% after exposure to 1 mg L-1 MC-LR to 90%, while chlorination treatment evidenced no reduction in cytotoxicity with the same reaction time.

Decomposition of Iodinated Pharmaceuticals by UV-254 nm-assisted Advanced Oxidation Processes.

Iodinated pharmaceuticals, thyroxine (a thyroid hormone) and diatrizoate (an iodinated X-ray contrast medium), are among the most prescribed active pharmaceutical ingredients. Both of them have been reported to potentially disrupt thyroid homeostasis even at very low concentrations. In this study, UV-254 nm-based photolysis and photochemical processes, i.e., UV only, UV/H2O2, and UV/S2O82-, were evaluated for the destruction of these two pharmaceuticals. Approximately 40% of 0.5µM thyroxine or diatrizoate was degraded through direct photolysis at UV fluence of 160mJcm-2, probably resulting from the photosensitive cleavage of C-I bonds. While the addition of H2O2 only accelerated the degradation efficiency to a low degree, the destruction rates of both chemicals were significantly enhanced in the UV/S2O82- system, suggesting the potential vulnerability of the iodinated chemicals toward UV/S2O82- treatment. Such efficient destruction also occurred in the presence of radical scavengers when biologically treated wastewater samples were used as reaction matrices. The effects of initial oxidant concentrations, solution pH, as well as the presence of natural organic matter (humic acid or fulvic acid) and alkalinity were also investigated in this study. These results provide insights for the removal of iodinated pharmaceuticals in water and/or wastewater using UV-based photochemical processes.

Degradation of dibutyl phthalate (DBP) by UV-254 nm/H2O2 photochemical oxidation: kinetics and influence of various process parameters.

Degradation of dibuytl phthalate (DBP), a plasticizer and also a widely distributed endocrine disruptor, by UV-254 nm/H2O2 advanced oxidation process (AOP) was investigated in this study. A significant DBP removal of 77.1 % at an initial concentration of 1.0 µM was achieved at UV fluence of 160 mJ/cm2, initial H2O2 dosage of 1.0 mM, and pH of 7.6 ± 0.1. The DBP degradation exhibited a pseudo-first-order reaction kinetic pattern, with the rate constants linearly increasing with increasing H2O2 dosage while decreasing with increasing initial DBP concentration and pH value in a specific range. DBP destruction was significantly inhibited in the presence of alkalinity and natural organic matter (NOM), two known factors that should be taken a serious consideration of in the research and design of UV/H2O2-based AOPs. Presence of common inorganic anions (i.e., Cl-, SO42-, and NO3-) and metal cations (i.e., Fe3+ and Zn2+) had a slight impact on the degradation of DBP, although Cu2+ could improve the degradation efficiency even at a concentration as low as 0.01 mg/L, suggesting a strong potential of applying UV/H2O2 for the removal of DBP with an environmental relevant level of copper.

Significant role of UV and carbonate radical on the degradation of oxytetracycline in UV-AOPs: Kinetics and mechanism.

Carbonate radical (CO3(•-)), a selective oxidant, reacts readily with electron-rich compounds through electron transfer and/or hydrogen abstraction. In this study, the role of CO3(•-) in degrading oxytetracycline (OTC) by UV only, UV/H2O2 and UV/persulfate (UV/PS) advanced oxidation processes (AOPs) in the presence of HCO3(-) or CO3(2-) was investigated. For UV only process, the presence of photosensitizers, i.e., nitrate (NO3(-)) and natural organic matter (NOM), had different impacts on OTC degradation, i.e., an enhancing effect by NO3(-) due to the generation of HO(•) and a slight inhibiting effect by NOM possibly due to a light scattering effect. Differently for UV/H2O2 and UV/PS processes, the presence of NO3(-) hardly influenced the destruction of OTC. Generation of CO3(•-) presented a positive role on OTC degradation by UV/NO3(-)/HCO3(-). Such influence was also observed in the two studied AOPs in the presence of both bicarbonate and other natural water constituents. When various natural water samples from different sources were used as reaction matrices, UV only and UV/H2O2 showed an inhibiting effect while UV/PS demonstrated a comparable or even promoting effect in OTC decomposition. After elucidating the potential contribution of UV direct photolysis via excited state OTC* at an elevated reaction pH condition, putative OTC transformation byproducts via CO3(•-) reaction were identified by ultra-high definition accurate-mass quadrupole time-of-flight tandem mass spectrometry (QTOF/MS). Five different reaction pathways were subsequently proposed, including hydroxylation (+16 Da), quinonization (+14 Da), demethylation (-14 Da), decarbonylation (-28 Da) and dehydration (-18 Da). The significant role of UV at high pH and CO3(•-) on OTC removal from contaminated water was therefore demonstrated both kinetically and mechanistically.

Degradation and mineralization of organic UV absorber compound 2-phenylbenzimidazole-5-sulfonic acid (PBSA) using UV-254nm/H2O2.

Various studies have revealed the non-biodegradable and endocrine disrupting properties of sulfonated organic UV absorbers, directing people's attention toward their risks on ecological and human health and hence their removal from water. In this study, UV-254nm/H2O2 advanced oxidation process (AOP) was investigated for degrading a model UV absorber compound 2-phenylbenzimidazole-5-sulfonic acid (PBSA) and a structurally similar compound 1H-benzimidazole-2-sulfonic acid (BSA), with a specific focus on their mineralization. At 4.0mM [H2O2]0, a complete removal of 40.0µM parent PBSA and 25% decrease in TOC were achieved with 190min of UV irradiation; SO4(2-) was formed and reached its maximum level while the release of nitrogen as NH4(+) was much lower (around 50%) at 190min. Sulfate removal was strongly enhanced by increasing [H2O2]0 in the range of 0-4.0mM, with slight inhibition in 4.0-12.0mM. Faster and earlier ammonia formation was observed at higher [H2O2]0. The presence of Br(-) slowed down the degradation and mineralization of both compounds while a negligible effect on the degradation was observed in the presence of Cl(-). Our study provides important technical and fundamental results on the HO based degradation and mineralization of SO3H and N-containing UV absorber compounds.