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Since the combination of anticancer drugs and opioids is very common, apatinib and tramadol are likely to be used in combination clinically. This study evaluated the effects of apatinib on the pharmacokinetics of tramadol and its main metabolite O-desmethyltramadol in Sprague-Dawley (SD) rats and the inhibitory effects of apatinib on tramadol in rat liver microsomes (RLMs), human liver microsomes (HLMs) and recombinant human CYP2D6.1. The samples were determined by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The in vivo results showed that compared with the control group, apatinib increased the AUC (0-t) , AUC (0-∞) and C max values of tramadol and O-desmethyltramadol, and decreased the values of V Z /F and CLz/F. In addition, the MRT (0-t) , MRT (0-∞) values of O-desmethyltramadol were increased. In vitro , apatinib inhibited the metabolism of tramadol by a mixed way with IC 50 of 1.927 µM in RLMs, 2.039 µM in HLMs and 15.32 µM in CYP2D6.1. In summary, according to our findings, apatinib has a strong in vitro inhibitory effect on tramadol, and apatinib can increase the analgesic effect of tramadol and O-desmethyltramadol in rats., Competing Interests: The authors declare that they have no competing interests., (© 2023 Bao et al.)

The objective of this study was to determine the effect of flavonoids on midostaurin disposition considering co-administration and metabolic enzyme gene polymorphism. Enzymatic incubation assays were performed in vitro, while in vivo experiments were conducted in Sprague-Dawley rats. The analytes were determined via UPLC-MS/MS. We found that myricetin was the most potent among the investigated 10 flavonoids in suppressing the metabolism of midostaurin, with an IC 50 at a low μM level. After co-administration of midostaurin and myricetin, the plasma concentration of midostaurin's primary metabolite CGP62221 was reduced corresponding to myricetin exposure. Furthermore, CYP3A4 homologous rat protein CYP3A2 was reduced significantly in the co-administration group. Thereafter, the kinetic parameters of 23 recombinant human CYP3A4 variants were determined using midostaurin. The relative intrinsic clearance varied from 269.63% in CYP3A4.29-8.95% in CYP3A4.17. In addition, the inhibitory potency of myricetin was substantially different for CYP3A4.29 and CYP3A4.17 compared with wild type, with IC 50 values of 9.85 ± 0.27 μM and 90.99 ± 16.13 μM, respectively. Collectively, our data demonstrated that flavonoids, particularly myricetin, can inhibit the metabolism of midostaurin. Additionally, CYP3A4 genetic polymorphism may contribute to stratification of midostaurin blood exposure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

To improve the performance of the conventional coagulation process, a permanganate (Mn(VII)) pre-oxidation combined with Fe(III)/peroxymonosulfate (PMS) coagulation process (Mn(VII)-Fe(III)/PMS) that can significantly improve the removal of dissolved organic carbon (DOC), turbidity, and micropollutants is proposed in this study. Compared with conventional Fe(III) coagulation, the Mn(VII)-Fe(III)/PMS process can also significantly enhance the removal of iohexol and sulfamethoxazole in raw water. During this process, the primary reduction product, Mn(IV), after Mn(VII) pre-oxidation was adsorbed on the floc surfaces and involved in the Fe(III)/PMS process. The natural organic matter (NOM) in raw water mediated the redox cycle of iron. The synergistic effect of NOM, Fe, and Mn facilitated the redox cycle of Mn(III)/Mn(IV) and Fe(III)/Fe(II) to promote the activation of PMS. The sulfate radical (SO 4 •- ) played an important role in the degradation of micropollutants. The formation potential of the detected volatile disinfection by-product (DBP) during the subsequent chlorination was reduced by 21.9% after the Mn(VII)-Fe(III)/PMS process. This study demonstrated the promising application of the Mn(VII)-Fe(III)/PMS process for coagulation and micropollutant control and illustrated the reaction mechanism. This study provides guidance for improving conventional drinking water treatment processes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

Almonertinib was approved for the first-line treatment of advanced NSCLC patients with EGFR-TKI-sensitive genetic mutations by National Medical Products Administration (NMPA) in 2021.The purpose of this study was to establish and validate a fast, accurate, stable and facile ultra-performance liquid chromatography-tandem mass spectrometry method for the quantification of almonertinib in rat plasma, it was employed to explore the effect of Paxlovid on the pharmacokinetics of almonertinib in rats. Zanubrutinib was used as an internal standard (IS), and the plasma samples were prepared by the protein precipitation method using acetonitrile. Chromatographic separation was carried out on a Shimadzu LC-20AT ultra-performance liquid chromatography system using a Shim-pack velox C18 (2.1× 50 mm, 2.7 μM) column. The mobile phase consisted of methanol and 0.1% formic acid-water. Mass spectrum analysis was executed using Shimadzu 8040 Triple quadrupole mass spectrometry. The precursor and product ions of the analyte and internal standard were detected in multiple reaction monitoring (MRM) mode. The typical fragment ions were m/z 526.20 → 72.10 for almonertinib and m/z 472.15 → 290.00 for zanubrutinib (IS). The method was validated to have good linearity for quantifying almonertinib in rat plasma from 0.1-1000 ng/ml (R 2 = 0.999), and the LLOQ was 0.1 ng/ml. The validity of this method was sufficiently verified for selectivity, specificity, extraction recovery, matrix effect, accuracy, precision and stability. The validated UHPLC-MS/MS method was successfully applied to the drug interaction study of almonertinib with Paxlovid in rats. Paxlovid significantly inhibits the metabolism of almonertinib and increased the exposure of almonertinib. This study can help us to understand the metabolic profile of almonertinib better, and further human trials should be conducted to validate the results., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Tang, Bao, Gao, Shao, Xie, Wu, Zhao and Xiao.)

Permanganate (Mn(VII)) is widely used as a mild oxidant in water treatment. However, the reaction rates of some emerging contaminants with Mn(VII) are extremely low. In this study, benzoquinone (BQ), a redox mediator with the important component in dissolved organic matter (DOM), enhanced the oxidation of bisphenol A (BPA) by Mn(VII) in a wide pH range of 4.0-10.0. The redox cycle of BQ would produce semiquinone radicals, which could act as ligands to stabilize the formed Mn(III) in the system to promote the oxidation of BPA. Notably, the presence of BQ might promote the formation of MnO 2 . A novel mechanism was proposed that singlet oxygen ( 1 O 2 ), Mn(III)-ligands (Mn(III)-L) and in-situ formed MnO 2 were the main contributors to accelerate BPA degradation in the Mn(VII)/BQ system. Under acidic conditions, the in-situ formed MnO 2 involved in the redox reaction and part of the Mn(IV) was reduced to Mn(III), indicating that the electron transfer of BQ promoted the formation of active Mn species and enhanced the Mn(VII) oxidation performance. Semiquinone radicals generated by BQ transformation would couple with the hydrogen substitution products of BPA to inhibit BPA self-coupling and promote the ring-opening reactions of BPA. Mn(VII)/BQ had better effect in raw water than in pure water, indicating that the Mn(VII)/BQ system has high potential for practical application. This study provided insights into the role of DOM in enhancing the Mn(VII) oxidation in water treatment., (Copyright © 2022. Published by Elsevier Ltd.)

Iodinated trihalomethanes (I-THMs) have drawn increasing concerns due to their higher toxicity than those of their chlorinated and brominated analogues. In this study, I-THM formation was firstly evaluated for three treatment scenarios - (i) chlorine alone, (ii) chloramine alone, and (iii) mixed chlorine/chloramine - in the presence and absence of UV irradiation for the iodide-containing humic acid solution or natural water. The results indicated that I-THM formation decreased in the order of mixed chlorination/chloramination > chloramination > > chlorination, which fitted the trend of toxicity evaluation results using Chinese hamster ovary cells. Conversely, total organic halide concentration decreased in the order of chlorination > > chloramination ≈ mixed chlorination/chloramination. Besides, I-THM formation can be efficiently controlled in a UV-activated mixed chlorine/chloramine system. Influencing factors including pH values and Br - /I - molar ratios were also systematically investigated in a mixed chlorine/chloramine system. Enhanced I-THM formation was observed with increasing pH values (6.0-8.0) and Br - /I - molar ratios (1: 1-10: 1). The results obtained in this study can provide new insights into the increasing risk of I-THM formation in a mixed chlorine/chloramine system and the effective control of I-THMs in the iodide-containing water using UV irradiation., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this study, electrochemically activated peroxymonosulfate (EC/PMS) with a sacrificial iron electrode was used for the removal of chloramphenicol (CAP) from water. Compared to electrolysis alone, peroxymonosulfate (PMS) alone, and Fe 2+ /PMS, EC/PMS significantly enhanced the CAP degradation. Various parameters, such as the applied current, electrolyte concentration, and PMS dose, were investigated to optimize the process. In addition, acidic conditions facilitated the CAP degradation. The presence of Cl - slightly enhanced the CAP degradation, while both HCO 3 - and NO 3 - exhibited an inhibitory effect on the CAP degradation. The floccules were also analyzed after the reaction by XPS and XRD. Quenching experiments indicated that both sulfate radicals (SO 4 ●- ) and hydroxyl radicals (•OH) were responsible for the CAP degradation. In addition, the degradation products were identified by LC/TOF/MS, and the degradation pathways were proposed accordingly. These results indicated that EC/PMS is a promising treatment process for the remediation of water polluted by CAP., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The present study comparatively investigated the ultrasonic degradation of ketoprofen (KET) and paracetamol (PCT) in water. Ultrasonic irradiation at 555 kHz achieved rapid degradation of KET and PCT in water, the removal efficiencies of KET (2.5-80 μM) and PCT (2.5-80 μM) reached 87.7%-100% and 50.6%-86.9%, respectively, after 10 min of reaction under an ultrasonic power of 60 W. The degradation behaviors of both KET and PCT followed the Langmuir-Hinshelwood model. KET was eliminated faster than PCT because of its higher hydrophobicity. Acidic media favored ultrasonic degradation of KET and PCT. Organic compounds in water matrices exerted a great negative effect on the ultrasonic degradation rates of KET and PCT major by competing with target compounds with the generated radicals at the bubble/water interfacial region. The effects of anions were species dependent. The introduction of ClO 4 - and Cl - enhanced KET and PCT degradation to different extents, while the introduction of HCO 3 - posed a negative effect on both KET and PCT. KET and PCT degradation are accompanied by the generation of several transform intermediates, as identified via LC/MS/MS analysis, and corresponding reaction pathways have been proposed. A human umbilical vein endothelial cell (HUVEC) toxicity evaluation indicated that ultrasonic treatment was capable of controlling the toxicity of KET or PCT degradation. Of note, the enhanced formation of disinfection byproducts (DBPs), i.e., trichloromethane (TCM) and trichloronitromethane (TCNM), was found due to chlorination after ultrasonic treatment for both KET and PCT., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Pyrimidine and purine bases (adenine, cytosine, guanine and thymine) are important precursors of organic chloramines (OC) and disinfection by-products (DBPs) during chlor(am)ination. In this study, OC and DBP formation derived from pyrimidine and purine bases during chlor(am)ination, post-chlor(am)ination after pretreated by UV alone and UV/chlorination were systematically investigated with ultraviolet light-emitting diodes (UV-LEDs, 265 and 275 nm) and low pressure mercury lamp (LPUV, 254 nm). The results revealed that higher OC formation was observed during chlorination than that during chloramination of pyrimidine and purine bases. The degradation of pyrimidine and purine bases followed the pseudo-first-order kinetics. Both solution pH and UV wavelength played vital influence on the degradation of pyrimidine and purine bases. In terms of fluence-based rate constants (k obs ), the degradation rates of pyrimidine and purine bases decreased in the order of 275 nm > 265 nm > 254 nm in alkaline conditions. The synergistic effects of k obs, chlorine, k obs, •OH and k obs, RCS contributed to the differences of pyrimidine and purine bases degradation at different pH values and UV wavelengths. A vital suppression of OC formation was observed during post-chlorination after pretreated by 275 nm UV-LED/chlorination. In addition, compared with LPUV (254 nm), less DBP formation was observed at UV-LED (275 nm), especially during the UV/chlorine process. The phenomena obtained in this study indicated that 275 nm UV-LED combined with chlorine could be a preferred method to promote pyrimidine and purine bases degradation and control OC and DBP formation in practical water treatment., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In this study, molybdenum disulfide (MoS 2 ) was chosen as a co-catalyst to enhance the removal efficiency of phenacetin (PNT) in water by a ferrous ion-activated peroxymonosulfate (Fe 2+ /PMS) process. Operating parameters, such as the initial solution pH and chemical dose on PNT degradation efficiency were investigated and optimized. Under an initial pH of 3, an Fe 2+ dose of 25 μM, a PMS dose of 125 μM and a MoS 2 dose of 0.1 g L -1 , the degradation efficiency of PNT reached 94.3%, within 15 min. The presence of common water constituents including Cl - , HCO 3 - , SO 4 2- and natural organic matter (NOM) will inhibit degradation of PNT in the MoS 2 /Fe 2+ /PMS system. Radical quenching tests combined with electron paramagnetic resonance (EPR) results indicated that in addition to free radical species (˙OH, SO 4 ˙ - and O 2 ˙ - ), nonradical reactive species ( 1 O 2 ) were also crucial for PNT degradation. The variations in the composition and crystalline structure of the MoS 2 before and after the reaction were characterized by XPS and XRD. Further, the degradation pathways of PNT were proposed according to the combined results of LC/TOF/MS and DFT calculations, and primarily included hydroxylation of the aromatic ring, cleavage of the C-N bond of the acetyl-amino group, and cleavage of the C-O bond of the ethoxy group. Finally, toxicity assessment of PNT and its products was predicted using the ECOSAR program., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Odors and tastes have become universal problems related to drinking water quality. In addition to the typical odor problems caused by algae or microorganisms, the occurrence of odors derived from drinking water disinfection have attracted attention. The chlor(am)ination-derived odor substances have certain toxicity and odor-causing characteristics, and would enter the tap water through water distribution systems, directly affecting drinking water safety and customer experience. This study provided a comprehensive overview of the occurrence, detection, and control of odor substances derived from drinking water chlor(am)ination disinfection. The occurrence and formation mechanisms of several typical types of disinfection derived odor substances were summarized, including haloanisoles, N-chloroaldimines, iodotrihalomethanes, and halophenoles. They are mainly derived from specific precursors such as halophenols, anisoles, and amino acids species during the disinfection or distribution networks. In addition, the change of disinfectant during chlor(am)ination was also one of the causes of disinfection odors. Due to the extremely low odor threshold concentrations (OTCs) of these odor substances, the effective sample pre-enrichment for instrument identification and quantification are essential. The control strategies of odor problems mainly include adsorption, chemical oxidation, and combined processes such as ozonation and biological activated carbon processes (O 3 /BAC) and ultraviolet-based advanced oxidation processes (UV-AOPs). Finally, the challenges and possible future research directions in this research field were discussed and proposed., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study was to evaluate the effect of resveratrol on the pharmacokinetics of ticagrelor in rats and the metabolism of ticagrelor in human cytochrome P450 (CYP) 3A4 (CYP3A4) and liver microsomes. Eighteen Sprague-Dawley rats were randomly divided into three groups: group A (control group), group B (50 mg/kg resveratrol), and group C (150 mg/kg resveratrol). After 30 min administration of resveratrol, a single dose of ticagrelor (18 mg/kg) was administered orally. The in vitro experiment was performed to examine the influence of resveratrol on ticagrelor metabolism in CYP3A4*1, human, and rat liver microsomes. Serial biological samples were assayed by validated ultra high-performance liquid chromatography - tandem mass spectrometer methods. For the in vivo study, the area under the concentration-time curve and mean peak plasma concentrations of ticagrelor in group B and C appeared to be significantly higher than the control group, while volume of distribution in terminal phase and apparent clearance of ticagrelor in group B and C were significantly decreased. For the in vitro study, resveratrol exhibited an inhibitory effect on CYP3A4*1, human and rat liver microsomes. The half-maximal inhibitory concentration values of resveratrol were 56.75 μM, 69.07 μM, and 14.22 μM, respectively. Our results indicated that resveratrol had an inhibitory effect on the metabolism of ticagrelor in vitro and in vivo. Further research should focus on the clinical combination of resveratrol with ticagrelor, and ticagrelor plasma concentration should be monitored to avoid the occurrence of adverse reaction.

A novel light source UV-C laser was applied in persulfate (PS) activation to effectively remove iodinated X-ray contrast medias (ICMs) including iohexol (IOX), iopamidol (IPM) and diatrizoate (DTZ) in this study. Significant ICMs degradation was observed in UV-C laser/PS systems with pseudo first-order rate constants of 0.022-0.067 s -1 . Sulfate radicals (SO 4 •- ) were the main active species in the three ICMs degradation, and the steady-state concentrations ([SO 4 •- ] ss ) were 3.629 × 10 -11  M (IOX), 1.702 × 10 -11  M (IPM) and 1.148 × 10 -11  M (DTZ), respectively. Under the high intensity of UV-C laser, the optimal reaction efficiency was achieved at pH = 7.0 with PS concentration of 1.0 mM, and the degradation efficiency for IOX reached 93.8% within only 40 s. Both bicarbonate and chloride ions could inhibit the three ICMs degradation and the inhibition rate increased with the increase of ions concentration. The kinetic models were established and the steady-state concentrations of radicals were calculated. Density functional theory (DFT) calculations combined with experiments were used to derive the reaction pathways for three ICMs. Cyclic voltammetry measurements detected a lower redox potential peak in IOX degradation, revealing the existence of electron shuttles under the UV-C laser irradiation to promote the redox reaction. This study is the first report of UV-C laser activation of persulfate. It is a new advanced oxidation process mediated by very effective photolysis and active species formation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This study investigated the mechanisms of mixed IO 3 - /I - system under UV irradiation in drinking water and compared the iodinated trihalomethanes (I-THMs) formation of a mixed IO 3 - /I - system to that of single I - and IO 3 - systems during subsequent chloramination. The effects of initial I - /IO 3 - molar ratio, pH, and UV intensity on a mixed IO 3 - /I - system were studied. The introduction of I - enhanced the conversion rate of IO 3 - to reactive iodine species (RIS). Besides, IO 3 - degradation rate increased with the increase of initial I - concentration and UV intensity and the decrease of pH value. In a mixed IO 3 - /I - system, IO 3 - could undergo direct photolysis and photoreduction by hydrated electron (e aq - ). Moreover, the enhancement of I-THM formation in a mixed IO 3 - /I - system during subsequent chloramination was observed. The I-THM yields in a mixed IO 3 - /I - system were higher than the sum of I-THMs produced in a single IO 3 - and I - systems at all the evaluated initial I - concentrations and pH values. The difference between I-THM formation in a mixed IO 3 - /I - system and the sum of I-THMs in a single IO 3 - and I - systems increased with the increase of initial I - concentration. As the initial pH decreased from 9 to 5, the difference of I-THM yields enhanced, while the total I-THM yield of a mixed IO 3 - /I - system and single I - and IO 3 - systems decreased slightly. Besides, IO 3 - -I - -containing water with DOC concentration of 2.5-4.5 mg-C/L, which mainly contained humic-acid substances, had a higher risk in I-THMs formation than individual I - -containing and IO 3 - -containing water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The conversion mechanisms of chlorine species (including free chlorine, monochloramine (NH 2 Cl), dichloramine, and total chlorine), nitrogen species (including ammonium (NH 4 + ), nitrate (NO 3 - ), and nitrite (NO 2 - )) as well as the formation of disinfection by-products (DBPs) in a UV-activated mixed chlorine/chloramines system in water were investigated in this work. The consumption rates of free chlorine and NH 2 Cl were significantly promoted in a HOCl/NH 2 Cl coexisting system, especially in the presence of UV irradiation. Moreover, the transformation forms of nitrogen in both ultrapure and HA-containing waters were considerably affected by UV irradiation and the mass ratio of free chlorine to NH 2 Cl. NO 3 - and NO 2 - can be easily produced under UV irradiation, and the removal efficiency of total nitrogen with UV was obvious higher than that without UV when the initial ratio of HOCl/NH 2 Cl was less than 1. The roles of different radicals in the degradation of free chlorine, NH 2 Cl and NH 4 + were also considered in such a UV-activated mixed chlorine/chloramines system. The results indicated that OH• was important to the consumption of free chlorine and NH 2 Cl, and showed negligible influence on the consumption of NH 4 + . Besides, the changes of DOC and UV 254 in HA-containing water in UV-activated mixed chlorine/chloramines system indicated that the removal efficiency of DOC (24%) was much lower than that of UV 254 (94%). The formation of DBPs in a mixed chlorine/chloramines system was also evaluated. The yields of DBPs decreased significantly as the mass ratio of HOCl/NH 2 Cl varied from 1 : 0 to 0 : 1. Moreover, compared to the conditions without UV irradiation, higher DBPs yields and DBP-associated calculated toxicity were observed during the UV-activated mixed chlorine/chloramine process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The effect of bromide and iodide on the transformation of humic acid (HA) and algal organic matter (AOM), and the formation of disinfection by-products (DBPs) during UV/chlorination were investigated. Experimental results indicated that the halides effectively inhibited mineralization, with multiple changes in organic molecule transformation due to differences in formation and speciation of reactive halogen species and free halogen. As a consequence, bromide and iodide also played important roles in DBP formation. The DBP yields in HA-containing water during UV/chlorination decreased in the order of iodide loaded > freshwater ≫ bromide loaded, whereas DBP formation in AOM-containing water decreased remarkably with halides added (freshwater > bromide loaded ≫ iodide loaded) at high UV fluence. Moreover, Pearson correlation analysis exhibited weaker correlation between DBPs and water parameters in AOM-containing water, while DBPs in HA-containing water exhibited better correlation with water parameters. For both simulated waters, the theoretical toxicity was calculated and peaked in bromide-containing water, whereas the calculated toxicity in iodide-containing water was comparable or slightly higher than that in freshwater. Therefore, UV/chlorine treatment may achieve good quality water with reduced DBP-associated toxicity in freshwater or iodide-containing water (iodide only), but careful consideration is needed when purifying source waters containing bromide (bromide only), especially for AOM/bromide-containing water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this study, nano zero-valent iron (nZVI) was utilized to activate persulfate (PS) for the degradation of metoprolol (MTP), a commonly used drug for curing cardiovascular diseases, in water. Quenching tests indicated that both the sulfate radical (SO 4 ˙ - ) and hydroxyl radical (˙OH) contributed to the degradation of MTP, while SO 4 ˙ - seemed to play a large role under natural pH conditions. Batch tests were conducted to investigate the effects of several influencing factors, such as PS concentration, initial MTP concentration, pH, temperature and common anions, on the degradation performance of MTP. Generally, lower MTP concentration and pH values, and higher PS concentration and temperature favoured MTP degradation. HCO 3 - , NO 3 - and SO 4 2- were found to inhibit MTP degradation, while Cl - enhanced MTP degradation. Several corrosion products of nZVI, including Fe 3 O 4 , Fe 2 O 3 and FeSO 4 , were formed during the reaction, which was reflected by the combined XRD and XPS analysis. Degradation pathways of MTP were proposed according to the identified transformation products, and the peak areas of the major products along with the time were also monitored. Finally, the toxicity of the reaction solution was assessed by experiments using Aliivibrio fischeri . Overall, it could be concluded that nZVI/PS might be a promising method for the rapid treatment of MTP-caused water pollution., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

With increasing shortage of clean water, rainwater has been considered as a precious alternative drinking water source. The processes applied to rainwater treatment are responsible for the safety of drinking water. Therefore, we systematically compared different disinfection processes to evaluate the control of disinfection by-product (DBP) formation and integrated cyto- and genotoxicity of the treated rainwater for the first time. The evaluated disinfection processes included chlorination and chloramination, pre-oxidation by potassium permanganate (KMnO 4 ) and potassium ferrate (K 2 FeO 4 ), ultraviolet/hydrogen peroxide (UV/H 2 O 2 ), and ultraviolet/persulfate (UV/PS) processes. The results revealed that chloramination was effective for controlling the formation of carbonaceous DBPs (C-DBPs), but not nitrogenous DBPs (N-DBPs). Compared to KMnO 4 pre-oxidation, better reduction of almost all DBPs was observed during K 2 FeO 4 pre-oxidation. According to the calculation of cytotoxicity index (CTI) and genotoxicity index (GTI), cyto- and genotoxicity of the samples decreased obviously at the dosage of ≥ 2.0 mg/L KMnO 4 and K 2 FeO 4 . The control of the cyto- and genotoxicity of the formed DBPs from the two UV-related AOPs was more effective at the dosage of ≥ 1.0 mM PS and ≥ 5.0 mM H 2 O 2 . Moreover, UV/PS was much more powerful to alter the structure of DBP precursors in rainwater., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The degradation of metoprolol (MTP), a β-blocker commonly used for cardiovascular diseases, by UV/chlorine and UV/H 2 O 2 processes was comparatively evaluated. MTP direct photolysis at 254 nm could be neglected, but remarkable MTP degradation was observed in both the UV/chlorine and UV/H 2 O 2 systems. Compared with UV/H 2 O 2 , UV/chlorine has a more pronounced MTP degradation efficiency. In addition to primary radicals (OH and Cl), secondary radicals (ClO and Cl 2 - ) played a pivotal role in degrading MTP by UV/chlorine process. The relative contributions of hydroxyl radicals (OH) and reactive chlorine species (RCS) in the UV/chlorine system varied at different solution pH values (i.e., the contribution of RCS increased from 57.7% to 75.1% as the pH increased from 6 to 8). The degradation rate rose as the oxidant dosage increased in the UV/chlorine and UV/H 2 O 2 processes. The presence of Cl - slightly affected MTP degradation in both processes, while the existence of HCO 3 - and HA inhibited MTP degradation to different extents in both processes. In terms of the overall cost of electrical energy, UV/chlorine is more cost efficient than UV/H 2 O 2 . The degradation products during the two processes were identified and compared, and the degradation pathways were proposed accordingly. Compared with the direct chlorination of MTP, pre-oxidation with UV/chlorine and UV/H 2 O 2 significantly enhanced the formation of commonly known DBPs. Therefore, when using UV/chlorine and UV/H 2 O 2 in real waters to remove organic pollutants, the possible risk of enhanced DBP formation resulting from the degradation of certain pollutants during post-chlorination should be carefully considered., Competing Interests: Declaration of competing interest We declare that we have no conflict of interest., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The formation and control of haloacetamides (HAcAms) in drinking water have raised high attention due to their high genotoxicity and cytotoxicity, especially the most cytotoxic one, diiodoacetamide (DIAcAm). In this study, the degradation of DIAcAm by UV/chlorination was investigated in terms of degradation kinetics, efficiency, influencing factors, oxidation products and toxicity evaluation. Results revealed that the degradation of DIAcAm by UV/chlorine process followed pseudo-first-order kinetics, and the rate constant between DIAcAm and OH radicals was determined as 2.8 × 10 9  M -1  s -1 . The contribution of Cl to DIAcAm degradation by UV/chlorine oxidation was negligible. Increasing chlorine dosage and decreasing pH significantly promoted the DIAcAm degradation during UV/chlorine oxidation, but the presence of bicarbonate (HCO 3 - ) and natural organic matter (NOM) inhibited it. The mass balance analysis of iodine species was also evaluated during UV/chlorine oxidation of DIAcAm. In this process, with DIAcAm decreasing from 16.0 to 0.8 μM-I in 20 min, IO 3 - , I - and HOI/I 2 increased from 0 to 6.3, 6.1 and 0.5 μM-I, respectively. The increase of CHO cell viability during DIAcAm degradation indicated that the toxicity of DIAcAm could be decreased by chlorination, UV irradiation and UV/chlorine oxidation treatments, in which UV/chlorine oxidation was more effective on toxicity reduction than chlorination and UV irradiation alone., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study compared the degradation of dissolved organic matter (DOM) by UV/chlorine advanced oxidation processes (AOPs) with emerging ultraviolet light-emitting diode (UV-LED, 275 nm) and traditional low pressure UV (LPUV, 254 nm) as UV sources. Excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and two-dimensional (2D) correlation gel permeation chromatograph were applied to explore the evolutions of DOM during oxidation processes. The degradation behaviors of DOM indicated by UV absorbance at 254 nm (UV 254 ), dissolved organic carbon (DOC), and fluorophores fitted the pseudo-first-order kinetics well. The removal efficiency of DOM was similar under UV-LED and LPUV irradiation alone. However, UV-LED exhibited much higher degradation rates (increased by 29-160%) than LPUV regardless of the tracking variables during UV/chlorine processes. For three PARAFAC components, humic-like fluorescences were preferentially degraded by UV/chlorine oxidation compared with protein-like fluorescence potentially due to the differences of electronic moieties and molecular weight (MW). The decline in UV 254 , DOC, and fluorophores increased with increasing chlorine dosage; linear correlations between those indicators were observed during the two AOPs. Moreover, UV-LED/chlorine could achieve greater extents of MW change. Our study demonstrated that UV-LED could be a superior alternative for the future selection of UV source in the UV/chlorine process., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ultraviolet light-emitting diodes (UV-LEDs) are promising alternatives to conventional low-pressure UV (LPUV) lamps, mainly because they contain no toxic mercury and have a potential for less energy consumption and longer lifetime. In this study, UV sources including UV-LEDs (265, 275 and 285 nm) and LPUV (254 nm) were compared in UV/chlorine degradation of an organic contaminant, ronidazole (RNZ). UV-LED/chlorine performed better than LPUV/chlorine at neutral and alkaline pH values for RNZ degradation considering the fluence-based rate constant. However, the wall plug efficiencies of UV-LEDs are relatively low at present and must reach about 20-25% to achieve the same electrical energy per order as the LPUV in UV/chlorine degradation of RNZ at pH 7.5 and 9. Neither the contribution of radical (HO· or Cl·) nor the quantum yield of chlorine could explain the different RNZ degradation rate by UV/chlorine at different wavelengths and pH values, while the chlorine photolysis rate should be the key factor for these phenomena. The effects of common co-existing substances in real water (chloride, bicarbonate and natural organic matter) on UV/chlorine degradation of RNZ were similar at different UV wavelengths. Opposite to other oxidants or reductants, the molar absorption coefficient of chlorine increases when the UV wavelength increases from 254 to 285 nm at neutral and alkaline pH, which makes UV-LED/chlorine one of the best choices for UV-LED-based advanced oxidation/reduction processes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The efficiency of the ultraviolet (UV)/chlorine process strongly depends on UV wavelength because chlorine photolysis and its subsequent radical formation are highly wavelength-dependent. This study compared the degradation of humic acid (HA) during the UV/chlorine process by low pressure mercury lamp (LPUV, 254 nm) and ultraviolet light-emitting diode (UV-LED, 275 and 310 nm). The results indicated that HA degradation followed the pseudo-first-order kinetics, and the fluence-based degradation rate constants (k obs ) were significantly affected by UV wavelength and solution pH. HA degradation decreased greatly with increasing solution pH during the UV/chlorine process at 254 nm, while the opposite trend was observed at 275 and 310 nm. In the meantime, k obs decreased in the order of 275 nm > 254 nm > 310 nm at pH > 7.0. The changes of chlorine molar absorption coefficients at different UV wavelengths resulted in the variation of chlorine photodecay rates (k obs, chlorine ), and the synergistic effects of k obs, chlorine and chlorine quantum yields (Φ chlorine ) affected HA reduction. The formation of disinfection by-products (DBPs) during the UV/chlorine process was also evaluated. A significant suppression on DBP formation and DBP-associated calculated theoretical cytotoxicity were observed at 275 nm high UV fluence and alkaline pHs. These findings in this study demonstrate that UV wavelength at 275 nm is more suitable for HA degradation by the UV/chlorine advanced oxidation process in practical applications., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Pulsed ultraviolet (UV) irradiation has presented enhanced inactivation efficiency in water disinfection and food decontamination. As an emerging UV source, UV light-emitting diodes (UV-LEDs) are an attractive alternative for pulsed irradiation because they can be turned on and off with a high and adjustable frequency. In this study, disinfection efficiencies of pulsed and continuous UV-LED irradiation were compared for Escherichia coli (E. coli) inactivation in water using a high power 285 nm LED and low power 265 and 280 nm LEDs. Factors including various duty cycles, pulse frequencies and UV irradiances were evaluated. The log-inactivation of E. coli increased substantially as the duty cycle decreased from 100% to 5% at the same UV dose. For 265 and 280 nm LEDs, the log-inactivation enhancements of pulsed UV irradiation were similar. When a higher irradiance was applied, the energy efficiency enhancement of pulsed UV irradiation became more obvious. The log-inactivation of E. coli enhanced remarkably using high current pulsed irradiation of 280 nm LEDs. Compared to continuous UV irradiation, pulsed UV-LED irradiation is an attractive alternative for E. coli inactivation in water considering energy efficiency., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Ultraviolet (UV) irradiation has been widely used in drinking water treatment processes, but its influence on the formation of disinfection by-products (DBPs), especially the emerging iodinated trihalomethanes (I-THMs) during post-chloramination remains unclear. This study evaluated the impact of low pressure (LP) UV treatment on the formation of I-THMs during post-chloramination through two pathways. The first pathway is through the transition of DOM structure and composition during UV-chloramination, resulting significant increase of I-THM formation with increasing UV dosage in different dissolved organic matter (DOM)-containing water (49.7%-90.5% at 1160 mJ/cm 2 ). With the application of excitation emission matrix-parallel factor analysis (EEM-PARAFAC), we found that I-THM formation in UV-chloraminated water correlated well with two ratios of three PARAFAC humic-like components (C3/C2 and C1/C2, R 2  = 0.958-1.000), suggesting that the ratios of fluorescent components can be used as reliable indicators for I-THM formation. Moreover, the shift in these fluorescent components is crucial for I-THM formation during UV-chloramination. Another pathway for UV irradiation to affect I-THM formation during post-chloramination is through the transformation of iodine species. Large amounts of reactive iodine species (HOI/I 2 and I 3 - ) can be generated directly in the mixed iodine system by UV light, leading to the enhancement of iodine utilization factor (IUF) (up to 0.040) after post-chloramination. These results suggest that UV application to DOM-containing water may induce changes in organic precursors and iodine species so as to enhance I-THM formation during post-chloramination., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study investigated the heat activated persulfate (heat/PS) process in the degradation of propranolol from water. Various factors ( e.g. , temperature, persulfate dose, initial pH and natural water constituent) on PRO degradation kinetics have been investigated. The results showed that the PRO degradation followed a pseudo-first-order kinetics pattern. As temperature rises, the pseudo-first-order rate constant ( k obs ) was improved significantly, and the k obs determined at 40-70 °C satisfied the Arrhenius equation, yielding an activation energy of 99.0 kJ mol -1 . The radical scavenging experiments and the EPR tests revealed that both SO 4 ˙ - and ·OH participated in degrading PRO, with SO 4 ˙ - playing a dominant role. Higher PS concentration and neutral pH favored PRO degradation. The impact of Cl - and HCO 3 - were concentration-dependent. A lower concentration of Cl - and HCO 3 - could accelerate PRO degradation, while the presence of HA showed inhibitory effects. Seven degradation products were recognized through LC/MS/MS analysis. Cleavage of ether bond, hydroxylation, and ring-opening of naphthol moiety are involved in the PRO's degradation pathway. Finally, the formation of disinfection byproducts (DBPs) before and after pre-treated by heat/PS was also evaluated. Compared with direct chlorination of PRO, the heat/PS pre-oxidation greatly impacted the DBPs formation. The higher PRO removal efficiency in natural water indicated the heat/PS process might be capable of treating PRO-containing water samples, however, its impacts on the downstream effect on DBPs formation should be also considered., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

This study investigated the degradation of propranolol (PRO), a beta (β)-blockers, by nano zero-valent iron (nZVI) activated persulfate (PS) under ultrasonic irradiation. Effects of several critical factors were evaluated, inclusive of PS concentration, nZVI dosage, ultrasound power, initial pH, common anions, and chelating agent on PRO degradation kinetics. Higher PS concentration, nZVI dosage and ultrasound power as well as acidic pH favored the PRO degradation. Conversely, anions and chelating agent took on the inhibitory effect towards PRO degradation to different extents. Furthermore, the variations of morphology and surface composition of nZVI before and after the reaction were characterized by TEM, XRD and XPS. Finally, on the basis of identified degradation intermediates by LC/MS/MS analysis, this work tentatively proposed the degradation pathways. These encouraging results suggest that US/nZVI/PS process is a promising strategy for the treatment of PRO-induced water pollutant., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Chloramine disinfection is one of the most common disinfection methods in drinking water treatment. In this study, the temporal variability of water odors during monochloramine auto-decomposition was investigated to elucidate the characteristics of odor problems caused by adopting chloramine disinfection in tap water. Odor intensities and dominant odorant contributions were determined using the flavor profile analysis (FPA) and odor active value (OAV), respectively. During auto-decomposition of monochloramine, Cl 2 /N molar ratio, pH, temperature, and the presence of NOM all affected odor intensity and odor temporal variation in drinking water. In general, decreasing pH from 8.5 to 6.0 led to increasing perceived odor intensity due to the formation of dichloramine. The major odorants responsible for chlorinous odor under acidic and non-acidic conditions were dichloramine and monochloramine, respectively. Chloraminated water with a Cl 2 /N molar ratio of 0.6 or NOM concentration <2 mg-C L -1 inhibited odor intensity. Furthermore, the influence of rechlorination on chlorinous odor intensity for chloraminated water should not be neglected. The results of this study will be beneficial for the control of chlorinous odors caused by chloramine disinfection in drinking water., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study investigated the formation of toxic iodinated trihalomethanes (I-THMs) during breakpoint chlorination of iodide-containing water. Impact factors including I - concentration, natural organic matter (NOM) concentration and type, pH as well as Br - /I - molar ratio were systematically investigated. Moreover, the incorporation of I - into I-THM formation was also calculated. The results showed that I-THM formation varied in different zones of the breakpoint curves. I-THMs increased with increasing chlorine dosage to breakpoint value and then dropped significantly beyond it. Iodoform (CHI 3 ) and chlorodiiodomethane (CHClI 2 ) were the major I-THMs in the pre-breakpoint zone, while dichloroiodomethane (CHCl 2 I) was the dominant one in the post-breakpoint zone. The formation of I-THMs increased remarkably with I - and dissolved organic carbon (DOC) concentrations. More bromine-containing species were formed as Br - /I - molar ratio increased from 0.5 to 5. In addition, the major I-THM compound shifted from CHCl 2 I to the more toxic CHClBrI. As pH increased from 6.0 to 8.0, I-THM formation kept increasing in the pre-breakpoint zone and the speciation of I-THMs changed alongside the breakpoint curves. The incorporation of I - during breakpoint chlorination was highly dependent on chlorine, I - , and NOM concentrations, NOM type, solution pH and Br - /I - molar ratio., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this study, the degradation of propranolol (PRO) by UV/persulfate process was systematically investigated. Direct photolysis of PRO was limited due to its low quantum yield, while the PRO degradation efficiency can be greatly promoted by the combination of persulfate and UV irradiation. Radical scavenging tests showed that both SO 4 - and OH contributed to the removal of PRO, with SO 4 - playing a more important role. The degradation rate of PRO was improved by increasing the persulfate dose and initial solution pH consistent with pseudo-first-order reaction kinetics. The effects of common water constituents were species dependent. HCO 3 - and Cl - promoted PRO degradation. By contrast, NO 3 - and HA were found to inhibit PRO degradation. A total of nine degradation products were identified by LC/MS/MS, which mainly derived from the ring-opening attack on the naphthalene group or oxidation of the amino moiety by SO 4 - and OH. Finally, the toxicity of the reaction mixtures was also assessed using luminescent bacteria Vibrio fischeri, and the results indicated that UV/persulfate is capable of controlling the toxicity of PRO degradation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Acrylamide is a monomer of polyacrylamide, which is widely used in the water treatment process as a flocculant. The degradation kinetics and formation of disinfection by-products (DBPs) during acrylamide chlorination were investigated in this study. The reaction between chlorine and acrylamide followed a pseudo-first-order kinetics. A kinetic model regarding acrylamide chlorination was established and the rate constants of each predominant elementary reaction (i.e., the base-catalyzed reaction of acrylamide with ClO - as well as the reactions of acrylamide with HOCl and ClO - ) were calculated as 7.89×10 7 M -2 h -1 , 7.72×10 1 M -1 h -1 , and 1.65×10 3 M -1 h -1 , respectively. The presence of Br - in water led to the formation of HOBr and accelerated the rate of acrylamide degradation by chlorine. The reaction rate constant of acrylamide with HOBr was calculated as 1.33×10 3 M -1 h -1 . The degradation pathways of acrylamide chlorination were proposed according to the intermediates identified using ultra-performance liquid chromatography and electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). Five chlorinated DBPs including chloroform (CF), dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), dichloroacetamide (DCAcAm), and trichloroacetamide (TCAcAm) were identified during acrylamide chlorination. The formation of CF, DCAN, DCAcAm, and TCAcAm kept increasing, while that of TCAN increased and then decreased with increasing reaction time. As the chlorine dosage increased from 0.75 to 4.5mM, DCAN became the dominant DBP. Large amounts of CF, DCAN, and TCAN were formed at basic pHs. The hydrolysis of DCAN and TCAN led to the formation of DCAcAm and TCAcAm, respectively. The results of this study elucidated that acrylamide can be a precursor for the formation of haloacetonitriles (HANs) and haloacetamides (HAcAms) during drinking water treatment., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Iodide (I - ) and iodinated X-ray contrast media (ICM) are the primary iodine sources for the formation of iodinated disinfection byproducts (I-DBPs), and iodate (IO 3 - ) is believed to be a desired sink of iodine in water. This study found that highly cytotoxic iodinated trihalomethanes (I-THMs) also can be generated from iodate-containing waters (without any other iodine sources) in the presence of zero valent iron (ZVI) during chloramination, which could be a big issue in the wide usage of iron pipes. The effect of major factors including ZVI dosage, NH 2 Cl and IO 3 - concentrations, initial pH, Br - /IO 3 - molar ratio, phosphate concentration, iron corrosion scales (goethite and hematite) on the formation of I-THMs were investigated. Formation of I-THMs from IO 3 - increased with the increase of ZVI dosage, IO 3 - and NH 2 Cl concentrations. Chloramines can also remarkably accelerate the reduction of IO 3 - by ZVI. Peak I-THM formation was found at pH 8. As the Br - /IO 3 - molar ratio increased from 0 to 20, I-THM formation considerably enhanced, especially for the bromine-incorporated species. Goethite and hematite enhanced the formation of I-THMs in the presence of ZVI. Additionally, a significant suppression on I-THM formation was observed with the addition of phosphate. Considering that a large number of water distribution networks contain unlined cast iron pipes, transformation of IO 3 - in the presence of ZVI during chloramination may contribute to the formation of I-THMs in such systems., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The degradation of acrylamide (AA) during UV/chlorine advanced oxidation process (AOP) was investigated in this study. The degradation of AA was negligible during UV irradiation alone. However, AA could be effectively degraded and mineralized during UV/chlorination due to the generation of hydroxyl radicals (OH). The degradation kinetics of AA during UV/chlorination fitted the pseudo-first order kinetics with the rate constant between AA and OH radicals being determined as 2.11 × 10 9  M -1  s -1 . The degradation rate and mineralization of AA during UV/chlorination were significantly promoted at acidic conditions as well as increasing chlorine dosage. The volatile degradation products of AA during UV/chlorination were identified using gas chromatography-mass spectrometry and the degradation pathways were then proposed accordingly. The formation of disinfection by-products (DBPs) in Milli-Q water and tap water during UV/chlorination of AA was also investigated. The DBPs included chloroform, dichloroacetonitrile, trichloroacetonitrile, 2,2-dichloroacetamide and 2,2,2-trichloroacetamide. Furthermore, the variations of AA degradation during UV/chlorination in different real water samples were evaluated., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The degradation kinetics, pathways and disinfection by-products (DBPs) formation of iopamidol by chlorine and chloramines were investigated in this paper. The chlorination kinetics can be well described by a second-order model. The apparent second-order rate constants of iopamidol chlorination significantly increased with solution pH. The rate constants of iopamidol with HOCl and OCl - were calculated as (1.66 ± 0.09) × 10 -3  M -1  s -1 and (0.45± 0.02) M -1  s -1 , respectively. However, the chloramination of iopamidol fitted well with third-order kinetics and the maximum of the apparent rate constant occurred at pH 7. It was inferred that the free chlorine (i.e., HOCl and OCl - ) can react with iopamidol while the combined chlorine species (i.e., NH 2 Cl and NHCl 2 ) were not reactive with iopamidol. The main intermediates during chlorination or chloramination of iopamidol were identified using ultra performance liquid chromatography - electrospray ionization-mass spectrometry (UPLC-ESI-MS), and the destruction pathways including stepwise deiodination, hydroxylation as well as chlorination were then proposed. The regular and iodinated DBPs formed during chlorination and chloramination of iopamidol were measured. It was found that iodine conversion from iopamidol to toxic iodinated DBPs distinctly increased during chloramination. The results also indicated that although chloramines were much less reactive than chlorine toward iopamidol, they led to the formation of much more toxic iodinated DBPs, especially CHI 3 ., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

UV activated sodium persulfate was employed to remove triclosan (TCS) in aqueous solution. The effects of several factors such as UV wavelength,UV 254 intensity,sodium persulfate dosage,pH value,and HA on TCS degradation were investigated. The second-order rate constants of free radicals (·OH, SO 4 ·- ) reacting with TCS and their contributions to TCS removal were determined,respectively. The dominant free radical was also identified. Furthermore, the TCS degradation efficiency in natural water by UV 254 /SPS and UV 254 /H 2 O 2 was compared. Finally,the possible pathway and intermediate products of TCS degradation were analyzed with GC/MS. The results indicated that UV 254 activated sodium persulfate could effectively remove TCS. The removal rate of TCS could reach 98.15% within 100s under the conditions of UV wavelength of 254 nm,UV intensity of 11.5μW·cm -2 ,sodium persulfate dosage of 1mmol·L -1 ,and TCS initial concentration of 275 μg·L -1 . TCS degradation followed the pseudo-first-order kinetic model and the pseudo-first-order rate constant was determined to be 0.0392 s -1 . Pseudo-first-order rate constant for TCS degradation increased with the increase of UV 254 intensity(I)and sodium persulfate dosage within experiment ranges. The effect of UV wavelength on TCS removal was not notable. Neutral condition was detrimental to TCS degradation. TCS removal was inhibited in the presence of HA. The reaction rate constants for·OH and SO 4 ·- reacting with TCS were 7.62×10 9 L·mol -1 ·s -1 and 9.86×10 9 L·mol -1 ·s -1 ,respectively. SO 4 ·- was the dominant free radical and its contribution rate to TCS removal was 97.63 % in UV 254 /SPS system . The K value of UV 254 /SPS was 4.13 times higher than that of UV 254 /H 2 O 2 process,which demonstrated that UV 254 /SPS process could remove TCS more effectively than UV 254 /H 2 O 2 . The main intermediate products found were 2,4-DCP and phenol in the degradation process of TCS in Milli-Q water by UV 254 /SPS.

The illustrated azomethine ylide, produced through a Schiff base condensation of the corresponding aldehyde-containing C3a-arylhexahydroindole with ethyl l-leucinate, engages in a stereoselective intramolecular cycloaddition reaction to give adduct 23 that has been elaborated, over eight steps, into the racemic modification of the alkaloid derivative gracilamine (1). The formation of this ylide and its conversion into isomer 23 mimics the proposed biogenesis of the pentacyclic framework of compound 1.

Three-dimensional ordered mesoporous Co 3 O 4 was prepared by nanocasting method with porous silicon KIT-6 as the hard template and firstly used to activate peroxymonosulfate for the degradation of rhodamine B. The structural properties were characterized by BET, H-TEM, XRD, XPS, FT-IR. The results showed that three-dimensional ordered mesoporous Co 3 O 4 presented far superior catalytic activity over conventional nanoscale Co 3 O 4 due to its abundant space mesoporous channel structure and the large specific surface areas. Higher catalyst dosage and higher peroxymonosulfate concentration favored the decolorization of rhodamine B. The removal of rhodamine B could be accelerated in the presence of Cl - and H 2 PO 4 - ; however, the decolorization of rhodamine B would be inhibited in the presence of NO 3 - , SO 4 2- and HCO 3 - . Sulfate radicals were identified as the dominant active species for the decolorization of rhodamine B through radicals quenching experiments. Three-dimensional ordered mesoporous Co 3 O 4 showed excellent catalytic activity even after five consecutive cycles.

Surface water are frequently subjected to problems of algal blooms and release of algae organic matter (AOM) from the algae cells, which cause many water quality issues. This study investigated the formation of organic chloramines and nitrogenous disinfection by-products (N-DBPs) during chlor(am)ination and UV/chlor(am)ination of AOM in drinking water. AOM caused higher organic chloramine formation than humic acid and fulvic acid during chlor(am)ination. The formation of organic chloramines increased first and then decreased with the increase of free chlorine dosage, but kept increasing with the increase of NH2Cl dosage. During AOM chlorination, the formation of organic chloramines kept decreasing as the reaction time went by, and the maximum organic chloramine proportion (79.1%) in total chlorine occurred at 8 h. However, during AOM chloramination, the formation of organic chloramines increased first, decreased in the following and then increased again as the reaction time went by, and the maximum organic chloramine proportion (22.1%) in total chlorine occurred at 24 h. UV irradiation pretreatment did not effectively influence organic chloramine formation during AOM chlor(am)ination, but accelerated the degradation of organic chloramines during chloramination. Besides, UV pretreatment enhanced the formation of N-DBPs during the subsequent chlor(am)ination of AOM, especially dichloroacetonitrile., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Iodinated trihalomethanes (I-THMs) are a group of emerging disinfection by-products with high toxicity, and iodide (I(-)) as well as iodinated organic compounds are expected to be their iodine sources. Nevertheless, in this study, iodate (IO3(-)) was proven to be a new iodine source of I-THM formation during UV/chloramination. In the iodate-containing waters (without any other iodine sources), I-THM formation increased with the increase of UV dose, IO3(-) and NH2Cl concentrations. With the increase of Br(-)/IO3(-) molar ratio, I-THM formation (especially for the brominated species) increased. Besides, NOM species could affect I-THM formation from IO3(-) during UV/chloramination. Fulvic acid could promote IO3(-) phototransformation to I(-) but humic acid impeded the production of I(-) during UV irradiation. Under realistic drinking water treatment conditions (DOC = 5.0 mg-C/L, IO3(-) = 12.7 μg-I/L, UV dose = 50 mJ/cm(2), NH2Cl = 5 mg-Cl2/L), CHCl2I was detected as 0.17 μg/L using solid-phase microextraction method, and the production rate of I-THMs from IO3(-) was about 7% of that from I(-)., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This study investigated the changes of chlorine species and proportion of organic chloramines during the chlorination process after UV irradiation pretreatment in drinking water. It was found that the UV pretreatment could enhance the percentage of organic chloramines by increasing free chlorine consumption in the chlorination of raw waters. The percentage of organic chloramines in total chlorine increased with UV intensity and irradiation time in raw waters. However, for the humic acid synthesized water, the percentage of organic chloramines increased first and then decreased with the increase of UV irradiation time. The value of SUVA declined in both raw and humic acid synthesized waters over the UV irradiation time, which indicated that the decomposition of aromatic organic matter by UV could be a contributor to the increase of free chlorine consumption and organic chloramine proportion. The percentage of organic chloramines during chlorination of raw waters after 30-min UV irradiation pretreatment varied from 20.2% to 41.8%. Total chlorine decreased obviously with the increase of nitrate concentration, but the percentage of organic chloramines increased and was linearly correlated to nitrate concentration., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

UV irradiation-activated sodium persulfate (UV/PS) was studied to degrade florfenicol (FLO), a phenicol antibiotic commonly used in aquaculture, in water. Compared with UV/H2O2 process, UV/PS process achieves a higher FLO degradation efficiency, greater mineralization, and less cost. The quantum yield for direct photolysis of FLO and the second-order rate constant of FLO with sulfate radicals were determined. The effects of various factors, namely PS concentration, anions (NO3 (-), Cl(-), and HCO3 (-)), ferrous ion, and humic acid (HA), on FLO degradation were investigated. The results showed that the pseudo-first-order rate constant increased linearly with increased PS concentration. The tested anions all adversely affected FLO degradation performance with the order of HCO3 (-) > Cl(-) > NO3 (-). Coexisting ferrous ions enhanced FLO degradation at a Fe(2+)/PS molar ratio under 1:1. HA significantly inhibited FLO degradation due to radical scavenging and light-screening effect. Toxicity assessment showed that it is capable of controlling the toxicity for FLO degradation. These findings indicated that UV/PS is a promising technology for water polluted by antibiotics, and the treatment is optimized only after the impacts of water characteristics are carefully considered.

Objective: The aim of this cross-sectional study was to examine the relationship among pain and other symptoms intensity, and health-related quality of life (HRQoL) in Chinese patients with knee osteoarthritis (OA)., Methods: The study was cross-sectional, descriptive, and correlational. A convenience sample of 466 patients with knee OA was recruited in the study. Age, gender, body mass index (BMI), duration of disease, and Kellgren- Lawrence (KL) scores were recorded. HRQoL and symptoms were assessed using the 36-item Short Form Health Survey (SF-36) and the Western Ontario and McMaster (WOMAC) index in participants., Results: The sample was predominantly female (82%) with mean age 56.56 years and mean BMI 24.53 kg/m(2). We found that WOMAC subscale scores significantly negative correlated with the majority of SF-36 subscale scores in knee OA patients (P < 0.05). There were no correlations between BMI, duration of disease, KL score and the vast majority of SF-36 subscale scores in patients (P > 0.05). In addition, there was a significant correlation between age and PCS, gender and MCS in patients (P < 0.05). Regression analysis showed, WOMAC subscale scores significantly negative correlated with the vast majority of SF-36 subscale scores. WOMAC-pain score had the strongest relationship with SF-36 PCS and MCS scores., Conclusions: In summary, pain severity has a greater impact on HRQoL than patient characteristics, other joint symptoms and radiographic severity in Chinese knee OA patients. Relieving of knee symptoms may help to improve patients' HRQOL. The study provided the evidence that relieving pain should be the first choice of therapy for knee osteoarthritis.

Objective: Although chondroprotective activities have been documented for polysaccharides, the potential target of different polysaccharide may differ. The study was aimed to explore the effect of glucan HBP-A in chondrocyte monolayer culture and chondrocytes-alginate hydrogel constructs in vivo, especially on the expression of type II collagen., Methods: Chondrocytes isolated from rabbit articular cartilage were cultured and verified by immunocytochemical staining of type II collagen. Chondrocyte viability was assessed after being treated with HBP-A in different concentrations. Morphological status of chondrocytes-alginate hydrogel constructs in vitro was observed by scanning electron microscope (SEM). The constructs were treated with HBP-A and then injected to nude mice subcutaneously. Six weeks after transplantation, the specimens were observed through transmission electron microscopy (TEM). The mRNA expressions of disintegrin and metalloproteinase with thrombospondin motifs 5 (ADAMTs-5), aggrecan and type II collagen in both monolayer culture and constructs were determined by real time polymerase chain reaction (PCR). The expression of type II collagen and matrix metalloproteinases-3 (MMP-3) in chondrocyte monolayer culture was also tested through Western blot and enzyme linked immunosorbent assay (ELISA), respectively., Results: MMP-3 secretion and ADAMTs-5 mRNA expression in vitro were inhibited by HBP-A at 0.3 mg/mL concentration. In morphological study, there were significant appearance of collagen in those constructs treated by HBP-A. Accordingly, in both chondrocyte monolayer culture and chondrocytes-alginate hydrogel constructs, the expression of type II collagen was increased significantly in HBP-A group when compared with control group (P<0.001)., Conclusions: The study documented that the potential pharmacological target of glucan HBP-A in chondrocytes monolayer culture and tissue engineered cartilage in vivo may be concerned with the inhibition of catabolic enzymes MMP-3, ADAMTs-5, and increasing of type II collagen expression.

Iodinated trihalomethanes (I-THMs) formation during chlorination and chloramination of five iodinated X-ray contrast media (ICM) compounds (iopamidol, iopromide, iodixanol, histodenz, and diatrizoate) in the presence of natural organic matter (NOM) was evaluated and compared. Chlorination and chloramination of ICM in the absence of NOM yielded only a trace amount of I-THMs, while levels of I-THMs were enhanced substantially in raw water samples. With the presence of NOM, the order with respect to the maximum yield of I-THMs observed during chlorination was iopamidol >> histodenz > iodixanol > diatrizoate > iopromide. During chloramination, I-THM formation was enhanced for hisodenz, iodixanol, diatrizoate, and iopromide. The order with respect to the maximum yield of I-THMs observed during chloramination was iopamidol > diatrizoate > iodixanol > histodenz > iopromide. With the exception of iopamidol, I-THM formation was favored at relatively low chlorine doses (≤100 μM) during ICM chlorination, and significant suppression was observed with high chlorine doses applied (＞100 μM). However, during chloramination, increasing monochloramine dose monotonously increased the yield of I-THMs for the five ICM. During chlorination of iodixanol, histodenz, and diatrizoate, the yields of I-THMs exhibited three distinct trends as the pH increased from 5 to 9, while peak I-THM formation was found at circumneutral pH for chloramination. Increasing bromide concentration not only considerably enhanced the yield of I-THMs but also shifted the I-THMs towards bromine-containing ones and increased the formation of higher bromine-incorporated species (e.g., CHBrClI and CHBr2I), especially in chloramination. These results are of particular interest to understand I-THM formation mechanisms during chlorination and chloramination of waters containing ICM., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Degradation kinetics and pathways of ronidazole (RNZ) by chlorination (Cl2), UV irradiation and combined UV/chlorine processes were investigated in this paper. The degradation kinetics of RNZ chlorination followed a second-order behavior with the rate constants calculated as (2.13 ± 0.15) × 10(2) M(-2) s(-1), (0.82 ± 0.52) × 10(-2) M(-1) s(-1) and (2.06 ± 0.09) × 10(-1) M(-1) s(-1) for the acid-catalyzed reaction, as well as the reactions of RNZ with HOCl and OCl(-), respectively. Although UV irradiation degraded RNZ more effectively than chlorination did, very low quantum yield of RNZ at 254 nm was obtained as 1.02 × 10(-3) mol E(-1). RNZ could be efficiently degraded and mineralized in the UV/chlorine process due to the generation of hydroxyl radicals. The second-order rate constant between RNZ and hydroxyl radical was determined as (2.92 ± 0.05) × 10(9) M(-1) s(-1). The degradation intermediates of RNZ during the three processes were identified with Ultra Performance Liquid Chromatography - Electrospray Ionization - mass spectrometry and the degradation pathways were then proposed. Moreover, the variation of chloropicrin (TCNM) and chloroform (CF) formation after the three processes were further evaluated. Enhanced formation of CF and TCNM precursors during UV/chlorine process deserves extensive attention in drinking water treatment., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Restriction fragment length polymorphism (RFLP) technology was used to investigate the microbial diversity and structure of biological activated carbon (BAC) from different sources in drinking water advanced treatment process. Diversity indices of samples A, B and C, with relatively high tannic acid and humic acid adsorption capacity, were close to each other, which meant higher microbial diversity. However, samples D and E had relatively lower diversity indices with the low tannic acid and humic acid adsorption capacity. There were five species including β-Proteobacteria, α-Proteobacteria, Planctomycetes, γ-Proteobacteria, Bacteroidetes in the phylogenetic tree of BAC samples. Among them, β-Proteobacteria and α-Proteobacteria were the dominant microbial species in these BAC samples, which played an important role in organic matter removal. Planctomycetes, γ-Proteobacteria, and Bacteroidetes were the non-dominant microbial species. Bacteroidetes only existed in samples A, B, C and D, while did not occur in sample E. The BAC samples with the higher tannic acid and humic acid adsorption capacity had higher microbial diversity. This research should deepen the understanding of microbial community in BAC, and provide a theoretical basis for the safety of drinking water.

The photochemical degradation of iopamidol with low-pressure UV lamps and the formation of iodinated disinfection by-products (I-DBPs) during sequential oxidation processes including chlorine, monochloramine and chlorine dioxide were investigated in this study. Iopamidol can be effectively decomposed by UV irradiation with pseudo-first order reaction kinetics. The evaluated quantum yield was found to be 0.03318 mol einstein(-1). Results showed that iopamidol degradation rate was significantly increased by higher UV intensity and lower initial iopamidol concentration. However, the effect of solution pH was negligible. Degradation of iopamidol by UV photolysis was subjected to deiodination and hydroxylation mechanisms. The main degradation products including -OH substitutes and iodide were identified by UPLC-ESI-MS and UPLC-UV, respectively. Increasing the intensity of UV irradiation promoted the release of iodide. Destruction pathways of iopamidol photolysis were proposed. Enhanced formation of I-DBPs were observed after iopamidol photolysis followed by disinfection processes including chlorine, monochloramine and chlorine dioxide. With the increase of UV fluence, I-DBPs formation were significantly promoted., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Objective: To compare the clinical effects of close manipulative reduction combined with minimally invasive percutaneous plate fixation(MIPPO) and conventional open reduction and internal fixation (ORIF) for the treatment of proximal humerus fractures., Methods: From April 2008 to March 2013, among the 75 patients with fractures of proximal humerus, 26 patients were male and 49 patients were female, ranging in age from 22 to 80 years; 18 patients had injuries caused by traffic accident and 57 patients had injuries caused by falling down. According to Neer classification, there were 49 cases of two-part fractures and 26 cases of three-part fractures. All the patients were divided into two groups: MIPPO group and ORIF group. There were 12 males and 21 females in the MIPPO group,including 22 cases of Neer two parts and 11 cases of Neer three parts, who were treated with close manipulative reduction combined with MIPPO. While the other 42 patients were in the ORIF group,including 16 males and 26 females. Among those patients,27 cases belonged to Neer two parts and 15 cases of Neer three parts, who were treated with ORIF. Length of the incision, blood loss, operating time, early postoperative pain(recorded by VAS), neck-shaft angle of proximal humerus and postoperative function of shoulder(recorded by Constant-Murley score, including pain, function, ROM and muscle length) were compared., Results: The mean lengths of incision were (6.74 +/- 0.38) cm in MIPPO group and (16.82 +/- 1.74) cm in ORIF group;blood losses were (110.15 +/- 29.49) ml in MIPPO group and (326.19 +/- 59.71) ml in ORIF group; operation times were (48.60 +/- 10.18) min in MIPPO group and (68.84-16.22) min in ORIF group. VAS of patients in MIPPO group on the 1st and 3rd days postoperatively were lower than those of patients in the ORIF group. The postoperative radiographs verified good position of all screws and satisfactory reduction of bone fracture reduction in both groups. All the patients were followed up,and the durig ranged from 8 to 24 months (mean 14.2 months). In the MIPPO group, there was no humeral head necrosis and all patients gained bone union; while in the ORIF group, 3 patients sustained nonunion and received reoperation for bone grafting, and 2 patients sustained humeral head necrosis. The mean Constant-Murley scores of shoulder were 88.94 +/- 2.57 in the MIPPO group and 86.00 +/- 3.36 in the ORIF group., Conclusion: The close manipulative reduction combined with MIPPO is a better choice for fixation of proximal humerus fractures, compared with conventional plate. This method possesses such advantages as a shorter incision, less disturbance of the blood supply and stable fixation of the fracture, allowing early exercise so that the function of shoulder recovers rapidly.

A novel dual coagulant system of polyaluminum chloride sulfate (PACS) and polydiallyldimethylammonium chloride (PDADMAC) was used to treat natural algae-laden water from Meiliang Gulf, Lake Taihu. PACS (Aln(OH)mCl3n-m-2k(SO4)k) has a mass ratio of 10 %, a SO4 (2-)/Al3 (+) mole ratio of 0.0664, and an OH/Al mole ratio of 2. The PDADMAC ([C8H16NCl]m) has a MW which ranges from 5 × 10(5) to 20 × 10(5) Da. The variations of contaminants in water samples during treatments were estimated in the form of principal component analysis (PCA) factor scores and conventional variables (turbidity, DOC, etc.). Parallel factor analysis determined four chromophoric dissolved organic matters (CDOM) components, and PCA identified four integrated principle factors. PCA factor 1 had significant correlations with chlorophyll-a (r=0.718), protein-like CDOM C1 (0.689), and C2 (0.756). Factor 2 correlated with UV254 (0.672), humic-like CDOM component C3 (0.716), and C4 (0.758). Factors 3 and 4 had correlations with NH3-N (0.748) and T-P (0.769), respectively. The variations of PCA factors scores revealed that PACS contributed less aluminum dissolution than PAC to obtain equivalent removal efficiency of contaminants. This might be due to the high cationic charge and pre-hydrolyzation of PACS. Compared with PACS coagulation (20 mg L(-1)), the removal of PCA factors 1, 2, and 4 increased 45, 33, and 12 %, respectively, in combined PACS-PDADMAC treatment (0.8 mg L(-1) +20 mg L(-1)). Since PAC contained more Al (0.053 g/1 g) than PACS (0.028 g/1 g), the results indicated that PACS contributed less Al dissolution into the water to obtain equivalent removal efficiency.