Ketogenic diet combined with intermittent fasting: an option for type 2 diabetes remission?

With increasing attention to diabetes remission, various special dietary patterns have been found to be effective in achieving diabetes remission. The effect of a single dietary pattern on lowering blood glucose is clear, but studies on the synergistic effects of different dietary patterns are limited. This article describes the types of intermittent fasting and ketogenic diets, potential mechanisms, contraindications of combination diets, recommendations for combination diets, and their health outcomes. This paper aims to illustrate the evidence for intermittent fasting combined with a ketogenic diet on outcomes of diabetes remission and effect on blood glucose control. Knowledge of these findings can help doctors and patients determine dietary patterns for achieving diabetes remission and understanding their application.

Reinvestigation on High-Valent Cobalt for the Degradation of Micropollutants in the Co(II)/Peroxymonosulfate System: Roles of Co(III).

Recently, reactive cobalt (Co) species, including Co(IV)-oxo and Co(II)-OOSO3- complexes, were proposed to be the primary intermediates formed during the process of activating peroxymonosulfate (PMS) by Co(II), mainly based on the observation that the methyl phenyl sulfoxide (MPSO) probe was transformed to methyl phenyl sulfone (MPSO2) in this process. However, in this work, we rationalized the results of the MPSO probe assay based on the chemistry of aqueous Co(III), an alternative reactive Co species. Moreover, 18O-labeled water experiments and Raman spectroscopy analysis clearly proved the Co(III) formation in the Co(II)/PMS system. In parallel, sulfate radicals (SO4•-) and hydroxyl radicals (HO•) were also involved in this system. Further, the relative contribution of Co(III) to the abatement of carbamazepine (CBZ), a representative micropollutant, in the Co(II)/PMS system was significantly increased by increasing the Co(II) dosage but was dramatically decreased by improving the PMS dosage and increasing the pH from 3 to 7. Additionally, the degradation pathway of CBZ by Co(III) and the Co(II)/PMS system was comparatively explored, confirming that Co(III) participated in the hydroxylation, carbonylation, deacetylation, and ring reduction of CBZ by the Co(II)/PMS system. Our work addresses the controversy regarding the reactive Co species involved in the Co(II)/PMS system with evidence of Co(III) as the chief one, which highlights the significance of re-evaluating the relative contribution of Co(III) in relevant environmental decontamination processes.

Comprehensive Assessment of Reactive Bromine Species in Advanced Oxidation Processes: Differential Roles in Micropollutant Abatement in Bromide-Containing Water.

Reactive bromine species (RBS) are gaining increasing attention in natural and engineered aqueous systems containing bromide ions (Br-). However, their roles in the degradation of structurally diverse micropollutants by advanced oxidation processes (AOPs) were not differentiated. In this study, the second-order rate constants (k) of Br•, Br2•-, BrO•, and ClBr•- were collected and evaluated. Br• is the most reactive RBS toward 21 examined micropollutants with k values of 108-1010 M-1 s-1. Br2•-, ClBr•-, and BrO• are selective for electron-rich micropollutants with k values of 106-108 M-1 s-1. The specific roles of RBS in aqueous micropollutant degradation in AOPs were revealed by using simplified models via sensitivity analysis. Generally, RBS play minimal roles in the UV/H2O2 process but are significant in the UV/peroxydisulfate (PDS) and UV/chlorine processes in the presence of trace Br-. In UV/PDS with ≥1 µM Br-, Br• emerges as the major RBS for removing electron-rich micropollutants. In UV/chlorine, BrO• contributes to the degradation of specific electron-rich micropollutants with removal percentages of ≥20% at 1 µM Br-, while the contributions of BrO• and Br• are comparable to those of reactive chlorine species as Br- concentration increases to several µM. In all AOPs, Br2•- and ClBr•- play minor roles at 1-10 µM Br-. Water matrix components such as HCO3-, Cl-, and natural organic matter (NOM) significantly inhibit Br•, while BrO• is less affected, only slightly scavenged by NOM with a k value of 2.1 (mgC/L)-1 s-1. This study sheds light on the differential roles of multiple RBS in micropollutant abatement by AOPs in Br--containing water.

Enhancing the Abatement of Permanganate-inert Micropollutants: Multiple Roles of Nascent Manganese Dioxide in Permanganate Oxidation.

Permanganate (Mn(VII)) is widely used as an oxidant in water treatment and usually reduced to nascent manganese dioxide (MnO2), which could promote Mn(VII) oxidation for the Mn(VII)-reactive compounds such as phenols and anilines. However, the removal of micropollutants containing diverse functional groups and the underlying mechanisms remain largely unexplored. This study reveals that Mn(VII)/nascent MnO2 was effective for the degradation of Mn(VII)-inert micropollutants, including sulfonamide antibiotics, ß-blockers and trimethoprim, with observed first-order rate constants (k'obs) of 0.126 ∼ 9 min-1 at pH 4.0. The synergetic effect of Mn(VII) and nascent MnO2 on the degradation of Mn(VII)-inert micropollutants decreased significantly when pH increased from 4.0 to 9.5. MnO2 played multiple roles in micropollutant degradation, which acted as a catalyst to promote the Mn(VII) oxidation of trimethoprim and propranolol, as well as an oxidant in propranolol degradation. Besides, Mn(III) oxidation accounted for 58% of the overall degradation of propranolol, but was not important for trimethoprim oxidation. Hydroxylated products were common products formed in Mn(VII)/MnO2. Differently, trimethoprim tended to form single-ring products via MnO2-catalyzed Mn(VII) oxidation, while propranolol preferentially formed dimers via in situ formed MnO2 oxidation. This study is the first to report that MnO2 enhances the abatement of Mn(VII)-inert micropollutants during Mn(VII)-based water treatment and unravels the multiple roles of MnO2 in micropollutant degradation by Mn(VII)/MnO2.

Clinical characteristics and acute complication of COVID-19 patients with diabetes: a multicenter, retrospective study in Southern China.

Aims: This study aims to describe the clinical characteristics, laboratory data and complications of hospitalized COVID-19 patients with type 2 diabetes mellitus (T2DM) since epidemic prevention and control optimization was adjusted in December 2022 in China. Methods: This retrospective multicenter study included 298 patients with confirmed type 2 diabetes mellitus with or without COVID-19. We collected data from the first wave of the pandemic in The Fifth Affiliated Hospital of Guangzhou Medical University, Loudi Central Hospital and The First People's Hospital of Xiangtan from December 1, 2022 to February 1, 2023. We extracted baseline data, clinical symptoms, acute complications, laboratory findings, treatment and outcome data of each patient from electronic medical records. Results: For among 298 hospitalized patients with type 2 diabetes, 136 (45.6%) were COVID-19 uninfected, and 162 (54.4%) were COVID-19 infected. We found that the incidence of cough, fatigue, fever, muscle soreness, sore throat, shortness of breath, hyposmia, hypogeusia and polyphagia (all p<0.01) were significantly higher in the exposure group. They showed higher levels of ketone (p=0.04), creatinine (p<0.01), blood potassium (p=0.01) and more diabetic ketoacidosis (p<0.01). Patients with COVID-19 less use of metformin (p<0.01), thiazolidinediones (p<0.01) and SGLT2 (p<0.01) compared with patients without COVID-19. Conclusion: COVID-19 patients with diabetes showed more severe respiratory and constitutional symptoms and an increased proportion of hyposmia and hypogeusia. Moreover, COVID-19 patients with diabetes have a higher incidence of acute complications, are more prone to worsening renal function, and are more cautious about the use of antidiabetic drugs.

Multiple roles of UV/KMnO4 in cyanobacteria containing water treatment: Cell inactivation & removal, and microcystin degradation.

Cyanobacterial blooms present great challenges to drinking water treatment and human health. The novel combination of potassium permanganate (KMnO4) and ultraviolet (UV) radiation is engaged as a promising advanced oxidation process in water purification. This study investigated the treatment of a typical cyanobacteria, Microcystis aeruginosa by UV/KMnO4. Cell inactivation was significantly improved by UV/KMnO4 treatment, compared to UV alone or KMnO4 alone, and cells were completely inactivated within 35 min by UV/KMnO4 in natural water. Moreover, effective degradation of associated microcystins was simultaneously achieved at UV fluence rate of 0.88 mW cm-2 and KMnO4 dosages of 3-5 mg L-1. The significant synergistic effect is possibly attributable to the highly oxidative species produced during UV photolysis of KMnO4. In addition, the cell removal efficiency via self-settling reached 87.9 % after UV/KMnO4 treatment, without additional coagulants. The fast in situ generated manganese dioxide was responsible for the enhancement of M. aeruginosa cell removal. This study firstly reports multiple roles of UV/KMnO4 process in cyanobacterial cell inactivation and removal, as well as simultaneous microcystin degradation under practical conditions.

Unexpected trends for the formation of chlorate and bromate during the photolysis of chlorine in bromide-containing water.

Solar photolysis of free chlorine (solar/chlorine) in bromide-containing water occurs under various scenarios, such as chlorinated reservoirs and outdoor swimming pools, and the formation of chlorate and bromate is an important issue in the system. We reported unexpected trends for the formation of chlorate and bromate in the solar/chlorine system. Excess chlorine inhibited the formation of bromate, i.e., increasing chlorine dosages from 50 to 100 µM reduced the bromate yield from 6.4 to 1.2 µM in solar/chlorine at 50 µM bromide and pH 7. The yield of bromate in solar/chlorine at 100 µM chlorine and 50 µM bromide in 240 min was 18.8% of that at 50 µM bromine only. The underlying mechanism was that HOCl can react with bromite (BrO2-) to form HOClOBrO-, whose multi-step transformation finally formed chlorate as the major product and bromate as the minor product. This reaction overwhelmed the oxidation of bromite to form bromate by reactive species, such as •OH, BrO• and ozone. On the other hand, the presence of bromide greatly enhanced the formation of chlorate. Increasing bromide concentrations from 0 to 50 µM enhanced the chlorate yields from 2.2 to 7.0 µM at 100 µM chlorine. The absorbance of bromine was higher than that of chlorine, thus the photolysis of bromine formed higher levels of bromite at higher bromide concentrations. Then, bromite rapidly reacted with HOCl to form HOClOBrO- and it further transformed to chlorate. Additionally, 1 mg L-1 NOM had a negligible effect on bromate yields in solar/chlorine at 50 µM bromide, 100 µM chlorine and pH 7. This study demonstrated a new pathway of chlorate and bromate formation in the solar/chlorine system with bromide.

Characterization of UV/chlorine process for micropollutant abatement by probe compound-based kinetic models.

Micropollutant (MP) abatement efficiencies are critical information for optimizing water treatment process for cost-effective operations. Nevertheless, due to the vast number of MPs in real water matrices, it is infeasible to measure their abatement efficiencies individually in practical applications. In this study, a probe compound-based kinetic model was developed for generalized prediction of MP abatement in various water matrices by the ultraviolet (UV)/chlorine process. The results show that by measuring the depletion of three probe compounds (ibuprofen, primidone, and dimetridazole) spiked in the water matrix, the exposures of main reactive chlorine species (RCS including chlorine radicals (Cl•), dichloride radicals (Cl2-•) and chlorine oxide radicals (ClO•)) and hydroxyl radicals (•OH) during the UV/chlorine process could be calculated using the model. Based on the determined exposures, the abatement efficiencies of various MPs in different water matrices (e.g., surface water, groundwater, and wastewater) could generally be predicted with acceptable accuracy by the model without prior water-specific calibration. In addition, the relative contribution of UV photolysis and oxidation with active chlorine, RCS, and •OH to MP abatement could be quantitatively simulated using the model to clarify the abatement mechanism of MPs during the UV/chlorine process. The probe-based kinetic model can thus offer a useful tool to guide practical water and wastewater treatment for MP abatement and to explore the mechanism of UV/chlorine process.

Efficacy and tolerability of repetitive transcranial magnetic stimulation for late-life depression: A systematic review and meta-analysis.

BACKGROUND: Repetitive transcranial magnetic stimulation (rTMS) is a widely available treatment for major depression, but its efficacy and tolerability are uncertain for patients with late-life depression (LLD). To assess the existing evidence of rTMS for LLD treatment, we conducted a systematic review and meta-analysis of randomized controlled trials (RCTs) according to PRISMA guidelines. METHODS: We retrieved RCTs from four databases published between 1 January 2000 and 10 September 2021 comparing the effects of active and sham stimulation in LLD patients. We performed subgroup analyses to examine the impact of different parameters. The primary outcomes were the response and discontinuation rates of rTMS for LLD patients, representing for efficacy and tolerability, respectively. Secondary outcomes were remission and dropout rates. Discontinuation referred to patients who withdrew for any reason, while dropout referred to participants who withdrew early because of adverse events. RESULTS: Nine articles describing 11 studies (two articles each contained two studies) met the eligibility criteria. All outcomes were analyzed using a random-effects model. The summary analysis of nine suitable RCTs revealed a cumulative response rate of 2.86 (95 % confidence interval (95 % CI), 1.87-4.37) and a remission rate of 4.02 (95 % CI, 1.83-8.81) in the active group compared to the sham group. The pooled odds ratios (ORs) for discontinuation and dropout rates were not significantly different between the two groups. In addition, some rTMS parameters were associated with better efficacy. CONCLUSIONS: The meta-analysis suggested that rTMS is an effective, well-tolerated treatment for patients with LLD. Future efforts should enhance study methodologies to improve their efficacy and increase the homogeneity of rTMS parameters to promote comparability between studies.

UV/Chlorine Process: An Efficient Advanced Oxidation Process with Multiple Radicals and Functions in Water Treatment.

Because of the deterioration of global water quality, the occurrence of chemical and microbial contaminants in water raises serious concerns for the health of the population. Identifying and developing effective and environmentally friendly water treatment technologies are critical to obtain clean water. Among the various technologies for the purification of water, ultraviolet photolysis of chlorine (UV/chlorine), an emerging advanced oxidation process (AOP), has multiple functions for the control of contaminants via the production of hydroxyl radicals (HO·) and reactive chlorine species (RCS), such as Cl·, ClO·, and Cl2·-.This Account centers around the radical chemistry of RCS and HO· in different water matrices and their roles and mechanisms in the abatement of contaminants. The concentrations of Cl·, ClO·, and Cl2·- are comparable to or higher than those of HO· (10-14 to 10-13 M). The reactivities of RCS are more selective than HO· with a broader range of second-order rate constants (k). The k values of Cl· toward most aromatics are higher or similar as compared to those of HO·, while those of Cl2·- and ClO· are less reactive but more selective toward aromatics containing electron-donating functional groups. Their major reaction mechanisms with Cl· are electron transfer and addition, while those with ClO· and Cl2·- primarily involve electron transfer. As for aliphatics, their reactivities with both HO· and RCS are much lower than those of aromatics. The reaction mechanisms for most of them with Cl· and Cl2·- are hydrogen abstraction, except for olefins, which are addition. In addition, RCS greatly contribute to the inactivation of microbial contaminants.Toward future application, the UV/chlorine process has both pros and cons. Compared with the traditional HO·-based AOP of UV/H2O2, UV/chlorine is more efficient and energy-saving for oxidation and disinfection, and its efficiency is less affected by water matrix components. However, the formation of toxic byproducts in UV/chlorine limits its application scenarios. In dissolved organic matter (DOM)-rich water, the formation of halogenated byproducts is enhanced in UV/chlorine. In the presence of ammonia, reactive nitrogen species (RNS) (e.g., ·NO and ·NO2) are involved, and highly toxic nitro(so) products such as nitro(so)-phenolics and N-nitrosodimethylamine are generated. For a niche application, the UV/chlorine process is recommended to be utilized in water with low levels of DOM and ammonia.Strategies should be developed to make full use of highly reactive species (RCS and HO·) for the abatement of target contaminants and to reduce the formation of toxic byproducts. For example, the UV/chlorine process can be used in tandem with other treatments to create multiple barriers for the production of safe water. In addition, halogen radicals are very important in ecosystems as well as other areas such as medical therapy and organic synthesis. UV/chlorine is the most efficient homogeneous system to generate halogen radicals, and thus it provides a perfect system to investigate the fates of halogen radicals for interdisciplinary research.

Mechanistic and kinetic understanding of micropollutant degradation by the UV/NH2Cl process in simulated drinking water.

The UV/monochloramine (UV/NH2Cl) process has attracted increasing attention in water treatment, in which hydroxyl radicals (HO•), reactive chlorine species (RCS) and reactive nitrogen species (RNS) are produced. This study investigated the effects of water matrices including halides, natural organic matter (NOM), alkalinity and pH, on the degradation kinetic of a variety of micropollutants and radical chemistry in the UV/NH2Cl process. The presence of chloride blunted HO• and Cl• impacts, but enhanced Cl2•- effect on micropollutants reactive toward Cl2•-. The presence of 30 µM bromide led to an 82% decrease in the specific pseudo-first-order rate constants (k') by HO• (kHO•'), and significantly diminished RCS efficacy. Reactive bromine species (RBS) were formed in the presence of bromide, while the contribution could not compensate for the decrease of HO• and RCS due to their lower reactivity toward micropollutants. Iodide rapidly transformed to HOI via reacting with NH2Cl, which resulted in a 59% decrease of kHO•' and 12% ∼ 100% decreases of k' by reactive halogen species (RHS) and RNS (kRHS + RNS') for most micropollutants. Nevertheless, k' of phenolic compounds, such as paracetamol, bisphenol A and salbutamol, increased in the presence of iodide by 78%, 360% and 130%, respectively, due to the roles of HOI and reactive iodine species (RIS). Bicarbonate decreased the contributions of HO• and RCS, but enhanced that of CO3•- for micropollutants reactive toward CO3•-. The presence of 1 mg/L NOM scavenged over half the amount of HO•, and also consumed RCS and RNS, resulting in significantly decreased removal of micropollutants. High pH value witnessed enhanced degradation for those micropollutants reactive toward RCS and RNS through deprotonation. The degradation of most micropollutants was inhibited in real drinking water and in the coexistence of halides. This study provides a better understanding of radical chemistry in the UV/NH2Cl process under a practical water treatment condition.

Kinetics and pathways of the degradation of PPCPs by carbonate radicals in advanced oxidation processes.

The carbonate radical (CO3•-) is a typical secondary radical observed in engineering and natural aquatic systems. This study investigated the degradation kinetics of 20 pharmaceuticals and personal care products (PPCPs) by CO3•- and the transformation pathways of a typical PPCP (naproxen) that is susceptible to CO3•-. CO3•- is highly selective for compounds containing aniline and phenolic hydroxyl groups as well as naphthalene rings, such as sulfamethoxazole, sulfamethazine, salbutamol, propranolol, naproxen, and macrolide antibiotics such as azithromycin, for which the second-order rate constants range from 5.6 × 107 M-1s-1 to 2.96 × 108 M-1s-1. A good linear relationship is observed between the natural logarithms of kCO3•- and the negative values of the Hammett Σσp+ constant for aromatic PPCPs, indicating that electron-donating groups promote the attack of benzene derivatives by CO3•-. The contribution of CO3•- to naproxen degradation is significant in different processes such as UV/H2O2, UV/persulfate, UV/chlorine, and UV/monochloramine, in the presence of HCO3-, which compensates for the decreased contributions of primary radicals. In particular, the formation of CO3•- increases the first-order rate constant of naproxen by 127% in UV/monochloramine in the presence of 50 mM HCO3- compared to that without HCO3-. Natural organic matter (NOM) exerts a slight scavenging effect on CO3•-, decreasing the inhibition effect of NOM on the degradation of naproxen by UV/H2O2 in the presence of HCO3-. The pathways involved in the transformation of naproxen by CO3•- include decarboxylation, hydroxylation, ketonization, demethylation and aldolization. In addition, the alteration of the genotoxicity during naproxen degradation by CO3•- was negligible.

Roles of Bromine Radicals and Hydroxyl Radicals in the Degradation of Micropollutants by the UV/Bromine Process.

The inevitable occurrence of Br- in natural water affects the degradation kinetics of micropollutants in the UV/chlorine process, the radical chemistry of which, however, is largely unclear. As Br- in the UV/chlorine process first forms free bromine (HOBr/OBr-), this study investigated the radical chemistry of the UV/bromine process for the degradation of selected micropollutants resistant to bromine, i.e., ibuprofen and benzoate, to focus on the roles of radicals. The actual quantum yields of HOBr and OBr- by UV photolysis at 254 nm are 0.43 (±0.025) and 0.26 (±0.025) mol Einstein-1, respectively. Br• and HO• are generated first, and then, Br2•- is formed, with the signal detectable at 360 nm by laser flash photolysis. Compared with Cl• in the UV/chlorine system, Br• exists at higher concentrations (∼10-12 M) in the UV/bromine system while HO• exists at similar concentrations. In the UV/bromine process, reactive bromine species (RBS) dominates the degradation of ibuprofen, while HO• dominates the degradation of benzoate. Br• and Br2•- are reactive toward ibuprofen which second-order rate constants (k) were determined to be 2.2 × 109 and 5.3 × 107 M-1 s-1, respectively, by laser flash photolysis. Br• was the major RBS for ibuprofen degradation by the UV/bromine treatment, whereas Br2•- increasingly contributed to ibuprofen degradation with increasing free bromine or Br- concentrations. Br• could be scavenged by HCO3- and natural organic matter (NOM), and the k with NOM was determined to be 2.6 × 104 (mg/L)-1 s-1. Both Br• and Br2•- prefer to react with ibuprofen via electron transfer with activation energy barriers (Δ‡G0SET) of 1.35 and 7.78 kcal mol-1, respectively. RBS promoted the formation of hydroxylated products. Then free bromine, rather than RBS, was responsible for the formation of brominated products, increasing the total organic bromine (TOBr) and tribromomethane yields in the UV/bromine system. This study demonstrates for the first time the roles of RBS and HO• in micropollutant degradation in the UV/bromine process.

Solar irradiation combined with chlorine can detoxify herbicides.

The solar/chlorine process is an energy-efficient advanced oxidation process that can produce reactive species such as hydroxyl radical, reactive chlorine species and ozone. This study investigated the process' ability to detoxify the typical herbicides atrazine and mecoprop (methylchlorophenoxypropionic acid). Both herbicides are resistant to direct solar photolysis or chlorination alone, but they can be degraded by the solar/chlorine process effectively. Atrazine inhibited the development of Arabidopsis thaliana, but such inhibition was negligible after solar/chlorine treatment of an atrazine solution. The transformation of atrazine in the process was shown to be through hydroxylation, hydrogen abstraction and dechlorination but did not involve chlorine substitution or addition. Cl• reacts with atrazine and mecoprop with rate constants of 6.87 × 109 M-1s-1 and 1.08 × 1010 M-1s-1, respectively, while ClO• reacts with mecoprop with a rate constant of 1.11 × 108 M-1s-1. The degradation kinetics of atrazine and mecoprop by solar/chlorine was simulated by modeling, which fitted the experimental results well. Hydroxyl radicals (HO•) mainly contributed to the degradation of atrazine by solar/chlorine at pH 7 with the contribution of 65%, whereas ClO• and O3 were main species responsible for the degradation of mecoprop with the contribution of 72% and 17%, respectively. The pseudo-first-order rate constants (k's) of the two degradations increased substantially (by 28.8% for atrazine and by 198% for mecoprop) when the chlorine dosage was increased from 50 µM to 200 µM. The k's decreased with increasing pH. The presence of natural organic matter inhibited the degradation of both herbicides, while the presence of bromide enhanced their degradation. This work reveals a feasible method for the detoxifying herbicides by combining chlorine with solar radiation.

Feasibility of the solar/chlorine treatment for lipid regulator degradation in simulated and real waters: The oxidation chemistry and affecting factors.

This work investigated the feasibility and mechanisms of solar/chlorine process in the removal of a kind of emerging contaminants, lipid regulators (gemfibrozil (GFRZ), benzafibrate (BZF), and clofibric acid (CA)), in simulated and real waters. These lipid regulators could be effectively removed by solar/chlorine treatment, and their corresponding pseudo-first-order rate constants (k') increased with increasing chlorine dosage. The degradation of GFRZ and BZF was primarily ascribed to reactive chlorine species (RCS) and ozone, while that of CA was mainly attributable to hydroxyl radical (HO) and ozone. As pH rose from 5.0 to 8.4, kozone' of GFRZ and BZF increased, while kHO' decreased. However, kRCS' of GFRZ increased by 130%, while that of BZF decreased by 43.3%. These changes resulted in slight changes in the overall k's with increasing pH. k's of GFRZ, BZF, and CA by solar/chorine treatment were inhibited by natural organic matter (NOM) while the presence of bromide enhanced the degradation of GFRZ by solar/chlorine process. The degradation of lipid regulators was still effective in a secondary wastewater effluent sample and a sand-filtered water sample, although that was inhibited due to the dissolve organic matter (DOM) contained in real waters. The acute toxicity during the degradation of GFRZ by solar/chlorine treatment was comparable to that by treatment with chlorine alone. This study demonstrated that RCS played an important role in the degradation of micropollutants by the solar/chlorine treatment and the feasibility of solar/chlorine process in the application for the degradation of organic compounds in real waters.

PPCP degradation and DBP formation in the solar/free chlorine system: Effects of pH and dissolved oxygen.

The solar/chlorine process produces multiple reactive species by solar photolysis of chlorine, which can be used as an energy-efficient technology for water treatment. This study investigated the effects of pH and dissolved oxygen (DO) on the degradation of pharmaceuticals and personal care products (PPCPs) and on the formation of disinfection byproducts (DBPs) in the solar/chlorine system. The degradation of 24 structurally diverse PPCPs was enhanced appreciably in the solar/chlorine system compared to solar irradiation and dark chlorination. The reactive species in the solar/chlorine system were identified to be hydroxyl radicals (HO), reactive chlorine species (RCS, i.e., Cl and ClO) and ozone. With increasing pH from 6 to 8, the steady-state concentrations of HO and Cl decreased from 1.23 × 10-14 M to 4.79 × 10-15 M and from 9.80 × 10-16 M to 4.31 × 10-16 M, respectively, whereas that of ClO increased from 5.30 × 10-14 M to 2.68 × 10-13 M and the exposure of ozone increased from 0.44 µM min to 1.01 µM min in 90 min. Accordingly, the removal efficiencies of 6 PPCPs decreased and 11 PPCPs increased. The decreased removal of PPCPs with increasing pH was due to the decrease in HO and Cl, while the increased removal was attributed to the increased ClO and ozone. The presence of DO enhanced the degradation of most PPCPs, indicating the role of ozone on the degradation. The formation of total organic chlorine (TOCl) and known DBPs was enhanced by 60.7% and 159.4%, respectively, in the solar/chlorine system compared to chlorination in a simulated drinking water containing 2.5 mg L-1 natural organic matter (NOM). As the pH rose from 6 to 8, TOCl formation decreased by 16.2%, while that of known DBPs increased by 58.6% in solar/chlorine. The absence of DO slightly suppressed the formation of TOCl and known DBPs. This study illustrated the significant role of RCS in the solar/chlorine system, which enhanced the degradation of micropollutants but increased the formation of chlorinated DBPs.

Comparison of the UV/chlorine and UV/H2O2 processes in the degradation of PPCPs in simulated drinking water and wastewater: Kinetics, radical mechanism and energy requirements.

The degradation of pharmaceuticals and personal care products (PPCPs) by the UV/H2O2 and UV/chlorine processes was compared at practical concentrations in simulated drinking water and wastewater. In pure water, the UV/chlorine process performed better than the UV/H2O2 process for the degradation of 16 PPCPs among the investigated 28 PPCPs under neutral conditions. Interestingly, the UV/chlorine approach was superior to the UV/H2O2 approach for the removal of all PPCPs in simulated drinking water and wastewater at the same molar oxidant dosage. The radical sink by oxidants and/or H2O was 2-3 orders of magnitude higher in UV/chlorine than UV/H2O2 in pure water. Thus, the UV/chlorine process was less affected by the water and wastewater matrices than UV/H2O2. In UV/chlorine, the concentration of ClO• was calculated to be ∼3 orders of magnitude greater than that of HO• in pure water, and the reactivities of ClO• with some PPCPs were as high as > 108 M-1 s-1. ClO• was mainly scavenged by the effluent organic matter (EfOM) with a rate constant of 1.8 × 104 (mg L-1)-1 s-1 in wastewater. Meanwhile, secondary radicals such as Br•, Br2•-, ClBr•- and CO3•- further contributed to PPCP degradation by the UV/chlorine process in wastewater, whose concentrations were at least 2 orders of magnitude higher than that in UV/H2O2. Compared with the UV/H2O2 process, the UV/chlorine process saved 3.5-93.5% and 19.1%-98.1% electrical energy per order (EE/O) for PPCP degradation in simulated drinking water and wastewater, respectively.

Chlorate Formation Mechanism in the Presence of Sulfate Radical, Chloride, Bromide and Natural Organic Matter.

Halides and natural organic matter (NOM) are inevitable in aquatic environment and influence the degradation of contaminants in sulfate radical (SO4•-)-based advanced oxidation processes. This study investigated the formation of chlorate in the coexposure of SO4•-, chloride (Cl-), bromide (Br-) and/or NOM in UV/persulfate (UV/PDS) and cobalt(II)/peroxymonosulfate (Co/PMS) systems. The formation of chlorate increased with increasing Cl- concentration in the UV/PDS system, however, in the Co/PMS system, it initially increased and then decreased. The chlorate formation involved the formation of hypochlorous acid/hypochlorite (HOCl/OCl-) as an intermediate in both systems. The formation was primarily attributable to SO4•- in the UV/PDS system, whereas Co(III) played a significant role in the oxidation of Cl- to HOCl/OCl- and SO4•- was important for the oxidation of HOCl/OCl- to chlorate in the Co/PMS system. The pseudo-first-order rate constants ( k') of the transformation from Cl- to HOCl/OCl- were 3.32 × 10-6 s-1 and 9.23 × 10-3 s-1 in UV/PDS and Co/PMS, respectively. Meanwhile, k' of HOCl/OCl- to chlorate in UV/PDS and Co/PMS were 2.43 × 10-3 s-1 and 2.70 × 10-4 s-1, respectively. Br- completely inhibited the chlorate formation in UV/PDS, but inhibited it by 45.2% in Co/PMS. The k' of SO4•- reacting with Br- to form hypobromous acid/hypobromite (HOBr/OBr-) was calculated to be 378 times higher than that of Cl- to HOCl/OCl-, but the k' of Co(III) reacting with Br- to form HOBr/OBr- was comparable to that of Cl- to HOCl/OCl-. NOM also significantly inhibited the chlorate formation, due to the consumption of SO4•- and reactive chlorine species (RCS, such as Cl·, ClO· and HOCl/OCl-). This study demonstrated the formation of chlorate in SO4•--based AOPs, which should to be considered in their application in water treatment.

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO•) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 108 M-1 s-1 and 3.6 (±0.1) × 107 M-1 s-1, respectively, whereas UV photolysis and the hydroxyl radical (HO•) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO• concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br-, whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO• was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO• oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO•. This study is the first to report the transformation pathway of a micropollutant by ClO•.