Insights into the transformation of natural organic matter during UV/peroxydisulfate treatment by FT-ICR MS and machine learning: Non-negligible formation of organosulfates.

Natural organic matter (NOM) is a major sink of radicals in advanced oxidation processes (AOPs) and understanding the transformation of NOM is important in water treatment. By using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in conjunction with machine learning, we comprehensively investigated the reactivity and transformation of NOM, and the formation of organosulfates during the UV/peroxydisulfate (PDS) process. After 60 min UV/PDS treatment, the CHO formula number and dissolved organic carbon concentration significantly decreased by 83.4 % and 74.8 %, respectively. Concurrently, the CHOS formula number increased substantially from 0.7 % to 20.5 %. Machine learning identifies DBE and AImod as the critical characteristics determining the reactivity of NOM during UV/PDS treatment. Furthermore, linkage analysis suggests that decarboxylation and dealkylation reactions are dominant transformation pathways, while the additions of SO3 and SO4 are also non-negligible. According to SHAP analysis, the m/z, number of oxygens, DBE and O/C of NOM were positively correlated with the formation of organosulfates in UV/PDS process. 92 organosulfates were screened out by precursor ion scan of HPLC-MS/MS and verified by UPLC-Q-TOF-MS, among which, 7 organosufates were quantified by authentic standards with the highest concentrations ranging from 2.1 to 203.0 ng L‒1. In addition, the cytotoxicity of NOM to Chinese Hamster Ovary (CHO) cells increased by 13.8 % after 30 min UV/PDS treatment, likely responsible for the formation of organosulfates. This is the first study to employ FT-ICR MS combined with machine learning to identify the dominant NOM properties affecting its reactivity and confirmed the formation of organosulfates from sulfate radical oxidation of NOM.

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.

pH-dependent bisphenol A transformation and iodine disinfection byproduct generation by peracetic acid: Kinetic and mechanistic explorations.

Peracetic acid (PAA) is regarded as an environmentally friendly oxidant because of its low formation of toxic byproducts. However, this study revealed the potential risk of generating disinfection byproducts (DBPs) when treating iodine-containing wastewater with PAA. The transformation efficiency of bisphenol A (BPA), a commonly detected phenolic contaminant and a surrogate for phenolic moieties in dissolved organic matter, by PAA increased rapidly in the presence of I-, which was primarily attributed to the formation of active iodine (HOI/I2) in the system. Kinetic model simulations demonstrated that the second-order rate constant between PAA and HOI was 54.0 M-1 s-1 at pH 7.0, which was lower than the generation rate of HOI via the reaction between PAA and I-. Therefore, HOI can combine with BPA to produce iodine disinfection byproducts (I-DBPs). The transformation of BPA and the generation of I-DBPs in the I-/PAA system were highly pH-dependent. Specifically, acidic conditions were more favorable for BPA degradation because of the higher reaction rates of BPA and HOI. More iodinated aromatic products were detected after 5 min of the reaction under acidic and neutral conditions, resulting in higher toxicity towards E. coli. After 12 h of the reaction, more adsorbable organic iodine (AOI) was generated at alkaline conditions because HOI was not able to efficiency transform to IO3-. The presence of H2O2 in the PAA solution played a role in the reaction with HOI, particularly under alkaline conditions. This study significantly advances the understanding of the role of I- in BPA oxidation by PAA and provides a warning to further evaluate the potential environmental risk during the treatment of iodine-bearing wastewater with PAA.

Formation Mechanisms of Nitro Products from Transformation of Aliphatic Amines by UV/Chlorine Treatment.

Formation of nitrogenous disinfection byproducts from aliphatic amines is a widespread concern owing to the serious health risks associated with them. However, the mechanisms of transforming aliphatic amines and forming nitro products in the UV/chlorine process have rarely been discussed, which are investigated in this work. Initially, secondary amines (R1R2NH) are transformed into secondary organic chloramines (R1R2NCl) via chlorination. Subsequently, radicals, such as HO• and Cl•, are found to contribute predominantly to such transformations. The rate constants at which HO•, Cl•, and Cl2•- react with R1R2NCl are (2.4-5.1) × 109, (1.5-3.8) × 109, and (1.2-6.1) × 107 M-1 s-1, respectively. Consequently, R1R2NCl are transformed into primary amines (R1NH2/R2NH2) and chlorinated primary amines (R1NHCl/R2NHCl and R1NCl2/R2NCl2) by excess chlorine. Furthermore, primarily driven by UV photolysis, chlorinated primary amines can be transformed into nitroalkanes with conversion rates of ∼10%. Dissolved oxygen and free chlorine play crucial roles in forming nitroalkanes, and post-chlorination can further form chloronitroalkanes, such as trichloronitromethane (TCNM). Radicals are involved in forming TCNM in the UV/chlorine process. This study provides new insights into the mechanisms of transforming aliphatic amines and forming nitro products using the UV/chlorine process.

Roles of Activated Carbon in UV/Chlorine/Activated Carbon-TiO2 Process for Micropollutant Abatement and DBP Control.

The ultraviolet (UV)/chlorine process has attracted increasing attention for micropollutant abatement. However, the limited hydroxyl radical (HO•) generation and the formation of undesired disinfection byproducts (DBPs) are the two major issues in this process. This study investigated the roles of activated carbon (AC) in the UV/chlorine/AC-TiO2 process for micropollutant abatement and DBP control. The degradation rate constant of metronidazole by UV/chlorine/AC-TiO2 was 3.44, 2.45, and 1.58 times higher than those by UV/AC-TiO2, UV/chlorine, and UV/chlorine/TiO2, respectively. AC acted as an electron conductor and dissolved oxygen (DO) adsorbent, resulting in the steady-state concentration of HO• that was ∼2.5 times that of UV/chlorine. Compared with UV/chlorine, the formation of total organic chlorine (TOCl) and known DBPs in UV/chlorine/AC-TiO2 was reduced by 62.3 and 75.7%, respectively. DBP could be controlled via adsorption on AC, and the increased HO• and decreased chlorine radical (Cl•) and chlorine exposure reduced DBP formation. UV/chlorine/AC-TiO2 efficiently abated 16 structurally different micropollutants under environmentally relevant conditions owing to the enhanced generation of HO•. This study provides a new strategy for designing catalysts with photocatalytic and adsorption properties for UV/chlorine to promote micropollutant abatement and DBP control.

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.

Overlooked roles of Cl2O and Cl2 in micropollutant abatement and DBP formation by chlorination.

This study investigated the roles of diverse free available chlorine (FAC) species including HOCl/OCl-, H2OCl+, Cl2O, and Cl2 in the degradation of micropollutants. The degradation of 5 micropollutants was significantly affected by pH, FAC dosage, and chloride (Cl-) concentration. The reaction orders in FAC (n) of 5 micropollutants (acetaminophen, carbamazepine, naproxen, gemfibrozil, and mecoprop) ranged from 1.4 ± 0.2 to 2.1 ± 0.3 at pH 3 - 5, evidencing the importance of Cl2O and Cl2 for micropollutant abatement. A simplified method for the determination of second-order rate constants (k) of specific FAC species with micropollutants was developed. Herein, the k for neutral/dissociated forms of 5 micropollutants with Cl2 and Cl2O were determined in the ranges of 9.3 (± 0.2) × 102 ∼ 2.9 (± 0.2) × 109 M-1 s-1 and 1.8 (± 0.1) × 104 ∼ 3.7 (± 0.6) × 109 M-1 s-1, respectively. They were 4 - 7 orders of magnitude higher than those of HOCl, whereas those of OCl- and H2OCl+ were negligible. By using kinetic modeling, Cl2 was more important under acidic conditions and higher Cl- levels with contributions of 37.9 - 99.2% at pH 5 in pure water. Cl2O played a dominant role in micropollutant degradation in pure water (56.4 - 87.3%) under neutral conditions. Furthermore, both Cl2 and Cl2O played vital roles in the formation of disinfection byproducts (DBPs) during chlorination of carbamazepine and natural organic matter. This study highlights the overlooked roles of Cl2O and Cl2 in micropollutant abatement and DBP formation during chlorination.

Exploring Pathways and Mechanisms for Dichloroacetonitrile Formation from Typical Amino Compounds during UV/Chlorine Treatment.

The formation of disinfection byproducts (DBPs) during UV/chlorine treatment, especially nitrogenous DBPs, is not well understood. This study investigated the formation mechanisms for dichloroacetonitrile (DCAN) from typical amino compounds during UV/chlorine treatment. Compared to chlorination, the yields of DCAN increase by 88-240% during UV/chlorine treatment from real waters, while the yields of DCAN from amino compounds increase by 3.3-5724 times. Amino compounds with electron-withdrawing side chains show much higher DCAN formation than those with electron-donating side chains. Phenylethylamine, l- phenylalanine, and l-phenylalanyl-l-phenylalanine were selected to represent amines, amino acids, and peptides, respectively, to investigate the formation pathways for DCAN during UV/chlorine treatment. First, chlorination of amines, amino acids, and peptides rapidly forms N-chloramines via chlorine substitution. Then, UV photolysis but not radicals promotes the transformation from N-chloramines to N-chloroaldimines and then to phenylacetonitrile, with yields of 5.4, 51.0, and 19.8% from chlorinated phenylethylamine, l-phenylalanine, and l-phenylalanyl-l-phenylalanine to phenylacetonitrile, respectively. Finally, phenylacetonitrile is transformed to DCAN with conversion ratios of 14.2-25.6%, which is attributed to radical oxidation, as indicated by scavenging experiments and density functional theory calculations. This study elucidates the pathways and mechanisms for DCAN formation from typical amino compounds during UV/chlorine treatment.

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.

Insights into the effects of bromide at fresh water levels on the radical chemistry in the UV/peroxydisulfate process.

Bromide (Br-) is a typical scavenger to sulfate radical (SO4•-) and hydroxyl radical (HO•), which simultaneously forms secondary reactive bromine species (RBS) such as Br• and Br2•-. This study investigated the effects of Br- at fresh water levels (~µM) on the radical chemistry in the UV/peroxydisulfate (UV/PDS) process by combining the degradation kinetics of probe compounds (nitrobenzene, metronidazole, and benzoate) with kinetic model. Br- at 1 - 50 µM promoted the conversion from SO4•- to HO• and RBS in the UV/PDS process. At pH 7, the concentration of SO4•- monotonically decreased by 31.5 - 94.8% at 1 - 50 µM Br-, while that of HO• showed an increasing and then decreasing pattern, with a maximum increase by 171.7% at 5 µM Br-. The concentrations of Br• and Br2•- (10-12 - 10-10 M) were 2 - 3 orders of magnitude higher than SO4•- and HO•. Alkaline condition promoted the conversion from SO4•- to HO•, and drove the transformation from RBS to HO•, resulting in much lower concentrations of RBS at pH 10. Br- at 1 µM and 5 µM decreased the pseudo-first-order reaction rates (k's) of 15 pharmaceuticals and personal care products (PPCPs) by 15.2 - 73.9%, but increased k's of naproxen and ibuprofen by 13.7 - 57.3% at pH 7. The co-existence of 10 - 1000 µM Cl- with 5 µM Br- further promoted the conversion from SO4•- to HO• compared to Br- alone. Bicarbonate consumed SO4•- and HO• but slightly affected RBS, while natural organic matter (NOM) exerted scavenging effects on HO• and RBS more significantly than SO4•-. This study demonstrated that Br- at fresh water levels significantly altered the radical chemistry of the UV/PDS process, especially for promoting the formation of HO•.

DBP formation and toxicity alteration during UV/chlorine treatment of wastewater and the effects of ammonia and bromide.

The UV/chlorine process is efficient for the abatement of micropollutants; yet, the formation of disinfection by-products (DBPs) and the toxicity can be altered during the treatment. This study investigated effluent organic matter characterization, DBP formation and toxicity alteration after the UV/chlorine treatment of wastewater; particularly, typical water matrix components in wastewater, namely, ammonia and bromide, were studied. The raw wastewater contained low levels of ammonia (3 µM) and bromide (0.5 µM). The UV/chlorine treatment efficiently eliminated 90 - 94% of fluorescent components. Compared with chlorination alone, a 20 min UV/chlorine treatment increased the formation of trihalomethanes (THMs), haloacetic acids (HAAs), chloral hydrate (CH), haloacetonitriles (HANs), trichloronitromethane (TCNM) and haloacetamides (HAcAms) by 90 - 508%. In post-chlorination after the UV/chlorine treatment, the formation of CH, HANs, TCNM and HAcAms increased by 77 - 274%, whereas the formation of both THMs and HAAs increased slightly by 11%. Meanwhile, the calculated cytotoxicity and genotoxicity of DBPs increased considerably after the UV/chlorine treatment and in post-chlorination, primarily due to the increased formation of HAAs and nitrogenous DBPs (N-DBPs). However, the acute toxicity of the wastewater to Vibrio fischeri and genotoxicity determined by the umu test decreased by 19% and 76%, respectively, after the 20 min UV/chlorine treatment. An additional 200 µM ammonia decreased the formation of all detected DBPs during the UV/chlorine treatment and 24 h post-chlorination, except that TCNM formation increased by 11% during post-chlorination. The acute toxicity of wastewater spiked with 200 µM ammonia was 32% lower than that of raw wastewater after the UV/chlorine treatment, but the genotoxicity was 58% higher. The addition of 1 mg/L bromide to the UV/chlorine process dramatically increased the formation of brominated DBPs and the overall calculated cytotoxicity and genotoxicity of DBPs. However, the acute toxicity and genotoxicity of the wastewater decreased by 7% and 100%, respectively, when bromide was added to the UV/chlorine treatment. This study illuminated that UV/chlorine treatment can decrease acute and geno- toxicities of wastewater efficiently.

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.

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.

DBP alteration from NOM and model compounds after UV/persulfate treatment with post chlorination.

The UV/persulfate process is an effective advanced oxidation process (AOP) for the abatement of a variety of micropollutants via producing sulfate radicals (SO4•-). However, when this technology is used to reduce target pollutants, the precursors of disinfection byproducts (DBPs), such as natural organic matter (NOM) and organic nitrogen compounds, can be altered. This study systematically investigated the DBP formation from NOM and five model compounds after UV/H2O2 and UV/persulfate treatments followed with 24 h chlorination. Compared to chlorination alone, the yields of trichloromethane (TCM) and dichloroacetonitrile (DCAN) from NOM decreased by 50% and 54%, respectively, after UV/persulfate treatment followed with chlorination, whereas those of chloral hydrate (CH), 1,1,1-trichloropropanone (1,1,1-TCP) and trichloronitromethane (TCNM) increased by 217%, 136%, and 153%, respectively. The effect of UV/H2O2 treatment on DBP formation shared a similar trend to that of UV/persulfate treatment, but the DBP formation was higher from the former. As the UV/persulfate treatment time prolonged or the persulfate dosage increased, the formation of TCM and DCAN continuously decreased, while that of CH, 1,1,1-TCP and TCNM presented an increasing and then decreasing pattern. SO4•- activated benzoic acid (BA) to form phenolic compounds that enhanced the formation of TCM and CH, while it deactivated resorcinol to decrease the formation of TCM. SO4•- reacted with aliphatic amines such as methylamine (MA) and dimethylamine (DMA) to form nitro groups, which significantly increased the formation of TCNM in post chlorination, and the rate was determined to be higher than that of HO•. This study illuminated the diverse impacts of the structures of the precursors on DBP formation after UV/persulfate treatment, and DBP alteration depended on the reactivity between SO4•- and specific precursor.

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.

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•.