Emerging Disinfection By-products Research Articles

Formation potential of emerging disinfection by-products during ozonation and chlorination of sewage effluents

This study investigates the formation potential of emerging DBPs (haloacetonitriles, halonitromethanes and halopropanones) during ozonation and ozonation/hydrogen peroxide treatment and subsequent chlorination of sewage effluent under various experimental conditions. Estimation of possible risk due to DBPs by calculation of cytotoxicity and genotoxicity was attempted.The studied DBPs showed different formation behavior during chlorination, with maximum yields within 0.5–48 h. Maximum cytotoxicity and genotoxicity was observed after 4 h of chlorination with dibromoacetonitrile being the major contributor. Ozonation and O3/H2O2 treatment resulted in increase of trichloronitromethane followed by a decline at higher doses, and reduction of haloacetonitriles. High ozone doses reduced cytotoxicity and genotoxicity of treated effluents. The presence of bromide shifted to bromo-DBPs formation and enhanced both cytotoxicity and genotoxicity. Particulate fraction in effluents significantly contributed to the formation of DBPs and consequently to the their toxicity.

Occurrence, Formation, and Oxidative Stress of Emerging Disinfection Byproducts, Halobenzoquinones, in Tea.

Halobenzoquinones (HBQs) are frequently detected disinfection byproducts (DBPs) in drinking water with high toxicity and relevance to public health. In this study, we characterized the occurrence, formation, and oxidative stress of the HBQs in tea. 2,6-DCBQ and TetraC-1,2-BQ were identified in all prepared teas at total concentrations of 1.3-2.0 ng/L. 2,6-DCBQ originated from drinking water DBPs, while TetraC-1,2-BQ originated from tea leaves or were generated during tea polyphenol chlorination. HBQs in tea induced the formation of reactive oxygen species and semiquinone radicals, and the oxidative stress could be depleted by tea polyphenols, e.g., (-)-epigallocatechin gallate (EGCG). High-resolution mass spectrometry analysis indicated that the HBQs combined with EGCG and formed adducts at a ratio of 1:1 or 2:1 with the binding sites on the A ring and B ring of EGCG. The viability of HepG2 cells exposed to 50 μM 2,6-DCBQ was increased from 20.0% to 65.2% when 50 μM of EGCG was added. These results demonstrated that various HBQs can occur in tea due to the HBQ DBPs in drinking water, the leachate from tea leaves, and the chlorination of tea polyphenols; furthermore, the oxidative stress and cellular toxicity induced by HBQs in tea could be decreased by tea polyphenols. This is the first study to report HBQs in tea, elucidate the sources of HBQs, and assess relevant health risks.

Selective Recognition of Phenazine by 2,6‐Dibutoxylnaphthalene‐Based Tetralactam Macrocycle

Summary of main observation and conclusionA 2,6‐dibutoxylnaphthalene‐based tetralactam macrocycle was designed and synthesized. This macrocycle shows highly selective recognition to phenazine – a well‐known secondary metabolite in bacteria and an emerging disinfection byproduct in drinking water. In contrast, the macrocycle shows no binding to the structurally similar dibenzo‐1,4‐dioxin. It was revealed that hydrogen bonding, π‐π and σ‐π interactions are the major driving forces between phenazine and the new tetralactam macrocycle. A perfect complementarity in electrostatic potential surfaces may explain the high selectivity. In addition, the macrocycle shows fluorescent response to phenazine, demonstrating its potential in fluorescent detection of phenazine.

Towards the revision of the drinking water directive 98/83/EC. Development of a direct injection ion chromatographic-tandem mass spectrometric method for the monitoring of fifteen common and emerging disinfection by-products along the drinking water supply chain

According to the recent proposal released by the European Commission for the revision of the 98/83/EC Directive, water suppliers will be requested to monitor the nine bromine- and chlorine congeners of haloacetic acids, HAAs, as well as the oxyhalides chlorite and chlorate, as disinfection by-products (DBPs) originated during the potabilization process.In this work, we propose a direct-injection method based on ion chromatography and mass spectrometric detection for the determination of the mentioned DBPs as well as bromate (already included in the 98/83/EC), implemented also for the following emerging HAAs monoiodo-, chloroiodo- and diiodo-acetic acids. The method was optimized to include the fifteen compounds in the same analytical run, tuning the chromatographic (column and gradient) and detection conditions (suppression current, transitions, RF lens settings and collision energies). To avoid matrix effect and to manage the instrumental conditions, optimization was performed directly in drinking water matrix. The method quantitation limits satisfy the new limits imposed by the future directive and range from 0.08 μg/L (monobromoacetic acid) to 0.34 μg/L (trichloroacetic acid). The performance of the method was checked along different strategic sampling points of three potabilization plants serving the city of Turin (Italy), including intermediate treatments and finished waters. Recovery was checked according to the ±30% limit of acceptability set by EPA regulations. The effect of disproportionate concentrations of chlorite and chlorate in respect to HAAs on HAA signals was studied; this aspect is underestimated in literature. The method is routinely applied by the potabilization plant of the city of Turin to confirm the effectiveness of all control measures in abstraction, treatment, distribution and storage. This study represents the first example in Italy of development and use of a cutting-edge technique for HAAs analysis along the potabilization processes.

Effects of 2,2-dichloroacetamide (DCAcAm), an emerging disinfection by-product in drinking water, on the intestinal microbiota of adult zebrafish.

The presence of disinfection by-products (DBPs) increases the mutagenicity of water and may pose adverse health effects. Gut microbiota exerts a fundamental role on host physiology, and how extrinsic perturbations influence its composition has been increasingly examined. However, the effect of DBPs on gut microbiota is still poorly understood. In the present study, adult zebrafish were exposed to different concentrations of dichloroacetamide (DCAcAm, an emerging nitrogenous DBP) for 30 days. Sequencing of 16S rRNA amplicons revealed a significant change in the richness and diversity of microbiota in the gut of DCAcAm-exposed zebrafish. At the phylum level, the abundance of Proteobacteria decreased and the abundance of Fusobacteria and Firmicutes increased significantly in the gut after exposure to 100 and 500 μg/L DCAcAm. At the genus level, the abundances of several bacteria which are considered pathogens or opportunistic pathogens in fish and closely related to fish metabolism, disease and inflammation (Aeromonas, Stenotrophomonas, Bacteroides and Ralstonia) increased in the DCAcAm-treated groups. Our results reveal that DBPs in drinking water potentially affect gut microbiota composition, which may contribute to the toxicity assessment of DBPs in future and provide new insight into the complex interactions between the DBPs in drinking water and host health.

Emerging disinfection by-products’ formation potential in raw water, wastewater, and treated wastewater in Thailand

Raw water (RW) from the Bangkok and Sing Buri water treatment plants located on the Chao Phraya River, river water, domestic wastewater (WW), and treated wastewater (TWW) from two wastewater treatment plants in Thailand were collected three times to investigate disinfection by-products’ (DBPs) formation potential (FP) including trihalomethane FP (THMFP), iodo-THMFP (I-THMFP), haloacetonitriles FP (HANFP), and trichloronitromethane FP (TCNMFP). High THMFP levels were observed in river water, WW, and TWW. Considering average value, the THMFP of TWW was about two times higher than that of RW. Relatively high levels of I-THMFP were found in WW and TWW. The I-THMFP of TWW was three to seven times higher than that of RW. The HANFP of TWW was one to three times higher than that of RW. High levels of TCNMFP were found in WW and TWW. TCNMFP of TWW was six to thirteen times higher than that of RW. The discharge of TWW to RW must be prevented and controlled. The moderately positive linear relationship was obtained between dissolved organic carbon and TCNMFP in TWW. Considering measured weight concentration, THMFP was found as the highest DBPs. The highest lethal concentration 50-weighted and lowest cytotoxicity-weighted concentrations of DBPs were determined for HANFP.

Predicting the cytotoxicity of disinfection by-products to Chinese hamster ovary by using linear quantitative structure-activity relationship models.

A suitable model to predict the toxicity of current and continuously emerging disinfection by-products (DBPs) is needed. This study aims to establish a reliable model for predicting the cytotoxicity of DBPs to Chinese hamster ovary (CHO) cells. We collected the CHO cytotoxicity data of 74 DBPs as the endpoint to build linear quantitative structure-activity relationship (QSAR) models. The linear models were developed by using multiple linear regression (MLR). The MLR models showed high performance in both internal (leave-one-out cross-validation, leave-many-out cross-validation, and bootstrapping) and external validation, indicating their satisfactory goodness of fit (R2 = 0.763-0.799), robustness (Q2LOO = 0.718-0.745), and predictive ability (CCC = 0.806-0.848). The generated QSAR models showed comparable quality on both the training and validation levels. Williams plot verified that the obtained models had wide application domains and covered the 74 structurally diverse DBPs. The molecular descriptors used in the models provided comparable information that influences the CHO cytotoxicity of DBPs. In conclusion, the linear QSAR models can be used to predict the CHO cytotoxicity of DBPs.

Analytical methods for conventional and emerging disinfection by-products in fresh-cut produce

The formation of toxic disinfection by-products (DBPs) is among the main concerns in the use of chlorine sanitizers for washing fresh and fresh-cut produce to minimize microbial cross-contamination. Even so, robust analytical methods for measuring various DBPs in produce have been lacking. This study has established two liquid-liquid extraction methods, followed by gas chromatography with electron capture detection, to measure 32 conventional and emerging DBPs in different produce types including lettuce, cabbage and strawberry. Good recoveries (50–130%) were achieved for most DBPs in the different produce. The method detection limits were in the range of 0.3–10 ng/g for trihalomethanes, haloacetic acids, nitrogenous DBPs, and other carbonaceous DBPs. Preliminary screening analysis indicated one-third of the target DBPs were found in unwashed produce, and washing with chlorine significantly promoted DBPs’ formation and concentrations in the produce. The developed analytical methods will be useful tools for future research on food DBPs.

Effect of photochemical advanced oxidation processes on the formation potential of emerging disinfection by-products in groundwater from part of the Pannonian Basin

Abstract This study evaluates the effect of photochemical advanced oxidation processes (AOPs) (O3/UV, H2O2/UV and O3/H2O2/UV) on the formation potential (FP) of emerging disinfection by-products including nitrogenous by-products (N-DBPs) and haloketones (HKs) in groundwater from part of the Pannonian Basin (AP Vojvodina, Republic of Serbia). Among the N-DBPs, the haloacetonitrile (HAN) precursor contents were 9.83 ± 0.59 μg/L while precursors of halonitromethanes, particularly trichloronitromethane (TCNM) were not detected. Similarly, precursors of HKs as carbonaceous DBPs were also not detected in raw water. Ozonation alone and the H2O2/UV process with a lower UV dose maximally decomposed HAN precursors (about 70%) while during O3-based AOPs, HANFP varied significantly. Application of UV photolysis and H2O2/UV processes with increasing UV dose doubled the HANFP. Ozone alone, O3/UV and H2O2/UV slightly increased HK formation potential, particularly 1,1-dichloro-2-propanone FP (0.93 ± 0.21 to 2.01 ± 0.37 μg/L). None of the investigated treatments influenced the formation of TCNM precursors. The effect of the applied treatments on bromide incorporation was most evident for HANs.

Cytotoxicity induced by iodinated haloacetamides via ROS accumulation and apoptosis in HepG-2 cells

Iodinated haloacetamides (I-HAcAms) are emerging disinfection by-products and have received great concern due to their extremely high health risk. Previous studies have demonstrated the cytotoxicity of I-HAcAms, but the biological mechanism remained unclear. In this study, cytotoxicity mechanisms of 4 I-HAcAms species were preliminarily examined using HepG-2 cells. The results showed that the cytotoxicity could be ranked as follows: diiodoacetamide (DIAcAm)> iodoacetamide (IAcAm)> bromoiodoacetamide (BIAcAm)> chloroiodoacetamide (CIAcAm). Reactive oxygen species (ROS) and apoptosis played an important role in the cytotoxicity for all I-HAcAms species. Moreover, the ROS and cytotoxicity could be completely reversed by the addition of an antioxidant (N-acetylcysteine (NAC)), but the apoptosis could not. Specifically, the apoptosis induced by DIAcAm and IAcAm was partially reversed by NAC, suggesting that in addition to ROS, other pathways were also possible; While For BIAcAm and CIAcAm, the apoptosis was not reversed by NAC at all, which is potentially due to ROS-independent pathways. The apoptosis mechanisms were further analyzed via Bax and Bcl-2 gene expression and the corresponding protein expression in HepG-2 cells, that mitochondrial pathway was important in the apoptosis of HepG-2 cells induced by all I-HAcAms species. Overall, the mitochondrial pathway provided a potential explanation for BIAcAm and CIAcAm-induced apoptosis, while both ROS and mitochondrial pathways explained DIAcAm and IAcAm-induced apoptosis.

Rapid degradation of brominated and iodinated haloacetamides with sulfite in drinking water: Degradation kinetics and mechanisms

The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection.

Halobenzoquinone-Induced Alteration of Gene Expression Associated with Oxidative Stress Signaling Pathways.

Halobenzoquinones (HBQs) are emerging disinfection byproducts (DBPs) that effectively induce reactive oxygen species and oxidative damage in vitro. However, the impacts of HBQs on oxidative-stress-related gene expression have not been investigated. In this study, we examined alterations in the expression of 44 genes related to oxidative-stress-induced signaling pathways in human uroepithelial cells (SV-HUC-1) upon exposure to six HBQs. The results show the structure-dependent effects of HBQs on the studied gene expression. After 2 h of exposure, the expression levels of 9 to 28 genes were altered, while after 8 h of exposure, the expression levels of 29 to 31 genes were altered. Four genes ( HMOX1, NQO1, PTGS2, and TXNRD1) were significantly upregulated by all six HBQs at both exposure time points. Ingenuity pathway analysis revealed that the Nrf2 pathway was significantly responsive to HBQ exposure. Other canonical pathways responsive to HBQ exposure included GSH redox reductions, superoxide radical degradation, and xenobiotic metabolism signaling. This study has demonstrated that HBQs significantly alter the gene expression of oxidative-stress-related signaling pathways and contributes to the understanding of HBQ-DBP-associated toxicity.

Analysis of 40 conventional and emerging disinfection by-products in fresh-cut produce wash water by modified EPA methods

Chlorine sanitizers used in washing fresh and fresh-cut produce can lead to generation of disinfection by-products (DBPs) that are harmful to human health. Monitoring of DBPs is necessary to protect food safety but comprehensive analytical methods have been lacking. This study has optimized three U.S. Environmental Protection Agency methods for drinking water DBPs to improve their performance for produce wash water. The method development encompasses 40 conventional and emerging DBPs. Good recoveries (60–130%) were achieved for most DBPs in deionized water and in lettuce, strawberry and cabbage wash water. The method detection limits are in the range of 0.06–0.58 μg/L for most DBPs and 10–24 ng/L for nitrosamines in produce wash water. Preliminary results revealed the formation of many DBPs when produce is washed with chlorine. The optimized analytical methods by this study effectively reduce matrix interference and can serve as useful tools for future research on food DBPs.

Characterization of Mechanisms of Glutathione Conjugation with Halobenzoquinones in Solution and HepG2 Cells.

Halobenzoquinones (HBQs) are a class of emerging disinfection byproducts. Chronic exposure to chlorinated drinking water is potentially associated with an increased risk of human bladder cancer. HBQ-induced cytotoxicity involves depletion of cellular glutathione (GSH), but the underlying mechanism remains unclear. Here we used ultrahigh performance liquid chromatography-high resolution mass spectrometry and electron paramagnetic resonance spectroscopy to study interactions between HBQs and GSH and found that HBQs can directly react with GSH, forming various glutathionyl conjugates (HBQ-SG) in both aqueous solution and HepG2 cells. We found that the formation of HBQ-SG varies with the initial molar ratio of GSH to HBQ in reaction mixtures. Higher molar ratios of GSH to HBQ facilitate the conjugation of more GSH molecules to an HBQ molecule. We deduced the reaction mechanism between GSH and HBQs, which involves redox cycling-induced formation of halosemiquinone (HSQ) free radicals and glutathione disulfide, Michael addition, as well as nucleophilic substitution. The proposed reaction rates are in the following order: formation of HSQ radicals > substitution of bromine by GSH > Michael addition of GSH on the benzoquinone ring > substitution of chlorine by GSH > substitution of the methyl group by GSH. The conjugates identified in HBQ-treated HepG2 cells were the same as those found in aqueous solution containing a 5:1 ratio of GSH:HBQs.

Removal of the precursors of N-nitrosodiethylamine (NDEA), an emerging disinfection byproduct, in drinking water treatment process and its toxicity to adult zebrafish (Danio rerio)

N-nitrosodiethylamine (NDEA) is one of the emerging nitrogenous disinfection byproducts with probable cytotoxicity, genotoxicity, and carcinogenesis. Its potential toxicological effects have received extensive attention but remain to be poorly understood. In this study, changes in NDEA precursors in drinking water treatment process were studied using the trial of its formation potential (FP), and the toxicity induced by NDEA to adult zebrafish was investigated. NDEA FP in the raw water of Taihu Lake ranged from 46.9 to 68.3 ng/L. The NDEA precursors were removed effectively by O3/BAC process. Hydrophilic fraction and low-molecular-weight fraction (<1 kDa) had the highest NDEA FP. The toxicity results demonstrated that the acute lethal concentration of NDEA causing 50% mortality in 96 h (96-h LC50) was 210.4 mg/L, and NDEA was more likely to be accumulated in kidney, followed by liver and gill. NDEA induced oxidative stress and antioxidant defense to zebrafish metabolism system at concentrations over 5 μg/L. After a 42-day exposure, a significant DNA damage was observed in zebrafish liver cells at NDEA concentrations beyond 500 μg/L. This study investigated NDEA properties in both engineering prospective and toxicity evaluation, thus providing comprehensive information on its control in drinking water treatment process and its toxicity effect on zebrafish as a model animal.

Suspect screening of halogenated carboxylic acids in drinking water using ion exchange chromatography – high resolution (Orbitrap) mass spectrometry (IC-HRMS)

Retrospective in silico screening of analytical data for the identification of new or emerging disinfection by-products in drinking waters could be useful to assess quality and potential hazards, as well as help implement mitigation procedures more rapidly. Herein, the first study coupling ion exchange chromatography (IC) with high resolution mass spectrometry (HRMS) for the determination of halogenated carboxylic acid disinfectant by-products is reported. Separation was achieved using a Metrohm A Supp 5 column and a Na2CO3/NaHCO3 gradient eluent from 1/0.31 to 10/3.1mM. A variety of solid phase extraction (SPE) sorbents were tested for added selectivity to organic ions and Isolute ENV+ cartridges were selected because of their best overall extraction performance. Method LODs were in the μgL−1 concentration range, with R2 ≥ 0.99 for all the analytes, and isobaric ions could be easily discriminated using HRMS. The method was applied to municipal drinking water. Targeted quantitative analysis revealed the presence of 10 haloacetic acids at levels not exceeding the limits set by WHO and USEPA. Furthermore, suspect screening for additional halogenated carboxylic acids via retrospective HRMS data analysis also indicated the presence of other iodinated HAAs and chlorinated propionic acids, of which one (i.e. monochloropropionic acid) is discussed here for the first time. Most importantly, several potential suspects could be eliminated from further consideration through HRMS data analysis alone. To our knowledge, this represents the first time that a retrospective IC-HRMS screen of halogenated carboxylic acids in drinking water has been reported.

Transformation of halobenzoquinones with the presence of amino acids in water: Products, pathways and toxicity

The transformation and detoxification of halobenzoquinones (HBQs), a class of emerging disinfection byproducts (DBPs), was studied in the presence of amino acids (AAs). The reaction activity of three HBQs with AAs generally ranked as 2-chlorobenzoquinone (CBQ) < 2,6-dichlorobezoquinone (DCBQ) < tetrachloroquinone (TCBQ), consistent with their halogenation degree and the calculated electron affinity (EA) results. According to mass spectrometry and density functional theory (DFT) calculations, AAs can easily covalently incorporate into HBQs via nucleophilic addition (CBQ and DCBQ) or substitution (TCBQ) through CNC or CSC linkages. Hydroxylation, nucleophilic reaction and decarboxylation were proposed to be the three major reaction pathways for HBQs transformation with AAs. HBQs firstly underwent the spontaneous hydrolysis, resulting in OH-HBQs formation. Then, nucleophilic addition/substitution of AAs occurred on HBQs and OH-HBQs to produce AA-HBQs/AA-HBQs-OH adducts. These adducts were subsequently oxidized into their corresponding decarboxylated forms. Based on the results of Luminous bacterium Q67 acute toxicity test, the toxicity of HBQs solution greatly decreased with AAs presented. The toxicity change was well explained by the lowest unoccupied molecular orbital energy (ELUMO) of formed products. Notably, the step that AAs nucleophilic bonded with HBQs led to the highest rise of ELUMO, which should be the most effective pathway for HBQs detoxification. This study shows that binding with amino nitrogen compounds should be an important process for HBQs transformation and detoxification, which helps to better understand the fate of this typical DBP in surface water.

Characterization of N-nitrosodimethylamine formation from the ozonation of ranitidine

N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product which is formed during water disinfection in the presence of amine-based precursors. Ranitidine, as one kind of amine-based pharmaceuticals, has been identified as NDMA precursor with high NDMA molar conversion during chloramination. This study focused on the characterization of NDMA formation during ozonation of ranitidine. Influences of operational variables (ozone dose, pH value) and water matrix on NDMA generation as well as ranitidine degradation were evaluated. The results indicate high reactivity of ranitidine with ozone. Dimethylamine (DMA) and NDMA were generated due to ranitidine oxidation. High pH value caused more NDMA accumulation. NDMA formation was inhibited under acid conditions (pH≤5) mainly due to the protonation of amines. Water matrix such as HCO3− and humic acid impacted NDMA generation due to OH scavenging. Compared with OH, ozone molecules dominated the productions of DMA and NDMA. However, OH was a critical factor in NDMA degradation. Transformation products of ranitidine during ozonation were identified using gas chromatography–mass spectrometry. Among these products, just DMA and N,N-dimethylformamide could contribute to NDMA formation due to the DMA group in the molecular structures. The NDMA formation pathway from ranitidine ozonation was also proposed.

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.

Kinetics and modeling of iodoform degradation during UV/chlorine advanced oxidation process

Iodoform (CHI3) is an emerging disinfection by-product (DBP) that may be formed during pre-oxidation or disinfection processes in drinking water treatment. Degradation kinetics, modeling and mechanism of CHI3 by combined UV/chlorine advanced oxidation processes (AOPs) were studied in this manuscript. CHI3 was effectively removed by UV/chlorine process with the reactions followed pseudo-first order kinetics. The contributions of direct UV photolysis as well as indirect photolysis (hydroxyl radicals (OH) to CHI3 degradation during UV/chlorination under different experimental factors were investigated and determined as 20.3% and 79.7% at pH 5 to 97.1% and 2.9% at pH 9, respectively. Chlorine dosage and CHI3 concentration had slight effects on the contributions of different degradation pathways. NOM and bicarbonate have negative effects on CHI3 degradation. The degradation model of CHI3 during UV/chlorine processes was established, and the satisfactory match of the model calculation results and the experimental data were found. The reaction rate constant between CHI3 and UV light as well as CHI3 and OH were determined as 3.43×10−3s−1 and 7.7×109M−1s−1, respectively. On the basis of the iodine species (such as IO3−, HOI, I2 and I3−) mass balance analysis, the degradation pathways of CHI3 were proposed and IO3− contributed 13.7% of the total liberated iodine species during UV/chlorination. These results demonstrated that UV/chlorination process is a promising AOP technology for the treatment of water containing CHI3.