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Peptide-bound histidines and imidazoles are important constituents of dissolved organic matter in water, and understanding the formation of halogenated disinfection byproduct (DBP) formation from these compounds during disinfection is important for ensuring a safe drinking water supply. Previous studies suggested that histidine has low reactivity with chlorine only; this study indicates that iodide substantially enhances histidine reactivity with the disinfectant at a time scale from days to hours. Mono- and di-iodinated histidines were identified as dominant transformation products with cumulative molar yields of 3.3 % at 6 h and they were stable in water over 7 days. These products were formed via electrophilic substitution of iodine to imidazole ring when hypoiodous acid reacted with histidine sidechain. Bromide minimally influenced the formation yields of these iodinated products, and higher pH increased yields up to 12 % for pH in the range 5-9. The cumulative concentration of low-molecular-weight DBPs, such as trihalomethanes and haloacetic acids, was less than 0.3 % under the same conditions. Similar iodinated imidazole analogs were also identified from other imidazoles (i.e., imidazole-carboxylic and phenyl-imidazole-carboxylic acids). This study demonstrated that peptide-bound histidine and imidazoles can serve as important precursors to iodinated aromatic DBPs, facilitating the identification of less-known iodinated DBPs.

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Iodinated disinfection by-products (I-DBPs) exhibited potential health risk owing to the high toxicity. Our recent study demonstrated that I-DBPs from Laminaria japonica (Haidai), the commonly edible seaweed, upon simulated household cooking condition were several hundred times more than the concentration of drinking water. Here, the characterization of Haidai and its leachate tandem with the formation, identification and toxicity of I-DBPs from the cooking of Haidai were systemically investigated. The dominant organic matter in Haidai leachate were polysaccharides, while the highest iodine specie was iodide (∼90% of total iodine). Several unknown I-DBPs generated from the cooking of Haidai were tentatively proposed, of which 3,5-diiodo-4-hydroxybenzaldehyde was dominant specie. Following a simulated household cooking with real chloraminated tap water, the presence of Haidai sharply increased aggregate iodinated trihalomethanes, iodinated haloacetic acids, and total organic iodine concentrations to 97.4 ± 7.6 µg/L,16.4 ± 2.1 µg/L, and 0.53 ± 0.06 mg/L, respectively. Moreover, the acute toxicity of Haidai soup to Vibrio qinghaiensis sp.-Q67 was around 7.3 times higher than that of tap water in terms of EC50. These results demonstrated that the yield of I-DBPs from the cooking of Haidai and other seaweed should be carefully considered.

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In this study, we demonstrate that Fe(III)-doped g-C3N4 can efficiently activate peracetic acid (PAA) to degrade electron-rich pollutants (e.g., sulfamethoxazole, SMX) over a wide pH range (3-7). Almost ∼100% high-valent iron-oxo species (Fe(V)) was generated and acted as the dominant reactive species responsible for the micropollutants oxidation based on the analysis result of quenching experiments, 18O isotope-labeling examination and methyl phenyl sulfoxide (PMSO) probe method. Electrochemical testing (e.g., amperometric i-t and linear sweep voltammetry (LSV)) and density functional theory (DFT) calculations illustrated that the main active site Fe atom and PAA underwent electron transfer to form Fe(V) for attacking SMX. Linear free energy relationship (LFER) between the pseudo-first-order rates of different substituted phenols (SPs) and the Hammett constant σ+ depicted the electrophilic oxidation properties. The selective oxidation of Fe(V) endows the established system remarkable anti-interference capacity against water matrices, while the Fe(V) lead to the formation of iodinated disinfection by-products (I-DBPs) in the presence of I-. Fe(III)-doped g-C3N4/PAA system showed excellent degradation efficiency of aquaculture antibiotics. This study enriches the knowledge and research of high-valent iron-oxo species and provides a novel perspective for the activation of PAA via heterogeneous iron-based catalysts and practical environmental applications.

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Chlorination of water results in the formation of haloacetic acids (HAAs) as major disinfection byproducts (DBPs). Previous studies have reported some HAAs species to act as cytotoxic, genotoxic, and carcinogenic. This work aimed at further exploring the toxicity potential of the most investigated HAAs (chloroacetic (CAA), bromoacetic (BAA), iodoacetic (IAA) acid) and HAAs species with high content of bromine (tribromoacetic acid (TBAA)), and iodine in their structures (chloroiodoacetic (CIAA) and diiodoacetic acid (DIAA)) to human cells. Novel knowledge was generated regarding cytotoxicity, oxidative stress, endocrine disrupting potential, and genotoxicity of these HAAs by using human placental and lung cells as in vitro models, not previously used for DBP assessment. IAA showed the highest cytotoxicity (EC50: 7.5 µM) and ability to generate ROS (up to 3-fold) in placental cells, followed by BAA (EC50: 20-25 µM and 2.1-fold). TBAA, CAA, DIAA, and CIAA showed no significant cytotoxicity (EC50 > 250 µM). All tested HAAs decreased the expression of the steroidogenic gene hsd17b1 up to 40 % in placental cells, and IAA and BAA (0.01-1 µM) slightly inhibited the aromatase activity. HAAs also induced the formation of micronuclei in A549 lung cells after 48 h of exposure. IAA and BAA showed a non-significant increase in micronuclei formation at low concentrations (1 µM), while BAA, CAA, CIAA and TBAA were genotoxic at exposure concentrations above 10 µM (100 µM in the case of DIAA). These results point to genotoxic and endocrine disruption effects associated with HAA exposure at low concentrations (0.01-1 µM), and the usefulness of the selected bioassays to provide fast and sensitive responses to HAA exposure, particularly in terms of genotoxicity and endocrine disruption effects. Further studies are needed to define thresholds that better protect public health.

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Iodinated disinfection by-products (I-DBPs) have attracted extensive interests because of their higher cytotoxicity and genotoxicity than their chlorinated and brominated analogues. Our recent studies have firstly demonstrated that cooking with seaweed salt could enhance the formation of I-DBPs with several tens of µg/L level. Here, I-DBP formation and mitigation from the reaction of disinfectant with Laminaria japonica (Haidai), an edible seaweed with highest iodine content, upon simulated household cooking process was systematically investigated. The total iodine content in Haidai ranged from 4.6 mg-I/g-Haidai to 10.0 mg-I/g-Haidai, and more than 90% of iodine is soluble iodide. During simulated cooking, the presence of disinfectant simultaneously decreased iodide by 15.0-32.8% to 2.7-5.8 mg/L and increased total organic iodine by 1.3-10.9 times to 0.5-1.8 mg/L in Haidai soup, proving I-DBP formation. The concentrations of iodinated trihalomethanes and haloacetic acids were at the levels of several hundreds of µg/L and several µg/L, respectively, which are 2-3 orders and 1-2 orders of magnitude more than those in drinking water. Effects of key factors including disinfectant specie, disinfectant dose, temperature and time on I-DBP formation were also ascertained, and temperature and disinfectant specie played a decisive role in the formation and speciation of I-DBPs. In order to avoid the potential health risk from the exposure of I-DBPs in Haidai soup, it is prerequisite to soak and wash dry Haidai sample over 30.0 min before cooking, which could effectively remove major soluble iodide. In general, this study provided the new insight into I-DBP formation from daily household cooking with Haidai and the corresponding enlightenment for inhabitants to eat Haidai in daily life.

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The increasing occurrence of harmful algal blooms (HABs) in surface waters may increase the input of algal organic matter (AOM) in drinking water. The formation of halogenated disinfection byproducts (DBPs) during combined chlorination and chloramination of AOM and natural organic matter (NOM) in the presence of bromide and iodide and haloform formation during halogenation of model compounds were studied. Results indicated that haloform/halogen consumption ratios of halogens reacting with amino acids (representing proteins present in AOM) follow the order iodine > bromine > chlorine, with ratios for iodine generally 1-2 orders of magnitude greater than those for chlorine (0.19-2.83 vs 0.01-0.16%). This indicates that iodine is a better halogenating agent than chlorine and bromine. In contrast, chlorine or bromine shows higher ratios for phenols (representing the phenolic structure of humic substances present in NOM). Consistent with these observations, chloramination of AOM extracted from Microcystis aeruginosa in the presence of iodide produced 3 times greater iodinated trihalomethanes than those from Suwannee River NOM isolate. Cytotoxicity and genotoxicity of disinfected algal-impacted waters evaluated by Chinese hamster ovary cell bioassays both follow the order chloramination > prechlorination-chloramination > chlorination. This trend is in contrast to additive toxicity calculations based on the concentrations of measured DBPs since some toxic iodinated DBPs were not identified and quantified, suggesting the necessity of experimentally analyzing the toxicity of disinfected waters. During seasonal HAB events, disinfection practices warrant optimization for iodide-enriched waters to reduce the toxicity of finished waters.

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Iodinated disinfection byproducts (I-DBPs) formed in water treatment are of emerging concern due to their high toxicity and the tase-and-odor problems associated with iodinated trihalomethanes (I-THMs). Iodoacetic acid and dichloroiodomethane are currently regulated in Shenzhen, China and the Ministry of Health of the People's Republic of China has also been considering regulating I-DBPs. Iodide (I-), organoiodine compounds (e.g., iodinated X-ray contrast media [ICM]), and iodate (IO3-) are the three common iodine sources in aquatic environment that lead to I-DBP formation. While UV irradiation effectively inactivate a wide range of microorganisms in water, it induces the transformation of these iodine sources, enabling the formation of I-DBPs. This review focuses on the fate and transformation of these iodine sources in UV-based water treatment (i.e., UV irradiation and UV-based advanced oxidation processes [UV-AOPs]) and the formation of I-DBPs in post-disinfection. I- released in UV-based treatments of ICM and can be oxidized in subsequent disinfection to hypoiodous acid (HOI), which reacts with natural organic matter (NOM) to produce I-DBPs. Both UV and UV-AOPs are not able to fully mineralize ICM and completely oxidize the released I- to (except UV/O3). Results reveal that UV and UV-AOPs are adequate for I-DBP degradation but require high UV doses. While the ideal I-DBP mitigation strategy awaits to be developed, understanding their sources and formation pathways aids in informed selections of water treatment processes, empowers water suppliers to meet drinking water standards, and minimizes consumers' exposure to I-DBPs.

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Different groups of disinfection by-products (DBPs) were studied through the degradation of iopamidol by the sequential oxidation process of ozone-low pressure ultraviolet light (O3-LPUV) followed by chlorination. This paper investigates the attenuation of iopamidol under this sequential treatment and the effect of chlorine contact time (30 min versus 3 days) to control the formation potential of DBPs: trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetamides (HAMs). Thirty target DBPs among the 9 iodinated-DBPs (I-DBPs), were monitored throughout the sequential treatment. Results showed that O3-LPUV removed up to 99% of iopamidol, while ozone and LPUV alone removed only 90% and 76% respectively. After chlorine addition, O3-LPUV yielded 56% lower I-DBPs than LPUV. Increasing chlorine contact time resulted in higher concentrations of all DBP groups (THMs, HANs, and HAMs), with the exception of I-DBPs. One new iodinated-haloacetamide, namely chloroiodoacetamide (CIACM) and one iodoacetonitrile (IACN) were detected. These results suggest the iodine incorporated in iopamidol may be a precursor for iodinated-nitrogenous-DBPs, which are currently not well studied.

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Manganese dioxide (MnO2) is a Mn deposit widely accumulated in the corrosion layer of pipelines, and iodide (I-) is a halogen ion frequently detected in waters. The biofilm dwelling on the corrosion scales often secretes extracellular polymeric substances (EPS) into drinking water. The paper aimed to study the I- oxidation by MnO2 and iodinated disinfection byproducts (I-DBPs) formation with biofilm EPS as a precursor. More than 93% of formed free iodine was finally converted into organic iodine in the MnO2/I-/EPS system. Compared with humic acid, EPS had a lower carbonaceous I-DBPs (C-IDBPs) formation while a higher nitrogenous I-DBPs (N-IDBPs) formation. The formation of iodomethanes (I-THMs), iodoacetonitriles (I-HANs) and iodoacetic acids (I-HAAs) decreased with the increase of pH due to the weakening of polarization effect and redox potential, while the iodoacetamides (I-HAcAms) formation achieved the maximum at pH 6.0 due to the difference between the hydrolysis rate of I-HANs and decomposition rate of I-HAcAms. The I-DBPs formation was positively correlated with I- concentration, while negatively correlated with MnO2 dose. Protein components displayed a higher formation of N-IDBPs and C-IDBPs than polysaccharide components due to higher nitrogen proportion and more iodination sites. Among 20 protein monomers, aspartic acid was considered as the most important precursor of the four investigated I-DBPs species. The paper is helpful to understand the I-DBPs formation when I- in the bulk water come into contact with Mn deposits attached by biofilm.

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Iodinated contrast media (ICM) are drugs which are used in medical examinations for organ imaging purposes. Wastewater treatment plants (WWTPs) have shown incapability to remove ICM, and as a consequence, ICM and their transformation products (TPs) have been detected in environmental waters. ICM show limited biotransformation and low sorption potential. ICM can act as iodine source and can react with commonly used disinfectants such as chlorine in presence of organic matter to yield iodinated disinfection byproducts (IDBPs) which are more cytotoxic and genotoxic than conventionally known disinfection byproducts (DBPs). Even highly efficient advanced treatment systems have failed to completely mineralize ICM, and TPs that are more toxic than parent ICM are produced. This raises issues regarding the efficacy of existing treatment technologies and serious concern over disinfection of ICM containing waters. Realizing this, the current review aims to capture the attention of scientific community on areas of less focus. The review features in depth knowledge regarding complete environmental fate of ICM along with their existing treatment options.

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Lead dioxide (PbO2) is an important form of lead mineral scales in drinking water pipes. Iodide (I-) widely presents in source waters and can be thermodynamically oxidized by PbO2 to the reactive iodine species (I2/HOI). Biofilm extracellular polymeric substances (EPS) are nonnegligible precursors of disinfection byproducts (DBPs). The aim was to study the oxidation of I- by PbO2 and formation of iodinated DBPs (I-DBPs) from EPS. At a high molar ratio of PbO2 to I- (> 100), the observed rate constants of I- oxidation decreased as pH increased from 6.0 to 9.0 with an H+ dependence of 0.79, and the rate constant (k) was 1.6 × 1011 M-2.79 s-1. Most of formed I2/HOI (> 92%) was transformed to organic iodine in the presence of EPS. EPS had a lower formation potential (FP) of carbonaceous I-DBPs (C-IDBPs), while a higher that of nitrogenous I-DBPs (N-IDBPs) than HA, resulting in a higher Chinese Hamster Ovary cell cytotoxicity. Generally, the formation of I-DBPs decreased with the increase of pH due to the reduction of surface positive charge and electrochemical driving force. PbO2 dose and I- concentration also had a significant effect on the I-DBPs formation. EPS proteins had a higher FP of both C- and N-IDBPs than polysaccharides on account of more electrophilic sites and higher nitrogen content. In proteins, aspartic acid was the main contributor to triiodomethane and iodoacetic acids formation, whereas aspartic acid, asparagine and tyrosine were the major precursors of diiodoacetonitrile and diiodoacetamide. The study helps to improve the control strategy of I-DBPs when biofilm outbreaks in lead-containing water pipes.

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Iodinated disinfection by-products (I-DBPs) have recently emerged as part of the pool of DBPs of public health concern. Due to limitations in measuring individual I-DBPs in a water sample, the surrogate measure of total organic iodine (TOI) is often used to account for the sum of all I-DBPs. In this study, TOI and total iodine (TI) are quantified in raw and treated waters in treatment trains at three sites in the Northeast United States. The occurrence, magnitude, and seasonality of these species was investigated within each sampling train and across the different sites. A regression model was developed to explore how TOI occurrence varies with routinely measured physical and chemical parameters in a water sample. The TOI and TI concentration at the three sites ranged from below the method detection limit to 18 µg/L and from 3 and 18.9 µg/L, respectively. There was substantial inter-monthly variability in TOI without a clear seasonal signal, and the concentration of TOI did not increase upon treatment. The results of the multivariate regression model showed that dissolved organic carbon (DOC), specific UV254 absorbance (SUVA), combined chlorine residual (TCl2), and pH were all significantly related to TOI concentration to varying degrees. A Tobit model was fit to show TOI predictions against observed (measured) TOI values. The model could explain approximately 46% of the variance of TOI concentrations in the treated waters.

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Iopamidol (IPM) is a potential source of toxic iodinated byproducts (I-DBPs) during water disinfection. In this work, we determined the kinetics and mechanism of degradation of IPM by a combination of ozone (O3) and peroxymonosulfate (PMS, HSO5-), and assessed its effect on the formation of iodinated trihalomethanes (I-THMs) during chlorination treatment. The degradation of IPM was accelerated by the O3/PMS process, and the hydroxyl (HO•) and sulfate (SO4•-) radicals were major contributors to the degradation. Using identification of the second order reaction rate between SO4•- and IPM (kSO4•-, IPM = 1.6 × 109 M-1 s-1), the contribution of HO• to the degradation was determined to be 78.3%. The degradation of IPM was facilitated by pH > 7, and natural organic matter (NOM) and alkalinity had limited effects on the degradation of IPM in the O3/PMS process. The transformation products of IPM were determined and inferred by QTOF-MS/MS, and the degradation pathways were elucidated. These include amide hydrolysis, amino oxidation, hydrogen abstraction, deiodination, and hydroxyl radical addition. Interestingly, oxidation of IPM by O3/PMS also decreased its potential for formation of I-THMs. After oxidation of IPM, the I-THMs formed from 5-µΜ IPM decreased from 14.7 µg L-1 to 3.3 µg L-1 during chlorination. Although the presence of NOM provided the precursor of I-THMs during chlorination of IPM, the O3/PMS process decreased I-THMs formation by 71%, because oxidation of released iodide into iodate effectively inhibited I-THMs formation. This study provides a new approach for the accelerated degradation of IPM and control of the formation of I-DBPs.

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Oil and gas (O&G) production in the United States is expected to grow at a substantial rate over the coming decades. Environmental sustainability related to water consumption during O&G extraction can be addressed through treatment and reuse of water returning to the surface after well completion. Water quality is an important factor in reuse applications, and specific treatment technologies must be utilized to remove different contaminants. Among others, biological active filtration can remove dissolved organic matter as a pre-treatment for surface discharge or to facilitate reuse in such applications as hydraulic fracturing, dust suppression, road stabilization, and crop irrigation. Yet, the formation of byproducts during treatment of O&G wastewater remains a concern when evaluating reuse applications. In this study, we investigated the previously unnoticed biotic formation of iodinated organic compounds (IOCs) such as triiodomethane during biological treatment of O&G wastewater for beneficial reuse. Iodide and several IOCs were quantified in O&G produced water before and after treatment in biological active filters filled with different media types over 13 weeks of operation. While iodide and total IOCs were measured at concentrations <53 mg/L and 147 µg/L, respectively, before biological treatment, total IOCs were measured at concentrations close to 4 mg/L after biological treatment. Triiodomethane was the IOC that was predominantly present. IOC formation had a negative strong correlation (r = -0.7 to -0.8, p < 0.05, n = 9) with iodide concentration in the treated O&G wastewater, indicating that iodide introduced to the biological active filter system was utilized in various reactions, including biologically mediated halogenation of organic matter. Additionally, iodide-oxidizing bacteria augmented in the treated produced water pointed towards potential negative environmental implications when releasing biologically treated halide-rich wastewater effluents to the aquatic environment.

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This study investigated the VUV/UV photodegradation of three iodinated disinfection byproducts (I-DBPs), namely, triiodomethane (TIM), diiodoacetamide (DIAcAm) and triiodoacetic acid (TIAA), based on a mini-fluidic VUV/UV photoreaction system (MVPS). The pseudo-first-order rate constants (k) of TIM, DIAcAm and TIAA under VUV/UV irradiation (1769, 1301 and 1174 m2 einstein-1, respectively) were higher than those under UV irradiation (1003, 832 and 766 m2 einstein-1, respectively). The enhancement of photodegradation could be attributed to the indirect HO• oxidation rather than the direct VUV photolysis. As a whole, compared with the indirect HO• oxidation, the direct UV photolysis had a relatively greater contribution to the degradation of the three I-DBPs, especially DIAcAm and TIAA (ca. 57% and 60%, respectively). The two electron-withdrawing groups in DIAcAm and TIAA (i.e., acylamino and carboxyl) decreased the electron density of the C-I bonds, thus weakening the electrophilic attack of HO•. The iodine in the three I-DBPs was released to form I- and a small fraction (< 6%) of I- was oxidized to IO3-, indicating that HO• preferred to break the C-I bonds rather than oxidize I-. The direct UV photolysis proceeded via H2O-catalyzed deiodination reactions, while the indirect HO• oxidation proceeded via deiodination reactions along with HO• addition. The VUV/UV photodegradation of the three I-DBPs was more favored at an acidic pH but inhibited by the water matrix components (i.e., NOM, Cl- and alkalinity) to different extents.

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In this study, the degradation kinetics of iopamidol (IPM) by three different UV-based oxidation processes including UV/hydrogen peroxide (H2O2), UV/persulfate (PDS) and UV/chlorine (NaClO) were examined and the potential formation of iodinated disinfection byproducts (I-DBPs) in these processes followed by sequential chlorination was comparatively investigated. Increasing pH led to the decrease of IPM degradation rate in UV/NaClO, while it showed negligible impact in UV/PDS and UV/H2O2. Common background constituents such as chloride ions (Cl-), carbonate (HCO3-) and natural organic matter (NOM) inhibited IPM degradation in UV/H2O2 and UV/PDS, while IPM degradation in UV/NaClO was only suppressed by NOM but not Cl- and HCO3-. The differences in transformation products of IPM treated by hydroxyl radical (HO*), sulfate radical (SO4*-), as well as Cl2*- and ClO* generated in these processes, respectively, were also analyzed. The results suggested that hydroxyl radical (HO*) preferred to form hydroxylated derivatives. Sulfate radical (SO4*-) preferred to oxidize amino group of IPM to nitro group, while Cl2*- and ClO* favored the generation of chlorine-containing products. Moreover, specific I-DBPs (i.e., iodoform (IF) and monoiodacetic acid (MIAA)) were detected in the three processes followed by chlorination. The addition of NOM had little effect on IF formation of three processes, while MIAA formation decreased in all processes except UV/H2O2. Given that the formation of I-DBPs in UV/NaClO was less than those formed in the other two processes, UV/NaClO seems to be a more promising strategy for effectively removing IPM with alleviation of I-DBPs in treated water effluents.

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Haloacetamides (HAMs), an emerging class of disinfection by-products, have received increasing attention due to their elevated cyto- and genotoxicity. However, only limited information is available regarding the iodinated analogues. This study investigated the formation and speciation of iodinated haloacetamides (I-HAMs) and their chlorinated/brominated analogues during the chloramination of bromide and/or iodide-containing waters and a model compound solution over various time periods. The rapid formation of diiodoacetamide (DIAM) was observed during chloramination of three simulated samples, whereas brominated (Br-HAMs) and chlorinated haloacetamides (Cl-HAMs) increased slowly with increasing reaction time. To further understand the differences in the formation of HAMs containing different halogens, experiments with the model compound asparagine in the presence/absence of iodide were conducted. Moreover, iodine utilisation factors and iodine incorporation factors were observed to increase significantly faster and were substantially higher than those of bromine. This implied that, compared with bromide, iodide has substantially greater potential to be transformed to the corresponding HAMs during chloramination, similar to that of other classes of DBPs. That is, I-HAMs formed faster than the other species investigated, including Cl-HAMs and Br-HAMs, in the early reaction stages (0-3 h). The effect of the bromide/iodide ratio (i.e., constant iodide, increasing bromide) on I-HAM formation was also examined. With increasing bromide/iodide ratio, the formation of Br-HAMs increased and dichloroacetamide decreased, but the formation of DIAM was largely unchanged. This was consistent with the constant level of iodide in spite of the increasing bromide. Chlorine and ammonia are applied separately during chloramination in water treatment, so the effect of pre-chlorination (before adding ammonia) on the formation and speciation of I-HAMs during in situ chloramination was also evaluated. Effective mitigation of DIAM formation with in situ chloramination was achieved, and the efficiency improved with increasing pre-chlorination time, where iodide was oxidised to iodate. The HAM-associated cytotoxicity was calculated to determine the change in toxicity at different reaction times, bromide/iodide ratios, and pre-chlorination times. A similar trend as the formation of I-HAMs was observed, which increased rapidly in the first 3 h, but decreased somewhat subsequently. When the bromide/iodide ratio and pre-chlorination time was increased, the calculated toxicity of the HAMs increased (due to more formation of Br-HAMs and less Cl-HAMs) and decreased (due to less DIAM formation), respectively.

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Toxic and odorous iodinated disinfection byproducts (I-DBPs) could form in the chemical oxidation of iodine-containing water. A critical step for controlling the hazardous I-DBPs is to convert the iodine species into stable and harmless iodate (IO3-) while inhibiting the accumulation of highly reactive hypoiodous acid (HOI). Herein, the oxidation of I- and HOI with ferrate was investigated, and the formation profile of HOI was determined based on 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) coloring method through a stopped-flow spectrophotometer. The second-order rate constants (kapp) of ferrate with HOI decreased from 1.6 × 105 M-1s-1 to 8.3 × 102 M-1s-1 as the solution pH varied from 5.3 to 10.3, which were 7.5, 7.2 and 13.8 times higher than that of ferrate with I- at pH 6.0, 7.0 and 8.0, respectively. Compared with other oxidants such as ozone, hypochlorous acid, chloramine and potassium permanganate, ferrate would swiftly oxidize HOI formed in the I- oxidation process. For the ferrate oxidation of I-containing water, HOI was swiftly oxidized to IO3- from pH 5.0 to 9.0. Phosphate buffer promoted the oxidation of I- while inhibited the oxidation of HOI with ferrate. When 5 mgC/L of humic acids (HA) existed in the solution, no formation of iodoform and monoiodoacetic acid (MIAA) was observed in the oxidation of iodide (20 µM) with ferrate (from 10 µM to 80 µM). These results suggested that ferrate oxidation could be an effective method for the control of I-DBPs in iodine-containing water treatment.

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In order to reduce the formation of disinfection by-products (DBPs) during potabilization of water it is necessary to explore the potential of the source water and the applied treatment to generate these chemicals. This is actually more challenging in large drinking water networks that use different source waters to satisfy drinking water demand. In this regard, this work investigated the formation of DBPs in water matrices that are commonly supplied to the city of Barcelona and its metropolitan area. The regulated trihalomethanes and haloacetic acids were the most abundant DBP classes in these waters, followed by haloacetamides and haloacetonitriles or trihalogenated acetaldehydes (THALs). On the contrary, the formation potential of iodo-DBPs was minor. Mixing of drinking water treatment plant finished waters with desalinated water decreased the overall DBP formation potential of the water but resulted in the increased formation of brominated DBPs after long chlorine contact time. The formation of most DBPs was enhanced at high water temperatures (except for Br-THALs) and increasing residence times. Potential cytotoxicity and genotoxicity of the DBP mixtures were mainly attributed to the presence of nitrogen-containing DBPs and HAAs.

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Presence of iodinated X-ray contrast media (ICMs) in source water is of high concern, because of their potential to form highly toxic iodinated disinfection by-products (I-DBPs). This study investigated kinetics, mechanisms and products for oxidation of one ICMs, iopamidol (IPM) by ferrate (Fe(VI)). The obtained apparent second-order rate constants for oxidation of IPM by Fe(VI) ranged from 0.7 M-1 s-1 to 74.6 M-1 s-1 at pH 6.0-10.0, which were highly dependent on pH. It was found that the oxidation of IPM by Fe(VI) led to the formation of highly toxic I-DBPs. Iodoform (IF), iodoacetic acid and triiodoacetic acid formations were observed during the oxidation and IF dominated the formed I-DBPs. The formation of I-DBPs was also governed by pH and the maximum formation of I-DBPs occurred at pH 9.0. Transformation pathways of IPM by Fe(VI) oxidation were speculated to proceed through deiodination, amide hydrolysis and oxidation of amine reactions. The deiodination reaction during the oxidation of IPM by Fe(VI) contributed to the formation of I-DBPs. The formation of I-DBPs during the oxidation of IPM by Fe(VI) was significantly higher than those of iohexol, diatrizoate and iopromide, which was consistent with the lowest molecular orbital energy gap of IPM. Although Fe(VI) is considered as a green oxidant, the formation of highly toxic I-DBPs during the oxidation of IPM should receive great attention.

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