Halogenated Disinfection Byproducts Research Articles

The investigation of quenching conditions for the analysis of total organic halogen, aliphatic and aromatic halogenated disinfection byproducts formed from chlor(am)ination

Total organic halogen (TOX) is used to describe total amount of halogenated DBPs. Typically, once a chlor(am)inated water sample is collected, it is necessary to add a quenching agent to quench the residual disinfectant so that further reactions to form more DBPs during the holding time can be prevented. In this study, we evaluated the effects of four quenching agents: ammonium chloride (NH4Cl), ascorbic acid, sodium sulfite (Na2SO3), and sodium thiosulfate (Na2S2O3) on the decomposition of TOX, aliphatic and aromatic halogenated DBPs under various quenching conditions (quenching time, pH, quenching ratio, temperature). The results showed that ascorbic acid had the least impact on TOX. Ascorbic acid appeared to be the most suitable quenching agent for aliphatic halogenated DBPs, especially since it could preserve more haloacetonitriles than other quenching agents. Both ascorbic acid and Na2SO3 could be used for the analysis of aromatic halogenated DBPs. The lower pH (pH 6.0), not excessive quenching agents and lower temperature (4 ºC) were all conducive to the preservation of TOX and halogenated DBPs. Importantly, unknown TOX (UTOX) also contained significantly toxic components. It was also found that addition of quenching agents might lead to underestimation of UTOX by researchers. SynopsisThe quenching agents and quenching conditions for the analysis of total organic halogen, aliphatic and aromatic halogenated DBPs formed from chlor(am)ination were investigated.

Iodide enhances degradation of histidine sidechain and imidazoles and forms new iodinated aromatic disinfection byproducts during chlorination

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.

Progress in Analytical Methods of Halogenated Disinfection By-Products

Ensuring the health and safety of drinking water is crucial for both nations and their citizens. Since the 20th century, the disinfection of drinking water, effectively controlling pathogens in water sources, has become one of the significant advances in public health. However, the disinfectants used in the process, such as chlorine and chlorine dioxide, react with natural organic matter in the water to produce disinfection by-products (DBPs). Most of these DBPs contain chlorine, and if the source water contains bromine or iodine, brominated or iodinated DBPs, collectively referred to as Halogenated disinfection byproducts (X-DBPs), are formed. Numerous studies have found that X-DBPs pose potential risks to human health and the environment, leading to widespread concern. Mass spectrometry has become an important means of discovering new types of X-DBPs. This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.

Reaction sites of pyrimidine bases and nucleosides during chlorination: A computational study

As important components of soluble microbial products in water, nucleobases have attracted much attention due to the high toxicity of their direct aromatic halogenated disinfection by-products (AH-DBPs) during chlorination. However, multiple halogenation sites of AH-DBPs pose challenges to identify them. In this study, reaction sites of pyrimidine bases and nucleosides during chlorination were investigated by quantum chemical computational method. The results indicate that the anion salt forms play key roles in chlorination of uracil, thymine, and their nucleosides, while neutral forms make predominant contributions to cytosine and cytidine. In view of both kinetics and thermodynamics, C5 is the most reactive site for uracil and thymine, N3/C5 and N3 for respective uridine and thymidine, N1/C5/N4 and N4 for respective cytosine and cytidine, whose estimated apparent rate constants kobs-est of ∼103, 103/102, 106/102/104, and 103 M−1 s−1, respectively, in consistent with the known experimental results. C6 in all pyrimidine compounds is hardly attacked by Cl+ in HOCl ascribed to its positive charge, but readily attacked by OH‾ in hydrolysis and the N1=C6 bond was found to possess the highest reactivity in hydrolysis among all double bonds. In addition, the structure-kinetic reactivity relationship study reveals a relatively strong correlation between lgkobs-est and APT charge in all pyrimidine compounds rather than FED2 (HOMO). The results are helpful to further understand the reactivity of various reaction sites in aromatic compounds during chlorination.

Development and validation of a GC-MS/MS method for the determination of iodoacetic acid in biological samples.

Iodoacetic acid (IAA) is a halogenated disinfection by-product of growing concern due to its high cytotoxicity, genotoxicity, endocrine disruptor effects, and potential carcinogenicity. However, the data on distribution and excretion of IAA after ingestion by mammals are still scarce. Here, we developed a reliable and validated method for detecting IAA in biological specimens (plasma, urine, feces, liver, kidney, and tissues) based on modified QuEChERS sample preparation combined with gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS/MS). The detection method for IAA exhibited satisfactory recovery rates (62.6-108.0%) with low relative standard deviations (RSD < 12.3%) and a low detection limit for all biological matrices ranging from 0.007 to 0.032ng/g. The study showed that the proposed method was reliable and reproducible for analyzing IAA in biological specimens. It was successfully used to detect IAA levels in biological samples from rats given gavage administration. The results indicated that IAA was found in various tissues and organs, including plasma, thyroid, the liver, the kidney, the spleen, gastrointestinal tract, and others, 6h after exposure. This study provides the first data on the in vivo distribution inand excretion of IAA by mammals following oral exposure.

Impact of non-aged and UV-aged microplastics on the formation of halogenated disinfection byproducts during chlorination of drinking water and its mechanism

Microplastics (MPs) are ubiquitously present in source water and undergo ultraviolet (UV) aging in aquatic environments before entering drinking water treatment plants. The presence of MPs in drinking water can impact the formation of halogenated disinfection byproducts (DBPs) during chlorine disinfection, yet the exact effect of MPs on DBP formation remain unclear. In this study, we conducted an investigation into the influence of non-aged and UV-aged MPs on halogenated DBP formation in drinking water and unveiled the underlying mechanisms. In comparison to source water samples devoid of MPs, the total organic halogen concentration was reduced by 19%–43% and 4%–13% in the drinking water samples containing non-aged and aged MPs, respectively. The differing effects on halogenated DBP formation can be attributed to the alternation in physical and chemical characteristics of MPs following UV aging. Aged MPs exhibited larger surface area with signs of wear and tear, heightened hydrophilicity, surface oxidation, increased oxygen-containing functional groups and dechlorination during the UV aging process. Both non-aged and aged MPs possess the capability to adsorb natural organic matter, leading to a reduction in the concentration of DBP precursors in the source water. However, the release of organic compounds from aged MPs outweighed the adsorption of organics. Furthermore, as a result of the surface activation of MPs through the UV aging process, the aged MPs themselves can also serve as DBP precursors. Consequently, the presence of halogenated DBP precursors in source water increased, contributing to a higher level of DBP formation compared to source water containing non-aged MPs. Overall, this study illuminates the intricate relationship among MPs, UV aging, and DBP formation in drinking water. It highlights the potential risks posed by aged MPs in influencing DBP formation and offers valuable insights for optimizing water treatment processes.

Degradation of humic acid by UV/PMS: process comparison, influencing factors, and degradation mechanism.

In natural water bodies, humic acid (HA), generated during the chlorination disinfection process at water treatment plants, can produce halogenated disinfection by-products, increasing the risk to drinking water safety and posing a threat to human health. Effectively removing HA from natural waters is a critical focus of environmental research. This study established a synergistic ultraviolet/peroxymonosulfate (UV/PMS) system to remove HA from water. It compared the efficacy of various UV/advanced oxidation processes (AOPs) on HA degradation, and assessed the influence of different water sources, initial pH, oxidant concentration, and anions (HCO3 -, Cl-, NO3 -) on HA degradation. The degradation mechanism of HA by the UV/PMS process was also investigated. Results showed that under the conditions of 3 mmol L-1 PMS concentration, 10 mg L-1 HA concentration, initial solution pH of 7, and a reaction time of 240 minutes, the mineralization rate of HA by UV/PMS reached 94.15%. The pseudo-first-order kinetic constant (k obs) was 0.01034 and the single-electric energy (EE/O) was 0.0157 kW h m-3, indicating superior HA removal efficiency compared to other systems. Common anions (HCO3 -, Cl-, NO3 -) in water were found to inhibit the degradation of HA, and acidic conditions were more conducive to HA removal, with the optimal pH being 3. Free radical quenching experiments showed that both sulfate radical (SO4 -˙) and hydroxyl radical (˙OH) radicals were involved in HA degradation, with SO4 -˙ being the primary oxidant and ˙OH as the auxiliary species. Analyses using 3D-excitation-emission matrix (EEM), parallel factor analysis (PARAFAC), specific fluorescence index, and absorbance demonstrated that UV/PMS technology could effectively degrade HA in water. This study provides theoretical references for further research on the removal of HA and other organic substances using UV/PMS technology.

Comparative formation of chlorinated and brominated disinfection byproducts from chlorination and bromination of amino acids

Amino acids are the main components of dissolved organic nitrogen in algal- and wastewater-impacted waters, which can react with chlorine to form toxic halogenated disinfection by-products (DBPs) in the disinfection process. In the presence of bromide, the reaction between amino acids and secondarily formed hypobromous acid can lead to the formation of brominated DBPs that are more toxic than chlorinated analogues. This study compares the formation of regulated and unregulated DBPs during chlorination and bromination of representative amino acids (AAs) (e.g., aspartic acid, asparagine, tryptophan, tyrosine, and histidine). In general, concentrations of brominated DBPs (trihalomethanes, haloacetonitriles, and haloacetamides, 24.9–5835.0 nM) during bromination were higher than their chlorinated analogues (9.3–3235.3 nM) during chlorination. This indicates the greater efficacy of bromine as a halogenating agent. However, the formation of chlorinated haloacetic acids during chlorination was higher than the corresponding brominated DBPs from bromination. It is likely that an oxidation pathway is required for the formation of haloacetic acids and chlorine is a stronger oxidant than bromine. Moreover, chlorine forms higher levels of haloacetaldehydes (74.4–1077.8 nM) from amino acids than bromine (1.0–480.2 nM) owing to the instability of brominated species. The DBP formation yields depend on the types of functional groups in the side chain of AAs. Eight intermediates resulting from chlorination/bromination of tyrosine were identified by triple quadrupole mass spectrometer, including N-chlorinated/brominated tyrosine, 3-chloro/bromo-tyrosine, and 3,5-dichloro/dibromo-tyrosine. These findings provided new insights into the DBP formation during the chlorination of algal- and wastewater-impacted waters with elevated bromide.

Evaluating the photochemical reactivity of disinfection byproducts formed during seawater desalination processes

Reverse osmosis (RO) is widely used for seawater desalination but pre-chlorination of intake water produces halogenated disinfection byproducts (DBPs). The fate and environmental impacts associated with the discharge of DBP-containing RO brine wastewater are unknown. Therefore, to evaluate if photochemistry plays a role in DBP degradation in seawater, we collected samples at a desalination plant, which were desalted and concentrated using two-inline solid phase extraction (SPE) techniques combining reverse-phase polymeric (PPL) and weak anion exchange (WAX) resins. Both filtered water samples and SPE samples (extracts reconstituted in open ocean seawater) were exposed to simulated sunlight in a custom-built flow-through system. Optical property analysis during irradiation experiments did not provide distinguishing features between intake water and RO reject water (brine). Extractable organic bromine (organoBr) concentrations were low in intake water samples (7.8 μg Br L−1) and did not change significantly due to irradiation. OrganoBr concentrations in laboratory-chlorinated raw water were much higher (135 μg Br L−1) and on average decreased by 42 % after 24 h irradiation. However, while organoBr concentrations were highest in RO reject water (473 μg Br L−1), changes in organoBr concentrations in PPL SPE samples after 24 h irradiation were variable, ranging from a 1–46 % loss. Furthermore, most bromine-containing molecular ions identified by high resolution mass spectrometry that were present in RO reject water before irradiation were also found after both 24 h and 50 h exposures. Although only one RO reject water sample was tested in this study, results highlight that hundreds of yet to be identified brominated DBPs in RO reject water could be resistant to photodegradation or phototransform into existing DBPs in the environment. Future work examining the biolability of DBPs in RO reject water, as well as the interplay between photochemical and biological DBP cycling, is warranted.

Total organic halogen (TOX) in drinking water: Occurrence, correlation analysis, and precursor removal during drinking water treatment

Total organic halogen (TOX) in drinking water provides a measurement of the overall organic halogenated disinfection by-products (DBPs) formed during disinfection. Yangtze River Delta is one of the regions with the highest population density, the fastest urbanization process, and the most severe water pollution in China. Collecting water samples from full-scale drinking water treatment plants (DWTPs) in this region, this study firstly surveyed TOX occurrence in drinking water. Besides, the correlation of TOX formation potential (TOXFP) and trihalomethane formation potential (THMFP) with general water quality parameters (e.g., dissolved organic carbon [DOC], UV254, and specific ultraviolet absorbance) and the removal efficiencies of TOX precursors by different water treatment processes were also investigated. TOX levels in DWTP effluents (i.e., finished water) ranged from 29 to 165 μg/L (median 67 μg/L), and those in simulated distribution system waters ranged from 101 to 276 μg/L (median 158 μg/L). There were generally higher linear regression coefficient values for raw water (R2 = 0.51–0.88) than for treated water (R2 = 0.33–0.64) in terms of the relationship between DBP formation potentials and general parameters. However, a relatively stronger correlation between THMFP and TOXFP was observed for treated water (R2 = 0.80, p < 0.001) than for raw water (R2 = 0.64, p < 0.001). The overall treatment efficiencies of investigated parameters in DWTPs generally followed the order of UV254 > DOC > TOX precursors > THM precursors. Notably, the overall removal rates of DOC and TOX precursors in summer (averaging 59 % and 54 %, respectively) were obviously higher than those in winter (averaging 39 % and 38 %, respectively), which was assumed to be related to the seasonal variation of bioactivity in sand filter. These results could expand the knowledge of TOX in drinking water, and provide valuable perspectives to water industry and DBP research.

CuO Promotes the Formation of Halogenated Disinfection Byproducts during Chlorination via an Enhanced Oxidation Pathway.

Previous studies showed that cupric oxide (CuO) can enhance the formation of trihalomethanes (THMs), haloacetic acids, and bromate during chlorination of bromide-containing waters. In this study, the impact of CuO on the formation kinetics and mechanisms of halogenated disinfection byproducts (DBPs) during chlorination was investigated. CuO does not enhance the formation of DBPs (i.e., 1,1,1-trichloropropanone, chloroform, and trichloroacetaldehyde (TCAL) /dichloroacetonitrile) during chlorination of acetone, 3-oxopentanedioic acid (3-OPA), and aspartic acid, respectively. This indicates that the halogen substitution pathway cannot be enhanced by CuO. Instead, CuO (0.1 g L-1) accelerates the second-order rate constants for reactions of chlorine (HOCl) with TCAL, citric acid, and oxalic acid at pH 8.0 and 21 °C from <0.1 to 29.4, 7.2, and 15.8 M-1 s-1, respectively. Oxidation pathway predominates based on the quantification of oxidation products (e.g., a trichloroacetic acid yield of ∼100% from TCAL) and kinetic modeling. CuO can enhance the formation of DBPs (e.g., THMs, haloacetaldehydes, and haloacetonitriles) during chlorination of model compounds and dissolved organic matter, of which both halogen substitution and oxidation pathways are required. Reaction rate constants of rate-limiting steps (e.g., citric acid to 3-OPA, aromatic ring cleavage) could be enhanced by CuO via an oxidation pathway since CuO-HOCl complex is more oxidative toward a range of substrates than HOCl in water. These findings provide novel insights into the DBP formation pathway in copper-containing distribution systems.

Analyzing disinfection by-products yield and mechanisms in UV/Cl2 using response surface methodology and quantitative structure-activity relationship models

The study aimed to investigate the formation of halogenated disinfection byproducts (DBPs) during applying UV/chlorine (UV/Cl2) and unravel the interactive impacts of critical operational parameters and the mechanisms behind DBPs formation. Response surface methodology and quantitative structure-activity relationship models were developed to evaluate the contribution of electrophilic, nucleophilic, and free radical reactions to the formation of DBPs in UV/Cl2. The study found that Cl2 and its interactions dominated the total DBPs and non-Br-DBPs formation, while Br− and the Cl2–Br− interaction played a decisive role in the Br-DBPs formation. The study also observed significant interactions of Br, Cl2, and pH on chloroform, bromodichloromethane, dichloroacetonitrile, 1,1-dichloro-2-propanone, trichloroactic acid, and chlorodibromoacetic acid formations, while no evident interaction on chloral hydrate, dibromochloromethane, trichloroacetone, dibromoacetic acid, and bromodichloroacetic acid formations. The electrophilic substitution of HOBr mainly controlled the formation of trihalomethanes, and the contribution of nucleophilic, electrophilic, and free radical (•OH, Cl•, Cl2•- and ClO•) reactions depended on the molar ratio of Cl2 to Br, and pH-determined hydrolysis rate constants of DBPs and the types of free radicals. Overall, the response surface methodology and quantitative structure-activity relationship models provided a reference for revealing DBPs formation mechanisms in other disinfection processes.

Zerovalent Iron/Cu Combined Degradation of Halogenated Disinfection Byproducts and Quantitative Structure-Activity Relationship Modeling.

Previous studies have reported that zerovalent iron (ZVI) can reduce several aliphatic groups of disinfection byproducts (DBPs) (e.g., haloacetic acids and haloacetamides) effectively, and the removal efficiency can be significantly improved by metallic copper. Information regarding ZVI/Cu combined degradation of different types of halogenated DBPs can help understand the fate of overall DBPs in drinking water distribution and storage systems consisting of unlined cast iron/copper pipes and related potential control strategies. In this study, we found that, besides aliphatic DBPs, many groups of new emerging aromatic DBPs formed in chlorinated and chloraminated drinking water can be effectively degraded by ZVI/Cu; meanwhile, total organic halogen and total ion intensity were reduced significantly after treatment. Moreover, a robust quantitative structure-activity relationship model was developed and validated based on the ZVI/Cu combined degradation rate constants of 14 typical aromatic DBPs; it can predict the degradation rate constants of other aromatic DBPs for screening and comparative purposes, and the optimized descriptors indicate that DBPs possessing a lower value of the lowest unoccupied molecular orbital energy and a higher value of dipole moment tend to present higher degradation rate constants. In addition, toxicity data of 47 DBPs (belonging to 18 groups) were predicted by two previously established toxicity models, demonstrating that, although most DBPs exhibit higher toxicity than their dehalogenated products, some DBPs show lower toxicity than their lowly halogenated analogs.

High-molecular-weight by-products of chlorine disinfection

Although drinking water chlorination has reduced the incidence of waterborne disease, the reactions of chlorine with organic matter can lead to the formation of >700 halogenated disinfection by-products (DBPs). Epidemiological studies have linked the consumption of chlorinated drinking water with bladder cancer. With studies indicating that the one- and two-carbon-atom DBPs of current interest account for only ~16% of disinfected water cytotoxicity, there is a need to identify toxicity drivers within the poorly characterized higher-molecular-weight (more than two carbon atoms) DBP fraction. In this Review, we outline the current knowledge regarding this fraction and discuss novel analytical approaches to characterizing the much wider variety of structures that it contains. We detail the products formed from the reactions of chlorine with different categories of precursor, including the characteristics of the elemental formulae of products identified by high-resolution mass spectrometry, the halogenated aromatic DBPs formed from precursors in pristine waters and the products derived from biopolymer-bound monomers in algal- or wastewater-impacted waters. Finally, we discuss the key challenges for research into this important, but until recently, mostly overlooked by-product fraction. Recent toxicological studies have indicated that the poorly characterized high-molecular-weight fraction of disinfection by-products may contribute more to toxicity than the carbon disinfection by-products of current research interest. This Review summarizes what is known about the high-molecular-weight fraction and suggests pathways for future research in this area.

Remarkably efficient Pt/CeO2–Al2O3 catalyst for catalytic hydrodeiodination of monoiodoacetic acid: Synergistic effect of Al2O3 and CeO2

Monoiodoacetic acid (MIAA) is one of the highly toxic halogenated disinfection by-products, which is formed during water disinfection processes. Catalytic hydrogenation with supported noble metal catalyst is a green and effective technique for the transformation of halogenated pollutant, but its activity still needs to be identified. In this study, Pt nanoparticles were supported on CeO2 modified γ-Al2O3 (Pt/CeO2–Al2O3) by chemical deposition method and the synergistic effect of Al2O3 and CeO2 on catalytic hydrodeiodination (HDI) of MIAA was systematically studied. Characterizations revealed that Pt dispersion could be improved by the introduced CeO2 through the formation of Ce–O–Pt bond and MIAA adsorption could be facilitated by high Zeta potential of Al2O3 component. Furthermore, optimal Ptn+/Pt0 could be obtained by adjusting CeO2 deposition amount on Al2O3, which could effectively facilitate the activation of C–I bond. Therefore, Pt/CeO2–Al2O3 exhibited remarkable catalytic activities and TOF values compared with those of Pt/CeO2 and Pt/Al2O3. Through detailed kinetic experiments and characterization, the extraordinary catalytic performance of Pt/CeO2–Al2O3 can be attributed to the abundant Pt sites as well as the synergistic effect between CeO2 and Al2O3.

Algae impacted drinking water: Does switching to chloramination produce safer drinking water?

Harmful algal (cyanobacterial) blooms (HABs) are increasing throughout the world. HABs can be a direct source of toxins in freshwater sources, and associated algal organic matter (AOM) can act as precursors for the formation of disinfection by-products (DBPs) in drinking water. This study investigated the impacts of algae on DBP formation using treatment with chloramine, which has become a popular disinfectant in the U.S. and in several other countries because it can significantly lower the levels of regulated DBPs formed. Controlled laboratory chloraminations were conducted using live field-collected algal biomass dominated by either Phormidium sp. or Microseira wollei (formerly known as Lyngbya wollei) collected from Lake Wateree and Lake Marion, SC. Sixty-six priority, unregulated or regulated DBPs were quantified using gas chromatography (GC)-mass spectrometry (MS). The presence of HAB-dominated microbial communities in source waters led to significant increases in more toxic nitrogen-containing DBPs (1.5–5 fold) relative to lake waters collected in HAB-free waters. Compared to chlorinated Phormidium-impacted waters, chloraminated waters yielded lower total DBP levels (up to 123 μg/L vs. 586 μg/L for low Br−/I− waters), but produced a greater number of brominated, iodinated, and mixed halogenated DBPs in high Br−/I− waters. Among the DBPs formed in Phormidium-impacted chloraminated waters, dichloroacetic acid, trichloromethane, chloroacetic acid, chloropropanone, and dichloroacetamide were dominant. For Microseira wollei-impacted chloraminated waters, total DBP concentrations ranged from 33 to 145 μg/L (approximately 3–5 times lower than chlorination), with dichloroacetic acid, dichloroacetamide, and trichloromethane dominant. Overall, chloramination significantly reduced calculated cytotoxicity and genotoxicity in low Br− and I− waters, but produced 1.3 fold higher calculated cytotoxicity (compared to chlorine) with high Br−/I− waters due to increased formation of more toxic iodo- and mixed halogenated DBPs.

Comparative assessment of embryotoxicity of 2,4,6-triiodophenol to mouse blastoid and pre-implantation embryo models

Embryonic developmental effects of disinfection by-products, which are generated during drinking water treatment and widely detected in environment, have gained more and more attention nowadays, calling for construction of in vitro research models which can mimic early embryonic development to evaluate the embryotoxicity. The embryonic stem cell test offers a promising assay to predict embryotoxicity of environmental pollutions. However, it is not appropriate for the toxicological study of preimplantation embryos. Here, we used mouse extended stem cells (mEPS) to reconstruct embryo-like structures (blastoid), furtherly attempting to evaluate the reliability of this model for the prediction of possible developmental toxicity of 2,4,6-triiodophenol (TIP, 5–50 μM), a novel halogenated disinfection byproduct widely detected in water and even drinking water, to mammalian preimplantation embryo. To verify this, we treated mouse embryo derived from in vitro fertilization (IVF-embryo) as reference. The results showed that mEPS-blastoid was like natural blastocyst in morphology, cell composition, and could recapitulate key developmental events happened during mouse preimplantation stage. When blastoid and IVF-embryo models were separately exposed to TIP, their final blastocyst formation rates were not impaired, according to morphological features, meanwhile that TIP exposure caused slight cell apoptosis. Besides, TIP induced an ICM cell bias in cell fate decision, resulting in cell proportion change, which implied abnormal developmental potential. Though we could not evaluate TIP’s embryotoxicity before 8-cell stage using blastoid model, its viability as a novel and high-throughput assessment platform for increasing environmental pollutants was still recognized.

Control of Pre-formed Halogenated Disinfection Byproducts with Reuse Biofiltration.

Disinfection byproduct (DBP) pre-formation is a major issue when prechlorination is used before or during advanced treatment of impacted drinking water sources. Control strategies for pre-formed DBPs before final disinfection, especially for currently nonregulated although highly toxic DBP species, are not yet established. This study evaluated the biodegradation potential of pre-formed DBPs, including haloacetonitriles (HANs), haloacetamides (HAMs), and haloacetaldehydes (HALs), during biofiltration with sand, anthracite, and biological activated carbon of three wastewater effluents under potable reuse conditions. Up to 90%+ removal of di- and trihalogenated HANs, HAMs, and HALs was observed, and removal was associated with active heterotrophic biomass and removal of biodegradable organic carbon. Unlike the microbial dehalogenation pathway of haloacetic acids (HAAs), removal of HANs and HAMs appeared to result from a biologically mediated hydrolysis pathway (i.e., HANs to HAMs and HAAs) that may be prone to inhibition. After prechlorination, biofiltration effectively controlled pre-formed DBP concentrations (e.g., from 271 μg/L to as low as 22 μg/L in total) and DBP-associated calculated toxicity (e.g., 96%+ reduction). Abiotic residual adsorption capacity in biological activated carbon media was important for controlling trihalomethanes. Overall, the toxicity-driving DBP species exhibited high biodegradation potential and biofiltration showed significant promise as a pre-formed DBP control technology.

Comparing risk of disinfection byproducts in drinking water under variable scenarios of seawater intrusion

The higher levels of halides in seawater increase bromide and iodide in the coastal aquifers, leading to higher concentrations of halogenated disinfection byproducts (DBPs). The populations in the coastal areas are susceptible to increased concentrations of DBPs while many DBPs are cyto- and genotoxic to mammalian cells, and are possible/probable human carcinogens. The implications of seawater intrusion on the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs), and the risks were analyzed by adding 0.0–2.0 % seawater (SW) (by volume) and chlorine to groundwater. Bromide and iodide concentrations in groundwater (0.0 %SW) were observed as 42.5 and non-detected (ND) μg/L respectively. With 2.0 %SW, these were spiked up to 1100 and 2.1 μg/L respectively. The most common THMs (THM4), iodinated THMs (I-THMs) and HAAs were 30.4, 0.13 and 27.9 μg/L for 0.0 % SW respectively. With 2.0 %SW, these values were 106.3, 1.6 and 72.9 μg/L, respectively. At 0.0 %SW, averages of chronic daily intakes (CDI) for THM4, HAAs and I-THMs were 2.61 × 10−4, 2.26 × 10−4 and 7.69 × 10−7 mg/kg/day respectively, which were increased to 9.97 × 10−4, 4.70 × 10−4 and 9.47 × 10−6 mg/kg/day, respectively for 2.0 %SW. For 0.0 %SW, overall cancer risks from few DBPs was 3.09 × 10−5 (6.46 × 10−6 - 7.23 × 10−5) while at 1.0 % and 2.0 %SW, risks were 4.88 × 10−5 (1.26 × 10−5–1.08 × 10−4) and 4.11 × 10−5 (1.21 × 10−5–9.28 × 10−5) respectively. The reduction of risks for 2.0 %SW was due to the increase of bromoform (TBM), and decrease in bromodichloromethane (BDCM) and dibromochloromethane (DBCM) at 2.0 %SW. The disability-adjusted life years (DALY) loss showed an increasing trend from 0.0 %SW (DALY: 77.30) to 1.0 %SW (DALY: 122.0) while an increase to 2.0 %SW showed a decrease in DALY (DALY: 102.8). Future study on toxicity of other regulated and emerging DBPs is warranted to better predict cancer risks.

Decomposition of Total Organic Halogen Formed during Chlorination: The Iceberg of Halogenated Disinfection Byproducts Was Previously Underestimated.

Total organic halogen (TOX) is widely used as a surrogate bulk parameter to measure the overall exposure of halogenated disinfection byproducts (DBPs) in drinking water. In this study, we surprisingly found that the level of TOX in chlorinated waters had been significantly underestimated under common analytical conditions. After the addition of quenching agent sodium thiosulfate, total organic chlorine and total organic bromine exhibited a two-phase decomposition pattern with increasing contact time, and a significant decomposition was observed for different types of quenching agents, quenching doses, and pH conditions. More importantly, the decomposed TOX closely correlated with the acute toxicity of quenched water against luminous bacteria, implying that the DBPs responsible for TOX decomposition could be of important toxicological significance. Based on nontarget analysis by using high-resolution mass spectrometry, molecular formulas for the decomposed TOX were determined. After re-examining the mass balance of TOX in the context of unintentional decomposition, it was found that both the level and percentage of unknown TOX in chlorinated waters were considerably higher than historically thought. Overall, this study brings new insights into the knowledge of TOX formed during chlorination, providing important clues on the identification of toxicity driver in drinking water.