Toxicity Of Disinfection Byproducts Research Articles

Determining high priority disinfection byproducts based on experimental aquatic toxicity data and predictive models: Virtual screening and in vivo study

Only about 100 disinfection byproducts (DBPs) have been tested for their potential aquatic toxicity. It is not known which specific DBPs, DBP main groups, and DBP subgroups are more toxic due to the lack of experimental toxicity data. Herein, high priority specific DBPs, DBP main groups, DBP subgroups, most sensitive model aquatic species, potential PBT and PMT (persistent, bioaccumulative/mobile, and toxic) DBPs were virtually screened for 1187 updated DBPs inventory. Priority setting based on experimental and predicted acute and chronic aquatic toxicity data found that the aromatic and alicyclic DBPs in four DBPs main groups showed high priority because larger proportions of aromatic and alicyclic DBPs are in high hazard categories (i.e. Acute and/or Chronic Toxic-1 or Toxic-2) according to the criteria in GHS system compared to the aliphatic and heterocyclic DBPs. The halophenols, estrogen-DBPs, nonhalogenated esters, and nonhalogenated aldehydes were recognized as high priority DBPs subgroups. For specific DBPs, 19 and 31 DBPs should be highly concerned in the future study because both acute and chronic toxicity of those DBPs to all of the three aquatic life (algae, Daphnia magna, fish) were classified as Toxic-1 and Toxic-2, respectively. The Daphnia magna and algae were sensitive to the acute toxicity of DBPs, while the fish and Daphnia magna were sensitive to the chronic toxicity of DBPs. One potential PBT (Tetrachlorobisphenol A) and four potential PMT DBPs were identified. For verification, the acute toxicity of four DBPs on three aquatic organism were performed, and their tested acute toxicity data to three aquatic organisms were consistent with the predictions. Our results could be beneficial to government regulators to adopt effective measures to limit the discharge of high priority DBPs and help the scientific community to develop or improve disinfection processes to reduce the production of high priority DBPs.

Enhanced degradation of para-nitrophenol during the UV/chlorine process with the addition of Fe(III): Performance, reaction mechanisms, and DBPs formation

Para-nitrophenol (PNP) enters aquatic environments through wastewater discharge, potentially threatening ecological security and public health. This work investigated the enhanced degradation of PNP in wastewater during the UV/chlorine process with the addition of Fe(III) (UV/chlorine/Fe(III)). The UV/chlorine/Fe(III) process (61.85 %) exhibited higher performance in PNP degradation in 10 min compared to the UV/chlorine process (40.00 %) because the synergistic effect of Fe(III) and free chlorine enhanced hydroxyl radicals (OH) and reactive chlorine species (RCSs) production. Furthermore, OH and RCSs were identified as the primary contributors to degrade PNP during the UV/chlorine/Fe(III) process, and their corresponding contributions accounted for 40.09 % and 37.10 %, respectively. Besides, the degradation efficiencies of PNP were promoted by increasing the dosages of Fe(III) and free chlorine and declined by increasing pH and PNP concentration. Also, Cl− could promote PNP degradation, while SO42− and HCO3− inhibited it. Then, the reaction mechanisms of PNP degradation during the UV/chlorine/Fe(III) process were proposed based on the identified transformation products (TPs) and the density functional theory (DFT) calculation. Meanwhile, PNP, TPs, and other possible intermediate products presented different ecotoxicity. Finally, the formation and toxicity of disinfection by-products (DBPs) with different Fe(III) concentrations, chlorine dosages, initial pHs, and PNP concentrations were explored. Overall, the obtained findings can provide deep insights into the mechanisms of PNP degradation and a new approach to enhancing PNP degradation in wastewater.

Disinfection by-products control in wastewater effluents treated with ozone and biological activated carbon followed by UV/Chlor(am)ine processes

Sequential utilization of ozone (O3) and biological activated carbon (BAC) followed by UV/chlor(am)ine advanced oxidation process (AOP) has drawn attention in water reuse. However, the formation of disinfection by-products (DBPs) in this process is less evaluated. This study investigated the DBP formation and the relevant toxicity during the O3-BAC-UV/chlor(am)ine treatment of sand-filtered municipal secondary effluent. DBP formation in UV/chlorine and UV/dichloramine (NHCl2) processes were compared, where the impact of key operational parameters (e.g., UV wavelength, pH) on DBP formation were comprehensively evaluated. O3-BAC significantly reduced DBP formation potential (DBPFP) (58.2 %). Compared to UV/chlorine AOP, UV/NHCl2 AOP reduced DBP formation by 29.7 % in short-time treatment, while insignificantly impacting on DBPFP (p > 0.05). UV/NHCl2 AOP also led to lower calculated cytotoxicity (67.7 %) and genotoxicity (55.9 %) of DBPs compared to UV/chlorine AOP. Compared to 254 nm UV light, the utilization of 285 nm UV light decreased the formation of DBPs in wastewater treated with the UV/chlorine AOP and UV/NHCl2 AOP by 31.3 % and 19.2 %, respectively. However, the cytotoxicity and genotoxicity in UV/NHCl2 AOP using 285 nm UV light increased by 83.4 % and 58.5 %, respectively, compared to 254 nm. The concentration of DBPs formed in the UV/NHCl2 AOP at pH 8 was 54.3 % lower than that at pH 7, suggesting a better control of DBPs at alkaline condition. In the presence of bromide, UV/NHCl2 AOP tended to generate more brominated DBPs than UV/chlorine AOP. Overall, UV/NHCl2 AOP resulted in lower concentration and toxicity of DBPs compared to UV/chlorine AOP.

Enhanced antibiotic degradation via photo-assisted peroxymonosulfate over graphitic carbon nitride nanosheets/CuBi2O4: Highly efficiency of oxygen activation and interfacial charge transfer

Improving the activation capacity of peroxymonosulfate (PMS) to increase radical and non-radical production is critical for antibiotic degradation. However, how to boost reactive oxygen species (ROS) and speed interfacial charge transfer remains an essential challenge. We report a coupling system of 10 %CNNS/CuBi2O4 photocatalyst and sulfate radical-based advanced oxidation processes (SO4−-AOPs) to enhance the activation of PMS and improve antibiotic degradation. Owing to highly efficient oxygen activation and interfacial charge transfer, the degradation efficiency of the photo-assisted PMS system was as high as 51.6 times and 2.8 times that of photocatalyst and SO4−-AOPs alone, respectively. Importantly, the highly efficient oxygen activation resulted in the production of O2−, which in turn could utilize the excess electrons generated through efficient interfacial charge transfer to convert into non-radical 1O2. The total organic carbon (TOC) elimination effectiveness of the photo-assisted PMS system reached 82 % via the synergy of radicals and non-radicals (O2−, OH, 1O2, SO4−, h+). This system also had excellent potential for reducing the generation and toxicity of disinfection by-products (DBPs), as evidenced through significant reductions in concentrations of trichloromethane (TCM), dichloroacetic acid (DCAA), and trichloronitromethane (TCNM) by 76 %, 64 %, and 35 %, respectively, providing an effective and eco-friendly strategy for antibiotic treatment.

Gastrointestinal Degradation and Toxicity of Disinfection Byproducts in Drinking Water Using In Vitro Models and the Roles of Gut Microbiota.

Disinfection byproducts (DBPs) in drinking water are mainly exposed to the human body after oral ingestion and degradation in the gastrointestinal tract. The role of gastrointestinal degradation in the toxic effects of DBPs still needs further investigation. In this study, the degradation of five categories of DBPs (22 DBPs) in the stomach and small intestine was investigated based on a semicontinuous steady-state gastrointestinal simulation system, and 22 DBPs can be divided into three groups based on their residual proportions. The degradation of chloroacetonitrile (CAN), dibromoacetic acid (DBAA), and tetrabromopyrrole (FBPy) was further analyzed based on the Simulator of the Human Intestinal Microbial Ecosystem inoculating the gut microbiota, and approximately 60% of CAN, 45% of DBAA, and 80% of FBPy were degraded in the stomach and small intestine, followed by the complete degradation of remaining DBPs in the colon. Meanwhile, gastrointestinal degradation can reduce oxidative stress-mediated DNA damage and apoptosis induced by DBPs in DLD-1 cells, but the toxicity of DBPs did not disappear with the complete degradation of DBPs, possibly because of their interferences on gut microbiota. This study provides new insights into investigating the gastrointestinal toxic effects and mechanisms of DBPs through oral exposure.

Impact of boiling on chemical and physical processes for reduction of halomethanes, haloacetonitriles, and haloacetic acids in drinking water

Tap water is boiled by families across the globe in their daily life for cooking food and beverages, as well as for controlling some chlorine-resistant organisms to improve the water quality. However, the effects of boiling methods (heating temperature, heating modes, open or closed containers) on water quality, in particular the reduction of disinfection byproducts (DBPs), are unclear. This comprehensive research demonstrates that during the heating process, trihalomethanes (THMs) were markedly decreased, haloacetonitriles (HANs) were drastically reduced and sometimes completely removed, while haloacetic acids (HAAs) were reduced the least. Heating to boiling in open containers reduced DBPs concentrations more than heating in the closed containers. Residual chlorine from 0.1 to 5.0 mg/L did not affect the removal of HANs, but could increase concentrations of HAAs likely due to reaction of organic matter with chlorine at elevated temperatures. THMs demonstrated good removal at 0.1–1 mg/L residual chlorine, but less removal at 5 mg/L residual chlorine. Sodium chloride (salt), often added as seasoning agent in the process of family cooking, was found to have little effect on the removal of DBPs during cooking and boiling. Compared with the toxicity of DBPs in tap water, boiling could greatly reduce both the cytotoxicity and carcinogenicity through removal of DBPs. Consequently, boiling of tap water had a significant effect on reducing human exposure to DBPs and their associated toxicities.

Stormwater discharge: An overlooked source of disinfection byproduct precursors

Discharge from the stormwater system is as an important pathway for contaminant transport, impacting the quantity and characteristics of dissolved organic matter (DOM) in surface water, and thus the formation of disinfection byproducts (DBPs) during downstream drinking water disinfection. In this study, DOM in stormwater pipes was characterized by size-exclusion chromatography, and the formation of 27 DBPs and halogen-specific total organic halogen (TOX) following chlorination was investigated. Overall, DOM in stormwater pipes was characterized by low molecular weight compounds and microbial-derived organics. Total DBP concentrations in chlorinated stormwaters were ∼1–15 times higher than in chlorinated surface waters. DBPs formed in stormwaters were dominated by trihalomethanes and haloacetic acids. Moreover, the DBP-associated toxicity of chlorinated stormwaters was ∼1–38 times higher than in chlorinated surface waters, and mainly due to the presence of large amount of haloacetaldehydes and haloacetonitriles. Sampling during a rainfall event suggested that stormwater discharge significantly increased DBP precursors in the surface water. The high formation and estimated toxicity of DBPs in stormwater discharge indicates this is an overlooked source of DBP precursors, posing a threat to the aquatic environment and potentially drinking water quality.

Investigation on toxicity and mechanism to Daphnia magna for 14 disinfection by-products: Enzyme activity and molecular docking

Exposure to disinfection by-products (DBPs) has been found to induce a range of toxic effects in aquatic organism. Previous studies have consistently demonstrated that a majority of DBPs have the ability to induce in vivo toxicity in aquatic organisms. However, the impact of DBPs on the metabolic processes of Daphnia magna (D. magna) and the underlying molecular toxicity mechanisms are still not well understood. Therefore, we investigated the effects of 14 DBPs on two oxidative stress enzymes and malondialdehyde (MDA) levels in D. magna. Additionally, we employed molecular docking to simulate the toxicity of DBPs to D. magna at the molecular level. This comprehensive analysis allowed us to gain further insights into the toxicity of DBPs on D. magna. The results showed that among the aliphatic DBPs, the more bromine substituents, the lower the toxicity effect, and it's opposite in the aromatic DBPs. In the detection of oxidative stress level, catalase (CAT) enzyme and superoxide dismutase (SOD) enzyme in D. magna under compound stress showed a low increase and decrease with the increase of concentration. The level of MDA showed a positive correlation with the concentration. In the last, molecular docking simulations have shown promise in predicting the toxicity of DBPs and providing insights into their toxic effects to a certain extent, and the docking situation of P53 is slightly different. Hence, it is imperative to further regulate the presence of aromatic DBPs due to their pronounced toxic effects on D. magna, and these simulations can be complemented with actual experiments to enhance our understanding of the toxicity mechanisms of DBPs.

Effects of dissolved organic matter removal and molecular transformation in different water treatment processes on formation of disinfection byproducts

Alterations in molecular composition of dissolved organic matter (DOM) during water treatments can influence the composition and toxicity of disinfection by-products (DBPs) in subsequent chlorination disinfection process. In this study, the impacts of DOM composition after various water treatment techniques (coagulation, adsorption, nanofiltration, biological aerated filter (BAF), and their integrated processes) on the generation mechanisms of DBPs were comprehensively explored by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in combination with GC–MS and LC-MS analysis. The results indicated that coagulation preferentially removed unsaturated (low H/C) and oxidized (high O/C) compounds, whereas adsorption was prone to remove the reduced (low O/C) component that was more reactive with chlorine, leading to lower yields (μg DBP/mg DOC) of trihalomethanes (THMs) and haloacetic acids (HAAs) during subsequent chlorination. The coagulation-adsorption technique exhibited a relatively high removal of both known and unknown DBPs, demonstrating that coagulation and adsorption were complementary for DOM removal at the molecular level. Nanofiltration selectively removed molecules with relatively high O/C, however, those with very low O/C that were more reactive with chlorine could pass through the nanofiltration membrane, resulting in the highest yields of THMs and HAAs. Although BAF was inefficient in removing DBPs precursors, it could convert molecules with low degree of oxidation and unsaturation into highly oxidized and unsaturated ones, thereby significantly enhancing the removal of DBPs precursors in the subsequent coagulation-adsorption process. These findings are instrumental in developing and selecting more effective techniques to minimize the formation of DBPs in water treatment.

Investigation on toxicity mechanism of halogenated aromatic disinfection by-products to zebrafish based on molecular docking and QSAR model

Halogenated aromatic disinfection by-products (DBPs) are a new type of DBPs that have been detected in various water bodies. Previous studies have shown that most of them can induce in vivo toxicity in aquatic organisms. In this study, in order to further investigate the toxic effects and mechanisms of aromatic DBPs, the toxicity and ecological risks of 10 halogenated aromatic DBPs were assessed using the model organism zebrafish. It was found that the toxicity of DBPs was related to the number, type, and position of halogen and the type of substituent, and the 24 h-toxicity value of DBPs in this experiment could replace their 96 h-toxicity value to reduce the test time and save the test cost. Halogenated phenol and halogenated nitrophenol were more toxic, but the current ecological risks of DBPs were relatively low. In addition, the toxicity mechanism of DBPs was analyzed based on molecular docking and quantitative structure-activity relationship (QSAR) models. The molecular docking results showed that all 10 DBPs could bind to zebrafish's catalase (CAT), cytochrome P450 (CYP450), p53, and acetylcholinesterase (AChE), thereby affecting their normal life activities. QSAR models indicated that the toxicity of halogenated aromatic DBPs to zebrafish mainly depended on their hydrophobicity (log D), the interaction with CAT (ECAT), and hydrogen bonding acidity (A).

Oxidative stress as a key event in 2,6-dichloro-1,4-benzoquinone-induced neurodevelopmental toxicity

2,6-dichloro-1,4-benzoquinone (DCBQ) has been identified as an emerging disinfection byproducts (DBPs) in drinking water and has the potential to induce neurodevelopmental toxicity. However, there is rarely a comprehensive toxicological evaluation of the neurodevelopmental toxicity of DCBQ. Here, neural differentiating SH-SY5Y cells were used as an in vitro model. Our results have found that DCBQ has decreased cell viability and neural differentiation, generated higher level of reactive oxygen species (ROS), increased the percentage of apoptosis and lowered the level of mitochondrial membrane potential, suggesting the neurodevelopmental toxicity of DCBQ. In addition, antioxidant N-acetyl-L-cysteine (NAC) could significantly attenuate these DCBQ-induced neurotoxic effects, supporting our hypothesis that the neurodevelopmental toxicity may be related with oxidative stress induced by DCBQ. We further demonstrated that DCBQ-induced neurodevelopmental toxicity could promote the mitochondrial apoptosis pathway and inhibit the prosurvival PI3K/AKT/mTOR pathway through inducing ROS, which ultimately inhibited cell proliferation and induced apoptosis in neural differentiating SH-SY5Y cells. These findings have provided novel insights into the risk of neurodevelopmental toxic effects associated with DCBQ exposure, emphasizing the importance of assessing the potential neurodevelopmental toxicity of DBPs.

Contributions of Pharmaceuticals to DBP Formation and Developmental Toxicity in Chlorination of NOM-containing Source Water.

Pharmaceuticals have been considered a priority group of emerging micropollutants in source waters in recent years, while their role in the formation and toxicity of disinfection byproducts (DBPs) during chlorine disinfection remains largely unclear. In this study, the contributions of natural organic matter (NOM) and pharmaceuticals (a mixture of ten representative pharmaceuticals) to the overall DBP formation and toxicity during drinking water chlorination were investigated. By innovatively "normalizing" chlorine exposure and constructing a kinetic model, we were able to differentiate and evaluate the contributions of NOM and pharmaceuticals to the total organic halogen (TOX) formation for source waters that contained different levels of pharmaceuticals. It was found that at a chlorine contact time of 1.0 h, NOM (2 mg/L as C) and pharmaceuticals (total 0.0062-0.31 mg/L as C) contributed 79.8-99.5% and 0.5-20.2%, respectively, of TOX. The toxicity test results showed that the chlorination remarkably increased the toxicity of the pharmaceutical mixture by converting the parent compounds into more toxic pharmaceutical-derived DBPs, and these DBPs might contribute significantly to the overall developmental toxicity of chlorinated waters. This study highlights the non-negligible role of pharmaceuticals in the formation and toxicity of overall DBPs in chlorinated drinking water.

Unravelling High-Molecular-Weight DBP Toxicity Drivers in Chlorinated and Chloraminated Drinking Water: Effect-Directed Analysis of Molecular Weight Fractions.

As disinfection byproducts (DBPs) are ubiquitous sources of chemical exposure in disinfected drinking water, identifying unknown DBPs, especially unknown drivers of toxicity, is one of the major challenges in the safe supply of drinking water. While >700 low-molecular-weight DBPs have been identified, the molecular composition of high-molecular-weight DBPs remains poorly understood. Moreover, due to the absence of chemical standards for most DBPs, it is difficult to assess toxicity contributions for new DBPs identified. Based on effect-directed analysis, this study combined predictive cytotoxicity and quantitative genotoxicity analyses and Fourier transform ion cyclotron resonance mass spectrometry (21 T FT-ICR-MS) identification to resolve molecular weight fractions that induce toxicity in chloraminated and chlorinated drinking waters, along with the molecular composition of these DBP drivers. Fractionation using ultrafiltration membranes allowed the investigation of <1 kD, 1-3 kD, 3-5 kD, and >5 kD molecular weight fractions. Thiol reactivity based predictive cytotoxicity and single-cell gel electrophoresis based genotoxicity assays revealed that the <1 kD fraction for both chloraminated and chlorinated waters exhibited the highest levels of predictive cytotoxicity and direct genotoxicity. The <1 kD target fraction was used for subsequent molecular composition identification. Ultrahigh-resolution MS identified singly charged species (as evidenced by the 1 Da spacing in 13C isotopologues), including 3599 chlorine-containing DBPs in the <1 kD fraction with the empirical formulas CHOCl, CHOCl2, and CHOCl3, with a relative abundance order of CHOCl > CHOCl2 ≫ CHOCl3. Interestingly, more high-molecular-weight CHOCl1-3 DBPs were identified in the chloraminated vs chlorinated waters. This may be due to slower reactions of NH2Cl. Most of the DBPs formed in chloraminated waters were composed of high-molecular-weight Cl-DBPs (up to 1 kD) rather than known low-molecular-weight DBPs. Moreover, with the increase of chlorine number in the high-molecular-weight DBPs detected, the O/C ratio exhibited an increasing trend, while the modified aromaticity index (AImod) showed an opposite trend. In drinking water treatment processes, the removal of natural organic matter fractions with high O/C ratio and high AImod value should be strengthened to minimize the formation of known and unknown DBPs.

Removal and transformation of disinfection by-products in water during boiling treatment

Disinfection by-products (DBPs) remain an ongoing issue because of their widespread occurrence and toxicity. Boiling is the most popular household water treatment method and can effectively remove some DBPs. However, the transformation behavior of DBPs during boiling is still unclear, and the key contributors to toxicity have not been identified. In this study, the changes in the concentrations of DBPs in the single-DBP systems and the multi-DBP systems during boiling were monitored, and in-depth discussions on the removal and transformation of DBPs in both systems were carried out. The results showed that boiling was effective in removing volatile DBPs (over 90% for TCAL, TCAN, and DCAN, and over 60% for TCM), but ineffective for non-volatile DBPs (around 20% for TCAA and below 10% for DCAA and MCAA). By hydrolysis and decarboxylation, the transformation occurred among DBPs, i.e., 55% TCAL to TCM, followed by 23% DCAN to DCAA, 22% TCAN to TCAA, and 10% TCAA to TCM. The transformations were found to be significantly influenced by other co-existing DBPs. In multi-DBP systems, the transformations of DCAN to DCAA and TCAN to TCAA were both promoted, while the transformation of TCAN to TCAA was inhibited. Transformation and volatilization are the two processes responsible for DBP removal. Toxicity estimates indicated that boiling was effective in reducing the toxicity of DBPs and improving the safety of the water, despite the interconversion of DBPs in drinking water during boiling. This study emphasized the importance of studying the interconversion behaviors of DBPs in drinking water during boiling and provided practical information for end-use drinking water safety.

Toxicity evaluation of chlorinated natural water using Photobacterium phosphoreum: Implications for ballast water management

Chlorination of ballast water could produce harmful disinfection by-products (DBPs) and total residual oxidants. The International Maritime Organization calls for toxicity testing of discharged ballast water with fish, crustacea and algae to reduce the risk, but it is difficult to evaluate the toxicity of treated ballast water in a short time. Therefore, the purpose of this study was to analyze the applicability of luminescent bacteria to the assessment of residual toxicity of chlorinated ballast water. The toxicity unit for all treated samples were higher for Photobacterium phosphoreum than for microalgae (Selenastrum capricornutum and Chlorella pyrenoidosa), after adding neutralizer, all samples showed little effect on the luminescent bacteria and microalgae. For the DBPs, except for 2,4,6-Tribromophenol, Photobacterium phosphoreum could produce more sensitive and rapid test results than other species, the results in Photobacterium phosphoreum showed that the toxicity of DBPs in order of: 2,4-Dibromophenol > 2,6-Dibromophenol > 2,4,6-Tribromophenol > Monobromoacetic acid > Dibromoacetic acid > Tribromoacetic acid, and most binary mixtures (aromatic DBPs and aliphatic DBPs) presented synergistic effects based on the CA model. The aromatic DBPs in ballast water deserve more attention. In general, for ballast water management, the use of luminescent bacteria to evaluate the toxicity of treated ballast water and DBPs is desirable, this study could provide beneficial information for enhancing ballast water management.

Comparison of disinfection by-products formed by preoxidation of sulfamethazine by K2FeO4 and O3 and the influence on cytotoxicity and biological toxicity.

This study researched the formation of disinfection by-products (DBPs) in sulfamethazine (SMZ) chlorination after preoxidation by K2FeO4 and O3 and the influence of preoxidation on cytotoxicity and biological toxicity. Then, the study emphatically analyzed the influencing factors such as NaClO dosage, pH value, reaction temperature, fulvic acid (FA), and bromide and iodide ions. The results showed that preoxidation by K2FeO4 effectively inhibited the formation of DBPs of haloketones (HKS) and trihalomethanes (THMs), with an average inhibition rate of over 60%. The formation of DBPs after preoxidation by O3 was higher than that by K2FeO4; preoxidation by K2FeO4 reduced the influence of NaClO dosage, temperature, and pH value on the production of DBPs after SMZ chlorination. The cytotoxicity and biological toxicity of SMZ chlorination after preoxidation were evaluated and compared by calculating the LC50 value of DBPs and the luminescent bacteria method. The results of both calculation methods showed that the toxicity of DBPs after preoxidation by K2FeO4 was lower than that by O3 preoxidation. K2FeO4 and O3 preoxidation improved the SMZ removal efficiency by 8.41 and 10.49%, respectively, and inhibited the formation of most DBPs, but the preoxidation promoted the formation of highly toxic DBPs (HANs). The toxicity of DBPs formed in SMZ chlorination after preoxidation by K2FeO4 and O3 was slightly higher than that of chlorination disinfection alone, but it was still within the safe range. This study provides more new details about the formation and toxicity changes of DBPs in the process of SMZ chlorination after preoxidation.

Evaluation of disinfection byproducts for their ability to affect mitochondrial function

In the race to deliver clean water to communities through potable water reuse, disinfection and water quality assessment are and will continue to be fundamental factors. There are over 700 disinfection byproducts (DBPs) in water; evaluating each compound is practically impossible and very time consuming. A bioanalytical approach could be an answer to this challenge. In this work, the response of four major classes of DBPs toward mitochondrial membrane potential (ΔΨm) and cytoplasmic adenosine triphosphate (C-ATP) was investigated with human carcinoma (HepG2) cells. Within 90 min of cell exposure, only the haloacetic acid (HAA) mixture caused a cytotoxic response as measured by C-ATP. All four groups (haloacetonitriles (HANs), trihalomethanes (THMs), nitrosamines (NOAs), and HAAs) responded well to ΔΨm, R2 > 0.70. Based on the half-maximum concentration that evoked a 50% response in ΔΨm, the response gradient was HANs >> HAAs ∼ THM > NOAs. The inhibition of the ΔΨm by HANs is driven by dibromoacetonitrile (DBAN), while dichloroacetonitrile (DCAN) did not cause a significant change in the ΔΨm at less than 2000 µM. A mixture of HANs exhibited an antagonistic behavior on the ΔΨm compared to individual compounds. If water samples are concentrated to increase HAN concentrations, especially DBAN, then ΔΨm could be used as a biomonitoring tool for DBP toxicity.

Comparative Toxicity Analyses from Different Endpoints: Are New Cyclic Disinfection Byproducts (DBPs) More Toxic than Common Aliphatic DBPs?

In recent years, dozens of halogenated disinfection byproducts (DBPs) with cyclic structures were identified and detected in drinking water globally. Previous in vivo toxicity studies have shown that a few new cyclic DBPs possessed higher developmental toxicity and growth inhibition rate than common aliphatic DBPs; however, in vitro toxicity studies have proved that the latter exhibited higher cytotoxicity and genotoxicity than the former. Thus, to provide a more comprehensive toxicity comparison of DBPs from different endpoints, 11 groups of cyclic DBPs and nine groups of aliphatic DBPs were evaluated for their comparative in vitro and in vivo toxicity using human hepatoma cells (Hep G2) and zebrafish embryos. Notably, results showed that the in vitro Hep G2 cytotoxicity index of the aliphatic DBPs was nearly eight times higher than that of the cyclic DBPs, whereas the in vivo zebrafish embryo developmental/acute toxicity indexes of the cyclic DBPs were roughly 48-50 times higher than those of the aliphatic DBPs, indicating that the toxicity rank order differed when different endpoints were applied. For a broader comparison, a Pearson correlation analysis of DBP toxicity data from nine different endpoints was conducted. It was found that the observed Hep G2 cytotoxicity and zebrafish embryo developmental/acute toxicity in this study were highly correlated with the previously reported in vitro CHO cytotoxicity and in vivo toxicity in aquatic organisms (P < 0.01), respectively. However, the observed in vitro toxicity had no correlation with the in vivo toxicity (P > 0.05), suggesting that the toxicity rank orders obtained from in vitro and in vivo bioassays had large discrepancies. According to the observed toxicity data in this study and the candidate descriptors, two quantitative structure-activity relationship (QSAR) models were established, which help to further interpret the toxicity mechanisms of DBPs from different endpoints.

Degradation of sulfamethazine in UV/monochloramine process: Kinetics, by-products formation, and toxicity evaluation

Ultraviolet combined monochloramine (UV/NH2Cl) process is a promising advanced oxidation process (AOP) to remove organic micropollutants effectively through the generation of various reactive species e.g., hydroxyl radicals (HO•), reactive chlorine species (RCS), and reactive nitrogen species (RNS). This study investigated the kinetics, transformation pathways, DBPs formation, and toxicity alternation in the degradation of sulfamethazine (SMT). Based on the calculation of degradation kinetic models, RNS was proved to be the most important reactive species in the degradation of SMT in UV/NH2Cl. The contribution of RNS, HO• and RCS were approximately 56.6%, 38.8%, and 4.5%, respectively. With the NH2Cl dosage increased from 100 to 800 µmol L-1, degradation rate increased from 37% to 73% in 10 min. Significantly alternation was not observed with the changing of pH. Natural organic matter (NOM) remarkably inhibited the degradation rate to 48.6% and 32.8% in the presence of 1 and 2 mg L-1 NOM. Degradation reactions of SMT in UV/NH2Cl system primarily comprised of hydroxylation, nitrosation, and ring opening reactions. The total theoretical toxicity of degradation system increased in the first 20 min and decreased eventually. Comparing with UV/free chlorine (UV/Cl2) process, less disinfection by-products (DBPs) generated in UV/NH2Cl treatment. Thus, the theoretical toxicity of DBPs formed in UV/NH2Cl was much lower than UV/Cl2. Within 40 min degradation, the theoretical toxicity value reached maximum at pH 7.1 due to the mass production of dicloroacetonitrile (DCAN). Bromide ions (10 µmol L-1) significantly promoted the formation of brominated DBPs especially dibromoacetonitrile (DBAN). This study provided insight into the important role of RNS in the SAs’ transformation in UV/NH2Cl process and reference to benefits and disadvantages when selecting the process for disinfection in drinking water treatment.

Toxicity of 17 Disinfection By-products to Different Trophic Levels of Aquatic Organisms: Ecological Risks and Mechanisms.

Intensified disinfection of wastewater during the COVID-19 pandemic increased the release of toxic disinfection by-products (DBPs). However, studies relating to the ecological impacts of DBPs on the aquatic environment remain insufficient. In this study, we comparatively investigated the toxicities and ecological risks of 17 typical, halogenated DBPs to three trophic levels of organisms in the freshwater ecosystem, including phytoplankton (Scenedesmus sp.), zooplankton (Daphnia magna), and fish (Danio rerio). Toxicity of DBPs was found to be species-specific: Scenedesmus sp. was the most sensitive to haloacetic acids, while D. magna was the most sensitive to haloacetonitriles and trihalomethanes. Specific to each DBP, toxicities were also related to their classes and substituted halogen atoms. Damage to photosystems and oxidative stress served as the potential mechanisms for DBPs toxicity to microalgae. The different sensitivities to DBPs indicate that a battery of bioassays with organisms at different trophic levels is necessary to determine the ecotoxicity of DBPs. Furthermore, the ecological risks of DBPs were assessed by calculating the risk quotients (RQs) based on toxicity data from multiple bioassays. The cumulative RQs of DBPs to all the organisms were greater than 1.0, indicating high ecological risks of DBPs in wastewater effluents.