Aromatic Disinfection Byproducts Research Articles

Chlorination of Aromatic Amino Acids: Elucidating Disinfection Byproducts, Reaction Kinetics, and Influence Factors.

In the face of ongoing water pollution challenges, the intricate interplay between dissolved organic matter and disinfectants like chlorine gives rise to potentially harmful disinfection byproducts (DBPs) during water treatment. The exploration of DBP formation originating from amino acids (AA) is a critical focus of global research. Aromatic DBPs, in particular, have garnered considerable attention due to their markedly higher toxicity compared to their aliphatic counterparts. This work seeks to advance the understanding of DBP formation by investigating chlorination disinfection and kinetics using tyrosine (Tyr), phenylalanine (Phe), and tryptophan (Trp) as precursors. Via rigorous experiments, a total of 15 distinct DBPs with accurate molecular structures were successfully identified. The chlorination of all three AAs yielded highly toxic chlorophenylacetonitriles (CPANs), and the disinfectant dosage and pH value of the reaction system potentially influence chlorination kinetics. Notably, Phe exhibited the highest degradation rate compared to Tyr and Trp, at both the CAA:CHOCl ratio of within 1:2 and a wide pH range (6.0 to 9.0). Additionally, a neutral pH environment triggered the maximal reaction rates of the three AAs, while an acidic condition may reduce their reactivity. Overall, this study aims to augment the DBP database and foster a deeper comprehension of the DBP formation and relevant kinetics underlying the chlorination of aromatic AAs.

Effects of ozone dose on brominated DBPs in subsequent chlor(am)ination: A comprehensive study of aliphatic, alicyclic and aromatic DBPs

Ozone‒chlor(am)ine is a commonly used combination of disinfectants in drinking water treatment. Although there are quite a few studies on the formation of some individual DBPs in the ozone‒chlor(am)ine disinfection, an overall picture of the DBP formation in the combined disinfection is largely unavailable. In this study, the effects of ozone dose on the formation and speciation of organic brominated disinfection byproducts (DBPs) in subsequent chlorination, chloramination, or chlorination‒chloramination of simulated drinking water were investigated. High-molecular-weight, aliphatic, alicyclic and aromatic brominated DBPs were selectively detected and studied using a powerful precursor ion scan method with ultra performance liquid chromatography/electrospray ionization triple quadrupole mass spectrometry (UPLC/ESI-tqMS). Two groups of unregulated yet relatively toxic DBPs, dihalonitromethanes and dihaloacetaldehydes, were detected by the UPLC/ESI-tqMS for the first time. With increasing ozone dose, the levels of high-molecular-weight (m/z 300–500) and alicyclic and aromatic brominated DBPs generally decreased, the levels of brominated aliphatic acids were slightly affected, and the levels of dihalonitromethanes and dihaloacetaldehydes generally increased in the subsequent disinfection processes. Despite different molecular compositions of the detected DBPs, increasing ozone dose generally shifted the formation of DBPs from chlorinated ones to brominated analogues in the subsequent disinfection processes. This study provided a comprehensive analysis of the impact of ozone dose on the DBP formation and speciation in subsequent chlor(am)ine disinfection.

Differences in the degradation behavior of disinfection by-products in UV/PDS and UV/H2O2 processes and the effect of their chemical properties

In this work, sixteen typical chlorinated and brominated aromatic disinfection by-products (DBPs) were selected as examples to investigate their different degradation mechanisms initiated by HO• and SO4•-. Addition reactions were the main mode of degradation of DBPs by HO•, while SO4•- dominated H-abstraction reactions and single electron transfer reactions. Chlorinated compounds had higher reactivity than brominated compounds. Furthermore, substituents with stronger electron-donating effects promoted the electrophilic reaction of DBPs with the two radicals. In addition, we developed a model based on the chemical properties LUMO, fmax−, and hardness for predicting the average reaction energy barriers for the initial reactions of DBPs with HO• and SO4•-. The model had good predictive performance for the difficulty of degradation of different DPBs by HO• and SO4•-, with R2 values of 0.85 and 0.87, respectively. Through the degradation efficiency simulation, we found that longer reaction times, higher oxidant concentrations and lower pollutant concentrations were more favorable for the removal of DBPs. The UV/PDS process showed better degradation of DBPs than the UV/H2O2 process. In addition, most degradation products of DBPs exhibited less toxicity to aquatic organisms than their parent compounds. This study provided theoretical guidance for the degradation and removal of other aromatic DBPs at the molecular level.

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.

Ozone mechanism, kinetics, and toxicity studies of halophenols: Theoretical calculation combined with toxicity experiment

Aromatic disinfection by-products (DBPs), which are generally more toxic than aliphatic DBPs, have attracted increasing attention. The toxicity of 13 typical halophenols on Scenedesmus obliquus was experimentally investigated, and the ozonation mechanism and kinetics of representative halophenols were further studied by quantum chemical calculations. The results showed that the EC50 values of halophenols ranged from 2.74 to 60.23 mg/L, and their toxicity ranked as follows: di-halogenated phenols > mono-halogenated phenols, mixed halogen-substituted phenols > single halogen-substituted phenols, and iodophenols > bromophenols > chlorophenols. The toxicity of halophenols was well described by the electronegativity index (ω) as lg(EC50)−1 = 6.228ω – 3.869, indicating halophenols capturing electrons as their potential toxicity mechanism. The reactions of O3 with halophenolate anions were dominated by three mechanisms: 1,3-dipolar cycloaddition, oxygen addition, and single electron transfer. The kinetic calculation indicated that O3 oxidized aqueous halophenols by reacting with halophenolate anions with the reaction rate constants as high as (0.91–3.47) × 1010 M−1 s−1. The number of halogen substituents affected the kO3, cal values of halophenolate anions, which are in the order of 2,4-dihalophenolate anions >4-halophenolate anions > 2,4,6-trihalophenolate anions. During the ozonation of 2,4,6-tribromophenol (246TBP), the toxic products (dimers and brominated benzoquinones) could be synergistically degraded by O3 and HO•. Thus, ozonation is feasible as a strategy to degrade aromatic DBPs.

Molecular interactions between bovine serum albumin (BSA) and trihalophenol: Insights from spectroscopic, calorimetric and molecular modeling studies

The issue of disinfection byproducts (DBPs) in the water has received critical attention due to the health effects on humans. In the water environment, interactions between bovine serum albumins (BSA), the most abundant water-soluble protein, and DBPs unavoidably occur. In this study, comparative binding interactions of two aromatic DBPs − 2,4,6-trichlorophenol (TCP) and 2,4,6-tribromophenol (TBP) with BSA were investigated systematically utilizing fluorescence spectrometry, UV absorption spectrometry, isothermal titration calorimetry and molecular docking approach. The fluorescence quenching results indicated that TCP/TBP could quench the endogenous fluorescence of BSA through static quenching mechanisms, and TBP showed a more substantial quenching effect. The binding constants were determined for TCP-BSA (3.638 × 105 L/mol, 303 K) and TBP-BSA (6.394 × 105 L/mol, 303 K) complexes, with TBP showing higher binding affinity than TCP. The thermodynamic study and docking analysis suggested that hydrogen bonding and van der Waals forces were the primary interaction forces. Both of TCP and TBP were located in the subdomain IIIA of BSA, and TBP could form more stable complex than TCP. The results of the present study contributed valuable information on the environmental behaviors of halophenols in water environment from perspectives of binding with BSA.

Synergistic cytotoxicity of binary combinations of inorganic and organic disinfection byproducts assessed by real-time cell analysis

Chlorine, chlorine dioxide, and ozone are widely used as disinfectants in drinking water treatments. However, the combined use of different disinfectants can result in the formation of various organic and inorganic disinfection byproducts (DBPs). The toxic interactions, including synergism, addition, and antagonism, among the complex DBPs are still unclear. In this study, we established and verified a real-time cell analysis (RTCA) method for cytotoxicity measurement on Chinese hamster ovary (CHO) cell. Using this convenient and accurate method, we assessed the cytotoxicity of a series of binary combinations consisting of one of the 3 inorganic DBPs (chlorite, chlorate, and bromate) and one of the 32 regulated and emerging organic DBPs. The combination index (CI) of each combination was calculated and evaluated by isobolographic analysis to reflect the toxic interactions. The results confirmed the synergistic effect on cytotoxicity in the binary combinations consisting of chlorite and one of the 5 organic DBPs (2 iodinated DBPs (I-DBPs) and 3 brominated DBPs (Br-DBPs)), chlorate and one of the 4 organic DBPs (3 aromatic DBPs and dibromoacetonitrile), and bromate and one of the 3 organic DBPs (2 I-DBPs and dibromoacetic acid). The possible synergism mechanism of organic DBPs on the inorganic ones may be attributed to the influence of organic DBPs on cell membrane and cell antioxidant system. This study revealed the toxic interactions among organic and inorganic DBPs, and emphasized the latent adverse outcomes in the combined use of different disinfectants.

Occurrence, influencing factors, toxicity, regulations, and abatement approaches for disinfection by-products in chlorinated drinking water: A comprehensive review.

Disinfection is considered as a vital step to ensure the supply of clean and safe drinking water. Various approaches are adopted for this purpose; however, chlorination is highly preferred all over the world. This method is opted owing to its several advantages. However, it leads to the formation of certain by-products. These chlorination disinfection by-products (DBPs) are genotoxic, carcinogenic and mutagenic. Still chlorination is being practiced worldwide. Present review gives insights into the occurrence, toxicity and factors affecting the formation of regulated (THMs, HAAs) and emerging DBPs (N-DBPs, HKs, HAs and aromatic DBPs) found in drinking water. Furthermore, remediation techniques used to control DBPs have also been summarized here. Key findings are: (i) concentration of regulated DBPs surpassed the permissible limit in most of the regions, (ii) high chlorine dose, high NOM, more reaction time (up to 3h) and high temperature (up to 30°C) enhance the formation of THMs and HAAs, (iii) high pH favors the formation of THMs while low pH is suitable of the formation of HAAs, (iv) high NOM, low temperature, low chlorine dose and moderate pH favors the formation of unstable DBPs (N-DBPs, HKs and HAs), (v) DBPs are toxic not only for humans but for aquatic fauna as well, (vi) membrane technologies, enhanced coagulation and AOPs remove NOM, (vii) adsorption, air stripping and other physical and chemical methods are post-formation approaches (viii) step-wise chlorination is assumed to be an efficient method to reduce DBPs formation without any treatment. Toxicity data revealed that N-DBPs are found to be more toxic than C-DBPs and aromatic DBPs than aliphatic DBPs. In majority of the studies, merely THMs and HAAs have been studied and USEPA has regulated just these two groups. Future studies should focus on emerging DBPs and provide information regarding their regulation.

Ferrate(VI) pretreatment before disinfection: An effective approach to controlling unsaturated and aromatic halo-disinfection byproducts in chlorinated and chloraminated drinking waters

Disinfection is an essential process of drinking water treatment to eliminate harmful pathogens, but it generates potentially toxic disinfection byproducts (DBPs). Ferrate (FeO42-, Fe(VI)) was used to pre-oxidize natural organic matter (NOM, the precursor of DBPs) in source water to control DBP formation in subsequent chlorine or chloramine disinfection. Currently, it is unclear how Fe(VI) changes the structure of NOM, and no information details the effect of Fe(VI) pretreatment on the aromatic DBPs or the speciation of overall DBPs generated in subsequent disinfection of drinking water. In the present paper, Fe(VI) was applied to pretreat simulated source water samples at a Fe(VI) to dissolved organic carbon mole ratio of 1:1 at pH 8.0. 13C nuclear magnetic resonance spectroscopy was newly employed to characterize NOM in simulated source waters with and without Fe(VI) treatment, and it was demonstrated that Fe(VI) converted unsaturated aromatic C functional groups in NOM to saturated aliphatic ones. High-resolution mass spectrometry (HRMS) and high performance liquid chromatography/triple quadrupole MS were applied to analyze the DBPs generated in chlorination and chloramination of the source waters with and without Fe(VI) pretreatment. It was confirmed that Fe(VI) pretreatment followed by chlorination (or chloramination), generated DBPs containing less unsaturated, halogenated, and aromatic moieties than chlorination (or chloramination) without pretreatment by Fe(VI). Finally, the cytotoxicity of disinfected drinking water samples were assessed with the human epithelial colorectal adenocarcinoma Caco-2 cell line (a model of the intestinal barrier for ingested toxicants), and the results show that Fe(VI) pretreatment detoxified the chlorinated and chloraminated drinking waters.