Disinfection By-products Research Articles

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.

Removal of Anabaena by ultrasonic pretreatment enhancing-coagulation and water treatment processes

Cyanobacteria bloom brings great challenges to the safety of the drinking water process. Ultrasonic pretreatment can effectively enhance coagulation to remove algae cells from algae-laden water. However, due to the special chain-like structure of Anabaena, the removal characteristics of Anabaena in water treatment process are quite different from those of unicellular cyanobacteria. No study has yet systematic studied on the enhancement effect of ultrasonic enhanced water treatment process on Anabaena. Therefore, this paper studied the characteristics and mechanism of ultrasonic pretreatment to enhance the removal of Anabaena, and carried out pilot experiments. The results showed that ultrasound irradiation at 740 kHz and 1.12 MHz had a great effect on the destruction of the chain-like structure and cell structure of Anabaena. After 15 min, the removal rate of Anabaena cells reached 16.0% and 30.4%, respectively, and the release of intracellular organic matter (IOM) reached 4.3 and 6.0 mg/L, in which phycocyanin released more. The damage of dynamic ultrasound irradiation on algae cells is weak, which can avoid the influence of uneven ultrasound irradiation on algae cells. The enhanced coagulation effect was better after 740 kHz ultrasonic pretreatment for 1 min, and the removal rates of algal cells, turbidity and dissolved organic carbon (DOC) increased by 7%, 9.4% and 12.6%, respectively. Pilot scale experiments demonstrate that ultrasonic pretreatment leads to a notable enhancement in the removal efficiency during the coagulation and sedimentation stages. After 4 h of operation, the turbidity and algal cell removal in the sedimentation stage increased by 6.1% and 14.0%, respectively. In addition, the removal of DOC in the final treated water increased by 6.7%. Furthermore, the disinfection by-products (DBPs) concentration experiences a reduction exceeding 200 μg per liter. Together, these results show a substantial improvement in filtration efficiency and effluent quality. This study provides guidance for the ongoing study of ultrasonic pretreatment to remove chain-like cyanobacteria.

Formation of nitrogen-containing disinfection by-products during the chloramination treatment of an emerging pollutant

Chloramination was commonly used as disinfectant for killing pathogens in water. However, in this process, nitrogen-containing disinfection by-products (N-DBPs) would accidently form and subsequently rise toxicity. Here, we investigated acute toxicity variation and by-products formation during chloramination treatment on UV filter 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone (BP-4). Under alkaline conditions, the acute toxicity of this system had significant increase. A total of 17 transformation products were tentatively identified, and for them, plausible transformation pathways were proposed. Noticeably, numerous aniline and nitrosobenzene analogs were detected, and the dramatic increase of acute toxicity in this system might be primarily attributed to the formation of benzoquinone and aniline analogs. Besides, bromophenol, iodophenol and iodobenzoquinone analogs exhibiting high toxicity were generated in the presence of bromine and iodide ions. This study indicates that chloramination treatment may significantly increase potential health risk, further management on disinfection system is reasonable.

A universal model to predict yields of THMs and HAAs based on UV–Visible absorption spectra

Differential absorption spectroscopy (DAS) quantifies changes in the UV–Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV–Visible spectrum of DOM. A new function (f(−DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(−DA350) and ln([THMs]), as well as f(−DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

Effect of exposure to disinfection by-products during swimming exercise on asthma-related immune responses.

Swimming is a widely practiced exercise in modern society, where there is a heightened interest in health. The exceptional benefits of swimming are well-known, yet the issue of water quality management inevitably arises due to its nature as an aquatic exercise. Several studies reported that chlorine disinfectants commonly used in swimming pool water disinfection could degrade into toxic disinfection by-products (DBPs) and suggested that the DBPs might induce respiratory disorders, including asthma. Conversely, there were also reports that the DBPs had no significant effects on respiratory conditions. In this study, we investigated the influence of swimming exercise and DBPs on asthma. The decomposition products had little effect on the number of T cells in various immune organs. However, swimming exercise was found to increase the cell count in proportion to the exercise duration. Nevertheless, there were no significant changes in other immune cells and the secretion of asthma-related cytokines. These findings indicate that the effects of swimming pool DBPs on respiratory conditions during swimming exercise are either negligible or absent, and instead, the immunological benefits gained through consistent swimming exercise outweigh any potential drawbacks.

Occurrence and fate of N-nitrosamines in full-scale domestic wastewater treatment plants and their impact on receiving waters along the Lijiang River, China

Domestic wastewaters contaminated with N-nitrosamines pose a significant threat to river ecosystems worldwide, particularly in urban areas with riparian cities. Despite widespread concern, the precise impact of these contaminants on receiving river waters remains uncertain. This study investigated eight N-nitrosamines in wastewater treatment plants (WWTPs) and their adjacent receiving river, the Lijiang River in Guilin City, Southwest China. By analyzing thirty wastewater samples from five full-scale WWTPs and twenty-three river water samples from Guilin, we quantified the mass loads of N-nitrosamines discharged into the surrounding watershed via domestic effluents. The results revealed that N-nitrosodimethylamine (10–60 ng/L), N-nitrosodiethylamine (3.4–22 ng/L), and N-nitrosopyrrolidine (not detected–4.5 ng/g) were predominant in influents, effluents, and sludge, respectively, with the overall removal efficiencies ranging from 17.7 to 65.6% during wastewater treatment. Cyclic activated sludge system and ultraviolet disinfection were effective in removing N-nitrosamines (rates of 59.6% and 24.3%), while chlorine dioxide disinfection promoted their formation. A total of 30.4 g/day of N-nitrosamine mass loads were observed in the Lijiang River water, with domestic effluents contributing about 31.3% (19.4 g/day), followed by livestock breeding wastewater (34.5%, 12.0 g/day), and unknown sources (24.7%, 7.5 g/day). These findings highlight the critical role of WWTPs in transporting N-nitrosamines to watersheds and emphasize the urgent need for further investigation into other potential sources of N-nitrosamine pollution within watersheds.

N-doped porous carbon modified by polyacrylic acid for efficient removal of disinfection products in environmental waters under extensive conditions

In this work, a novel porous carbon nanocomposite was successfully prepared by creatively using polyacrylic acid to modify N-doped porous carbon, which was used to adsorb and remove new cyclic chlorine disinfection by-products in various water environments. The high-temperature calcination process at 1000 °C created a hierarchical pore structure that contained both micropores and mesopores. This structure significantly increased the mass transfer efficiency of the target on the adsorbent. The incorporation of N atoms enhanced NC's binding affinity and furnished target adsorption sites. The dispersion of N-doped porous carbon was significantly improved after polyacrylic acid modification. Moreover, the surface charge of NC-1000 was also altered, facilitating easier electrostatic interaction with DBPs. Subsequently, faster adsorption kinetics was obtained within 2 min, and the removal efficiency of 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were promoted to 94.10 % and 98.71 %, respectively. Characterization and data analysis revealed that the primary adsorption mechanism was chemical (electrostatic interaction, hydrophobic interaction, π-π interaction, and hydrogen bond). Surprisingly, factors such as ionic strength, natural organic matter and pH had minimal impact on the adsorption process, indicating that NC-1000@PAA had excellent anti-interference performance. Despite undergoing four adsorption–desorption cycles, NC-1000@PAA upheld a steady composition along with a remarkable adsorption capability. Furthermore, NC-1000@PAA had negligible cytotoxicity, which was assessed by cell experiments. The application of NC-1000@PAA was attested in various environmental waters. The proposed method provided a new strategy to pollutant removal by NC-1000@PAA under extensive conditions, which had wide perspective and practicability on the purification treatment of environmental water.

Spatiotemporal dynamics of dissolved organic matter and disinfection by-products formation potential of Shengzhong Lake in southwest China.

The quality and quantity of dissolved organic matter (DOM) in lakes as well as its environmental effects associated with the unintended disinfection by-products (DBPs) have received continuous attention. This work investigated the spatiotemporal dynamics of DOM in Shengzhong Lake in southwest China and the formed DBPs during the chlorine disinfection process. The results showed that lake water in summer had significantly higher dissolved oxygen and dissolved organic carbon than that in winter. In contrast, DOM in winter demonstrated an obviously higher aromaticity and molecular weight than that in summer. Four fluorescence components, i.e., terrestrial humic-like substances (C1), protein-like substances (C2), and microbial humic-like substances (C3 and C4), were identified, and their relative abundance followed in the order of C3 > C4 > C2 > C1 in winter and C4 > C3 > C1 > C2 in summer. The formation potential of trihalomethanes and haloacetic acids in winter was higher and lower than that in summer, which was mainly ascribed to the content of aromatic and hydrophobic substances. Compared to the significant seasonal dynamic, the spatial variation of DOM and the formed DBPs was not obvious. This work sheds light on the spatial-temporal distribution of DOM and the potentially formed DBPs in Shengzhong Lake, and will be helpful for understanding the biogeochemical cycle of carbon and assessing the drinking water safety.

Emerging disinfection byproducts 3-bromine carbazole induces cardiac developmental toxicity via aryl hydrocarbon receptor activation in zebrafish larvae

3-bromine carbazole (3-BCZ) represents a group of emerging aromatic disinfection byproducts (DBP) detected in drinking water; however, limited information is available regarding its potential cardiotoxicity. To assess its impacts, zebrafish embryos were exposed to 0, 0.06, 0.14, 0.29, 0.58, 1.44 or 2.88 mg/L of 3-BCZ for 120 h post fertilization (hpf). Our results revealed that ≥1.44 mg/L 3-BCZ exposure induced a higher incidence of heart malformation and an elevated pericardial area in zebrafish larvae; it also decreased the number of cardiac muscle cells and thins the walls of the ventricle and atrium while increasing cardiac output and impeding cardiac looping. Furthermore, 3-BCZ exposure also exhibited significant effects on the transcriptional levels of genes related to both cardiac development (nkx2.5, vmhc, gata4, tbx5, tbx2b, bmp4, bmp10, and bmp2b) and cardiac function (cacna1ab, cacna1da, atp2a1l, atp1b2b, atp1a3b, and tnnc1a). Notably, N-acetyl-L-cysteine, a reactive oxygen species scavenger, may alleviate the failure of cardiac looping induced by 3-BCZ but not the associated cardiac dysfunction or malformation; conversely, the aryl hydrocarbon receptor agonist CH131229 can completely eliminate the cardiotoxicity caused by 3-BCZ. This study provides new evidence for potential risks associated with ingesting 3-BCZ as well as revealing underlying mechanisms responsible for its cardiotoxic effects on zebrafish embryos.

PFAS promotes disinfection byproduct formation through triggering particle-bound organic matter release in drinking water pipes

Loose deposit particles in drinking water distribution system commonly exist as mixtures of metal oxides, organic materials, bacteria, and extracellular secretions. In addition to their turbidity-causing effects, the hazards of such particles in drinking water are rarely recognized. In this study, we found that trace per- and polyfluoroalkyl substances (PFASs) could dramatically promote the formation of disinfection byproducts (DBPs) by triggering the release of particle-bound organic matter. Carboxylic PFASs have a greater ability to increase chloroacetic acid than sulfonic PFASs, and PFASs with longer chains have a greater ability to increase trichloromethane release than shorter-chain PFASs. Characterization by organic carbon and organic nitrogen detectors and Fourier transform ion cyclotron resonance mass spectrometry revealed that the released organic matter was mainly composed of proteins, carbohydrates, lignin, and condensed aromatic structures, which are the main precursors for the formation of DBPs, particularly highly toxic aromatic DBPs. After the release of organic matter, the particles exhibit a decrease in surface functional groups, an increase in surface roughness, and a decrease in particle size. The findings provide new insights into the risks of loose deposits and PFASs in drinking water, not only on PFASs per se but also on its effect of increasing toxic DBPs.

Impact of changes in biofilm composition response following chlorine and chloramine disinfection on nitrogenous disinfection byproduct formation and toxicity risk in drinking water distribution systems

In practical drinking water treatment, chlorine and chloramine disinfection exhibit different mechanisms that affect biofilm growth. This study focused on the influence of biofilm composition changes, especially extracellular polymeric substance (EPS) fractions, on the potential formation and toxicity of nitrogenous disinfection by-products (N-DBP). Significant differences in microbial diversity and community structure were observed between the chlorine and chloramine treatments. Notably, the biofilms from the chloramine-treated group had higher microbial dominance and greater accumulation of organic precursors, as evidenced by the semi-quantitative confocal laser-scanning microscopy assay of more concentrated microbial aggregates and polysaccharide proteins in the samples. Additionally, the chloramine-treated group compared with chlorine had a higher EPS matrix content, with a 13.5 % increase in protein. Furthermore, the protein distribution within the biofilm differed; in the chlorine group, proteins were concentrated in the central region, whereas in the chloramine group, proteins were primarily located at the water–biofilm interface. Notably, functional prediction analyses of protein fractions in biofilms revealed specific functional regulation patterns and increased metabolism-related abundance of proteins in the chlorine-treated group. This increase was particularly pronounced for proteins such as dehydrogenases, reductases, transcription factors, and acyl-CoA dehydrogenases. By combining the Fukui function and density functional calculations to further analyse the effect of biofilm component changes on N-DBP production under chlorine/chloramine and by assessing the toxicity risk potential of N-DBP, it was determined that chloramine disinfection is detrimental to biofilm control and the accumulation of protein precursors has a higher formation potential of N-DBPs and toxicity risk, increasing the health risk of drinking water.

Formation and control of disinfection by-products during the trichloroisocyanuric acid disinfection in swimming pool water

The increasing demand for trichloroisocyanuric acid (TCCA) in swimming pool disinfection highlights the need to evaluate its applicability in terms of disinfection by-product (DBP) formation. Nevertheless, there is limited understanding of DBP formation and control during TCCA disinfection, particularly concerning the effects of various management parameters. This study aimed to fill this knowledge gap by comprehensively investigating DBP formation during TCCA chlorination, with a particular focus on assessing the contribution and interaction of influencing factors using Box-Behnken Design and response surface methodology. Results indicated that the concentrations of trichloroacetaldehyde, chloroform, dichloroacetic acid, trichloroacetic acid, and dichloroacetonitrile produced by TCCA disinfectant were 42.5%, 74.0%, 48.1%, 94.7% and 42.6% of those by the conventional sodium hypochlorite disinfectant, respectively. Temperature exhibited the most significant impact on chloroform formation (49%), while pH played a major role in trichloroacetaldehyde formation (44%). pH2 emerged as the primary contributor to dichloroacetic acid (90%) and trichloroacetic acid (93%) formation. The optimum water quality conditions were determined based on the minimum total DBPs (pH = 7.32, Temperature = 23.7 °C, [Cl−] = 437 mg/L). Chlorine dosage and contact time exhibited greater influence than precursor concentration on chloroform, dichloroacetonitrile, trichloroacetaldehyde, trichloroacetic acid, and total DBPs. Although the interaction between water quality parameters was weak, the interaction between disinfection operating parameters demonstrated substantial effects on DBP formation (8.56–19.06%). Furthermore, the DBP predictive models during TCCA disinfection were provided for the first time, which provides valuable insights for DBP control and early warning programs.

Natural Disinfection-like Process Unveiled in Soil Microenvironments by Enzyme-Catalyzed Chlorination.

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.

Rapid degradation of brominated haloacetaldehydes at elevated temperature: Kinetics and newly discovered mechanisms

As an important class of disinfection byproducts (DBPs) of emerging concern, haloacetaldehydes (HALs) undergo degradation and transformation under environmentally relevant conditions. In this study, the stability of chlorinated and brominated HALs was investigated at different pHs and water temperatures. Results indicated that the degradation of HALs followed second-order kinetics. Surprisingly, rapid degradation of Br-HALs at elevated temperature was newly discovered in this study. At 50 °C and pH 7.5, over 90 % of TBAL degraded in 8 min, while the degradation of TCAL was ∼1 %. Moreover, increasing pH also facilitated the degradation of HALs and the alkaline degradation rate constants (KOH−) were found to be 7–9 orders of magnitude higher than their neutral degradation rate constants (KH2O). Under conditions relevant to environment and DBP measurement, HALs mainly degraded to form corresponding trihalomethanes and formate via decarburization pathway, which accounted for 70–93 % of HALs loss. The remaining 7–30 % of HAL loss was attributed to the dehalogenation pathway newly proposed in this study, successfully closing halogen balance during HAL degradation. In addition, a quantitative structure-activity relationship (QSAR) model was established for HAL degradation and the degradation rate constants for three mono-HALs were predicted at different temperature. The kinetic models and reaction rate constants obtained in this study can be used for quantitative predictions of HAL concentrations in drinking water, which is beneficial for monitoring and control of these emerging DBPs. Furthermore, considering the rapid degradation of Br-HALs into corresponding products, the temperature during sample pre-treatment can have a significant impact on DBP analysis.

Interactions of ferrate(VI) and aquatic humic substances in water treatment

Aquatic humic substances, encompassing humic acid (HA) and fulvic acid (FA), can influence the treatment of ferrate(VI), an emerging water treatment agent, by scavenging Fe(VI) to accelerate its decomposition and hinder the elimination of target micro-pollutants. Meanwhile, HA and FA degrade the water quality through the transformation to disinfection byproducts over disinfection, contribution to water color, and enhanced mobility of toxic metals. However, the interplay with ferrate(VI) and humic substances is not well understood. This study aims to elucidate the interactions of ferrate(VI) with HA and FA for harnessing ferrate(VI) in water treatment. Laboratory investigations revealed distinctive biphasic kinetic profiles of ferrate(VI) decomposition in the presence of HA or FA, involving a 2nd order kinetic reaction followed by a 1st-order kinetic reaction. Both self-decay and reactions with the humic substances governed the ferrate(VI) decomposition in the initial phase. With increasing dissolved organic carbon (DOC), the contribution of self-decomposition to ferrate(VI) decay declined, while humic substance-induced ferrate(VI) consumption increased. To assess relative contributions of the two factors, DOC50% was first introduced to represent the level at which the two factors equally contribute to the ferrate(VI) loss. Notably, DOC50% (11.90 mg/L for HA and 13.10 mg/L for FA) exceeded typical DOC in raw water, implying that self-decay predominantly governs ferrate(VI) consumption. Meanwhile, ferrate(VI) could degrade and remove HA and FA across different molecular weight (MW) ranges, exhibiting treatment capabilities that are either better or, at least, equivalent to ozone. The ferrate(VI) treatment attacked high MW, hydrophobic organic molecules, accompanied by the production of low MW, more hydrophilic compounds. Particularly, FA was more effectively removed due to its smaller molecular sizes, higher solubility, and lower carbon contents. This study provides valuable insights into the effective utilization of ferrate(VI) in water treatment in presence of humic substances.

The formation and control of disinfection by-products by two-step chlorination for sewage effluent: Role of organic chloramine decomposition among molecular weight fractions

With the increasing discharge of wastewater effluent to natural waters, there is an urgent need to achieve both pathogenic microorganism inactivation and the mitigation of disinfection by-products (DBPs) during disinfection. Studies have shown that two-step chlorination, which injected chlorine disinfectant by splitting into two portions, was more effective in inactivating Escherichia coli than one-step chlorination under same total chlorine consumption and contact time. In this study, we observed a substantial reduction in the formation of five classes of CX3R-type DBPs, especially highly toxic haloacetonitriles (HANs), during two-step chlorination of secondary effluent when the mass ratio of chlorine-to-nitrogen exceeded 2. The shift of different chlorine species (free chlorine, monochloramine and organic chloramine) verified the decomposition of organic chloramines into monochloramine during second chlorination stage. Notably, the organic chloramines generated from the low molecular weight (< 1 kDa) fraction of dissolved organic nitrogen in effluent organic matter tended to decompose during the second step chlorination leading to the mitigation of HAN formation. Furthermore, the microbiological analysis showed that two-step chlorinated effluent had a slightly lower ecological impact on surface water compared to one-step chlorination. This work provided more information about the two-step chlorination for secondary effluent, especially in terms of organic chloramine transformation and HAN control.

Transformation pathways of enrofloxacin chlorination disinfection by-products in constructed wetlands

Antibiotic residues and their chlorinated disinfection by-products (Cl-DBPs) have adverse effects on organisms in aquaculture water. Taking enrofloxacin (ENR) as target antibiotic, this study investigated the degradation and transformation of ENR Cl-DBPs in constructed wetlands (CWs). Results showed that, ENR and its Cl-DBPs affected the biodegradation of CWs at the preliminary stage, but did not affect the adsorption by plant roots, substrates, and biofilms. The piperazine group of ENR had great electronegativity, and was prone to electrophilic reactions. The carboxyl on quinolone group of ENR had strong nucleophilicity, and was prone to nucleophilic reactions. C atoms with significant negative charges on the aromatic structure of quinolone group were prone to halogenation. During the chlorination of ENR, one pathway was the reaction of quinolone group, in which nucleophilic substitution reaction by chlorine occurred at C26 atom on carboxyl group, then halogenation occurred under the action of Cl+ at C17 site on the aromatic ring; the other pathway was the reaction of piperazine group, in which N7 atom was firstly attacked by HOCl, resulting in piperazine ring cleavage, then followed by deacylation, dealkylation, and halogenation. During the biodegradation of ENR Cl-DBPs, the reactivity of piperazine structure was strong, especially at N6, N7, C13, and C14 sites, while the ring structure of quinolone group was quite stable, and only occurred decyclopropyl at N5 site. Overall, the biodegradation of ENR Cl-DBPs in CWs went through processes including piperazine ring cleavage, tertiary amine splitting, dealkylation, and aldehyde oxidation under the action of coenzymes, in which metabolites such as ketones, aldehydes, carboxylic acids, amides, primary amines, secondary amines, tertiary amines and acetaldehyde esters were produced. Most ENR Cl-DBPs had greater bioaccumulation potential and stronger toxicity than their parent compound, fortunately, CWs effectively reduced the environmental risk of ENR Cl-DBPs through the cooperation of adsorption and biodegradation.

Photochemical Transformation of Dissolved Organic Matter in Surface Water Augmented the Formation of Disinfection Byproducts

Photochemical Transformation of Dissolved Organic Matter in Surface Water Augmented the Formation of Disinfection Byproducts

Formation of halonitromethanes from benzylamine during UV/chlorination: Impact factors, toxicity alteration, and pathways.

Halonitromethanes (HNMs), a representative nitrogen-containing disinfection byproduct, have gained significant concerns due to their higher cytotoxicity and genotoxicity. UV/chlorination is considered a promising alternative disinfection technology for chlorination. This study aimed to investigate the HNMs formation from benzylamine (BZA) during UV/chlorination. The experimental results revealed that the yields of HNMs initially raised to a peak then dropped over time. Higher chlorine dosage and BZA concentration promoted the formation of HNMs, whereas alkaline pH inhibited their formation. The presence of bromine ion (Br-) not only converted chlorinated-HNMs (Cl-HNMs) to brominated (chlorinated)-HNMs Br (Cl)-HNMs) and brominated-HNMs (Br-HNMs) but also enhanced the total concentration of HNMs. Besides, the calculated cytotoxicity index (CTI) and genotoxicity index (GTI) of HNMs were elevated by 68.97% and 60.66% as Br- concentration raised from 2 to 6µM. The possible formation pathways of HNMs from BZA were proposed based on the intermediates identified by a gas chromatography/mass spectrometry (GC/MS). In addition, the formation rules of HNMs in actual water verified the results in deionized water during UV/chlorination. The results of this study provide basic data and a theoretical basis for the formation and control of HNMs, which is conducive to applying UV/chlorination.

Comparison of Fe‐based and Al‐based coagulants in the removal of organic and disinfection by‐product precursors

AbstractSurface water is renowned for its natural organic matter, constituting approximately 45% of total dissolved organic carbon (DOC) which can be removed in water treatment plants. However, residual DOC in water can react with chlorine to form several carcinogenic disinfectant by‐products (DBPs). This study aimed to examine the molecular weight of organic fractions dissolved in three different water sources that act as precursors to the formation of DBPs species. The coagulants used were Al‐ and Fe‐based, frequently used in water treatment plants to remove organic fractions. Characterization of DOC in source water served as the first step in determining the performance of both coagulants in terms of organic properties. The results showed that the selected surface waters had similar DOC characteristics, including biopolymers, humic substances, building blocks, and a low molecular weight. These fractions contributed to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs). The Fe‐based coagulant was more effective than the Al‐based coagulant in removing all organic fractions and reducing THMs compared to HAAs. Furthermore, one‐way ANOVA analysis showed a significant difference in the average removal of organic fractions and DBP species between the Fe‐based and Al‐based coagulants. The Fe‐based coagulant showed higher efficiency in removing biopolymers, dibromochloromethane, and chlorodibromoacetic acid than the Al‐based coagulant. In contrast, the Al‐based coagulant had better performance in reducing dibromo HAA and tribromo HAA. Both coagulants had no significant difference in extracting other organic fractions or DBPs species.