Chlorinated Disinfection Byproducts Research Articles

Point-of-use chlorine residuals and disinfection byproduct occurrences in rural households served by public water utilities in Appalachian Virginia

ABSTRACT We characterized concentrations of trihalomethanes (THMs), a measure of disinfection byproducts (DBPs), in tap water samples collected from households with utility-supplied water in two rural counties in Appalachian Virginia, and assessed associations with pH, free chlorine, and metal ions which can impact THM formation. Free chlorine concentrations in all samples (n = 27 homes) complied with EPA drinking water guidelines, though 7% (n = 2) of first draw samples and 11% (n = 3) of 5-min flushed-tap water samples exceeded the US Safe Drinking Water Act (SDWA) maximum contaminant level (MCL) for THM (80 ppb). Regression analyses showed that free chlorine and pH were positively associated with the formation of THM levels above SDWA MCLs (OR = 1.04, p = 0.97 and OR = 1.74, p = 0.79, respectively), while temperature was negatively associated (OR = 0.78, p = 0.38). Of the eight utilities serving study households, samples from water served by three different utilities exceeded the EPA MCL for THM. Overall, these findings do not indicate substantial exposures to DBPs for rural households with utility-supplied water in this region of southwest Virginia. However, given the observed variability in THM concentrations between and across utilities, and established adverse health impacts associated with chronic and acute DBP exposure, more research on DBPs in rural Central Appalachia is warranted.

Reaction mechanisms of chlorinated disinfection byproducts formed from nitrophenol compounds with different structures during chlor(am)ination and UV/post-chlor(am)ination

Nitrophenol compounds (NCs) have high formation potentials of disinfection byproducts (DBPs) in water disinfection processes, however, the reaction mechanisms of DBPs formed from different NCs are not elucidated clearly. Herein, nitrobenzene, phenol, and six representative NCs were used to explore the formation mechanisms of chlorinated DBPs (Cl-DBPs) during chlor(am)ination and UV/post-chlor(am)ination. Consequently, the coexistence of nitro and hydroxy groups in NCs facilitated the electrophilic substitution to produce intermediates of Cl-DBPs, and the different positions of nitro and hydroxy groups also induced different yields and formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Besides, the amino, chlorine, and methyl groups significantly influenced the formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Furthermore, the total Cl-DBPs yields from the six NCs followed a decreasing order of 2-chloro-3-nitrophenol, 3-nitrophenol, 2-methyl-3-nitrophenol, 2-amino-4-nitrophenol, 2-nitrophenol, and 4-nitrophenol during chlorination and UV/post-chlorination. However, the total Cl-DBPs yields from the six NCs during chloramination and UV/post-chloramination followed a quite different order, which might be caused by additional reaction mechanisms, e.g., nucleophilic substitution or addition might occur to NCs in the presence of monochloramine (NH2Cl). This work can offer deep insights into the reaction mechanisms of Cl-DBPs from NCs during the chlor(am)ination and UV/post-chlor(am)ination processes.

Nanobubbles improve peroxymonosulfate-based advanced oxidation: High efficiency, low toxicity/cost, and novel collaborative mechanism

Cl- activated peroxymonosulfate (PMS) oxidation technology can effectively degrade pollutants, but the generation of chlorinated disinfection byproducts (DBPs) limits the application of this technology in water treatment. In this study, a method of nanobubbles (NBs) synergistic Cl-/PMS system was designed to try to improve this technology. The results showed the synergistic effects of NBs/Cl-/PMS were significant and universal while its upgrade rate was from 12.89% to 34.97%. Moreover, the synergistic effects can be further improved by increasing the concentration and Zeta potential of NBs. The main synergistic effects of NBs/Cl-/PMS system were due to the electrostatic attraction of negatively charged NBs to Na+ from NaCl, K+ from PMS, and H+ from phenol, which acted as a "bridge" between Cl- and HSO5- as well as phenol and Cl-/HSO5-, increasing active substance concentration. In addition, the addition of NBs completely changed the oxidation system of Cl-/PMS from one that increases environmental toxicity to one that reduces it. The reason was that the electrostatic attraction of NBs changed the active sites and degradation pathway of phenol, greatly reducing the production of highly toxic DBPs. This study developed a novel environmentally friendly oxidation technology, which provides an effective strategy to reduce the generation of DBPs in the Cl-/PMS system. Environmental ImplicationCl- activated peroxymonosulfate (PMS) oxidation technology results in the formation of chlorinated disinfection byproducts (DBPs), limiting its application in water treatment. In this study, the nanobubbles (NBs) synergistic Cl-/PMS system was designed to enhance the degradation and mineralization rates of ionizable pollutants. Based on luminescent bacterial toxicity tests, the inhibition rate of the NBs/Cl-/PMS system was (9.35%) much lower than that of the control (only phenol, 30.96%) or Cl-/PMS system (100%). This study developed a novel environmentally friendly oxidation technology, which provides an effective strategy to reduce the generation of DBPs in the Cl-/PMS system.

Control of chlorination disinfection by-products in drinking water by combined nanofiltration process: A case study with trihalomethanes and haloacetic acids

Disinfection by-products (DBPs) are prevalent contaminants in drinking water and are primarily linked to issues regarding water quality. These contaminants have been associated with various adverse health effects. Among different treatment processes, nanofiltration (NF) has demonstrated superior performance in effectively reducing the levels of DBPs compared to conventional processes and ozone-biological activated carbon (O3-BAC) processes. In this experiment, we systematically investigated the performance of three advanced membrane filtration treatment schemes, namely "sand filter + nanofiltration" (SF + NF), "sand filter + ozone-biological activated carbon + nanofiltration" (SF + O3-BAC + NF), and "ultrafiltration + nanofiltration" (UF + NF), in terms of their ability to control disinfection by-product (DBP) formation in treated water, analyzed the source and fate of DBP precursors during chlorination, and elucidated the role of precursor molecular weight distribution during membrane filtration in relation to DBP formation potential (DBPFP). The results indicated that each treatment process reduced DBPFP, as measured by trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP), with the SF + O3-BAC + NF process being the most effective (14.27 μg/L and 14.88 μg/L), followed by the SF + NF process (21.04 μg/L and 16.29 μg/L) and the UF + NF process (26.26 μg/L and 21.75 μg/L). Tyrosine, tryptophan, and soluble microbial products were identified as the major DBP precursors during chlorination, with their fluorescence intensity decreasing gradually as water treatment progressed. Additionally, while large molecular weight organics (60–100,000 KDa) played a minor role in DBPFP, small molecular weight organics (0.2–5 KDa) were highlighted as key contributors to DBPFP, and medium molecular weight organics (5–60 KDa) could adhere to the membrane surface and reduce DBPFP. Based on these findings, the combined NF process can be reasonably selected for controlling DBP formation, with potential long-term benefits for human health.

Effects of cupric ions on the formation of chlorinated disinfection byproducts from nitrophenol compounds during UV/post-chlorination

Cupric ions (Cu2+) are ubiquitous in surface waters and can influence disinfection byproducts (DBPs) formation in water disinfection processes. This work explored the effects of Cu2+ on chlorinated DBPs (Cl-DBPs) formation from six representative nitrophenol compounds (NCs) during UV irradiation followed by a subsequent chlorination (i.e., UV/post-chlorination), and the results showed Cu2+ enhanced chlorinated halonitromethane (Cl-HNMs) formation from five NCs (besides 2-methyl-3-nitrophenol) and dichloroacetonitrile (DCAN) and trichloromethane (TCM) formation from six NCs. Nevertheless, excessive Cu2+ might reduce Cl-DBPs formation. Increasing UV fluences displayed different influences on total Cl-DBPs formation from different NCs, and increasing chlorine dosages and NCs concentrations enhanced that. Moreover, a relatively low pH (5.8) or high pH (7.8) might control the yields of total Cl-DBPs produced from different NCs. Notably, Cu2+ enhanced Cl-DBPs formation from NCs during UV/post-chlorination mainly through the catalytic effect on nitro-benzoquinone production and the conversion of Cl-DBPs from nitro-benzoquinone. Additionally, Cu2+ could increase the toxicity of total Cl-DBPs produced from five NCs besides 2-methyl-3-nitrophenol. Finally, the impacts of Cu2+ on Cl-DBPs formation and toxicity in real waters were quite different from those in simulated waters. This study is conducive to further understanding how Cu2+ affected Cl-DBPs formation and toxicity in chlorine disinfection processes and controlling Cl-DBPs formation in copper containing water.

Sunlight enhanced the formation of tribromomethane from benzotriazole degradation during the sunlight/free chlorine treatment in the presence of bromide

The coexistence of free chlorine and bromide under sunlight irradiation (sunlight/FC with Br−) is unavoidable in outdoor seawater swimming pools, and the formation of brominated disinfection byproducts could act more harmful than chlorinated disinfection byproducts. In this study, benzotriazole was selected as a model compound to investigate the degradation rate and the subsequent formation of disinfection byproducts via sunlight/FC with Br− process. The rate constants for the degradation of benzotriazole under pseudo first order conditions in sunlight/FC with Br− and sunlight/FC are 2.3 ± 0.07 × 10−1 min−1 and 6.0 ± 0.7 × 10−2 min−1, respectively. The enhanced degradation of benzotriazole can be ascribed to the generation of HO•, bromine species, and reactive halogen species (RHS) during sunlight/FC with Br−. Despite the fact that sunlight/FC with Br− process enhanced benzotriazole degradation, the reaction results in increasing tribromomethane (TBM) formation. A high concentration (37.8 μg/L) of TBM was detected in the sunlight/FC with Br−, which was due to the reaction of RHS. The degradation of benzotriazole was notably influenced by the pH value (pH 4 − 11), the concentration of bromide (0 − 2 mM), and free chlorine (1 − 6 mg/L). Furthermore, the concentration of TBM increased when the free chlorine concentrations increased, implying the formation potential of harmful TBM in chlorinated seawater swimming pools.

Comparative analysis of chlorinated disinfection byproducts formation from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination

Nitrophenol compounds (NCs) are widely distributed in water environments and regarded as important precursors of disinfection byproducts (DBPs). Herein, 4-nitrophenol and 2-amino-4-nitrophenol were selected as representative NCs to explore chlorinated DBPs (Cl-DBPs) formation during UV/post-chlorination. Dichloronitromethane (DCNM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), and trichloromethane (TCM) were formed from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination, and the yields of individual Cl-DBPs from 2-amino-4-nitrophenol were higher than those from 4-nitrophenol. Meantime, increasing chlorine contact time, UV fluence, and free chlorine dose could enhance Cl-DBPs formation, while much higher values of the three factors might decrease the yields of Cl-DBPs. Besides, alkaline pH could decrease the yields of halonitromethane (HNMs) and DCAN but increase the yields of TCM. Also, higher concentrations of 4-nitrophenol and 2-amino-4-nitrophenol would induce more Cl-DBPs formation. Subsequently, the possible formation pathways of DCNM, TCNM, DCAN, and TCM form 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination were proposed according to transformation products (TPs) and density functional theory (DFT) calculation. Notably, Cl-DBPs formed from 2-amino-4-nitrophenol presented higher toxicity than those from 4-nitrophenol. Among these generated Cl-DBPs, DCAN and TCNM posed higher cytotoxicity and genotoxicity, respectively. Furthermore, 4-nitrophenol, 2-amino-4-nitrophenol, and their TPs exhibited ecotoxicity. Finally, 4-nitrophenol and 2-amino-4-nitrophenol presented a high potential to produce DCNM, TCNM, DCAN, and TCM in actual waters during UV/post-chlorination, but the Cl-DBPs yields were markedly different from those in simulated waters. This work can help better understand Cl-DBPs formation from different NCs during UV/post-chlorination and is conducive to controlling Cl-DBPs formation.

Electrochemical reductive removal of trichloroacetic acids by a three-dimensional binderless carbon nanotubes/ CoP/Co foam electrode: Performance and mechanism

Numerous chlorinated disinfection by-products (DBPs) are produced during the chlorination disinfection of water. Among them, chloroacetic acids (CAAs) are of great concern due to their potential human carcinogenicity. In this study, effective electrocatalytic dechlorination of trichloroacetic acids (TCAA), a typical CAAs, was achieved in the electrochemical system with the three-dimensional (3D) self-supported CoP on cobalt foam modified by carbon nanotubes (CNT/CoP/CF) as the cathode. At a 10 mA cm−2 current density, 74.5% of TCAA (500 μg L−1) was converted into AA within 100 min. In-situ growth of CoP increased the effective electrochemical surface area of the electrode. Electrodeposited CNT promoted electron transfer from the electrode surface to TCAA. Therefore, the production of surface-adsorbed atomic hydrogen (H*) on CNT/CoP/CF was improved, further resulting in excellent electrochemical dechlorination of TCAA. The dechlorination pathway of TCAA proceeded into acetic acids via direct electronic transfer and H*-mediated reduction on CNT/CoP/CF electrode. Additionally, the electroreduction efficiency of CNT/CoP/CF for TCAA exceeded 81.22% even after 20 cycles. The highly efficient TCAA reduction performance (96.57%) in actual water revealed the potential applicability of CNT/CoP/CF in the complex water matrix. This study demonstrated that the CNT/CoP/CF is a promising non-noble metal cathode to remove chlorinated DBPs in practice.

Valorization of Field-Spent Granular Activated Carbon as Heterogeneous Ozonation Catalyst for Water Treatment.

Developing sustainable cost-effective strategies for valorization of field-spent granular activated carbon (s-GAC) from industrial water treatment has gained much interest. Here, we report a cost-effective strategy for the regeneration of s-GAC as an adsorbent in a large-scale drinking water treatment plant and used as an efficient and durable ozonation catalyst in water. To achieve this, a series of samples is prepared by subjecting s-GAC to thermally controlled combustion treatments with and without pyrolysis. The catalytic performance of the optimized sample is evaluated for oxalic acid degradation as the model pollutant under batch (>15 h) and continuous flow operations (>200 h). The partially deactivated catalyst upon reuse is restored by thermal treatment. Electron paramagnetic resonance and selective quenching experiments show the formation of singlet oxygen (1O2) during catalytic ozonation. The GAC-ozonation catalyst is efficient to minimize the formation of chlorinated disinfection by-products like trihalomethanes and haloacetic acids in an urban wastewater effluent.

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.

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.

Degradation products and transformation pathways of sulfamethoxazole chlorination disinfection by-products in constructed wetlands

Antibiotics and available chlorine coexist in multiple aquatic environments, and thus antibiotics and their chlorinated disinfection by-products (Cl-DBPs) have been a great concern for the nature and human health. Herein, the degradation intermediates and transformation pathways of sulfamethoxazole (SMX) Cl-DBPs in constructed wetlands (CWs) were investigated. A total of five SMX Cl-DBPs and their twenty degradation products in CWs was identified in this study. SMX and its Cl-DBPs influenced the biodegradation rather than the adsorption process in CWs. S1 atom on sulfonyl group of SMX had the strongest nucleophilicity, and was most vulnerable for nucleophilic attack. N5 and N7 on amino groups, and C17 on the methyl group had great electronegativity, and were susceptible to electrophilic reactions. S1–N5 and S1–C8 bonds of SMX are the most prone to cleavage, followed by C11–N5, C16–C17, and C12–N7. The chlorination of SMX mainly occurred at S1, N5, and N7 sites, and went through S–C cleavage, S–N hydrolysis, and desulfonation. The biodegradation of SMX Cl-DBPs in CWs mainly occurred at S1, N5, N7, C8, and C17 sites, and went through processes including oxidation of methyl, hydroxyl and amino groups, desulfonation, decarboxylation, azo bond cleavage, benzene ring cleavage, β-oxidation of fatty acids under the action of coenzymes. Over half of the SMX Cl-DBPs had greater bioaccumulation potential than their parent SMX, but the environmental risk of SMX Cl-DBPs was effectively reduced through the degradation by CWs.

ChloroDBPFinder: Machine Learning-Guided Recognition of Chlorinated Disinfection Byproducts from Nontargeted LC-HRMS Analysis.

High-resolution mass spectrometry (HRMS) is a prominent analytical tool that characterizes chlorinated disinfection byproducts (Cl-DBPs) in an unbiased manner. Due to the diversity of chemicals, complex background signals, and the inherent analytical fluctuations of HRMS, conventional isotopic pattern (37Cl/35Cl), mass defect, and direct molecular formula (MF) prediction are insufficient for accurate recognition of the diverse Cl-DBPs in real environmental samples. This work proposes a novel strategy to recognize Cl-containing chemicals based on machine learning. Our hierarchical machine learning framework has two random forest-based models: the first layer is a binary classifier to recognize Cl-containing chemicals, and the second layer is a multiclass classifier to annotate the number of Cl present. This model was trained using ∼1.4 million distinctive MFs from PubChem. Evaluated on over 14,000 unique MFs from NIST20, this machine learning model achieved 93.3% accuracy in recognizing Cl-containing MFs (Cl-MFs) and 92.9% accuracy in annotating the number of Cl for Cl-MFs. Furthermore, the trained model was integrated into ChloroDBPFinder, a standalone R package for the streamlined processing of LC-HRMS data and annotating both known and unknown Cl-containing compounds. Tested on existing Cl-DBP data sets related to aspartame chlorination in tap water, our ChloroDBPFinder efficiently extracted 159 Cl-containing DBP features and tentatively annotated the structures of 10 Cl-DBPs via molecular networking. In another application of a chlorinated humic substance, ChloroDBPFinder extracted 79 high-quality Cl-DBPs and tentatively annotated six compounds. In summary, our proposed machine learning strategy and the developed ChloroDBPFinder provide an advanced solution to identifying Cl-containing compounds in nontargeted analysis of water samples. It is freely available on GitHub (https://github.com/HuanLab/ChloroDBPFinder).

A comparison of typical ultrafiltration processes in drinking water treatment: Implications for fouling control and disinfection performance

Despite the rapid proliferation of ultrafiltration (UF) membranes in drinking water treatment, the long-term operational performance of various hybrid UF processes remains inadequately understood. Herein, three typically applied hybrid UF processes were directly compared on a pilot scale, focusing on effluent quality, fouling control and subsequent disinfection performance. Water quality analysis revealed that the direct UF process exhibited significant removal of high molecular weight and hydrophobicity fractions, while the integration of UF with conventional water treatment processes further enhanced the removal of medium molecular weight and transition fractions, as well as fluorescent organic matter. The augmentation of pretreatment processes resulted in the hybrid UF process featuring enhanced anti-fouling properties, characterized by decreased reversible and irreversible resistances under the constant flux condition. This improvement was attributed to reduced interaction between the membrane and foulants. Furthermore, the subsequent disinfection performance of hybrid UF processes was evaluated using chlorine and chlorine dioxide as disinfectants. The chlorine decay rate and disinfection by-product formation indicated that chlorine dioxide was more suitable for the UF process, whereas chlorine was better for the hybrid UF process with low organic matter content in the effluent. These comprehensive comparisons offer valuable insights for making informed decisions in adopting suitable hybrid UF processes for practical water treatment applications.

Enhanced Removal of Dissolved Effluent Organic Matter in Wastewater Using Lignin-Based Biochar Supported Fe–Cu Bimetallic Oxide Catalyst

The effluent discharged from wastewater treatment facilities frequently enters the ocean, posing a considerable threat to the health of marine life and humans. In this paper, an alkali lignin-based biochar-loaded modified Fe–Cu catalyst (FeCu@BC) was prepared to remove soluble microbial products (SMP) from secondary effluent as disinfection by-products precursors at ambient temperature and pressure. The humic acid (HA) was taken as the representative substance of SMP. The results showed that the maximum removal efficiency of HA reached 93.2% when the FeCu@BC dosage, pH, initial HA concentration, and dissolved oxygen concentration were 5.0 g/L, 7, 100 mg/L, and 1.75 mg/L, respectively. After three cycles, the removal efficiency of HA could be maintained at more than 70%. The quenching experiments and electron spin resonance (EPR) results showed that •OH and 1O2 were involved in the degradation of HA in the FeCu@BC catalyst reaction system, with 1O2 playing a dominant role. Theoretical calculations confirmed that •OH and 1O2 were more prone to attack the C=O bond of the side chain of HA. After processing by the FeCu@BC catalyst, the yield of chlorinated disinfection by-products from secondary effluent had decreased in an obvious manner. This study provides a new solution to efficiently solve the problem of chlorinated disinfection by-products from HA.

Sulfadiazine chlorination disinfection by-products in constructed wetlands: Identification of biodegradation products and inference of transformation pathways

Disinfection by-products (DBPs) formed from chlorination of antibiotics have greater toxicity than their parent compounds. Herein, this study investigated the biotransformation process of sulfadiazine Cl-DBPs in constructed wetlands (CWs). Results showed that, S atom on sulfonyl group, and N atoms on primary and secondary amine groups were the most reactive sites of sulfadiazine molecule. S1–N4 and S1–C8 of sulfadiazine are the most vulnerable bonds to cleave, followed by C14–N4 and C11–N5 bonds. In the chlorination process, sulfadiazine went through C–N bond cleavage, N-reductive alkylation, halogenation, and desulfonation to produce two aromatic Cl-DBPs. In the biodegradation process in CWs, sulfadiazine Cl-DBPs went through processes mainly including dechlorination, S–N bond cleavage, aniline-NH2 oxidation, desulfonation, phenol-OH oxidation, benzene ring cleavage, C–N bond cleavage, and β-oxidation of fatty acids under the action of a variety of oxidoreductases and hydrolases, during which a total of ten biodegradation products was identified. Moreover, sulfadiazine affected the biodegradation rather than the adsorption process in CWs. The two aromatic sulfadiazine Cl-DBPs had much higher bioaccumulation potentials than their parent sulfadiazine, but for the ten biodegradation products of sulfadiazine Cl-DBPs in CWs, 70% and almost 100% of them had lower bioaccumulation potentials than sulfadiazine and their parent sulfadiazine Cl-DBPs, respectively. The CWs were effective in reducing the environmental risk of sulfadiazine Cl-DBPs.

Peracetic Acid to Reduce Disinfection By-product Formation in Drinking Water

Laboratory experiments were conducted to evaluate the ability of peracetic acid (PAA—containing 10% hydrogen peroxide by weight in equilibrium) to reduce subsequent chlorination disinfection by-product (DBP) formation (trihalomethanes, haloacetic acids,...

Curbing chlorine disinfection byproduct formation with a biomimetic FeTAML oxidation catalyst

An [Fe(TAML)]− catalyst boosts the oxidising power of chlorine disinfectants to clear a model organic pollutant and inhibits formation of trihalomethane disinfection byproducts.

Tailoring the topology of ZIF-67 metal-organic frameworks (MOFs) adsorbents to capture humic acids

Chlorination is a versatile technique to combat water-borne pathogens. Over the last years, there has been continued research interest to abate the formation of chlorinated disinfection by-products (DBPs). To prevent hazardous DBPs in drinking water, it is decided to diminish organic precursors, among which humic acids (HA) resulting from the decomposition and transformation of biomass. Metal-organic frameworks (MOFs) such as zeolitic imidazolate frameworks (ZIFs) have recently received tremendous attention in water purification. Herein, customized ZIF-67 MOFs possessing various physicochemical properties were prepared by changing the cobalt source. The HA removal by ZIF-67-Cl, ZIF-67-OAc, ZIF-67-NO3, and ZIF-67-SO4 were 85.6%, 68.9%, 86.1%, and 87.4%, respectively, evidently affected by the specific surface area. HA uptake by ZIF-67-SO4 indicated a removal efficiency beyond 90% in 4 <pH< 8, while a drop was observed when pH reached ∼10. A parametric study revealed that the adsorption efficiency was a function of dosage; moreover, the removal percentage remained > 90% after 60 min mixing the solution with 0.3 g L−1 ZIF-67-SO4. Notably, an acceptable removal performance (∼72.3%) was obtained even at HA concentrations up to 100 mg L−1. The equilibrium data fitted well with the isotherm models in the order of Langmuir> Hill > BET> Khan > Redlich-Peterson> Jovanovic> Freundlich > and Temkin. The maximum adsorption capacity qm for HA uptake by ZIF-67-SO4 was 175.89 mg g−1, well above the majority of adsorbents. The pseudo-first-order model described the rate of HA adsorption by time. In conclusion, ZIF-67-SO4 presented promising adsorptive properties against HA. Further studies would be needed to minimize cobalt leaching from the ZIF-67-SO4 structure and improve its reusability safely, to ensure its effectiveness and the economy of adsorption system.

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.