Formation Of Disinfection By-products Research Articles

Advances in environmental analysis of high molecular weight disinfection byproducts.

The disinfection of drinking water, while critical for public health, leads to the formation of disinfection byproducts (DBPs). Toxicological and epidemiological studies have demonstrated that exposure to disinfected water samples may pose adverse effects on human health. Recent research highlights the potential greater toxicity contribution of DBP fractions with high molecular weight (MW) (with more than two carbon atoms) compared to regulated low MW DBPs, emphasizing the need for advanced analytical techniques to identify and characterize these fractions. In this review, we summarize different analytical techniques for indirectly assessing DBP precursors and directly analyzing DBPs, discussing their advantages and limitations. Additionally, since identifying DBP toxicity agents in complex water mixtures is crucial for further optimizing water disinfection and controlling DBP formation, key DBP identification methods based on both chemical and bioassay metrics are also included and discussed. Finally, we highlight three important aspects for the future development of analytical methods to enhance the understanding of high MW DBP formation.

Characterization of Disinfection By-Products Originating from Residual Chlorine-Based Disinfectants in Drinking Water Sources

In this study, samples from the Yangtze River, Han River, and Liangzi Lake in Wuhan City were utilized to characterize the formation of disinfection by-products (DBPs) from chlorine-based disinfection residues in drinking water sources. The results indicated that the main DBPs in drinking water sources were trichloromethane (TCM) and trichloroacetic acid (TCAA). The generation of DBPs was significantly positively correlated with oxidative substances, aromatic compounds, pH, and ammonia nitrogen (NH3-N) content in the water. The concentration of TCAA increased from 0 to 2.45 ± 0.31 mg/L when the reaction time increased to 72 h. As the NaClO concentration increased from 5 mg/L to 15 mg/L, the concentrations of TCAA, TBM, and DCAN increased from 2.03 ± 0.04 mg/L, 0 mg/L, and 0 mg/L to 2.49 ± 0.34 mg/L, 0.21 ± 0.07 mg/L, and 0.10 ± 0.04 mg/L before decreasing to 1.75 ± 0.19 mg/L, 0.17 ± 0.07 mg/L, and 0.04 ± 0.05 mg/L, respectively. The orthogonal experimental results showed that Br−, NH3-N, and pH all had significant influences on the TCM generation, whereas temperature affected the formation of TCAA in the Han River. This work reveals the factors influencing the generation of DBPs from chlorine-based disinfection residues, offering a prevention and control method for DBPs in drinking water sources from a theoretical perspective.

Magnesium Bicarbonate-Walnut Shell Dual-Template Synthesis of Multifunctional Layered Porous Carbon for Enhanced Adsorption of Aqueous Chlorinated Organic Compounds.

Chloride ions readily react with organic matter and other ions, resulting in the formation of disinfection by-products (DBPs) that exhibit heightened levels of toxicity, carcinogenicity, and mutagenicity. This study creatively employed waste walnut shells as self-templates and low-cost magnesium bicarbonate as a rigid template to successfully synthesize multifunctional porous carbon derived from walnut shells. Employing a series of characterization techniques, it was ascertained that the porous carbon material (WSC/Mg) synthesized via the dual-template method exhibited a distinct layered microscopic surface structure, with a predominance of C and O elements on the surface. The material displayed a high degree of graphitization, significant specific surface area, and abundant oxygen-containing surface functional groups. The incorporation of magnesium bicarbonate as a hard template improved the structure of the walnut shell porous carbon, resulting in a significant enhancement in mass transfer efficiency for the target product on the adsorbent and a substantial improvement in removal efficiency. In comparison with walnut shell-derived carbon using only self-templating, WSC/Mg exhibited a 17.26-fold increase in adsorption capacity for 2,4-dichlorophenol. Furthermore, even after four adsorption-desorption cycles, WSC/Mg-12 maintained an adsorption efficiency above 90%. It is remarkable that WSC/Mg-12 demonstrated exceptional resistance to interference from natural organic matter and pH variations. Moreover, the adsorbed saturated WSC/Mg-12 effectively treated real coke wastewater, resulting in an 80% color removal rate, 20% COD removal rate, and 15% ammonia nitrogen removal rate. In conclusion, this study presents an innovative approach for cost-effective and versatile porous carbon materials with extensive applications in water environment purification and biomass utilization.

Unveiling the optical and molecular characteristics of aging microplastics derived dissolved organic matter transformed by UV/chlor(am)ine oxidation and its potential for disinfection byproducts formation

The investigations into the existence and behavior of microplastics (MPs) in water environment were widely conducted, while the characteristics of dissolved organic matter derived from MPs (MPs-DOM) during advanced oxidation have garnered comparatively little attention. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was employed along with multiple statistical analyses to gain a deeper understanding of the conversion of MPs-DOM in UV/chlor(am)ine advanced oxidation processes (AOPs). The diverse treatments exhibited varying degrees of augmentation in both aging and fragmentation of MPs with the order of UV/Cl2 > UV > UV/NH2Cl. The fragmentation degree of MPs upon two UV-based AOPs (UV-AOPs) was dependent on their monomer chemical structure. The highest TOC values of three MPs-DOM were observed after UV/Cl2 AOP and the lowest after UV/NH2Cl AOP. Polyvinyl chloride (PVC) displayed a greater release of MPs-DOM under varying leaching conditions. UV/Cl₂ AOP favored the reaction with saturated MPs-DOM, while UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating disinfection byproducts (DBPs) formation after chlorination. The precursors generated by UV/Cl₂ AOP owned lower H/C, higher modified aromatic index (AImod), and lower molecular weight (MW) products after chlorination. PVC-DOM with fewer CH₂ groups was more reactive. -H₂O, +O and -CH₂ reactions dominated in PVC-DOM (CHO compounds), while -2H, +O, -CH₂ did in PVC-DOM (CHON compounds). The dominant chlorine addition/substitution reactions occurred in PVC-DOM treated by UV/Cl₂ AOP, identifying 195 Cl-DBPs with 220 precursor-product pairs. Mass difference analyses showed that +2H and +O reactions were the most frequent of the 24 reaction types. Environmental ImplicationMicroplastics derived dissolved organic matters (MPs-DOM) transformed into disinfection byproducts (DBPs) under advanced oxidation processes (AOPs), heightening environmental risks. In this study, Fourier transform ion cyclotron resonance mass spectrometry was employed to gain a deeper understanding of MPs-DOM conversion in UV/chlor(am)ine AOPs. MPs fragmentation and fluorescent components varied with monomer chemistry and polymers. UV/Cl₂ AOP reacted with saturated MPs-DOM. UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating DBPs formation. DBPs precursors generated by UV/Cl₂ AOP owned higher modified aromatic index, lower H/C and molecular weight. Unveiling the MPs-DOM transformation during AOPs can mitigate the negative environmental impacts of MPs and their derivatives.

A convenient reduction method for the detection of low concentration free available chlorine——utilizing sodium sulfite as a quencher

Chlorine, serving as the mainstream disinfectant, can react with dissolved organic matter (DOM) to form undeserved disinfection by-products (DBPs). Free available chlorine (FAC) concentration is crucial to ensure effective disinfection while minimizing the formation of toxic DBPs. In this study, we propose a convenient method using sodium sulfite (Na2SO3) to reduce oxidized chlorine in FAC. The molar concentration of reduced chloride ion (Cl−) was quantified directly by ion chromatography to reflect FAC concentration. Compared with common FAC detection techniques including DPD colorimetry, iodometric, and UV methods, this novel reduction method exhibits a lower detection limit and is more resistant to interference. Common water matrices, such as DOM and anions did not affect the method accuracy (< 3.6%). Furthermore, carbonaceous DBPs (C-DBPs) like regulated trihalomethanes and halogenacetic acids, unregulated aromatic chlorophenols, did not interfere with the determination of FAC by using this reduction method. This lack of interference can be attributed to the low redox potential of Na2SO3, which does not readily react with these C-DBPs. However, nitrogenated DBPs (N-DBPs) like dichloroacetonitrile displayed slight interference (the effect of common dichloroacetonitrile concentration in water on FAC was less than 0.0007 μM). This suggests that this method is well-suited for determining FAC in chlorination processes where the C-DBPs predominated. Overall, the reduction method enables precise determination of FAC and proves valuable in assessing residual chlorine levels in both laboratory and real disinfected water samples dominated by C-DBPs.

Optimizing natural organic matter removal at the Koka water treatment plant, Ethiopia, using soil–alum composite material

ABSTRACT Conventional water treatment methods often fail to remove natural organic matter (NOM), leading to the formation of harmful disinfection by-products in chlorinated water. This study aimed to develop a synergistic, local soil–aluminum sulfate (alum) composite material to enhance NOM removal from real water samples. Locally derived soil (Chalaltu) samples were collected from selected locations and subjected to thermal treatment at elevated temperatures. The thermally treated soil was then combined with alum at varying mixing percentages to create the composite material. The synthesized composite materials were thoroughly characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy, Fourier transform infrared, and Brunauer–Emmett–Teller techniques. The alum-treated soil, obtained through thermal treatment at 500 °C with a mixing ratio of 50%, a dosage of 25 mg/L, and a settling time of 25 min, exhibited impressive removal efficiencies. The composite material increased removal efficiency by 1.5 times for both UV254 absorbance (91.1%) and dissolved organic carbon (90%), while reducing the alum dose by 58% compared to the existing Koka water treatment plant process. Reducing alum usage could lead to cost savings and alleviate concerns about its association with Alzheimer's disease. This technique is essential within the context of water treatment technology.

Formation and estimated cytotoxicity of trihalomethanes and haloacetic acids during ozonation of nonylphenol in bromide-containing water after chlorination process: Impact of ozonation initial pH

The presence of nonylphenol (NP) in bromide-containing water contributed to the formation of regulated disinfection by-products (DBPs): trihalomethanes-4 (THM4) and haloacetic acids-5 (HAA5). This study investigates the effects of ozonation pH on the degradation of NP, DBP formation, and DBP-estimated cytotoxicity. The ozonation pH was varied to 5, 7, and 9 to determine the effect of acidic, neutral, and alkaline conditions. The increase of ozonation initial pH improved the NP degradation. Ozonation of all initial pH conditions could decrease TCM, BDCM, and BDCM formation but increase the TBM formation at alkaline conditions. The formation of mono-HAA5 on the other hand, increased at all ozonation initial pH. Ozonation at acidic and neutral initial conditions can reduce the estimated cytotoxicity of the total formation of THM4 and HAA5 by 74.34 % and 93.31 %, respectively. In contrast, DBP's estimated cytotoxicity was raised by 33.72 % upon ozonation at an initial pH of alkaline. According to the study's findings, lowering the cytotoxicity of DBPs in acidic or alkaline environments can be achieved without changing the ozonation's pH. Based on these findings, pH changes are not required to reduce DBP during ozonation of NP-bromide-containing water. Future research on the impact of natural organic matter is recommended to investigate ozonation's capacity to reduce DBP production during ozonation of NP-containing natural water.

Ozone disinfection of waterborne pathogens: A review of mechanisms, applications, and challenges.

Water serves as a critical vector for the transmission of pathogenic microorganisms, playing a pivotal role in the emergence and propagation of numerous diseases. Ozone (O3) disinfection technology offers promising potential for mitigating the spread of these pathogens in aquatic environments. However, previous studies have only focused on the inactivated effect of O3 on a single pathogenic microorganism, lacking a comprehensive comparative analysis of various influencing factors and different types of pathogens, while the cost-effectiveness of O3 technology has not been mentioned. This review synthesized the migration characteristics of various pathogenic microorganisms in water bodies and examined the properties, mechanisms, and influencing factors of O3 inactivation. It evaluated the efficacy of O3 against diverse pathogens, namely bacteria, viruses, protozoa, and fungi, and provided a comparative analysis of their sensitivities to O3. The formation and impact of harmful disinfection by-products (DBPs) during the O3 inactivation process were assessed, alongside an analysis of the cost-effectiveness of this method. Additionally, potential synergistic treatment processes involving O3 were proposed. Based on these findings, recommendations were made for optimizing the utilization of O3 in water inactivation in order to formulate better inactivation strategies in the post-pandemic eras.

Aromatic Structures Govern the Formation of Chlorinated Byproducts in Dichlorine Radical Reactions.

Radical-induced disinfection byproduct (DBP) formation is drawing attention with increasing applications of advanced oxidation processes (AOPs). Cl2•- represents one of the extensively generated radicals in AOPs, whose behavior in DBP formation remains unknown. In this study, we found that aromatic structures serve as the main DBP precursors in Cl2•- reactions by employing diverse groups of model compounds. At a typical Cl2•- exposure of 1.2 × 10-9 M·s, the sum concentrations of 7 regulated aliphatic DBPs (e.g., trichloromethane, chloroacetic acids) are ∼0.10 to 0.48 μM for aromatic precursors and <0.05 μM for aliphatic ones. The DBP formation mechanisms from Cl2•- reactions involved the formation of chlorinated aromatics, radical-induced oxygen incorporation followed by ring cleavage, and the interactions of Cl2•- with ring-cleavage intermediates. In reacting with DOM, Cl2•- reactions produced much fewer aliphatic DBPs (5% of the total organochlorine vs 40% for chlorination) and chloroacetic acids dominated the aliphatic DBPs (usually trihalomethane for chlorination), which can be well interpreted by the precursors and mechanisms proposed. This work comprehensively reveals the precursors, formation patterns, and mechanisms of DBPs during the less-studied Cl2•- reactions, highlighting the importance of eliminating the aromatic structures of DOM before the AOPs.

Reduction of organic matter and disinfection by products formation at surface water treatment plants in Egypt

ABSTRACT Although the removal of colloidal particles continues to be an important reason for using coagulation, currently a newer approach, the removal of organic matter to reduce the formation of disinfection byproducts (DBPs) such as trihalomethanes (THMs) are suspected carcinogens. Inefficient removal of total organic carbon (TOC) leads to the formation of carcinogenic THMs. This motivates the research efforts to find a way to reduce them in potable water. The first objective of this research is monitoring the water quality (raw and produced) for selected three water treatment plants within Giza Governorate to reveal the most polluted site (high TOC in the raw water and THMs in the treated water) in the study areas. The second objective of this study is enhancing coagulation to reduce TOC and THMs from surface water treating. In this study, two different coagulants aluminum sulfate (alum), and ferric chloride were tested under different conditions of pH and coagulant concentration to determine their effectiveness for removal of TOC, THMs and turbidity. Optimum values for the mentioned conditions were used to achieve the maximum reduction for TOC and THMs in Al-Ayat drinking water treatment plant (DWTP) which recorded the highest concentration of TOC and THMs. Ferric chloride as a coagulant achieved the maximum removal percentage % of TOC, THMs and turbidity as 79%, 82% and 94%, respectively, at ferric chloride dose 100 mg/L, while alum as a coagulant recorded the maximum removal percentage % of TOC, THMs and turbidity as 46%, 52% and 91%, respectively, at alum dose 100 mg/L. The results indicated that ferric chloride as a coagulant has the highest efficiency reduction of TOC, THMs and turbidity if compared to alum with the same dose added.

In-depth analysis of natural organic matter fractions in drinking water treatment performance: Fate and role of humic substances in trihalomethanes formation potential

In this study we investigate the compositional changes in dissolved organic matter (DOM) fractions across diverse water sources and treatment processes in three Drinking Water Treatment Plants (DWTPs). High-Performance Size Exclusion Chromatography coupled with Diode Array Detection and Organic Carbon Detection (HPSEC-DAD-OCD) was employed to characterize DOM fractions, offering insights into treatment optimization. We examine bulk water parameters, DOM distributions, and the efficiency of treatment trains in reducing DOM fractions. Results reveal distinct DOM composition profiles in river-sourced versus reservoir-sourced waters, with implications for treatment processes. Coagulation, Granular Activated Carbon (GAC) adsorption, Electrodialysis Reversal (EDR), and Ion Exchange (IEX) were evaluated for their efficacy in removing DOM fractions. The analysis highlights the effectiveness of coagulation in reducing high molecular weight (MW) fractions, while GAC filtration targets lower MW fractions. EDR shows significant removal of anions and aromatics, while IEX demonstrates high removal efficiencies for removing humic substances (HS) fractions. Spectroscopic analysis further elucidates changes HS sub-fractions and their role in disinfection by-products (DBP) formation. To quantitatively assess the relationship between HS sub-fractions and trihalomethane formation potentials (THMFP), Pearson correlation analysis were conducted, unveiling robust associations between HS sub-fractions and THM-FP that can be predicted by surrogate parameters such as A254.

Reactivity, Pathways, and Iodinated Disinfection Byproduct Formation during Chlorination of Iodotyrosines Derived from Edible Seaweed.

Iodine derived from edible seaweed significantly enhances the formation of iodinated disinfection byproducts (I-DBPs) during household cooking. Reactions of chlorine with monoiodotyrosine (MIT) and diiodotyrosine (DIT) derived from seaweed were investigated. Species-specific second-order rate constants (25 °C) for the reaction of hypochlorous acid with neutral and anionic MIT were calculated to be 23.87 ± 5.01 and 634.65 ± 75.70 M-1 s-1, respectively, while the corresponding rate constants for that with neutral and anionic DIT were determined to be 12.51 ± 19.67 and 199.12 ± 8.64 M-1 s-1, respectively. Increasing temperature facilitated the reaction of chlorine with MIT and DIT. Based on the identification of 59 transformation products/DBPs from iodotyrosines by HPLC/Q-Orbitrap HRMS, three dominant reaction pathways were proposed. Thermodynamic results of computational modeling using density functional theory revealed that halogen exchange reaction follows a stepwise addition-elimination pathway. Among these DBPs, 3,5-diiodo-4-hydroxy-benzaldehyde and 3,5-diiodo-4-hydroxy-benzacetonitrle exhibited high toxic risk. During chlorination of MIT and DIT, iodinated trihalomethanes and haloacetic acids became dominant species at common cooking temperature (80 °C). These results provide insight into the mechanisms of halogen exchange reaction and imply important implications for the toxic risk associated with the exposure of I-DBPs from household cooking with iodine-containing food.

Halogenation of Anilines: Formation of Haloacetonitriles and Large-Molecule Disinfection Byproducts.

Aniline-related structures are common in anthropogenic chemicals, such as pharmaceuticals and pesticides. Compared with the widely studied phenolic compounds, anilines have received far less assessment of their disinfection byproduct (DBP) formation potential, even though anilines and phenols likely exhibit similar reactivities on their respective aromatic rings. In this study, a suite of 19 aniline compounds with varying N- and ring-substitutions were evaluated for their formation potentials of haloacetonitriles and trihalomethanes under free chlorination and free bromination conditions. Eight of the aniline compounds formed dichloroacetonitrile at yields above 0.50%; the highest yields were observed for 4-nitroaniline, 3-chloroaniline, and 4-(methylsulfonyl)aniline (1.6-2.3%). Free bromination generally resulted in greater haloacetonitrile yields with the highest yield observed for 2-ethylaniline (6.5%). The trihalomethane yields of anilines correlated with their haloacetonitrile yields. Product analysis of aniline chlorination by liquid chromatography-high-resolution mass spectrometry revealed several large-molecule DBPs, including chloroanilines, (chloro)hydroxyanilines, (chloro)benzoquinone imines, and ring-cleavage products. The product time profiles suggested that the reaction pathways include initial ring chlorination and hydroxylation, followed by the formation of benzoquinone imines that eventually led to ring cleavage. This work revealed the potential of aniline-related moieties in micropollutants as potent precursors to haloacetonitriles and other emerging large-molecule DBPs with the expected toxicity.

Disinfectant control in drinking water networks: Integrating advection–dispersion–reaction models and byproduct constraints

Effective disinfection is essential for maintaining water quality standards in distribution networks. Chlorination, as the most used technique, ensures safe water by maintaining sufficient chlorine residuals but also leads to the formation of disinfection byproducts (DBPs). These DBPs pose health risks, highlighting the need for chlorine injection control (CIC) by booster stations to balance safety and DBPs formation. Prior studies have followed various approaches to address this research problem. However, most of these studies overlook the changing flow conditions and their influence on the evolution of the chlorine and DBPs concentrations by integrating simplified transport-reaction models into CIC. In contrast, this paper proposes a novel CIC method that: (i) integrates multi-species dynamics, (ii) allows for a more accurate representation of the reaction dynamics of chlorine, other substances, and the resulting DBPs formation, and (iii) optimizes for the regulation of chlorine concentrations subject to EPA mandates thereby mitigating network-wide DBPs formation. The novelty of this study lies in its incorporation of time-dependent controllability analysis that captures the control coverage of each booster station. The effectiveness of the proposed CIC method is demonstrated through its application and validation via numerical case studies on different water networks with varying scales, initial conditions, and parameters.

Periodic membrane fractionation of freshwater organic matter reveals various reactivity patterns during chlorine/chloramine disinfection

Although drinking water disinfection has significantly reduced mortality from waterborne diseases, the formation of potentially harmful disinfection by-products (DBPs) remains a concern today. These DBPs emerge from the reaction of dissolved organic matter (DOM) with chlor(am)ine during disinfection. Identifying these DBP precursors from heterogeneous and complex DOM mixtures is challenging and to address this, a novel membrane fractionation protocol was developed to isolate and identify the organic DBP precursors from fresh water sources. A tight ultrafiltration and nanofiltration membrane were carefully selected to partition DOM into three molecular weight (MW) fractions: high (>20 kDa), medium (0.3–20 kDa) and low (<0.3 kDa) as defined by high performance-size exclusion chromatography- total organic carbon analysis. A mathematical tool was developed to optimize the fractionation protocol. Therefore, ultrafiltration was executed before nanofiltration and the concentration factor was maximized without inducing fouling to obtain the purest fractions. The mathematical tool was also set in place to predict the necessary diafiltration factor for each individual fractionation experiment based on the initial organic matter composition of the surface water allowing the fractionation protocol to be effective at all times. The protocol was applied to surface water samples collected six times across three seasons yielding a fraction enriched in high MW compounds (up to 50 %), a fraction having more than 80 % of medium MW compounds and a fraction only containing low MW compounds. Although the medium MW fraction showed the highest reactivity for the majority of the investigated DBPs, the low MW fraction showed high reactivity for iodinated trihalomethanes during chlorination and for haloacetonitriles during chloramination. The high MW fraction had the lowest reactivity towards DBPs, which can have important implications for a drinking water treatment since this fraction is generally the most effectively removed by e.g. coagulation, while the more important fractions for DBP formation such as the medium and low MW compounds remain in the water until the disinfection step.

Persistent free radicals in natural organic matter activated by iron particles enhanced disinfection byproduct formation

The widespread presence of iron (Fe) particles and natural organic matter (NOM) in drinking water distribution systems (DWDS) can significantly affect tap water quality, contributing to aesthetic issues and potentially generating harmful disinfection byproducts (DBPs). This study revealed that Fe particles, when combined with humic acid (HA), substantially increased DBP formation during chlorination. Fe particles (particularly preformed Fe particles) significantly increased haloacetic acid (HAA) formation by activating the persistent free radicals (PFRs) in the HA. Compared with the control system without Fe particles, greater than 2 times of HAA increase were observed for the system with Fe pariticles. PFRs accumulated on Fe particle surface could generate hydroxyl radicals, facilitating the decomposition of HA into smaller molecules, which were more reactive with chlorine disinfectants, thus elevated the DBP formation including both known and unknown N-DBPs and Cl-DBPs. The DBP promotion effect of in-situ formed Fe particles was much less than that of preformed Fe particles although both in-situ formed and preformed Fe particles could accumulate PFRs from HA. In-situ formed particles primarily accumulated carbon-centered PFRs, while preformed particles accumulated oxygen-centered PFRs. To mitigate the Fe particle induced water quality risks, it is crucial to control iron pipe corrosion and iron release in DWDS. In addtion, the optimization of treatment processes such as coagulation and filtration to more completely remove NOM and Fe particles could help minimize the DBP formation.

Seasonal natural organic matter removal and implications for disinfection by-product formation at the Koka water treatment plant: Upper Awash, Ethiopia

ABSTRACT This study evaluated the seasonal performance of the Koka water treatment plant in removing natural organic matter (NOM) and the implications for disinfection by-product (DBP) formation potential. Raw and treated water samples were collected during the dry and wet seasons and analyzed using physicochemical parameters and fluorescence spectroscopy. The results revealed significant seasonal variations in raw water (RW) quality, with higher turbidity, pH, temperature, conductivity, total organic carbon (TOC), dissolved organic carbon (DOC), and UV254 absorbance during both seasons and across treatment processes. The NOM removal efficiency of the treatment plant was poor, with mean TOC removal of 46 and 43% and DOC removal of 15.8 and 15.2% during dry and wet seasons, respectively. The sedimentation unit demonstrated negative TOC removal, indicating NOM accumulation likely due to biochemical reactions in the unit. Fluorescence analysis and the correlation between specific ultraviolet absorbance (SUVA) and DBP formation potential suggest a higher risk of DBP formation in chlorinated drinking water. These findings highlight the influence of seasonal variations, RW quality, and the treatment process dynamics on the plant's performance in removing NOM. There is a need to implement adaptable strategies to enhance NOM removal, accounting for seasonal fluctuations in RW quality.

Insights into the degradation of sulfamethoxazole in UV/nitrite system: Mechanism, transformation process and disinfection by-products formation

Antibiotics removal from wastewater by conventional methods is limited, and their lingering presence in the environment can be hazardous to both human health and the ecosystem. Sulfamethoxazole (SMX) is one of the primary study subjects for antibiotic contamination, the degradation behavior, mechanism, transformation pathway, disinfection byproducts (DBPs) formation and variations about toxicity in UV/nitrite (NO2−) system were examined in this study. Compared with UV irradiation, the first-order reaction rate of SMX in UV/NO2− system rose from 0.0397 to 0.0528 min−1. This enhancement was linked to the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS), which promoted the degradation. SMX removal was more favorable under high dissolved oxygen (DO) levels and acidic conditions. When NO2− concentrations ranged from 0.1 to 1.0 mM, the higher concentration was more favorable to the degradation. The addition of 10 mM of HA and HCO3− hindered the oxidation of SMX by 48.46 % and 26.85 %, respectively, while the addition of Cl− slightly accelerated the decay of SMX at certain concentrations (5, 10 mM). The results of HPLC-ESI-MS and DFT computation suggested three possible SMX degradation pathways, including nitrification, hydroxylation, and bond breaking (such as sulfonamide cleavage). The primary DBPs produced by the post-chlorination of SMX in UV/NO2− system were TCM (87.02 % of the total detected DBPs) with a minor quantity of DBPs containing nitrogen. The presence of bromide ions (Br−) can lead to the production of highly toxic bromine containing disinfection by-products (Br-DBPs). After adding Br− in UV/NO2− system, 100 % of N-DBPs (TCNM, DCAN) and 93.43 % of C-DBPs (TCM, DCAA, TCAA) were converted to Br-DBPs (TBM, DBAA, TBAA, BDCM, DBCM), with the production of Br-DBPs accounting for 82.63 % of the detected DBPs.

Different impacts of natural and anthropogenic factors on dissolved organic matter chemistry in coastal rivers: Implications for water management

The chemical composition of dissolved organic matter (DOM) exerts significant influence on aquatic energy dynamics, pollutant transportation, and carbon storage, thereby playing pivotal roles in the local water quality and regional-global biogeochemical cycling. However, the effects of natural climate change and local human activities on watershed characteristics and in-river processes have led to uncertainties regarding their contributions to DOM chemistry in coastal rivers, creating challenges for effective water management and the study of organic matter cycling. In this investigation, we employed a combination of stable isotopic analysis, optical techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to elucidate the sources, optical properties, and molecular composition of DOM in three South China coastal rivers. Our results suggest that terrestrial DOM entering the three rivers through natural or anthropogenic pathways is gradually diluted by in situ primary production as it moves downstream, ultimately being influenced by seawater intrusion near the estuary. Additionally, terrestrial processes influenced by temperature likely govern DOC concentration, while seawater intrusion promotes the natural production of S-containing organic compounds. In contrast, human-altered landcover significantly impacts DOM molecular composition. Increased water areas lead to the enrichment of lignins with high disinfection byproduct formation potential, and agricultural residue burning appears to be the dominant source of pyrogenic DOM in these coastal rivers. Our distinct results suggest that the development of specific water management plans that consider the combined effects of temperature, seawater intrusion, landcover changes, and agricultural practices will be essential to ensure sustainable water resource.

Revisiting the chloramination of phenolic compounds: Formation of novel high-molecular-weight nitrogenous disinfection byproducts

Disinfection is critical for ensuring water safety; however, the potential risks posed by disinfection byproducts (DBPs) have raised public concern. Previous studies have largely focused on low-molecular-weight DBPs with one or two carbon atoms, leaving the formation of high-molecular-weight DBPs (HMW DBPs, with more than two carbon atoms) less understood. This study explores the formation of HMW DBPs during the chloramination of phenolic compounds using a novel approach that combines high-resolution mass spectrometry with density functional theory (DFT) calculations. For the first time, we identified nearly 100 previously unreported HMW nitrogenous DBPs (N-DBPs), with nearly half of those being halogenated N-DBPs. These N-DBPs were tentatively identified as heterocyclic (e.g., pyrrole and pyridine analogs) and coupling heterocyclic N-DBPs. Through detailed structure analysis and DFT calculations, the key formation steps of heterocyclic N-DBPs (monochloramine-mediated ring-opening reactions of halobenzoquinones) and new bonding mechanisms (C–N, C–O, and C–C bonding) of the coupling heterocyclic N-DBPs were elucidated. The selective formation of these novel N-DBPs was significantly influenced by factors such as contact time, monochloramine dosage, pH, and bromide concentration. Our findings emphasize the occurrence of diverse HMW heterocyclic N-DBPs, which are likely toxicologically significant, underscoring the need for further research to evaluate and mitigate their potential health risks in water disinfection.