Rapid Mass Conversion for Environmental Microplastics of Diverse Shapes.

Rivers have been recognized as the primary conveyors of microplastics to the oceans, and seaward transport flux of riverine microplastics is an issue of global attention. However, there is a significant discrepancy in how microplastic concentration is expressed in field occurrence investigations (number concentration) and in mass flux (mass concentration). Of urgent need is to establish efficient conversion models to correlate these two important paradigms. Here, we first established an abundant environmental microplastic dataset and then employed a deep neural residual network (ResNet50) to successfully separate microplastics into fiber, fragment, and pellet shapes with 92.67% accuracy. We also used the circularity (C) parameter to represent the surface shape alteration of pellet-shaped microplastics, which always have a more uneven surface than other shapes. Furthermore, we added thickness information to two-dimensional images, which has been ignored by most prior research because labor-intensive processes were required. Eventually, a set of accurate models for microplastic mass conversion was developed, with absolute estimation errors of 7.1, 3.1, 0.2, and 0.9% for pellet (0.50 ≤ C < 0.75), pellet (0.75 ≤ C ≤ 1.00), fiber, and fragment microplastics, respectively; environmental samples have validated that this set is significantly faster (saves ∼2 h/100 MPs) and less biased (7-fold lower estimation errors) compared to previous empirical models.

Advancing illicit connection diagnosis of urban stormwater pipes: Comprehensive analysis with EEM fluorescence spectroscopy.

Urban drainage systems are significant contributors to the issue of black-odorous water bodies. The current application of stormwater pipe inspection technologies faces substantial limitations, especially in industrial areas with diverse wastewater. This study introduced an innovative approach using excitation-emission matrix (EEM) fluorescence spectroscopy for rapid and accurate diagnosis, providing a new perspective for diagnosing illicit connections. In single wastewater-type areas like residential zones, the method achieved a remarkable 91.5 % accuracy solely through spectra observation and fluorescence peak intensity comparison, outperforming conventional NH3-N-based techniques, which reached an accuracy of only 68.1 %. For regions with complex wastewater scenarios, after EEM subtraction, the residual spectra can be roughly categorized into four distinctive categories based on characteristics. This provides a preliminary assessment and helps in initially identifying the types and sources of inflowing wastewater. Furthermore, the least squares (LS) method refines diagnosis results, offering calculated coefficients reflecting the probability and severity of suspected wastewater intrusion. Simulation experiments and field sample analyses validated the feasibility and accuracy of the EEM-based method, highlighting its advantages for diagnosing illicit connections in both single and mixed wastewater scenarios. The results can significantly narrow down the investigation scope and enhance the confirmation of wastewater sources, exhibiting promising application prospects.

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 ( [Formula: see text] ) were found to be 7-9 orders of magnitude higher than their neutral degradation rate constants ( [Formula: see text] ). 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.

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.

How to achieve adequate quenching for DBP analysis in drinking water?

Quenching is an important step to terminate disinfection during preparation of disinfected water samples for the analysis of disinfection byproducts (DBPs). However, an incomplete quenching might result in continued reactions of residual chlorine, whereas an excessive quenching might decompose target DBPs. Therefore, an adequate quenching to achieve simultaneous disinfection termination and DBP preservation is of particular importance. In this study, the two-stage reaction kinetics of chlorine and three commonly used quenching agents (i.e., ascorbic acid, sodium thiosulfate, and sodium sulfite) were determined. Stopping quenching during the first stage prevented interactions of residual chlorine with natural organic matter. Complete quenching was achieved by minimizing the quenching time for ascorbic acid and sodium sulfite, while limiting the quenching time to less than 3 min for sodium thiosulfate. At the optimized quenching times, the molar ratios (MRs) of quenching agent to chlorine were 1.05, 1.10, and 0.75 for ascorbic acid, sodium sulfite, and sodium thiosulfate, respectively. The destructive effects of the three quenching agents on total organic halogen (TOX) followed the rank order of ascorbic acid (33.7-64.8 %) < sodium sulfite (41.6-72.8 %) < sodium thiosulfate (43.3-73.2 %), and the destructive effects on aliphatic DBPs also followed the rank order of ascorbic acid (29.5-44.5 %) < sodium sulfite (34.9-51.9 %) < sodium thiosulfate (46.9-53.2 %). For total organic chlorine (TOCl) and aliphatic DBPs, the quenching behavior itself had more significant destructive effect than the quenching agent type/dose and quenching time, but for total organic bromine (TOBr), the destructive effect caused by quenching agent type/dose and quenching time was more significant. High-dose, long-duration quenching enhanced the reduction of TOX, but had little effect on aliphatic DBPs. Additionally, the three quenching agents reduced the levels of halophenols (except for tribromophenol), while maintained or increased the levels of tribromophenol, halobenzoic/salicylic acids, and halobenzaldehydes/salicylaldehydes. To achieve adequate quenching for overall DBP analysis in chlorinated water samples, it is recommended to use ascorbic acid at a quenching agent-to-chlorine MR of 1.0 for a quenching time of < 0.5 h.

Tracking the source of antibiotic resistome in the stormwater network drainage in the presence of sewage illicit connections.

Stormwater pipes are illicitly connected with sewage in many countries, which means that sewage enters stormwater pipes and the drainage is discharged to surface water without any treatment. Sewage contains more pathogens and highly risky antibiotic resistance genes (ARGs) than surface runoff. Therefore, sewage may alter the microbial and ARG compositions in stormwater pipe drainage, which in turn leads to an increased risk of resistance in surface water. However, the effects of sewage on ARGs in the drainage of stormwater networks have not been systematically studied. This study characterized the microbial and ARG composition of several environmental compartments of a typical stormwater network and quantified their contributions to those in the drainage. This network transported ARGs and microorganisms from sewage, sediments in stormwater pipes, and surface runoff into the drainage and thus into the river. According to metagenomic analysis, multidrug resistance genes were most abundant in all samples and the numbers and relative abundance of ARGs in the drainage collected during wet weather were comparable to that of sewage. The results of SourceTracker showed that the relative contribution of sewage was double that of rainwater and surface runoff in the drainage during wet weather for both microorganisms and ARGs. Desulfovibrio, Azoarcus, and Sulfuritalea were connected with the greatest number of ARGs and were most abundant in the sediments of stormwater pipes. Furthermore, stochastic processes were found to dominate ARG and microbial assembly, as the effects of high hydrodynamic intensity outweighed the effects of environmental filtration and species interactions. The findings of this study can increase our understanding of ARGs in stormwater pipe drainage, a crucial medium linking ARGs in sewage to environmental ARGs.

Identification of high oxygen-consuming substances in stormwater drainage systems illicitly connected with sewage system.

The dissolved oxygen content in water is an important indicator for assessing the quality of the water environment, and maintaining a certain amount of dissolved oxygen is essential for the healthy development of the ecological environment. When a water body is anoxic, the activity of anaerobic microorganisms increases and organic matter is decomposed to produce a large number of blackening and odorizing substances, resulting in black and odorous water bodies, which is a very common and typical phenomenon in China. Presently, there is still a relatively universal occurrence of illicitly connected stormwater and sewage pipes in the urban drainage pipe network in China, which makes oxygen-consuming substances be directly discharged into rivers through stormwater pipes and consume the dissolved oxygen in the water bodies, resulting in an oxygen deficiency of the water. This induces seasonal or year-round black and stink phenomena in urban rivers. Hence, identifying high oxygen-consuming substances, which lays the foundation for the subsequent removal of oxygen-consuming substances, is essential. Through a series of comparisons of water quality indicators and analysis of organic characteristics, it was found that the oxygen consumption capacity of domestic sewage was higher than that of industrial wastewater in the selected area of this study, and the oxygen-consuming substances of domestic sewage were small molecular amino acids. By comparing 20 conventional free amino acids, it was found that seven of them consumed oxygen easily, and compared with chemical oxygen consumption, biological oxygen consumption was in a leading position.

Alkaline chlorination of drinking water: A trade-off between genotoxicity control and trihalomethane formation.

The pH of chlorination is an important factor affecting the formation of disinfection byproducts (DBPs). In this study, we discovered that the genotoxicity induced by chlorination can be effectively reduced under alkaline conditions. As the pH of chlorination increased from 6.5 to 8.5, the genotoxicity of investigated waters reduced by ∼30-90 %. By assessing the genotoxicity of the mixture of measured DBPs, it was found that the contribution of measured DBPs to the overall genotoxicity was lower than 5 %, and the significant reduction of genotoxicity was largely associated with unknown DBPs. The result of Pearson's correlation analysis indicated that humified organics and soluble microbial byproducts were likely responsible for the genotoxicity, and their derived genotoxic compounds (i.e., unknown DBPs) tended to decompose during alkaline chlorination. However, the control of genotoxicity by alkaline chlorination was achieved at the expense of promoting trihalomethane (THM) formation. The highest genotoxicity reduction (93 %) was observed for chlorinated granular activated carbon-treated waters, but the formation of THMs was promoted to a level approaching that in untreated waters. The inconsistent trend of overall genotoxicity and THM concentration during alkaline chlorination suggested the inadequacy of THMs as metric for DBP exposure, and considerations should also be given to the toxicity of bulk water in addition to regulated DBPs.

Residual chlorine persistently changes antibiotic resistance gene composition and increases the risk of antibiotic resistance in sewer systems.

During the COVID-19 pandemic, excessive amounts of disinfectants and their transformation products entered sewer systems worldwide, which was an extremely rare occurrence before. The stress of residual chlorine and disinfection by-products is not only likely to promote the spread of antibiotic resistance genes (ARGs), but also leads to the enrichment of chlorine-resistant bacteria that may also be resistant to antibiotics. Therefore, the potential impact of such discharge on ARG composition should be studied and the health risks should be assessed. Thus, this study combined high-throughput 16S rRNA gene amplicon sequencing and metagenomic analysis with long-term batch tests that involved two stages of stress and recovery to comprehensively evaluate the impact of residual chlorine on the microbial community and ARG compositions in sewer systems. The tests demonstrated that the disturbance of the microbial community structure by residual chlorine was reversible, but the change in ARG composition was persistent. This study found that vertical propagation and horizontal gene transfer jointly drove ARG composition succession in the biofilm, while the driving force was mainly horizontal gene transfer in the sediment. In this process, the biocide resistance gene (BRG) subtype chtR played an important role in promoting co-selection with ARGs through plasmids and integrative and conjugative elements. Moreover, it was further shown that the addition of sodium hypochlorite increased the risk of ARGs to human health, even after discontinuation of dosing, signifying that the impact was persistent. In general, this study strengthens the co-selection theory of ARGs and BRGs, and calls for improved disinfection strategies and more environmentally friendly disinfectants.

Total organic halogen (TOX) in drinking water: Occurrence, correlation analysis, and precursor removal during drinking water treatment.

Total organic halogen (TOX) in drinking water provides a measurement of the overall organic halogenated disinfection by-products (DBPs) formed during disinfection. Yangtze River Delta is one of the regions with the highest population density, the fastest urbanization process, and the most severe water pollution in China. Collecting water samples from full-scale drinking water treatment plants (DWTPs) in this region, this study firstly surveyed TOX occurrence in drinking water. Besides, the correlation of TOX formation potential (TOXFP) and trihalomethane formation potential (THMFP) with general water quality parameters (e.g., dissolved organic carbon [DOC], UV254, and specific ultraviolet absorbance) and the removal efficiencies of TOX precursors by different water treatment processes were also investigated. TOX levels in DWTP effluents (i.e., finished water) ranged from 29 to 165 µg/L (median 67 µg/L), and those in simulated distribution system waters ranged from 101 to 276 µg/L (median 158 µg/L). There were generally higher linear regression coefficient values for raw water (R2 = 0.51-0.88) than for treated water (R2 = 0.33-0.64) in terms of the relationship between DBP formation potentials and general parameters. However, a relatively stronger correlation between THMFP and TOXFP was observed for treated water (R2 = 0.80, p < 0.001) than for raw water (R2 = 0.64, p < 0.001). The overall treatment efficiencies of investigated parameters in DWTPs generally followed the order of UV254 > DOC > TOX precursors > THM precursors. Notably, the overall removal rates of DOC and TOX precursors in summer (averaging 59 % and 54 %, respectively) were obviously higher than those in winter (averaging 39 % and 38 %, respectively), which was assumed to be related to the seasonal variation of bioactivity in sand filter. These results could expand the knowledge of TOX in drinking water, and provide valuable perspectives to water industry and DBP research.

Simultaneous modulation of CHO cell cytotoxicity, turbidity, and DOC by coagulation with or without pre-oxidation in water from the Pearl River Delta region, China.

Coagulation with or without pre-oxidation are important drinking water treatment processes. However, the efficacy of these processes in mitigating water toxicity remains unknown. To further improve drinking water safety, we employed water from the Pearl River Delta region of southern China to investigate a treatment approach consisting of coagulation with or without pre-oxidation to simultaneously modulate health-relevant cytotoxicity to CHO cells, on top of the conventional foci of turbidity and dissolved organic carbon (DOC) during water treatment. Three coagulants (two aluminum-based and one iron-based salts) and three pre-oxidants (ozone, permanganate, and peroxymonosulfate) were studied. For coagulation without pre-oxidation, intermediate coagulant doses and pH reached optimum cytotoxicity to CHO cells, turbidity, and DOC control simultaneously. Introducing oxidants reduced cytotoxicity to CHO cells significantly, enhanced by increasing oxidant concentrations and pre-oxidation duration. The cytotoxicity to CHO cells mitigation capabilities of three pre-oxidants were: ozone > peroxymonosulfate > potassium permanganate. Modulation of water cytotoxicity to CHO cells was mostly attributable to controlling DOC (specifically humic-acid like substances, tyrosine, tryptophan). However, the addition of pre-oxidants led to significant shifts in water cytotoxicity to CHO cells forcing drivers, rendering humic-acid like substances the sole decisive cytotoxicity-inducing fluorophores. For the first time, 'sweet spots' were identified to simultaneously monitor cytotoxicity to CHO cells alongside turbidity and DOC. These methods better modulate water cytotoxicity to CHO cells without sacrificing conventional water treatment goals while shedding light onto the mechanisms behind.

Disinfection by-product precursors introduced by sandstorm events: Composition, formation characteristics and potential risks.

Sandstorms, a natural meteorological event, occur repeatedly during the dry season and can accumulate large amounts of natural/anthropogenic pollutants during the deposition process, potentially introducing disinfection by-product (DBP) precursors into surface waters. In this study, the characteristics of sandstorm-derived dissolved organic matter (DOM) and its DBP formation potential were elucidated. Overall, sandstorm-derived DOM mainly consisted of low-molecular-weight, low-aromaticity, high-nitrogen organic matter, with a dissolved organic carbon (DOC) release yield of 14.4 mg-DOC/g. The halogenated DBP formation potential (calculated as total organic halogen) of sandstorm-derived DOM was comparable to that of surface water, while the normalized DBP-associated toxicity was 1.96 times higher. Similar to DOM introduced by other depositional pathways, sandstorm-derived DOM also had higher yields of highly cytotoxic DBPs (haloacetaldehydes [HALs], haloacetonitriles [HANs] and halonitromethanes [HNMs]). The average atmospheric deposition flux for DOM during the sandstorm event (50.4 ± 2.1 kg km-2 day-1) was 6.95 times higher than that of dry deposition, indicating a higher probability of contaminant input. Simultaneously, the estimation revealed that the sandstorm will increase the formation potential of toxicity forcing agents, such as HALs, HANs and HNMs, in surface water by 3.87%, 2.39% and 9.04%, respectively. Considering the high frequency of sandstorm events and the sorption of other organic pollutants by sand and dust, the impact of sandstorms on surface water quality should be of concern.

Leaching of organic matter and iodine, formation of iodinated disinfection by-products and toxic risk from Laminaria japonica during simulated household cooking.

Iodinated disinfection by-products (I-DBPs) exhibited potential health risk owing to the high toxicity. Our recent study demonstrated that I-DBPs from Laminaria japonica (Haidai), the commonly edible seaweed, upon simulated household cooking condition were several hundred times more than the concentration of drinking water. Here, the characterization of Haidai and its leachate tandem with the formation, identification and toxicity of I-DBPs from the cooking of Haidai were systemically investigated. The dominant organic matter in Haidai leachate were polysaccharides, while the highest iodine specie was iodide (∼90% of total iodine). Several unknown I-DBPs generated from the cooking of Haidai were tentatively proposed, of which 3,5-diiodo-4-hydroxybenzaldehyde was dominant specie. Following a simulated household cooking with real chloraminated tap water, the presence of Haidai sharply increased aggregate iodinated trihalomethanes, iodinated haloacetic acids, and total organic iodine concentrations to 97.4 ± 7.6 µg/L,16.4 ± 2.1 µg/L, and 0.53 ± 0.06 mg/L, respectively. Moreover, the acute toxicity of Haidai soup to Vibrio qinghaiensis sp.-Q67 was around 7.3 times higher than that of tap water in terms of EC50. These results demonstrated that the yield of I-DBPs from the cooking of Haidai and other seaweed should be carefully considered.

Zerovalent Iron/Cu Combined Degradation of Halogenated Disinfection Byproducts and Quantitative Structure-Activity Relationship Modeling.

Previous studies have reported that zerovalent iron (ZVI) can reduce several aliphatic groups of disinfection byproducts (DBPs) (e.g., haloacetic acids and haloacetamides) effectively, and the removal efficiency can be significantly improved by metallic copper. Information regarding ZVI/Cu combined degradation of different types of halogenated DBPs can help understand the fate of overall DBPs in drinking water distribution and storage systems consisting of unlined cast iron/copper pipes and related potential control strategies. In this study, we found that, besides aliphatic DBPs, many groups of new emerging aromatic DBPs formed in chlorinated and chloraminated drinking water can be effectively degraded by ZVI/Cu; meanwhile, total organic halogen and total ion intensity were reduced significantly after treatment. Moreover, a robust quantitative structure-activity relationship model was developed and validated based on the ZVI/Cu combined degradation rate constants of 14 typical aromatic DBPs; it can predict the degradation rate constants of other aromatic DBPs for screening and comparative purposes, and the optimized descriptors indicate that DBPs possessing a lower value of the lowest unoccupied molecular orbital energy and a higher value of dipole moment tend to present higher degradation rate constants. In addition, toxicity data of 47 DBPs (belonging to 18 groups) were predicted by two previously established toxicity models, demonstrating that, although most DBPs exhibit higher toxicity than their dehalogenated products, some DBPs show lower toxicity than their lowly halogenated analogs.

Reevaluation for UV photolysis of Fe(III) inducing tetracycline abatement: Overlooked significance of complexation-assistance in environmental fates of antibiotics.

Interaction of antibiotics with metal ions in aquatic environments, commonly occurring to form complexes, may affect the migration, transformation and reactivity of residual antibiotics. This study demonstrates the photolysis of Fe(III) by UV irradiation at pH 3.5, as an advanced oxidation process, to produce •OH for the abatement of a common broad-spectrum antibiotic compound, tetracycline (TET). The dimethylamino (-N(CH3)2) and hydroxyl (-OH) groups of TET were determined as the binding sites for the complexation with Fe(III) via a series of novel characterization approaches. The complexation stoichiometry of Fe(III)-TET complexation, including the complexation ratio, constants and percentages, was determined via a complexometric titration based on the UV differential spectroscopy. The complexation constant was determined to be 21,240 ± 1745 L·mol-1 under the designed conditions. Complexation of TET with Fe(III) enhanced its degradation in the UV/Fe(III) process, through the promotion of the •OH generation by inhibiting hydrolysis-precipitation process of Fe(III) and enhancing Fe(III)/Fe(II) cycle and the acceleration of mass transfer between •OH and TET. This finding provides new insights into the role of complexation in the fate of residual antibiotics in the UV/Fe(III) process. The reduced overall ecotoxicity during the TET abatement, evaluated by the toxicity variation through ECOSAR program, provides the UV/Fe(III) process with a theoretical feasibility for water decontamination in actual applications.

Direct discharge of sewage to natural water through illicitly connected urban stormwater systems: An overlooked source of dissolved organic matter.

The illicit connection of sewage pipes to stormwater pipes commonly occurs in urban stormwater systems. This brings problems that sewage might be directly discharges into natural water and even drinking water sources without treatment, posing risks to ecological safety. Sewage contains various unknown dissolved organic matter (DOM), which could react with disinfectants and lead to the formation of carcinogenic disinfection byproducts (DBPs). Thus, understanding the impacts of illicit connections on downstream water quality is of significance. This study firstly investigated the characteristics of DOM using fluorescence spectroscopy and the formation of DBPs after chlorination in an urban stormwater drainage system in the case of illicit connections. The results found that the concentrations of dissolved organic carbon and dissolved organic nitrogen ranged from 2.6 to 14.9 mg/L and from 1.8 to 12.6 mg/L, respectively, with the highest levels occurring at the illicit connection points. Concerning DBP precursors, pipe illicit connections introduced considerable precursors of highly toxic haloacetaldehydes and haloacetonitriles into the stormwater pipes. Furthermore, illicit connections introduced more contents of tyrosine-like and tryptophan-like aromatic proteins, which may be related to foods, nutrients, personal care products, etc. in the untreated sewage. This indicated that the urban stormwater drainage system was a significant input source of DOM and DBP precursors to natural water. The results of this study are of great significance for protecting the security of water sources and promoting the sustainability of urban water environment.

Adsorption of highly toxic chlorophenylacetonitriles on typical microplastics in aqueous solutions: Kinetics, isotherm, impact factors and mechanism.

Microplastics (MPs) widely exist in all kinds of water bodies. The physical and chemical properties of MPs make them easy to become the carrier of pollutants, but the interaction between disinfection by-products (DBPs) and MPs has not been studied yet. In this study, the occurrence of emerging high-toxic chlorophenylacetonitriles (CPANs) in wastewater treatment plant (WWTP) effluents was determined. CPANs ubiquitously existed in WWTP effluents, and the concentration ranged from 88 ± 5 ng/L to 219 ± 16 ng/L. The typical MPs (i.e., polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS)) were selected to study their adsorption of CPANs. Adsorption kinetics and isotherm analysis were carried out. The maximum Langmuir adsorption capacities were 8.602 ± 0.849 to 9.833 ± 0.946 µg/g for PE, 13.340 ± 1.055 to 29.405 ± 5.233 µg/g for PET, and 20.537 ± 1.649 to 43.597 ± 1.871 for PS. Dichloro-CPANs had higher adsorption capacity than monochloro-CPANs. After that, the specific surface area, contact angle, FTIR spectrum, crystallinity, and glass transition temperature (Tg) of MPs were measured. Based on the analysis of the properties of both MPs and CPANs, the mechanism of adsorption was studied. The adsorption of CPANs on PE was mainly affected by pore-filling and van der Waals force. In addition to these two factors, the adsorption of PET was also affected by hydrophobic interaction. Due to the substituents on the benzene ring, there was π-π interaction between PS and CPANs, which might be the reason why PS had the highest adsorption capacity for CPANs. Finally, the effects of pH and dissolved organic matter were studied, and their effects were relatively limited. The results indicated that MPs may adsorb CPANs in actual WWTP effluents, and special attention should be paid to the possible impacts on the aquatic environment caused by the transfer of CPANs on MPs.

Effects of UV-based oxidation processes on the degradation of microplastic: Fragmentation, organic matter release, toxicity and disinfection byproduct formation.

The occurrence and transformation of microplastics (MPs) remaining in the water treatment plants has recently attracted considerable attention. However, few efforts have been made to investigate the behavior of dissolved organic matter (DOM) derived from MPs during oxidation processes. In this study, the characteristics of DOM leached from MPs during typical ultraviolet (UV)-based oxidation was focused on. The toxicity and disinfection byproduct (DBP) formation potentials of MP-derived DOM were further investigated. Overall, UV-based oxidation significantly enhanced the aging and fragmentation of highly hydroscopic MPs. The mass scales of leachates to MPs increased from 0.03% - 0.18% at initial stage to 0.09% - 0.71% after oxidation, which were significantly higher than those leached by natural light exposure. Combined fluorescence analysis with high resolution mass spectrometer scan confirmed that the dominant MP-derived DOM are chemical additives. PET-derived DOM and PA6-derived DOM showed inhibition of Vibrio fischeri activity with corresponding EC50 of 2.84 mg/L and 4.58 mg/L of DOC. Bioassay testing with Chlorella vulgaris and Microcystis aeruginosa showed that high concentrations of MP-derived DOM inhibited algal growth by disrupting the cell membrane permeability and integrity. MP-derived DOM had a similar chlorine consumption (1.63 ± 0.41 mg/DOC) as surface water (1.0 - 2.0 mg/DOC), and MP-derived DOM mainly served as precursors for the investigated DBPs. Contrary to the results of previous studies, the DBP yields from MP-derived DOM were relatively lower than those of aquatic DOM under simulated distribution system conditions. This suggests that MP-derived DOM itself rather than serving as DBP precursor might be potential toxic concern.

Effects of phosphate addition on the removal of disinfection by-product formation potentials by biological activated carbon filtration.

In drinking water treatment plants (DWTPs), the widely used biological activated carbon filters (BACFs), as the last barrier before disinfection, can remove dissolved organic matter (DOM) known as precursors of disinfection by-products (DBPs). Whether phosphate addition can improve water purification and DBP control of BACFs is still controversial. This study investigated short-term and long-term effects of phosphate addition on controlling DBP formation potentials (FPs) by BACFs via column and batch experiments. The BAC columns presented good water purification performance: they removed around 50 % DOM, nearly all fulvic acid-likes and humic acid-likes as well as 5 %-70 % chlor(am)innated THM4, HAA9 and HAN4 FPs (except chloraminated THM4 FPs)， which was mainly contributed by aerobic bacteria not anoxic bacteria. Phosphate addition within 7-14 days further improved removals of DOM, aromatic organics, fluorescence fractions in DOM as well as HAA9 and HAN4 FPs (especially TCAA FP and TCAN FP) to different extent. However, this improvement did not last longer, and removals of DOM, aromatic organics, two fluorescence fractions (soluble microbial byproduct-likes and humic acid-likes) and DBP FPs decreased despite long-term phosphate addition. Oxic and anoxic batch experiments showed that the positive response of water purification to short-term phosphate addition was also mainly attributed to aerobic bacteria and not to anoxic bacteria. For example, the former decreased DOM and DBP FPs, while the latter increased protein- and tryptophan-like substances as well as chloraminated THM4 FPs. Phosphate addition resulted in EPS increase in anoxic reactors and decrease in oxic reactors. These results indicated that a high dissolved oxygen in BACFs may be helpful for water purification and DBP control. Overall, short-term phosphate addition into phosphorus-limited water is beneficial for BACFs to control DBPs while long-term addition has no effect. Therefore, an intermittent phosphate addition into BACFs is suggested to control DBPs in DWTPs.

Degradation kinetics and formation of regulated and emerging disinfection by-products during chlorination of two expectorants ambroxol and bromhexine.

Ambroxol hydrochloride (AMB) and bromhexine hydrochloride (BRO) are classic expectorants and bronchosecretolytic pharmaceuticals. In 2022, both AMB and BRO were recommended by medical emergency department of China to alleviate cough and expectoration for symptoms caused by COVID-19. The reaction characteristics and mechanism of AMB/BRO with chlorine disinfectant in the disinfection process were investigated in this study. The reaction of chlorine with AMB/BRO were well described by a second-order kinetics model, first-order in both AMB/BRO and chlorine. The second order rate reaction constant of AMB and BRO with chlorine at pH 7.0 were 1.15 × 102 M-1s-1 and 2.03 × 102 M-1s-1, respectively. During chlorination, a new class of aromatic nitrogenous disinfection by-products (DBPs) including 2-chloro-4, 6-dibromoaniline and 2, 4, 6-tribromoaniline were identified as the intermediate aromatic DBPs by gas chromatography-mass spectrometry. The effect of chlorine dosage, pH, and contact time on the formation of 2-chloro-4, 6-dibromoaniline and 2, 4, 6-tribromoaniline were evaluated. In addition, it was found that bromine in AMB/BRO were vital bromine source to greatly promote the formation of classic brominated DBPs, with the highest Br-THMs yields of 23.8% and 37.8%, respectively. This study inspired that bromine in brominated organic compounds may be an important bromine source of brominated DBPs.