Boosting the Performance of Nanofiltration Membranes in Removing Organic Micropollutants: Trade-Off Effect, Strategy Evaluation, and Prospective Development.

In view of the high risks brought about by organic micropollutants (OMPs), nanofiltration (NF) processes have been playing a vital role in advanced water and wastewater treatment, owing to the high membrane performance in rejection of OMPs, permeation of water, and passage of mineral salts. Though numerous studies have been devoted to evaluating and technically enhancing membrane performance in removing various OMPs, the trade-off effect between water permeance and water/OMP selectivity for state-of-the-art membranes remains far from being understood. Knowledge of this effect is significant for comparing and guiding membrane development works toward cost-efficient OMP removal. In this work, we comprehensively assessed the performance of 88 NF membranes, commercialized or newly developed, based on their water permeance and OMP rejection data published in the literature. The effectiveness and underlying mechanisms of various modification methods in tailoring properties and in turn performance of the mainstream polyamide (PA) thin-film composite (TFC) membranes were quantitatively analyzed. The trade-off effect was demonstrated by the abundant data from both experimental measurements and machine learning-based prediction. On this basis, the advancement of novel membranes was benchmarked by the performance upper-bound revealed by commercial membranes and lab-made PA membranes. We also assessed the potentials of current NF membranes in selectively separating OMPs from inorganic salts and identified the future research perspectives to achieve further enhancement in OMP removal and salt/OMP selectivity of NF membranes.

Kinetics and mechanism of haloacetaldehyde formation from the reaction of acetaldehyde and chlorine.

Haloacetaldehydes (HALs) are the third prevalent group of disinfection by-products (DBPs) by weight in drinking water, and their cytotoxicity and genotoxicity are higher than regulated DBPs. In order to understand their formation mechanism during chlorination and ozonation-chlorination, this study examined the reaction kinetics of chloral hydrate (CH), dichloroacetaldehyde (DCA), chloroacetaldehyde (CA) and acetaldehyde by chlorine at different pH values and chlorine doses. The results showed that the reaction rate constants increased with pH and chlorine dose, except that the degradation of CH would not be affected by the presence of free chlorine. At the same pH and chlorine dose, the half-lives of CH, DCA, CA and acetaldehyde were in the order of CH > acetaldehyde â‰« DCA > CA. A kinetic model used to predict the formation of HALs and chloroform during chlorination of acetaldehyde was developed, and the predicted data fitted well with the measured data. As pre-ozonation could oxidize natural organic matter to acetaldehydes, the concentration of acetaldehyde formed after pre-ozonation was used to calculate the HAL yields during ozonation-chlorination by the kinetic model, which fitted the experimental results well. The kinetic model elucidated that the formation mechanism of HALs was a stepwise substitution process on the α-hydrogen of acetaldehyde during chlorination.

Study on the influence of operational and management processes of a water reclamation plant since COVID-19 situation.

Reusing treated wastewater can effectively alleviate water shortages and water contamination problems but depends on ensuring the safety of the reclaimed water that is produced. The operating and management conditions for water reclamation plants in China have been changed since the outbreak of the COVID-19 epidemic in China at the end of 2019 to prevent emerging viruses being spread through wastewater treatment processes and the reclaimed water that is produced. Removal of pathogens and trace organic compounds (e.g., pharmaceuticals and personal care products and endocrine disrupting chemicals) in a real water reclamation plant after the start of COVID-19 epidemic was studied. Disinfection byproduct formation caused by chlorine being added to meet disinfection requirements was also assessed. The pathogenic microorganism concentrations in effluent were <2 (most probable number)/L, and the removal rates for most trace organic compounds were >80% when advanced treatments were performed using ozone, ultraviolet light, and chlorine doses of 2 mg/L, 20.5 mJ/cm2, and 2-3 mg/L, respectively. The main disinfection byproduct produced at a chlorine dose of 2 mg/L and a residence time of 1 h was chloroform (at concentrations <15 µg/L). The results indicated that the water reclamation processes with modified conditions gave high pathogen and trace organic compound removal rates and reasonably well-controlled disinfection byproduct concentrations.

Optimization of ozone dosage in an ozone contact tank using a numerical model.

Ozone has been widely applied in drinking water and wastewater treatment plants, and it is essential to determine the ozone dosage and its ratio in ozone contact tank to increase the ozone absorption and utilization rates. Batch experiments were performed to determine the first-order reaction rate coefficient of ozone (k1) in different raw water qualities. Results showed that k1 had an exponential decaying relationship with the ozone consumption amount (ΔO3). Based on the ozone mass transfer and decomposition kinetics, a numerical model was developed to optimize the total ozone dosage and its ratio in three aeration parts by calculating the ozone absorption and utilization rates in an ozone contact tank. The ozone absorption rate was little affected by the water quality, and an even distribution of ozone could greatly increase the ozone absorption rate. However, the ozone utilization rate was tightly related with the water quality. For waters that consumed ozone quickly, ozone should be dosed equally in three aeration parts to increase the ozone utilization rate up to 94.3%. Otherwise, more ozone should be dosed in the first aeration part. An increase in ozone utilization rate would induce an increase in the degree of water purification. This model could give theoretical support for the determination of ozone dosage and its ratio in water treatment plants rather than experience.

A Facile and Scalable Fabrication Procedure for Thin-Film Composite Membranes: Integration of Phase Inversion and Interfacial Polymerization.

Conventional dense thin-film composite (TFC) membranes evince a universally low water permeability, the increase of which typically relies on introducing additional transport channels based on intricate steps within a membrane preparation process. In this study, we reported a novel and simplified procedure for the fabrication of high-performance TFC membranes. Specifically, the dissolution of aqueous monomers in the casting solution was utilized for the following interfacial polymerization (IP). Since the monomers diffused to the water bath during phase inversion, the control of precipitation time enabled an effective regulation of the monomer concentration in the formed polymeric substrates, where the IP reaction was initiated by the addition of the organic phase. The entire and uniform embedment of aqueous monomers inside the substrates contributed to the formation of ultrathin and smooth selective layers. An excellent separation performance (i.e., water permeability: 34.7 L m-2 h-1 bar-1; Na2SO4 rejection: ∼96%) could be attained using two types of aqueous monomers (i.e., piperazine and ß-cyclodextrin), demonstrating the effectiveness and universality of this method. Compared to the conventional immersion-based process, this novel procedure shows distinct advantages in reducing monomer usage, shortening the production cycle, and achieving a more superior membrane performance, which is highly promising for large-scale membrane manufacture.

Synergistic effects of combining ozonation, ceramic membrane filtration and biologically active carbon filtration for wastewater reclamation.

In this study, we proposed to apply an integrated process which is comprised of in situ ozonation, ceramic membrane filtration (CMF) and biologically active carbon (BAC) filtration to wastewater reclamation for indirect potable reuse purpose. A pilot-scale (20 m3/d) experiment had been run for ten months to validate the prospect of the process in terms of treatment performance and operational stability. Results showed that the in situ O3 + CMF + BAC process performed well in pollutant removal, with chemical oxygen demand, ammonia, nitrate nitrogen, total phosphorus and turbidity levels in the treated water being 5.1 ±â€¯0.9, 0.05 ±â€¯0.01, 10.5 ±â€¯0.8, <0.06 mg/L, and <0.10 NTU, respectively. Most detected trace organic compounds were degraded by>96%. This study demonstrated that synergistic effects existed in the in situ O3 + CMF + BAC process. Compared to pre-ozonation, in situ ozonation in the membrane tank was more effective in controlling membrane fouling (maintaining operational stability) and in degrading organic pollutants, which could be attributed to the higher residual ozone concentration in the tank. Because of the removal of particulate matter by CMF, water head loss of the BAC filter increased slowly and prolonged the backwashing interval to 30 days. BAC filtration was also effective in removing ammonia and N-nitrosodimethylamine from the ozonated water.

The haloacetic acid leap in effluent of a biologically active carbon filter experiencing a disinfectant switch.

Water utilities must disinfect their water despite the formation of carcinogenic disinfection byproducts (DBPs) such as haloacetic acids (HAAs) upon chlorination. Although employment of a biologically active carbon (BAC) filtration process is able to reduce the HAA level preventively by removing the HAA precursors and correctively by removing the already-formed HAAs, this research reported an HAA leap in a bench-scale BAC filter effluent upon a disinfectant switch from chlorine to chloramine, posing a pressure of meeting the stringent HAA regulations. The HAA6 (sum of six HAAs) tripled from a 5 µg/L base level to a maximum of 17 µg/L during progressive switches with 3 chloramine doses at 5, 25, and 50 mg/L. Dichloroacetic acid (DCAA) accounted for the majority of the leap, which also influenced the bromine substitution factor during the HAA formation. Filtration of distilled water using heat-deactivated media evidenced slight HAA desorption and suggested potential roles of soluble microbial products from biofilms as new HAA precursors for a real BAC filter experiencing a disinfectant switch.

Mechanism of ozonation enhanced formation of haloacetaldehydes during subsequent chlorination.

Haloacetaldehydes (HAs) are the third prevalent group of disinfection by-products of great health concern. A bench-scale study was performed to investigate the formation and speciation of HAs in raw and treated waters after chlorination and ozonation-chlorination. Pre-ozonation resulted in enhanced HA formation during subsequent chlorination, and the HA yields from ozonation-chlorination were 1.66 and 1.63 times higher than that from chlorination of raw and treated waters. The mechanism about the increase of HA formation during ozonation-chlorination was systematically investigated in this study. The results showed that acetaldehyde formed after ozonation was the dominant precursor for the enhanced HA formation during subsequent chlorination. Increase in pH and chlorine dose increased HA formation during acetaldehyde chlorination. Based on the kinetic studies on the HA formation during acetaldehyde chlorination and the HA stabilities with and without free chlorine, it was found that chlorine was incorporated into the α-hydrogen in acetaldehyde to form a sequence of mono-, di- and tri-chloroacetaldehyde. During this process, these three chlorinated acetaldehydes would also undergo base-catalyzed hydrolysis through decarburization and dehalogenation pathways. This study elucidated that acetaldehyde formed after ozonation resulted in the increase of HA formation during subsequent chlorination. This study also revealed the formation pathway of HA during chlorination of acetaldehyde, which would help to minimize HA formation at drinking water plants.

Impacts of Metal-Organic Frameworks on Structure and Performance of Polyamide Thin-Film Nanocomposite Membranes.

Metal-organic frameworks (MOFs), a class of hybrid organic-inorganic materials, have recently attracted tremendous interests in the fabrication of thin-film nanocomposite (TFN) membranes with exceptional permselectivity. However, the structure-performance relationship of such membranes, which is a function of both MOF type and membrane fabrication procedure, has not been elucidated in the literature. In this study, three types of hydro-stable MOFs, namely, MIL-53(Al), NH2-UiO-66, and ZIF-8, were used to fabricate TFN nanofiltration membranes via both blending (BL) and preloading interfacial polymerization methods. Results show that the incorporation of MOFs could enhance water permeability of TFN membranes to 7.2 L/(m2·h·bar) at most ( TFNNH2-UiO-66-BL-0.10%), about 1.3 times of the corresponding thin-film composite membranes, without sacrificing their selectivity to reject NaCl (>40%) and xylose (>65%). Membrane characterization revealed that MOFs decreased the cross-linking degree while increasing the membrane thickness, surface negative charge, and roughness of the polyamide active layer. MIL-53(Al) were found to bind with polyamide via reacting with piperazine, whereas weaker polyamide-MOF interactions were observed for NH2-UiO-66 and ZIF-8. This difference, along with the hydrophilicity of MOF particles, explained the varied permselectivity of different TFN membranes. Compared to pristine polyamide membranes, the TFN membranes demonstrated higher or comparable efficiencies in removing a set of six pharmaceuticals (PhACs), which were determined by the molecular properties of PhACs and membrane structure. The findings of this study deepen our understanding of the roles that MOFs play in regulating membrane performance, promoting molecular design of MOF-incorporated TFN membranes via precise control of MOF-polymer interactions.

Enhanced organic removal for shale gas fracturing flowback water by electrocoagulation and simultaneous electro-peroxone process.

Colloids and organics in shale gas fracturing flowback water (SGFFW) during shale gas extraction are of primary concerns. Coagulation combined with oxidation might be a promising process for SGFFW treatment. In this study, a novel electrocoagulation-peroxone (ECP) process was developed for SGFFW treatment by simultaneous coagulation and oxidation process with a Al plate as the anode and a carbon-PTFE gas diffusion electrode as the cathode, realizing the simultaneous processes of coagulation, H2O2 generation and activation by O3 at the cathode. Compared with electrocoagulation (EC) and peroxi-electrocoagulation (PEC), COD removal efficiency mainly followed the declining order of ECP, PEC and EC under the optimal current density of 50 mA cm-2. The appearance of medium MW fraction (1919 Da) during ozonation and PEC but disappearance in ECP indicated that these intermediate products couldn't be degraded by ozonation and PEC but could be further oxidized and mineralized by the hydroxyl radical produced by the cathode in ECP, demonstrating the hydroxyl radical might be responsible for the significant enhancement of COD removal. The pseudo-first order kinetic model can well fit ozonation and EC process but not the PEC and ECP process due to the synthetic effect of coagulation and oxidation. However, the proposed mechanism based model can generally fit ECP satisfactorily. The average current efficiency for PEC was 35.4% and 12% higher than that of ozonation and EC, respectively. This study demonstrated the feasibility of establishing a high efficiency and space-saving electrochemical system with integrated anodic coagulation and cathodic electro-peroxone for SGFFW treatment.

Formation of disinfection by-products under influence of shale gas produced water.

Accidental spills and surface discharges of shale gas produced water could contaminate water resources and generate health concerns. The study explored the formation and speciation of disinfection by-products (DBPs) during chlorination of natural waters under the influence of shale gas produced water. Results showed the presence of produced water as low as 0.005% changed the DBP profile measurably. A shift to a more bromine substitution direction for the formation of trihalomethanes, dihaloacetic acids, trihaloacetic acids, and dihaloacetonitriles was illustrated by exploring the individual DBP species levels, bromine substitution factors, and DBP species fractions, and the effect was attributable to the introduction of bromide from produced water. The ratio of dichloroacetic and trichloroacetic acids also increased, which was likely affected by different bromination degrees at elevated bromide concentrations. Increasing blend ratios of produced water enhanced the formation of DBPs, especially the brominated species, while such negative effects could be alleviated by pre-treating the produced water with ozone/air stripping to remove bromide. The study advances understandings about the impacts of produced water spills or surface discharges regarding potential violation of Stage 2 DBP rules at drinking water treatment facilities.

Impacts of shale gas production wastewater on disinfection byproduct formation: An investigation from a non-bromide perspective.

The rapid rise of shale gas development has triggered environmental and human health concerns due to its impacts on water resources, especially on disinfection byproduct (DBP) formation upon chlorination. Despite the recently reported results on bromide, the effects of non-bromide ions in production wastewater at extremely high levels are vaguely defined. In this study, we investigated the effects of production wastewater, with bromide and non-bromide species, on the formation of DBPs when production wastewater was spiked into surface waters at various percentages. Results showed that the introduction of debrominated production wastewater led to increased formation of some chlorinated DBP species in selected surface water and wastewater. As the spiking percentage of debrominated production wastewater increased, the chlorinated DBP species increased. The contributions of individual cations to DBP formation followed a sequence of magnesium > calcium > barium at 0.10% spiking percentage due to the different catalytic effects of their chelates with organic precursors. The study of anions suggested that the discharge of treated production wastewater containing elevated sulfate may further enhance DBP formation. The significance of this study lies in the fact that in addition to bromide concerns from production wastewater, non-bromide species also contributed to DBP formation. The gas production wastewater management decision should consider the negative impacts from both bromide and non-bromide species to better protect the receiving water resources.

Adsorption of pharmaceuticals onto isolated polyamide active layer of NF/RO membranes.

Adsorption of trace organic compounds (TrOCs) onto the membrane materials has a great impact on their rejection by nanofiltration (NF) and reverse osmosis (RO) membranes. This study aimed to investigate the difference in adsorption of various pharmaceuticals (PhACs) onto different NF/RO membranes and to demonstrate the necessity of isolating the polyamide (PA) active layer from the polysulfone (PS) support layer for adsorption characterization and quantification. Both the isolated PA layers and the PA+PS layers of NF90 and ESPA1 membranes were used to conduct static adsorption tests. Results showed that apparent differences existed between the PA layer and the PA+PS layer in the adsorption capacity of PhACs as well as the time necessary to reach the adsorption equilibrium. PhACs with different physicochemical properties could be adsorbed to different extents by the isolated PA layer, which was mainly attributed to electrostatic attraction/repulsion and hydrophobic interactions. The PA layer of ESPA1 exhibited apparently higher adsorption capacities for the positively charged PhACs and similar adsorption capacities for the neutral PhACs although it had significantly less total interfacial area (per unit membrane surface area) for adsorption compared to the PA layer of NF90. The higher affinity of the PA layer of ESPA1 for the PhACs could be due to its higher capacity of forming hydrogen bonds with PhACs resulted from the modified chemistry with more -OH groups. This study provides a novel approach to determining the TrOC adsorption onto the active layer of membranes for the ease of investigating adsorption mechanisms.

Effects of conventional ozonation and electro-peroxone pretreatment of surface water on disinfection by-product formation during subsequent chlorination.

The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H2O2) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O3) to hydroxyl radicals (OH) by electro-generated H2O2, the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO3-) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation.

A comparison of genotoxicity change in reclaimed wastewater from different disinfection processes.

Effluents before disinfection from four wastewater reclamation plants were treated with chlorine (Cl2), ozone (O3), chlorine dioxide (ClO2), medium-pressure ultraviolet (MPUV) and four different combinations of the above, to evaluate the effect of disinfection processes on the genotoxicity removal by the SOS/umu test. Results showed that the genotoxicity increased after MPUV irradiation (10-100 mJ/cm2), but declined when adopting other disinfection processes. The effectiveness of genotoxicity reduction by five chemical disinfectants was identified as: O3 > pre-ozonation with Cl2 ≈ ClO2 > combination of ClO2 and Cl2 > Cl2. The sequential combination of MPUV, Cl2 and O3 reduced the genotoxicity to a level similar to the source water. The influence of differential disinfection process varied on iodinated wastewater, which is closely related to the competitive reactions between disinfectants, iodine and dissolved organic matters. The removal of genotoxic pollutants and the formation of genotoxic disinfection by-products are the two major factors that lead to the change in genotoxicity during disinfection.

Role of adsorption in combined membrane fouling by biopolymers coexisting with inorganic particles.

This study was conducted in order to obtain a better understanding of the combined fouling by biopolymers coexisting with inorganic particles from the aspects of fouling index, fouling layer structure and biopolymer-particle interactions. Calcium alginate was used as the model biopolymer and Fe2O3, Al2O3, kaolin, and SiO2 were used as model inorganic particles. Results showed that the combined fouling differed greatly among the four types of inorganic particles. The differences were attributed particularly to the different adsorption capacities for calcium alginate by the particles with this capacity decreasing in the order of Fe2O3, Al2O3, kaolin and SiO2. Particle size measurement and electron microscopic observation indicated the formation of agglomerates between calcium alginate and those inorganic particles exhibiting strong adsorption capacity. A structure was proposed for the combined fouling layer comprised of a backbone cake layer of alginate-inorganic particle agglomerates with the pores partially filled with discontinuous calcium alginate gels. The filterability of the fouling layer was primarily determined by the abundance of the gels. The strength of physical interaction between calcium alginate and each type of inorganic particle was calculated from the respective surface energies and zeta potentials. Calculation results showed that the extent of physical interaction increased in the order of Al2O3, Fe2O3, kaolin and SiO2, with this order differing from that of adsorption capacity. Chemical interactions may also play an important role in the adsorption of alginate and the consequent combined fouling. High-resolution XPS scans revealed a slight shift of electron binding energies when alginate was adsorbed.

The role of solubility on the rejection of trace organics by nanofiltration membrane: exemplified with disinfection by-products.

Interactions of trace organic compounds (TOrCs) with polymeric nanofiltration (NF) membrane can affect their rejection. It is desirable to investigate whether solubility which depends on the free energy of interaction between these solutes and water correlates with rejection/adsorption and the potential to be incorporated in the partitioning terms of current NF model. A total of ten neutral disinfection by-products (DBPs) were selected as the model compounds for TOrCs to comprehensively investigate the role of solubility on rejection and adsorption. Pearson correlation analysis indicated that the correlation between MW and rejection ratio was highly significant (r = 0.778, p = 0.008) and that between solubility and rejection ratio was moderately significant (r = -0.636, p = 0.48) in a cross-flow system. By fitting Freundlich equation from adsorption isotherm experiment, the adsorption affinity (K f) of DBPs was roughly correlated with their solubility with regard to the comparison of n value with 1. α was then introduced as a parameter of solute-membrane interaction from the perspective of partitioning term in the hydrodynamic model. Exponential relationship can be observed between the solubility and α, demonstrating the possibility of incorporating solubility into the partitioning terms in NF model to accurately predict the rejection of DBPs.

Mechanism and kinetics of halogenated compound removal by metallic iron: Transport in solution, diffusion and reduction within corrosion films.

A detailed kinetic model comprised of mass transport (ktra), pore diffusion (kdif), adsorption and reduction reaction (krea), was developed to quantitatively evaluate the effect of corrosion films on the removal rate (kobs) of halogenated compounds by metallic iron. Different corrosion conditions were controlled by adjusting the iron aging time (0 or 1 yr) and dissolved oxygen concentration (0-7.09 mg/L DO). The kobs values for bromate, mono-, di- and tri-chloroacetic acids (BrO3-, MCAA, DCAA and TCAA) were 0.41-7.06, 0-0.16, 0.01-0.53, 0.10-0.73 h-1, with ktra values at 13.32, 12.12, 11.04 and 10.20 h-1, kdif values at 0.42-5.82, 0.36-5.04, 0.30-4.50, 0.30-3.90 h-1, and krea values at 14.94-421.18, 0-0.19, 0.01-1.30, 0.10-3.98 h-1, respectively. The variation of kobs value with reaction conditions depended on the reactant species, while those of ktra, kdif and krea values were irrelevant to the species. The effects of corrosion films on kdif and krea values were responsible for the variation of kobs value for halogenated compounds. For a mass-transfer-limited halogenated compound such as BrO3-, an often-neglected kdif value primarily determined its kobs value when pore diffusion was the rate-limiting step of its removal. In addition, the value of kdif might influence product composition during a consecutive dechlorination, such as for TCAA and DCAA. For a reaction-controlled compound such as MCAA, an increased krea value was achieved under low oxic conditions, which was favorable to improve its kobs value. The proposed model has a potential in predicting the removal rate of halogenated compounds by metallic iron under various conditions.

Azo compound degradation kinetics and halonitromethane formation kinetics during chlorination.

The chlorination of azo compounds can produce halonitromethanes (HNMs), which have attracted increasing concern due to their high genotoxicity. By impacting the speciation of chlorine and azo compounds, pH impacts apparent second-order rate constants of Methyl Orange (MO, 27.5-1.4 × 103 M-1 s-1), Acid Orange II (AO, 16.7-99.3 M-1 s-1), and Acid Red 1 (AR 1, 3.7-72.5 M-1 s-1) (pH range 6.3-9.0). The two-compartment first-order model successfully described the chloropicrin (TCNM) formation kinetics, suggesting that both fast- and slow-reacting precursors of TCNM are generated from the chlorination of azo compounds. The ratios between fast and slow formation rate constants for MO and AO were 15.6-5.4 × 102, while that of AR 1 was 9.8-19.4 (pH range 6.5-9.0). The fraction of the fast-reacting TCNM precursors decreased with increasing pH for MO and AO; while that for AR 1 decreased when pH increased from 6.5 to 8.0, and then increased when pH increased from 8.0 to 9.0. The impact of pH on TCNM formation was also precursor-specific. The highest molar yields of TCNM predicted from the model in this study were 2.4%, 2.5%, and 1.5% for MO, AO, and AR 1, respectively. The study demonstrates that azo compounds are important HNM precursors, and pose a potential threat to drinking water safety.

Effect of bromide on the transformation and genotoxicity of octyl-dimethyl-p-aminobenzoic acid during chlorination.

Octyl-dimethyl-p-aminobenzoic acid (ODPABA), one of the most commonly used organic UV filters, can undergo considerable transformation in water when entering into the disinfection process. The impacts of bromide on degradation kinetics, formation and speciation of transformation products, regulated disinfection by-products (DBPs) as well as genotoxicity changes during ODPABA chlorination were investigated in this study. Results indicated that the reaction of ODPABA with chlorine followed pseudo-first-order and second-order kinetics. Adding bromide noticeably enhanced the degradation rate of ODPABA, but reduced the impact of chlorine dose. Four halogenated transformation products (Cl-ODPABA, Br-ODPABA, Cl-Br-ODPABA and Br2-ODPABA) were detected by LC-MS/MS. Mono-halogenated products were stable during 24-h chlorination, while di-halogenated products constantly increased. The total yields of trihalomethanes (THMs) and haloacetic acids (HAAs) were both low, but predominated by bromine substitution at high levels of bromide. In addition, SOS/umu tests showed that genotoxicity was generated after ODPABA chlorination, which was increased at least 1.5 times in the presence of bromine. Whereas, no significant genotoxicity variation was observed following bromide concentration change.