Nitrogenous Disinfection By-products Research Articles

FT-ICR/MS deciphers formation of unknown macromolecular disinfection byproducts from algal organic matters after plasma oxidation

Algal organic matter (AOM) is a potential precursor of disinfection byproducts (DBPs) in water treatment. It is a major challenge to identify macromolecular DBPs due to the diversity of AOM. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) was applied to diagnose the AOM diversity after algae removal by plasma oxidation and to recognize the macromolecular DBPs in subsequent chlorination. Significant removal of AOM released by M. aeruginosa, C. raciborskii, and A. spiroies was achieved by plasma oxidation, accompanied by decrease in the proportion of CHNO formulas and increase in CHO formulas. Without plasma treatment, chlorination generated approximately 2486 macromolecular carbonaceous DBPs (C-DBPs) and 1984 nitrogenous DBPs (N-DBPs), with C11HnOmClx and C18HnNmOzClx as the most abundant DBPs. The numbers of C-DBPs and N-DBPs decreased by 63.3% and 62.9%, respectively, if plasma treatment was applied prior to chlorination. Network computational analysis revealed that Cl substitution was the main formation pathway of AOM-derived DBP formation rather than HOCl addition. The precursors of macromolecular DBPs contained a characteristic atomic number of C and O (7 ≤ C ≤ 18; 3 ≤ O ≤ 11). This study firstly disclosed the relationship between AOM diversity and novel macromolecular DBPs during algae-laden water treatment.

Degradation pathways and kinetics of chloroacetonitriles by UV/persulfate in the presence of bromide

Chloroacetonitriles (CANs) are highly toxic nitrogenous disinfection by-products (N-DBPs), which frequently appear in water supply systems and have attracted widespread attention. UV/persulfate (PS) is an effective method to degrade CANs. Bromide (Br−) is widespread in aquatic environments and reacts with oxidative radicals to produce secondary reactive bromine species (RBS), which affects the degradation of CANs by UV/PS. It was found that the degradation of CANs was highly inhibited by Br−. The apparent first-order reaction rate constants of monochloroacetonitrile (MCAN), dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN) decreased from 2.63 × 10−3, 2.00 × 10−3 and 8.66 × 10−4 s−1 to 2.58 × 10−4, 1.61 × 10−4 and 1.59 × 10−4 s−1, respectively after adding 20 μM of Br−. HO• was the main radicals contributing to the degradation of CANs when the concentration of Br− was less than 10 μM, compared with SO4•− and direct photolysis. When the concentration of Br− was up to 20 μM, the contributions of RBS accounted for 85.7%, 90.7% and 89.9% of the apparent degradation rate constants of CANs, respectively. During the reaction, about 65% of nitrogen atoms were transformed into NO3− by the CC bond cleavage and oxidation. The yields of Cl− by dechlorination reaction accounted for 83.5%, 71.0% and 41.2% of the chlorine contents in MCAN, DCAN and TCAN, respectively. It was verified that CANs react with free bromine (HOBr) to produce bromochloroacetonitrile (BCAN). DCAN and TCAN are hydrolyzed to produce corresponding haloacetamides (HAMs), which are further reacted with HOBr to produce bromodichloroacetic acid (BDCAA). Furthermore, the generation of bromate was also worth noting via the oxidation of Br− in the UV/PS system.

Single-step mixotrophic algal wastewater treatment: Microbial assessment of effluent

Viability of a single-step mixotrophic algal wastewater treatment (A-WWT) system in delivering discharge-quality effluent has been previously demonstrated. This report presents inactivation performance of the A-WWT system and compares it with that of high-rate algal ponds, activated sludge, and membrane bioreactors. Log reduction per unit energy input/volume of wastewater by the A-WWT system is shown to range 6.4–14.6 m3/kWh, while that in the above alternatives ranged 1.3–3.5 m3/kWh. Pathogenicity and virulence of the algal effluent and the potential for formation of disinfection byproducts (DBPs) under chlorination are discussed. Concentrations of seven of the common nitrogenous DBPs in the algal effluent were <50 ng/L.

Automated headspace solid-phase microextraction-gas chromatography-mass spectrometry of trihalomethane and typical nitrogenous disinfection by-products in water

Disinfection by-products (DBPs) are detrimental to public health owing to their carcinogenicity and mutagenesis. Fast and reliable determination of DBPs is essential for ascertaining their formation, characteristics, and occurrence. This study reported an automated headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) method for quantifying typical nitrogenous-DBPs, including haloacetonitriles (HANs), trichloronitromethane, and trihalomethanes (THMs). The analysis was further optimized by selecting SPME fiber coatings, extraction/desorption time and temperature, and salt addition. The optimized method examined the occurrence and stability of the selected DBPs in aqueous samples under different preservation conditions and showed good sensitivity (limit of detection: 0.010–0.320 µg/L) and precision. Most THMs and HANs with high recovery were preserved in ultrapure water under dark and low-temperature conditions. However, real samples exhibited greater analytical biases due to comprehensive effects of photochemistry, biochemistry, and physiochemistry. Based on the findings of this study, we recommend that tested samples should be preserved in a frozen state and analyzed within three days.

Fermentation liquid as a carbon source for wastewater nitrogen removal reduced nitrogenous disinfection byproduct formation potentials of the effluent

Sludge alkaline fermentation liquid (SAFL) is an alternative to sodium acetate (NaAc) in enhancing wastewater nitrogen removal. Upon SAFL addition, dissolved organic nitrogen (DON) can be externally introduced or biologically synthesized during nitrogen removal, which is an important precursor to toxic nitrogenous disinfection by-products (N-DBPs). This study aims to evaluate the effects of different carbon source addition on effluent DON concentration, composition, and N-DBP formation potentials. A lab-scale A2O system treating real municipal wastewater was operated with NaAc or SAFL as external carbon sources. DON molecules and potential N-DBP precursors were identified by Orbitrap mass spectrometry. Subsequently, major microorganisms contributing to DON biosynthesis were suggested based on metagenomics. It was found that effluent DON was higher with SAFL as the carbon source than NaAc (1.51 ± 0.24 v.s. 0.56 ± 0.08 mg N/L, p < 0.05). Nevertheless, dichloroacetonitrile and nitrosamine formation potentials (7.14 ± 1.02 and 1.57 ± 0.07 μg/mg DON-N, respectively) of the effluent with SAFL addition were 42.79 ± 2.42% and 54.89 ± 1.70% lower than those of NaAc. Protein- and lignin-like compounds were the most abundant DON molecules in the effluent, where alanine, glycine and tyrosine were important precursors to N-DBPs. Azonexus and Flavobacterium spp. were positively correlated with these precursors, and possessed key genes involved in precursor synthesis. SAFL is a promising carbon source, not only for achieving efficient inorganic nitrogen and DON removals, but also for reducing N-DBP formation potentials of chlorinated effluent.

Removal of disinfection byproducts and toxicity of chlorinated water by post-treatments of ultraviolet/hydrogen peroxide and ultraviolet /peroxymonosulfate

Post-treatment of ultraviolet (UV) irradiation is not efficient in eliminating toxicity of chlorinated water. Removal of disinfection byproducts (DBPs) and toxicity of chlorinated water by UV/hydrogen peroxide (UV/H2O2) and UV/peroxymonosulfate (UV/PMS) was investigated. In the absence of bromide, adding H2O2 or PMS enhanced the removal of nitrogenous DBPs and total organic chlorine (TOCl) than UV alone (1200 mJ/cm2). UV/PMS decreased the cytotoxicity from 10.6 to 4.4 mg-Phenol/L and genotoxicity from 7.1 to 2.0 μg-4-NQO/L, more efficient than UV/H2O2. However, results were quite different in the presence of bromide. PMS led to the increased formation of total organic bromine (TOBr) in chlorinated water. UV/PMS was therefore less efficient in toxicity removal than UV/H2O2. In the presence of bromide, UV/H2O2 decreased the cytotoxicity and genotoxicity by 85% and 68%, while UV/PMS only removed the cytotoxicity and genotoxicity by 59% and 46%. In the UV/PMS process, SO4˙- was more efficient on toxicity removal than ˙OH. Contributions of UV irradiation, ˙OH and SO4˙- were 55%, 14% and 31% to cytotoxicity removal, and 49%, 15% and 36% to genotoxicity removal. This study demonstrated the feasibility of using UV/H2O2 and UV/PMS as post-treatments to enhance the removal of DBPs and toxicity of chlorinated water.

Insight into the degradation of ciprofloxacin by medium-pressure UV-activated monochloramine process

The degradation efficiency and mechanisms of ciprofloxacin (CIP), a typical antibiotic, by a medium-pressure ultraviolet/chloramine (MPUV/NH2Cl) treatment were investigated. The results showed that CIP degradation by MPUV/NH2Cl was significantly higher than that by NH2Cl oxidation and MPUV photolysis, and that this degradation processes were consistent with pseudo-first-order kinetics. The initial CIP concentration (7.5–30.2 μM) and the presence of HCO3− (0.5–10 mM) significantly inhibited CIP degradation with kobs,CIP 0.0090–0.0069 and 0.0078–0.0048 cm2/mJ. In contrast, NO3− (50–500 μM) and Br− (0.5–10 mM) significantly promoted the degradation with kobs,CIP 0.0078–0.0102 and 0.0078–0.0124 cm2/mJ. The effect of Cl− (0.5–10 mM) and natural organic matter (1–5 mg/L) were negligible. The NH2Cl dosage (30–60 μM) presented a dual effect, in which its increase within the optimal concentration range (30–40 μM) accelerated CIP degradation due to the formation of reactive radicals, whereas an excessive increase (40–60 μM) quenched the free radicals, ultimately quenching the free radicals and inhibiting the degradation. The optimum pH for CIP degradation under MPUV/NH2Cl treatment was 7.0. The contribution of reactive halogen species (i.e., reactive chlorine species and reactive nitrogen species) to CIP degradation was substantially greater than that of hydroxyl radicals under acidic or neutral conditions. We identified the degradation products of CIP and proposed degradation pathways, which included defluorination and cracking of the piperazine ring, with the latter being dominant. Compared to haloacetic acid (HAA) and nitrogenous disinfection byproducts (N-DBPs), MPUV/NH2Cl significantly reduced trihalomethane (THM) production and theoretical cytotoxicity by 80.1% and 78.4% respectively, compared to the background experiment in natural water at a UV dose of 300 mJ/cm2.

Identification, Occurrence, and Cytotoxicity of Haloanilines: A New Class of Aromatic Nitrogenous Disinfection Byproducts in Chloraminated and Chlorinated Drinking Water.

Identifying disinfection byproducts (DBPs) with high health risk is an unresolved challenge. In this study, six members of a new class of aromatic nitrogenous DBPs─2-chloroaniline, 2-bromoaniline, 2,4-dichloroaniline, 2-chloro-4-bromoaniline, 4-chloro-3-nitroaniline, and 2-chloro-4-nitroaniline─are reported as DBPs in drinking water for the first time. Haloanilines completely degraded within 1 h in the presence of chlorine (1 mg/L), while about 20% remained in the presence of chloramine (1 mg/L) after 120 h. Haloanilines showed high stability in the absence of disinfectants, with <30% degradation at pH 5-9 over 120 h. Eight haloanilines were determined in chloraminated finished water and tap water at total concentrations of up to 443 ng/L. The most abundant was 2-bromoaniline, with a median concentration of 104 ng/L. The cytotoxicity of eight haloanilines and regulated trichloromethane and dichloroacetic acid (DCAA) was evaluated using Hep G2 cell assay. The EC50 values of eight haloanilines were 1-2 orders of magnitude lower than those of the regulated DBPs. The lowest toxic concentration of 2-chloro-4-nitroaniline was 1 μM, 500 times lower than that of DCAA. The formation and control of haloanilines in drinking water warrant further investigation.

Kinetics and Transformations of Diverse Dissolved Organic Matter Fractions with Sulfate Radicals.

Dissolved organic matter (DOM) scavenges sulfate radicals (SO4•-), and SO4•--induced DOM transformations influence disinfection byproduct (DBP) formation when chlorination follows advanced oxidation processes (AOPs) used for pollutant destruction during water and wastewater treatment. Competition kinetics experiments and transient kinetics experiments were conducted in the presence of 19 DOM fractions. Second-order reaction rate constants for DOM reactions with SO4•- (kDOM,SO4•-) ranged from (6.38 ± 0.53) × 106 M-1 s-1 to (3.68 ± 0.34) × 107 MC-1 s-1. kDOM,SO4•- correlated with specific absorbance at 254 nm (SUVA254) (R2 = 0.78) or total antioxidant capacity (R2 = 0.78), suggesting that DOM with more aromatics and antioxidative moieties reacted faster with SO4•-. SO4•- exposure activated DBP precursors and increased carbonaceous DBP (C-DBP) yields (e.g., trichloromethane, chloral hydrate, and 1,1,1-trichloropropanone) in humic acid and fulvic acid DOM fractions despite the great reduction in their organic carbon, chromophores, and fluorophores. Conversely, SO4•--induced reactions reduced nitrogenous DBP yields (e.g., dichloroacetonitrile and trichloronitromethane) in wastewater effluent organic matter and algal organic matter without forming more C-DBP precursors. DBP formation as a function of SO4•- exposure (concentration × time) provides guidance on optimization strategies for SO4•--based AOPs in realistic water matrices.

Formation of disinfection byproducts from chlorinated soluble microbial products: Effect of carbon sources in wastewater denitrification processes

Carbon sources are crucial for biological denitrification in wastewater treatment that significantly affects the production of soluble microbial products (SMPs), thereby affecting the formation of disinfection byproducts (DBPs) during subsequent chlorination. However, the effect of carbon sources on DBPs formation has not been studied. In this work, sodium acetate, sodium lactate, and glucose were used as carbon sources, and denitrifying SMPs derived from different carbon sources were used as DBPs precursors to investigate the formation potential (FP) of 16 carbonaceous DBPs and 19 nitrogenous DBPs. Results showed that the carbonaceous DBPs FP of SMPs derived from acetate, lactate, and glucose were 502.1–584.3, 250.3–288.9, and 374.7–439.1 μg/L, respectively, and the nitrogenous DBPs FP were 19.1–45.6, 12.8–21.9, and 7.9–9.0 μg/L, respectively. After chlorination, the genotoxicity of SMPs measured by the SOS/umu test was also evaluated with 364 ng 4-NQO/L for acetate, 212 ng 4-NQO/L for lactate, and 138 ng 4-NQO/L for glucose. Based on X-ray photoelectron spectroscopy, chemical structures of SMPs were characterized, and their relationship with DBPs FP was investigated to explain the mechanism of DBPs formation. Aromatic C and C-O were found to be the major precursor structures to form carbonaceous DBPs, and their lowest proportions in lactate-derived SMPs caused the lowest carbonaceous DBPs FP. Organic nitrogen, including aromatic N, amide/peptide N, and primary amine N, was the precursor of nitrogenous DBPs. The lowest concentration of dissolved organic nitrogen for glucose-derived SMPs caused the lowest nitrogenous DBPs FP and genotoxicity. Glucose may be a better choice among the three carbon sources in terms of reducing genotoxicity.

Flume and single-pass washing systems for fresh-cut produce processing: Disinfection by-products evaluation

Free chlorine is widely used in fresh-cut produce washing to minimize microbial cross-contamination, but its application can also lead to the formation of harmful disinfection byproducts (DBPs). This study compared DBPs in process water and washed produce during commercial operation. Samples of shredded lettuce and diced cabbages washed in chlorinated water in the traditional double-flume wash and novel immersion-free single-pass wash systems were collected at multiple time points and locations from the processing lines. A suite of 33 conventional and emerging DBPs, including 4 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 9 nitrogenous DBPs (N-DBPs), and 11 carbonaceous DBPs (C-DBPs), were investigated. Overall, N-DBPs and HAAs dominated the concentration of detected DBPs. Wash water in the flumes contained 7–111 folds higher DBP levels compared to that in the single-pass system, with the abundance of DBPs following the order of N-DBPs > HAAs > C-DBPs > THMs. DBPs were detected on washed produce, presenting primarily in the forms of N-DBPs and HAAs followed by C-DBPs and THMs. While higher levels of DBPs were detected in flume-washed produce, the final potable water rinse significantly reduced the DBP concentration in these products. The concentrations of THMs and HAAs on these washed products were used to estimate potential exposure via consumption of fresh-cut produce and the levels were below the daily allowable exposure for drinking water standard established by the U.S. Environmental Protection Agency. The detected high concentration and potential toxicity of N-DBPs indicate the need for further research. The findings of this study advance the understanding of the formation and removal of DBPs during wash processes, and identify additional research opportunities for further reduction in DBPs and food safety improvement.

Nitrite-enhanced N-nitrosamines formation during the simulated tetracycline polluted groundwater chlorination: Experimental and theoretical investigation

N-nitrosamines (NAs), a class of emerging nitrogenous disinfection byproducts, have been detected remarkably in drinking/reclaimed water. There is a significant risk of excessive levels of NAs in the chlorination of the polluted source water, especially in the direct chlorination of nitrite-enriched groundwater. Considering the co-pollution of nitrite and micro-organic pollutants on groundwater, experiments were conducted on chlorination of nitrite-enriched water with precursor of antibiotics, and it was confirmed that the Cl 2 : N (molar ratio of chlorine to nitrite), contacting time, pH, and DO appreciably influenced the NAs formation potential. The molecular electric potential revealed that different dissociation status of precursors has a specific correlation with NAs formation potential (FP). The nitrite significantly increased the NAs FP because the reactive nitrogen species (RNS) formed in the oxidation process from nitrite to nitrate. Sequences of transformation products are determined to support the RNS promoted hypothesis of N-nitrosodimethylamine (NDMA) formation mechanism; furthermore, theoretical investigation in the reaction of dimethylamine (DMA) with different RNS verified the above hypothesis. • NDMA FP significantly promoted in chlorination of nitrite-enriched groundwater. • DO is not a key factor to NDMA formation in nitrite-enriched situation. • RNS enhanced-nitrosation pathway was proposed. • NDEA has been detected along with NDMA formation.

Developmental toxicity of bromoacetamide via the thyroid hormone receptors-mediated disruption of thyroid hormone homeostasis in zebrafish embryos

Bromoacetamide (BAcAm) is a nitrogenous disinfection by-product. We previously found that BAcAm induced developmental toxicity in zebrafish embryos, but the underlying mechanisms remain to be elucidated. Since thyroid hormones (THs) homeostasis is crucial to development, we hypothesized that disruption of THs homeostasis may play a role in the developmental toxicity of BAcAm. In this study, we found BAcAm exposure significantly increased mortality and malformation rate, decreased hatching rate and body length, inhibited the locomotor capacity in zebrafish embryos. BAcAm elevated TSH, T3 and T4 levels, down-regulated T3/T4 ratios, and up-regulated mRNA expression changes of THs related genes (trh, tsh, tg, nis, tpo, dio1, dio2, ugt1ab，klf9 and rho), but down-regulated mRNA expression changes of TH receptors (tr α and tr β). Up-regulated tr α and tr β mRNAs by rescue treatment confirmed that both tr α and tr β were involved in the developmental toxicity of BAcAm. In conclusion, our study indicates disruption of THs homeostasis via the thyroid hormone receptors was responsible for the developmental toxicity of BAcAm.

Degradation Kinetics and Disinfection By-Product Formation of Iopromide during UV/Chlorination and UV/Persulfate Oxidation

As the detection of micropollutants in various water resources is commonly reported, developing an efficient technology to remove them to maintain water safety has become a major focus in recent years. The degradation kinetics of iopromide, one of a group of iodinated X-ray contrast media (ICM), using advanced oxidation processes of ultraviolet/chlorination (UV/Cl2) and UV/persulfate (UV/PS) oxidation were investigated in this research. The results show that iopromide degradation fitted pseudo-first-order kinetics, and the rate constants were calculated as 2.20 (± 0.01) × 10−1 min−1 and 6.08 (± 0.10) × 10−2 min−1 in UV/Cl2 and UV/PS, respectively. In the two systems, the degradation rates were positively correlated with the initial concentrations of HOCl and PS, respectively. In the UV/Cl2 system, the degradation rate of iopromide reached a maximum at pH 7, while in the UV/PS system, pH had only a slight effect on the degradation rate. Chloride in water had a negligible effect on iopromide degradation, whereas bromide inhibited iopromide degradation in the UV/Cl2 system. The contributions of UV irradiation, •OH, and RCS to iopromide degradation during UV/Cl2 treatment were calculated as 20.8%, 54.1%, and 25.1%, respectively. One carbonated and three nitrogenated disinfection by-products (C-DBP (chloroform) and N-DBPs (dichloroacetonitrile, trichloronitromethane, and trichloroacetone)) were detected at relatively high levels, along with three emerging iodinated DBPs (dichloroiodomethane, monochlorodiiodomethane, and triiodomethane). More C- and N-DBPs were generated in the UV/Cl2 and UV/PS systems than in UV irradiation, while considerably higher I-DBPs were generated in UV irradiation than in the other two systems. Thus, it is essential to pay attention to DBP formation when UV/Cl2 or UV/PS is used to treat iopromide in water. In order to better control the generation of carcinogenic and toxic I-DBPs, Cl2 or PS combined with UV should be adopted for iopromide degradation, instead of UV alone, for providing safe drinking water to the public.

Synergistic Control of Nitrogenous Disinfection By-products and Opportunistic Pathogens in Drinking Water by Iron-Modified Quartz Sand Filtration

The main function of quartz sand in drinking water treatment has been to remove turbidity, while the microbial effect of its solid-liquid interface has been ignored. In order to solve the limitations of control of the disinfection by-products (DBPs) and opportunistic pathogens (OPs) in common quartz sand, the common quartz sand was modified to iron sand. The maximum DBPs formation potential of typical nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products was determined using gas chromatography-ECD. Compared with those of sand, the inhibition effects of halonitromethanes, haloacetamides, and haloacetonitriles by the Fe-sand were increased by 51.51%, 43.66%, and 90.6%, respectively. In addition, the gene copy numbers of Hartmanella vermiformis, Legionella spp., Mycobacterium spp., M. avium, and Naegleria spp. were detected via quantitative qPCR, and the results indicated that the Fe-sand did have a similar significant inhibitory effect on OPs. The Fe-sand had limited ability to enhance the removal of NOM. However, the Fe-sand effectively inhibited the continuous contribution of biofilm to N-DBPs and opportunistic pathogens. The distribution of biofilms on the surface of the Fe-sand filter media was uniform, not likely to fall off, and more stable; however, the suspended biofilms in the effluent were more difficult to aggregate. In addition, the α-helix of the secondary structure in the extracellular protein disappeared in the effluent of the Fe-sand. Therefore, the whole suspended biofilm was easily penetrated by chlorine. The Fe-sand solid-liquid interface did significantly change the microbial community structure and suspended biofilm characteristics, which provides a new concept to ensure the safety of drinking water quality and plays a good theoretical supporting role in the improvement and transformation of the existing process in drinking water treatment plants.

Permanganate/Bisulfite Pre-Oxidation of Natural Organic Matter Enhances Nitrogenous Disinfection By-Products Formation during Subsequent Chlorination

The permanganate/bisulfite (PM/BS) process is a novel oxidation process, which can degrade micropollutants within several seconds. As natural organic matter (NOM) ubiquitously exists in an aquatic environment, the PM/BS process will inevitably react with NOM, which may impact the disinfection-by-products (DBPs) formation during subsequent chlorination. This study investigated the effect of PM/BS pre-oxidation of NOM on DBP formation. It was found that TOC removal reached a plateau when the molar ratio of PM to BS was 1:5. Increasing ratios of PM to BS decreased the intensity and area of fluorescence spectroscopy. PM and BS doses, pre-oxidation time, pH of solutions and concentration of Br− impacted the formation potential of various DBPs. PM/BS pre-oxidation decreased the formation of TCM while increasing the yields of N-DBPs, thus increasing the risk of water quality. Calculated toxicity analysis showed that a general increase in CTI was observed with PM/BS pre-oxidation, indicating that PM/BS pre-oxidation had a negative effect on risk control of overall cytotoxicity. Although the PM/BS process could accelerate the degradation of micropollutants, the elevated DBPs formation, especially highly toxic N-DBPs, needs enough attention to control water-quality risk.

Transformation mechanism and fate of dissolved organic nitrogen (DON) in a full-scale drinking water treatment

Dissolved organic nitrogen (DON) has attracted much attention in drinking water treatment due to its potential to produce nitrogenous disinfection by-products (N-DBPs). This work was designed to explore the transformation and fate of DON and dissolved inorganic nitrogen (DIN) in drinking water treatment. The changes of DON and formation of N-DBPs were evaluated along the water treatment route (i.e., pre-ozonation and biological-contact oxidation, delivery pipes’ transportation, coagulation-sedimentation, sand filtration, post-ozonation, biological activated carbon, ultrafiltration and disinfection) of drinking water treatment plant (DWTP). The transformation mechanism of DON was comprehensively investigated by molecular weight fractionation, three-dimensional fluorescence, LC-OCD (Liquid Chromatography-Organic Carbon Detection), total free amino acids. A detailed comparison was made between concentrations and variations of DON and DIN affected by seasons in the drinking water treatment. Regardless of seasonal variation in raw water concentration, the DON removal trends between different treatment processes remain constant in the present study. Compared to other treatment processes, pre-ozonation and coagulation-sedimentation exhibited the dominant DON removal in different seasons, i.e., 11.13%-14.45% and 14.98%-22.49%, respectively. Contrary, biological-contact oxidation and biological activated carbon negatively impacted the DON removal, in which DON increased by 1.76%-6.49% in biological activated carbon. This may be due to the release of soluble microbial products (SMPs) from bacterial metabolism, which was further validated by the rise of biopolymers in LC-OCD.

Advanced oxidation processes (AOPs) based wastewater treatment - unexpected nitration side reactions - a serious environmental issue: A review

• Unexpected nitration processes led to formation of several nitro-derivatives. • Nitrogen fixation importantly contributes to formation of reactive nitrogen species in sonolysis. • Denitration and renitration processes in persulfate based AOPs causes nitration of intermediates. • Post-treatment and nitro-derivatives monitoring are important in AOPs. • Risk of low water quality in case of unexpected nitration during treatment process. Chemical compounds containing nitro group (nitro-products) are a one of toxic by-products, that can be formed during wastewater treatment processes. In case of presence of nitrite or nitrate ions, the formation of nitro-products during advanced oxidation processes (AOPs) is very common. It is caused by the reactive nitrogen species (RNs) such as nitrate radical (NO 3 • ), nitrite radical (NO 2 • ), nitrogen oxide radical (NO • ) and peroxynirite (ONOO–). In fact, the oxidative degradation of N-containing pollutants releases nitrate, nitrite and ammonium ions. In some cases, secondary reactions of mineralised nitrogen species (nitrate and nitrite ions) with the parent or intermediate compound generate next several nitro-products. The nitro-products are more toxic comparing to the primary pollutants and act as the precursors of the nitrogenous disinfection by-products. Moreover, some studies reported unexpected nitro-products formation during the oxidative degradation. In case of such processes a special attention should be made to monitor and minimize these effects. De-nitration of the initial nitro-compounds induces the formation of various nitro-products in AOPs. It was observed for UV light driven, Fenton and persulfate based AOPs. The sonochemical nitrogen fixation is a key mechanism for the formation of nitro-compounds in ultrasounds based AOPs. Therefore, this paper is focused on comparison of various AOPs in terms of nitro-products formation mechanisms and the associated environmental issues.

Comparison of UV and UV/chlorine system on degradation of 2,4-diaminobutyric acid and formation of disinfection byproducts in subsequent chlorination

• UV/chlorine system showed extremely excellent performance in degrading DAB. • C-C bond and C-N bond fracture were the main reactions of DAB degradation by UV. • RCS produced by UV/chlorine system preferentially attacked amino groups on DAB. • N-DBPs had great formation potential when UV/chlorine was used as pretreatment. • THMs were more prone to bromine substitution than HANs. 2,4-diaminobutyric acid (DAB) is a common non-protein amino acid with extremely high neurotoxicity in water environment, posing a serious threat to human health and animal welfare around the world. Therefore, it is necessary to take appropriate measures to remove it. In this paper, degradation of DAB in UV and UV/chlorine system were studied, and transformation pathways of DAB were preliminarily proposed based on the identified transformation products. Moreover, formation of disinfection byproducts (DBPs) during post-chlorination under different conditions were also discussed. The results indicated that the presence of reactive substances in UV/chlorine system significantly promoted the degradation of DAB, but more DBPs and their precursors were produced at the same time. UV irradiation time, pH and Cl 2 /N affected the formation of DBPs during post-chlorination to various degrees. Notably, precursors of carbonaceous DBPs were mainly formed during UV irradiation, while those of nitrogenous DBPs were mainly formed during UV/chlorine system. In the presence of bromide, brominated DBPs were the absolute dominant species, while formation of chlorinated DBPs were inhibited. Furthermore, total trihalomethane and total haloacetonitrile increased with increasing bromide concentration. Overall, special attention should be paid to DBP formation when selecting UV or UV/chlorine system as pretreatment to eliminate DAB.

Study on the Control of Dichloroacetonitrile Generation by Two-Point Influent Activated Carbon-Quartz Sand Biofilter.

Aiming at the problem of highly toxic Nitrogenous disinfection by-products (N-DBPs) produced by disinfection in the process of drinking water, two-point influent activated carbon-quartz sand biofilter, activated carbon-quartz sand biofilter, and quartz sand biofilter are selected. This study takes typical N-DBPs Dichloroacetonitrile (DCAN) as the research object and aromatic amino acid Tyrosine (Tyr), an important precursor of DCAN, as the model precursor. By measuring the changes of conventional pollutants in different biofilters, and the changes of Tyr, the output DCAN formation potential of the biofilters, this article investigates the control of DCAN generation of the two-point influent activated carbon-quartz sand biofilter. The results show that the average Tyr removal rate of the three biofilters during steady operation is 73%, 50%, and 20%, respectively, while the average effluent DCAN generation potential removal rate is 78%, 52%, and 23%, respectively. The two-point influent activated carbon-sand biofilter features the highest removal rate. The two-point water intake improves the hypoxia problem of the lower filter material of the activated carbon-quartz sand biofilter, and at the same time, the soluble microbial products produced by microbial metabolism can be reduced by an appropriate carbon sand ratio, which is better than traditional quartz sand filters and activated carbon-quartz sand biofilters in the performance of controlling the precursors of N-DBPs.