Formation Of Nitrogenous Disinfection By-products Research Articles

Effects of cast iron pipe corrosion on nitrogenous disinfection by-products formation in drinking water distribution systems via interaction among iron particles, biofilms, and chlorine

The effects of cast iron pipe corrosion on nitrogenous disinfection by-products formation (N-DBPs) in drinking water distribution systems (DWDSs) were investigated. The results verified that in the effluent of corroded DWDSs simulated by annular reactors with corroded cast iron coupons, typical N-DBPs, including haloacetamides, halonitromethanes, and haloacetonitriles, increased significantly compared with the influent of DWDSs. In addition, more dissolved organic carbon, adenosine triphosphate, and iron particles were simultaneously detected in the bulk water of corroded DWDSs, thereby indicating that abundant iron particles acted as a “protective umbrella” for microorganisms. Under the condition of corroded DWDSs, the extracellular polymeric substances gradually exhibited distinct characteristics, including a higher content and lower flocculation efficiency, thereby resulting in a large supply of N-DBPs precursors. Corroded cast iron pipes, equivalent to a unique microbial interface, induced completely distinct microbial community structures and metabolic functions in DWDSs, thereby enhancing the formation of N-DBPs. This is the first study to successfully reveal the interactions among iron particles, biofilms, and chlorine in DWDSs, which may help to fully understand the biofilm transformation and microbial community succession in DWDSs.

Removal performance and mechanism of typical amino acids in water by the peroxymonosulfate/Fe3O4 nanoparticles

Abstract Dissolved organic nitrogen (DON) as precursors of nitrogenous disinfection byproducts (N-DBPs) has become a serious issue for drinking water treatment. Here, Fe3O4/peroxymonosulfate (PMS) system was used to examine the amino acid removal and formation of N-DBPs in the system and the corresponding mechanisms. Results showed a remarked variation in removal efficiency of three typical amino acids, i.e., glutamate (78%), histidine (53%) and phenylalanine (27%) in Fe3O4/PMS system at optimum conditions (0.1 g/L Fe3O4, 1.5 mM PMS, 1 h). Notably, Fe3O4/PMS treatment led to dichloroacetonitrile (DCAN) formation caused by the chlorination of glutamate, phenylalanine and histidine being reduced by 53.3%, 9.7% and 41.9%, respectively. The degradation and subsequent N-DBPs formation in the Fe3O4/PMS system mainly depended on the types and properties of the amino acids. The formation of dichloroacetamide (DCAcAm) exhibited different trends, which may be due to the different R group structure of the three amino acids and the special aromaticity of the imidazole ring in the histidine side chain that facilitates its quick electrophilic substitution and ring-opening reaction. This study highlights that the Fe3O4/PMS system is a promising strategy to remove DON and efficiently eliminate N-DBPs formation in the drinking water treatment process depending on the amino acid type.

Formation of nitrogenous disinfection byproducts in MP UV-based water treatments of natural organic matters: The role of nitrate

UV-based water treatment processes have been reported to induce genotoxicity during the treatments of surface water, drinking water and artificial water with natural organic matters (NOMs), causing genotoxicity concerns for the drinking water safety. Nitrogenous disinfection byproducts (N-DBPs) were generally reported to be much more genotoxic than their non-nitrogenous analogues, and might be responsible for the genotoxicity in UV processes. Although nitrate-rich water was getting attention for the possibility of genotoxicity and N-DBPs during UV treatments, the impact mechanism of nitrate on the degradation of NOMs, the formation of N-DBPs and genotoxicity has not been explicated. Here simulation experiments of NOM degradation under medium-pressure (MP) UV and MP UV/H2O2 treatments were conducted to explore the effect of nitrate on the molecular characteristics of NOM, the nitrate-derived N-DBPs and the potential genotoxicity through non-targeted analysis and CALUX® reporter gene assays. The results showed that nitrate can accelerate the degradation of NOMs in the MP UV process but inhibit the degradation of NOMs in the MP UV/H2O2 process. During the degradation of NOMs, the molecular compositions varied by the effect of nitrate on oxygen atoms, molecule analogs, and saturation. A total of 105 and 374 nitrate-derived N-DBPs were identified in the MP UV and MP UV/H2O2 treatment, respectively. Most of these N-DBPs contain one nitrogen atom, and the representative features are nitro-, methoxy- (or hydroxyl-) and ester- groups on benzene. No genotoxicity was observed without nitrate spiking, whereas genotoxicity was induced after both MP UV and MP UV/H2O2 treatments when nitrate was spiked, which is worthy of attention for the drinking water safety management.

Formation of nitrogenous disinfection by-products (N-DBPs) in drinking water: emerging concerns and current issue

Nitrogenous disinfection by-product (N-DBPs) has always been one of the most concerned disinfection by-products (DBPs) in recent years. The toxicity of regulated DBPs is generally less than that of N-DBPs, which have been widely detected in finished drinking water. Despite the fact that N-DBPs are highly toxic, there are currently no N-DBPS species officially regulated by governments around the world. This paper provides a review of the formation mechanism and precursors of nitrogen-containing disinfection by-products in drinking water treatment. Also, the spcieces and inducing factors of N-DBPs were summarized. The data were mainly collected from 2000-2002 and 2006-2007 US Survey in effluents of US WTPs. Because nitrogen source is a prerequisite for the formation of nitrogen-DBP in drinking water, the occurrence of N-DBPS may increase due to the influence of sewage and algae blooms on water sources. Chloramine disinfection are used in most of developed countries for preferred secondary disinfection to reduce the formation of chlorine-related by-products, but this increases the formation potential of N-DBPs. Furthermore, the safety control of N-DBPs and suggestions for the further exploration of for efficient drinking water are discussed. Coagulation and filtration are not very effective in removing precursors (such as amino acids) of N-DBPs and the precursors need to be removed before disinfection.

UV254 irradiation of N-chloro-α-amino acids: Kinetics, mechanisms, and N-DBP formation potentials

This study explores the degradation kinetics and mechanisms of N-chloro-α-amino acids and the changes in the formation potential of nitrogenous disinfection byproducts (N-DBPs) upon UV254 irradiation. UV254 irradiation significantly accelerated the degradation of all the tested N-chloro-α-amino acids compared to those in the dark. Both direct photolysis-induced cleavage of the N-Cl bonds and radical oxidation (e.g., Cl• and Cl2•−) involved reactions that contributed to their enhanced degradation. The fluence-based photolysis rate constants of the N-chloro-α-amino acids varied in the range of (1.06—5.47) × 10−3 cm2 mJ−1 at pH 6.0 and (0.74—2.79) × 10−3 cm2 mJ−1 at pH 8.0. The apparent quantum yields (Φapp) of the majority of the N-chloro-α-amino acids were in the range of 0.41−0.95 at pH 6.0 and 0.22−0.79 at pH 8.0, except N-chloroaspartic acid, N-chlorohistidine, and N-chloroalanine. UV254 irradiation significantly enhanced the formation of trichloronitromethane (TCNM) from the tested N-chloro-α-amino acids after post-chlorination, but exhibited various effects on the formation of dichloroacetonitrile (DCAN). A longer UV254 irradiation time generated more TCNM, and a lower pH produced more DCAN from the N-chloro-α-amino acids. The degradation pathways of N-chlorotyrosine, as a representative N-chloro-α-amino acid, are proposed, and the β-scission and 1,2-H shift pathways led to the formation of different precursors of TCNM and DCAN. The results of this study improve our understanding of the fate of N-chloro-α-amino acids under UV254 irradiation and post-chlorination.

Enhanced formation of dichloroacetamide and dichloroacetonitrile during chloramination of drinking water and model organic matters in the presence of copper corrosion products

The formation of nitrogenous disinfection byproducts (N-DBPs) occurs in chloraminated water in drinking water distribution systems and may be affected by metal pipe materials and their corrosion products. The effect of copper corrosion products, including Cu2+, CuO, and Cu2O, on the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) was investigated during chloramination of natural organic matter (NOM), model precursors (carboxylic acids and amino acids), and real water samples. Copper corrosion products enhanced DCAN and DCAcAm formation during chloramination of NOM by 33%–72% and 11%–80%, respectively. Addition of 15N-labeled monochloramine showed that the copper corrosion products primarily enhanced the formation of DCAN using organic nitrogen and monochloramine as nitrogen sources, and the formation of DCAcAm using monochloramine as the nitrogen source, but had a limited impact on the formation of DCAcAm using organic nitrogen as the nitrogen source. A distinct N-DBP formation pathway in the presence of Cu2+ and CuO was observed using tyrosine as a model compound, which included the formation of 1,4-benzoquinone as a dominant intermediate. On reaction with monochloramine, the 1,4-benzoquinone greatly contributed to enhancement of DCAN and DCAcAm formation using monochloramine as the nitrogen source. During chloramination of real water samples, Cu2+ and CuO enhanced DCAN formation by 9–40% and DCAcAm formation by 16–33%. This study increases our knowledge of copper catalyzed DCAN and DCAcAm formation in copper pipes, which will be meaningful for water safety in distribution systems using chloramine disinfection.

Characterization of algal organic matter as precursors for carbonaceous and nitrogenous disinfection byproducts formation: Comparison with natural organic matter

Algal organic matter (AOM) and natural organic matter (NOM) from a typical eutrophic lake were comprehensively investigated in terms of their physico-chemical property, components and disinfection byproduct formation potentials (DBPFPs). The relationships between specific chemical properties of AOM and NOM with their corresponding DBPFPs were further evaluated during chlorination. Results indicated that AOM had lower specific UV absorbance (SUVA) but richer organic nitrogen contents than NOM. Fluorescence excitation emission matrix spectroscopy further demonstrated that AOM were chiefly composed of aromatic protein-like and soluble microbial byproduct-like matters, while NOM were mainly contributed from humic acid-like and soluble microbial byproduct-like substances. Although the molecular weight (MW) distribution of AOM and NOM showed no significant difference, size-exclusion chromatography with organic carbon as well as organic nitrogen detection (LC-OCD-OND) revealed that AOM were concentrated with the fraction of building blocks and NOM had higher concentrations of biopolymers and humics (HS). Moreover, AOM displayed higher DBPFPs than NOM, especially for nitrogenous DBPFP (N-DBPFP). MW < 1 kDa fractions both in AOM and NOM contributed the largest proportion to the formation of carbonaceous disinfection byproducts (C-DBPs). In addition, Pearson correlation analysis showed that bulk parameter SUVA was significantly relevant to the formation potentials of trihalomethane both in AOM and NOM, but was ineffective for carbonaceous DBPFP (C-DBPFP) prediction. Dissolved organic nitrogen contents in biopolymer and HS characterized by LC-OCD-OND had strong correlations with N-DBPFPs from AOM and NOM, indicating that LC-OCD-OND quantitative analysis could improve the prediction accuracy of the DBP formation than bulk parameters during NOM and AOM chlorination.

Dissolved organic nitrogen in wastewater treatment processes: Transformation, biosynthesis and ecological impacts.

With the upgrade of wastewater treatment plants (WWTPs) to meet more stringent discharge limits for nutrients, dissolved organic nitrogen (DON) is present at an increasing percentage (up to 85%) in the effluent. Discharged DON is of great environmental concern due to its potentials in stimulating algal growth and forming toxic nitrogenous disinfection by-products (N-DBPs). This article systematically reviewed the characteristics, transformation and ecological impacts of wastewater DON. Proteins, amino acids and humic substances are the abundant DON compounds, but a large fraction (nearly 50%) of DON remains uncharacterized. Biological treatment processes play a dominant role in DON transformation (65-90%), where DON serves as both nutrient and energy sources. Despite of the above progress, critical knowledge gaps remain in DON functional duality, relationship with dissolved inorganic nitrogen (DIN) species, and coupling/decoupling with the dissolved organic carbon (DOC) pool. Development of more rapid and accurate quantification methods, modeling transformation processes, and assessing DON-associated eutrophication and N-DBP formation risks should be given priority in further investigations.

Release of nitrogenous disinfection by-product precursors in algae-laden water under UV radiation

Abstract Nitrogen-containing organic compounds and nitrogenous disinfection by-products (N-DBPs) in drinking water have attracted attention in the field of water treatment. Metabolites released during algae growth contain a variety of organic nitrogen species, which are called N-DBP precursors. The aim of this paper is to elucidate how N-DBP precursors are released under UV radiation, as well as investigate the variations of their chemical properties. The results show that through UV radiation, the physiological metabolism of algal cells was disordered and the properties of their metabolites were changed. The dissolved organic nitrogen (DON) compound concentration increased rapidly from 5.38 at the beginning to 11.11 mg/L after 30 min of radiation, and then increased steadily from 11.11 to 23.71 mg/L during a further 210 min of radiation. Derivation results of the curves for algae and DON concentration variations shows that when 1 × 1010 algal cells were destroyed, 8.31 mg DON was released into the solution during the first 30 min of radiation. Low dose UV radiation brought a slight decline of the specific N-DBP formation potential due to changes in the extracellular organic matter (EOM) structure without destroying the algal cells, which was conducive to controlling the formation potential of N-DBPs. Long-time UV radiation can bring a significant increase in N-DBP formation potential. After 4 hours of ultraviolet radiation, the total formation potential of N-DBPs in the solution increased from about 84.9 μg/L to about 213.5 μg/L, 2.5 times higher than the initial solution. The N-DBP formation potential increases obviously during the first 10–30 min UV radiation, and then decreases slightly in the subsequent 30–240 min radiation.

Identification of N-Nitrosamines and Nitrogenous Heterocyclic Byproducts during Chloramination of Aromatic Secondary Amine Precursors.

With diminishing pristine water, wastewater-affected waters that contain complex anthropogenic compounds are becoming important sources of drinking water and the compounds will inevitably react with disinfectants to form disinfection byproducts (DBPs). Secondary amines such as diphenylamine (DPA) analogues are considered as potential precursors of N-nitrosamines. In this study, an in situ 14N/15N-labeling and screening workflow was used to systematically investigate the formation of nitrogenous DBPs (N-DBPs) and putative reaction pathways. Twenty-four pairs of N-DBPs were generated and identified from chloramination of DPA through two main pathways, in which chloramines reacted with the amino and phenyl functional groups to form N-nitrosodiphenylamine and monochlorinated 5,10-dihydro-phenazine (Cl-DiH-Phe), respectively. Cl-DiH-Phe could further produce phenazine and the coupling products with another DPA molecule. Selective N-DBP formation was pH and dose-dependent, and the same reactions were observed for additional two aromatic DPA analogues. Effects of alkyl substituents on the formation pathways were investigated using a series of dialkyl and N-alkyl aromatic analogues. Only the amino pathway to form nitrosamines was noticed for dialkyl amines, nevertheless, both the main reactions occurred for N-alkyl aromatic amines. These findings suggested that the reaction with chloramines through a phenyl pathway was likely to be crucial for novel nitrogenous heterocyclic byproducts.

Formation of disinfection byproducts during chlorination of mixed nitrogenous compounds in swimming pools

Disinfection byproducts (DBPs) in swimming pool waters are receiving increasing attention because of their toxicity and widespread occurrence. Current studies rarely investigate the formation of DBPs from typical precursors in swimming pools under mixed exposure. They also rarely investigate the formation of carbonaceous DBPs (C-DBPs) and nitrogenous DBPs (N-DBPs) simultaneously. In this study, the formation of C-DBPs and N-DBPs were investigated during chlorination of mixed precursors (i.e., tryptophan, urea, creatinine, and ammonia). The effects of precursors and operation parameters were also investigated. Among the four precursors, tryptophan had the highest DBP formation potential. Urea and ammonia restrained the formation of C-DBPs but promoted the formation of more toxic N-DBPs. C-DBP yields were significantly higher than N-DBP yields under all experimental conditions. Longer reaction time and higher chlorine dosage promoted the formation of C-DBPs, while higher temperature decreased the concentration of N-DBPs. The presence of bromide not only improved the sum yields of DBPs, but also shifted chlorinated DBPs to brominated species.

ClO2 pre-oxidation impacts the formation and nitrogen origins of dichloroacetonitrile and dichloroacetamide during subsequent chloramination

Chlorine dioxide (ClO2) can be used as a pre-oxidant when chloramination is performed in water treatment plants. However, the effects of ClO2 pre-oxidation on the formation of nitrogenous disinfection by-products, such as dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm), during chloramination are not well understood. In this study, the effects of ClO2 pre-oxidation on the formation of DCAN and DCAcAm during chloramination of 28 model compounds and seven real water samples were investigated. The sources of nitrogen for DCAN and DCAcAm formation were investigated using 15N-labeled monochloramine. ClO2 pre-oxidation affected DCAN and DCAcAm formation during chloramination of model compounds in different ways. ClO2 pre-oxidation increased unlabeled and 15N-labeled DCAN and DCAcAm formation during chloramination of six amino acids and peptides and five indoles and tertiary amines. ClO2 pre-oxidation decreased DCAN formation but increased DCAcAm formation during chloramination of three hydroxybenzamide compounds, but had the opposite effects for four tetracyclines. ClO2 pre-oxidation generally decreased DCAN and DCAcAm formation during chloramination of the phenolic compounds that are precursors not containing nitrogen. 2-Aminoacetophenone, formamid-trans-muconic acid, and unsaturated ketones were found to be transformation products of ClO2 oxidation of 3-methylindole, salicylamide, and resorcinol, respectively. Possible DCAN and DCAcAm formation pathways during chloramination after ClO2 oxidation were identified. For most of the water samples, ClO2 pre-oxidation decreased the amounts of DCAN and DCAcAm formed during chloramination by 36%–70% and 11%–59%, respectively. This may have been caused by ClO2 oxidation destroying phenolic precursors and macromolecular proteins rather than amino acids in the water samples.

Impact of backwash on biofiltration-related nitrogenous disinfection by-product formation

Previous studies have reported that biofilm extracted from full-scale biofilters can serve as nitrogenous disinfection by-product (N-DBP) precursors. Detached biofilm materials could escape during filter ripening and form N-DBP upon chloramination. This study examined the potential breakthrough of biofilm and N-DBP precursors during filter ripening at two water treatment plants (WTPs). The presence of biofilm material in aqueous samples was estimated by total adenosine triphosphate (tATP) levels; N-DBP formation potential (FP) tests were conducted under uniform formation conditions to quantify N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN4) precursors. While tATP peaks in filter effluent were observed post backwash at both WTPs, temporary increases of effluent NDMA FP were only observed during filter ripening where particle-associated NDMA precursors served as the dominant contributor. Overall, biofilters examined in this study demonstrated a consistent removal of NDMA FP regardless of the filter ripening process.

Effects of Pre-Oxidation on Haloacetonitrile and Trichloronitromethane Formation during Subsequent Chlorination of Nitrogenous Organic Compounds.

The reaction between organic matter and disinfectants leads to the formation of disinfection byproducts (DBPs) in drinking water. With the improvement of detection technology and in-depth research, more than 1000 kinds of DBPs have been detected in drinking water. Nitrogenous DBPs (N-DBPs) are more genotoxic and cytotoxic than the regulated DBPs. The main methods are enhanced coagulation, pretreatment, and depth technologies which based are on conventional technology. Amino acids (AAs) are widely found in surface waters and play an important role by providing precursors from which toxic nitrogenous disinfection by-products (N-DBPs) are generated in chlorinated drinking water. The formation of N-DBPs, including dichloroacetonitrile, trichloroacetonitrile, and trichloronitromethane (TCNM), was investigated by analyzing chlorinated water using ozone (OZ), permanganate (PM), and ferrate (Fe(VI)) pre-oxidation processes. This paper has considered the control of pre-oxidation over N-DBPs formation of AAs, OZ, PM, and Fe(VI) pre-oxidation reduced the haloacetonitrile formation in the downstream chlorination. PM pre-oxidation decreased the TCNM formation during the subsequent chlorination, while Fe(VI) pre-oxidation had no significant influence on the TCNM formation, and OZ pre-oxidation increased the formation. OZ pre-oxidation formed the lowest degree of bromine substitution during subsequent chlorination of aspartic acid in the presence of bromide. Among the three oxidants, PM pre-oxidation was expected to be the best choice for reducing the estimated genotoxicity and cytotoxicity of the sum of the measured haloacetonitriles (HANs) and TCNM without bromide. Fe(VI) pre-oxidation had the best performance in the presence of bromide.

Stable Isotopic Labeling and Nontarget Identification of Nanogram/Liter Amino Contaminants in Water.

We report a new combinatorial approach of stable isotopic labeling (SIL)-solid phase extraction (SPE)-liquid chromatography-tandem high-resolution mass spectrometry (LC-HRMS/MS) for identification of amino-containing contaminants at trace levels in source water. The new SIL method requires small amounts of formaldehyde (CH2O) and deuterated formaldehyde (CD2O) to efficiently label ng/L amino compounds in 1 L of water and improves SPE recovery, enabling environmental analysis of trace amino-compounds. Isotopically methylated components were confirmed using LC-MS/MS based on their retention times, and characteristic isotope patterns of the molecular and product ions. Using the characteristic isotope patterns, we established a data prioritization process to identify the amino compounds in thousands of mass peaks in raw data. Analysis of a labeled authentic source water detected 8952 m/z peaks and tentatively identified 154 amino compounds. Our SIL-methylation prioritization approach effectively reduced the complexity of data. Manual spectrum interpretation identified 77 of the 154 components as amino acids and peptides. We confirmed 8 of the 77 compounds using commercially available standards to demonstrate the feasibility and reliability of our SIL-SPE-LC-HRMS/MS method for environmental analysis of trace amino-containing contaminants. The method can efficiently identify amino-precursors in source water, enabling other studies of nitrogenous disinfection byproduct formation.

Conversion of chlorine/nitrogen species and formation of nitrogenous disinfection by-products in the pre-chlorination/post-UV treatment of sulfamethoxazole

Pre-chlorination and UV disinfection are two common processes in drinking water treatment plants. Sulfamethoxazole (SMX), an antibiotic widely detected in source water, was selected as a precursor to study the conversion of chlorine/nitrogen species and DBP formation in pre-chlorination/post-UV process. The combined chlorine (mainly organic chloramines) produced in pre-chlorination of SMX can self-degrade and release free chlorine back again as pre-chlorination time goes on. With free chlorine dose increasing, the self-degradation rate of combined chlorine increased obviously. But the combined chlorine stopped self-degrading and remained stable around 1 mg-Cl2/L after adding 0.30 mM chlorine for 30 min. Post-UV treatment after pre-chlorination can enhance the degradation and achieve a complete removal of combined chlorine (including organic chloramines). Deamination occurred during pre-chlorination/post-UV process and deamination amount (-NH2) per SMX concentration was 0.19 M/M. Radicals in this process had no obvious influence on chlorine/nitrogen species conversion. Direct chlorination of SMX had the lowest DBP formation potentials while the application of pre-chlorination and UV enhanced them. Compared with UV treatment only, dichloroacetonitrile formation potential of SMX reduced by 1.58 × 10−3 mol/mol-SMX (17.37 μg/l) after pre-chlorination/post-UV treatment. During pre-chlorination/post-UV/final-chlorination treatment of SMX, Br− and natural organic matter can enhance DBP formation and toxicity-weighted values. Acid conditions showed a very high DBP risk, while alkaline conditions could cut this risk obviously, especially for the toxicity-weighted values of these DBPs.

Microbial degradation of typical amino acids and its impact on the formation of trihalomethanes, haloacetonitriles and haloacetamides during chlor(am)ination

Nitrogenous disinfection by-products (N-DBPs) in chlorinated drinking water are receiving increasing attention due to their elevated toxicities. An effective strategy to control the formation of N-DBPs is to reduce their nitrogenous precursors (e.g., amino acids [AAs], believed to be the important N-DBP precursors) before disinfection. So far, little information is available about the effectiveness of conventional microbial degradation at controlling the formation of N-DBPs. In this study, the biodegradability of 20 AAs was investigated, and the impacts of microbial degradation for the selected 6 typical AAs on the formation of N-DBPs (haloacetonitriles and haloacetamides) and traditional carbonaceous DBP (chloroform) were investigated. The results indicated that glycine, arginine, aspartic acid, asparagine, alanine and serine were susceptible to biodegradation, and the formation potentials (FPs) of DBPs were remarkably reduced after biodegradation. The highest chloroform FP reduction rates from tryptophan and tyrosine were 85.4% and 56.2%, respectively. The FPs of dichloroacetonitrile and trichloroacetamide were also reduced after biodegradation of the all selected AA samples during chlor(am)ination. Dichloroacetamide FPs decreased continuously with incubation time during chlorination for phenylalanine, asparagine, aspartic acid, and the mixed AAs, and the highest reduction rates were 78.7%, 74.6%, 46.7% and 35.3% respectively. The results of integrated toxicity analysis indicated that the pre-treatment of microbial degradation significantly decreased the integrated toxicity of DBPs formed from AAs. Moreover, the microbial community analysis revealed that Proteobacteria was predominant at phylum level in the mixed AA sample, and the dominant genera were Acinetobacter and Pseudomonas. Proteobacteria may play an important role in controlling DBP precursor.

Transformation and fate of dissolved organic nitrogen in drinking water supply system: A full scale case study from Yixing, China

The transformation of dissolved organic nitrogen (DON) in the drinking water treatment plants could be closely associated with nitrogenous disinfection by-product (N-DBP) formation. In this study, we have assessed the molecular transformation of DON and its impact on N-DBP formation in a full scale drinking water treatment plant. Based on the result of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis, DON compounds with low molecular weight (<1 kDa) were classified as CHON, CHON2 and CHON3 according to the number of nitrogen atoms. Via the analytical window of van Krevelen diagrams, we found that the molecular structural features of CHON, CHON2 and CHON3 were not altered before the chlorination process. In detail, the CHON2 and CHON3 compositions were concentrated on the regions assigned to a lignin-structure while CHON compositions were also distributed in other compounds including proteins, carbohydrates and tannin. Furthermore, CHON formation was more difficult to be removed before the V-filter process. For N-DBP, chlorine-containing DON (Cl-DON) composition was likely to be removed through flocculation and sedimentation processes, whereas N-nitrosamine compounds were removed in V-filter and biological activated carbon filter processes. The health risks of aromatic structure N-nitrosamines due to the pre-chlorination of the raw water should be further studied.

Impact of UV irradiation on Chlorella sp. damage and disinfection byproducts formation during subsequent chlorination of algal organic matter

The frequent occurrence of algal blooms in surface water has attracted more and more attention, which caused many water quality problems, including disinfection byproducts (DBPs). Algal organic matter (AOM) including intracellular organic matter (IOM) and extracellular organic matter (EOM), was a well-known precursor to DBPs formation in drinking water. This study evaluated the effect of ultraviolet (UV) irradiation on the cell integrity, IOM release and DBPs formation during subsequent chlorination of Chlorella sp. Results showed the damage rates of algal cells increased to 40.1% after the high UV irradiation of 528 mJ/cm2, which contributed to the release of IOM. In addition, UV irradiation was effective in reducing the formation of haloacetic acids (HAAs) both in AOM and IOM, but promoted the formation of nitrogenous DBPs (N-DBPs) from AOM in subsequent chlorination. Furthermore, neutral pH exerted a positive effect on the formation of DBPs. UV irradiation decreased the bromine substitution factor (BSF) value of AOM at a high bromide level. The BSF values increased with increasing of the concentration of bromide. Moreover, more amino acids and low molecular weight precursors were produced after UV irradiation in filtered supernatant, which contributed to the formation of N-DBPs with algal chlorination. Overall, this information demonstrated pre-oxidation of UV irradiation could be used to treat the algal-rich drinking water.

The contribution of biofilm to nitrogenous disinfection by-product formation in full-scale cyclically-operated drinking water biofilters

Biofiltration has been shown to be effective for disinfection by-product (DBP) precursor control, however few studies have considered its role in the potential formation of DBPs. Biofilm is composed of heterogeneous bacteria as well as extracellular polymeric substances (EPS). The objective of this study was to determine the contribution of biofilm-related materials such as EPS to form nitrogen-containing DBPs upon chloramination, and to determine the influence of cyclical (scheduled on-off) biofilter operation on DBP precursor removal. Biologically active media was sampled from a full-scale biofilter operating under cold-water conditions (3.6 ± 0.5 °C) and extracted using a cation exchange resin into a phosphate buffer solution. Biomass concentrations, as determined using adenosine triphosphate (ATP) measurements, remained stable at 298 ± 55 ng ATP/g media over the trial period. N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN4) formation potential (FP) tests conducted under uniform formation conditions (UFC) using extracted biofilm yielded 0.80 ± 0.27 ng NDMA/g media and 18.7 ± 3.3 ng dichloroacetonitrile (DCAN)/g media. Further analyses of extracted biofilm using fluorescence spectroscopy and liquid chromatography-organic carbon detection indicated the presence of proteins above 20 kDa and humic-like substances. Extracted proteins (93.5 ± 8.1 μg/g media) correlated well (R = 0.90) with UV 280 measurements, indicating that spectrophotometry may serve as a valuable tool to quantify proteins in extracted biofilms. While substances in biofilms can serve as NDMA and DCAN precursors, the full-scale cyclically-operated biofilter that was examined did not show release of NDMA precursors during start-up following stagnation periods of 6 h or more. These biofilters consistently removed 6.9 ± 4.3 ng/L of NDMA precursors; typical NDMA UFC-FP of biofilter effluent was 8.5 ± 2.6 ng/L.