Identification, occurrence, concentration and composition profile of fiproles in municipal wastewater treatment plants.

Although fipronil and several of its transformation products are ubiquitous in aquatic environments, limited information is available on the structural identities, detection frequencies, concentrations and composition profiles of fiproles (fipronil and its known and unknown transformation products) in municipal wastewater treatment plants (WWTPs). In this study, a suspect screening analysis was applied to identify and characterize fipronil transformation products in 16 municipal WWTPs from three cities in China. In addition to fipronil and its four transformation products (fipronil amide, fipronil sulfide, fipronil sulfone and desulfinyl fipronil), fipronil chloramine and fipronil sulfone chloramine were detected for the first time in municipal wastewater. Moreover, the cumulative concentrations of six transformation products were 0.236 ng/L and 3.44 ng/L in wastewater influents and effluents, and accounted for one-third (in influents) to half (in effluents) of fiproles. Of those transformation products, two chlorinated byproducts (fipronil chloramine and fipronil sulfone chloramine) were major transformation products in both municipal wastewater influents and effluents. Notably, the log Kow and bioconcentration factor (evaluated by EPI Suite software) of fipronil chloramine (log Kow = 6.64, and BCF = 11,200 L/kg wet-wt) and fipronil sulfone chloramine (log Kow = 4.42, and BCF = 382.9 L/kg wet-wt) were greater than that of their parent compound. Considering the persistence, bioaccumulation potential and toxicity, the high detection rates of fipronil chloramine and fipronil sulfone chloramine in urban aquatic systems need to be specifically considered in future ecological risk assessments.

Overlooked Iodo-Disinfection Byproduct Formation When Cooking Pasta with Iodized Table Salt.

Iodized table salt provides iodide that is essential for health. However, during cooking, we found that chloramine residuals in tap water can react with iodide in table salt and organic matter in pasta to form iodinated disinfection byproducts (I-DBPs). While naturally occurring iodide in source waters is known to react with chloramine and dissolved organic carbon (e.g., humic acid) during the treatment of drinking water, this is the first study to investigate I-DBP formation from cooking real food with iodized table salt and chloraminated tap water. Matrix effects from the pasta posed an analytical challenge, necessitating the development of a new method for sensitive and reproducible measurements. The optimized method utilized sample cleanup with Captiva EMR-Lipid sorbent, extraction with ethyl acetate, standard addition calibration, and analysis using gas chromatography (GC)-mass spectrometry (MS)/MS. Using this method, seven I-DBPs, including six iodo-trihalomethanes (I-THMs) and iodoacetonitrile, were detected when iodized table salt was used to cook pasta, while no I-DBPs were formed with Kosher or Himalayan salts. Total I-THM levels of 11.1 ng/g in pasta combined with cooking water were measured, with triiodomethane and chlorodiiodomethane dominant, at 6.7 and 1.3 ng/g, respectively. Calculated cytotoxicity and genotoxicity of I-THMs for the pasta with cooking water were 126- and 18-fold, respectively, compared to the corresponding chloraminated tap water. However, when the cooked pasta was separated (strained) from the pasta water, chlorodiiodomethane was the dominant I-THM, and lower levels of total I-THMs (retaining 30% of the I-THMs) and calculated toxicity were observed. This study highlights an overlooked source of exposure to toxic I-DBPs. At the same time, the formation of I-DBPs can be avoided by boiling the pasta without a lid and adding iodized salt after cooking.

Novel insights into formation mechanism of organic chloramines from pre-oxidized algae-laden water: Multiple roles of dissolved organic nitrogen.

Organic chloramines posed significant risks to drinking water safety. However, the formation mechanism of algae-derived organic chloramines remained unclear. In this study, it was observed that pre-oxidation of algal suspensions increased organic chloramine formation during chlorination. Compared to KMnO4 pre-oxidation, O3 significantly increased the organic chloramine formation potential of algal suspensions. Characterization was performed with size exclusion chromatography-multiple detectors (SEC-MDs) to better understand the organic chloramine formation mechanism. The results revealed that low molecular weight proteins (AMW ≤ 0.64 kDa) were the main precursors of organic chloramines after conventional water treatment processes. We then focused on 14 essential amino acids involved in protein formation. Their concentrations and organic chloramine formation potentials were determined, based on which the theoretical organic chloramine formation potentials of the studied samples were evaluated. However, dramatic gaps between theoretical and experimental organic chloramine formations were observed, which suggested that not all organic nitrogen could react with chlorine to form organic chloramine. The condensed dual descriptor (CDD) was calculated to predict the electrophilic substitution reaction sites on peptides. Furthermore, the activation barrier of each proposed reaction was computed to confirm that the reaction sites for chlorine were located on amino groups. This study clarified the formation mechanism of algal-derived organic chloramines, which could provide a powerful theoretical foundation for controlling organic chloramine formation in drinking water processes.

The "Burn": water quality and microbiological impacts related to limited free chlorine disinfection periods in a chloramine system.

To control microbial proliferation and nitrification within distribution systems, utilities practicing secondary disinfection chloramination often discontinue their ammonia feed and provide a short, free chlorine disinfection period (FClP), commonly referred to as a "chlorine burn". However, the success and practicality of this approach is often criticized because of the return to nitrification; yet, previous studies conducted in full-scale distribution systems do not contain the sampling frequency to determine how quickly nitrification can return. In this research, a total of 15 hydrants distributed across hydraulically modeled water ages were sampled for 21 sampling events over a period spanning two annual FClPs (2018 and 2019) to investigate the water quality, planktonic community, and, using a new sampling technique, established biofilm community impacts within a single, distribution system pressure zone. Hydrants measured elevated nitrite only 10 weeks after the end of the FClP and live cell counts in the bulk and scour samples statistically significantly increased within two weeks after the FClP ended and chloramine disinfection resumed, indicating limited impacts from a FClP. Furthermore, the FClP significantly increased iron concentrations during the period of free chlorine disinfection creating a consumer water quality concern. Microbial fingerprint analysis using flow cytometry revealed that beta diversity did not significantly change for sampling locations that experienced even periodic low total chlorine concentrations. Only locations that maintained high chlorine residuals throughout both chloramine and free chlorine disinfection periods demonstrated significant changes in bulk water microbial community. Even for these locations, microbial communities of the scoured biofilms remained similar over the course of the study.

Reactivity-directed analysis - a novel approach for the identification of toxic organic electrophiles in drinking water.

Drinking water consumption results in exposure to complex mixtures of organic chemicals, including natural and anthropogenic chemicals and compounds formed during drinking water treatment such as disinfection by-products. The complexity of drinking water contaminant mixtures has hindered efforts to assess associated health impacts. Existing approaches focus primarily on individual chemicals and/or the evaluation of mixtures, without providing information about the chemicals causing the toxic effect. Thus, there is a need for the development of novel strategies to evaluate chemical mixtures and provide insights into the species responsible for the observed toxic effects. This critical review introduces the application of a novel approach called Reactivity-Directed Analysis (RDA) to assess and identify organic electrophiles, the largest group of known environmental toxicants. In contrast to existing in vivo and in vitro approaches, RDA utilizes in chemico methodologies that investigate the reaction of organic electrophiles with nucleophilic biomolecules, including proteins and DNA. This review summarizes the existing knowledge about the presence of electrophiles in drinking water, with a particular focus on their formation in oxidative treatment systems with ozone, advanced oxidation processes, and UV light, as well as disinfectants such as chlorine, chloramines and chlorine dioxide. This summary is followed by an overview of existing RDA approaches and their application for the assessment of aqueous environmental matrices, with an emphasis on drinking water. RDA can be applied beyond drinking water, however, to evaluate source waters and wastewater for human and environmental health risks. Finally, future research demands for the detection and identification of electrophiles in drinking water via RDA are outlined.

Inactivation of Rhizoctonia solani in fertigation water using regenerative in situ electrochemical hypochlorination.

The capture and re-use of greenhouse fertigation water is an efficient use of fertilizer and limited water resources, although the practice is not without risk. Plant pathogens and chemical contaminants can build up over successive capture and re-use cycles; if not properly managed they can lead to reduced productivity or crop loss. There are numerous established and emerging water treatment technologies available to treat fertigation water. Electrochemical processes are emerging as effective means for controlling pathogens via in situ regenerative hypochlorination; a process that is demonstrated here to achieve pathogen control in fertigation solutions without leading to the accumulation of potentially phytotoxic free chlorine residuals associated with other chlorination processes. An electrochemical flow cell (EFC) outfitted with ruthenium dioxide (RuO2) dimensionally stable anodes (DSA) was characterized and evaluated for free chlorine production and Rhizoctonia solani inactivation in both irrigation and fertigation solutions. Pathogen inactivation was achieved at low current densities and short residence or cell contact times. Effluent free chlorine concentrations were significantly lower than commonly reported phytotoxic threshold values (approximately 2.5 mg/L) when fertilizer (containing ammonium) was present in the test solution; an effect attributable to reactions associated with breakpoint chlorination, including chloramine formation, as well as the presence of other oxidizable compounds in the fertilizer. Chloride concentrations were stable under the test conditions suggesting that the EFC was operating as a regenerative in situ electrochemical hypochlorination system. No significant changes to macronutrient concentrations were found following passage through the EFC.

N-chlorination mediates protective and immunomodulatory effects of oxidized human plasma proteins.

Hypochlorous acid (HOCl), a powerful antimicrobial oxidant, is produced by neutrophils to fight infections. Here, we show that N-chlorination, induced by HOCl concentrations encountered at sites of inflammation, converts blood plasma proteins into chaperone-like holdases that protect other proteins from aggregation. This chaperone-like conversion was reversible by antioxidants and was abrogated by prior methylation of basic amino acids. Furthermore, reversible N-chlorination of basic amino acid side chains is the major factor that converts plasma proteins into efficient activators of immune cells. Finally, HOCl-modified serum albumin was found to act as a pro-survival molecule that protects neutrophils from cell death induced by highly immunogenic foreign antigens. We propose that activation and enhanced persistence of neutrophils mediated by HOCl-modified plasma proteins, resulting in the increased and prolonged generation of ROS, including HOCl, constitutes a potentially detrimental positive feedback loop that can only be attenuated through the reversible nature of the modification involved.

Factors affecting the water odor caused by chloramines during drinking water disinfection.

Chloramine disinfection is one of the most common disinfection methods in drinking water treatment. In this study, the temporal variability of water odors during monochloramine auto-decomposition was investigated to elucidate the characteristics of odor problems caused by adopting chloramine disinfection in tap water. Odor intensities and dominant odorant contributions were determined using the flavor profile analysis (FPA) and odor active value (OAV), respectively. During auto-decomposition of monochloramine, Cl2/N molar ratio, pH, temperature, and the presence of NOM all affected odor intensity and odor temporal variation in drinking water. In general, decreasing pH from 8.5 to 6.0 led to increasing perceived odor intensity due to the formation of dichloramine. The major odorants responsible for chlorinous odor under acidic and non-acidic conditions were dichloramine and monochloramine, respectively. Chloraminated water with a Cl2/N molar ratio of 0.6 or NOM concentration <2 mg-C L-1 inhibited odor intensity. Furthermore, the influence of rechlorination on chlorinous odor intensity for chloraminated water should not be neglected. The results of this study will be beneficial for the control of chlorinous odors caused by chloramine disinfection in drinking water.

The Henry's constant of monochloramine.

Monochloramine is a secondary disinfectant used in drinking water and is also formed in chlorinated wastewater. While known to hydrolyze over time and react with dissolved organic matter, its partitioning between the aqueous and gas phase has not been extensively studied. Preliminary experiments demonstrated that monochloramine concentrations in solutions open to the atmosphere or actively aerated decreased more rapidly than in sealed solutions, indicating significant losses to the atmosphere. For example, a monochloramine solution open to the atmosphere yielded a loss rate constant of 0.08 d-1, a value twice that for sealed samples without headspace (0.04 d-1) where loss occurs exclusively as a result of hydrolysis. A solution aerated at 10 mL s-1 had a loss rate constant nearly 10× greater than that for hydrolysis alone (0.35 d-1). To better understand partitioning of monochloramine to the gas phase and potential for volatilization, the dimensionless Henry's law constants of monochloramine (KH) were determined using an equilibrium headspace technique at five different temperatures (11, 16, 21, 27, and 32 °C). The resulting values ranged from 8 × 10-3 to 4 × 10-2, indicating a semi-volatile compound, and were found to be consistent with quantitative structure activity relationship predictions. At 20 °C, monochloramine exhibits a dimensionless Henry's constant of about 1.7 × 10-2 which is 35 times greater than ammonia but comparable to the Henry's constant of inorganic semi-volatile compounds such sulfur dioxide. The Henry's constant values for monochloramine suggests that volatilization could be a relevant loss process in open systems such as rivers receiving chlorinated wastewater effluent, swimming pools and cooling towers.

Monochloramine dissipation in storm sewer systems: field testing and model development.

Monochloramine (NH2Cl), as the dominant disinfectant in drinking water chloramination, can provide long-term disinfection in distribution systems. However, NH2Cl can also be discharged into storm sewer systems and cause stormwater contamination through outdoor tap water uses. In storm sewer systems, NH2Cl dissipation can occur by three pathways: (i) auto-decomposition, (ii) chemical reaction with stormwater components, and (iii) biological dissipation. In this research, a field NH2Cl dissipation test was conducted with continuous tap water discharge into a storm sewer. The results showed a fast decrease of NH2Cl concentration from the discharge point to the sampling point at the beginning of the discharge period, while the rate of decrease decreased as time passed. Based on the various pathways involved in NH2Cl decay and the field testing results, a kinetic model was developed. To describe the variation of the NH2Cl dissipation rates during the field testing, a time coefficient fT was introduced, and the relationship between fT and time was determined. After calibration through the fT coefficient, the kinetic model described the field NH2Cl dissipation process well. The model developed in this research can assist in the regulation of tap water outdoor discharge and contribute to the protection of the aquatic environment.

Concentrations of disinfection by-products in swimming pool following modifications of the water treatment process: An exploratory study.

The formation and concentration of disinfection by-products (DBPs) in pool water and the ambient air vary according to the type of water treatment process used. This exploratory study was aimed at investigating the short-term impact of modifications of the water treatment process on traditional DBP levels (e.g., trihalomethanes (THMs), chloramines) and emerging DBPs (e.g., Halonitromethanes, Haloketones, NDMA) in swimming pool water and/or air. A sampling program was carried to understand the impact of the following changes made successively to the standard water treatment process: activation of ultraviolet (UV) photoreactor, halt of air stripping with continuation of air extraction from the buffer tank, halt of air stripping and suppression of air extraction from the buffer tank, suppression of the polyaluminium silicate sulfate (PASS) coagulant. UV caused a high increase of Halonitromethanes (8.4 fold), Haloketones (2.1 fold), and THMs in the water (1.7 fold) and, of THMs in the air (1.6 fold) and contributed to reducing the level of chloramines in the air (1.6 fold) and NDMA in the water (2.1 fold). The results highlight the positive impact of air stripping in reducing volatile contaminants. The PASS did not change the presence of DBPs, except for the THMs, which decrease slightly with the use of this coagulant. This study shows that modifications affecting the water treatment process can rapidly produce important and variable impacts on DBP levels in water and air and suggests that implementation of any water treatment process to reduce DBP levels should take into account the specific context of each swimming pool.

Occurrence and formation of disinfection by-products in the swimming pool environment: A critical review.

Disinfection of water for human use is essential to protect against microbial disease; however, disinfection also leads to formation of disinfection by-products (DBPs), some of which are of health concern. From a chemical perspective, swimming pools are a complex matrix, with continual addition of a wide range of natural and anthropogenic chemicals via filling waters, disinfectant addition, pharmaceuticals and personal care products and human body excretions. Natural organic matter, trace amounts of DBPs and chlorine or chloramines may be introduced by the filling water, which is commonly disinfected distributed drinking water. Chlorine and/or bromine is continually introduced via the addition of chemical disinfectants to the pool. Human body excretions (sweat, urine and saliva) and pharmaceuticals and personal care products (sunscreens, cosmetics, hair products and lotions) are introduced by swimmers. High addition of disinfectant leads to a high formation of DBPs from reaction of some of the chemicals with the disinfectant. Swimming pool air is also of concern as volatile DBPs partition into the air above the pool. The presence of bromine leads to the formation of a wide range of bromo- and bromo/chloro-DBPs, and Br-DBPs are more toxic than their chlorinated analogues. This is particularly important for seawater-filled pools or pools using a bromine-based disinfectant. This review summarises chemical contaminants and DBPs in swimming pool waters, as well as in the air above pools. Factors that have been found to affect DBP formation in pools are discussed. The impact of the swimming pool environment on human health is reviewed.

Organic chloramines in chlorine-based disinfected water systems: A critical review.

This paper is a critical review of current knowledge of organic chloramines in water systems, including their formation, stability, toxicity, analytical methods for detection, and their impact on drinking water treatment and quality. The term organic chloramines may refer to any halogenated organic compounds measured as part of combined chlorine (the difference between the measured free and total chlorine concentrations), and may include N-chloramines, N-chloramino acids, N-chloraldimines and N-chloramides. Organic chloramines can form when dissolved organic nitrogen or dissolved organic carbon react with either free chlorine or inorganic chloramines. They are potentially harmful to humans and may exist as an intermediate for other disinfection by-products. However, little information is available on the formation or occurrence of organic chloramines in water due to a number of challenges. One of the biggest challenges for the identification and quantification of organic chloramines in water systems is the lack of appropriate analytical methods. In addition, many of the organic chloramines that form during disinfection are unstable, which results in difficulties in sampling and detection. To date research has focussed on the study of organic monochloramines. However, given that breakpoint chlorination is commonly undertaken in water treatment systems, the formation of organic dichloramines should also be considered. Organic chloramines can be formed from many different precursors and pathways. Therefore, studying the occurrence of their precursors in water systems would enable better prediction and management of their formation.

Monochloramine Loss Mechanisms in Tap Water.

Chloramination has been widely applied for drinking water disinfection, with monochloramine (NH2Cl) the dominant chloramine species. However, under neutral pH, NH2Cl can autodecompose and react with chemical components in drinking water, thus decreasing disinfection efficiency. In tap water, the NH2Cl loss rate can be influenced by temperature, pH, Cl/N molar ratio, the initial NH2Cl concentration, and the natural organic matter (NOM) concentration. A good prediction of NH2Cl loss can assist in the operation of drinking water treatment plants. In this research, a kinetic rate constant )and a reactive site fraction (S = 0.43 ± 0.06) for the reaction between free chlorine released from NH2Cl autodecoposition and tap water NOM were derived from a kinetic model to predict the NH2Cl loss under various conditions. A temperature-dependent model was also developed. The model predictions match well with the experimental results, which demonstrates the validity of the model and provides a convenient and accurate method for NH2Cl loss calculations.

Formation of known and unknown disinfection by-products from natural organic matter fractions during chlorination, chloramination, and ozonation.

Natural organic matter (NOM) is the main precursor of disinfection by-products (DBPs) formed during drinking water treatment processes. Previous studies of the relationships between DBP formation and NOM fractionation have mainly been focused on currently regulated DBPs and a few certain emerging DBPs. In this work, the Suwannee River NOM solution was fractionated into groups with different hydrophobicities using DAX-8 resins, and volatile and semi-volatile DBPs formed during the chlorination, chloramination and ozonation of the NOM fractions were examined by a nontargeted screening of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry procedure. The results showed that a total of 302 DBPs representing nine chemical classes were detected, of which 266 were possibly newly detected, based on library searching with NIST 08 library (using similarity and reverse values of at least 600 and 700, respectively) and linear retention indices. The characterization of DBP precursors suggests that hydrophobic (HPO) NOM contains the major fraction of precursor for the formation of nitrogenous DBPs (contributing about 60% of the total nitrogenous DBPs) during all three disinfection processes. Much larger amounts of heterocyclic DBPs were formed from the HPO fraction than from the hydrophilic fraction during chlorination. During chloramination and ozonation, 5-15 times more ketones were formed from the hydrophilic fraction than from the HPO fraction. During ozonation, more than twice the amounts of esters and alcohols were formed from the hydrophilic fraction than from the HPO fraction. Three-dimensional excitation-emission matrix spectra suggest that similar to the formation of regulated DBPs, humic acid-like substances are probably the precursors of halogen-containing DBPs. Relatively higher nitrogenous DBPs formation from the HPO fraction might be because of the existence of protein-like materials.

Synergistic integration of sonochemical and electrochemical disinfection with DSA anodes.

This work focuses on the disinfection actual urban wastewater by the combination of ultrasound (US) irradiation and electrodisinfection with Dimensionally Stable Anodes (DSA). First, the inactivation of Escherichia coli (E. coli) during the sonochemical disinfection was studied at increasing ultrasound power. Results showed that it was not possible to achieve a complete disinfection, even at the highest US power (200 W) dosed by the experimental device used. Next, the electrodisinfection with DSA anodes at different current densities was studied, finding that it was necessary a minimum current density of 11.46 A m(-2) to reach the complete disinfection. Finally, an integrated sonoelectrodisinfection process was studied. Results showed a synergistic effect when coupling US irradiation with DSA electrodisinfection, with a synergy coefficient higher than 200% of the disinfection rate attained for the highest US power applied. In this process, hypochlorite and chloramines were identified as the main reagents for the disinfection process (neither chlorate nor perchlorate were detected), and the presence of trihalomethanes was far below acceptable values. Confirming this synergistic effect with DSA anodes opens the door to novel efficient disinfection processes, limiting the occurrence of hazardous disinfection by-products.

Assessment of air and water contamination by disinfection by-products at 41 indoor swimming pools.

This study was aimed at assessing the profiles (occurrence and speciation) of disinfection by-product (DBP) contamination in air and water of a group of 41 public indoor swimming pools in Québec (Canada). The contaminants measured in the water included the traditional DBPs [i.e., four trihalomethanes (THMs), six haloacetic acids (HAAs)] but also several emergent DBPs [i.e., halonitriles, halonitromethanes, haloketones and nitrosodimethylamine (NDMA)]. Those measured in the air comprised THMs and chloramines (CAMs). Overall, extremely variable DBP levels were found from one pool to another (both quantitatively and in terms of speciation). For instance, in water, among the four THMs, chloroform was usually the most abundant compound (37.9±25.7µg/L). Nevertheless, the sum of the three other brominated THMs represented more than 25% of total THMs at almost half the facilities visited (19 cases). In 13 of them, the levels of brominated THMs (66±24.2µg/L) even greatly outweighed the levels of chloroform (15.2±6.31µg/L). Much higher levels of HAAs (294.8±157.6µg/L) were observed, with a consistent preponderance of brominated HAAs in the swimming pools with more brominated THMs. NDMA levels which were measured in a subset of 8 pools ranged between 2.8ng/L and 105ng/L. With respect to air, chloroform was still the most abundant THM globally (119.4±74.2µg/m(3)) but significant levels of brominated THMs were also observed in various cases, particularly in the previously evoked group of 13 swimming pools with preponderant levels of brominated THMs in water. CAM levels (0.23±0.15mg/m(3)) varied highly, ranging from not detected to 0.56mg/m(3). Overall, the levels were generally relatively high compared to current guidelines or reference values from several countries, and they point to a relatively atypical presence of brominated compounds, and to significant levels of emergent DBPs for which health risk is less documented.

Ternary Model of the Speciation of I-/Br-/Cl-Trihalomethanes Formed in Chloraminated Surface Waters.

This study examined the effects of the iodide concentration and pH on yields and speciation of the entire group of 10 species of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) formed at pH values from 6.5 to 8.5 in chloraminated surface waters in the presence of bromide and iodide. Pathways of iodine, bromine, and chlorine incorporation in the active sites in dissolved organic matter (DOM) were examined on the basis of a ternary halogenation/THM speciation model. The model assumed the occurrence of sequential three-step halogenation of the active site and competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. A comparison of experimentally measured and modeled speciation coefficients and also iodine and bromine incorporation factors calculated for 10 THM species showed that the developed approach was sufficient to closely model the observed trends. Interpretation of preferred iodine incorporation pathways associated with the generation of THMs in all examined conditions showed that the susceptibility of the halogenated intermediates to iodine incorporation increases rapidly with the number of iodine atoms that have already been incorporated into the reaction site. In contrast, the incorporation of bromine and chlorine atoms in the intermediates involved in the generation of THMs makes them largely inactive in iodine incorporation reactions. The presented approach allows for a further understanding of the mechanisms of DOM/halogen interactions and prediction of the speciation of THMs formed at varying pH values, iodide concentrations, and other system conditions.

Effect of UV irradiation on the proportion of organic chloramines in total chlorine in subsequent chlorination.

This study investigated the changes of chlorine species and proportion of organic chloramines during the chlorination process after UV irradiation pretreatment in drinking water. It was found that the UV pretreatment could enhance the percentage of organic chloramines by increasing free chlorine consumption in the chlorination of raw waters. The percentage of organic chloramines in total chlorine increased with UV intensity and irradiation time in raw waters. However, for the humic acid synthesized water, the percentage of organic chloramines increased first and then decreased with the increase of UV irradiation time. The value of SUVA declined in both raw and humic acid synthesized waters over the UV irradiation time, which indicated that the decomposition of aromatic organic matter by UV could be a contributor to the increase of free chlorine consumption and organic chloramine proportion. The percentage of organic chloramines during chlorination of raw waters after 30-min UV irradiation pretreatment varied from 20.2% to 41.8%. Total chlorine decreased obviously with the increase of nitrate concentration, but the percentage of organic chloramines increased and was linearly correlated to nitrate concentration.

Contribution of N-Nitrosamines and Their Precursors to Domestic Sewage by Greywaters and Blackwaters.

N-nitrosamines and their precursors are significant concerns for water utilities exploiting wastewater-impacted water supplies, particularly those practicing potable reuse of wastewater. Previous efforts to identify specific precursors in municipal wastewater accounting for N-nitrosamine formation have met with limited success. As an alternative, we quantified the relative importance of greywater (i.e., shower, kitchen sink, bathroom washbasin, and laundry) and blackwater (i.e., urine and feces) streams in terms of their loadings of ambient specific and total N-nitrosamines and chloramine-reactive and ozone-reactive N-nitrosamine precursors to domestic sewage. Accounting for the volume fractions of individual greywater and blackwater streams, laundry water represented the most significant source of N-nitrosamines and their precursors, followed by shower water and urine. Laundry water was particularly important for ozone-reactive N-nitrosamine precursors, accounting for ∼99% of N-nitrosodimethylamine (NDMA) precursors and ∼69% of precursors for other uncharacterized N-nitrosamines. For the other greywater streams, consumer products contributed additional N-nitrosamines and precursors, but the remarkable uniformity across different products suggested the importance of common macroconstituents. The consumption of a standard dose of the antacid ranitidine substantially increased NDMA and its chloramine-reactive precursors in urine. Nevertheless, nearly 40% of the American population would need to consume ranitidine daily to match the NDMA loadings from laundry water.