Effects of Br−on NDMA Formation During Chloramination:a Review of Influencing Factors,Mechanisms,and Control

For the invasion of seawater and the stress of human activities,bromide ion(Br−)exists widely in drinking water sources,and it was found to influence the formation of non-brominated but carcinogenic nitrogen-containing disinfection by-product nitroso-dimethylamine(NDMA)during chloramination(NH2Cl).The presence of Br−leads to the formation of bromine-active species,such as bromamines(NH2Br),bromochloramine(NHClBr),as well as hypobromous acid(HOBr),which are more reactive with NDMA precursors than chlorine-active species,so might promote NDMA generation.This review mainly focuses on the influencing laws,as well as the factors(disinfection conditions and characteristics of water matrixes)that affected NMDA formation during chloramination with Br−.In addition,the possible influencing pathways are discussed.Finally,based on the above summary,measures pertaining to reduce the impact of Br−on NDMA production are concluded.This review would provide a theoretical reference for drinking water treatment plants to deal with bromine-containing water during chloramination.

Insight into the formation of iodinated tr ihalomethanes dur ing chlor ination,monochloramination, and dichloramination of iodide-containing water

In this study, the formation of iodinated trihalomethanes(I-THMs) was systematically evaluated and compared for three treatment processes-(i) chlorination,(ii) monochloramine, and(iii) dichloramination-under different p H conditions. The results demonstrated that ITHM formation decreased in the order of monochloramination > dichloramination > chlorination in acidic and neutral p H. However, the generation of I-THMs increased in the dichloramination < chlorination < monochloramination order in alkaline condition. Specifically, the formation of I-THMs increased as p H increased from 5 to 9 during chlorination and monochloramination processes, while the maximum I-THM formation occurred at pH 7 during dichloramination. The discrepancy could be mainly related to the stability of the three chlor(am) ine disinfectants at different p H conditions. Moreover, in order to gain a thorough insight into the mechanisms of I-THM formation during dichloramination, further investigation was conducted on the influencing factors of DOC concentration and Br/Imolar ratio. I-THM formation exhibited an increasing and then decreasing trend as the concentration of DOC increased from 1 to 7 mg-C/L, while the yield of I-THMs increased with increasing Br/Imolar ratio from 5:0 to 5:10. During the three processes mentioned above, similar I-THM formation results were also obtained in real water, which indicates that the excessive generation of I-THMs should be paid special attention during the disinfection of iodide-containing water.

Formation and cytotoxicity of a new disinfection by-product (DBP) phenazine by chloramination of water containing diphenylamine

Disinfection by-products （DBPs） in drinking water have caused worldwide concern due to their potential carcinogenic effects. The formation of phenazine from diphenylamine （DPhA） chloramination was studied and its cytotoxicities for two human cancer cells were also investigated. Phenazine was detected synchronously with the consumption of DPhA by chloramination, which further confirmed that the new DBP phenazine can be produced along with N-nitrosodiphenylamine （NDPhA） from DPhA chloramination. The formation of phenazine had a maximum molar yield with solution pH increasing from 5.0 to 9.0, with phenazine as the main product for DPhA chloramination at lower pH, but higher pH favored the formation of NDPhA. Thus, solution pH is the key factor in controlling the formation of phenazine and NDPhA. Both the initial DPhA and chloramine concentrations did not show a significant effect on the molar yields of phenazine, although increasing the chloramine concentration could speed up the reaction rate of DPhA with chloramines. The cytotoxicity assays showed that phenazine had significant cell-specific toxicity towards T24 （bladder cancer cell lines） and HepG2 （hepatic tumor cell lines） cells with IC50 values of 0.50 and 2.04 mmol/L, respectively, and T24 cells being more sensitive to phenazine than HepG2 cells. The ICs0 values of phenazine, DPhA, and NDPhA for T24 cells were of the same order of magnitude and the cytotoxicity of phenazine for T24 cells was slightly lower than that of NDPhA （IC50, 0.16 mmol/L）, suggesting that phenazine in drinking water may have an adverse effect on human health.

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter(AOM) and effluent organic matter(Ef OM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts(DBPs) during chlorination and chloramination from various types of dissolved organic matter(DOM, e.g., natural organic matter(NOM), AOM, and Ef OM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes(THMs) and haloacetic acids(HAAs) was observed in NOM than AOM and Ef OM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes(HALs), haloacetonitriles(HANs) and haloacetamides(HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor(BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance(SUVA) increased. AOM favored the formation of iodinated THMs(I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor(ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.

Chloramination of wastewater effluent: Toxicity and formation of disinfection byproducts

The reclamation and disinfection of waters impacted by human activities（e.g., wastewater effluent discharges） are of growing interest for various applications but has been associated with the formation of toxic nitrogenous disinfection byproducts（N-DBPs）. Monochloramine used as an alternative disinfectant to chlorine can be an additional source of nitrogen in the formation of N-DBPs. Individual toxicity assays have been performed on many DBPs, but few studies have been conducted with complex mixtures such as wastewater effluents. In this work, we compared the cytotoxicity and genotoxicity of wastewater effluent organic matter（Ef OM） before and after chloramination. The toxicity of chloraminated Ef OM was significantly higher than the toxicity of raw Ef OM, and the more hydrophobic fraction（HPO）isolated on XAD-8 resin was more toxic than the fraction isolated on XAD-4 resin.More DBPs were also isolated on the XAD-8 resin. N-DBPs（i.e., haloacetonitriles or haloacetamides） were responsible for the majority of the cytotoxicity estimated from DBP concentrations measured in the XAD-8 and XAD-4 fractions（99.4% and 78.5%, respectively）.Measured DBPs accounted for minor proportions of total brominated and chlorinated products, which means that many unknown halogenated compounds were formed and can be responsible for a significant part of the toxicity. Other non-halogenated byproducts（e.g.,nitrosamines） may contribute to the toxicity of chloraminated effluents as well.

Influencing factors of disinfection byproducts formation during chloramination of Cyclops metabolite solutions

Effects of reaction time, chlorine dosage, pH and temperature on the formation of disinfection byproducts （DBPs）, were investigated during the chloramination of Cyclops metabolite solutions. The results showed that some species of DBPs like trichloromethane （TCM）, dichloroacetic acid （DCAA） and trichloroacetic acid （TCAA） could accumulate to their respective stable values with a progressive elevation in reaction time and monochloramine concentration. And 1,1,1-2-trichloropropanone （1,1,1- TCP） content decreased correspondingly with a continuous increase of reaction time. The amounts of chloral hydrate （CH）, chloropicrin （TCNM）, 1,1,1-TCP and DCAA firstly increased and then decreased with increasing monochloramine doses. Higher temperature resulted in a decrease of CH, dichloroacetonitrile （DCAN）, 1,1-dichloropropanone （1,1-DCP）, 1,1,1-TCP, DCAA and TCAA concentration, pH affected the formation of the different DBPs distinctly. TCM accumulateded with the increase of pH under 9, and DCAA, TCAA, CH and 1,1-DCP decreased continuously with increasing pH from 5 to 10, and other DBPs had the maximum concentrations at pH 6-7.

Comparative mammalian cell cytotoxicity of wastewater with elevated bromide and iodide after chlorination,chloramination, or ozonation

Recycling wastewater is becoming more common as communities around the world try to better control their water resources against an increased frequency of either prolonged droughts or intense flooding. For communities in coastal areas, wastewaters may contain elevated levels of bromide（Br^-） and iodide（I^-） from seawater intrusion or high mineral content of source waters. Disinfection of such wastewater is mandatory to prevent the spread of pathogens, however little is known about the toxicity of wastewater after disinfection in the presence of Br^-and I^-. In this study we compared the induction of chronic cytotoxicity in mammalian cells in samples of municipal secondary wastewater effluent amended with elevated levels of Br^-/I^-after disinfection by chlorine, chloramines or ozone to identify which disinfection process generated wastewater with the lowest level of adverse biological response. Chlorination increased mammalian cell cytotoxicity by 5times as compared to non-disinfected controls. Chloramination produced disinfected wastewater that expressed 6.3 times more cytotoxicity than the non-disinfected controls and was 1.3 times more cytotoxic than the chlorinated samples. Ozonation produced wastewater with cytotoxicity comparable to the non-disinfected controls and was at least 4times less cytotoxic than the chlorine disinfected wastewaters. These results indicate that compared to chlorination and chloramination, ozonation of wastewater with high Br^-/Ilevels yielded the lowest mammalian cell cytotoxicity, suggesting its potential as a more favorable method to disinfect wastewater with minimizing the biological toxicity in mind.

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products（I-DBPs） and haloacetaldehydes（HALs） are emerging disinfection by-product（DBP） classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes（I-THMs）,iodo-haloacetic acids（I-HAAs） and selected HALs（mono-HALs and di-HALs species, including iodoacetaldehyde） were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.

Importance of Bromine-Substituted DBP’s in Drinking Water

Significant fractions of bromine-substituted disinfection byproducts (DBPs)—particularly trihalomethanes (THMs)— have been observed to form during treatment of water from the Missouri River. THM speciation was also noted to follow a seasonal pattern during a 2.5-year period, during which samples were collected multiple times per month. Although some treatment processes were effective at reducing the chloroform formation potential, no treatment used at this utility significantly reduced the formation of the three bromine-substituted THM species. Using chloramination rather than free chlorination for secondary disinfection, however, was effective at limiting increases in the concentration of all four regulated THM species in the distribution system.

Simultaneous Control of Microorganisms and Disinfection By-products by Sequential Chlorination

Objective To introduce a new sequential chlorination disinfection process in which short-term free chlorine and chloramine are sequentially added. Methods Pilot tests of this sequential chlorination were carried out in a drinking water plant. Results The sequential chlorination disinfection process had the same or better efficiency on microbe （including virus） inactivation compared with the free chlorine disinfection process. There seemed to be some synergetic disinfection effect between free chlorine and monochloramine because they attacked different targets. The sequential chlorination disinfection process resulted in 35.7%-77.0% TTHM formation and 36.6%-54.8% THAA5 formation less than the free chlorination process. The poorer the water quality was, the more advantage the sequential chlorination disinfection had over the free chlorination. Conclusion This process takes advantages of free chlorine＇s quick inactivation of microorganisms and chloramine＇s low disinfection by-product （DBP） yield and long-term residual effect, allowing simultaneous control of microbes and DBPs in an effective and economic way.

Biological stability in drinking water: a regression analysis of influencing factors

Some parameters, such as assimilable organic carbon(AOC), chloramine residual, water temperature, and water residence time, were measured in drinking water from distribution systems in a northern city of China. The measurement results illustrate that when chloramine residual is more than 0.3 mg/L or AOC content is below 50 μg/L, the biological stability of drinking water can be controlled. Both chloramine residual and AOC have a good relationship with Heterotrophic Plate Counts(HPC)(log value), the correlation coefficient was -0.64 and 0.33, respectively. By regression analysis of the survey data, a statistical equation is presented and it is concluded that disinfectant residual exerts the strongest influence on bacterial growth and AOC is a suitable index to assess the biological stability in the drinking water.

Formation and speciation of disinfection byproducts during chlor(am)ination of aquarium seawater

The chemistry associated with the disinfection of aquarium seawater is more complicated than that of freshwater, therefore limited information is available on the formation and speciation of disinfection byproducts（DBPs） in marine aquaria. In this study, the effects of organic precursors, bromide（Br-） and pre-ozonation on the formation and speciation of several typical classes of DBPs, including trihalomethanes（THM4）, haloacetic acids（HAAs）,iodinated trihalomethanes（I-THMs）, and haloacetamides（HAc Ams）, were investigated during the chlorination/chloramination of aquarium seawater. Results indicate that with an increase in dissolved organic carbon concentration from 4.5 to 9.4 mg/L, the concentrations of THM4 and HAAs increased by 3.2-7.8 times under chlorination and by 1.1-2.3 times under chloramination. An increase in Br-concentration from 3 to 68 mg/L generally enhanced the formation of THM4, I-THMs and HAc Ams and increased the bromine substitution factors of all studied DBPs as well, whereas it impacted insignificantly on the yield of HAAs. Pre-ozonation with 1 mg/L O3 dose substantially reduced the formation of all studied DBPs in the subsequent chlorination and I-THMs in the subsequent chloramination. Because chloramination produces much lower amounts of DBPs than chlorination, it tends to be more suitable for disinfection of aquarium seawater.

Formation and control of nitrogenous DBPs from Western Australian source waters: Investigating the impacts of high nitrogen and bromide concentrations

We studied the formation of four nitrogenous DBPs（N-DBPs） classes（haloacetonitriles,halonitromethanes, haloacetamides, and N-nitrosamines）, as well as trihalomethanes and total organic halogen（TOX）, after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone–biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection.

Impact of total organic carbon and chlorine to ammonia ratio on nitrification in a bench-scale drinking water distribution system

Nitrification occurs in chloraminated drinking water systems and is affected by water quality parameters.The aim of this study was to investigate the impact of total organic carbon and chlorine to ammonia ratio on nitrification potential in a simulated drinking water distribution system as during chloramination.The occurrence of nitrification and activity of nitrifying bacteria was primarily monitored using four rotating annular bioreactors(RAB)with different chlorine to ammonia ratios and total organic carbon(TOC)levels.The results indicated that nitrification occurred despite at a low influent concentration of ammonia,and a high concentration of nitrite nitrogen was detected in the effluent.The study illustrated that reactors 1(R1)and 3(R3),with higher TOC levels,produced more nitrite nitrogen,which was consistent with the ammonia-oxidizing bacteria(AOB)counts,and was linked to a relatively more rapid decay of chloramines in comparison to their counterparts(R2 and R4).The AOB and HPC counts were correlated during the biofilm formation with the establishment of nitrification.Biofilm AOB abundance was also higher in the high TOC reactors compared with the low TOC reactors.The chlorine to ammonia ratio did not have a significant impact on the occurrence of nitrification.Bulk water with a high TOC level supported the occurrence of nitrification,and AOB development occurred at all examined chlorine to ammonia dose ratios(3:1 or 5:1).

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.

Biostability in distribution systems in one city in southern China: Characteristics, modeling and control strategy

This study investigated the bacterial regrowth in drinking water distribution systems receiving finished water from an advanced drinking water treatment plant in one city in southem China. Thirteen nodes in two water supply zones with different aged pipelines were selected to monitor water temperature, dissolved oxygen （DO）, chloramine residual, assimilable organic carbon （AOC）, and heterotrophic plate counts （HPC）. Regression and principal component analyses indicated that HPC had a strong correlation with chloramine residual. Based on Chick-Watson＇s Law and the Monod equation, biostability curves under different conditions were developed to achieve the goal of HPC 100 CFU/mL. The biostability curves could interpret the scenario under various AOC concentrations and predict the required chloramine residual concentration under the condition of high AOC level. The simulation was also carded out to predict the scenario with a stricter HPC goal （≤50 CFU/mL） and determine the required chloramine residual. The biological regrowth control strategy was assessed using biostability curve analysis. The results indicated that maintaining high chloramine residual concentration was the most practical way to achieve the goal of HPC ≤ 100 CFU/mL. Biostability curves could be a very useful tool for biostability control in distribution systems. This work could provide some new insights towards biostability control in real distribution systems.

A balancing act: Optimizing free chlorine contact time to minimize iodo-DBPs, NDMA, and regulated DBPs in chloraminated drinking water

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane(THM) and haloacetic acid(HAA) disinfection byproducts(DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodoacids, iodo-THMs, and N-nitrosodimethylamine(NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes(iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon(DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both p Hs, but the regulated DBPs could exceed the regulations at pH 7.

Developing a chloramine decay index to understand nitrification:A case study of two chloraminated drinking water distribution systems

The management of chloramine decay and the prevention of nitrification are some of the critical issues faced by water utilities that use chloramine as a disinfectant.In this study,potential association between high performance size exclusion chromatography（HPSEC）data obtained with multiple wavelength Ultraviolet（UV） detection from two drinking water distribution systems in Australia and nitrification occurrence was investigated.An increase in the absorbance signal of HPSEC profiles with UV detection at λ = 230 nm between apparent molecular weights of 200 to 1000 Da was observed at sampling sites that experienced rapid chloramine decay and nitrification while its absorbance signal at λ =254 nm decreased.A chloramine decay index（C.D.I） defined as the ratio of area beneath the HPSEC spectra at two different wavelengths of 230 and 254 nm,was used in assessing chloramine decay occurrences.The C.D.Is of waters at locations that experienced nitrification were consistently higher than locations not experiencing nitrification.A simulated laboratory study showed that the formation of nitrite/nitrate and/or soluble microbial products and/or the release of extracellular polymeric substances（EPS） during nitrification may contribute to the C.D.I.increase.These findings suggest that C.D.I derived from HPSEC with multiple wavelength UV detection could be an informative index to track the occurrence of rapid chloramine decay and nitrification.

Characteristics of typical dissolved black carbons and their influence on the formation of disinfection by-products in chlor(am)ination

Dissolved black carbon(DBC)released from biochar can be one of the potential disinfection by-products(DBPs)precursors in the dissolved organic matter pool.However,the physiochemical and structural properties of DBC and the effects on the development of DBPs and DBP formation potential(DBPFP)during the disinfection process remain unclear.In this study,the characteristics of two kinds of DBC,namely,animal-derived DBC(poultry litter DBC,PL-DBC)and plant-derived DBC(wheat straw DBC,WS-DBC),were investigated.The effects of different kinds of DBC on the evolution of DBPs and DBPFP in chlorine and chloramine disinfection processes were compared with natural organic matter(NOM).The results showed that the total DBPs concentrations derived from PL-DBC,WS-DBC and NOM were similar during chlorination(i.e.,61.23µg/L,64.59µg/L and 64.66µg/L,respectively)and chloramination(i.e.,44.63µg/L,44.42µg/L and 45.58µg/L,respectively).The lower total DBPs and DBPFP concentrations in chloramination could be attributed to the fact that the introduction of ammonia in chloramine inhibited the breaking of the bond between the disinfectant and the active group of the precursor.Additionally,DBC presented much lower total DBPFP concentrations than NOM in both chlorination and chloramination.However,both kinds of DBC tended to form more monochloroacetic acids and haloacetamides than NOM,which could result from the higher organic strength,higher protein matter,and nitrogen-rich soluble microbial products of DBC.

Chloramine demand estimation using surrogate chemical and microbiological parameters

A model is developed to enable estimation of chloramine demand in full scale drinking water supplies based on chemical and microbiological factors that affect chloramine decay rate via nonlinear regression analysis method.The model is based on organic character（specific ultraviolet absorbance（SUVA）） of the water samples and a laboratory measure of the microbiological（Fm） decay of chloramine.The applicability of the model for estimation of chloramine residual（and hence chloramine demand） was tested on several waters from different water treatment plants in Australia through statistical test analysis between the experimental and predicted data.Results showed that the model was able to simulate and estimate chloramine demand at various times in real drinking water systems.To elucidate the loss of chloramine over the wide variation of water quality used in this study,the model incorporates both the fast and slow chloramine decay pathways.The significance of estimated fast and slow decay rate constants as the kinetic parameters of the model for three water sources in Australia was discussed.It was found that with the same water source,the kinetic parameters remain the same.This modelling approach has the potential to be used by water treatment operators as a decision support tool in order to manage chloramine disinfection.