Progress in Analytical Methods of Halogenated Disinfection By-Products

Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.

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.

Removal of disinfection by-products formation potential by biologically intensified process

The removal of disinfection by-products formation potential(DBPFP) in artificially intensified biological activated carbon(IBAC) process which is developed on the basis of traditional ozone granular activated carbon was evaluated. By IBAC removals of 31% and 68% for THMFP and HAAFP were obtained respectively. Under identical conditions, the removals of the same substances were 4% and 32% respectively only by the granular activated carbon(GAC) process. Compared with GAC, the high removal rates of the two formed potential substances were due to the increasing of bioactivity of the media and the synergistic capabilities of biological degradation cooperating with activated carbon adsorption of organic compounds. A clear linear correlation(R 2=0.9562 and R 2=0.9007) between DOC HAAFP removal rate and Empty Bed Contact Time(EBCT) of IBAC process was observed, while that between THMFP removal rate and EBCT of GAC was R 2=0.9782. In addition certain linear correlations between THMFP, HAAFP and UV 254 (R 2=0.855 and R 2=0.7702) were found for the treated water. For IBAC process there are also more advantages such as long backwashing cycle time, low backwashing intensity and prolonging activated carbon lifetime and so on.

Removal characteristics of disinfection by-products formation potential by bioaugmentation activated carbon process

The high-active bacteria were screened from 8 dominant bacteria obtained from the natural water body,and then the bioaugmentation activated carbon was formed by hydraulic immobilization of the high-active bacteria. Plant-scale studies on removal characteristics of disinfection by-products formation potentials (DBPFP) by bioaugmentation activated carbon process were conducted for micro-polluted raw water treatment. The results show that the bioaugmentation activated carbon process has adopted better purification efficiency to THMFP and HAAFP than traditional biological activated carbon process,and that average removal efficiencies of THMFP and HAAFP can reach 35% and 39.7% during the test period,increasing by more than 10% compared with traditional biological activated carbon process. The removal efficiencies of THMFP and HAAFP are stable because of the biodegradation of the high-active bacteria and the adsorption of active carbon. The biodegradability of CHCl3 formation potential is better as compared with that of CHCl2Br and CHClBr2 formation potentials among THMFP,and high removal efficiency of CHCl3formation potential is obtained by bioaugmentation degradation of the high-active bacteria. The biodegradability of HAAFP is better in comparison with that of THMFP,and the chemical properties of HAAFP are propitious to adsorption of activated carbon. Thus,HAAFP is on predominance during the competitive removal process with THMFP.

Characterization of dissolved organic matter fractions and its relationship with the disinfection by-product formation

Dissolved organic matter （DOM） has been identified as precursor for disinfection by-products （DBPs） formation during chlorination. Recently, it has been demonstrated that the characteristics of DOM influence the DBPs formation mechanism. A study was, therefore, initiated to investigate the effects of DOM fractions on DBPs formation mechanism. In the chlorination process, organic acids are dominant precursors of total thihalomethanes （TTHM） because of the vc-o and unsaturated structures. Furthermore, the TTHM formation of organic acids was affected by pH more greatly. Based on the fluorescence spectroscopy analysis, DOM fractions contained several fluorescence substances. During chlorination, humic acid-like substances were found to exhibit high chlorine reactivity and hydrophobic organics decomposed to smaller molecules faster than hydrophilic organics even at lower chlorine dosages. Unlike hydrophobic fractions, hydrophilic organics showed no toxicity following chlorination, suggesting that the toxic structures in hydrophihc organics showed high chlorine reactivity during chlorination.

Less pressure contributes to gravity-driven membrane ultrafiltration with greater performance:Enhanced driving efficiency and reduced disinfection by-products formation potential

Gravity-driven membrane(GDM)systems have been well developed previously;however,impacts of driving(i.e.,transmembrane)pressure on their performance received little attention,which may infuence GDM performance.In this study,we evaluated 4 GDM systems via altering the transmembrane pressure from 50 mbar to 150 mbar with 2 groups,treating surface water in Beijing,China.Results showed that less driving pressure was more favorable.Specifically,compared to groups(150 mbar),groups under a pressure of 50 mbar were found to have greater normalized permeability and lower total resistance.During the whole operation period,the quality of effuents was gradually improved.For example,the removal efficiency of UV254was significantly improved;particularly,under low driving pressure,the removal efficiency of UV254in PES GDM system increased by 11.91%,as compared to the corresponding system under high driving pressure.This observation was consistent with the reduction on disinfection by-products(DBPs)formation potential;groups under 50 mbar achieved better DBPs potential control,indicating the advantages of lower driving pressure.Biofilms were analyzed and responsible for these differences,and distinct distributions of bacteria communities of two GDM systems under 50 and 150 mbar may be responsible for various humic-like substances removal efficiency.Overall,GDM systems under less pressure should be considered and expected to provide suggestions on the design of GDM systems in real applications.

Disinfection of swimming pools with chlorine and derivatives: formation of organochlorinated and organobrominated compounds and exposure of pool personnel and swimmers

Chlorination of pool water leads to the forma-tion of many by-products, chloroform usually being the most abundant. The paper reports the results of a study evaluating exposure of bath-ers and pool employees to trihalomethanes (chloroform, bromodichloromethane, dibromo-chloromethane, bromoform) in four indoor swimming pools with chlorinated water. Chlo-roform concentrations in environmental air samples when the pool was in use (about 9 h), in the range 1-182 μg/m3, were greater near the pool than in the change rooms, passageways and offices. Chloroform concentrations in per-sonal air samples of pool employees were in the range 18-138 μg/m3. Urinary concentrations of chloroform averaged (geometric means) 0.123 and 0.165 μg/l and 0.404 and 0.342 μg/l prior and at the end of exposure during in water and out of water activities, respectively. The significant increase in urinary excretion of chloroform confirms that the source of the contaminant was pool water. Absorption of chloroform, estimated from airborne and water concentrations, was significantly correlated with delta chloroform (after/before exposure) and urinary concentra-tions of chloroform at the end of exposure. As chloroform is a toxic and possibly carcinogenic substance, these observations pose a problem principally for the general population of pool users.

Identification of key precursors contributing to the formation of CX_(3)R-type disinfection by-products along the typical full-scale drinking water treatment processes

Identification and characterization of disinfection by-product(DBP)precursors could help optimize drinkingwater treatment processes and improve the quality of finishedwater.This study comprehensively investigated the characteristics of dissolved organic matter(DOM),the hydrophilicity and molecule weight(MW)of DBP precursor and DBP-associated toxicity along the typical full-scale treatment processes.The results showed that dissolved organic carbon and dissolved organic nitrogen content,the fluorescence intensity and the SUVA254 value in raw water significantly decreased after the whole treatment processes.Conventional treatment processes were in favor of the removal of high-MW and hydrophobic DOM,which are important precursors of trihalomethane and haloacetic acid.Compared with conventional treatment processes,Ozone integrated with biological activated carbon(O3-BAC)processes enhanced the removal efficiencies of DOM with different MW and hydrophobic fractions,leading to a further decrease in almost all DBP formation potential and DBP-associated toxicity.However,almost 50%of the detected DBP precursors in raw water has not been removed after the coagulation-sedimentation-filtration integrated with O3-BAC advanced treatment processes.These remaining precursors were found to be mainly hydrophilic and low-MW(<1.0 kDa)organics.Moreover,they would largely contribute to the formation of haloacetaldehydes and haloacetonitriles,which dominated the calculated cytotoxicity.Since current drinking water treatment process could not effectively control the highly toxic DBPs,the removal of hydrophilic and low-MW organics in drinking water treatment plants should be focused on in the future.

Bacteria inactivation by sulfate radical:progress and non-negligible disinfection by-products

Sulfate radicals have been increasingly used for the pathogen inactivation due to their strong redox ability and high selectivity for electron-rich species in the last decade.The application of sulfate radicals in water disinfection has become a very promising technology.However,there is currently a lack of reviews of sulfate radicals inactivated pathogenic microorganisms.At the same time,less attention has been paid to disinfection by-products produced by the use of sulfate radicals to inactivate microorganisms.This paper begins with a brief overview of sulfate radicals’properties.Then,the progress in water disinfection by sulfate radicals is summarized.The mechanism and inactivation kinetics of inactivating microorganisms are briefly described.After that,the disinfection by-products produced by reactions of sulfate radicals with chlorine,bromine,iodide ions and organic halogens in water are also discussed.In response to these possible challenges,this article concludes with some specific solutions and future research directions.

Genotoxicity Induced by Low Dose and Mixed Exposure to Haloacetaldehydes,an Emerging Class of Drinking Water Disinfection By-products

Haloacetaldehydes(HALs)are the third largest disinfection by-products(DBPs)class by mass in drinking water.Most of them alone in high doses are more cytotoxic and genotoxic than regulated DBPs.However,the toxic effects of mixed exposure to HALs at environmentally relevant levels are still unknown.Given that genotoxicity is critical for risk assessment,we employed multiple genotoxic tests including the Salmonella typhimurium revertant mutation assay(Ames assay),the single cell gel electrophoresis(SCGE)assay,the cytoplasmic blocking micronucleus(CBMN)assay,and theγ-H2AX assay to investigate the genotoxicity of HALs based on the HALs concentrations and components detected in the finished drinking water of Shanghai,China.The results demonstrated the concentrations of HALs were low,ranging from 0.04µg/L to 4.47µg/L,and the total concentration was 10.85µg/L.Although the mutagenicity of HALs was negative even at 1000-fold concentrations in the real world,mixed exposure to 100 and 1000-fold concentrations HALs resulted in DNA and chromosomal damage in human hepotocyte(HepG2)cells.HALs significantly increased the levels of reactive oxygen species(ROS)andγ-H2AX and activated nuclear factor erythroid-derived factor 2-related factor 2(NRF2)pathway-related protein expressions in HepG2 cells.The antioxidant NAC could ameliorate NRF2 pathway-related protein expression and DNA damage caused by HALs,suggesting that the genotoxicity of mixed exposure to HALs involved cellular oxidative stress and NRF2 pathway activation.

Research progress of disinfection and disinfection by-products in China

Disinfection is an indispensable water treatment process for killing harmful pathogens and protecting human health. However, the disinfection has caused significant public concern due to the formation of toxic disinfection by-products(DBPs). Lots of studies on disinfection and DBPs have been performed in the world since 1974. Although related studies in China started in1980 s, a great progress has been achieved during the last three decades. Therefore, this review summarized the main achievements on disinfection and DPBs studies in China, which included:(1) the occurrence of DBPs in water of China,(2) the identification and detection methods of DBPs,(3) the formation mechanisms of DBPs during disinfection process,(4) the toxicological effects and epidemiological surveys of DBPs,(5) the control and management countermeasures of DBPs in water disinfection, and(6) the challenges and chances of DBPs studies in future. It is expected that this review would provide useful information and reference for optimizing disinfection process, reducing DBPs formation and protecting human health.

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration （UF） and biologic activated carbon （BAC） filtration was investigated for the removal of organic matter and disinfection by-products （DBPs） precursors from micropolluted surface water. A pilot scale plant with the capacity of 120 m3 per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m2 and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid （HoA）, base （HOB） and neutral （HoN）, weakly hydrophobic acid （WHOA） and hydrophilic matter （HIM） by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon （DOC）, 87% of UV254, 77% of trihalomethane （THMs） precursors, 76% of haloacetic acid （HAAs） precursors, 83%of trichloracetic aldehyde （CH） precursor, 77% of dichloroaeetonitrile （DCAN） precursor, 51% of trichloroacetonitrile （TCAN） precursor, 96% of 1,1,1- trichloroacetone （TCP） precursor and 63% of trichloroni- tromethane （TCNM） precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000-3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200-500 Da. DOC had a close linear relationship with the formation potential of DBPs.

Disinfection By-Products in Drinking Water, Recycled Water and Wastewater： Formation, Detection, Toxicity and Health Effects： Preface

The disinfection of drinking water was an outstanding（and perhaps the most important）public health achievement of the 20^（th） century.According to the United Nations World Health Organization,

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.

The impact of iodinated X-ray contrast agents on formation and toxicity of disinfection by-products in drinking water

The presence of iodinated X-ray contrast media（ICM） in source waters is of high concern to public health because of their potential to generate highly toxic disinfection by-products（DBPs）. The objective of this study was to determine the impact of ICM in source waters and the type of disinfectant on the overall toxicity of DBP mixtures and to determine which ICM and reaction conditions give rise to toxic by-products. Source waters collected from Akron,OH were treated with five different ICMs, including iopamidol, iopromide, iohexol,diatrizoate and iomeprol, with or without chlorine or chloramine disinfection. The reaction product mixtures were concentrated with XAD resins and the mammalian cell cytotoxicity and genotoxicity of the reaction mixture concentrates was measured. Water containing iopamidol generated an enhanced level of mammalian cell cytotoxicity and genotoxicity after disinfection. While chlorine disinfection with iopamidol resulted in the highest cytotoxicity overall, the relative iopamidol-mediated increase in toxicity was greater when chloramine was used as the disinfectant compared with chlorine. Four other ICMs（iopromide, iohexol, diatrizoate, and iomeprol） expressed some cytotoxicity over the control without any disinfection, and induced higher cytotoxicity when chlorinated. Only iohexol enhanced genotoxicity compared to the chlorinated source water.

Evaluation of N-acetylcysteine and glutathione as quenching agents for the analysis of halogenated disinfection by-products

Disinfection by-products(DBPs), formed from the reactions of disinfectants with natural organic matter and halides in drinking water, were considered to be cytotoxic and genotoxic, and might trigger various cancers. The relatively low concentration of DBPs in finished water(low μg/L or even ng/L levels) and the interference from water matrix inhibited in situ determination of DBPs. Moreover, the further formation and degradation of DBPs by disinfectants during the holding time(several hours to several days) from sample collection to analysis could adversely affect the determination of DBPs. To obtain accurate, precise and reliable data of DBP occurrence and formation, robust and reliable sample preservation is indispensable. However, the commonly used quenching agents(e.g., sodium sulfite, sodium thiosulfate, and ascorbic acid) for sample preservation can decompose reactive DBPs by reductive dehalogenation. This study evaluated the performance of N-acetylcysteine(NAC) and glutathione(GSH) as quenching agents for the analysis of halogenated DBPs by investigating the stoichiometry of the disinfectant-quenching agent reaction, the formation of DBPs during chlor(am)ination of NAC or GSH, and the effects of NAC or GSH on the stability of 18 individual DBPs and total organic halogen(TOX). Based on the results of this study, NAC and GSH were considered to be ideal quenching agents for the analysis of most DBPs and TOX, except halonitromethanes.

Concentration levels of disinfection by-products in 14 swimming pools of China

Swimming has become a popular exercising and recreational activity in China but little is known about the disinfection by-products （DBPs） concentration levels in the pools. This study was conducted as a survey of the DBPs in China swimming pools, and to establish the correlations between the DBP concentrations and the pool water quality parameters. A total of 14 public indoor and outdoor pools in Beijing were included in the survey. Results showed that the median concentrations for total tfihalomethanes （TTHM）, nine haloacetic acids （HAA9）, chloral hydrate （CH）, four haloacetonitriles （HAN4）, 1,1- dichloropropanone, 1,1,1-trichloropropanone and trichlor- onitromethane were 33.8, 109.1, 30.1, 3.2, 0.3, 0.6 pg＇L-1 and below detection limit, respectively. The TTHM and HAA9 levels were in the same magnitude of that in many regions of the world. The levels of CH and nitrogenous DBPs were greatly higher than and were comparable to that in typical drinking water, respectively. Disinfection by chlorine dioxide or trichloroisocyanuric acid could sub- stantially lower the DBP levels. The outdoor pools had higher TTHM and HAA9 levels, but lower trihaloacetic acids （THAA） levels than the indoor pools. The TTHM and HAA9 concentrations could be moderately correlated with the free chlorine and total chlorine residuals but not with the total organic carbon （TOC） contents. When the DBP concentration levels from other survey studies were also included for statistical analysis, a good correlation could be established between the TTHM levels and the TOC concentration. The influence of chlorine residual on DBP levels could also be significant.

Zebrafish embryo toxicity of 15 chlorinated, brominated, and iodinated disinfection by-products

Disinfection to protect human health occurs at drinking water and wastewater facilities through application of non-selective oxidants including chlorine. Oxidants also transform organic material and form disinfection by-products（DBPs）, many of which are halogenated and cyto-and genotoxic. Only a handful of assays have been used to compare DBP toxicity,and researchers are unsure which DBP（s） drive the increased cancer risk associated with drinking chlorinated water. The most extensive data set employs an in vitro model cell,Chinese hamster ovary cells. Traditionally, most DBP research focuses on the threat to human health, but the effects on aquatic species exposed to DBPs in wastewater effluents remain ill defined. We present the developmental toxicity for 15 DBPs and a chlorinated wastewater to a model aquatic vertebrate, zebrafish. Mono-halogenated DBPs followed the in vivo toxicity rank order： acetamides 〉 acetic acids 〉 acetonitriles ~ nitrosamines, which agrees well with previously published mammalian in vitro data. Di-and tri-halogenated acetonitriles were more toxic than their mono-halogenated analogues, and bromine-and iodine-substituted DBPs tended to be more toxic than chlorinated analogues. No zebrafish development effects were observed after exposure to undiluted or non-concentrated,chlorinated wastewater. We find zebrafish development to be a viable in vivo alternative or confirmatory assay to mammalian in vitro cell assays.

A new technique helps to uncover unknown peptides and disinfection by-products in water

Environmental water samples can be extremely complex,with potentially thousands of molecules that can derive from natural organic matter（NOM）and thousands that derive from anthropogenic contaminants.As complex as these samples are,drinking water can be even more complex.Due to disinfectants that are used to treat drinking water（e.g.,chlorine,chloramines,