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.

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.

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.

Health Risk Assessment of Employees Exposed to Chlorination By-products of Recreational Water in Large Amusement Parks in Shanghai

Objective Chlorination is often used to disinfect recreational water in large amusement parks;however,the health hazards of chlorination disinfection by-products(DBPs)to occupational populations are unknown.This study aimed to assess the exposure status of chlorinated DBPs in recreational water and the health risks to employees of large amusement parks.Methods Exposure parameters of employees of three large amusement parks in Shanghai were investigated using a questionnaire.Seven typical chlorinated DBPs in recreational water and spray samples were quantified by gas chromatography,and the health risks to amusement park employees exposed to chlorinated DBPs were evaluated according to the WHO's risk assessment framework.Results Trichloroacetic acid,dibromochloromethane,bromodichloromethane,and dichloroacetic acid were detected predominantly in recreational water.The carcinogenic and non-carcinogenic risks of the five DBPs did not exceed the risk thresholds.In addition,the carcinogenic and non-carcinogenic risks of mixed exposure to DBPs were within the acceptable risk limits.Conclusion Typical DBPs were widely detected in recreational water collected from three large amusement parks in Shanghai;however,the health risks of DBPs and their mixtures were within acceptable limits.

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.

Studies of non-metallic organic disinfectants on inactivation of avian influenza viruses

Six different kinds of non-metallic or organic disinfectants were obtained in this research study including “Neutral Electrolyzed Water”, “M22” organic disinfectant solution, Superoxy Food Wash disinfectant, Hydrogen Peroxide, Clorox Germicidal Bleach and Clidox-S. The effectiveness of these disinfectants was studied against various subtypes of avian influenza virus (AIV). The virus-disinfectant mixtures were prepared in serial dilutions of each disinfectant with a constant virus titer and incubated at ambient temperature in different time intervals for virus inactivation. The virus inactivation results were determined by virus recovery in embryonating chicken eggs. Among the six different kinds of nonmetallic disinfectants obtained for this research project, Neutral Electrolyzed Water, “M22” solution, Clorox Germicidal Bleach and Clidox-S were effectively inactivated AIV with appropriate working dilutions and reaction times. Superoxy Food Wash disinfectant and Hydrogen Peroxide were found having limited effect on virus inactivation with extended exposure times of more than 2 hours. These research findings provide scientific data to poultry industry with guidelines to select and use non-metallic organic disinfectants for poultry flock sanitation and disinfection to effectively prevent and control of avian influenza outbreaks.

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.

Waste Water Disinfection During SARS Epidemic for Microbiological and Toxicological Control

Objective To evaluate the disinfection of wastewater in China. Methods During the SARS epidemic occurred in Beijing, a study of different disinfection methods used in the main local wastewater plants including means of chlorine, chlorine dioxide, ozone, and ultraviolet was carried out in our laboratory. The residual coliform, bacteria and trihalomethanes, haloacetic acids were determined after disinfection. Results Chlorine had fairly better efficiency on microorganism inactivation than chlorine dioxide with the same dosage. Formation of THMs and HAAs does not exceed the drinking water standard. UV irradiation had good efficiency on microorganism inactivation and good future of application in China. Organic material and ammonia nitrogen was found to be significant on inactivation and DBPs formation. Conclusion Chlorine disinfection seems to be the best available technology for coliform and bacteria inactivation. And it is of fairly low toxicological hazard due to the transformation of monochloramine.

Enhanced Disinfection Effect of a Compound Disinfectant against Bovine Herpes Virus Type 1 at Low Temperature

A compound disinfectant, which consisted of didecyldimethylammonium chloride (DDAC), ortho-dichlorobenzene (1,2-dichlorobenzene, ODB), and chlorocresol (4-chloro-3-methylphenol, CC), and its component chemicals were individually tested for effectiveness against bovine herpes virus type 1 (BHV-1). DDAC, DDAC+ODB, DDAC+CC, and DDAC+ODB+CC showed effectiveness against BHV-1 at room temperature. However, ODB, CC, and ODB+CC showed no virucidal effects. The effects of all disinfectants tested were decreased at low temperature. DDAC showed disinfectant effects at a dilution of 1/800 and DDAC+ODB, DDAC+CC, and DDAC+ODB+CC at dilutions of 1/800 and 1/1600 at low temperature in the presence of 2% fetal bovine serum (FBS) but ODB, CC, and ODB+CC showed no virucidal effects. At low temperature and in the presence of 10% FBS, DDAC, DDAC+ODB, and DDAC+CC showed disinfectant effects at dilutions of 1/800, whereas ODB, CC, and ODB+CC showed no virucidal effects. DDAC+ ODB+CC was more effective (at 1/800 and 1/1600) than the other disinfectants under these conditions. In conclusion, a combination of three disinfectant components (DDAC+ODB+CC), enhanced the disinfectant effects at low temperature and in organic matter contamination.

Reduction of Trihalomethanes Forming Potential by Adsorption of Natural Organic Matter on Ionic Exchange Resins

In a sanitation process of drinking water, carbon from the organic matter reacts with chlorine, forming by-products, among which are trihalomethanes (THM). These substances are carriers of mutagenic and can-cerogenic potential and hence should be removed in drinking water treatment. Since the natural organic mat-ters are precursors of THM formation, their removal from the water decreases the concentration of THMs. The THM forming potential is the most reliable indicator in evaluation of organic matter removal during drinking water treatment processes. The results have shown that the reaction producing THMs follows sec-ond order kinetics. The second order rate constant ranged from 0.024 M-1s-1 to 0.065 M-1s-1 at 22 °C and pH = 8.2 for 96 hours. The removal of 78.4% of natural organic matter, by adsorption on anionic exchange res-ins, resulted in the THM forming potential reduction by 63.1%. Various fractions of natural organic matter differ in their reactivity with chlorine, which is important when it comes to selection of the adsorption me-dium in the drinking water treatment processes.

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.

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter（DOM） and bromide ion concentration have a significant influence on the formation of disinfection by-products（DBPs）. In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight（MW）, trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes（pre-chlorination, coagulation, sand filtration,disinfection） were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW 1 k Da and fraction with MW 3-10 k Da, and the DBP＇s generation ability of lower molecular weight DOM（ 10 k Da） was higher than that of higher molecular weight DOM. During different processes,pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes（THMs） were mainly generated in pre-chlorination and disinfection, while haloacetic acids（HAAs） were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.

Characterization of natural organic matter in water for optimizing water treatment and minimizing disinfection by-product formation

Introduction Natural organic matter（NOM）present in source water has significant impact on water treatment processes and on the quality of drinking water.NOM is a complex mixture of diverse groups of organic compounds,humic and fulvic acids,proteins,peptides,carbohydrates,and heterogeneous materials

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.

Enhanced removal of organic matter and typical disinfection byproduct precursors in combined iron–carbon micro electrolysis-UBAF process for drinking water pre-treatment

The organic matter and two types of disinfection byproduct(DBP) precursors in micropolluted source water were removed using an iron–carbon micro-electrolysis(ICME)combined with up-flow biological aerated filter(UBAF) process. Two pilot-scale experiments(ICME-UBAF and UBAF alone) were used to investigate the effect of the ICME system on the removal of organic matter and DBP precursors. The results showed that ICME pretreatment removed 15.6% of dissolved organic matter(DOM)and significantly improved the removal rate in the subsequent UBAF process. The ICME system removed 31% of trichloromethane(TCM) precursors and 20% of dichloroacetonitrile(DCAN) precursors. The results of measurements of the molecular weight distribution and hydrophilic fractions of DOM and DBP precursors showed that ICME pretreatment played a key role in breaking large-molecular-weight organic matter into low-molecular-weight components, and the hydrophobic fraction into hydrophilic compounds, which was favorable for subsequent biodegradation by UBAF.Three-dimensional fluorescence spectroscopy(3D-EEM) further indicated that the ICME system improved the removal of TCM and DCAN precursors. The biomass analysis indicated the presence of a larger and more diverse microbial community in the ICME-UBAF system than for the UBAF alone. The high-throughput sequencing results revealed that domination of the genera Sphingomonas, Brevundimonas and Sphingorhabdus contributed to the better removal of organic matter and two types of DBP precursors. Also, Nitrosomonas and Pseudomonas were beneficial for ammonia removal.

Impact of chlorine exposure time on disinfection byproduct formation in the presence of iopamidol and natural organic matter during chloramination

Chloramines,in practice,are formed onsite by adding ammonia to chlorinated drinking water to achieve the required disinfection.While regulated disinfection byproducts(DBPs)are reduced during chloramine disinfection,other DBPs such as iodinated(iodo-)DBPs,that elicit greater toxicity are formed.The objective of this study was to investigate the impact of prechlorination time on the formation of both halogen-specific total organic halogen(TOX)and iodo/chlorinated(chloro-)DBPs during prechlorination/chloramination in source waters(SWs)containing iopamidol,an X-ray contrast medium.Barberton SW(BSW)and Cleveland SW(CSW)containing iopamidol were prechlorinated for 5–60 min and afterwards chloraminated for 72 hr with ammonium chloride.Chlorine contact time(CCT)did not significantly impact total organic iodine(TOI)concentrations after prechlorination or chloramination.Concentrations of total organic chlorine(TOCl)formed during prechlorination did not significantly change regardless of pH and prechlorination time,whileTOClappearedtodecreaseafter 72 hrchloraminationperiod.Dichloroiodomethane(CHCl_2I)formation during prechlorination did not exhibit any significant trends as a function of p H or CCT,but after chloramination,significant increases were observed at pHs 6.5 and 7.5 with respect to CCT.Iodo-HAAs were not formed during prechlorination but were detected after chloramination.Significant quantities of chloroform(CHCl_3)and trichloroacetic acid(TCAA)were formed during prechlorination but formation ceased upon ammonia addition.Therefore,prechlorination studies should measure TOX and DBP concentrations prior to ammonia addition to obtain data regarding the initial conditions.

Effects of reductive inorganics and NOM on the formation of chlorite in the chlorine dioxide disinfection of drinking water

Chlorine dioxide(ClO_(2))disinfection usually does not produce halogenated disinfection byproducts,but the formation of the inorganic by-product chlorite(ClO^(–)_(2))is a serious consideration.In this study,the ClO^(–)_(2)formation rule in the ClO_(2)disinfection of drinking water was investigated in the presence of three representative reductive inorganics and four natural organic matters(NOMs),respectively.Fe^(2+)and S^(2–)mainly reduced ClO_(2)to ClO^(–)_(2)at low concentrations.When ClO_(2)was consumed,the ClO^(–)_(2)would be further reduced by Fe^(2+)and S^(2–),leading to the decrease of ClO^(–)_(2).The reaction efficiency of Mn^(2+)with ClO_(2)was lower than that of Fe^(2+)and S^(2–).It might be the case that Mn O 2 generated by the reaction between Mn^(2+)and ClO_(2)had adsorption and catalytic oxidation on Mn^(2+).However,Mn^(2+)would not reduce ClO^(–)_(2).Among the four NOMs,humic acid and fulvic acid reacted with ClO_(2)actively,followed by bovine serum albumin,while sodium alginate had almost no reaction with ClO_(2).The maximum ClO^(–)_(2)yields of reductive inorganics(70%)was higher than that of NOM(around 60%).The lower the concentration of reductive substances,the more ClO^(–)_(2)could be produced by per unit concentration of reductive substances.The results of the actual water samples showed that both reductive inorganics and NOM played an important role in the formation of ClO^(–)_(2)in disinfection.

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.