Modeling the Formation of Chlorination By-Products During Enhanced Coagulation

Because of increasing need to balance health risks for pathogen control and disinfection by-products (DBP) formation in drinking water supplies, water utilities are forced to closely examine and optimize their disinfection practices. This research was designed to investigate the effects of independent variables of dissolved organic carbon (DOC), ferric chloride dosage, chlorine dose, and reaction time on trihalomethanes (THMs) formation in Terkos Lake Water (TLW) of Istanbul City. A statistically-based empirical model was developed for predicting THM formation during enhanced coagulation. The R ² and F value of model were 0.762 and 460, respectively. The model was found to be statistically significant for all four variables, and model predictions appear to be most accurate for this study. A multiple linear model exhibited the best fit of data. It was observed that THM formation depended primarily on DOC removal. Model calibration, testing and validation were accomplished by using independent data set.     

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.     

Degradation of chlortoluron in water disinfection processes: a kinetic study

The kinetics of the reaction between chlortoluron, a phenylurea herbicide [N'-(2-hydroxy-4-methyl-5-chlorophenyl)-N,N-dimethylurea], and hypochlorite, the active species in water disinfection processes involving chlorine, were investigated by HPLC-UV and HPLC-electrospray ionisation mass spectrometry (HPLC-ESI-MS). In particular, the concentrations of the main chlortoluron by-products were monitored as a function of time by HPLC-ESI-MS and a kinetic model was developed to fit the relevant curves. The results showed that chlortoluron degradation starts with two parallel pathways, namely, chlorination and hydroxylation of the aromatic ring, which are then followed by consecutive chlorination reactions, and after almost 2 weeks by ring opening and partial mineralisation, as confirmed by head-space solid-phase microextraction gas chromatography-MS (SPME-GC-MS) and total organic carbon (TOC) measurements. Kinetic constants for the first reactions of the overall process, under pseudo-first-order conditions (hypochlorite excess), were estimated by a fitting procedure.     

Determination of an acceptable assimilable organic carbon (AOC) level for biological stability in water distribution systems with minimized chlorine residual

There is considerable interest in minimizing the chlorine residual in Japan because of increasing complaints about a chlorinous odor in drinking water. However, minimizing the chlorine residual causes the microbiological water quality to deteriorate, and stricter control of biodegradable organics in finished water is thus needed to maintain biological stability during water distribution. In this investigation, an acceptable level of assimilable organic carbon (AOC) for biologically stable water with minimized chlorine residual was determined based on the relationship between AOC, the chlorine residual, and bacterial regrowth. In order to prepare water samples containing lower AOC, the fractions of AOC and biodegradable organic matter (BOM) in tap water samples were reduced by converting into biomass after thermal hydrolysis of BOM at alkaline conditions. The batch-mode incubations at different conditions of AOC and chlorine residual were carried out at 20°C, and the presence or absence of bacterial regrowth was determined. The determined curve for biologically stable water indicated that the acceptable AOC was 10.9 μg C/L at a minimized chlorine residual (0.05 mg Cl₂/L). This result indicated that AOC removal during current water treatment processes in Japan should be significantly enhanced prior to minimization of the chlorine residual in water distribution.     

Laboratory-scale chlorination to estimate the levels of halogenated DBPs in full-scale distribution systems

Occurrence of halogenated disinfection by-products (DBPs) (trihalomethanes –THMs– and haloacetic acids –HAAs–) in the waters of two utilities in Quebec City (Canada) was investigated using two approaches: experimental chlorination studies and full-scale sampling within distribution systems. Experimental studies were designed to reproduce treatment plant and distribution system conditions (chlorine dose, water temperature, pH and water residence time). Differences in halogenated DBPs in the two distribution systems under study were significant and comparable to those observed in experimental laboratory studies. For the waters of both utilities, chlorination studies better reproduced the occurrence of halogenated DBPs in points of the distribution system located near the treatment plant (low residence time of water) than in other points. Multivariate regression models for THMs, HAAs and their species were developed using the data from experimental studies in order to predict halogenated DBP levels measured in the distribution system. Models were all statistically significant, but showed low ability to predict full-scale halogenated DBPs, particularly in points located at distribution system extremities. Specifically, experimental chlorination-based models are not able to simulate the decrease of HAA levels. Results of this research suggest that the use of experimental data to predict halogenated DBP levels in full-scale distribution systems – for operational, regulatory and epidemiological purposes – must be done with caution.     

Assessment of chlorine tolerance profile of <Emphasis Type="BoldItalic">Citrobacter</Emphasis> species recovered from wastewater treatment plants in Eastern Cape,South Africa

This present study assessed the chlorine tolerance of some Citrobacter species recovered from secondary effluents from the clarifiers of two wastewater treatment plants in the Eastern Cape, South Africa. The bacterial survival, chlorine lethal dose and inactivation kinetics at lethal doses were examined. Inactivation of the test bacteria (n = 20) at the recommended dose of 0.5 mg/l for 30 min exposure showed a progressive reduction in bacterial population from 4 to 5 log reduction and residuals ranged between 0.12 and 0.46 mg/l. The bactericidal activity of chlorine increased at higher dosages with a substantial reduction in viability of the bacteria and complete inactivation of the bacterial population at a lethal dose of 0.75 and 1.0 mg/l in 30 min. For the inactivation kinetics, bactericidal activity of chlorine increased with time showing a 3.67–5.4 log reduction in 10 min, 4.0–5.6 log reduction in 20 min and above 6.3 log reductions to complete sterilization of bacterial population over 30 min for all the entire test Citrobacter isolates used in this study. Furthermore, there was a strong correlation (R ² > 0.84) between bacteria inactivation and increase in contact time. This study appears to have provided support for laboratory evidence of bacterial tolerance to chlorine disinfection at current recommended dose (0.5 mg/l for 30 min), and chlorine concentration between 0.75 and 1.0 mg/l was found to have a better disinfecting capacity to check tolerance of Citrobacter species.     

Evaluation of biological stability and corrosion potential in drinking water distribution systems: a case study

The appearance of assimilable organic carbon (AOC), microbial regrowth, disinfection by-products (DBPs), and pipe corrosion in drinking water distribution systems are among those major safe drinking water issues in many countries. The water distribution system of Cheng-Ching Lake Water Treatment Plant (CCLWTP) was selected in this study to evaluate the: (1) fate and transport of AOC, DBPs [e.g., trihalomethanes (THMs), haloacetic acids (HAAs)], and other organic carbon indicators in the selected distribution system, (2) correlations between AOC (or DBPs) and major water quality parameters [e.g. dissolved oxygen (DO), free residual chlorine, and bacteria, and (3) causes and significance of corrosion problems of the water pipes in this system. In this study, seasonal water samples were collected from 13 representative locations in the distribution system for analyses of AOC, DBPs, and other water quality indicators. Results indicate that residual free chlorine concentrations in the distribution system met the drinking water standards (0.2 to 1 mg l(-1)) established by Taiwan Environmental Protection Administration (TEPA). Results show that AOC measurements correlated positively with total organic carbon (TOC) and UV-254 (an organic indicator) values in this system. Moreover, AOC concentrations at some locations were higher than the 50 microg acetate-C l(-1) standard established by Taiwan Water Company. This indicates that the microbial regrowth might be a potential water quality problem in this system. Higher DO measurements (>5.7 mg l(-1)) might cause the aerobic biodegradation of THMs and HAAs in the system, and thus, low THMs (<0.035 mg l(-1)) and HAAs (<0.019 mg l(-1)) concentrations were observed at all sampling locations. Results from the observed negative Langelier Saturation Index (LSI) values, higher Ryznar Stability Index (RSI) values, and high Fe3+ concentrations at some pipe-end locations indicate that highly oxidative and corrosive conditions occurred. This reveals that pipe replacement should be considered at these locations. These findings would be helpful in managing the water distribution system for maintaining a safe drinking water quality.     

饮水中挥发性卤代烃成因研究

对影响饮水生成挥发性卤代烃的各种因素进行了研究.发现源水腐殖质等有机物的存在和加氯消毒处理是产生挥发性卤代烃的主要原因,而氯化消毒的温度、时间、源水pH值对其生成有重要影响.     

Formation and modeling of disinfection by-products in drinking water of six cities in China

Water quality parameters including TOC, UV(254), pH, chlorine dosage, bromide concentration and disinfection by-products were measured in water samples from 41 water treatment plants of six selected cities in China. Chloroform, bromodichloromethane, dibromochloromethane, dichloroacetic acid and trichloroacetic acid were the major disinfection by-products in the drinking water of China. Bromoform and dibromoacetic acid were also detected in many water samples. Higher concentrations of trihalomethanes and haloacetic acids were measured in summer compared to winter. The geographical variations in DBPs showed that TTHM levels were higher in Zhengzhou and Tianjin than other selected cities. And the HAA5 levels were highest in Changsha and Tianjin. The modeling procedure that predicts disinfection by-products formation was studied and developed using artificial neural networks. The performance of the artificial neural networks model was excellent (r > 0.84).     

Multi-level modelling of chlorination by-product presence in drinking water distribution systems for human exposure assessment purposes

During drinking water treatment and distribution, chlorine reacts with organic matter occurring in water to form various chlorination by-products (CBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). This paper presents the occurrence of THMs and HAAs in different water distribution systems (DS) of the same region and their modelling for exposure assessment purposes. This study was conducted in eight DS supplying chlorinated water to the population of Québec City, Canada. These systems differ in type of water source (i.e. surface, ground or mixed water), in treatment applied at the plant, and in size and structure of the DS. Two spatio-temporal databases for THMs and HAAs were implemented, one for model development and the other for model validation. The analysis of the data demonstrates significant seasonal and spatial variations of these compounds. A multi-level statistical modelling approach was applied to estimate the ranges for occurrence of THMs and HAAs in the eight DS (i.e. a single model for the study region for each CBP species). The modelling approach integrates available or easily measurable parameters. For both THMs and HAAs, a two-level model considering a sampling-site random effect was selected among various models initially developed. The model capacity for estimating the presence of THMs and HAAs in drinking water and its usefulness for exposure assessment purposes in the studied region was demonstrated.     

Optimizing booster chlorination in water distribution networks: a water quality index approach

The optimization of chlorine dosage and the number of booster locations is an important aspect of water quality management in distribution networks. Booster chlorination helps to maintain uniformity and adequacy of free residual chlorine concentration, essential for safeguarding against microbiological contamination. Higher chlorine dosages increase free residual chlorine concentration but generate harmful by-products, in addition to taste and odor complaints. It is possible to address these microbial, chemical, and aesthetic water quality issues through free residual chlorine concentration. Estimating a water quality index (WQI) based on regulatory chlorine thresholds for microbial, chemical, and aesthetics criteria can help engineers make intelligent decisions. An innovative scheme for maintaining adequate residual chlorine with optimal chlorine dosages and numbers of booster locations was established based on a proposed WQI. The City of Kelowna (BC, Canada) water distribution network served to demonstrate the application of the proposed scheme. Temporal free residual chlorine concentration predicted with EPANET software was used to estimate the WQI, later coupled with an optimization scheme. Preliminary temporal and spatial analyses identified critical zones (relatively poor water quality) in the distribution network. The model may also prove useful for small or rural communities where free residual chlorine is considered as the only water quality criterion.     

Investigation of pollution characteristics of polychlorinated biphenyls in the typical drinking water sources in Jiangsu Province, China

Concentration and composition of polychlorinated biphenyls (PCBs) in the typical drinking water sources in Jiangsu Province were studied by scene investigation and physical and chemical analyses as well. Total amount of PCBs in some surface water and surface microlayers exceeded the standard (20 ng/l) in the "Environmental Quality Standard of Surface Water". There were less PCBs in suspended substances and bottom mud. It reflected that there was less PCB pollution in drinking water sources in Jiangsu Province for quite a long period. The main kind of PCBs in the typical drinking water sources was dichlorobiphenyl. Monochlorobiphenyl and trichlorobiphenyl ranked next to dichlorobiphenyl. In the study of PCB distribution in drinking water sources, it was found that the concentration of PCBs in surface microlayer was higher than that in deep water. The concentration of PCBs along the Yangtze River bank was more than that in the middle of Yangtze River. PCBs in the typical drinking water sources mostly came from by-products in industrial production.     

Disinfection by-product formation and mutagenic assay caused by preozonation of groundwater containing bromide

Brominated organic and inorganic by-products are generated during ozonation of groundwater containing high bromide concentrations. This study measured concentrations of bromate, bromoform, bromoacetic acids, bromoacetonitriles, bromoacetone, 2,4-dibromophenol and aldehyde generated by ozonation. The potential mutagenicity of ozonated waters was assessed using the Ames and Microtox tests. Test results for the 18 ozonated groundwater samples demonstrate that bromate formation is associated with high pH, bromide and alkalinity content, low levels of dissolved organic carbon (DOC) and ammonia, and low alkalinity. Brominated organic by-products were correlated with high bromide ion and natural organic matter content, and low ammonia concentrations. The Ames test results demonstrate that all extracts from ozonated water have mutagenic activity; however, the 18 raw groundwater samples had no mutagenicity. The Microtox test results also show that the ozonated water samples were highly toxic. Generally, both bromide and DOC content promoted the formation of ozonation by-products and mutagenicity. Controlling of bromide and DOC concentrations is an effective method of reducing potential by-product formation and eliminating mutagenicity problems associated with groundwater ozonation.     

Ecological risk analysis of polycyclic aromatic hydrocarbons (PAHs) in surface sediments from Laizhou Bay

The current research aims at developing predictive models for trihalomethane (THM) formation in Lebanon based on field-scale investigations as well as laboratory controlled experimentations. Statistical analysis on field data revealed significant correlations for TTHM with chlorine dose, Specific UV-A, and UV(254) absorbing organics. Simulated distribution system-THM tests showed significant correlations with applied chlorine dose, total organic carbon, bromides, contact time, and temperature. Predictive models, formulated using multiple regression approaches, exhibiting the highest coefficients of determination were quadratic for the directly after chlorination (DAC; r(2) = 0.39, p < 0.036) and network (r(2) = 0.33, p < 0.064) THM databases, and logarithmic for the laboratory simulated THM database (r(2) = 0.70, p < 0.001). Computed r(2) values implied low correlations for the DAC and network THM database, and high correlation for the laboratory simulated THM database. Significance of the models were at the 0.05 level for DAC database, 0.10 level for the network database, and very high (<0.01 level) for the laboratory simulated THM database. It is noteworthy to mention that no previous attempts to assess, monitor, and predict THM concentrations in public drinking water have been reported for the country although a large fraction of the population consumes chlorinated public drinking water.     

Monitoring the Trihalomethanes Present in Water After Treatment with Chlorine Under Laboratory Condition

In this work assays involving chlorinated water samples, which were previous spiked with humic substances or algae blue green and following the production of the THMs for 30 days is described. To implement the assays, five portions of 1,000 ml of water were stored in glass bottles. The water samples were treated with solutions containing 2, 3, 4 and 5 mg l⁻¹ chlorine. The samples aliquots (60 ml) were transferred into the glass vials, 10 ml were removed to have a headspace and 100 μl of the 10 mg l⁻¹ pentafluortoluene bromide solution was added to each vial. The extraction step was performed by adding 10 g of Na₂SO₄ followed by 5 ml of n-pentane. The vials were stopped with a TFE-faced septum and sealed with aluminum caps. The generated THMs were determined by gas chromatography with electron capture detector using reference solutions with concentration ranging from 8 to 120 μg l⁻¹ THMs. Three assays were monitored during 30 days and chloroform was the predominant compound found in the water samples, while other species of THMs were not detected. The results showed that when the chlorine concentration was increased in water samples containing algae the concentration of THM varied randomly. Nevertheless, in water samples containing humic substances the increase of the THM concentration presented a relationship with the chlorine concentration. It was also observed that chloroform concentration increased with the elapsed time up to one and six days to water samples spiked with humic substances and algae blue green, respectively and decreased along 30 days. By other hand, assays performed using water samples containing decanted algae material showed that THM was not generated by the chlorine addition.     

Monochloramine loss in the presence of humic acid

Free chlorine has been used extensively as a primary and secondary disinfectant for potable water. Where it is difficult to maintain a free chlorine residual or when disinfection by-products (DBPs) are of concern, monochloramine has been used to provide a stable disinfectant residual in distributions systems. Reactions of disinfectants, free chlorine or monochloramine, with natural organic matter (NOM) consequently result in the formation of DBPs such as trihalomethanes and haloacetic acids. However, few studies have focused on the fate and kinetics of monochloramine loss in the presence of reactive constituents such as NOM. Monochloramine is inherently unstable and decays even without reactive constituents present via a mechanism known as autodecomposition. Therefore, to predict monochloramine concentrations in the presence of NOM is clearly associated with the ability to adequately model autodecomposition. This study presents the results of a semi-mechanisiic model capable of predicting the loss of monochloramine in the presence of humic material in the pH range of 6.55-8.33. The model accounts for both fast and a slow monochloramine demand to explain the loss of monochloramine over the pH range of this study. The formation of dichloroacetic acid was also predicted due to the ability of the model to differentiate monochloramine reaction pathways in the presence NOM. The results shown here demonstrate the ability of a semi-mechanistic model to predict monochloramine residuals and DBP formation in the presence of humic material.     

Ascorbic acid reduction of active chlorine prior to determining Ames mutagenicity of chlorinated natural organic matter (NOM)

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all compounds in samples from potable water supplies or laboratory studies of DBP formation. Reduction of oxidizing disinfectants is required since these compounds can kill the bacteria or react with the agar, producing chlorinated byproducts. When mutagens are collected by passing potable water through adsorbing resins, active chlorine compounds react with the resin, producing undesirable mutagenic artifacts. The bioanalytical and chemoanalytical needs of drinking water DBP studies required a suitable reductant. Many of the candidate compounds failed to meet those needs, including 2,4-hexadienoic (sorbic) acid, 2,4-pentanedione (acetylacetone), 2-butenoic (crotonic) acid, 2-butenedioic (maleic and fumaric) acids and buten-2-ol (crotyl alcohol). Candidates were rejected if they (1) reacted too slowly with active chlorine, (2) formed mutagenic byproducts, or (3) interfered in the quantitation of known chlorination DBPs. L-Ascorbic acid reacts rapidly and stoichiometrically with active chlorine and has limited interactions with halogenated DBPs. In this work, we found no interference from L-ascorbic acid or its oxidation product (dehydroascorbic acid) in mutagenicity assays of chlorinated NOM using Salmonella typhimurium TA100, with or without metabolic activation (S9). This was demonstrated for both aqueous solutions of chlorinated NOM and concentrates derived from the involatile, ether-extractable chlorinated byproducts of those solutions.     

Drinking water treatment is not associated with an observed increase in neural tube defects in mice

Disinfection by-products (DBPs) arise when natural organic matter in source water reacts with disinfectants used in the water treatment process. Studies have suggested an association between DBPs and birth defects. Neural tube defects (NTDs) in embryos of untreated control mice were first observed in-house in May 2006 and have continued to date. The source of the NTD-inducing agent was previously determined to be a component of drinking water. Tap water samples from a variety of sources were analyzed for trihalomethanes (THMs) to determine if they were causing the malformations. NTDs were observed in CD-1 mice provided with treated and untreated surface water. Occurrence of NTDs varied by water source and treatment regimens. THMs were detected in tap water derived from surface water but not detected in tap water derived from a groundwater source. THMs were absent in untreated river water and laboratory purified waters, yet the percentage of NTDs in untreated river water were similar to the treated water counterpart. These findings indicate that THMs were not the primary cause of NTDs in the mice since the occurrence of NTDs was unrelated to drinking water disinfection.     

新疆主要城市集中式饮用水源地水质评价

2007年新疆环保系统的调查和评价结果表明,新疆16个主要城市的31个现役集中式饮用水源地总供水量为4.47×10^8m^3,担负着供应420万常住城市人口的生活饮用水、部分工业用水和城市生态用水的责任;城市饮用水源地总体水质良好,水质达标比例为83.9%,不同地区、不同水源类型间存在差异;由于受原生土壤地质条件和人类活动的影响,目前有5个集中式饮用水源地超过国家规定的水质标准,而且部分饮用水源地中有机污染物有多项检出;受水源保护区划工作滞后、监管力度不够等因素影响,部分城市饮用水源地存在一定的环境安全隐患。