Understanding data requirements for trihalomethane formation modelling in water supply systems

Tighter regulatory standards for trihalomethanes in drinking water have been introduced in many countries in response to improved epidemiological evidence. This has led to the need to model better the THM concentrations in water distribution systems in order to manage efficiently economic, chemical and microbiological factors. THM modelling is a challenging process given the complex chemistry and dependence on river catchment, water treatment works and distribution system characteristics. It is demonstrated that a good understanding of the system from raw water to tap is needed if cost effective models of appropriate fidelity are to be produced. For appropriate systems models can incorporate, through empirical relationships, raw water quality variations based on river flow predictions, aspects of unit process management decision making variables as well as distribution system characteristics. In many systems model fidelity and hence efficient management is constrained by a lack of knowledge of system response.     

Carbohydrates as trihalomethanes precursors. Influence of pH and the presence of Cl(-) and Br(-) on trihalomethane formation potential

Upon chlorination carbohydrates can give trihalomethanes (THMs). In the present work, we have studied the influence of pH, chloride or bromide concentration on the formation of THMs from carbohydrates. We have observed that THMs are not formed at acidic pH, while basic pH values only increase slightly the THM content, although the consumption of chlorine increases up to 100% with respect to pH 8. The presence of chloride in ppm increases the THM formation from carbohydrates without influence of the chlorine consumption. In the same manner, the presence of bromide ions in ppb also increases remarkably the THMs formed upon chlorination of saccharides. Even more, we have observed that at bromide concentrations below 100ppb, complete incorporation of bromide in THMs occurs. Overall, the results obtained show that saccharides widely present in natural waters can give rise to significant THM concentrations in the disinfection process by chlorine.     

A retrospective cohort study of trihalomethane exposure through drinking water and cancer mortality in northern Italy

A few epidemiologic studies have suggested that consumption of drinking water with high trihalomethane content increases the risk of cancer. We investigated the mortality of a cohort of 5144 residents in Guastalla, northern Italy, who were supplied tap water with high chloroform and trihalomethane content between 1965 and 1987. Using death rates of a nearby community as reference rates, the standardized mortality ratio from all cancers between 1987 and 1999 was slightly increased for both males (1.2, 95% confidence interval 1.1-1.4) and females (1.1, 95% confidence interval 1.0-1.3). This was mainly due to a higher mortality from stomach, liver, lung, prostate and bladder cancer in males and from stomach, pancreas, breast and ovarian cancer and lymphocytic leukemia in females. We also noted excess mortality from melanoma in both males and females. Overall, our findings were consistent with an association between trihalomethane exposure and increased cancer risk at some sites. However, the point estimates were statistically imprecise, due to the limited number of deaths for some site-specific cancers. In addition, we were unable to rule out the possibility of confounding due to smoking and other life-style factors with regard to some of the excess rates.     

Multivariate statistical relationships between routine water plant data and trihalomethane levels. Implications for studies of human health

Routine water treatment plant data were used to construct a mathematical/statistical model of trihalomethane formation during lime-soda ash softening. Chemical characteristics of the raw water, such as temperature and color, and several treatment parameters, including chlorine dose, were significant predictors for chloroform and total trihalomethanes. The pattern of prediction was notably different for the brominated species. The results of this preliminary study support the view that routine water plant data can be used to estimate retrospectively, and with accuracy, trihalomethane levels for past time periods in which only the routine plant data are available. Possible limitations of the approach and the prospects for improving epidemiologic health effects studies of trihalomethanes in drinking water are discussed.     

Multiple linear regression modeling of disinfection by-products formation in Istanbul drinking water reservoirs

Oxidation of raw water with chlorine results in formation of trihalomethanes (THM) and haloacetic acids (HAA). Factors affecting their concentrations have been found to be organic matter type and concentration, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with water reservoirs from Terkos, Buyukcekmece and Omerli lakes, Istanbul, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, contact time, chlorine dose, and specific ultraviolet absorbance (SUVA). The determination of disinfection by-products (DBP) was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total THM and total HAA based on the use of pH, contact time, chlorine dose, and SUVA. The developed models provided satisfactory estimations of the concentrations of the DBP and the model regression coefficients of THM and HAA are 0.88 and 0.61, respectively. Further, the Durbin-Watson values confirm the reliability of the two models. The results indicate that under these experimental conditions which indicate the variations of pH, chlorine dosages, contact time, and SUVA values, the formation of THM and HAA in water can be described by the multiple linear regression technique.     

Variations in trihalomethane levels in three French water distribution systems and the development of a predictive model

Epidemiological studies have demonstrated that chlorination by-products in drinking water may cause some types of cancer in humans. However, due to differences in methodology between the various studies, it is not possible to establish a dose-response relationship. This shortcoming is due primarily to uncertainties about how exposure is measured—made difficult by the great number of compounds present—the exposure routes involved and the variation in concentrations in water distribution systems. This is especially true for trihalomethanes for which concentrations can double between the water treatment plant and the consumer tap.The aim of this study is to describe the behaviour of trihalomethanes in three French water distribution systems and develop a mathematical model to predict concentrations in the water distribution system using data collected from treated water at the plant (i.e. the entrance of the distribution system).In 2006 and 2007, samples were taken successively from treated water at the plant and at several points in the water distribution system in three French cities. In addition to the concentrations of the four trihalomethanes (chloroform, dichlorobromomethane, chlorodibromomethane, bromoform), many other parameters involved in their formation that affect their concentration were also measured.The average trihalomethane concentration in the three water distribution systems ranged from 21.6 μg/L to 59.9 μg/L. The increase in trihalomethanes between the treated water at the plant and a given point in the water distribution system varied by a factor of 1.1-5.7 over all of the samples. A log-log linear regression model was constructed to predict THM concentrations in the water distribution system. The five variables used were trihalomethane concentration and free residual chlorine for treated water at the plant, two variables that characterize the reactivity of organic matter (specific UV absorbance (SUVA), an indicator developed for the free chlorine consumption in the treatment plant before distribution δ) and water residence time in the distribution system.French regulations impose a minimum trihalomethane level for drinking water and most tests are performed on treated water at the plant. Applied in this context, the model developed here helps better to understand trihalomethane exposure in the French population, particularly useful for epidemiological studies.     

Modeling of trihalomethane cometabolism in nitrifying biofilters

The computer program AQUASIM was used to model biofilter experiments seeded with Lake Austin, Texas mixed-culture nitrifiers. These biofilters degraded four trihalomethanes (THMs) (trichloromethane (TCM) or chloroform, bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM) or bromoform) commonly found in treated drinking water. Apparent steady-state data from the biofilter experiments and supporting batch experiments were used to estimate kinetic parameters for TCM, DBCM and ammonia degradation. Subsequently, the model was verified against other experimental biofilter data. To allow for full-scale simulations, BDCM and TBM rate constants were estimated using data from batch kinetic studies. Finally, the model was used to simulate full-scale filter performance under different filter surface loading rates and THM speciation seen in practice. Overall, total THM removals ranged from 16% to 54% in these simulations with influent total THM concentrations of 75-82microg/L, which illustrates the potential of THM cometabolism to have a significant impact on treated water quality.     

Chlorine demand-based predictive modeling of THM formation in water distribution networks

The potential carcinogenicity of trihalomethanes (THMs) has led to increasingly stricter regulation of drinking water supplies. This has led to the need to manage better the chemical and microbiological risk balance in chlorinated supplies. The use of empirical equations to predict THM concentrations in water quality models is challenging and expensive due to the numerous temporally and spatially dependent uncertainties involved. In this paper, the benefits of a simple predictive method using a THM productivity parameter based on chlorine consumed by bulk free chlorine reactions are explored using extensive field data from a water distribution system in the Midlands region of the UK. It is concluded that the productivity parameter provides an appropriate, relatively robust, yet straightforward alternative to the use of an empirical equation based on regression analyses to predict THM concentrations in distribution, and that the method has the potential to help distribution system water quality model calibration.     

Effect of bromide on the formation of disinfection by-products during wastewater chlorination

The effect of bromide ion on the formation and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) during the chlorination of biologically treated wastewaters was investigated. The experimental results showed that the formation of total THMs and total HAAs during chlorine disinfection increased with increasing bromide levels in wastewater. The formation of CHBr₃ increased nearly linearly with increasing bromide ion levels, while CHCl₂Br and CHClBr₂ increased with increasing bromide concentration from 0 to 3.2 mg L⁻¹ and thereafter remained constant or slightly decreased. Increasing initial bromide levels up to 12.8 mg L⁻¹ resulted in sharp decrease of the concentration of CHCl₃ and chloro- HAAs. The mixed bromochloro- HAAs and bromo-only species replaced chloro- HAAs as the dominated species of HAA with increasing bromide levels. The distribution of monohalogenated, dihalogenated and trihalogenated species of HAAs in chlorinated wastewater at high concentration of bromide (>2 mg L⁻¹) is different from that of drinking/natural water. The values of the bromine incorporation factors, n (Br) and n′ (Br), increased with increasing bromide concentration and remained constant or slightly decreased with increasing contact time under the studied range of bromide ion concentrations during chlorination. Moreover, the bromine incorporation into THMs was higher than that of HAAs with bromide levels ranging from 1.0 to 12.8 mg L⁻¹, indicating the dissimilar formation mechanisms of THMs and HAAs involving bromide.     

给排水工程的绿色环保

近年来,节能环保问题,已经成了建筑行业可持续发展的关键性问题。建筑给水排水作为建筑内部的重要组成部分,设计人员在设计时除了要满足人们可居住性和舒适性的要求外,更应该注意给排水的绿色环保。     

The impact of water consumption, point-of-use filtration and exposure categorization on exposure misclassification of ingested drinking water contaminants

The use of population-level indices to estimate individual exposures is an important limitation of previous epidemiologic studies of disinfection by-products (DBPs). We examined exposure misclassification resulting from the use of system average DBP concentrations to estimate individual-level exposures. Data were simulated (n=1000 iterations) for 100 subjects across 10 water systems based on the following assumptions: DBP concentrations ranged from 0-99 microg/L with limited intra-system variability; water intake ranged from 0.5-2.5 L/day; 20% of subjects used bottled water exclusively; 20% of subjects used filtered tap water exclusively; DBP concentrations were reduced by 50% or 90% following filtration. DBP exposure percentiles were used to classify subjects into different exposure levels (e.g., low, intermediate, high and very high) for four classification approaches. Compared to estimates of DBP ingestion that considered daily consumption, source type (i.e., unfiltered tap, filtered tap, and bottled water), and filter efficiency (with 90% DBP removal), 48-62% of subjects were misclassified across one category based on system average concentrations. Average misclassification across at least two exposure categories (e.g., from high to low) ranged from 4-14%. The median classification strategy resulted in the least misclassification, and volume of water intake was the most influential modifier of ingestion exposures. These data illustrate the importance of individual water use information in minimizing exposure misclassification in epidemiologic studies of drinking water contaminants.     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

饮用水中氯化消毒副产物的控制研究进展

探讨了DBPs的形成机理及其种类,然后介绍了DBPs对人体的健康风险,并总结了目前国内外控制DBPs的方法,为饮用水高效安全消毒技术的进一步研究提出了意见和建议。     

Empirical rate equation for trihalomethane formation with chlorination of humic substances in water

Trihalomethane (THM) in drinking water is formed by chlorination of humic substances. In this study, the rates of THM formation in aqueous solution of humic acid were examined under various conditions. The following rate equation was obtained empirically. [THM] = k (pH − a)[TOC][Cl₂]₀^mtⁿ.

Here, [THM] is the concentration of total THM after t h, [TOC] and [Cl₂]₀ are the concentrations of total organic carbon and chlorine dose, k is the rate constant and a, m and n are parameters. The values of k, a, m and n for humic acid as reagent were obtained as 8.2 × 10⁻⁴ (l^mmg^−mh⁻ⁿ), 2.8, 0.25 and 0.36, respectively. The activation energy was obtained as 37 kJ mol⁻¹. Further, it was proved that the above equation could be applied to the rates of THM formation from precursors in actual river and lake waters.     

Behavior of trihalomethanes and haloacetic acids in a drinking water distribution system

This investigation focused on the seasonal variation and spatial fate of chlorination disinfection by-products (CDBPs) in a drinking water distribution system located in a region where very significant seasonal variations in water temperature and surface water quality occur. The analysis of a large number of collected samples showed that the seasonal and geographical variations of both groups of CDBPs under study—trihalomethanes (THMs) and haloacetic acids (HAAs)—were particularly important in this region. THM levels in summer and fall were, on average, about five times higher than in winter, whereas average HAAs in spring were about four times higher than in winter. THMs increased and stabilized in the extremities of the distribution system, whereas HAAs begin to increase, and then decrease (mainly due to a reduction of dichloroacetic acid). This decrease was significantly higher in warm waters than in cold waters, which led to the hypothesis of microbial degradation of HAAs as water approaches the system extremities. In fact, regression models for the occurrence of both CDBPs showed that the residence time of water was one important parameter in explaining the fate of both CDBPs. The spatio-temporal portrait of both groups of CDBPs that was generated demonstrates that, due to their high intra-seasonal changes, the calculation of average annual levels of these substances for compliance with regulations can vary widely. The results used in the portrait of CDBP behavior are also relevant in terms of exposure assessment for future epidemiological studies on human reproductive outcomes in the region.     

Changes of trihalomethane formation potentials in the tone river

The changes of trihalomethane formation potentials (THMFPs) in the Tone River were examined. There were clear differences not in THMFPs but in THMFP loading (THMFP × flow rate) between the winter and the summer. The ratio of THMFP loading caused by artificial pollution was estimated. This ratio increased sharply with increases in watershed area and reached about 80% for a watershed area of about 2000 km² (with a population density of about 65 persons km²). Further, two formulas were obtained to estimate the THMFP and THMFP loading of the Tone River in the future.     

Solar disinfection (SODIS): simulation of solar radiation for global assessment and application for point-of-use water treatment in Haiti

Haiti and other developing countries do not have sufficient meteorological data to evaluate if they meet the solar disinfection (SODIS) threshold of 3-5 h of solar radiation above 500 W/m2, which is required for adequate microbial inactivation in drinking water. We have developed a mathematical model based on satellite-derived daily total energies to simulate monthly mean, minimum, and maximum 5-h averaged peak solar radiation intensities. This model can be used to assess if SODIS technology would be applicable anywhere in the world. Field measurements were made in Haiti during January 2001 to evaluate the model and test SODIS efficacy as a point-of-use treatment option. Using the total energy from a measured solar radiation intensity profile, the model recreated the intensity profile with 99% agreement. NASA satellite data were then used to simulate the mean, minimum, and maximum 5-h averaged peak intensities for Haiti in January, which were within 98.5%, 62.5%, and 86.0% agreement with the measured values, respectively. Most of the discrepancy was attributed to the heterogeneous nature of Haiti's terrain and the spatial resolution of the NASA data. Additional model simulations suggest that SODIS should be effective year-round in Haiti. Actual SODIS efficacy in January was tested by the inactivation of total coliform, E. coli, and H2S-producing bacteria. Exposure period proved critical. One-day exposure achieved complete bacterial inactivation 52% of the time, while a 2-day exposure period achieved complete microbial inactivation 100% of the time. A practical way of providing people with cold water every morning that has undergone a 2-day exposure would be to rotate three groups of bottles every morning, so two groups are out in the sun and one is being used for consumption.     

三种饮用水消毒副产物形成模型对比研究

选取反应时间(t)、水温(T)、pH、总有碳(TOC)、特别紫外吸光度(UV254)、溴离子浓度(Br-)及反应的氯剂量(Cl2)等相关的水质参数,构建了三卤甲烷及卤乙酸两大类消毒副产物的多元线性回归、非线性回归及神经网络预测模型。结果表明,消毒副产物的多元线性回归模型能逐步筛选回归因子,得出影响消毒副产物形成的主要因素及影响程度,各消毒副产物的多元线性回归方程的线性非常显著(p≤0.05);消毒副产物的非线性回归模型能分析预测各种对消毒副产物的影响不呈线性关系的因素;各消毒副产物神经网络预测的判定参数均大于0.83,表明采用神经网络预测消毒副产物的形成可以获得较精确的预测值。     

Trihalomethane occurrence in chlorinated reclaimed water at full-scale wastewater treatment plants in NE Spain

Total trihalomethane (TTHM) concentrations were determined in three chlorinated effluents (i.e. secondary and tertiary) from full-scale wastewater treatment plants (WWTP) in NE Spain over a 2-year monitoring period (May 2003-February 2005). Low TTHM concentrations (2-30 microg L(-1)), according to international standards for drinking water (80-150 microg L(-1)), were obtained in all samples analysed. The effects of (a) ammonia nitrogen and bromide concentrations, (b) UV light exposure, (c) tank storage, and (d) water temperature were evaluated. Two chlorination strategies were adopted: low chlorine dosages (2-5 mg Cl2 L(-1)) and a high-chlorine dosage (16 mg Cl2 L(-1)). The effects of storing chlorinated reclaimed water and of UV light exposure before chlorination were also evaluated. Samples collected over the 2-year monitoring period offered the possibility to assess the numerous variables affecting THM formation. A statistical evaluation of Platja d'Aro WWTP data set shows a low TTHM formation in the presence of high ammonia nitrogen concentration (p<0.05). That result can be attributed to the formation of chloramines by reaction with added chlorine, at doses below breakpoint chlorination. An increase in TTHM concentration in the presence of bromide (0-1 mg L(-1)) was also recorded (p<0.05). In contrast to published reports, TOC had a negative effect on TTHM formation. COD and turbidity had no statistical significance on TTHM formation. As expected, chlorination promoted TTHM formation in the three water reclamation plants monitored. Nevertheless, no statistical difference was observed when chlorinated effluents were kept in storage tanks. Exposure to UV light did not affect either formation or removal of TTHM. The relative production of TTHM during warm and cold seasons was also evaluated. TTHM production decreased with higher temperatures, but that could be attributed to the increase of ammonia nitrogen concentration observed during the warm summer seasons.     

Impact of water stagnation in residential cold and hot water plumbing on concentrations of trihalomethanes and haloacetic acids

This study demonstrates that levels of trihalomethanes (THMs) increase considerably when cold water stagnates in residential pipes and, more significantly, when water remains in the hot water tank. Levels of haloacetic acids (HAAs) increase as well in both cases, but less significantly in comparison to THMs. The study also demonstrates that in both the plumbing system and residential hot water tank, chlorinated and brominated DBP species do not behave in the same manner. Finally, the study shows that sustained use of water in households helps to maintain THM and HAA levels close to those found in water of the distribution system. The results are useful to identify methods of indoor water use that minimize population exposure to DBPs and improve DBP exposure assessment for epidemiological studies.