Levels Of Disinfection By-products Research Articles

Algal-derived organic matter as precursors of disinfection by-products and mutagens upon chlorination

Algal-derived organic materials (including algal cells, hydrophilic and hydrophobic proteins) from Chlamydomonas sp. (a common green alga in local reservoirs), were chlorinated in the laboratory (20 °C, pH 7, Cl2/DOC ratio of 20 mg Cl2 mg−1). Levels of disinfection by-products and mutagenicity (via Salmonella T100 mutation assay, -S9) over 2 h of chlorination time were determined. The hydrophilic proteins were more effective precursors of chloroform (35.9 μmol L−1 at 120 min), 35 times greater than that from the hydrophobic proteins; whereas the hydrophobic proteins were more potent precursors of direct-acting mutagens (maximum level of 50.1 rev μL−1 at 30 s) than the hydrophilic proteins (maximum level of 3.38 rev μL−1 at 60 min). The mutagenicity of the chlorinated solutions generally reached a peak level shortly after chlorination and then declined afterwards, a pattern different from that of chloroform generation. The results indicate that algal hydrophilic proteins, containing low aromaticity and difficult to be removed via coagulation/flocculation, are important chloroform precursors. It is also suggested that hydrophobic organic intermediates with low molecular weight formed during chlorination may serve as the direct-acting mutagens.

Pooling Data on Pools: Genotoxicity of Chemicals in Indoor Swimming Pools

Disinfection by-products (DBPs) form in swimming pool water from reactions between disinfectants such as chlorine and organic matter such as sweat, skin cells, and urine. A new study described in a set of three articles provides the first comprehensive characterization of DBPs in an indoor pool environment and offers initial evidence of cellular-level effects of these chemicals in swimmers in an indoor chlorinated pool [EHP 118(11):1523–1530; Richardson et al.; EHP 118(11):1531–1537, Kogevinas et al.; EHP 118(11):1538–1544, Font-Ribera et al.]. The authors assessed short-term changes in 49 healthy adults after they swam for 40 minutes in a public indoor chlorinated pool. They observed increases in two biomarkers of genotoxicity relative to the concentration of brominated trihalomethanes (THMs) in exhaled breath, which were used as a proxy of the swimmers’ total DBP exposures. Those biomarkers were micronuclei in blood lymphocytes (which have been associated with cancer risk in healthy subjects) and urine mutagenicity (a biomarker of exposure to genotoxic agents). The team also took detailed measurements of THMs in air around the pool and in exhaled breath of the swimmers before and after swimming. The investigators measured several biomarkers of respiratory effects after swimming and found changes in only one—a slight increase in serum CC16, which suggests an increase in lung epithelium permeability. However, they found no evidence that DBP exposure affected lung function. The research team identified more than 100 DBPs in the water of the chlorinated pool as well as another indoor pool disinfected with bromine. Some of these compounds had never been reported previously in swimming pool water and/or chlorinated drinking water. In vitro assays showed the swimming pool water was mutagenic at levels similar to that of drinking water but was more cytotoxic (could kill cells at a lower concentration) than drinking water. The researchers acknowledge the need for further research on a variety of swimming pools under various conditions of maintenance and use as well as more complete evaluations of the uptake and potential effects of the compounds present in pool water. They also note the importance of timing in the collection of biological samples—a parameter for which there was no precedent, given the lack of previous studies of this type with swimmers. Above all, they emphasize that positive health effects of swimming can be maintained by minimizing pool levels of DBPs.

Spatial and temporal evaluations of disinfection by-products in drinking water distribution systems in Beijing, China

Disinfection by-products were determined in 15 water treatment plants in Beijing City. The effects of different water sources (surface water source, mixture water source and ground water source), seasonal variation and spatial variation were examined. Trihalomethanes and haloacetic acids were the major disinfection by-products found in all treated water samples, which accounted for 42.6% and 38.1% of all disinfection by-products respectively. Other disinfection by-products including haloacetonitriles, chloral hydrate, haloketones and chloropicrin were usually detected in treated water samples but at lower concentrations. The levels of disinfection by-products in drinking water varied with different water sources and followed the order: surface water source > mixture water source > ground water source. High spatial and seasonal variation of disinfection by-products in the drinking water of Beijing was shown as a result.

Concentration, Chlorination, and Chemical Analysis of Drinking Water for Disinfection Byproduct Mixtures Health Effects Research: U.S. EPA’s Four Lab Study

The U.S. Environmental Protection Agency's "Four Lab Study" involved participation of researchers from four national Laboratories and Centers of the Office of Research and Development along with collaborators from the water industry and academia. The study evaluated toxicological effects of complex disinfection byproduct (DBP) mixtures, with an emphasis on reproductive and developmental effects that have been associated with DBP exposures in some human epidemiologic studies. This paper describes a new procedure for producing chlorinated drinking water concentrate for animal toxicology experiments, comprehensive identification of >100 DBPs, and quantification of 75 priority and regulated DBPs. In the research reported herein, complex mixtures of DBPs were produced by concentrating a natural source water with reverse osmosis membranes, followed by addition of bromide and treatment with chlorine. By concentrating natural organic matter in the source water first and disinfecting with chlorine afterward, DBPs (including volatiles and semivolatiles) were formed and maintained in a water matrix suitable for animal studies. DBP levels in the chlorinated concentrate compared well to those from EPA's Information Collection Rule (ICR) and a nationwide study of priority unregulated DBPs when normalized by total organic carbon (TOC). DBPs were relatively stable over the course of the animal studies (125 days) with multiple chlorination events (every 5-14 days), and a significant portion of total organic halogen was accounted for through a comprehensive identification approach. DBPs quantified included regulated DBPs, priority unregulated DBPs, and additional DBPs targeted by the ICR. Many DBPs are reported for the first time, including previously undetected and unreported haloacids and haloamides. The new concentration procedure not only produced a concentrated drinking water suitable for animal experiments, but also provided a greater TOC concentration factor (136×), enhancing the detection of trace DBPs that are often below detection using conventional approaches.

DRINKING WATER QUALITY: Better Biomarker of DBP Exposure

DRINKING WATER QUALITY: Better Biomarker of DBP Exposure

A comparison of disinfection by-products found in chlorinated and chloraminated drinking waters in Scotland

Seven water treatment works were selected to compare disinfection by-products (DBPs) formed when using chlorination and chloramination. DBPs measured included trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), trihalonitromethane, iodinated THMs and nitrosamines. Generally treatment works that used chloramination were able to meet the European THM regulatory limit of 100 μg L −1 whereas the chlorinated works found it significantly more difficult. There were no significant differences in the levels of nitrogenous DBPs between the treatment works using chlorination or chloramination with the exception of the nitrosamine N-nitrosodimethylamine (NDMA) which was present at one treatment works in one season.

Presence and formation of disinfection by-products in Cairo residential water supply

A sampling program was conducted in a residential community in Cairo, Egypt in order to determine the presence of chlorine disinfection by-products (DBPs) in treated water and to observe the impact of the distribution system on DBP levels. Five campaigns were conducted over a 15-month period during 2005–2006. Trihalomethanes (THMs) and haloacetic acids (HAAs) exceeded local and international limits depending upon the season. Tap water concentrations of THMs were considerably higher in summer than during the rest of the year. In the Summer 2005 event, the average for the 20 tap water locations was 158 μg/l Total-THMs, well in excess of the U.S. EPA limit of 80 μg/L and the current Egyptian standard of 100 μg/l; all 20 locations exceeded the 100 μg/l limit. For the following event in late Fall 2005, the average dropped to 84 μg/l with 11 and 6 sites exceeding the U.S. EPA and Egyptian limits, respectively. HAA levels tended to be complementary to Total-THM values in that they were lower in summer but higher during fall and spring. The U.S. EPA limit on a select set of 5 HAAs (HAA5) is 60 μg/l (Egypt does not currently regulate HAAs). The average for HAA5 in the Summer 2005 event was 52 μg/l with 8 of the 20 tap samples equalling or exceeding the 60 μg/l standard. By contrast, in Fall 2005, the HAA5 average increased to 89 μg/l, with 15 of 20 sites exceeding the limit. THM and HAA concentrations generally increased with distance from the WTP along a targeted distribution main, while chlorine and natural organic matter tended to decrease.

Drinking Water Disinfection By-Product Exposure and Duration of Gestation

Recent studies suggest elevated exposure to drinking water disinfection by-products (DBPs) may be associated with decreased risk of preterm birth. We examined this association for exposure to total trihalomethanes (TTHMs), 5 haloacetic acids (HAA5), and total organic halides. Analysis included 2039 women in a prospective pregnancy study conducted from 2000 through 2004 in 3 study sites. Water samples were collected and analyzed for DBP concentrations. Participant data were collected through interviews, an early ultrasound, and birth records. We assessed the associations between DBPs and preterm birth (<37-weeks' gestation) using log-binomial regression. Discrete-time hazard analysis was used to model the conditional odds of delivery each week in relation to DBP exposure. Average second trimester DBP levels were associated with lower risk of preterm birth. Adjusted risk ratios for TTHM levels of 33.1-55.0, 55.1-66.3, 66.4-74.8, and 74.9-108.8 microg/L versus 2.2-4.6 microg/L were 0.8 (95% confidence intervals = 0.5-1.3), 0.9 (0.6-1.4), 0.7 (0.4-1.1), and 0.5 (0.3-0.9), respectively. Risk ratios for HAA5 levels of 17.9-22.0, 22.1-31.5, 31.6-40.4, and 40.5-52.8 microg/L versus 0-0.9 microg/L were 1.1 (0.8-1.7), 0.8 (0.5-1.2), 0.5 (0.3-0.8), and 0.7 (0.4-1.1), respectively. The conditional odds of delivery each week were decreased for the highest TTHM and HAA5 exposure groups versus the low exposure group for gestational weeks 33-40. The probability of preterm birth was not increased with high DBP exposure.

Drinking Water Disinfection By-Products and Time to Pregnancy

Laboratory evidence suggests tap water disinfection by-products (DBPs) could have an effect very early in pregnancy, typically before clinical detectability. Undetected early losses would be expected to increase the reported number of cycles to clinical pregnancy. We investigated the association between specific DBPs (trihalomethanes, haloacetic acids, brominated-trihalomethanes, brominated-haloacetic acids, total organic halides, and bromodichloromethane) and time to pregnancy among women who enrolled in a study of drinking water and reproductive outcomes. We quantified exposure to DBPs through concentrations in tap water, quantity ingested through drinking, quantity inhaled or absorbed while showering or bathing, and total integrated exposure. The effect of DBPs on time to pregnancy was estimated using a discrete time hazard model. Overall, we found no evidence of an increased time to pregnancy among women who were exposed to higher levels of DBPs. A modestly decreased time to pregnancy (ie, increased fecundability) was seen among those exposed to the highest level of ingested DBPs, but not for tap water concentration, the amount absorbed while showering or bathing, or the integrated exposure. Our findings extend those of a recently published study suggesting a lack of association between DBPs and pregnancy loss.

Chlorinated disinfection by-products in drinking water according to source, treatment, season, and distribution location

The occurrence of the most prevalent chlorinated disinfection by-products (DBPs) was investigated in three Quebec City distribution systems that deliver drinking water subjected to different treatment strategies. Trihalomethanes (THMs), haloacetic acids (HAAs), and other complementary parameters were monitored in several locations representing variable water residence times over 16 months. The occurrence of chlorinated DBPs levels was considerably lower in the system where raw water is subjected to pre-ozonation instead of pre-chlorination (as pre-treatment) or direct chlorination. Seasonal analysis of the data showed that according to the system and to the group of chlorinated DBPs, the average DBP concentrations in winter were two to four times lower than the average DBP levels of the entire period under study. Considerable variations of both DBP groups were observed according to the water residence time in the distribution system, but the behavior was not the same for THMs as for HAAs. In fact, correlations between THM and HAA levels were good only for cold water and low residence time conditions. Seasonal and spatial variations of DBPs documented in this study have important implications on regulatory issues and from an epidemiological point of view. Key words: trihalomethanes, haloacetic acids, drinking water, distribution system, water treatment, source, season, location.

IDSE and beyond: Application of computer modeling to distribution system water quality

Computer modeling has long been touted as a cost‐effective tool with which to study distribution systems for master planning, system deficiency analysis, and other such activities. This article demonstrates full‐scale applications of computer modeling to ensure regulatory compliance with disinfection byproduct levels and optimize drinking water distribution system water quality. In addition, computer modeling was used to predict the effects of water utility operations and water treatment processes on distribution system water quality, thus allowing utilities to examine multiple operational changes safely and efficiently before pilot‐scale testing or full‐scale implementation.

The Healthy Men Study: An Evaluation of Exposure to Disinfection By-Products in Tap Water and Sperm Quality

BackgroundChlorination of drinking water generates disinfection by-products (DBPs), which have been shown to disrupt spermatogenesis in rodents at high doses, suggesting that DBPs could pose a reproductive risk to men. In this study we assessed DBP exposure and testicular toxicity, as evidenced by altered semen quality.MethodsWe conducted a cohort study to evaluate semen quality in men with well-characterized exposures to DBPs. Participants were 228 presumed fertile men with different DBP profiles. They completed a telephone interview about demographics, health history, water consumption, and other exposures and provided a semen sample. Semen outcomes included sperm concentration and morphology, as well as DNA integrity and chromatin maturity. Exposures to DBPs were evaluated by incorporating data on water consumption and bathing and showering with concentrations measured in tap water. We used multivariable linear regression to assess the relationship between exposure to DBPs and adverse sperm outcomes.ResultsThe mean (median) sperm concentration and sperm count were 114.2 (90.5) million/mL and 362 (265) million, respectively. The mean (median) of the four trihalomethane species (THM4) exposure was 45.7 (65.3) μg/L, and the mean (median) of the nine haloacetic acid species (HAA9) exposure was 30.7 (44.2) μg/L. These sperm parameters were not associated with exposure to these classes of DBPs. For other sperm outcomes, we found no consistent pattern of increased abnormal semen quality with elevated exposure to trihalomethanes (THMs) or haloacetic acids (HAAs). The use of alternate methods for assessing exposure to DBPs and site-specific analyses did not change these results.ConclusionsThe results of this study do not support an association between exposure to levels of DBPs near or below regulatory limits and adverse sperm outcomes in humans.

Exposure to Drinking Water Disinfection By-Products and Pregnancy Loss

Previous research has suggested that exposure to elevated levels of drinking water disinfection by-products (DBPs) may cause pregnancy loss. In 2000-2004, the authors conducted a study in three US locations of varying DBP levels and evaluated 2,409 women in early pregnancy to assess their tap water DBP concentrations, water use, other risk factors, and pregnancy outcome. Tap water concentrations were measured in the distribution system weekly or biweekly. The authors considered DBP concentration and ingested amount and, for trihalomethanes only, bathing/showering and integrated exposure that included ingestion. On the basis of 258 pregnancy losses, they did not find an increased risk of pregnancy loss in relation to trihalomethane, haloacetic acid, or total organic halide concentrations; ingested amounts; or total exposure. In contrast to a previous study, pregnancy loss was not associated with high personal trihalomethane exposure (> or =75 micro g/liter and > or =5 glasses of water/day) (odds ratio = 1.1, 95% confidence interval: 0.7, 1.7). Sporadic elevations in risk were found across DBPs, most notably for ingested total organic halide (odds ratio = 1.5, 95% confidence interval: 1.0, 2.2 for the highest exposure quintile). These results provide some assurance that drinking water DBPs in the range commonly encountered in the United States do not affect fetal survival.

Occurrence of disinfection by-products in low DOC surface waters in Turkey

A total of 29 surface waters from different regions of Turkey were sampled once a month during 2004. Filtered raw water samples were characterized, chlorinated and the concentrations of disinfection by-products (DBPs) were measured. All waters were low in DOC ranging from 0.91 to 4.42 mg/L. The range of annual average trihalomethanes (THMs) and haloacetic acids (HAAs) concentrations in all waters was 21–189 and 18–149 μg/L, respectively. Total mass contributions of halides in THMs and HAAs to absorbable organic halides (AOX) ranged between 10 and 56% in all waters on annual average basis, indicating that significant amounts of other DBPs are being formed in the majority of the tested waters. A strong linear correlation was obtained between the concentrations of THMs and HAAs. Rather poor correlations were found for THMs–AOX and HAAs–AOX levels. For both THMs and HAAs, chlorinated species dominated over brominated ones since the majority of water sources had very low bromide levels. While chloroform and trichloroacetic acid were the major THM and HAA compounds, respectively; the extent of formation and speciation of DBPs varied greatly by season and water source. No consistent general trends were observed in terms of seasonal variations in DBP levels, suggesting that the characteristics of NOM moieties and their chlorine reactivity vary by season in almost all waters tested.

Chlorination Disinfection By-products in Drinking Water and the Risk of Adult Leukemia in Canada

The authors conducted a population-based case-control study of 1,068 incident leukemia cases and 5,039 controls aged 20-74 years during 1994-1997 to examine the association between exposure to drinking water chlorination disinfection by-products and adult leukemia risk in Canada. Residence and drinking water source histories and data from municipal water supplies were used to estimate individual chlorination disinfection by-product exposure according to water source, chlorination status, and chlorination disinfection by-product levels during the 40-year period before the interview. The analysis included 686 cases and 3,420 controls for whom water quality information was available for at least 30 of these years. Increased risk of chronic myeloid leukemia was associated with increasing years of exposure to different chlorination disinfection by-product indexes, with an adjusted odds ratio of 1.72 (95% confidence interval: 1.01, 3.08) for the highest exposure duration to total trihalomethanes of more than 40 microg/liter. In contrast, the risk of the other studied leukemia subtypes was found to decrease with increasing years of exposure to chlorination disinfection by-products. A protective effect was noted for chronic lymphoid leukemia (odds ratio = 0.60, 95 percent confidence interval: 0.41, 0.87) associated with the highest exposure duration to total trihalomethanes of more than 40 microg/liter. More studies with long-term exposure measures and large enough to evaluate leukemia subtypes are needed to further understanding of the issue.

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.

Mixing it up: Integrated disinfection scenarios in drinking water treatment

This column discusses the quandry water utilities face when attempting to concurrently achieve higher levels of pathogen disinfection and lower levels of disinfection byproducts (DBPs). Integrated disinfection, one such strategy utilities can use to achieve this goal, is the focus of this article. Two case studies, examples of integrated disinfection, are also discussed: Evaluation of chlorine dioxide and ozone; and, evaluation of ozone and ultraviolet (UV) light.

Analysis of disinfection by-products in drinking water by LC–MS and related MS techniques

Current research indicates that much of the unidentified fraction of drinking water disinfection by-products (DBPs) is highly polar and of high molecular weight. The combination of liquid chromatography and mass spectrometry (LC–MS) is being increasingly used for the direct analysis of these highly polar, hydrophilic DBPs and for the exploration of high molecular weight by-products. Further, improvements in LC–MS instrumentation and analytical techniques are providing low μg/L and ng/L detection limits, which allow trace levels of DBPs to be measured. This review covers recent applications of LC–MS and other related techniques, such as flow injection-atmospheric pressure chemical ionization and electrospray ionization (ESI)-MS, high-field asymmetric waveform ion mobility spectrometry–ESI–MS, membrane-introduction MS, and ion chromatography–ESI–MS for measuring known DBPs and exploring the nature of previously uncharacterized DBPs.

Formation of disinfection by-products and applicability of differential absorbance spectroscopy to monitor halogenation in chlorinated coastal and deep ocean seawater

Formation of disinfection by-products (DBPs) in chlorinated coastal (CS) and deep ocean (sampled at a 1500-m depth) seawater (DO) was explored using conventional chromatographic methods and differential absorbance spectroscopy. It was determined that trihalomethanes (THMs) predominated by bromoform, haloacetonitriles and haloacetic acids (HAA) form in chlorinated seawater. The yield of identified DBPs, especially THMs, was higher in CS, while in DO seawater the relative contribution of HAAs was almost four times higher than that of THMs. The fraction of consumed chlorine incorporated into the identified DBPs in DO natural organic matter (NOM) was much lower than that for coastal marine NOM, which was also more active in forming brominated DBPs. The kinetics of seawater chlorination was relatively rapid, and high levels of DBPs were released within the first 20–30 min of reaction. The kinetics of THMs and HAAs release could be approximated using a logarithmic function of reaction time. Absorbance measurements showed that chlorination caused the absorbance of DO and CS to decrease at wavelengths >250 nm. The features of the differential absorbance spectra of chlorinated seawater were close to those reported for drinking water, but their intensity was lower. The concentrations of CHBr 3, CHBr 2Cl and CHBrCl 2 formed in CS and DO chlorinated at varying chlorine doses and reaction times were well correlated with the corresponding — ΔA 272 and/or — ΔA 405 values. (The differential absorbance at 405 nm can be measured in the presence of residual chlorine). These results show that differential absorbance provides a number of sensitive surrogate parameters that can be used to monitor and quantify the formation of halogen-containing DBPs in seawater.

Considerations for improving the accuracy of exposure to disinfection by-products by ingestion in epidemiologic studies

Disinfection by-product (DBP) exposure characterization studies are often based on the analysis of a limited number of samples collected from a distribution system (DS) in which DBP levels are variable over time and space. A compositing technique was developed to simplify the sample collection procedures for integrating over temporal variations in DBPs measured in terms of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halogen (TOX). Over the course of 5 days analysis, the single composited sample was within 94–100% of the average THM concentration in all grab samples, 92–105% of HAAs, and 130% of the TOX concentration. Additionally, temporal variability factors such as timing of sample collection and the handling of tap water prior to consumption were found to influence DBP levels in consumers' drinking water. Included in our study of home water use are the effects of boiling which removed up to 98% of THMs and point of use (POU) devices which all showed DBP removal but differed depending on the device used. These factors should be taken into consideration in DBP exposure characterization for epidemiologic studies.