Exposure estimates to disinfection by-products of chlorinated drinking water

Exposure to disinfection by-products (DBPs) of drinking water is multiroute and occurs in households serviced by municipal water treatment facilities that disinfect the water as a necessary step to halt the spread of waterborne infectious diseases. Biomarkers of the two most abundant groups of DBPs of chlorination, exhaled breath levels of trihalomethanes (THMs) and urinary levels of two haloacetic acids, were compared to exposure estimates calculated from in-home tap water concentrations and responses to a questionnaire related to water usage. Background THM breath concentrations were uniformly low. Strong relationships were identified between the THM breath concentrations collected after a shower and both the THM water concentration and the THM exposure from a shower, after adjusting for the postshower delay time in collecting the breath sample. Urinary haloacetic acid excretion rates were not correlated to water concentrations. Urinary trichloroacetic acid excretion rates were correlated with ingestion exposure, and that correlation was stronger in a subset of individuals who consumed beverages primarily within their home where the concentration measurements were made. No correlation was observed between an average 48-hr exposure estimate and the urinary dichloroacetic acid excretion rate, presumably because of its short biological half-life. Valid biomarkers were identified for DBP exposures, but the time between the exposure and sample collection should be considered to account for different metabolic rates among the DBPs. Further, using water concentration as an exposure estimate can introduce misclassification of exposure for DBPs whose primary route is ingestion due to the great variability in the amount of water ingested across a population.     

Impact of Booster Chlorination on Chlorine Decay and THM Production: Simulated Analysis

The effect of conventional and booster chlorination on chlorine residuals and trihalomethane (THM) formation in drinking water distribution systems was modeled using the EPANET hydraulic modeling software. The model results suggest that booster chlorination may allow utilities to meet disinfection goals better by carrying chlorine residuals to remote points in the distribution system while lowering the total mass of chlorine applied to the system. The model results suggest that booster chlorination may provide the greatest advantages to points in the distribution system located near storage tanks by providing a more consistent chlorine residual and possibly reducing THM formation. A new version of the EPANET model, the EPANET Multispecies model, was also used to compare chlorine decay due to reactions in the bulk fluid and reactions occurring at the pipe wall. The results suggest that chlorine decay due to wall reactions can be very significant at remote points in the distribution system. Additionally, if THMs are assumed to form primarily through reactions in the bulk fluid, use of the new EPANET Multispecies software allows for calculation of THM formation based solely on chlorine reactions in the bulk fluid rather than on overall chlorine decay.     

Secondary Benefits of Aquifer Storage and Recovery: Disinfection By-Product Control

The potential of biological processes during aquifer storage to reduce disinfection by-products (DBP), and DBP precursors were examined under controlled conditions. Finished water treated by conventional water treatment practice was pumped into a sand media column for up to 34 days of residence time. Two experiments were conducted where the finished water was chlorinated or ozonated prior to injection. Chlorination of water withdrawn from simulated aquifer storage conditions resulted in reduced formation of trihalomethane (THM) concentrations for all three treated water types. Ozonation of finished water resulted in a 70% decrease in TTHM formation. Aquifer storage of finished water resulted in a 26–28% reduction in TTHM formation and the removal of preformed THM species was as high as 40%. Overall, aquifer storage of chlorinated finished water resulted in a 44% reduction in TTHM formation when additionally chlorinated after withdrawal. Bromate formed during ozonation was reduced by approximately 54%. This study indicates that the sequencing of chlorination or ozonation with respect to aquifer storage and recovery operations can impact DBP formation.     

Effects of Bromide Ion and Natural Organic Matter Fractions on the Formation and Speciation of Chlorination By-Products

The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA254) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV254 absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254?nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (>54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60–110?μg/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500?μg/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.     

Cultured astrocytes express proteins involved in vesicular glutamate release

The objective of this study is to analyze volatile organic compound (VOC) concentrations in Taiwan's drinking water supply. Focusing on Taiwan's three major metropolitan areas--Taipei, Taichung and Kaohsiung (in the north, middle and south, respectively)--171 samples were taken from tap water and 68 from boiled water. Tests showed VOC concentrations were highest in Kaohsiung. This is due to different water sources and methods of treatment. Except for bromoform, trihalomethane (THM) concentrations were highest. Detection rates of toluene and 1,2-dichloroethane were slightly higher than other VOC compounds. VOC concentrations decreased significantly after water was boiled. THMs had a removal rate from 61% to 82%. The authors conclude that the three metropolitan areas contain significantly different levels of VOCs and that boiling can significantly reduce the presence of VOCs. Other sources of pollution that contaminate drinking water such as industrial plants and gas stations must be further investigated.     

Methotrexate suppresses nitric oxide production ex vivo in macrophages from rats with adjuvant-induced arthritis

This review discusses the relation between by-products of drinking water chlorination and cancer in the light of present toxicological and epidemiologic evidence. During the chlorination of drinking water, a complex mixture of by-products forms from chlorine and the organic and inorganic compounds present in raw water. The quality and quantity of such compounds depend on the specific nature of the organic material in raw waters, the inorganic material in raw water, pH, temperature, other water treatment practices, and the chlorine timing and dose added. Chlorination by-products are important mainly when surface water is used for drinking water as more organic compounds are present in surface waters than in ground waters. The gastrointestinal and urinary tract are the cancer sites that are most often associated with the use of chlorinated surface water or with the quantity of chlorination by-products in the water-supply network. Yet the microbial quality of drinking water should not be compromised by excessive caution over the potential long-term effects of disinfection by-products because the risk of illness and death resulting from exposure to pathogens in untreated drinking water may be several orders of magnitude greater than the cancer risks from chlorination by-products.     

Dose-dependent vehicle differences in the acute toxicity of bromodichloromethane

Bromodichloromethane (BDCM) is a disinfection by-product of drinking water chlorination and is the second most common trihalomethane (THM) in finished drinking water. THMs have generally been administered to experimental animals in corn oil, rather than drinking water, which can influence the site and magnitude of toxicity. To examine the effects of gavage vehicle on the acute renal and hepatic toxicity of orally administered BDCM, 95-day-old male F344 rats were given single doses of 0, 200, or 400 mg BDCM/kg in corn oil or an aqueous 10% Emulphor solution. Activities of serum hepatoxicity indicators were significantly greater 48 hr after administration of 400 mg BDCM/kg in corn oil compared to the aqueous vehicle, but delivery of the low dose in either dosing vehicle had little effect on serum enzymes. In contrast, significant elevations in urinary renal toxicity indicators were noted at 200 and 400 mg BDCM/kg in both vehicles after 24 hr, indicating that the kidney is more sensitive to low doses of BDCM than the liver. Significantly greater increases were observed in urinary indicators after delivery of 200 mg BDCM/kg in 10% Emulphor compared to corn oil. However, administration of the high dose in corn oil resulted in greater nephrotoxicity than in the aqueous vehicle. Significant interactions between vehicle of administration and BDCM dose observed for both urinary and serum parameters further indicate that vehicle differences noted in BDCM acute toxicity are dose dependent. This observation may be due to pharmacokinetic differences in gastrointestinal rates of absorption of BDCM from corn oil as compared to an aqueous solution.     

Trihalomethane and Haloacetic Acid Disinfection By-Products in Full-Scale Drinking Water Systems

Trihalomethane (THM), haloacetic acid (HAA5), and total organic carbon (TOC) data provided by the Missouri Dept. of Natural Resources for drinking water treatment systems in the State of Missouri was analyzed for the years 1997–2001. These data indicated that a significant portion of systems exceeded the current regulatory limits of 80 and 60?μg/L for THM and HAA5 in these years. The vast majority of the treatment plants exceeding the regulatory limits were small plants with service populations less than 10,000 people. No significant temporal trend in either THM or HAA5 was noted for the years 1997–2001. This work suggests that the proposed use of a locational running annual average may have a significant effect on compliance. The use of chloramines (combined chlorine) versus free chlorine (HOCl/OCl?) as a residual disinfectant was shown to significantly reduce both THM and HAA5 in systems that treat their own water (primary systems), but did not have a significant effect in systems which purchase their water from primary systems (secondary systems). Comparison of finished water at the treatment plant versus in the distribution system suggested that a majority of THM and HAA5 may be produced within the plant as opposed to the distribution system. Hence, reducing these chlorinated disinfection byproducts within the treatment plant itself should be a key focus for achieving compliance, and supports Environmental Protection Agency disinfection byproducts compliance guidelines using enhanced coagulation.     

Assessment of the carcinogenic potential of chlorinated water: experimental studies of chlorine, chloramine, and trihalomethanes

BACKGROUND: Water chlorination has been one of the major disease prevention treatments of this century. While epidemiologic studies suggest an association between cancer in humans and consumption of chlorination byproducts in drinking water, these studies have not been adequate to draw definite conclusions about the carcinogenic potential of the individual byproducts. PURPOSE: The purpose of this study was to investigate the carcinogenic potential of chlorinated or chloraminated drinking water and of four organic trihalomethane byproducts of chlorination (chloroform, bromodichloromethane, chlorodibromomethane, and bromoform) in rats and mice. METHODS: Bromodichloromethane, chlorodibromomethane, bromoform, chlorine, or chloramine was administered to both sexes of F344/N rats and (C57BL/6 x C3H)F1 mice (hereafter called B6C3F1 mice). Chloroform was given to both sexes of Osborne-Mendel rats and B6C3F1 mice. Chlorine or chloramine was administered daily in the drinking water for 2 years at doses ranging from 0.05 to 0.3 mmol/kg per day. The trihalomethanes were administered by gavage in corn oil at doses ranging from 0.15 to 4.0 mmol/kg per day for 2 years, with the exception of chloroform, which was given for 78 weeks. RESULTS: The trihalomethanes were carcinogenic in the liver, kidney, and/or intestine of rodents. There was equivocal evidence for carcinogenicity in female rats that received chlorinated or chloraminated drinking water; this evidence was based on a marginal increase in the incidence of mononuclear cell leukemia. Rodents were generally exposed to lower doses of chlorine and chloramine than to the trihalomethanes, but the doses in these studies were the maximum that the animals would consume in the drinking water. The highest doses used in the chlorine and chloramine studies were equivalent to a daily gavage dose of bromodichloromethane that induced neoplasms of the large intestine in rats. In contrast to the results with the trihalomethanes, administration of chlorine or chloramine did not cause a clear carcinogenic response in rats or mice after long-term exposure. CONCLUSION: These results suggest that organic byproducts of chlorination are the chemicals of greatest concern in assessment of the carcinogenic potential of chlorinated drinking water.     

Improved Real-Coded GA for Groundwater Bioremediation

Cost-effective ways of remediating contaminated ground water by in situ bioremediation or other methods can be identified by coupling optimization and simulation methods. However, application of these methods to field-scale problems is limited by computational efficiency and by ease of use. In this paper, a more efficient genetic algorithm is developed and applied to in situ bioremediation of ground water. The algorithm involves a real-coded genetic algorithm (GA) coupled with two newly developed operators: directive recombination and screened replacement. This paper is the first application of a real-coded genetic algorithm (RGA) to ground-water remediation. The numerical results obtained for two bioremediation examples indicate that the directive recombination and screened replacement significantly improve the performance of RGA and that RGA performs much better than the standard binary-coded GA for the ground-water remediation problem. Because of the incorporation of interactions between the degrading microbes, oxygen, and contaminant concentrations, the equations for bioremediation are highly nonlinear. The RGA developed would also be expected to be more efficient for other highly nonlinear water resources problems.     

Particulate and THM Precursor Removal with Ferric Chloride

Pilot-scale experiments were performed to investigate the effectiveness of enhanced coagulation in removing particles and trihalomethane (THM) precursors from two surface source waters: California State Project water and Colorado River water. The removal of suspended particles and natural organic matter at various ferric chloride doses and coagulation pHs was assessed through source water and filter effluent measurements of turbidity, particle count, UV254, TOC, and THM formation potential. Overall, it was found that optimal removal of particles and THM precursors by enhanced coagulation with ferric chloride is obtained at high coagulant doses (>16 mg∕L) and low pH conditions. Generally, turbidity removal is more efficient and head loss is more moderate at ambient pH compared with pH 5.5. Additionally, filter effluent particle counts were found to be consistent with residual turbidity data. The removal of THM precursors by enhanced coagulation is significantly enhanced at pH 5.5 compared with ambient pH. The reduction in THM formation potential is consistent with the trends observed for the THM precursor removal data (i.e., UV254 and TOC data). Furthermore, specific UV absorbance was used to estimate the proportion of humic substances in the raw waters. Enhanced coagulation was found to be less effective for the source water with the lower specific UV absorbance.     

Effects of dichloroacetate on glycogen metabolism in B6C3F1 mice

Dichloroacetate (DCA) is a by-product of drinking water chlorination. Administration of DCA in drinking water results in accumulation of glycogen in the liver of B6C3F1 mice. To investigate the processes affecting liver glycogen accumulation, male B6C3F1 mice were administered DCA in drinking water at levels varying from 0.1 to 3 g/l for up to 8 weeks. Liver glycogen synthase (GS) and glycogen phosphorylase (GP) activities, liver glycogen content, serum glucose and insulin levels were analyzed. To determine whether effects were primary or attributable to increased glycogen synthesis, some mice were fasted and administered a glucose challenge (20 min before sacrifice). DCA treatments in drinking water caused glycogen accumulation in a dose-dependent manner. The DCA treatment in drinking water suppressed the activity ratio of GS measured in mice sacrificed at 9:00 AM, but not at 3:00 AM. However, net glycogen synthesis after glucose challenge was increased with DCA treatments for 1-2 weeks duration, but the effect was no longer observed at 8 weeks. Degradation of glycogen by fasting decreased progressively as the treatment period was increased, and no longer occurred at 8 weeks. A shift of the liver glycogen-iodine spectrum from DCA-treated mice was observed relative to that of control mice, suggesting a change in the physical form of glycogen. These data suggest that DCA-induced glycogen accumulation at high doses is related to decreases in the degradation rate. When DCA was administered by single intraperitoneal (i.p.) injection to na?ve mice at doses of 2-200 mg/kg at the time of glucose challenge, a biphasic response was observed. Doses of 10-25 mg/kg increased both plasma glucose and insulin concentrations. In contrast, very high i.p. doses of DCA (> 75 mg/kg) produced progressive decreases in serum glucose and glycogen deposition in the liver. Since the blood levels of DCA produced by these higher i.p. doses were significantly higher than observed with drinking water treatment, we conclude that apparent differences with data of previous investigations is related to substantial differences in systemic dose and/or dose-time relations.     

Determination of N-nitrosodimethylamine at part-per-trillion levels in drinking waters and contaminated groundwaters

The carcinogen N-nitrosodimethylamine (NDMA) may be quantitated routinely at ultratrace (ng/L) levels in drinking water or contaminated groundwater. The aqueous sample is passed through a preconditioned Empore C18 filter disk to remove neutral nonpolar species and then extracted continuously overnight with highest purity dichloromethane. The latter is then concentrated to 1 mL, and a large aliquot (up to 200 microL) is loaded onto a dual-stage carbon sorbent trap, after which the solvent is removed with ultrapure helium. The concentrated residues are then injected onto a gas chromatographic column using a short-path thermal desorber. NDMA is selectively detected using a chemiluminescent nitrogen detector (CLND) operated in its nitrosamine-selective mode. The reporting limit for this procedure, evaluated using two independent statistically unbiased protocols, is 2 ng of NDMA/L. A related procedure, employing an automatic sampler instead of the short-path thermal desorber, provides convenient analysis of heavily contaminated samples and exhibits a reporting limit (same protocols cited previously) of 110 ng of NDMA/L. When the two methods are used together in a "two-tiered" protocol, NDMA concentrations spanning 4 orders of magnitude (ng/L to microgram/L levels) may be measured routinely. The low-level procedure employing only the short-path thermal desorber was applied successfully to three sources of drinking water, where NDMA concentrations ranged between 2 and 10 ng of NDMA/L. The two-tiered protocol was applied to a series of contaminated groundwaters whose NMDA concentrations ranged between approximately 10-7000 ng of NDMA/L. The results agreed with those obtained from an independent collaborating laboratory, which used a different analytical procedure.     

Source of drinking water at home and site-specific cancer incidence in Washington County, Maryland

A nonconcurrent prospective study was conducted to investigate the postulated relationship between organic chemical by-products of water chlorination and risk of human cancer. Vital records and nonofficial census data available for each of nearly 31,000 study subjects were used to compute selected sex- and site-specific cancer incidence rates in a well-defined county population. Age, socioeconomic status, smoking history, source of drinking water at home, and other individual characteristics of the study population were examined in relation to the cancer rates. The drinking water source variable consisted of three historical cohorts, each distinguished by a different degree of exposure to chloroform and other chlorination byproducts. Incidence rates for cancer of the bladder among men and for cancer of the liver among women were nearly twofold higher in the drinking water cohort that had been supplied chlorinated surface water at home when compared to the cohort with a history of consumption of unchlorinated ground water. The differences, however, were not statistically significant. A complementary mortality study also suggested an association of chlorinated water with cancer of the liver and urinary tract. The findings in Washington County indicate the need for further studies of individuals with different histories of exposure to chlorinated and unchlorinated drinking water.     

Predicting the Formation of Chlorinated and Brominated By-Products

Although disinfection was one of the major public health advances in the last century and continues to be so in the twenty-first century, the disinfectants themselves may react with naturally occurring materials in treated water to form unintended by-products, which may themselves pose risks. This is of particular concern with regard to the use of chlorine. Generation of disinfection by-products (DBPs) has been shown to be a function of various factors including total organic carbon concentration, type of organic precursor, chlorination level, pH, temperature, reaction time, and UV-254 absorbance. Another factor affecting DBP formation is the presence and concentration of the bromide ion in the raw or finished water. Bromine substitutes for chlorine to produce bromine-containing homologues of the more familiar chlorine species. The current list of by-products targeted for regulation contains brominated and mixed bromine-chlorine species of total trihalomethanes and haloacetic acids. These are known to form in bromide-containing waters when chlorinated. To control chlorination DBPs therefore requires an understanding of the factors that influence their formation. This paper presents a model that can be used to predict the formation of chlorinated, brominated, and mixed species compounds based on initial chlorine concentration, chlorine consumption, bromide ion concentration, and pH. The model clearly shows that higher levels of bromide in the water favor the formation of brominated compounds. Brominated compounds also form faster than chlorinated compounds.     

Drinking in rhesus monkeys: Roles of presystemic and systemic factors in control of drinking.

Determined the effect of 24-hr water deprivation and subsequent drinking on systemic fluid balance in 4 male rhesus monkeys prepared with indwelling cardiac catheters. Significant intra- and extracellular depletions, as indicated by increased plasma sodium concentrations, osmolality, and plasma protein concentrations, resulted from the deprivation. An early attenuation in rehydrational drinking rate (2–4 min) was not associated with changes in systemic fluid balance, which suggests presystemic influences on behavior at this time. When drinking terminated, however, plasma dilution was significant. In experiments in which Ss were sham drinking (open gastric cannula), water but not isotonic saline infusions, given through an intestinal cannula, reduced drinking rate and produced significant plasma dilution. Iv water infusions reduced drinking to only a comparable extent despite more rapid and substantial plasma dilution. Thus, systemic absorption does not account entirely for the effect of intestinal water infusions on drinking. It is concluded that stimulation of mechanisms both presystemically and systemically is important in the control and termination of rehydrational drinking in this species. (21 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

GA-QP Model to Optimize Sewer System Design

Sanitary sewer systems are fundamental and expensive facilities for controlling water pollution. Optimizing sewer design is a difficult task due to its associated hydraulic and mathematical complexities. Therefore, a genetic algorithm (GA) based approach has been developed. A set of diameters for all pipe segments in a sewer system is regarded as a chromosome for the proposed GA model. Hydraulic and topographical constraints are adopted in order to eliminate inappropriate chromosomes, thereby improving computational efficiency. To improve the solvability of the proposed model, the nonlinear cost optimization model is approximated and transformed into a quadratic programming (QP) model. The system cost, pipe slopes, and pipe buried depths of each generated chromosome are determined using the QP model. A sewer design problem cited in literature has been solved using the GA-QP model. The solution obtained from the GA model is comparable to that produced by the discrete differential dynamic programming approach. Finally, several near-optimum designs produced using the modeling to generate alternative approach are discussed and compared for improving the final design decision.     

Spinal analgesia for cesarean section

Over a twelve-month period, 47 of a total of 127 women had spinal anaesthesia (SA) for caesarean section (SC). Data from the anaesthesia and the postoperative period were collected and a questionnaire was sent to the mothers after discharge. The analgesia was sufficient in 45 patients. Two had general anaesthesia (GA). One further patient had GA because of overwhelming anxiety. Despite crystalloid preloading, 45% had a significant decrease in systolic blood pressure. Hypotensive cases were treated with a bolus of ephedrine i.v. Forty-one of the new-born babies scored Apgar 10/1 and all scored 10/5. No postdural puncture headaches were observed during the patients' stay in hospital. Forty women answered the questionnaire, and of these, 38 said they would prefer SA in the event of future SC. Six out of eight women who had previously had epidural analgesia preferred SA. We find that SA is a safe, easy, and reliable method for SC, although supplementary analgetic and antiemetic may be needed, but it is mandatory to maintain the systolic blood pressure (cardiac output) close to the preanalgetic values.     

Inactivation Kinetics of the Cyanobacterial Toxin Microcystin-LR by Free Chlorine

Worldwide, the increasing occurrence of toxins produced by cyanobacteria in water bodies used as source waters for drinking water has become an important public health issue. Microcystin-LR is one of the most commonly found cyanotoxins. A detailed evaluation of the free chlorine induced inactivation kinetics of extracellular microcystin-LR is presented in this study. Rate constants needed for chlorine inactivation of the toxin were derived from the data. The effects of varied pH, chlorine dose, toxin concentration, and temperature on the rate of inactivation were evaluated. Batch chlorination experiments were run using carbonate-buffered Milli-Q water at three different initial toxin concentrations (1, 2, and 8?μg/L), three different chlorine doses (1, 3, and 9?mg/L), and three different pH values (6.0, 7.5, and 9.0) at 11, 20 and 29°C. The study showed that extracellular microcystin-LR was inactivated by free chlorine and the inactivation rate was affected by pH. The highest inactivation rates were observed at pH 6.0 and the lowest at pH 9.0.     

Epidermal growth factor (EGF) and EGF receptor in hypospadias

Environmental oncology is a discipline concerned with studies of multi-aspect relationships between environment and living organisms exposed to the modifying influence of carcinogenic agents. It also deals with general biological regularities involved in neoplasm development as well as their prevention in different species including man, animals and plants. Various investigations conducted at the Laboratory and supported with Russian and foreign grants (1991-1996) are briefly discussed. Among them are biotesting environmental carcinogens (aminoanthraquinons, by-products of drinking water chlorination, development of new testing systems and objects of detection involved in identification of genotoxic substances (criteria for formation of short-term test batteries and evaluation of perspectives, methods and results), investigation of xenobiotic metabolic activation (enzyme imprinting in adult animals), search for anticarcinogens (classification of carcinogenesis inhibitors, development of testing systems for modifiers selection), and establishing environment-related regularities of tumor growth. Vistas in environmental oncology development are discussed.