Trihalomethanes aqueous solutions sono-oxidation

Ultrasonic (US) irradiation, hydrogen peroxide (H(2)O(2)), Fenton's oxidation and the combination of the processes were investigated for destruction and removal of the following trihalomethanes (THMs) compounds from aqueous solutions: CHCl(3), CHBrCl(2), CHBr(2)Cl, CHBr(3), and CHI(3). H(2)O(2) had no significant effect on the THMs sonodegradation. The coupled US and Fenton processes did not affect the CHCl(3), CHBrCl(2), and CHBr(2)Cl sonolysis efficiency. Nevertheless, the sonodegradation of CHBr(3) was enhanced. CHI(3) was degraded by Fenton's oxidation rather than by the US irradiation during the sonication/Fenton treatment. The combination of sonication with H(2)O(2) or Fenton's reagent did not affect the mineralization of the THMs aqueous mixture.     

城市污水再生水氯消毒副产物比较研究

比较分析了对城市污水再生水采用液氯和二氧化氯消毒前后消毒副产物的变化。结果表明:城市污水再生水本身含有少量的氯代有机物,经液氯消毒后二氯甲烷、三氯甲烷含量大幅增加,为进水的3～4倍,同时产生了新的消毒副产物二氯一溴甲烷;经二氧化氯消毒后未出现新的消毒副产物,且原有副产物浓度基本不变。因此,再生水使用二氧化氯消毒具有明显优势。     

Chemometric modeling and prediction of trihalomethane formation in Barcelona's water works plant

Formation and occurrence of trihalomethanes (CHCl3, CHBr3, CHCl2Br, and CHBr2Cl) are investigated in water chlorination disinfection processes in the Barcelona's water works plant (WWP). Twenty-three WWP variables were measured and investigated for correlation with trihalomethane formation. Multivariate statistical methods including principal component analysis (PCA), multilinear regression (MLR), stepwise MLR (SWR), principal component regression (PCR) and partial least squares regression (PLSR) have been used and compared to model and predict the complex behavior observed for the measured trihalomethane concentrations. The results, obtained by PCA as well as the evaluation of the statistical significance of the coefficients in the linear regression vectors, revealed that the most important WWP variables for trihalomethane formation were: water temperature, total organic carbon, added chlorine concentrations, UV absorbance and turbidity at different sites of the WWP, as well as other variables like wells supply flow levels and carbon filters age. Overall, MLR and PLSR methods performed the best and gave similar good predictive properties. Best results were obtained for the total sum of trihalomethane concentrations, TTHM, with average modeling and prediction relative errors of 12% and 16%, respectively. Among the individual trihalomethanes, the concentrations of CHBr3 were the worst predicted ones with average modeling and prediction relative errors between 21-25% and 29-31%, respectively, followed by CHCl2Br with 23-26% and 25-27%. Better predictions were obtained for the concentrations of CHBr2Cl with relative modeling and prediction errors varying between 14-17% and 21%, and for the concentrations of CHCl3 with 21-24% and 23-25% errors, respectively.     

Photodegradation of chlorinated hydrocarbons in the presence and absence of dissolved oxygen in water

The photodegradation rates of seven chlorinated hydrocarbons; C2Cl4, C2HCl3, C2H4Cl2, 1,1,1-C2H3Cl3, 1,1,2-C2H3Cl3, CHCl3, CCl4 were investigated under the UV bandwidths of 185 and 254 nm in the presence and absence of dissolved oxygen (DO) in water. These hydrocarbons are possible contaminants of groundwater. This study confirms that the degradation rates of all chlorinated hydrocarbons are elevated in the absence of DO. This was especially apparent for chlorinated methane and ethane. Tetrachloroethylene's rate was the highest among the seven hydrocarbons regardless of the DO levels. It was clear that the concentration of intermediate trichloroethylene produced by photodegradation of tetrachloroethylene in the absence of DO was 1/50th of that in the presence of DO. Photodegradation in the presence of DO resulted in the formation of O3 and hydroxyl radicals. Alternatively, the photodegradation in the absence of DO resulted in the formation of organic radicals and a dissociation of the bond. It is discussed that DO acts as an "inner filter" or "scavenger" that reduces the UV light intensity in the photoreactor. Molecular O2 has absorption bands at 185 and 254 nm, the former being stronger. The processes of degradation depend on the degradation rate relative to the presence and absence of DO.     

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.     

A possible new disinfection by-product--2-chloro-5-oxo-3-hexene diacyl chloride (COHC)--in formation of MX by chlorinating model compounds

MX was widely considered as one of the most important disinfection by-products (DPBs) and as the strong carcinogen in the chlorinated drinking water. Some model compounds which have been classified into four families were chlorinated at laboratory conditions. MX was produced only in the chlorinated substituted aromatic aldehydes and amino acids, while a possible new compound (COHC) was found in some substituted aromatic aldehydes, chlorinated substituted aromatic acids and phenols. Through the analysis of the peaks presented in mass spectrum, the composition and structure of the new compound are proposed as 2-chloro-5-oxo-3-hexene diacyl chloride (COHC) which could cause interference in the detection of MX. COHC has also been found in drinking water and extracted chlorinated fulvic acid solution from the sediment and water of Tai Lake, so it should bring about more attention.     

Potential impact of chlorination of Sandy bottom swimming areas on drinking water sources

The concentrations of trihalomethanes and haloacetic acids, disinfection by‐products (DBPs) of chlorine, were measured in sandy bottom swimming areas to determine their potential impact on surface and ground water that are sources of drinking water. Total trihalomethanes and individual haloacetic acid concentrations in several swimming area samples were higher than the drinking water standards (current and proposed). Individual trihalomethanes (except bromoform) also exceeded ground and surface water release standards. No release standard exists for haloacetic acids. The DBPs, while exceeding standards, would be diluted by the ground water and microbially degraded prior to reaching the drinking water plant. So while DBPs from swimming areas contributed to groundwater concentrations, the current drinking water standards could still be met using source waters impacted by chlorinated swimming areas. It is suggested, though, that any release of chlorinated DBPs to surface and ground water be minimized to obtain the highest quality water sources for drinking water.     

Chemical water quality in Thailand and its impacts on the drinking water production in Thailand

In Thailand, surface water and groundwater are the main water sources for tap water and drinking water production. Thirty-six different samples from surface waters from Chao Praya and Mae Klong rivers, tap waters, bottled drinking waters, groundwaters and commercial ice cubes from around the Bangkok area were collected. Water samples were also taken from two waterworks in the Chonburi province. The extensive survey showed that, overall in all water samples investigated, there was only a minor pollution which could be traced back to the analyses performed including amongst others total organic carbon, inorganics and heavy metals, pesticides, organochlorine compounds, volatile organic compounds, surfactants, pharmaceuticals and disinfection by-products. However, whenever organic micropollutants could be detected in surface water, such as, e.g. the herbicide atrazine, they were also present in the tap water produced thereof proving that the present treatment steps are not sufficient for removal of such pollutants. The concentration of disinfection by-products was higher in tap water produced from Chao Praya river than from Mae Klong river. Disinfection by-products were also found in bottled drinking water. Commercial ice cubes contained anionic surfactants and their metabolites at elevated concentrations. The data of this study constitute the first set of homogenous data for the chemical water quality and also aid development of new water quality criteria in Thailand.     

Disinfection by-product formation after biologically assisted GAC treatment of water supplies with different bromide and DOC content

Chlorination of drinking water in the presence of bromide and dissolved organic carbon (DOC) leads to the formation of brominated and chlorinated disinfection by-products (DBP). The concentration of bromide ions in the raw water is a significant factor in the speciation of DBP formed, and causes shifts in trihalomethane (THM) formation from chlorinated to brominated species. Drinking water treatment techniques that remove organic contaminants without affecting bromide ion concentrations cause increases in the brominated THM. For the present study, three water supplies containing different DOC and ambient bromide concentrations were filtered through biologically assisted granular activated carbon (BGAC). Similar to adsorption and coagulation treatment, this treatment does not remove bromide from drinking water; also, THMFP (trihalomethane formation potential) analysis indicated that the chlorinated effluent contained higher concentrations of brominated THM in comparison to the influent. Although BGAC may increase the brominated THM, which may be more toxic than the chlorinated THM, the overall reduction of THMFP by DOC removal far exceeds this negative change, thereby producing a much less toxic finished drinking water. This work is part of a study to make high DOC surface waters on the Canadian prairie safe and palatable for small volume users (individuals or small communities).     

The impact of bromide on the formation of neutral and acidic disinfection by-products (DBPs) in Mediterranean chlorinated drinking water

By using the Grob closed loop stripping analysis technique a wide variety of disinfection by-products (DBPs) was determined, in finished drinking water of 15 important cities of Greece distributed in the southern, northern, west continental land and in the islands of Aegean and Ionian Seas. Trihalomethanes, haloacetonitriles, haloacetic acids, chloropicrin, halogenated ketons and chloral hydrate were the main DBPs determined. In chlorinated drinking water of coastal cities brominated DBPs were most abundant than their chlorinated homologues due to the higher bromide concentration in raw waters of these areas. Factor analysis with principal component extraction of the results demonstrated a clear differentiation between the examined drinking waters on the basis of their DBPs content and vicinity to the sea.     

再生水用于地下回灌的加氯消毒研究

针对城市污水厂二级出水用于地下回灌的两种深度处理工艺,确定了达到消毒要求的加氯量,并且研究了加氯消毒对有关水质参数DOC、AOX、CHCl3、CCl4、UV254等的影响。研究发现,有效氯投加量在8mg/L左右时,水中细菌总数与总大肠菌群数均能达到我国饮用水卫生标准。加氯后水的DOC值变化不大,AOX值则有较明显的增大,CHCl3浓度略有增加,CCl4基本维持在加氯前的水平,UV254值也较加氯前有所增大。研究结果还表明,粒状活性炭处理工艺在污水深度处理流程中对去除消毒副产物（AOX）及其前驱物发挥着重要的作用。     

Nucleic acid fluorochromes and flow cytometry prove useful in assessing the effect of chlorination on drinking water bacteria

Flow cytometry (FCM), combined with staining using two fluorochromes (propidium iodide, PI, or SYBR Green II RNA gel stain, SYBR-II), was used to assess nucleic acid injuries to chlorinated drinking water bacteria. Highly fluorescent SYBR-II-stained bacteria were converted to bacteria with low fluorescence after chlorination. PI staining of bacteria exposed to different doses of chlorine showed membrane permeabilisation ([Cl2] < 0.2 mg L(-1)) and nucleic acid damage at higher doses ([Cl2] > 0.3 mg L(-1)). Above a threshold dose (between 1.5 and 3 mg Cl2 L(-1)), nucleic acids appeared severely damaged and incapable of being stained by PI or SYBR-II. These results constitute evidence that FCM is a promising tool for assessing drinking water bacteria injuries and for controlling chlorine disinfection efficiency much more rapidly than the standard sensitive but time-consuming heterotrophic plate count method.     

ClO_2和Cl_2对城市污水再生水消毒效果的比较

采用Cl02和C12对西安市的城市污水再生水进行消毒,中试结果表明:当Cl02投加量>7.67mg/L时,经30min接触消毒后,出水中未检出总大肠菌群,以氯代有机物为代表的消毒副产物(DBPs)较进水没有明显增加,出水的COD和浊度分别平均降低了13.2%和17.9%,色度平均减少了5倍当Cl2投加量>6mg/L时,经30min接触消毒后,出水中未检出总大肠菌群,出水中的二氯甲烷和三氯甲烷浓度是进水中的2-3倍,三卤甲烷含量则达到进水的4-6倍,同时生成少量的二氯一溴甲烷,出水的COD和浊度分别平均降低了17.8%和8.75%,色度减少了5-10倍.     

Electrochemical removal of bromide and reduction of THM formation potential in drinking water

Trihalomethanes (THMs), a by-product of the chlorination of natural waters containing dissolved organic carbon and bromide, are the focus of considerable public health concern and regulation due to their potential as a carcinogen by ingestion. This paper presents a promising new water treatment process that lowers the concentration of bromide in drinking water and thus, lowers the THM formation potential. Bromide is oxidized by electrolysis to bromine and then the bromine apparently volatilized. The electrolyzed water, when chlorinated, produces measurably lower amounts of THMs and proportionately fewer brominated THMs, which are of greater public health concern than the chlorinated THMs. Removing bromide should also reduce the formation of other disinfection by-products such as bromate and haloacetic acids.     

Seasonal variation in drinking water concentrations of disinfection by-products in IZMIR and associated human health risks

Seasonal variation in concentrations of two different disinfection by-product groups, trihalomethanes (THMs) and haloacetonitriles (HANs), was investigated in tap water samples collected from five sampling points (one groundwater and four surface water sources) in Izmir, Turkey. Estimates of previously published carcinogenic and non-carcinogenic risks through oral exposure to THMs were re-evaluated using a probabilistic approach that took the seasonal concentration variation into account. Chloroform, bromoform, dibromochloromethane and dichloroacetonitrile were the most frequently detected compounds. Among these, chloroform was detected with the highest concentrations ranging from 0.03 to 98.4 microg/L. In tap water, at the groundwater supplied sampling point, brominated species, bromoform and dibromoacetonitrile, were detected at the highest levels most probably due to bromide ion intrusion from seawater. The highest total THM and total HAN concentrations were detected in spring while the lowest in summer and fall. The annual average total THM concentration measured at one of the surface water supplied sampling points exceeded the USEPA's limit of 80 microg/L. While all non-carcinogenic risks due to exposure to THMs in Izmir drinking water were negligible, carcinogenic risk levels associated with bromodichloromethane and dibromochloromethane were higher than one in million.     

Correlations between differential absorbance and the formation of individual DBPs

This study examined correlations between the differential absorbance at 272nm (deltaA272) and the formation of disinfection by-products (DBPs) in chlorinated water from the Tolt River, a water source for Seattle, WA. The DBPs investigated included chloroform (CHCl3), dichlorobromomethane (CHCl2Br), mono-, di- and trichloroacetic acids (MCAA, DCAA, and TCAA, respectively), chloral hydrate (CH), dichloroacetonitrile (DCAN) and 1,1,1-trichloropropanone (TCP). Whereas the kinetics of DBP formation are complex and are non-linear, the same DBP data represented as a function of deltaA272 are quite simple. Absorbance decreases when the water is chlorinated, i.e., deltaA272 is always negative. The DBP vs. -deltaA272 correlations can almost always be quantified by linear equations, at least above some threshold value of -deltaA272, with R2 values > 0.95. The only DBP that did not follow this trend was CH, for which an exponential relationship better described the data. TCP and DCAN were unstable at pH 7 and 8, but at pH 6 linear correlations between their concentrations and -deltaA272 were as strong as those for the more stable DBPs. The threshold -deltaA272 value is approximately the same for many of the DBPs studied, supporting the hypothesis that individual DBPs are released following the formation of a common intermediate, or at least a small group of similar intermediates. The DBP vs. -deltaA272 correlations may have practical value since they provide an alternative approach for monitoring the formation of individual DBP species on-line, but the generality of the relationships needs to be further examined.     

Toxicity evaluation of surface water treated with different disinfectants in HepG2 cells

It is well known that water disinfection through chlorination causes the formation of a mixture of disinfection by-products (DBPs), many of which are genotoxic and carcinogenic. To demonstrate the formation of such compounds, a pilot water plant supplied with water from Lake Trasimeno was set up at the waterworks of Castiglione del Lago (PG, Italy). The disinfectants, continuously added to pre-filtered lake water flowing into three different basins, were sodium hypochlorite, chlorine dioxide and peracetic acid, an alternative disinfectant used until now for disinfecting waste waters, but not yet studied for a possible use in drinking water treatment. The aim of this study was to evaluate the formation during the disinfection processes of some toxic compounds that could explain the genotoxic effects of drinking waters. Differently treated waters were concentrated by solid-phase adsorption on silica C(18) columns and toxicity was assessed in a line of human hepatoma cells (HepG2), a metabolically competent cellular line very useful for human risk evaluation. The seasonal variability of the physical-chemical water characteristics (AOX, UV 254 nm, potential formation of THM, pH and temperature) made indispensable experimentation with water samples taken during the various seasons. Autumn waters cause greater toxicity compared to those of other seasons, in particular dilution of the concentrate at 0.5l equivalent of disinfected waters with chlorine dioxide and peracetic acid causes a 55% reduction in cellular vitality while the cellular vitality is over 80% with the all other water concentrates. Moreover it is very interesting underline that non-cytotoxic quantities of the autumnal water concentrates cause, after 2h treatment, a decrease in GSH and a statistically significant increase in oxygen radicals, while after prolonged treatment (24h) cause a GSH increase, without variations in the oxygen radical content. This phenomenon could be interpreted as the cellular adaptation response to an initial oxidative stress.     

氯化消毒副产物NDMA的生成与控制研究进展

NDMA（N-Nitrosodimethylamine）是水处理领域新近发现的一种氯化消毒副产物,由于其具有检出率高、致癌风险大、难以有效去除等特性,已成为国际关注的重要水质问题之一。饮用水中的NDMA主要产生于氯化消毒过程,尤为严重的是氯胺消毒过程,而臭氧和过氧化氢氧化基本不产生NDMA。NDMA为亲水性小分子有机物,常规处理和深度处理均难于有效去除,而且管网中的浓度显著高于出厂水。目前控制饮用水中NDMA的常用方法是紫外线照射,但能耗较高。其他方法如延长自由氯接触时间和采用高铁酸盐预氧化、反渗透、臭氧／过氧化氢高级氧化工艺等也可以不同程度地控制NDMA及其前体物。     

Volatile disinfection by-product analysis from chlorinated indoor swimming pools

Chlorination of indoor swimming pools is practiced for disinfection and oxidation of reduced compounds that are introduced to water by swimmers. However, there is growing concern associated with formation for chlorinated disinfection by-products (DBPs) in these settings. Volatile DBPs are of particular concern because they may promote respiratory ailments and other adverse health effects among swimmers and patrons of indoor pool facilities. To examine the scope of this issue, water samples were collected from 11 pools over a 6 month period and analyzed for free chlorine and their volatile DBP content. Eleven volatile DBPs were identified: monochloramine (NH₂Cl), dichloramine (NHCl₂), trichloramine (NCl₃), chloroform (CHCl₃), bromoform (CHBr₃), dichlorobromomethane (CHBrCl₂), dibromochloromethane (CHBr₂Cl), cyanogen chloride (CNCl), cyanogen bromide (CNBr), dichloroacetonitrile (CNCHCl₂), and dichloromethylamine (CH₃NCl₂). Of these 11 DBPs, 10 were identified as regularly occurring, with CHBrCl₂ only appearing sporadically. Pool water samples were analyzed for residual chlorine compounds using the DPD colorimetric method and by membrane introduction mass spectrometry (MIMS). These two methods were chosen as complementary measures of residual chlorine, and to allow for comparisons between the methods. The DPD method was demonstrated to consistently overestimate inorganic chloramine content in swimming pools. Pairwise correlations among the measured volatile DBPs allowed identification of dichloromethylamine and dichloroacetonitrile as potential swimming pool water quality indicator compounds.     

Carcinogenic and mutagenic properties of chemicals in drinking water

Isolated cases of careless handling of industrial and domestic waste has lead to a wide variety of dangerous chemicals being inadvertently introduced into drinking water. However, chemicals with established carcinogenic and mutagenic properties that occur with a high frequency and in multiple locations are limited in number. To date, the chief offenders have been chemicals of relatively low carcinogenic potency. Some of the more common chemicals are formed as by-products of disinfection. The latter process is generally regarded as essential to the production of a “microbiologically safe” drinking water. Consequently, any reductions in what may be a relatively small carcinogenic risk must be balanced against a potential for a higher frequency of waterborne infectious disease.The results of recent toxicological investigations will be reviewed to place the potential carcinogenic and mutagenic hazards frequently associated with drinking water into perspective. First, evidence for the carcinogenicity of certain volatile organic compounds such as trichloroethylene, tetrachloroethylene and carbon tetrachloride is considered. Second, the carcinogenic activity that can be ascribed to various by-products of chlorination is reviewed in some detail. Finally, recent evidence that other chemicals derived from the treatment and distribution of drinking water is highlighted as an area requiring move systematic attention.