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.     

三种消毒剂的灭活效果及其消毒副产物分析

选择次氯酸钠、高锰酸钾和单过硫酸氢钾饮用水消毒粉作为消毒剂,考察了三种消毒剂的灭活效果及其消毒副产物的产生情况.结果表明,次氯酸钠对细菌的灭活效果明显,用量少,但产生的消毒副产物种类多、含量高,且会产生大量的氯仿;单过硫酸氢钾的灭活效果比较明显,用量比次氯酸钠多,但产生的消毒副产物种类少、含量低;高锰酸钾对细菌有一定的灭活效果,用量明显比前两种消毒剂多,但无消毒副产物生成.在实际应用时,应根据具体水质特点和不同场合合理使用三种消毒剂.     

Chlorination disinfection by-products, public health risk tradeoffs and me

Since 1974 when trihalomethanes (THMs) were first reported as disinfection by-products (DBPs) in drinking water, there has been an enormous research effort directed at understanding how DBPs are formed in the chlorination or chloramination of drinking water, how these chlorination DBPs can be minimized and whether they pose a public health risk, mainly in the form of cancer or adverse reproductive outcomes. Driven by continuing analytical advances, the original DBPs, the THMs, have been expanded to include over 600 DBPs that have now been reported in drinking water. The historical risk assessment context which presumed cancer could be mainly attributed to exposure to environmental carcinogens played a major role in defining regulatory responses to chlorination DBPs which, in turn, strongly influenced the DBP research agenda. There are now more than 30 years of drinking water quality, treatment and health effects research, including more than 60 epidemiology studies on human populations, directed at the chlorination DBP issue. These provide considerable scope to reflect on what we know now, how our understanding has changed, what those changes mean for public health risk management overall and where we should look to better understand and manage this issue in the future.     

氯化消毒副产物的控制研究进展

探讨了CDBPs的形成机理,总结了目前国内外控制CDBPs的方法,并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,以确保饮用水的安全性。     

Disinfectant decay and disinfection by-products formation model development: chlorination and ozonation by-products

Comprehensive disinfectant decay and disinfection by-product formation (D/DBP) models in chlorination and ozonation were developed to apply to various types of raw and treated waters. Comparison of several types of models, such as empirical power function models and empirical kinetic models, was provided in order to choose more robust and accurate models for the D/DBP simulations. An empirical power function model based on dissolved organic carbon and other parameters (Empirically based models for predicting chlorination and ozonation by-products: haloacetic acids, chloral hydrate, and bromate, EPA Report CX 819579, 1998) showed a strong correlation between measured and predicted trihalomethane (THM) and haloacetic acid (HAA) formation for raw waters. Internal evaluation of kinetic-based models showed good predictions for chlorine decay and THM/HAA formation, but no significant improvements were observed compared to the empirical power function model simulations. In addition, several empirical models for predicting ozone decay and bromate (ozonation disinfection by-product) formation were also evaluated and/or developed. Several attempts to develop kinetic-based and alternative models were made: (i) a two-stage model (two separate decay models) was adapted to ozone decay and (ii) an ozone demand model was developed for bromate formation. Generally, internal evaluation of kinetic-based models for ozone decay showed significant improvements, but no significant improvements for the simulation of bromate formation were observed compared to the empirical power function model simulations. Additional efforts were performed to reduce the gaps between specific models and their actual application. For instance, temperature effects and configuration of ozone contactors were considered in actual application.     

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。     

Human health risk assessment of chlorinated disinfection by-products in drinking water using a probabilistic approach

The presence of chlorinated disinfection by-products (DBPs) in drinking water is a public health issue, due to their possible adverse health effects on humans. To gauge the risk of chlorinated DBPs on human health, a risk assessment of chloroform (trichloromethane (TCM)), bromodichloromethane (BDCM), dibromochloromethane (DBCM), bromoform (tribromomethane (TBM)), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in drinking water was carried out using probabilistic techniques. Literature data on exposure concentrations from more than 15 different countries and adverse health effects on test animals as well as human epidemiological studies were used. The risk assessment showed no overlap between the highest human exposure dose (EXP(D)) and the lowest human equivalent dose (HED) from animal test data, for TCM, BDCM, DBCM, TBM, DCAA and TCAA. All the HED values were approximately 10(4)-10(5) times higher than the 95th percentiles of EXP(D). However, from the human epidemiology data, there was a positive overlap between the highest EXP(D) and the lifetime average daily doses (LADD(H)) for TCM, BDCM, DCAA and TCAA. This suggests that there are possible adverse health risks such as a small increased incidence of cancers in males and developmental effects on infants. However, the epidemiological data comprised several risk factors and exposure classification levels which may affect the overall results.     

Formation of disinfection by-products after pre-oxidation with chlorine dioxide or ferrate

The effect of pre-oxidation with chlorine dioxide (ClO₂) or ferrate (Fe(VI)) on the formation of disinfection by-products (DBPs) during chlorination or chloramination was tested with natural waters from 12 sources (9 surface waters, 1 groundwater, and 2 wastewater effluents). DBPs investigated included trihalomethanes (THM), chloral hydrate (CH), haloketones (HK), haloacetonitriles (HAN) and trichloronitromethane (TCNM), chlorite and chlorate. Chlorite and chlorate were found in the ClO₂-treated waters. Application of 1 mg/L ClO₂ ahead of chlorination reduced the formation potential for THM by up to 45% and the formation of HK, HAN and TCNM in most of the samples. The CH formation results were mixed. The formation of CH and HK was enhanced with low doses of Fe(VI) (1 mg/L as Fe), but was greatly reduced at higher doses (20 mg/L Fe). Fe(VI) reduced the formation of THM, HAN and TCNM in most of the samples. Reduced potential for the formation of NDMA was observed in most of the samples after both ClO₂ and Fe(VI) pre-oxidation.     

Comparison of disinfection byproduct formation from chlorine and alternative disinfectants

Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.     

Disinfection and formation of disinfection by-products in a photoelectrocatalytic system

In this study, disinfection and formation of disinfection by-products (DBPs) were studied in a photoelectrocatalytic (PEC) treatment system. Disinfection performance of titanium dioxide (TiO₂) in the PEC system was determined through Escherichia coli (E. coli) inactivation. Humic acid (HA) was used as a model organic compound and its removal was monitored by total organic carbon (TOC) measurements using 410 nm (color) and 254 nm (UV₂₅₄) wavelengths. Trihalomethanes (THMs) were measured for the evaluation of DBPs formation during PEC treatment of chloride and HA mixture. It was found that unlike photocatalytic treatment, THMs might form in the PEC system. To investigate the effects of anions on the PEC treatment, chloride (Cl⁻), sulfate (SO₄²⁻), phosphoric acid (H₂PO₄⁻)/hydrogen phosphate (HPO₄²⁻) and bicarbonate (HCO₃⁻) ions were added separately to the HA and bacterial suspensions. Presence of H₂PO₄⁻/HPO₄²⁻ and HCO₃⁻ ions resulted in inhibitory effects on both HA degradation and E. coli inactivation, which were also examined in the photoanode. It was observed that the presence of HA had a strong inhibitory effect on the disinfection of E. coli.     

Occurrence and control of nitrogenous disinfection by-products in drinking water--a review

The presence of nitrogenous disinfection by-products (N-DBPs), including nitrosamines, cyanogen halides, haloacetonitriles, haloacetamides and halonitromethanes, in drinking water is of concern due to their high genotoxicity and cytotoxicity compared with regulated DBPs. Occurrence of N-DBPs is likely to increase if water sources become impacted by wastewater and algae. Moreover, a shift from chlorination to chloramination, an option for water providers wanting to reduce regulated DBPs such as trihalomethanes (THMs) and haloacetic acids (HAAs), can also increase certain N-DBPs. This paper provides a critical review of the occurrence and control of N-DBPs. Data collated from surveys undertaken in the United States and Scotland were used to calculate that the sum of analysed halonitromethanes represented 3-4% of the mass of THMs on a median basis; with Pearson product moment correlation coefficients of 0.78 and 0.83 between formation of dihaloacetonitriles and that of THMs and HAAs respectively. The impact of water treatment processes on N-DBP formation is complex and variable. While coagulation and filtration are of moderate efficacy for the removal of N-DBP precursors, such as amino acids and amines, biofiltration, if used prior to disinfection, is particularly successful at removing cyanogen halide precursors. Oxidation before final disinfection can increase halonitromethane formation and decrease N-nitrosodimethylamine, and chloramination is likely to increase cyanogen halides and NDMA relative to chlorination.     

Fate of toxic cyanobacterial cells and disinfection by-products formation after chlorination

Drinking water sources in many regions are subject to proliferation of toxic cyanobacteria (CB). Chlorination of source water containing toxic cyanobacterial cells for diverse treatment purposes might cause cell damage, toxin release and disinfection by-products (DBP) formation. There is limited information available on chlorination of different toxic CB cells and DBP formation potentials. This work: (1) determines the extent of lysis and toxins/taste and odor compound release in chlorinated natural water from CB cells (Anabaena circinalis, Microcystis aeruginosa, Cylindrospermopsis raciborskii, and Aphanizomenon issatsckenka) from laboratory cultures and natural blooms; (2) assesses the rates of oxidation of toxins by free chlorine under environmental conditions; (3) studies the DBP formation associated with the chlorination of CB cell suspensions. With chlorine exposure (CT) value of <4.0 mg min/L >60% cells lost viability causing toxin release. Cell membrane damage occurred faster than oxidation of released toxins. Kinetic analysis of the oxidation of toxins in natural water revealed significant differences in their susceptibility to chlorine, saxitoxins being the easiest to oxidize, followed by cylindrospermopsin and microcystin-LR. Furthermore, concentrations of trihalomethanes and haloacetic acids (<40 μg/L) and N-nitrosodimethylamine (<10 ng/L) as chlorination by-products were lower than the guideline values even at the highest CT value (220 mg min/L). However, the DBP concentrations in environmental bloom conditions with very high cell numbers were over the guideline values.     

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。     

二氧化氯消毒副产物亚氯酸盐及氯酸盐的测定

概述了ClO_2消毒技术的特点及消毒副产物对人体健康存在的隐患,介绍了离子色谱仪测饮用水中消毒副产物的检测方法和检测条件,并对某水厂近半年的出厂水中的ClO_2消毒副产物进行检测,结果表明该水厂的出厂水中的消毒副产物符合卫生标准。     

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.     

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.     

Occupational exposure and health risks of volatile organic compounds of hotel housekeepers: Field measurements of exposure and health risks

Hotel housekeepers represent a large, low-income, predominantly minority, and high-risk workforce. Little is known about their exposure to chemicals, including volatile organic compounds (VOCs). This study evaluates VOC exposures of housekeepers, sources and factors affecting VOC levels, and provides preliminary estimates of VOC-related health risks. We utilized indoor and personal sampling at two hotels, assessed ventilation, and characterized the VOC composition of cleaning agents. Personal sampling of hotel staff showed a total target VOC concentration of 57 ± 36 µg/m³ (mean ± SD), about twice that of indoor samples. VOCs of greatest health significance included chloroform and formaldehyde. Several workers had exposure to alkanes that could cause non-cancer effects. VOC levels were negatively correlated with estimated air change rates. The composition and concentrations of the tested products and air samples helped identify possible emission sources, which included building sources (for formaldehyde), disinfection by-products in the laundry room, and cleaning products. VOC levels and the derived health risks in this study were at the lower range found in the US buildings. The excess lifetime cancer risk (average of 4.1 × 10⁻⁵) still indicates a need to lower exposure by reducing or removing toxic constituents, especially formaldehyde, or by increasing ventilation rates.     

Removal of precursors for disinfection by-products (Dbps)--differences between ozone- and OH-radical-induced oxidation

Pre-oxidation is often applied to reduce the formation of disinfection by-products (DBPs). The aim of pre-oxidation is to remove the centers of natural organic matter (NOM) which are responsible for the formation of DBPs. In this paper, the differences between ozone- and OH-radical-induced oxidation to remove DBP-precursors are compared. The experiments were done with water of the River Ruhr (Germany) with a concentration of dissolved organic carbon (DOC) of 2 mg/l. Ozonation was able to remove DBP precursors selectively. After application of an absorbed ozone mass of 1.5 mg/mg DOC, a reduction in the formation potential for (THM-FP) and in the formation potential for organic halogen adsorbable on activated carbon (AOX-FP) down to 68 and 73% of the initial concentration was achieved, respectively. A removal of NOM was not achieved using absorbed ozone masses between 0.5 and 1.5 mg/mg DOC. In the hydrogen peroxide/UV process, in which OH-radicals are the reactive species, an increase in the THM concentration was measured after application of this process with short irradiation times. The maximum value of the THM-FP was 20% higher than the initial THM-FP. After an irradiation time of 1,050 min and a hydrogen peroxide consumption of 5.6 mg/l, the THM-FP and AOX-FP decreased to 75 and 71% of the initial formation potential, respectively. There was no selective removal of DBP precursors because the DOC concentration decreased also to 75% of the initial DOC-concentration after 1,050 min of irradiation.     

Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa

Formation of carbonaceous disinfection by-products (C-DBPs), including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs), chloral hydrate (CH), and nitrogenous disinfection by-products (N-DBPs), including haloacetonitriles (HANs) and trichloronitromethane (TCNM) from chlorination of Microcystis aeruginosa, a blue-green algae, under different conditions was investigated. Factors evaluated include contact time, chlorine dosages, pH, temperature, ammonia concentrations and algae growth stages. Increased reaction time, chlorine dosage and temperature improved the formation of the relatively stable C-DBPs (e.g., THM, HAA, and CH) and TCNM. Formation of dichloroacetonitrile (DCAN) followed an increasing and then decreasing pattern with prolonged reaction time and increased chlorine dosages. pH affected DBP formation differently, with THM increasing, HKs decreasing, and other DBPs having maximum concentrations at certain pH values. The addition of ammonia significantly reduced the formation of most DBPs, but TCNM formation was not affected and 1,1-dichloropropanone (1,1-DCP) formation was higher with the addition of ammonia. Most DBPs increased as the growth period of algal cells increased. Chlorination of algal cells of higher organic nitrogen content generated higher concentrations of N-DBPs (e.g., HANs and TCNM) and CH, comparable DCAA concentration but much lower concentrations of other C-DBPs (e.g., THM, TCAA and HKs) than did natural organic matter (NOM).