饮用水氯化消毒副产物与出生缺陷

饮用水氯化消毒处理过程中可形成多种类型的消毒副产物(DBPs)．包括三卤甲烷、卤代乙酸、卤代乙腈、卤代酮及氯代呋喃酮等。一系列研究显示DBPs与神经管缺陷、先天性心脏病、泌尿系统畸形、头面部缺陷等有相关性。但是．以往的一些研究无法正确估计暴露水平及各种DBPs之间或与饮水中其他物质之间的联合作用。因此．有必要通过正确的暴露估计和流行病学研究及合理的毒理学试验．深入探索氯化消毒副产物对出生缺陷的影响。     

Assessment of disinfection by-products in drinking water in Korea.

The main purpose of applying the chlorination process during water treatment is for disinfection. Research results, however, indicate that disinfection byproducts (DBPs) including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HKs), and chloropicrin (CP) can be produced by the chlorination process. Some of these DBPs are known to be potential human carcinogens. This 3-year project is designed to establish a standard analysis procedure for DBPs in drinking water of this country and investigate the distribution and sources of specific DBPs. The occurrence level of DBPs in drinking water was below 50 micrograms/l in most cases. THMs in plant effluent accounted for 60% of all DBPs measured, whereas HAAs accounted for 20%, HANs 12%, HKs 5% and CP 3%. Chloroform was found to be the major THMs compound (77%), followed by bromodichloromethane (BDCM, 18%) and bromoform (BF, 3%). The concentration of DBPs formed in distribution systems increased from those detected in plant effluent. Comparison of humic acid and sewage as precursors for THMs formation showed that humic acid was the major THMs precursor. Results would play an important role in exposure assessment as a part of the risk assessment process, and would give basic information for establishment of DBPs reduction and management procedures.     

Reproductive and developmental effects of disinfection by-products in drinking water.

Recent epidemiologic studies have reported associations between the consumption of chlorinated drinking water and reproductive and developmental effects. Here we review the available epidemiologic data, assess the hazard potential posed by exposure to disinfection by-products, identify critical data gaps, and offer recommendations for further research. The epidemiologic evidence supporting associations between exposure to water disinfection by-products (DBPs) and adverse pregnancy outcomes is sparse, and positive findings should be interpreted cautiously. The methods used during the early stages of research in this area have been diverse. Variability in exposure assessment and endpoints makes it difficult to synthesize or combine the available data. Exposure misclassification and unmeasured confounding may have lead to bias in risk estimation. Future studies of reproductive outcome and exposure to chlorinated water should use improved methods for exposure assessment to 1) assure selection of appropriate exposure markers, 2) assess seasonal and annual fluctuations in DBPs, 3) assess variability within the distribution system, and 4) assess exposure through multiple routes such as bathing and showering, as well as consumption. Population-based studies should be conducted to evaluate male and female fertility, conception delay, growth retardation, and specific birth defects. The reproductive and developmental effects of exposure to DBPs could be efficiently explored in ongoing investigations by incorporating valid exposure markers and relevant questionnaire information. Future studies should make use of naturally occurring variability in the concentrations of DBPs and may incorporate biomarkers of exposure and effect in their design. Epidemiologic investigations should be conducted in parallel with laboratory-based and animal studies in a coordinated, multidisciplinary approach.     

饮用水中消毒副产物研究进展

从饮用水中消毒副产物 (DBPS)种类、毒性、流行病学调查以及饮用水中的分布状况 ,综述了DBPS研究的进展 ;并且从相应的卫生标准或限量值的制定以及去除方法等方面 ,综述了管理和治理情况。结果发现 ,经加氯消毒后的饮用水中DBPS 的种类很多 ,饮用水中存在的主要物质为三卤甲烷和卤乙酸类的物质 ,对人体毒性较大的物质是三卤甲烷、卤乙酸、溴酸盐和亚氯酸盐。国内外饮用水中DBPS 卫生标准或限量值在不断修改或补充 ,监测指标在不断增多 ,限量值在不断加严 ,其目的是利用消毒剂消灭病原体的同时 ,将其对人体危害降至最低。     

Exposure to water disinfection by-products and adverse pregnancy outcomes: results of a case-control study carried out in Modena (Italy)

Chlorination By Products (CBPs) in drinking water have been associated with an increased risk of adverse pregnancy outcomes, such as small term birth (STB) and preterm delivery. Up to date epidemiological evidence is weakened by a generally inaccurate exposure assessment, often at an ecological level: in this study the exposure is evaluated at the individual level. A case control study with incident cases was performed in Modena between October 1999-September 2000. 332 subjects were enrolled: 93 preterm births (26th-37th week of pregnancy), 73 STB (from 38th week, and weight less than the lowest 10th percentile) and 166 controls. Exposure was assessed both by applying a questionnaire on personal habits and by personal water sampling directly at subjects' home. THMs were analysed in all samples, chlorite and chlorate in water samples treated with chlorine dioxide. Subjects usually drinking tap water were few (5.2%): most of them were living in areas supplied by water treated with chlorine dioxide (87%). Levels of THMs were low (mean: 0.73 microgram/l), while chlorite and chlorate concentrations were relatively high (mean: 217.8 microgram/l for chlorites and 95.2 microgram/l for chlorates). Preterm birth did not show any significant association with CBPs, while STB appeared significantly associated, after adjusting for many potential confounders, with CBPs induced by chlorine dioxide treatment, especially with levels of chlorate higher than 200 microgram/l (OR: 4.7; 95%CI: 1.15-19.72). The association between STB and chlorate must be investigated further as the number of water utilities applying chlorine dioxide as disinfection treatment is increasing.     

Mutagenicity and disinfection by-products in surface drinking water disinfected with peracetic acid

The aims of this research were to study the influence of peracetic acid (PAA) on the formation of mutagens in surface waters used for human consumption and to assess its potential application for the disinfection of drinking water. The results obtained using PAA were compared to those found with sodium hypochlorite (NaClO) and chlorine dioxide (ClO2). The Ames test, root anaphase aberration assay, and root/micronuclei assay in Allium cepa and Tradescantia/micronuclei test were used to evaluate the mutagenicity of disinfected samples. Microbiological tests were also performed, and disinfection by-products (DBPs) were identified using gas chromatography/mass spectrometry (GC/MS). A slight bacterial mutagenicity was found in raw lake and river water, and similar activity was detected in disinfected samples. A plant test revealed genotoxicity in raw river water, and microbiological analysis showed that PAA has bactericidal activity but lower than that of the other disinfectants. The DBPs produced by PAA were mainly carboxylic acids, which are not recognized as mutagenic, whereas the waters treated with the other disinfectants showed the presence of mutagenic/carcinogenic halogenated DBPs. However, additional experiments should be performed with higher concentrations of PAA and using water with higher organic carbon content to better evaluate this disinfectant.     

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.     

江苏省城市饮用水氯化消毒副产物的健康风险评估

目的 了解江苏省城市饮用水中氯化消毒副产物三卤甲烷、卤乙酸暴露水平,评估饮用水中氯化消毒副产物经口摄入途径对人体健康潜在危害,为制定饮水安全保障政策提供参考.方法 2017-2019年,选取全省氯化消毒的市政水厂51座,在枯水期(3-5月)、丰水期(7-9月)采集出厂水、末梢水192份,检测水中三卤甲烷(三氯甲烷、一氯二溴甲烷、二氯一溴甲烷、三溴甲烷)、卤乙酸(二氯乙酸、三氯乙酸)暴露水平,使用美国环保署推荐的健康风险评价模型,对氯化消毒副产物经口摄入途径的健康风险进行评估.结果 所有水样氯化消毒副产物检出值均低于国标限值.氯化消毒副产物对成年男性、成年女性、儿童终身致癌风险分别为3.13×10-5、3.16×10-5、2.91×10-5,其中二氯一溴甲烷致癌风险最高,对成年男性、成年女性、儿童致癌风险分别为1.12×10-5、1.13×10-5、1.04×10-5,分别占总致癌风险的35.78％、35.76％、35.74％.副产物终身致癌风险液氯消毒高于次氯酸钠消毒,末梢水高于出厂水,丰水期高于枯水期.对成年男性、成年女性、儿童非致癌风险健康危害指数分别为7.30×10-2、7.40×10-2、6.80×10-2,其中三氯甲烷非致癌风险最高.结论 江苏省城市饮用水氯化消毒副产物终身致癌风险、非致癌风险均在可接受范围内,二氯一溴甲烷、一氯二溴甲烷是风险管理重点指标.     

Multipathway risk assessment on disinfection by-products of drinking water in Hong Kong

The lifetime cancer risk and the hazard index of trihalomethanes (THMs) through oral ingestion, dermal absorption, and inhalation exposure from tap water in 19 districts in Hong Kong are estimated. The most dominant THMs are chloroform and bromodichloromethane (BDCM) in Hong Kong tap water. Among the three different pathways, residents have a higher risk of cancer through oral ingestion than through the other two pathways. The lifetime cancer risks through oral ingestion and dermal absorption for BDCM make the highest percentage contribution (59%) to total risks, followed by chloroform (24%). The chloroform and BDCM are at or above the negligible risk level of 10(-6) by a factor of 10 or more in most districts. Among the 19 districts, people living in Sai Kung have the highest risk of cancer due to the THM exposure through the multipathways, mainly because of the exposure to BDCM and dibromochloromethane (DBCM). The total cancer risk analysis indicates that each year approximately 10 out of the seven million Hong Kong residents could get cancer from the daily intake of water.     

饮用水消毒副产物暴露评价研究进展

介绍了饮用水消毒副产物暴露评价的基本定义,对饮用水暴露评价的主要消毒副产物进行了归纳总结,综述了现阶段饮用水消毒副产物暴露评价方法的进展及不足,并结合具体案例对饮用水消毒副产物暴露评价的具体步骤进行较为详细阐述,并对饮用水消毒副产物暴露评价研究的发展趋势及将来研究的重点进行了展望。     

潍坊市饮用水中消毒副产物的水平及其健康风险评价

目的了解潍坊市居民生活饮用水中消毒副产物的种类和分布水平,并对其健康风险进行评价。方法于2018年丰水期(8月)和枯水期(3月)采集潍坊市区12家市政水厂的出厂水和相应的末梢水水样共86份,对水样中18种消毒副产物进行浓度水平检测和健康风险评价。检测结果评价参考国家生活饮用水标准(GB5749—2006),并参照美国USEPA的致癌风险模型评估DBPs经饮水途径对潍坊市居民造成的健康危害。结果潍坊市饮用水中主要检测到的消毒副产物为THMs(TCM、BDCM、DBCM和TBM);丰水期与枯水期消毒副产物的浓度在不同季节分布均无差异(P>0.05);出厂水和末梢水中消毒副产物引起的致癌风险分别为11.1×10~(-7)～7.73×10~(-5)和7.86×10~(-7)～1.07×10~(-4),非致癌风险分别为1.82×10~(-3)～0.13和1.64×10~(-3)～0.18,致癌风险均来自三卤甲烷类物质。结论三卤甲烷是2018年潍坊市主城区饮用水中的主要消毒副产物。     

饮用水卤乙醛类消毒副产物的生成及毒效应研究进展

卤乙醛类消毒副产物是饮用水中新发现的消毒副产物,位居饮用水中消毒副产物总量第三,其生成与水中天然有机物和卤化物水平、饮用水处理工艺和消毒剂类型有关。新近研究显示卤乙醛类消毒副产物比饮用水中受控的三卤甲烷类消毒副产物和卤乙酸类消毒副产物有更强的细胞毒性和遗传毒性。目前仅有少数国家和地区对饮用水中检出率高的三氯乙醛设定了限值,但日益积累的证据表明非受控的卤乙醛类消毒副产物对人群健康的潜在风险更高。本文综述了当前饮用水中卤乙醛类消毒副产物的生成与转化、细胞毒性、遗传毒性等方面的研究进展,展望了未来卤乙醛类消毒副产物毒理学研究应关注的问题,以支撑科学的饮用水卫生标准研制。     

生活饮用水中消毒副产物及阴离子的离子色谱测定法

目的 建立生活饮用水中几种常见阴离子和消毒副产物测定的离子色谱法。方法 水样经Metrosup A Supp 7-250/4.0阴离子色谱柱(250mm×4.0mm)分离,以3.2mmol/L Na2CO3-2.1mmol/L NaHCO3为淋洗液在流速为1.0ml/min条件下等度洗脱,抑制型电导检测器检测。结果 该法各目标物相关系数r>0.996,检出限在0.0002mg/L~0.0033mg/L之间,加标回收率为88.08%~107.8%,相对标准偏差在2.31%以内(n=6)。结论 该法直接进样,只需22min即可实现生活饮用水中7种阴离子的定量测定,满足国家限量标准要求,适合基层单位大批量多批次样品的测定。     

自动顶空—气相色谱法快速测定生活饮用水中6种消毒副产物残留

通过优化顶空气相分析中的平衡温度、平衡时间、加盐量及固液比等实验参数,建立自动顶空—气相色谱快速测定生活饮用水中6种消毒副产物残留的方法。结果表明:在固液比为1∶1,加氯化钠量为3 g,70℃下平衡15 min后进行顶空自动进样分析,6种消毒副产物灵敏度大幅提高,该法操作简单,可节省大量时间,适用于水样批量检测。通过方法学验证的结果显示,6种目标物在相应浓度范围内的线性关系良好(R~20.998),检出限为0.004μg/L(四氯化碳)~0.342μg/L(二氯甲烷),定量限为0.013μg/L(二氯一溴甲烷)~1.34μg/L(二氯甲烷);不同浓度水平的加标回收率在82.9%~97.5%范围内,相对标准偏差为0.86%~3.25%(n=5)。方法适用于基层疾控中心对生活饮用水卫生监测的需要。     

烟台市政供水中消毒副产物污染状况及控制措施研究

目的:了解烟台市政供水中消毒副产物(CDBPs)污染状况及季节分布,寻找有效控制消毒副产物生成量的水处理方式。方法:选取水源水、水厂水及末梢水等进行调查研究,对主要消毒副产物三卤甲烷(THMs)和卤乙酸(HAAs),以及pH、游离余氯、水温进行监测。通过控制氯投入量的干预措施,了解不同余氯浓度下水中CDBPs的变化情况。结果:目前烟台市政供水中消毒副产物指标未超出GB5749-2006饮用水卫生要求,但一氯二溴甲烷含量偏高。水厂水余氯夏季应保持在0.6 mg/L～0.7 mg/L,冬季节应在0.4 mg/L～0.5 mg/L,春秋季应在0.5 mg/L～0.6 mg/L为宜。结论:目前烟台市政供水中消毒副产物指标污染状况不严重;消毒副产物的产生量随季节有所不同,夏季最高,冬季最低;减少或避免预氯化,不同季节按各自适宜的用量投氯,可有效降低消毒副产物的产生量,有效控制二次污染。     

吹扫捕集-气相色谱/质谱法测定饮用水中挥发性氯化消毒副产物

目的:建立适用于饮用水中挥发性氯化消毒副产物的分析方法。方法:利用吹扫捕集-气相色谱/质谱联用技术,全扫描方式进行质谱定性,外标法定量。结果:方法在试验浓度范围内线性良好(r>0.9991),检出限为0.02μg/L～0.13μg/L,样品平均回收率在95%～103%,相对标准偏差(RSD)在3.3%～9.5%。结论:该方法具有分析快速、简单,准确、灵敏、无干扰等优点,适合于饮用水中氯化消毒副产物的检测。     

Disinfection of drinking water,disinfection by-products and cancer: what about Australia?

Abstract: Chlorine, commonly used to disinfect drinking water, produces by-products known from animal studies to be carcinogenic and mutagenic. Most epidemiological studies into the possible association between chlorination by-products in drinking water and cancer have been ecological in nature, or have relied on case-control designs based on death certificates. Interpretation of results arising from these studies is limited. Individual levels of toxicant exposure and many potential confounders and effect modifiers are unable to be accounted for in the analyses. At best, these studies generate hypotheses that require more definitive investigation. Misclassification of individuals based on inaccurate assessment of the level of exposure is probable. The few analytic studies able to overcome or minimise these problems suggest a clear link between exposure to chlorinated drinking water and the development of urinary bladder cancer. They also suggest a possible link with rectal cancer. However, these studies have classified subjects by exposure to chlorinated drinking water, rather than to levels of chlorine and its by-products in drinking water. To date, the link between levels of chlorine and its by-products in water, levels of consumption and cancer has not been made. Information on the levels of chlorine and some by-products is available in many water jurisdictions in Australia. Further, epidemiological methods can be employed to quantify water consumption. Case-control studies linking these parameters would help us to understand the magnitude of the risk to human populations and provide a basis to investigate mechanisms for risk reduction.     

Health impacts of long-term exposure to disinfection by-products in drinking water in Europe: HIWATE

There appears to be very good epidemiological evidence for a relationship between chlorination by-products, as measured by trihalomethanes (THMs), in drinking water and bladder cancer, but the evidence for other cancers, including colorectal cancer appears to be inconclusive and inconsistent. There appears to be some evidence for a relationship between chlorination by-products, as measured by THMs, and small for gestational age (SGA)/intrauterine growth retardation (IUGR) and preterm delivery, but evidence for other outcomes such as low birth weight (LBW), stillbirth, congenital anomalies and semen quality appears to be inconclusive and inconsistent.     

离子色谱法测定饮用水消毒副产物亚氯酸盐、氯酸盐和溴酸盐

目的建立饮用水中消毒副产物（DBP）亚氯酸盐、溴酸盐、氯酸盐的离子色谱检测方法。方法用IonPac23（4×250mm）型阴离子分析柱和（4×50mm）型阴离子保护柱。DS6抑制型电导检测器,抑制器采用ASRS3004mm型,淋洗液浓度：4.5mmol/L Na2CO3~0.8 mmol/L NaHCO3,流速：1.0ml/min。结果本方法线性关系良好（r≥0.999）,精密度高,5.0μg/L添加水平相对标准偏差（RSD）〈10%。在10.0μg/L、50.0μg/L、150.0μg/L三种浓度添加水平下,平均回收率在96.9%~99.1%之间。亚氯酸盐、溴酸盐、氯酸盐最低检测浓度分别为3.1μg/L、3.0μg/L、3.7μg/L。结论该方法操作简单,灵敏度高,适用于饮用水中亚氯酸盐、溴酸盐、氯酸盐的检测。