Fe3+和Br-对饮用水氯消毒过程中挥发性卤代烃生成的影响

以腐殖酸模拟天然水体中的活性消毒副产物的前体物,研究了含腐殖酸水样中溴离子和三价铁离子对氯消毒反应过程中挥发性卤代烃三卤甲烷(THMs)的生成量和相对分布的影响.结果表明,水样中的溴离子浓度增加将增加溴代三卤甲烷和总三卤甲烷的生成量, 在Br^-离子浓度1.0 mg/L时,THMs的总量为不含Br^-时的2.7倍;当水样中含有溴离子时,在偏酸性条件下三价铁对三卤甲烷的生成有一定的抑制作用,在偏碱性条件下三价铁离子提高了溴离子与腐殖酸的反应活性,从而提高了三卤甲烷的生成总量.Fe³⁺浓度为5 mg/L时,三溴甲烷的生成量与无Fe³⁺存在时相比,由51.7 μg/L增加到79.4 μg/L, 增加幅度达54%,THMs的总量从113.49 μg/L增加到162.09 μg/L.溴离子对饮用水的安全性具有较大的负面影响,溴离子和三价铁离子共存于偏碱性环境中时对加氯消毒后饮用水的致癌风险的影响显著增大,当Br^-含量为0.2 mg/L、Fe³⁺含量为5 mg/L时,在pH为6和8的条件下,致癌风险比饮用水中不含Br^-和Fe³⁺时分别增加2.5和5.1倍.     

Photodegradation of methylmercury in Jialing River of Chongqing,China

Photodegradation (PD) of methylmercury (MMHg) is a key process of mercury (Hg) cycling in water systems, maintaining MMHg at a low level in water systems. However, we possess little knowledge of this important process in the Jialing River of Chongqing, China. In situ incubation experiments were thus performed to measure temporal patterns and influencing factors of MMHg PD in this river. The results showed that MMHg underwent a net demethylation process under solar radiation in the water column, which predominantly occurred in surface waters. For surface water, the highest PD rate constants were observed in spring (12 × 10^− 3 ± 1.5 × 10^− 3 m²/E), followed by summer (9.0 × 10^− 3 ± 1.2 × 10^− 3 m²/E), autumn (1.4 × 10^− 3 ± 0.12 × 10^− 3 m²/E), and winter (0.78 × 10^− 3 ± 0.11 × 10^− 3 m²/E). UV-A radiation (320–400 nm), UV-B radiation (280–320 nm), and photosynthetically active radiation (PAR, 400–700 nm) accounted for 43%–64%, 14%–31%, and 16%–45% of MMHg PD, respectively. PD rate constants varied substantially with the treatments that filtered the river water and amended it with chemicals (i.e., Cl⁻, NO₃⁻, dissolved organic matter (DOM), Fe(III)), which reveals that suspended particulate matter and water components are important factors in affecting the PD process. For the entire water column, the PD rate constant determined for each wavelength range decreased rapidly with water depth. UV-A, UV-B, and PAR contributed 27%–46%, 6.2%–12%, and 42%–65% to the PD process, respectively. PD flux was estimated to be 4.7 μg/(m²·year) in the study site. Our results are very important to understand the cycling characteristics of MMHg in the Jialing River of Chongqing, China.     

Cancer risk assessment from exposure to trihalomethanes in tap water and swimming pool water

We investigated the concentration of trihalomethanes （THMs） in tap water and swimming pool water in the area of the Nakhon Path- om Municipality during the period April 2005-March 2006. The concentrations of total THMs, chloroform, bromodichloromethane, dibromochloromethane and bromoform in tap water were 12.70-41.74, 6.72-29.19, 1.12-11.75, 0.63-3.55 and 0.08-3.40 μg/L, respectively, whereas those in swimming pool water were 26.15-65.09, 9.50-36.97, 8.90-18.01, 5.19-22.78 and ND-6.56 μg/L, respectively. It implied that the concentration of THMs in swimming pool water was higher than those in tap water, particularly, brominated-THMs. Both tap water and swimming pool water contained concentrations of total THMs below the standards of the World Health Organization （WHO）, European Union （EU） and the United States Environmental Protection Agency （USEPA） phase Ⅰ, but 1 out of 60 tap water samples and 60 out of 72 swimming pool water samples contained those over the Standard of the USEPA phase Ⅱ. From the two cases of cancer risk assessment including Case Ⅰ Non-Swimmer and Case Ⅱ Swimmer, assessment of cancer risk of nonswimmers from exposure to THMs at the highest and the average concentrations was 4.43×10^-5 and 2.19×10^-5, respectively, which can be classified as acceptable risk according to the Standard of USEPA. Assessment of cancer risk of swimmers from exposure to THMs at the highest and the average concentrations was 1.47×10^-3 and 7.99×10^-4, respectively, which can be classified as unacceptable risk and needs to be improved. Risk of THMs exposure from swimming was 93.9%-94.2% of the total risk. Cancer risk of THMs concluded from various routes in descending order was： skin exposure while swimming, gastro-intestinal exposure from tap water intake, and skin exposure to tap water and gastro-intestinal exposure while swimming. Cancer risk from skin exposure while swimming was 94.18% of the total cancer risk.     

长江南京段水源水中有机磷酸酯的污染特征与风险评估

为探究长江南京段水源水中有机磷酸酯(organophosphate esters,OPEs)的污染特征、时空分布、生态风险和健康风险,利用固相萃取-高效液相色谱-串联质谱法测定了13种OPEs.结果表明,除磷酸三(2,3-二溴丙基)酯外,其余12种OPEs均有不同程度的检出,总浓度范围为85. 21～1 557. 96 ng·L~(-1),氯代烷基磷酸酯是主要化合物,其中检出浓度最高的是磷酸三(2-氯乙基)酯[tri(2-chloroethyl) phosphate,TCEP],高达447. 08 ng·L~(-1).长江南京段水源水中OPEs呈现明显的季节变化特征,夏季总检出浓度为220～1557. 96 ng·L~(-1),平均浓度是493. 78 ng·L~(-1),是春秋季的1. 7～2. 6倍.生态风险评估显示磷酸三甲苯酯和2-乙基己基二苯基磷酸酯对有机体(藻类,甲壳类动物和鱼类)具有中或高等风险.高暴露浓度下,OPEs的总非致癌风险为4. 41×10~(-3)～2. 91×10~(-2),均小于1,0～3个月的婴儿最高,总致癌风险值为5. 88×10~(-7)～3. 89×10~(-6),其中TCEP和磷酸三(1,3-二氯-2-丙基)酯对儿童有潜在的致癌风险.长江南京段水源水中OPEs对儿童的长期暴露风险需引起高度重视.     

崇左响水地区地下水水质分析及健康风险评价

以崇左响水地区为研究区域,对区域内60个地下水样品中的常规指标和金属元素进行测定和分析,运用内梅罗综合指数法分析了不同类型地下水环境质量,应用健康风险评价模型评价了不同类型地下水的健康风险.结果表明,井水、泉水和地下河水的常规指标和金属元素均出现不同程度的超标现象,水质级别均为较差级别,地下河水的综合评价分值(F=4. 26)最低,井水和泉水的综合评价分值(F=7. 10)相同.高硬度和高矿化度利于Cr的富集,还原环境利于As的富集,Zn、Pb、Cd和Cu经过的环境地球化学作用相似,Fe、Al和Mn来源相似.健康风险评价表明,3种类型地下水的健康总风险偏高,大小顺序为井水地下河水泉水,主要来源于致癌性金属元素Cr.致癌总风险比非致癌总风险高4～6个数量级,致癌总风险均高于最大可接受风险水平(5. 0×10~(-5)a~(-1)),非致癌总风险均小于可接受的健康风险水平(10~(-6)a~(-1)).儿童健康总风险大于成人,经饮水途径引起的健康风险比皮肤接触途径高2～3个数量级.从饮水安全考虑,在饮用前需对井水、地下河水和泉水进行适当处理并实施对Cr污染物的控制.     

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW < 1 kDa and fraction with MW 3−10 kDa, and the DBP''s generation ability of lower molecular weight DOM (< 10 kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.     

Effect of ferric and bromide ions on the formation and speciation of disinfection byproducts during chlorination

The e ects of ferric ion, pH, and bromide on the formation and distribution of disinfection byproducts (DBPs) during chlorination were studied. Two raw water samples from Huangpu River and Yangtze River, two typical drinking water sources of Shanghai, were used for the investigation. Compared with the samples from Huangpu River, the raw water samples from Yangtze River had lower content of total organic carbon (TOC) and ferric ions, but higher bromide concentrations. Under controlled chlorination conditions, four trihalomethanes (THMs), nine haloacetic acids (HAAs), total organic halogen (TOX) and its halogen species fractions, including total organic chlorine (TOCl) and total organic bromide (TOBr), were determined. The results showed that co-existent ferric and bromide ions significantly promoted the formation of total THMs and HAAs for both raw water samples. Higher concentration of bromide ions significantly changed the speciation of the formed THMs and HAAs. There was an obvious shift to brominated species, which might result in a more adverse influence on the safety of drinking water. The results also indicated that high levels of bromide ions in raw water samples produced higher percentages of unknown TOBr.     

东江流域典型乡镇饮用水源地重金属污染健康风险评价

为阐明东江流域典型乡镇饮用水源地重金属污染物的分布特征与风险水平,对研究区域内9个区县45个水样中的常规水质指标和铁、铜、锰、锌、砷、铬、汞、铅、镉等金属污染物浓度进行了分析检测,并应用美国环境保护署推荐的环境健康风险评价模型,对不同类型的水源地进行了健康风险评价.结果表明,该研究区域的金属致癌风险较高,其中最高的致癌风险来自水库中的铬,成人和儿童分别达到1.14×10-4.a-1和2.14×10-4.a-1,江河、水库和地下水的金属总致癌风险超过了ICRP推荐的可接受风险水平5.0×10-5.a-1;该区域金属非致癌风险较低,均在EPA推荐的可接受范围内.该研究区域金属污染物的优先控制顺序为铬>砷>铅>铁>锌,饮用水源地的风险值排序为水库>江河>地下水>山泉.     

饮用水中三卤甲烷的生成特性及控制技术研究

水源中的腐殖酸等有机物在氯消毒过程中通常会与消毒剂发生反应生成三卤甲烷,且饮用水中卤代烷含量往往高于水源水,包括三氯甲烷(TCM)、一溴二氯甲烷(DCBM)、二溴一氯甲烷(DBCM)以及溴仿(TBM)等,以三氯甲烷为主.三卤甲烷(THMs)已被证实与动物体的癌症、畸形及遗传病密切相关.文章主要从三卤甲烷的生成特性与机理、影响因素及其去除控制技术等几方面对国内外有关研究进行具体综述和介绍,为今后更深入地研究THMs的生成机理及其前体有机物来源提供理论依据,以便寻求更经济实用、切实可行的控制与去除THMs的新技术,同时也应加强THMs暴露的健康风险等方面的评价.     

Enhanced photoelectrocatalytic degradation of ammonia by in situ photoelectrogenerated active chlorine on TiO2 nanotube electrodes

TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.     

黄河下游引黄灌区地下水重金属分布及健康风险评估

为了解黄河下游引黄灌区地下水重金属污染水平,在引黄灌区豫、鲁两省采集59个地下水样品,定量分析了11种重金属元素(Ba、Cd、Cr、Cu、Fe、Mn、Mo、Ni、Pb、Se和Zn)的含量及空间分布特征,应用健康风险评价模型评价了地下水中重金属污染所引起的健康风险.结果表明,地下水中Fe和Zn的平均浓度较高,分别为0.496 mg·L-1和0.445 mg·L-1.Fe、Mn、Se和Zn出现超标现象,超标率分别为:27.12%、27.12%、15.25%和5.09%.采用Inverse Distance Weighted插值法得到了黄河下游引黄灌区地下水重中金属含量的空间分布,发现地下水中超标的重金属主要分布在武城县、范县、东阿县、禹城市和冠县等区域.健康风险评价表明,非致癌物质通过饮水途径引起的健康风险高于皮肤暴露,但致癌物质的皮肤暴露致癌风险高于饮水途径.饮水和皮肤暴露途径中,致癌物质的个人年风险均以Cr最大,分别是Cd的7倍和28倍,但二者均低于最大可接受风险水平(5×10-5a-1).非致癌物质(Ba、Cu、Fe、Mn、Mo、Ni、Pb、Se和Zn)的饮用水健康风险集中在1.13×10-9～6.06×10-8a-1,皮肤接触健康风险集中在1.73×10-13～3.46×10-10a-1,均小于最大可接受风险水平.     

淮河流域典型癌病高发区土壤和地下水重金属积累及健康风险

分别采集淮河沿岸某癌病高发区土壤和地下水样品,分析和探讨了土壤和地下水重金属的含量、分布和季节变化,以及土壤和地下水重金属积累的生态与健康风险.结果表明,除Zn外,土壤和地下水重金属含量旱季均高于雨季,癌病高发村庄高于其他村庄,河流污染是沿岸土壤和地下水重金属积累的主要原因.除土壤Cd达到中度潜在生态风险外,土壤中其余重金属的潜在生态风险总体为轻微级.癌病高发村庄居民饮水中重金属致癌和非致癌健康风险明显高于其他村庄居民,均为其他村庄居民的2倍以上,其中,重金属非致癌健康风险达到93.09×10-10a-1,接近国际健康组织推荐的最大可忽略风险,重金属致癌健康风险达到27.82×10-5a-1,分别为ICRP和US EPA推荐的最大可接受风险的5倍和2倍以上.各种重金属中,Pb和Cr是主要的非致癌健康风险因子,Cr是主要的致癌健康风险因子.癌病高发村庄土壤和地下水重金属积累明显,存在较高的饮水重金属暴露健康风险.     

水中溴离子对氯化消毒副产物的影响

根据我国某城市饮用水中三卤甲烷类物质的现状，对水中Ｂｒ＾－的存在，Ｂｒ＾－对ＴＨＭｓ，卤代乙酸类物质形成的影响以及ＴＨＭｓ，ＨＡＡｓ形成的机理等进行综述，且提出了控制饮用水氯化消毒副产物的相应对策。     

氟化工园区及周边地下水健康风险及脆弱性评价

以阜新市某氟化工园区为研究对象,对园区及周边地下水样品中的Cr、As、Cu、Hg、Mn及F 6种元素分季节进行测定分析,采用美国环保署（US EPA）推荐的人体健康风险评价模型对重金属Cr、As、Cu、Hg、Mn及F进行地下水环境的人体健康风险评价,并应用DRASTIC模型评价该区域地下水的脆弱性.结果表明,研究区地下水受到重金属和氟化物的污染.健康风险评价表明,总致癌风险数量级在10^-5~10^-4之间,处于Ⅱ~Ⅳ级风险评价标准区间,总非致癌风险大于1,经饮水摄入途径引起的非致癌危害比皮肤接触途径高3~4个数量级.脆弱性评价表明,研究区的脆弱性指数DI范围为4.30~5.91,整体脆弱性处于Ⅲ级中等脆弱性水平.     

Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems

The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments, oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of pH, Fe(II) and Cr(III) on the intermediates and redox rate was investigated. SO₄^2 − and elemental S were formed as the major and minor products, respectively, during the oxidation processes. Ferric (hydr) oxides including Fe(OH)₃ and goethite were formed with low degree of crystallinity. Low pH and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air (oxygen), and Fe(II) ions played a key role in the redox process. The addition of Fe(II) ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr(III) ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe(II) ions to form a Fe(III)/Fe(II) redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe(II) ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.     

Particulate matter assessment of a wetland in Beijing

To increase the knowledge on the particulate matter of a wetland in Beijing, an experimental study on the concentration and composition of PM₁₀ and PM_2.5 was implemented in Beijing Olympic Forest Park from 2013 to 2014. This study analyzed the meteorological factors and deposition fluxes at different heights and in different periods in the wetlands. The results showed that the mean mass concentrations of PM₁₀ and PM_2.5 were the highest at 06:00–09:00 and the lowest at 15:00–18:00. And the annual concentration of PM₁₀ and PM_2.5 in the wetland followed the order of dry period (winter) > normal water period (spring and autumn) > wet period (summer), with the concentration in the dry period significantly higher than that in the normal water and wet periods. The chemical composition of PM_2.5 in the wetlands included NH₄⁺, K⁺, Na⁺, Mg^2 +, SO₄^2 −, NO₃⁻, and Cl⁻, which respectively accounted for 12.7%, 1.0%, 0.8%, 0.7%, 46.6%, 33.2%, and 5.1% of the average annual composition. The concentration of PM₁₀ and PM_2.5 in the wetlands had a significant positive correlation with relative humidity, a negative correlation with wind speed, and an insignificant negative correlation with temperature and radiation. The daily average dry deposition amount of PM₁₀ in the different periods followed the order of dry period > normal water period > wet period, and the daily average dry deposition amount of PM_2.5 in the different periods was dry period > wet period > normal water period.     

贵州草海沉积物重金属元素分布特征及健康风险评价

为研究贵州威宁草海重金属污染现状,对该区域内20个采样点表层沉积物中的6种重金属元素（Pb、Cd、Cu、Zn、Fe、Mn）进行检测和分析.结果表明,表层沉积物中Cd、Zn和Pb的含量分别为贵州省土壤背景值的32.44、614.45和185.30倍,主要来源为采矿及矿物加工.此外,县城污水排放对Cu分布有一定的影响.Cd、Zn和Pb主要以可还原态及可氧化态存在,形态分布受Fe元素影响较大;Mn则以弱酸可提取态为主,具有较高的生物有效性.健康风险评价结果表明,表层沉积物对儿童造成的非致癌风险值（1.2×10¹ a^-1）超过限值（1.0×10⁰ a^-1）,对成人（7.91×10^-5 a^-1）和儿童（1.11×10^-3 a^-1）造成的致癌风险超过了可接受水平,其中,Cd是主要的致癌风险元素.综合来看,草海表层沉积物的重金属污染较为严重.     

Determination of photochemically-generated reactive oxygen species in natural water

Reactive oxygen species(ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment.ROS may participate in the indirect photolysis of trace organic pollutants,therefore resulting in changes in their environmental fates and ecological risks in natural water systems.Bisphenol A(BPA),an endocrine-disrupting chemical,exits widely in natural waters.The photodegradation of BPA promoted by ROS(.OH,1O2,HO2./O2·-),which were produced on the excitation of ubiquito...     

传统给水处理厂氯消毒模型的开发与应用

以建立给水处理过程的风险分析方法为目标,提出了适用于传统给水处理工艺的氯消毒概率机理模型.模型既考虑氯消毒过程中有机物、余氯、氨氮、溴离子之间化学反应,又考虑水厂混凝、沉淀和过滤工艺过程中的物理和生物作用.典型水厂的现场监测数据表明,该模型能够较好地模拟水厂中高锰酸盐指数、氨氮以及4种三卤甲烷的浓度概率分布.Monte Carlo模拟的结果表明,与我国城市供水水质标准相比,该水厂高锰酸盐指数和单种三卤甲烷的超标概率极低,但总三卤甲烷的超标概率略高,约为2.3%.     

Composition and source apportionment of dust fall around a natural lake

The aim of this study was to determine the source apportionment of dust fall around Lake Chini, Malaysia. Samples were collected monthly between December 2012 and March2013 at seven sampling stations located around Lake Chini. The samples were filtered to separate the dissolved and undissolved solids. The ionic compositions(NO-3, SO2-4, Cl-and NH+4) were determined using ion chromatography(IC) while major elements(K, Na, Ca and Mg) and trace metals(Zn, Fe, Al, Ni, Mn, Cr, Pb and Cd) were determined using inductively coupled plasma mass spectrometry(ICP-MS). The results showed that the average concentration of total solids around Lake Chini was 93.49 ± 16.16 mg/(m2·day). SO2-4, Na and Zn dominated the dissolved portion of the dust fall. The enrichment factors(EF) revealed that the source of the trace metals and major elements in the rain water was anthropogenic, except for Fe. Hierarchical agglomerative cluster analysis(HACA) classified the seven monitoring stations and 16 variables into five groups and three groups respectively. A coupled receptor model, principal component analysis multiple linear regression(PCA-MLR), revealed that the sources of dust fall in Lake Chini were dominated by agricultural and biomass burning(42%),followed by the earth's crust(28%), sea spray(16%) and a mixture of soil dust and vehicle emissions(14%).