饮用水源水中致嗅物质去除技术研究进展

土臭素和2-甲基异莰醇是饮用水中存在的主要致嗅味物质,活性炭吸附是目前研究最多、应用最广泛的嗅味物质去除技术,文章重点介绍了影响活性炭吸附的各种因素,对化学氧化法和生物降解法去除嗅味物质的研究进展进行了简述。     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L⁻¹ and gave detection limits of 0.5–1.5 ng·L⁻¹ for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

典型水环境微生物源异嗅物研究进展

致嗅微生物主要包括放线菌、藻类和黏细菌等,广泛存在于水源水库、湖泊、溪流和海洋等典型水生态系统中,代谢产生的异嗅化合物痕量即可造成严重的异嗅味,威胁供水安全.目前,大量研究集中在异嗅化合物的有效控制上,投入使用的有物理和化学等方法,但存在问题,有待改进与完善,微生物法对环境友好,因此具有广阔的应用前景.本文从异嗅化合物的种类、生物源、检测方法、控制措施、影响因素及产嗅机制等方面的研究进行综述,并进行展望,讨论今后研究热点,旨在推进异嗅化合物的相关研究,保障城镇供水安全.     

生物过滤饮用水深度处理:机遇与挑战

源水水质的恶化给传统的饮用水处理工艺带来了挑战.生物过滤是饮用水消毒输配之前管理、维护及增强颗粒滤料表面生物活性以去除有机和无机物的过程.由于具有高效、低成本等优点，生物过滤在饮用水深度处理工艺中逐渐得到广泛的应用.本文综述了生物过滤在饮用水处理过程中对水中溶解性有机质（消毒副产物前体物）的去除、微量污染物的削减、嗅味化合物及氨氮的去除等.此外，针对生物过滤在水深度处理过程中存在的问题，本文详细讨论了含氮消毒副产物前体物的生成、低温下生物过滤效能下降等挑战，并提出了今后需要研究的问题.     

Identification of causative compounds and microorganisms for musty odor occurrence in the Huangpu River, China

There are regular problems of musty odor in the Huangpu River,a major source of drinking water for Shanghai,China.In this study,the musty odor and its main causative compounds in the Huangpu River source water were confirmed through a yearly investigation using flavor profile analysis combined with HSPME-GC-MS analysis.The investigation showed that 2-methylisoborneol (2-MIB) with a concentration level between 28.6 and 71.0 ng/L was responsible for the musty odor in summer from July to September.Microscopic observation confirmed with the cloning results showed that Phormidium spp.,which accounted for 80%-95% of the algal cell density,was the microorganisms responsible for the production of 2-MIB and the estimated 2-MIB yield was 0.022 pg/cell.Results from a wide-area sampling campaign in the Huangpu River watershed showed that,other than the large tributaries receiving water from Tai Lake,several small creeks close to the intake may have contributed most of the 2-MIB and the Phormidium spp.to the Huangpu River source water.This study provides methodology for the investigation of odor causing compounds and microorganisms in river-type source water,and the result will be useful for water quality control in both source water and drinking water.     

地表水体放线菌分离鉴定与致嗅能力研究

原水中的嗅味是饮用水中嗅味的主要来源之一.从中国南方地区某水库中分离纯化放线菌并进行菌种鉴定及产致嗅物质2-甲基异莰醇(2-MIB)和土臭素(GSM)能力研究.使用膜滤法和高氏一号培养基分离纯化水体中的放线菌.结合菌落菌丝形态特征、碳源利用、菌株生理生化特征及16S rRNA同源性序列分析对从该水库中分离纯化的40株放线菌进行菌种鉴定,结果表明有38株链霉菌、1株气微菌和1株假诺卡氏菌.分别使用高氏一号液体培养基和水库水体对这40株放线菌进行摇床发酵,结合顶空固相微萃取(SPME)和气质联用(GC-MS)方法检测发酵液中致嗅物质2-MIB和GSM含量,发现不同放线菌甚至链霉菌属内不同菌种产生致嗅物质的能力不同,且相差较大.放线菌在液体培养基中产致嗅物质2-MIB和GSM能力并不完全代表在水库中对水体2-MIB和GSM的贡献大小.     

Quantitative method to determine the regional drinking water odorant regulation goals based on odor sensitivity distribution：Illustrated using 2-MIB

Taste and odor （T/O） in drinking water often cause consumer complaints and are thus regulated in many countries. However, people in different regions may exhibit different sensitivities toward WO. This study proposed a method to determine the regional drinking water odorant regulation goals （ORGs） based on the odor sensitivity distribution of the local population. The distribution of odor sensitivity to 2-methylisobomeol （2-MIB） by the local population in Beijing, China was revealed by using a normal distribution function/model to describe the odor complaint response to a 2-MIB episode in 2005, and a 2-MIB concentration of 12.9 ng/L and FPA （flavor profile analysis） intensity of 2.5 was found to be the critical point to cause odor complaints. Thus the Beijing ORG for 2-MIB was determined to be 12.9 ng/L. Based on the assumption that the local FPA panel can represent the local population in terms of sensitivity to odor, and that the critical FPA intensity causing odor complaints was 2.5, this study tried to determine the ORGs for seven other cities of China by performing FPA tests using an FPA panel from the corresponding city. ORG values between 12.9 and 31.6 ng/L were determined, showing that a unified ORG may not be suitable for drinking water odor regulations. This study presents a novel approach for setting drinking water odor regulations.     

洞庭湖水体异味物质及其与藻类和水质的关系

以洞庭湖水体中异味物质为研究对象,开展异味物质调查,并结合藻类结构、水质及其营养状况等因素,深入分析洞庭湖异味物质的来源和变化情况. 结果表明,DMS(dimethylsulfide,甲硫醚)、DMTS(dimethyltrisulfide,二甲基三硫醚)、β-cyclocitral(β-环柠檬醛)、MIB(2-methylisoborneol,二甲基异冰片)和GSM(geosmin,土嗅素)在全湖广泛存在,其最高质量浓度分别达到500.80、28.80、21.84、14.50和22.40 ng/L. 结合与藻类生物量的相关分析发现,直链藻、冠盘藻等硅藻可能是洞庭湖中DMS、DMTS和β-cyclocitral的重要来源,湖区土壤、沉积物中的微生物和死亡分解的藻类是MIB和GSM主要来源. 洞庭湖水体绝大部分处于中营养水平,其中东洞庭湖TLI(综合营养状态指数,为48.3)最高,南洞庭湖(为47.3)其次,西洞庭湖(为42.7)最低. 异味物质含量和水质的相关分析发现,异味物质质量浓度与TLI、水温、pH、ρ(DO)、ρ(TN)和ρ(COD_Mn)显著相关,说明水质对异味物质含量有重要影响.      

上海市饮用水中痕量土臭素和二甲基异冰片年变化规律及来源研究

采用液液微萃取-气相色谱/质谱联用测定饮用水中痕量异嗅物质--土臭素(geosmin,GSM)和二甲基异冰片(2-Methylisoborneol,2-MIB或MIB).对上海市饮用水水源以及某水厂工艺出水进行调查发现,土霉昧的来源主要为2-MIB,异嗅问题暴发季节为7～10月,7、8月份达到顶峰,原水中2-MIB的最高检出浓度可达152.82 ng/L.水厂出水中最高检出浓度为97.94 ng/L.初步的来源分析推断2-MIB为水中颤藻的代谢产物.     

有机物分子结构与味觉的关系研究

水是人们生活中不可或缺的重要物质,随着人民生活水平的不断提高,对饮用水水质的要求越来越高。而饮用水水源的污染却日益加重,给水处理工作带来了较大困难。饮用水的嗅和味源自水中某些物质,直接影响水的可饮性,产生嗅和味的某些合成化合物,有害人体健康。因此,如何有效地减少饮用水中的嗅和味,是水处理工作不可忽视的一个方面,而了解产生嗅味的物质组成及其产生的过程,对有效地去除和减少饮用水中的嗅味有很重要的指导意义,文章就二者的关系进行了初步的研究和探讨。     

臭氧-接种生物滤池组合工艺去除饮用水中典型致嗅物质

通过在生物滤池表面接种MIB(2-甲基异茨醇)及geosmin(土臭素)降解菌,增强生物滤池的作用,并探讨臭氧-生物滤池组合工艺对MIB和geosmin的处理效果. 结果表明:单独接种生物滤池可使ρ(MIB)和ρ(geosmin)从初始的500ng/L分别降至125和112ng/L,MIB和geosmin的去除效果先随EBCT(空床停留时间)的延长而显著增加,但当EBCT大于20min后无明显变化;随着滤料深度的增加,滤池生物量逐渐降低,对污染物的去除率增加缓慢.在接种生物滤池前增加臭氧单元,当EBCT为20min、臭氧投加量为2mg/L时,臭氧-接种生物滤池组合工艺可去除84%的MIB和94%的geosmin,其中接种生物滤池单元中生物量随滤池深度的增加呈先增后减的趋势,滤料深度为100~200mm时,单位高度滤料的去除率最高. 采用臭氧-接种生物滤池组合工艺可有效去除水中的MIB和geosmin.      

γ-Al2Ｏ3催化臭氧氧化水中嗅味物质MIB效能研究

以γ- Al₂Ｏ₃粉末为催化剂,研究了催化臭氧氧化去除水体中典型嗅味物质2-甲基异茨醇（MIB）的效能及相关影响因素.研究表明,γ- Al₂Ｏ₃在蒸馏水和自来水本底中,均表现出显著的催化活性.在蒸馏水本底条件下,催化氧化可提高MIB去除率47个百分点;而在自来水本底条件下,可提高MIB去除率40个百分点以上.臭氧浓度、催化剂投加量和MIB的初始浓度对催化氧化过程具有明显的影响作用.水的硬度对γ- Al₂Ｏ₃催化臭氧氧化MIB影响不大,但水中无机阴离子对催化效果影响显著.天然水体中的重碳酸盐/碳酸盐碱度可以抑制催化臭氧氧化过程中产生的羟基自由基,对γ- Al₂Ｏ₃催化臭氧氧化MIB起到了抑制作用.低浓度的腐殖酸能够促进催化氧化过程,而高浓度时则有抑制作用.通过pH值对催化氧化MIB的影响和叔丁醇对催化氧化的抑制作用,间接地证明γ- Al₂Ｏ₃催化氧化MIB的作用机理是以羟基自由基为主的间接氧化过程.     

冬季水库水源中MIB和土嗅素的产生与降解机理

2-甲基异冰片(MIB) 和土嗅素(geosmin)由放线菌,真菌和蓝绿藻代谢产生,这两种物质是目前造成饮用水具有霉味和土味的主要原因.以包头市画匠水库为研究对象,运用推流式反应器基本模型和OriginPro 9.0线性拟合法,分析冬季水源水库水中MIB和土嗅素净产率与损失率;运用双膜理论计算嗅味物质挥发速率常数.结果表明,冬季画匠水库0.55m冰层下,透射光照强度(Surface PAR)为70 ~ 636W/m2,平均光照强度为114.8W/m2,存在合适藻类代谢产生异味物质的光照条件.封冻前后,水库水中MIB和土嗅素浓度逐渐增高,并以60~102ng/L的较高浓度水平维持到来年解冻,此后二者浓度逐渐降低到较低水平,呈规律性变化.曲线拟合结果显示,冬季画匠水库水中MIB/土嗅素的产生与减少均符合准一级反应动力学模型(R2为0.941~0.989).由于低温与冰层阻碍等原因,影响水库中MIB/土嗅素的损失主要因素是出流携带;冰层融化后,挥发和出流携带是MIB/土嗅素减少的主要原因.MIB和土嗅素冬季产生速率常数为4.119, 2.146ng/(L×d),水流携带损失速率常数为0.032d-1.冰层融化后,MIB产生速率为1.012ng/(L×d),损失速率为0.072d-1,藻细胞产率4.57×10-8ng/(L×d×cell);土嗅素产生速率常数为1.638ng/(L×d),损失速率为0.083d-1,藻细胞产率5.46×10-8ng/(L×d×cell).     

Simultaneous determination of ten taste and odor compounds in drinking water by solid-phase microextraction combined with gas chromatography-mass spectrometry

Taste and odor （T＆O） problems in drinking water frequently occur because of many compounds present in the water, of which trans-1,10-dimethyl-trans-9-decalol （geosrnin） and 2-methylisoborneol （MIB） are well-known. In this study, a fast and effective method was established for simultaneous determination of 10 T＆O compounds, including geosmin, MIB, 2,4,6-trichloroanisole （TCA）, 2-methylbenzofuran, 2-isopropyl-3-methoxypyrazine （IPMP）, 2-isobutyl-3-methoxypyrazine （IBMP）, cis-3-hexenyl acetate, trans,trans-2,4-heptadienal, trans, cis-2,6-nonadienal, and trans-2-decenal in water samples by headspace solid-phase microextraction （SPME） coupled with gas chromatography-mass spectrometry. An orthogonal array experimental design was used to optimize the effects of SPME fiber, extraction temperature, stirring rate, NaC1 content, extraction time, and desorption time. The limits of detection ranged from 0.1 to 73 ng/L were lower than or close to the odor threshold concentrations （OTCs）. All the 10 T＆O compounds were detected in the 14 water samples including surface water, treatment process water and tap water, taken from a waterworks in Lianyungang City, China. MIB and geosmin were detected in most samples at low concentration. Six T＆O compounds （IPMP, IBMP, trans,cis-2,6-nonadienal, 2-methylbenzofuran, trans-2-decenal, and TCA） were effectively decreased in water treatment process （sedimentation and filtration） that is different from cis-3-hexenyl acetate, MIB and geosmin. It is noted that the TCA concentrations at 15.9-122.3 ng/L and the trans,cis-2,6-nonadienal concentrations at 79.9-190.1 ng/L were over 10 times higher than their OTCs in tap water. The variation of the analytes in the all water samples, especially distribution system indicated that distribution system cannot be ignored as a T＆O compounds source.     

反渗透膜在分散型农村饮用水深度处理中开发应用研究

以反渗透膜为主,综合集成超滤、微滤、砂滤、活性碳吸附、紫外线消毒等技术措施．设计安装了适合农村自来水、井水、河水不同饮用水源深度净化处理的3套设备。运行结果表明,设备对于饮用水源中的有机物、微生物、色味臭,以及自来水中的余氯,处理效果非常明显。研究成果为解决分散型农村安全饮用水问题．提供了比较好的技术方案。     

我国部分商品瓶装饮用水中挥发性有机物的研究

应用Tekmar3000吹扫捕集-气相色谱质谱组合分析仪,参照USEPA的标准分析方法,对我国某些商品瓶装饮用水中挥发性有机物进行了定量分析,结果表明,其含量一般在1～8μg/L,其中普遍含有具三致潜力的卤代烃与苯系物。虽然这些毒理性指标均可达到我国瓶装饮用纯净水卫生标准,但与国外优质瓶装饮用水相比,存在明显的差距。瓶装饮用水中挥发性有机物主要与深度处理技术和组合工艺有关,可通过改进这些技术而得以有效控制。      

厌氧-混凝-高级氧化对转运站污水恶臭处理效果

以总还原硫(TRS)为考察指标,分析了基于厌氧-混凝-高级氧化工艺的中试系统各处理单元对转运站污水中恶臭物质的处理效果。转运站污水中,TRS总量为0.602 mg/L水,而经过厌氧、混凝、高级氧化等处理单元后依次为4.167,3.513,0.168 mg/L水。厌氧对含硫有机物的降解是恶臭物质产生的重要过程,混凝过程对污水恶臭去除作用很小。相比于混凝出水,高级氧化对恶臭物质去除率在95%以上。     

氯灭活地下水源中3种优势真菌的效能与机制

地下水源中真菌大量繁殖会产生嗅味,引发毒性反应以及产生大量肉眼可见的絮状物,严重影响供水水质.以地下水源中3种优势真菌木霉属、青霉属、枝孢属为研究对象,以氯为消毒剂,通过研究真菌孢子胞内物质泄漏,胞外三磷酸腺苷(ATP),脱氧核糖核酸(DNA)和蛋白质增加及孢子形态变化,探明了氯灭活3种真菌孢子的效能与机制.结果表明,氯灭活真菌孢子符合一级动力学,满足Chick模型,3种真菌的耐氯性为:木霉属青霉属枝孢属,真菌孢子尺寸越大,亲水性越强,灭活效果越好.氯灭活后,胞内物质泄漏,胞外特征物质(ATP、DNA、蛋白质)显著增加;氯对细胞表面破坏严重,灭活后真菌孢子凹陷,表面褶皱.综上所述,氯首先作用于孢子表面,降低孢子的可培养性,进一步作用使细胞的通透性屏障受损,导致胞内特征物质释放,以致孢子死亡.     

密云水库微生物相变化对水质及嗅味的影响

研究北京市地表水源密云水库微生物相变化对水质及嗅味的影响.结果表明:密云水库细菌密度和种类相对稳定,对水质影响较小.2005—2006年,平均细菌密度约300 mL－1,多为革兰氏阴性菌,放线菌与霉菌较少.密云水库藻类生长与水质嗅味呈正相关性.年平均浮游微藻密度为655×104 L－1,全年有2个藻类生长高峰期,即9月和5月,藻密度分别为1　665×104和988×104 L－1.高峰期,水库中出现大量蓝绿藻(如颤藻、鱼腥藻、微囊藻等)以及颗粒直链藻,直接导致水体嗅味.2005—2006年,密云水库有机碳含量明显增加,总氮、总磷含量变化不大.      

Identification of odorous compounds in reclaimed water using FPA combined with sensory GC-MS

Odorous compounds in the influent of a reclaimed water treatment plant (RWTP), consisting of coagulation, sedimentation, continuous micro-filtration (CMF), and chlorination in succession, in a north China city, were identified by combining flavor profile analysis (FPA) with sensory gas chromatograph-mass spectrometry (GC-MS). The sewery/swampy/septic odor with an odor intensity of 6.4 was found to be the major odor group in the RWTP influent, and the existence of well-known odorant including dimethyl disulfide, dimethyl trisulfide, indole and skatole were confirmed using GC-MS. The result of a spiking test showed that the intensity (3.6) of the sewery/swampy/septic odor caused by these four chemicals contributed to over 50% of the odor intensity of the influent. The FPA intensity for sewery/swampy/septic odor in the RWTP effluent was 3.8, showing that the treatment process was not efficient for the removal of odorants, particularly indole and skatole.