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.     

武汉市饮用水中阿特拉津及降解产物浓度特征

为了解武汉市政水厂水源水和出厂水中阿特拉津及降解产物的浓度水平和去除率,该文采用超高效液相色谱-串联质谱法,对10家市政水厂在丰水期和枯水期采集的水源水和出厂水中的阿特拉津及降解产物进行检测,检测物质分别为阿特拉津(ATZ)、异丙基阿特拉津（DIA）、二丁基阿特拉津(DEA)、二氨基氯代阿特拉津（DACT）和羟基阿特拉津(OH-ATZ)。研究结果显示,水源水中ATZ的浓度中位数是37.2 ng/L,降解产物浓度依次为DEA(5.88 ng/L)、OH-ATZ(5.07 ng/L)、DIA(3.12 ng/L)和DACT(1.26 ng/L),阿特拉津及降解产物在汉江水中的含量是长江水的3～5倍。水源水和出厂水中DIA和DEA在丰水期7月浓度较高,而DACT在枯水期5月浓度较高。经过常规水处理工艺流程后,ATZ几乎未被去除,DIA和DACT出现去除率负增长,建议在常规水处理工艺中增加颗粒活性炭和臭氧等工艺,以降低饮用水中阿特拉津及降解产物的浓度。     

洪季珠江三角洲水系烷基酚污染状况研究

对夏季珠江三角洲河流及珠江口表层水中溶解态的壬基酚(NPs)和辛基酚(OP)的污染状况进行了分析.结果表明,河流样品中除珠江正干平洲水道口、沙湾水道口及西江虎跳门处NPs值较高分别达98.84、129.82和164.98 ng/L外,其他地点均为<20～40ng/L;伶仃洋及近海表层水NPs含量较低为<10～14ng/L.OP值以澳门内港处最高为8.54ng/L,另外在白鹅潭、沙湾水道口和虎跳门处分别为2.89、2.44、2.12ng/L,其余采样点均低于检测限2ng/L,伶仃洋及近海表层水样OP值低于检测限1ng/L.     

ABR—SBR工艺处理中成药制药废水

将厌氧折流板反应器一序批式活性污泥法(ABR-SBR)应用于中成药废水处理工程中.运行结果表明,在进水质量农度CODGr为438～2 300 mg/L,BOD5为310-824 mg/L,SS为86～229 mg/L和色度为50～220倍时,处理后出水可达到GB 21906-2008<中药类制药工业水污染物排放标准>要求,该工艺操作简便、抗冲击负荷能力强、运行费用低.     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

umu试验研究饮用水氯和氯胺消毒过程中遗传毒性的变化以及消毒条件的影响

采用umu遗传毒性测试方法考察了消毒剂投加量、反应时间和消毒剂氯氮比对某饮用水厂臭氧-生物活性炭出水加氯或氯胺消毒前后遗传毒性的影响.结果表明,炭后水具有一定的遗传毒性(20～70 ng/L),加氯或氯胺消毒后遗传毒性增加.反应时间为24 h,在相同投加量下氯消毒遗传毒性(40～95 ng/L)高于氯胺消毒遗传毒性(20～40 ng/L);当氯初始投加量从0 mg/L增加到10 mg/L时,炭后水的遗传毒性先迅速增加,在0.5～1 mg左右达到极大值,然后再降低,在3～5 mg左右达到极小值后缓慢上升,但是氯胺消毒后水样遗传毒性变化规律不如氯消毒的明显.当投加量为3 mg/L时,随着反应时间从0 h延长至72 h,无论是氯消毒还是氯胺消毒,炭后水遗传毒性均是先迅速增加,在2 h时达到极大值后再下降,在18 h左右达到极小值然后缓慢上升,而且任意反应时间内,氯胺消毒的遗传毒性(20～62 ng/L)均小于氯消毒(83～120 ng/L).本试验还研究了消毒剂氯氮比对炭后水氯消毒后遗传毒性的影响.在本试验条件下,从遗传毒性的角度看,对于饮用水消毒氯胺比氯更安全,而且2种消毒方式的遗传毒性的变化规律均不同于总HAAs的变化规律.     

广州污水厂磺胺和喹诺酮抗生素污染特征研究

采用固相萃取(SPE)-高效液相色谱(HPLC)法分析了广州市3个污水处理厂进出水中磺胺类和喹诺酮类抗生素共10种化合物的含量特征,并探讨其去除效果和环境排放量。结果表明,进水和出水中磺胺类抗生素总含量分别为3591.9～7782.5ng/L和2216.6～3591.9ng/L,喹诺酮类抗生素总含量分别为1539.4～2700.2ng/L和1284.4～5080.1ng/L。单个化合物的检出率在37.5%～97.5%,其中磺胺类抗生素以SMT、SM2和SM1为主,喹诺酮类抗生素以CIP和LOM为主。磺胺类和喹诺酮类抗生素的最高去除率分别为69.2%和27.2%,环境排放量分别为487.7～1512.3g/d和329.3～1117.6g/d。     

罗时江中5种环境内分泌干扰物的分布特征

以典型的农业面源污染河流——大理洱海罗时江作为研究对象,采用固相萃取、超声萃取和气相色谱质谱联用技术,对河流水体和表层沉积物样品中5种EDCs〔环境内分泌干扰物,包括BPA(双酚A)、E1(雌酮)、E2(17β-雌二醇)、EE2(乙炔基雌二醇)和E3(雌三醇)〕进行分析测定.结果表明,罗时江水体中普遍存在EDCs,其中ρ(BPA)为1.01～43.64 ng/L,ρ(E1)为2.54～20.53 ng/L,ρ(E2)为nd～23.18 ng/L,ρ(EE2)为1.16～13.74 ng/L,ρ(E3)为nd～26.55 ng/L.各采样点EDCs污染通量结果显示,右所、邓川2个乡镇对EDCs污染贡献量最为显著,之后由于湿地截留以及河流的自净作用EDCs污染通量有所削减.罗时江对洱海的入湖EDCs贡献量为1.35～3.70μg/s.在城镇下游处沉积物中E1和E3的富集倍数均为各采样点中最高,这与河流水体中的污染通量变化趋势一致,进一步说明该处污染负荷的加剧,并且说明EDCs会在污染发生时于下游就近沉积.沉积物中w(E3)最高(1.48～28.44μg/kg),其次为w(E1)(0.36～2.95μg/kg),E2因迅速降解不易富集.      

水解酸化-UBF-接触氧化组合工艺处理聚醚生产污水工程实践

介绍了水解酸化-UBF-接触氧化组合工艺处理聚醚多元醇生产污水的工艺设计和运行效果。经一段时间的调试及运行表明:该工艺处理聚醚多元醇生产综合污水是切实可行的。在进水ρ(COD)为8000～12000mg/L,ρ(BOD5)为1200～1500mg/L的条件下,经过该工艺处理,出水ρ(COD)为250～300mg/L,ρ(BOD5)在50～80mg/L以下,出水水质达GB8978-1996《污水综合排放标准》Ⅲ级。     

大亚湾海域多氯联苯及有机氯农药研究

1999年 8月 4日采集了大亚湾次表层水、悬浮颗粒物和表层沉积物并用气相色谱 (电子捕集检测器 )分析了其中 12个多氯联苯 (PCBs)和 18个有机氯农药样品。总PCBs含量 ,水体中介于 91.1～ 135 5 .3ng/L ,沉积物中为 (0 .85～ 2 7.37)× 10 -9;总HCHs含量水体中介于 35 .5～ 12 2 8.6ng/L ,沉积物中则为 (0 .32～ 4 .16 )×10 -9;总DDTs含量在水体中介于 2 6 .8～ 975 .9ng/L ,沉积物中为 (0 .14～ 2 0 .2 7)× 10 -9;而在悬浮颗粒物中均未检出。水体和沉积物中DDT/(DDE DDD)比值较大 ,表明近期仍有此类化学物质输入大亚湾海域。本研究为大亚湾养殖海区提供难降解有机污染物的现状资料。     

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.      

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.     

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.      

Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS)and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS)

Two sample preparation methods were introduced and compared in this paper to establish a simple, quick and exact analysis of geosmin and 2-methylisoborneol. LC-18 column was employed in solid phase extraction (SPE), 1.0 mL of hexane was adopted in liquid-liquid extraction (LLE), and the extracts were analyzed by gas chromatograph mass spectrum (GCMS) in selected ion mode. Mean recoveries of SPE were low for 2-methylisoborneol (2-MIB) and geosmin (GSM) with values below 50%. For LLE, the recoveries were satisfyingly above 50% for 2-MIB and 80% for GSM. Detection limits of the LLE method were as low as 1.0 ng/L for GSM and 5.0 ng/L for 2-MIB. A year-long investigation on odor chemicals of drinking water in Shanghai demonstrated that in the summer, there was a serious odor problem induced by a high concentration of 2-MIB. The highest concentration of 152.82 ng/L appeared in July in raw water, while GSM flocculation was minimal with concentrations below odor threshold.     

Biodegradation of geosmin in drinking water by novel bacteria isolated from biologically active carbon

Three strains of Gram-negative bacteria capable of removing geosmin from drinking water were isolated from biologically active carbon and identified to be Chryseobacterium sp., Sinorhizobium sp. and Stenotrophomonas sp. based on physio-biochemistry analysis and 16S rRNA gene sequence analysis. Removal e ciencies of 2 mg/L geosmin in mineral salts medium were 84.0%, 80.2% and 74.4% for Chryseobacterium sp., Sinorhizobium sp. and Stenotrophomonas sp., respectively, while removal e ciencies of 560 ng/L geosmin in filter influent were 84.8%, 82.3% and 82.5%, respectively. The biodegradation of geosmin was determined to be a pseudo first-order reaction, with rate constants at 2 mg/L and 560 ng/L being 0.097 and 0.086 day??1, 0.089 and 0.084 day??1, 0.074 and 0.098 day??1 for the above mentioned degraders, respectively. The biomass of culture in the presence of geosmin was much higher than that in the absence of geosmin.     

密云水库水的预氧化研究

针对北京密云水库水的水质特征,分别进行了实验室预氧化实验和现场中试研究。室内预氧化实验结果表明,预臭氧化对水中UV254的去除率明显高于高锰酸钾和次氯酸钠,并且还能有效降低原水中的THMFP。在1.0 mg/L臭氧剂量时,嗅味物质MIB的浓度从98.0 ng/L降为73.0 ng/L,去除率为26.0%。中试试验结果表明,预臭氧化工艺与常规工艺的THMFP的去除率分别是25.6%和14.9%,预臭氧化能大幅度杀灭大肠杆菌,去除率高达94%,并能够显著降低砂滤出水颗粒数,从而减少砂滤出水微生物、病原体出现的几率,对改善水质有积极影响。     

Treatment of taste and odor causing compounds 2-methyl isoborneol and geosmin in drinking water: A critical review

Problems due to the taste and odor in drinking water are common in treatment facilities around the world. Taste and odor are perceived by the public as the primary indicators of the safely and acceptability of drinking water and are mainly caused by the presence of two semi-volatile compounds – 2-methyl isoborneol (MIB) and geosmin. A review of these two taste and odor causing compounds in drinking water is presented. The sources for the formation of these compounds in water are discussed alongwith the health and regulatory implications. The recent developments in the analysis of MIB/geosmin in water which have allowed for rapid measurements in the nanogram per liter concentrations are also discussed. This review focuses on the relevant treatment alternatives, that are described in detail with emphasis on their respective advantages and problems associated with their implementation in a fullscale facility. Conventional treatment processes in water treatment plants, such as coagulation, sedimentation and chlorination have been found to be ine ective for removal of MIB/geosmin. Studies have shown powdered activated carbon, ozonation and biofiltration to be e ective in treatment of these two compounds. Although some of these technologies are more e ective and show more promise than the others, much work remains to be done to optimize these technologies so that they can be retrofitted or installed with minimal impact on the overall operation and e ectiveness of the treatment system.     

Interference of iron as a coagulant on MIB removal by powdered activated carbon adsorption for low turbidity waters

Powered activated carbon (PAC) is widely used in water treatment plants to minimize odors in drinking water. This study investigated the removal of 2-methylisoborneol (MIB) by PAC adsorption, combined with coagulation using iron as a coagulant. The adsorption and coagulation process were studied through different case scenarios of jar tests. The analysis evaluated the effect of PAC dosing in the liquid phase immediately before or after the coagulant addition. Ferric sulphate was used as the coagulant with dosages from 10 to 30 mg/L, and PAC dosages varied from 10 to 40 mg/L. The highest MIB removal efficiency (about 70%) was achieved without the coagulant addition and with the highest PAC dosage (40 mg/L). Lower MIB removal efficiencies were observed in the presence of coagulant, showing a clear interference of the iron precipitate or coagulant in the adsorption process. The degree of interference of the coagulation process in the MIB removal was proportional to the ratio of ferric hydroxide mass to the PAC mass. For both cases of PAC dosing, upstream and downstream of the coagulant injection point, the MIB removal efficiency was similar. However, MIB removal efficiency was 15% lower when compared with experiments without the coagulant application. This interference in the MIB adsorption occurs potentially because the coagulant coats the surface of the carbon and interferes with the MIB coming in contact with the carbon’s surface and pores. This constraint requires an increase of the PAC dosage to provide the same efficiency observed without coagulation.     

臭氧氧化分解饮用水中嗅味物质2-甲基异莰醇

比较了几种常见氧化剂对饮用水中嗅味物质2-甲基异莰醇(2-methylisoborneol,MIB)的氧化去除效果.结果表明,KMnO₄、NaClO、H₂O₂等氧化剂的氧化作用对水中MIB的去除效果均较差,而臭氧却能有效地将其氧化;考察了pH对臭氧化去除MIB的影响规律,发现pH在7.0～10.0条件下,随着pH值增加MIB去除率增加,但当pH达到10.0左右时,MIB的去除率反而下降;MIB的臭氧化去除效果随着自由基捕获剂(重碳酸盐和叔丁醇)的浓度增加而明显地降低,说明臭氧化去除水中MIB主要遵循自由基作用机理;以松花江江水为本底进行试验和与蒸馏水进行试验的结果相差不大,原因可能是由于松花江水体中碳酸盐浓度较低(小于50 mg/L),对自由基捕获能力较小,同时江水中的部分腐殖质(NOM)对臭氧去除MIB的过程起到了促进作用.