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.     

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).     

上海某黄浦江原水供水系统中主要致嗅物质的迁移规律分析

采用顶空固相微萃取-气相色谱质谱联用研究了上海市某黄浦江水源供水系统中2-甲基异莰醇(M1B)、土味素(GSM)和余氯的迁移变化规律.结果表明,黄浦江源水及其各级净水工艺处理水、管网水和二次供水系统末端水中均含有MIB和GSM,分别在2～18 ng/L和2.68～5.06 ng/L之间;其浓度经水厂各级工艺处理后明显下...     

Characterization of typical taste and odor compounds formed by Microcystis aeruginosa

Production and characteristics of typical taste and odor (T&O) compounds by Microcystis aeruginosa were investigated. A few terpenoid chemicals, including 2-MIB, β-cyclocitral, and β-ionone, and a few sulfur compounds, such as dimethyl sulfide and dimethyl trisulfide, were detected. β-Cyclocitral and β-carotene concentrations were observed to be relevant to the growth phases of Microcystis. During the stable growth phase, 41-865 fg/cell of β-cyclocitral were found in the laboratory culture. β-Cyclocitral concentrations correlated closely with β-carotene concentrations, with the correlation coefficient R2 = 0.96, as it is formed from the cleavage reaction of β-carotene. For dead cell cases, a high concentration of dimethyl trisulfide was detected at 3.48-6.37 fg/cell. Four T&O compounds, including β-cyclocitral, β-ionone, heptanal and dimethyl trisulfide, were tested and found to be able to inhibit and damage Microcystis cells to varying degrees. Among these chemicals, β-cyclocitral has the strongest ability to quickly rupture cells.     

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.      

不同营养源条件下螺旋鱼腥藻生长与产嗅特征研究

蓝藻次生代谢产物所导致的嗅味问题已成为饮用水的主要水质问题之一,然而不同种属蓝藻的产嗅特征往往差别明显.本研究将从洋河水库中分离得到的可高产土臭素（geosmin）的螺旋鱼腥藻（Anabaena sp.）进行扩大化培养,通过测定不同营养源条件下的生物量及土臭素等各项指标的变化,探讨了不同营养盐条件对该螺旋鱼腥藻生长及产...     

江苏水源地型水库异味物质发生风险及影响因素

为认知水源地型水库异味发生风险及其规律,本研究于异味风险高危期(夏季),对江苏17个省级水源地型水库开展了水质、浮游生物和异味物质状况调查.结果表明,本次调查的17个水库普遍存在富营养化程度偏高(如藻类生物量偏大和水体透明度偏低)的问题,约三分之一的水库出现部分水层异味物质2-甲基异莰醇(MIB)浓度超标,MIB平均浓度为(13. 7±20. 7) ng·L-1,表明江苏省水库型水源地普遍存在MIB风险;多个水库检出土臭素(GSM),但其浓度均没有超过10ng·L-1的饮用水标准浓度(最大浓度为4. 6 ng·L-1);同步水质调查及统计分析表明,MIB浓度和水体叶绿素a浓度、水体透明度、悬浮颗粒物浓度、富营养化指数等重要水质指标及浮游植物生物量(特别是蓝藻生物量)相关性显著(P 0. 05),其中MIB与叶绿素a、富营养化指数呈极显著的相关关系(P 0. 01).因此,水源地型水库的异味物质风险与水库的富营养化密切相关;实施营养盐外源输入削减、提高流域植被覆盖度、科学调控渔业养殖规模等水体富营养化控制措施是水库异味物质控制的关键.     

典型血吸虫病疫区表层水中酚类化合物的污染特征及潜在风险

为研究典型血吸虫病疫区酚类化合物的污染现状,通过采集枯水期松澧洪道、藕池河下游和沱江这3条河的南县段27个表层水样,采用高灵敏的GC-MS/MS技术对水样中14种酚类化合物进行分析,结果表明松澧洪道、藕池河下游和沱江表层水样中Σ酚类的浓度分别为878.05、148.36和594.49 ng.L-1.松澧洪道水样中Σ氯代酚的浓度为203.03 ng.L-1,Σ非氯代酚的浓度为97.21 ng.L-1,在这3条河流水样中都是最高的;t-检验的结果显示3条河流水样中的Σ氯代酚之间以及Σ非氯代酚之间都不存在显著性差异(P>0.05).五氯酚、2-硝基酚、2,6-二氯酚和苯酚是松澧洪道水样中主要的污染物,分别占这条河流总酚类污染物质量分数的27%、54%、4.4%和1%;2-硝基酚和2,6-二氯酚是藕池河下游与沱江水样中主要的污染物,这2类污染物分别占藕池河下游水样中总酚类污染物质量分数的61%和4.3%,占沱江水样中总酚类污染物质量分数的30%和2%.研究结果中五氯酚的检出浓度与文献报道的国内血吸虫病疫区水样中的浓度相比较,表明该研究区水样中五氯酚的浓度处于各疫区的中等污染水平,说明因五氯酚及其降解产物的污染会给当地水环境带来潜在风险.     

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.     

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.     

Products and mechanisms of the reactions of the nitrate radical (NO3) with isoprene, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene in air

Products and mechanisms of the reaction of NO₃ with isoprene have been studied under simulated atmospheric conditions with in situ FTIR spectroscopy as analytical technique. The study addressed also the reactions of NO₃ with 1,3-butadiene and 2,3-dimethyl-1,3-butadiene as well as with the deuterated species 1,1,4,4-d₄-1,3-butadiene, d₆-1,3-butadiene and 4,4-d₂-2-methyl-1,3-butadiene (d₂-isoprene). The dienes examined apparently follow very similar reaction pathways. The decay of the intermediate peroxynitrates formed after the addition of NO₃ to one of the methylene groups, leads to unsaturated ketone-nitrate, aldehyde-nitrate, alcohol-nitrate and perhaps also dinitrate species. The yield of unsubstituted carbonyl compounds was insignificant in the reactions of NO₃ with 1,3-butadiene and isoprene. In the case of isoprene, NO₃ reacts adding preferentially to the 1-position and 3-methyl-4-nitroxy-2-butenal appears to be the main product. 1,3-Butadiene predominantly reacts with NO₃ via trans-1,4-addition and 1,2-addition while the cis-1,4-addition path is of minor importance. trans-4-Nitroxy-2-butenal and 1-nitroxy-3-buten-2-one were found as main products. Contrary to the daytime OH-initiated degradation of isoprene, the nighttime oxidation of isoprene by NO₃ leads to formation of large quantities of organic nitrate compounds; this may have consequences for the tropospheric NO_y budget as briefly discussed.     

枯草芽孢杆菌对土臭素和2-甲基异冰片的降解动力学特性

土臭素(geosmin,GSM)和2-甲基异冰片(2-methylisoborneol,2-MIB)是2种普遍存在于养殖水体中的土腥异味化合物,微生物降解是去除这两种物质的有效途径.本文研究了枯草芽孢杆菌(Bacillus subtilis)降解GSM和2-MIB的动力学特性.结果表明,枯草芽孢杆菌对GSM(1 000~2 000 ng·L-1)和2-MIB(1 000~2 000 ng·L-1)具有较好的降解性能,降解率均达90%以上;枯草芽孢杆菌对这些异味化合物的降解符合伪一级反应动力学,其生物降解速率常数(K)范围为0.14~0.41,降解速率不随GSM和MIB初始浓度的变化而变化;枯草芽孢杆菌对GSM降解的最大比生长速率umax为0.311,Monod常数KS为1.73,而在降解MIB过程中枯草芽孢杆菌的生长不符合Monod方程(R2=0.781).     

三峡库区丰水期表层水中酚类的分布特征及潜在风险

采用GC/MS技术对三峡库区干流及22条支流的47个表层水样中的15种酚类化合物进行分析,结果表明库区干流和支流表层水样中酚类总浓度的几何均值分别为52.47和87.99 ng.L-1.干流和支流中非氯酚类总浓度的几何均值均大于氯酚类,库区表层水以非氯代酚组分为主.苯酚、邻甲酚和2-硝基酚是库区干流水样中主要的酚类,分别占干流Σ酚类的79.1%、3.7%和3.6%.苯酚、邻甲酚、2,6-二氯酚和2-硝基酚是库区支流水样中的优势污染物,分别占支流Σ酚类的77.5%、5.4%、3.8%和2.2%.本研究中苯酚和2-硝基酚的检出浓度与《国家污染物环境健康风险名录》中的标准限值相比较,远低于可能导致生物毒性危害的标准限值,与国内外其他地区水体中苯酚含量相比也处于较低污染水平,说明表层水样中苯酚与2-硝基酚污染给研究区水环境带来的潜在风险较小.     

A fishy odor episode in a north China reservoir：Occurrence, origin, and possible odor causing compounds

A significant outbreak of fishy odor occurred in a reservoir located in Inner Mongolia, China, in the winter of 2011, and the odor rating, algal density and concentrations of some potential odorous compounds were monitored over a period of two months. The peak odor rating of the fishy odor was 7 according to flavor profile analysis. Among the dominant algal species （two diatom and one chrysophyte species） observed during the survey, the chrysophyte Dinobryon sp. was the most abundant species, with the peak density recorded at 88,520 cells/mL. Seven potential algal metabolites including heptanal, 2,4-heptadienal, 2,4-decadienal, nonanal, 2-octenal, 2,6- nonadienal and hexanal were detected. The principal component analysis result showed that n-hexanal, n-heptanal and 2,4-decadienal, possibly the metabolites of diatoms, and 2,4-heptadienal, possibly the metabolite of Dinobryon sp., might have contributed to the fishy odor episode. This study demonstrated that the fishy odor episode in this reservoir might be caused by the abnormal growth of chrysophytes and diatoms under the ice-cover.     

Microcystis aeruginosa/Pseudomonas pseudoalcaligenes interaction effects on off-flavors in algae/bacteria co-culture system under different temperatures

We conducted an experiment to study the interaction effects of Microcystis aeruginosa and Pseudomonas pseudoalcaligenes on off-flavors in an algae/bacteria co-culture system at three temperatures (24, 28 and 32°C). Gas chromatography–mass spectrometry was applied to measure off-flavor compounds dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), 2-methylisoborneol, geosmin (GEO) and β-cyclocitral. During the lag phase of co-cultured M. aeruginosa (first 15 days), P. pseudoalcaligenes significantly increased the production of DMS, DMTS and β-cyclocitral at all three temperatures. In the exponential phase of co-cultured M. aeruginosa (after 15 days), M. aeruginosa became the main factor on off-flavors in the co-culture system, and β-cyclocitral turned to the highest off-flavor compound. These results also indicated that DMS, DMTS and β-cyclocitral were the main off-flavor compounds in our M. aeruginosa/P. pseudoalcaligenes co-culture system. Univariate analysis was applied to investigate the effects of M. aeruginosa and P. pseudoalcaligenes on the production of off-flavors. The results demonstrated that both M. aeruginosa and P. pseudoalcaligenes could increase the production of DMS and DMTS, while β-cyclocitral was mainly determined by M. aeruginosa. Our results also provide some insights into understanding the relationship between cyanobacteria and heterotrophic bacteria.     

凤眼莲对富营养化水体硝化、反硝化脱氮释放N2O的影响

以往有关大型水生漂浮植物消减富营养化水体氮(N)的研究主要侧重于植物对N的吸收效果,而忽略了硝化、反硝化反应途径对水体脱氮的贡献.基于此,本研究中借助具创新性的收集凤眼莲种植水体释放N₂O的装置和方法,通过模拟实验研究了凤眼莲对富营养化水体硝化、反硝化脱氮中间产物N₂O的影响.结果表明,凤眼莲可以促进富营养化水体的硝化、反硝化、成对硝化-反硝化反应过程,在本实验条件下凤眼莲种植水体在整个培养期内释放的N₂O气体浓度累积升高幅度较大,为453~4055 nL·L^-1(未加硝化抑制剂处理),通过释放N₂O而脱除氮素的量占整个水体N消减量的1.36%,为相应未种植凤眼莲水体的4.31倍.种植凤眼莲水体试验期间释放N₂O-N的量与水体氨态氮或硝态氮浓度的变化量均存在显著相关关系(p<0.05),说明N₂O释放量受到水体中NH₄⁺、NO₃^-浓度变化的影响.种植凤眼莲在实验中后期可以增加水体中硝化、反硝化细菌的数量,但其数量远低于凤眼莲根系附着的硝化反硝化细菌.水体中反硝化细菌数量与水体释放N₂O浓度之间并无显著相关性,说明种植凤眼莲水体反硝化脱氮释放N₂O过程可能主要是由根系共生微生物驱动的.     

黄浦江原水中土臭素冬季超标机制研究

基于黄浦江原水中土臭素浓度出现的季节性超标现象,采用高通量测序技术对比分析了夏、冬季微生物群落结构差异,发现夏、冬季水样中微生物群落结构差异显著.土臭素浓度较低的夏季水样中相对丰度较高的微生物为Microcystis、Synechococcus等蓝藻类微生物,其与嗅味物质的合成相关且易于汇集到沉积物内,导致夏季水样与冬季沉积物微生物种群相关;冬季水样中丰度较高的微生物主要为Flavobacterium、Candidatus Pelagibacter、Limnohabitans等水华蓝藻分解微生物,由此推测夏季增殖并汇集于沉积物的水华蓝藻分解是导致原水冬季土臭素超标的主要原因.本研究基于微生物种群结构分析提出了冬季原水中嗅味物质超标的可能机制,为饮用水原水嗅味污染控制提供了理论参考.     

Identification of unknown disinfection byproducts in drinking water produced from Taihu Lake source water

Although disinfection byproducts(DBPs) in drinking water have been suggested as a cancer causing factor, the causative compounds have not yet been clarified. In this study, we used liquid chromatography quadrupole-time-of-flight spectrometry(LC-QTOF MS) to identify the unknown disinfection byproducts(DBPs) in drinking water produced from Taihu Lake source water, which is known as a convergence point for the anthropogenic pollutants discharged from intensive industrial activities in the surroundi...     

卫河新乡市区段春季溶解CH4与N2O浓度特征

对卫河新乡市区段春季CH_4与N_2O浓度进行调查分析,初步探讨了城市河流中典型温室气体的溶存量空间变化及其影响因素.结果表明,受到水中污染物质浓度及人类活动影响,春季卫河表层水中CH_4与N_2O浓度处于超饱和状态,饱和度分别为147.59~2 667.85和4.06~188.25.影响市区内N_2O浓度的主要环境因素为NH~+_4-N(P0.01),而新区污水处理厂排水输入显著提高了N_2O的溶存量,说明污染物类型影响温室气体的产生和积累,NH~+_4-N的硝化过程是城市河流N_2O产生的主要来源.逐步回归分析表明CH_4浓度是NH~+_4-N浓度与水温的相关函数,其中CH_4浓度与NH~+_4-N极显著相关(R2=0.70,P0.01),说明春季卫河中NH~+_4-N浓度是影响卫河春季CH_4溶存的关键因素.此外研究结果显示在NO~-_3-N浓度较低并且NH~+_4-N浓度高时水中CH_4与N_2O浓度具有显著正相关关系,表明有效态氮浓度差异影响CH_4与N_2O产生过程的耦合机制.