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.     

超声活化过硫酸盐降解水中典型嗅味

为有效解决饮用水嗅味污染问题,选取水中典型致嗅物质二甲基异莰醇（2-MIB）和土臭素（GSM）作为目标污染物,系统研究了超声（US）活化过硫酸盐（PS）高级氧化技术对两种致嗅物质的降解规律及其影响因素.结果表明,在15 min内超声/过硫酸盐联用工艺能有效去除水中典型嗅味,与单独超声处理相比,2-MIB和GSM的去除率分别可提高57.0%和63.6%;2-MIB与GSM浓度在100~800 ng·L^-1范围内US/PS联用工艺均有较高的去除率,且在100 ng·L^-1时降解效果最佳,去除率分别可达88.7%和93.3%;典型致嗅物质的降解速率随PS浓度（0.25~2mmol·L^-1）和US声强（0.33~0.53 W·cm^-2）的增加而加快;水体中腐殖酸存在会竞争消耗自由基使嗅味降解受到抑制但影响效果不显著;在反应体系中分别加入甲醇与叔丁醇（自由基清除剂）后,2-MIB与GSM去除率明显下降,且甲醇对嗅味降解抑制程度强于叔丁醇,表明US/PS高级氧化技术对嗅味快速的降解主要是硫酸根自由基与羟基自由基共同作用的结果.     

Optimization of enrichment processes of pentachlorophenol (PCP) from water samples

The method of enriching PCP( pentachlorophenol ) from aquatic environment by solid phase extraction (SPE) was studied.Several factors affecting the recoveries of PCP, including sample pH, eluting solvent, eluting volume and flow rate of water sample, were optimized by orthogonal array design(OAD). The optimized results were sample pH 4; eluting solvent, 100% methanol; eluting solvent volume, 2 ml and flow rate of water sample, 4 ml/min. A comparison is made between SPE and liquid-liquid extraction(LLE) method. The recoveries of PCP were in the range of 87.6%-133.6% and 79%-120.3% for SPE and LLE, respectively. Important advantages of the SPE compared with the LLE include the short extraction time and reduced consumption of organic solvents. SPE can replace LLE for isolating and concentrating PCP from water samples.     

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).     

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.     

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...     

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.     

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.     

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.      

真空紫外/氯处理饮用水典型致嗅物质

为有效去除常规水处理工艺难以去除的典型致嗅物质二甲基异莰醇（2-MIB）和土臭素（GSM）,采用真空紫外/氯高级氧化技术,探讨该技术降解致嗅物质的效能,研究在不同紫外光强、氯浓度、pH、重碳酸盐浓度、腐殖酸浓度条件下致嗅物质的降解效果,分析羟基自由基在致嗅物质降解中起到的作用,目标物浓度采用吹扫捕集-气质联用法（GC/MS）测定.结果表明,真空紫外/氯高级氧化技术可以有效去除饮用水典型致嗅物质,相比紫外/氯高级氧化技术而言,在30 min内2-MIB和GSM的去除率分别提高15%和8%;随着氯浓度和紫外光强度的增加,致嗅物质的降解速率加快;在弱酸性条件下,致嗅物质的去除效果明显,在pH为5时,2-MIB和GSM的去除率在反应10 min后分别可以达到95%和96%;水体中重碳酸盐和腐殖酸的存在,竞争消耗反应体系中的自由基,对致嗅物质的降解起到抑制作用;在反应体系中投加1 mmol·L^-1羟基自由基抑制剂叔丁醇后,2-MIB和GSM的去除率下降明显,分别下降40%和31%,表明羟基自由基在致嗅物质的去除中起到主要作用.     

SPE-GC-MS/SIM测定水节霉发生地河水中半挥发性有机物

为测定水节霉发生地河水中ρ(SVOCs)(SVOCs为半挥发性有机物),比较了LLE(液液萃取)和SPE(固相萃取)前处理法提取加标空白水样中ρ(SVOCs)的GC-MS/SIM测定结果,确定并采用重现性好的SPE-GC-MS/SIM法测定了水节霉发生地河水中的ρ(SVOCs). 结果表明,LLE和SPE法对SVOCs的加标回收率分别为41.8%~121.5%和31.5%~124.4%,相对标准偏差分别为6.0%~18.0%和0.9%~14.5%,二者回收率相差不大,但SPE法的相对标准偏差小于LLE法,SPE法重现性较好,因此采用SPE-GC-MS/SIM法测定2011年2月水节霉发生地河水中的ρ(SVOCs),共检出29种SVOCs,其中ρ(邻苯二甲酸二乙酯)、ρ(∑PAHs)、ρ(硝基苯)、ρ(1,2-二氯苯)和ρ(1,4-二氯苯)分别为1 020.59、532.14、43.39、38.52和19.57 ng/L,均未超出GB 5749—2006《生活饮用水卫生标准》相关限值,表明水节霉发生地未发生SVOCs污染.      

硝酸钙对河流底泥中含硫化合物嗅味原位控制

以硝酸钙作为氧化剂,对深圳河污染底泥典型嗅味物质AVS（酸挥发性硫化物）和GEM（土臭素）及2 MIB（2 甲基异莰醇）进行原位控制. 结果表明,当硝酸钙投加量（以单位质量AVS所需NO3- N质量计）为1.68 g/g,AVS去除率达到92%,且可有效避免硝酸钙向上覆水释放,适合工程应用. 但是,硝酸钙对河流底泥GEM和2 MIB等典型嗅味物质的原位控制效果较差. 硝酸钙能够引起底泥中微生物多样性增加,16S rDNA指纹图谱显示,优势菌株包括去除AVS的脱氮硫杆菌(Thiobacillus thioparus),反硝化细菌(Simplicispira sp.和Rhodanobacter sp).以及降解有机物的菌株(Simplicispira sp.、Lysobacter sp.、Pseudoxanthomonas sp.)等.      

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.     

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.     

GC-ECD测定地表水中的硝基苯类和氯苯类化合物

文章分别以液液萃取法和固相萃取法作为预处理方法,建立了地表水中12种硝基苯类和氯苯类化合物的气相色谱-电子捕获检测器(GC-ECD)分析检测方法,其中包括1,2-二硝基苯、1,3-二硝基苯、1,4-二硝基苯,2-硝基氯苯、3-硝基氯苯、4-硝基氯苯、1,2,3,4-四氯苯、1,2,3,5-四氯苯、1,2,4,5-四氯苯、2,4-二硝基甲苯、2,4-二硝基氯苯、2,4,6-三硝基甲苯。通过对实验条件的优化,对100 mL水样的方法检出限为液液萃取0.05⁰.15μg/L,固相萃取0.100.15μg/L,固相萃取0.10⁰.16μg/L范围内,加标回收率分别为80.7%0.16μg/L范围内,加标回收率分别为80.7%⁸8.0%和74.2%88.0%和74.2%¹01%,相对标准偏差分别在1.8%101%,相对标准偏差分别在1.8%⁵.3%和3.7%5.3%和3.7%⁵.5%之间。应用所建立的方法,对上海市地表水样进行监测分析,12种目标物质仅检出硝基氯苯,浓度为ND5.5%之间。应用所建立的方法,对上海市地表水样进行监测分析,12种目标物质仅检出硝基氯苯,浓度为ND⁰.52μg/L,样品加标回收率为液液萃取72.5%0.52μg/L,样品加标回收率为液液萃取72.5%⁸1.9%,固相萃取67.0%81.9%,固相萃取67.0%⁹1.0%。     

固相萃取和高效液相色谱联用测定污水中的五氯苯酚

采用固相萃取和高效液相色谱相结合的方法对污水中五氯苯酚的含量进行定量检测。结果表明,污水的pH值为4,流速控制在4mL/L以内,C18固相萃取柱对五氯苯酚有良好的吸附保留性能,以2mL的甲醇洗脱,洗脱效率在85%~95%之间。与传统的液液萃取相比,固相萃取的优势在于操作时间缩短、有机溶剂的使用量减少。     

典型城市河流中嗅味物质和微生物菌落特征

对某城市河流沿程水质、典型嗅味物质以及微生物群落结构进行了调查分析. 结果表明:河水中2种嗅味物质〔二甲基异莰醇(2-MIB)和土臭素(Geosmin)〕的质量浓度均受到ρ(DO)的显著影响. 绝对厌氧条件〔ρ(DO)<0.2 mg/L〕水体中,ρ(二甲基异莰醇)和ρ(土臭素)的平均值分别为794.8和269.8 ng/L;好氧条件〔ρ(DO)>2.0 mg/L〕水体中,二者的平均值分别为91.6 和104.7 ng/L;而且ρ(DO)较低时,水体中的可疑致病菌含量升高,微生物安全性降低. 控制该河流水体ρ(DO)在2.0 mg/L以上,有利于抑制水体中嗅味物质的产生,可提高河流水体的微生物安全性.      

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.      

液相色谱质谱法测定水体及土壤中的类固醇激素

建立了水体和土壤中类固醇激素的液相色谱质谱分析方法。水样采用固相萃取方法富集,土壤样经加速溶剂萃取后由固相萃取净化和富集。处理好的样品经丹磺酰衍生化后上仪器分析。结果表明,类固醇激素在水体和土壤中的检出限分别为0.01~0.6ng/L和0.01~0.19ng/g,回收率分别为77%~97%和62%~119%,RSD小于6.04%和15.5%。该方法具有较高的准确度和精密度,适用于环境水体及土壤中类固醇激素残留的分析。