SPME-GC/MS/MS法测定水中2-甲基异莰醇和土臭素

研究了固相微萃取-气相色谱/二级质谱联用法测定水中2-甲基异坎醇(2-MIB)和土臭素(GSM)的方法.确定了最佳固相微萃取条件,NaCl加入量3 g,萃取温度60 ℃,搅拌时间30 min,搅拌速度800 r/min.在优化的仪器条件对臭味物质的测定结果显示,此方法灵敏度高,具有良好的精密度和准确度.2-MIB和GSM的相关系数均大于0.999;检出限及RSD分别为0.2 ng/L、0.4 ng/L和5.86%、6.50%;加标回收率分别为100.6%和92.3%.该方法操作简单省时,可满足水中痕量异臭物质的测定.     

Comparison between ozone and ferrate in oxidising geosmin and 2-MIB in water.

Among the chemicals causing taste and odour (T&O) in drinking water, the most commonly identified and problematic ones are geosmin and 2-MIB (2-methylisoborneol). Since the reported odour thresholds of geosmin and 2-MIB are as low as 4 and 8.5 ng/L, respectively, they are not readily removed by conventional water treatment processes. In this study, ozone (O3) and ferrate (Fe(VI)) were applied to oxidise geosmin and 2-MIB. Their performances were compared in terms of removal efficiency of geosmin and 2-MIB. In the case of O3, removal efficiency of geosmin and 2-MIB ozonation at different initial O3 doses, H2O2/O3 ratios and water temperatures were evaluated. The oxidation rates of geosmin and 2-MIB by Fe(VI) were measured within pH 6-8. The effect of H2O2 addition was also evaluated. In summary, O3, especially with H2O2, could almost completely oxidise geosmin and 2-MIB, while Fe(VI) could not oxidise them more than 25% at any pH that was considered in this study. This was attributed to the structure of the organics and high reaction selectivity of Fe(VI). Further study should be conducted to find the reason of inhibition of oxidation by Fe(VI).     

The effect of oxidants on 2-MIB concentration with the presence of cyanobacteria.

In this study, the effect of three oxidants, sodium hypochlorite, potassium permanganate, and ozone, were tested for the removal of 2-MIB with presence of cyanobacteria. Algae in water samples from the source water of Feng-Shen waterworks (FSW), Taiwan were cultivated at 30 degrees C with continuous light at an intensity between 2,500 and 3,400 lux. During the cultivating process, water samples were analyzed for nutrients, light absorbance at 665 nm (A665), and 2-MIB concentration. The 2-MIB concentrations within the incubated samples increased to as high as 1,000 ng/L to 2,000 ng/L, although no extra nutrients were added to the raw water. After 2 to 3 days incubation, the intracellular 2-MIB concentration was as high as 70% of the total 2-MIB in the samples. The algae that developed were mainly cyanobateria, and more than 90% belonged to the Genus Oscillatorias. An almost 100% removal of both 2-MIB and geosmin in the raw water was observed after ozonation for 10 minutes at a dosing rate of 0.91 mg/l-min. Chlorine and permanganate were much less effective, both removing only about 11% of the 2-MIB within 60 minutes at oxidant concentration of 10 mg/l. Oxidation of the cultivated samples showed that chlorine and permanganate may damage algae cells causing them to release intracellular 2-MIB. During the 60 minutes of reaction time, the total 2-MIB concentrations (intracellular plus dissolved) varied by no more than 10%, however, the ratios between dissolved and total 2-MIB concentrations increased. Two effects of ozonation on the 2-MIB concentration in the cultivated samples were observed when the algae were young, namely 2-MIB release from damaged cells and 2-MIB oxidization. The rates of 2-MIB release and 2-MIB destruction were similar. However, old algae cells were more easily damaged. As a result, intracellular 2-MIB was released faster, and the soluble 2-MIB was destroyed more quickly by ozonation.     

混凝-气浮-过滤工艺中粉末活性炭投加效果与投加点研究

对投加粉末活性炭(PAC)预处理黄河原水进行了现场中试研究,确定了PAC适宜的投加位置和投量。结果表明,PAC最佳投加点为混合池,投加PAC使气浮出水浊度提高0.4NTU左右,滤后出水浊度略有升高(<0.1NTU);在絮凝池投加会造成气浮、过滤出水浊度的明显增加;在预氧化前投加PAC较之在混合池投加其有机物去除率略有下降;在混合池投加,当PAC的投加量为10mg/L时,滤后水的CODMn去除率提高15%-20%,可取得满意的结果;滤后水的色、臭和味等指标可完全达到国家饮用水标准的要求。     

金门水厂原水中臭味物质去除的中试研究

金门地区水库富营养化严重影响饮用水水质。夏天藻类所产生的臭味以土霉味为主。土霉味主要来自于藻类代谢物二甲基异冰片和土臭素。利用活性炭处理工艺分别使二甲基异冰片、土臭素及嗅值的去除率达92%、83%及72%;而利用臭氧一生物活性炭工艺则可使二甲基异冰片、土臭素及嗅值的去除率分别达96.3%、100%及96.7%。组合工艺可有效去除臭味物质,但清水池加氯消毒所产生的氯臭味,使嗅值无法达到台湾地区的饮用水水质标准,因此要特别注意控制加氯量。     

Fenton高级氧化技术去除水中有机污染物2-MIB的影响因素研究

针对目前比较关注的致嗅物质污染问题,选用Fenton高级氧化技术研究了其对水中致嗅物质2-甲基异莰醇（2-MIB）的去除,探讨了Fenton反应对水中致嗅物质的去除效能及H2O2/Fenton摩尔比、Fe2＋浓度、反应时间和溶液pH值各因素对氧化反应的影响。提出了Fenton氧化反应去除2-MIB的最佳反应条件。实验结果表明：Fenton高级氧化能有效去除水中的2-MIB。在H2O2/Fenton摩尔比为3.0、Fe2＋浓度10 mg/L、反应时间10 min和溶液pH值为3.0时,去除效率达到97.9%。Fenton氧化反应的操作条件（浓度、pH值等）比较容易实现,因此Fenton氧化技术在实际污染处理中有很大的应用前景。     

Ability of humans to smell geosmin, 2-MIB and nonadienal in indoor air when using contaminated drinking water.

The most common compounds responsible for off flavours are geosmin, 2-MIB, and nonadienal which are poorly removed by conventional water treatment operations and hence result in customer complaints. Because these odourants are moderately volatile and have very low odour threshold values, it is necessary to determine their concentrations in air when water is used indoors. If the detectable aqueous concentrations for these odourants are known, the utilities may take action to treat their water at times when the concentration of the raw water exceeds the threshold concentration. To predict the concentration in the shower stall and bathroom air after showering, recently published Henry's law constants for the selected odourants and a model developed to determine the volatilization of the odourous compounds by applying two-resistance theory were used. Then the results were compared with the odour threshold concentration data to determine under which conditions the odourants become detectable. For parameters representing a typical bathroom and shower stall setting, the results showed that the odourants become detectable when the aqueous concentration of geosmin and nonadienal exceed 10 ng/L at 42 degrees C. As the aqueous concentration increases, geosmin and nonadienal become detectable at lower temperatures, however 2-MIB is only detectable above 20 ng/L and at 42 degrees C.     

Advanced treatment for taste and odour control in drinking water: case study of a pilot scale plant in Seoul, Korea.

Taste and odour problems of tap water in Seoul are attributed to 2-methylisoborneol (2-MIB) and trans-1,10-dimethyl-trans-9-decalol (geosmin), which are the result of metabolism of algae and chlorine for disinfection. This study was carried out to measure 2-MIB and geosmin in the raw water from the Han River, to investigate removal efficiency of GAC and BAC integrated with post-ozonation, and to minimise and quantify the required chlorine concentration as a final disinfectant through the candidate process.     

O_3和O_3/H_2O_2氧化对饮用水中痕量臭味物质的处理效果研究

研究了O3、O3/H2O2深度氧化法对饮用水中的Geosmin、MIB、IBMP、IPMP及TCA等痕量异味物质的去除效能。当O3投加量为4.66mg/L时,对痕量异味物质的去除率按IBMP、TCA、Geosmin、IPMP和MIB的排列,其中对Geosmin的绝对去除量最大,达到了140ng/L。投加O30.43mg/L和H2O210mg/L氧化去除5种痕量异味物质,对IBMP和TCA去除率分别达到75%和67.2%,去除效率较高;但在O3及O3/H2O2这样的投加量下,痕量异味物质尚不能达到标准中对嗅阈值的要求,还需配合后续处理工艺。     

吴淞江微污染水源水处理工艺的比较研究

采用预臭氧生物活性炭滤池、生物接触预氧化、PAC吸附预处理三种工艺对吴淞江微污染水源水处理进行研究;常温下,臭氧投加量2 mg/L,预臭氧生物活性炭滤池对氨氮的去除率维持在70%以上,出水NH3-N约1 mg/L,CODMn平均去除率34.16%;生物接触预氧化对氨氮去除率可达80%以上,但CODMn平均去除率只有7.6%;PAC对色度及臭味有良好的去除效果,但对其他物质去除率较低.三种工艺相比,作为水厂改造或备用应急方案,预臭氧生物活性炭滤池为最佳选择.     

石灰软化法处理地下水源水硬度试验研究

采用石灰软化法处理某地下水源水硬度,结果表明,当石灰投加量为220mg/L,pH为8.7～8.9时,可使原水硬度和碱度分别由300mg/L和250mg/L降至115mg/L和80mg/L以下,去除率分别为61.7%和68%,沉淀和过滤对硬度去除效果影响不大;投加石灰后出水浊度明显升高,投加PAC(聚氯化铝)40mg/L,并与常规工艺联用,可使出水浊度稳定降低至0.15～0.65NTU;试验证明"石灰+PAC+常规工艺"能有效去除水中硬度和浊度,出水煮沸后不再生成沉淀和悬浮物,符合现行《生活饮用水卫生标准》(GB 5749—2006)和用户使用要求,石灰软化法药耗成本估算为0.246元/m3。     

水源水质标准中嗅味标准的研究

在我国现有的《生活饮用水水源水质标准》(CJ3020-93)标准中并未对嗅味做定性和定量的规定。嗅味层次分析方法能够对水样中的嗅味种类以及嗅味强度做出定性和定量化的判断,通过嗅味层次分析方法以及SPME-GC/MS化学分析的结果,给出了饮用水嗅味的推荐值。按不同水源地类型对二甲基异莰醇(2-MIB)的标准进行了研究,综合考虑感官分析和化学分析结果,水厂可处理程度以及消费者可接受情况,给出2-MIB标准的推荐值,一级、二级水源地的标准推荐值为10 ng/L,三级水源地的标准推荐值为50 ng/L。二甲基异莰醇(2-MIB)嗅味标准推荐值的给出在一定程度上对水源地的划分又提供了一个参考依据,开辟了水质感官分析的新思路,为我国城市水源中2-MIB含量的划分提供了参考。     

Occurrence of the Odor Compounds, 2-Methylisoborneol and Geosmin in Eastern Lake Ontario and the Upper St. Lawrence River

Unpleasant tastes and odors in drinking water from the upper St. Lawrence River were investigated in the fall of 1996 and 1997 as the result of increasing taste and odor events in recent years. Taste and odor events resulted in widespread public reaction to the earthy/musty tasting water produced and a need for accurate information to assist water treatment efforts. The presence of geosmin, (trans, trans-1,10-dimethyl-9-decalol) and 2-methylisoborneol (MIB2, 1,2,7,7-tetramethyl-exobicyclo[2.2.1]heptan-2-ol), the most common causes worldwide of earthy and musty odors in water, were investigated in eastern Lake Ontario and the upper St. Lawrence River. Gas chromatography-mass spectrometry was used for quantitation and confirmation of the presence of these compounds in water samples. Both geosmin and MIB2 were detected in river water samples at concentrations ranging from 5 to 20 ng/L and 2 to 25 ng/L, respectively. The compounds were also detected in southern coastal lake water which serves as a source to the St. Lawrence River, but not in mid-lake samples. Similar levels of geosmin and MIB2 were detected in untreated Lake St. Lawrence water, in samples taken following pre-chlorination for zebra mussel control, and in samples taken following conventional treatment at a water filtration plant.     

Efficient taste and odour removal by water treatment plants around the Han River water supply system.

Seven major water treatment plants in Seoul Metropolitan Area, which are under Korea Water Resources Corporation (KOWACO)'s management, take water from the Paldang Reservoir in the Han River System for drinking water supply. There are taste and odour (T&O) problems in the finished water because the conventional treatment processes do not efficiently remove the T&O compounds. This study evaluated T&O removal by ozonation, granular activated carbon (GAC) treatment, powder activated carbon (PAC) and an advanced oxidation process in a pilot-scale treatment plant and bench-scale laboratory experiments. During T&O episodes, PAC alone was not adequate, but as a pretreatment together with GAC it could be a useful option. The optimal range of ozone dose was 1 to 2 mg/L at a contact time of 10 min. However, with ozone alone it was difficult to meet the T&O target of 3 TON and 15 ng/L of MIB or geosmin. The GAC adsorption capacity for DOC in the three GAC systems (F/A, GAC and O3 + GAC) at an EBCT of 14 min is mostly exhausted after 9 months. However, substantial TON removal continued for more than 2 years (>90,000 bed volumes). GAC was found to be effective for T&O control and the main removal mechanisms were adsorption capacity and biodegradation.     

Behaviour of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) in oxidative water treatment processes.

Endocrine disrupting chemicals (EDCs) such as natural and synthetic hormones or industrial chemicals can adversely affect the endocrine system at very low concentrations. As such substances can be present in raw water used for drinking-water production, they potentially pose a health risk to humans. In this study laboratory tests were performed to determine removal efficiencies of selected oxidative drinking water treatment processes, namely ozonation (1.4 mg/l O3) and chlorination, using sodium hypochlorite (0.5 mg/l NaClO) and chlorine dioxide (0.4-0.6 mg/l ClO2) under conditions applied in technical plants. 500-300,000 ng/l of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol-n-ethoxylates (NPnEO) were selected for investigations and measured by HPLC/FLD and HPLC/MS. To investigate possible oxidation by-products, adsorbable organic halogens (AOX) were determined and estrogenic activities were assessed with the help of an estrogen receptor binding assay (YES). Ozonation and chlorination with ClO2 removed both 4-NP and BPA below detection limits, corresponding with AOX and estrogenic activity. Concerning NPnEO ozonation removed NP1EO and NP2EO up to 28% and 30%, respectively, whereas ClO2 showed high removal efficiencies, eliminating >94% and 92%, respectively. NaCIO removed 4-NP and BPA below detection limits, but estrogenic activities increased and AOX could be measured. NP1EO and NP2EO were only marginally reduced corresponding to the slight decrease of estrogenic potential.     

粉末活性炭处理抗生素污染原水试验研究

探讨了粉末活性炭对抗生素的去除效果.在对水体中30种常见抗生素污染调研的基础上,选取萘啶酸、土霉素、林可霉素3种代表性抗生素进一步分析所需粉末活性炭的投加量.研究结果表明:当污染物在1 mg/L时,粉末活性炭的投加量分别为115 mg/L(萘啶酸)、75 mg/L(土霉素)、25mg/L(林可霉素),去除率均在99％以上,并根据其他抗生素的吸附难易度,推导出在相同污染程度下粉末活性炭的投加量;当原水中出现小于1 μg/L的持续性污染时,粉末活性炭的投加量应保持在1～35 mg/L,以保证稳定高效的去除效果.     

水中天然有机物对粉末活性炭吸附2-MIB的影响

粉末活性炭(PAC)对2-MIB的吸附过程更接近于Freundich吸附等温模式。用树脂富集方法将松花江水中的天然有机物(NOM)分为憎水性酸(HOA)、憎水性碱(HOB)、憎水中性物(HON)、亲水酸(HIA)、亲水碱(HIB)、亲水中性物(HIN)等六类,原水中有机碳的回收率为84.7%(以TOC计)。不同组分NOM不同程度地降低了PAC的吸附容量。以松花江水为本底,利用等背景化合物模式进行试验,结果表明,活性炭的吸附容量与2-MIB初始浓度成正比。利用HSDM模型能很好地预测PAC吸附松花江原水中2-MIB的动力学过程,在PAC投加量适当的情况下,吸附时间为4h时的吸附量占吸附平衡总量的70%左右,与实测结果接近。     

A fast stir bar sorptive extraction method for the analysis of geosmin and 2-methylisoborneol in source and drinking water.

The presence of unpleasant taste and odour in drinking water is an ongoing aesthetic concern for water providers worldwide. The need for a sensitive and robust method capable of analysis in both natural and treated waters is essential for early detection of taste and odour events. The purpose of this study was to develop and optimise a fast stir bar sorptive extraction (SBSE) method for the analysis of geosmin and 2-methylisoborneol (MIB) in both natural water and drinking water. Limits of detection with the optimised fast method (45 min extraction time at 60 degrees C using 24 microL stir bars) were 1.1 ng/L for geosmin and 4.2 ng/L for MIB. Relative standard deviations at the detection limits were under 17% for both compounds. Use of multiple stir bars can be used to decrease the detection limits further. The use of 25% NaCl and 5% methanol sample modifiers decreased the experimental recoveries. Likewise, addition of 1 mg/L and 1.5 mg/L NaOCI decreased the recoveries and this effect was not reversed by addition of 10% thiosulphate. The optimised method was used to measure geosmin concentrations in treated and untreated drinking water. MIB concentrations were below the detection limits in these waters.     

Enhancing flexible fiber filter (3FM) performance using in-line coagulation.

A new packing for deep bed filtration using Flexible Fibers has been proposed and developed on a very large scale for tertiary treatment of wastewater. The purpose of this study is to check the possibility of using this technology for the production of drinking water from surface water. In this study, the feasibility of the fiber filter application on water treatment was examined and the removal efficiency of fiber filter was improved using an in-line coagulant injection method. The experiments were carried out at pilot scale. The filter was packed with bundles of polyamide fibers with a bed porosity of 93%. Nak-dong River was used as the filter influent water and alum, PSOM, and PAC were used as the coagulants. The coagulants were injected by the in-line injection method. Small dosages (1-5 mg/L) of the polymeric coagulants (PSOM and PAC) showed an increase of removal efficiency compared to the operation without coagulants. Specifically, 1 mg/L of PAC showed the longest filtration time. Considering filtration time, filtrate quality, and filtered volume, the filtration velocity of 120 m/hr was chosen as an optimum value. For long-term operations, the effluent quality was 0.4 NTU and the removal efficiency was stable for the given optimum conditions.     

高盐景观水体除磷、除藻药剂优选及复配

淡水盐碱化是全球范围内面临的一个新兴环境问题,其中城镇内人工景观水体表现尤为突出。高盐景观水体盐度大,导致植物不易生长,藻类逐渐成为优势种群,影响观感。通过絮凝法同时除磷、除藻,使景观水体恢复藻类爆发前的状态。研究11种絮凝药剂对TP、Chla(叶绿素a)的去除效率,其中PAC除磷效果很好,CPAM可以有效除藻。经过浓度梯度优选实验,优选出PAC和CPAM的最优投加浓度,并进行复配试验。复配结果为当PAC投加浓度10mg/L、CPAM投加浓度3mg/L时组合除磷、除藻效果最佳,TP平均去除率为92.52%,Chla平均去除率为98.32%。