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).     

Treatment of taste and odor material by oxidation and adsorption.

Massive blooms of blue-green algae in reservoirs produce the musty-earthy taste and odor, which are caused by compounds such as 2-MIB and geosmin. 2-MIB and geosmin are rarely removed by conventional water treatment. Their presence in the drinking water, even at low levels (ng/L), can be detected and it creates consumer complaints. So those concentrations have to be controlled as low as possible in the drinking water. The removals by oxidation (O3, Cl2, ClO2) and adsorption (PAC, filter/adsorber) were studied at laboratory and pilot plant (50 m3/d) to select suitable 2-MIB and geosmin treatment processes. The following conclusions were derived from the study. Both of the threshold odor levels for 2-MIB and geosmin appeared to be 30 ng/L as a consequence of a lab test. For any given PAC dosage in a jar-test, removal efficiencies of 2-MIB and geosmin were increased in proportion to PAC dosage and were independent of their initial concentration in raw water for the tested PAC dosages. In comparison of geosmin with 2-MIB, the adsorption efficiency of geosmin by PAC was superior to that of 2-MIB. The required PAC dosages to control below the threshold odor level were 30 mg/L for geosmin and 50 mg/L for 2-MIB at 100 ng/L of initial concentration. Removal efficiencies of odor materials by Cl2, ClO2, and O3 were very weak under the limited dosage (1.5 mg/L), however increased ozone dosage (3.8 mg O3/L) showed high removal efficiency (84.8% for 2-MIB) at contact time 6.4 minutes. According to the initial concentrations of 2-MIB and geosmin, their removal efficiencies by filter/adsorber differed from 25.7% to 88.4%. For all those, however, remaining concentrations of target materials in finished waters were maintained below 30 ng/L. The longer run-time given for the filter/adsorber, the higher the effluent concentration generated. So it is necessary that the run-time of the filter/adsorber be decreased, when 2-MIB or geosmin occurs in raw water.     

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.     

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.     

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.     

Effects of chlorine and chloramines on earthy and musty odors in drinking water.

Water treatment plants in the US may operate under the assumption that chlorine masks earthy and musty odors from geosmin and 2-methylisoborneol (MIB) in drinking water. To test this hypothesis, we evaluated the effects of chlorine and chloramines on geosmin and MIB by two sensory analysis approaches--a statistical Pairwise Comparison Test, and Flavor Profile Analysis (FPA). All Pairwise Ranking test statistics were significant (p<0.05); we conclude that panelists can differentiate minor differences in geosmin and MIB concentrations in a Pairwise Comparison Test even in the presence of chlorine. FPA appeared to be more challenging in discerning subtle differences in concentrations of geosmin or MIB than did the Pairwise Comparison Test, and the presence of chlorine (0.5-20 mg/L) and chloramines (3-24 mg/L) confused the panelists (i.e showed a larger error in the intensity of response reported by the panel), but did not necessarily mask geosmin or MIB.     

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。     

Removal of geosmin and 2-methylisoborneol by biological filtration.

The quality of drinking water is sometimes diminished by the presence of certain compounds that can impart particular tastes or odours. One of the most common and problematic types of taste and odour is the earthy/musty odour produced by geosmin (trans-1, 10-dimethyl-trans-9-decalol) and MIB (2-methylisoborneol). Taste and odour treatment processes including powdered activated carbon, and oxidation using chlorine, chloramines, potassium permanganate, and sometimes even ozone are largely ineffective for reducing these compounds to below their odour threshold concentration levels. Ozonation followed by biological filtration, however, has the potential to provide effective treatment. Ozone provides partial removal of geosmin and MIB but also creates other compounds more amenable to biodegradation and potentially undesirable biological instability. Subsequent biofiltration can remove residual geosmin and MIB in addition to removing these other biodegradable compounds. Bench scale experiments were conducted using two parallel filter columns containing fresh and exhausted granular activated carbon (GAC) media and sand. Source water consisted of dechlorinated tap water to which geosmin and MIB were added, as well as, a cocktail of easily biodegradable organic matter (i.e. typical ozonation by-products) in order to simulate water that had been subjected to ozonation prior to filtration. Using fresh GAC, total removals of geosmin ranged from 76 to 100% and total MIB removals ranged from 47% to 100%. The exhausted GAC initially removed less geosmin and MIB but removals increased over time. Overall the results of these experiments are encouraging for the use of biofiltration following ozonation as a means of geosmin and MIB removal. These results provide important information with respect to the role biofilters play during their startup phase in the reduction of these particular compounds. In addition, the results demonstrate the potential biofilters have in responding to transient geosmin and MIB episodes.     

Correlating 2-MIB and microcystin concentrations with environmental parameters in two reservoirs in South Taiwan.

Cyanobacteria are present in many drinking water reservoirs in Taiwan, and some of them may produce off-flavour compounds and natural toxins. To investigate the correlation among two groups of cyanobacterial metabolites, microcystins and 2-methylisoborneol (2-MIB), and other environmental parameters, approximately 22 water quality and meteorological parameters were monitored for two source waters (Moo-Tan and Tseng-Wen reservoirs) in south Taiwan from August 2003 to April 2005. Monitoring results showed that the two groups of cyanobacterial metabolites were present in the source waters. Concentrations of 2-30 ng/L of 2-MIB was observed for the two reservoirs, while that of the total concentrations of the five microcystin congeners measured were between 30 and 340 ng/L. The concentration of both 2-MIB and microcystins showed higher concentrations in warmer seasons. A stepwise regression technique was employed to correlate 2-MIB and microcystins concentrations with all the corresponding water quality and meteorological parameters. Correlations among 2-MIB concentration, microcystin concentration, water temperature and air temperature were found in the water samples collected from both reservoirs. The correlations may provide a simple means for the water utility to anticipate the two groups of cyanobacterial metabolites in the two source waters.     

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。     

ph and Mg/Ca control for biological treatment of an offensive flavour (2-MIB)

From a series of experimental observations, it was found that removal rates of the offensive flavor 2-methylisoborneol(2-MIB) and ammonia by a biological treatment for water supply were rather unstable and that the removal rates of them often became reverse such as low removal in 2-MIB and high removal of ammonia. One reason for the reverse phenomenon was found that the affinities of sludge around bacteria with 2-MIB and ammonia often became reversed. The affinities of sludge with 2-MIB and ammonia were found to be changeable depending upon pH along with magnesium (Mg) and calcium (Ca) concentrations in sludge. From these findings, control of pH and magnesium calcium ratio (Mg/Ca) of raw water was recommended for simultaneous and stable removal of 2-MIB and ammonia. From plant scale experiments equipped with automatic pH controller, the effects of pH and Mg/Ca control for biological treatment of 2-MIB and ammonia were observed in a biological activated filtration. Here, a biological activated carbon filtration means a longer filtration than 40 to 50 days from the beginning. The obtained results were almost as expected, showing high removal rates of both 2-MIB and ammonia.     

Interlaboratory comparison of geosmin and 2-methylisoborneol in municipal tap water.

An interlaboratory comparison ("round-robin") for geosmin and 2-methylisoborneol (MIB) was carried out between six laboratories of the Ontario Water Works Research Consortium (OWWRC). Municipal tap water was found to be a suitable medium for distribution of samples. To test stability, geosmin and MIB were added to tap water and stored at 2-4 degrees C. Under these conditions, geosmin concentrations declined by approximately 5% per month for the first 2 months. MIB concentrations were stable over a 158-day period. Three round-robins were carried out individually in 2001, 2003 and 2004. Two levels of geosmin and MIB were used: nominally 10 and 100 ng/l. In 2003 the relative standard deviation for all six participating laboratories were 34, 21, 21 and 22% for low and high level MIB, and low and high level geosmin, respectively. For all but MIB at the low level, there was a marked improvement in agreement between laboratories from 2001 to 2004. However, we recommend use of common analytical standards in order to potentially further reduce interlaboratory variability.     

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。     

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。     

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.     

Optimization of stir bar sorptive extraction applied to the determination of odorous compounds in drinking water.

The off-flavour compounds 2-methylisoborneol (MIB), geosmin, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, 2,3,4-trichloroanisole and 2,4,6-tribromoanisole were analyzed in water samples by Stir Bar Sorptive Extraction (SBSE) followed by on-line thermal desorption (TD)-capillary GC/MS. Quantification was performed using MS in the single ion monitoring mode (SIM) with 2,4,6-trichloroanisol-D5 as internal standard. Quantification limits are 0.1 ng/l to 0.2 ng/l for the haloanisoles, 0.5 ng/l for geosmin and 1 ng/l for MIB. The relative standard deviations at the quantification limit are ranging from 7 to 14.6%. SBSE-recovery was evaluated by spiking real water samples and varied from 87 to 117%. More than twenty samples per day can be analyzed by SBSE-TD-capillary GC-MS. The same technique in combination with olfactometry was used to elucidate unknown odorous compounds in water samples.     

Geosmin and MIB events in a new reservoir in southern California.

Diamond Valley Lake is a large drinking water reservoir in western Riverside County, California near the city of Hemet. In almost 6 years since filling began in 1999, this reservoir has experienced five episodes involving either geosmin or 2-methylisoborneol (MIB). The first one was a short-lived but intense geosmin event in May 2000, associated with a planktonic cyanobacterium, Anabaena circinalis. Geosmin levels reached 750 ng/L at the surface. All the other episodes involved benthic proliferations in the littoral zone. In September 2002, an MIB-producing growth developed in a shallow area near the outlet tower, dominated by Oscillatoria cf. curviceps and O. limosa. A similar event occurred in October 2003. In March 2004, an extensive growth of cyanobacteria that included two geosmin producers developed at the east dam, but had minimal effect on geosmin levels in the water. Finally, there was a major MIB episode in October 2004, in which the primary causative organism was again Oscillatoria cf. curviceps. A band of benthic cyanobacteria developed all around the shoreline from 3-9 m deep, and surface MIB levels reached 63 ng/L. These events showed that a new reservoir in a mild climate can be colonised by benthic cyanobacteria that produce MIB and geosmin, within a relatively short time.     

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.     

Biofilm in water pipelines; a potential source for off-flavours in the drinking water.

Volatile organic compounds (VOC) are identified in natural biofilm established in plastic pipes used at the drinking water supply. Odour potent VOCs such as ectocarpene, dictyopterene A and C', geosmin, beta-ionone, 6-methyl-5-hepten-2-one, menthol and menthone were prominent compounds in biofilm in the distribution network and at raw water test sites, and are associated with algae and cyanobacteria present in the raw water source.     

An analytical method for shipboard extraction of the odour compounds, 2-methylisoborneol and geosmin.

Extractions for the analysis of geosmin and 2-methylisoborneol (MIB) were carried out on board a research vessel by extracting water samples in the collection bottles with dichloromethane. The extracts are stable and can be stored for up to two months with no apparent loss of analytes. Workup and analysis could be done at the rate 15-20 samples per week. Approximately 150 samples from Lake Ontario were analyzed in 2000 and 120 samples in 2001. Concentrations as low as 1 ng/L could be detected, but reliable determination was only attained above 5 ng/L (> 80% qualifier ion match within +/- 50%). Reproducibility between duplicates was generally better than 10%, and recovery of surrogate standards from reagent water averaged ca. 80% and from lake water ca. 60%. In early September, 2000, geosmin concentrations in Lake Ontario ranged from 1-13 ng/L and MIB from 1-31 ng/L. In 2001, the ranges were 1-47 and 1-56 ng/L for geosmin and MIB, respectively. Lowest concentrations occurred in the western and central regions and highest concentrations in the eastern region and St Lawrence River.