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.     

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).     

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.     

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.     

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.     

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.     

Synthesis and odour thresholds of mixed halogenated anisoles in water.

Earthy-musty off-flavour compounds in water samples are usually associated with the presence of geosmin and 2-methylisoborneol. However, the presence of 2,3,6- and 2,4,6-trichloroanisoles or other halogenated anisoles can impart objectionable tastes and odours to the water even at very low trace levels. This paper shows the synthesis of non-commercial 2,3,6- and 2,4,6- mixed chloro/bromoanisoles which can be present in bromide rich waters and could also be suspected of imparting earthy-musty off-flavours to the water. All the synthesized compounds were subjected to the flavour profile analysis (FPA) method and their odour threshold concentrations (OTC) in water were carried out giving values in the low ng/L range.     

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.     

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.     

A review of taste and odour events in Barcelona's drinking water area (1990-2004).

The main, relevant, solved problems associated with taste and odour incidents in Barcelona's drinking water area in the last 14 years are reviewed. Events produced by creosote, dioxanes and dioxolanes, dicylopentadiene, and diacetyl, among the anthropogenic compounds; geosmin, MIB and iodinated trihalomethanes and chlorobromoanisoles as examples of compounds of natural origin are exemplified. The determination of the odour threshold concentrations of selected odorous compounds is also shown as a tool to gain a better knowledge of future taste and odour events.     

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。     

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.     

Design and application of a GC-SNIff/MS system for solving taste and odour episodes in drinking water.

This paper describes the implementation of a GC-Sniff/MS system that allows the simultaneous determination of the odorous properties of compounds eluting from a GC column and their identification by MS. The technique was first tested with standard compounds then applied to real cases of taste and odour episodes. This approach allowed the identification of geosmin at low levels and suggested the possible implication of methylnaphthalene in the development of chemical odours. It provided the first clue of the presence of a halophenol with a very low odour threshold involved in a chlorophenolic odour episode. The chemical was finally identified as 2,6-dibromophenol. The method was also applied to the characterization of a complex mixture of additives leaching from a flexible rubber pipe. In the latter case, Time-of-Flight MS was also used to confirm the identity of the additives.     

Annual dynamics and origins of the odorous compounds in the pilot experimental area of Lake Dianchi, China.

Lake Dianchi is the sixth largest freshwater lake in China. The pilot experimental area (6 km2) in Lake Dianchi is one of the most severely polluted areas in the lake with heavy cyanobacteria blooms. During June 2002 to May 2003, the algal composition and number, and odorous compounds were identified monthly and monitored in the area. Meanwhile, physicochemical parameters such as total phosphorus (TP), total nitrogen (TN), 5-day biochemical oxygen demand (BOD5), chemical oxygen demand (COD(Mn)), dissolved oxygen (DO), pH, transparency, temperature and chlorophyll a (chla) were determined. Four odorous compounds: 2-methylisoborneol (MIB), geosmin, beta-cyclocitral and beta-ionone were found in the lake water. Both the concentration of particulate beta-cyclocitral and that of beta-ionone correlated significantly with the annual variation of Chla, biomass of total phytoplankton, cyanobacteria and Microcystis. The concentration of particulate MIB correlated significantly with the biomass of Oscillatoria, while the concentration of particulate geosmin correlated significantly with the biomass of Anabaena. Off-flavour in the pilot area was found to be caused by a combination of beta-cyclocitral- and beta-ionone-producing Microcystis, MIB-producing Oscillatoria and geosmin-producing Anabaena. beta-ionone, MIB and geosmin contributed collectively to the odour intensity in the lake water.     

Understanding medicinal taste and odour formation in drinking waters.

The formation of bromophenols during chlorination of phenol- and bromide-containing waters can be critical for taste and odour problems in drinking waters. The work performed has confirmed that flavour threshold concentrations of some bromophenols are in the ng/L range. In addition, under typical drinking water conditions, kinetic experiments and model simulations performed have shown that (1) bromination is the predominant reaction pathway, (2) bromophenol reaction kinetics are rapid leading to taste-and-odour episodes that last for short periods of 10-20 min, (3) increasing phenol concentration and pH tends to increase taste and odour intensity, (4) increasing chlorine or bromide concentrations tends to shorten the duration of the taste-and-odour episode.     

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.     

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.     

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.     

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.     

A re-evaluation of the taste and odour of methyl tertiary butyl ether (MTBE) in drinking water.

Methyl tertiary butyl ether (MTBE) is a gasoline additive that has been found in groundwater when an underground gasoline storage tank leaks. Although dependent on the clean-up standards that are applied, clean-up costs have been estimated in the US alone to be in the billions of dollars. MTBE is considered primarily a taste and odour concern and not a toxicity issue at concentrations found in drinking water. Thus, the clean-up of MTBE problems is controlled by the MTBE odour threshold concentration (OTC). The level of clean-up and associated differential of millions of dollars is a matter of concern for water purveyors and well owners. A 1993 study of nine OTC studies showed the OTC of MTBE in water to be between 0.04 and 0.06 microg/L, a level over two orders of magnitude less than eight other studies. This 1993 study was repeated at the original laboratory in 2004 and is reported in this paper. The laboratory's quality control programme and ability to repeat one of the eight other studies indicated the laboratory was qualified to repeat its original OTC study. The flavour and odour detection threshold range in the 1993 study, however, could not be confirmed by trained assessors repeating the original study in 2004. The inconsistencies in the data and the high detection on water blanks indicate that the dilution series of the test solutions for the 1993 study were mainly at subthreshold levels. Therefore, the original study of 1993 is not a valid OTC study for MTBE and should not be used to develop drinking water and clean-up standards. The OTC of MTBE is over 15 microg/L for the eight valid studies.