UV-based advanced oxidation processes for the treatment of odour compounds: Efficiency and by-product formation

The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O₃ yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m⁻³ and without the risk of the formation of nitrite or bromate above the maximum contaminant level.     

Sensory properties and analysis of two muddy odour compounds, geosmin and 2-methylisoborneol, in water and fish

Muddy or earthy odours are a problem in water supplies and fisheries. Some species of aquatic actinomycetes and blue-green algae are generally indicated as sources of muddy odour in natural waters. These organisms are capable of producing the muddy-smelling compounds geosmin and 2-methylisoborneol.The sensory properties of geosmin and 2-methylisoborneol in water and in the flesh of four species of fish were studied. Threshold odour concentrations are presented, and they indicate that both compounds have strong odour characteristics. The intensity of the muddy odour as perceived by the judges was proportional to the logarithm of the concentration of muddy odour compounds in the concentration ranges tested (for geosmin, up to 100 μgkg⁻¹, and for 2-methylisoborneol, up to 10 μg kg⁻¹). The results indicate that it may be possible to quantify muddy odour compounds in water and fish by sensory methods.     

Cause and identification of taste and odour compounds in water

Odour compounds in water may originate from industrial and municipal sewage effluents or from biological activities of algae and heterotrophic micro-organisms. The relative importance of these two sources of odour substances is discussed for the situation in The Netherlands. A number of organic compounds that have been proved to be responsible for odour problems in effluent water, river water and drinking water are presented. Different types of chlorinated compounds are shown to be of importance in relation to offensive water odour. Some recommendations tentative for maximum allowable concentrations of odour compounds in effluents, surface waters and drinking water are given.     

Actinomycetes in relation to taste and odour in drinking water: myths, tenets and truths

Actinomycetes are a complex group of bacteria present in a wide variety of environments, either as dormant spores or actively growing. Some actinomycetes produce two potent terpenoids (geosmin and 2-methylisoborneol (MIB)) and pyrazines, common causes of drinking water off flavours, and have been implicated in taste and odour episodes. However, isolation from a water source is not evidence that actinomycetes caused a taste and odour event. Dormant spores of actinomycetes may be isolated from aquatic environments in high concentrations, despite production in the terrestrial environment. Similarly, odourous compounds produced by actinomycetes may be produced terrestrially and washed into aquatic environments, with or without the actinomycetes that produced them. Actinomycetes may exist as actively growing mycelium in small, specialized habitats within an aquatic system, but their odourous compounds may influence a wider area. This paper attempts to elucidate the types and activities of actinomycetes that may be found in, or interact with, drinking water supplies.     

Effect of residual chlorine on the analysis of geosmin, 2-MIB and MTBE in drinking water using the SPME technique

The effect of chlorine on the analysis of three organic compounds (geosmin, 2-methylisoborneol (2-MIB) and methyl tert-butyl ether (MTBE)) in drinking water is elucidated. Three fibers for solid-phase microextraction (SPME) were employed for the extraction of the organic compounds from drinking water samples with and without free residual chlorine present. A gas chromatograph coupled with a mass spectrometer was used to analyze the compounds trapped by the fibers. The presence of chlorine substantially reduces the observed geosmin, 2-MIB, and MTBE concentrations. Depending on the analyte and chlorine concentrations, an experimental error of 10-70% may be observed due to the presence of free residual chlorine. The impact is larger for lower organic compound concentrations, and under higher residual chlorine conditions. To counteract the effect from residual chlorine, sodium thiosulfate was used to dechlorinate the water. After dechlorination the experimental error was less than 10%, suggesting that dechlorination is necessary when applying SPME for the extraction of organic compounds from chlorinated drinking water.     

Spatio-temporal distribution of cell-bound and dissolved geosmin in Wahnbach Reservoir: Causes and potential odour nuisances in raw water

In many lakes and reservoirs, problems caused by off-flavours are known to be particularly associated with the occurrence of planktonic and benthic cyanobacteria. Frequently observed objectionable taste and odorous products of cyanobacteria are geosmin and 2-methylisoborneol.Investigations focused on the littoral zone of Wahnbach Reservoir (Germany) revealed that benthic cyanobacteria were present in this oligotrophic drinking water reservoir. Benthic cyanobacteria were found in the depth horizon between 1.75 m and 11 m, particularly on south-exposed slopes. This spatial distribution indicates a possible key role of the underwater light climate. Moreover, cell-bound and dissolved geosmin were detected in corresponding littoral samples. Both fractions were subjected to spatial and primarily temporal variations with maximum concentrations at the end of summer. However, a substantial lowering of the water level caused a diminution of cyanobacterial growth. Due to the drawdown of the water level concentrations of cell-bound geosmin and pigments (as a proxy of cyanobacterial biomass) were remarkably reduced, and dissolved geosmin was never detected during this phase. Except for the influence of water level fluctuation no other abiotic variables had a significant influence on pigment and geosmin concentrations. From geosmin concentrations detected in the littoral zone, the probability of serious episodes of odour events in the raw water of the Wahnbach Reservoir was estimated. Hence, the probability that the raw water was affected by geosmin was minor, which was supported by routine flavour profiles. Nevertheless, the study shows that odorous episodes caused by benthic cyanobacteria are likely to develop even in an oligotrophic lake or reservoir when these cyanobacteria, and consequently odorous production, proliferate. In principle, such a proliferation cannot be excluded as nutrients are available from the sediment pore water, and underwater light at the sediment surface in the sub-littoral is sufficiently high due to very low phytoplankton-induced turbidity under oligotrophic conditions. Thus, management-induced fluctuations of the water level seem to be the main control variable to generate light conditions at the sediment surface fluctuating in a given depth horizon faster than cyanobacteria can develop there.     

Enhancing the biofiltration of geosmin by seeding sand filter columns with a consortium of geosmin-degrading bacteria

Geosmin is a secondary metabolite that can be produced by many species of cyanobacteria and Actinomycetes. It imparts a musty/earthy taste and odour to drinking water which can result in consumer complaints and a general perception that there is a problem with the water quality. As geosmin is recalcitrant to conventional water treatment, processes are sought to ensure effective removal of this compound from potable water. Biological filtration (biofiltration) is an attractive option for geosmin removal as this compound has been shown to be biodegradable. However, effective biofiltration of geosmin can be site specific as it is highly dependent upon the types of organism present and there is often an extended acclimation period before efficient removals are achieved. We report here, a novel approach to enhance the biofiltration of geosmin by seeding sand filter columns with a bacterial consortium previously shown to be capable of effectively degrading geosmin. Geosmin removals of up to 75% were evident through sand columns which had been inoculated with the geosmin-degrading bacteria, when compared with non-inoculated sand columns where geosmin removals were as low as 25%. These low geosmin removals through the non-inoculated sand columns are consistent with previous studies and were attributed to physical/abiotic losses. The presence of an existing biofilm was shown to influence geosmin removal, as the biofilm allowed for greater attachment of the geosmin-degrading consortium (as determined by an ATP assay), and enhanced removals of geosmin. Minimal difference in geosmin removal was observed when the geosmin-degrading bacteria were inoculated into the sand columns containing either an active or inactive biofilm.     

Development of predictive models for geosmin-related taste and odor in Kansas, USA, drinking water reservoirs

The presence of taste and odor compounds can greatly reduce the quality of drinking water supplies. Because the monetary costs associated with the removal of these compounds can be high, it is impractical for most facilities to continuously treat their raw water. Instead, new tools are needed to help predict when taste and odor events may be most likely to occur. Water quality data were collected between June and October in 2006-2007 from five Kansas (USA) reservoirs in order to develop predictive models for geosmin, a major taste and odor compound; two of these reservoirs were also sampled during specific taste and odor events in December 2006 and January 2007. Lake trophic state alone was not a good predictor of geosmin concentrations as the highest average geosmin concentration was observed in the reservoir with the lowest nutrient and chlorophyll a concentrations. In addition, taste and odor events were not confined to summer months; elevated geosmin concentrations were observed in several reservoirs during the winter. Growth limitation by inorganic phosphorus appeared to be the primary determinant of geosmin production by algal cells in these reservoirs.     

Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: influence of NOM and process modelling

The adsorption of the taste and odour (T&O) compounds geosmin and 2-methylisoborneol (2-MIB) onto powdered activated carbon (PAC) has been studied under conditions which are typical for a drinking water treatment plant that uses reservoir water for drinking water production. The reservoir water as well as the pre-treated water (after flocculation) contains NOM that competes with the trace compounds for the adsorption sites on the carbon surface. Although the DOC concentrations in the reservoir water and in the pre-treated water were different, no differences in the competitive adsorption could be seen. By using two special characterisation methods for NOM (adsorption analysis, LC/OCD) it could be proved that flocculation removes only NOM fractions which are irrelevant for competitive adsorption.Different model approaches were applied to describe the competitive adsorption of the T&O compounds and NOM, the tracer model, the equivalent background compound model, and the simplified equivalent background compound model. All these models are equilibrium models but in practice the contact time in flow-through reactors is typically shorter than the time needed to establish the adsorption equilibrium. In this paper it is demonstrated that the established model approaches can be used to describe competitive adsorption of T&O compounds and NOM also under non-equilibrium conditions.The results of the model applications showed that in particular the simplified equivalent background compound model is a useful tool to determine the PAC dosage required to reduce the T&O compounds below the threshold concentration.     

Disinfection by-product formation after biologically assisted GAC treatment of water supplies with different bromide and DOC content

Chlorination of drinking water in the presence of bromide and dissolved organic carbon (DOC) leads to the formation of brominated and chlorinated disinfection by-products (DBP). The concentration of bromide ions in the raw water is a significant factor in the speciation of DBP formed, and causes shifts in trihalomethane (THM) formation from chlorinated to brominated species. Drinking water treatment techniques that remove organic contaminants without affecting bromide ion concentrations cause increases in the brominated THM. For the present study, three water supplies containing different DOC and ambient bromide concentrations were filtered through biologically assisted granular activated carbon (BGAC). Similar to adsorption and coagulation treatment, this treatment does not remove bromide from drinking water; also, THMFP (trihalomethane formation potential) analysis indicated that the chlorinated effluent contained higher concentrations of brominated THM in comparison to the influent. Although BGAC may increase the brominated THM, which may be more toxic than the chlorinated THM, the overall reduction of THMFP by DOC removal far exceeds this negative change, thereby producing a much less toxic finished drinking water. This work is part of a study to make high DOC surface waters on the Canadian prairie safe and palatable for small volume users (individuals or small communities).     

Toxicological relevance of emerging contaminants for drinking water quality

The detection of many new compounds in surface water, groundwater and drinking water raises considerable public concern, especially when human health based guideline values are not available it is questioned if detected concentrations affect human health. In an attempt to address this question, we derived provisional drinking water guideline values for a selection of 50 emerging contaminants relevant for drinking water and the water cycle. For only 10 contaminants, statutory guideline values were available. Provisional drinking water guideline values were based upon toxicological literature data. The maximum concentration levels reported in surface waters, groundwater and/or drinking water were compared to the (provisional) guideline values of the contaminants thus obtained, and expressed as Benchmark Quotient (BQ) values. We focused on occurrence data in the downstream parts of the Rhine and Meuse river basins. The results show that for the majority of compounds a substantial margin of safety exists between the maximum concentration in surface water, groundwater and/or drinking water and the (provisional) guideline value. The present assessment therefore supports the conclusion that the majority of the compounds evaluated pose individually no appreciable concern to human health.     

The application of powdered activated carbon for MIB and geosmin removal: predicting PAC doses in four raw waters

Blooms of blue-green algae in reservoirs often produce the musty-earthy taste and odour algal metabolites 2-methylisoborneol (MIB) and geosmin. MIB and geosmin are not removed by conventional water treatment and their presence in the distribution system, even at low ng L-1 levels, can result in consumer complaints. Powdered activated carbon (PAC) can effectively remove MIB and geosmin when the correct dose is applied. The homogeneous surface diffusion model (HSDM) was used to predict PAC doses required to reduce MIB and geosmin concentrations to below 10 ng L-1 at four water treatment plants in Adelaide, South Australia. In jar tests, undertaken under treatment plant conditions, the predicted doses were found to produce water of the desired quality in three of the four waters. The poor predictions found in the fourth water, which had a considerably higher turbidity, were attributed to the incorporation of PAC in a larger, denser floc, leading to a reduced effective contact time of the adsorbent. It was found that higher doses of PAC were required for both compounds to produce acceptable quality water when turbidities rose above 26 NTU.     

Simultaneous degradation of disinfection byproducts and earthy-musty odorants by the UV/H2O2 advanced oxidation process

Advanced treatment technologies that control multiple contaminants are beneficial to drinking water treatment. This research applied UV/H₂O₂ for the simultaneous degradation of geosmin, 2-methylisoborneol, four trihalomethanes and six haloacetic acids. Experiments were conducted in de-ionized water at 24 ± 1.0 °C with ng/L amounts of odorants and μg/L amounts of disinfection byproducts. UV was applied with and without 6 mg/L H₂O_2. The results demonstrated that brominated trihalomethanes and brominated haloacetic acids were degraded to a greater extent than geosmin and 2-methylisoborneol. Tribromomethane and dibromochloromethane were degraded by 99% and 80% respectively at the UV dose of 1200 mJ/cm² with 6 mg/L H₂O₂, whereas 90% of the geosmin and 60% of the 2-methylisoborneol were removed. Tribromoacetic acid and dibromoacetic acid were degraded by 99% and 80% respectively under the same conditions. Concentrations of trichloromethane and chlorinated haloacetic acids were not substantially reduced under these conditions and were not effectively removed at doses designed to remove geosmin and 2-methylisoborneol. Brominated compounds were degraded primarily by direct photolysis and cleavage of the C-Br bond with pseudo first order rate constants ranging from 10⁻³ to 10⁻² s⁻¹. Geosmin and 2-methylisoborneol were primarily degraded by reaction with hydroxyl radical with direct photolysis as a minor factor. Perchlorinated disinfection byproducts were degraded by reaction with hydroxyl radicals. These results indicate that the UV/H₂O₂ can be applied to effectively control both odorants and brominated disinfection byproducts.     

Removal of MIB and geosmin using granular activated carbon with and without MIEX pre-treatment

This study assessed the impact of MIEX pre-treatment, followed by either coagulation or microfiltration (MF), on the effectiveness of pilot granular activated carbon (GAC) filters for the removal of the taste and odour compounds, 2-methylisoborneol (MIB) and geosmin, from a surface drinking water source over a 2-year period. Complete removal of MIB and geosmin was achieved by all GAC filters for the first 10 months, suggesting that the available adsorption capacity was sufficient to compensate for differences in dissolved organic carbon (DOC) entering the GAC filters.Reduction of empty bed contact time (EBCT), in all but one GAC filter, resulted in breakthrough of spiked MIB and geosmin, with initial results inconclusive regarding the impact of MIEX pre-treatment. MIB and geosmin removal increased over the ensuing 12 months until complete removal of both MIB and geosmin was again achieved in all but one GAC filter, which had been pre-chlorinated. Autoclaving and washing the GAC filters had minimal impact on geosmin removal but reduced MIB removal by 30% in all but the pre-chlorinated filter, confirming that biodegradation impacted MIB removal. The impact of biodegradation was greater than any impact on GAC adsorption arising from DOC differences due to MIEX pre-treatment. It is not clear whether, at a lower initial EBCT, MIEX pre-treatment may have impacted on the adsorption capacity of the virgin GAC.The GAC filter maintained at the longer EBCT, which was also pre-chlorinated, completely removed MIB and geosmin for the period of the study, suggesting that the greater adsorption capacity was compensating for any decrease in biological degradation.     

Relationship between intensity, concentration, and temperature for drinking water odorants

Odor analyses experiments indicated that, for the concentrations and temperatures tested, odor intensity was a function of both aqueous concentration and water temperature for water containing 1-butanol, free available chlorine, geosmin, n-hexanal, 2-methylisoborneol, and trans-2, cis-6 nonadienal. At weak odorant concentrations (approximately 4 on the flavor profile rating scale) the perceived odor intensity of these six chemicals was greater when the temperature was 45 degrees C than was 25 degrees C. Both of these temperatures are commonly encountered by consumers when they use tap water. Odor response to water containing isobutanal was affected by concentration but not water temperature. Experiments also revealed that reduction in aqueous concentration did not consistently reduce odor intensity; for some aqueous concentrations and chemicals an increase in odor intensity occurred at lower concentrations.     

Factors influencing the effect of bleached kraft mill effluents on drinking water quality

The taste and odour of drinking waters contaminated with bleached kraft mill effluent (BKME) were investigated. Mill effluents with a wide range of odour thresholds were selected and the effects of biological treatment, conventional water purification, carbon filtration, residual chlorine concentration, and recipient water quality were evaluated. No correlation was found between the original odour of BKME and the drinking water impairment. The taste and odour of drinking water prepared from pure glacial-fed river water to which biotreated BKMEs from three separate pulp mills were added was found to be impaired at effluent concentrations ranging from 0.1 to 0.4%. Effluent biotreatment, conventional water purification, and carbon filtration significantly reduced, but did not completely eliminate, BKME-associated taste and odour in potable water samples. The concentration of residual chlorine in the finished drinking water samples was an important factor influencing the degree of taste impairment.     

Development of the revised drinking water standard for chromium

Comprehensive regulations are being developed to limit human exposure to contamination in drinking water by the United States Environmental Protection Agency (EPA) under the authority of the Safe Drinking Water Act (SDWA). These regulations are being developed in several phases and include synthetic organic chemicals, inorganic chemicals, microbiological contaminants and radionuclides. This paper addresses the fundamental concepts and approaches used by EPA in setting drinking water regulations and how EPA is using these concepts to revise the drinking water standard for chromium.     

Seasonal occurrence and degradation of 2-methylisoborneol in water supply reservoirs

Methylisoborneol (MIB) and geosmin are cyanobacterial metabolites that occur at nanograms per liter levels in surface water supplies and are responsible for many taste and odor complaints about the aesthetics of drinking water. This study evaluated three water supply reservoirs with bottom-release (hypolimnion) outlet structures in Arizona. MIB concentrations were always higher than geosmin concentrations, but both followed similar seasonal trends. MIB concentrations increased from spring to late summer, and stratified vertically with depth in the water column; the highest concentrations were always in the upper 10 m of the water column. Thermal destratification in the autumn increased MIB concentrations released from the outlet of reservoirs and impacted downstream utilities for several months. By winter of each year MIB concentrations were non-detectable. Mass balance analyses on MIB indicated that in-reservoir reactions were more important in changing MIB concentrations than conservative hydraulic "flushing" of the reservoir. Maximum net loss rates for MIB in the field (R(F,max)) were on the order of 0.23-1.7 ng/L-day, and biodegradation appeared more important than volatilization, photolysis or adsorption. Using lake water in laboratory experiments, bacterial biodegradation rates (R(L)) ranged from 0.5-1 ng/L-day and were comparable to R(F,max) values. Based upon these rates, MIB concentrations in a reservoir would decrease by approximately 30 ng/L over a period of 1 month. This was the magnitude change in MIB concentrations commonly observed after autumn thermal destratification of the reservoirs.     

Origins and implications of drinking water odours in lakes and reservoirs of British Columbia, Canada

The relationship between commonly measured limnological parameters and odours was examined in 16 reservoirs and lakes used as sources for drinking water and three reference lakes. Odour analysis was conducted using flavour profile analysis (FPA) and, on select lakes, gas chromatography ion-trap mass spectrometry (GC-ITMS) for target compounds. Total phosphorus (TP) was the best single predictor of FPA intensity and multiple regression models accounted for 37-39% of intensity variance in the epilimnion and metalimnion, respectively. Earthy odours were more prevalent in reservoirs and lakes with higher TP, whereas decomposing vegetation and green vegetation+grassy odours almost exclusively occurred when TP was lower (<13 microg P/L). Only geosmin was identified with GC-ITMS, and it was found to occur in lakes and reservoirs of higher trophic status (e.g. more algal biomass). Infrequent episodic events in the Greater Victoria's principal reservoir (e.g. algal blooms) have previously been linked with taste and odour problems in their tap water. However, analysis of odours under the conditions of this study (i.e. no strong odour episodes in the source reservoir) suggest that typical odours prevalent in tap water originating from Sooke Lake Reservoir are derived from treatment processes or the distribution system, not directly from the reservoir. This study demonstrates the utility of employing relatively simple and established methods to better understand management issues of a drinking water system.     

Identification and assessment of hazardous compounds in drinking water

The identification of organic chemicals in drinking water and their assessment in terms of potential hazardous effects are two very different but closely associated tasks. In relation to both continuous low-level background contamination and specific, often high-level, contamination due to pollution incidents, the identification of contaminants is a pre-requisite to evaluation of significant hazards. Even in the case of the rapidly developing short-term bio-assays which are applied to water to indicate a potential genotoxic hazard (for example Ames tests), identification of the active chemicals is becoming a major factor in the further assessment of the response.Techniques for the identification of low concentrations of organic chemicals in drinking water have developed remarkably since the early 1970s and methods based upon gas chromatography-mass spectrometry (GC-MS) have revolutionised qualitative analysis of water. Such techniques are limited to “volatile” chemicals and these usually constitute a small fraction of the total organic material in water. However, in recent years there have been promising developments in techniques for “non-volatile” chemicals in water. Such techniques include combined high-performance liquid chromatography-mass spectrometry (HPLC-MS) and a variety of MS methods, involving, for example, field desorption, fast atom bombardment and thermospray ionisation techniques. In the paper identification techniques in general are reviewed and likely future developments outlined.The assessment of hazards associated with chemicals identified in drinking and related waters usually centres upon toxicology - an applied science which involves numerous disciplines. The paper examines the toxicological information needed, the quality and deployment of such information and discusses future research needs.Application of short-term bio-assays to drinking water is a developing area and one which is closely involved with, and to some extent dependent on, powerful methods of identification. Recent developments are discussed.