ARTICLE IN PRESS

Water Research 38 (2004) 1520–1529

Occurrence and fate modeling of MTBE and BTEX compounds in a Swiss Lake used as drinking water supply
Torsten C. Schmidta,*, Stefan B. Haderleina,1, Rolf Pfisterb, Richard Forsterb
a

Swiss Federal Institute for Environmental Science and Technology (EAWAG) and Swiss Federal Institute of Technology, Zurich (ETHZ), P.O. Box 611, Ueberlandstr. 133, CH-8600 Duebendorf, Switzerland b Wasserversorgung Zurich, Hardhof 9, CH-8023 Zurich, Switzerland Received 28 April 2003; received in revised form 8 December 2003; accepted 17 December 2003

Abstract Emissions of fuel components from boating use on multiple-use lakes and reservoirs are of high concern with regard to the drinking water supply from such water bodies. We report results of a detailed study on the occurrence, sources and fate of aromatic hydrocarbons and methyl tert-butyl ether (MTBE) in a typical holomictic lake, Lake Zurich, that supplies drinking water for the largest Swiss city. Emphasis of the investigation was on the fuel oxygenate MTBE, which was found in concentrations up to 1.4 mg/L in the epilimnion and up to 0.05 mg/L in the hypolimnion of the lake. The concentration difference was due to the stratification of the lake during the boating season with very limited water exchange across the thermocline. MTBE and BTEX nearly completely volatilized before vertical lake mixing occurred in winter. Spatial and temporal variations of MTBE concentrations in the lake were observed and successfully predicted using two complementary box models (MASAS Light and Aquasim). The drinking water supply from holomictic lakes is not at risk for the scenarios studied if water is extracted from well below the thermocline. Since emissions of unburned gasoline into such water bodies are caused predominantly by boating activities, restrictions of highly emitting twostroke engines could substantially reduce the MTBE and BTEX load of the epilimnion during the boating season. r 2004 Elsevier Ltd. All rights reserved.
Keywords: MTBE; BTEX; Gasoline; Drinking water; Boating; Lake

1. Introduction The concentration of fuel-derived hydrocarbons in lakes, rivers, and coastal waters has been intensively studied in the past [1]. The major emission source was found to be boating traffic, in particular emissions of unburned fuel from two-stroke-engines mainly used in small motor and sailing boats [2–4]. More recently,
*Corresponding author. Present address: Center for Applied Geoscience, Eberhard-Karls-University Tuebingen, Wilhelmstr. 56, D-72074 Tuebingen, Germany. Tel.: +49-7071-29-73147; fax: +49-7071-29-5139. E-mail address: torsten.schmidt@uni-tuebingen.de (T.C. Schmidt). 1 Center for Applied Geoscience, Eberhard-Karls-University Tuebingen, Wilhelmstr. 56, D-72074 Tuebingen, Germany.

oxygenates added to gasoline such as methyl tert-butyl ether (MTBE) have been the focus of investigations in the US. Reported peak concentrations of MTBE in the epilimnion of (shallow) freshwater lakes were as high as 31 mg/L [5,6], which is well above the odor threshold of about 15 mg/L. As for other hydrocarbons, MTBE concentrations were strongly correlated with the number of boats in use. Consequently, various communities have restricted the use of personal watercraft on multiple-use lakes, in particular in California [7]. Pankow et al. [8] modeled volatilization rates for MTBE and benzene in surface water as a function of the three parameters depth, wind speed and water flow velocity. The calculated half-lifes ranged from 0.1 to 85 days for MTBE and from 0.005 to 42 days for benzene. Thus, a fairly rapid air/water exchange is generally expected for MTBE in shallow surface waters. In

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2003.12.027

Reuter et al.05–2.4–30. of samples 4 5 16 118 430 6 132 172 59 200 na 14 40 na na 54 estimate if boating use may lead to disturbance of wildlife.29. . boating seasond Lake Zurich.01–0. e.030–0. which ranges from 0.01–2. 1–20c 2.16 0.02 mg/L). year round Cranberry Lake. LOD: limit of detection. year round Lake Tahoe. Such carbureted two-stroke engines emit up to 25–30% of the fuel unburned into the water or the atmosphere [7]. year round Lake Zurich.9 Reference [12] [13] [14] [15] [16] [17] [18] This study This study This study [9] [19] [5] [10] [20] [6] na: not available. o0. o0. In Europe. regarding boating use. year roundf Lake Donner. a Note that % positives depends heavily on the LOD. 0. epilimnion data. However. The few reports.8b 0.1–12 0.05–9.59 na.4 0.2 13. which was corroborated by comparing model results based on MTBE loss via volatilization with measured data in two lakes [10]. data from US lakes is often used to Table 1 Reported concentrations of MTBE in surface water bodies Country Denmark Finland Germany Germany Germany Germany Switzerland Switzerland Switzerland Switzerland US US US US US US Water body (if specified) Various lakes Creeks and rivers Helsinki area Various rivers and ponds Various rivers Various rivers Various rivers Various rivers.036–0.g. off-seasone Lake Zurich. e Measurements from October 2002 to April 2003 and October to November 2003 at all depths (lower LOD of 0. o0. c Estimated value. Due to the lack of MTBE concentration data for European lakes. together with data for other surface water bodies and US lakes. Of particular concern in the US are personal water crafts for high-speed boating with carbureted or nondirect fuel injection two-stroke engines (essentially all jet skis and wave runners manufactured before 1999). boating season California lakes.10–1. h Data set partially overlapping with [5].62 0. In Europe. primarily due to boating activities. 0. oLOD–0. o0.19–0.02 mg/L). / Water Research 38 (2004) 1520–1529 1521 conclusion.10 0. 0.. Bradley et al.01 to 1 mg/L. 0. are summarized in Table 1.C. much less information on the occurrence of MTBE in freshwater lakes is available than in the US. g Outlier of 2.15.21. 0. Lake Zurich is a typical mid-European multiple-use lake with intense boating activities during summer. [11] suggested microbial degradation of MTBE in lake sediments as an additional sink for MTBE in stratified lakes. and only might become a future source of fuel (and MTBE) input in lakes. human activities or poses a risk for drinking water supplies [13]. At the same time. Recently. such watercrafts are hardly seen yet on freshwater lakes and streams. year round Lake Texoma. hypolimnion data. o0. elevated concentrations of MTBE. [9] studied in detail the potential sources of MTBE at Lake Donner and have shown that neither road runoff nor precipitation contributed much to the MTBE load. boating season New Jersey lakes.53g 0.038. Regarding lake hydraulics. i. Kanton Zurich.18–4.4 0. o0.1 na.4c. They found MTBE concentrations rapidly decreasing after the end of the boating season and attributed the MTBE loss mainly to volatilization. during the boating season at marinas and resorts.2–28. About 45 million m3 per % Positivesa na 5 81 97 87 67 45 100 100 100 na 100 98 na 20c 100 Concentration average and range (in mg/L) na.. they have hardly any outflow. New Jersey.53 mg/L not included in average. climate and lake hydraulics.8 mg/L not included in average as suggested by the authors. o0.2 14. f Measurements from April 2002 to November 2003 at depth >20 m (lower LOD of 0.2 0. 0.ARTICLE IN PRESS T.047 na. o1–10.01–0. Schmidt et al. it serves as the main drinking water supply for the city of Zurich. epilimnion data. many of the lakes in the southwestern US studied over the last years are nearly stagnant in summer. may only be expected during periods of high input.11.5.059. there are major differences between the US and a typical mid-European situation. d Measurements 1999–2003 from mid-May to September at depth 0–5 m.e.06. year roundh No.90.17. b Outlier of 9.

Lake Zurich is separated by a dam from Lake Obersee. The aims of this study were therefore: (i) to determine the content of MTBE and other fuel-derived aromatic hydrocarbons in Lake Zurich depending on spatial and temporal distribution. depth profiles from 0 to 30 m were measured on two sunny Sundays in June and July with intense boating traffic (one sampling round in the morning.5 Â 106 0. where boats cross only occasionally. toluene. 1. glacio-fluvial lake of wellknown hydraulics and morphology (Table 2). one in the afternoon). In order to study in more detail daily and spatial variations of MTBE concentrations in the lake. Basel. mxylene. at the deepest point of the lake (Fig.49 Â 106 [21] 5 3. o-xylene. ethylbenzene. Switzerland).C.3 Â 109 66. Riesbach is located near the outflow of Lake Zurich with intense boating traffic arising from the various marinas in or near the city.ARTICLE IN PRESS 1522 T. Lake Zurich is holomictic with regular deep-mixing over winter (from January to April) and a (theoretical) mean water residence time of 430 days. Schmidt et al. 2. Due to the reports from the US.3 . 2. depth profiles for MTBE were measured in Thalwil and Zollikon in February. At these sites. water exchange by inflow and outflow is almost completely confined to the epilimnion. 2.6 Â 106 29 Â 103 4/2.3 Â 103 136/51 430 7. 1.5%). August and November (sampling always in the morning). 1).1. (iii) to model the behavior of these compounds over time and space. Since inflow during the deepmixing phase is about 50% of the summer inflow. which results in a residence time of less than 3 months. however. Its length from Rapperswil to Zurich is about 30 km in north west direction (Fig. Zurich water works (WVZ) were concerned about impacts of boating on the quality of the extracted water. This mixture contains all seven analytes at a concentration of 1 g/L in methanol (certified maximum concentration error 70.7 Â 106. 1). two sites were selected for further measurements: Riesbach. Lake Zurich Lake Zurich is a prealpine. In summer. we provide data for a risk assessment of MTBE and aromatic hydrocarbons in a holomictic lake used as drinking water supply. close to Zurich harbor.3. Thalwil is about 8 km further up the lake. (ii) to identify the major immission and elimination pathways for such compounds in a holomictic lake and.and ether mix 30 from Dr.4-dichlorobenzene Table 2 Characteristic data of Lake Zurich Lake morphology Volume (m3) Surface area (m2) Length (m) Max/mean width (m) Max/mean depth (m) Lake hydraulics Theoretical mean residence time of water (d) Mean. From 2001 on.2. Experimental section 2. 2. Water and methanol used for standard preparations were HPLC-grade from Baker (Stehelin. max and min throughflow of water (m3/d) Mean water exchange rate epilimnion/hypolimnion (summer) (m3/d) Mean epilimnion depth (summer) (m) Mean epilimnion volume (summer) (m3) Mean temperature in epilimnion (summer) ( C) 3. Study site and sampling points Preliminary investigations were carried out in 1999 at various sampling points near Zurich harbor and in summer and winter 2000 during two regular sampling campaigns. Fig. Chemicals MTBE. At Rapperswil. more than 6 years are actually needed for the total renewal of the lake water [22]. benzene. Ehrenstorfer (Augsburg. which is the main inflow to the lake. May. Germany). The outflow of Lake Zurich is the river Limmat in the city of Zurich. Thus.3 Â 108 16. 2=Thalwil) and filling stations (). and Thalwil. / Water Research 38 (2004) 1520–1529 year are extracted by two drinking water treatment plants from 30 m below surface. 23 Â 106. Lake Zurich with location of sampling points (1=Riesbach. and p-xylene were purchased as aromatics.

5–10 vol. Varian. ffikon. This very userfriendly program was used to model situations where horizontal concentration gradients were negligible.50 atm L molÀ1 at 16 C. Switzerland) was used as internal standard. The following temperature program was used: 5 min at 40 C. Due to the limited availability of experimental data.85 17. In the case of MTBE.5 mg/m3 assumed as average value for Switzerland [27].4. The reliability of the method was validated in two round-robin tests for the determination of MTBE at low concentrations. Netherlands). Since water exchange with the hypolimnion during this phase is very small and does not influence epilimnion concentrations. at the outer boundary of and Pfa reactor 2. Switzerland).%) and Measurement uncertainty (%) 715 710 710 710 710 710 Recoveries (%) 110 110 105 105 105 108 Retention time (min) 5. Consequently.10 0. headspace SPME with a Combi-PAL autosampler (CTC.10–10 0. 2. Zug.74 18. net losses of MTBE from reactor 2 occurred neither by advection nor by diffusion across the outer boundary.50–10 0. no input (20 days). 2. desorption time was 20 min at an injector temperature of 280 C (split open after 60 s). the concentration gradient was assumed to be zero. Subsequent SPME enrichments were done with a 75 mm Carboxen/ PDMS fiber (Supelco.ARTICLE IN PRESS T.8 mm (Chrompack/Varian. For the FID the following settings were used: temperature 300 C. The relevant elimination processes and overall concentrations in epi. (IV) stratified lake. no input (105 days). it was neglected. two wellmixed reactors representing two sections of the epilimnion of the lake during the input phase (boating season) were coupled with an advective and a diffusive link. Analytical methods All analytes (MTBE and BTEX) were quantified using gas chromatography with split-/splitless injector 1177 and flame ionization detection (Varian GC 3800. and synthetic air at 300 mL/min. Separation of analytes was carried out with a GC column CP-Select 624. respectively. The Henry constants KH of the compounds were extrapolated to 16 C where possible.and hypolimnion of Lake Zurich were modeled with MASAS Light. Major uncertainties regarding MTBE input comprise the average MTBE content of gasoline used for boats (2. Therefore. Both reactors were in contact with an air compartment with a constant MTBE concentration of 0. The MTBE content in these gasoline samples was 2. Schmidt et al. Fluka. Carrier gas was helium at a constant flow of 2 mL/min.50 0. In order to model the spatial distribution of MTBE in Lake Zurich.10–10 Squillace et al.49 9. (III) stratified lake. input (153 days). Bellefonte. yielding KH=0. hydrogen at 30 mL/min.13 .5. Input parameters for both models are summarized in Table 4. / Water Research 38 (2004) 1520–1529 1523 (purum. Quantitation was done with an external calibration curve after correction by the internal standard. (II) stratified lake. Selected gasoline samples from boat filling stations were analyzed by the Swiss Federal Institute for Testing and Materials (EMPA) according to the European regulation EN 228. Buchs. make-up gas (nitrogen) at 25 mL/min. [23] were used.10–10 0. the following equation was derived for the temperature dependency of KH from measurements in a temperature range from 5 C to 35 C [24]: ln KH=À5041 1/T+9. df 1.10 Working range (mg/L) 0.83. The two reactors comprised only half of the total lake volume because at the upper end of the lake another area of intense boating exists at the cities of Rapperswil . 5 min at 250 C. to 150 C at 5 C/min. Modeling approach For all model calculations physico-chemical parameters of MTBE and BTEX compounds published by Table 3 Analytical method parameters Substance MTBE Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene Limit of quantitation (LOQ) (mg/L) 0. no input (87 days).32 mm.08 19. A time frame with the following four phases was implemented to predict contaminant concentrations: (I) mixed lake. Ten milliliter of a sample was filled in a 20-mL headspace vial and 1 mL of an internal standard solution was added.10 0.5 and 9.20–10 0. The conceptual model of the lake used for Aquasim simulations is shown in Fig. 30 m  0. a spreadsheet-based program developed at EAWAG [25]. PA). Switzerland) was used.33 13. The atmospheric background concentration could only be considered in Aquasim.10 0.10–10 0. 2.20 0.8 vol% for a regular and premium grade gasoline. Equilibration time was 15 min at room temperature. Important parameters of the analytical method are summarized in Table 3.C. For enrichment and injection. to 250 C at 40 C/min. Zwingen. Middleburg. the more sophisticated program Aquasim [26] had to be used.

Khor: horizontal diffusivity.e.1.ARTICLE IN PRESS 1524 T.and hypolimnion is small. Because off-season and hypolimnion concentrations of MTBE always were below the limit of quantitation (0.C. Estimated from [28]. A summary of all MTBE measurements obtained from 1999–2003 is included in Table 1. Note that the model comprises only half of the total epilimnion volume (see text for details). Emissions from four-stroke engines were neglected. i.4 mg/L during summer the fluctuations of MTBE concentrations over time and space were subsequently studied in more detail. For hypolimnion and off-season epilimnion measurements included in Table 1. hence the hypolimnion was not considered as an additional compartment. 2. 3. they do not depend on the MTBE input in the epilimnion. Results and discussion Value 4’600 3. Water exchange between epi.004 mg/L.6 vol% 20% 80% 153 d 6. / Water Research 38 (2004) 1520–1529 Fig. which provided a five-fold improvement in sensitivity. This is nearly 10 times lower than the average epilimnion concentrations during the boating season.1 to 1. the analytical method was changed from FID to MS detection. only measurements from May 2002 on are therefore included.1 mg/L). Schmidt et al. Since preliminary investigations in 1999 and 2000 indicated that concentrations of MTBE in Lake Zurich ranged from 0. Seasonal and daily fluctuations 193’000 L/a 4.6 m/s 5m 16 C 5 cm/s 80%/20% Estimated from [28] and regional boat registry. The concentrations in the hypolimnion are remarkably constant at both sampling points and over time. MTBE was always detected in the epilimnion at concentrations >0. Conceptual model of Lake Zurich epilimnion for modeling spatial distribution of MTBE and BTEX with Aquasim. The average concentration in 200 samples taken from the lake hypolimnion since April 2002 is 0. Table 4 Model input parameters for calculations with MASAS Light and Aquasim Parameters for estimating MTBE input into the lake Number of boats with two-stroke enginesa Gasoline consumption of all twostroke engines on Lake Zurichb Average MTBE content of gasoline used in boats Emission rate of unburned gasoline from two-stroke engines Dissolution rate of unburned gasoline emitted by two-stroke engines Boating season from May to September Resulting MTBE input in Lake Zurich during boating season Other model input parameters Wind speed Epilimnion depth Average epilimnion temperature during summer Average flow velocity in epilimnion Fraction of MTBE released in source and non-source zone (Aquasim only)c a b the share of fuel emitted unburned from two-strokeengines (4–50%). During the boating season.038 7 0. c These fractions are estimates based on observations of boat numbers during sample campaigns. The average off-season .. vtot: mass transfer coefficient for air–water exchange.1 mg/L.9 kg/d 1.

Thus. maximum epilimnion concentrations were about 10 times lower than reported from US lakes. over the day a steep concentration gradient developed in the upper few meters that concurred with the temperature gradient.07. LOQ: limit of quantitation (see Table 3). concentrations were nearly constant in the epilimnion (see above for exemption) and decreased rapidly with depth. summer concentra- tions of MTBE did not exceed 0. / Water Research 38 (2004) 1520–1529 1525 epilimnion concentrations are only slightly elevated compared with hypolimnion concentrations (less than a factor of 2).1 0. 3a and b) revealed that MTBE concentration profiles very well matched the corresponding temperature profiles (data not shown).07. with much less intense boating use. Vertical mixing within the epilimnion during the night presumably destroyed the epilimnic concentration gradient.80 1. Depth profiles of MTBE at the two sampling points Riesbach (a) and Thalwil (b).3 0. a similar correlation of MTBE concentrations with boating use as already described for multiplepurpose lakes in the US [9.08.2 0.01 AM 24.07.01 AM 29.40 0. Schmidt et al.20 1. Thus. in µg/L 0. Diurnal fluctuations of MTBE concentrations at Lake Zurich during the two sampling campaigns on June 24 and July 29 were significant.. Spatial distribution Depth profiles measured at Riesbach and Thalwil (Fig.01 AM 29.01 PM 08.01 AM LOQ (b) Fig. Temperature profiles are not shown to enhance legibility. Whereas MTBE concentrations in the epilimnion were rather constant during the morning measurements.06. This MTBE conc.07.06.5 0.e.C. in µg/L 0 0 5 Depth in m 10 15 20 25 0.06. .20 0.06.2.14 mg/L and BTEX could never be detected.10] was found.00 0 5 Depth in m 10 15 20 25 24. morning and afternoon sampling campaigns were carried out on two days in June and July 2001 with intense boating traffic. Very similar depth profiles for MTBE were measured on other sampling dates during the boating season and at other sampling sites of the WVZ water quality monitoring at Lake Zurich.ARTICLE IN PRESS T. However. 3.40 (a) MTBE conc.01 PM LOQ 0.4 0. i. Lake Walen.60 0.00 1. diurnal epiliminic stratification with reduced vertical mixing might explain the higher MTBE concentrations beneath the lake surface.01 PM 29. 3. To investigate if MTBE input over the day resulted in significant diurnal concentration patterns. 3a (Riesbach) and b (Thalwil).6 24.01 PM 29. which substantiates the rapid decrease of the MTBE load in the lake after the end of the boating season. which might be explained by the lower MTBE input due to a lower average content of MTBE in gasoline and less emitting boating types. The depth profiles for MTBE obtained during these four sampling events at both sites are shown in Fig. At another lake nearby.01 AM 24.

001 o0. however.66 mg/l in August [18].080  Toluene 0. In that study.02.23 mg/L. In 2001/2002. 1.05 (sum of all isomers) mg/L.051 o0.47.1 mg/L.001 o0. and 2.5 m below the surface BTEX concentrations were below the limit of quantitation (0. our finding is consistent with results by Wick et al.047 o0.4 times higher at the highly frequented site Riesbach in June and July.1 mg/l). were 0.023 0.05 mg/L.8 times higher on both sampling dates. Comparison of MTBE concentrations in the epilimnion of Lake Zurich at the two sampling sites Riesbach and Thalwil shows clearly a correlation of MTBE concentrations with boating traffic intensity.0015 — 0. During day time.001 0.45 mg/l in August 2001. Schmidt et al. Purge & Trap-GC/MS was used with a lower limit of detection (LOD) of 0.0015 — 0.055 o0.001 0. In contrast. 2. Modeling results The modeling with MASAS Light and Aquasim served several purposes: first. c No hydrolysis at lake pH (7.023 0.e.C.001 o0. e Microbial degradation was neglected for all compounds since no rate constants appropriate for a lake epilimnion were available.39.050 o0. the MTBE concentration at Riesbach was 1. differed from the pattern seen for MTBE. BTEX were only detected between May and August above 0. In particular for the BTEX compounds this is a worst-case scenario since degradation might considerably contribute to overall loss [29]. this does not change the result more than 3%. river Limmat. the major elimination processes for MTBE and BTEX were identified with the use of lake and substance-specific data (using MASAS Light). The vertical distribution of BTEX.001 o0.0015 — 0.001 o0. Aquasim also allowed to include a non-zero air concentration. MTBE was detected year round but from October to May concentrations were below 0.0015 o0. In the morning sampling campaigns.023 0. i.001 o0. respectively) was lower due to horizontal mixing during the night when no MTBE input occurred. The Aquasim model was used to analyze the differences in concentration found at the two sampling sites Thalwil (non-source zone) and Riesbach (source zone). In agreement with the modeling results (see below). shortly after the boating season commenced. the concentration difference between the two sites (1.001 0.6) [30]. 3. BTEX concentrations decreased more rapidly with depth than MTBE concentrations. however. d Using Henry constants extrapolated to 16 C (where data for extrapolation was available).001 o0.05 mg/L. . after cessation of the boating season. ethylbenzene and xylenes were 0.001 0. 2 3 of total À1Á elimination rate) and flushing 3 (Table 5). MTBE was measured several times in the outflow of Lake Zurich. toluene..073 kw kex khyd kgas ksed kphotod kphotoi kbio k dÀ1 dÀ1 dÀ1 dÀ1 dÀ1 dÀ1 dÀ1 dÀ1 dÀ1 0.001 o0. 0.001 o0. respectively. and rose to 0. For BTEX compounds.ARTICLE IN PRESS 1526 T.8–8. Elimination Table 5 Average first-order rate constants for elimination of MTBE and BTEX in the epilimnion of Lake Zurich during summera Rate constant Symbol Units Compound MTBE Flushing through outflow Water exchange with hypolimnionb Abiotic hydrolysis Gas exchanged Sedimentation Direct photochemical transformation Indirect photochemical transformation Biological transformatione Total elimination rate constant a b Benzene 0. Frequently.1 and 1.076 o-Xylene 0. Second. / Water Research 38 (2004) 1520–1529 concentration profile is consistent with previously published data from Lake Donner [9]. This indicates that the assumption of horizontally homogenous concentrations in the epilimnion is an oversimplification of the system which tends to underestimate peak diurnal concentrations in boating areas. This result is consistent with monthly monitoring data of the regional authorities in 2000 that gave maximum MTBE concentrations of 0.023 0. a simulation over several years was run to evaluate long-term trends of MTBE in the lake.3. a similar but less-pronounced trend was observed. Peak concentrations in August for benzene.001 o0. in addition to the monitoring of MTBE and BTEX in Lake Zurich. Though the reason for this behavior is not exactly clear.001 o0. [29] who attributed the loss of benzene in the metalimnion of a lake to a stable community of benzene degrading bacteria in this region.001 0.001c 0. The major elimination processes from the lake epilimnion were air–water exchange (approx. no MTBE was detected in river Limmat in November 2001 and February 2002. The small hypolimnion concentrations were neglected. Concentrations in May 2001.075 Estimated from model calculations with MASAS Light using physico-chemical parameters at 25 C (see text). The results were then used to predict average epiand hypolimnion concentrations in the whole lake.

which represents the average lake concentrations better than the source-zone site (Riesbach). The obtained value of 5. 5.015 mg/L. Fig. Over 4 years of constant MTBE input during Phase 3 (P3). considering that the Henry constants differ by more than one order of magnitude between MTBE and the three BTEX compounds. The effective horizontal diffusivity Khor was used as a fitting parameter. Schmidt et al.038 mg/L.C. P3. for MTBE and BTEX. The upper limit of predicted concentrations is obtained by simply assuming equilibrium between the mixed lake and the atmosphere and no net changes in the hypolimnion after stratification. However. respectively (details see text). Aquasim prediction of epilimnion concentrations of MTBE at the two sampling points Riesbach (within source zone) and Thalwil (within non-source zone). 4 shows MASAS Light predictions of MTBE concentrations in the epilimnion and hypolimnion of the lake (assumed to be horizontally well mixed) in comparison with measured concentrations. In contrast to studies on US lakes that involved a calculation of MTBE loss [9. The reason is mainly that a zero concentration for air had to be assumed due to constraints of the MASAS Light program. 5. For parameters not listed in Table 4 the following values were used: vtot=0. hypolimnion concentrations remain o0. flushing via the outflow needs to be considered for Lake Zurich as for most other mid-European lakes. P2.038 mg/L. Note that air concentrations could not be considered in this model and are therefore assumed to be 0.5 mg/m3 is about 0. This is evident by the rather high concentrations of MTBE in the lake outflow. The predicted epilimnion concentrations at Riesbach are at the higher end of the measured data. 1.18 Â 106 m2/d. river Limmat. P1. l=6000 m. This might be due to the fact that MTBE concentrations were measured in the morning. microbial degradation in lake bottom sediments may not contribute substantially to the overall elimination of MTBE. P4: phases 1–4. Predicted epilimnion concentrations for the whole lake are well within the range of experimental results at the Thalwil site.4%). except for indirect photochemical transformation via reaction with OH-radicals in the case of o-xylene (approx.249 m/d. and no MTBE was emitted in Fig. The Aquasim prediction of horizontal segmentation in the lake is shown in Fig.ARTICLE IN PRESS T. Fig. 4.28 mg/L is reached 40 days after the boating season (and thus the MTBE input) commences (75%). w=2000 m. sedimentation is not an important elimination process.18 Â 106 m2/d (or 60 m2/s) is at the upper end of turbulent horizontal diffusivities found in lakes [31] but can be explained by the fact that in addition to horizontal diffusivity other horizontal exchange processes are included in the effective parameter. The measured hypolimnic concentrations of 2002 and 2003 are about 2. For this case (using KH=0. / Water Research 38 (2004) 1520–1529 1527 rates were surprisingly similar for all compounds. . Since hardly any MTBE reaches the lake sediment.and hypolimnion concentrations of MTBE in Lake Zurich over 4 years compared with measurement results at Thalwil in August 2001. [11] recently suggested microbial degradation of MTBE in lake sediments as a potential sink for MTBE in stratified lakes. during summer (see above). Bradley et al. MASAS Light prediction of epi. The equilibrium concentration of 0. A further model prediction shows that even after 15 years (MTBE has been used in Switzerland in substantial amounts since about 1985). Water exchange with the hypolimnion contributed only about 2% to the total removal from the epilimnion. 2001 are given (data from the morning sampling campaign were used).10]. This perfectly matches the average measured hypolimnion concentration of 0. For comparison.5 times higher than the predicted ones. the range of measured MTBE concentrations in the epilimnion on July 29.304 atm L molÀ1 at 8 C from our own measurements) the predicted equilibrium concentration in water assuming a constant air concentration of 0. under the given assumptions. Other elimination processes were not of importance (o1%). Khor=5. there is hardly a rise in hypolimnic concentrations due to the small vertical water exchange during stratification (see Table 2) and since most of the MTBE has already been eliminated from the lake before complete mixing occurs. With this model it is possible to match the measured concentrations at the Riesbach (source zone) and Thalwil (diffusive-linked zone) site.

[5] Baehr AL. Grundwasser 2001. If contaminants are almost completely eliminated during the stratification period. either based on local data or on literature values. 3. [4] Juttner .2:51–60. Environ Sci Technol 2001. Pyle SM.126(12):1131–6. Environmental significance Due to the density stratification of holomictic lakes there is hardly any water exchange in summer and thus transport of dissolved contaminants between epi. J Environ Eng ASCE 2000. Calculated volatilization rates of fuel oxygenate compounds and other gasoline-related compounds from rivers and streams. California Department of Boating and Waterways. Environment and quality of life. Impact on water quality. the uncertainty in MTBE input in the lake was most important. Zogorski JS. a sensitivity analysis was carried out with Aquasim to identify which of these parameters dominate uncertainties in the model result. and the effective horizontal diffusivity Khor determine the concentration difference between both compartments. Kobenhavn. Environ Sci Technol 2000.37(15):3756–66. and fate of the gasoline oxygenate methyl tert-butyl ether (MTBE) in a multiple-use lake. Frank Peeters and Heinz Singer for helpful comments on the manuscript.29(8):1976–82. Quantification of gases and VOC. twelve hours before sampling whereas the model assumes a constant input over the whole boating season. Water Res 1995. Summer 1998. Gschwend PM. Concentrations. Zafiriou OC. F. Light. Seasonal and daily variations in concentrations of methyltertiarybutyl ether (MTBE) at Cranberry Lake. Weiss H. Emissions of two. Environ Sci Technol 1998. MTBE input is governed by several factors: gasoline consumption of boats. Modeling volatilization of MTBE from standing surface waters. [11] Bradley PM. Sussex County. et al. Water Res 2003. Two-stroke and MTBE issues. Water Res 1995. Furthermore.and hypolimnion. for both lake compartments.34(3):368–72. In order to further reduce emissions of unburned fuel into surface water. Schmidt et al. We thank Markus Ulrich. Handlingsplan for MTBE. Landmeyer JE. Environ Sci Technol 1982. Since there are a number of model input parameters that could only be estimated. chenwasser in Deutsch(MTBE) in Grund. New Jersey. 1998. Reilly T. Volatile organic compounds at a coastal site.C. 282pp. average emission rate of unburned gasoline and dissolution rate of MTBE in water from unburned gasoline. it is advisable to include benzene and other BTEX when studying boating emissions since substantial amounts of these toxicologically more relevant compounds are emitted along with MTBE and total elimination rates are similar.og Energiministeriet Miljostyrelsen. [7] Anonymous. Emissions of two. [6] Toran L.dbw. [3] Juttner .33(5):921–37.35(4):658–62. Luxembourg: Office for Official Publications of the European Communities.and four-stroke outboard engines—II. Acknowledgements We thank Frank Peeters for his help in the conceptual model and its implementation in AQUASIM for the modeling of spatial distribution. editors. Financial support has been provided by Com! ne ! rale des Eaux (CGE). [12] Anonymous. Untersu. 2002. 19. r-butylether chungen zum Benzininhaltstoff Methyltertia . average MTBE content of gasoline used in these boats. MTBE input and water throughflow influence concentrations in both lake compartments in the same direction whereas the fraction of MTBE released in the source and non-source zone.htm.16:38–45. sources. Overall. Schirmer M. The frequently used assumption of horizontal homogeneity in lakes is not always valid on a diurnal time scale as shown for the spatial MTBE distribution in Lake Zurich. their concentration in the hypolimnion will remain very low even over long time periods. [2] Gabele PA. EUR 20417 EN—European Union Risk Assessment Report on Tert-butyl methyl ether. [13] Hansen BG. [9] Reuter JE. therefore no risk is expected for the drinking water supply in such lakes.ca. US Geological Survey. Rathbun RE. Available at http://www. et al. Miljo. F. New Jersey. river water below multiple-use lakes may be contaminated with MTBE at the sub-mg/L level as is the case in river Limmat. West Trenton. [14] Effenberger M. pagnie Ge References [1] Mantoura RFC. Baehr A. Clarke KR.4. et al. Rowena Crockett is acknowledged for the analysis of gasoline samples from one of the boat filling stations. Chapelle FH. Several students have provided valuable input during a case study about MTBE in Lake Zurich using MASAS Light. Zapecza OS.32(23): 3666–72. Widespread potential for microbial MTBE degradation in surfacewater sediments. Drinking water is typically extracted well below the thermocline. [10] Stocking AJ. Markus Ulrich helped with all features of modeling with his program MASAS . 2003. Emissions from two outboard engines operating on reformulated gasoline containing MTBE. et al. Methyl tert-butyl ether (MTBE) and other volatile organic compounds in lakes in Byram township. Lipka C. Short-term variations. Popp P. vol.und Oberfla land. 1998. Although elimination rates of VOC in running water are higher than in lakes. [8] Pankow JF. limitations of the use of high-emitting two-stroke engine types in motorboats should be considered.gov/mtbe.ARTICLE IN PRESS 1528 T.and four-stroke outboard engines—I. Chemosphere 1996. For all of these parameters estimated values had to be used. / Water Research 38 (2004) 1520–1529 the approx. 984264. Baker R. Kavanaugh MC. 2.29(8):1983–7.

36(17):3652–61. 1998. Zimmermann U. Bundesamt fur . r[15] Klinger J. 1998.ARTICLE IN PRESS T. Determination of methyl tertbutyl ether in surface water by use of solid-phase microextraction. [19] Boughton CJ.30(2):21–30. W. [25] Ulrich MM. Swiss Federal Institute for Environmental Science and Technology (EAWAG).143(3):166–71. 2002. 2001. Methyl tert-butyl ether (MTBE) in river and wastewater in Germany—1. [17] Achten C. Bern. Abscha vanz von Methyl-tert-butylether (MTBE). Baudirektion Kanton Zurich. / Water Research 38 (2004) 1520–1529 . McNeill K. Puttmann . Environ Sci Technol 2001. Kampbell DH. . Medilanski E. 1996.34(20): 4354–62. Brauch H-J. Hyman MR. MASAS light. Pankow JF. Eberhard-Karls-University. Environmental organic chemistry. Balsiger C. . Umwelt.34(7):1359–64. EAWAG/ETH. Taylor CD. Gihr R. Ulrich M. 1972–1996. Nr. [31] Schwarzenbach RP. Duebendorf. [16] Achten C. Environ Sci Technol 2000. Seel P. Sewell GW. Zurich.35(19): 3954–61. 1994. Puttmann W. 2004. Lico MS. Bundesamt fur . [29] Wick LY. Smith CA. Carson City. 2003. Environ Toxicol Chem 1997. . Environ Poll 2002. Rojo M. Schriftenreihe Umwelt Nr. Moir ME. Untersuchung von Fliessgewa auf VOC im Kanton Zurich. Wasserversorgung Zurich (WVZ). Imboden DM. Kolb A. tzung der Altlastenrele[27] Lothenbach B. Reduktion der VOC-Emissionen bei der Bootsbetankung. [30] O’Reilly KT. Master thesis. Schmidt et al. P. US Geological Survey. Wald und Landschaft. 1997. Zurich. July–September 1997. Forster R. [22] Gammeter S. . Umweltmaterialien. Review of the environmental behavior and fate of methyl tertbutyl ether. Korte NE. Zogorski JS.C. ssern [18] Pfister H. Umwelt. 254. Environ Sci Technol 2000. Gschwend PM.16(9):1836–44. 151. [21] Dzambas Z. Bern. Hydrolysis of tert-butyl methyl ether the (MTBE) in dilute aqueous acid. [23] Squillace PJ. Environ Sci Technol 2002.118(3):331–6. AWEL. MTBE (methyl-tertia butylether)—Ein Problemstoff fur . USGS Fact Sheet FS-055-98. Tuebingen. die Wasserversorgung? gwf-Wasser/Abwasser 2002. Nevada and California. Volatile organic compounds in Lake Tahoe. Duebendorf. NV. [26] Reichert P. Wald and Landschaft. Water quality at five marinas in Lake Texoma as related to methyl tert-butyl ether (MTBE). Gschwend PM. Limnologische Untersuchung des Zurichsees . . sserschutz. Munz C. Water Sci Technol 1994. New York: Wiley. Sacher F. [20] An YJ. Fate of benzene in a stratified Lake receiving contaminated groundwater discharges from a Superfund site. [28] Schurmann . 1529 [24] Arp HP. MASAS library files for Swiss lakes. AQUASIM—a tool for simulation and data analysis of aquatic systems. . Abteilung Gewa .