Occurrence and fate modeling of MTBE and BTEX compounds in a Swiss Lake used as drinking water supply

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 microg/L in the epilimnion and up to 0.05microg/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 two-stroke engines could substantially reduce the MTBE and BTEX load of the epilimnion during the boating season.     

Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins

Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.     

Comparison of MTBE concentrations in groundwater of urban and nonurban areas in Germany

The occurrence of the gasoline oxygenate methyl tert-butyl ether (MTBE) in groundwater samples from known fuel-contaminated sites (n=29 samples), nonurban (n=74) and urban sites (n=67) in Germany was investigated. The analyses revealed detection frequencies of 58% (contaminated sites), 24% (nonurban sites) and 63% (urban sites) at a detection limit of 0.01 microgL(-1). Median (maximum) MTBE concentrations were calculated for nonurban and urban samples as 0.18 microgL(-1) (2.2 microgL(-1)) and 0.06 microgL(-1) (48 microg L(-1)). The data from nonurban samples revealed MTBE detections mainly at public supply wells with higher pumping rates than monitoring wells. MTBE was more frequently detected in urban samples, most probably due to the higher atmospheric input and direct liquid emissions from motorways or gas stations. Higher concentrations above 1.0 microgL(-1) in urban areas were found in wells located at industrial sites, where also a MTBE plume was accidentally detected during the study. The prevalence of MTBE in shallow aquifers was comparable to those in the USA.     

Seasonal variations in the concentrations of ethylene,acetylene and propylene at Trombay,Bombay

Concentrations of ethylene, acetylene and propylene at Trombay, Bombay for the year 1982 are given in this paper. The method of measurement consisted of pre-concentrating the atmospheric hydrocarbons in short U-columns kept at dry ice temperature and then analysing in a gas chromatograph with a chemiluminescent detector. The data is based on 2-h samples collected daily in the forenoon and afternoon periods. A minimum concentration of 0.2 ppb of ethylene could be detected by this method. The ground level ozone concentrations at Trombay correlated with ethylene concentrations (correlation coefficient = 0.70) and with the product of ethylene and propylene (correlation coefficient = 0.40). These correlations are significant at 99.5 and 95% confidence levels respectively, and indicate that these reactive hydrocarbons contribute to ground level ozone concentrations.Measurements at Trombay showed that the concentrations of the hydrocarbons are below the air quality standards. The chemiluminescent method of detection was found to be very convenient for selective determination of ethylene and other reactive hydrocarbons.     

Contamination by heavy metals in silver fish (Rastreneobola argentea) caught from Lakes Kyoga and Victoria,Uganda

Little information exists on heavy metal contamination in silver fish (Rastreneobola argentea) caught from Lake Victoria. A large number of Ugandans consume the species. Sun‐dried silver fish were collected from 10 landing sites on Lake Victoria, and from five control sites along Lake Kyoga. The finely ground fish was digested with analytical reagent grade nitric acid. Analyses were performed by atomic absorption spectrophotometry. The specimens were found to contain significantly higher levels (p ≤ 0.05) of zinc, Zn (86.1%), copper, Cu (99.1%), cadmium, Cd (99.3%) and lead, Pb (94.6%) compared with those from the control sites. The fish contamination was attributed to discharge into Lake Victoria of untreated industrial and anthropogenic effluent. Although mean Zn, Cu and Pb concentrations were still below, those of Cd were higher than the maximum permissible levels recommended by the World Health Organization (WHO). Overconsumption of the silver fish could pose Cd‐related health risks.     

Sexual difference in PCB concentrations of lake trout (Salvelinus namaycush) from Lake Ontario

We determined polychlorinated biphenyl (PCB) concentrations in 61 female lake trout (Salvelinus namaycush) and 71 male lake trout from Lake Ontario (Ontario, Canada and New York, United States). To estimate the expected change in PCB concentration due to spawning, PCB concentrations in gonads and in somatic tissue of lake trout were also determined. In addition, bioenergetics modeling was applied to investigate whether gross growth efficiency (GGE) differed between the sexes. Results showed that, on average, males were 22% higher in PCB concentration than females in Lake Ontario. Results from the PCB determinations of the gonads and somatic tissues revealed that shedding of the gametes led to 3% and 14% increases in PCB concentration for males and females, respectively. Therefore, shedding of the gametes could not explain the higher PCB concentration in male lake trout. According to the bioenergetics modeling results, GGE of males was about 2% higher than adult female GGE, on average. Thus, bioenergetics modeling could not explain the higher PCB concentrations exhibited by the males. Nevertheless, a sexual difference in GGE remained a plausible explanation for the sexual difference in PCB concentrations of the lake trout.     

Visible-light-induced photocatalysis of low-level methyl-tertiary butyl ether (MTBE) and trichloroethylene (TCE) using element-doped titanium dioxide

While the photocatalytic degradation of various volatile organic compounds in conjunction with UV light has been widely reported, visible-light-induced photocatalytic degradation of low-levels of the pollutants MTBE and TCE, which have been linked to potential adverse health effects, is rarely reported. The present study examined whether visible-light-activated S- or N-doped TiO₂ photocatalytic technology can be used to control indoor concentrations of MTBE and TCE. This study consists of the characterization of the doped TiO₂ powders, as well as an investigation of their photocatalytic activities. In regards to both powders, a shift of the absorbance spectrum towards the visible light region was observed. An activity test suggested that these photocatalysts exhibited reasonably high degradation efficiencies towards MTBE and TCE under visible light irradiation. The degradation efficiencies of MTBE and TCE by S- and N-doped photocatalysts exceeded 75 and 80%, respectively, at input concentrations (IC) of 0.1 ppm. Degradation efficiency was dependent on both IC and relative humidity. TCE could enhance the degradation efficiency of MTBE even under visible-light irradiation. The estimated mineralization efficiencies (MEs) were comparable to those of previous studies conducted with UV/TiO₂ systems. Similar to the relative degradation efficiencies, the ME of TCE was higher in comparison to that of MTBE. The CO production measured during the photocatalytic processes represented a negligible addition to indoor CO levels. These results suggest that visible-light-activated S- and N-doped TiO₂ photocatalysts may prove a useful tool in the effort to improve indoor air quality.     

Seasonal variation and impact factors of available phosphorus in typical paddy soils of Taihu Lake region,China

Phosphorus loss from soil can play an important role in eutrophication of aquatic bodies. The seasonal variation of available phosphorus in soil profiles of three major paddy soils (Bai soil, Huangni soil and Wushan soil) during wheat and rice growth seasons was studied in the Taihu Lake region of China. The results were as follows: the available phosphorus contents differed in the three paddy soils. Available phosphorus content in Bai soil was the lowest in these soils. The available phosphorus content decreases rapidly with depth from the soil surface and reach the minimum value at approximately 45 cm before increasing slightly near the groundwater. The contents of available phosphorus were higher in February (tillering and shooting period of wheat) and in September (full heading time of rice) than in other months. The total phosphorus content strongly affects available phosphorus content in the studied soils. During the period of wheat cultivation, they show a typical power function relationship with correlation coefficient r = 0.6492** (n = 13), a significant positive linear correlation. In addition, available phosphorus content has a remarkable positive linear correlation with organic matter content, r = 0.9111** (n = 13), and a remarkable negative linear correlation with pH value, r = ?0.5945* (n = 13). In Wushan soil, there is a negative linear correlation between clay content and available phosphorus content, r = ?0.9289* (n = 4). Therefore, total phosphorus content, organic matter content and pH value are major impact factors on available phosphorus content in these soils.     

Elucidation and short-term forecasting of microcystin concentrations in Lake Suwa (Japan) by means of artificial neural networks and evolutionary algorithms

Non-supervised artificial neural networks (ANN) and hybrid evolutionary algorithms (EA) were applied to analyse and model 12 years of limnological time-series data of the shallow hypertrophic Lake Suwa in Japan. The results have improved understanding of relationships between changing microcystin concentrations, Microcystis species abundances and annual rainfall intensity. The data analysis by non-supervised ANN revealed that total Microcystis abundance and extra-cellular microcystin concentrations in typical dry years are much higher than those in typical wet years. It also showed that high microcystin concentrations in dry years coincided with the dominance of the toxic Microcystis viridis whilst in typical wet years non-toxic Microcystis ichthyoblabe were dominant. Hybrid EA were used to discover rule sets to explain and forecast the occurrence of high microcystin concentrations in relation to water quality and climate conditions. The results facilitated early warning by 3-days-ahead forecasting of microcystin concentrations based on limnological and meteorological input data, achieving an r(2)=0.74 for testing.     

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.     

Assessing sediment and water quality issues in expanding African wetlands: the case of the Mara River,Tanzania

Climatological influences and catchment pressures have altered the natural energy regime in the lower Mara River in Tanzania, creating conditions favourable for sedimentation. Wetland growth in the lower Mara River is investigated through particle size analyses and high resolution micro-XRF screening of sediment cores from the area. Geochemical profiling indicates that the Mara wetlands serve as an important trap for contaminated sediments originating the North Mara Gold Mine complex. Heavy metals and arsenic (As) appear to be reasonably well bound in alluvial stores of the wetlands but selected elements (e.g. Cr) may become progressively mobile over time. Human activity in the catchment presents risks to the biodiversity of the wetland area, and also to its ability to buffer Lake Victoria by assimilating pollutants. Changes to the hydrological regime of the Mara wetlands could reverse the patterns of sedimentation and adversely affect water and sediment quality in Lake Victoria. Furthermore, the study highlights a deficit of data relating to sediment sources, deposition patterns and associated contamination, which must be understood before effective management strategies on sediment and contaminants can be applied.     

西湖风景名胜区新农村建设的实践与思考

通过分析杭州西湖风景名胜区农村的特点,阐述风景名胜区资源保护和农村居民生产、生活发展的辩证关系,提出衡量风景名胜区新农村建设成功与否的3条标准和风景名胜区新农村建设的发展思路,并结合近几年杭州西湖风景名胜区农村村庄整治的实践,总结风景名胜区实施新农村建设的体会与成效。     

Patterns and mechanisms of phytoplankton variability in Lake Washington (USA)

Temporal variability in lake phytoplankton is controlled largely by a complex interplay between hydrodynamic and chemical factors, and food web interactions. We explored mechanisms underlying phytoplankton interannual variability in Lake Washington (USA), using a 25-yr time series of water quality data (1975-1999). Time-series analysis and PCA were used to decompose chlorophyll data into modes of variability. We found that phytoplankton dynamics in Lake Washington were characterized by four seasonal modes, each of which was associated with different ecological processes. The first mode coincided with the period when the system was light limited (January-March) and phytoplankton patterns were driven by the amount of available solar radiation. The second mode (April-June) coincided with the peak of the spring bloom and the subsequent decline of phytoplankton biomass, and was largely controlled by total phosphorus levels and grazing pressure from cladoceran zooplankton. Evidence of co-dependence and tight relationship between phytoplankton and cladoceran dynamics were also found from July to October when a large portion of the phosphorus supply in the mixed layer was provided by zooplankton excretion. The fourth mode (November-December) was associated with the transition to thermal and chemical homogeneity and the winter phytoplankton minima (2-2.5 microg/l). Finally, we examined the effects of meteorological forcing and large-scale oceanic climate fluctuations (ENSO and PDO) on phytoplankton dynamics and assessed the significance of their role on the interannual variability in the lake.     

Polybrominated diphenyl ether (PBDE) concentrations and resulting exposure in homes in California: relationships among passive air,surface wipe and dust concentrations,and temporal variability

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in furniture foam, electronics, and other home furnishings. A field study was conducted that enrolled 139 households from California, which has had more stringent flame retardant requirements than other countries and areas. The study collected passive air, floor and indoor window surface wipes, and dust samples (investigator collected using an HVS3 and vacuum cleaner) in each home. PentaBDE and BDE209 were detected in the majority of the dust samples and many floor wipe samples, but the detection in air and window wipe samples was relatively low. Concentrations of each PBDE congener in different indoor environmental media were moderately correlated, with correlation coefficients ranging between 0.42 and 0.68. Correlation coefficients with blood levels were up to 0.65 and varied between environmental media and age group. Both investigator‐collected dust and floor wipes were correlated with serum levels for a wide range of congeners. These two sample types also had a relatively high fraction of samples with adequate mass for reliable quantification. In 42 homes, PBDE levels measured in the same environmental media in the same home 1 year apart were statistically correlated (correlation coefficients: 0.57–0.90), with the exception of BDE209 which was not well correlated longitudinally.     

Composition of bacterial and archaeal communities in freshwater sediments with different contamination levels (Lake Geneva, Switzerland)

The aim of this study was to compare the composition of bacterial and archaeal communities in contaminated sediments (Vidy Bay) with uncontaminated sediments (Ouchy area) of Lake Geneva using 16S rRNA clone libraries. Sediments of both sites were analysed for physicochemical characteristics including porewater composition, organic carbon, and heavy metals. Results show high concentrations of contaminants in sediments from Vidy. Particularly, high contents of fresh organic matter and nutrients led to intense mineralisation, which was dominated by sulphate-reduction and methanogenesis. The bacterial diversity in Vidy sediments was significantly different from the communities in the uncontaminated sediments. Phylogenetic analysis revealed a large proportion of Betaproteobacteria clones in Vidy sediments related to Dechloromonas sp., a group of dechlorinating and contaminant degrading bacteria. Deltaproteobacteria, including clones related to sulphate-reducing bacteria and Fe(III)-reducing bacteria (Geobacter sp.) were also more abundant in the contaminated sediments. The archaeal communities consisted essentially of methanogenic Euryarchaeota, mainly found in the contaminated sediments rich in organic matter. Multiple factor analysis revealed that the microbial community composition and the environmental variables were correlated at the two sites, which suggests that in addition to environmental parameters, pollution may be one of the factors affecting microbial community structure.     

Seasonal and diurnal variations of volatile organic compounds (VOCs) in the atmosphere of Hong Kong

Ambient VOCs samples were collected at three locations (PolyU campus (PU), Kwun Tong (KT), Hok Tsui (HT)) in Hong Kong during the periods of November 2000-February 2001 and June 2001-August 2001. Also the concentrations of VOCs in Cross Harbor tunnel in Hong Kong were obtained in order to determine the vehicular sources of VOCs. Toluene was the most abundant VOC detected in Hong Kong. At the PU station, which is close to a main road, the concentrations of most VOCs were higher in summer than in winter. However, at the background location HT, the concentrations of all VOCs except tetrachloroethene were higher in winter than in summer. Regional physical dispersion/transportation and mixing depth may be the reasons for higher VOC concentrations in winter at HT. The BTEX (benzene:toluene:ethylbenzene:xylene) ratios of PU and KT during winter period were (1.9:10.1:1.0:1.8) and (1.9:10.4:1.0:1.5), and (0.9:8.3:1.0:2.2) and (0.8:29.6:1.0:1.8) for summer season, respectively. The xylene/ethylbenzene (X/E) ratio was used to assess the relative age of the air parcels in this study. The concentrations of VOCs in the atmosphere in Hong Kong were mainly affected by direct emissions from vehicles, evaporation of fuels, photochemical reactions and few industrial emissions. The BTEX ratio in the tunnel was 2:10.4:1:3.2. The BTEX ratios at PU and KT during the winter period were similar to that in tunnel (except for xylenes). The X/E ratio in the tunnel was higher than that in the ambient air. This indicated that the freshly emitted xylenes in the tunnel decayed at different rates from OH-oxidation in the atmosphere. Good BTEX correlations (r>0.8) were found at PU and KT in winter (**P<0.01). Vehicular exhaust was the dominant source at PU and KT stations, and less evaporation of fuel or additive occurred at low temperature in winter. Diurnal variations of mean BTEX concentrations at the roadside monitoring station (PU) showed two peaks associated with traffic density and vehicle type.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediments from the Mersey Estuary, U.K

Sediments from the Mersey Estuary were analysed for polycylic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Total PAH concentrations ranged from 626 to 3766 microg/kg and total PCB concentrations ranged from 36 to 1409 microg/kg. These concentrations are intermediate in comparison to other U.K estuaries with similar histories of industrialisation and urbanisation. The distribution of individual PAHs were consistent throughout the Mersey Estuary, this together with molecular indices suggests mainly pyrolitic inputs, augmented by a variety of industrial petrogenic sources. Comparison of tri-to-hepta PCB congeners revealed multiple sources and inputs throughout the estuary. A sediment core collected in close proximity to Garston Docks revealed the take-off, peak pollutant input and recent decline of PCB pollution. However, a second depth profile of sediments at Ellesmere Port showed little change in total or individual PCB concentrations due to extensive sediment reworking and mixing.     

Mercury in the air, water and biota at the Great Salt Lake (Utah, USA)

The Great Salt Lake, Utah (USA), is the fourth largest terminal lake on Earth and a stop-over location for 35 million birds on the Pacific Flyway. Recently, the Utah Department of Health and Utah Division of Wildlife Resources issued tissue mercury (Hg) consumption advisories for several species of birds that consume the lake's brine shrimp. We hypothesized that the chemistry of the atmosphere above the Great Salt Lake would facilitate atmospheric deposition of Hg to the water. Because little information was available on Hg at the Great Salt Lake, and to begin to test this hypothesis, we measured atmospheric elemental (Hg(0)) and reactive gaseous mercury (RGM) concentrations as well as Hg concentrations in water and brine shrimp five times over a ~year. Surrogate surfaces and a dry deposition model were applied to estimate the amount of Hg that could be input to the lake surface, and HYSPLIT model back trajectories were developed to investigate potential sources of RGM to the lake. Atmospheric Hg(0) concentrations were similar to global ambient background values and RGM concentrations were similar to those reported for rural areas. Both Hg(0) and RGM exhibited regular diel variability. Model estimated deposition velocities for RGM to the lake ranged from 0.9 to 3.0 cm s(-1) while that determined for surrogate surfaces ranged from 2.8 to 7.8 cm s(-1). Filtered total and methyl Hg concentrations in Great Salt Lake surface waters were consistent throughout the year (3.6+/-0.8 ng L(-1) and 0.93+/-0.59 ng L(-1), respectively), while brine shrimp concentrations had a statistically significant increase from summer to fall. Data collected and data analyses indicated no direct local or regional source of Hg to the lake and that factors within the Great Salt Lake basin are important in controlling Hg(0) and RGM concentrations.     

Spatial and temporal patterns in metal levels in eggs of common terns (Sterna hirundo) in New Jersey

Seabirds are excellent subjects for examination of metals because they feed at different trophic levels, including as top-level piscivores, they are long-lived, and many are abundant and widely distributed. In this paper we examine the levels of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in eggs from common terns (Sterna hirundo) nesting on five saltmarsh islands in Barnegat Bay, New Jersey from 2000 to 2002. We test the null hypothesis that there were no locational or temporal differences from 2000 to 2002. There were significant locational differences in all metals in some years, although the differences were not large. The levels of most metals do not seem sufficiently high to cause adverse effects, although the levels of mercury in eggs of some common terns from the bay are within the range known to cause adverse effects. Mercury in common tern eggs may be a contributing cause to their local decline.     

Seasonal variations and annual fluxes of arsenic in the Garonne, Dordogne and Isle Rivers, France

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly analyses for arsenic were conducted from 1999 to 2005 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Despite the known historical polymetallic pollution affecting the Lot-Garonne River system, the highest As concentration level was observed in the Isle River. This was explained by the geological context and various Au/As deposits in this watershed. In the three studied rivers, dissolved As concentrations showed important seasonal variations with maximum values in summer. The dissolved As concentrations were closely related to water temperature and their increase in spring/summer appeared to be induced by water temperatures above approximately 15 degrees C, independently from discharge. The reduction of As(V) to more soluble As(III) and/or destruction of solid As carrier phases by micro-organisms could explain this observation, suggesting that temperature-dependent biogeochemical processes play an important role in controlling As partition and speciation in fluvial systems. Water and SPM fluxes in the Garonne River mainly control arsenic inputs into the Gironde Estuary and the downstream coastal zones. Based on the present data, we propose an empirical model to roughly estimate the annual dissolved and particulate As fluxes in the Garonne, Dordogne and Isle Rivers from annual water and SPM fluxes. The comparison of observed As fluxes and those estimated from the empirical model suggests that resuspension of historical, polluted reservoir sediments during a major flood accounted for approximately 50% of the annual As fluxes in 2003.