Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.     

Trimethylbenzoic acids as metabolite signatures in the biogeochemical evolution of an aquifer contaminated with jet fuel hydrocarbons

Evolution of trimethylbenzoic acids in the KC-135 aquifer at the former Wurtsmith Air Force Base (WAFB), Oscoda, MI was examined to determine the functionality of trimethylbenzoic acids as key metabolite signatures in the biogeochemical evolution of an aquifer contaminated with JP-4 fuel hydrocarbons. Changes in the composition of trimethylbenzoic acids and the distribution and concentration profiles exhibited by 2,4,6- and 2,3,5-trimethylbenzoic acids temporally and between multilevel wells reflect processes indicative of an actively evolving contaminant plume. The concentration levels of trimethylbenzoic acids were 3-10 orders higher than their tetramethylbenzene precursors, a condition attributed to slow metabolite turnover under sulfidogenic conditions. The observed degradation of tetramethylbenzenes into trimethylbenzoic acids obviates the use of these alkylbenzenes as non-labile tracers for other degradable aromatic hydrocarbons, but provides rare field evidence on the range of high molecular weight alkylbenzenes and isomeric assemblages amenable to anaerobic degradation in situ. The coupling of actual tetramethylbenzene loss with trimethylbenzoic acid production and the general decline in the concentrations of these compounds demonstrate the role of microbially mediated processes in the natural attenuation of hydrocarbons and may be a key indicator in the overall rate of hydrocarbon degradation and the biogeochemical evolution of the KC-135 aquifer.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

Sediment evidence of early eutrophication and heavy metal pollution of Lake Mälaren, central Sweden

Lake M?laren is the water supply and recreation area for more than 1 million people in central Sweden and subject to considerable environmental concern. To establish background data for assessments of contemporary levels of trophy and heavy metal pollution, sediment cores from the lake were analyzed. Diatom-inferred lake-water phosphorus concentrations suggest that pre-20th century nutrient levels in S?dra Bj?rkfj?rden, a basin in the eastern part of M?laren, were higher (c. 10-20 micrograms TP L-1) than previously assumed (c. 6 micrograms TP L-1). Stable lead isotope and lead concentration analyses from 3 basins (S. Bj?rkfj?rden, Gisselfj?rden and Ask?fj?rden) show that the lake was polluted in the 19th century and earlier from extensive metal production and processing in the catchment, particularly in the Bergslagen region. The lake has experienced a substantial improvement of the lead pollution situation in the 20th century following closure of the mining and metal industry. The lead pollution from the old mining industry was large compared to late-20th century pollution from car emissions, burning of fossil fuels and modern industries.     

Exploiting plant metabolism for the phytoremediation of persistent herbicides

Weed control by herbicides has helped us to create the green revolution and to provide food for at least the majority of human beings living today. However, some herbicides remain in the environment and pose an ecological problem. The present review describes the properties and fate of four representative herbicides known to be presistent in ecosystems. Metabolic networks are depicted and it is concluded that removal of these compounds by the ecologically friendly technique of phytoremediation is possible. The largest problem is seen in the uptake of the compounds into suitable plants and the time needed for such an approach.     

EuroBionet: a pan-European biomonitoring network for urban air quality assessment

EuroBionet, the 'European Network for the Assessment of Air Quality by the Use of Bioindicator Plants', is an EU-funded cooperative project currently consisting of public authorities and scientific institutes from 12 cities in 8 countries. In 2000, the bioindicator plants tobacco (Nicotiana tabacum Bel W3), poplar (Populus nigra 'Brandaris'), spiderwort (Tradescantia sp. clone 4430), Italian rye grass (Lolium multiflorum italicum) and curly kale (Brassica oleracea acephala) were exposed to ambient air at 90 monitoring sites according to standardised methods. Visible injuries and growth parameters were assessed and the accumulation of toxic substances in leaves determined. The exposure of tobacco resulted in a gradient with low levels of ozone-induced foliar injury in N and NW Europe, and medium to high values in the southern and central regions. The results of heavy metal and sulphur analyses in rye grass samples generally showed low to very low sulphur and low to medium heavy metal concentrations in leaves. In some cities, however, local hot spots of heavy metal contamination were detected. Analyses of the PAH contents in curly kale leaves gave low to medium values, with locally elevated levels at traffic-exposed sites.     

Transfer of the fungicide vinclozolin from treated to untreated plants via volatilization

Head lettuce plantlets (Lactuca sativa L. var. capitata) were potted, treated with vinclozolin at the six-leaf stage according to application standards and allowed to dry for 24 h. The potted plantlets were then placed in either growth chambers with controlled temperature (20 and 25 degrees C, respectively) or in a greenhouse (approximately 12 degrees C), together with untreated spinach (Spinacia oleracea L.) and standardized grass cultures (Lolium multiflorum Lam. ssp.) While the treated lettuce pots remained in the respective growing compartments until the end of the experiments, spinach and grass were exposed to the compartment air for 24 h and their shoot material was analyzed for vinclozolin by GC-ECD and GC-high resolution mass spectrometry. Exposure and analysis of untreated spinach and grass were carried out at two- or three-day intervals during the course of the experiments. Also, air samples were taken from the compartments at intervals and analyzed for vinclozolin. Maximum vinclozolin concentration in the growth chamber air was about 330 ng m(-3) while vinclozolin contamination of the untreated plants ranged from 50 to 200 microg kg(-1) FW (fresh weight). In the greenhouse atmospheric vinclozolin concentration reached approximately 15 ngm(-3) and maximum contamination of spinach and grass were 30-40 microg kg(-1) FW. Our data clearly show that unintended contamination of plants growing in the vicinity of vinclozolin-treated plants can occur even if the fungicide layer is completely dry. Implications for safety testing and food plants are discussed.