Comparison of dioxin and furan TEQ determination in contaminated soil using chemical,micro-EROD,and immunoassay analysis

High resolution mass spectrometry gas chromatography (GC/MS) is the standard method for dioxin and furan analysis in environmental matrices. Considered as very accurate, this method is however time consuming and expensive. Methods based on biological interactions have the necessary sensitivity but began only recently to be investigated in the context of environmental applications. We have compared dioxin and furan toxicity levels (expressed as toxic equivalent quantities (TEQs)) in soil samples by three analytical approaches: the micro-ethoxyresorufin-o-deethylase (EROD) bioassay (a receptor-based method), an immunoassay (antibody-based method) and GC/MS analysis (used as a reference) using a shortened extraction-purification method. Both biological methods were sensitive to interferences from compounds co-extracted from samples. Most samples were underestimated by the immunoassay and, at a greater extent, overestimated by the EROD bioassay. The average accuracy of TEQ estimation (86 +/- 45% of values established by GC/MS) and the absence of false-negatives showed by the immunoassay suggest the usefulness of this method for semi-quantitative, preliminary characterization of potentially contaminated sites.     

Transport and degradation of toluene and o-xylene in an unsaturated soil with dipping sedimentary layers

A lysimeter trench was established at the Gardermoen delta (50 km north of Oslo, Norway) to study the flow of water and transport and degradation of aromatic jet fuel components (toluene and o-xylene) in the undisturbed unsaturated zone. Site investigations with ground-penetrating radar revealed the presence of dipping sedimentary layers within the foreset unit. This study has shown that the foreset bed of the Gardermoen delta structure provided a preferential flow path for the transport of the solute plumes, but did not have dramatic effects on the degradation potential under the current conditions. The degradation potential for toluene and o-xylene in the unsaturated zone at Gardermoen was very high and almost all of the injected hydrocarbons were biodegraded before reaching the saturated zone. However, the horizontal displacement of the plume showed that knowledge about sedimentary structures in the unsaturated zone is important for a sufficient monitoring of contaminant transport and for remediation purposes. Carbon dioxide and O2 were measured in situ simultaneously with extraction of water samples, and indicated aerobic biodegradation of toluene and o-xylene. Overall, first-order degradation coefficients were calculated to be in the range of 0.19 to 0.21 d(-1) and 0.10 to 0.11 d(-1) for toluene and o-xylene, respectively.     

Rhizosphere acidification and cadmium uptake by strawberry clover

Strawberry clover (Trifolium fragiferum L.) is a hardy legume found in indigenous or introduced populations throughout the world. Tolerance to saline and alkaline soils, flooding, and heavy metals make it a good prospect for reclamation projects. The research, described here, was conducted to: (i) characterize the morphological variation in plants from available seed sources, (ii) evaluate cadmium uptake and tolerances over a wide range of morphological variants, and (iii) elucidate the variability in the effects of roots on rhizosphere pH and the relationship to cadmium uptake. Seeds from selected accessions were planted in the greenhouse for comparison of morphological variation. The accessions examined had a mean height of 10.7+/-7 cm. Accessions 254916 and 237925 are tall with high rhizosphere pH values and might be useful in phytoremediation. Strawberry clover accessions were also grown hydroponically to examine differences in cadmium uptake. The ability of strawberry clover roots to change rhizosphere pH and take up cadmium was examined using culture tubes containing nutrient agar, a moderate level of cadmium, and a pH indicator dye. The results provided evidence for a negative correlation between rhizosphere pH and cadmium uptake.     

Stray field nuclear magnetic resonance of soil water: development of a new, large probe and preliminary results

Development, characterization, and preliminary results of a recent technique capable of local measurements of pore-size distribution by a spatially resolved low resolution nuclear magnetic resonance (NMR) technique are described. Potential environmental uses include studying the change in pore-size distribution caused by surface compaction, which influences surface runoff, and obtaining information on the physical state of non-aqueous compounds in porous materials, which should aid the selection of appropriate soil remediation methods. Stray field (STRAFI) imaging is an NMR technique that allows distortion-free imaging of materials with short NMR relaxation times. The sample is placed in the strong axial fringe field gradient of a superconducting NMR magnet. We report on a new, unique, large 5-cm-diameter STRAFI probe, and its use for three preliminary test cases: water in ceramics of known pore size, paraffin wax and oil in sandstone rock, and water in soil at different matric potentials. The imaging is confined to one dimension with a spatial resolution of the order of 100 microm for protons. The optimum position for imaging occurs at 2.62 T and a gradient of 12.1 T/m. Water relaxation decay curves can be measured at any position in the 8-cm-long sample. These curves are decomposed into a series of terms each corresponding to a different pore size. Preliminary results show continuum fits to decay curves for a soil drained to three different matric potentials. Such information will be useful for interpreting water retention curves and will lead to understanding of the behavior of fluids in the vadose zone.     

Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Spatial and temporal modeling of microbial contaminants on grazing farmlands

This paper introduces an integrated spatial and temporal modeling system developed mathematically for assessing microbial contaminants on animal-grazed farmlands. The model uses fecal coliform, specifically Escherichia coli, as an indicator of fecal contamination and describes the sources, sinks, transport processes, and fate of E. coli contaminants in catchments and associated streams. Spatial features include grazing location, land topography, distance to a nearby stream, and distance through the stream network to the outlet. Temporal features are population dynamics on the land surface, in flow, and on streambeds. The model applies the principles of conservation of mass balance on two different types of pools: grid cells on land surfaces and networked stream segments. The model aims to improve the prediction of the effects of different land management strategies on the fecal contamination of waterways. This is achieved by characterizing the movement of fecal contaminants from land to streams and in-stream mobilization. Processes of attenuation, diffusion, and transport govern the movement. Our study site is a hill land catchment with an area of 140 ha and is used exclusively for animal grazing. The model was calibrated with previous research results, and then tested using the data collected at the outlet of the catchment. The sensitivity of the model predictions was analyzed for different scenarios: effect of stock rate, attenuation rate, and flow volumes. The similar pattern between monitored and predicted E. coli concentration proved that the model captures the key features that control the population dynamics of fecal contaminants. Further experiments are required to expand the model's functionality for covering more mitigation options.     

The measurement of cholinesterase activities as a biomarker in chub (Leuciscus cephalus): the fish length should not be ignored

Biomarkers are early warning systems of the exposure of aquatic organisms to pollutants. Among them, the measurement of the cholinesterase (ChE) activities in fish muscle is a biomarker of the exposure to organophosphosphates and carbamates pesticides. As such it has been used in numerous field studies both in marine and continental waters. Cyprinids (chub, Leuciscus cephalus) were sampled in river sites (France) in relatively clean and polluted areas. We performed the statistical analysis of the ChE activities and we generally observed a statistical relationship between ChE activities and fish length, the larger fish having the lower ChE activities. We concluded that the great majority of the significant differences in ChE activities between sites could be due in fact to differences in fish length between field samples. We stress the importance of taking into account the fish length whenever differences in ChE levels between field sites must be interpreted.     

Radioactive contamination in the Arctic--sources, dose assessment and potential risks

Arctic residents, whose diets comprise a large proportion of traditional terrestrial and freshwater foodstuffs, have received the highest radiation exposures to artificial radionuclides in the Arctic. Doses to members of both the average population and selected indigenous population groups in the Arctic depend on the rates of consumption of locally-derived terrestrial and freshwater foodstuffs, including reindeer/caribou meat, freshwater fish, goat cheese, berries, mushrooms and lamb. The vulnerability of arctic populations, especially indigenous peoples, to radiocaesium deposition is much greater than for temperate populations due to the importance of terrestrial, semi-natural exposure pathways where there is high radiocaesium transfer and a long ecological half-life for this radionuclide. In contrast, arctic residents with diets largely comprising marine foodstuffs have received comparatively low radiation exposures because of the lower levels of contamination of marine organisms. Using arctic-specific information, the predicted collective dose is five times higher than that estimated by UNSCEAR for temperate areas. The greatest threats to human health and the environment posed by human and industrial activities in the Arctic are associated with the potential for accidents in the civilian and military nuclear sectors. Of most concern are the consequences of potential accidents in nuclear power plant reactors, during the handling and storage of nuclear weapons, in the decommissioning of nuclear submarines and in the disposal of spent nuclear fuel from vessels. It is important to foster a close association between risk assessment and practical programmes for the purposes of improving monitoring, formulating response strategies and implementing action plans.     

Temporal trends for 99Tc in Norwegian coastal environments and spatial distribution in the Barents Sea

The objective of this study was to reassess 99Tc transit times and transfer factors, from Sellafield to northern Norway, and to determine the extent of 99Tc migration to the Barents Sea. Filtered seawater samples were collected on a monthly basis from Hilles?y, northern Norway, and in February 1999 from the Barents Sea. Results showed an increase in levels of 99Tc at Hilles?y where activity concentrations have increased from a baseline of 0.2-0.4Bq m(-3) to a maximum of 1.6 Bq m(-3). A transit time of 42 months and a transfer factor of 6Bq m(-3) per PBq a(-1) have been derived, using cross-correlation analysis. The current study predicts that future levels are unlikely to increase dramatically over the levels observed in 1998. Levels of 99Tc in the Barents Sea ranged from 0.2 Bq m(-3) to 1.1 Bq m(-3) showing the influence of new 99Tc inputs by early 1999.