Anomalous transport of colloids and solutes in a shear zone

Transport experiments with colloids and radionuclides in a shear zone were conducted during the Colloid and Radionuclide Retardation experiment (CRR) at Nagra's Grimsel Test Site. Breakthrough curves of bentonite colloids and uranine, a non-sorbing solute, were measured in an asymmetric dipole flow field. The colloid breakthrough is earlier than that of uranine. Both breakthrough curves show anomalously long late time tails and the slope of the late time tails for the colloids is slightly higher. Anomalous late time tails are commonly associated with matrix diffusion processes; the diffusive interaction of solutes transported in open channels with the adjacent porous rock matrix or zones of stagnant water. The breakthrough curves for different colloid size classes are very similar and show no signs of fractionation due to their (size-dependent) diffusivity. It is proposed that tailing of the colloids is mainly caused by the structure of the flow field and that for the colloid transport, matrix diffusion is of minor importance. This has consequences for the interpretation of the uranine breakthrough. Comparisons of experimental results with numerical studies and with the evaluation of the colloid breakthrough with continuous time random theory imply that the tailing in the conservative solute breakthrough in this shear zone is not only caused by matrix diffusion. Part of the tailing can be attributed to advective transport in fracture networks and advection in low velocity regions. Models based on the advection-dispersion equation and matrix diffusion do not properly describe the temporal and spatial evolution of colloid and solute transport in such systems with a consistent set of parameters.     

Wirkung subakuter PCB-Exposition (Aroclor 1254) auf Sauerstoffverbrauch, Schwimmbewegung und Biotransformation (GST-Aktivität) des Karpfens (Cyprinus carpio)

Objective and Background

PCB (polychlorinated biphenyle) are typical man-made environmental pollutants that cause a broad spectrum of effects in vertebrates. Although a lot has been studied about the toxic effects of xenobiotic substances on aquatic organisms, their subacute effects are not yet well known. Fish occupies a central position in freshwater food webs and therefore, carp was chosen to be our test organism. The aim of our study was the investigation of subacute effects of Aroclor 1254 (22μg ^l?1) on respiration, swimming activity, and biotransformation, allowing discussion of changed interaction between the available energy resources.

Methods

The respiration experiments under controlled laboratory conditions were run for 29 days (5 d before, 16 d with and 8 d after chemical exposure) with exposed carp compared to the non-exposed fish. Furthermore, the BehavioQuant system quantitatively monitors the positions of each individual fish before (8 d) and during (21 d) PCB exposure and swimming activity (number of horizontal turnings s^?1) of animals was calculated. Thereafter, liver samples were taken from animals for analysis of the phase 2 enzyme activity (glutathione-S-transferase). In the respiration experiments were 6 exposure, 6 controll, and 3 solubilizer controll groups (12 animals each group); in the behavioral experiments were 9 exposure, 6 controll- und 3 solubilizer controll groups (6 animals each group), and in the enzyme activity measurements were 9 exposure, 6 controll and 3 solubilizer controll groups (6 animals each group) examined.

Results and Discussion

A clearly increased (33%) oxygen consumption due to the PCB-exposure is found to be reversible; after the exposure period the respiration of carp shows a level comparable to the oxygen consumption during non-exposure time. By evaluating quantitative behavioral parameters of animals, it becomes evident that the exposure to PCB also causes a reversible change in their swimming behavior. Chemical stress leads to a decrease of mean daily swimming activity combined with an increase of the mean number of turnings during the night. Thereafter, the swimming activity shifts to the circadian swimming behavior under control conditions. Furthermore, our measurement of soluble and microsomal glutathione-S-transferase activity of fish liver shows a significant elevation after exposure period.

Conclusion

Our results prove that it was feasible to detect sublethal effects of PCB-mixture on all parameters under these conditions successfully. Our findings imply that fish are able to cope with the chemicals and we purse the hypothesis that the higher physiological energy demand caused by increased activity of enzymes, which are involved in biotransformation of foregin substances, may be related to a higher respiration of fish stressed by xenobiotics.

Recommendation and Outlook

Further experiments should investigate the effects of PCB on ecophysiological parameters of carp fed with exposed natural food allowing discussion of ecological consequences.     

New beach in a shallow estuarine lagoon: a model-based <Emphasis Type="Italic">E. coli</Emphasis> pollution risk assessment

A 3D hydrodynamic model has been applied to the Curonian Lagoon to study the pollution impact of E. coli on a new beach that might be opened in the lagoon. Through a field survey the E. coli inputs were measured and then used in the numerical model, and through laboratory experiments the decay rate of E. coli was established. The model has been calibrated and validated for the year 2015, and several scenarios have been studied, such as sewage system breakdown, severe weather conditions or high river loads. The model has then been run for a period of 12 years to obtain a robust statistics for the pollution on the planned beach. Results show that the decay rate of E. coli is between 0.55 days and 2.3 days and the modeled decay times are compatible with these numbers. The only scenario that would create a risk for the bathing waters of the beach is a breakdown of the sewage system on the Curonian Spit. In this case the hours (and days) over legally allowable bathing threshold were computed in order to estimate the number of days the beach could be closed. These results have been confirmed by the 12 year simulations. With an influence map analysis the two most critical sewage systems could be identified.     

Empirical relationship between precision and ultra-trace concentrations of PCDD/Fs and dioxin-like PCBs in biological matrices

Dioxin analysis in food and feed can be characterized as an analytical application where very high accuracy is required at very low levels of contamination. Gas chromatography (GC) in combination with 13C-label isotope dilution (ID) high resolution mass spectrometry (HRMS) is the reference congener-specific technique characterized by pronounced selectivity, precision and trueness at parts-per-trillion (ppt) and sub-parts-per-trillion (sub-ppt) levels. The quality of the analytical data produced routinely by a laboratory should be adequate for its intended purpose, i.e., one will seek a compromise between the cost and time needed and the consequences of incorrect decisions due to erroneous results. The requirements for reproducibility are usually dependent on the analyte concentrations and have been expressed in various empirical functions. While Horwitz or modified functions are widely useful for many purposes, it would be difficult to expect these functions to cover every analytical problem. This study reports on precision characteristics achieved by the GC-ID-HRMS reference method for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in food and feed in two interlaboratory method-performance studies among expert laboratories with long-standing experience in this field. Striking linear functions in log scale between reproducibility standard deviation and congener's level over a concentration range of 10(-8)-10(-14)g per g fresh weight are observed. The data fit very well to a Horwitz-type function of the form sR=0.153c0.904, where sR and c are dimensionless mass ratios expressed in pg g(-1) on fresh weight, regardless of the nature of the toxic congeners, food and feed matrices, or sample preparation methods. We demonstrate that the proposed function is suitable for use as a fitness-for-purpose criterion for proficiency assessment in interlaboratory comparisons on dioxins and related compounds in food.