Adverse effects in wild fish living downstream from pharmaceutical manufacture discharges

A set of biochemical and histological responses was measured in wild gudgeon collected upstream and downstream of urban and pharmaceutical manufacture effluents. These individual end-points were associated to fish assemblage characterisation. Responses of biotransformation enzymes, neurotoxicity and endocrine disruption biomarkers revealed contamination of investigated stream by a mixture of pollutants. Fish from sampled sites downstream of the industrial effluent exhibited also strong signs of endocrine disruption including vitellogenin induction, intersex and male-biased sex-ratio. These individual effects were associated to a decrease of density and a lack of sensitive fish species. This evidence supports the hypothesis that pharmaceutical compounds discharged in stream are involved in recorded endocrine disruption effects and fish population disturbances and threaten disappearance of resident fish species. Overall, this study gives argument for the utilisation of an effect-based monitoring approach to assess impacts of pharmaceutical manufacture discharges on wild fish populations.     

Methylmercury levels and bioaccumulation in the aquatic food web of a highly mercury-contaminated reservoir

The low Ebro River basin (NE Spain) represents a particular case of chronic and long-term mercury pollution due to the presence of an industrial waste (up to 436 μg/g of Hg) coming from a chlor-alkali plant Albeit high total mercury (THg) levels have been previously described in several aquatic species from the surveyed area, methylmercury (MeHg) values in fish individuals have never been reported. Accordingly, in order to investigate bioaccumulation patterns at different levels of the aquatic food web of such polluted area, crayfish and various fish species, were analysed for THg and MeHg content. At the hot spot, THg mean values of crayfish muscle tissue and hepatopancreas were 10 and 15 times, respectively, greater than the local background level. Higher mean THg concentrations were detected in piscivorous (THg=0.848 ± 0.476 μg/g wet weight (ww); MeHg=0.672 ± 0.364 μg/g ww) than in non-piscivorous fish (THg=0.305 ± 0.163 μg/g ww; MeHg=0.278 ± 0.239 μg/g ww). Although these results indicated that THg in fish increased significantly with increasing trophic position, the percentage of the methylated form of Hg was not strongly influenced by differences in relative trophic position. This is an important finding, since the fraction of THg as MeHg in the top fish predator was unexpectedly lower than for other species of the aquatic food chain. Moreover, mean THg concentrations in piscivorous fish exceed the maximum level recommended for human consumption. From our findings, it is clear that for this specific polluted system, speciation becomes almost mandatory when risk assessment is based on MeHg, since single measurements of THg are inadequate and could lead to an over- or under-estimation of contamination levels.     

Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.     

Antlers of Cervus elaphus as biomonitors of ⁹⁰Sr in the environment

Adequate radioprotection of the environment requires the identification of biomonitors sensitive to the variation of its radionuclide content. Due to the chemical similarities between calcium and strontium, calcified tissues of mammals are considered to be good ⁹⁰Sr biomonitors. This work considered Cervus elaphus antlers which, being shed annually, can give information about the importance of radiostrontium contamination in an ecosystem in the time period required for the growth of the antler. The samples were collected at various points of W and SW Spain. The mean value of their ⁹⁰Sr content was (70 ± 43 (S.D.)) Bq/kg d.w., range (16-218) Bq/kg d.w., and the radionuclide was evenly distributed in the different parts of the antler. There was a good correlation between the antlers’ ⁹⁰Sr content and the ⁹⁰Sr deposited in the soil. The antlers’ content of ²²⁶Ra (from the natural uranium series) and the contents of some stable elements (Ca, Mg, Sr, and K) were also determined. The values for these stable elements were practically constant in the analyzed samples, and the concentrations measured decreased in the following order:Ca » Mg > K > Sr » ⁹⁰Sr > ²²⁶Ra     

Realistic retrospective dose assessments to members of the public around Spanish nuclear facilities

In the frame of an epidemiological study carried out in the influence areas around the Spanish nuclear facilities (ISCIII-CSN, 2009. Epidemiological Study of The Possible Effect of Ionizing Radiations Deriving from The Operation of Spanish Nuclear Fuel Cycle Facilities on The Health of The Population Living in Their Vicinity. Final report December 2009. Ministerio de Ciencia e Innovación, Instituto de Salud Carlos III, Consejo de Seguridad Nuclear. Madrid. Available from: http://www.csn.es/images/stories/actualidad_datos/especiales/epidemiologico/epidemiological_study.pdf), annual effective doses to public have been assessed by the Spanish Nuclear Safety Council (CSN) for over 45 years using a retrospective realistic-dose methodology. These values are compared with data from natural radiation exposure. For the affected population, natural radiation effective doses are in average 2300 times higher than effective doses due to the operation of nuclear installations (nuclear power stations and fuel cycle facilities). When considering the impact on the whole Spanish population, effective doses attributable to nuclear facilities represent in average 3.5 × 10⁻⁵ mSv/y, in contrast to 1.6 mSv/y from natural radiation or 1.3 mSv/y from medical exposures.     

Improvement of electrical resistivity tomography for leachate injection monitoring

Leachate recirculation is a key process in the scope of operating municipal waste landfills as bioreactors, which aims to increase the moisture content to optimize the biodegradation in landfills. Given that liquid flows exhibit a complex behaviour in very heterogeneous porous media, in situ monitoring methods are required. Surface time-lapse electrical resistivity tomography (ERT) is usually proposed. Using numerical modelling with typical 2D and 3D injection plume patterns and 2D and 3D inversion codes, we show that wrong changes of resistivity can be calculated at depth if standard parameters are used for time-lapse ERT inversion. Major artefacts typically exhibit significant increases of resistivity (more than +30%) which can be misinterpreted as gas migration within the waste. In order to eliminate these artefacts, we tested an advanced time-lapse ERT procedure that includes (i) two advanced inversion tools and (ii) two alternative array geometries. The first advanced tool uses invariant regions in the model. The second advanced tool uses an inversion with a “minimum length” constraint. The alternative arrays focus on (i) a pole–dipole array (2D case), and (ii) a star array (3D case). The results show that these two advanced inversion tools and the two alternative arrays remove almost completely the artefacts within +/?5% both for 2D and 3D situations. As a field application, time-lapse ERT is applied using the star array during a 3D leachate injection in a non-hazardous municipal waste landfill. To evaluate the robustness of the two advanced tools, a synthetic model including both true decrease and increase of resistivity is built. The advanced time-lapse ERT procedure eliminates unwanted artefacts, while keeping a satisfactory image of true resistivity variations. This study demonstrates that significant and robust improvements can be obtained for time-lapse ERT monitoring of leachate recirculation in waste landfills.     

Fractions and background concentrations of potentially toxic elements in Hungarian surface soils

This work established background concentrations for the pseudo total (HNO₃ + H₂O₂-soluble), mobilisable (NH₄-acetate + EDTA-soluble) and mobile (1?M NH₄NO₃-soluble) element fractions of Hungarian surface soils that can be used as reference values for the soil quality standards. The 193 soils investigated were taken from the Hungarian Soil Information and Monitoring System. The background values for Al, As, B, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn were given as a range covering 95% of the variance of the representative samples. The differences between observed element concentrations and the calculated background values indicated anthropogenic or pedogenic impact in each fraction. The comparison of the calculated background values with the Hungarian quality standards and the contamination limit values of other countries showed that the limit values of a certain region or country are not suitable for other areas. Generally, Mn and Al had the highest, while Cd had the lowest concentration in each fraction. Cr and Al were the least and Sr was the most mobile element. The principal component analysis indicated different geochemical and physico-chemical behaviour of the elements in the fractions; the pseudo total fraction was influenced more by the geological behaviour, while mobilisable and mobile fraction explained a much higher proportion of the total variance of soil physico-chemical properties than soil geochemical properties. The Cd–Ni and Co–Mn element pairs were always in the same principal component in each fractions indicating similar geogenic origin and showing that their solubility changes are similar in function of soil properties.