Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Assimilation efficiencies of Cd and Zn in the common carp (Cyprinus carpio): effects of metal concentration, temperature and prey type

The impact of several factors on the assimilation efficiency (AE) of Cd and Zn from food in the common carp (Cyprinus carpio) was studied. Tested prey species were midge larvae (Chironomus riparius), zebra mussels (Dreissena polymorpha) and oligochaetes (Tubifex tubifex). The Cd load of the larvae did not affect the Cd AE in the carp. The Zn AE however, was negatively related to the Zn load of the prey. Food quantity and starvation of the carp did not significantly affect the Cd AE. For Zn, a significant decrease in AE was found when carp were fed ad libitum. Decreasing the temperature from 25 degrees C to 15 degrees C did not influence the Cd AE, while for Zn a significant decrease of the AE was measured. Carp assimilated Cd from both zebra mussels and oligochaetes with a significantly lower efficiency in comparison to the midge larvae, although Zn AEs was prey independent.     

Differential responses of the freshwater wetland species Juncus effusus L. and Caltha palustris L. to iron supply in sulfidic environments

Sulfur pollution can lead to serious problems in freshwater wetlands, including phosphorus eutrophication and sulfide toxicity. We tested the effects of anaerobic iron-rich groundwater discharge in fens, simulated by iron injection, on two characteristic species (Juncus effusus and Caltha palustris) in a sulfidic environment. Biomass production of C. palustris roots showed an optimum response to the combined addition of iron and sulfide, with highest values at intermediate concentrations of both substances. Iron deficiency apparently occurred at low iron concentrations, while at high iron concentrations, growth was decreased. For J. effusus, in contrast, no toxic effects were found of both iron and sulfide. This could be explained by larger radial oxygen loss (ROL) of J. effusus and could not be explained by differences in phosphorous concentrations. The results of our experiments confirm that iron-rich groundwater discharge has the potential to affect vegetation composition through toxicity modification in sulfidic environments.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Dairy washwater treatment using a horizontal flow biofilm system

In Ireland, dairy farmyard washwater commonly comprises farmyard run-off and dairy parlour washings. Land-spreading is the most widely used method for treating this wastewater. However, this method can be labour intensive and can cause, in some cases, the degradation of surface and ground waters, mainly due to nitrogen contamination. In this study, a horizontal flow biofilm reactor (HFBR) with step-feed was constructed and tested in the laboratory, to remove organic carbon and nitrogen from a agricultural strength synthetic washwater (SWW). The HFBR had an average top plan surface area (TPSA) of 0.1002 m(2) and consisted of a stack of 45 polystyrene horizontal sheets--15 sheets embedded with 25 mm deep frustums above 30 sheets with 10 mm deep frustums. The frustums acted as miniature reservoirs. The sheets were alternately offset to allow the wastewater to flow horizontally along each sheet and vertically from sheet to sheet down through the reactor. Biofilms developed on the sheets and treated the wastewater. During the 212-d study, the total hydraulic loading rate based on the TPSA of the sheets was 35 l m(-2) d(-1). SWW was pumped for 10 min each hour, in a step feed arrangement at a rate of 23.33 l m(-2) d(-1) on to the top sheet during Phases 1 and 2, and 11.67 l m(-2) d(-1) onto Sheet 16 during Phase 1 (days 1-92) and onto Sheet 30 during Phase 2 (days 93-212). The substrate loading rate during Phases 1 and 2 was 94.8 g total chemical oxygen demand (COD) m(-2) d(-1) and 10.5 g total nitrogen (TN) m(-2) d(-1), based on the TPSA. At steady state in Phase 2, the unit achieved excellent carbon removal of 99.7% 5-day biochemical oxygen demand (BOD(5)) and 96.7% total COD, equivalent to TPSA removal rates of 67.5 g BOD(5)m(-2)d(-1) and 91.7 g COD m(-2) d(-1). The nitrogen removal percentages were 98.3% total ammonium-nitrogen (NH(4)-N(t)) and 72.8% TN, which equated to TPSA removal rates of 4.8 g NH(4)-N(t) m(-2) d(-1) and 7.6g TN m(-2) d(-1). No sloughing of solids or clogging of media occurred during the study. The unit was simple to construct and operate, with little maintenance.     

Relationships between street characteristics and perceived attractiveness for walking reported by elderly people

Walking is important for the health of elderly people. Previous studies have found a relationship between neighbourhood characteristics, physical activity and related health aspects. The multivariate linear regression model presented here describes the relationships between the perceived attractiveness of streets for walking along and (physical) street characteristics. Two hundred and eighty-eight independently living elderly people (between 55 and 80 years old) participated in the study. Street characteristics were assessed along homogeneous street subsections defined as ‘links’. Positively related to perceived attractiveness of links were the following street characteristics: slopes and/or stairs, zebra crossings, trees along the route, front gardens, bus and tram stops, shops, business buildings, catering establishments, passing through parks or the city centre, and traffic volume. Litter on the street, high-rise buildings, and neighbourhood density of dwellings were negatively related to perceived link attractiveness. Overall, the results suggest that three main aspects affect perceived attractiveness of streets for walking, namely tidiness of the street, its scenic value and the presence of activity or other people along the street. The results are discussed within the context of these three aspects.     

Images of war: using satellite images for human rights monitoring in Turkish Kurdistan

In areas of war and armed conflict it is difficult to get trustworthy and coherent information. Civil society and human rights groups often face problems of dealing with fragmented witness reports, disinformation of war propaganda, and difficult direct access to these areas. Turkish Kurdistan was used as a case study of armed conflict to evaluate the potential use of satellite images for verification of witness reports collected by human rights groups. The Turkish army was reported to be burning forests, fields and villages as a strategy in the conflict against guerrilla uprising. This paper concludes that satellite images are useful to validate witness reports of forest fires. Even though the use of this technology for human rights groups will depend on some feasibility factors such as prices, access and expertise, the images proved to be key for analysis of spatial aspects of conflict and valuable for reconstructing a more trustworthy picture.