Marine sponges with contrasting life histories can be complementary biomonitors of heavy metal pollution in coastal ecosystems

In this study, we compared the usefulness of a long-living sponge (Hymeniacidon heliophila, Class Demospongiae) and a short-living one (Paraleucilla magna, Class Calcarea) as biomonitors of metallic pollution. The concentrations of 16 heavy metals were analyzed in both species along a gradient of decreasing pollution from the heavily polluted Guanabara Bay to the less impacted coastal islands in Rio de Janeiro, SE Brazil (SW Atlantic). The levels of most elements analyzed were higher in H. heliophila (Al, Co, Cr, Cu, Fe, Mn, Ni, Hg, Ni, and Sn) and P. magna (Ni, Cu, Mn, Al, Ti, Fe, Pb, Co, Cr, Zn, and V) collected from the heavily polluted bay when compared with the cleanest sites. Hymeniacidon heliophila accumulates 11 elements more efficiently than P. magna. This difference may be related to their skeleton composition, histological organization, symbiont bacteria and especially to their life cycle. Both species can be used as a biomonitors of metallic pollution, but while Hymeniacidon heliophila was more effective in concentrating most metals, Paraleucilla magna is more indicated to detect recent pollutant discharges due to its shorter life cycle. We suggest that the complementary use of species with contrasting life histories can be an effective monitoring strategy of heavy metals in coastal environments.     

Operating problems in anaerobic digestion plants resulting from nitrogen in MSW

Organic waste and municipal solid waste usually contain considerable amounts of different nitrogen compounds, which may inhibit anaerobic degradation processes and cause problems in the downstream and peripheral devices. This refers particularly to the different process stages of anaerobic digestion, to wastewater treatment, and to exhaust air treatment. Neither the knowledge about nitrogen problems nor the technologies for elimination of nitrogen compounds from the wastewater or the exhaust air of anaerobic digestion can be regarded as state-of-the-art. Most of the technologies in question have already been applied in other areas, but are barely tested for application in anaerobic digestion plants. The few performance data and experiences at hand were mainly derived from pilot and demonstration facilities. In this paper, the problem of nitrogen will be discussed in detail according to the separate problem fields based on the authors' experience, as well as on the basis of a review of the relevant literature. Furthermore, possible solutions will be proposed and the need for further research and development will be formulated.     

Internal ecosystem feedbacks enhance nitrogen-fixing cyanobacteria blooms and complicate management in the Baltic Sea

Eutrophication of the Baltic Sea has potentially increased the frequency and magnitude of cyanobacteria blooms. Eutrophication leads to increased sedimentation of organic material, increasing the extent of anoxic bottoms and subsequently increasing the internal phosphorus loading. In addition, the hypoxic water volume displays a negative relationship with the total dissolved inorganic nitrogen pool, suggesting greater overall nitrogen removal with increased hypoxia. Enhanced internal loading of phosphorus and the removal of dissolved inorganic nitrogen leads to lower nitrogen to phosphorus ratios, which are one of the main factors promoting nitrogenfixing cyanobacteria blooms. Because cyanobacteria blooms in the open waters of the Baltic Sea seem to be strongly regulated by internal processes, the effects of external nutrient reductions are scale-dependent. During longer time scales, reductions in external phosphorus load may reduce cyanobacteria blooms; however, on shorter time scales the internal phosphorus loading can counteract external phosphorus reductions. The coupled processes inducing internal loading, nitrogen removal, and the prevalence of nitrogen-fixing cyanobacteria can qualitatively be described as a potentially self-sustaining "vicious circle." To effectively reduce cyanobacteria blooms and overall signs of eutrophication, reductions in both nitrogen and phosphorus external loads appear essential.     

Crystal structure analysis of enantiomerically pure (+) and (-) beta-hexabromocyclododecanes

The molecular structures of individual HBCD stereoisomers are not elucidated yet. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and tentatively assigned their relative configurations. Herein we report on the isolation of enantiomerically pure (+) and (-) beta-HBCDs, both obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations determined from X-ray diffraction analysis. The absolute configuration of (+) beta-HBCD was found to be (1S,2S,5S,6R,9S,10R), while the one of (-) beta-HBCD was assigned to (1R,2R,5R,6S,9R,10S). The given structural information allows, for the first time, the unambiguous identification of these two important HBCD stereoisomers, which are typically found in technical products at proportions of about 3-5% for each enantiomer.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD stereoisomers suggest that the presented isomerization mechanism is of relevance for those stereoisomers as well.     

Investigation of the antibacterial effects of silver-modified TiO2 and ZnO plasmonic photocatalysts embedded in polymer thin films

Nanosilver-modified TiO₂ and ZnO photocatalysts were studied against methicillin-resistant Staphylococcus aureus on the surface and against naturally occurring airborne microorganisms. The photocatalysts/polymer nanohybrid films were prepared by spray coating technique on the surface of glass plates and on the inner surface of the reactive light source. The photoreactive surfaces were activated with visible light emitting LED light at λ?=?405 nm. The optical properties of the prepared photocatalyst/polymer nanohybrid films were characterized by diffuse reflectance measurements. The photocatalytic properties were verified with the degradation of ethanol by gas chromatography measurements. The destruction of the bacterial cell wall component was examined with transmission electron microscope. The antibacterial effect of the photocatalyst/polymer nanohybrid films was tested with different methods and with the associated standard ISO 27447:2009. With the photoreactive coatings, an extensive disinfectant film was developed and successfully prepared. The cell wall component of S. aureus was degraded after 1 h of illumination. The antibacterial effect of the nanohybrid films has been proven by measuring the decrease of the number of methicillin-resistant S. aureus on the surface and in the air as the function of illumination time. The photocatalyst/polymer nanohybrid films could inactivate 99.9 % of the investigated bacteria on different thin films after 2 h of illumination with visible light source. The reactive light source with the inner-coated photocatalyst could kill 96 % of naturally occurring airborne microorganisms after 48 h of visible light illumination in indoor air sample. The TEM results and the microbiological measurements were completed with toxicity tests carried out with Vibrio fischeri bioluminescence bacterium.     

Protected area characteristics that help waterbirds respond to climate warming

Protected area networks help species respond to climate warming. However, the contribution of a site's environmental and conservation-relevant characteristics to these responses is not well understood. We investigated how composition of nonbreeding waterbird communities (97 species) in the European Union Natura 2000 (N2K) network (3018 sites) changed in response to increases in temperature over 25 years in 26 European countries. We measured community reshuffling based on abundance time series collected under the International Waterbird Census relative to N2K sites’ conservation targets, funding, designation period, and management plan status. Waterbird community composition in sites explicitly designated to protect them and with management plans changed more quickly in response to climate warming than in other N2K sites. Temporal community changes were not affected by the designation period despite greater exposure to temperature increase inside late-designated N2K sites. Sites funded under the LIFE program had lower climate-driven community changes than sites that did not received LIFE funding. Our findings imply that efficient conservation policy that helps waterbird communities respond to climate warming is associated with sites specifically managed for waterbirds.