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.     

Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol

The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α₂-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S_N2-like substitution reaction. Only α₂-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism.     

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.     

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.     

The Solling roof revisited--slow recovery from acidification observed and modeled despite a decade of "clean-rain" treatment

Soil chemistry under the Solling clean-rain roof was simulated using the dynamic multi-layer soil chemistry model SAFE, including sulfate adsorption. Soil was sampled in order to parameterize the pH and sulfate concentration dependent sulfate adsorption isotherm used in SAFE. Modeled soil solution chemistry was compared to the 14 year long time-series of monthly measurements of soil solution data at 10 and 100cm depth. The deposition of N and S under the roof has been reduced by 68% and 53%, respectively, compared to the surrounding area. Despite this the soil solution concentrations of sulfate are still high (a median of 420mumol(c)/L at 100cm depth between 2000 and 2002) and the soil base saturation low (approximately 3% in the whole profile in 1998). Sulfate adsorption is an important process in Solling. The soil capacity to adsorb sulfate is large, the modeled adsorbed pool in 2003 down to 100cm was 1030kg S/ha, and the measured sulfate concentration is high, due to release of adsorbed sulfate. The addition of sulfate adsorption improved the modeled sulfate dynamics although the model still slightly underestimated the sulfate concentration at 100cm. Model predictions show no recovery, based on the criteria of Bc/Al ratio above 1 in the rooting zone, before the year 2050, independent of future deposition cuts.     

Bendiocarbamate induced structural alterations in rabbit thymus after experimental peroral administration

In this study histological structure of rabbit thymus after bendiocarbamate (2,3–isopropyledene–dioxyphenyl methylcarbamate) administration was studied. Bendiocarbamate was perorally administered for 90 days. At Day 3, 10, 20, 30, 60, 90 morphometric analysis was realized. Quantitative evaluation showed that in the control group thymus cortex forms 57.94 ± 7.10% and medulla 35.94± 7.38%. In almost all experimental groups significantly higher relative volume of cortex and lower relative volume of medulla was detected. Detail morphometric analysis found that the number of thymocytes per constant area and the diameter of tymocytes was decresed after bendiocarbamate administration. The number and diameter of reticular cells was not affected. Results of this study suggest negative effect of bendiocarbamate on the formation of thymus structures.     

Dose estimation and radon action level problems due to nanosize radon progeny aerosols in underground manganese ore mine

One of the essential parameters influencing of the dose conversion factor is the ratio of unattached short-lived radon progeny. This may differ from the value identified for indoor conditions when considering special workplaces such as mines. Inevitably, application of the dose conversion factors used in surface workplaces considerably reduces the reliability of dose estimation in the case of mines.This paper surveyed the concentration of radon and its short-lived radon progeny and identified the unattached fraction of short-lived radon progeny. As well equilibrium factor during the month of August was calculated simultaneously at two extraction faces in a manganese ore mine.During working hours the average radon concentrations were 220 Bq m⁻³ and 530 Bq m⁻³ at Faces 1 and 2; the average short-lived progeny concentration was 90 Bq m⁻³ and 190 Bq m⁻³, the average equilibrium factors were 0.46 and 0.36, and the average unattached fractions were 0.21 and 0.17, respectively. The calculated dose conversion factor was between 9 and 27 mSv WLM⁻¹, but higher values could also be possible.     

Naturwissenschaften aktuell

Naturwissenschaften aktuell     

The Impact of Map and Data Resolution on the Determination of the Agricultural Utilisation of Organic Soils in Germany

Due to its nature, agricultural land use depends on local site characteristics such as production potential, costs and external effects. To assess the relevance of the modifying areal unit problem (MAUP), we investigated as to how a change in the data resolution regarding both soil and land use data influences the results obtained for different land use indicators. For the assessment we use the example of the greenhouse gas (GHG) emissions from agriculturally used organic soils (mainly fens and bogs). Although less than 5 % of the German agricultural area in use is located on organic soils, the drainage of these areas to enable their agricultural utilization causes roughly 37 % of the GHG emissions of the German agricultural sector. The abandonment of the cultivation and rewetting of organic soils would be an effective policy to reduce national GHG emissions. To assess the abatement costs, it is essential to know which commodities, and at what quantities, are actually produced on this land. Furthermore, in order to limit windfall profits, information on the differences of the profitability among farms are needed. However, high-resolution data regarding land use and soil characteristics are often not available, and their generation is costly or the access is strictly limited because of legal constraints. Therefore, in this paper, we analyse how indicators for land use on organic soils respond to changes in the spatial aggregation of the data. In Germany, organic soils are predominantly used for forage cropping. Marked differences between the various regions of Germany are apparent with respect to the dynamics and the intensity of land use. Data resolution mainly impairs the derived extent of agriculturally used peatland and the observed intensity gradient, while its impact on the average value for the investigated set of land-use indicators is generally minor.