Influence of the amendment of corn straw on the degradation behaviour of the fungicide dithianon in soil

Degradation studies were conducted with the fungicide (14)C-dithianon under standard conditions for 64 days in soil. The compound is characterized by mineralization losses of approx. 33% and the formation of non-extractable (bound) residues of approx. 63% in 64 days. The microbial activity of the soil was stimulated by an amendment of corn straw simulating post-harvest conditions. This addition of straw decreased the mineralization of the compound initially. At the end of the incubation period, however, the mineralization rate was higher in the straw amended soil compared to the control. The addition of straw increased the amount of radiocarbon in the desorption solutions. Thus higher amounts of incorporated radiocarbon could be found in the biomass of the amended soil. Model calculations show that the straw amendment has a sustained influence on the mineralization of the compound. Potential mechanisms of the effect of dissolved organic matter on the sorption/desorption equilibrium are discussed.     

Characterization of non-extractable residues of the fungicide dithianon in soil using 13C/14C-labelling techniques

The fate of the (14)C-labelled fungicide dithianon in soil is characterized by the formation of non-extractable, "bound" residues of approximately 63% of applied amount in 64 d. Humic acids containing these "bound" residues were isolated after conducting degradation studies of the active ingredient in an orthic luvisol under standardized conditions. In the same way, (13)C-labelled dithianon was incubated in an artificial soil which was produced by humification of (13)C-depleted straw in an incinerated soil. The "bound" residues of the (13)C-labelled dithianon in the humic acid fraction of the artificial soil were analyzed using (13)C-NMR techniques. There was no evidence of a covalent bonding of the residues to the humic substances. Results of polarity gradient high performance thin layer chromatography (AMD-HPTLC) of "bound" residues of the (14)C-labelled dithianon in the humic acid fraction indicate a sequestration process of metabolites into the humic substance as a possible binding mechanism.     

Temporal variation of fluoride concentration in antlers of roe deer (Capreolus capreolus) living in an area exposed to emissions from iron and steel industry, 1948-2000

Temporal changes of environmental fluoride concentration in the industrialized area of Siegen, western Germany were assessed by studying the fluoride content of antlers (n=116) collected between 1948 and 2000 from the resident roe deer (Capreolus capreolus) population. During the analyzed period, major fluoride emission sources in the study area have been iron- and steelworks. Fluoride concentrations in the antlers ranged between 118 and 5428 mg/kg of bone ash. There was an overall increase in antler fluoride content from the late 1940s/early 1950s to the late 1950s/mid-1960s. Thereafter, antler fluoride levels overall steadily declined. For statistical analysis, the data were grouped into five periods (1948–1959, 1960–1969, 1970–1979, 1980–1989, and 1990–2000). Geometric mean fluoride concentrations of the samples ranged from 323 (period 1990–2000) to 2096 mg/kg of bone ash (period 1960–1969). Sample means for the periods 1980–1989 and 1990–2000, respectively, were always significantly lower than those of older samples. The decrease in antler fluoride concentrations during recent decades suggests a drop of ambient fluoride levels, that is hypothetically attributed to a reduction in the number of emission sources in the area and a decline of fluoride discharges from both local and more distant sources due to improved emission control measures. Comparison with antler fluoride data for other roe deer populations from western Germany further suggests that the roe deer from the Siegen area were recently exposed to an only moderate additional fluoride load from industrial sources. Studying antler fluoride concentrations is a convenient and cost-effective method of monitoring temporal changes in ambient fluoride levels.     

Evaluating and expanding the European Union's protected-area network toward potential post-2020 coverage targets

The Convention on Biological Diversity's (CBD) strategic plan will expire in 2020, but biodiversity loss is ongoing. Scientists call for more ambitious targets in the next agreement. The nature-needs-half movement, for example, has advocated conserving half of Earth to solve the biodiversity crisis, which has been translated to protecting 50% of each ecoregion. We evaluated current protection levels of ecoregions in the territory of one of the CBD's signatories, the European Union (EU). We also explored the possible enlargement of the Natura 2000 network to implement 30% or 50% ecoregion coverage in the EU member states’ protected area (PA) network. Based on the most recent land-use data, we examined whether ecoregions have enough natural area left to reach such high coverage targets. We used a spatially explicit mixed integer programing model to estimate the least-cost expansion of the PA network based on 3 scenarios that put different emphasis on total conservation cost, ecological representation of ecosystems, or emphasize an equal share of the burden among member states. To realize 30% and 50% ecoregion coverage, the EU would need to add 6.6% and 24.2%, respectively, of its terrestrial area to its PA network. For all 3 scenarios, the EU would need to designate most recommended new PAs in seminatural forests and other semi- or natural ecosystems. Because 15 ecoregions did not have enough natural area left to implement the ecoregion-coverage targets, some member states would also need to establish new PAs on productive land, allocating the largest share to arable land. Thirty percent ecoregion coverage was met by protecting remaining natural areas in all ecoregions except 3, where productive land would also need to be included. Our results support discussions of higher ecoregions protection targets for post-2020 biodiversity frameworks.     

Sequentielle Schwermetallextraktion aus Staubniederschlägen und Stra\ensedimenten

For the application of our method for the sequential extraction of heavy metals from microsamples presented in part 1 (“Sequentielle Schwermetallextraktion von Mikroproben” — “Sequential Extraction of Heavy Metals from Micro Samples”) an investigation was carried out to evaluate airborne dust fallout and street sediments at two urban sites where different heavy metal immission rates occur due to traffic influence. In the street sediments the total concentrations of zinc, copper and lead was three to fivefold higher in the silt and clay fraction (< 63 μm) than in the particle size fraction (< 1,12 mm), but showed nearly the same mobilisation behaviour. The dust samples showed equal mobilisation behaviour as the street sediments for copper and lead, while zinc was considerably more mobile in the dust samples: In extraction steps I–IV (I: mobile fraction; II: easily deliverable fraction; III: fraction bound to manganese oxides; IV: fraction bound organic to matter) zinc, copper and lead in street sediments, as well as copper and lead in dust samples, were dissolved to 40–70%, whereas about 80% of zinc in the dust samples was already dissolved in extraction step I.     

Mild hydrolysis of 2-trifluoromethylphenol: kinetics, mechanism and environmental relevance

2-Trifluoromethylphenol was hydrolysed in a phosphate buffer at neutral pH. At mild temperatures ranging from 34 degrees C to 69 degrees C this compound liberates consecutively fluorine anions to form salicylic acid. This process is energetically driven by the hydration of the fluorine anions. No intermediates have been detected by HPLC and (19)F-NMR and this was confirmed by computer calculations which favor the first step in the whole reaction sequence being rate-limiting. Accordingly, the reaction energy of the first dehalogenation of the trifluoromethyl anion is 28.4 kcal mol(-1) higher than for the second dehalogenation. The pseudo-first-order kinetic was determined and from an Arrhenius diagram an activation energy of E(a)=25.1 kcal mol(-1) has been estimated. At 37 degrees C and a pH of 7.4 the half-life was 6.9 h. The rate of hydrolysis was favored at higher pH and it was not influenced by oxygen, sunlight or trace elements found in natural water. The latter was shown by incubations with lake water instead of distilled water.     

Transport and anaerobic biodegradation of propylene glycol in gravel-rich soil materials

Continued input of airplane de-icing/anti-icing fluids (ADAF) to runway adjacent soils may result in the depletion of soil-borne terminal electron acceptors. We studied the transport and transformation of propylene glycol (PG), the major constituent of many ADAF, in topsoil and subsoil samples using saturated column experiments at 4 degrees C and 20 degrees C. The export of soil-borne DOC was generally high, non-exhaustive and rate limited. Retardation of added PG was negligible. Rapid PG degradation was observed only in topsoil materials high in organic matter at 20 degrees C. At 4 degrees C, no significant degradation was observed. Thus, under unfavorable, i.e., wet and cold conditions typical for winter de-icing operations, PG and its metabolites will be relocated to deeper soil horizons or even to the groundwater. In subsoil materials, PG degradation was very slow and incomplete. We found that subsoil degradation depended on the import of active microorganisms originating from the organic-rich topsoil material. The degradation efficiency is strongly influenced by the flow velocity, i.e., the residence time of PG in the soil column. Poorly crystalline iron(III) and manganese(IV) (hydr)oxides are used during microbial respiration acting as terminal electron acceptors. This results in the formation and effective relocation of reduced and mobile Fe and Mn species. Long-term application of ADAF to runway adjacent soil as well as the lasting consumption of Fe and Mn will tend to decrease the soil redox potential. Without proper counteractive measures, this will eventually favor the development of methanogenic conditions.