First evidence for a stereoselective incorporation of nonylphenol diastereomers in soil-derived organo-clay complexes

Environmental processes can affect the stereochemical properties of organic pollutants. In particular, biotic processes like microbial transformations or membrane penetration alter the ratios of enantiomers as well as diastereomers. These effects have been intensively used not only in environmental studies but also in medicine, toxicology, pharmacy, and agricultural sciences. However, in order to identify unambiguously biotic-initiated alteration of organic compounds, the knowledge on the stereoselective effect of all relevant processes is mandatory. Therefore, here we report the first evidence for a stereospecific formation of non-extractable residues of a xeniobiotic in a highly relevant soil subfraction, the organo-clay complexes. In this study, soils were spiked with labeled and unlabeled nonylphenol isomer, and incubation experiments were performed to study its long-term incorporation behavior into soil-derived organo-clay complexes under abiotic and biotic conditions. Besides the extractable particle-associated proportion especially the humic fractions comprising the bound residues have been analyzed by GC/MS. Our results from biotic experiments revealed alterations of the diastereomeric composition of the contaminant in the different soil humic subfractions. A depletion of the first eluting diastereomer as expressed by diastereomeric ratios around 0.6 has been observed for the extractable fraction, whereas the non-extractable proportion was enriched in the first diastereomer (diasteremoric ratio around 1.0). On the contrary, the diastereomeric ratios remained unaffected during the abiotic experiments (diasteremoric ratio around 0.8). These systematic observations give clear evidence that the process of microbial-assisted incorporation of nonylphenol into soil organo-clay complexes is a stereoselective process. To our knowledge, this is the first report on a stereoselective incorporation process of organic substances forming non-extractable residues. Consequently, the formation of non-extractable residues has to be considered in environmental studies dealing with stereoselective analysis of organic pollutants in soils to study their microbial transformation.     

GIS-gestützte Analysen zur möglichen Gefährdung von Naturschutzgebieten durch den Anbau gentechnisch veränderter Kulturpflanzen

Background, Aim, and Scope The introduction of genetically modified plants (GMP) into the European agriculture primarily has been investigated in respect of economical aspects, its impacts on conventional crops, and direct or indirect effects on human health. Potential ecological impacts, especially their long term and large scale implications, were out of focus, usually. A special task is to protect the integrity of nature reserves. According to §?23 of the German Nature Protection Law (BNatSchG) nature reserves are to protect nature and landscape properties by preserving and developing existing as well as by re-establishing biotopes of wild and endangered species. According to §?34a of the BNatSchG the use of GMP has to be accompanied by an environmental impact analysis of possible risks like it has to be done in projects affecting the integrity of Flora-Fauna-Habitats (FFH) or European bird sanctuaries. Considering this, the joint research project “Recommendations for isolation distances concerning the cultivation of genetically modified plants in the neighbourhood of protected areas” which was promoted by the Federal Agency for Nature Conservation (BfN) aimed at describing possible risks for biocoenoses in conservation areas that could be caused by the cultivation of GMP in their vicinity and at evaluating measures which could mitigate or hinder negative effects. The article at hand concentrates on describing the implications which would emerge when introducing different isolation distances concerning the cultivation of herbicide resistant oil seed rape (HR-OSR) and insect resistant maize (B.?t.-maize) near protection areas. On the other hand, a methodology is introduced which was developed to classify the German nature reserves according to their potential endangerment by GMP cultivation and to minimise calculation efforts for modelling possible impacts. Materials and Methods In 2003, there were around 7,400 nature reserves which covered 3?% of the whole territory of Germany. A geographical information system (GIS) was used to integrate geometries of conservation areas, land use data (CORINE landcover), agricultural information on district level as well as a map of German ecoregions. At first, it was evaluated how much arable land for B.?t.-maize or HR-OSR cultivation would remain if introducing different isolation distances around nature reserves (NSG). Furthermore, the NSG were aggregated to several homogenous classes reflecting different levels of cultivation intensities in their vicinity and different geometric properties. This was realised calculating a geometric coefficient (GC) which describes the ratio of periphery and area of each NSG in order to abstract the risk of GMP invasion. The density of maize and rape cropping near the NSG was expressed by a cultivation coefficient (CC). According to regional agricultural surveys, this was calculated by adding up the area of maize and rape fields within a radius of 1,000?m (maize) and 4,000?m (rape), respectively, around the NSG. Results Considering an isolation distance of 1,000?m around the NSG, 90?% of the farmland in Germany would be available for GMP cultivation. 50?% would remain when establishing an isolation distance of 4,000 m. The combination of GC and CC resulted in a total of nine risk categories (RC) describing the potential risk of endangerment by GMP cultivation in the vicinity of NSG. Areas with highest risk were grouped in RC nine where the smallest NSG (+ GC) in the main cultivation areas of maize or corn (+ CC) were summarised. With a numerical proportion of 7?% those sites cover only 0.4?% of total area of all NSG. All nature reserves showing highest CC values had a total proportion of 60?%. Discussion The derivation of GC and CC was based on a hierarchical approach and was implemented by complex GIS procedures. This makes it easy to calculate additional values for different GMP, protection areas or isolation distances. The RC were useful for choosing representative modelling sites in order to minimise calculation efforts when modelling possible impacts of GMP cultivation in vicinity of nature reserves. Conclusions The assessment of isolation distances around protection areas should be performed for each area individually concerning the GMP specific effects and dispersal properties as well as the protected organisms and the main protection targets. Especially HR-OSR is critical because of its volunteers and hybridisation partners. Another main source of GMP dispersal into protection areas might be the contamination of conventional seeds with transgene OSR seeds. Recommendations and perspectives Before defining and applying particular measures in order to protect conservation areas from possible impacts due to GMP cultivation a political and societal discussion is necessary in order to assess which GMP induced impacts may be tolerated. This has to be supported by additional scientific studies based on empirical and estimated data evaluating possible dispersal distances of GM pollen and possible environmental impacts of released transgenes and their toxins. According to the EU Directive 2001/18/EC the cultivation of GMP should be accompanied by a case-specific monitoring and general surveillance, as well. It should be realised as soon as possible, since the release and the cultivation of GMP in Germany have been started, already. The monitoring should be complemented by the implementation of a web-based geoinformation system (WebGIS) which enables the compilation and evaluation of the data and relevant geodata.     

A Framework for Analyzing Longitudinal and Temporal Variation in River Flow and Developing Flow-Ecology Relationships1

Larned, Scott T., David B. Arscott, Jochen Schmidt, and Jan C. Diettrich, 2010. A Framework for Analyzing Longitudinal and Temporal Variation in River Flow and Developing Flow-Ecology Relationships. Journal of the American Water Resources Association (JAWRA) 46(3):541-553. DOI: 10.1111/j.1752-1688.2010.00433.x Abstract: We propose a framework for analyzing longitudinal flow variation and exploring its ecological consequences in four steps: (1) generating longitudinally continuous flow estimates; (2) computing indices that describe site-specific and longitudinal flow variation, including intermittence; (3) quantifying and visualizing longitudinal dynamics; (4) developing quantitative relationships between hydrological indices and ecological variables (flow-ecology relationships). We give examples of each step, using data from a New Zealand river and an empirical longitudinal flow model, ELFMOD. ELFMOD uses spot-gauging data and flow or proxy variable time series to estimate flow magnitude and state (flowing or dry) at user-defined intervals along river sections. Analyses of flow-ecology relationships for the New Zealand river indicated that fish and benthic and hyporheic invertebrate communities responded strongly to variation in mean annual flow permanence, flow duration, dry duration, drying frequency, inter-flood duration, and distances to flowing reaches. To put longitudinal flow variation into a broader context and guide future research, we propose a conceptual model that combines elements of two contrasting perspectives: rivers as longitudinal continua, and rivers as patch mosaics. In this conceptual model, hydrologically complex rivers are composed of linear sequences of nested hydrological gradients, which are bordered by hydrogeomorphic discontinuities, and which collectively generate hydrological dynamics at river-section scales.     

Biodegradability testing of synthetic ester lubricants--effects of additives and usage

The optimised biodegradability test system "O2/CO2 Headspace Test with GC-TCD" is used for the assessment of synthetic ester lubricants. The effects of both additives and usage on biodegradability are examined and discussed. Ester based cutting fluids and hydraulic fluids with and without additives are used under defined conditions at machine tools and hydraulic and plain bearing test benches. The lubricants are characterised additionally with respect to kinematic viscosity, acidity and elemental composition. Furthermore, a formulated mineral oil is characterised before and after usage at an hydraulic test bench. The results clearly show that the mineral oil is far less biodegradable than the ester oils and that their biodegradability is not affected by usage. Biodegradability of the ester oils is mainly depending on the characteristics of the base fluids and not affected by the additives. Antioxidants are influencing stability respectively biodegradability indirectly, since they prevent oxopolymerisation effects. Other effects of usage on biodegradation are not detected. In this context, the antioxidants ensure ready biodegradability and have a positive effect on the environmental fate of synthetic ester lubricants.     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

Biodegradation of low aqueous concentration pentachlorophenol (PCP) contaminated groundwater

Bioremedial treatment to remove low level organic contamination to regulatory standards has met with limited success. In this study source water from a contaminated surficial aquifer at a former wood treatment facility was used to evaluate the potential for indigenous microorganisms to degrade low level (< 1.0 mg) pentachlorophenol (PCP) to a regulatory drinking water standard of 0.001 mg/L. PCP degradation was evaluated in series of batch reactors in a two phase study to (a) determine the rate and extent of PCP removal and (b) evaluate the impact of nutrient amendment (N and P) on removal rate. All reactors with the exception of the abiotic control demonstrated PCP removal to a level < 0.002 mg/L within a maximum period of 32 d with and without nutrient amendment. A regression analysis of reactive phosphate (ortho-P) concentration versus removal rate produced an R2 of 0.94 (p = 0.006) indicating a significant correlation between the level of available phosphate and PCP degradation rate. Selective bacterial enumeration (for PCP degrading bacteria) revealed PCP-degrading bacteria increased in abundance prior to and in conjunction with the degradation phase to a density of between 10(3) to 10(4) CFU/ml. Isolates were also analyzed for total fatty acids using Fatty Acid Methyl Ester (FAME) methodology and the results indicated that PCP degrading bacteria were present in the aquifer and consisted of predominately fluorescent, oxidase positive Pseudomonas species. Overall, data indicate that autochthonous microbes are capable of removing low level PCP (< 1.0 mg/L) to approach if not reach the regulatory standard of 0.001 mg/L with the addition of oxygen, with or without nutrient amendment. Results of this research can be applied to full-scale implementation of in-situ or ex-situ bioremediation of groundwater at former wood treatment facilities.