Brominated flame retardants and related chlorinated persistent organic pollutants in fish from river Elbe and its main tributary Vltava

Brominated flame retardants (BFRs) are widely used industrial chemicals, residues of which can be nowadays found in all environmental compartments. The widespread presence of BFRs in various environmental compartments and food chain is a consequence of both their broad application area and physico-chemical properties, such as resistance to degradation and high lipophilicity. Alike in the case of other halogenated persistent organic pollutants (POPs), fish can be used as a bioindicator of aquatic environment pollution. In presented study, conducted in the year 2005, altogether 80 samples representing the most abundant fresh water fish species, viz. chub (Leuciscus cephalus), bream (Abramis brama), and perch (Perca fluviatilis) collected in 11 sampling sites located at Elbe and Vltava (Moldau) rivers were examined for levels of major BFRs. Without any exception, BFRs were detected in all fish samples. BDE 47 was the dominating congener in all fish species. This fact was not surprising, since it used to be the main component in various kinds of technical mixtures. With regard to relatively high levels of BDE 47 in fish tissue, as compared to other BFRs, and considering strong correlation with the total PBDEs content, simplified laboratory examination and, consequently, increased samples throughput can be obtained when only this congener is monitored. The potential of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), to provide more comprehensive information on the bioaccumulating chemicals occurring in fish samples, has been demonstrated in this study.     

Metal accumulation in the earthworm Lumbricus rubellus. Model predictions compared to field data

The mechanistic bioaccumulation model OMEGA (Optimal Modeling for Ecotoxicological Applications) is used to estimate accumulation of zinc (Zn), copper (Cu), cadmium (Cd) and lead (Pb) in the earthworm Lumbricus rubellus. Our validation to field accumulation data shows that the model accurately predicts internal cadmium concentrations. In addition, our results show that internal metal concentrations in the earthworm are less than linearly (slope<1) related to the total concentration in soil, while risk assessment procedures often assume the biota-soil accumulation factor (BSAF) to be constant. Although predicted internal concentrations of all metals are generally within a factor 5 compared to field data, incorporation of regulation in the model is necessary to improve predictability of the essential metals such as zinc and copper.     

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.     

Electrochemical treatment of a simple azodye and analysis of the degradation products using high performance liquid chromatography-diode array detection-tandem mass spectrometry

The simple, low molecular weight, azodye acid yellow 9 (AY9) is electrochemically treated in a suitable electrolytic cell using NaCl as a supporting electrolyte, carbon fleece as cathode and platinated titanium as anode. Samples from certain time periods of treatment are analysed. HPLC-UV chromatograms demonstrate the degradation of the initial azodye, while diode array detector (DAD) spectra give evidence concerning the aromaticity of the degradation products and tandem mass spectrometry (MS(2)) offer structural information on some final products. In order to distinguish cathodic and anodic processes, separated cells connected with electrolytic junction are used, clarifying the oxidative and reductive decomposition pathways of the studied azodye. Several intermediate products are identified in very low concentrations such as hydrazo-derivatives, chlorinated aromatic and aliphatic compounds as well as amino- and hydroxyl-products. Experiments in separated electrolytic cells show that azodye degradation proceeds mainly oxidatively, since cathodic action is extremely limited, while treatment in common cells results in complete decoloration and presence of degradation products in very low concentration. Finally, simple degradation mechanisms are suggested based on tandem mass spectrometric identification of several degradation products.     

Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid

A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) (13)C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time (T(CH)) and proton spin-lattice relaxation time in the rotating frame (T(1rho)(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T(CH) values and the longest T(1rho)(H) values which suggested, respectively, one. an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two. consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T(CH) values and shorter T(1rho)(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.     

Modeling organic carbon dynamics and cadmium fate in long-term sludge-amended soil

A model is described that may help to resolve uncertainty and controversy over the long-term consequences of sludge applications to arable land, especially with regard to the effects of sludge adsorption characteristics on trace metal solubility and bioavailability (e.g., the sludge "time bomb" or sludge "protection" hypotheses). Mass balances of organic and inorganic material derived from sludge and crop residues are simulated. Each pool has a potentially different adsorption affinity for trace metals, and this leads to changes in the adsorption capacity of sludge-amended soil that influence leaching and crop uptake. Model simulations were compared with measured changes in organic carbon and ethylenediaminetetraacetic acid (EDTA)-extractable cadmium contents in a clay loam soil following 41 years of sludge applications. The model adequately reproduced the data, although discrepancies in the vertical distribution of Cd were attributed to the effects of macropore transport and root-uptake driven recirculation. A Monte Carlo sensitivity analysis demonstrated that the most important parameters affecting leaching and crop uptake were the Cd loading and parameters controlling adsorption, especially the partition coefficient for sludge-derived inorganic material and the exponent regulating the effect of pH on sorption. Scenario simulations show that no general conclusions can be drawn with respect to the validity of the sludge "time bomb" and sludge "protection" hypotheses. Either may occur, or neither, depending on three key system parameters: the ratio of sludge adsorption capacity to the initial adsorption capacity of the soil, the proportion of the sludge adsorption capacity contributed by the inorganic fraction, and the sludge Cd loading.     

Verbleib von spurenschadstoffen bei der methylesterherstellung aus altspeisefett im technikumsmaßstab

Aims and Scope

In Germany, 120,000 tons per year of waste edible fats are collected from the catering and the food industry Until recently, these fats have widely been used as a nutritional additive for poultry and other animals fodder. Due to the BSE crisis and some affairs based on dioxins in feeding stuff, waste fats are now barely used as fodder. Currently, these fats substitute fresh vegetable oils in the chemical industry and are used as raw material for the production of biodiesel. Therefore, alternative fields of application are required. In this context, the Deutsche Bundesstiftung Umwelt (DBU) is sponsoring a joint research project which deals with the production and testing of cooling lubricants based on monoesters made from waste edible fats.

Methods

In a first step, characteristics and quality of wasteedible fats of different origins were chemically analysed and monitored. The investigations covered the following fat specific parameters: total contamination, sulphate ash, water content, peroxide number, iodine value, kinematical viscosity, neutralisation number (free fatty acids) and fatty acid spectra. In the next step, a process development/optimisation was carried out for the production of methylesters based on the raw material waste fat, leading to the construction of a pilot plant. To investigate the fate of trace pollutants during the production process of waste-fat methylester, samples were systematically contaminated with polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and the elements Al, Cd, Cr, Cu, Ni, P, Pb, Sn, and Zn. These contaminated fat samples were transesterified in laboratory scale. The primary and by-products were analysed subsequently.

Results

Valuable hints on the design of the technical process of fatty adid methylester production based on waste edible fats were gained by regarding the fat specific parameters. For example, filtration and dewatering of the waste fats proved necessary. The saturated fatty acids, most wanted for the production of cooling lubricants due to their high oxidation stability, were present in the range of 11,3% to 31,6%. Due to the low content of free fatty acids, a base catalysed process occurred more suitable for the transesterification of the waste edible fats. Trace analytical investigations concerning inorganic and organic pollutants proved a low basic contamination of the waste edible fats. Experiments with systematic contamination of the fats indicated an accumulation of the heavy metals in the glycerol phase during the transesterification process, whereas the organic pollutants were detected in the methylester fraction by amounts of 80% to 95%.

Outlook

In a next step, the further processing of the methylesters to monoesters with alcohols of the chain length C2 to C8 will be presented. Associated results of chemical-analytical investigations on the process and the application of the cooling lubricants will also be given.     

Global-scale vs. regional-scale scenario assumptions: implications for estimating future water withdrawals in the Elbe River basin

In this paper, we explore how scenarios of future water withdrawals in a river basin are influenced by scale-dependent quantifications of the driving forces for two global-scale storylines. Either global-scale information or region-specific information is used to do the quantifications. In addition, we analyze the impact of including or not some restricted regional-scale information in the employed water use model. To develop scenarios of water withdrawals in the German part of the Elbe River basin, we applied the modules for domestic, thermoelectric power and manufacturing water use of the global water model WaterGAP, using scale-dependent driving forces scenarios and other scale-dependent model input. In the global-scale quantitative interpretations of the storylines of the IPCC SRES scenarios A1 and B2, all major driving forces of water withdrawals in the basin—population, thermoelectric power production and industrial gross domestic product—show vigorous increases between 2000 and 2025, while from the regional perspective, smaller increases but mostly decreases appear to be plausible. These discrepancies are partly due to the fact that for the global-scale interpretations only the historic developments until 1990 were taken into account, and not until 2000 as in the regional case. The resulting scenarios of sectoral water withdrawals in 2025 differ strongly between the two scale-dependent interpretations of the storylines, with the global one leading to much higher absolute water withdrawals and much lower withdrawal decreases between 2000 and 2025. Therefore, for regional assessments of water withdrawals, we recommend to embed the scenario analysis in global-scale storylines by performing regional-scale quantifications of the global qualitative driving forces scenarios, based on a limited amount of region-specific information.     

Decolorization of RBBR by plant cells and correlation with the transformation of PCBs

An extracellular H2O2-requiring Remazol Brilliant Blue R (RBBR) decolorizing enzyme activity was detected after cultivation of cells of various plant species both in liquid medium and when growing on agar plates containing RBBR. Level of the enzyme activity was compared with the ability to metabolize polychlorinated biphenyls (PCBs). The ability to decolorize RBBR was tested in the presence and absence of PCBs. The cultures with high PCB-transforming activity proved to exhibit RBBR oxidase much more resistant towards the influence of PCBs. In addition low activities of lignin peroxidase (LiP) and manganese dependent peroxidase (MnP) were detected in medium and in plant cells. No correlation of MnP and LiP activities with PCB degradation could be found. The RBBR decolorization could be used as a rough screening method for plant cultures able to metabolize PCBs.