Characterization of model melanoidins by the thermal degradation profile

Different types of model melanoidins were thermally degraded, with subsequent identification of the volatiles produced, to obtain and compare the thermal degradation profile of various melanoidins. At first, the volatiles produced from heated glucose/glycine standard melanoidins were compared with glucose/glutamic acid and L-(+)-ascorbic acid/glycine standard melanoidins. In the headspace of heated glucose/glycine melanoidins, mainly furans, were detected, accompanied by carbonyl compounds, pyrroles, pyrazines, pyridines, and some oxazoles. Heating of L-(+)-ascorbic acid/glycine melanoidins resulted in relatively more N-heterocycles, while from glucose/glutamic acid melanoidins no N-heterocycles were formed. In a second part, a chemical treatment was applied to glucose/glycine melanoidins prior to the thermal degradation. Acid hydrolysis was performed to cleave glycosidically linked sugar moieties from the melanoidin skeleton. Nonsoluble glucose/glycine melanoidins were also subjected to an oxidation. The results indicate that the thermal degradation profile is a useful tool in the characterization of different types of melanoidins.     

Amino acid catalysis of 2-alkylfuran formation from lipid oxidation-derived α,β-unsaturated aldehydes

The formation of 2-alkylfurans from the corresponding lipid-derived α,β-unsaturated aldehydes under dry-roasting conditions was investigated in detail. The addition of an amino acid to an α,β-unsaturated aldehyde drastically increased 2-alkylfuran formation. Peptides and proteins as well were able to catalyze 2-alkylfuran formation from the corresponding α,β-unsaturated aldehydes. Further investigation of 2-alkylfuran formation showed the need of oxidizing conditions and the involvement of radicals in the reaction. This way, the formation of 2-methylfuran from 2-pentenal, 2-ethylfuran from 2-hexenal, 2-propylfuran from 2-heptenal, 2-butylfuran from 2-octenal, 2-pentylfuran from 2-nonenal, and 2-hexylfuran from 2-decenal was shown. The impact of amino acids on 2-alkylfuran formation from lipid-derived α,β-unsaturated aldehydes represents an interesting example of the complex role of amino acids in the multitude of chemical reactions occurring during thermal processing of lipid-rich foods.     

A Method for Determining Phosphate Diffusion Coefficients by Bulk Diffusion in Soil

A method is described for the determination of phosphate diffusion coefficients by bulk diffusion in soil using the concentration distance method. Two soil blocks only differing in phosphate concentration are brought into contact. After a diffusion period of two weeks the soil blocks are separated, frozen in liquid nitrogen and sliced into layers about 0.02 cm thick by means of a refrigerated microtome. The soil samples are extracted with 4 N HCl, a procedure which fully recovers the added amount of fertilizer P and thus includes the total amount of P that diffuses from one soil block to the other. A concentration distance profile for P and a calculation of the P diffusion coefficient is presented.     

Effect of land use types on decomposition of 14C-labelled maize residue (Zea mays L.)

The effect of three land use types on decomposition of ¹⁴C-labelled maize (Zea mays L.) residues and soil organic matter were investigated under laboratory conditions. Samples of three Dystric Cambisols under plow tillage (PT), reduced tillage (RT) and grassland (GL) collected from the upper 5 cm of the soil profile were incubated for 159 days at 20 °C with or without ¹⁴C-labelled maize residue. After 7 days cumulative CO₂ production was highest in GL and lowest in PT, reflecting differences in soil organic C (SOC) concentration among the three land use types and indicating that mineralized C is a sensitive indicator of the effects of land use regime on SOC. ¹⁴CO₂ efflux from maize residue decomposition was higher in GL than in PT, possibly due to higher SOC and microbial biomass C (MBC) in GL than in PT. ¹⁴CO₂ efflux dynamics from RT soil were different from those of PT and GL. RT had the lowest ¹⁴CO₂ efflux from days 2 to 14 and the highest from days 28 to 159. The lowest MBC in RT explained the delayed decomposition of residues at the beginning. A double exponential model gave a good fit to the mineralization of SOC and residue-¹⁴C (R² > 0.99) and allowed estimation of decomposition rates as dependent on land use. Land use affected the decomposition of labile fractions of SOC and of maize residue, but had no effect on the decomposition of recalcitrant fractions. We conclude that land use affected the decomposition dynamics within the first 1.5 months mainly because of differences in soil microbial biomass but had low effect on cumulative decomposition of maize residues within 5 months.     

Die Forstwirtschaft der Ostmark und ihre Beziehungen zur gesamtdeutschen volkswirtschaft

Ohne Zusammenfassung     

Accumulation of metals in macrophytes from water reservoirs of a power supply plant, Rio de Janeiro State, Brazil

Aquatic macrophytes are well known accumulators for heavy metals, the reason why they are used as bioindicators for water quality and in phytoremediaton strategies. This study reports on the elemental concentrations in four free-floating aquatic macrophytes (S. auriculata; P. stratiotes; E. crassipes and E. azurea) growing in two water reservoirs (Santana e Vigário, Rio de Janeiro State, Brazil) of an electric power plant that receive input from the polluted Paraíba do Sul River. Filtered water samples and water suspended solids from these environments were also analysed. Inductively coupled plasma mass spectrometry was used as the principal method, allowing the determination of up to 41 elements, including the rare-earth elements (REEs) and other trace metals not assayed before in these macrophytes. The results show that all elements studied are accumulated by the macrophytes with concentration ratios (CR = [plant]: [water]) varying from about 1,000 to 200,000, based on the dry weight of the plant species. With a few exceptions, highest accumulations were observed in E. crassipes in which CRs increase in the sequence: Cu < Mo < Cr < Pb < Tl < Fe < La < Zn < Ce< Mn. Surprisingly high CRs (e.g. Ce: 74,000) and corresponding mass concentrations were observed for the rare-earth elements (e.g. ∑REE: 112 mg kg^?1), also measured in the water suspended particle fraction. The results show that this fraction acts as an effective sink for trace metals in the aquatic system studied and seems to play also an important role in the transfer of metals from water to the plant species.     

Growth and phosphorus uptake of maize cultivated alone,in mixed culture with other crops or after incorporation of their residues

Intercropping or rotating of P‐efficient crop species which mobilize sparingly soluble P by their root exudates can have beneficial effects on growth and P uptake of P‐inefficient species. We aimed at studying the effect of intercropping or incorporating of crop residues of P‐efficient crops on the components of maize P‐uptake, i.e. the root‐system size and P influx (P‐uptake rate per unit root length). This was studied in 3 pot experiments in a low‐P sandy soil. In the first experiment, maize was intercropped with white lupine, sugar beet or oilseed rape, and with groundnut in the second experiment. In the third experiment, maize was grown after incorporating the crop residues of white lupine, sugar beet or oilseed rape. Maize growth and yield was strongly inhibited when intercropped with white lupine, sugar beet or oilseed rape, probably because of competition for nutrients. But with groundnut as the accompanying species, maize yield was increased by a factor of 3, mainly because of an enhanced P influx. Crop residues of oilseed rape and sugar beet increased the yield of maize by factors 2 and 1.6, respectively, because of a 3 and 2 times higher P uptake as compared to maize grown after maize without incorporation of crop residue. The reason for the higher maize P‐uptake after oilseed rape was an 11 times higher P influx as compared to maize without crop residues, and after sugar beet residues because of an enhanced root growth and a 4 times higher P influx. Lupine residues did not improve maize growth, mainly because of a low P influx, which was even less than that of maize grown without crop residues. The soil solution P concentration and calcium acetate lactate‐extractable P (CAL P) measured in this study did not reflect the P availability as indicated by the plants (P uptake, P influx). This indicates that other mechanisms such as P mobilization in the rhizosphere by root exudates or cell‐wall components were responsible for the increased P availability. These mechanisms need further investigation.     

A method for determining Michaelis-Menten kinetic parameters of nutrient uptake for plants growing in soil

The relationship between nutrient influx (I_n) and solution concentration at the root surface (C_lo) has not yet been determined for roots growing in soil because of difficulties in measuring C_lo. Corn was grown on two soils with 12 and 21% clay. Each soil had five K levels ranging from low to very high. Potassium influx (I_n) was determined from K uptake between two harvests and root length. C_lo was then calculated from the average soil solution concentration and I_n by assuming that diffusion is the main transport mechanism for K to the root. Potassium influx plotted against C_lo showed a saturation curve, typical of a Michaelis-Menten kinetic relationship. The Michaelis-Menten uptake parameters, maximum influx (I_max) and Michaelis constant (K_m), were obtained by the “Hanes” plot. There was close agreement, without lack of fit, between calculated and observed data. The proposed procedure therefore appears to be suitable for estimating the uptake kinetics of roots growing in soil. Requirements for applications of the method are discussed.     

Bioassay-directed Fractionation of Organic Extracts of Marine Surface Sediments from the North and Baltic Sea - Part II: Results of the biotest battery and development of a biotest index (8 pp)

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Part I: Determination and identification of organic pollutants Part II: Results of the biotest battery and development of a biotest index

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Preamble. This series of two papers presents the results of an interdisciplinary research project (ISIS) dealing with bioassay-directed fractionation of marine sediment extracts. Part I presents the extraction and fractionation procedure as well as the results of chemical analysis, including non-target analysis of sediments. Part II describes the results of the biotest battery in relation to chemicals possibly causing parts of the observed effects. A biotest index is used to compare the toxicities of the samples.

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AUTHORS / AFFILIATIONS Ninja Reineke (3), Werner Wosniok (4), Dirk Danischewski (1), Heinrich Hühnerfuss (3), Angelika Kinder (5), Arne Sierts-Herrmann (5), Norbert Theobald (2), Hans-Heinrich Vahl (6), Michael Vobach (1), Johannes Westendorf (6) and Hans Steinhart (5).

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(1) Federal Research Centre for Fisheries, Institute for Fishery Ecology, Palmaille 9, 22767 Hamburg, Germany (2) Federal Maritime and Hydrographic Agency, Bernhard-Nochtstr. 78, 20359 Hamburg, Germany (3) University of Hamburg, Institute for Organic Chemistry, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany (4) University of Bremen, Institute of Statistics, Bibliothekstr. 1, 28334 Bremen, Germany (5) University of Hamburg, Institute for Food Chemistry, Grindelallee 117, 20146 Hamburg, Germany (6) University of Hamburg, University Hospital Hamburg-Eppendorf, Department for Toxicology, Vogt-Kölln-Str. 30, 22527 Hamburg, Germany (7) Eurofins Wiertz-Eggert-Jörissen, Stenzelring 14b, 21107 Hamburg, Germany

Goal, Scope and Background

The ecological relevance of contaminants in mixtures is difficult to assess, because of possible interactions and due to lacking toxicity data for many substances present in environmental samples. Marine sediment extracts, which contain a mixture of environmental contaminants in low concentrations, were the object of this study. The extracts were investigated with a set of different biotests in order to identify the compound or the substance class responsible for the toxicity. For this goal, a combination of biotests, biotest-directed fractionation and chemical analysis has been applied. Further on, a strategy for the development of a biotest index to describe the toxicity of the fractions without a prior ranking of the test results is proposed. This article (Part II) focuses on the biological results of the approach.

Methods

The toxicological potential of organic extracts of sediments from the North Sea and the Baltic Sea was analyzed in a bioassay-directed fractionation procedure with a set of biotests: luciferase reporter gene assays on hormone receptor and Ah receptor, arabinose resistance test, fish embryo test (Danio rerio), comet assay, acetylcholinesterase inhibition test, heat-shock protein 70 induction, oxidative stress and luminescence inhibition test (Vibrio fischeri). The test results provided the basis for the calculation of a biotest index by factor analysis to compare the toxicity of the samples and fractions.

Results and Discussion

Results of 11 biotests on different fractionation levels of the samples were described and discussed with regard to the occurrence of contaminants and their toxic potentials. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons, quinones, brominated indoles and brominated phenols were in the focus of interest. A biotest index was constructed to compare the toxic responses in the samples and to group the biotest results.

Conclusion

The procedure presented in this study is well suited for bioassay-directed fractionation of marine sediment extracts. However, in relatively low contaminated samples, high enrichment factors and sufficient fractionation is necessary to allow identification of low concentrations of contaminants which is required to link effects and possible causes. In the present case, the relation between substances and effects was difficult to uncover due to relatively low concentrations of pollutants compared to the biogenic matrix and to the remaining complexity of the fractions. The results, with respect to the brominated phenols and indoles in the samples, highlight the successful use of bioassay directed fractionation in the case of high concentrations and high toxicity.

Recommendation and Outlook

In general, it has been shown that a marine risk assessment requires focusing on the input of diffuse sources and taking into account the fact of mixture toxicity. Effects resulting from biogenic substances will make the assessment of the influence of anthropogenic substances even more difficult.     

Phosphorylation networks regulating JNK activity in diverse genetic backgrounds

Cellular signaling networks have evolved to enable swift and accurate responses, even in the face of genetic or environmental perturbation. Thus, genetic screens may not identify all the genes that regulate different biological processes. Moreover, although classical screening approaches have succeeded in providing parts lists of the essential components of signaling networks, they typically do not provide much insight into the hierarchical and functional relations that exist among these components. We describe a high-throughput screen in which we used RNA interference to systematically inhibit two genes simultaneously in 17,724 combinations to identify regulators of Drosophila JUN NH(2)-terminal kinase (JNK). Using both genetic and phosphoproteomics data, we then implemented an integrative network algorithm to construct a JNK phosphorylation network, which provides structural and mechanistic insights into the systems architecture of JNK signaling.