Contamination history of suspended river sediments accumulated in oxbow lakes over the last 25 years

Background, aims, and scope  Embankment of meandering river systems in many industrial areas results in the formation of artificial oxbow lakes that may act as perennial or intermittent traps for river sediments. Their deposits can be dated using a combination of historical and stratigraphic data, providing a good means to study historical records of contamination transported by rivers. Contamination history over the last few decades is of special significance for Central and Eastern Europe as it can reflect high pollutant levels in the second half of the twentieth century and the subsequent improvement after the fall of the Iron Curtain. The purpose of this study was to investigate recent sediments of an oxbow lake of the Morava River, Czech Republic, their stratigraphic records, sediment architecture, and history of contamination. Materials and methods  Seven ground-penetrating radar (GPR) profiles and three sediment cores up to 4 m deep were studied. The stratigraphy of the cores was inferred from visible-light spectrophotometry, X-ray radiography, grain size analysis, and semiquantitative modal analysis of sandy fractions. The sediments were dated using the ¹³⁷Cs mass activity and combinations of stratigraphic and historical data. The cores were sampled for concentrations of heavy metals and persistent organic pollutants. Wet sampled, lyophilized, and sieved sediments were extracted and analyzed for heavy metals by inductively coupled plasma mass spectrometry (ICP-MS) of aqua regia leachate and for persistent organic pollutants by gas chromatography (GC-ECD and GC-MS). Results  Three distinct sedimentary sequences (S1, S2, and S3) were identified. The basal sequence S1 represents river channel sediments deposited before the formation of the oxbow lake, most likely before the 1930s. The boundary between the S1 and S2 sequence correlates with the level of sediment dredging from 1981 evidenced from historical data. The overlying sequences S2 and S3 represent a postdredging sediment wedge, which progrades into the lake. ¹³⁷Cs dating revealed a distinct Chernobyl 1986 peak at ∼150 cm depth inferring sedimentation rates up to 7.7 cm/year. Sediment contamination abruptly increased from the pre-1930s deposits to the post-1981 deposits. The concentration levels increased two to five times for Pb, As, Zn, and Cu, about 10 to 15 times for Cr, Sb, and Hg, up to 34 times for Cd, and 25 to 67 times for DDTs, PCBs, and PAHs. The concentrations of most contaminants remained approximately constant until the late 1980s when they started to decrease slowly. The decreasing trends were most prominent for heavy metals and anthracene, less prominent for DDTs, and almost absent for PCBs and most PAHs. Discussion  Different temporal and spatial patterns for various contaminants make it possible to distinguish between anthropogenic point sources from local industry (anthracene, Cr, Cd), possible diffuse sources (most PAHs), and geological background (V, Co, Ni, and Mo). The observed recent trends in heavy metal and persistent organic pollutant contamination are generally consistent with data from other Central European rivers. The roughly balanced contamination levels in sediments from the lake and the adjacent river channel suggest that the oxbow lake deposits reflect immediate levels of the contamination bound to suspended particulate matter passing through the river. Conclusions  The investigated oxbow lake accumulated suspended sediment from Morava River, developing a thick sedimentary body. The sediments offer a good time framework to study historical contamination of the river on a decade time scale. Continuous contamination trends can be traced back to the early 1980s. The results show that stratigraphic analysis of cores has a good potential for identification of uninterrupted historical trends and unconformities, e.g., due to dredging. Recommendations and perspectives  Oxbow lakes may provide an alternative to floodplains and reservoir deposits when studying river contamination history. High sedimentation rates of up to 7.7 cm/year offer a very good stratigraphic resolution, making it possible to study contamination patterns on annual or even seasonal time scales. On the other hand, oxbow lakes may represent long-term contamination stores, which are unlikely to be redistributed by river erosion and, hence, may possess significant environmental risks for the farther future.     

New approach to border line evaluations for whole sample of Williams pear (Pyrus communis)

In many processes of heat exchange, as well as in other processes of biomaterial handling, physical properties of fruit such as dimensions, shape, surface area and volume are of crucial importance. The objective of this work was to find a function which approximates pear border line, as precisely as possible, in order to calculate the surface area and volume of a pear by means of integral calculus. Previously described estimation of an average pear border line was based on the sixth order polynomial and proposed algorithm. Two new ways to calculate the Williams pear border line are the focus of this study. The first way includes spline functions as an estimation of a pear border line (i.e. four third order polynomials), while the second one uses regression function obtained by nonlinear regression method. The regression function has two independent variables, length and total length of a pear. The most precise approximation of a pear border line was obtained by nonlinear regression with R² = 97.48. This was more obvious when total pear length was smaller or greater than average total pear length. Border lines of all tested pears were determined by one regression function with large precision. Therefore, it is safe to calculate surface area and volume of a pear based on regression function and total pear length, only. Calculated volumes of the pears were compared with volumes measured by Archimedes’ method. The smallest relative error has been obtained when the volumes were calculated using the regression function as approximation of pear border line.     

Botanical pesticides and their human health safety on the example of Citrus sinensis essential oil and Oulema melanopus under laboratory conditions

Biopesticides derived from plants have recently received increasing interest as an alternative to conventional chemicals suitable for integrated pest management and organic farming. In this study, Citrus sinensis (Osbeck) essential oil was tested for its potential for wheat protection against Oulema melanopus (L.). The chemical composition of the essential oil was analyzed by gas chromatography-mass spectrometry (GC-MS). Twenty-four compounds were identified in the oil among which d-limonene was a predominant component, followed by myrcene, α-pinene, linalool, sabinene, decanal, and other minor components. Direct contact toxicity assay showed the effectiveness of the essential oil against O. melanopus larvae causing the mortality of 85% during 48 hours. The persistence study revealed high dissipation rate of the oil from treated plants, whereas concentrations lower than 0.01 g/kg were detected by GC-MS 5 min after the application of the oil, suggesting its environmental and food safety. These results, together with previous literature reports reviewed in this study, indicate the great potential of the C. sinensis essential oil for future use in crop protection against insect pests.     

Über die Schädlichkeit einiger Borkenkäferarten auf der AprikosePrunus armniaca L.)

Ohne Zusammenfassung     

Exploration of beer proteome using OFFGEL prefractionation in combination with two-dimensional gel electrophoresis with narrow pH range gradients

Two-dimensional gel electrophoresis in combination with mass spectrometry has already been applied successfully to study beer proteome. Due to the abundance of protein Z in beer samples, prefractionation techniques might help to improve beer proteome coverage. Proteins from four lager beers of different origins were separated by two-dimensional electrophoresis (2-DE) followed by tandem mass spectrometric analysis. Initially 52 proteins mostly from Hordeum vulgare (22 proteins) and Saccharomyces species (25 proteins) were identified. Preparative isoelectric focusing by OFFGEL Fractionator was applied prior to 2-DE to improve its resolution power. As a result of this combined approach, a total of 70 beer proteins from Hordeum vulgare (30 proteins), from Saccharomyces species (31 proteins), and from other sources (9 proteins) were identified. Of these, 37 proteins have not been previously reported in beer samples.     

Deoxynivalenol oligoglycosides: new "masked" fusarium toxins occurring in malt, beer, and breadstuff

The co-occurrence of deoxynivalenol-3-glucoside with its parent toxin, deoxynivalenol, has been recently documented in many cereal-based foods, especially in those produced by enzyme-catalyzed processes. The presence of this masked mycotoxin in the human diet has become an issue of health concern, mainly because of its assumed bioavailability. A selective immunoaffinity-based preconcentration strategy, followed by ultrahigh-performance liquid chromatography coupled with high-resolution orbitrap mass spectrometry, revealed that, in addition to the most common deoxynivalenol-3-glucoside, also oligoglycosylated deoxynivalenols with up to four bound hexose units were present in cereal-based products. The structure, origination, and fate of these deoxynivalenol conjugates during malt/beer production and bread baking have been thoroughly investigated. Special attention has been paid to the changes of deoxynivalenol conjugates enabled by industrial glycosidase-based enzymatic preparations. To the authors' best knowledge, this is the first study documenting the complexity of masked deoxynivalenol issue.     

Cultivar variability of patatin biochemical characteristics: table versus processing potatoes (Solanum tuberosum L.)

Biochemical characteristics of patatin proteins purified by ion-exchange and affinity chromatography from tubers of 20 potato cultivars were studied to evaluate their genotype differences with respect to utility groups, table potato cultivars (TPCs) and processing potato cultivars (PPCs). Both groups of cultivars showed similar values of protein content in dry matter (3.98-7.39%) and of patatin relative abundance (5.40-35.40%). Three mass levels (～40.6, 41.8, and 42.9 kDa) of purified patatins were found by MALDI-TOF MS within all cultivars. Differences among mass levels corresponding with the mass of sugar antenna (～1.2 kDa) confirmed the previous concept of different glycosylation extentsin patatin proteins. It was showed that the individual types of patatin varying in their masses occur in the patatin family in a ratio specific for each of the cultivars, with the lowest mass type being the major one. Electrophoretic analyses demonstrated wide cultivar variability in number of patatin forms. Especially 2D-PAGE showed 17-23 detected protein spots independently on the utility group. Specific lipid acyl hydrolase (LAH) activity of purified patatins from the individual tested cultivars varied between 0.92 and 5.46 μmol/(min mg). Patatin samples within most of the TPCs exhibited higher values of specific LAH activity than samples of PPCs. It may be supposed that individual patatin forms do not have similar physiological roles.     

Insect pest management agents: hormonogen esters (juvenogens)

The chemical part of this investigation focused on designing structures and synthesizing a series of six new esters (juvenogens), derived from biologically active insect juvenile hormone bioanalogues (juvenoids, JHAs) and unsaturated short-chain linear and branched fatty acids for possible application as biochemically targeted insect hormonogen agents. The structures of the new compounds were assigned on the basis of a detailed NMR analysis of their (1)H and (13)C NMR spectra. The biological part of this investigation focused on introductory biological screening tests with these compounds against the red firebug (Pyrrhocoris apterus), termites (Reticulitermes santonensis and Prorhinotermes simplex), and the blowfly (Neobellieria bullata). The biological activity of the juvenogens was studied in relation to the fatty acid functionality in the structures. Notable biological activity in topical tests and medium activity in peroral tests was found for the juvenogens 3 and 7 with P. apterus. The compounds 6 and 8 showed the lowest activity in both topical and oral assays with P. apterus. Considerable effect of all tested juvenogens was observed in P. simplex; however, the juvenogens 5 and 6 (derivatives of the only branched short-chain fatty acid) showed no activity against R. santonensis. The effect of the compounds 3-8 on larval hatching of N. bullata was only moderate (larval hatching 80-90%); however, the proliferation effect caused by 5, 6, and 8 is more pronounced than the effect caused by 3, 4, and 7.     

A new approach for cytokinin isolation from Arabidopsis tissues using miniaturized purification: pipette tip solid-phase extraction

ABSTRACT: BACKGROUND: We have developed a new analytical approach for isolation and quantification of cytokinins (CK) in minute amounts of fresh plant material, which combines a simple one-step purification with ultra-high pressure liquid chromatography-fast scanning tandem mass spectrometry. RESULTS: Plant tissue samples (1-5 mg FW) were purified by stop-and-go-microextraction (StageTip purification), which previously has only been applied for clean-up and pre-concentration of peptides. We found that a combination of two reverse phases and one cation-exchange phase, was the best tool, giving a total extraction recovery higher than 80%. The process was completed by a single chromatographic analysis of a wide range of naturally occurring cytokinins (bases, ribosides, O- and N-glucosides, and nucleotides) in 24.5 minutes using an analytical column packed with sub-2-microne particles. In multiple reaction monitoring mode, the detection limits ranged from 0.05 to 5 fmol and the linear ranges for most cytokinins were at least five orders of magnitude. The StageTip purification was validated and optimized using samples of Arabidopsis thaliana seedlings, roots and shoots where eighteen cytokinins were successfully determined. CONCLUSIONS: The combination of microextraction with one-step high-throughput purification provides fast, effective and cheap sample preparation prior to qualitative and quantitative measurements. Our procedure can be used after modification also for other phytohormones, depending on selectivity, affinity and capacity of the selected sorbents.