Adsorption—desorption and/or precipitation—dissolution processes of zinc in soils

The concentrations of trace and toxic metals in soil solutions are explained by several authors either in terms of adsorption—desorption or precipitation—dissolution reactions in soils. Data have been given for zinc to test the applicability of both concepts. The results show that the concentrations of zinc in equilibrium solutions with soil clay fractions and whole soil samples at pH values below 7 are determined exclusively by adsorption—desorption reactions for various pH's, contents of bound zinc and compositions of soils. At neutral to alkaline pH values precipitation—dissolution reactions of zinc may take place. There is some evidence that formation of zinc silicates may control the zinc concentration in solution provided natural complexing agents are absent, the affinity of the soil for zinc is low and the content of reaching zinc is high (> ～ 100 ppm). Even at pH values above 7, the formation of other zinc compounds is unlikely in most soils because additions of large amounts of zinc are required to ensure saturation of the adsorption sites of different soil components before the zinc concentration in the soil solution can increase sufficiently to bring about the precipitation of definite compounds. Model experiments in CaCO₃-buffered systems showed that the adsorption capacity for specifically adsorbed zinc (in μmole/g) by the following components increased in the order CaCO₃ (0.44), bentonite (44), humic acid (842), amorphous Fe- and Al-oxides (1190, 1310) and δ -MnO₂ (1540) and demonstrated the importance of Mn-, Fe-, and Al-oxides and humic substances for the binding of zinc in soils containing carbonates, and thus indicate the special role of these components in limiting precipitation reactions.     

Isolation and identification of the metolachlor stereoisomers using high-performance liquid chromatography, polarimetric measurements, and enantioselective gas chromatography

Because of the presence of two chiral elements (an asymmetrically substituted carbon and a chiral axis), the herbicide metolachlor consists of four stereoisomers stable at ambient temperature with aSS-, aRS-, aSR-, and aRR-configurations (aSS, the isomer with aS,1'S-configuration, etc.). Metolachlor, initially introduced into the market as the racemic product containing all four stereoisomers, is currently being replaced worldwide by S-metolachlor, the product enantiomerically enriched with the herbicidally active 1'S-isomers (aSS, aRS). The isomer-specific analysis of metolachlor requires not only enantioselective ("chiral") analytical techniques but also suitable reference compounds. In this study, two of the four metolachlor isomers were isolated from rac-metolachlor in enantio- (ee > 98%) and diastereomerically pure forms by a combination of achiral and chiral high-performance liquid chromatography (HPLC). The two isomers were identified as the aSS- and the aRR-isomers by polarimetric measurements, in reference to previous data. The two isomers were then thermally equilibrated to 1:1 mixtures of the aSS/aRS and aRR/aSR diastereomers, respectively, so that analytical data of all four metolachlor isomers became available; they were then used to identify these isomers in technical products by chiral high-resolution gas chromatography (HRGC). The kinetics of the thermally induced interconversion of the atropisomers was studied and the consequences, such as for GC analysis, are discussed. A comparison of on-column and split/splitless injection indicated that the latter technique results in significant isomerization prior to separation and, therefore, cannot be used for accurate isomer analysis.     

Species concepts and systematics of domesticated cereals

Summary Cultivated cereals are domesticated grasses. Wild progenitors of domestic cereals are aggressive natural colonizers and often become weedy in man disturbed habitats. Hybridization between cultivated cereals and their close wild relatives gives rise to mimetic cereal weeds that often accompany the domestic species well beyond its natural range. Similar weeds may also evolve from abandoned cultivars as a result of mutations that restore their ability for natural seed dispersal. Cultivated complexes of domestic species are typically variable. Man selects and isolates phenotypes to suit his fancies, with the result that different phenotypes of a cereal are often grown for different uses in the same village, and adjacent villages often grow different phenotypes for similar uses. Conventional species concepts do not hold for domestic species. It is proposed that wild, weed and cultivated complexes of individual domestic species be recognized respectively as subspecies. Major discontinuities in variation within the weed or cultivated subspecies are then identified as races without formal taxonomic recognition.

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Artbegriff und Systematik bei domestizierten Getreiden

Zusammenfassung Kultivierte Getreide sind domestizierte Gräser. Die wilden Vorfahren der domestizierten Getreide sind aggressive natürliche Besiedler und werden oft zu Unkräutern in vom Menschen beeinflußten Standorten. Bastardierung zwischen kultivierten Getreiden und ihren wilden Verwandten läßt mimetische Getreideunkräuter entstehen, die oft die domestizierten Arten außerhalb ihres natürlichen Verbreitungsgebietes begleiten. Ähnliche Unkräuter können sich auch aus aufgegebenen Sorten entwickeln als ein Ergebnis von Mutationen, die ihre Fähigkeit zur natürlichen Samenausstreuung wiederherstellen. Kultivierte Komplexe domestizierter Arten sind in typischer Weise variabel. Der Mensch selektiert und isoliert Phänotypen nach seinen Vorstellungen mit dem Ergebnis, daß verschiedene Phänotypen eines Getreides oft zu verschiedenen Zwecken im selben Dorf angebaut werden, und benachbarte Dörfer oft verschiedene Phänotypen für ähnliche Zwecke kultivieren. Der herkömmliche Artbegriff bewährt sich nicht bei domestizierten Arten. Es wird vorgeschlagen, daß Wild-, Unkraut- und Kulturformen einer domestizierten Art als entsprechende Unterarten angesehen werden. Größere Gruppen innerhalb der Unkraut- oder Kultur-Unterart sollten als Rassen ohne formale taxonomische Bezeichnung gehandhabt werden.

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LC-MS/MS quantification of sulforaphane and indole-3-carbinol metabolites in human plasma and urine after dietary intake of selenium-fortified broccoli

This study aimed at developing a sensitive LC-MS/MS method for the quantification of sulforaphane (SFN) and indole-3-carbinol metabolites in plasma and urine after dietary intake of regular and selenium-fertilized broccoli using stable isotope dilution analysis. In a three-armed, placebo-controlled, randomized human intervention study with 76 healthy volunteers, 200 g of regular (485 μg of total glucosinolates and <0.01 μg of selenium per gram fresh weight) or selenium-fertilized broccoli (589 μg of total glucosinolates and 0.25 μg of selenium per gram fresh weight) was administered daily for 4 weeks. Glucoraphanin and glucobrassicin metabolites quantified in plasma and urine were SFN-glutathione, SFN-cysteine, SFN-cysteinylglycine, SFN-acetylcysteine, and indole-3-carboxaldehyde, indole-3-carboxylic acid, and ascorbigen, respectively. Dietary intake of selenium-fertilized broccoli increased serum selenium concentration analyzed by means of atomic absorption spectroscopy by up to 25% (p < 0.001), but affected neither glucosinolate concentrations in broccoli nor their metabolite concentrations in plasma and urine compared to regular broccoli.     

Colluvisols under cultivation in Schleswig-Holstein. 2. Carbon distribution and soil organic matter composition

Soils under intensive cultivation have altered due to water erosion. This study was conducted to determine whether soil organic matter (SOM) composition of the colluvial source (Ap horizons) differs from the colluvial sink (M horizons). The SOM of a sandy Catena with erodic Cambisols and colluvic soils (Colluvisols) in Schleswig-Holstein, Northwest Germany, was investigated. A wet chemical analysis was combined with CPMAS ¹³C-NMR spectroscopy. In one case a significant correlation between the SOM composition of the Ap horizon of the erodic Cambisol and the M horizon of the Colluvisol was high (r² = 0.904^-), whereas the correlation for the other set was much weaker (r² = 0.640*). Two possible paths of pedogenesis are discussed. About 70% of the SOM of the colluvial source is decomposed during translocation or after deposition. A selective preservation or new formation of humins in the M material is probable. These humins contain, obviously, large amounts of polysaccharides, which were not detected by the wet chemical analysis. Further investigations of colluvic and erodic soils are necessary in order to specify the SOM quality and its possible modification due to soil translocation and accumulation.     

Phosphorus speciation of forest‐soil organic surface layers using P K‐edge XANES spectroscopy

The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water‐logging (Stagnosol, Rheic Histosol) was analyzed by P K‐edge XANES and subsequent Linear Combination Fitting. In both soils, ≈ 70% of the P was inorganic phosphate and ≈ 30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water‐logging in the Histosol compared to the Stagnosol did not affect P speciation.     

Hydrological parameterization of piping in loess‐rich soils in the Bergisches Land,Nordrhein‐Westfalen,Germany

Pedohydrological properties were investigated on a piped slope in the Bergisches Land in the Rhenish Slate Mountains (Nordrhein‐Westfalen, Germany). The study confirmed that genesis and development of pipes decisively depend on hydrological conditions in the soils. Vertical water permeability of saturated samples was very high. This promoted fast seepage. Many macropores produced by earthworms also caused high transport capacity for soil water. Even more efficient were the burrows of moles and mice, enabling immediate infiltration and direct vertical and lateral water movement. On the contrary, the horizontal saturated permeability was low indicating no correlation with piping. Porosity of piped soils was not different to that of other soils of the region without pipes.     

Ash and biochar amendment of coarse sandy soil for growing crops under drought conditions

Appropriate soil amendments may increase plant available water and crop yields on coarse sandy soils under drought conditions. In this study, we applied straw ash or straw biochar from gasification to a Danish coarse sandy subsoil to assess the effects on soil water retention, evapotranspiration and crop yields. Spring barley (2016, 2017) and winter wheat (2018) were grown over three years in columns containing 25cm of organic matter-rich topsoil, 80 cm of amended coarse sandy soil (1.5%, 3%, 6% wt. ash or 1% wt. biochar or control soil) and 45 cm of un-amended subsoil. Precipitation, evaporative demands and soil moisture were recorded across the growth seasons, with 2018 having severe drought conditions. This year evapotranspiration levels increased with increasing ash and biochar content (by 54% and 33% for the 6% ash- and 1% biochar-amended soils, respectively), and plant dry matter increased by 18% in both the 1% biochar- and 6% ash-treated soils compared to the untreated control. A linear relationship was established between in situ field capacity and ash dosage (R² = .96), showing an increase of 2.2% per percentage (wt.) of ash added, while the 1% biochar treatment increased the capacity by 3.5%, indicating a higher efficiency than for ash. However, we did not find significant positive effects on grain yields. The results show that ash and biochar have the potential to significantly increase soil water retention, evapotranspiration and total dry matter yield in drought conditions, but that this may not correspond to an increase in grain yield.     

Detection of phloridzin in strawberries (Fragaria x ananassa Duch.) by HPLC-PDA-MS/MS and NMR spectroscopy

The phenolic profile of strawberry fruits (Fragaria x ananassa Duch., Rosaceae) was investigated by high-performance liquid chromatography with photodiode array detection. A peak displaying retention time and UV spectral data identical to those of phloridzin (phloretin 2'-O-beta-d-glucoside), a dihydrochalcone glucoside so far considered characteristic of apples, was monitored. For further characterization, crude extracts of strawberries were purified on polyamide, and the target compound was isolated by preparative and analytical HPLC. Structure elucidation was performed on the basis of APCI- and ESI-MS in the negative ion mode as well as by 1D and 2D NMR spectroscopy using authentic phloridzin for comparison. The d-configuration of the sugar moiety was established by HPLC analysis of the corresponding acyclic 1-deoxy-1-(N-acetyl-alpha-methylbenzylamino)alditol acetate. Apart from its chemotaxonomic relevance, this first report on the occurrence of phloridzin in strawberries is of particular interest for the authenticity control of strawberry products such as juices, jams, and fruit preparations since phloridzin has so far been used for the detection of fraudulent admixtures.     

Rapid surface plasmon resonance-based inhibition assay of deoxynivalenol

Deoxynivalenol belongs to a group of highly toxic fungal metabolites produced by Fusarium species that may contaminate food and animal feed, mostly grains. Three different monoclonal mouse anti-deoxynivalenol antibodies were compared for the development of a surface plasmon resonance (SPR)-based immunoassay for the selective and quantitative determination of deoxynivalenol in naturally contaminated matrices. A conjugate of deoxynivalenol with the protein casein was prepared and immobilized on the sensor chip surface. An excess of antibody was added to each test solution before the measurement. The assay was based on the competition for antibody binding between the immobilized deoxynivalenol conjugate on the sensor and the free deoxynivalenol molecules in the test solution. The deoxynivalenol-casein sensor could be reused more than 500 times without significant loss of activity using 6 M guanidine chloride solution for regeneration. The cross-reactivity of the three antibodies in the SPR assay was tested with other trichothecene mycotoxins (3-acetyl-deoxynivalenol, 15-acetyl-deoxynivalenol, nivalenol, HT2-toxin, and T2-toxin). The only sample preparation was extraction with max 80 vol % acetonitrile and 10-fold dilution with the running buffer. The assay had an optimal range between 2.5 and 30 ng/mL deoxynivalenol in the test solution. Most results of the SPR-based assay were in agreement with liquid chromatography/tandem mass spectrometry measurements of naturally contaminated wheat samples.