Photodegradation of phosmet in wool wax models and on sheep wool: determination of wool wax bound phosmet by means of isotope ratio mass spectrometry

The photochemical reactions of phosmet, an organophosphorus insecticide used for plant protection and for control of ectoparasites on productive livestock, were studied in the presence of wool wax. Induced by UV light, phosmet features numerous degradation pathways as well as photoaddition reactions with lipid structure moieties. In model irradiation experiments of phosmet in mixtures of solvents (cyclohexane, cyclohexene, 2-propanol) and fatty acid methyl esters (methyl stearate, methyl oleate, 12-hydroxymethyl stearate), both adjusted to the hydroxyl and iodine values of wool wax, half-lives were determined to be approximately 7 and 16 h, respectively. Irradiation of phosmet on crude sheep wool resulted in a degradation rate of 65% after 24 h. In tracer studies with stable isotope labeled phosmet ([15N]phosmet) in commercial lanolin and on raw sheep wool, employing a sunlight simulator and natural sunlight, wool wax bound phosmet was formed. After extraction and measurement by elemental analyzer/isotope ratio mass spectrometry, delta15N values of the phosmet-free wool wax fractions were notably increased as compared to the value of natural lanolin. Calculated from the delta15N values, an average of 13.9/15.6% (sunlight simulator/natural sunlight) was bound to wool wax lipids after irradiation of thin films of commercial lanolin. In experiments with sheep wool, 13.2 and 15.4%, respectively, were detected as wax-bound.     

Einfluss assoziativer rhizosphärenbakterien auf die äHrstoffaufnahme und den Ertrag von Mais

In mehrjährigen Feldversuchen (1990–1995) in Nordostdeutschland wurde der Einfluß selektierter assoziativer Rhizosphärenbakterien auf den Ertrag und die Nährstoffaufnahme bei Mais untersucht.

Der Trockenmasse‐ und Kolbenertrag zur Siloreife bzw. der Samenertrag wurde durch die Bakterienstämme Pseudomonas fluorescens (PsIA12), Agrobacterium rhizogenes (A1A4), Rhizobium trifolii (R39) und z.T. durch Stenotrophomonas maltophilia (PsIB2) in den Jahren 1990 bis 1995 auf lehmigen Sandböden wiederholt signifikant, auf sandigem Lehm zum Teil signifikant erhöht. Maissorten können unterschiedlich auf die Bakterieninokulation reagieren. Die Bakterien stimulierten insbesondere bei Jungpflanzen die Wurzelentwicklung und die Nährstoffaufnahme (N, P, K) aus dem Boden. Sie bildeten Phytohormone (Auxine und z.T. Cytokinine) und überlebten, auch unter Feldbedingungen, im Rhizosphärenraum von Mais während der gesamten Vegetation.     

Nutrient limitation of alpine plants: Implications from leaf N : P stoichiometry and leaf δ15N

Nitrogen (N) deposition can affect grassland ecosystems by altering biomass production, plant species composition and abundance. Therefore, a better understanding of the response of dominant plant species to N input is a prerequisite for accurate prediction of future changes and interactions within plant communities. We evaluated the response of seven dominant plant species on the Tibetan Plateau to N input at two levels: individual species and plant functional group. This was achieved by assessing leaf N : P stoichiometry, leaf δ¹⁵N and biomass production for the plant functional groups. Seven dominant plant species—three legumes, two forbs, one grass, one sedge—were analyzed for N, P, and δ¹⁵N 2 years after fertilization with one of the three N forms: NO$ _3^- $ , NH$ _4^+ $ , or NH₄NO₃ at four application rates (0, 7.5, 30, and 150 kg N ha^–1 y^–1). On the basis of biomass production and leaf N : P ratios, we concluded that grasses were limited by available N or co‐limited by available P. Unlike for grasses, leaf N : P and biomass production were not suitable indicators of N limitation for legumes and forbs in alpine meadows. The poor performance of legumes under high N fertilization was mainly due to strong competition with grasses. The total above‐ground biomass was not increased by N fertilization. However, species composition shifted to more productive grasses. A significant negative correlation between leaf N : P and leaf δ¹⁵N indicated that the two forbs Gentiana straminea and Saussurea superba switched from N deficiency to P limitation (e.g., N excess) due to N fertilization. These findings imply that alpine meadows will be more dominated by grasses under increased atmospheric N deposition.     

Langjähriger witterungseinfluss auf das grünland in zwei verschiedenen landschaftsgebieten

Langjährige Beobachtungen der Witterungsfaktoren Temperatur und Niederschlag auf Ertrag und Pflanzenbestand von zwei Dauergrünlandstandorten verschiedener Klimagebiete wurden ausgewertet. Anlaß war das Phänomen, daß im Erzgebirge der Ertrag trotz hoher Stickstoffdungung nach dem 3. Versuchsjahr sukzessive abfiel und nach dem 12. Jahr wieder anstieg. Als Vergleich bot sich nahezu gleich bewirtschaftetes Grünland im Havelländischen Luch an.

Die Ursache fur die Ertragsdepression wurde zunächst in einer Umschichtung der Pflanzenbestände vermutet. Schließlich wurde ein Zusammenhang zwischen Witterung und Ertrag am Beispiel der Abweichungen von den Mittelwerten gefunden.     

Short‐term response of the Ca cycle of a montane forest in Ecuador to low experimental CaCl2 additions

The tropical montane forests of the E Andean cordillera in Ecuador receive episodic Sahara‐dust inputs particularly increasing Ca deposition. We added CaCl₂ to isolate the effect of Ca deposition by Sahara dust to tropical montane forest from the simultaneously occurring pH effect. We examined components of the Ca cycle at four control plots and four plots with added Ca (2 × 5 kg ha^–1 Ca annually as CaCl₂) in a random arrangement. Between August 2007 and December 2009 (four applications of Ca), we determined Ca concentrations and fluxes in litter leachate, mineral soil solution (0.15 and 0.30 m depths), throughfall, and fine litterfall and Al concentrations and speciation in soil solutions. After 1 y of Ca addition, we assessed fine‐root biomass, leaf area, and tree growth. Only < 3% of the applied Ca leached below the acid organic layer (pH 3.5–4.8). The added CaCl₂ did not change electrical conductivity in the root zone after 2 y. In the second year of fertilization, Ca retention in the canopy of the Ca treatment tended to decrease relative to the control. After 2 y, 21% of the applied Ca was recycled to soil with throughfall and litterfall. One year after the first Ca addition, fine‐root biomass had decreased significantly. Decreasing fine‐root biomass might be attributed to a direct or an indirect beneficial effect of Ca on the soil decomposer community. Because of almost complete association of Al with dissolved organic matter and high free Ca²⁺ : Al³⁺ activity ratios in solution of all plots, Al toxicity was unlikely. We conclude that the added Ca was retained in the system and had beneficial effects on some plants.     

GC-based analysis of plant stanyl fatty acid esters in enriched foods

Approaches for the capillary gas chromatographic (GC) based analysis of intact plant stanyl esters in enriched foods were developed. Reference compounds were synthesized by enzyme-catalyzed transesterifications. Their identities were confirmed by means of mass spectrometry. Using a medium polar trifluoropropylmethyl polysiloxane stationary phase, long-chain plant stanyl esters could be separated according to their stanol moieties and their fatty acid chains. Thermal degradation during GC analysis was compensated by determining response factors; calibrations were performed for ten individual plant stanyl esters. For the analysis of low-fat products (skimmed milk drinking yogurts), the GC separation was combined with a "fast extraction" under acidic conditions. For fat-based foods (margarines), online coupled LC-GC offered an elegant and efficient way to avoid time-consuming sample preparation steps. The robust and rapid methods allow conclusions on both, the stanol profiles and the fatty acid moieties, and thus provide a basis for the authentication of this type of functional food ingredients.     

Short-term competition between crop plants and soil microbes for inorganic N fertilizer

Agricultural systems that receive high amounts of inorganic nitrogen (N) fertilizer in the form of either ammonium (NH₄⁺), nitrate (NO₃⁻) or a combination thereof are expected to differ in soil N transformation rates and fates of NH₄⁺ and NO₃⁻. Using ¹⁵N tracer techniques this study examines how crop plants and soil microbes vary in their ability to take up and compete for fertilizer N on a short time scale (hours to days). Single plants of barley (Hordeum vulgare L. cv. Morex) were grown on two agricultural soils in microcosms which received either NH₄⁺, NO₃⁻ or NH₄NO₃. Within each fertilizer treatment traces of ¹⁵NH₄⁺ and ¹⁵NO₃⁻ were added separately. During 8 days of fertilization the fate of fertilizer ¹⁵N into plants, microbial biomass and inorganic soil N pools as well as changes in gross N transformation rates were investigated. One week after fertilization 45-80% of initially applied ¹⁵N was recovered in crop plants compared to only 1-10% in soil microbes, proving that plants were the strongest competitors for fertilizer N. In terms of N uptake soil microbes out-competed plants only during the first 4 h of N application independent of soil and fertilizer N form. Within one day microbial N uptake declined substantially, probably due to carbon limitation. In both soils, plants and soil microbes took up more NO₃⁻ than NH₄⁺ independent of initially applied N form. Surprisingly, no inhibitory effect of NH₄⁺ on the uptake and assimilation of nitrate in both, plants and microbes, was observed, probably because fast nitrification rates led to a swift depletion of the ammonium pool. Compared to plant and microbial NH₄⁺ uptake rates, gross nitrification rates were 3-75-fold higher, indicating that nitrifiers were the strongest competitors for NH₄⁺ in both soils. The rapid conversion of NH₄⁺ to NO₃⁻ and preferential use of NO₃⁻ by soil microbes suggest that in agricultural systems with high inorganic N fertilizer inputs the soil microbial community could adapt to high concentrations of NO₃⁻ and shift towards enhanced reliance on NO₃⁻ for their N supply.