Gas chromatography-mass spectrometry of the trimethylsilyl (oxime) ether/ester derivatives of cholic acids: Their presence in the aquatic environment

This paper presents a derivatization, mass fragmentation study relating to the most common six cholic acids, such as cholic, lithocholic, chenodeoxycholic, Ursodeoxycholic, 3-hydroxy,7-ketocholanic and dehydrocholic acids, identified and quantified as pollutants in the aquatic environment at the first time. Derivatizations have been performed with the two-step process (1: oximation, 2: silylation) varying the time and temperature of both reactions. Optimum responses have been obtained after 30 min oximation with hydroxylamine HCl and 90 min silylation with hexamethyldisilazane and trifluoroacetic acid at 70 degrees C. Fragmentation patterns of the trimethylsilyl (oxime) ether/ester derivatives Of all six cholic acids provided the theoretically expected, fully derivatized compounds. Reproclucibility/linearity of derivatives calculated oil the basis of the corresponding selective fragment ions, characterized by the relative standard deviation percentages of measurements, proved to be <= 4.9(RSD%). The practical utility of the method was shown by the identification and quantification of cholic acids as pollutants in the aquatic environment. Subsequently to a solid phase extraction study varying the pH of extractions (pH 2, pH 4 and pH 7), applying the OASIS cartridges, it has been confirmed that the recoveries for all six cholic acids are acceptable, varying between 77% and 104%, and are independent on the pH. The total cholic acid content of a Hungarian wastewater plants' influent wastewater varied between 184 mu g/L and 356 mu g/L, while the Danube rivers' cholic acid content was 4.1 mu g/L, only. (C) 2008 Elsevier B.V. All rights reserved.Hungarian Academy of Sciences [OTKA T0-47199]This work was supported by the Hungarian Academy of Sciences (Project No. OTKA T0-47199)

Nitrogen partitioning in orchard-grown Macadamia integrifolia

Nut yield is highly variable in commercial macadamia production, and to ensure that nitrogen (N) Supply does not limit yield, high rates of N fertilizer are generally applied. To elucidate N source and sink relations in mature Macadamia integrifolia Maiden et Betche trees, we traced (15)N label after injection into individual branches and, after soil application, analysed xylem sap and examined the effects of hedging on tree N relations. Xylem sap N and sugar composition and concentration changed in relation to phenology and tree management. Canopy position did not affect xylem sap N concentration but sampling date had a significant effect. Hedging in spring was associated with a rapid and dramatic reduction of the concentration of xylem sap N until the following autumn, but unhedged trees were not available to unequivocally assess the significance of the results. Following (15)N-branch injection in winter, most (15)N label was incorporated into flushing leaves and into bark. After (15)N injection in spring, flushing leaves and flowers were most strongly (15)N-labelled. In late spring, (15)N label was equally incorporated by developing nuts that were retained or later abscised. Soil (15)N application in summer resulted in (15)N-labelling of outer and mid-canopy leaves. In the following spring, (15)N label was translocated to flushing leaves, flowers and developing nuts. The results indicate that outer and mid-canopy leaves are the main N sink for soil-derived N during the vegetative phase and a N Source for developing tissues during the reproductive phase. Our study provides evidence that N supply to developing nuts is not a primary cause for nut abscission, supporting the notion that high N fertilizer application rates do not improve nut retention. We propose that current orchard design and hedging practices should be reviewed in context of the role of outer canopy leaves as a source of N for reproductive tissues