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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 26 (1997), S. 1-15 
    ISSN: 1432-0789
    Keywords: Key words Analytical pyrolysis ; Humic substances ; Heterocyclic nitrogen ; 15N NMR ; Mass spectrometry ; Soil organic matter ; Model structure ; Unidentified nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract 1. From the data presented herein it is possible to deduce the following distribution of total N in humic substances and soils: proteinaceous materials (proteins, peptides, and amino acids) – ca. 40%; amino sugars – 5–6%; heterocyclic N compounds (including purines and pyrimidines) – ca. 35%; NH3–19%; approximately 1/4 of the NH3 is fixed NH4 +. Thus, proteinaceous materials and heterocyclics appear to be major soil N components. 2. Natural 15N abundance levels in soils and humic materials are so low that direct analysis by 15N NMR is very difficult or impossible. To overcome this difficulty, the soil or humic material is incubated with 15N-enriched fertilizer. Even incubation in the laboratory for up to 630 days does not produce the same types of 15N compounds that are formed in soils and humic materials over hundreds or thousands of years. For example, very few 15N-labelled heterocyclics are detected by 15N NMR. Does this mean that heterocyclics are not present? Or are the heterocyclics that are present not labelled under these experimental conditions and therefore not detected by the 15N NMR spectrometer ? Another possibility is that a large number of N heterocyclics occur in soils, but each type occurs in very low concentrations. Until the sensitivity is improved, 15N NMR will not provide results that can be compared with data obtained from the same soil and humic material samples by chemical methods and mass spectroscopy. 3. What is most important with respect to agricultural is that all major N forms in soils are available to organisms and are sources of NH3 or NH4 + for plant roots and microbes. Naturally, some of the NH3 will enter the N cycle. 4. From chemical and pyrolysis-mass spectrometric analyses it appears that N heterocylics are significant components of the SOM, rather than degradation products of other molecules due to pyrolysis. The arguments in favor of N heterocyclics as genuine SOM components are the following: a) Some N-heterocyclics originate from biological precursors of SOM, such as proteinaceous materials, carbohydrates, chlorophyll, nucleic acids, and alkaloids, which enter the soil system as plant residues or remains of animals. b) In aquatic humic substances and dissolved organic matter (DOM) at considerably lower pyrolysis temperatures (200 to 300°C), free and substituted N-heterocyclics such as pyrroles, pyrrolidines, pyridines, pyranes, and pyrazoles, have been identified by analytical pyrolysis (Schulten et al 1997b). c) Their presence in humic substances and soils was also detected without pyrolysis by gel chromatography – GC/MS after reductive acetylation (Schnitzer and Spiteller 1986), by X-ray photoelectron spectroscopy (Patience et al. 1992), and also by spectroscopic, chromatographic, chemical, and isotopic methods (Ikan et al. 1992). 5. While we can see light at the end of the tunnel as far as soil-N is concerned, further research is needed to identify additional N-containing compounds such as N- heterocyclics, to determine whether these are present in the soil or humic materials in the form in which they were identified or whether they originate from more complex structures. If the latter is correct, then we need to isolate these complex N-molecules and attempt to identify them.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 20 (1995), S. 17-23 
    ISSN: 1432-0789
    Keywords: Soil organic matter ; Hot water extract ; Field experiment ; Soil biomass ; Temporal variations ; Soil fertility ; NMR ; Analytical pyrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Hot water-soluble organic matter was extracted from soil samples collected weekly between April and October in untreated and NPK+farmyard manure-fertilized plots in the 88-year-old Static Experiment (Loess Chernozem) at Bad Lauchstädt, Germany. As shown by solid-state 13C-nuclear magnetic resonance spectroscopy (13C-NMR) combined with pyrolysis-field ionization mass spectrometry this organic matter fraction was largely composed of carbohydrates and N-containing compounds, in particular amino-N species and amides. This composition and the low pyrolysis temperatures (mainly between 300 and 500°C) indicated its origin from soil biomass and root exudates and lysates, and its presence in the soil solution or weakly adsorbed by soil minerals and humic macromolecules. Long-term fertilization with NPK+farmyard manure resulted in larger mean concentrations of hot water-extracted C and N (0.933 and 0.094 g kg-1) than soil management without fertilization (0.511 and 0.056 g kg-1). The C and N extracted by hot water were in the range of 3–5% of total soil C and N. In the two treatments distinct temporal changes were observed, which appeared to be related to population dynamics of soil organisms, root growth and decomposition, and climatic influences on soil.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 24 (1997), S. 249-254 
    ISSN: 1432-0789
    Keywords: Key words Acid hydrolysis ; Agriculture ; Analytical pyrolysis ; Field ionization mass spectrometry ; Gas chromatography/mass spectrometry ; Heterocyclics ; Mineral soils ; Unknown nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Curie-point pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and in-source pyrolysis-field ionization mass spectrometry (Py-FIMS) were applied for the first time to the structural characterization of organic nitrogen in hydrolyzates and hydrolysis residues resulting from the classical 6M HCl hydrolysis of mineral soils. Two well-described soils of widely different origin (i.e., a Gleysol Ah and a Podzol Bh) were investigated. Py-GC/MS was performed using a nitrogen-selective detector to detect and identify N-containing pyrolysis in the hydrolyzate (e.g., pyrazole and/or imidazole, N,N-dimethylmethanamine, benzenacetonitrile, propane- and propenenitriles) and the hydrolysis residue (e.g., pyrroles, pyridines, indoles, N-derivatives of benzene, benzothiazol, and long-chain aliphatic nitriles). Moreover, temperature-resolved Py-FIMS allowed us to record the thermal evolution of the N-containing compounds during pyrolysis. These were characterized by a particularly high thermostability compared to their thermal release from whole soils. The combination of pyrolysis with mass spectrometric methods permitted analyses of the identities and thermal stabilities of complex nitrogen compounds in hydrolysis residues of whole soils, which cannot be done by wet-chemical methods. Pyrolysis-methylation GC/MS with tetramethyl-ammonium hydroxide (TMAH) as methylating agent enabled the identification of N,N-dimethylbenzenamine and so confirmed the identification of benzeneamine by Py-GC/MS in nonmethylated hydrolysis residues. The described N-derivatives of benzene and long-chain nitriles are usually not detectable by pyrolysis-mass spectrometry of plants and microorganisms. These compounds are characteristic of soils, terrestrial humic substances and hydrolysis residues and seem to be specific, stable transformation products of soil nitrogen.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Analytical and Applied Pyrolysis 27 (1993), S. 169-185 
    ISSN: 0165-2370
    Keywords: Analytical pyrolysis ; humic compounds ; plant litter ; pyrolysis ; soil organic matter ; soil science ; wet chemistry.
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 14 (1975), S. 403-415 
    ISSN: 0570-0833
    Keywords: Mass spectrometry ; Analytical methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Field desorption (FD) enables mass-spectrometric investigation of large organic molecules without their vaporization. The present state of our theoretical understanding of the ionization of these molecules in the adsorbed state on organic emitters is described. The special problems of the technique and prospective developments in the apparatus for future analytical problems are outlined. The present progress report concentrates on analytical studies of biochemical model compounds and degradation products from environmental chemicals and drugs. The method is particularly suitable for the detection and identification of submicrogram quantities of underivatized polar substances present in complex mixtures or pre-purified extracts from biological materials.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 17 (1978), S. 221-238 
    ISSN: 0570-0833
    Keywords: Mass spectrometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The current state of quantitative analysis with the mass spectrometer in biochemistry and medicine is reviewed. The basic principles of mass spectrometry, the latter's combination with chromatography, the development of sensitive, exact, and in particular specific mass-spectrometric methods of detection, and the principle of dilution with stable isotopes are illustrated by examples. The most important fields of application are: the pharmacokinetics of drugs and active metabolites, investigation of metabolic pathways, supporting of medical diagnoses and enhancement of their specificity, and finally checking the quality of simpler quantitative processes in clinical chemistry.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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