Use of 15N-depleted artificial compost in bound residue studies.
Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.
Berns
Anne
A
Forschungszentrum Juelich GmbH, Institute of Chemistry and Dynamics of the Geosphere, Institute IV: Agrosphere, 52425, Juelich, Germany. a.berns@fz-juelich.de
Vinken
Ralph
R
Bertmer
Marko
M
Breitschwerdt
Andrea
A
Schäffer
Andreas
A
D002850:Chromatography, Gel; D006812:Humic Substances / Q000032:analysis; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D009587:Nitrogen Isotopes; D010573:Pesticide Residues / Q000737:chemistry*; D012839:Simazine / Q000737:chemistry*; D012987:Soil / Q000032:analysis*; D014297:Trimethylsilyl Compounds
D006812:Humic Substances; D009587:Nitrogen Isotopes; D010573:Pesticide Residues; D012987:Soil; D014297:Trimethylsilyl Compounds; C039293:trimethylchlorosilane; D012839:Simazine