Soil microbes are central to many soil processes, but due to the structural complexity of soil organic matter, the accurate quantification of microbial biomass contributions continues to pose a significant analytical challenge. In this study, microbes from a range of soils were cultured such that their molecular profile could be compared to that of soil organic matter and native vegetation. With the use of modern NMR spectroscopy, the contributions from microbial species can be discerned in soil organic matter and quantified. On the basis of these studies, the contributions of microbial biomass to soil organic matter appear to be much higher than the 1-5% reported by other researchers. In some soils, microbial biomass was found to contribute >50% of the extractable soil organic matter fractions and approximately 45% of the humin fraction and accounted for >80% of the soil nitrogen. These findings are significant because organic matter is intimately linked to nutrient release and transport in soils, nitrogen turnover rates, contaminant fate, soil quality, and fertility. Therefore, if in some cases soil organic matter and soil organic nitrogen are predominately of microbial origin, it is likely that this fraction, whether in the form of preserved material or living cells, plays an underestimated role in several soil processes.
Contaminant-soil interaction studies have indicated that physical conformation of organic matter atthe solid-aqueous interface is important in governing hydrophobic organic compound (HOC) sorption. To testthis, organo-clay complexes were constructed by coating montmorillonite and kaolinite with peat humic acid (PHA) in Na+ or Ca2+ dominated solutions with varying pH and ionic strength values. The solution conditions encouraged the dissolved PHA to adopt a "coiled" or "stretched" conformation prior to interacting with the clay mineral surface. Both kaolinite and montmorillonite organo-clay complexes exhibited higher phenanthrene sorption (Koc values) with decreasing pH, indicating that the coiled configuration provided more favorable sorption conditions. Evidence from 1H high-resolution magic angle spinning (HR-MAS) nuclear magnetic resonance (NMR) indicated that polymethylene groups were prevalent at the surface of the organo-clay complexes and may enhance sorptive interactions. Preferential sorption of polymethylene groups on kaolinite and aromatic compounds on montmorillonite may also contribute to the difference in phenanthrene sorption by PHA associated with these two types of clay. This study demonstrates the importance of solution conditions in the sorption of nonionic, hydrophobic organic contaminants and also provides evidence for the indirect role of clay minerals in sorption of contaminants at the soil-water interface.
Nuclear magnetic resonance (NMR) is arguably the most powerful and versatile tool in modern science. It has the capability to solve complex structures and interactions in situ even in complex heterogeneous multiphase samples such as soil, plants, and tissues. NMR has vast potential in environmental research and can provide insight into a diverse range of environmental processes at the molecular level be it identifying the binding site in human blood for a specific contaminant or the compositional dynamics of soil with climate change. Modern NMR-based metabonomics is elucidating contaminant toxicity and toxic mode of action rapidly and at sub lethal concentrations. Combined modern NMR approaches provide a powerful framework to better understand carbon cycling and sustainable agriculture, as well as contaminant fate, bioavailability, toxicity, sequestration, and remediation.
This article presents research targeted toward the isolation and detection of unique molecular structures from what is believed to be the world's most complex organic mixture: dissolved organic matter (DOM). Hydrophilic interaction chromatography (HILIC) was used to separate Suwannee River DOM (SRDOM) into 80 fractions, simplified to the extent that detection with nuclear magnetic resonance spectroscopy (NMR) results in many sharp signals that are indicative of individual compounds, some of which are identifiable with multidimensional NMR. Parallel factor analysis (PARAFAC) of fluorescence excitation-emission matrices (EEMs) was additionally employed on HILIC-simplified fractions to further confirm the effectiveness of the HILIC separations as well as draw insight into how structural characteristics relate to DOM fluorescence signals. Findings suggest that material believed to be derived from both cyclic and linear terpenoids was dominant in the most hydrophobic fractions as were the majority of the fluorescence signals, whereas hydrophilic material was highly correlated with carbohydrate-type structures as well as high contributions from amino acid fluorescence. NMR spectra of DOM, typically featureless mounds, are substantially more detailed with HILIC-simplified fractions to the point where hundreds of signals are present and 2D NMR correlations permit significant structural identifications.
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