Soil organic matter (SOM) contains about twice the amount of carbon in the atmosphere. With global changes, the potential shifts in SOM quantity and quality are a major concern. Due to its heterogeneity, SOM remains largely unknown in terms of its molecular composition and responses to climatic events. Traditional bulk soil analysis cannot depict the structural changes in SOM. This thesis applies two complementary molecular-level methods, i.e., SOM biomarker gas chromatography/mass spectrometry (GC/MS) and nuclear magnetic resonance (NMR) spectroscopy, to examine the origin and degradation of various SOM components in grassland and temperate forest soils, and to investigate the shifts in microbial community and SOM composition with both laboratory- and field-simulated global changes, such as frequent freeze-thaw cycles, increasing soil temperatures, elevated atmospheric CO2 levels, and nitrogen (N) deposition. This thesis has several major findings. First, as the most active component in soil, microbial communities were sensitive to substrate availability changes resulting from prolonged soil incubation, freeze-thaw-induced cell lyses, N fertilization and increased plant inputs under elevated CO2 or soil warming. Microbial community shifts have direct impacts on SOM decomposition patterns. For instance, an increased fungal community was believed to contribute to the enhanced lignin oxidation in an in situ soil warming experiment as the primary degrader of lignin in terrestrial environments. Second, contrast to the conventional belief that aromatic structure was recalcitrant and stable in SOM, ester-bond aliphatic lipids primarily originating from plant cutin and suberin were preferentially preserved in the Canadian Prairie grassland soil profiles as compared with lignin-derived phenols. Cutin- and suberin-derived compounds also demonstrated higher stability during soil incubation. With an increased litter production under elevated CO2 or global warming, an enrichment of alkyl structures that had strong contributions from leaf cuticles was observed in the Duke Forest Free Air CO2 Enrichment (FACE) and soil warming experiments, suggesting an accumulation of plant-derived recalcitrant carbon in the soil. These results have significant implications for carbon sequestration and terrestrial biogeochemistry. Overall, this thesis represents the first of its kind to employ comprehensive molecular-level techniques in the investigation of SOM structural alterations under global changes.

Soil organic matter (SOM) contains about twice the amount of carbon in the atmosphere. With global changes, the potential shifts in SOM quantity and quality are a major concern. Due to its heterogeneity, SOM remains largely unknown in terms of its molecular composition and responses to climatic events. Traditional bulk soil analysis cannot depict the structural changes in SOM. This thesis applies two complementary molecular-level methods, i.e., SOM biomarker gas chromatography/mass spectrometry (GC/MS) and nuclear magnetic resonance (NMR) spectroscopy, to examine the origin and degradation of various SOM components in grassland and temperate forest soils, and to investigate the shifts in microbial community and SOM composition with both laboratory- and field-simulated global changes, such as frequent freeze-thaw cycles, increasing soil temperatures, elevated atmospheric CO2 levels, and nitrogen (N) deposition. This thesis has several major findings. First, as the most active component in soil, microbial communities were sensitive to substrate availability changes resulting from prolonged soil incubation, freeze-thaw-induced cell lyses, N fertilization and increased plant inputs under elevated CO2 or soil warming. Microbial community shifts have direct impacts on SOM decomposition patterns. For instance, an increased fungal community was believed to contribute to the enhanced lignin oxidation in an in situ soil warming experiment as the primary degrader of lignin in terrestrial environments. Second, contrast to the conventional belief that aromatic structure was recalcitrant and stable in SOM, ester-bond aliphatic lipids primarily originating from plant cutin and suberin were preferentially preserved in the Canadian Prairie grassland soil profiles as compared with lignin-derived phenols. Cutin- and suberin-derived compounds also demonstrated higher stability during soil incubation. With an increased litter production under elevated CO2 or global warming, an enrichment of alkyl structures that had strong contributions from leaf cuticles was observed in the Duke Forest Free Air CO2 Enrichment (FACE) and soil warming experiments, suggesting an accumulation of plant-derived recalcitrant carbon in the soil. These results have significant implications for carbon sequestration and terrestrial biogeochemistry. Overall, this thesis represents the first of its kind to employ comprehensive molecular-level techniques in the investigation of SOM structural alterations under global changes.