In this dissertation, the intermolecular interactions between soil organic matter (SOM) and organofluorine compounds have been studied at the molecular-level using Nuclear Magnetic Resonance (NMR) spectroscopy. NMR probes the local magnetic environment surrounding atomic nuclei, and is uniquely capable as an analytical tool to probe molecular environments in complex disordered materials, such as soils. Several NMR techniques were employed in this work, including Pulse Field Gradient (PFG)-NMR based diffusion measurements, solid-state cross-polarization (CP), saturation transfer difference (STD) spectroscopy, and reverse-heteronuclear saturation transfer difference (RHSTD) spectroscopy. Using organofluorine compounds as molecular probes, xenobiotic interactions with SOM were studied. Using 1H{19F} RHSTD, the interaction sites in humic acid for organofluorine compounds were identified by direct molecular-level methods. Protein and lignin were identified as major binding sites, with different preferences exhibited for these sites by dissimilar organofluorine compounds: aromatic organofluorine compounds display varied preference for aromatic humic acid sites while perfluorooctanoic acid exhibits near total selectivity for protein-derived binding sites. The mechanisms underlying these preferences were probed in the solution state. Using crucial knowledge from the humic acid studies, a detailed molecular-level investigation of xenobiotic interactions in an intact and unmodified whole soil was made possible. A direct and in situ elucidation of the components in soil organic matter that interact with small organofluorine xenobiotic molecules has been presented, allowing, for the first time, resolution of multiple interactions occurring for xenobiotics simultaneously at different sites within a whole soil.

In this dissertation, the intermolecular interactions between soil organic matter (SOM) and organofluorine compounds have been studied at the molecular-level using Nuclear Magnetic Resonance (NMR) spectroscopy. NMR probes the local magnetic environment surrounding atomic nuclei, and is uniquely capable as an analytical tool to probe molecular environments in complex disordered materials, such as soils. Several NMR techniques were employed in this work, including Pulse Field Gradient (PFG)-NMR based diffusion measurements, solid-state cross-polarization (CP), saturation transfer difference (STD) spectroscopy, and reverse-heteronuclear saturation transfer difference (RHSTD) spectroscopy. Using organofluorine compounds as molecular probes, xenobiotic interactions with SOM were studied. Using 1H{19F} RHSTD, the interaction sites in humic acid for organofluorine compounds were identified by direct molecular-level methods. Protein and lignin were identified as major binding sites, with different preferences exhibited for these sites by dissimilar organofluorine compounds: aromatic organofluorine compounds display varied preference for aromatic humic acid sites while perfluorooctanoic acid exhibits near total selectivity for protein-derived binding sites. The mechanisms underlying these preferences were probed in the solution state. Using crucial knowledge from the humic acid studies, a detailed molecular-level investigation of xenobiotic interactions in an intact and unmodified whole soil was made possible. A direct and in situ elucidation of the components in soil organic matter that interact with small organofluorine xenobiotic molecules has been presented, allowing, for the first time, resolution of multiple interactions occurring for xenobiotics simultaneously at different sites within a whole soil.

Overall soil productivity is declining in the U.S. due to loss of soil organic matter (SOM). Decreased SOM lowers soil water storage, reduces water infiltration, slows aggregate formation, and depletes soil of nutrients. In many systems, crop nutrients are replaced by expensive synthetic fertilizers that can lead to environmental concerns. This practice is not economically or environmentally sustainable in the long term. To secure future soil use and crop production, sustainable management practices are needed to prevent further SOM depletion. Incorporating legumes into cropping systems is one alternative that can bolster soil organic C (SOC) (key indicator of SOM) and reduce N fertilizer applications through symbiotic legume N fixation. Three studies were conducted over multiple years at the Texas A&M AgriLife Research and Extension Center near Overton, TX. Annual cool- and warm-season legumes were evaluated as potential green manure crops and intercrops under grain sorghum [Sorghum bicolor (L.) Moench], high-biomass sorghum [Sorghum bicolor (L.) Moench], and annual forage cropping systems. These studies quantified legume soil moisture usage and C and N contributions to the soil and subsequent crop yields in East Texas. Primary project objectives were to maintain or maximize primary crop yields at reduced N fertilizer rates and to build SOC through the integration of legume green manures and intercrops. Green manuring cool-season legumes showed the most beneficial effect on SOC, soil total N, and crop yields; however, significant increases in yield were only detected after three years in rotation. Intercropping Iron-and-Clay cowpea (Vigna unguiculata L. [Walp]) decreased yield of both high-biomass sorghum and grain sorghum due to competitive vegetative growth. Iron-and-Clay did however improve biomass yields of high-biomass sorghum in two subsequent years when implemented as a green manure. Despite large N yields as high as 310 kg ha-1, impacts of legumes on annual forage crops was limited. Poor response was likely a result of previous field history in which a permanent warm-season grass pasture was cultivated for site preparation and mineralized SOC released substantial amounts of available N. Under low soil N conditions, legume green manures produce enough N to likely reduce N fertilizer requirements cost-effectively for subsequent crops in East Texas.

Diss. (sammanfattning). Uppsala : Sveriges lantbruksuniv., 2003. / Härtill 3 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2004. / Härtill 5 uppsatser.

Diss. (sammanfattning) Uppsala : Univ., 2003. / Härtill 5 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2004. / Härtill 4 uppsatser.

Diss. (sammanfattning) Alnarp : Sveriges lantbruksuniversitet, 2006. / Härtill 4 uppsatser.

Diss. (sammanfattning) Umeå : Sveriges lantbruksuniv., 2006. / Härtill 4 uppsatser.

Le radiocarbone (14C) et le tritium (3H) sont libérés dans l'environnement de manière naturelle et par les activités nucléaires. Les rejets devant perdurer pendant les prochaines décennies, il est primordial de prévoir leur devenir et leur temps de résidence dans les sols. L'objectif de cette thèse est de proposer une prévision quantitative et une modélisation simple du devenir de 14C et 3H dans les matières organiques du sol (MOS). L'originalité de ce travail est double: nous faisons l'hypothèse que l'incorporation et le devenir des atomes d'hydrogène non-échangeable (HNE) dans le sol sont couplés à la dynamique du carbone; l'approche choisie est le traçage naturel ou artificiel par les isotopes stables 13C et 2H.A travers le traçage naturel par le 13C in situ, nous avons quantifié le carbone récemment incorporé par la végétation sur quelques décennies. Nous avons alors adapté le modèle RothC à la dynamique du C profond des sols. Cela nous a permis de prévoir que 10% du C persisteront pendant plusieurs siècles dans les couches profondes. Les expériences croisées d'incubation de composés marqués en 13C et 2H nous a permis de montrer que l’activité microbienne est le moteur de l’incorporation d’hydrogène de l’eau dans les MOS et nous a permis d'établir la stœchiométrie CH des biotransformations. Ces expérimentations ont permis de proposer un modèle de la dynamique couplée de C et H des MOS à court et moyen terme (décennies). Une méta-analyse des corrélations entre les teneurs en 13C et 14C de sols mondiaux nous a permis de démontrer que l'enrichissement en 13C des MOS peut être expliqué en totalité par le rapport 13C/12C de la végétation dont elles sont issues. / Radiocarbon (14C) and tritium (3H) are naturally released into the environment but also through nuclear activities. The releases are expected to persist for the next decades, it is important to predict their fate and their residence time in soils. The objective of this thesis is to propose a quantitative prediction and a simple modeling of the fate of 14C and 3H in soil organic matter (SOM). The originality of this work is twofold: first, we hypothesize that the incorporation and fate of NEH atoms in the soil are coupled to the carbon dynamics. Second, we chose to trace carbon and hydrogen by natural or artificial 13C and 2H tracing.Through natural in situ 13C tracing, we quantified the carbon recently incorporated by vegetation in few decades. Deep horizons contain a large part of this carbon (typically 20 to 30%). We adapted the RothC model to the deep soil C dynamics. This allowed us to predict that 10% of C will persist for several centuries in the deeper layers. The labelling experiments showed that the microbial activity is driving the incorporation of hydrogen from water into SOM, and allowed us to establish the CH stoichiometry of biotransformations. These experiments were a mean to propose a model of the coupled C and H dynamics of the SOM in the short and medium term (decades). The results of this thesis contribute as well to the improvement of the interpretation of natural abundances in 13C and 2H stable isotopes. A meta-analysis of the correlations between the 13C and 14C concentrations of global soils has demonstrated that the 13C enrichment of deep organic matter can be fully explained by the 13C/12C ratio of the vegetation from which they are derived.