Fabian Jaeger

Proton Nuclear Magnetic Resonance (NMR) Relaxometry in Soil Science Applications

Proton NMR relaxometry is a very powerful tool for investigating porous media and their interaction with wa- ter or other liquids and the mobility and interaction of organic molecules in solution. It is commonly used in material sci- ence or earth science. However, it is only scarcely applied in soil science although it shows great potential for helping to understand water uptake into the soil matrix and processes occurring at the solid-liquid interface at soil particle surfaces. This review introduces proton NMR relaxometry in the context of soil science and discusses the most important applica- tions of the method in this field. Relevant results from different applications of NMR relaxometry in soils are described and research gaps identified. Some original data is presented concerning biofilm formation in soils, which was investi- gated using proton NMR relaxometry. NMR relaxometry is a sensitive, informative and promising method to study pore size distribution in soils as well as many kinds of soil physicochemical processes, among which are wetting, swelling or changes in macromolecular status. It is further a very helpful method to study interactions between molecules in soil or- ganic matter and can serve to study the state of binding of water or organic chemicals to soil organic matter. Relaxation times determined by NMR relaxometry are sensitive to various factors that play a role in soil-water interaction which is both an advantage and shortcoming of the method: NMR relaxometry can be applied to numerous investigations in soil science, but at the same time interpretation of the results may be very difficult in such complex and heterogeneous sys- tems like soils.

Proton NMR Relaxometry as a Useful Tool to Evaluate Swelling Processes in Peat Soils~!2009-07-26~!2009-12-04~!2010-06-15~!

Dramatic physical and physico-chemical changes in soil properties may arise due to temperature and moisture variations as well as swelling of soil organic matter (SOM) under constant conditions. Soil property variations may influence sorption/desorption and transport processes of environmental contaminants and nutrients in natural-organic-matterrich soils. Notwithstanding the studies reported in literature, a mechanistic model for SOM swelling is unavailable yet. The objective of the present study was the evaluation of the swelling of peat soils, considered as SOM models, by 1 H NMR relaxometry and differential scanning calorimetry (DSC). Namely, information on the processes governing physical and physicochemical changes of peat during re-hydration were collected. The basic hypothesis of the present study was that the changes are slow and may affect water state as well as amounts of different water types into the peats. For this reason, such changes can be evidenced through the variations of mobility and thermal behaviour of the involved H2O molecules by using 1 H NMR relaxometry and DSC. According to the experimental results, a mechanistic model, describing the fundamental processes of peat swelling, was obtained. Two different peats re-wetted at three temperatures were used. The swelling process was monitored by measuring spin-spin relaxation time (T2) over a hydration time of several months. Moreover, DSC, T1 – T2 and T2 – D correlation measurements were done at the beginning and at the end of the hydration. Supplementary investigations were also done in order to discriminate between the swelling effects and the contributions from soil solution, internal magnetic field gradients and/or soil microorganisms to proton relaxation. All the results revealed peat swelling. It was evidenced by pore size distribution changes, volumetric expansion and redistribution of water, increasing amounts of nonfreezable and loosely bound water, as well as formation of gel phases and reduction of the translational and rotational mobility of H2O molecules. All the findings implied that changes of the physical and physicochemical properties of peats were obtained. In particular, three different processes having activation energies comprised in the interval 5 – 50 kJ mol -1 were revealed. The mechanistic model which was, then, developed included water reorientation in bound water phases, water diffusion into the peat matrix and reorientation of SOM chains as fundamental processes governing SOM swelling. This study is of environmental significance in terms of re-naturation and re-watering of commercially applied peatlands and of sorption/desorption and transport processes of pollutants and nutrients in natural organic matter rich soils.

Proton NMR Relaxometry as a Useful Tool to Evaluate Swelling Processes in Peat Soils

Dramatic physical and physico-chemical changes in soil properties may arise due to temperature and moisture variations as well as swelling of soil organic matter (SOM) under constant conditions. Soil property variations may influ- ence sorption/desorption and transport processes of environmental contaminants and nutrients in natural-organic-matter- rich soils. Notwithstanding the studies reported in literature, a mechanistic model for SOM swelling is unavailable yet. The objective of the present study was the evaluation of the swelling of peat soils, considered as SOM models, by 1 H NMR relaxometry and differential scanning calorimetry (DSC). Namely, information on the processes governing physical and physicochemical changes of peat during re-hydration were collected. The basic hypothesis of the present study was that the changes are slow and may affect water state as well as amounts of different water types into the peats. For this reason, such changes can be evidenced through the variations of mobility and thermal behaviour of the involved H2O molecules by using 1 H NMR relaxometry and DSC. According to the experimental results, a mechanistic model, describ- ing the fundamental processes of peat swelling, was obtained. Two different peats re-wetted at three temperatures were used. The swelling process was monitored by measuring spin-spin relaxation time (T2) over a hydration time of several months. Moreover, DSC, T1 - T2 and T2 - D correlation measurements were done at the beginning and at the end of the hydration. Supplementary investigations were also done in order to discriminate between the swelling effects and the con- tributions from soil solution, internal magnetic field gradients and/or soil microorganisms to proton relaxation. All the re- sults revealed peat swelling. It was evidenced by pore size distribution changes, volumetric expansion and redistribution of water, increasing amounts of nonfreezable and loosely bound water, as well as formation of gel phases and reduction of the translational and rotational mobility of H2O molecules. All the findings implied that changes of the physical and phys- icochemical properties of peats were obtained. In particular, three different processes having activation energies com- prised in the interval 5 - 50 kJ mol -1 were revealed. The mechanistic model which was, then, developed included water reorientation in bound water phases, water diffusion into the peat matrix and reorientation of SOM chains as fundamental processes governing SOM swelling. This study is of environmental significance in terms of re-naturation and re-watering of commercially applied peatlands and of sorption/desorption and transport processes of pollutants and nutrients in natural organic matter rich soils.