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Institute
Gel effect induced by mucilage in the pore space and consequences on soil physical properties
(2020)
Water uptake, respiration and exudation are some of the biological functions fulfilled by plant roots. They drive plant growth and alter the biogeochemical parameters of soil in the vicinity of roots, the rhizosphere. As a result, soil processes such as water fluxes, carbon and nitrogen exchanges or microbial activity are enhanced in the rhizosphere in comparison to the bulk soil. In particularly, the exudation of mucilage as a gel-like substance by plant roots seems to be a strategy for plants to overcome drought stress by increasing soil water content and soil unsaturated hydraulic conductivity at negative water potentials. Although the variations of soil properties due to mucilage are increasingly understood, a comprehensive understanding of the mechanisms in the pore space leading to such variations is lacking.
The aim of this work was to elucidate the gel properties of mucilage in the pore space, i.e. interparticulate mucilage, in order to link changes of the physico-chemical properties in the rhizosphere to mucilage. The fulfilment of this goal was confronted to the three following challenges: The lack of methods for in situ detection of mucilage in soil; The lack of knowledge concerning the properties of interparticulate mucilage; The unknown relationship between the composition and the properties of model substances and root mucilage produced by various species. These challenges are addressed in several chapters.
In a first instance, a literature review picked information from various scientific fields about methods enabling the characterization of gels and gel phases in soil. The variation of soil properties resulting from biohydrogel swelling in soil was named the gel effect. The combined study of water entrapment of gels and gel phases in soil and soil structural properties in terms of mechanical stability or visual structures proved promising to disentangle the gel effect in soil.
The acquired methodical knowledge was used in the next experiments to detect and characterize the properties of interparticulate gel. 1H NMR relaxometry allows the non-invasive measure of water mobility in porous media. A conceptual model based on the equations describing the relaxation of water protons in porous media was developed to integrate the several gel effects into the NMR parameters and quantify the influence of mucilage on proton relaxation. Rheometry was additionally used to assess mucilage viscosity and soil microstructural stability and ESEM images to visualize the network of interparticulate gel. Combination of the results enabled to identify three main interparticulate gel properties: The spider-web effect restricts the elongation of the polymer chains due to the grip of the polymer network to the surface of soil particles. The polymer network effect illustrates the organization of the polymer network in the pore space according to the environment. The microviscosity effect describes the increased viscosity of interparticulate gel in contrast to free gel. The impact of these properties on soil water mobility and microstructural stability were investigated. Consequences on soil hydraulic and soil mechanical properties found in the literature are further discussed.
The influence of the chemical properties of polymers on gel formation mechanism and gel properties was also investigated. For this, model substances with various uronic acid content, degree of esterification and amount of calcium were tested and their amount of high molecular weight substances was measured. The substances investigated included pectic polysaccharides and chia seed mucilage as model polymers and wheat and maize root mucilage. Polygalacturonic acid and low-methoxy pectin proved as non-suitable model polymers for seed and root mucilage as ionic interactions with calcium control their properties. Mucilage properties rather seem to be governed by weak electrostatic interactions between the entangled polymer chains. The amount of high molecular weight material varies considerably depending on mucilage´s origin and seems to be a straight factor for mucilage’s gel effect in soil. Additionally to the chemical characterization of the high molecular weight compounds, determination of their molecular weight and of their conformation in several mucilages types is needed to draw composition-property profiles. The variations measured between the various mucilages also highlight the necessity to study how the specific properties of the various mucilages fulfill the needs of the plant from which they are exuded.
Finally, the integration of molecular interactions in gel and interparticulate gel properties to explain the physical properties of the rhizosphere was discussed. This approach offers numerous perspectives to clarify for example how water content or hydraulic conductivity in the rhizosphere vary according to the properties of the exuded mucilage. The hypothesis that the gel effect is general for all soil-born exudates showing gel properties was considered. As a result, a classification of soil-born gel phases including roots, seeds, bacteria, hyphae and earthworm’s exuded gel-like material according to their common gel physico-chemical properties is recommended for future research. An outcome could be that the physico-chemical properties of such gels are linked with the extent of the gel effect, with their impact on soil properties and with the functions of the gels in soil.
Organic substances play an essential role for the formation of stable soil structures. In this context, their physico-chemical properties, interactions with mineral soil constituents and soil-water interactions are particu-larly important. However, the underlying mechanisms contributing to soil particle cementation by swollen or-ganic substances (hydrogels) remains unclear. Up to now, no mechanistic model is available which explains the mechanisms of interparticulate hydrogel swelling and its contribution to soil-water interactions and soil structur-al stability. This mainly results from the lack of appropriate testing methods to study hydrogel swelling in soil as well as from the difficulties of adapting available methods to the system soil/hydrogel.
In this thesis, 1H proton nuclear magnetic resonance (NMR) relaxometry was combined with various soil micro- and macrostructural stability testing methods in order to identify the contribution of hydrogel swelling-induced soil-water interactions to the structural stability of water-saturated and unsaturated soils. In the first part, the potentials and limitations of 1H NMR relaxometry to enlighten soil structural stabilization mechanism and vari-ous water populations were investigated. In the second part, 1H-NMR relaxometry was combined with rheologi-cal measurements of soil to assess the contribution of interparticulate hydrogel swelling and various polymer-clay interactions on soil-water interactions and soil structural stability in an isolated manner. Finally, the effects of various organic and mineral soil fractions on soil-water interactions and soil structural stability was assessed in more detail for a natural, agriculturally cultivated soil by soil density fractionation and on the basis of the experiences gained from the previous experiments.
The increased experiment complexity in the course of this thesis enabled to link physico-chemical properties of interparticulate hydrogel structures with soil structural stability on various scales. The established mechanistic model explains the contribution of interparticulate hydrogels to the structural stability of water-saturated and unsaturated soils: While swollen clay particles reduce soil structural stability by acting as lubricant between soil particles, interparticulate hydrogel structures increase soil structural stability by forming a flexible polymeric network which interconnects mineral particles more effectively than soil pore- or capillary water. It was appar-ent that soil structural stability increases with increasing viscosity of the interparticluate hydrogel in dependence on incubation time, soil texture, soil solution composition and external factors in terms of moisture dynamics and agricultural management practices. The stabilizing effect of interparticulate hydrogel structures further in-crease in the presence of clay particles which is attributed to additional polymer-clay interactions and the incor-poration of clay particles into the three-dimensional interparticulate hydrogel network. Furthermore, the simul-taneous swelling of clay particles and hydrogel structures results in the competition for water and thus in a mu-tual restriction of their swelling in the interparticle space. Thus, polymer-clay interactions not only increase the viscosity of the interparticulate hydrogel and thus its ability to stabilize soil structures but further reduce the swelling of clay particles and consequently their negative effects on soil structural stability. The knowledge on these underlying mechanisms enhance the knowledge on the formation of stable soil structures and enable to take appropriate management practices in order to maintain a sustainable soil structure. The additionally out-lined limitations and challenges of the mechanistic model should provide information on areas with optimization and research potential, respectively.