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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.
The use of agricultural plastic covers has become common practice for its agronomic benefits such as improving yields and crop quality, managing harvest times better, and increasing pesticide and water use efficiency. However, plastic covers are suspected of partially breaking down into smaller debris and thereby contributing to soil pollution with microplastics. A better understanding of the sources and fate of plastic debris in terrestrial systems has so far been hindered by the lack of adequate analytical techniques for the mass-based and polymer-selective quantification of plastic debris in soil. The aim of this dissertation was thus to assess, develop, and validate thermoanalytical methods for the mass-based quantification of relevant polymers in and around agricultural fields previously covered with fleeces, perforated foils, and plastic mulches. Thermogravimetry/mass spectrometry (TGA/MS) enabled direct plastic analyses of 50 mg of soil without any sample preparation. With polyethylene terephthalate (PET) as a preliminary model, the method limit of detection (LOD) was 0.7 g kg−1. But the missing chromatographic separation complicated the quantification of polymer mixtures. Therefore, a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method was developed that additionally exploited the selective solubility of polymers in specific solvents prior to analysis. By dissolving polyethylene (PE), polypropylene (PP), and polystyrene (PS) in a mixture of 1,2,4-trichlorobenzene and p-xylene after density separation, up to 50 g soil became amenable to routine plastic analysis. Method LODs were 0.7–3.3 mg kg−1, and the recovery of 20 mg kg−1 PE, PP, and PS from a reference loamy sand was 86–105%. In the reference silty clay, however, poor PS recoveries, potentially induced by the additional separation step, suggested a qualitative evaluation of PS. Yet, the new solvent-based Py-GC/MS method enabled a first exploratory screening of plastic-covered soil. It revealed PE, PP, and PS contents above LOD in six of eight fields (6% of all samples). In three fields, PE levels of 3–35 mg kg−1 were associated with the use of 40 μm thin perforated foils. By contrast, 50 μm PE films were not shown to induce plastic levels above LOD. PP and PS contents of 5–19 mg kg−1 were restricted to single observations in four fields and potentially originated from littering. The results suggest that the short-term use of thicker and more durable plastic covers should be preferred to limit plastic emissions and accumulation in soil. By providing mass-based information on the distribution of the three most common plastics in agricultural soil, this work may facilitate comparisons with modeling and effect data and thus contribute to a better risk assessment and regulation of plastics. However, the fate of plastic debris in the terrestrial environment remains incompletely understood and needs to be scrutinized in future, more systematic research. This should include the study of aging processes, the interaction of plastics with other organic and inorganic compounds, and the environmental impact of biodegradable plastics and nanoplastics.
The global problematic issue of the olive oil industry is in its generation of large amounts of olive mill wastewater (OMW). The direct discharge of OMW to the soil is very common which presents environmental problems for olive oil producing countries. Both, positive as well as negative effects on soil have been found in earlier studies. Therefore, the current study hypothesized that whether beneficial effects or negative effects dominate depends on the prevailing conditions before and after OMW discharge to soil. As such, a better understanding of the OMW-soil interaction mechanisms becomes essential for sustainable safe disposal of OMW on soil and sustainable soil quality.
A field experiment was carried out in an olive orchard in Palestine, over a period of 24 months, in which the OMW was applied to the soil as a single application of 14 L m-2 under four different environmental conditions: in winter (WI), spring (SP), and summer with and without irrigation (SUmoist and SUdry). The current study investigated the effects of seasonal conditions on the olive mill wastewater (OMW) soil interaction in the short-term and the long-term. The degree and persistence of soil salinization, acidification, accumulation of phenolic compounds and soil water repellency were investigated as a function of soil depth and time elapsed after the OMW application. Moreover, the OMW impacts on soil organic matter SOM quality and quantity, total organic carbon (SOC), water-extractable soil organic carbon (DOC), as well as specific ultraviolet absorbance analysis (SUVA254) were also investigated for each seasonal application in order to assess the degree of OMW-OM decomposition or accumulation in soil, and therefore, the persisting effects of OMW disposal to soil.
The results of the current study demonstrate that the degree and persistence of relevant effects due to OMW application on soil varied significantly between the different seasonal OMW applications both in the short-term and the long-term. The negative effects of the potentially hazardous OMW residuals in the soil were highly dependent on the dominant transport mechanisms and transformation mechanisms, triggered by the ambient soil moisture and temperature which either intensified or diminished negative effects of OMW in the soil during and after the application season. The negative effects of OMW disposal to the soil decreased by increasing the retention time of OMW in soil under conditions favoring biological activity. The moderate conditions of soil moisture and temperature allowed for a considerable amount of applied OMW to be biologically degraded, while the prolonged application time under dry conditions and high temperature resulted in a less degradable organic fraction of the OMW, causing the OMW constituents to accumulate and polymerize without being degraded. Further, the rainfall during winter season diminished negative effects of OMW in the soil; therefore, the risk of groundwater contamination by non-degraded constituents of OMW can be highly probable during the winter season.
Abstract The present work investigates the wetting characteristics of soils with regard to their dependence on environmental parameters such as water content (WC), pH, drying temperature and wetting temperature of wettable and repellent soils from two contrasting anthropogenic sites, the former sewage disposal field Berlin-Buch and the inner-city park Berlin-Tiergarten. The aim of this thesis is to deepen the understanding of processes and mechanisms leading to changes in soil water repellency. This helps to gain further insight into the behaviour of soil organic matter (SOM) and identifying ways to prevent or reduce the negative effects of soil water repellency (SWR). The first focus of this work is to determine whether chemical reactions are required for wetting repellent samples. This hypothesis was tested by time and temperature dependence of sessile drop spreading on wettable and repellent samples. Additionally, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to determine whether various drying regimes cause changes in the relative abundance of hydrophobic and hydrophilic functional groups in the outer layer of soil particles and whether these changes can be correlated with water content and the degree of SWR. Finally, by artificially altering the pH in dried samples applying acidic and alkaline reagents in a gaseous state, the influence of only pH on the degree of SWR was investigated separately from the influence of changes in moisture status. The investigation of the two locations Buch and Tiergarten, each exceptionally different in the nature of their respective wetting properties, leads to new insights in the variety of appearance of SWR. The results of temperature, water content and pH dependency of SWR on the two contrasting sites resulted in one respective hypothetical model of nature of repellency for each site which provides an explanation for most of the observations made in this and earlier studies: At the Tiergarten site, wetting characteristics are most likely determined by micelle-like arrangement of amphiphiles which depends on the concentration of water soluble amphiphilic substances, pH and ionic strength in soil solution. At low pH and at high ionic strength, repulsion forces between hydrophilic charged groups are minimized allowing their aggregation with outward orientated hydrophobic molecule moieties. At high pH and low ionic strength, higher repulsion forces between hydrophilic functional groups lead to an aggregation of hydrophobic groups during drying, which results in a layer with outward oriented hydrophilic moieties on soil organic matter surface leading to enhanced wettability. For samples from the Buch site, chemical reactions are necessary for the wetting process. The strong dependence of SWR on water content indicates that hydrolysis-condensation reactions are the controlling mechanisms. Since acid catalyzed hydrolysis is an equilibrium reaction dependent on water content, an excess of water favours hydrolysis leading to an increasing number of hydrophilic functional groups. In contrast, water deficiency favours condensation reactions leading to a reduction of hydrophilic functional groups and thus a reduction of wettability. The results of the present investigation and its comparison with earlier investigations clearly show that SWR is subject to numerous antagonistically and synergistically interacting environmental factors. The degree of influence, which a single factor exerts on SWR, is site-specific, e.g., it is dependent on special characteristics of mineral constituents and SOM which underlies the influence of climate, soil texture, topography, vegetation and the former and current use of the respective site.
The (un-)controlled application of olive oil mill wastewater (OMW) has positive and negative effects on soil quality. On the one hand it can be used as fertilizer, on the other hand especially the occurrence of soil water repellency is problematic. Due to this fact the objective of this study was to characterize the effects of OMW application on soil and to investigate the mechanisms that are in combination with changes of soil organic matter quality responsible for soil water repellency depending on the climatic conditions.
At first several locations of uncontrolled OMW disposal were screened for positive and negative im-pacts. Then, laboratory incubation experiments and finally a field experiment in Israel were conducted in order to determine the influence of climatic conditions. Besides standard soil parameters (pH, elec-tric conductivity, total carbon, dissolved organic carbon , specific UV-Absorption) it was focused on the determination of phenolic compounds, the carbon isotope ratio, the water drop penetration time and the contact angle as well as the thermal analysis.
This thesis shows that soil water repellency of OMW-polluted soils depends on the climatic conditions, i.e. the application season. In the laboratory as well as in the field the wettability of the soil was strongly reduced under hot and dry conditions. It was observed, that the stable carbon fraction characterized by a high calorific value is responsible for soil water repellency. In particular, amphiphilic substances, e.g. fatty acids, may interact with soil particles as a consequence of drying. On the contrary, no reduc-tion of the wettability of the soil was determined under moist conditions and degradation of organic matter of the OMW was enhanced. Nevertheless, too strong irrigation or rainfall, e.g. in winter, may leach phenolic ingredients of the OMW into the groundwater.
At the same time the application led to an increase of organic and inorganic nutrients, which should be emphasized as a positive effect. Due to these results, a controlled application of olive oil mill wastewater as alternative, low-cost and sustainable treatment option is recommended. But, instead of the current application season winter, the olive mill wastewater should be stored and not be spread before spring in order to avoid negative impacts on the soil.
A fundamental understanding of attachment of engineered nanoparticles to environmentalrnsurfaces is essential for the prediction of nanoparticle fate and transport in the environment.
The present work investigates the attachment of non-coated silver nanoparticles and citraterncoated silver nanoparticles to different model surfaces and environmental surfaces in thernpresence and absence of humic acid. Batch sorption experiments were used for this investigation.
The objective of this thesis was to investigate how silver nanoparticles interactrnwith surfaces having different chemical functional groups. The effect of presence of HA, on the particle-surface interactions was also investigated. In the absence of humic acid, nanoparticle-surface interactions or attachment was influencedrnby the chemical nature of the interacting surfaces. On the other hand, in the presence ofrnhumic acid, nanoparticle-surface attachment was influenced by the specific surface area of the sorbent surfaces. The sorption of non-coated silver nanoparticles and citrate coatedrnnanoparticles to all the surfaces was nonlinear and best described by Langmuir isotherm, indicating monolayer sorption of nanoparticles on to the surfaces. This can be explained as due to the blocking effect generated by the particle-particle repulsion. In the presence of humic acid, sorption of nanoparticles to the surfaces was linear. When the humic acid was present in the interacting medium, both the nanoparticles and surfaces were getting coated with humic acid and this masks the chemical functionalities of the surfaces. This leads to the change in particle-surface interactions, in the presence of humic acid. For the silver nanoparticle sorption from an unstable suspension, the sorption isotherms did not follow any classical sorption models, suggesting interplay between aggregation and sorption. Citrate coated silver nanoparticles and humic acid coated silver nanoparticles showed arndepression in sorption compared to the sorption of non-coated silver nanoparticles. In therncase of citrate coated silver nanoparticles the decrease in sorption can be explained by thernmore negative zeta potential of citrate coated nanoparticles compared to non-coated ones. For humic acid coated nanoparticles the sorption depression can be due to the steric hindrance caused by the free humic acid molecules which may coat the sorbent surface or due to the competition for sorption sites between the nanoparticle and free humic acid molecules present in the suspension. Thus nanoparticle surface chemistry is an important factor that determines the attachment of nanoparticles towards surfaces and it makes the characterization of nanoparticle surface an essential step in the study of their fate in the environment.
Another aim of this study was to introduce the potential of chemical force microscopy for nanoparticle surface characterization. With the use of this technique, it was possible to distinguish between bare silver nanoparticles, citrate coated silver nanoparticles, and humic acid coated silver nanoparticles. This was possible by measuring the adhesion forces between the nanoparticles and five different AFM probes having different chemical functionalization.
Soil organic matter (SOM) is a key component responsible for sequestration of organic molecules in soil and regulation of their mobility in the environment. The basic structure of SOM is a supramolecular assembly responding dynamically to the environmental factors and the presence of interacting molecules. Despite of the advances in the understanding of sorption processes, the relation between sorbate molecules, SOM supramolecular structure and its dynamics is limited. An example of a dynamic nature of SOM is a physicochemical matrix aging that is responsible for SOM structural arrangement. The underlying process of the physicochemical aging is the formation of water molecule bridges (WaMB) between functional groups of molecular segments. Since WaMB influence the stiffness of SOM structure, it was hypothesized that formation of WaMB contributes to the sequestration of organic molecules. However, this hypothesis has not been tested experimentally until now. Furthermore, the knowledge about the influence of organic molecules on WAMB is based solely on computer modeling studies. In addition, the influence of organic molecules on some physical phases forming SOM is not well understood. Especially, the interactions between organic molecules and crystalline phases represented by aliphatic crystallites, are only presumed. Thus, the investigation of those interactions in unfractioned SOM is of high importance.
In order to evaluate the involvement of WaMB in the sequestration of organic molecules and to increase our understanding about interactions of organic chemicals with WaMB or aliphatic crystallites, the following hypotheses were tested experimentally. 1) Similarly to crystalline phases in synthetic polymers, aliphatic crystallites, as a part of SOM, cannot be penetrated by organic molecules. 2) The stability of WaMB is determined by the ability of surrounding molecules to interact with water forming WaMB. 3) WaMB prevent organic molecules to leave the SOM matrix and contribute thus to their immobilization. In order to test the hypotheses 1 and 2, a set of experiments including treatment of soils with chosen chemicals was prepared. Interaction abilities of these chemicals were characterized using interaction parameters from the Linear Solvation Energy Relationship theory. WaMB characteristics were monitored using Differential Scanning Calorimetry (DSC) allowing to measure the WaMB thermal stability and the rigidity of SOM matrix; which in turn was determined by the heat capacity change. In addition, DSC and 13C NMR spectroscopy assessed thermal properties and the structure of aliphatic crystallites. The spiking of samples with a model compound, phenol, and measurements of its desorption allowed to link parameters of the desorption kinetics with WaMB characteristics.
The investigation showed that the WaMB stability is significantly reduced by the presence of molecules with H-donor/acceptor interaction abilities. The matrix rigidity associated with WaMB was mainly influenced by the McGowan’s volume of surrounding molecules, suggesting the importance of dispersion forces. The desorption kinetics of phenol followed a first order model with two time constants. Both of them showed a relation with WaMB stability, which supports the hypothesis that WaMB contribute to the physical immobilization of organic molecules. The experiments targeted to the crystallites revealed their structural change from the ordered to the disordered state, when in contact with organic chemicals. This manifested in their melting point depression and the decrease of overall crystallinity. Described structural changes were caused by molecules interacting with specific as well as non-specific forces, which suggests that aliphatic crystallites can be penetrated and modified by molecules with a broad range of interaction abilities.
This work shows that chosen organic molecules interact with constituents of SOM as exemplified on WaMB and aliphatic crystallites, and cause measurable changes of their structure and properties. These findings show that the relevance of aliphatic crystallites for sorption in soil may have been underestimated. The results support the hypothesis that physicochemical matrix aging significantly contributes to the immobilization of organic chemicals in SOM.
