Measurement of the size distribution of water-filled pores at different matric potentials by stray field nuclear magnetic resonance

The water retention characteristic provides the traditional data set for the derivation of a soil's pore‐size distribution. However, the technique employed to achieve this requires that assumptions be made about the way pores interconnect. We explore an alternative approach based on stray field nuclear magnetic resonance (STRAFI‐NMR) to probe the water‐filled pores of both saturated and unsaturated soils, which does not require information relating to pore connectivity. We report the relative size distributions of water‐occupied pores in saturated and unsaturated samples of two sets of glass beads of known particle size, two sands, and three soils (a silty loam, a sandy loam and a loamy sand), using measurements of the NMR T₁ proton relaxation time of water. The T₁ values are linearly related to pore size and consequently measured T₁ distributions provide a measure of the pore‐size distribution. For both the sands and the glass beads at saturation the T₁ distributions are unimodal, and the samples with small particle sizes show a shift to small T₁ values indicating smaller voids relative to the samples with larger particles. Different matric potentials were used to reveal how the water‐occupied pore‐size distribution changes during drainage. These changes are inconsistent with, and demonstrate the inadequacies of, the commonly employed parallel‐capillary tube model of a soil pore space. We find that not all pores of the same size drain at the same matric potential. Further, we observe that the T₁ distribution is shifted to smaller values beyond the distribution at saturation. This shift is explained by a change in the weighted average of the relaxation rates as the proportion of water in the centre of water‐filled pores decreases. This is evidence for the presence of pendular structures resulting from incomplete drainage of pores. For the soils the results are similar except that at saturation the T₁ distributions are bimodal or asymmetrical, indicative of inter‐aggregate and intra‐aggregate pore spaces. We conclude that the NMR method provides a characterization of the water‐filled pore space which complements that derived from the water retention characteristic and which can provide insight into the way pore connectivity impacts on drainage.     

Transformation of the structural organization of clay sediments and soils under the impact of polyelectrolytes

The effects of polyacrylic acid (PAAc) and polyacrylamide (PAA) adsorption by quartz sand, montmorillonite, kaolinite, gray forest soil, and chernozem on the texture of the sorbents were studied. It was shown that the polymolecular adsorption was typical of the applied polyelectrolytes. The addition of PAA in a concentration of 0.05% to the solution resulted in consolidation of the sediments with a decrease in their volume. In the case of montmorillonite, a loose gel precipitate formed; its volume decreased by about 6% during the experiment. The adsorption of polyelectrolytes slightly affected the average radii, total surface area, and volume of the pore space (within 4–20%). The transformation of the surface of minerals and soils under the action of polyelectrolytes resulted in a significant change in the differential pore volume. The number of pores of about 0.0014 μm in size hardly changed at all. However, wider pores (0.011–0.45 μm) appeared. The adsorption of PAAc resulted in the appearance of wide pores (1.6–22.0 μm), and the adsorption of PAA resulted in the appearance of two narrow classes of micropores. A much more even distribution of differential porosity in the range of 3.6–4.5 μm was revealed. Thus, the transformation of the surface of adsorbents by polyelectrolytes led to changes in the pore-size distribution.     

MEASUREMENT OF PORE SIZES IN FINE-TEXTURED SOILS: A REVIEW OF EXISTING TECHNIQUES

Pore size distributions obtained from the relationship between moisture content and suction are not dependable in fine-textured soils because of shrinkage. To overcome this problem, methods such as nitrogen sorption, mercury intrusion porosimetry, non-polar liquid desorption and thin sectioning have been used. In order to pre-dry samples without changes in the pore system, freeze-drying, organic liquid replacement of soil water, and critical point drying techniques have been employed. These methods of soil drying and pore size measurement are described and compared, and the validity of their use in soil studies is examined. The measurement of pore sizes by water desorption is also discussed.     

Evaluation of 1H NMR relaxometry for the assessment of pore‐size distribution in soil samples

¹H NMR relaxometry is used in earth science as a non‐destructive and time‐saving method to determine pore size distributions (PSD) in porous media with pore sizes ranging from nm to mm. This is a broader range than generally reported for results from X‐ray computed tomography (X‐ray CT) scanning, which is a slower method. For successful application of ¹H NMR relaxometry in soil science, it is necessary to compare PSD results with those determined from conventional methods. The PSD of six disturbed soil samples with various textures and soil organic matter (SOM) content were determined by conventional soil water retention at matric potentials between −3 and −390 kPa (pF 1.5–3.6). These PSD were compared with those estimated from transverse relaxation time (T₂) distributions of water in soil samples at pF 1.5 using two different approaches. In the first, pore sizes were estimated using a mean surface relaxivity of each soil sample determined from the specific surface area. In the second and new approach, two surface relaxivities for each soil sample, determined from the T₂ distributions of the soil samples at different matric potentials, were used. The T₂ distributions of water in the samples changed with increasing soil matric potential and consisted of two peaks at pF 1.5 and one at pF 3.6. The shape of the T₂ distributions at pF 1.5 was strongly affected by soil texture and SOM content (R² = 0.51 − 0.95). The second approach (R² = 0.98) resulted in good consistency between PSD, determined by soil water retention, and ¹H NMR relaxometry, whereas the first approach resulted in poor consistency. Pore sizes calculated from the NMR data ranged from 100 μm to 10 nm. Therefore, the new approach allows ¹H NMR relaxometry to be applied for the determination of PSD in soil samples and for studying swelling of SOM and clay and its effects on pore size in a fast and non‐destructive way. This is not, or only partly, possible by conventional soil water retention or X‐ray CT.     

MODIFICATION OF CALCINED CLAY AND ITS PHYSICAL PROPERTIES FOR USE AS A SUBSIDIARY MATERIAL FOR GROWING MEDIA

Calcined clay is a granular agglomerate of clay. It has a large surface area and myriad small pores, but also has a low easily available water (EAW) and water-buffering capacity (WBC). In this research, calcined clay was modified to enhance its low EAW and WBC and to allow it to substitute for subsidiary materials like perlite and vermiculite in growing media. To determine the proper size of the unit particles constituting the agglomerates for the matric potential of 1–10 kPa, several sizes of feldspar were agglomerated, and water suction tests were conducted. Based on the proper size, calcined clay was modified and made with kaolin through two steps. The first step consisted in consolidating kaolin by mixing it with water and drying it. It was then crushed and classified into the proper size. The second step consisted in agglomerating the kaolin spherically using a pan-type pelletizer. The fabrication of the modified calcined clay (MCC) was completed by heating it at 900°C for 2 hrs. The granule of MCC was found to have bimodal pores: small pores with diameters of about 1 μm, and pores larger than 10 μm. Through the water suction tests of MCC and its mixture with Canadian sphagnum that were conducted, it was verified that MCC has higher EAW and WBC values compared to the typical calcined clay in growing media.     

太白山北坡土壤的粘土矿物

太白山位于陕西省西部,绝顶海拔近4000米,是秦岭山脉的主峰,属于我国西北中部地区最高名山之一。地理位置约为北纬33.9-34.15度,东经107.4-108.0度。由于秦岭的屏障使潮湿的海洋气团不易深入西北,同时也阻挡了北方的寒潮不致长驱南下,所以秦岭已成为自然地理上划分我国东部南北的重要界线。太白山的气候具有南温带的温和气候和北亚热带的温暖气候特点,属于温带和亚热带过渡性地带。     

Untersuchung der potentiellen Stickstoff-Mineralisation in Trumao-Böden und einem Pseudogley

Total porosity and pore size distribution in untilled and tilled loess soils . Soil core samples were taken from untilled and tilled soils of a no-tillage experiment to determine total porosity and pore size distribution. The soil samples were collected at short time intervals during 1969–1971 from 2–6 cm depth of a Grey Brown Podzolic Soil (Typudalf) deriverd from loess. 1. Total porosity differed in untilled and tilled plots on the average by 4.7 vol.% (table 2). The seasonal changes are more pronounced on the tilled soil. Higher values of total porosity are observed during spring and fall, as compared to summer. Values are influenced by soil cultivation, rainfall and green manure crops (fig. 1a, b). 2. The changes of the fraction of large pores (> 30 μ), expressed on a volume basis, are similar to the changes in total porosity in direction but greater in extent. On the contrary the seasonal changes of the fractions of medium pores (3–30 μ), small pores (0,2–3,0 μ) and very small pores (< 0, 2 μ) appear to be independent from changes in total porosity (fig. la, b). 3. Fig. 2, showing the relation between total porosity and pore size distribution, may induce the wrong impression, that a decrease in total porosity results in an increase of the quantity of small and very small pores, accompanied with an excessive reduction of the quantity of large pores. If this relation is based on weight (100 g of solid soil particles) and not on volume (100 cm³ of soil particles and pores), it becomes clear, that compacting and loosening the soil investigated affect mainly the amount of large pores. 4. The seasonal changes of soil water content in the field influence pore size distribution. Under the condition of constant total porosity increasing water content at sampling date induces a pore size redistribution in favour of the pores > 300 μ and 1,5–3,0 μ (table 3). 5. A decrease in total porosity does not induce an increase in the homogeneity of the soil investigated (fig. 3). 6. The average total porosity of the untilled and tilled soil is near the lower and upper limit respectively of the range, which is considered to be the optimum for air capacity.     

Morphological determination of pore connectivity as a function of pore size using serial sections

The geometry of pore space in soil is considered to be the key in understanding transport of water, gas and solute. However, a quantitative and explicit characterization, by means of a physical interpretation, is difficult because of the geometric complexity of soil structure. Pores larger than 40 μm within two soil horizons have been analysed morphologically on 3-dimensional digital representations of the pore space obtained by serial sections through impregnated specimens. The Euler-Poincaré characteristic has been determined as an index of connectivity in three dimensions. The pore connectivity is quantified as a function of the minimum pore diameter considered leading to a connectivity function of the pore space. Different pore size classes were distinguished using 3-dimensional erosion and dilation. The connectivity function turned out to differentiate between two soil materials. The pore space in an upper Ah horizon is intensely connected through pores between 40 and 100 μm, in contrast to the pore space in the AhBv beneath it. The morphological pore-size distributions were compared to the pore-size distribution obtained by water retention measurements. The discrepancy between these different methods corresponds to the expectation due to pore connectivity.     

THE INFLUENCE OF MAGNESIUM IN SALINE AND SODIC SOILS: A SPECIFIC EFFECT OR A PROBLEM OF CATION EXCHANGE?

Na-Mg and Na-Ca exchange isotherms were determined at electrolyte concentrations of 500, 50, 5 and 1 meq per litre for illite, vermiculite and montmorillonite and for three soils containing illite and montmorillonite. This enabled comparisons to be made of clay swelling, dispersion and soil hydraulic conductivity changes between the Na-Mg and Na-Ca systems at known SAR, ESP and electrolyte concentration. Na-Mg montmoriUonite and a montmorillonitic soil behaved identically to the Na-Ca systems at the same ESP and electrolyte concentration: there was no specific effect. At the same SAR, the higher ESP in the Na-Mg system caused greater changes than in the Na-Ca systems. The Na-Mg vermiculite, illite, illitic soil and mixed illite-montmorillonitic soil showed greater changes than the Na-Ca systems at the same ESP, and there was a specific effect. At the same SAR, the higher ESP in all the Na-Mg systems apart from vermiculite increased the differences, but for vermiculite with a lower ESP, the differences were reduced. The lack of a specific effect for montmorillonite is probably related to the demixing of cations with the divalent ions concentrated on the non-swelling (internal) surfaces of the crystals.     

基于低场核磁技术研究土壤持水性能与孔隙特征

为研究常规水稻土和设施蔬菜地土壤持水性能与孔隙分布特征,利用低场核磁共振技术,获取田间持水量状态的土壤T_2谱线特征,在此基础上分析了土壤失水时信号幅值、弛豫时间与土壤含水量和孔隙大小分布的关系。结果表明:水稻土和设施蔬菜地土壤中孔隙分布均比较分散,小孔隙居多,大孔隙较少,水稻田转化为设施蔬菜地后,土壤孔隙半径整体变小,土壤结构恶化。在土壤失水过程中,波峰消减与谱线偏移同时发生,小峰优先消失且消减速率大于主峰,表明该过程中孔隙收缩与水分散失同时发生,土壤孔隙由大到小依次不断排水。低场核磁共振作为一种快速、无损的测量工具,能够更直接、更准确地反映出土壤水分迁移过程和孔隙分布规律,从而为设施栽培土壤退化机理和土壤改良提供新的理论和技术支撑。     

TOWARDS AN OBJECTIVE CLASSIFICATION OF SOIL STRUCTURE

A classification of structural condition in surface soils is proposed, based on the volumes of two categories of pore size, termed air capacity (pores greater than 60 μm diameter) and available water (pores of 60 to 0.2 μm diameter. Relationships of pore volumes to particle size class, organic carbon content and soil water regime are examined. Soil structural conditions are mainly affected by water regime and organic carbon and, apart from the extremes of sandy or clayey textures, less influenced by particle size distribution.     

A numerical experiment on pore size,pore connectivity,water retention,permeability, and solute transport using network models

Network models are idealized geometrical representations of porous media. They allow the simulation of effective hydraulic properties and of solute transport for well‐defined porous structures. In this paper, the relation between pore structure and effective properties is studied using a network model which can be adjusted to predefined pore‐size distributions and pore topologies. I show that pore topology can be adjusted such that quite different pore‐size distributions lead to essentially identical water retention curves. This puts into question the common interpretation of the retention curve as being indicative of the pore‐size distribution. However, I also found that both the hydraulic conductivity and the dispersion of a solute depend on the water retention curve and not on the particular combination of pore‐size distribution and topology which make it up. This corroborates the widely used approach of inferring relative permeabilities from water retention data.     

A MINERALOGICAL CHARACTERIZATION OF SOME VERTISOLS IN THE GEZIRA AND THE KENANA CLAY PLAINS OF THE SUDAN

Examination of the clay fraction of the Gezira and Kenana soils of the Sudan revealed montmorillonite as the dominant clay mineral, accompanied by kaolinite. The presence of illite and vermiculite is questionable. Quartz was found as an accessory mineral. Most of the kaolinite is concentrated in the ‘coarse clay’ (2–0.2 μm), whereas more than 90 per cent of the ‘fine clay’ consists of montmorillonite.     

PORE SIZE DISTRIBUTION IN CRITICAL POINT AND FREEZE DRIED AGGREGATES FROM CLAY SUBSOILS

Using aggregates from 2 clay soils over a range of water contents from pF 1 to oven dry, shrinkage and water release curves were measured and pore size distributions found by mercury porosimetry after critical point and after freeze drying. Freeze drying caused less shrinkage, the maximum being 6 cm³ 100 g^?1 from pF 1, but gave a large increase, up to 10 cm³ 100 g^?1, of pores in the 0.1–10 μm size range. Critical point drying produced more shrinkage from pF 1, more than half of which was attributed to loss of interlamellar water and the rest to the collapse of pores larger than 10 μm. In these clays the volume of pores of over 3 μm diameter was very small (<3 cm³ 100 g^?1) and most of the plant available water was released by collapse of narrower pores and not by pore emptying.     

Mercury porosimetry of compacted clay minerals

The clay minerals, kaolin and montmorillonite, were compacted at different pressures up to 300 MPa. The textural characteristics (pore radius, surface area and porosity) of the clay minerals were measured after compaction and related to the particle size and the cation exchange capacity of these clays. Kaolins and montmorillonites with and without compaction were characterized by mercury intrusion using a porosimeter within the range 0.1 MPa to 200 MPa. A negative linear correlation was obtained between the mean pore radius of compacted clays and the cation exchange capacity. A larger percentage of fine particles originated compacts with small pore sizes. The pore radius and the porosity of the clay minerals diminished with increasing compaction pressure, whereas the surface area increased.     

Bestimmung von Benetzungswinkeln an verschiedenen Korn- und Aggregatfraktionen

Determination of wetting angles on different particle and aggregate size fractions With investigations of water tension, capillary rise and infiltration the wetting angles of soil are usually assumed to be zero degrees. This assumption however is very often not valid. The estimation of wetting angles in soils of different grain-size distribution must take into account the interaction of grain-sizes with pore sizes. Therefore a correcting factor was worked out using 12 separated grain fractions. This factor effectively eliminated the influence of grain-size distribution when applied to fractions in the range between 2000 and 35 μm at angles between 0 and ?90°. Some examples of results are given.     

Effects of organic carbon and clay contents on structure-related properties of arable soils with high clay content

Understanding of factors governing soil structural features is necessary for managing key processes affecting crop productivity and environmental impacts of agriculture, for example, soil water balance, aeration, and root penetration. Organic matter is known to act as a major binding agent in soil aggregation and thus constitutes a central pillar in soil structure formation. However, knowledge of the structural role of organic matter or carbon (OC) in soils highly rich in clay-sized particles (<0.002 mm) is limited. In this study, the effects of clay and OC contents on aggregate stability, water holding capacity, near-saturated hydraulic conductivity, total porosity, and pore size distribution were assessed in cultivated fields with high clay content located in private crop production farms in southern Finland. Significant positive correlations were found between OC content and proportion of water stable aggregates and specific pore sizes from the range of 30 μm up to 1 mm diameter determined by image analysis. Porosities on a smaller size range derived from water retention measurements likewise showed a positive correlation with OC in <0.2 μm sizes. On the range of 0.2–1 μm, a negative relationship was observed, which induced a negative effect of OC on soil plant available water reserves. In line with the positive correlation between OC and larger soil pores, free water, representing the amount of water that can be drained by gravity, exhibited a positive relationship with OC suggesting that OC content can enhance aeration of soils with high clay content. Compared to OC, clay content tended to have an adverse effect on soil structural properties. Clay correlated negatively with pores larger than 30 μm, free water content, and extrapolated field saturated hydraulic conductivity. Further, our imaging results showed how saturated hydraulic conductivity was controlled by pore morphology, and there was a power law relationship between the conductivity and critical pore diameter. $K\propto d_c^2$ in agreement with the percolation theory. Overall, the structural impacts and hydrological implications of OC and clay in heavy clay soils vary by pore size ranges and their emergent practical impacts are thus not straightforward.     

Structural change induced by wetting and drying in seedbeds of a hardsetting soil with contrasting aggregate size distribution

Hardsetting has been related to two main processes: (i) development of strength when the soil is still moist (–100 kPa) due to matric suction acting within interparticle and interaggregate bridges and (ii) temporary cementation of dry soil by poorly ordered silica and aluminosilicates. In both cases, hardsetting of a seedbed should depend on geometric aspects of macro- and micro-structure. This study deals with aggregate breakdown and/or deformation on wetting and with the structural changes which follow on drying. Repacked seedbeds of a hardsetting red-brown earth were wetted by capillary rise. Seedbeds with a coarse and a fine aggregate size distribution were examined. Before and after wetting, the bulk density of the seedbeds was measured at 5-mm increments using a gamma probe. Replicate samples were air dried, gamma scanned and impregnated. Binary images of pore space (> 107 μm) of vertical faces were used to generate depth functions of structure attributes, including macroporosity. Bulk density measurements combined with image analysis resulted in successful structure characterization. Thin-section observations were used to interpret the quantified changes in terms of physical processes. In both coarse and fine seedbeds the physical processes which determined structural change occurred upon wetting rather than on drying. Coalescence of aggregates under plastic conditions, partly due to overburden pressure and enhanced by microcracking and partial slaking, occurred at the bottom of the coarse seedbed. In the fine seedbed, the fine material agglomerated due to matric suction. These different processes led to rather similar, microporous microstructures which exhibited similar strength properties after drying.     

Einfluss des Porenwasserdruckes auf die Zugfestigkeit von Bodenproben

Effect of pore water pressure on tensile strength Direct tensile testing with measurements of the pore water suction was used to investigate the relationship between tensile strength and suction. The tests were conducted on a till and a clayey soil, both homogenized. A closer view is focused on the relationship between material strain and the development of suction. Beyond, the factor χ of the effective stress equation for unsaturated soils by Bishop (1959), which was calculated by the data of tensile strength and corresponding matric suction is compared to the volumetric χ of the tested soil specimens. It could be shown, that the pore water pressure changes with strain. Therefore, not the initial suction of a soil is relevant for its failure but the actual one that can be measured in the failure zone at the moment of fracture. In addition the application of the volumetric χ in the effective stress equation compared to the χ derived from tensile testing leads to an 1.6 to 2.8 fold overestimation of the contribution of matric suction to soil tensile strength.     

An index for soil pore size distribution

An index for classifying soil pore size distribution is proposed. The arithmetic mean change in percent soil water content by weight as the tension changes from zero to 1.5 bars is used as the index. This number characterizes the size distribution of pores with a radius of one micron or greater. A simple equation is presented to calculate the index from soil water contents at pressure plate settings of zero, 0.2, and 1.5 bars. Moisture release curves from 3 different soils show that the index does tend to characterize the shape of the release curve and that it is sensitive to past management which affects the distribution of large soil pores. When all other conditions are optimum, it appears that there exists a specific value of the index which indicates when the soil pore size distribution may be expected to limit plant growth. It is further suggested that the index, together with penetrometer measurements made at the 1.5-bar water content, may be used as “soil test values” for making practical management decisions and for predicting the stability of soils under varying field conditions.