Development of a mineralogical matrix at the adsorption of polyelectrolytes on soil minerals and soils

The formation of the adsorption layers of polyelectrolytes (PEs) with the development of a mineralogical matrix on the surface of soil minerals and soils (kaolinite, montmorillonite, quartz sand, gray forest soil, and a chernozem) were established on the basis of direct measurements and IR spectroscopy. The differences in the adsorption kinetics of polyacrylamide (PAM) and polyacrylic acid (PAA) were revealed depending on the mineral nature, which were confirmed by the calculated values of the effective adsorption constants. It was found that the limit values of the PAM and PAA adsorption derived from experimental measurements for all the minerals were significantly higher than the values calculated for the formation of a monomolecular layer, which indicated adsorption on the surface of not only separate macromolecules but also secondary PE structures such as packets or fibrils. The IR spectroscopy studies confirmed the differences in the adsorption mechanism of PEs on soil minerals (from physical adsorption to chemisorption with the formation of surface compounds due to polar groups of PEs and surface groups of mineral particles). As a result, a cluster-matrix structure controlling the physicochemical properties of the modified surface was developed on the surface of natural aluminosilicates and soils.     

Pore size distribution measurements in swell-shrink soils

A method for the determination of pore size distribution in swell-shrink soils was described. Undisturbed core samples, saturated and drained at 1.5 MPa suction, were filled with a non-polar liquid (xylol), and its retention at suctions lower than 1.5 MPa was measured. Oven dry samples were analyzed in the same way. Derived pore size distributions were compared with those obtained by water desorption. Pore size distributions and their relative changes as a function of water content were related to some soil constituents and properties. Stability factor and sum of montmorillonite and vermiculite significantly influenced the pore size distribution by water release, A higher stability factor resulted in lower relative changes (ratios) in the pore size classes <10 μm and 0.2–10 μm when the samples were drained from saturation to 1.5 MPa suction, however, at extreme dryness, the relative changes were positively correlated to the sum of montmorillonite and vermiculite.     

使用自由软件和便携式光学显微镜研究土壤孔隙特征

Total porosity (TP), determined by image analysis, pore type and pore size distribution were evaluated on impregnated soil blocks from an undisturbed Brazilian sandy loam soil using a digital portable optical microscope. The free software Image J (version 1.40g) was used for image analysis. Procedures for soil image collection and analysis were presented. The image analysis allowed the evaluation of pore sizes with diameters ranging from 20 to >1 000 μm. The following types of pores were also obtained: rounded, elongated and intermediate. The results allowed the characterization of the soil as moderately porous (TP=21.6%). Rounded, intermediate and elongated pores were responsible for 11.6%, 31.7% and 56.7% of TP. In relation to pore size 51.1% of TP was in the 100-500 μm size class and a third of TP came from the pores larger than 500 μm.     

聚乙烯包膜肥料控释膜层结构特征研究

【目的】包膜肥料控释膜层结构和孔隙性质直接影响其养分释放速率。研究包膜肥料膜层结构特征,可以明确膜层结构参数与养分释放速率的关系,揭示包膜肥料控释机制,为建立养分释放数理模型提供理论依据。【方法】以聚乙烯包膜肥料控释膜层作为研究对象,量化研究了聚乙烯喷涂控释膜层的结构特征参数。利用扫描电镜,观测了在不同放大倍数下,采用喷涂工艺制备的聚乙烯包膜肥料膜层的外表层、横断面和内表层特征;以压汞仪测定了膜上孔隙的大小和分布;采用泡点法研究了大孔隙的最大孔径。【结果】不同放大倍数下的扫描电镜观测结果表明,喷涂法制备的包膜肥料控释膜层外表面整体上光滑、平整、均匀、疏松,但局部存在少量孔隙,孔径主要分布在1000～50 nm的范围内;在放大倍数很高的情况下,整体上膜层无细微孔隙结构。控释膜层厚度约为60～100 μm,断面形貌疏松无孔。膜层内表面粗糙,高低起伏不平、犬牙交错。膜壳材料堆密度为0.4～0.8 g/mL,低于聚乙烯密度,属于疏松结构。孔隙结构分析结果表明,聚乙烯控释膜层的中值孔径为4.5～5.3 nm,与对比的聚乙烯薄膜基本一致,说明两种膜分子链间的细微结构没有差异;但是聚乙烯控释膜层中存在占比18%的直径约为1000～50 nm的较大孔,孔径小于10 nm的间隙占82%,进一步说明占比少的大孔影响控释膜层释放性能。喷涂控释膜层总孔体积在0.4686～1.2260 mL/g,平均孔径在25.1～86.8 nm范围内,孔隙率为33.0%～50.6%,显著高于拉伸工艺制备的聚乙烯薄膜。释放期在1～6个月的包膜控释肥料,最大孔径在990～480 nm的范围,随包膜肥料释放期的增加,膜孔直径逐步减小,说明包膜控释肥料养分释放速率与其最大孔径存在内在联系。【结论】综合3种方法的测定结果,聚乙烯控释膜层可以看作是膜层均匀致密且局部有孔隙,膜壳直径3 mm,膜层厚度约为50 μm,最大孔径为1 μm,平均孔径为50 nm的密闭球形壳体。最大孔是水分和养分进出膜层的主要通道,决定了包膜肥料养分释放速率的快慢。     

Horvath-Kawazoe Model Based Evaluation of Pore Volume of Nanoporous Clinoptilolite

A liquid nitrogen (N₂) adsorption isotherm was employed to understand the differential pore-volume distribution (PVD) patterns of commercial Clinoptilolite (zeolite) fractions (<125 µ (Z8; fine or micro), 125–250 µ (Z9; medium) and >250 µ (Z10; coarse). The differential PVD of the fractions were calculated from the original Horvath-Kawazoe (HK) model. A full spectrum of pore volume distribution has exhibited “curves symmetric around the origin” irrespective of the Clinoptilolite fractions. However, the fractions exhibited a definite pattern of curves for each of the micro, meso and macropore region. Although, ultramicropores couldn’t be seen in any of the fractions, super micropore region exhibited uni-modal distribution curve with mono-disperse pores for all the fractions with varying pore volumes, while multimodal and tri-modal for meso and macro pore region respectively. Irrespective of the pore region, fine fraction (Z8) exhibited higher differential pore volume than other fractions. It was evident from the differential PVD that particle size has a major role in determining the textural properties of Clinoptilolite fractions.     

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.     

Pore-size distribution in loamy soils: A comparison between microtomographic and capillarimetric determination methods

Pore-size distribution in a soddy-podzolic silt loamy soil developing from mantle loesslike loam (Eutric Albic Retisol (Loamic, Cutanic)) was calculated from the water retention curve according to Jurin’s equation and directly determined in microtomographic experiments. Rounded macropores with the diameter of their sections from 75 to 1000 μm predominate in horizontal sections if the studied soil samples. A larger part of the soil pores (>30–35%) belongs to micro- and nanopores, and they cannot be quantitatively determined by the tomographic method, because their sizes are smaller than the detection limit of the applied X-ray microtomography (8.75 μm per pixel). This leads to a significantly larger pore volume determined from the water retention curve in comparison with the “tomographic” pore volume. A comparative analysis of pore-size distribution curves obtained by these methods shows that the major regularities of the pore-size distribution in the range from 30 to 5000 μm are similar in both cases. Fine macropores and, partly, mesopores predominate. Common characteristics of the pore-size distribution curves obtained by these methods, including the coincidence of the peaks, attest to the validity of classical approaches, according to which the hydrology of soil pore space can be perceived as a physical model of cylindrical capillaries of different sizes with capillary-sorbed water.     

Spatial location of carbon decomposition in the soil pore system

We sought to examine the distribution of carbon (C) decomposition within the framework of the soil pore system. Soils were sampled from a transect having a natural gradient in pore‐size distribution. After the addition of labelled wheat straw (¹³C) the repacked soil columns were incubated (25°C) at soil water matric potentials of either ?75 kPa or ?5 kPa and for either 4 or 90 days. Pore‐size distribution was determined for each soil column after incubation and soils were then analysed for soluble C, label‐derived residual C, label‐derived and native biomass C, nematode abundance, and ergosterol concentration as an indicator of fungal biomass. Overall, the data suggested that pore‐size distribution and its interaction with soil water give rise to a highly stratified biogeography of organisms through the pore system. This results in different rates of decomposition in pores of different size. Added plant material seemed to decompose most rapidly in soils with a relatively large volume of pores with neck diameters c. 15–60 µm and most slowly in soils with large volumes of pores with neck diameters < 4 µm. Regression analysis suggested that at matric potentials of both ?75 kPa and ?5 kPa the fastest decomposition of organic substrate occurred close to the gas–water interface. This analysis also implied that slower rates of decomposition occur in the pore class 60–300 µm. Correlations between the mass of soil biota and the pore volume of each pore class point to the importance of fungi and possibly nematodes in the rapid decomposition of C in the pores c. 15–60 µm during the early stages of decomposition.     

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.     

The Impact of Multiple Freeze–Thaw Cycles on the Microstructure of Aggregates from a Soddy-Podzolic Soil: A Microtomographic Analysis

With the help of computed X-ray microtomography with a resolution of 2.75 μm, changes in the microstructure and pore space of aggregates of 3 mm in diameter from the virgin soddy-podzolic soil (Glossic Retisol (Loamic)) in the air-dry, capillary-moistened, and frozen states after five freeze–thaw cycles were studied in a laboratory experiment. The freezing of the samples was performed at their capillary moistening. It was shown that capillary moistening of initially air-dry samples from the humus (AY), eluvial (EL), and illuvial (BT1) horizons at room temperature resulted in the development of the platy, fine vesicular, and angular blocky microstructure, respectively. The total volume of tomographically visible pores >10 μm increased by 1.3, 2.2, and 3.4 times, respectively. After freeze–thaw cycles, frozen aggregates partly preserved the structural arrangement formed during the capillary moistening. At the same time, in the frozen aggregate from the AY horizon, the total tomographic porosity decreased to the initial level of the air-dry soil. In the frozen aggregate from the EL horizon, large vesicular pores were formed, owing to which the total pore volume retained its increased values. The resistance of aggregate shape to the action of freeze–thaw cycles differed. The aggregate from the EL horizon completely lost its original configuration by the end of the experiment. The aggregate from the AY horizon displayed definite features of sagging after five freeze–thaw cycles, whereas the aggregate from the BT1 horizon preserved its original configuration.     

Image analysis and three-dimensional modelling of pores in soil aggregates

Three cross-sections of soil aggregates (2–5 mm diameter) were digitized at 5 μm resolution from montages (× 100) of scanning electron micrographs to produce binary images representing the soil pores and soil matrix. A three-dimensional random Boolean process was chosen as a model of the soil pores and matrix. The soil matrix was simulated by randomly positioned, overlapping spheres with radii drawn from an exponential distribution. Simulation of a 1 mm cube of one soil aggregate showed that all but 0.1 % of the pore space was connected to the exterior, although only 50% appeared to be connected to the exterior in a cross-sectional image. Pore spaces able to accommodate different sizes of microorganisms were also investigated. For example, a protozoan with a cross-sectional diameter of 20 μm could be accommodated in 17% of the pores in a 1 mm³ soil cube, although only 11 % of the pores would be accessible to those protozoa on the exterior of the cube.     

Interaction between clay microstructure, decomposition of plant residues and humification

We have studied microstructural changes in montmorillonite and kaolinite, which were amended with organic debris (leaves of chestnut or beech), microbial inoculum and nutrients and subjected, for 30 days at 25°C, to alternate drying and wetting (D–W) or kept continuously moist at water-holding capacity (WHC). The objective was to evalute the interactions between the decomposition of plant residues and clay microstructural organization in different pore–water regimes. The microstructure was studied by Hg porosimetry, N adsorption at 77 K, and scanning electron microscopy. Decomposition was assessed by measuring residual C and N, the amount of humified material, the relative contents of humic (HA) and fulvic (FA) acids, and their molecular weight distribution. The structural organization at the end of the experiments was different for the two clays, and new classes of pores were found as the result of the microbial metabolism. The decomposition was also significantly affected by clay type. Decomposition of the organic matter (OM) was rapid in the montmorillonite. The humified material occured mainly as low molecular weight FAs. By contrast, transformation was slow in kaolinite, leaving much residual C, and more of the humified material consisted of HAs. Alternate D–W had little effect on microstructure and decomposition. Samples that were kept moist and amended with chestnut leaves produced the greatest amount of humified substances. The dynamics of the decomposition was significantly affected by the nature of the leaves as indicated by the differences in residual C, humified material and C/N ratio. By contrast, changes in pore size distribution (PSD) were litle influenced by the type of organic debris.     

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.     

蒙脱石纳米复合物的制备及其吸附作用研究

对天然蒙脱石(M)矿物进行钠化改型和柱撑复合,制备了蒙脱石纳米复合物(MN),并对其进行表征,同时研究其对黄曲霉毒素的吸附作用。结果表明：与M相比,MN的层间距和比表面积明显增大,d₍₀₀₁₎值增加到1.96 nm,比表面积达到149.68m²/g,而且孔体积增加,孔直径缩小,微孔比例提高。吸附试验表明：复合改性后,MN对黄曲霉毒素的吸附容量和吸附速率均明显优于M。这些结果提示MN可望成为性能优越的黄曲霉毒素吸附剂。     

气化过程中谷壳焦颗粒孔隙结构及分形特性的演化

为了深入揭示生物质焦在气化反应中的行为变化及反应机理,该文利用氮气物理吸附法和扫描电镜等技术研究了气化过程中谷壳焦颗粒孔隙结构和表面形态的演化,并用分形维数描述了焦颗粒内部孔隙表面形态的复杂程度。结果表明,谷壳气化焦的吸附特性曲线在整体上均呈现出II型等温线特征,表明焦颗粒具有较为连续和完整的孔分布系统。随着气化反应的进行,谷壳焦的BET比表面积和微孔比表面积均呈现出先增大后减小的变化趋势,并在气化转化率为48.6%时取得最大值210.45和147.14m2/g。孔容积的变化规律与比表面积相近。随着气化转化率的增大,焦颗粒的平均孔径迅速减小,在转化率为35.4%时达到最小值2.94nm,之后稍有增大。分形FHH(Frenkel-Halsey-Hill)模型适用于生物质气化焦颗粒孔隙表面分形特征的研究。气化过程中焦颗粒孔隙表面分形维数的变化趋势与平均孔径的变化趋势相反,两者呈现出较好的线性关系。研究结果可为实际生物质气化过程的数值模拟和运行参数的优化等提供参考。     

Relationship between soil organic matter and micropores in a long-term experiment at Ultuna,Sweden

Our study showed that long‒term addition of organic matter to a fine textured soil (36.5% clay, 41% silt, 22.5% sand) resulted in an increase of both macro‒ and microporosity in the top soil layer. In terms of changes of the absolute pore volume, macropores were of main importance. However, in relative terms, the increase of microporosity was comparable to that of macroporosity (75% and 90%). Changes in porosity upon different organic matter levels had a marginal effect on the water storage capacity. Micropores with diameters in the range of 1—30 μm were highly significantly correlated to soil organic matter characteristics showing that there is a non‒uniform distribution in relation to pores. Mechanisms leading to disproportionally high concentrations of soil organic matter in relation to micropores are discussed.     

Uptake and Distribution of Lead (Pb) and Cadmium (Cd) in the Freshwater Crab,Potamonautes Perlatus (Crustacea) in the Eerste River,South Africa

This paper evaluates the effects of organic amendments and ironprecipitation on pore size distribution and mechanical resistancein sulphide mine tailings, as related to plant habitat requirements. Unaltered tailings, oxidised tailings collected from untreated, fertilized and sludge-amended plots in the field,and mixtures of unaltered tailings and organic amendments prepared in the laboratory, were analysed for pore size distribution. The organic amendments (sewage sludge, peat mossand paper mill sludge) were each applied at the rates of 0, 16 and 33% by volume. A difference in pore-size distribution between untreated and treated samples was shown in both field and laboratory samples. Both inorganic and organic amendments caused a decrease in pores holding water at soil water potentials–10 to –60 kPa, but increased the pores holding water at tensions below –60 kPa. This resulted in a decreased or unchanged content of plant available water (W_a) in all laboratory samples and in the fertilized field samples. Penetration studies in the field showed that additions of fertilizer, without any organic matter, had resulted in hardpans in the oxidised tailings that significantly increased themechanical resistance in the surface horizon. Thus, this studyindicates that the physical influence of the oxidation processestaking place in sulphide mine tailings can be magnified by additions of soil amendments. The aggregation of iron oxides and negatively charged particles such as organic substances orphosphate anions may cement the tailings, which can result inimpeded root growth.     

Evaluation of Differential Pore-Volume Distribution (DPVD) Patterns of Porous Clinoptilolite Fractions

Analysis of differential pore-volume distribution (DPVD) patterns of a commercial Clinoptilolite has been conducted experimentally using an analyzer by measuring the N₂ adsorption isotherm. The commercial material was fractionated by sieving through sequential sieves: <125 µ (Z8; fine), 125–250 µ (Z9; medium), and >250 µ (Z10; coarse). The DPVD of the fractions were calculated from the hysteresis loop according to the adsorption and desorption curves of Dollimore-Heal (DH) model. The adsorption cycle had produced dissimilar differential pore volume distribution patterns. For the 10-nm pore width, fine and medium fractions had a maximum pore volume up to 0.0016 cm³/g nm, while the coarse fraction had a little greater value up to 0.002 cm³/g nm. Moreover, the medium fraction had too many hills and valleys in the DPVD. However, the desorption cycle–based DH analysis did not show any marked variation in the DPVD pattern.     

Der Einfluß langjähriger Düngungsmaßnahmen auf die Dynamik der Bodenstruktur

The influence of a long term fertilizer experiment on the dynamic of soil structure In a long term manurial experiment at Dikopshof the dynamic of the structure of a Luvisol from loess during the growing seasons 1981 and 1982 was investigated. Farmyard manure effected the greatest variations in pore volume, amount of pores > 50 μm, air and water permeability, aggregate stability and dehydrogenase activity. Higher amounts of mineral fertilizer, that is additional mineral fertilization equivalent to the mineral contents of farmyard manure, could change the soil structure only for a short period. The yield of winter wheat was in close relation to the pore volume, the amount of pores > 50 μm and the dehydrogenase activity of the topsoil.     

Micromorphometric and micromorphological investigations of a clay loam soil in viticulture under zero and conventional tillage

Porosity, pore size distribution and the orientation pattern of pores were measured on thin sections prepared from undisturbed soil samples by means of electro-optical image-analysis. Total porosity was significantly higher at all sampling times in conventionally tilled plots, but the proportion of pores ranging from 30 to 500 μm, which are considered the most important both in soil-water-plant relationships and in maintaining a good soil structure, was higher in no-tilled plots. Modifications of pore orientation pattern were also observed. Micromorphological observations revealed some differences between the two series of soil samples; the formation of surface soil crusts was strongly reduced in no-tilled plots.