土壤胶体对蛋白质的吸附

土壤有机-无机复合体是土壤肥力的物质基础之一,不仅依随成土过程而发生变化,人类耕作利用也可产生影响。     

Bildung und Eigenschaften amorpher Tonbestandteile in Böden des gemäßigt-humiden Klimabereichs

Formation and properties of amorphous clay constituents in soils of the temperate-humid climate region A review of literature and of some own work was given on formation and properties of amorphous clay constituents which occur along with crystalline clay minerals in soils. By that the importance of soil amorphous material with respect to pedologic-agricultural and social-environmental problems was tried to emphasize. At the beginning some clarification of the different terms used for inorganic amorphous clay constituents and a sort of difinition of the different kinds of amorphous materials seemed to be evident. Then, the occurence and the formation of amorphous material in soils of the temperate-humid climate region was commentated. As a result of this it was stated that amorphous clay constituents occur mainly as coatings on negatively charged surfaces of crystalline layer silicates. From the grouping of amorphous substances around negatively charged cores (layer silicates or Al^IV-cores in allophanic soils, respectively) it was deduced that the organisation of amorphous clay constituents and allophanes as well as synthetic aluminosilicates might be due to an unique structural principle, which was tried to explain more detailed. The methods used for determination of amorphous materials, especially allophanes, were discussed. Since the determination of amorphous clay constituents by chemical dissolution techniques is ambiguous with respect to soils containing different weathering stages of crystalline layer silicates as well, some suggestions were made for characterizing amorphous substances in soils by cation exchange and anion adsorption properties. Finally the importance of exchange-reactions caused by specific adsorption of ions and molecules (e.g. nutrients and pesticides) was indicated. Furthermore, the possibility was mentioned that harmful environmental substances might be bound (neutralized) and waste nutrients might be recycled by specific adsorption on amorphous soil constituents.     

Sulfometuron incorporation in cationic micelles adsorbed on montmorillonite

The aim of this study was to understand the interactions between alkylammonium cations present as monomers and micelles and a clay mineral, montmorillonite, to develop slow release formulations of anionic herbicides, such as sulfometuron (SFM) whose leaching in soils is an environmental and economic problem. In the proposed formulation the herbicide is incorporated in positively charged micelles of quaternary amine cations, which in turn adsorb on the negatively charged clay. The adsorption of hexadecyltrimethylammonium (HDTMA) and octadecyltrimethylammonium (ODTMA) on montmorillonite was studied above and below their critical micelle concentrations (CMC). At concentrations above the CMC, the loading exceeded the clay's cation exchange capacity (CEC) and indicated higher affinity of the cation with the longer alkyl chain. An adsorption model could adequately simulate adsorption at concentrations below the CMC, and yield fair predictions for the effect of ionic strength. The model indicated that above the CMC adsorbed micelles contributed significantly to the amount of ODTMA adsorbed. Evidence for adsorption of ODTMA micelles on montmorillonite was provided by X-ray diffraction, freeze-fracture electron microscopy, and dialysis bag measurements. SFM was not adsorbed directly on the clay mineral, and adsorbed at low levels, when the organic cation was adsorbed as monomers. In contrast, a large fraction of SFM adsorbed on the clay mineral when incorporated in micelles that adsorbed on the clay.     

THE REACTIONS OF SOLUBLE ALUMINIUM WITH MONTMORILLONITE

The amount of aluminium sorbed by calcium bentonite from basic aluminium chloride solutions depends on the ratio of OH to A1 in the original solution. Except when OH/A1 = 0, only part of the sorbed A1 is exchanged by dilute solutions of barium or calcium chlorides and the exchange capacity of the clay decreases in proportion to the amount of aluminium retained by the clay. Al-bentonite appears to contain a mixture of A1³⁺ and a basic cation in which OH/Al is 2.5. Neutralizing Al-bentonite with calcium acetate of pH 7.2 restores only part of the exchange capacity and some charged interlayer aluminium is thought to remain in the clay at this pH. It seems possible, therefore, that charged interlayer aluminium may be found even in soils with a neutral reaction.     

Origin of the pH-dependent cation exchange capacities of Irish soil clays

Values of cation exchange capacity determined at pH 4.8 and at pH 8.2 are reported for peroxidized clay separates from a group of Irish soils derived from a variety of parent materials. The correlation between the two measurements was poor. The differences between the values (pH-dependent CEC's) ranged from 0.1 to 58.6 mequiv./100 g, with a mean of 12.9 mequiv./100 g. The highest values were associated with clays from spodic horizons and clays from basalt-derived soils. CEC at pH 8.2 and pH-dependent CEC were highly correlated with citrate-dithionite-bicarbonate (CDB) extractable Al. In contrast, CEC at pH 4.8 was negatively correlated with this parameter, suggesting that hydrous oxides reduced CEC at low pH values.Values of CEC of pH 4.8 and pH 8.2 are also reported for a selection of 16 clays subjected to sequential extraction with CDB and NaOH. CDB treatment reduced mean pH-dependent CEC from 20.4 to 9.0 mequiv./100 g, which was reduced to 3.9 mequiv./100 g by subsequent extraction with NaCH. The material removed by CDB was apparently positively charged at pH 4.8 and negatively charged at pH 8.2. Most of the pH-dependent CEC remaining after CDB treatment was associated with the clays from spodic horizons. The material extracted by NaOH was apparently negatively charged at both pH 4.8 and pH 8.2. No direct evidence of the physical nature of this material was obtained but it was present in sufficient amounts to suggest that it existed in particular forms in some of the clays from the spodic horizons. Following the dissolution treatments, the correlation between CEC values at pH 4.8 and pH 8.2 was very good (r = 0.99).     

Improving on the Prediction of Cation Exchange Capacity for Highly Weathered and Structurally Contrasting Tropical Soils from Their Fine-Earth Fractions

The roles of fine-earth materials in the cation exchange capacity (CEC) of especially homogenous units of the kaolinitic and oxyhydroxidic tropical soils are still unclear. The CEC (pH 7) of some coarse-textured soils from southeastern Nigeria were related to their total sand, coarse sand (CS), fine sand (FS), silt, clay, and organic-matter (OM) contents before and after partitioning the dataset into topsoils and subsoils and into very-low-, low-, and moderate-/high-stability soils. The soil-layer categories showed similar CEC values; the stability categories did not. The CEC increased with decreasing CS but with increasing FS. Silt correlated negatively with the CEC, except in the moderate- to high-stability soils. Conversely, clay and OM generally impacted positively on the CEC. The best-fitting linear CEC function (R², 68%) was attained with FS, clay, and OM with relative contributions of 26, 38, and 36%, respectively. However, more reliable models were attained after partitioning by soil layer (R², 71–76%) and by soil stability (R², 81–86%). Notably FS's contribution to CEC increased while clay's decreased with increasing soil stability. Clay alone satisfactorily modeled the CEC for the very-low-stability soils, whereas silt contributed more than OM to the CEC of the moderate- to high-stability soils. These results provide new evidence about the cation exchange behavior of FS, silt, and clay in structurally contrasting tropical soils.     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

Poorly ordered hydrous Fe oxides, colloidal dispersion and soil aggregation. II. Modification of silty soil aggregation with Fe(III) polycations and model humic macromolecules

Poorly ordered ferrihydrites, more or less associated with synthetic humic macro-molecules, were added to a poorly structured temperate silty soil. Manipulation of the net soil charge through these additions was measured by potentiometric titration and cation exchange capacity. The consequences of anchoring positively charged Fe hydrous oxides on negative permanent clay surface charges were studied. Both cementation and aggregate water-stability increased with increase in adsorbed iron. The aggregation process was studied by using micromorphology and ultramicromorphology, water retention curves, mercury porosimetry and a fractal approach. Aggregate water-stability was studied when the soils were air-dried, with some irreversible aggregation, and oven-dried or wetted from – 1.5 MPa to – 1 kPa thereafter. Soils with added Fe(III) polycation–humic macro-molecule associations were less positively charged, less cemented and less stable than soils amended with Fe(III) polycations alone. The effect of these treatments on slaking is discussed.     

Characteristics of fragipan B horizons developed on different parent material in North-Western Italy

A Fragipan (Bx) is a soil horizon hard when dry and brittle when moist, that undergoes slaking upon water immersion, forming a barrier to roots and limiting land use. Brittleness and slaking depend on soil porosity and particle arrangement, but still no agreement exists on the inorganic components responsible for such arrangement. We hypothesized that the same kind of particle arrangement may originate from different soil components, ultimately depending on the lithology of parent material, and evaluated the soil and clay characteristics that best differentiate Bx from B horizons. Thirty-six samples were taken from Typic Fragiudalfs developed on the two sides of an alluvial fan characterized by different amounts of ultramafic materials. Discriminant Analysis evidenced that pedogenic Fe oxides were fundamental in discriminating Bx from B horizons on pure ultramafic parent material, while clay mineralogy was more important in soils with less ultramafic materials. In the first case, the association between clay minerals and self-assembling oxides systems may lead to brittleness, while in the second case the higher abundance of kaolinite may contribute to weak associations between pH-dependent sites and negatively charged surfaces. The only common feature to fragipans on both river sides was a higher degree of weathering.     

Factors affecting aggregate instability of Greek agricultural soils

Abstract

The aggregate stability of several surface soils from Thessaly plain, Central Greece, was studied using an instability index which classified the soils according to the stability of their aggregates to water. This index was correlated to the basic soil properties influencing aggregate stability. It was found that soil aggregate stability was positively correlated with clay content, total specific surface area, cation exchange capacity, base saturation, and free silicon oxides content. Silt, very fine and fine sand, and the ratio (sand+silt)/clay influenced negatively the aggregate stability. Organic matter content and sesquioxides have no effect on aggregate stability. It was also observed that the fraction of carbonates with silt dimension influenced negatively the aggregate stability. From the results of this study it was concluded that the factors affecting water aggregate stability were specific surface area and cation exchange capacity of the soils.     

THERMODYNAMICS OF SINGLY CHARGED ION EXCHANGES IN THE TRACE REGIONS ON CAMP BERTEAU MONTMORILLONITE

Ion exchange equilibria for seven pairs of singly charged ions between aqueous chloride solutions and a montmorillonite clay have been studied at 25 °C for low values of the total normality of the equilibrium solution. Only the trace region for the preferred ion was investigated. Since the analogue of Henry's law was found to be valid, the exchanges being almost ideal, standard free energies were calculated from experimental data in the region where the analogue of Henry's law is obeyed by extrapolating to half-loading with one of the ions. The results satisfy the requirement of additivity and are in good agreement with known values.     

Predicting carbon content in illitic clay fractions from surface area, cation exchange capacity and dithionite-extractable iron

We used the specific surface area (SSA), the cation exchange capacity (CEC) and the content of dithionite‐extractable iron (Fe_d) to predict the content of organic carbon in illitic clay fractions of topsoils from loess. We determined SSA (BET‐N₂ method) and CEC of clay fractions after removing organic C or reducing oxides or both. The CEC and the SSA of the carbon‐ and oxide‐free clay fraction explained 56% and 54% of the variation in C content, respectively. The Fe_d content of the clay fractions was strongly and negatively related to the C content, and with the SSA of the carbon‐free clay fraction it predicted C content almost completely (R² = 0.96). The results indicate that the amount of cations adhering to the silicate clay minerals and the size of the silicate mineral surface area are important properties of the mineral phase for the storage potential of C. The reason for the negative relation between iron oxides and C content remains unclear.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.     

Evaluation of ferrolysis in soil formation

The concept of ferrolysis as defined in the 1970s by Brinkman and co‐workers is mentioned in the recent literature as a dominant process to explain clay disintegration, interlayering of clay minerals, and strong texture contrast of duplex soils, in which bleaching and mottling are predominant features. Ferrolysis is based on biochemical reduction of free iron(III) oxides to Fe²⁺ and re‐oxidation of Fe²⁺ during alternating reducing and oxidizing conditions in the soil. The acidity produced during the oxidation is assumed to release cations from silicates which results in the destruction of clay minerals. A detailed analysis of data from chemical analyses, laboratory experiments, and mineralogical and micromorphological investigations, which have been considered to sustain the ferrolysis theory, has been carried out. Some soils in Belgium and France, which have been considered to be formed mainly by ferrolysis, show strong textural contrast or albeluvic features. It has been shown that the development of these soils is due to clay translocation rather than to clay destruction by ferrolysis. Fine quartz and chlorite, assumed to be secondary minerals formed during ferrolysis, are more likely formed by disintegration of larger quartz and chlorite particles.     

POTASSIUM-CALCIUM EXCHANGE EQUILIBRIA IN SOILS: THE LOCATION OF NON-SPECIFIC (GAPON) AND SPECIFIC EXCHANGE SITES

Several studies (e.g. Bolt et al., 1963; Beckett, 1964a) of the exchange equilibria between K and Ca on soil colloids or pure clay minerals have drawn attention to the presence of sites with different affinities for K. There is so far no evidence to indicate the location of sites with the highest affinity, though several workers (e.g. van Schouwenburg and Schuffelen, 1963) have assumed that they lie on the edge-faces of stacks of clay plates, or in the spaces between the expanded leaves of partially weathered stacks of clay plates. Earlier work has resolved the K: Ca exchange isotherms of soils and clays into a curved part at low values of aK/√aCa, attributed to exchange at sites with a high specific affinity for K, and an upper linear part commonly described by the Gapon equation and attributed to non-specific sites. The present work on soil clays and clay minerals shows that Na hexametaphosphate or changes in pH affect the curved but not the linear part; cetyl trimethyl ammonium bromide and changes in the amount or charge of exchangeable Al affect the linear but not the curved part of the isotherms. At low pH, the linear but not the curved part of the kaolinite isotherm obeys Schofield's Ratio Law. Grinding has more effect on the curved than on the linear part. So the specific sites are attributed to the edges or peripheral interstices of stacks of clay plates, and the non-specific sites to their planar surfaces. The specific sites take up K more slowly from solution than the non-specific sites. The isotherms of completely dispersed bentonites have no curved part. The specific sites are attributed to the wedge-shaped interstices opened between clay plates by weathering, from which exchange is diffusion-controlled. Added organic cations reduce the numbers of both kinds of site; peroxide treatment increases them. This paper confirms that the exchange sites with highest affinity for K are indeed associated with the edges, rather than the faces, of stacks of clay plates.     

Arabinogalactan proteins are incorporated in negatively charged coffee brew melanoidins

The charge properties of melanoidins in high molecular weight (HMw) coffee brew fractions, isolated by diafiltration and membrane dialysis, were studied. Ion exchange chromatography experiments with the HMw fractions showed that coffee brew melanoidins were negatively charged whereas these molecules did not expose any positive charge at the pH of coffee brew. Fractions with different ionic charges were isolated and subsequently characterized by means of the specific extinction coefficient (K(mix 405nm)), sugar composition, phenolic group content, nitrogen content, and the arabinogalactan protein (AGP) specific Yariv gel-diffusion assay. The isolated fractions were different in composition and AGP was found to be present in one of the HMw fractions. The AGP accounted for 6% of the coffee brew dry matter and had a moderate negative charge, probably caused by the presence of uronic acids. As the fraction that precipitated with Yariv was brown (K(mix 405nm) = 1.2), compared to a white color in the green bean, it was concluded that these AGPs had undergone Maillard reaction resulting in an AGP-melanoidin complex. The presence of mannose (presumably from galactomannan) indicates the incorporation of galactomannans in the AGP-melanoidin complex. As the uronic acid content in the more negatively charged melanoidin-rich, AGP-poor HMw fractions decreased, it was hypothesized that acidic groups are formed or incorporated during melanoidin formation.     

Chemistry of soil aluminum

Abstract

Better understanding of soil aluminum has had dramatic effects on the interpretation of many aspects of soil chemistry. Aluminum is a Group III element, metallic in nature, and exhibits both ionic and cuvaient bonding. It is the most plentiful of all metallic cations of the earth's crust. It is released from octahedral coordination with oxygen in minerals by weathering processes. Once released, the trivalent Al ion assumes octahedral coordination with six OH₂ groups each of which dissociates a H ion in sequence as pH increases. The resulting hydroxy‐Al ions are absorbed to the cation exchange capacity of the soil. Here they polymerize on charged surfaces and in the interlayers of the clay minerals obstructing both the contraction of the clay lattice and the exchange of cations. Soluble Al is toxic to most plants, and reacts readily with soluble phosphates converting them to relatively insoluble and plant‐unavailable forms. Adsorbed and polymerized aluminum affects actual lime requirements of soils by its acidic nature and indicated lime requirements by its effect on the buffers of the lime requirement test. The level of exchangeable Al has been suggested as an Index of lime requirement of acid soils, but this may be an adequate Index for liming only on highly weathered soils.     

CLAY MINERAL DISTRIBUTION AND ORIGIN IN THE SOIL TYPES OF ISRAEL

The mineralogical composition of clays (< 2μm) in representative profiles of all soil types of Israel was investigated. The soils were classified according to their clay mineral assemblages into three groups. I. Montmorillonitic soils. Montmorillonite is the dominant mineral and exceeds 65 per cent of the total minerals found; each of the other minerals comprises less than 15 per cent. 2. Montmorillonitic-kaolinitic soils. The soil clay fractions contain 50-60 per cent montmorillonite and 15-25 per cent kaolinite, generally adding up to more than 75 per cent of the clay fraction. 3. Montmorillonitic-calcitic soils. The clays contain more than 10 per cent calcite. Montmorillonite is the dominant clay mineral (except for one soil type, mountain rendzina, where calcite is dominant). The first and second assemblages are typical of the soils of the Mediterranean zone, whereas the soils of the desert zone are characterized by the third assemblage. The origin of montmorillonite, kaolinite, and illite, the three main clay minerals, was found to be detritic, as was the origin of palygorskite which was mainly found in the calcite rich soils of the desert zone. The cation exchange capacity of montmorillonite seems to be higher under higher precipitation. Montmorillonite content and cation exchange capacity of the clays were found to be highly correlated. The carbonate content of the clay fraction and the amount of carbonate in the soil were also highly correlated.     

Effect of soil composition on adsorption of lead as reflected by a study on a natural forest soil profile

The adsorption characteristics of lead on each genetic horizon of a natural brown forest soil profile were studied to recognize the possible immobilizing effect of a mineralogical diverse soil profile in the case of a possible lead contamination. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate and organic matter free variant. TEM-EDS analyses were performed to characterize the adsorption capacity of individual mineral phases. The most important lead adsorbents in order of importance are the organic matter, the clay minerals, and the iron oxides. The most significant process is the ion exchange of calcium by lead with the respect to adsorption. The organic matter adsorbs more lead than clay minerals, and clay fractions adsorb more lead as compared to the whole soil samples. Among mixed layer clay minerals, those containing swelling component have the highest lead adsorption capacity, but the exact distinguishing of the individual clay mineral particles with the respect to their adsorption capacity is not possible. The calcite influences the lead adsorption through its buffering capacity: high calcite content results in lead precipitation. Soils characterized by high amount of organic matter, swelling clay mineral accumulation horizon and calcareous subsoil are suitable medium to immobilize a significant lead pollution.     

CLAY DISPERSION IN TYPICAL SOILS OF NORTH CAMEROON AS A FUNCTION OF PH AND ELECTROLYTE CONCENTRATION

Knowledge of clay dispersion behaviour [which is highly influenced by ion concentration in the aqueous phase and by related surface charge (SC) of colloids] is important for rating soil erosion risk (by water). It can also be useful for improving soil management systems. Clay fractions separated from samples of the A‐horizon of a Vertisol, Ultisol and Oxisol were collected, representing typical soils of North Cameroon. These soils were very different in physicochemical and mineral parameters. The effect of pH and the multivalent ions Ca²⁺, SO₄²⁻ and PO₄³⁻ on SC and dispersion characteristics were determined. The water dispersible clay was found to be higher in the Vertisol and Ultisol than in the Oxisol, indicating that the <2 µm fractions from the Vertisol and Ultisol are more dispersible than that from the Oxisol. The clay dispersion ratio together with the dispersion ratio were found to be in good agreement with water dispersible clay and are negatively correlated with the amount of organic matter and dithionite citrate bicarbonate soluble Fe and Al. Generally, SC of the <2 µm fraction was found to be negative when the pH was in the region of 3 to 9; thus the absolute value is highly pH‐dependent. At pH 6 and 8, CaCl₂, Na₂SO₄ and Na₂HPO₄ additions had antagonistic effects on SC: Ca²⁺ increased SC, whereas SO₄²⁻ and PO₄³⁻decreased SC indicating the adsorption of positively as well as negatively charged multivalent ions by soil colloids. Along with the increase of SC, there was a fall in repulsive forces and formation of Ca‐bridges, the addition of Ca²⁺ induced flocculation more rapidly than SO₄²⁻ and PO₄³⁻ amendments. Copyright © 2011 John Wiley & Sons, Ltd.