THE EFFECT OF PROLONGED CROPPING ON THE EXCHANGE SURFACES OF THE CLAYS OF BROADBALK FIELD

Earlier studies have shown that the K-(Ca+Mg) exchange isotherms of field soils are not greatly changed by cropping, by additions of K-fertilizer, nor by moderate release of K from fixed forms. The present work shows that very prolonged K-enrichment or depletion in the Broadbalk trials has led to substantial differences between the exchange isotherms of soils from adjacent plots in proportion to the severity of their K-depletion. It is suggested that the changes result from the removal of inter-lamellar K and the consequent increases in the inter-lamellar spacings of parts of the clay crystals, which have increased the extent of the surface areas accessible to K-(Ca+Mg) exchange. It is possible that increases sufficient to cause substantial changes in the exchange isotherms may not be apparent in X-ray diffraction diagrams. Treatment of the K-depleted clays with m CaCl₂ appears to contract the newly expanded parts of the clay crystals, so that exchange on the occluded surfaces is once again too slow to be observed by the procedures used.     

THERMODYNAMICS OF CATION EXCHANGE ON CLAY: Ca-K-MONTMORILLONITE

Radioactive elution and batch equilibration techniques have been used to obtain isotherms at 30° C, 50°C, and 70° C for the exchange of Ca for K on K-montmorillonite. From these the changes in enthalpy and entropy were + 3.87 kcal/mole and +6.7 e.u./mole of Ca respectively. The activity coefficient for K decreased from approximately 1.5 to 1 and for Ca from 1 to approximately 0.5 as the fraction of K on the clay increased from 0 to 1. The results are discussed especially in relation to hydration of the ions and adsorption of water on the clay. The entropy of adsorbed water is inferred, from the results, to be less than that for liquid water.     

CALCIUM: ALUMINIUM EXCHANGE EQUILIBRIA IN CLAY MINERALS AND ACID SOILS1

Exchange reactions between 0.0in AlCl₃ solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al³⁺ and Al(OH)₂⁺ were adsorbed from solutions of pH > 4.0 and Al³⁺ and H⁺ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al³⁺ was strongly preferred to Ca²⁺ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl₃ solution. This proved the validity of the procedure used for calculating exchangeable Al³⁺. K values for Ca:Al exchange favoured Al³⁺ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.     

SODIUM-CALCIUM EXCHANGE EQUILIBRIA IN SALT-AFFECTED AND NORMAL SOILS

Sodium-calcium exchange equilibria in soils with a range of cation exchange capacity (CEC) and surface charge density (SCD), showed calcium preference whether the results were interpreted by a thermodynamic treatment, by an electric diffuse double layer equation, or by an empirical approach. Surface soils preferred Ca more than the corresponding sub-soils, which was mainly attributed to their higher SCDs and organic carbon contents (OC). Significant correlations between OC and (ΔG_o)c_a→_Na, and OC and SCD, suggest the effect of OC on Ca preference to be mainly through increased SCD rather than to specific ion exchange sites. Significant correlations between ΔG_o and SCD, ΔG_o and K_G (the Capon constant), and between corrected SCD and K_G, suggest that all three approaches can be used to describe Na:Ca exchange equilibria in these soils, and that the equilibria are related to intrinsic soil properties.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

THERMODYNAMICS OF K–Ca ION EXCHANGE IN SOILS1

Cation exchange characteristics of the K:Ca saturated forms of five soils were measured at 25°C and 50°C. The rates of isotopic exchange of ⁴²K and ⁴⁵Ca were too fast to be measured except that of ⁴²K in the K:Ca Harwell soil at 25°C. The slower isotopic exchange of K in this soil was attributed to the presence of a zeolite, clinoptilolite. The intra-particle diffusion coefficient, D_i, of K in this soil increased with K-saturation to a maximum at about 40 per cent K, probably because of the ‘blocking’ action of the larger hydrated Ca ions at small K-saturations in clinoptilolite. The CEC, measured by isotopic exchange along the K:Ca adsorption isotherm, decreased with increasing temperature probably because some interlayer spaces collapsed. The standard free energy, enthalpy, and entropy changes were negative for the reaction Ca-soil+2K⁺? 2K-soil+Ca⁺⁺. These results seem to show that K is more strongly bound than Ca by the soil and that the Ca-preference shown by the isotherm at small external electrolyte concentration is caused by entropy changes in solution. Calculated activity coefficients of the exchangeable ions changed with K-saturation similarly at both temperatures but values at 50°C were smaller than at 25°C.     

Quantity/intensity and quantity/potential studies in Na–Ca exchange system in some salt-affected soils

The Q/I curves for Na in the Na–Ca system in some salt-affected soils of Malaprabha and Ghataprabha river valleys lacked the curvature commonly seen in the Q/I curve for potassium. The Malaprabha soils showed lower AR₀^Na , Na_L and BC₀^Na values and higher energies of replacement of calcium by sodium than the Ghataprabha soils; the latter showed a higher affinity for Na than Ca. Two distinct linear parts of the quantity/ potential curves, with different slopes, indicated that Na is held in these soils in two characteristic types of exchange sites having different affinities for sodium. The intersection of the two linear parts corresponded to ESP values in the range of 13 to 64%. The change in the affinity at such a high degree of Na saturation was attributed to the presence of chloritized smectitic clays and sodium-selective zeolite, such as analcite, reported in these soils.     

ION EXCHANGE IN SOILS FROM THE ION PAIRS K–Ca,K–Rb,AND K–Na1

Isotopic exchange of ⁴³K, ²⁴Na, ⁸⁶Rb, and ⁴⁵Ca was used to measure the equilibria between some arable soils and mixed chloride solutions of the ion pairs, K–Ca, K–Rb, and K–Na; the results were interpreted by a thermodynamic treatment of the exchange isotherm (Gaines and Thomas, 1953). The cation exchange capacities of the soils were not constant for the three ion pairs and decreased appreciably with K-saturation in the K–Ca systems because Ca ions were trapped inside the interlayer spaces. That soils preferred K to Na in the K–Na systems and Rb to K in the K–Rb systems, was explained in terms of the standard free-energy changes of the exchange reactions. The activity coefficients of the adsorbed ions, f, changed with K-saturation differently for the three ion pairs: fNa and fCa decreased continuously with increasing K-saturation whereas fRb remained almost constant. However, with increasing K-saturation, fK increased in the K–Na systems, remained unchanged in the K–Rb systems, and first increased and then decreased in the K–Ca systems. These changes are interpreted in terms of the effect of the various ions on the interlayer space of 2 : 1 type clay minerals and the possible distribution of adsorbed ions between the Gouy and Stern layers.     

不同土壤对钾的选择吸附特性

用K Ca交换平衡法对砖红壤、红壤、土、黑土和水稻土K的选择吸附特性研究结果表明 :KG 和KV 系数随着K Ca平衡体系中吸附相中钾与钙比率的变化而改变 ,其曲线特征说明土壤胶体存在着对K亲和力不同的吸附点位。在低钾饱和度时 ,土壤对K的高选择吸附主要归于粘粒矿物楔形区域电荷点位吸附 ,五种土壤楔形区域相对吸附点位顺序为 :黑土 >土 >水稻土 >红壤 >砖红壤 ,该相对吸附点位顺序与土壤含有风化云母和蛭石有关。在高钾饱和度时 ,五种土壤对K的吸附主要发生于粘粒矿物的晶层表面电荷点位 ,粘粒矿物的晶层表面电荷起源也许起决定作用 ,此时KG 选择系数的大小顺序为 :砖红壤 >红壤 >黑土 >土 >水稻土     

Adsorption and binding of amino acids on homoionic montmorillonite and kaolinite

The adsorption and binding of amino acids (aspartic acid, cysteine, glycine, proline and arginine), ranging in molecular weight from 115 to 174 and in isoelectric point from pH 2.8 to 10.8, to montmorillonite [M] and kaolinite [K] homoionic to H, Na, Ca, Zn, La or Al were studied in unbuffered suspensions. Aspartic acid was adsorbed and bound on M homoionic to Ca or Zn but only adsorbed to K homoionic to Ca or Zn. Cysteine was only adsorbed on M homoionic to Al and adsorbed and bound on M homoionic to Zn and on K homoionic to H or Zn. Proline was adsorbed and bound on M homoionic to H, Ca or Zn and on K homoionic to H; it was adsorbed but not bound on both M and K homoionic to Al. Arginine was adsorbed and bound on M homoionic to H or Al and only adsorbed on K homoionic to Ca or Zn. Glycine was not bound on any of the clays. The amounts of amino acid adsorbed and bound (measured by the loss of amino acid from solution) and the class (Giles et al., 1974a and b) of both the adsorption and binding isotherms (retention against ultimate washing with water) were dependent on the type of amino acid, the type of clay, the type of cation predominant on the clays and the basicity or the additional function moiety (e.g. carboxyl, thiol, guanido) of the amino acid. The relative values of the non-standard free energy of clay-amino acid complexes that had isotherms of the Giles C-class were dependent on the type and molecular weight of the amino acid and on the exchangeable cation on the clay.     

Sorption and catalytic hydrolysis of diethatyl-ethyl on homoionic clays

Sorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were studied in aqueous media. The Freundlich sorption coefficient, K(f), measured from isotherms on clay followed the order of Na(+) approximately K(+) > Mg(2+) approximately Ca (2+). Analysis of FT-IR spectra of diethatyl-ethyl sorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for sorption, indicating that sorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by sorption on the clay surface.     

Characterization of clay and fine silt fractions of forest soils by standardized K/Ca sorption isotherms

For better comparison of selectivity characteristics of clay and fine silt fractions sorption isotherms standardized on the cation exchange capacity (CEC) are useful. Due to the effect of the CEC on the sorption isotherms, it is necessary to characterize the exchanging substance with regard to different ion selectivities with standardized potassium/calcium‐(K/Ca) sorption isotherms. This procedure helps to complete the knowledge about the mineralogical composition, which is obtained by X‐ray powder diffractometry. A Haplic Luvisol from boulder marl shows distinct differences in its K selectivity both between different particle size fractions and different horizons. This is partly due to the presence of smectites and vermiculites which are differently distributed within the particle size fractions. The increase of K selectivity with increasing particle diameter in the calcareous C horizon can be attributed to the marginal expansion of mica/illite by Ca²⁺ ions. The K selectivity of individual particle size fractions in different horizons of a Gleyic Cambisol from glacial sand shows major similarities. If pedogenic chlorite is formed, no changes in selectivity characteristics can be observed.     

Potassium additions on ionic equilibria,selectivity and diffusion of cations in soils

Abstract

In a soil system variation in the concentration of any one ion as induced by external addition might bring changes in the ionic‐equilibria, diffusion rate and strength of adsorption of all the ions involved. In four Indiana soils the changes in ionic equilibria, selectivity coefficient and rate of diffusion coefficient for K, Na, Ca and Mg were investigated at 5 levels of added K. The experiments were carried out under controlled laboratory conditions by incubating soils for 3 weeks at 25C. All soils had a greater fraction of Ca and Mg on the exchange phase than in solution, whereas with K and Na the reverse occurred. Potassium adsorption isotherms for all the soils differed indicating the difference in the nature of soil materials involved. Chalmers soil with high clay content with high exchange capacity had high differential buffer value for K. In all the soils, K was adsorbed preferentially to Na at all the levels of K addition, Calcium was adsorbed preferentially to Mg on the Zanesville and Toronto soils. However, in Chalmers and Raub soils, reverse was observed when the level of K addition was exceeded 1.0 and 0.5 me K/100g soil, respectively. This difference in Mg for Ca is attributed to smaller proportion of Mg saturation on the exchange surface. Divalent cations were preferentially adsorbed over monvalent ions. Increasing levels of K addition increased the diffusion rates of all the ions under consideration. The rate of diffusion for K and Ca were governed by concentrations of these ions on the exchange and solution phase.     

THE POTASSIUM STATUS OF MALAWI SOILS

Twenty surface soils from four main Soil Groups in Malawi and their sub-soils were divided into three groups based on cation exchange capacity (group I, CEC < 50; group II, 50–100; and group III > 100μeq g^–1). In each soil group the maximum amounts of K removed by successive extraction with 0.005 M CaCl₂ solution were well related to the potassium potential pK–0.5p(Ca + Mg), exchangeable K, ‘step K’, and the quotient ‘step K’/CR.K, where CR.K is ‘constant-rate’potassium. In Group III soils only, ‘step K’/CR.K values were significantly correlated with pH, clay, and CEC, and this suggested that the soils were relatively rich in K⁺ specific binding sites. In 27 soils from an NPK factorial experiment on tea, the rate of depletion of extractable K reserve increased with ammonium sulphate treatment, whereas K fertilizers tended to off-set significantly (P= 0.001) the depletion of K reserve. The values for the change in free energy ΔG =RT In a_K/ (a_(Ca+Mg)) ^½, ranged from –12 to –16 kJ mol^–1, and field observations showed that tea plants growing on soils having ΔG values less than –15 kJ mol^–1 responded to K fertilizers. The investigation has indicated that heavily cropped soils are likely to show crop responses if the intensive cropping system does not include supplementation of K.     

Adsorption of the Bacillus thuringiensis toxin (Cry1Ab) on Na‐montmorillonite and on the clay fractions of different soils

The adsorption of the toxin from Bacillus thuringiensis (Bt‐toxin), which is synthesized in genetically modified maize, on sterilized Na‐montmorillonite and on H₂O₂‐treated and untreated clay fractions of three soils from different sites were studied. All adsorption isotherms can be described by a linear isotherm. Although all clay fractions from the different soils show nearly the same mineralogical composition, we found different affinities ranging from k = 47.7 to k = 366.7 of the adsorbates for the Bt‐toxin. The H₂O₂‐treated clay fractions show no correlation between the adsorption affinity and the amount of soil organic matter. On the other hand, there is a correlation between the content of organic carbon and the adsorption affinity of the untreated clay fractions. This can be explained by the fact that due to the coatings of soil organic matter on aggregates, the Bt‐toxin polymers are not able to adsorb within the clay aggregates.     

DIFFUSE DOUBLE LAYER THEORY APPLIED TO Na-Ca EXCHANGE EQUILIBRIA IN TEMPERATE AND SEMI-ARID TROPICAL SOILS

A cation exchange equation based on diffuse double layer (DDL) theory was tested on 26 surface and sub-surface soils from 6 field experiments in temperate and semi-arid tropical regions. Sodification (the fraction of total charge on the surface neutralised by the excess of Na⁺ plus the deficit of Cl^?), or the exchangeable Na percentage, ESP, of these soils in relation to SAR, the molar ratio (Na]/[Ca + Mg] ^1/2, was evaluated from the observed data on Na:Ca exchange in two ways, using the DDL equation: (1) by multiplying the surface charge density of the soil with a mean correction factor f (based on the whole isotherm) assuming no interaction between adjacent clay platelets; this predicted the sodification of the soils satisfactorily between 0–30 ESP, though at the highest SAR values (i.e. > 60), predicted ESP values were significantly smaller than the experimental values for 23 of the 26 soils; (2) by assigning values to the extent of interaction Y_d (directly related to the electric potential Ψ_d midway between adjacent clay platelets) over the whole isotherm; Y_d was found to increase by varying degrees in different soils with SAR and ESP. Also in 12 of the 15 pairs of soils compared, the mean value, _d, over the whole Ca-Na exchange isotherm was appreciably larger for surface soils (which had higher surface charge densities) than for the subsoils from the same sites. The suggestion that the Y_d parameter provides a better criterion than the f parameter for characterising and comparing Na:Ca exchange equilibria in contrasting soils is discussed in relation to the effects of soil components.     

Plant Availability Index by Potassium Exchange Isotherms in Selected Rice Soils of Lesser Himalayas

Potassium (K) exchange isotherms (quantity–intensity technique, Q/I) and K values derived from the Q/I relationship provide information about soil K availability. This investigation was conducted to study Q/I parameters of K, available K extracted by 1 N ammonium acetate (NH₄AOc) (exchangeable K plus solution K), K saturation percentage (K index, %), and the properties of 10 different agricultural soils. In addition, the relationship of mustard plant yield response to the K requirement test based on K exchange isotherms was investigated. The Q/I parameters included readily exchangeable K (ΔK₀), specific K sites (K_X), linear potential buffering capacity (PBC^K), and energy of exchange of K (E_K). The results of x-ray diffraction analysis of the oriented clay fractions indicated that some mixed clay minerals, illite clay minerals, along with chlorite/hydroxy interlayered vermiculite and kaolinite were present in the soils. The soil solution K activity ratio at equilibrium (AR₀) ranged from 8.0 × 10^?4 to 3.1 × 10^?3 (mol L^?1)^0.5. The readily exchangeable K (ΔK₀) was between 0.105 to 0.325 cmol_ckg^?1 soil, which represented an average of 88% of the exchangeable K (K_ex). The soils showed high capacities to maintain the potential of K against depletion, as they represented high linear potential buffering capacities (PBC^K) [13.8 to 50.1 cmol_c kg^?1/(mol L^?1)^0.5. The E_K values for the soils ranged from ?3420 to ?4220 calories M^?1. The percentage of K saturation (K index) ranged from 0.7% to 2.2%. Analysis of variance of the dry matter (DM), K concentrations, and K uptake of mustard plants indicated that there were no significant differences among the adjusted levels of K as determined by the exchange-isotherm curve.     

Effect of Al hydroxide polymers on cation exchange of montmorillonite

Al hydroxide polymers (AlHO) can significantly influence the cation exchange behaviour of clays. We have determined the effect of synthesized AlHO on Ca–Na, Zn–Na and Pb–Na exchange for a series of exchanger compositions and two Al loadings at pH 6.0 and an ionic strength of 0.01  m . The preference for Ca on the siloxane surface of the clay–AlHO system (CAlHO) was greater than for the pure clay, and the average K _V (Vanselow selectivity coefficient) was determined to be 2.16 and 1.24, respectively. The selectivity coefficients for the exchange reactions Zn–Na and Pb–Na were not directly determined in CAlHO systems, because heavy-metal ions bind as well to the clay surface as to the AlHO over a wide range of pH. We have estimated the effect of the presence of AlHO on the selectivity coefficients of Zn–Na and Pb–Na exchange by extrapolation of the experimental results of Ca–Na, Zn–Na and Pb–Na exchange for pure clay and Ca–Na exchange for CAlHO. The average K _V was increased by the presence of the AlHO from 1.23 to 2.16 for Zn–Na exchange and from 1.59 to 2.77 for Pb–Na exchange. The increase in the preference for the divalent cations is probably caused by parallel alignment of clay platelets by sorption of AlHO. Increasing the amount of AlHO did not change the selectivity for Ca–Na exchange, and probably the structure of the system or the arrangement of the clay platelets and AlHO particles was not substantially changed. This was supported by the linear reduction of the cation exchange capacity with amount of AlHO present at pH 6.6. It seems likely that the selectivity coefficients for Ca–Na, Zn–Na and Pb–Na exchange that we found apply in naturally occurring montmorillonite–AlHO systems.     

Competitive Effect of Copper,Zinc, Cadmium and Nickel on Ion Adsorption and Desorption by Soil Clays

This study evaluated the effect of competing copper, zinc, cadmium and nickel ions in 0.01 M Ca(NO₃)₂ on heavy metal sorption and desorption by soil clay fractions. Initial Cu addition levels varied from 99 mg kg^-1 to 900 mg kg^-1 and Zn, Cd and Ni levels were 94, 131 and 99 mg kg^-1, respectively. Sorption of Cu conformed to a Freundlich equation. The amounts of metals not displaced by successive 48 h desorption cycles with 0.01 M Ca(NO₃)₂ were considered ‘specifically adsorbed’. Total sorption of Zn and Cd generally decreased in the order: Vertisol > Gleyic Acrisol > Planosol clay. More than 70% of the copper was specifically sorbed. Specific sorption of Zn was depressed by competition with Cu in the three clays investigated. At surface coverages higher than 200 mg Cu per kg of soil clay, zinc sorption in the Planosol and Gleyic Acrisol clays took place at low affinity sites. The exchangeable component of sorbed cadmium accounted for >:60% of the sorption in the Vertisol clay, >70% in the Gleyic Acrisol clay and was almost 100% in the Planosol clay. Nickel was not retained by the Planosol and Gleyic Acrisol clays and was ionexchangeably adsorbed by the Vertisol clay. At the conditions studied, Ni and Cd remain a ready source of pollution hazard.     

Sorption of L-methionine-sulphoximine on humic acids and clay minerals

 The sorption of L-methionine-sulphoximine (MSX) on soil-extracted humic fractions (MW>20,000 Da), and mined clays (kaolinite and montmorillonite) was studied by a reversed-phase high-performance liquid chromatography method. The molecule, acting as an inhibitor of glutamine synthetase activity, was recently used in soil incubation assays for the determination of gross rates of N mineralization. Equilibrium data of MSX adsorbed on humic fractions and clay minerals were described by both the Freundlich and Langmuir sorption isotherms. It was observed that humic fractions were more effective than mined clay minerals in removing MSX from water. Most isotherms were of Langmuir type, indicating a higher affinity of MSX for sorbing sites which become increasingly saturated at higher equilibrium concentrations. Analysis of Langmuir empirical constants revealed that different adsorbing mechanisms took place. Results showed that when MSX is applied in soil incubation assays, sorption of MSX on soil colloids considerably reduces the availability of the inhibitor to target microorganisms, and renders the method unsuitable for the determination of the gross rate of N mineralization, especially when high levels of both organic matter and clay minerals are present in the soil. Received: 19 April 1999