Cation exchange capacity measurements

Abstract

Soil cation exchange capacity (CEC) measurements are important criteria for soil fertility management, vaste disposal on soils, and soil taxonomy. The objective of this research was to compare CEC values for arable Ultisols from the humid region of the United States as determined by procedures varying widely in their chemical conditions during measurement. Exchangeable cation quantities determined in the course of two of the CEC procedures were also evaluated. The six procedures evaluated were: (1) summation of N NH₄OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus BaCl₂ ‐ TEA (pH 8.0) exchangeable acidity; (2) N Ca(OAc)₂ (pH 7.0) saturation with Mg(OAc)₂ (pH 7.0) displacement of Ca²⁺; (3) N NH₄OAc (pH 7.0) saturation with NaCl displacement of NH₄ ⁺; (4) N MgCl₂ saturation with N KCl displacement of Mg²⁺; (5) compulsive exchange of Mg²⁺ for Ba²⁺; and (6) summation of N NH₄OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus N KCl exchangeable AJ. The unbuffered procedures reflect the pH dependent CEC component to a greater degree than the buffered methods. The compulsive exchange and the summation of N NH₄OAc exchangeable cations plus N KCl exchangeable Al procedures gave CEC estimates of the same magnitude that reflect differences in soil pH and texture. The buffered procedures, particularly the summation of N NH₄OAc exchangeable cations plus BaCl₂ ‐ TEA (pH 8.0) exchangeable acidity, indicated inflated CEC values for these acid Ultisols that are seldom limed above pH 6.5. Exchangeable soil Ca and Mg levels determined from extraction with 0.1 M BaCl₂ were consistently greater than values for the N NH₄Oac (pH 7.0) extractions. The Ba²⁺ ion is apparently a more efficient displacing agent than the NH₄ ⁺ ion. Also, the potential for dissolving unreacted limestone is greater for the Ba₂ ⁺ procedures than in the NH₄ ⁺ extraction.     

The effects of feeding byOniscus asellus (Isopoda) on nutrient cycling in an incubated hardwood forest soil

Summary Oniscus asellus produced changes in the nutrients leached from Oie and Oa horizons of a hardwood forest soil. Soil with isopods lost more K⁺ (54%) from the Oie horizon and more Ca²⁺ (25%), Mg²⁺ (40%), and water-extractable S (23%) from the Oa horizon than soil without isopods. In contrast, soils with isopods lost less Ca²⁺ (39076) from the Oie horizon and less dissolved C-bonded S (33%) from the Oa horizon than soil without isopods. In addition, the Oia and Oa horizons exhibited different nutrient dynamics. When isopods were present, the Oa horizon leachates accumulated more Na⁺ K⁺, Ca²⁺, Mg²⁺, NO₃ ^– , water-soluble SO₄ ^2–, and dissolved C-bonded S, and the Oie horizon retained more of these nutrients. The type of leaching solution also had a major effect on nutrients. Leaching with a simulated soil solution resulted in smaller nutrient losses for K⁺ and Mg²⁺ in both horizons and for Na⁺, Ca²⁺, and NO₃ ^– in the Oa horizon than leaching with distilled water.     

Characterization and evaluation of chabazite- and mordenite-rich tuffs,and their mixtures as soil amendments and slow release fertilizers

In the present study, zeolite tuffs of diverse chemistry, mineralogy and origin were characterized and tested for their efficiency as slow release fertilizers (SRF) through a series of leaching tests. Mixtures of zeolite tuffs were created and tested as loamy soil additives, in order to evaluate any synergistic effect on their cation exchange capacity (CEC) and SRF properties. The studied materials were a chabazite-rich tuff (SOR), a mordenite-rich tuff (KIM), 3 mixtures of them (SOR/KIM 30/70, 50/50 and 70/30) and a commercial clinoptilolite-rich tuff (BLG). CEC (sodium acetate method) was 95.7 for BLG, 100.9 for KIM and 92.2 cmol kg^?1 for SOR, while their mixtures displayed intermediate values. SRF values vary, with the SOR/KIM 30/70 exhibiting the slowest NH₄⁺ release in 29 days (1.7%) compared to the control sample (19%). Zeolites promoted PO₄^?3 release, while their selectivity for Mg²⁺ and K⁺ was clearly affected by their different structure and chemistry. BLG exhibited the strongest selectivity for Mg²⁺, having the lowest release (39%). The results demonstrate that mixtures of zeolite tuffs could have a potential use in agricultural processes, by improving parameters like: chemistry, mineralogy, CEC and SRF efficiency, and resulting in the production of a competitive and functional soil additive.     

铁铝氢氧化物对两种土壤和高岭石表面K+和NH4+解吸的影响

Potassium (K) and nitrogen (N) are essential nutrients for plants. Adsorption and desorption in soils affect K+ and NH + 4 availabilities to plants and can be affected by the interaction between the electrical double layers on oppositely charged particles because the interaction can decrease the surface charge density of the particles by neutralization of positive and negative charges. We studied the effect of iron (Fe)/aluminum (Al) hydroxides on desorption of K+ and NH + 4 from soils and kaolinite and proposed desorption mechanisms based on the overlapping of diffuse layers between negatively charged soils and mineral particles and the positively charged Fe/Al hydroxide particles. Our results indicated that the overlapping of diffuse layers of electrical double layers between positively charged Fe/Al hydroxides, as amorphous Al(OH) 3 or Fe(OH) 3 , and negatively charged surfaces from an Ultisol, an Alfisol, and a kaolinite standard caused the effective negative surface charge density on the soils and kaolinite to become less negative. Thus the adsorption affinity of these negatively charged surfaces for K+ and NH + 4 declined as a result of the incorporation of the Fe/Al hydroxides. Consequently, the release of exchangeable K+ and NH +4 from the surfaces of the soils and kaolinite increased with the amount of the Fe/Al hydroxides added. The greater the positive charge on the surfaces of Fe/Al hydroxides, the stronger was the interactive effect between the hydroxides and soils or kaolinite, and thus the more release of K+ and NH + 4 . A decrease in pH led to increased positive surface charge on the Fe/Al hydroxides and enhanced interactive effects between the hydroxides and soils/kaolinite. As a result, more K+ and NH + 4 were desorbed from the soils and kaolinite. This study suggests that the interaction between oppositely charged particles of variable charge soils can enhance the mobility of K+ and NH + 4 in the soils and thus increase their leaching loss.     

Simulated effects of acid deposition on podzolic soils: Consequences of process and parameter aggregation

Solution cation concentrations and base cation leaching were simulated for a homogenous soil block and a soil showing five horizons of a podzolic forest soil. The dynamic model ACIDIC simulated water flow, nutrient uptake for tree growth, and cation exchange between H⁺, Al³⁺, Ca²⁺, Mg²⁺ and K⁺ in forest soil. In the multi-layer simulations exchangeable base cation concentrations changed most in the O horizon. The subsoil had a decisive effect on the pH of the runoff and base cation leaching from the soil. The one-layer model underestimated Ca and Mg leaching and overestimated H⁺ and Al concentrations in the runoff. In the eluvial and the top of illuvial horizon the solution Al / (Ca + Mg) ratio exceeded that in one-layer structure more than 10-fold. Cases with the horizon-specific cation exchange coefficient values and mean coefficient values for all layers showed only minor differences in Al / (Ca + Mg) ratio. The vertical variation in the soil chemical properties should be accounted for even if some details of processes and parameters were unavailable.     

Fixed ammonium and potassium release from two soils

Abstract

Release of native and added K⁺ and NH⁺ ₄ from two soils was monitored during a 166 day incubation/leaching experiment. One soil (Brookston) represented a major soil series In Ontario whereas the other (Harriston) was suspected having a relatively large fixation capacity. Treatments were imposed involving addition of 50 μM g^‐1 soil of K⁺(KCl) or NH⁺ ₄ (NH₄Cl) only or one added after the other on successive days. The addition of either K⁺ or NH⁺ ₄ on day 2 tended to inhibit the release of the other added on day I. Also the addition of either K⁺ or NH⁺ ₄ on day 1 tended to inhibit the sorption or fixation of the other on day 2. The release rate of K⁺ during the 10 to 166 day period was almost constant and not affected by the addition of NH⁺ ₄. Alternatively, the addition of K⁺ on day 2 slowed the release rate of NH⁺ ₄ measured by NO^? ₃ appearance from day 10 to 40 but had no effect thereafter. At the end of the experiment considerably more K⁺ than NH⁺ ₄ was retained suggesting that K⁺ was more firmly fixed. However, the continuing nitrification of NH⁺ ₄ must be contrasted with periodic removal of K⁺ by leaching with 0.01 M CaCl₂ solution since the equilibrium between exchangeable and fixed ions was affected. There were no notable differences between the two soils inspite of a considerable difference in clay content.     

Changes in Chemical Properties of an Oxisol Due to Gypsum Application

The increasing demand for fertilizers and the fact that the world reserves of phosphorus (P) and potassium (K) are depletable make appropriate soil management a critical factor in agriculture. Techniques for the fertilizer use and soil acidity corrective are becoming increasingly necessary to minimize the cost of yield and increase the nutrient efficiency. In view of the aforementioned, the present study aimed to assess the effects of gypsum application on the leaching of cations in the soil profile. A completely randomized design in a 5 × 4 factorial arrangement, with five replicates, was used. The treatments corresponded to five gypsum rates (0, 1, 2, 4, and 8 magnesium (Mg) ha^?1) applied on broadcast of soil and at four depth sampled (0–5, 6–10, 11–15, and 16–20 cm). Gypsum application increased the fertility in depth, with the leaching of cations. There was an increase in soil pH, exchangeable K⁺ and calcium (Ca²⁺), sulfur (S–SO₄^2?), P, boron (B), and manganese (Mn) concentration, cation exchange capacity (CEC), K⁺ and Ca²⁺ saturation, Ca²⁺/Mg²⁺, Ca²⁺/K⁺, and K⁺/(Ca²⁺ + Mg²⁺) ratios, and electrical conductivity in soil depth. On the other hand, there was a decrease in exchangeable Mg²⁺ and potential acidity hydrogen and aluminum (H⁺ + Al³⁺), available silicon (Si), Mg²⁺ saturation, and Ca²⁺/K⁺ and Mg²⁺/K⁺ ratio. These results demonstrate that the gypsum application in an Oxisol with 690 g kg^?1 of clay improves the root system with a significant increase in the soil fertility in the profile.     

Influence of surface‐applied poultry manure on topsoil and subsoil acidity and salinity: A leaching column study

It has been suggested that surface applications of animal manure can ameliorate both top and subsoil acidity. For that reason, the effects of surface incorporation (0–5 cm) of a high rate of poultry manure to an acid soil on pH and exchangeable and soluble Al in the top‐ and subsoil were investigated in a leaching column study. During the experimental period of 108 d, columns received a total of 875 mm with leaching events occurring after 9, 37, 58, and 86 d. Incorporation of poultry manure into the surface 5 cm resulted in a large rise in pH measured in both 1M KCl and in soil solution. This liming effect was attributed primarily to the substantial CaCO₃ content of poultry manure. In the 15–45 cm layer, pH_KCl was not significantly different between poultry manure and control treatments but surprisingly, soil‐solution pH was substantially less in the poultry‐manure treatments. Exchangeable Al was significantly less in poultry manure than in control in all soil layers although the effect was most marked in the 0–5 cm layer. However, although concentrations and activities of monomeric Al (Al_mono), and the proportion of total Al present as Al_mono, in soil solution were lower under poultry manure than in control in the 0–5 cm layer, the reverse was, in fact, the case in lower soil horizons. This was attributed to a soluble‐salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. Indeed, electrical conductivity and concentrations of Ca²⁺, Mg²⁺_, K⁺, and Na⁺ in soil solution were substantially higher in the poultry‐manure than in the control treatments at all soil depths. Poultry‐manure applications also resulted in substantial increases in the concentrations of Ca²⁺_, Mg²⁺_, K⁺, Na⁺, Al_mono, NH , and NO in leachates, particularly at the fourth leaching. It was concluded that although surface application of poultry manure can raise soil pH in the topsoil, increases in soluble‐salt concentrations in soil solution can greatly modify this effect in the subsoil.     

Soil Solution as Affected by Plant Residues and Nitrogen Rates

Cation mobility in acidic soils with low organic‐matter contents depends not only on sorption intensity but also on the solubility of the species present in soil solution. In general, the following leaching gradient is observed: potassium (K⁺) > magnesium (Mg²⁺) > calcium (Ca²⁺) > aluminum (Al³⁺). To minimize nutrient losses and ameliorate the subsoil, soil solution must be changed, favoring higher mobility of M²⁺ (metal ions) forms. This would be theoretically possible if plant residues were kept on the soil surface. An experiment was conducted in pots containing a Distroferric Red Latosol, with soil solution extractors installed at two depths. Pearl millet, black oat, and oilseed radish residues were laid on the soil surface, and nitrogen (as ammonium nitrate) was applied at rates ranging from 0 to 150 mg kg^?1. Corn was grown for 52 days. Except for K⁺ and ammonium (NH₄ ⁺), nitrogen rates and plant residues had little effect upon the concentrations and forms of the elements in the soil solution. Presence of cover crop residues on soil surface decreased the effect of nitrogen fertilizer on Ca leaching. More than 90% of the Ca²⁺, Mg²⁺, and K⁺ were found as free ions. The Al³⁺ was almost totally complexed as Al(OH₃)⁰. Nitrogen application increased the concentrations of almost all the ions in soil solution, including Al³⁺, although there was no modification in the leaching gradient.     

Contribution of separate solid-phase components to the formation of the cation exchange capacity in the main genetic horizons of meadow-chestnut soils

Different types of cation exchange capacity (CEC) and related chemical properties were determined in the main genetic horizons of meadow-chestnut soils in the mesodepressions at the Dzhanybek Research Station of the Institute of Forestry of the Russian Academy of Sciences. In the A horizon, the CEC is mainly due to the organic matter from the clay and coarse fractions, which provides 36% of the soil CEC, and to labile silicates and other clay minerals of the clay fraction. In the Bt horizon, the CEC is mainly provided by the labile minerals of the clay fraction and organic matter of the clay and coarse fractions. The standard soil CEC was found to be significantly higher than the sum of the exchangeable cations in the A horizon and slightly lower than the sum of the exchangeable cations in the Bt and Bca2 horizons. This difference can be related to the fact that the NH₄⁺ ion, which is selectively adsorbed by clay minerals, is used as a displacing cation during the determination of the exchangeable bases, while the Ba²⁺ ion, which is more selectively adsorbed by organic matter, is used during the determination of the standard CEC. In all the genetic horizons, the experimentally determined value of the standard CEC almost coincides with the CEC value obtained by summing the standard CECs of the different particle-size fractions with account for their contents; hence, this parameter is additive in nature.     

Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

Exchangeable cations and CEC determinations of some highly weathered soils

Abstract

Eight methods to determine exchangeable cations and cation exchange capacity (CEC) were compared for some highly weathered benchmark soils of Alabama. The methods were: (1) 1N NH₄OAc at pH 7.0 by replacement (for CEC only), (2) 1N NH₄OAc at pH 7.0 (summation of basic cations plus 1N KCl extractable Al), (3) 1N NH₄OAc at pH 7.0 (summation of basic cations plus exchangeable H⁺), (4) 0.1M BaCl₂ (summation of basic cations plus exchangeable Mn, Fe and Al), (5) Mehlich 1 (summation of basic cations plus 1N KCl extractable Al), (6) Mehlich 1 (summation of basic cations plus exchangeable H⁺), (7) Mehlich 3 (summation of basic cations plus 1N KCl extractable Al), and (8) Mehlich 3 (summation of basic cations plus exchangeable H⁺). The 0.1M BaCl₂ was chosen as the standard method for the highly weathered soils and the other methods compared to it. The results indicated that the 1N NH₄OAc replacement method gave significantly higher CEC values compared to the summation methods. This was probably due to the overestimation of the field CEC caused by measurement of pH dependent cation exchange sites in these soils. There was, however, close agreement between the BaCl₂ method and the summation methods that included extractable Al. The generally good agreement between these summation methods suggests that the Mehlich 1 and Mehlich 3 extractants, commonly used to determine available nutrients in the southeastem USA, may also be used to measure effective CEC of some acid‐rich sesquioxide benchmark soils of Alabama. However, 1N KCl extractable Al as opposed to exchangeable H⁺ should be included in the computation.     

Ammonium fixation by soils saturated with different cations

A laboratory experiment was conducted to study the influence of saturation of specific cations (Ca²⁺, Na⁺, Ba²⁺ and K⁺) on NH₄⁺ fixation in six soil samples with differing physicochemical and mineralogical characteristics. The study showed that their effects were in the following order: Ba²⁺ > Na⁺ > Ca²⁺ > control > K⁺. Treatment with K⁺ apparently removed some NH₄⁺ fixed in the soils prior to sampling. The fixing capacity of the six samples was in the following order: Hoogly > Malda > Haringhata > Canning > Coochbihar > Jalpaiguri. The fixing behaviour was found to parallel the amount of clay present except in one sample.     

Leaching behaviour of a sandy soil amended with natural and NH4+ and K+ saturated clinoptilolite and chabazite

Using saturated or enriched zeolites as slow release fertilizers (SRFs) is considered as an environmental-friendly strategy to enhance use of macronutrients in sandy soils. In this paper, two natural zeolites, clinoptilolite (CLI) and chabazite (CHA) were used as mineral precursors to prepare NH₄⁺/K⁺ saturated clinoptilolite (NH₄⁺/K⁺-CLI) and chabazite (NH₄⁺/K⁺-CHA) as zeolitic nutrient sources (ZNSs). Comparison between the nutrient retention capabilities of these ZNSs was one of the main objectives of this study. The NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA were prepared by soaking the zeolites in NH₄Cl and KCl solutions, respectively. Leaching tests were performed on a sandy soil amended with chemical fertilizers (CFs), NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA to evaluate the leaching properties of them. The results indicated that approximately 84% and 88% of the NH₄⁺ and K⁺ of soils fertilized with CFs were lost during the experiment, respectively. While, the NH₄⁺ and K⁺ losses from soils amended with NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA were 29%, 23%, and 14%, 24%, respectively. Despite of drastic changes in leaching behavior of CFs, nutrient losses from ZNSs were more uniform during the experiments. No significant difference was found between the two studied zeolites on reduction of K⁺ loss. However, CHA was more effective in preventing NH₄⁺ loss during leaching.     

Release of sulphate-sulphur, potassium, calcium and magnesium from spent mushroom compost under field conditions

 The release of SO₄ ^2–-S, K⁺, Ca²⁺ and Mg²⁺ from soil amended with spent mushroom compost (SMC), a byproduct of mushroom production, was measured in leachate from field lysimeters for 30 weeks. Rates of application were 0 and 80 t ha^–1 moist SMC. The SMC contained 1.7% K, 6.5% Ca, 0.4% Mg and 1.2% S (of which 87% is SO₄ ^2–-S), and has a C : S ratio of 26. The break-through curves of ion leaching were polymodal indicating the preservation of soil structure in the lysimeters and its influence on leaching. SO₄ ^2–-S release from SMC was rapid (first-order exponential) and was very similar to the release from a laboratory incubation. The release of K⁺, Ca²⁺ and Mg²⁺ was described using first/zero-order models which were also used to describe their release in the laboratory. The rate and amount of Ca²⁺ release was similar in the field and laboratory, but the amount of K⁺ (and to a lesser extent Mg²⁺) release was less in the field than in the laboratory. Recoveries of SMC applied nutrients in leachate were 80% of S (263 kg ha^–1), 3% of K (14 kg ha^–1), 16% of Ca (284 kg ha^–1) and 37% of Mg (40 kg ha^–1). Little if any S was mineralised. Using SMC could provide plants with S, K, Ca and Mg but there is potential for SO₄ ^2–-S losses via leaching. Received: 7 April 1999     

Nutrient balance in Scots pine (Pinus sylvestris L.) forest. 2. Effects of plant growth and N-deposition on soil solution and leachate chemistry in a lysimeter experiment

Three years of N application to a Cambic arenosol (Typic Udorthent) in two lysimeter series, one with and one without young saplings of Pinus sylvestris L. have produced significant changes in soil solution and leachate chemistry. An application of 30 kg N/ha^*yr^?1 significantly increased NO₃ ^? leaching from the soil. This N load was also sufficient to significantly increase the mobility of the phyto-toxic elements Al³⁺ and Mn²⁺, likewise to increase leaching of the important plant nutrients Ca²⁺, Mg²⁺ and K⁺. At a N load of 90 kg N/ha^*yr^?1 significant increase in NH₄ ⁺ leaching was observed, but total leaching of NH₄ ⁺ was still very low compared to NO₃ ^? leaching. No significant treatment effects were found for SO₄ ^2?, Fe²⁺ and Cl^? in the leachate. Trees grown in the lysimeters buffered the acidifying effect of N application and increased the leachate pH by 0.2 pH units compared to lysimeters without trees.     

Element Budgets in a Forested Watershed in Southern China: Estimation of a Proton Budget

We evaluated the element budgets in a forested watershed in Jiulianshan, southern China. The element input in bulk precipitation was characterized by high depositions of H⁺, NH₄ ⁺, Ca²⁺, and SO₄ ^2?, i.e., 400, 351, 299, and 876 eq/ha/yr, respectively. The outputs of H⁺, NH₄ ⁺, and SO₄ ^2? from the watershed were very low, while those of Ca²⁺ and Mg²⁺ were high, 712 and 960 eq/ha/yr, respectively. The element budgets suggested that i) the net retentions of H⁺, NH₄ ⁺, and SO₄ ^2? in this watershed were high, and ii) the net release of Mg²⁺ from this watershed was high mainly due to weathering. The net release of Ca²⁺ was not so high because of the high atmospheric deposition, while atmospheric deposition of Mg²⁺ was not so high (130 eq/ha/yr). Decrease of acid neutralizing capacity in the soil, i.e., net soil acidification, was caused mainly by the net release of Mg²⁺. Moreover, the net retention of SO₄ ^2? also contributed to soil acidification.     

Calcium-Ammonium Selectivity of Two Benchmark Soils from Botswana as Assessed by Competing Semi-empirical Ion Exchange Equations

The effectiveness of lime-ammonium-nitrate (LAN) as a nitrogen (N) fertilizer in weathered soils depends on the respective selectivity for ammonium (NH₄) and calcium (Ca) by the soils. The study assessed Ca²⁺/NH₄⁺ exchange selectivity of two benchmark soils from Botswana and examined the soil fertility management implications. Surface horizons (0–20 cm) of Pellustert and Haplustalf were equilibrated with 50 ml stock solution containing variable concentrations of Ca²⁺ and NH₄⁺. The Ca²⁺/NH₄⁺ exchange data were fitted into the Vanselow (K_V), Gaines and Thomas (K_GT), Davies (K_D), and the regular solution (K_RS) equations. The selectivity coefficients for the Ca²⁺/NH₄⁺ exchange reactions varied widely with the soil exchanger composition except for the relatively stable K_RS. The selectivity coefficients indicated strong preference for NH₄⁺ to Ca²⁺. The thermodynamic exchange constant, K_ex, was 5.75 ± 1.24 in the Pellustert, indicating preferential adsorption of NH₄⁺, but not in the Haplustalf with K_ex = 0.92 ± 0.27. The free energy for Ca²⁺/NH₄⁺ exchange (ΔG°_ex) was negative (?4.26 ± 0.59 kJ mol^?1) in the Pellustert but slightly positive in the Haplustalf (0.34 ± 0.87 kJ mol^?1). In conclusion, the soil-NH₄ complex was more stable than soil-Ca complex in the Pellustert, indicating LAN as a N fertilizer would have greater potential effectiveness in the Pellustert than in the Haplustalf.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

REACTIONS OF AMMONIA WITH SOIL. I

Heats of adsorption and adsorption isotherms of ammonia gas were measured at 300 K (27 °C) on outgassed soil saturated with Na⁺, K⁺, NH₄⁺, Ca²⁺, or Mg²⁺ ions. The Ca and Mg soils adsorbed apparently one more NH₂ molecule per exchangeable ion than the Na and K soils, mostly in the relative pressure range o to 0.005, but not much more than the NH₄ soil. The initial heat of adsorption was c. 75 kJ mol^-1 on the Ca and Mg soils and c. 60 kJ mol^-1 on the other soils. The results suggest that most NH, is sorbed on these soils through reactions not involving exchangeable cations.