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1.
The retention of NH4+ and Ca2+ on soil and weathered pumice samples containing constant and/or variable charge components was measured in different NH4CI-CaCl2 solutions. The NH4+/Ca2+ selectivity of each sample was evaluated using a quotient of the partition of NH4+ on the exchange sites and in the solution relative to that of Ca2+. It increased with decreasing pH and increasing NH4Cl-CaCl2 concentration for a given equivalent fraction of NH4+ in the solution. These effects were quantitatively explained in terms of the changes of NH4+ and Ca2+ concentrations in the solution and in the diffuse double-layer of the ion-exchange material as predicted by the law of mass action and the electric double layer theory. The NH4+/Ca2+ selectivity of different exchange materials showed a similar variation among their exchange sites and increased in the order humus, allophane and imogolite (Si/Al ratio 0.5) < allophane (Si/Al ratio 1.0), montmorillonite < vermiculite, illite < halloysite. The origin of negative charge, the steric features around the exchange sites and clay-humus interaction are suggested as being important in determining the NH4+/Ca2+ selectivity.  相似文献   

2.
The interactions of potassium and calcium ions with two variable charge soils and one constant charge soil were examined by measuring the pK-0.5pCa value with two ion-selective electrodes, together with measurements of single ion activities. The constant charge soil showed a much higher preference for calcium relative to potassium than the variable charge soils. The relative affinities of potassium, calcium, sodium and aluminum ions with exchange sites were not constant, but were a function of surface properties of the soil. pH affected the pK-0.5pCa value in both the variable charge soil and the constant charge soil. The strong competition of aluminum ions for exchange sites was the major cause of the higher preference of soils for calcium ions relative to potassium ions at low pH. The pK-0.5pCa value was always smaller in sulfate systems than in chloride systems, with the difference more distinct in variable charge soils. In addition to an initial fast reaction, some potassium ions were immobilized at later times, even for the highly weathered variable charge soil.  相似文献   

3.
Abstract

A simple and precise method for determination of surface charge density of soils is described. It involves saturating the negative and positive exchange sites with NH+ 4 and NO 3 ions, respectively, removing the excess solution by centrifugation, and determining the ions on the exchange sites by a steam distillation method. Results showed that the concentration and type of saturating ions and the extractant used significantly affected the surface negative charge densities. The average value of surface negative charge densities of 10 surface soils from Iowa, Chile, and Costa Rica by the proposed method agreed closely with that obtained by the original method proposed by Schofield in 1949 (14.6 vs. 13.7 cmol(‐) kg‐1 soil). The advantages of the proposed method are no need for the laborious extraction steps and simplicity of the steam distillation method for determination of NH+ 4 and NO 3 in soil samples.  相似文献   

4.
The dissolution of a reactive phosphate rock (Gafsa, GPR) was evaluated in a range of UK soils which varied considerably in calcium (Ca) status and in a soil that had been amended with different amounts of a cation exchange resin (CER) to provide a Ca sink of varying size. As expected, but not apparently previously reported, increasing solution Ca concentration caused a decrease in the dissolution of GPR, consistent with the solubility product principle. At 40 d, the extent of GPR dissolution was correlated more closely with soil solution Ca concentration (r=?0.91) than with either the number of unoccupied exchange sites for Ca or the Ca-exchange capacity (CaEC) of the soil (r=0.61 and r=?0.35, respectively). Unoccupied exchange sites for Ca were only effective in influencing GPR dissolution when solution Ca concentration was sufficiently low (< 1 mmol dm?3) for the sites to be operating on the well-buffered portion of the Ca-exchange isotherm. The combined effects of an initial low solution Ca concentration and the presence of unoccupied Ca exchange sites caused the relationship between GPR dissolution and solution Ca concentration to become curvilinear, whereby the proportion of GPR dissolved at 40 d could be related to the initial soil solution Ca concentration by an exponential equation. A similar interaction was obtained for the relationship between GPR dissolution and CaEC (operating at solution Ca concentrations ≥0.6 mmol dm?3) following the addition of CER to the soil. The effectiveness of the additional sites for Ca in maintaining the product of ionic concentrations below the solubility product of GPR was such that the amount of GPR dissolved at 40 d correlated linearly and strongly (r= 1.00) with the CaEC of the soil-CER mixtures.  相似文献   

5.
This work is the first of several projects concerned with the study of higher-affinity reactions of Cd, Zn and Ni ions with soil clay fractions. Procedures for the separation of sorbed metals into fractions of lower and higher affinity for soil surfaces are described and evaluated.Various concentrations of Cd, Zn and Ni were allowed to react in the presence of 0.01 M Ca(NO3)2 with soil clays for 1 week after stabilization of suspension pH. The adsorbed metals were partitioned by a brief extraction with 0.01 M Ca(NO3)2 and the resultant fractions, called specifically and non-specifically sorbed metals, were measured by radioisotopic procedures.Measured separation factors showed that the fraction of sorbed metals that was desorbed by a rapid Ca(NO3)2 extraction still had a preference, sometimes marked, over Ca on the soil clay fraction. Separation of fractions of sorbed metals on the basis of affinity was reproducible, but the boundary conditions defined by separation factors vary appreciably between adsorbents, with values in the range 3–20 for amounts sorbed equivalent to ≦ 0.05% of cation exchange capacity and for pH values < 7.The proportions of Cd, Zn and Ni bound at high-affinity sites were strongly dependent on experimental conditions of pH, equilibrium time and surface saturation in relation to each soil clay. Hence, comparisons of affinities of trace metals for soils by reliance on measures of total sorption only, without assessing the contribution of lower-affinity forms, may prejudice conclusions and predictions arising from studies of the possible retention of metal pollutants in soils and fixation of micronutrients from fertilizers.  相似文献   

6.
The influence of organic matter in the translocation of metals between soil and soil solution of an acid forest soil Water extracts were prepared from soil samples which were collected from a soil profile showing very little variation in the texture down to a depth of 120 cm and thus only little translocation of clay in the soil profile. The aim of the study was to describe the distribution between soil and soil solution of several metals like Cu, Pb, Cd, Zn, Al and Mn as a function of humic substances, electrolyte concentration and pH. From the experimental results the following hypothesis on the reaction mechanisms involving metals and humus derived substances has been deduced. The metals Cu, Fe, Al and Pb are mobilized through complexation by soluble humus substances in addition to the usual pH dependent desorption and dissolution of hydroxides. This mobilization determines the solution concentration of Cu and Fe at pH > 3.7 and Al and Pb at pH > 4.2. Al, Fe and Pb are complexed selectively by high molecular weight humus derived substances which undergo adsorption on soil mineral surfaces. Cu interacts with low molecular weight humus derived substances which are not easily adsorbed by the mineral surfaces. Zn, Cd and Mn primarily undergo sorption and are thus controlled by pH and electrolyte concentration of solutions because their complexation with humus derived substances seems to be weak or nonexistant. It is further postulated that the humus derived substances mobilize Al3+ and Fe3+ ions. By this, other metals like Cd, Zn, Mn, Ca and Mg can occupy the free exchange sites.  相似文献   

7.
The Ca concentration of the soil solution influences K plant nutrition by its influence on K concentration of the soil solution and on soil buffer power through ion exchange and K release or fixation. The effects of the imposed solution Ca concentration on the estimates of these parameters and on these two phenomena were studied on a loamy soil. Potassium sorption and desorption experiments were conducted for 16 h at five initial Ca concentrations (from 0 to 10?1 M) and followed by the measurement of soil exchangeable K (ammonium acetate extraction). Soil K-Ca exchange properties and the contributions of exchangeable K and non-exchangeable K to K dynamics of the soil-solution system were estimated. The‘Ratio Law’ applied for the medium range of Ca concentrations, i.e. 10?1 M to 10?3 M. But, it failed for some experiments at small initial Ca concentrations (0 M and 10?4 M). This failure went with a decrease of the number of sites of great affinity for K in K-Ca ion exchange and/or a decrease of the amount of K not in exchange equilibrium with Ca but extracted by M ammonium acetate. Release of K increased and fixation of K decreased when Ca concentration increased. The relation between the change in the amount of non-exchangeable K during the experiment and the initial constraint (ø) was curvilinear on the large range of ø investigated. But, this relation was independent of Ca concentration. The K concentration of the solution for which neither sorption of K by the soil nor desorption of K from the soil occurred decreased and the slope of the sorption-desorption curve at this K concentration increased when the solution Ca concentration decreased. These two parameters can be considered the K concentration of the soil solution of the soil and the buffer power of the soil, respectively, only if the initial Ca concentration imposed during the sorption-desorption experiments is close to the Ca concentration of the soil solution of the soil. A predictive model of the soil buffer power based on ion exchange and release-fixation properties is proposed. Despite some discrepancies at very low Ca concentrations (<0·5 mM Ca) when‘Ratio Law’did not apply the agreement between calculated and observed values was good. The model permits the correction of the experimentally obtained buffer power for the bias related to the great solution volume: soil weight ratio commonly used during the sorption-desorption experiments.  相似文献   

8.
Measurements of pH and A1 concentration were made on 10-2 M CaCl2, suspensions of a number of acid soils that had been limed to give 3 range of pH values, and exchangeable A1 and Ca+Mg were determined in 1.0 M NH4Cl extracts. The variation of pH with A1 concentration did not support the theory that pH is controlled by the solubility of Al(OH)3. For some of the soils, proton release on hydrolysis of A13+ions in solution accounted for the pH values, and explained quantitatively the variation of pH with the Ca:Al balance of the exchange complex, taking account of the selectivity coefficient for exchange, Kca→A1 Although Kca→A1 was smaller for soils containing more humus, their pH values were also less than those predicted by the hydrolysis of A13+ in solution, indicating that they contained other sources of protons, presumably the carboxyl groups in humus.  相似文献   

9.
Adsorption of Potassium and Calcium Ions by Variable Charge Soils   总被引:1,自引:1,他引:1  
Interactions of potassium and calcium ions with four typical variable charge soils in South China were examined by measuring pK-0.5pCa value with a potassium ion-selective electrode and a calcium ion-selective electrode,and pK value with a potassium ion-selective electrode.The results showed that adsorption of potassium and calcium ions increased with soil suspension pH,and the tendency of the pK-0.5pCa value changing with pH differed with respect to pH range and potassium to calcium ratio.Adsorption of equal amount of calcium and potassium ions led to release of an identical number of protons,suggesting similar adsorption characteristics of these two ions when adsorbed by variable charge soils.Compared with red soil,latosol and lateritic red soil had higher adsorption selectivities for calcium ion.The red soil had a greater affinity for potassium ion than that for calcium ion at low concentration,which seems to result from its possession of 2:1 type minerals,such as vermiculite and mica with a high affinity for potassium ion.The results indicated that adsorption of potassium and calcium ions by the variable charge soils was chiefly caused by the electrostatic attraction between the cations and the soil surfaces.Moreover,it was found that sulfate could affect the adsorption by changing soil surface properties and by forming ion-pair.  相似文献   

10.
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.  相似文献   

11.
Anion retention is important in highly weathered soils that contain large amounts of iron and aluminium oxides with surfaces of variable charge. Sorption mechanisms retard anionic solute transfer through these soils. We determined the retardation factor for nitrate in highly weathered Ferralsols from New Caledonia from dynamic experiments using a transient‐flow method, and we evaluated the effect of soil solution concentration and organic matter content. A simple method with sectionable tubes was used to determine the nitrate isotherm during non‐steady‐state water flow under unsaturated conditions. The topsoil retarded the movement of nitrate, and the sorption followed a linear isotherm. In subsoils, retardation factors were larger and increased from 1.15 to 2.05 at soil pH as the NO3‐N concentration of the input solution decreased from 71.43 to 0.35 mm , indicative of a non‐linear isotherm. Positive surface charge sites were considered to be of two types: one with strong affinity for nitrate at small concentrations and one with weak affinity for adsorption of nitrate at larger concentrations. This type of isotherm with high‐ and low‐energy sites is similar to those found for oxyanions and heavy metals. The related anion exchange capacity was larger than that usually observed in soils of variable charge. Not all exchange sites were detected with our method, and some sites were obviously not available for nitrate retention.  相似文献   

12.
茶多酚和铜对可变电荷土壤钙镁释放的影响   总被引:1,自引:0,他引:1  
通过批平衡试验,研究茶多酚、铜和体系pH对可变电荷土壤释放钙镁离子的影响。研究发现,铜离子初始浓度为2.0mmol/L,最终体系pH为5.0时,随着茶多酚添加量的增加,可变电荷土壤表面的负电荷增加,土壤表面释放的钙镁离子量减少。茶多酚初始添加量为20 g/kg,最终体系pH为5.0时,随着铜离子初始浓度的升高,可变电荷土壤对铜离子的吸附量增加,铜离子通过与钙镁离子发生离子交换,形成对吸附位点的竞争,从而增加钙镁离子的释放。茶多酚初始添加量为20 g/kg,铜离子浓度为2.0 mmol/L,随着pH的升高,可变电荷土壤钙镁离子释放量下降。在相同pH条件下,茶多酚可以通过自身的吸附增加可变电荷土壤表面负电荷,减少可变电荷土壤钙镁离子的释放量。研究结果可为茶园土壤酸化和污染控制提供参考。  相似文献   

13.
It is hypothesized that episodic introductions of road salt severely disrupt the soil nitrogen cycle at a range of spatial and temporal scales. A field-scale study has confirmed impacts on the nitrogen cycle in soil, soil solution and river samples. There is evidence that ammonium-N retention on cation exchange sites has been reduced by the presence of sodium ions, and that ammonium-N has been flushed from the exchange sites. Increases in soil pH have been caused in naturally acidic uplands. These have enhanced mineralization of organic-N, especially nitrification, leading to a reduction in the mineralizable-N pool of roadside soils. There is evidence to support the hypothesis that organic matter content has been lowered over decades either through desorption or dispersal processes. Multiple drivers are identified that contribute to the disruption of nitrogen cycling processes, but their relative importance is difficult to quantify unequivocally. The influence of road salt on soil and soil solution declines with distance from the highway, but impacts on water chemistry in a local stream are still strongly evident at some distance from the road.  相似文献   

14.
A sample of Harwell soil containing 36 percent fine clay (< 0.3 μm) and 14 per cent coarse clay plus fine silt (0.3–5μm) was separated into fractions, and the K-supplying power of soil and fractions measured by cropping with ryegrass, exchange with Ca resin and double-label isotopic exchange with 42K and 45Ca ions. Mineralogical examination of the fractions coupled with the cropping experiments showed that the K-supplying power of the soil to ryegrass can be explained by the presence of a zeolite, clinoptilolite-heulandite, in addition to the clay minerals, mica, and interstratified illitic smectite, commonly found in a glauconitic clay-rich soil. The 0.3–5 μm fraction, containing much zeolite, has an exchange diffusion coefficient for K ions to Ca resin of 1.8 × 10?16 cm2sec?1 compared with a value of 5.7 × 10?20 for the < 0.3μm fractions in which interstratified illitic smectite is the dominant mineral. Isotopic exchange shows that all Ca ions in fractions < 50μm are isotopically exchangeable. In fractions coarser than 20μm, some of the K ions in felspar and mica were not exchangeable within the duration of the experiments.  相似文献   

15.
The effects of soil pH on sorption of cadmium, zinc, nickel and cobalt were studied by changing the pH of a soil and measuring sorption. Results were compared with published results for effects of pH on sorption of cadmium, zinc and nickel by goethite. In a further experiment, the effects of pH on the uptake of zinc and cobalt by subterranean clover were measured. Effects of pH on sorption were described in terms of the concentration of metal ions required to produce equal sorption. Where the metal ions were incubated with the soil, unit increase in pH decreased the concentration of metal ions required about 10-fold for zinc, about 7-fold for nickel, about 6-fold for cobalt, and about 4-fold for cadmium. When the soil was mixed with a large volume of solution, the effects were similar for zinc and cadmium but slightly smaller for cobalt and slightly larger for nickel. In all cases, the magnitude of the effect varied somewhat with pH. Sorption was greater with a dilute background electroiyte than with a concentrated one and the effects of pH were greater. The effects for soil were smaller than effects of pH on sorption by iron oxides for which unit increase in pH can decrease the required concentration of Zinc 35-fold and cadmium 11-fold. These results are consistent with adsorption of divalent ions on a variable charge surface that is negatively charged. They are not consistent with the adsorption of monovalent metal ions on a variable charge surface. This mechanism requires at least a 10-fold effect of pH. They show that the change in electric potential with change in pH is smaller for reacting surfaces in soil than for goethite. The effects of changing pH on the amounts of zinc and cobalt fertilizer required for equal uptake by plants was even smaller with unit increase in pH, causing a 1.4-fold increase in the amount of fertilizer required, that is, a 1.4-fold decrease in fertilizer effectiveness.  相似文献   

16.
Potassium-calcium exchange equilibria in, and the kinetics of K release from, soil from the Nil and PK treatments of the Saxmundham Experiment, Rotation 1, and the Ga, Ca + K and K saturated panicle size fractions of the soils were investigated. The free energy and enthalpy ot exchange showed K preference in all the solids. Selectivity for K decreased with increasing particle size and pre-treatment with K salts. A comparison of the ‘differential enthalpy of exchange: per cent K saturation’ relationship for the whole soil with those of the particle size fractions suggests that soil dispersion during particle size separation also decreased K selectivity significantly. When related to the mineralogical composition of the soil, the differential enthalpy data suggest that maximum K. selectivity is associated with a vermiculite/smectite component of inter-stratified minerals in the soil. Isotopic exchange using 4sCa on the decalcified solids showed a measurable rate of exchange for the Ca forms of the <0.2 and 0.2–2 /μm fractions. This is attributed to traces of blocking materials (CaCO3 or hydroxy-aluminium polymers), which are removed or rendered porous during treatment with dilute KCl solution, so that isotopic exchange with Ca is then much more rapid. The kinetics of K extraction with a Ca saturated resin, interpreted on the basis of a three-compartment model, suggest that sorbed K and K released by ‘fast’ and slow processes, representing sites of low and high K selectivity, were associated with minera-logically distinct phases in the various particle size fractions.  相似文献   

17.
Abstract

The objective of this study was to determine the effects of pH and ionic strength on the distribution and speciation of zinc (Zn), copper (Cu), and cadmium (Cd) in surface soil samples from two Brazilian Oxisols amended with biosolids. Soils and biosolids were equilibrated in an experimental dual‐chamber diffusion apparatus that permits the soils and biosolids to react through a solution phase via diffusion across a membrane. After equilibrium was reached, soil and biosolids samples were sequentially fractionated to identify various solid forms of Zn, Cu, and Cd. Metal concentrations in the solution phase were determined and mass balance calculated. Equilibrating pH had no major effect on Cu solubility from biosolids and, at pH range from 4 to 7, most Cu remained in the biosolids. Soluble Zn and Cd concentration increased with decreasing pH because of the increased solubility of the biosolids. Copper and Zn were primarily associated with the residual fraction and Fe oxides in one soil, but were primarily associated with chemically unstable fractions, or adsorbed to the surface of oxides, in the other soil. In both soils, Cd was primarily associated with readily bioavailable fractions. The effect of pH on the metal distribution was more evident than the ionic strength effect. Free ions were the predominant metal species in solution, especially at lower pH values.  相似文献   

18.
Competitive adsorption of K and Ca in a Mn oxide (birnessite) system was investigated using a double indicator electrode technique. The data showed that Ca was more competitive than K for adsorption sites on the Mn oxide. The preference of the oxide for Ca over K was partially attributed to the specific adsorption of Ca on the oxide. The extent of the preference did not consistently increase as the amount of K and Ca was continuously added to the system, possibly due to a decrease in the availability of the specific adsorption sites as these sites were increasingly occupied by the added Ca. The pK-0.5pCa value for the system significantly increased when the solution to solid ratio was above 16 (mL g?1). Raising pH caused an increase in the solution K/Ca equivalent activity ratio and a linear decrease in the pK-0.5pCa value, though the influence of the pH on the K/Ca equivalent activity ratio was not substantial until the pH was above 5.23. These results demonstrate an unique interaction of K and Ca on the surface of the Mn oxide, which cannot be solely interpreted by the classical ratio law. This study is of significance in the chemistry of K in soils which have properties of variable charge and specific adsorption of the competitive cations.  相似文献   

19.
Charge characteristics and Cu^2 adsorption-desorption of soils with variable charge(latosol)and permanent charge(brown soil)and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively.The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system,but the opposite trend occurred in the points of zero charge(PZCs).The amount of Cu^2 ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu^2 concentration within a certain range in the equilibrium solution.The amount of Cu^2 ions desorbed with KCl from permanent-charge soil was more than that from variable-charge soil,but the amount of Cu^2 ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil.The increase of PZC of soils with variable or permanent change varied with the increment of Cu^2 ions added.When the same amount of Cu^2 ions was added,the increments of PZC and variable negative surface chargc of permanent-charge soil were different from those of variable-charge soil.  相似文献   

20.
The objective of this study was to investigate possible ways of mobilizing residual fertilizer P as a result of local pH elevation caused by urea hydrolysis. The response of water-soluble P (Pw) and dissolved organic C (DOC) to urea hydrolysis was monitored in three cultivated soils and at two P levels for up to 127–135 d and compared with corresponding changes in soils limed with Ca(OH)2. Hydrolysis of urea was complete in 8–15d during which soil pH increased by 1–1.5 units at the maximum. Subsequently, the pH decreased to or below the original level owing to nitrification. Mobilization of soil P was enhanced substantially in parallel with the increase in pH, the peak Pw occurring simultaneously with the highest pH value. In all urea-treated soils, Pw remained at an elevated level for at least 60d. As compared to urea, elevation of soil pH with Ca(OH)2 had only a minor and inconsistent influence on Pw. In mobilization of soil P, the urea-induced increase in pH and a simultaneous production of NH4+ ions proved to be superior to liming with Ca(OH)2. It was hypothesized that when an acid soil is amended with urea, phosphate is first displaced by OH? ions, resulting in elevated solution P concentrations. A simultaneous dissolution of organic matter contributes to the persistence of high P concentration by competition for sorption sites on Fe and Al oxides, and thus retards the resorption of P.  相似文献   

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