The effects of electrolyte concentrations on calcium-sodium exchange equilibria in two soil samples of india

The effects of total electrolyte concentrations of the equilibrium solutions (t.e.c.) on Ca²⁺-Na⁺ exchange equilibria in two soil samples (high and low in organic matter, clay content and CEC) were studied. Homoionic (Na⁺-saturated) soil samples were equilibrated with solutions having a large range in sodium adsorption ratio (SAR) at 25, 50, 75 and 100 meq. 1^-1 t.e.c. The exchange equilibria data were analysed, using a thermodynamic approach and the selectivity coefficients of Gapon (1933), Vanselow (1932) and Krishnamoorthy et al. (1948) (K_G, K_V and K_KDO). At a given proportion of Ca²⁺: Na⁺ in the equilibrium solution, the development of the exchangeable sodium percentage (ESP) in both soil samples increased with the increase in t.e.c. At a given SAR, the effect of t.e.c. on the development of ESP was less on a soil sample with high organic matter (O.M.), clay content and cation exchange capacity (CEC) than on a soil sample with low O.M., clay content and CEC. The values of exchange selectivity coefficients decreased with the increase in t.e.c, and did not remain constant throughout the exchange isotherm for any of the t.e.c. tried.     

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。     

Interactions of allophane with humic acid and cations

Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl₂ or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl₂ than in NaCl of the same ionic strength. Apparently Ca²⁺ ions were more effective than Na⁺ ions in screening the negative charge on HA. In CaCl₂ the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl₂ sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca²⁺ or Na⁺) for charge balance. The Ca²⁺ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca²⁺ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.     

High monosilicic acid supply rapidly increases Na accumulation in maize roots by decreasing external Ca2+ activity

Both calcium (Ca²⁺) and silicon (Si) improve plant performance under salt (NaCl) stress. Although these two mineral elements share numerous similarities, the information on how their extracellular interactions in the root apoplast affect uptake of sodium (Na⁺) is still lacking. Here, we investigated the effect of high Si supply in the bioavailable form of monosilicic acid (H₄SiO₄) on the activity of Ca²⁺ in the external root solution, and subsequent root uptake and compartmentation of Na in maize (Zea mays L.). In the short‐term experiments (6 h), 14‐d‐old maize plants were exposed to various concentrations of Ca²⁺ at three different pH‐values (6.5, 7.5, and 8.5) and two Si concentrations, i.e., low (1 mM) and high (4 mM) supply of H₄SiO₄. The activity of Ca²⁺ and Na⁺ in the external solution as well as the root concentrations of total and cell sap and BaCl₂‐exchangeble apoplastic fractions of both elements were analyzed. The pH of the nutrient solution affected neither the ion activities nor the root accumulation of both Ca²⁺ and Na⁺. At higher pH values (7.5 and 8.5) the interactions of Ca²⁺ and Si at high Si supply led to a decrease of Ca²⁺ activity and, hence, an increase of Na⁺ : Ca²⁺ activity ratio in the external root solution. Concomitantly, despite the elevated exchangeable apoplastic fraction of both Ca²⁺ and Na⁺, the total and cell sap concentrations were remarkably decreased for Ca²⁺ and increased for Na⁺ by the addition of 4 mM H₄SiO₄. This work demonstrates that at high Si supply extracellular Ca‐Si interactions leading to lowered activity of Ca²⁺ might rapidly compromise the ameliorative effect of Ca²⁺ on Na⁺ accumulation in roots. Practically, Si over‐fertilization of saline and, in particular, sodic soils may further promote the accumulation of Na⁺ in root tissues hours after Si application and, hence, increase a potential risk of Na⁺ toxicity.     

Influence of Aluminum Hydroxide on Potassium Release from Two Colombian Soils

Abstract

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non‐exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2∶1 clay minerals and High Terrace with predominantly 1∶1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl‐Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K₂O, respectively. They were used either untreated or prepared by adding AlCl₃ and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10 mM NH₄OAc at pH 7.0 and 10 mM CaCl₂ at pH 5.8 for 120 h at 6 mL h^?1 to examine the release of Kex and Knex. In the untreated soils, NH₄ ⁺ and Ca²⁺ released the same amounts of Kex from Caribia, whereas NH₄ ⁺ released about twice as much Kex as Ca²⁺ from High Terrace. This study proposes that the small ionic size of NH₄ ⁺ (0.54 nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca²⁺ (0.96 nm) cannot have access. As expected for a soil dominated by 2∶1 clay minerals, Ca²⁺ caused Knex to be released from Caribia with no release by NH₄ ⁺. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca²⁺ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl₃ which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH₄ salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.     

THERMODYNAMICS AND THERMOCHEMISTRY OF THE EXCHANGE REACTION BETWEEN NH4+ AND Mn2+ IN A MONTMORILLONITE CLAY

The exchange reaction between NH₄⁺ and Mn³⁺ was studied on a montmorillonite clay at several temperatures and different ionic strengths. Manganese was preferred to ammonium; this preference increased with the temperature and dilution of the dialysate. Comparison with published data concerning exchanges involving NH₄⁺ and the alkaline-earths showed that in the sequence of increasing selectivity: Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺, Mn²+ lies between Mg²⁺ and Ca²⁺. The enthalpy change was measured calorimetrically and calculated by application of the van't Hoff law to the temperature coefficient of the equilibrium constants. Both values were in good agreement. The excellent recoveries of Mn²⁺ at the end of the exchange reaction and the constancy of the cation exchange capacity over the whole range of surface composition ruled out the possibility of significant adsorption in the MnOH⁺ form. The behaviour of manganese was very similar to that of the alkaline-earth cations.     

Sodium‐calcium interactions with growth,water, and photosynthetic parameters in salt‐treated beans

Calcium (Ca²⁺) amelioration of the plant's growth response to salinity depends on genetic factors. In this work, supplemental Ca²⁺ did not improve growth in Phaseolus vulgaris L. cv. Contender under high‐saline conditions and negatively affected several physiological parameters in nonsalinized plants. The response to supplemental Ca²⁺ was examined using plants grown in 25% modified Hoagland solution at different Na⁺ : Ca²⁺ ratios. In control plants (1 mM Ca²⁺; 1 mM Na⁺) surplus Ca²⁺ (4 or 10 mM) was associated with stomatal closure, decrease of hydraulic conductivity, sap flow, leaf specific dry weight, leaf K⁺ and leaf Mg²⁺ concentrations, and inhibition of CO₂ assimilation. Leaf water content was enhanced, while water‐use efficiency and dry matter were unaffected during the 15 d experimental period. The Ca²⁺ effect was not cation‐specific since similar results were found in plants supplied with high external Mg²⁺ or with a combination of Ca²⁺ and Mg²⁺. Relative to control plants, salinization (50 and 100 mM NaCl) caused a decrease in dry matter, hydraulic conductivity, sap flow, leaf Mg²⁺ activity, and inhibition of stomatal opening and CO₂ assimilation. However, NaCl (50 and 100 mM NaCl) enhanced leaf K⁺ concentration and water‐use efficiency. At 100 mM NaCl, leaf water content also significantly increased. Supplemental Ca²⁺ had no amelioration effect on the salt‐stress response of this bean cultivar. In contrast, the 50 mM–NaCl treatment improved stomatal conductance and CO₂‐assimilation rate in plants exposed to the highest Ca²⁺ concentration (10 mM). Phaseolus vulgaris is classified as a very NaCl‐sensitive species. The similarities in the effects caused by supplemental Ca²⁺, supplemental Mg²⁺, and NaCl salinity suggest that P. vulgaris cv. Contender has a high non‐ion‐specific salt sensitivity. On the other hand, the improvement in gas‐exchange parameters in Ca²⁺‐supplemented plants by high NaCl could be the result of specific Na⁺‐triggered responses, such as an increase in the concentration of K⁺ in the leaves.     

不同白榆品系对滨海盐碱地的改良效果及盐分离子的分布与吸收

为揭示不同白榆(Ulmus pumila L.)品系对滨海盐碱地土壤盐分的改良作用及盐分离子在土壤-白榆系统中的分布与吸收特征,筛选适宜在滨海盐碱地造林的耐盐白榆品系,以中度盐渍化生境下4年生的6种白榆品系(1,5,28,30,46,105号)为试验材料,采用野外取样与室内测试相结合的方法,研究了Na+、K+、Ca2+、Mg2+等盐离子在土壤及白榆品系各器官(根、茎、叶)中的分布特征。结果表明:(1)白榆可降低滨海盐碱地土壤中盐离子及全盐含量,不同白榆品系较对照的土壤全盐含量降低了55.0%～63.1%,30号白榆降幅最大。(2)不同白榆品系将Na+、K+、Ca2+、Mg2+优先积累到叶中,且叶中维持较高的K+/Na+、Ca2+/Na+、Mg2+/Na+比值,不同白榆品系通过建立新的离子平衡以适应盐胁迫环境。(3)不同白榆品系的离子吸收选择性系数均为SK,NaSCa,NaSMg,Na,其对K+的吸收选择性大于对Ca2+、Mg2+吸收选择性;种内差异导致不同白榆品系对Na+、K+、Ca2+、Mg2+吸收选择能力不同,28号白榆根系对K+的吸收性最强,5号白榆根系对Ca2+、Mg2+的吸收性最强。     

Driving forces for sodium removal during phytoremediation of calcareous sodic and saline–sodic soils: a review

Abstract. Sodic and saline–sodic soils are characterized by the occurrence of sodium (Na⁺) at levels that result in poor physical properties and fertility problems, adversely affecting the growth and yield of most crops. These soils can be brought back to a highly productive state by providing a soluble source of calcium (Ca²⁺) to replace excess Na⁺ on the cation exchange complex. Many sodic and saline–sodic soils contain inherent or precipitated sources of Ca²⁺, typically calcite (CaCO₃), at varying depths within the profile. Unlike other Ca²⁺ sources used in the amelioration of sodic and saline‐sodic soils, calcite is not sufficiently soluble to effect the displacement of Na⁺ from the cation exchange complex. In recent years, phytoremediation has shown promise for the amelioration of calcareous sodic and saline–sodic soils. It also provides financial or other benefits to the farmer from the crops grown during the amelioration process. In contrast to phytoremediation of soils contaminated by heavy metals, phytoremediation of sodic and saline–sodic soils is achieved by the ability of plant roots to increase the dissolution rate of calcite, resulting in enhanced levels of Ca²⁺ in soil solution to replace Na⁺ from the cation exchange complex. Research has shown that this process is driven by the partial pressure of CO₂ (P_CO2) within the root zone, the generation of protons (H⁺) released by roots of certain plant species, and to a much smaller extent the enhanced Na⁺ uptake by plants and its subsequent removal from the field at harvest. Enhanced levels of P_CO2 and H⁺ assist in increasing the dissolution rate of calcite. This results in the added benefit of improved physical properties within the root zone, enhancing the hydraulic conductivity and allowing the leaching of Na⁺ below the effective rooting depth. This review explores these driving forces and evaluates their relative contribution to the phytoremediation process. This will assist researchers and farm advisors in choosing appropriate crops and management practices to achieve maximum benefit during the amelioration process.     

Effect of water quality on exchange phase — solution phase behavior of three soils

The effect of total electrolyte concentration (TEC) and sodium adsorption ratio (SAR) of water on ESR‐SAR relationships of clay (Typic Haplustert), clay loam (Vertic Haplustept) and silt loam (Lithic Haplorthent) soils was studied in a laboratory experiment. Twenty four solutions, encompassing four TEC levels viz., 5, 10, 20, and 50 mmol_c l^—1 and six SAR levels viz., 2.5, 5, 10, 15, 20, and 30 mmol^1/2l^—1/2 were synthesized to equilibrate the soil samples using pure chloride salts of calcium, magnesium, and sodium at Mg:Ca = 1:2. SAR of equilibrium solution decreased as compared to the equilibrating solution and more so in waters of low salt concentration and high SAR. At low electrolyte concentration, high SAR values were not attained in the equilibrium solution because of addition of calcium and magnesium from the mineral dissolution and from the exchange phase. Irrespective of TEC, exchangeable sodium in all the soils increased by about 4.5 to 5‐fold and irrespective of SAR, it increased by about 1.4‐ to 1.8‐fold. A positive interaction of TEC and SAR influenced the ESP build‐up and CEC played a major role in the visual disparity in sodication of these soils. At higher TEC levels, considerable increase in ESP was observed when it was corrected for anion exclusion and more so in silt loam followed by clay loam and clay soils. The values for Gapons' constant were in the range 0.0110—0.0176, 0.0142—0.0246, and 0.0189—0.0344 mmol^—1/2l^1/2 in clay, clay loam, and silt loam soils, respectively. Increase in TEC from 5 to 50 mmol_c l^—1 resulted in 5.84, 8.33, and 9.77 % decrease in Gapons' constant of clay, clay loam, and silt loam soils, respectively. The soils exhibited differential affinity for Ca²⁺, Mg²⁺ or Na⁺ under different quality waters. Regression coefficients of ESR‐SAR relationship were lower for low TEC as compared with high TEC waters. The exchange equilibrium was strongly affected by TEC of the solution phase. Variation in soil pH was gradual with respect to TEC and SAR of equilibrating solution and no sharp change was observed. Soluble salt concentration was doubled upon equilibration with low salt waters at all SAR levels in all the soils. However, the salt concentration remained unchanged upon equilibration with high salt waters. Considering pH 8.5 a boundary between soil salinity and sodicity, ESP values attained at TEC 5 mmol_c l^—1 were 7.34, 8.02, and 14.32 for clay, clay loam, and silt loam soils, respectively.     

Phosphate adsorption by Na−, Mg− and Ca−saturated soil clays

Phosphate adsorption by the homoionic clay (Na, Ca, Mg) of three soils with widely varying mineralogy obeyed the Langmuir isotherm. The Langmuir constants b and k were a function both of the nature of the dominant clay mineral present and of the saturating cations following the order: Ca⁺⁺ ? Mg⁺⁺ ? Na⁺. This order was in agreement with those predicted by the diffuse double layer theory. The sample having montmorillonite when saturated with sodium, exhibited a negative adsorption of phosphorus which changed to a large positive adsorption in the presence of 0.1 N NaCl; It was concluded that the exchangeable cations influenced the extent of P adsorption by controlling the accessibility of the edge clay surfaces to phosphate ions.     

Proton release by N2‐fixing plant roots: A possible contribution to phytoremediation of calcareous sodic soils

With a world‐wide occurrence on about 560 million hectares, sodic soils are characterized by the occurrence of excess sodium (Na⁺) to levels that can adversely affect crop growth and yield. Amelioration of such soils needs a source of calcium (Ca²⁺) to replace excess Na⁺ from the cation exchange sites. In addition, adequate levels of Ca²⁺ in ameliorated soils play a vital role in improving the structural and functional integrity of plant cell walls and membranes. As a low‐cost and environmentally feasible strategy, phytoremediation of sodic soils — a plant‐based amelioration — has gained increasing interest among scientists and farmers in recent years. Enhanced CO₂ partial pressure (P_CO2) in the root zone is considered as the principal mechanism contributing to phytoremediation of sodic soils. Aqueous CO₂ produces protons (H⁺) and bicarbonate (HCO₃^‐). In a subsequent reaction, H⁺ reacts with native soil calcite (CaCO₃) to provide Ca²⁺ for Na⁺ Ca²⁺ exchange at the cation exchange sites. Another source of H⁺ may occur in such soils if cropped with N₂‐fixing plant species because plants capable of fixing N₂ release H⁺ in the root zone. In a lysimeter experiment on a calcareous sodic soil (pH_s = 7.4, electrical conductivity of soil saturated paste extract (EC_e) = 3.1 dS m^‐1, sodium adsorption ratio (SAR) = 28.4, exchangeable sodium percentage (ESP) = 27.6, CaCO₃ = 50 g kg^‐1), we investigated the phytoremediation ability of alfalfa (Medicago sativa L.). There were two cropped treatments: Alfalfa relying on N₂ fixation and alfalfa receiving NH₄NO₃ as mineral N source, respectively. Other treatments were non‐cropped, including a control (without an amendment or crop), and soil application of gypsum or sulfuric acid. After two months of cropping, all lysimeters were leached by maintaining a water content at 130% waterholding capacity of the soil after every 24±1 h. The treatment efficiency for Na⁺ removal in drainage water was in the order: sulfuric acid > gypsum = N₂‐fixing alfalfa > NH4NO3‐fed alfalfa > control. Both the alfalfa treatments produced statistically similar root and shoot biomass. We attribute better Na+ removal by the N₂‐fixing alfalfa treatment to an additional source of H⁺ in the rhizosphere, which helped to dissolve additional CaCO₃ and soil sodicity amelioration.     

Clay Dispersion of Hardsetting Inceptisols in Southeastern Nigeria as Influenced by Soil Components

Abstract

Hardsetting soil properties are undesirable in agricultural soils because they hamper moisture movement and soil aeration. The soils of the floodplain of Niger River in eastern Nigeria hardsets upon drying, following dispersion, puddling, and slaking during the waterlogged period. Ten soil samples collected from a depth of 0–20 cm were analyzed for their properties. The soils are classified as Fluvaquentic Eutropepts or Dystric Gleysol (FAO). The objective was to investigate the influence of some soil properties on water‐dispersible clay (WDC) of the soils, which is the precursor of the hardsetting process. The total clay content (TC) correlated significantly with WDC (r=0.94??), whereas the water‐dispersible silt (WDSi) was higher than its corresponding total silt content. The WDC showed a positive correlation with dithionite extractable Fe (Fed), Al (Ald), and oxalate extractable Fe (Feo) (r=0.75?, 0.89??, and 0.76? respectively). Exchangeable Mg²⁺ correlated significantly with WDSi (r=0.70). Principal component analysis of the soil variables indicates that 15 soil components, which influence WDC as hardsetting properties, were reduced to 5 orthogonal components. The parameters that influence hardsetting properties are exchangeable Na⁺, K⁺, Ca²⁺, Mg²⁺, Fed, Alo, and Feo. Other soil properties are kaolinite, smectite, illite, and WDC, including soil organic carbon (OC), electrical conductivity (EC), and ESP. Therefore, those soil properties, which explain hardsetting characteristics most, are exchangeable Na⁺, Fed, OC, Mg²⁺, and Alo. There are negative consequences on the erodibility, runoff, infiltration and tillage of the soils at both submerged and dry conditions due to clay dispersion, low OC, and hardsetting behavior of the soil.     

Growth and ion uptake of four Brassica species as affected by Na/Ca ratio in saline sand culture

The influence of supplemental Ca² in saline nutrient solutions on germination, growth, and ion uptake of four Brassica species, B. campestris L., B. carinata, A.Br., B. juncea (L.) Czern. and Coss., and B. napus L. was studied in sand culture. The addition of 11.25 mM CaC1² to nutrient solution containing 225 mM NaC1 improved percentage of germination of B. napus and B. juncea, but had no significant effect on the germination speed of the four species. There was no significant effect of additional amount of Ca² in the saline medium (150 mM NaC1) on the shoot biomass and seed yield of B. carinata and B. campestris. By contrast, shoot dry matter of B. napus and B. juncea increased significantly with the increased in Ca² concentration of the growth medium, but their seed yield remained unaffected. Decreased Ca² concentrations of the saline growth medium reduced percent oil content in B. carinata, B. juncea, and B. campestris. Increasing Na/Ca ratio of the external medium affected ion uptake differently in different species. In B. carinata, a relatively salt-tolerant species, the concentrations of Na⁺ and K⁺ in the shoots remained unaffected, but the C1 concentration was reduced linearly with the increase in external Na/Ca ratios. Root K⁺ and Ca²⁺ of the species decreased with the decrease in Ca²⁺ supply. In B. campestris increasing Na/Ca ratios of the saline medium had no effect on the concentrations of Na⁺, C1, and Ca²⁺ in the shoots and Na⁺, C1, and K⁺ in the roots. Only shoot K⁺ and root Ca²⁺ decreased consistently. In the highly salt-sensitive species, B. napus, the shoot Na⁺ was reduced by the addition of Ca²⁺ in the salt treatment, whereas the C1 and Ca²⁺ uptake was promoted by supplemental Ca²⁺. The root K⁺ concentrations decreased with the increase in Na/Ca. In B. juncea, which was similar to B. napus in biomass production, high Ca²⁺ concentration in the salt treatment reduced the shoot Na⁺ and root C1 concentrations and promoted the K⁺ uptake. Shoot Na/Ca and Na/K ratios were increased in B. napus and B. juncea at the highest Na/Ca ratio of the growth medium. Shoot K⁺ selectivity, S^K,Na (determined as molar ratio of K: Na in tissue to molar ratio of K:Na in external medium) of all species remained unaffected except for B. juncea in which it decreased significantly at the highest Na/Ca ratio. The root K⁺ selectivity increased in B. carinata.     

Evaluating the fraction of electrically associated cations on surfaces of soil particles by extrapolation of strong-field Wien effect measurements in dilute suspensions

Purpose

For agricultural production and environment protection, it is cations loosely bound to the soil particles that have a great significance in short-term processes of adsorption–desorption, exchange, and transport. It is beneficial to be able to evaluate the fractions of these cations in order to correctly predict potential pollution of soils by heavy metals and availability of plant nutrients.

Materials and methods

The homionic suspensions of yellow-brown soil (YB) and black soil I (BI) saturated with Na⁺ and Ca²⁺ and three subsamples of black soil II (BII) saturated with Ca²⁺ and Cd²⁺ were prepared to determine the electrical conductivity (EC) of the suspensions. On the basis of electrical conductivity vs. field strength (EC-E) curve, the fraction of electrically associated cations on surfaces of soil particles was evaluated by extrapolation of strong-field Wien effect measurements in dilute suspensions.

Results and discussion

The maximum dissociation degree (α _max) of Na⁺ adsorbed on surfaces of yellow-brown soil and black soil I was about 0.21, which is approximately twice as much as those of Ca²⁺ (0.07–0.10) adsorbed on surfaces of two soils. The soil type was not the main factor in evaluating α _max, and the valence of the cations was. For divalent cations, α _max of Ca²⁺ and Cd²⁺ adsorbed on soil particles with different contents of organic matter descended in the order: top black soil II?>?bottom black soil II?>?OM-free bottom black soil II.

Conclusions

The relatively small fractions of electrically adsorbed cations—about 0.2 for Na⁺ and 0.1 for Ca²⁺ on yellow-brown and black soils particles indicated that even for the more loosely adsorbed Na⁺ ions, most of the cations in the double layers of soil particles were adsorbed strongly by other, more specific mechanisms and cannot be stripped off into the solution, which would increase its electrical conductivity in a strong applied field.

     

Sodium removal from a calcareous saline–sodic soil through leaching and plant uptake during phytoremediation

Saline–sodic and sodic soils are characterized by the occurrence of sodium (Na⁺) to levels that can adversely affect several soil properties and growth of most crops. As a potential substitute of cost‐intensive chemical amelioration, phytoremediation of such soils has emerged as an efficient and low‐cost strategy. This plant‐assisted amelioration involves cultivation of certain plant species that can withstand ambient soil salinity and sodicity levels. It relies on enhanced dissolution of native calcite within the root zone to provide adequate Ca²⁺ for the Na⁺ Ca²⁺ exchange at the cation exchange sites. There is a lack of information for the Na⁺ balance in terms of removal from saline–sodic soils through plant uptake and leaching during the phytoremediation process. We carried out a lysimeter experiment on a calcareous saline–sodic soil [pH of saturated soil paste (pH_s) = 7.2, electrical conductivity of the saturated paste extract (EC_e) = 4.9 dS m⁻¹, sodium adsorption ratio (SAR) = 15.9, CaCO₃ = 50 g kg⁻¹]. There were three treatments: (1) control (without application of a chemical amendment or crop cultivation), (2) soil application of gypsum according to the gypsum requirement of the soil and (3) planting of alfalfa (Medicago sativa L.) as a phytoremediation crop. The efficiency of treatments for soluble salt and Na⁺ removal from the soil was in the order: gypsum ≈ alfalfa > control. In the phytoremediation treatment, the amount of Na⁺ removed from the soil through leaching was found to be the principal cause of reduction in salinity and sodicity. Copyright © 2003 John Wiley & Sons, Ltd.     

Charge properties of mixtures of minerals with variable and constant surface charge

Surface charge of mixtures of lepidocrocite and illite determined by adsorption of potential-determining and electrolyte ions is studied as a function of pH and NaCl concentration. Deviations between results obtained by both methods were a function of the illite content of the mixtures, and can be mainly attributed to coatings of hydroxyaluminium complexes on the constant charge surfaces of the clay mineral, which can react with H⁺ ions or release exchange sites by precipitation of well-formed hydroxides. These coatings of aluminium complexes can cause H⁺ consumptions similar to those due to lepidocrocite. Some ideas are put forward for modelling charge properties of mixed systems.     

Ammonium-calcium exchange equilibria in soils and weathered pumices that differ in cationexchange materials

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.     

Influence of soil ESP and electrolyte concentration of permeating water on hydraulic properties of a Vertisol

The effect of soil ESP on soil moisture retention and volume change of montmorillonitic type clay soil (vertisol) in the 10–58 ESP range showed increase in moisture retention with soil ESP in 10-bar suction range. Soil moisture suction (h) – water content (θ)relationship of the form h = h_o(θ/θ_s)^?b, where ‘h_o’is air entry suction and ‘b’ is a constant, was obtained at all ESP levels. Soil bulk density at low moisture contents increased considerably with soil ESP due to dispersion and decreased linearly with increase in soil water content because of mineral swelling. The soil water diffusivity and conductivity in the 0.15–0.35 g/g moisture content range followed an exponential increase with soil moisture content recording a sharp decrease at soil ESP 10. The effect of high exchangeable sodium, however, was mitigated, to a large extent, by the increase in electrolyte concentration of permeating water to 5 mmhos/cm or greater. Decrease in water transmission parameters ascribed to exchangeable Na⁺ in the drier moisture regime was accounted for by dispersion of soil particles at low ESP. Whereas adsorbed Na⁺ – induced swelling was regarded as the major factor modifying soil water relations at relatively high ESP under wet moisture regime. Soil ESP of 10 may be treated as critical for swelling clay soil from soil and water – management view point.     

Implication of Gypsum Rates to Optimize Hydraulic Conductivity for Variable‐Texture Saline–Sodic Soils Reclamation

Sodium (Na⁺) dominated soils reduce saturated hydraulic conductivity (K_s) by clay dispersion and plugging pores, while gypsum (CaSO₄•2H₂O) application counters these properties. However, variable retrieval of texturally different saline–sodic soils with gypsum at soil gypsum requirement (SGR) devised to define its quantity best suited to improve K_s, leach Na⁺ and salts. This study comprised loamy‐sand (LS), sandy loam (SL), and clay loam (CL) soils with electrical conductivity of saturation extract (EC_e) of ~8 dS m⁻¹, sodium adsorption ratio (SAR) of ~44 (mmol L⁻¹)^1/2 and exchangeable sodium of ~41%, receiving no gypsum (G₀), gypsum at 25% (G₂₅), 50% (G₅₀) and 75% (G₇₅) of SGR. Soils packed in lysimeters were leached with low‐carbonate water [EC at 0·39 dS m⁻¹, SAR at 0·56 (mmol L⁻¹)^1/2 and residual sodium carbonate at 0·15 mmol_c L⁻¹]. It proved that a rise in gypsum rate amplified K_s of LS ≫ SL > CL. However, K_s of LS soil at G₂₅ and others at G₇₅ remained efficient for salts and Na⁺ removal. Retention of calcium with magnesium (Ca²⁺ + Mg²⁺) by LS and SL soils increased by G₅₀ and decreased in G₇₅, while in CL, it also increased with G₇₅. The enhanced Na⁺ leaching efficiency in LS soil with G₂₅ was envisaged by water stay for sufficient time to dissolve gypsum and exchange and leach out Na⁺. Overall, the superiority of gypsum for LS at G₂₅, SL at G₅₀ and CL at G₇₅ predicted cost‐effective soil reclamation with a decrease in EC_e and SAR below 0·97 dS m⁻¹ and 5·92 (mmol L⁻¹)^1/2, respectively. Copyright © 2015 John Wiley & Sons, Ltd.