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.     

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.     

几种土壤交换性酸测定方法的效果比较

为真实地反映酸性土壤交换性酸含量水平,探讨了KCl淋溶法、BaCl_2淋溶法、NaAc淋溶法、KCl-三乙醇胺(Triethanolamine,TEA)提取法和BaCl_2-TEA提取法对紫色土、黄壤、红壤和砖红壤4种土壤的交换性酸测定效果。结果表明:5种方法测得的土壤交换性酸大小关系为:BaCl_2-TEA提取法KCl-TEA提取法NaAc淋溶法BaCl_2淋溶法KCl淋溶法。BaCl_2淋溶法能较为真实地反映出土壤交换性酸水平,其次为KCl淋溶法。受土壤有机酸和铝氧化物的影响,NaAc淋溶法、KCl-TEA提取法和BaCl_2-TEA提取法测得的土壤交换性酸含量偏高。但由于尚无标准方法对测定结果进行验证,因此,还需进一步对土壤交换性酸测定方法及其影响因素开展研究。     

Cation exchange capacity and base saturation of imperfectly drained surface coastal plain soils

Abstract

Testing three imperfectly drained forest soils (Alfisols and Ultisol) by nine methods showed that cation exchange capacities were highly pH dependent. Adding lime increased CEC values obtained by buffered and unbuffered methods but decreased CEC values when total bases were added to total acidity or salt replaceable acidity. No method tested completely explained the change in CEC caused by liming. Fractionation of the whole soil CEC Indicated an appreciable masked charge caused by an apparent complexing of amorphous metal oxides with clay or organic matter. In both buffered and unbuffered solutions, calcium saturation usually gave higher CEC values than monovalent ion saturation.     

Extractable Acidity by a Centrifuge Method

Abstract

Titratable or extractable acidity is a measure of the acidity released by a soil to a buffered extraction solution. The United States Natural Resources Conservation Service (NRCS) Soil Survey Laboratory (SSL) routinely measures extractable acidity on soils that are carbonate free. In this study, a centrifuge method for measuring acidity extracted by barium chloride triethanolamine (BaCl₂‐TEA), pH 8.2, is described. Compared with the SSL vacuum extraction method, the proposed method provides better reproducibility for highly acidic soils, typically organic or andic materials. Key variables resolved while developing this method were extraction time and sample mass. Soil chemistry can significantly affect the pH of the extraction solution. It was concluded that checking postextraction pH is an effective way to identify samples that should be rerun by using a smaller sample size.     

Comparison of five methods to determine the cation exchange capacity of soil

Background

Cation exchange capacity (CEC) is a routinely measured soil fertility indicator. The standard NH₄OAc (pH 7) extraction procedure is time-consuming and overestimates actual CEC values of variable charge soils. Unbuffered extractants have been developed to measure the effective CEC (eCEC), but they differ in the type of index cation and extraction procedures.

Aim

This study was set up to systematically compare CEC values and exchangeable cation concentrations among different procedures and evaluate their practical aspects.

Methods

Five procedures were compared for (e)CEC, that is, silver thiourea (AgTU), cobalt(III) hexamine (Cohex), compulsive exchange (CE, i.e., BaCl₂/MgSO₄), BaCl₂ (sum of cations in single-extract), and NH₄OAc (pH 7). We applied these methods to a set of 25 samples of clay minerals, peat, or samples from soils with contrasting properties.

Results

The CEC values correlated well among methods (R² = 0.92–0.98). Median ratios of eCEC (AgTU as well as CE) to the corresponding eCEC (Cohex) value were 1.0, showing good agreement between eCEC methods, but NH₄OAc exceeded Cohex values (ratios up to 2.5 in acid soil). For BaCl₂-extracteable cations, the ratio ranged from low (<1.0) in acid soils (acid cations not measured) to high (>1.0) in high-pH soil (dissolution of carbonates). Multiple-extraction methods (CE and NH₄OAc) yielded more variation and increased labor.

Conclusions

The chemical properties of the sample cause method-specific interactions with chemical components of extractants. We found the Cohex method with ICP-MS detection to be the most efficient and cost-effective technique for determination of eCEC and exchangeable cations.     

Eignung von 0,1 M BaCl2-Lösung zur Bestimmung der Kationenaustauscheigenschaften kalkhaltiger Böden

Determination of the CEC of carbonate soils with unbuffered 0.1 M BaCl₂ Soils containing carbonates and precipitated calcium carbonate, respectively, were percolated with unbuffered 0.1 M BaCl₂ followed by 0.1 M MgCl₂ and anorganic acids of the same concentration. The measured concentration of bases (including Ba⁺⁺) in the percolates indicates, that precipitation of Ba⁺⁺ or exchange with Ca⁺⁺/Mg⁺⁺ on carbonate surfaces occurs during percolation, which leads to an overestimation of exchangeable bases. From the total amount of Ba⁺⁺ bounded in such a way the less part is dissolved/exchanged by MgCl₂ solution in the following leaching step. So the CEC of carbonate soils seems to be generally overestimated too, by the method applied in a not exactly measurable degree.     

Calcium requirements of citrus

Abstract

A close relationship was found between the pH of soil suspensions in the SMP buffer solution (pH_smp) and the potential acidity of soils (H + Al) extracted by a neutral calcium acetate solution (r = 0.98), for twenty six soil samples of the State of Sao Paulo, Brazil, This relationship was represented by the equation lnY = 7.76 ‐ 1.053X, which allowed for the calculation of H + Al directly from the values of pH_smp.

With the values of H + Al and the sum of bases, calcium, magnesium and potassium, the cation exchange capacity (CEC), and the base saturation (V) were calculated. Relationships between the base saturation of the soils and the active acidity of soil suspensions were close, both for pH determined in water (r=0.94) and pH determined in 0.01M CaCl₂ solution (r ‐ 0.97). Thus the lime requirement (LR) of soils could be calculated, for given values of pH or base saturation, using the equation LR = CEC (V₂ ‐ V₁)/100, in which V₁ is the base saturation of the soil and V₂ is the expected value upon liming.

The predicted values for lime required to increase the soil pH in water to either 5.5 or 6.0 were comparable to those obtained by the direct use of the SMP buffer method, and were, respectively, two and four times higher than the amounts required to neutralize exchangeable aluminum, considering the criterion LR = Al × 1.5.

The proposed method to determine lime requirement of soils is described in detail and the advantages of its use are discussed.     

Release of Al by hydroxy-interlayered vermiculite and hydroxy-interlayered smectite during determination of cation exchange capacity in fine earth and rock fragments fractions

The fine earth (<2 mm) and rock fragments (>2 mm) fractions of two soils derived from Oligocene sandstone have been examined to assess the origin of the discrepancies between cation exchange capacity (CEC) and effective CEC (ECEC). The soils differ in terms of acidity: soil A is more acid than soil B. When the A samples are treated with BaCl₂, the solution became sufficiently acid (pH < 4·5) to dissolve and to maintain Al in solution. From these samples more Al is released than base cations. Aluminium was continuously replenished even after 192 h, so that the ECEC was always larger than the CEC. Samples from soil B contain less H and Al ions, and the BaCl₂ solution could not lower the pH below 5·0. In these samples little Al is released, and the base cations dominate the exchangeable pool of ions. This Al can be considered to be exchangeable, and a good agreement exists between the ECEC and the CEC. The source of non-exchangeable Al in the A samples is the OH-Al polymers of the hydroxy-interlayered vermiculite (HIV) and hydroxy-interlayered smectite (HIS) that tend to dissolve during the BaCl₂ treatments. In the less acid B samples the Al polymers are not affected by BaCl₂ treatment. Different results were obtained when the clays, extracted from an Na-dispersed suspension, were treated with BaCl₂ solution. Because the clays are no longer acid, no H⁺ is released, and the OH-Al polymers are not dissolved. Therefore, the saturating ions play an important role in the dissolution of the OH-Al polymers and cause differences between the CEC and ECEC. We discount organic matter and specifically Al-organo complexes as a source of non-exchangeable Al. Both A and B soils contain very similar pyrophosphate-extractable Al, but show substantial differences in the amount of exchangeable Al.     

Determination of exchangeable acidity,carbonate ions and change of buffer in triethanolamine‐buffered solutions percolated through soil samples containing carbonates

Abstract

The content of dissolved carbonates and exchanged acidity in triethanolamine‐buffered BaCl₂‐solutions which were percolated through soil samples containing carbonates is determined by two titration‐procedures to pH 4.0 and 10.25. because a single titration value gives no information of the amounts of both ionic species in solution. The amount of dissolved carbonates calculated on the bases of these titration‐procedures, however, is smaller than that determined by measuring the content of inorganic carbon in solution. The difference is attributed to the sorption of protonized triethanolamine‐buffer during percolation, which leads to an underestimation of CEC when measured by re‐exchanged Ba⁺⁺, whereas the amount of exchangeable bases is overestimated due to dissolution of carbonates. The amount of exchanged acidity calculated from the data obtained is surprisingly high and is at least partly attributed to the existence of HCO₃ ^‐ ‐sorbed on the surface of (wet) soils.     

Simplified methylene blue method for rapid determination of cation exchange capacity of mineral soils

Abstract

Rapid determination of cation exchange capacity (CEC) of soils can be useful for soil testing to improve efficiency of fertilizer use. The methylene blue (MB) method of Wang et al. (1989) has been simplified for rapid determination of CEC of mineral soils in field. For the temperate and tropical soils used, the relationships between the CEC by the ammonium acetate (NH₄OAc) method and the simplified MB method were linear (r² = 0.97) with a slope ranging from 0.84 to 1.02. These results suggest that the simplified MB method has the potential for a rapid determination of the CEC of mineral soils.     

Cation exchange capacity variations in acidic forest soils from Sutton,Québec,Canada

Abstract

Single values of the cation exchange capacity (CEC) are widely used in modeling soil solution chemistry in soil and water ecosystems. Our aim was to determine the CEC as a function of pH and ionic strength in an acidic forest soil. We examined the cation exchange of two Humo‐Ferric Podzols (Haplorthods) equilibrated with artificial soil solutions of different concentrations. Aliquots of acid (HC1) or base (NaOH) were added to generate a pH range of 3 to 6. The CEC, determined by displacement with BaCl₂ showed little or no increase with increasing pH and a definite increase with lower pH. This anomalous behavior was attributed to the precipitation of aluminum (Al) at high pH and to its dissolution at low pH.     

Influence of Different Forms of Iron and Aluminum on the Nature of Soil Acidity of Some Inceptisols,Alfisols, and Ultisols

Abstract

Fifteen acid soils of Mizoram representing Ultisols and Inceptisols, and Madhya Pradesh, representing Alfisols, were studied to characterize the nature of acidity in relation to different forms of iron (Fe) and aluminum (Al). The mean contents of Fe and Al were extracted by various extracting reagents and were found to be in descending order as followed: dithionite>oxalate>pyrophosphate>ammonium acetate>KCl. The electrostatically bonded EB‐H⁺ and EB‐Al³⁺ acidity comprised 28.3 and 71.7% of exchangeable acidity whereas EB‐H⁺, EB‐Al³⁺, exchangeable, and pH‐dependent acidities comprised 9.8, 30.7, 40.5, and 59.5% of total potential acidity. All forms, of acidity showed significant correlation with pH_k and organic carbon. Among the different forms, Fe and Al caused most of the variations in different forms of soil acidity but the effect of different forms of Al are more active and directly participate in the formation of EB‐H⁺, EB‐Al³⁺, and exchangeable acidity.     

A computer‐assisted method for CEC estimation and quality control in a routine soil‐test operation

Abstract

Cation‐exchange capacity (CEC) of 30 Alabama soils was estimated by two different methods based or routine soil‐test results consisting of soil‐water pH, Adams‐Evans buffer pH, and Mehlich‐1 extractable cations (K, Mg, and Ca), which were obtained automatically by a computerized data acquisition system. In one method, CEC was calculated by solving a quadratic equation involving soil‐water and buffer pH's; in the other, CEC was estimated as the summation of extractable cations and exchangeable acidity. The two estimated CEC's agreed well with each other and also had the same magnitude as CEC determined by the normal NaOAc, pH 8.2 method. By averaging the two calculated values, an even closer estimation of the measured CEC was found. These calculations and comparisons can be accomplished quickly and efficiently by a minicomputer via a simple FORTRAN program.

In addition, a discrepancy between the two estimated CEC's would indicate possible errors in analytical determinations and/or the inadequacy of the soil testing procedures. Therefore, an additional means for quality control in a routine soil‐test operation can be obtained by comparing the two CEC values.     

Extractability of previously‐applied zinc as influenced by properties of calcareous soils

Abstract

The recovery of applied zinc (Zn) by plants is relatively small. Coupled with lack of leaching, this leads to accumulation of Zn in topsoil which may result in unfavorable growth conditions for the subsequent plants. Different extractants may be used for assessing the Zn status of soils previously treated with Zn sources. The extractability of retained Zn is influenced by soil properties. This experiment was conducted to study the influence of selected properties of calcareous soils on extractability of Zn by three popular Zn soil tests. Twenty samples from surface horizons (0–20 cm) of highly calcareous soils of southern Iran (pH 7.9 to 8.5; calcium carbonate equivalent 16 to 58%) previously treated with three levels of Zn (0, 10, and 20 mg Zn kg^‐1 soil as ZnSO₄#lb7H₂O) in triplicate and under one crop of corn (Zea mays L.) were extracted with DTPA, EDTA‐(NH₄)₂CO₃ and Na₂‐EDTA. Extractability (EXT) in a particular extractant was defined as the slope of the regression line, relating extractable Zn of each soil to the rate of applied Zn, multiplied by 100. The EXT values of soils ranged from 24.9 to 73.0% for DTPA, 47.2 to 84.4% for EDTA‐(NH₄)₂CO₃, and 28.2 to 56.7% for Na₂‐EDTA. Stepwise regression equations showed that cation exchange capacity (CEC) and calcium carbonate equivalent (CCE) followed by clay content were the most influential soil properties in EXT of retained Zn of highly calcareous soils. The EXT values decreased with increase in CEC, and CCE but increased with increase in clay.     

Kinetics of ammonia volatilization of anhydrous ammonia applied to a vertisol as influenced by Farm Yard manure,sorbed cations and cation exchange capacity

Abstract

In laboratory experiments, effects of added Farm Yard Manure (FYM), sorbed cations and cation exchange capacity (CEC) on NH₃ volatilization of anhydrous ammonia applied to a Vertisol were studied at 0.3 bar soil Moisture Tension and 25 ± 1°C. On addition of FYM or with increase in CEC the volatilization of retained ammonia was reduced while the effect of the sorbed cations was in the order : K‐Soil > Na‐Soil > Ca‐Soil > Mg‐Soil. The results suggest that the volatilization of retained NH₃ followed First order reaction kinetics, with a rapid rate of volatilization in the initial 8 to 10 h followed by a retarded rate up to 144 h.     

Availability of extractable boron in some acid soils,west Bengal,India

Abstract

A relatively small range between deficiency and toxic limits of boron (B) necessitates precise evaluation of the availability of extractable boron before applying B in deficient soils. Keeping this in view, laboratory and greenhouse experiments were conducted to assess the availability of native B in soils. For this purpose, 25 acid soils with diverse properties and varying hot water extractable B content, were selected from lateritic and alluvial tracts of Southern West Bengal. A greenhouse pot experiment with four rates of B (0, 0.5, 1.0, and 2.0 mg kg^‐1) was conducted in completely randomized design to study the response of soybean (Glycine max L.) to native and applied B in all 25 soils. The suitability of nine extractants for determining available soil B was assessed by correlating the amount of extractable B in untreated soils with Bray's percent yield, uptake, and tissue B concentration of soybean plants. Optimization of salicylic acid concentration is described and the advantages of this extractant are discussed. The interference of amethyst color (produced by iron and salicylic acid) with the colorimetric estimation of B is studied. Hot CaCl₂ was found to be the most suitable extractant for the determination of available B in these soils, followed by hot water, salicylic acid, and ammonium acetate. However, salicylic acid appeared to be the most efficient extractant for routine soil analysis for available B, where a large number of samples are analyzed. The critical values in respect to sufficiency of extractable B for soybean plants were 0.51 for hot water, 0.61 for hot CaCl₂, 0.27 for ammonium acetate and 0.45 mg kg^‐1 for salicylic acid. The critical B concentration in soybean plants was 18 mg kg^‐1 on dry weight basis. Multiple regression equations relating soil properties to native soil B extracted by various extractante were developed. It was observed that organic carbon and clay contributed positively to B extracted by hot water, hot CaCl₂, and ammonium acetate, while salicylic acid extractable B showed positive relationships with cation exchange capacity (CEC) and clay. The CEC and Fe₂O₃ were found to have positive influence on tartaric acid extractable B. Implications of the influences of soil properties on the extractable B content of soils are discussed.     

Modelling cation exchange in columns of disturbed and undisturbed subsoil

Cation exchange is often studied with disturbed and dried soils, but the applicability of the results to undisturbed soils is not straightforward. We investigated the value of exchange coefficients obtained from standard procedures for predicting cation exchange in soil. Columns of undisturbed and disturbed subsoil of a Luvisol (SBt horizon) were leached under saturated conditions with 0.4, 4, 20, 41, 102 and 205 mm BaCl₂ at a Darcy velocity of 1400 mm day^?1. The model PHREEQC was used to calculate one‐dimensional transport, inorganic complexation and multiple cation exchange. Two model variants were tested: m1 (exchangeable cations obtained by percolation with NH₄Cl) and m2 (exchangeable cations obtained by shaking the soil with BaCl₂). The exchange coefficients (Gaines–Thomas formalism) were calculated from the ion activities in solution and exchangeable cations obtained by NH₄Cl percolation (m1) or shaking with BaCl₂ (m2). Variant m1 predicted cation exchange of the disturbed (homogenized) soil for the entire BaCl₂ concentration range, whereas variant m2 resulted in a two‐fold overestimation of desorbed K for all experiments, which was related to large amounts of K released from the soil by shaking with BaCl₂. In experiments with undisturbed soil, variant m1 predicted the concentrations of Mg, Ca, K, and Na in the solution phase and the sum of cations released from exchange sites. However, variant m2 predicted changes in ion concentrations and exchangeable cations somewhat less well. This study suggests that the amounts of exchangeable cations and exchange coefficients obtained from experiments with homogenized soil by percolation are useful to predict cation concentrations in column experiments with undisturbed soils.     

A comparison of methods used for determination of cation exchange capacity

Abstract

Cation exchange capacity of ten non‐calcareous and non‐saline soils from Queensland, Australia, has been determined by the ammonium acetate method using different procedures, by an ammonium chloride method at pH8.5, and by three methods which attempt to approximate field conditions. Procedural differences in the ammonium acetate method produced variation in results, and methods using approximate field conditions gave much lower values for those soils considered to have variable charge properties.     

Fractionation of extractable aluminum in acid soils: A review and a proposed procedure

Abstract

Different forms of soil aluminum (Al) are involved in the retention of anions and cations, phytotoxicity of Al in acid soils, CEC reduction and soil physical properties such as aggregate stability and water infiltration. Therefore it is desirable to quantify the different forms of Al in soil especially acidic soils. A rationale was developed from a literature survey to identify the following fractions of Al: (a) exchangeable quantified by 1M KC1 extraction; (b) organic bound quantified by 0.1M CuCl₂ + 0.5M KCl extraction; (c) sorhed Al extractable with 1M NE₄OAc at pH 4.0; (d) amorphous Al oxide and hydroxide and amorphous aluminosilicates (if present) extractable with 0.2M ammonium oxalate at pH 3.0; and (e) interlayered Al extractable with 0. 33M sodium citrate at pH 7.3. Pools (a), (b), and (c) are extracted sequentially. Amorphous Al oxide and hydroxide (pool d) is calculated from ammonium oxalate extractable Al minus (a + b + c). Interlayered Al is calculated from sodium citrate extractable Al minus ammonium oxalate extractable Al. The latter two extractions are done on separate subsamples of soils. From preliminary studies and data for 13 soil samples it is suggested that this fractionation of soil Al is more meaningful than that obtained by the KCl ‐> K₄P₂O₇ ‐> ammonium oxalate > citrate‐bicarbonate‐dithionite extraction sequence.