Comparison of some methods for determination of sulfate in soils

Abstract

Sulfate (SO₄ ^2‐) is present in soils as salts of various metals, and the different metals associated with sulfate may influence adsorption of SO₄ ^2‐by soils. The analytical method used for determination of SO₄ ^2‐could be affected by the type of metal associated with the SO₄ ^2‐. Four analytical methods based on different principles were evaluated for determination of SO₄ ^2‐in different metal salts and in soil extracts obtained with three extractants {0.1M lithium chloride (LiCl), 0.15% calcium chloride (CaCl₂), and 500 mg P/L as calcium phosphate [Ca(H₂PO₄)2]}. The analytical methods were: (i) a methylene blue (MB) colorimetric method after the reduction of SO₄ ^2‐to hyrogen sulfide (H₂S), (ii) an ion Chromatographie (IC) method, (iii) a turbidimetric (TD) method, and (iv) an indirect barium (Ba) atomic absorption spectrophotometric (SP) method. The recovery of SO₄ ^2‐associated with various mono‐, di‐, and tri‐valent metals was quantitative by the MB method. But, trivalent metals, such as aluminum (Al), indium (In), lanthanum (La), and scandium (IC), decreased the recovery of SO₄ ^2‐by the other three methods. The MB and IC methods gave similar values for SO₄ ^2‐in soils by using the three extractants. The TD and SP methods gave variable results and, in general, underestimated the amounts of SO₄ ^2‐in soils. Among the four methods, the MB and IC methods were the most accurate and precise.     

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.     

Measurement of Cation Exchange Capacity of Organic‐Matter Fractions from Soils using a Modified Compulsive Exchange Method

Abstract

This article describes a modified compulsive exchange method suitable for the determination of cation exchange capacity (CEC) over a pH range on solid, separated organic‐matter fractions. The method is demonstrated to be a reproducible and relatively simple means of measuring CEC on fractions separated by physical means in conjunction with hydrofluoric acid (HF) treatment. By including a modification for measuring the residual magnesium (Mg²⁺) content by dilution and conductivity, the method is simplified to measure CEC versus pH using a single sample; the only laboratory instruments required are pH and conductivity meters and a balance. The lack of agreement between this method and the silver thiourea (AgTU) method for some fractions at low pH is attributed to the uncontrolled variation in solution ionic strength when acid is introduced to effect solution pH changes in the AgTU method.     

New buffer pH method for rapid estimation of exchangeable acidity and lime requirement of soils

Abstract

A new buffer pH method (BpH) for the rapid estimation of unbuffered salt‐exchangeable acidity (ACe) and lime requirement (LR) has been developed. The buffer reagent, consisting of sodium glycerophosphate, acetic acid, trletlianolamine, ammonium chloride and barium chloride, was useful within the pH range 3.8 to 6.6. Delta values from BpH were converted into buffer pH acidity values (AC) and calibrated against ACe of 91 mineral soils and 100 acid Histosols. The correlation coefficients between AC and ACe were 0.966 and 0.956 for the mineral soils and Histosols, respectively. The corresponding regression equations in terms of meq/100 cm were ACe ‐ ‐0.54 + 0.96 AC and ACe = ‐7.4 + 1.6 AC for mineral soils and Histosols, respectively.

To predict lime requirement of mineral soils a curvilinear equation was required. The equation, LR in meq CaCO₃/100 cm³ = 0.1 (AC)² + AC, was tested successfully against rates of lime carried out under laboratory conditions and against crop response in the greenhouse. Field studies on acid Histosols with maize and soybeans showed optimum yield when the rate of lime added was approximately equivalent to ACe.     

Adsorption complex,pH relationships in some acid mediterranean forest soil profiles

Acid soils in some mediterranean forests were investigated for the composition of the adsorption complex and the gradients in soil pH. The effective CEC (235–838 mmol_c kg^?1) and base saturation (93–98 %) are highest in ectorganic horizons. In the mineral horizons the effective CEC (23–52 mmol_c kg^?1) and base saturation (11–40 %) are much lower. The exchange complex of mineral horizons consists for 90 (AEh) to 40 percent (Bw2) of organic matter. The effective CEC of the mineral clay fraction is low (60 mmol_c kg^?1 clay). The clear trends in soil pH within the ectorganic layer of deciduous and sclerophyllous oak forests are attributed to vertical spatial separation of nitrogen mineralization (ammonification and strongly impeded nitrification) and nutrient uptake by roots (mainly NH₄). This leads to a high effective CEC in the fermentation layer and acidification of the uppermost part of the mineral soil. In contrast to the situation in temperate forests this process is impeded in mediterranean coniferous forests, where litter decomposition is extremely slow and both proton production and consumption take place in the organic rich mineral horizon.     

Elimination of chloride interference in the phenoldisulphonic acid method of nitrate determination in soils

Abstract

A technique was developed to eliminate chloride interference using antimony (III) in the determination of nitrates in soils by phenoldisulphonic acid method. This method was found effective upto nearly 300 ppm Cl^‐ in soils ranging in pH from 5.6 to 8.3. By avoiding repeated filtrations of chloride precipitates, this method allowas quick analysis of soils for nitrates in single soil extracts containing other mineral nitrogen fractions.     

Carbon content in soil particle size and consequence on cation exchange capacity of Alfisols

Abstract

Many of the cultivated soils of sub‐Saharan Africa typically have a surface horizon low in clay and with a low cation exchange capacity (CEC). In these soils, CEC is largely due to the soil organic matter (SOM). Measurements made on long‐term trials show that changes in CEC and SOM are positively correlated to one another, but not of same magnitude, suggesting that not all of the SOM plays an equal role as regards the soil CEC. To study the influence of the different SOM size fractions on the CEC, soils with or without application of manure or compost coming from trials in Chad and Côte d'Ivoire were separated without destruction of the SOM into five organo‐mineral fractions: “coarse sand”;, “fine sand”;, “coarse silt”;, “fine silt”;, and “clay”; made up of particles of sizes between 2,000 and 200, 200 and 50, 50 and 20, 20 and 2, and 2 and 0 μm, respectively. Fractionation was carried out by mechanical dispersion of the soil, wet sieving of the fractions larger than 20 μm, and decanting of the “clay”; and “fine silt”; fractions. The CEC of these fractions increases inversely with their size. The “clay”; fraction which contains half of the SOM contributes about 80% of the CEC of the soils. The CEC of the fractions is largely a function of their carbon (C) content, but the organic CEC per unit C of the “clay”; fraction appears to be four times greater than that of the other fractions (1,000 as against 270 cmol_c kg^‐1). Applications of manure or compost increase the CEC of the soils by increasing the soil C only when this C increase concerns the fine fractions of the SOM.     

An evaluation of cation exchange capacity measurements for soils in the tropics

Abstract

Comparisons of CEC and exchange acidity neasurements were made on a group of selected West African soils using three commonly used analytical procedures, namely, neutral‐acetate displacement, BaCl₂‐TEA leaching at pH 8, and unbuffered KCl extraction.

The three methods gave large differences in CEC values which followed the order of BaCl₂‐CEC>>NH₄OAc‐CEC> KCl‐CEC. Results of exchange acidity also followed the same order. The high exchange acidity values obtained by the BaCl₂‐TEA (pH 8) method were mainly due to changes in surface charge characteristics of Fe and Al oxides and hydrous oxides. The effective CEC method is recommended for routine soil analysis for highly weathered soils in the tropics.

Regression analysis of the base saturation values obtained from the three methods indicated the data followed a curvilinear relationship. The acetate method was more highly correlated with the effective CEC method than with the BaCl₂ method.     

Carbon storage in loess derived surface soils from Central Germany: Influence of mineral phase variables

The influence of the soil mineral phase on organic matter storage was studied in loess derived surface soils of Central Germany. The seven soils were developed to different genetic stages. The carbon content of the bulk soils ranged from 8.7 to 19.7 g kg^—1. Clay mineralogy was confirmed to be constant, with illite contents > 80 %. Both, specific surface area (SSA, BET‐N₂‐method) and cation exchange capacity (CEC) of bulk soils after carbon removal were better predictors of carbon content than clay content or dithionite‐extractable iron. SSA explained 55 % and CEC 54 % of the variation in carbon content. The carbon loadings of the soils were between 0.57 and 1.06 mg C m^—2, and therefore in the ”︁monolayer equivalent” (ME) level. The increase in SSA after carbon removal (ΔSSA) was significantly and positively related to carbon content (r² = 0.77). Together with CEC of carbon‐free samples, ΔSSA explained 90 % of the variation in carbon content. Clay (< 2 μm) and fine silt fractions (2—6.3 μm) contained 68—82 % of the bulk soil organic carbon. A significantly positive relationship between carbon content in the clay fraction and in the bulk soil was observed (r² = 0.95). The carbon pools of the clay and fine silt fractions were characterized by differences in C/N ratio, δ¹³C ratio, and enrichment factors for carbon and nitrogen. Organic matter in clay fractions seems to be more altered by microbes than organic matter in fine silt fractions. The results imply that organic matter accumulates in the fractions of smallest size and highest surface area, apparently intimately associated with the mineral phase. The amount of cations adhering to the mineral surface and the size of a certain and specific part of the surface area (ΔSSA) are the mineral phase properties which affect the content of the organic carbon in loess derived arable surface soils in Central Germany most. There is no monolayer of organic matter on the soil surfaces even if carbon loadings are in the ME level.     

Zur Bestimmung austauschbarer Kationen in sauren Waldböden

On the determination of exchangeable cations in acid forest soils Different samples from acid forest soils were percolated with large amounts of H₂O. Significant amounts of anions, especially sulfate, were found in the percolates mainly accompanied by Na. K, Ca and Mg (M_b-cations). The dissolution of Al-Sulfates and subsequent exchange of M_b-cations by Al as dominant mechanism is proposed. Thus the common method for determination of the cation exchange capacity (CEC) of acid forest soils, the percolation with NH₄Cl may overestimate the CEC. The overestimation may be related to the sulfate content of the soil and also influences the calculation of relative CEC proportions of individual cations.     

Determination of organic matter content in arid‐zone soils using a simple “loss‐on‐ignition” method

Abstract

A simple and rapid procedure for the determination of organic matter content in mineral soils by loss‐on‐ignition without pretreatment was studied. Attention was given to the possible effect of inorganic compounds abundant in mineral soils on the estimation of organic matter content by this method. Both fast heating (DTA‐TGA type) studies and prolonged heating procedures were employed on natural and “synthetic”; soils. The results were compared to those obtained by the dichromate wet‐oxidation method widely used in soil laboratories for organic matter determination. In a group of 91 soils collected from various mineral soils in Israel, and having OM contents between 0.09 and 13.23%, a correlation coefficient of 0.972 was obtained for the linear regression between organic matter content measured by the proposed method and organic carbon measured by the dichromate wet‐oxidation method.     

Soil microstructure and factors of its formation

The microstructural stability of soils of different geneses (steppe soils, tropical soils, and subtropical soils) developed from marine clay, loess, and weathering crusts was studied by the method of successive treatments with chemical reagents destroying the particular clay-aggregating components. The following dispersing agents were used: (1) H₂O (pH 5.5), (2) 0.1 N NaCl (pH 6), (3) 0.002% Na₂CO₃ (pH 8.7), (4) 0.1 N NaOH (pH 11.5), (5) the Tamm reagent (pH 3.2), and (6) 0.1 N NaOH (pH 11.5). The properties of the clay subfractions obtained in the course of these treatments were studied by a set of analytical methods, including X-ray diffractometry, Mössbauer spectroscopy, and magnetic measurements. It was shown that soil microaggregates are formed under the impact of a number of physicochemical processes; the content and properties of inorganic components (clay minerals in soils with a high CEC and iron oxides in soils with a low CEC) are the controlling factors. The structure of the parent materials is transformed to different degrees to form the soil structure. For example, autonomous nondifferentiated soils inherit, to some extent, the specific microorganization of the parent material. At the same time, the redistribution of substances in the soil profile and in the landscape may exert a substantial influence on the soil structure and microstructure. This is particularly true for autonomous differentiated soils, turbated soils, accumulative soils, polylithogenic soils, and polygenetic soils. The properties of the obtained subfractions of the clay (the mineralogical composition, the Fe²⁺/(Fe²⁺ + Fe³⁺) ratio, the magnetic susceptibility, and the Cha/Cfa ratio) attest to the spatial heterogeneity of the composition and properties of the mineral and organic aggregated compounds in soils.     

Time‐dependent zinc desorption in soils

Abstract

Time dependent zinc (Zn) desorption in eight benchmark soils of India was studied in relation to various pH values and ionic strengths. Soil samples were equilibrated in solutions containing 10 μg Zn g^‐1 soil at pH 5.5,6.5, and 7.5 for 48 h at 25±2°C, and adsorbed Zn extracted with calcium chloride (CaCl₂) for various periods of time. Desorption of Zn decreased with increasing pH, and the desorption rate decreased abruptly at pH 7.5. In contrast, an increase in the equilibration period and ionic strength of the background electrolyte increased Zn desorption. Four rival kinetic models were fitted and evaluated for their suitability for describing the Zn desorption process. Reaction rate constant (ß) calculated from the Elovich model for the different soils ranged from 9.99 to 25 (mg Zn kg^‐1)^‐1. The different kinetic models tested indicated that Zn desorption in soils was a diffusion controlled process. The desorption was rapid in the first 4 h, followed by slower phase in the rest of the time at all the pH values indicating a biphasic desorption, characteristic of a diffusion controlled process. The ß value for the Elovich equation showed a strong association with soil clay content and cation exchange capacity (CEC). Further, the best prediction of Zn desorption reaction rate constant could be made using multiple‐regression equation with soil clay content and CEC as variables.     

Soil slaking sensitivity as influenced by soil properties in alluvial and residual humid tropical soils

Purpose

In the humid Caribbean region characterized by high-intensity tropical rainfall, soil aggregate breakdown and pore blocking due to slaking pressures are major land degradation mechanisms. In this research, we investigated the susceptibility of soils to slaking pressures under rapid wetting as influenced by soil properties and the depositional origin from which the soil is formed using water-stable aggregates (WSAr) and percolation stability (PSc) as indices of the strength of aggregate inter-particle cohesion.

Materials and methods

Wet sieving and percolation stability analyses were employed to investigate WSAr and pore blocking, respectively. The combined effect of soil properties of clay, organic matter (OM), cation exchange capacity (CEC), and exchangeable sodium percentage (ESP) was used to determine the slaking sensitivity score (SSc) of 14 physiogeographically important soils in Trinidad, comprising of nine alluvial and five residual soils.

Results and discussion

Results showed that irrespective of alluvial or residual depositional nature of the parent material, samples had high SSc with an average WSAr of 37.8% and PSc of 6.0 mm/10 min. The linear relationships between SSc with WSAr (r²?=???0.12) and SSc with PSc (r²?=???0.012) of all the 14 soils although negative were weak. Clay content accounted for 94.0% of the variation in CEC in alluvial soils and had strong negative relationships with WSAr (r²?=???0.74) and PSc (r²?=???0.79) in residual soils. Additionally, OM with WSAr (r²?=?0.52) and PSc (r²?=?0.24), and CEC with WSAr (r²?=?0.46) and PSc (r²?=?0.39) showed significant positive linear relationships in residual soil.

Conclusions

The predominantly micaceous and kaolinitic clay mineralogy of these soils, coupled with the low OM contents, increases the proneness of the soils to slaking. This suggests that clay mineralogy is responsible for the high slaking sensitivity rather than clay content or just the depositional origin of the soils. As CEC increases, an accompanying increase in OM is required to increase inter-particle cohesion and to impart partial hydrophobicity, which in turn decreases mineralogically induced susceptibility of individual aggregates to slaking.

     

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.     

Effects of changes in pH, ionic strength, and sulphate concentration on the CEC of temperate acid forest soils

As the acidity of rain diminishes, changes in the pH, ionic strength, and ion activities of the soil solution will influence the charge characteristics of soil. We have investigated the response of cation exchange capacity (CEC) of three acid forest soils of variable charge to small changes in pH, ionic strength, and SO^2?₄ concentration. The variable charge for these temperate soils has the same significance as for tropical soils and those from volcanic ash. Maximum absolute increase in CEC on increasing pH by 0·2–0·5 units reached 5 cmol_c kg^-1 in O horizons. The increase in CEC on doubling ionic strength in EA and Bsh horizons of a Cambic Podzol was about half that amount, but relative gains compared to effective CEC were 65 and 46%, respectively. For other soil horizons, absolute changes were smaller, and relative changes were between 10 and 30%. Halving the SO^2?₄ concentration significantly influenced CEC only in some samples. Both pH and ionic strength must be adjusted with care when determining CEC_c of acid forest soils. Decreasing acid deposition will not inevitably increase CEC_c because in some soils pH effects may be balanced by simultaneous decrease in ionic strength.     

A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Zinc Sorption in Selected Soils

Abstract

The adsorption of nutrient elements is one of the most important solid‐ and liquid‐phase interactions determining the retention and release of applied plant nutrients and the efficiency of fertilization. The study showed that the soils with high cation exchange capacity (CEC), CaCO₃, organic matter contents, and heavy texture adsorbed more zinc (Zn). The alkaline soils from Pakistan adsorbed more Zn than English acidic soils. Langmuir and Freundlich isotherm fit was excellent, and r² values for the Langmuir isotherm were highly significant (r²=0.84 to 0.99). The Langmuir b values, representing the adsorptive capacity of a soil, increased as the texture fineness increased in the soil, with increases in the concentration of adsorptive material (such as organic matter and CaCO₃) and with increases in CEC and pH. The alkaline soils from Pakistan had higher bonding energy constant and higher log Kf values than the acidic English soils. Sequential extraction of Zn in these soils showed that most of the Zn was held in CaCO₃ pool in the alkaline soils, whereas in acidic soils adsorbed Zn was in exchangeable form.     

Mutual relationships of biochar and soil pH,CEC, and exchangeable base cations in a model laboratory experiment

Purpose

The majority of biochar studies use soils with only a narrow range of properties making generalizations about the effects of biochar on soils difficult. In this study, we aimed to identify soil properties that determine the performance of biochar produced at high temperature (700 °C) on soil pH, cation exchange capacity (CEC), and exchangeable base cation (Ca²⁺, K⁺, and Mg²⁺) content across a wide range of soil physicochemical properties.

Materials and methods

Ten distinct soils with varying physicochemical properties were incubated for 12 weeks with four rates of biochar application (0.5, 2, 4, and 8% w/w). Soil pH, CEC, and exchangeable base cations (Ca²⁺, K⁺, and Mg²⁺) were determined on the 7th and 84th day of incubation.

Results and discussion

Our results indicate that the highest biochar application rate (8%) was more effective at altering soil properties than lower biochar rates. Application of 8% biochar increased pH significantly in all incubated soils, with the increment ranging up to 1.17 pH unit. Biochar induced both an increment and a decline in soil CEC ranging up to 35.4 and 7.9%, respectively, at a biochar application rate of 8%. Similarly, biochar induced increments in exchangeable Ca²⁺ up to 38.6% and declines up to 11.4%, at an 8% biochar application rate. The increment in CEC and exchangeable Ca²⁺ content was found in soils with lower starting exchangeable Ca²⁺ contents than the biochar added, while decreases were observed in soils with higher exchangeable Ca²⁺ contents than the biochar. The original pH, CEC, exchangeable Ca²⁺, and texture of the soils represented the most crucial factors for determining the amount of change in soil pH, CEC, and exchangeable Ca²⁺ content.

Conclusions

Our findings clearly demonstrate that application of a uniform biochar to a range of soils under equivalent environmental conditions induced two contradicting effects on soil properties including soil CEC and exchangeable Ca²⁺ content. Therefore, knowledge of both biochar and soil properties will substantially improve prediction of biochar application efficiency to improve soil properties. Among important soil properties, soil exchangeable Ca²⁺ content is the primary factor controlling the direction of biochar-induced change in soil CEC and exchangeable Ca²⁺ content. Generally, biochar can induce changes in soil pH, CEC, and exchangeable Ca²⁺, K⁺, and Mg²⁺ with the effectiveness and magnitude of change closely related to the soil’s original properties.

     

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.