Vorstellung der SrCl2-Methode nach Bach zur Bestimmung der effektiven Kationenaustauschkapazität und Vergleich mit der NH4Cl-Methode

Presentation of the SrCl₂-method after Bach for the determination of the effective cation exchange capacity and comparison with the NH₄Cl-method The SrCl₂-method for the determination of the effective cation exchange capacity CEC_eff has been developed by Dr. H. Bach, a former geochemist of the “Geologisches Landesamt Schleswig-Holstein”. Exchangeable metallic cations in soils are displaced by a 0, 1 M SrCl₂-solution and analyzed from the percolate. Reexchange of strontium by a 0, 1 M MgCl₂-solution allows to determine the CEC_eff by analyzing for strontium in the second percolate. In comparison with the customary application of NH₄Cl, SrCl₂ shows the following advantages:

• 1 The nearly unbuffered SrCl₂-solution adopts instantly the pH of the soil.
• 2 In contrast to the weakly acid NH₄Cl-solution, no H₃O⁺-cations compete with the exchange cation. Furthermore, partial dissolution of clay minerals is prevented because of the near-neutral character of the SrCl₂-solution.
• 3 The SrCl₂-method can be applied on all types of soils including carbonate- and salt-bearing soils.
• 4 The amount of free (dissolved) cations can be approximated.

     

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.     

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.     

Eine Methode zur Bestimmung austauschbarer Kationen in Waldböden

A Method for the Determination of Exchangeable Cations in Forest Soils A simple extraction method with NH₄Cl was developed for determining exchangeable cations in forest soils. The influence of selected parameters (reaction time, concentration of NH₄Cl, filter medium etc.) affecting the amount of extractable cations was tested and a standardisation was done. The cation exchange was completed in less than 4 h. For a quantitative extraction of K, Mg, Ca, and Mn a concentration of 0.05 M NH₄Cl was sufficient. The extractable amount of these cations was always clearly defined. However, extracted Al and Fe increased with the NH₄Cl-concentration. Depending on the soil samples, the exchange is not quantitative even when using a saturated solution. The extractable H⁺ is nearly independent of the NH₄Cl-concentration. Probably considerable amounts are dissociated from organic acids. The optimized method is feasible and can be used for K, Mg, Ca, and Mn as an alternative to percolation methods.     

Die Bestimmung der effektiven Kationenaustauschkapazität von Gesteinen

The determination of the effective cation exchange capacity of rocks The extractable cations (1 N NH₄Cl) of broken, mortared, and ground rocks (Sandstone, Clay schist, Diabase, Alkali-Olivinbasalt) were determined using vibration extraction and percolation. These methods were evaluated by re-exchange experiments. In addition mineralogical components, specific surface and effective porosity of the rocks were determined. Al-silicates which are cation exchangers like Illite and Zeolite minerals were found in these rocks. Mortaring and grinding increased the specific surface and the exchange capacity of the rocks which have a low porosity (Clay schist and Basalt). For example, the CEC of broken Clay schist was 27 μmol_c g^?1 and increased to ≈ 40 μmol_c g^?1 after mortaring. The CEC of the rocks with a high porosity (Diabase and Sandstone) did not depend on the particle size. Therefore we assume, that inner parts of the broken rocks were reached by extraction. The CEC amounts to ≈ 50–80% of the sum of the cations, which could be extracted with NH₄Cl. This difference is probably due to the dissolution of salts. Mortaring and grinding increased the amount of cations derived from dissolving of salts. The results show, that rocks are of signficance not only for silicate weathering, but also for the cation exchange.     

Acidification of Solid and Solution Phases at Greater Depths (> 150 cm) at Solling Spruce Site

The acidification of the soil and percolation water at soildepths from 150 to 500 cm was studied at the Solling spruce sitefrom 1991 to 1996. NH₄Cl exchangeable cations of the fineearth and bedrock fractions were obtained from different depthsand the soil solution composition was monitored at 150, 200,300, 400 and 500 cm depths using seven suction lysimeters at each depth.In the seepage water collected from 150 and 200 cm depth, pHvalues decreased in the period 1991 to 1996, but no significantchanges were observed in solutions collected below 200 cm depth.Element budgets of Al and M_b (Na, K, Mg, Ca) cationsindicated that buffering by exchange of Al with M_b cationsoccurred mainly in surface 200 cm soil depth. High variabilities in concentrations of SO₄ (at 150 cm) andM_a (Al, Mn, H, Fe) cations (at 300 and 500 cm) wereobserved. High variabilities in M_a cations could beassigned to one of the lysimeters at each depththat extracted low pH solutions. The amount of exchangeablecations in the fine earth and the bedrock fractions indicatedthat the acidification front (exchangeable M_b cations < 80equivalent percent) had occurred to soil depth of more than 360cm, but the extent of acidification that might have occurred inthe preindustrial period is not known. In both fine earth andbedrock fractions, depthwise changes of exchangeable M_a andM_b cations were quite similar, suggesting that rockfractions have contributed to proton buffering not only bysilicate weathering but also by cation exchange.     

Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.     

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.     

A comparison of buffered and unbuffered ammonium salts to determine exchangeable base cations in acid soils

Abstract

In soil samples from two study sites in southern Norway, exchangeable cations were determined using two different ammonium (NH₄)‐salts as extractant. As expected, the cation exchange capacity (CEC) determined in 1M ammonium acetate (NH₄OAc), buffered at pH 7.0 was higher than the CEC measured in ammonium nitrate (NH₄NO₃). By contrast, the amount of exchangeable calcium (Ca), magnesium (Mg), and barium (Ba) was lowest in the NH₄OAc extract, in particular in the upper soil horizons high in organic matter (O‐ and E‐horizon). This suggests that NH₄ in 1M NH₄OAc does not compete effectively with multivalent base cations. The relatively high levels of exchangeable base cations in NH₄NO₃ could not be explained by increased weathering. An increase in selectivity of especially divalent cations may explain the relatively low amount of exchangeable base cations extracted by NH₄OAc, as this involves increased deprotonation and thus a higher negative charge.     

The sensitivity of Swiss forest soils to acidification and the risk of aluminum toxicity

In the context of pollution‐control strategies to minimize the detrimental effects of soil acidification, there is a need to know how and to what extent soils respond to acidifying substances. The purposes of this study were to assess the sensitivity of soil to acidification, in particular to a decrease in pH and in base saturation (BS), and the risk of Al toxicity for vulnerable plants using chemical indicators. These indicators were derived from soil data (pH, exchangeable cations, amount of fine earth) measured in the mineral horizons of 257 soil profiles throughout Switzerland. Based on the analysis of the distribution of pH and BS values in the soil collective, we assessed the sensitivity of soils to a decrease in pH and in BS. Soils that were considered sensitive to a decrease in pH had pH values between 4.8 and 7.0. The degree of sensitivity was estimated with the proportion of fine earth in the critical pH range to a depth of 100 cm. Soils that were considered sensitive to a decrease in BS had pH values between 3.6 and 5.5 and a BS between 10% and 95%. Since the effective cation‐exchange capacity (CEC_eff) of the fine earth might dampen the decrease in BS when acidity is added, the disposition for a decrease in BS was related to the relative amount of fine earth in the sensitive BS and to the mean CEC_eff of this fine‐earth fraction. The risk of Al toxicity for vulnerable plants was estimated using the ratio of base cations to Al at the cation‐exchange sites (BC : Al_exc). A BC : Al_exc of 0.2 was taken as a threshold value below which the risk for sensitive plants increases. The degree of risk was based on the proportion of fine earth in the critical BC : Al range (≤0.2) in the soil profile. These indicators taking into account the various aspects of soil acidification are derived from usually available data and represent therefore a cost‐effective tool to assess the sensitivity of soils to an input of acidity.     

Extraction of mobile element fractions in forest soils using ammonium nitrate and ammonium chloride

The extraction of earth alkaline and alkali metals (Ca, Mg, K, Na), heavy metals (Mn, Fe, Cu, Zn, Cd, Pb) and Al by 1 M NH₄NO₃ and 0.5 M NH₄Cl was compared for soil samples (texture: silt loam, clay loam) with a wide range of pH(CaCl₂) and organic carbon (OC) from a forest area in W Germany. For each of these elements, close and highly significant correlations could be observed between the results from both methods in organic and mineral soil horizons. The contents of the base cations were almost convertible one‐to‐one. However, for all heavy metals NH₄Cl extracted clearly larger amounts, which was mainly due to their tendency to form soluble chloro complexes with chloride ions from the NH₄Cl solution. This tendency is very distinct in the case of Cd, Pb, and Fe, but also influences the results of Mn and Zn. In the case of Cd and Mn, and to a lower degree also in the case of Pb, Fe, and Zn, the effect of the chloro complexes shows a significant pH dependency. Especially for Cd, but also for Pb, Fe, Mn, Zn, the agreement between both methods increased, when pH(CaCl₂) values and/or contents of OC were taken into account. In comparison to NH₄Cl, NH₄NO₃ proved to be chemically less reactive and, thus, more suitable for the extraction of comparable fractions of mobile heavy metals. Since both methods lead to similar and closely correlated results with regard to base cations and Al, the use of NH₄NO₃ is also recommended for the extraction of mobile/exchangeable alkali, earth alkaline, and Al ions in soils and for the estimation of their contribution to the effective cation‐exchange capacity (CEC). Consequently, we suggest to determine the mobile/exchangeable fraction of all elements using the NH₄NO₃ method. However, the applicability of the NH₄NO₃ method to other soils still needs to be investigated.     

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.     

Acidiphily in pteridophytes: Assessment of the role of root cation‐exchange properties

The soil preference with respect to soil acidity of Asplenium scolopendrium L., Dryopteris filix‐mas (L.) Schott, Pteridium aquilinum (L.) Kuhn as well as of subspecies of the Asplenium trichomanes L. and Polypodium vulgare L. complexes were studied in relation to root cation‐exchange properties. Data were collected for substrate acidity, soil exchangeable cations, and root cation‐exchange capacity. Acidiphilous pteridophytes were characterized by low cation‐exchange capacities. It is unlikely that cation‐exchange properties protect plants from potentially harmful cations such as aluminium or hydrogen, which are abundant under acid soil conditions, through immobilization. It is postulated that cation‐exchange properties are a secondary adaptation to soil acidity, in addition to major adaptations which determine the apparent soil preference. Possibly, a limited variation in cation‐exchange capacity as a function of soil conditions could prevent harmful interactions of soil exchangeable cations with the cation‐exchange sites, such as displacement of cell wall calcium by aluminium or hydrogen ions in acid soils.     

Considerations on cross‐linking by bivalent cations in soil organic matter with low exchange capacity

A soil's cation exchange capacity (CEC) is expected to be relatively inert against changes in cation loading. In this study, we treated a soil sample originating from the organic layer of a forest soil with various bivalent cations after removing the native cations. Sorption isotherms and cation exchange capacity were determined, the latter using the BaCl₂ method. Sorption showed Langmuir characteristics, with the maximum coverage (Q_max) increasing in the order Ba²⁺ < Ca²⁺ < Mg²⁺, but being clearly smaller than the initial load of native exchangeable cations. The Langmuir coefficient, k_Me, depended oppositely to the order obtained for Q_max. CEC increased upon cation treatment and it varied by a factor of almost two. The unexpected variation of CEC was explained by the low cation exchange capacity of the organic matter such that not all functional groups are close enough to be bridged and the second charge of a bivalent cation is not neutralized by the organic functional group. The Langmuir sorption type, and Q_max being smaller than the content of sorption sites and being largest for Mg, suggested that only a part of the sites can be cross‐linked and at least part of the cross‐links are formed by hydrated cations. Thermodynamic considerations allowed reconstruction of two contrasting processes during CEC determination by Ba²⁺: Case A: the disruption of cross‐links, which increases with the cationic strength and the cation load before CEC determination, but does not require structural re‐orientation in the SOM matrix, and Case B: the formation of new cross‐links during CEC determination, depending only on the content of unoccupied sites before CEC determination and requiring structural re‐organization of the matrix and thus a minimum matrix flexibility. The use of bivalent cations for CEC determination may thus result in an overestimation of CEC for organic matter with low CEC. This has, however, promising potential when comparing CEC determined with monovalent cations and bivalent cations. Using a set of bivalent cations, may allow probing distribution of distances between functional groups in the organic matter and even characterize the matrix rigidity of the cation‐cross‐linked network.     

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.     

Soil physical properties affected by long-term fertilization

According to the literature, soil physical properties are linked mainly with organic constituents that are often considered as the first indicator of soil fertility. But the use of fertilizers and amendments can change soil properties independently of the organic matter content. In a long‐term experiment at Versailles, fertilizers and amendments have been applied each year to uncultivated plots. After 70 years, the plots had the same low organic matter content except those which were treated with manure. However, the physico‐chemical environment had become strongly differentiated. Physical properties, especially soil water relations, were also greatly affected. The use of ammoniacal fertilizers strongly decreased soil pH and cation exchange capacity (CEC_soil). Plots treated in this way were more sensitive to the degradation of their hydraulic properties and became unstable in spite of the preservation of their porosity. Basic amendments (i.e. bases added as CO₃^2–, OH^–, O^2– or silicate anions) increased soil pH, CEC_soil and its saturation by exchangeable calcium. The increase in CEC_soil improved soil structural cohesion and water flow properties. After basic treatment, there is greater structural stability, and water moves faster through the soil. In potassic and sodic plots, K⁺ and Na⁺ affected water movement and increased the soil's sensitivity to degradation. Manure treatment increased water retention and soil stability. The cation exchange capacity, measured at soil pH, can be used as a good indicator of soil stability, in combination with the organic matter content and the kinds of exchangeable cation (especially K⁺ and Na⁺).     

Cation exchange properties of acid forest soils of the northeastern USA

Negative correlations between soil pH and cation exchange capacity (CEC) or base saturation in soils of the northeastern USA and Scandinavia have raised questions regarding the nature of cation exchange in acid forest soils. Using data from three small‐catchment studies and an extensive regional survey of soils in the northeastern USA, I examined relationships among total carbon, effective CEC (CEC_e), soil pH_s (in 0.01 m CaCl₂) and base saturation. Organic matter is the predominant source of soil surface charge in these coarse‐grained, glacially derived soils. Correlation coefficients (r) between total carbon and CEC_e ranged from 0.43 to 0.74 in organic horizons and from 0.46 to 0.83 in mineral horizons. In all cases, the intercepts of functional relations between CEC_e and total C were near zero. In O horizons, the CEC_e per unit mass of organic carbon (CEC_e:C) was positively correlated with pH_s in three of the four data sets, consistent with the weak‐acid behaviour of the organic matter. However, CEC_e:C was negatively correlated with pH_s in mineral soils in two data sets, and uncorrelated in the other two. The CEC_e in mineral soils represents the portion of total CEC not occupied by organically bound Al. The negative correlations between CEC_e:C and pH_s can therefore be explained by increased Al binding at higher pH_s. Aluminium behaves like a base cation in these soils. When Al was considered a base cation, the relation between base saturation and pH_s could be effectively modelled by the extended Henderson–Hasselbalch equation. When modelled without Al as a base cation, however, there were no consistent relationships between pH_s and base saturation across sites or soil horizons. Because of the non‐acidic behaviour of Al, it is difficult to predict the effect of ongoing reductions in acid deposition on the base status of soils in the northeastern USA.     

The determination of ammonium and chloride by an auto‐analyser for the measurement of cation exchange capacity of soils

Abstract

An auto‐analyser method has been developed for the simultaneous determination of NH₄ ⁺ and Cl^‐ in Ca(NO₃)₂/KNO₃ extracts of NH₄Cl treated soils for cation exchange capacity measurements. The method gives satisfactory agreement with manual titration procedures.     

Relationship between water soluble and exchangeable soil cations for estimating plant uptake and leaching potential

Abstract

The relationship between water soluble and exchangeable cations (Ca, Mg, Na, and K) was investigated for surface horizons of 195 soils including many taxonomic categories and a wide range in physical and chemical properties from around the world. This will provide information on exchangeable soil cation solubility for use in estimating plant uptake and leaching potential. Amounts of water soluble and exchangeable cations were not consistently related (r² of 0.50, 0.08, 0.77, and 0.49 for Ca, Mg, Na, and K). High correlations were biased by high water soluble and exchangeable cation levels of a few soils that had 3.8‐ and 2.5‐fold greater mean than median values. The ratio of exchangeable to water soluble cations was closely related to cation saturation (r² of 0.87, 0.95, 0.95, and 0.93 for Ca, Mg, Na, and K, respectively). As the degree of saturation of the exchange complex by a certain cation increased, solubility Increased. A change in saturation had less effect on K than on Na, Mg, and Ca solubility. Only exchangeable soil cations (NH₄OAc extractable) are routinely measured and reported in soil survey reports, thus, water soluble levels may be determined from cation saturation. This will allow estimation of the amounts of cation that can potentially move in solution through the soil or be taken up by plants. Use of cation saturation, in addition to exchangeable content, will better characterize soil cation availability by representing quantity, intensity, and buffer factors.     

Sequential Leaching of Volcanic Soil to Determine Plant-Available Cations and the Provence of Soil Minerals Using Sr Isotopes

Sequential leaching experiments using H₂O, H₂O₂, NH₄Cl, and HCl were performed on surface soils on an andesite substrate at four sites in the Kawakami mountainous area, central Japan. The solutions extracted from the dehydrated soil by H₂O, H₂O₂, and NH₄Cl have relatively constant ratios with respect to Ca, Mg, and Sr, while they have variable ⁸⁷Sr/⁸⁶Sr ratios depending on the site. The elemental ratios and Sr isotopes in the extracted solution are different from those of the soil minerals but identical to those of the soil solution and the plants. Sr isotopic data indicate that the residues after extraction from fine-grained minerals by NH₄Cl and HCl are a mixture of acid-resistant minerals derived from bedrock and from arid areas in China. We suggest that there is a vital exchange of Sr and other cations between plants and the soil pool of exchangeable cations through the soil solution, while soil minerals, except chlorite, do not participate in the exchange reaction.