Cation exchange capacity and reactions

Donald S Rossa and Ulf Skyllbergb, aDepartment of Plant & Soil Science, Jeffords Hall, University of Vermont, Burlington, VT, United States;
b
Department of Forest Ecology and Management, Swedish University of Agricultural Sciences, Umeå, Sweden
© 2022 Elsevier Ltd. All rights reserved.

Introduction 1
Sources of charge in soils 2
Permanent negatively charged mineral surfaces 2
Variably charged mineral surfaces 3
Charges of soil organic matter functional groups 3
Cation exchange concept and models 4
Cation exchange equations 4
Extension of the cation exchange concept to variably charged soils 6
Exchangeable and non-exchangeable aluminum and hydrogen ions 6
Base saturation and CEC definitions 7
Cation exchange in acidic forest soils 8
Cation exchange in highly weathered tropical soils 10
Summary and outlook 10
References 11

Key points
• Cation exchange is an important chemical reaction in soils that governs the plant availability of nutrients such as calcium,
magnesium and potassium.
• The source of negative surface charge in soils is permanently charged clay minerals, variably charged metal oxides and soil
organic matter functional groups.
• Different soils may be dominated by different types of cation exchange. Sodium–calcium exchange may be important in
high-pH clay soils and aluminum–hydrogen ion exchange in low-pH forest soils.
• Cation exchange can be described quantitatively with reversible, thermodynamic equations. Constants for these equations
are conditional because of difficulties in estimating the activity of cations adsorbed by surfaces and occupying the electrical
double layer.
• The term ‘base cation’ can easily be misleading for calcium, magnesium, potassium and sodium. In a relatively narrow pH
range, the saturation of soil negative charges by these cations (‘base saturation’) is often positively related to pH.
• The pH-dependent chemistry of aluminum hydrolysis and bonding to soil organic matter complicates cation exchange
modeling in low-pH soils. This could be overcome by introducing operationally defined exchangeable and
non-exchangeable fractions of Al (aluminum) cations.
• In moderately acidic soils, aluminum hydrolysis buffers change in soil pH. In highly acidic soils, exchange between
aluminum and hydrogen cations is an important pH buffering process.

Introduction

The study of cation exchange is often credited as the beginning of the discipline of soil chemistry. Early work by H.S. Thompson,
followed closely by J.T. Way, was published in 1850 in the Journal of the Royal Agricultural Society of England (Thompson, 1850;
Way, 1850). They observed that a cation such as NH+4 (ammonium) will displace Ca2+ (calcium) from soil and do so rapidly,
reversibly and quantitatively. These results still hold essentially true for many soils and combinations of common exchangeable
cations, e.g. Na+ (sodium), K+ (potassium), NH+4, Mg2+ (magnesium), and Ca2+. These cations can be modeled as being held in the
soil by weak, electrostatic interactions with negatively charged surfaces. In this idealized representation, the cations remain hydrated
in a diffuse swarm or layer close to the soil surface but do not directly bond. The sum of the negative charges is termed the cation
exchange capacity (CEC) of soil. Early work focused on agricultural soils in which the source of the negative charge was largely from
clay minerals with isomorphic substitution, e.g. an Al atom with +3 charge substituting in the crystal structure where a Si (silicon)
atom with a +4 charge is usually located. This type of charge is termed ‘permanent,’ because it is independent of pH. Cation
exchange processes were relatively straightforward to study in these settings, but are more complex in soils with ‘variably’ (pH-
dependent) charged minerals, such as iron (Fe) oxyhydroxides, and in acidic soils where aluminum is more soluble and reactive.
The only finding from Way’s early work that has not held up is his assertion that soil organic matter (SOM) had no charge.
Subsequent work has shown the importance of SOM, and in fact, it is the primary source of CEC in many soils, especially those with

Encyclopedia of Soils in the Environment, Second Edition https://doi.org/10.1016/B978-0-12-822974-3.00063-X 1

2 Cation exchange capacity and reactions

a low clay content. Research on cation exchange processes has continued for the past 170 years with many advances in both our
conceptualization and mathematical description of exchange reactions, although much of the focus has remained on clay minerals
as the source of negative charge.
The preponderance of cations that are held in an exchangeable form in soils, Ca2+, Mg2+, K+, and sometimes NH+4, are important
plant nutrients. Their availability for plant uptake is primarily a function of a soil’s CEC, although some K+ and NH+4 can be fixed
and only slowly released from the interlayers of some 2:1 clay minerals. These cations are relatively small and weakly polarizable
(hard) Lewis acids (accept a pair of electrons) and interact electrostatically with negatively charged soil surfaces (similar to hard
Lewis bases). Because of its prevalence in most parent material, its divalent charge and its energy of hydration, Ca2+ is usually the
dominant exchangeable cation in the normal pH range of agricultural soils, e.g. pH 5.5–7.5 (Table 1). The CEC of more acidic soils
can be dominated by exchangeable Al3+, whereas more alkaline soils may be sodic and dominated by exchangeable Na+. The
currently used unit for CEC is centimole of charge per kilogram (cmolc kg−1) and most soils range between 5 and 20 cmolc kg−1. This
unit was inherited from the commonly used, and numerically equivalent, pre-SI unit of milliequivalent per 100 g of soil and is likely
to be the only instance when one will use the cmol notation. The range of CEC in different soils is quite wide, but higher is not
necessarily better (in an agricultural sense) as long as sufficient nutrient cations are retained. Coarse-textured soils, low in clay and
SOM, may have very low CEC and not be able to retain sufficient calcium for optimal plant growth. The relative affinity of soil
surfaces for Ca2+ over Na+ is of global significance because these two elements have similar abundance in the Earth’s crust; most of
the Na+ released from weathering ends up in the oceans while Ca2+ is retained in soils.

Sources of charge in soils

Permanent negatively charged mineral surfaces
Early researchers recognized that clay was a source of negative charge in soils, but the structure of clay minerals, a subgroup of
phyllosilicates, was not understood until the advent of X-ray diffraction techniques in the 1930s. Based on the work of Linus Pauling
and others, the layered structure of some common clay minerals was found to have cations substituted by a different cation of
similar size but lower charge. For example, the Si4+ cation in a silica sheet could be substituted by Al3+, or an Al3+ cation in an
aluminum sheet could be substituted by Mg2+ or Fe2+. Most clay minerals that develop charge have two silica sheets sandwiching
one aluminum sheet (2:1 layer) and this isomorphic substitution results in a net negative layer charge. In some geologically-derived
phyllosilicates, such as muscovite, the layer charge is balanced exactly by an interlayer cation, such as K+, that is part of the crystal
structure, and the overall mineral charge is zero. In many soil-derived clays and weathered inherited phyllosilicates, the layers are no
longer held tightly together and water and associated dissolved ions can enter, e.g. illite, a hydrous mica. The exposed clay surfaces
have a negative charge that must be balanced by cations in the soil solution. The geometry, distribution and strength of the negative
charge is not sufficient to form inner-sphere bonds (strong ionic or covalent associations excluding water molecules) with the
cations and a diffuse swarm of hydrated cations balances the charge. This negative charge is considered permanent because it is
usually not affected by soil pH, ionic strength, or the type of exchangeable cations present. This permanence may be somewhat less
so in acidic soils that foster the precipitation of positively charged polynuclear Al-hydroxides in the clay interlayers, which block
some of the permanent charge. The types of soil clay minerals that display this permanent charge tend to dominate the clay-size soil

Table 1 Median CEC, exchangeable cations, organic carbon, and pH for selected World Reference Base (WRB) soil groups compiled from the World Inventory of
Soil Emission Potential (WISE) database (Batjes, 2009).

WRB group approx. USDA n CECe CECt Exch-Ca Exch-Mg Exch-K Exch-Na Exch-Al Org-C pHw
cmolc/kg g/kg

Acrisol Ultisol, Oxisol 244 3.9 8.8 1.14 0.60 0.20 0.10 0.80 17.0 4.80
Andosol Andosol 99 7.6 25.0 4.80 1.90 0.40 0.20 0.10 43.2 6.00
Arenosol sandy Entisol 158 4.0 4.3 2.75 0.60 0.20 0.10 0.10 3.0 6.90
Calcisol Aridisol 99 27.9 17.1 23.40 2.80 0.70 0.30 0.00 6.8 8.20
Cambisol Inceptisol 372 14.9 18.6 10.40 2.20 0.40 0.20 0.10 13.0 6.90
Ferralsol Oxisol 225 2.7 9.2 0.40 0.30 0.10 0.05 1.04 18.0 4.76
Fluvisol alluvial Entisol 184 17.8 17.0 12.30 2.90 0.50 0.30 0.00 11.0 7.30
Luvisol Alfisol 357 11.2 11.7 7.50 1.90 0.40 0.20 0.10 8.0 7.00
Phaeozem humid Mollisol 168 23.8 23.5 18.00 3.20 0.60 0.20 0.00 14.8 7.05
Regosol Entosols 107 6.0 9.0 4.10 1.20 0.30 0.10 0.00 9.9 7.00
Solonetz natric Aridisol 117 15.8 13.5 8.80 2.80 0.60 0.90 0.00 8.0 8.00
Vertisol Vertisol 436 49.8 46.5 34.10 11.00 0.70 0.66 0.00 9.0 7.60

Podzols were not well represented in this database (see Table 2).
WRB groups are from WRB (2006). The approximate equivalent in USDA soil taxonomy (approx.. USDA) is also provided. The effective CEC (CECe) was calculated from the sum of
exchangeable (Exch-) cations and the total CEC (CECt) was measured at a reference pH of 7.0 or 8.2. The pH (pHw) is the pH in water.
 Cation exchange capacity and reactions 3

fraction in soils of the temperate regions, such as Europe (including Russia) and the USA, where most of the initial research on soils
was performed.

Variably charged mineral surfaces

There are clay minerals, which are a class of phyllosilicates, and there are clay-sized minerals, which include non-silicates such as Al,
Fe and Mn (manganese) (oxy)(hydr)oxides. This may be confusing because, in soil science, the word clay is used for two different
purposes—particle size and mineralogy. The non-silicates are much more prevalent in acidic and highly weathered soils, such as
found in the tropics. The charge on these oxide surfaces is not derived from structural substitution but, instead, from surface
functional groups. These are usually –OH groups that can lose or gain an H+ (hydrogen) and take on a negative or positive charge.
The propensity to dissociate and create a negative charge depends on a number of factors that include the nature of the metal, the
structure of the mineral and the ionic strength and pH of the solution. Different ions can also affect the charge, but the ion
determining primary electrical potential is H+ and thus pH is usually the controlling factor. Some of the variably charged minerals
can have a net positive charge, especially at low pH, and there is a pH at which the overall net charge is zero. These variably charged
minerals were not widely researched until the last part of the 20th century, when there was more focus on acidic subtropical and
tropical soils. However, Sante Mattson, working with a variety of soil types in Sweden, clearly showed variable charge in his 1931
paper: ‘The laws of soil colloidal behavior: VI. Amphoteric behavior’ (Mattson, 1931). Most other work during this decade, and for
many to follow, focused on phyllosilicates that have only minor variable charge on the edges of the Al and Si sheets.

Charges of soil organic matter functional groups

The importance of SOM for the CEC of soils, similar to variably charged minerals, was documented in the early part of the 20th
century by a few researchers, including Mattson, but its general importance for CEC was only recognized decades later. It is now clear
that both clay-size minerals (phyllosilicates and metal oxyhydroxides) and SOM contribute to the negative charge of soils and SOM
can be the primary source of charge. This is especially true in many forest soils developed from coarse textured parent material, e.g.
glacial drift, where surface horizons can be quite low in clay content but quite high in SOM, and higher CEC is strongly correlated
with higher SOM (Fig. 1) (Johnson, 2002). The charge on SOM develops from the dissociation of H+ from primarily carboxylic
groups and to a lesser extent phenolic groups. These functional groups have been found to have a wide range of acid strengths (pKa

Fig. 1 Relationship between soil organic matter and effective cation exchange capacity (CECe) at three different forested watersheds in the northeastern USA
(Spodosols and Inceptisols in USDA Taxonomy). Open circles are O horizons and ‘+’ are mineral horizons. Organic matter was measured in the top panel by loss-
on-ignition and a direct measurement of carbon (
58% of SOM) was used in the bottom two panels. The effective CEC (CECe) was determined by the sum of
exchangeable cations. The source is Johnson CE (2002) Cation exchange properties of acid forest soils of the Northeastern USA. European Journal of Soil Science
53: 271–282, part of Fig. 2, which is reproduced with permission.
4 Cation exchange capacity and reactions

values, which measure the propensity of an acid to release H+) so that raising or lowering the pH will usually increase or decrease the
negative charge of soil linearly, and buffer its pH value. What is not widely recognized, however, is that the negative charge per
amount of SOM does not vary much in field soils below a pH of about 5.5 even though adjusting the pH of an individual soil
sample will cause a dramatic change (Ross et al., 2008). This is the result of the interplay between Al, pH, and the development of
SOM-associated charge, and will be discussed further below. The SOM does not develop detectable positive charge at any pH. Thus,
it is not amphoteric like the metal oxyhydroxides. Adding organic residues, manure or compost to soil can bring about many
physical and chemical improvements and is an effective means of increasing a soil’s CEC. This can be especially important for
sustainable agricultural production on low-clay soils where increased SOM may be needed to maintain soil fertility.

Cation exchange concept and models

Conceptual and mathematical models of cation exchange reactions were developed in the early part of the 20th century with the
assumption of an idealized, permanently charged surface. An early approximation, the Helmholtz model, describes the particle–soil
solution interface as a charged surface with associated, adsorbed cations. Experimental results were however better described by an
exponential decrease in the concentration of cations from the negatively charged particle surface into the bulk solution. This so
called diffuse double layer (DDL) is explained by the Guoy–Chapman theory. The DDL, later renamed the electrical double layer
(EDL) to be more explanatory, extends out into the soil solution to a distance at which there is no longer any electric force from the
surface and the cationic and anionic charges cancel out. Thus, two opposing forces act on ions in the soil particle–bulk solution
interface—the electrostatic attraction of cations toward the negatively charged surface (together with repulsion of anions) and
diffusion forces by which the excess of cations near the surface migrate along the concentration gradient toward the bulk solution
(anions migrate in the opposite direction). The thickness of the EDL can be calculated by the Guoy–Chapman theory, and it varies
not only with the magnitude of surface charge but also with the valence and concentration of the ions in the bulk solution. Divalent
cations will create a thinner double layer than monovalent cations, as will a larger concentration of ions (a higher ionic strength).
The EDL model and associated equations help to explain flocculation and dispersion of charged soil particles as influenced by the
relative abundance of cations such as Ca2+ (promotes thinner EDL that allows flocculation of soil particles) and Na+ (promotes
thicker EDL that keeps particles dispersed). To improve the fit further to experimental data, several modifications of the Guoy–-
Chapman theory have been proposed. The Stern modification adds a layer of strongly adsorbed cations, also referred to as the
Helmholtz layer that effectively decreases surface charge and thus the EDL thickness. In the ideal case, cations adsorbed in the Stern
layer are imagined as inner-sphere bonded (non-hydrated), whereas the cations in the EDL are considered fully hydrated (Fig. 2).
The propensity of a cation to be adsorbed is a function not only of charge but also the energy of hydration, i.e. the energy released
when the cation reacts with water; this reflects the strength of the bond between the cation and the first shell of water molecules. A
cation from the same group in the periodic table, e.g. the alkali metals or the alkaline-earth metals, will be preferentially adsorbed in
its non-hydrated state if its atomic number and ionic radius are higher and therefore its energy of hydration is lower. Thus K+, atomic
number 19, will be adsorbed more strongly than Na+, atomic number 11, and Ca2+, atomic number 20, will be more strongly
adsorbed than Mg2+, atomic number 12. This is the basis for cation selectivity, discussed further in the next section. The theory and
equations used to describe the EDL were initially based on the premise of permanently charged surfaces of clay minerals, but have
since been adapted for variably charged minerals and functional groups of SOM to cover cation exchange and surface complexation
reactions of metals and their ions in soils (Goldberg, 1992; McBride, 1994; Sparks, 1995; Tipping, 2002; Evangelou and Phillips,
2005; Essington, 2015; Strawn et al., 2015).

Cation exchange equations

A variety of equations have been developed to describe exchange reactions between cations in the bulk solution and cations in the so
called exchange phase (weakly adsorbed at the surface or in the EDL) of soils. In its simplest form, reactions are restricted to
exchange between two cations of the same charge (homovalent, e.g. Na+ and K+) or different charge (heterovalent, e.g. Ca2+ and K+)
taking place on permanently charged clay mineral surfaces. These reactions take the form of simple chemical equilibria equations,
but differ primarily in how the exchange phase is expressed. The difficulty in developing true equilibrium constants, i.e. thermo-
dynamic stability constants, is primarily because of uncertainty in how to calculate the activity of the cations (in principal their
effective concentrations) at the surface and in the EDL. It is also difficult to account for electrostatic effects at the surface, i.e. the work
required to migrate cations from the EDL into the bulk solution. No suitable method is known. When applied to soils, the
heterogeneity of permanent and variably charged surfaces also limits transferability of equilibrium constants. Because the constant
in a cation exchange equation incorporates all these factors and uncertainties it is termed a selectivity coefficient and is referred to as
conditional rather than being constant. In systems with variably charged particles it also depends strongly on pH and ionic strength.
Nonetheless, these equations have been useful in applications such as the soil fertility of the common nutrient cations, effects of
liming and in predicting the effect of Na+ in irrigation water on soil dispersion. Two of the most commonly used equations are
presented below and the reader is referred to soil chemistry text books such as Essington (2015) for additional permutations and
discussion. Some of the more recently developed equations have a stronger footing in thermodynamics but do not necessarily
provide better results.
 Cation exchange capacity and reactions 5

Fig. 2 Conceptual description of the particle surface–soil solution interface of a theoretical soil composed of negatively, permanently charged clay and variably
charged natural organic matter (NOM) functional groups and metal oxide surfaces. Anions in solution are for simplicity represented by chloride. The electrical
double layer (EDL) has a thickness on the nanometer scale depending on pH and ionic strength. The effective cation exchange capacity (CECe) is composed of cations
held in the EDL: mono- and di-valent base cations (at pH 7.0, left), and H+, Al(OH)3-n
n and BC (at pH 4.5–5.0, right). The total CEC (CECt) in addition includes
non-exchangeable RCOOH functional groups (Ht–He) with a pKa value of a reference pH (7.0 or 8.2) and below, as well as chemisorbed Ca and Al cations.

The Vanselow equation expresses the exchange phase cations as the mole fraction of the total CEC. For a homovalent exchange
reaction, this is the same as moles of charge, but this is not the case for heterovalent exchange. In the equation below, the mole
fraction of Na+, NNa, is the moles of Na+ in the exchange phase divided by the sum of the exchange phase moles of Ca2+ + Na+.
Vanselow


KV ¼ NCa ðNa + Þ2 =NNa 2 Ca2 + ,

where KV is the Vanselow constant, N is the mole fraction in the exchange phase and () is the solution activity.
Gapon
   1=2
Kg ¼ Ca1=2 X ½Na + =½NaX Ca2 + ,

where Kg is the Gapon constant, X is the exchange phase and the solution cations are expressed as concentrations [].
The Gapon equation expresses the exchange phase in moles of charge instead of a simple mole fraction and uses molar
concentration instead of activity in the solution phase. It is probably evident that these two equations will provide different results,
but they do not differ dramatically over the normal range of CEC and exchangeable cation concentrations.
What becomes clear when applying these equations is that there is a strong selectivity for different cations, even those of the same
valence. For example, at equal concentrations of Ca2+ and Na+ in solution, the equilibrated exchange phase would be over 95%
Ca2+. The constant for Ca2+/K+ exchange tends to be a factor of 10 different from that for Ca2+/Na+, and the exchange phase for K+ is
commonly much higher than that of Na+. The relative selectivity for common exchangeable cations, also known as the lyotropic
series, is Al3+ > Ca2+ > Mg2+ > K+  NH+4 > Na+. The effect of valence is much stronger than that of different hydration energies
within a valence, but the latter is also important. Additional cations could be added to this list but these six dominate the exchange
phase across a range of soil types and pH. Many other divalent cations found in soils are transition metals, such as Cu2+ (copper),
Zn2+ (zinc), Cd2+ (cadmium) and Pb2+ (lead), and their interaction with soil surfaces is usually more complex (due to inner-sphere
and hydrolysis reactions) than the outer-sphere hydrated ionic behavior assumed for exchange reactions. This complexity is also
true for the behavior of Al3+ in soils, discussed further below.
6 Cation exchange capacity and reactions

Extension of the cation exchange concept to variably charged soils

When the cation exchange concept, originally developed for reactions taking place at the surfaces of permanently charged clays in
agricultural soils, was applied to a wider range of soils cations other than Na, K, Mg and Ca had to be considered. In acidic forest
soils (e.g. Alfisols, Inceptisols, Spodosols) and highly weathered soils (Oxisols and Ultisols) dominated by variably charged metal
oxide minerals and functional groups of SOM, the ‘major cations’ taking part in cation exchange reactions at surface charges of soil
components would include H+ and Al cations (Al3+ and its hydrolysis products, collectively written Al(OH)(3-n)+ n ; n ¼ 0–3). During
the “acid rain research era” (roughly 1970s to 1990s) simplified models were developed in which the cation exchange between Al3+
and the so called base cations (BC: Na+, K+, Ca2+, Mg2+) was linked to the pH-dependent solubility of the Al(OH)3 (s) mineral
gibbsite. This process was described as a major pH buffering mechanism by which soils neutralized H+ in acid rain and indirectly
controlled the nutrient availability and acidity in runoff from soils to surface waters (Christophersen et al., 1982 [ILWAS model];
Cosby et al., 1985 [MAGIC model]; Reuss, 1983). This type of model fits data from B horizons of Spodosols affected by acid rain
and with a pH exceeding approximately 4.0–4.5 (Fig. 3), but fails at lower pH as discussed below.
Somewhat earlier, research on clay mineral chemistry conducted at pH values well below neutrality had revealed that the
hydrolysis of Al and its products (the cations Al(OH)(3-n)+ n ) also played a previously overlooked role at permanently charged
surfaces (Harwood and Coleman, 1954; Low, 1955). Hydroxy-interlayered vermiculite (HIV) and smectite (HIS) minerals denote
permanently charged minerals with part of their negative charge ‘blocked’ by Al(OH)(3-n)+ n cations and or layers of positively charged
polynuclear Alx(OH)(3x-n)+
n polymers. This effect is largest at pH values in the approximate range of 4.5–6.0 (cf. Fig. 2). When pH is
raised further, the hydrolysis of Al and nucleation of non-charged Al-oxyhydroxide minerals, e.g. gibbsite Al(OH)3(s), reaches
completion and covers the interlayers of these minerals, with the permanent negative charge of the clay restored (Bertsch and
Bloom, 1996). Similar to Al cations blocking interlayers of HIV and HIS, Al(OH)(3-n)+ n cations may form thermodynamically very
stable complexes with functional groups of SOM, e.g. di/tri carboxyls, phenol and quinone (McColl and Pohlman, 1986). These
strongly bonded Al cations are not considered readily exchangeable against other cations. When the cation exchange concept was
extended to variably charged minerals and soils dominated by such minerals, the CEC concept therefore required some redefinition
and extension.

Exchangeable and non-exchangeable aluminum and hydrogen ions

One important extension of the cation exchange concept for variably charged soils is the division of Al into exchangeable and
non-exchangeable forms. Aluminum chemistry is markedly different from that of the other major metal cations in soils, which are
alkali and alkali-earth metals. It is a primary component of most clay minerals and one of the major elements in the Earth’s crust
(third most abundant after oxygen and silicon) but is relatively insoluble at a pH above about 5.5 – 6.0. Below this pH, Al can be
solubilized but is also quite reactive and will readily form strong complexes with oxygen-containing functional groups of SOM and
oxygen-containing anions such as sulfate and phosphate, and will also hydrolyze to form soluble and insoluble Al-hydroxy
polymers. Even though Al participates in numerous reactions in soils, an exchangeable fraction may be operationally defined. A
selection of neutral salts of cations that are non-specifically adsorbed to soil particles (e.g. KCl, NH4Cl, BaCl2) will extract a similar
amount of Al from a soil, and this is operationally defined as exchangeable Al. Repeated extractions or leaching with a neutral salt,

5
Gapon
1:2 CaCl2
pH

R2 = .894
4

3
0 0.2 0.4 0.6 0.8 1
Ca Satura on
Fig. 3 Relationship between Ca saturation of CECe and pH (measured in 0.002 M CaCl2) in mineral horizons of Spodosols. A model based on cation exchange
between Al and Ca, depicted by the Gapon equation, linked to pH dependent solubility of gibbsite, Al(OH)3(s), fits observations in B horizon samples (black squares
and black curve). In the E horizon samples (open symbols), the model cannot explain the observations. This is because when pH drops below 4.0 (corresponding to

4.5 at pH in water), Al exchanges with H rather than with Ca (or other BCs), and the model collapses. Printed with permission from Reuss JO, Hopper RWE, Walthall
PM, and Roswall EC (1990) Aluminum solubility, calcium-aluminum exchange, and pH in acid forest soils. Soil Science Society of America Journal 54: 374–380.
 Cation exchange capacity and reactions 7

or the use of stronger extractants (i.e. more acidic and or containing polyvalent metal cations competing with Al for oxygen groups
or ligands complexing with Al cations) will however extract more Al. This suggests that there is a continuum of strengths of adsorbed
Al in soils, but with a neutral-salt-defined fraction assumed to participate in exchange reactions similar to other exchangeable
cations. Notably, this fraction will be strongly pH dependent.
Non-exchangeable Al is represented by Al cations (Al3+ and partly hydrolyzed forms collectively captured by the formula
Al(OH)(3-n)+
n ) strongly complexed by SOM functional groups, as well as Al(OH)(3-n)+ n cations and or layers of positively
charged Alx(OH)(3x-n)+
n polymers captured in interlayers of permanently charged minerals and amorphous Al-oxyhydroxide
minerals. Notably, this non-exchangeable fraction is still a minor fraction of the total quantity of Al in soils, dominated by
aluminosilicate minerals which can only be extracted by total digestion in very strong acid (e.g. concentrated HF, hydro-
fluoric acid). In forest surface soils with a naturally low pH (<5.0), conditions at which permanently charged clay minerals
are not stable, 0.5 M CuCl2 (copper chloride) has been successfully used as a quantitative extractant of organically absorbed
Al (Juo and Kamprath, 1979), and the difference between 0.5 M CuCl2 and 1.0 M KCl extractable Al has been used as a
measure of non-exchangeable forms of Al in these types of soil (Skyllberg, 1999).
Most productive agricultural soils, including those studied in the first century of soil chemistry research, have a pH above 5.5 and
no or very little exchangeable Al3+. More acidic agricultural soils of the tropics and subtropics can have sufficient exchangeable Al+3
to cause toxicity to sensitive crops. Because of the hydrolysis reactions of Al (transformation of Al3+ to Al(OH)(3-n)+
n cations and H+)
over the pH range of about 4.2 to 5.5 (even higher pH if complexed by SOM, which suppresses hydrolysis), Al has been considered
to be an acid cation. With decreased pH below 5.5, exchangeable Al3+ should increase in concentration and become a higher
percentage of the CEC, but at pH 4.2 and lower, Al hydrolysis is minimal. In this relatively narrow pH range (4.2–5.5), the Al3+
fraction of the CEC can be a good predictor of soil pH (negative correlation).
Similar to Al, hydrogen ions become important in the exchange processes of more acidic soils. This is particularly true when pH
decreases below 4.2 and Al(OH)3(s) is not a stable mineral. At such a low pH, H+ is a major cation in soil solutions, readily taking
part in cation-exchange reactions. Highly acidic Oa horizons can have exchangeable H+ greater than 10 cmolc kg−1, occupying over a
third of the exchange sites (Table 2). In many forest soils with a natural pH below 4.5 in the organic surface horizons and A/E
horizons, cation exchange between H+ and Al3+ is the major pH buffering process (Skyllberg, 1999; Ross et al., 2008) and H+ and Al3+
dominate the CEC over Na+, K+, Mg2+ and Ca2+ (Figs. 4 and 5).
A non-exchangeable pool of H can also be defined, similar to Al. It is composed of H+ that is not dissociated from SOM
functional groups at the pH of the soil or extraction solution (i.e. these functional groups have a pKa value well above the pH of the
soil, Fig. 2). In SOM-dominated soils, e.g. Oa (H) horizons and Histosols, the pool of non-exchangeable H+ is large, as represented
by the protonated carboxyl and phenol functional groups of SOM. This pool is denoted Ht, an abbreviation for total or titratable H+.
The latter is understood to be non-exchangeable H+ released from soil by the reaction with OH− under formation of water during
base titration.

Base saturation and CEC definitions

There are two important CEC definitions: the total (CECt) and the effective (CECe). Total CEC represents all potential negative
charges on soil particles when the soil is raised to a reference pH of 7.0 or 8.2 (the latter often used because it is the pH reached in
equilibrium with calcite) and is determined as the sum of total H+ (Ht), total charges of Al(OH)3-n n (Alt) and the sum of charges of
the BC. The effective CEC is the sum of neutral salt (1.0 M KCl or equivalent) extractable charges pertaining to H, Al and BC. The
sum of these neutral salt extractable cations is intended to represent the negative charge of soil at ambient conditions. Alternative
methods for the determination of a soil’s ambient CEC have also been developed, where pH and ionic strength are kept buffered at
the ambient conditions during the extraction (Gillman and Sumpter, 1986).
The term base cation does not mean the cations Na+, K+, Mg2+ and Ca2+are bases. The term originates from describing soil
components as fully hydrolyzed metal oxides, where Na2O, K2O, MgO and CaO are indeed bases giving a pH > 10 in reaction with
water, while Al2O3 and Fe2O3 are considered acidic oxides. The BCs are in fact hard Lewis acids that preferentially adsorb to hard

Table 2 The mean effective CEC (CECe), major exchangeable cations, organic carbon, and pH from acidic podzols in the northeastern USA.

Soil horizons n CECe Exch-Ca2+ Exch-Al3+ Exch-H+ Org-C pHw

cmolc/kg g/kg
Oa (H) 142 32.3 9.14 7.77 11.92 46.9 3.55
B 26 9.9 0.37 7.72 1.50 8.2 3.96
Oa and A 48 16.4 4.74 7.99 4.71 35.0 3.74

The CECe was calculated by the sum of exchangeable cations for the 142 Oa and 26 B horizons, and by the compulsive exchange method of Gillman and Sumpter (1986) for the 48 Oa
and A horizons. The CECt was not measured for these soils but would include Ht (titratable acidity) and some non-exchangeable Al (Alt). The pH (pHw) is the soil pH measured in water.
Data are from two sampling campaigns of regional forest soils described in Ross DS, David MB, Lawrence GB, and Bartlett RJ (1996) Exchangeable hydrogen explains the pH of
Spodosol Oa horizons. Soil Science Society of America Journal 60: 1926–1932, used with permission.
8 Cation exchange capacity and reactions

Fig. 4 The positive relationship between total adsorbed log (Al/H+) on the x-axis and neutral salt (1.0 M KCl) exchangeable log (Al/3H+) on the y-axis demonstrates
that total adsorbed Al (defined by 0.5 M CuCl2 extraction) and H titrated to pH 7.0 dictates the ratio of Al and H in solution. In the absence of permanent clay minerals
and metal oxides (pH is lower than 4.0 in all soil samples where these minerals are not stable), Al3+ versus H+ exchange by soil organic matter functional groups is
the process behind the relationship. The 18 soil samples shown in the plot represent 1-cm layers of O and E horizons of two Spodosols. The numbers 1–5 represent
1-cm layers of the E horizon with the zero level set at the interface between O and E. The figure is from Skyllberg U (1999) pH and solubility of aluminium in acidic
forest soils: A consequence of reactions between organic acidity and aluminium alkalinity. European Journal of Soil Science 50(1): 95–106 and is reproduced with
permission.

Lewis bases (i.e. oxygen atoms of minerals or SOM functional groups). While Al3+ readily hydrolyzes in most soils, and thus releases
3 H+ under the formation of Al(OH)3, the cations Na+, K+, Mg2+ and Ca2+ do not hydrolyze below pH values of 10.
The base saturation (BS) is the fraction of CEC accounted for by base cations: BC/CECe and BC/CECt.
Because of the differences in hydrolysis of BC and Al, the relationship between pH and BS (i.e. BC/CECe and BC/CECt) in a
population of soil samples would be expected to be positively correlated if pH exceeds approximately 4.5 (cf. Fig. 3). Such a positive
relationship is a prerequisite for the models developed during the acid rain era (e.g. Christophersen et al., 1982; Reuss, 1983; Cosby
et al., 1985) to succeed as pH buffering models in soils.
A related concept is the ideal basic cation saturation ratio (BCSR). Many soil tests will report the saturation of the individual
‘base’ cations in relation to CECt. One can easily find recommendations in the popular literature for attaining ideal saturation ratios
of Ca2+ charges at 65% (i.e. exch-Ca2+/CECt  100), Mg2+ at 10% and K+ at 5%. These ratios are not only proposed to provide
proper chemical fertility but also to achieve maximum physical and biological fertility. These ratios are, again, based on historical
research that has not withstood the test of time and they may be quite expensive for the agricultural producer to maintain (Kopittke
and Menzies, 2007). While it is clear that there can be an imbalance in these exchangeable nutrient cations, numerous studies have
shown that the ranges of the BC saturation ratios needed to achieve optimal plant growth are quite wide and encompass those
usually found in agricultural soils. Some soils are naturally high or low in Mg, inherited from parent material, and adjusting the Mg2
+
saturation of CECt to 10% could be difficult, expensive and unnecessary. Only excessive additions of one of these BCs can actually
cause problems.

Cation exchange in acidic forest soils

In most soils pH is buffered and kept well above pH 4.5 because of kinetically driven weathering (solubilization) reactions with an
abundance of aluminosilicate minerals. Exceptions are in the case of inputs of extreme mineral acidity, such as acid mine drainage,
or in organic soil horizons such as the Oe (F) and Oa (H) that lack weatherable minerals. It can also be the case in some mineral E
and B horizons in forest soils where the abundance, as well as the slow kinetics of aluminosilicate dissolution, is not enough to
overcome the instant pH buffering by acidic organic functional groups (carboxylic acids) associated with SOM, contributed by the
deposition and turnover of plant litter. In these soils the pH is well below the range for hydrolysis of Al, and the Al3+ cation cannot
be considered acidic. Under these conditions BS is not positively related to pH (Fig. 5C). It is not difficult to find parallel increases
by depth in both pH and exchangeable Al3+. The reason is that H+ and Al3+ ions dominate CECe and CECt, and the major cation
exchange process in these soils is H+ versus Al3+. At low pH, the minor contribution from BCs and the sites they are associated with,
seldom play any role in pH buffering. This is clearly shown by plots of BC, Ale and He vs CECe where BC simply increases with
increased CECe (as controlled by the quantity of SOM) while Ale increases at the expense of He, indicative of H+–Al3+ exchange
(c.f. Skyllberg, 1999).
Reuss et al. (1990) demonstrated with a simple model that exchange between Ca and Al is the dominant cation exchange process
in the B horizons of acid forest soil with a pH above 4.5–5.0. As expected, in these soils pH is positively correlated to BS when
AldCa exchange is the dominant cation exchange reaction (Fig. 3). However, in E horizons, where the pH value falls below 4.5, the
model applied by Reuss clearly fails, and BS is negatively correlated to pH. This observation was not explained at the time but was
later shown to be due to HdAl exchange being the dominant cation exchange process in the O and E horizons of Spodosols
 Cation exchange capacity and reactions 9

(A)

(B)

(C)

Fig. 5 (A) Relationship between pH and CECe in five high-SOM forest soil samples in which pH was adjusted in the laboratory in six different subsamples.
(B) Relationship between pH and CECe in 105 forest soil samples in which the pH was not adjusted in the laboratory. (C) Change in Al3+ saturation of the CECe with
increasing depth and pH in an idealized Spodosol forest soil profile. Lower Al saturation at lower pH coincides with a higher quantity of SOM. Notably the increase in
pH with depth from Oa into Bhs is due to AldH exchange and the rise in pH above 4.5 is due to CadAl exchange. The figures are from Ross DS, Matschonat G, and
Skyllberg U (2008) Cation exchange in forest soils: The need for a new perspective. European Journal of Soil Science 59(6): 1141–1159, doi:10.1111/j.1365-
2389.2008.01069.x and are reproduced with permission.

(e.g. Skyllberg, 1999; Ross et al., 2008). This interpretation was supported experimentally by the work of Hargrove and Thomas
(1984) and Walker et al. (1990) on HdAl exchange in acid-washed peats. In Fig. 4, HdAl exchange at SOM sites, with a
stoichiometry of 2.47, is the dominant cation exchange process in O and E horizons of two Spodosols. Deviation from the expected
value of 3.0 (three H+ in exchange for one Al3+) is a common observation in studies of AldH exchange (Hargrove and Thomas,
1984; Walker et al., 1990) and can be explained either by some organically complexed Al retaining a positive charge (R–Al+) and or
by electrostatic effects in the EDL, not accounted for in the model. Regardless, it is clear that exchange processes in highly acidic
forest soils are better modeled by Al3+–H+ exchange rather than by exchange involving BC.
At such a low pH of 3.0, the soil solution activity of H+ is 1 mmol L−1 which is likely to be higher than any other aqueous phase
cation. This H+ can be considered exchangeable and, in fact, measurements of CEC in these soils relate better to the sum of
exchangeable cations if an estimate of exchangeable H+ is included. The source of charge, however, is the dissociation of H+ from
10 Cation exchange capacity and reactions

organic functional groups and this confounds the view of being truly exchangeable. Nonetheless, due to dissociated acid organic
functional groups these organic horizons in forest soils can have quite a large CECe (c.f. Table 2) even though BC may not buffer pH.
Thus, the CECe is also critical for retaining and recycling Ca, Mg and K in these naturally acidic ecosystems.
One other interesting aspect of acidic forest soils is that, unless strongly affected by mineral acidity, the CECe per kg of carbon
does not appear to vary greatly with pH (Ross et al., 2008). While adjusting pH in the laboratory will cause significant changes in
CECe, a collection of samples from the field will not usually show an effect of pH below about pH 5 (Fig. 5B). This is, again, related
to Al chemistry and pH buffering as discussed above. Highly acidic organic surface horizons will necessarily have lower Alt,e and thus
higher He,t because Al is minerogenic and is not recycled by litter to any great extent. Here H+ will accumulate as a consequence of
plant BC uptake and exchange for H+. At greater depth in the soil profile the availability of minerogenic Al increases. This will make
Al available for reactions. Exchange of H for Al results in an increase in pH but not necessarily in an increase in CECe, because most
Al bonded to SOM in these horizons is non-exchangeable (Alt > Ale). Deeper into the mineral soil horizons of acid forest soils pH
will generally increase because H+ is consumed by weathering reactions. This results in an increase in BS (Fig. 5B and C) and AldBC
exchange is the dominant cation exchange reaction (Figs. 3 and 5B). Soils receiving large inputs of H+ may also be depleted of Al at
depth in mineral soils, as revealed in some heavily acidified Dutch soils during the acid rain era (Mulder and Stein, 1994). Large
inputs of mineral acidity, concentrated by stemflow, were also found to acidify forest soils rapidly in southern Sweden, lowering the
CECe (Matschonat and Falkengren-Grerup, 2000). Apart from these highly impacted areas, it is difficult to find an effect of pH on
CEC in acid forest soils because of the interplay between Al and H.

Cation exchange in highly weathered tropical soils

Soils in the tropics are diverse, possibly more so than at higher latitudes, reflecting a broad range in parent material, climate and age.
While many tropical soils contain 2:1 layered clay minerals and permanent CEC, highly weathered soils may develop in humid,
older landscapes. In these soils, Oxisols in USDA Taxonomy and primarily Ferralsols in WRB groups (Table 1), the loss of Si from
weathering results in the clay size fraction being dominated by 1:1 clay minerals (usually kaolinite) and enriched in Al oxides
(primarily gibbsite) and Fe oxides and hydroxides (e.g. goethite and hematite). These minerals have been termed ‘low-activity’ clays
because of the virtual lack of permanent charge (Uehara and Gillman, 1981). This process of desilication (leaching of silicic acid:
H4SiO4) was historically termed ‘laterization’ with resulting ‘lateritic’ soils low in CECt (<10 cmolc kg−1), low in nutrient cations,
high in exchangeable Al, and with a relatively low pH (<5) (Pincus et al., 2017). The most weathered of these soils may be depleted
of 2:1 clays, but any small remnant could contribute disproportionately to the CEC (Nakao et al., 2017).
The ‘low activity’ mineral fraction means that much of the CEC in the surface horizons can be derived from SOM, accumulated
through litter and root turnover or through added amendments. The charge on SOM varies with pH, but always results in a negative
charge within the normal pH range of these soils. Subsurface horizons, lower in SOM, may have quite a low CECe (<2 cmolc kg−1).
The pH-dependent variably charged minerals are amphoteric, as discussed above, and Oxisols can therefore develop substantial
anion exchange capacity (AEC). The various metal oxides (Mn and Ti (titanium), in addition to the dominant Al and Fe) have a
wide range in the pH of their zero point of charge (ZPC). The definitions of ZPC, and the methods for measuring it, have evolved
over time and a recent soil chemistry text such as Essington (2015) or Strawn et al. (2015) should be consulted for in depth
discussion. The overall net charge of these highly weathered soils evolves toward zero through loss of silica and permanent charge
(Chadwick and Chorover, 2001) with SOM being the primary determinant of negative charge by coating the low activity Fe and Al
oxyhydroxides minerals (Chorover et al., 2004).
Oxisols (Ferralsols) generally have low native fertility and may be difficult to manage partly because of their low CEC and pH,
and therefore have low ability to retain nutrient cations. They occur worldwide throughout the tropics, but are most prevalent in
South America and central Africa (Buol and Eswaran, 1999). The dominance of variable charge and the native acidity of these soils
results in a wide divergence between the CECe and CECt. For example, the 225 Ferrasol samples in Table 1 had an average CECe of
2.7 cmolc kg−1 and CECt of 9.2 cmolc kg−1. Thus additions of lime or other materials to raise the soil pH can increase the retention of
nutrient cations by increasing the CEC. However, this may create other soil physical and chemical problems related to flocculation
or dispersion and anion (e.g. phosphate) retention due to changes in AEC.

Summary and outlook

Cation exchange reactions are long-studied, fundamental soil chemical processes. In near-neutral soils dominated by clay minerals
with permanent negative charge, cation exchange between Ca, Mg, K and Na can be described by relatively simple stoichiometric
equations. Cation exchange in soils with variably charged minerals and soil organic matter is more complicated, but can still be
modeled by incorporating the effects of pH and ionic strength on surface charge. In acidic soils, H ions and Al cations become
important in cation exchange reactions. In forest soils with a pH below 4.5, cation exchange concepts developed for less-acid soils,
such as a positive relationship between pH and base saturation, do not apply. In these soils, reactions involving the operationally
defined fractions of exchangeable and non-exchangeable H and Al can explain pH buffering through AldH exchange. Development
of geochemical models applicable across the full range of soils found worldwide, and in which all the major ion exchange and pH
buffering processes are captured and integrated, remains a challenge in the field of soil science.
 Cation exchange capacity and reactions 11

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