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Measurements and
mechanisms in acid soils
a
Bryon W. Bache
a
Department of Applied Biology , Cambridge,
CB2 3DX, U.K.
Published online: 11 Nov 2008.

To cite this article: Bryon W. Bache (1988) Measurements and mechanisms in

acid soils, Communications in Soil Science and Plant Analysis, 19:7-12, 775-792,
DOI: 10.1080/00103628809367975

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 Downloaded by [Cornell University Library] at 16:11 17 November 2014

,yf
PART 1

SOIL ACIDIFICATION
 COMMUN. IN SOIL SCI. PLANT ANAL., 19(7-12), 775-792 (1988)

MEASUREMENTS AND MECHANISMS IN ACID SOILS

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Key Words: soil pH, buffering, charge, base saturation, lime

requirement

Bryon W. Bache

Department of Applied Biology, Cambridge CB2 3DX, U.K.

ABSTRACT

This overview outlines some conceptual and practical problems

associated with the important variables in s o i l acidity research,
and makes some suggestions for improvement where appropriate.

INTRODUCTION

The central problem in soil acidity is the relationship between

the t o t a l acidity of the system (i.e. the nature and amounts of the
proton donors in the solid phase) and the intensity of acidity (i.e.
the a c t i v i t y of hydrogen ions in s o l u t i o n ) . When expressed
numerically, this relationship is the soil buffer capacity, but in a
broader sense it involves definitions, measuring techniques,
chemical mechanisms and eventually a quantitative description that
can unite theory and practice.

775

Copyright © 1988 by Marcel Dekker, Inc.

 776 BACHE

The plant scientist needs to define fairly precisely the

factors affecting crop growth that depend on soil acidity, in order
to compare different soils, crop species and varieties. But simpler
procedures, provided they are based on sound concepts, are adequate
for the agronomist, who only needs to apply sufficient lime to
obtain optimum yields.

CHARACTERISING SOIL REACTION

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pH is the most frequently-performed chemical measurement on

soil. I t is surprising, then, that there are no agreed definitions
or standards either for i t s measurement or for its interpretation.
Some confusion s t i l l exists about "soil pH".
The definition pH = -log a^, where aH is the hydrogen ion
activity is a term derived from a chemical potential and can be
applied only to a solution. The thermodynamic impossibility of
evaluating the a c t i v i t y of a single ion i s overcome by the
operational definition of pH, which t i e s i t to an agreed pH of a
reference solution.
Soil, however, is a multiphase heterogenous system. At field
capacity moisture content i t contains at most about a third of i t s
volume as solution. Additions necessary to give sufficient liquid to
measure pH can dilute the solution several fold. The measured pH
then varies with four experimental variables: the soil:solution
ratio, the type and concentration of electrolyte in the solution,
the position of the electrodes in the suspension, and whether the
suspension is stirred or not during the measurement.
These salt and suspension effects have been attributed to two
causes: the liquid junction potential of the reference electrode,
and the presence of the e l e c t r i c a l double layer surrounding the
negatively-charged colloids in soils. In common with other cations,
the hydrogen ion concentration will be higher near the charged
surface than in the bulk solution, but one might expect its
activity, determined by interaction with nearby electric charges, to
be constant throughout the system. The fact that measured soil pH
 ACID SOIL MEASUREMENTS AND MECHANISMS 777

values vary as explained above, shows that they are not reflecting a
thermodynamic potential.
This apparent dilemma can be resolved by considering the
electrochemical potential of a pair of ions . This leads to the
result that the "reduced ratio" of the activities of a pair of
similarly-charged cations, e.g. afj/(aca) has
some thermodynamic
meaning, in contrast to the activity of a single ion which does not.
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Experiments convincingly support the theory in that the logarithm of

this activity ratio, pH-1/2pCa, is reasonably constant over
considerable variation in soil: solution ratio and electrolyte
concentration.
This was first discovered by Schofield and Taylor , who called
pH-1/2pCa the lime potential of soil. Values for lime potential are
not often reported, but soil pH is now frequently measured in 0.01 M
CaCl2 solution, so that 1/2pCa remains approximately constant and
the measured pH is directly proportional to the lime potential.
There are practical advantages in measuring soil pH in this way:
there is no need to separate the solution to get reasonably steady
readings, because the suspension and stirring effects are
practically eliminated at this electrolyte concentration, and there
is very little variation with soil:solution ratio.
It has been suggested that the Ca concentration in 0.01M CaCl«
is close to that of the soil solution. While this may be so for
slightly acid highly fertile soils, it is not so for calcareous
soils in which the solubility of calcite maintains the Ca
concentration at approximately 0.005M (depending on CO 2 partial
pressure), nor for soils of humid temperate or tropical regions
where considerable leaching occurs.
A recent study on Western Australian soils illustrates very
well the effects of salt concentration on the pH of separated
solutions that had been equilibrated with soils at a range of ionic
strengths (I). The authors suggested using an extractant at
1=0.005, which was close to the ionic strength of the soil solution
at field capacity (Ig)f rather than at 1=0.03 given by 0.01 M CaClj
solution, to measure pH. Attractive though this may seem, it will
 778 BACHE

not give an absolute value because I will vary with changes in

s
electrolyte and moisture contents. Unfortunately, solution cation
concentrations were not reported, so that pH-1/2pCa cannot be
calculated for this otherwise comprehensive data set.
The essential requirement for a standard soil pH method is to
use an electrolyte concentration sufficiently high that it will not
greatly change on equilibration with most soils, but not too high to
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desorb much acidic exchangeable cations (H and Al ) and so give an

unrealistically low pH reading. Equilibration with 0.01 M CaCl2
solution is popular, but there is clearly a case for using a lower
concentration.

TOTAL AND EXCHANGEABLE ACIDITY

Measurement of total acidity may seem more straightforward than

soil reaction, but there are severe practical problems.
Soil titration curves do not generally show an inflexion or end
point, s"b there is no absolute pH at which to measure total acidity.
Bradfield and Allison suggested that pH 8.2 should be the criterion
of a fully base-saturated soil because this is the pH of a
calcareous soil suspension in equilibrium with the CO., partial
pressure of the air, 0.0003 atm (0.03%). This has been generally
accepted.
Total acidity is now determined by equilibrating soil with a
triethanolamine buffer at pH 8.2 in 0.25M B a C l 2 solution, and back
titrating the unreacted buffer with acid. The concentrated salt
solution is necessary to desorb proton donors from the soil surfaces
to speed up their reaction with the buffer solution. However, a
fully base-saturated calcareous soil in equilibrium with air has pH
about 7.5 in 0.25M BaCl 2 solution, rather than its natural pH of 8.2
in 0.005M C a ( H C O 3 ) 2 solution, so that 8.2 in 0.25M B a C l 2 is an
unrealistically high pH. A lower reference pH would also be more

appropriate because of the higher' partial pressure of CO2 in

19
biologically active soils. The current standard method also
suffers from the disadvantage of a short equilibration period, for a
system where reaction rates are notoriously slow.
 ACID SOIL MEASUREMENTS AND MECHANISMS 779

An absolute value for total acidity is not perhaps very

important. However, the use of a BaCl2-triethanolamine saturating
buffer at pH 8.2 has become a reference standard for measuring
negative charge and cation-exchange capacity/ so that this question
needs to be addressed critically.
Exchangeable acidity is the component of total acidity that can
be extracted from soil by a concentrated unbuffered salt solution
such as 1.0M KC1. The acidity in the extract is measured by
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titration with NaOH solution to an endpoint, which is around pH 8.

Much of this acidity is exchangeable Al, and if required this
component can be determined separately. This is an extremely useful
measurement, and is relatively uncomplicated except for
uncertainties over what constitutes "exchangeable Al" .

SURFACE CHARGE AND BUFFER CAPACITY

Proton transfer reactions involve charge transfer, so that

acidity is closely linked to the surface charges on soil colloids.
These depend on the nature and amounts of the soil components.

Methods for Measuring Charge

Surface charge determinations generally involve three stages,

(i) Saturating the soil with a concentrated solution of an
electrolyte buffered at the required pH. This also desorbs
exchangeable cations, the sum of which gives the effective cation-
exchange capacity, CECg, at that pH. (ii) Reducing the electrolyte
concentration to that required for the charge determination. (iii)
The measurement stage, in which the adsorbed ions are usually
displaced with a second electrolyte and their amounts determined.
Alternatively, the equilibrium established in (ii) can be labelled
with a suitable radioactive isotope, and its distribution between
the two phases determined.
Negative charge measured in buffered solutions at pH values of
7.0 or 8.2 gives the cation-exchange capacity (CEC) of soils at
 780 BACHE

these conventional pH values, but this may be different from CEC e

measured using unbuffered salts at the natural reaction of the
soil 1 1 .

Charge Mechanisms

The following mechanisms are thought to be mainly responsible

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for the development of surface charge and the acidity associated

with it.
(i) Isomorphous substitution within the lattices of crystalline
alumino-silicate clay minerals results in permanent negative charges
which are neutralized by exchangeable cations. Permanent charge
itself does not contribute to acid-base buffering, but as pH drops
below about 5.5, H + adsorption by clays breaks Al-0 bonds in the
aluminosilicates and eventually releases A l 3 + cations, increasingly
so as pH drops. These cations are adsorbed by the clay negative
charge and constitute the main source of acidity in many clay soils
7,11_

(ii) Many soils also contain pH-dependent charge. This is

particularly associated with organic matter and has therefore been
attributed to the dissociation of carboxylic acid groups on humus:

Ca(OH) 2
R(COOH) 2 » R(COO") 2 + Ca2+ + 2H 2 O

Carboxylic acids found in soils appear to have a range of p K &

values, and so contribute to buffering over the pH range from 2 to
7. Humus also contains weaker acid phenolic hydroxy groups that
g
control buffering at pH>7. There is now considerable evidence that
much of this organic pH-dependent charge may a r i s e from the
deprotonation of organically-complexed aluminium ions which have
formed during the course of soil development:

COO Ca(OH), COO"

R A10H > R. + Ca2+ + A1(OH) 3
COO COO"
 ACID SOIL MEASUREMENTS AND MECHANISMS 781

(iii) pH-dependent charge is also a feature of strongly-

18
weathered s u b s o i l s of i n t e r m e d i a t e pH . This has been a t t r i b u t e d
to the adsorption of positively-charged Al-hydroxy polymers in clay
i n t e r l a y e r s , p a r t i c u l a r l y in aluminous c h l o r i t e m i n e r a l s , thereby
blocking t h e clay n e g a t i v e charge. A r i s e in pH deprotonates t h e
polymers and releases the negative charge for neutralization by non-
hydrolysed base cations:
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clayl Ca(OH)2 clay_ [

2+
A16(OH)16 • 6A1(OH) 3 C a 2 +
clay" I clay"" |

(iv) Soils containing considerable amounts of Al and Fe

hydroxides, or allophane, in their clay fractions develop charges by
the adsorption of potential-determining ions, mainly H and OH .

H+ H+
+ C £
FeO HI- H 2 0 FeO .OH

OH" OH

This charge i s pH-dependent, but i t is also strongly affected by

ionic strength, which explains stage ( i i ) in the measurement
procedure above. Such colloids show a zero point of charge (ZPC).
In s o i l s , the positive charges developed at low pH often co-exist
with negative charges on silicate clays or humus, so that the soils
then show a point of zero net charge (PZNC). Fig. 1, taken from
Gillman and Sumpter illustrates these relationships. The amounts of
positive charge developed at pH 4 may amount to 20 mmol(+)/kg in the
subsoil horizons of oxic s o i l s , but t h i s i s a l l neutralized by pH
7.

Soil Buffer Capacity

Soil buffering has often been investigated by adjusting s o i l

samples to a range of pH values and then measuring charge as
 782 BACHE

large
neg.
o
Sur face

i
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FIG 1. Generation of positive and negative charge, and exchange

capacity, as a function of pH (Gillman and Sumpter )•

described above. However, this only measures charge variation with

pH and not the acid or base required to reach that pH. pH buffering
of soils can only be reliably determined by the batch method:
incremental additions of CaCO, are incubated with moist soil, at low
temperature to discourage acid production by mineralization and
nitrification, and when the reaction is complete the soils are
equilibrated with appropriate electrolye solutions for pH
measurement.
Conventional pH titration curves with Ca<0H>2 solution at a
controlled ionic strength are useful when an automatic titrator is
available, but even when slowly performed do not reach equilibrium.
For a soluble buffer, the buffer capacity is given by ß = ^AB/^pH
where J pH is the change in pH from the addition of ^ AB mol/1
of acid or base. A similar convention can be used for soils, with
appropriate units such as mmol( + )/kg soil. Values of this buffer
capacity for some soil components cover a very wide range, for
o n

example from 4 mmol( + )/kg for kaolinite to 1300 mmol( + )/kg for
soil organic matter .
The buffer capacity for a given s o i l is not constant over the
whole pH range. For most surface soils, pH-dependent charge
associated with organic matter is the main buffering mechanism over
the pH range 4.5-6.5, which is the most useful range for
 ACID SOIL MEASUREMENTS AND MECHANISMS 783

8.0

xa.
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5.0 -

4.0 -

3.0
-8 -6 - 4 - 2 0 2 4
O M BASIS A M E N D M E N T RATE
(mmollp'l g'1)

FIG 2. A generalised soil buffer curve derived from expressing

the acid or base amendment rate on the basis of organic
matter content (Magdoff and Bartlett 1 3 ).

agricultural soils, as shown in Fig.2. This is a composite curve for

all the soils studied by Magdoff and B a r t l e t t 1 3 in which buffer
capacity varied, but the curve is drawn on the basis of amendment
rate of acid or bicarbonate per gram of organic matter in soil. The
higher buffer capacity above pH 6.5 results from the effect of
increasing solubility of C 0 2 on bicarbonate equilibria. The higher
buffer capacity as pH drops below 4.5 is due mainly to aluminium
buffering as clays and hydrous oxides adsorb protons.
By contrast the buffer curve of acid-washed peat titrated in a
nitrogen atmosphere (Fig. 3) is well-buffered to a lower pH (2.5-
5.5) than the soils in Fig. 2, due to carboxy groups, and to a
higher pH (7-10) than in Fig. 2, due to phenolic hydroxy groups.
Buffer capacities over limited pH ranges may be determined very
simply in the laboratory, the main requirement being to control the
electrolyte concentration so that measured pH values are comparable.
 784 BACHE

10
pH
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0 1.0 2.0
m mol/g 0H~
FIG 3. pH titration curves of acid peat with Ca(OH)- solution
at electrolyte concentrations controlled by adding CaCl2
solution as shown.

The rate of approach to equilibrium needs to be studied because slow

reactions are particularly important for neutralizing acid inputs.

Anomalies

There is not an exact correspondence between charge generation

and base consumption during titration of acid soils. Evidence for
this occurs in the early literature, and a recent example is given
by Gillman and Sumpter , who measured lime requirement of some
trop cal Queensland soils by stepwise addition of Ca(0H)2# allowing
equilibrium to be reached before the next addition, and compared
this with their charge measurements. They found that "on average
about 50% of lime added is used in increasing CECg, (the basic
cation-exchange capacity obtained from Ca adsorption) indicating
that a substantial portion of added lime is consumed in reactions
not involving cation exchange". A similar but smaller effect was
shown for a group of 30 upland soils in Scotland , but here lime
 ACID SOIL MEASUREMENTS AND MECHANISMS 785

r e q u i r e m e n t exceeded CEC by a f a c t o r of only 1.12. Some of t h e added

Ca must be in organic combination, for in a Scottish h i s t o s o l an
increasing proportion of this Ca was non-exchangeable to 1.0M KCl as
the pH rose. Gillman and Sumpter's data indicate that 10-20 mmol/kg
of Ca i s non-exchangeable at pH 6 for s o i l s containing 1-3%C, and
for the Scottish histosol about 130 mmol/kg for about 50%C

pH BASE SATURATION RELATIONSHIPS

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Neutralisation of proton donors by bases always increases the

base saturation of soils, therefore intuitively we expect a
relationship b tween them. Although many workers have studied this,
no general relationship has appeared and Blosser and Jenny
concluded "no explanations of the discrepancies have been offered".
In fact, the suggestions made by early workers were not far off
our present understanding. Apart from experimental uncertainties
such as a valid determination of pH, the biggest differences are
between mineral and organic soils, and these clearly relate to
permanent-charge acidity (exchangeable Al) and pH-dependent acidity.
Data showing the differences between the mineral and organic
components are illustrated in Fig. 4.
To understand pH-base saturation relationships, the acid soil
system must be considered in two stages: dissociation of proton
donors, and the distribution of H + ions between the surface and the
solution.
Consider first the neutralization of carboxylic acids in humus,
as discussed above and illustrated in Fig.3 over the pH range 2-7.
The degree of dissociation of the weak acid, « ,is identical to the
base saturation of the soil. Complete dissociation implies complete
neutralization and a base saturation of 1.0, hence cC = CECe/CEC...
If the acid were soluble, pH would be related to the mean acid
dissociation constant p K m and the degree of dissociation,oC,by the
Henderson-Hasselbach equation: pH = p K m + nlog( oc/(1-ot)), but
for an insoluble anion such as a clay or humus particle, both the
dissociated hydrogen ions and the charge-neutralizing base cations
 786 BACHE

8.0

pH
7.0

6.0

5.0
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4.0

3.0
50 100
Base Saturation, %
FIG 4. Relationships between soil pH in 0.1 M KC1 and the degree
of base saturation of some German marsh soils
(Schachtschabel and Renger ).

will be adsorbed to the particle surface. They will only appear in

solution, to be detected by a glass electrode, if soluble anions are
present. The distribution of cations between the surface and
solution will then be governed by cation-exchange equilibria. For
the reaction:

R(COO~)2(H+)2 + Ca(NO3)2 — * R(COO")2Ca2+

the equivalent-fraction selectivity coefficient, K , is given by

where q indicates equivalents, Eq = mol(+), adsorbed at the surface,

q0 i s the negative char.ge or CEC, Eq = mol(-), and a indicates the
 ACID SOIL MEASUREMENTS AND MECHANISMS 787

activity of cations in solution. These relationships can be

combined in principle with q~ = CEC e = oC CEC t , to give a
quantitative relationship between base saturation and solution pH.
This does not yet appear to have been investigated in detail.
For permanent, charge acidity (exchangeable Al), the acid is
already dissociated and adsorbed at charged surfaces. Assuming that
its neutralization is by Ca(OH)2, its distribution is governed by
Ca-Al exchange equilibria, and pH can be brought into the equilibria
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21
either through the A1(OH)3 solubility equilibria , or through the
3+ 2+ + 1
hydrolysis reaction A l = A1OH + H . In the first case lime
potential, pH-1/2pCa, was related to base satuatlon expressed as the
balance between Al and (Ca+Mg) saturation of the exchange complex,
and in the second case pH was directed related to base saturation.
In both cases the selectivity coefficient for Ca-Al exchange was
critical for determining the solution pH, and as this can vary by
103 for different exchangers1, there is plenty of scope for
differences in the pH-base saturation relationship between different
soils for this reaction alone.
When pH-dependent and permanent charge components are combined
together, as they are in most soils, a complex set of relationships
will be required to adequately describe the situation.

ALUMINIUM SOLUBILITY

Aluminium is the key element in acid mineral soils • Its

solubility can be measured by extracting soil solution or by
equilibrating soils with dilute electrolytes. There has been much
discussion, however, on the mechanisms controlling its solubility in
soils • While pH is undoubtedly the master variable, relationships
between Al concentrations and pH are not straightforward . The
solubility equilibria of a number of Al-containing minerals controls
solubility when geochemical equilibrium is reached. At higher pH
values (5-7), soluble aluminium in excess of that expected from
solubility equilibria is due to the formation of soluble complexes
with silicate, fluoride and organic ligands. However, under the
 788 BACHE

rapid fluctuations of water content, temperature and electrolyte

concentration that occur in s o i l s , cation-exchange processess are
likely t o be more important than s o l u b i l i t y e q u i l i b r i a in
controlling the concentrations of uncomplexed mononuclear aluminium
ions (Al3+ and A1OH2 + ) 3 .

Exchangeable Al is thus an extremely important feature of acid

soils. Extraction with unbuffered neutral s a l t s gives a good
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indication of i t s amount, but i t varies more with experimental

conditions and the nature of the extracting salt than for the basic
exchangeable cations . Organically-complexed Al is not exchangeable
to neutral s a l t s , but can be extracted with copper s a l t s ; i t thus
seems less likely to be an immediate control on Al s o l u b i l i t y , but
Q

it is a major pH buffer in organic horizons of acid soils .

THE ROOT ENVIRONMENT

Determining t h e i o n i c environment of p l a n t r o o t s i s a s e p a r a t e
issue from general characterization of soil» Ideally, the soil
solution surrounding the roots should be extracted. Direct
centrifugation, or centrifugal displacement with a heavy non-polar
•liquid such as trifluoro trichloro ethane , are the preferred
methods. The soil saturation extract gives some indication of the
electrolyte concentration of the s o i l solution, and may be
sufficient for many purposes.
There is l i t t l e point trying to get a characteristic pH from
the s o i l solution because both acid-generating and acid-
neutralization processes occur during plant growth, and the
electrolyte concentration (and hence pH) varies because of nitrogen
transformations, fertilizer addition and nutrient uptake. These
short term variations are well known. More careful study of the
chemistry of the rhizosphere has revealed quite dramatic pH changes
in certain circumstances .
These l o c a l i s e d pH v a r i a t i o n s may produce considerable
differences in the solubility of nutrients and toxic elements. I t
seems likely that these pH gradients will equalize over a winter
 ACID SOIL MEASUREMENTS AND MECHANISMS 789

season by diffusion of the main proton carriers in the soil

solution, i.e. H and HCO,~ ions . They may thus make little
difference to the gross acidity of a reasonably well-buffered soil,
but may be extremely important for immediate plant response.
Critical work on plants growing in acid soil must therefore
give very careful consideration to appropriate characterization of
the root environment. The variations in moisture content,
electrolyte concentrations and pH that undoubtedly occur indicate
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that any single ion function will be unsatisfactory, and that ion
activity ratios or products are probably more reliable. For example,
when considering Al toxicity, pH-1/3pAl or 1/2pCa-1/3pAl should
remain approximately constant while individual ion concentrations
vary. This issue of soil characterization is quite separate from the
physiological response of plants to concentration or activity
ratios, which is beyond this overview.

LIME REQUIREMENT

Methods for estimating lime requirement have occupied soil

chemists for many years. The only reliable method is the batch
method with CaCO, additions described above, thus simulating field
p
liming . Many rapid methods have been devised for use in soil
testing programmes, mostly depending on the pH change of a buffer
solution, initially at pH 7.5 or 8.0, on reaction with an acid soil:
the greater the pH change, the more lime is needed. These methods
are calibrated against the absolute method or field liming trials.
A more rational approach to lime requirement follows from the
soil buffer capacity as defined above, and this underlies the
extension methods used in Britain. Lime requirement is derived from
the simple equation LR = B(pH. - pH Q ), where pHQ is the initial pH,
and pH t is the target pH. Which soil pH method is used is probably
immaterial. Both LR and B must be in the same units, such as mmol/kg
for laboratory soils or tonne/ha of CaCO3 in the field. The
transition from laboratory to field lime requirements must take
account of the bulk density of soil, varying from 0.4 g/cm for
 790 BACHE

cultivated histosols to 1.6 g/cm for some sands, and the depth to
which lime is to be incorporated.
Many correlations between LR, buffering and soil components
have been measured over the years, and the extension services in
acid soil areas have wide experience of liming. Hence it is rarely
necessary to measure B in the laboratory, provided a field texture
assessment is made that can also incorporate an approximate estimate
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of organic matter content. Values of B for such a system used in

Britain are as follows:

Soil texture: B (tonne/ha CaCO,)

sands (S,LS) 3
light textures (SL,SZL,SL) 5
medium textures (SCL,CL,ZCL) 7
heavy textures (SC,ZC,C) 9
organic soils (15-25% C) 10
peaty soils (25-40% C) 11
peats (>40% C) 12

The target pH to which soil should be limed depends on the

sensitivity of the crops to be grown and the nature of the soil. For
example, sensitive crops such as barley or sugar beet on mineral
soils in temperate regions require pH about 6 - 6.5. Liming to a
lower pH is adequate for less sensitive crops such as potatoes and
grassland, and for crops on organic or sandy-textured soils which
maintain lower concentrations of soluble Al. In poorly-buffered
nutrient-deficient soils, the dangers of trace element deficiencies
caused by overliming may be as great as those for Al toxicity.
The main problem affecting field liming in Britain is the
variability of soil. In some cases a range of two pH units has been
found within an area of a few hectares. This variability may have
been caused by uneven lime applications in the past, perhaps
accentuated by differences in texture.
In view of the uncertainties over pH measurements, liming
practice and the variability of soils in the field, complicated but
 ACID SOIL MEASUREMENTS AND MECHANISMS 791

short-term non-equilibrium buffering procedures in the laboratory

for determining lime requirement seem to be a waste of effort when
the simple system described here is highly effective in practice.

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 792 BACHE

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