SOIL CHEMISTRY
The chemistry of a soil determines its ability to supply available plant
nutrients and affects its physical properties and the health of its living
population. In addition, a soil's chemistry also determines its corrosivity,
stability, and ability to absorb pollutants and to filter water.
It is the surface chemistry of mineral and organic colloids that determines
soil's chemical properties. A colloid is a small, insoluble particle ranging in
size from one nanometer to one micrometer, so small enough to remain
suspended by Brownian motion in a fluid medium without settling.
Most soils contain organic colloidal particles called humus as well as the
inorganic colloidal particles of clays. The very high specific surface area of
colloids and their net electrical charges give soil its ability to hold and
release ions. Negatively charged sites on colloids attract and
release cations in what is referred to as cation exchange.
Cation-exchange capacity is the amount of exchangeable cations per unit
weight of dry soil and is expressed in terms of milliequivalents of positively
charged ions per 100 grams of soil (centimoles of positive charge per
kilogram of soil (cmolc/kg). Similarly, positively charged sites on colloids can
attract and release anions in the soil, giving the soil anion exchange
capacity.
Cation and Anion Exchange
The cation exchange which takes place between colloids and soil
water, buffers (moderates) soil pH, alters soil structure, and
purifies percolating water by adsorbing cations of all types, both useful and
harmful.The negative or positive charges on colloid particles make them able
to hold cations or anions, respectively, to their surfaces. The charges result
from four sources.
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1) Isomorphous substitution occurs in clay during its formation, when
lower-valence cations substitute for higher-valence cations in the crystal
structure. Substitutions in the outermost layers are more effective than
for the innermost layers, as the electric charge strength drops off as the
square of the distance. The net result is oxygen atoms with net negative
charge and the ability to attract cations.
2) Edge-of-clay oxygen atoms are not in balance ionically as the
tetrahedral and octahedral structures are incomplete.
3) Hydroxyls may substitute for oxygens of the silica layers, a process
called hydroxylation. When the hydrogens of the clay hydroxyls are
ionised into solution, they leave the oxygen with a negative charge
(anionic clays).
4) Hydrogens of humus hydroxyl groups may also be ionised into
solution, leaving, similarly to clay, oxygen with a negative charge.
Cations held to the negatively charged colloids resist being washed
downward by water and are out of reach of plant roots, thereby preserving
the soil fertility in areas of moderate rainfall and low temperatures. There is
a hierarchy in the process of cation exchange on colloids, as cations differ in
the strength of adsorption by the colloid and hence their ability to replace
one another (ion exchange).
If present in equal amounts in the soil water solution:Al 3+ replaces
H+ replaces Ca2+ replaces Mg2+ replaces K+ same as NH+ replaces Na+. If one
cation is added in large amounts, it may replace the others by the sheer
force of its numbers. This is called law of mass action. This is largely what
occurs with the addition of cationic fertilizers (potash, lime).
As the soil solution becomes more acidic (low pH, meaning an abundance of
H+), the other cations more weakly bound to colloids are pushed into solution
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as hydrogen ions occupy exchange sites (protonation). A low pH may cause
the hydrogen of hydroxyl groups to be pulled into solution, leaving charged
sites on the colloid available to be occupied by other cations.
This ionisation of hydroxy groups on the surface of soil colloids creates what
is described as pH-dependent surface charges. Unlike permanent charges
developed by isomorphous substitution, pH-dependent charges are variable
and increase with increasing pH.
Freed cations can be made available to plants but are also prone to be
leached from the soil, possibly making the soil less fertile. Plants are able to
excrete H+ into the soil through the synthesis of organic acids and by that
means, change the pH of the soil near the root and push cations off the
colloids, thus making those available to the plant.
Cation Exchange Capacity (CEC)
Cation exchange capacity is the soil's ability to remove cations from the soil
water solution and sequester those to be exchanged later as the plant roots
release hydrogen ions to the solution. CEC is the amount of exchangeable
hydrogen cation (H+) that will combine with 100 grams dry weight of soil and
whose measure is one milliequivalents per 100 grams of soil (1 meq/100 g).
Hydrogen ions have a single charge and one-thousandth of a gram of
hydrogen ions per 100 grams dry soil gives a measure of one milliequivalent
of hydrogen ion. Calcium, with an atomic weight 40 times that of hydrogen
and with a valence of two, converts to (40÷2) × 1milliequivalent=20
milliequivalents of hydrogen ion per 100 grams of dry soil or 20 meq/100g.
The modern measure of CEC is expressed as centimoles of positive charge
per kilogram (cmol/kg) of oven-dry soil.Most of the soil's CEC occurs on clay
and humus colloids, and the lack of those in hot, humid, wet climates (such
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as tropical rainforests), due to leaching and decomposition, respectively,
explains the apparent sterility of tropical soils. Live plant roots also have
some CEC, linked to their specific surface area.
Anion Exchange Capacity (AEC)
Anion exchange capacity is the soil's ability to remove anions (such
as nitrate, phosphate) from the soil water solution and sequester those for
later exchange as the plant roots release carbonate anions to the soil water
solution. Those colloids which have low CEC tend to have some AEC.
Amorphous and sesquioxide clays have the highest AEC,followed by the iron
oxides. Levels of AEC are much lower than for CEC, because of the generally
higher rate of positively (versus negatively) charged surfaces on soil colloids,
to the exception of variable-charge soils. Phosphates tend to be held at anion
exchange sites.Iron and aluminum hydroxide clays are able to exchange
their hydroxide anions (OH−) for other anions.
The order reflecting the strength of anion adhesion is as follows:The amount
of exchangeable anions is of a magnitude of tenths to a few milliequivalents
per 100 g dry soil. As pH rises, there are relatively more hydroxyls, which will
displace anions from the colloids and force them into solution and out of
storage; hence AEC decreases with increasing pH (alkalinity).
Reactivity (pH)
Soil reactivity is expressed in terms of pH and is a measure of
the acidity or alkalinity of the soil. More precisely, it is a measure
of hydronium concentration in aqueous solution and ranges in values from 0
to 14 (acidic to basic) but practically speaking for soils, pH ranges from 3.5
to 9.5, as pH values beyond those extremes are toxic to life forms.
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At 25°c aqueous solution that has a pH of 3.5 has
10−3.5 moles H3O+ (hydronium ions) per litre of solution (and also
10−10.5 moles per litre OH−). A pH of 7, defined as neutral, has 10 −7 moles of
hydronium ions per litre of solution and also 10 −7 moles of OH− per litre;
since the two concentrations are equal, they are said to neutralise each
other.
A pH of 9.5 has 10−9.5 moles hydronium ions per liter of solution (and also
10−2.5 moles per liter OH−). A pH of 3.5 has one million times more hydronium
ions per liter than a solution with pH of 9.5 (9.5 − 3.5 = 6 or 106) and is more
acidic.The effect of pH on a soil is to remove from the soil or to make
available certain ions. Soils with high acidity tend to have toxic amounts
of aluminum and manganese.
As a result of a trade-off between toxicity and requirement most nutrients
are better available to plants at moderate pH, while most minerals are more
soluble in acid soils. Soil organisms are hindered by high acidity, and most
agricultural crops do best with mineral soils of pH 6.5 and organic soils of
pH 5.5. Given that at low pH toxic metals (e.g. cadmium, zinc, lead) are
positively charged as cations and organic pollutants are in non-ionic form.
Thus both made more available to organisms, it has been suggested that
plants, animals and microbes commonly living in acid soils are pre-
adapted to every kind of pollution, whether of natural or human origin. In
high rainfall areas, soils tend to acidify as the basic cations are forced off the
soil colloids by the mass action of hydronium ions from usual or unusual rain
acidity against those attached to the colloids.
High rainfall rates can then wash the nutrients out, leaving the soil inhabited
only by those organisms which are particularly efficient to uptake nutrients in
very acid conditions, like in tropical rainforests. Once the colloids are
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saturated with H3O+, the addition of any more hydronium ions or aluminum
hydroxyl cations drives the pH even lower (more acidic) as the soil has been
left with no buffering capacity.
In areas of extreme rainfall and high temperatures, the clay and humus may
be washed out, further reducing the buffering capacity of the soil. In low
rainfall areas, unleached calcium pushes pH to 8.5 and with the addition of
exchangeable sodium, soils may reach pH 10. Beyond a pH of 9, plant
growth is reduced.
High pH results in low micro-nutrient mobility, but water-soluble chelates of
those nutrients can correct the deficit. Sodium can be reduced by the
addition of gypsum (calcium sulphate) as calcium adheres to clay more
tightly than does sodium causing sodium to be pushed into the soil water
solution where it can be washed out by an abundance of water.
Base Saturation
There are acid-forming cations (e.g. hydronium, aluminium, iron) and there
are base-forming cations (e.g. calcium, magnesium, sodium). The fraction of
the negatively-charged soil colloid exchange sites (CEC) that are occupied by
base-forming cations is called base saturation.
If a soil has a CEC of 20 meq and 5 meq are aluminium and hydronium
cations (acid-forming), the remainder of positions on the colloids (20 − 5 =
15 meq) are assumed occupied by base-forming cations, so that the base
saturation is 15÷20 × 100% = 75% (compliment 25% is assumed acid-
forming cations).
Base saturation is almost in direct proportion to pH (it increases with
increasing pH). It is of use in calculating the amount of lime needed to
neutralise an acid soil (lime requirement). The amount of lime needed to
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neutralize a soil must take account of the amount of acid forming ions on the
colloids (exchangeable acidity), not just those in the soil water solution (free
acidity).
The addition of enough lime to neutralize the soil water solution will be
insufficient to change the pH, as the acid forming cations stored on the soil
colloids will tend to restore the original pH condition as they are pushed off
those colloids by the calcium of the added lime. [132]
Buffering Capacity
The resistance of soil to change in pH, as a result of the addition of acid or
basic material, is a measure of the buffering capacity of a soil and (for a
particular soil type) increases as the CEC increases. Hence, pure sand has
almost no buffering ability, though soils high in colloids (whether mineral or
organic) have high buffering capacity.
Buffering occurs by cation exchange and neutralization. However, colloids
are not the only regulators of soil pH. The role of carbonates should be
underlined, too. More generally, according to pH levels, several buffer
systems take precedence over each other, from calcium carbonate buffer
range to iron buffer range.
The addition of a small amount of highly basic aqueous ammonia to a soil
will cause the ammonium to displace hydronium ions from the colloids, and
the end product is water and colloidally fixed ammonium, but little
permanent change overall in soil pH.
The addition of a small amount of lime, Ca(OH)2, will displace hydronium ions
from the soil colloids, causing the fixation of calcium to colloids and the
evolution of CO2 and water, with little permanent change in soil pH. The
above are examples of the buffering of soil pH.
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The general principal is that an increase in a particular cation in the soil
water solution will cause that cation to be fixed to colloids (buffered) and a
decrease in solution of that cation will cause it to be withdrawn from the
colloid and moved into solution (buffered). The degree of buffering is often
related to the CEC of the soil; the greater the CEC, the greater the buffering
capacity of the soil.
