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 1
nanometer to 1
micrometer, thus 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 (or 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, that 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. •
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. • Edge-of-clay oxygen atoms are not in balance ionically as the
tetrahedral and
octahedral structures are incomplete. •
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). • Hydrogens of humus hydroxyl groups may also be ionised into solution, leaving, similarly to clay, an oxygen with a negative charge. Cations held to the negatively charged colloids resist being washed downward by water and are at first 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: Al3+ replaces H+ replaces Ca2+ replaces Mg2+ replaces K+ same as 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
fertilisers (
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 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 cations (H+) that will combine with 100 grams dry weight of soil and whose measure is one
milliequivalent per 100 grams of soil (1 meq/100 g). Hydrogen ions have a single charge and one-thousandth of a gram (1 mg) 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 = 20 milliequivalents of hydrogen ion per 100 grams of dry soil or 20 meq/100 g. 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 as
tropical rainforests), due to fast leaching and decomposition, respectively, explains the apparent lack of
fertility 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.
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 an 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. At 25 °C an 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 litre of solution (and also 10−2.5 moles per litre OH−). A pH of 3.5 has one million times more hydronium ions per litre than a solution with pH of 9.5 ( or 106) and is thus 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
aluminium and
manganese. As a result of a trade-off between
toxicity and requirement most nutrients are better available to plants at moderate pH, although most minerals are more soluble (
weatherable) 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.
aluminium,
cadmium,
zinc,
lead) are positively charged as cations and organic pollutants are in non-ionic form, thus both are 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 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, 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 percentage 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 () are assumed occupied by base-forming cations, so that the base saturation is (the 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 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.
Buffering 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
neutralisation. 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.
Redox Soil chemical reactions involve some combination of proton and
electron transfer.
Oxidation occurs if there is a loss of electrons in the transfer process while
reduction occurs if there is a gain of electrons.
Reduction potential is measured in volts or millivolts. Soil
microbial communities develop along
electron transport chains, forming electrically conductive
biofilms, and developing networks of
bacterial nanowires. Redox factors act on soil development, with
redoximorphic color features providing critical information for soil interpretation. Understanding the
redox gradient is important to managing
carbon sequestration,
bioremediation,
wetland delineation, and
soil-based microbial fuel cells. == Nutrients ==