SOIL ACIDITY 2.

Accumulation of organic matter:

i) Formation of soluble complexes with non-acidic
Soil pH determines: cations subected to leaching
1. Plants dominate the natural landscape. ii) OM contains acid functional groups
2. Crops can be grown successfully in farmer’s fields. 3. Oxidation of Nitrogen (Nitrification). Ammonium oxidize ti
3. Elements are present at optimum, deficient or toxic levels nitrate ions releases 2H+ ions.
for plant growth. 4. Oxidation of Sulphur.
4. Affects aggregate stability & water movement. 5. Acid precipitation. Formation of strong acids leads to
5. Determines the destruction or movement of soil pollutanta dissociation to H+.
into th groundwater. 6. Plant uptake of cations. Balance between positive and
negative charges from soil solution.
Acidity (HUMID), Alkalinity (ARID)
SOIL ACIDIFICATION PROCESS:
Human activities can accelerate or slow down the natural changes.

Soil Acidification Process

Processes that add H+ ions to the soil system is acidification which

lowers the soil pH. Processes that consume H + ions reduce acidity H+ ions added The non-acid The exchange
and raise soil pH to neutral or higher is alkalinizing process. to the soil cations can complex and
solution then be the soil
Natural acidificatiom is driven by: exchange with exported in solution
non-acid ions leaching watre becomes
i) Production of organic acids (carbonic acids) held on humus along with increasingly
ii) Leaching away of non-acid cations (Ca2+, Mg2+, K+, Na+) and clay accompanying dominated by
colloids. anions. acid cations.
Emissions from power plants, vehicles amd inputs of nitrogen into
agricultural systems accelerates acidification.
Because of this seuence of events, H+ ion producing processes
Sources of H+ ions acidify soils in humid regions where leaching is extensive.

1. Carbonic and other organic acids – formation of organic acid

and dissociation of H+ from carbonic acids.
Long-term soil acidification in arid regions where the Ca 2+, Mg2+, K+,  Reducing effective CEC of the soil.
Na+ are mostly not removed by leaching. Remains in the soil and  As the pH is raised and the hydroxyl aluminum ions
reexchange with the acid cations, preventing a drop in pH level. precipitate as uncharged Al(OH)3
 The negative sites on the colloids become available for
Role of Aluminium
cation exchange.
The other principal acid cation besides hydrogen. Major constituent  The soil CEC increases - as the pH is raised from pH 4.5 to
of most soil minerals and clays. pH 7.0 (all aluminum cations have precipitated as Al(OH) 3o
 In Strongly acid soils the colloidal complex is dominated by:
H+ ions are adsorbed on clay surface, attack the mineral structure o Al3+ ions & associated hydroxy-aluminum ions (e.g.
and releasing Al3+ ions. Al(OH)2+).
o Al3+ & H+ is bound tightly in the organic matter & on
- Al3+ ions adsorbed on colloids cation exchange sites.
clay crystal edges; not readily exchangeable.
- In euilibrium with dissolved Al3+ in soil solution.
Pools of Soil Acidity
Critical roles in soil acidity:
Four pools of acidity are recognized:
 Highly toxic to soil organisms
 Al3+ ions have tendency to hydrolyze water molecules into 1. Active acidity
H+ and OH- 2. Salt-replaceable acidity – due to Al3+ and H+ ions that are
 Al3+ combines with OH-, leaving the H+ ion to lower pH of easily exchangeable by other cations in unbuffered salt
soil solution. solution.
 H+ ions are adsorbed on a clay surface, they usually attack 3. Residual acidity – can be neutralized by liming.
the structure of the minerals. 4. Potential acidity – arise upon oxidation of sulphur (acid
 A single Al3+ ion can thus release up to three H + ions as the sulfate soil)
following reversible reaction series proceeds to the right :
- Al3+ + H2O ↔ Al(OH)2+ + H+ Combination of all acidity = TOTAL ACIDY of soil
- Al(OH)2+ + H2O ↔ Al(OH)2+ + H+
+
- Al(OH)2 + H2O ↔ Al(OH)3 + H+
 The hydroxy aluminum ions (Al(OH)xy+) formed - adsorbed
on acid soil surfaces (colloidal complex)(internal & external)
& block cation exchange sites.
 3) Residual acidity – can be neutralize by liming
- Associated with H+ and Al3+ bound in nonexchangeable
forms by OM and clays.
- To partly neutralize residual – requires 5 to 10 metrics
tons/ha of limestone
4) Potential Acidity (less common) – arise upon oxidation of
sulphur (acid sulfate soil)

Adsorbed (exchangeable) and residual (bound) ions are much more

numerous > than soil solution. Aluminium ions, by hydrolysis of
water also supply H+ ions in the soil solution.

Neutralizing only the H+ and Al3+ ions in the soil solution will be of
little consequence – will be quickly replaced by ions associated with
the colloid – demonstrates high buffering capacity.

Soil Buffering
Pools of Soil Acidity
The total acidity in soils:
1) Active acidity – due to H+ and Al3+ ions in soil solution
- Size is very small 1) Active
- 2kg of Calcium Carbonate to neutralize it at pH 4 2) Exchangeable (Salt replaceable)
- Very important (determines solubility of substances in soil 3) Residual Soil Acidity
solution)
2) Salt-replaceable acidity – due to Al3+ and H+ ions that are Soils that tends to resist change in soil pH is called soil buffering.
easily exchangeable by other cations in unbufferred salt Any changes in the soil solution pH will be buffered by the presence
solution (e.g. KCl) of the other two pool (buffering).
- Only in very acidic soils.
In certain anaerobic soils and sediments, presence of reduced
- To neutralize acidity (100 times greater amount of CaCO 3
sulphur – potential of 4th pool of soil acidity. Especially if the
compares to active acidity.
material is exposed to air by drainage or excavation.
- The acidity is highest for smectites, vermiculities
(intermediate) and kaolinite (lowest)
Soil Buffering for Intermediate pH levels (pH 5-7)
Buffering can be explained through the equilibrium exists among
pools of acidity.
If lime is applied; to neutralize H+ ions in soil solution – reactions
move to the right; minimize pH change.
If OM decay/fertilizer application; addition of H+ ions in soil
solutions – reactions move to the left; to minimize pH change.
Soils with higher clay and OM content is better buffered.
Soil colloids and their reaction with H and Al carbonates accounts
for soil buffering (5 mechanisms involved)
Mechanisms of Soil Buffering
1) Aluminium hydrolysis
2) Organic matter reaction
3) pH dependent charge sites on clay
4) Cation exchange
5) Carbonate dissolution and precipitation
Importance of Soil Buffering Capacity
1) To ensure soil pH stability – preventing fluctuations that
detrimental to soil organisms.
2) Influences the amount of amendments required to change
soil pH.
The higher CEC of a soil, the greater its buffering capacity
Acidifying Agents
To reduce the extreme alkalinity in some arid region soils:
 Applying OM (e.g. pine needles, acid peat moss and some
saw dust – low in non acid-cations)
 Applying elemental sulphur; upon oxidation in the soil
produces sulphuric acid.
 Applying Ferrous Sulphate also reduces soil pH and provides
available iron.
Liming Considerations
Soil pH is largely controlled by humus, clay fractions and associated
exchaneable cations.
The maintenance of satisfactory soil fertility levels in humid regions
depends on lime to balance the losses of Ca and Mg from the soil.
Liming:
 Maintains the level of exchangeablr calcium and magnesium
 Provides a chemical and physical environment (encourage
growth of most common plants)
 3 types of Ca and Mg containing liming materials that are
used in humid regions, carbonates, oxides and hyroxides.
The amount of limestone required to increase the pH depends on
the buffer capacity of the soil.
The clay soil require more limestone because of their high cation
exchange capacities. Subsequent application can be made 2-3 years
intervals.
Repeated applications of limestones are required since leaching
losses and crop removal deplete the soils of calcium and magnesium
thus lowers the pH.
Limestone applications to the surface soil have a little effect on the
subsoil horizons as the carbonates do not move downward.
- To counteract aluminium toxicity and Ca deficiency in the
subsoil, apply gypsum.
- The gypsum slowly dissolves and leached into the subsoil
where it stimulates the penetration of plant roots and Ca
uptake.
Bulk application by specially equipped trucks is the most widespread
method of applying ground limestone. The scene pictured occurred
on a windy day and the dispersion by wind illustrates the finely
ground nature of the agricultural limestone applied. To avoid
problems with heavy trucks bogging down in soft, recently tilled
soils, it is often preferred to make lime applications to land that is in
sod, under no-till management, or frozen hard.
Biological effects of soil pH
Strongly acid soil presents problems to non-adapted plants;
 Toxicities of Al, Mn, H, Fe
 Deficiencies of Ca, Mg, Mo, P
Toxicities of Nutrients
Aluminium toxicity
- Common/severe problem associated with acid soils.
- Rarely a problem when soil pH > 5.2
- In most organic soils, Al toxicity is much less a problem due
to less Al available and bound to carboxylic acid and
phenolic sites on soil OM.
- Symptoms on plants – stunted root system, short, thick,
stubby roots, little branching, tips turn yellow; leaves
chlorotic.
Manganese toxicity
 Serious problem associated with acid soils – derived from
Mn rich parent materials.
 Toxic when taken up at excessive quantities.
 Common problem at soil pH 5.6
 Symptoms on plants – crinkling / cupping of leaves,
interveinal patches of chlorotic tissue.
Hydrogen ion toxicity
o Toxic concentrations of H+ at soil pH < 4.0 – 4.5
o Effects on planrs – damaging root membranes
o Kill beneficial soil bacteria
Iron toxicity
- Toxic concentration of oxidized / reduced (under anaerobic
condition) iron at soil pH < 4.0
- Fe (II) form are more soluble
pH, Nutrient availability and Plant Response
The availability of most essential nutrient are affected by soil pH. In
acid soils all nutrient elements are deficient except for iron,
manganese and zinc as they are present in toxic quantities.
In alkaline soil, low availability of iron, manganese, zinc, copper and
boron.
minerals near the root. In more acid soils, the reduced pH might
increase the toxicity of aluminum. A barrier membrane allowed soil
solution to pass through, but prevented root growth into the lower
soil where pH was measured. Plants were watered from the bottom
by capillary rise.

pH levels 5.5 – 7 is the most satisfactory range for plant nutrient

availability.

Nutrient Availability to plants

Availability of micronutrients is increased by low soil pH (toxicity).

In moderately alkaline soils:

- Mo, Ca, Mg, N, K, S are amply available.

- Fe, Mn, Zn, Cu, Co are low
- P, B availability is low in alkaline soils (deficiency level)

pH ranges of 5.5 – 7.0 may provide the most satisfactory plant

nutrient levels,

Soil pH at different distances from the roots of wheat plants

receiving either ammonium (NH4+) or nitrate (NO3-) or no nitrogen
fertilizer. Uptake of NH4+ cations causes the roots to release
equivalent positive charges in the form of H+ cations, which lower
the pH (see rxn. 9.7). When a NO3- anion is taken up, the roots
release a bicarbonate anion (HCO3-), which raises the pH (see rxn.
9.8). The soil used was a calcareous sandy clay loam in the Aridisols
order with pH = 8.1. In this experiment, the lowered pH near the
roots using NH4+ markedly enhanced the plant’s uptake of
phosphorus by increasing the solubility of calcium phosphate