SOIL CHEMICAL PROPERTIES 1

SOIL CHEMICAL PROPERTIES

Prepared by: NIKAH Q. DULATRE & SEPRIDA A. HALOG

 SOIL COLLOIDS

o The colloidal state refers to a two-phase system in which one material in a very finely
divided state is dispersed through second phase.
o Soils colloids are the most active constituent of the soil and it determine the physical and
chemical properties of the soil.
o They are made up of the smallest particles (<0.001mm) of humus and clay in the soil.

 CLASSIFICATION

o Inorganic colloids
o Organic colloids

Note: Both inorganic and organic colloids are intimately mixed with other soil solids.
Thus, the bulk of the soil solids are essentially inert and the majority of the soils physical
and chemical character is a result of the colloids present.

Inorganic soil colloids

o Layer aluminosilicates which consist of thin layers of repeated structural

units. These are the dominant clay minerals in temperate regions.
o Amorphous aluminosilicates that form from volcanic ash.
o Al and Fe oxides which may be crystalline or amorphous. These are
common in subtropical and tropical regions.

Organic soil colloids

o Include highly decomposed organic matter generally called humus.

o Organic colloids are more reactive chemically and generally have a greater
influence on soil properties per unit weight than the inorganic colloids.
o The negative charges of humus are associated with partially dissociated
enolic (-OH), carboxyl (-COOH), and phenolic groups; these groups in
turn are associated with central units of varying size and complexity.
o The complex humus colloids is composed of C, H and O rather than Al, Si
and O like the silicate clays.
o Humus is amorphous and its chemical and physical characteristics are not
well defined. The organic colloidal particles vary in size, but they may be
at least as small as the silicate clay particles.
o They are not stable as clay and thus more dynamic, being formed and
destroyed more rapidly than clay.
 SOIL CHEMICAL PROPERTIES 2

 GENERAL PROPERTIES OF SOIL COLLOIDS

1. SIZE
o The inorganic and organic colloids are extremely small size (< 2
micrometers in diameter).
o These particles cannot be seen using an ordinary light microscope but can
be seen only with an electron microscope.
2. SURFACE AREA
o Because of their small size, all soil colloids have a larger external surface
area per unit mass.
o The external surface area of 1g of colloidal clay is 1000x that of 1g of
coarse sand.
o Certain silicate clays have extensive internal surfaces occurring between
plate like crystal units that make up each particle and often greatly exceed
the external surface area.
o The total surface area of soil colloids ranges from 10 m 2 /g for clays with
only external surfaces to more than 800 m2 /g for clays with extensive
internal surfaces.
o The colloid surface area in the upper 15cm of a hectare of a clay soil could
be as high as 700,000 km2 g -1.
3. SURFACE CHARGES
o Both external and internal surfaces of soil colloids carry negative and/or
positive charges.
o Most of the organic and inorganic soil colloids carry a negative charge.
o When an electric current is passed through a suspension of soil colloidal
particles they migrate to anode, the positive electrode indicating that they
carry a negative charge.
o The magnitude of the charge is known as zeta potential.
o The presence and intensity of the particle charge influence the attraction
and repulsion of the particles towards each other, there by influencing both
physical and chemical properties.
o The sources of negative charge on clays comes from (i) ionizable
hydrogen ions and (ii) isomorphous substitutions.

i) Ionizable hydrogen ions: These are hydrogen from hydroxyl (OH) ions on
clay surfaces. The –Al-OH or –Si-OH portion of the clay ionizes the H
and leaves an unneutralized negative charge on the oxygen (-AlO- or –
SiO-). The extent of ionized hydrogen depends on solution pH and hence
these negative charges are pH dependent charges. More ionization occurs
in alkaline (basic) solutions.

ii) Isomorphous substitution: This is due to the substitution of a cation of

higher valence with another cation of lower valence but similar size in the
clay crystal structure. In clay crystals some ions fit exactly into mineral
lattice sites because of their convenient size and charge. Dominantly, clays
have Si4+ in tetrahedral sites and A13+ in octahedral sites. Other ions
present in large amounts during clay crystallization can replace some of
 SOIL CHEMICAL PROPERTIES 3

the A13+ and Si4+ cations. Common substitutions are the Si4+ replaced by
A13+, and replacement of A13+ by Fe3+, Fe2+, Mg2+ or Zn2+. As the total
negative charge from the anions (oxygen) remains unchanged, the lower
positive charge of the substituted cations result in excess negative charges
on clay crystals.
4. ADSORPTION OF CATIONS:
o As soil colloids possess negative charge they attract and attach the ions of
positive charge on the colloidal surfaces.
o They attract cations like H+, A13+, Ca2+ and Mg2+.
o This gives rise to an ionic double layer.
o The Isomorphous substitution in the colloidal particle makes the external
and internal layers of clay minerals negatively charged and these surfaces
act as huge anions, which form the inner layer of the double layer.
o The outer layer is made up of a swarm of loosely held (adsorbed) cations
attracted to the negatively charged surfaces.
5. ADSORPTION OF WATER:
o A large number of water molecules are associated with soil colloidal
particles.
o Some water molecules are attracted to the adsorbed cations and the cation
is said to be in hydrated state.
o Others water molecules are held in the internal surfaces of the colloidal
clay particles.
o These water molecules play a critical role in determining both the physical
and chemical properties of soil.
6. COHESION (Attractive force between similar molecules or materials):
o Cohesion indicates the tendency of clay particles to stick together.
o This tendency is due to the attraction of clay particles for water molecules
held between them.
o When colloidal substances are wetted, water first adheres to individual
clay particles and then brings about cohesion between two or more
adjacent colloidal particles.
7. ADHESION (Attractive force between different molecules or materials):
o Adhesion refers to the attraction of colloida1 materials to the surface of
any other body or substance with which it comes in contact.
8. SWELLING AND SHRINKAGE:
o Some soil clay colloids belonging to smectite group like Montmorillonite
swell when wet and shrink when dry.
o After a prolonged dry spell, soils high in smectite clay (e.g. Black soil -
Vertisols) often show crises-cross wide and deep cracks.
o These cracks first allow rain to penetrate rapidly.
o Later, because of swelling, the cracks will close and become impervious.
o But soils dominated by kaolinite, chlorite, or fine grained micas do not
swell or shrink.
o Vermiculite is intermediate in its swelling and shrinking characteristics.
 SOIL CHEMICAL PROPERTIES 4

9. DISPERSION AND FLOCCULATION:

o As long as the colloidal particles remain negatively charged, they repel
each other and the suspension remains stable.
o If on any account they loose their charge, or if the magnitude of the charge
is reduced, the particles coalesce, form flock or loose aggregates, and
settle down.
o This phenomenon of coalescence and formation of flocks is known as
flocculation.
o The reverse process of the breaking up of flocks into individual particles is
known as de-flocculation or dispersion.
10. BROWNIAN MOVEMENT:
o When a suspension of colloidal particles is examined under a microscope
the particles seem to oscillate.
o The oscillation is due to the collision of colloidal particles or molecules
with those of the liquid in which they are suspended.
o Soil colloidal particles with those of water in which they are suspended are
always in a constant state of motion.
o The smaller the particle, the more rapid is its movement.
11. NON PERMEABILITY:
o Colloids, as opposed to crystalloids, are unable to pass through a semi-
permeable membrane.
o Even though the colloidal particles are extremely small, they are bigger
than molecules of crystalloid dissolved in water.
o The membrane allows the passage of water and of the dissolved substance
through its pores, but retains the colloidal particles.

 TYPES OF SOIL COLLOIDS

1. Layer silicate clays
2. Iron and Aluminum oxide clays (sesquioxide clays)
3. Allophane and associated amorphous clays
4. Humus
Note: Layer silicate clays, iron and aluminium oxide clays, allophane and associated amorphous
clays are inorganic colloids while humus is an organic colloid.
1. LAYER SILICATE CLAYS
o These important silicate clays are also known as phyllosilicates (Phyllon - leaf)
because of their leaf-like or plate like structure.
o These are made up of two kinds of horizontal sheets. One dominated by silicon
and other by aluminum and/or magnesium.
Silica tetrahedron: The basic building block for the silica-dominated sheet is a unit
composed of one silicon atom surrounded by four oxygen atoms. It is called the silica
tetrahedron because of its four-sided configuration. An interlocking array or a series
of these silica tetrahedra tied together horizontally by shared oxygen anions gives a
tetrahedral sheet.
 SOIL CHEMICAL PROPERTIES 5

Alumina octahedron: Aluminium and/or magnesium ions are the key cations
surrounded by six oxygen atoms or hydroxyl group giving an eight sided building
block termed octahedron. Numerous octahedra linked together horizontally comprise
the octahedral sheet. An aluminum-dominated sheet is known as a di-octahedral
sheet, whereas one dominated by magnesium is called a tri-octahedral sheet. The
distinction is due to the fact that two aluminum ions in a di-octahedral sheet satisfy
the same negative charge from surrounding oxygen and hydroxyls as three
magnesium ions in a tri-octahedral sheet. The tetrahedral and octahedral sheets are
the fundamental structural units of silicate clays. These sheets are bound together
within the crystals by shared oxygen atoms into different layers. The specific nature
and combination of sheets in these layers vary from one type of clay to another and
control the physical and chemical properties of each clay.

2. IRON AND ALUMINUM OXIDE CLAYS (SESQUIOXIDE CLAYS)

o Under conditions of extensive leaching by rainfall and long- time intensive
weathering of minerals in humid warm climates, most of the silica and alumina in
primary minerals are dissolved and slowly leached away.
o The remnant materials, which have lower solubility, are called sesquioxides.
Sesquioxides (metal oxides) are mixtures of aluminum hydroxide, Al (OH)3, and
iron oxide, Fe2O3, or iron hydroxide, Fe(OH)3.
o The Latin word sesqui means one and one-half times, meaning one and one-half
times more oxygen than Al and Fe.
o These clays can grade from amorphous to crystalline. Examples of iron and
aluminum oxides common in soils are gibbsite (Al2O3.3H2O) and geothite
(Fe2O3.H2O).
o Less is known about these clays than about the layer silicates.
o These clays do not swell, not sticky and have high phosphorus adsorption
capacity.

3. ALLOPHANE AND OTHER AMORPHOUS MINERALS

o These silicate clays are mixtures of silica and alumina.
o They are amorphous in nature. Even mixture of other weathered oxides (iron
oxide) may be a part of the mixture.
o Typically, these clays occur where large amount of weathered products existed.
These clays are common in soils forming from volcanic ash (e.g., Allophane).
o These clays have high anion exchange capacity or even high cation exchange
capacity.
o Almost all of their charge is from accessible hydroxyl ions (OH-), which can
attract a positive ion or lose the H+ attached.
o These clays have a variable charge that depends on H+ in solution (the soil
acidity).

4. HUMUS (ORGANIC COLLOID)

o Humus is amorphous, dark brown to black, nearly insoluble in water, but mostly
soluble in dilute alkali (NaOH or KOH) solutions.
 SOIL CHEMICAL PROPERTIES 6

o It is a temporary intermediate
product left after considerable
decomposition of plant and
animal remains.
o They are temporary intermediate
because the organic substances
remain continue to decompose
slowly.
o The humus is often referred to as
an organic colloid and consists
of various chains and loops of
linked carbon atoms.
o The humus colloids are not
crystalline.
o They are composed basically of carbon, hydrogen, and oxygen rather than of
silicon, aluminum, iron, oxygen, and hydroxyl groups.
o The organic colloidal particles vary in size, but they may be at least as small as
the silicate clay particles.
o The negative charges of humus are associated with partially dissociated enolic (-
OH), carboxyl (-COOH), and phenolic groups; these groups in turn are associated
with central units of varying size and complexity.

 CATION EXCHANGE CAPACITY (CEC)

o CEC is a measure of the soil’s ability to hold positively charged ions.
o It is a very important soil property influencing soil structure stability, nutrient
availability, soil pH and the soil’s reaction to fertilizers and other ameliorants.
o Cations are positively charged ions such as calcium (Ca2+), magnesium (Mg2+), and
potassium (K+), sodium (Na+) hydrogen (H+), aluminum (Al3+), iron (Fe2+),
manganese (Mn2+), zinc (Zn2+) and copper (Cu2+).
o These cations are held by the negatively charged clay and organic matter particles in
the soil through electrostatic forces (negative soil particles attract the positive
cations).
o The cations on the CEC of the soil particles are easily exchangeable with other
cations and as a result, they are plant available.
o Thus, the CEC of a soil represents the total amount of exchangeable cations that the
soil can adsorb.

IMPLICATIONS
o The higher the CEC the more clay or organic matter present in the soil. This usually
means that high CEC (clay) soils have a greater water holding capacity than low CEC
(sandy) soils.
o Low CEC soils are more likely to develop potassium and magnesium (and other
cation) deficiencies, while high CEC soils are less susceptible to leaching losses of
these cations. So, for sandy soils, a large one-time addition of cations e.g. potassium
can lead to large leaching losses (soil isn’t able to hold on to the excess K). More
frequent additions of smaller amounts are better.
 SOIL CHEMICAL PROPERTIES 7

o The lower the CEC, the faster the soil pH will decrease with time. So, sandy soils
need to be limed more often than clay soils.
o The higher the CEC, the larger the quantity of lime that must be added to increase the
soil pH; sandy soils need less time than clay soils to increase the pH to desired levels.

 BASE SATURATION
o Base saturation indicates the balance between acid and base cations adsorbed by the
CEC of a soil such as potassium (K), magnesium (Mg), calcium (Ca), and sodium
(Na).
o It is a partial misnomer because a base is a chemical compound that can react with an
acid to form a salt like calcium hydroxide, Ca(OH)2.
o The base saturation percentages are calculated for each cation then added up to
determine base saturation. For example, suppose that the following soil test ppm
values were determined (Table 1).

AMENDMENT AND FERTILIZER RECOMMENDATIONS

o Limestone recommendations
- Limestone needs to be applied at a rate to neutralize all of the acidity on the soil
exchange sites. It takes 1000 lbs. of limestone for each meq/100g of soil acidity.

Limestone (tons/acre) = 0.5 x (CEC x H%)

- This assumes incorporation in the top 6 2/3 inches of soil. This factor needs to be
adjusted directly in proportion to the tillage depth.

o Gypsum Recommendations
- Soils containing more than 15% exchangeable sodium are prone to poor drainage
and salt buildup.
- Application of a soluble source of calcium, such as gypsum, is recommended to
replace the sodium off of the exchange sites and be leached out of the root zone.
- Gypsum recommendations are 3440 lbs. per meq/100g of sodium wanting to be
replaced per foot of soil.
Gypsum (tons/acre foot) = 1.7 x CEC x (Na% - 5%)
- This recommends
an amount of
gypsum that will
replace all but 5%
of the sodium in the
top foot of soil.
Sodium needs to be
corrected in the top
foot to ensure good
root growth in salt-
affected soils.
 SOIL CHEMICAL PROPERTIES 8

o Fertilizer Recommendations
- Soil cations become
increasingly soluble and
available to plants as the
exchangeable % increases.
- The goal is to maintain
adequate amounts of
nutrients for plant uptake
while minimizing nutrient
leaching loss.
- Optimum base saturation
percentages recommended
are: Na <10%; K 2-7%; Mg 15-20%; Ca 65-75%
- Fertilizer application rates can be adjusted to reach these optimum saturation
levels. This approach works well for soils with low CEC (<10). It does not work
well with CEC >40.
- For example, let’s assume soil test K value of 39 ppm, which calculates out to be
3.3% saturation for a soil with a CEC of 3. Based on these figures, perhaps a
maintenance amount of K is all that is needed.
- However, a fertilizer recommendation philosophy based on an optimum soil test
level of 130 ppm K would classify this soil as being severely deficient.
- Which is right? The problem with the critical soil test level approach is that a
coarse textured soil will not hold 130 ppm of K.
- Applying excessive amounts of K to sandy soils could overcorrect a nutrient
problem and create a potential nutrient imbalance.
- The base saturation ratio approach, on the other hand, would balance out the
fertility and prevent excessive K leaching.
- Further, heavy texture soils with a CEC of >40 require an excessive amount of K
depending on base saturation.
- The amount K required to obtain a desired K concentration of 2%, 3%, and 5%
for CEC ranging from 5 to 60 is shown in Table 2.

 EXCHANGEABLE SODIUM PERCENTAGE (ESP)

o ESP is the relative amount of the sodium ion present on the soil surface, expressed as
a percentage of the total CEC.
o ESP is, accordingly, the amount of adsorbed sodium on the soil exchange complex
expressed in percent of the CEC in milliequivalents per 100g of soil. Thus,

ESP = Exchangeable Na (me/100g soil) x 100

Cation exchange capacity (me/100g soil)

 SOIL pH
o Soil pH or soil reaction is an indication of the activity or alkalinity of soil and is
measured in pH units.
o It is defined as the negative logarithm of the hydrogen ion concentration.
o The pH scale goes from 0 to 14 with pH 7 as the neutral point.
 SOIL CHEMICAL PROPERTIES 9

o As the amount of hydrogen ions in the soil increases the soil pH decreases thus
becoming more acidic.
o From pH 7 to 0 the soil is increasingly more acidic and from pH 7 to 14 the soil is
increasingly more alkaline or basic.
o Descriptive terms commonly associated with certain ranges in soil pH are:
o Extremely acid: < 4.5; lemon = 2.5; vinegar = 3.0; stomach acid = 2.0;
soda = 2-4
o Very strongly acid: 4.5 – 5.0; beer = 4.5 – 5.0; tomatoes = 4.5
o Strongly acid: 5.1–5.5; carrots=5.0; asparagus=5.5; boric acid=5.2;
cabbage=5.3
o Moderately acid: 5.6–6.0; potatoes=5.6
o Slightly acid: 6.1–6.5; salmon=6.2; cow's milk=6.5
o Neutral: 6.6–7.3; saliva=6.6–7.3; blood=7.3; shrimp=7.0
o Slightly alkaline: 7.4–7.8; eggs=7.6–7.8
o Moderately alkaline: 7.9–8.4; sea water=8.2; sodium bicarbonate=8.4
o Strongly alkaline: 8.5–9.0; borax=9.0
o Very strongly alkaline: > than 9.1; milk of magnesia=10.5,
ammonia=11.1; lime=12

 SOURCES OF SOIL ACIDITY

1. Crop Removal
2. Fertilizer
3. Rainfall

Crop Removal
o Calcium, magnesium and potassium are essential nutrients for plant growth.
o Their uptake by plants and subsequent removal through harvest can have an
acidifying effect on soils.
o The amount of these nutrients removed by cropping depends on:
o Crop grown
o Part of crop harvested
o Stage of growth at harvest
o Removal is greater for hay crops than for grain crops (table 1)
 SOIL CHEMICAL PROPERTIES 10

Fertilizer
o Nitrogen fertilizers
have a greater
acidifying effect on
soils than other
fertilizers.
o Two processes are
involved. First,
commonly used
nitrogen fertilizers
contain ammonium
nitrogen (urea is an
ammonium
forming material).
Soil bacteria
convert ammonium
(NH4+) to nitrate
(NO3+) through a biochemical process called nitrification. Hydrogen (H+) is
released in this process, and free hydrogen ions cause an increase in acidity. The
second acidifying effect comes from nitrate that is not taken up by the growing
crop. Nitrates are very soluble and, if not taken up by plants, will move downward
with soil water and may be carried below the root zone. They take with them
other nutrients that have a positive charge-most likely calcium and magnesium-
and their removal in this manner has the same acidifying effect on soils as
removal by a crop.
o Table 2 shows the calculated amount of typical aglime needed to offset the acidity
potential of common nitrogen fertilizers. It is evident that applying more nitrogen
fertilizer than a crop can take up is not only wasteful and expensive from the
nitrogen standpoint but also increases the cost of a liming program and can be a
pollution hazard.

Rainfall
o Soils can become acid even in the absence of crop removal or fertilizer
applications.
o It is considered a natura cause of acidity because of the downward movement of
water through the soil profile and the remocal of nutrients from surface runoff and
erosion.
o As water moves down through the soil profile, it has a slow but persistent
acidifying affect.
o Weak acids (corresponding to vinegar) are produced in the soil when plant
residues and organic matter decompose.
o These weak acids react and combine with nutrients such as calcium, magnesium,
potassium, and sodium as the soil solution (water) moves down through and
below the root zone (leaching).
o Hydrogen, or aluminum if soil pH is less than 5.2, replace basic cations causing
the soil in the leached zone to become more acid.
 SOIL CHEMICAL PROPERTIES 11

 POOLS OF ACIDITY
Active acidity is the quantity of hydrogen ions that are present in the soil water
solution. The active pool of hydrogen ions is in equilibrium with the exchangeable
hydrogen ions that are held on the soil’s cation exchange complex. This pool most
readily affects plant growth. Active acidity may be directly determined using a pH
meter, such as an electron probe.
Exchangeable acidity refers to the amount of acid cations, aluminum and hydrogen,
occupied on the CEC. When the CEC of a soil is high but has a low base saturation,
the soil becomes more resistant to pH changes. As a result, it will require larger
additions of lime to neutralize the acidity. The soil is then buffered against pH
change.
Residual acidity comprised of all bound aluminum and hydrogen in soil minerals.
Out of all pools, residual acidity is least available.

 BUFFERING CAPACITY
o It quantifies the ability of a solution to resist changes in pH by either absorbing or
desorbing H+ and OH- ions.
o When an acid or base is added to a buffer system, the effect on pH change can be
large or small, depending on both the initial pH and the capacity of the buffer to
resist change in pH.
o Buffer capacity (β) is defined as the moles of an acid or base necessary to change
the pH of a solution by 1, divided by the pH change and the volume of buffer in
liters; it is a unitless number.
o A buffer resists changes in pH due to the addition of an acid or base though
consumption of the buffer.
o As long as the buffer has not been completely reacted, the pH will not change
drastically.
o The pH change will increase (or decrease) more drastically as the buffer is
depleted: it becomes less resistant to change.

 EFFECT OF SOIL PH ON NUTRIENT AVAILABILITY

o Soil pH affects nutrient availability by changing the form of the nutrient in
the soil. Adjusting soil pH to a recommended value can increase the
availability of important nutrients. Plants usually grow well at pH values
above 5.5 and pH 6.5 is considered the optimum nutrient availability.
o Lower pH increase the solubility of Al, Mn, and Fe, which are toxic to
plants in excess. A critical effect of excess soluble Al is the slowing or
stopping of root growth.
o Extreme pH values decrease the availability of most nutrients. Low pH
reduces the availability of the macro- and secondary nutrients, while high
pH reduces the availability of most micronutrients. Microbial activity may
also be reduced or changed.
 SOIL CHEMICAL PROPERTIES 12

 LIMING
o It is the application of calcium- and magnesium- rich materials to soil in various
forms, including marl, chalk, limestone, or hydrated lime.
o This neutralizes soil acidity and increases activity of soil bacteria.

 RELATIVE NEUTRALIZING VALUE (RNV)

o The percent of effective material in lime based on particle size can be combined
with lime purity values to calculate the overall quality of aglime.
o RNV is calculated using the lime purity value (CCE) and fineness values for
percent less than 50 mesh and percent between 10 and 50 mesh.
o The equation used is:

RNV = CCE/100 (% between 10 and 50 mesh + % less than 50 mesh)

2

o Where CCE is % calcium carbonate equivalent.

o The amount of particles between 10 and 50 mesh is divided by two because it is
only half as effective as those smaller than 50 mesh.
 SOIL CHEMICAL PROPERTIES 13

 SOIL SALINITY AND SODICITY

SOIL SALINITY
o Saline irrigation water contains dissolved substances known as salts.
o In much of the arid and semi-arid United States (including Montana), most
of the salts present in irrigation water are chlorides, sulfates, carbonates,
and bicarbonates of calcium magnesium, sodium, and potassium.
o While salinity can improve soil structure, it can also negatively affect
plant growth and crop yields.

SOIL SODICITY
o Sodicity refers specifically to the amount of sodium present in irrigation
water.
o Irrigating with water that has excess amounts of sodium can adversely
impact soil structure, making plant growth difficult.
o Highly saline and sodic water qualities can cause problems for irrigation,
depending on the type and amount of salts present, the soil type being
irrigated, the specific plant species and growth stage, and the amount of
water able to pass through the root zone.