CHEMISTRY OF SOIL 163

SOIL COMPONENTS

A soil is simply a porous medium consisting of minerals, water, gases, organic matter, and
microorganisms. The traditional definition is: Soil is a dynamic natural body having properties derived
from the combined effects of climate and biotic activities, as modified by topography, acting on parent
materials over time.

Soil is comprised of minerals, soil organic matter

(SOM), water, and air. The composition and proportion of these
components greatly influence soil physical properties, including
texture, structure, and porosity, the fraction of pore space in a
soil. In turn, these properties affect air and water movement in
the soil, and thus the soil’s ability to function.

Minerals and SOM make up the solid fraction, whereas

air and water comprise the pore space fraction. A typical
agricultural soil is usually around 50% solid particles and 50%
pores.

1. Mineral

The largest component of soil is the mineral portion, which makes up approximately 45% to 49%
of the volume. Soil minerals are derived from two principal mineral types. Primary minerals, such as
those found in sand and silt, are those soil materials that are similar to the parent material from which they
formed. They are often round or irregular in shape. Secondary minerals, on the other hand, result from the
weathering of the primary minerals, which releases important ions and forms more stable mineral forms
such as silicate clay. Clays have a large surface area, which is important for soil chemistry and water-
holding capacity. Additionally, negative and neutral charges found around soil minerals influences the
soil’s ability to retain important nutrients, such as cations, contributing to a soils cation exchange capacity
(CEC).

2. Water

Water is the second basic component of soil. Water can make up approximately 2% to 50% of the
soil volume. Water is important for transporting nutrients to growing plants and soil organisms and for
facilitating both biological and chemical decomposition. Soil water availability is the capacity of a
particular soil to hold water that is available for plant use.

The capacity of a soil to hold water is largely dependent on soil texture. The more small particles in
soils, the more water the soil can retain. Thus, clay soils having the greatest water-holding capacity and
sands the least. Additionally, organic matter also influences the water-holding capacity of soils because of
organic matter’s high affinity for water. The higher the percentage of organic material in soil, the higher the
soil’s water-holding capacity.

The point where water is held microscopically with too much energy for a plant to extract is called
the “wilting coefficient” or “permanent wilting point.” When water is bound so tightly to soil particles, it is
not available for most plants to extract, which limits the amount of water available for plant use. Although
clay can hold the most water of all soil textures, very fine micropores on clay surfaces hold water so tightly
that plants have great difficulty extracting all of it. Thus, loams and silt loams are considered some of the
most productive soil textures because they hold large quantities of water that is available for plants to use.

3. Organic matter

Organic matter is the next basic component that is found in soils at levels of approximately 1% to
5%. Organic matter is derived from dead plants and animals and as such has a high capacity to hold onto
and/or provide the essential elements and water for plant growth. Soils that are high in organic matter also
have a high CEC and are, therefore, generally some of the most productive for plant growth. Organic
matter also has a very high “plant available” water-holding capacity, which can enhance the growth
potential of soils with poor water-holding capacity such as sand. Thus, the percent of decomposed organic
matter in or on soils is often used as an indicator of a productive and fertile soil. Over time, however,
prolonged decomposition of organic materials can lead it to become unavailable for plant use, creating
what are known as recalcitrant carbon stores in soils.

4. Gases

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Gases or air is the next basic component of soil. Because air can occupy the same spaces as water,
it can make up approximately 2% to 50% of the soil volume. Oxygen is essential for root and microbe
respiration, which helps support plant growth. Carbon dioxide and nitrogen also are important for
belowground plant functions such as for nitrogen-fixing bacteria. If soils remain waterlogged (where gas is
displaced by excess water), it can prevent root gas exchange leading to plant death, which is a common
concern after floods.

5. Microorganisms

Microorganisms are the final basic element of soils, and they are found in the soil in very high
numbers but make up much less than 1% of the soil volume. A common estimate is that one thimble full of
topsoil may hold more than 20,000 microbial organisms. The largest of these organisms are earthworms
and nematodes and the smallest are bacteria, actinomycetes, algae, and fungi. Microorganisms are the
primary decomposers of raw organic matter. Decomposers consume organic matter, water, and air to
recycle raw organic matter into humus, which is rich in readily available plant nutrients.

Other specialized microorganisms such as nitrogen-fixing bacteria have symbiotic relationships

with plants that allow plants to extract this essential nutrient. Such “nitrogen-fixing” plants are a major
source of soil nitrogen and are essential for soil development over time. Mycorrhizae are fungal complexes
that form mutualistic relationships with plant roots. The fungus grows into a plant’s root, where the plant
provides the fungus with sugar and, in return, the fungus provides the plant root with water and access to
nutrients in the soil through its intricate web of hyphae spread throughout the soil matrix. Without
microbes, a soil is essentially dead and can be limited in supporting plant growth.

Soil Texture

Soil texture can have a profound effect on many other properties and is considered among the most
important physical properties. Texture is the proportion of three mineral particles, sand, silt and clay, in a
soil. These particles are distinguished by size, and make up the fine mineral fraction. Particles over 2 mm in
diameter (the ‘coarse mineral fraction’) are not considered in texture, though in certain cases they may
affect water retention and other properties. The relative amount of various particle sizes in a soil defines its
texture, i.e., whether it is a clay, loam, sandy loam or other textural category.

Soil Particle Diameter (mm)

Gravel >2.0
Sand 0.05-2.0
Silt 0.002-0.05
Clay <0.002

Texture is the result of ‘weathering,’ the physical and chemical breakdown of rocks and minerals.
Because of differences in composition and structure, materials will weather at different rates, affecting a
soil’s texture. For example, shale, an easily weathered rock, forms clay-rich soils, whereas granite, a slow
weathering rock, usually forms sandy, coarse soils. Since weathering is a relatively slow process, texture
remains fairly constant and is not altered by management practices.

Soil Colloids

‘Soil colloids’ refer to the finest clay and

SOM particles in a soil. Colloids are an important soil
fraction due to properties that make them the location
of most physical and chemical activity in the soil. One
such property is their large surface area. Smaller
particles have more surface area for a given volume
or mass of particles than larger particles. Thus, there
is increased contact with other colloids and with the
soil solution. This results in the formation of strong
friction and cohesive bonds between colloid particles
and soil water, and is why a clay soil holds together
better than a sandy soil when wet.

BASIC SOIL CHEMISTRY

Soils transport and move water, provide homes for thousands of bacteria and other creatures, and
have many different arrangements of weathered rock and minerals. When soils and minerals weather over
time, the chemical composition of soil also changes. However, nothing changes the chemistry of soils
faster than humans do. Many of today’s soil chemistry problems have to do with environmental sciences.
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1. SOIL PH

The soil pH is a measure of soil acidity or alkalinity. pH can range from 1 to 14, with values 0-7
being acidic, and 7-14 being alkaline. Soils usually range from 4 to 10. The pH is one of the most
important properties involved in plant growth, as well as understanding how rapidly reactions occur in the
soil. For example, the element iron becomes less available to plants a higher the pH is. This creates iron
deficiency problems. Crops usually prefer values between 5.5-8, but the value depends on the crop. The pH
of soil comes from the parent material during soil formation, but humans can add things to soils to change
them to better suit plant growth. Soil pH also affects organisms.

In the soil, availability of plant nutrients such as nitrogen (for foliage), phosphorus (for root
formation and energy transfer), and potassium (for seed formation/germination and sugar formation) are
affected by the pH of the soil. Soil pH is not a nutrient but does tell us how well plants can pull nutrients
from the soil. And microorganisms live in the soil and their activity is affected by soil pH around them.
These organisms are responsible for decomposition of leaves and other plant tissues, dead animals, and for
biodegrading of organic compounds in soil. Soil pH also affects the dissolution of soil minerals that are
then released as nutrients for growing plants.

When the soil pH is below the ideal, it can be raised by the addition of lime. The quantity of
limestone
(CaCO3) required to raise the pH of an acid soil to a desired pH level is referred to as lime requirement.

Liming

When the soil pH is below the ideal, it can be increased by liming. This is why people sometimes
spread white powder on their lawns or gardens. This white powder is lime. Calcitic limestone (CaCO )
provides a good source of Calcium (Ca) and helps neutralize soil acidity. Dolomitic limestone functions
similarly but also adds Magnesium (Mg). The best limestone will have the greatest calcium and magnesium
content and will be ground into very tiny particles. The smaller particles allow the limestone to correct soil
acidity more rapidly.

The chemistry to liming is quite simple. Hydrogen ions (H +) are attracted to soil and organic
material which have a negative charge. When lime is applied, these hydrogen ions are exchanged for
calcium or magnesium (Ca2+ or Mg2+) ions which have a greater positive charge. This helps to neutralize
the acidity of the soil. The free hydrogen ions are taken out of solution. This also helps to increase the pH.
This reaction demonstrates the process of liming:

In some cases when the soil pH is high, application of ammonium fertilizers, urea, sulfur/ferrous
sulfate, and using acidifying residues (e.g. pine needles, saw dust and acid moss) can help to reduce soil
pH. The addition of organic matter (plants and compost) can make soils more resistant to a drop or rise in
pH.

Buffering Capacity

This is the ability to withstand rapid pH fluctuation. The greater the buffering capacity, the greater
the quantity of acid or base which must be used to alter the pH. Soil types having low buffering capacities
include sandy soils with little clay or organic matter. Soils with a higher buffering capacity would have
large quantities of mineral clay and organic matter. Therefore, a thick rich soil with a high buffering
capacity would require more lime in order to raise the pH.

2. CATION EXCHANGE CAPACITY

Soil clay minerals and organic matter tend to be negatively charged, thus attracting positively
charged ions (cations) on their surfaces by electrostatic forces. As a result, the cations remain within the
soil root zone and are not easily lost through leaching. The adsorbed cations may easily exchange with
other cations in the soil solution, hence the term "cation exchange." The adsorbed cations replenish the ions
in the soil solution when concentrations decrease due to uptake by plant roots.

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Cation exchange capacity (CEC) is a measure of the total negative charges within the soil that
adsorb plant nutrient cations such as calcium (Ca 2+), magnesium (Mg2+) and potassium (K+). As such, the
CEC is a property of a soil that describes its capacity to supply nutrient cations to the soil solution for plant
uptake. Plant roots can remove nutrients from the soil solution, which results in nutrients moving away
from the clay particles. Addition of fertilizer to soil causes an initial increase in nutrient concentration in
the soil solution, which results in nutrients moving toward clay particles.

The nutrient cations plants use in the largest amounts are potassium (K +), calcium (Ca2+) and
magnesium (Mg2+). Other cations adsorbed on exchange sites are ammonium (NH 4+), sodium (Na+),
hydrogen (H+), aluminum (Al3+), iron (Fe2+ or Fe3+), manganese (Mn2+), copper (Cu2+) and zinc (Zn2+).
Micronutrient cations such as zinc, copper, iron and manganese are typically present at very low
concentrations in soils. Ammonium concentrations are also typically very low because microorganisms
convert ammonium to nitrate in a process called nitrification.

How CEC changes with Soil pH

The CEC of soil organic matter and some clay minerals varies with pH. Generally, the CEC is
lowest at soil pHs of 3.5 to 4.0 and increases as the pH is increased by liming an acid soil. Because CEC
may vary considerably with soil pH, it is a common practice to measure a soil’s CEC at a pH of 7.0. Also
note that some positive charges may occur on specific soil mineral surfaces at low pH. These positive
charges retain anions (negatively charged ions) such as chloride (Cl -) and sulfate (SO42-).

Typical CEC Values in Soils

In most soil reports, CEC is expressed as milliequivalents (meq) of charge (number of charges) per
100 grams of soil (meq/100 g or as cmol/kg when using International Scientific Units). The number of
milliequivalents is used rather than a weight (pounds, grams, etc.) of adsorbed cations because CEC
represents the total number of charges, which is a better standard of comparison of different soils because
each cation species has a different weight and soils differ in the proportions of the different cation species.

Because soil is a mixture of different particle sizes (sand, silt and clay), clay mineral types and
organic matter in various proportions, the dominant components and soil pH dictates the soil’s CEC.
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Cation exchange capacities at pH 7.0 of different soil types, textures and soil organic matter.

Soil and soil components CEC (meq/100 g)

Clay Type
Kaolinite 3 – 15
Illite 15 – 40
Montmorillonite 80 – 100
Soil Texture
Sand 1–5
Fine and Sandy Soil 5 – 10
Loam 5 – 15
Clay Loam 15 – 30
Clay >30
Organic Matter 200 – 400

3. PERCENT BASE SATURATION

Percent base saturation (BS) is the percentage of the CEC occupied by the basic cations Ca 2+, Mg2+
and K . Basic cations are distinguished from the acid cations H + and Al3+. At an approximate soil pH 5.4 or
+

less, Al3+ is present in a significantly high concentration that hinders growth of most plant species, and the
lower the soil pH, the greater the amount of toxic Al 3+. Therefore, soils with a high percent base saturation
are generally more fertile because:

 They have little or no acid cation Al3+ that is toxic to plant growth.
 Soils with high percent base saturation have a higher pH; therefore, they are more buffered against
acid cations from plant roots and soil processes that acidify the soil (nitrification, acid rain, etc.).
 They contain greater amounts of the essential plant nutrient cations K +, Ca2+ and Mg2+ for use by
plants.

The percentage base saturation is expressed as follows:

%BS = [(Ca2+ + Mg2+ + K+)/CEC] × 100

Significance of CEC and BS

A soil’s CEC affects fertilization and liming practices. For example, soils with high CEC retain
more nutrients than low-CEC soils. With large quantities of fertilizers applied in a single application to
sandy soils with low CEC, loss of nutrients is more likely to occur via leaching. In contrast, these nutrients
are much less susceptible to losses in clay soils.

Crop production releases acidity into soil. Soil pH will decrease more due to crop production on
low CEC soils. High CEC soils are generally well buffered such that pH changes much less from crop
production. Therefore, sandy soils low in CEC need to be limed more frequently but at lower rates of
application than clay soils. Higher lime rates are needed to reach an optimum pH on high CEC soils due to
their greater abundance of acidic cations at a given pH.

4. SORPTION AND PRECIPITATION

Soil particles have the ability to capture different nutrients and ions. Sorption is the process in
which one substance takes up or holds another. In this case, soils that have high sorption can hold a lot of
extra environmental contaminents, like phosporus, onto the particles. Soil precipitation occurs during
chemical reactions when a nutrient or chemical in the soil solution (water around soil particles) transforms
into a solid. This is really important if soils are really salty. Soil chemists study the speed of these reactions
under many different conditions.

5. OXIDATION AND REDUCTION REACTIONS

Soils that alternate between wet and dry go from having a lot of oxygen to not a lot of oxygen. The
presence or absence of oxygen determines how soils chemically react. Oxidation is the loss of electrons,
and reduction is the gaining of electrons at the soil surface. These type of reactions occur every day, and are
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responsible for creating things like rust. Soils, because they contain a lot of iron, can also rust, or if they
contain a lot of water, can turn a light gray color. This is partially responsible for all of the different colors
that are found, and creates the speckles usually found deeper in the soil.

Soil Color

Soil color can tell us a lot about the soil and the environment. Dark black top soil indicates high
organic mater contents as compare to light brown colors. The presence of gray colors in the soil is used to
determine the water table depth. This is done when assessing the site for many land uses related both to
agriculture and well as urban/ suburban development. Often the gray colors are referred to as wetness
mottles or redoximorphic features (formed from reduction and oxidation chemical reactions in the soil).
Many land use decision are based on these colors and the fact that they do not change season to season.
Thus in summer when water tables are deep gray colors indicate how high the water table will rise during
the wettest time of the year.

The color change from red (rusty) to gray observe in the soil is due to reduction and oxidation of
Fe. This process occurs in soil but in saturated soil this occurs when Fe 3+ is reduced to Fe2+ due to a
microbial mediated redox reaction.

If air (O2) is in the soil the soil is aerobic – rusty or oxidized color persist

4 e- + O2 + 4 H+  2 H2O

If all O2 is removed soil becomes anaerobic (saturation occurs)

• Denitrification – no color change

10 e- + 12 H+ + 2 NO3  N2 + 6 H2O

• Iron (Manganese) Reduction – soil turns gray

2 e- + 6 H+ + Fe2O3  2 Fe(II) + 3 H2O

• Sulfate Reduction – rotten egg odor

8 e- + 10 H+ + SO4  H 2S + 4 H2O

Once the gray colors due to Fe3+ reduction and removal have formed it is unlikely that the particles
will become coated again. Since this reaction occurs in saturated and reduced or anaerobic conditions the
presence of gray colors indicates where the water table is in that soil. This helps soil scientist identify
wetland or hydric soils and locate suitable soils for septic systems and related land use. This reaction only
occurs if there are sufficient numbers of microbes and a food source (carbon) present to cause anaerobic
conditions to occur.

SOIL NUTRIENT CYCLING

Each year the soil undergoes a series of cycles in which materials are added and then taken away.
Organic matter and nutrients, in various forms, are constantly being added to the soil. Nutrients are the
minerals required by plants to survive. It is very important that plants receive all the required nutrients.
There are a total of sixteen elements required for plant growth. Each is required in different amounts. The
most important nutrients are called macronutrients. Nutrients which are essential, but only needed in
small quantities are called micronutrients.

Carbon, Hydrogen, and Oxygen are the big three macronutrients. These are obtained in almost
unlimited amounts from the atmosphere and from the water around the plant. The other macronutrients are
nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S). These
nutrients should be available for plant uptake from the soil. Micronutrients are obtained from the soil. They
are boron (B), copper (Cu), chlorine (Cl), iron (Fe), manganese (Mn), molybdenum (Mo), and zinc (Zn).
They are all essential because the absence of any one of these will cause the plant to grow poorly or
develop disease.

Nitrogen Cycling in Soils

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Nitrogen is a key component of soil organic matter and is required by plants in large quantities. It is
often the first limiting nutrient in cropping systems. Nitrogen forms a part of every living cell. It is an
essential component of amino acids — the building blocks for proteins. The amount of N supplied to plants
influences the production of plant proteins such as enzymes, mitochondria and carrier, storage and
structural proteins.

Chlorophyll is the N-based plant component responsible for photosynthesis. The amount of
chlorophyll in a plant is reflected by the shade of green in plant leaves. Therefore, plant leaves can provide
a visual clue to the N status of a crop (e.g., lighter shades of green in plant leaves could suggest an
inadequate N supply).

In general, the nitrogen cycle has five steps:

1. Nitrogen fixation (N2 to NH3/ NH4+ or NO3-)

Nitrogen fixation is the process by which gaseous nitrogen (N 2) is converted to ammonia (NH3 or
NH ) via biological fixation or nitrate (NO 3-) through high-energy physical processes. N 2 is extremely
4
+

stable and a great deal of energy is required to break the bonds that join the two N atoms. N 2 can be
converted directly into NO 3- through processes that exert a tremendous amount of heat, pressure, and
energy. Such processes include combustion, volcanic action, lightning discharges, and industrial means.
However, a greater amount of biologically available nitrogen is naturally generated via the biological
conversion of N2 to NH3/ NH4+. A small group of bacteria and cyanobacteria are capable using the enzyme
nitrogenase to break the bonds among the molecular nitrogen and combine it with hydrogen.

Nitrogenase only functions in the absence of oxygen. The exclusion of oxygen is accomplished by
many means. Some bacteria live beneath layers of oxygen-excluding slime on the roots of certain plants.
The most important soil dwelling bacteria, Rhizobium, live in oxygen-free zones in nodules on the roots of
legumes and some other woody plants. Aquatic filamentous cyanobacteria utilize oxygen-excluding cells
called heterocysts.

2. Nitrification (NH3 to NO3-)

Nitrification is a two-step process in which NH 3/ NH4+ is converted to NO3-. First, the soil bacteria
Nitrosomonas and Nitrococcus convert NH3 to NO2-, and then another soil bacterium, Nitrobacter, oxidizes
NO2- to NO3-. These bacteria gain energy through these conversions, both of which require oxygen to occur.

3. Assimilation (Incorporation of NH3 and NO3- into biological tissues)

Assimilation is the process by which plants and animals incorporate the NO 3- and ammonia formed
through nitrogen fixation and nitrification. Plants take up these forms of nitrogen through their roots, and
incorporate them into plant proteins and nucleic acids. Animals are then able to utilize nitrogen from the
plant tissues.

4. Ammonification (organic nitrogen compounds to NH3)

Assimilation produces large quantities of organic nitrogen, including proteins, amino acids, and
nucleic acids. Ammonification is the conversion of organic nitrogen into ammonia. The ammonia produced
by this process is excreted into the environment and is then available for either nitrification or assimilation.
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5. Denitrification(NO3- to N2)

Denitrification is the reduction of NO3- to gaseous N2 by anaerobic bacteria. This process only
occurs where there is little to no oxygen, such as deep in the soil near the water table. Hence, areas such as
wetlands provide a valuable place for reducing excess nitrogen levels via denitrification processes.

Phosphorus Cycling in Soils

One of the main roles of P in plants is the storage and transfer of energy. The high-energy
phosphate bonds in molecules such as adenosine triphosphate (ATP) and adenosine diphosphate (ADP)
drive virtually every biochemical reaction in plants. Phosphorus is also part of important structural
components of plants, such as nucleic acids, phospholipids and coenzymes.

Phosphorus exists in different pools and pathways by which P may be taken up by plants or lost
from the soil. Phosphorus in soil exists in combination with other elements such as O and H. Plant roots
absorb P mainly as orthophosphate (H2PO4- or HPO42-). The primary orthophosphate form (H 2PO4-)
dominates in soils below pH 7.2, and the secondary form (HPO 42-) is prevalent in soils above pH 7.2. Plants
are able to absorb the primary form more rapidly than the secondary form.

In soils, P occurs in three pools: soil solution, mineral and organic. Plants can only use P from the
soil solution pool. The mineral and organic pools have stable components that change little with time (e.g.,
humus) and labile portions that gradually release P to the soil solution.

Phosphorus does not always “flow” toward the soil solution pool from the labile pool. It can move
from the soil solution to the labile pools or even directly into stable soil components. Similarly, labile P can
be tied up in nonlabile organic and mineral compounds.

Potassium Cycling in Soils

Unlike most essential nutrients, K is not an integral part of any plant structural component.
However, it does play a role in many processes vital to plant growth. Among the functions of K in plants
are enzyme activation, transport of sugars, plant water balance and regulation of stomata. Potassium
“activates” many different enzymes involved in plant growth. For example, photosynthesis as well as starch
and protein synthesis are key pathways that rely on K-influenced enzyme systems. The transport of sugars
produced during photosynthesis also depends on K. Inadequate K can result in a build-up of photosynthetic
products in the leaves, which can adversely affect the rate of photosynthesis and plant growth.

Potassium, along with sugars and other inorganic ions, influences the water balance within plants
and helps to maintain an inward concentration gradient between roots and the soil solution. Potassium also
influences the transpiration rate by controlling the size of the stomata openings in response to
environmental and internal plant conditions.

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Potassium, much like phosphorus, exists in pools with differing abilities to replenish crop available
K. In soil, K occurs in four pools: soil solution, exchangeable, fixed and parent minerals. The soil solution
and exchangeable pools of K are in equilibrium with each other. Plants absorb K exclusively as the K + ion,
which is the only form that exists in soil solution. Exchangeable K refers to ions adsorbed to exchange sites
on soil particles. It accounts for 1 to 2% of soil K. When K is removed from soil solution by plant uptake it
is replenished by K released from the exchangeable pool. Likewise, if the concentration of K in soil
solution exceeds that in the exchangeable pool, K will adsorb to the exchange sites. This equilibrium
ensures a steady pool of available K.

Potassium fixation is the entrapment of the K + ion in the structure of clay minerals. Fixation
accounts for 1 to 2% of soil K. The fixed pool is not able to release K at rates sufficient to meet the
demands of growing crops. However, a portion of this pool will become available as the exchangeable and
soil solution K supplies are depleted.

Sulfur Cycling in Soils

Sulfur is essential for the conversion of NO 3- to NH4+ in plants, and the synthesis of plant proteins.
Sulfur is an integral part of plant processes, including N fixation in legumes, synthesis and functioning of
chlorophyll, and oil formation in canola. Sufur requirements of crops remain high from germination
through to grain filling because it is required to support vegetative growth and grain formation.

Only 1 to 3% of the soil total S is in the plant available form (SO 42-). The bulk of soil S (200 to
1100
kg/ha) is in soil organic matter. Mineralization of organic S compounds is an important source of S for
growing
plants. The weathering of S-containing minerals such as gypsum (CaSO 4) can be a source of crop available
S particularly in dry regions where the amount of precipitation is too low to leach it from the soil profile.
Other primary and secondary minerals will release elemental S (S 0/S2-), which is converted to SO4 2- when
exposed to moisture, oxygen and microbial processes.

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Calcium and Magnesium Cycling in Soils

Calcium is a vital structural component of cell walls and influences membrane permeability. It also
plays a role in N metabolism as it enhances plant uptake of NO 3-. Other important functions of Ca include
the movement of carbohydrates and other nutrients within the plant and cell elongation and division.

Magnesium is a critical component of chlorophyll, and therefore essential for photosynthesis in the
plant. It acts as a catalyst and co-factor for many important enzyme systems within plants and also appears
to play a role in the production of oils and fats.

Plants absorb Ca and Mg as positively charged ions from the soil solution and they are replenished
from the exchangeable pool. Weathering of Ca and Mg minerals with time results in crop available Ca and
Mg entering the exchangeable pool. Generally, there is less Mg in the soil solution than Ca. Even though
plants require Mg in smaller amounts it is more likely to be deficient than Ca. This is partly because Mg
binding to cation exchange sites is weaker than competing cations such as K +, Ca2+, and NH4+.
Consequently, plants growing on soils with excesses of any of these cations are more likely to show
symptoms of Mg deficiency. Erosion is the main route of Mg and Ca loss from the soil.

Micronutrients

Although micronutrients (Cl, Fe, Mn, Zn, B, Cu, and Mo) are required in “micro” quantities, they
are significant in terms of their contribution to plant growth. Soil characteristics can influence
micronutrient availability. Clay soils are less likely to be deficient in micronutrients than sandy soils. Soils
with low (i.e., less than 1 to 2%) or very high organic matter content (i.e., greater than 30%) often have low
levels of micronutrient availability. As soil pH increases, availability of micronutrients tends to decrease.
The exception is molybdenum whose availability increases with soil pH.

Inorganic micronutrients occur naturally in mineral soils. As parent minerals break down during
soil formation, micronutrients slowly become available to plants. Organic matter is also an important
source of micronutrients. Microbial decomposition helps to release micronutrients into plant-available
forms.

Micronutrient Characteristics

Form Taken up by
Micronutrient Function in Plants
Plant
Associated with the suppression of leaf and root
Chlorine (Cl) Cl- ion
diseases.
A vital constituent of chlorophyll. Important for oxygen
Iron (Fe) Fe2+ / Fe3+ transfer within the plant system. Important for the
formation/activity of respiratory enzymes.
Mn2+ and as a
Seems to play a role in the uptake of the other nutrients
Manganese (Mn) component of organic
and the activation of a number of enzyme systems.
complexes
Plays a role in the formation of growth promoting
Zn2+ and as a
compounds, carbohydrate transformations, regulation of
Zinc (Zn) component of organic
sugar consumption, and is a constituent of several
complexes
enzyme systems.
Boron (B) Primarily boric acid Maintains plant cell wall integrity.

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(H3BO3)
Cu2+ and as a Essential for production of iron-containing compounds.
Copper (Cu) component of organic Facilitates synthesis of chlorophyll. Influences several
complexes metabolic reactions.
Enhance plant uptake of N, K, Ca required by legumes
Molybdenum (Mo) MoO42- for fixation of atmospheric nitrogen by nodular
bacteria.

WASTES AND POLLUTANTS IN SOILS

Soils are subject to both purposeful and accidental addition of numerous chemical by humans,
which can persist in soils for many decades.

Purposeful application includes:

 fertilizers (some “natural” fertilizers include elevated levels of heavy metals and organic
contaminants)
 pesticides (some are applied directly to the soil to control various pests; others reach the soil by
washing off leaves in rainstorms)

Accidental application includes:

Source from above (i.e., the atmosphere)

 enhanced mineral acid constituents of rain (H2SO4, HNO3)
 acid oxide gases (SO3, NO2)
 radioactive fallout (e.g., 134Cs, 137Cs, 89Sr, 90Sr, 131I,14C, etc.)
 volatile organic carbon compounds (benzene, toluene)
 particulate deposition (PAHs, F, volatile metals)

Sources from below (i.e., buried sources, groundwater)

 migration of landfill leachates (heavy metals, halocarbons, other organic contaminants)
 migration of spilled chemicals or leaking stored chemicals (petroleum, halocarbons, pesticides)
 Sewage spills or pipe leaks

Some materials may eventually washout of soils with through flowing groundwater or degas to the
atmosphere. Others (especially non-soluble, non-volatile compounds) will not. Instead these tend to build
up, unless they are subsequently biodegraded (in the case of organic contaminants)

There are 3 main chemical factors that control the fate and residence time of all pollutant materials
in soils.

1. Adsorption/interaction with solids

 affects mostly inorganic ions and small organic ions that can bind to exchangeable sites on
soil particles
 larger molecular weight organic molecules (particularly quaternary ammonium salts) that
binds to soil humus

2. Volatilization

 affects mostly low molecular weight hydrocarbons

 halocarbons
 aromatic hydrocarbons.

3. Decomposition/Reaction/Decay

 microbial decay of organic molecules

 abiotic chemical degradation of organic molecules
 photochemical degradation of organic molecules
 radioactive decay
 heavy metal bio-accumulation (removal of plant litter before re-mineralization prevents re-
addition of metals to the soil)

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 CHEMISTRY OF SOIL 174

 Redox/solubility change

Phytoremediation: Using Plants to Clean Up Soils

There are multiple applications that use plants to clean up or remediate soils contaminated with
heavy metals, organic contaminants and radioisotopes.

 Phytovolatilization: water and organic contaminants are taken up through plant roots, transported
to the leaves, and released into the atmosphere.

 Microorganism stimulation: Plants excrete enzymes and organic substances from their roots that
stimulate growth of microorganisms such as fungi and bacteria, which in turn metabolize the
organic contaminants.

 Phytostabilization: Plants prevent contaminants from migrating by reducing runoff, surface

erosion, and ground-water flow rates.

 Phytoaccumulation/extraction: Plant roots can remove metals from contaminated sites and
transport them to leaves and stems for harvesting and disposal or metal recovery through smelting
processes.

 Phytodegradation : Organic contaminants are absorbed inside the plant and metabolized (broken
down) to non-toxic molecules by natural chemical processes within the plant.

NAME: ________________________________________________ SCORE: ______________

YR & SEC: _______________ GROUP NO. _______ DATE: _______________

ACTIVITY NO. ____

CHEMISTRY OF SOIL

In the space provided, write the letter of the term or phrase that best matches the description.

A. soil colloids F. primary minerals K. fertilizer

B. nutrients G. buffering capacity L. secondary minerals
C. macronutrients H. soil M. micronutrients
D. alkaline I. lime N. organic matter
E. pH J. acid O. cation exchange capacity

1. material with a pH of less than 6.9

2. material with a pH of more than 7.1
3. the ability of the soil to withstand pH fluctuation
4. the ability of a soil to hold and exchange plant nutrient cations
5. material that supplies nutrients for plants
6. material that reduces the acid content of soil
7. elements used in relatively large quantities
8. elements used in very small quantities
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 CHEMISTRY OF SOIL 175

9. substances necessary for the functioning of an organism

10. dead plant and animal tissue that originates from living sources
11. measurement of alkalinity from 1 to 14
12. top layer of the earth’s surface suitable for plant life
13. refer to the finest clay and SOM particles in a soil.
14. soil materials that are similar to the parent material from which they formed
15. result from the weathering of the primary minerals

Illustrate and describe the steps that are involved in nitrogen cycle.

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