How soils supply plant

nutrients
An Introduction to Soil Chemistry

Prepared by:
Richard Stehouwer
Department of Agronomy
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 Our questions
1. What is in soil?
2. Where do soil nutrients come from?
3. How do plants get their nutrients?
4. Is there a difference in the
adsorption process for different
nutrients?
5. What about salinity?
What makes up the soil?
 Soil Components
The 4 parts of soil

Soil
Air
About ½ of the Mineral 25% About ½ of the
Matter
soil volume is 45% soil volume is
solid particles Soil
Water pore space
25%

Organic
Matter
5%
 Lets go back to 9 th grade…
• Important cell processes:
– Protein synthesis
– Photosynthesis
– Cell respiration
• What are the materials needed for these?
– Phosphate (ATP)
– Carbon
– Oxygen
– Nitrogen
– Carbon dioxide
 A. Supplying Plant Nutrients
Nutrients that plants obtain from the soil

Macronutrients: Micronutrients:
(needed in large amounts) (needed in small amounts)
• Nitrogen (N) • Chlorine (Cl)
• Phosphorus (P) • Cobalt (Co)
• Potassium (K) • Copper (Cu)
• Calcium (Ca) • Iron (Fe)
• Magnesium (Mg) • Manganese (Mn)
• Sulfur (S) • Molybdenum (Mo)
• Nickel (Ni)
• Zinc (Zn)
 2. Where do plant nutrients
come from?
A. Decaying plant litter

B. Breakdown of soil minerals

C. Addition by humans
– Commercial fertilizer
– Manure
– Lime
– Other
A. Recycling plant
nutrients
B. Breakdown of soil minerals

Water
Acid
Zn

Ca
K
Ni
Mg Cu
C. Nutrient additions by
humans

• Commercial fertilizers
– Nutrients are in a form that is available to plants
– Dissolve quickly and nutrients go into soil water
• Lime
– Dissolves slowly as it neutralizes soil acidity
– Releases calcium and magnesium
• Organic nutrient sources
– Manure, compost, sewage sludge
– Decay and nutrient release is similar to crop litter
How do plants get their
nutrients?
 A. The soil solution

• Soil water is a complex

solution that contains
– Many types of nutrients
– Other trace elements
– Complex organic molecules
• Nutrients in the soil
solution can be readily
taken up by plant roots N P K

• If nutrients remained in
solution they could all be Zn Ni Ca Mg Cu
quickly lost from the soil.
Another word for this loss of
nutrients is LEACHING.
 B. Adsorption
• Adsorption refers to the ability
of an object to attract and hold
particles on its surface.

+ - • Solid particles in soil have the

ability to adsorb
– Water (WHC)
– Nutrients and other chemicals

• The most important adsorbers in

soil are
– Clays
– Organic matter
Is there a difference in the
adsorption process?
A. Cation Exchange Capacity
• Cation exchange capacity
(CEC) is the total amount of
cations that a soil can retain

• The higher the soil CEC the

greater ability it has to
store plant nutrients

• Soil CEC increases as

1. The amount of clay increases
2. The amount of organic
matter increases
3. The soil pH increases
 1. Clay
a. Surface Area
¼ cup of clay has more surface area
¼ cup
than a football field

The large surface area of

clay allows it to
• Adsorb a lot of water
• Retain nutrients
• Stick to other soil particles
b. Clay has a negative
charge.
Clay particles are stacked
in layers like sheets of
paper.
Each clay sheet is slightly
separated from those on
either side.
Each sheet has negative
charges on it.
Negative charges have to
be balanced by positive
1/20,000 in charges called cations.
Cation Retention on
Soil Clays
Calcium, +2

Magnesium, +2

Potassium, +1

Ammonium, +1

Sodium, +1

Copper, +2
Aluminum, +3

Hydrogen, +1
 2/3. Organic Matter and
pH
Hydrogen
Nutrients

Increasing pH
increases cation
exchange capacity
of organic matter

Low pH, 4 - 5 Neutral pH, 7

(acidic soil) (“sweet” soil)
 B. Negatively Charged
Nutrients
(Anions)
• Some very important plant nutrients are anions.

Nitrate Phosphate Sulfate Chloride

• Soils are able to retain some of these nutrient

anions.
• Retention of nutrient anions varies from one anion
to another
 Phosphate retention in soil
3. Adsorption on oxide surfaces

Phosphate anions -
Each held by two
chemical bonds to the
iron oxide surface

Iron oxide surface

 Nitrate (NO3-)
retention in soils
Unlike phosphate, nitrate
is very weakly held by soils
• Nitrate does not react to NO3-
form new solids
• Nitrate is not held by oxide
surfaces

If nitrate is not taken

up by plants it is very
likely to be lost from
the soil
H. Moving nutrients from soil to plants
Nutrients in
soil solution

Plant
Root

Nutrients on soil clay

and organic matter
 Excessive Nutrient Loading
Nutrients in
soil solution

Plant
Root

Nutrients on soil clay

Nutrient loss in
and organic matter
drainage water
 What about salinity?
• Sometimes there is a build up of salt in the soil. (This
is caused by our irrigation practices… DON’T worry
we will look at it more next week)

• When this happens osmosis occurs and draws the

water out of the roots. This causes the plant to die.

• Only specially adapted plants can survive such

environments.
 The black box is open
• Soil consists of mineral and organic matter,
air and water
• Soils are able to adsorb nutrients and other
chemicals
• The most important adsorbers are clay and
organic matter
• Adsorbed nutrients are available
to plants
• Adsorbed nutrients are not prone
to loss in drainage water
• Soil adsorption capacity can be
exceeded leading to greater
nutrient loss
The Earth’s crust

Ca
Al Fe

Si K
Mg
Na

Others

Soil Analysis Ch5 30

O
 oxygen is negatively charged
 the other major elements are positively charged
 oxygen bonds with one or more of the cations, producing a
chemistry of oxides
 silicon oxides (silicates)
 aluminium oxides (aluminates)
 generally in combination as aluminosilicates
 these dominate the minerals
 low levels of other elements account for the differences in
minerals

Soil Analysis Ch5 31

 Si binds to four oxygens in a tetrahedron
 Al has six oxygens (often as OH) in an octahedron
 not a matter of individual SiO4 or Al(OH)6 units
 some Os are shared between the silicate or aluminate units
 most common structure in clay minerals is the formation of
sheets
 “flat” layers of silicate tetrahedra or aluminate octahedra
 these sheets stack on top of each other
 held together by hydrogen bonding or electrostatic attraction

Soil Analysis Ch5 32

Common sheet arrangement in clay minerals
(tetrahedrons in grey)

1:1 2:1 2:2

Soil Analysis Ch5 33

 real clay crystals are not pure silicates or aluminates
 some Si or Al atoms are substituted during the crystallisation
process
 creates spare charges which give the overall crystal a charge
 balanced by loose cations or anions

O has only 1 bond,

O O so has -ve charge;
Si replaced requires balancing
O Si O O Al O- positive charge from
by Al in crystal free cation
O O X+

Soil Analysis Ch5 34

 these cations generally are held on the surface of the clay
 are not strongly held
 can be exchanged for other cations in an equilibrium process
 measured as the cation exchange capacity (CEC)
 soil pH has no effect on the exchange capacity from the clay
minerals

Soil Analysis Ch5 35

 as minerals weather, they lose silicon
 this leads to increasing proportions of aluminate in
weathered clays
 Al-OH species are amphiprotic
 soils dominated by oxides of aluminium (and other
metals) can have positive sites in acidic soils
 this allows anion exchange

Al-OH + H+ <=> Al-OH2+ + X-

Soil Analysis Ch5 36

5.3 Ion exchange in soils

 when the loosely held cations or anions on the mineral

surfaces are replaced by ions of the same charge (sign and
magnitude) in solution
 cation exchange is by far the most common
 necessary for soil fertility
 as soils weather, they lose cation exchange capacity and lose
fertility

Soil Analysis Ch5 37

Cation Exchange
 clay minerals have negative charge due to substitution of aluminium
or silicon in the crystal lattice
 humus also contributes negative charge, due to the presence of
dissociated organic acids
 humus-COOH  humus-COO- + H+

Exercise 5.2
 What effect would soil pH have on the amount of cation sites
from humus?

 low pH, less dissociated acid, less sites

Soil Analysis Ch5 38

 a cation in solution replaces an adsorbed cation on the soil
particle
 eg soil-Na + K+ (aq)  soil-K + Na+ (aq)

 charges that are balanced, not number of charged species.

Class Exercise 5.3

 Write an equation for the exchange of adsorbed sodium with
solution calcium.

 soil-Na + soil-Na + Ca2+ (aq)  soil=Ca + 2Na+ (aq)

Soil Analysis Ch5 39

 exchange is equilibrium
 reversible and dependent on the levels of each of the species,
particularly the solution species
 eg if a soil solution becomes depleted in calcium, then
some calcium will desorb from an exchange site into
solution
 known as buffering
 in all but the most leached and infertile of soils, there will be a
balance between adsorbed and dissolved ions

Soil Analysis Ch5 40

Exercise 5.4
 What do you think would happen to a soil which is treated
with lime (calcium hydroxide), in addition to a pH change?

 high concentration of Ca in solution

 this would be partly reduced by exchange with the soil cations

Soil Analysis Ch5 41

Cation exchange capacity (CEC)

 the moles of exchangeable positive charge per unit mass 100

g of dry soil

 usually mmole/100g or cmole/kg (the same value)

 Ca & Mg contribute twice as much to the CEC as an equivalent

number of sodium and potassium ions because of their 2+
charges

Soil Analysis Ch5 42

Soil CEC Class Exercise 5.5
 Comment on the trend in CEC

Sand 2-4 in Table 5.1.

Sandy loam 2-12  CEC increases with higher clay

levels

Loam 7-16

Silt loam 9-26

Clay, clay loam 4-60

Soil Analysis Ch5 43

Significance of CEC
 uptake of nutrient ions from plant roots occurs from solution
only
 as cations are absorbed into the roots, they are replaced in the
soil solution by H+ ions
 when the exchange equilibrium is disturbed, some of that ion
will desorb from the soil particles
 replaced by another ion
 if the nutrient is a weakly adsorbed one, such as K, there may
not be enough adsorbed to replenish the soil, presenting a
fertility problem
 K is the most likely cation to be in short supply

Soil Analysis Ch5 44

Anion exchange
 the important soil anions, nitrate and phosphate, behave very
different at exchange sites
 nitrate and chloride are only weakly held at positive sites
 more likely to be found in soil solution
 phosphate and sulfate are very strongly bound to the exchange
sites
 phosphate can become covalently and irreversibly bound

Soil Analysis Ch5 45

Soil pH
 one of its most important properties
 it affects so many other soil properties, (eg ion exchange and
nutrient availability)
 soil pH comes about from a balance between acidic and
alkaline species
 reflects mainly the levels of dissolved H+ and OH-, but also
the adsorbed H+ on cation exchange sites
 normally ranges from 4-9

Soil Analysis Ch5 46

Sources of soil acidity
 rain - polluted or fresh will be slightly acidic due to dissolved
gases

 microbial and root respiration – this produces CO2, which is

slightly acidic in solution

 oxidation of organic matter – this produces organic acids

known as humic acids, together with nitric and sulfuric acids

Soil Analysis Ch5 47

Sources of soil alkalinity

 carbonate minerals – calcium and magnesium carbonate are

common materials in minerals
 they are slightly soluble in water, and produce OH- as they
dissolve
 these cations and Na & K are known as bases because of their
association with alkaline soils

 mineral weathering – many primary minerals as they

weather release hydroxide salts of the basic cations

Soil Analysis Ch5 48

Trends in soil pH
 as soils age by weathering and leaching, they tend to become
more acidic
 primary minerals that release alkaline materials are replaced
by neutral or slightly acidic secondary minerals
 leaching removes the carbonate minerals
 weathering occurs from the surface downwards so that the A
and B horizons will tend to be more acidic than the C horizon

Soil Analysis Ch5 49

Significance of soil pH
 nutrient availability – the ability of plants to take up
nutrients is very much dependent on the soil pH

Soil Analysis Ch5 50

Significance of soil pH
 effect on soil organisms – soil organisms prefer different pH
levels
 acid-sulfate soils - soils that are rich in inorganic sulfide
minerals, such as pyrites,
 can lead to the formation of excessive levels of sulfuric acid
through oxidation
 soil pH dives to very low levels
 causes solubilisation of toxic levels of aluminium,
manganese and iron from soil minerals
 plant preferences – most alkaline soils; a few which need
acidic soils

Soil Analysis Ch5 51

Soil pH management
 soils tend towards lower pH values as they age
 the main need for pH management is to making the soil more
alkaline
 most common method by liming
 agricultural lime is a mixture dominated by CaCO3, but also
containing MgCO3 and Ca(OH)2
 comes from ground limestone,
 add the nutrients calcium and magnesium to the soil
 dolomite lime has a higher proportion of magnesium
carbonate
 to reduce pH , add Fe, S or peat

Soil Analysis Ch5 52

Exercise 5.9
 What factors will affect the amount of liming required?

 buffering capacity
 pH

Soil Analysis Ch5 53

Redox potential (Eh)
 a measure of its ability to produce oxidation or reduction of
chemical species in it
 the most important soil property indicated by the soil Eh is
whether it is aerobic or anaerobic
 aerobic soils give a positive value
 the lower the value the more anaerobic the conditions
 a value that is affected by soil pH

Soil Analysis Ch5 54