Principles of Soil Science Module 3 Soil Chemistry

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SOIL CHEMISTRY

Ms. Rochelle Joie A. Saracanlao


Topics Covered
 Chemical nature of soil constituents
 Chemical properties of soils
 Problem soils
 Chemistry of flooded soils
Chemical Nature of
Soil Constituents
Chemical Nature of Soil Constituents
Three phases:
a. Solid
- Skeletal framework of soils
- Mixture of inorganic and organic materials
b. Liquid
- Soil solution, carries and moves dissolved nutrients
c. Gas
Chemical Nature of Soil Constituents
Three phases:
a. Solid
- Skeletal framework of soils
- Mixture of inorganic and organic materials
b. Liquid
- Soil solution, carries and moves dissolved nutrients
c. Gas
Chemical Nature of Soil Constituents
Percentage Composition by Volume

SOIL AIR ATMOSPHERIC


AIR
OXYGEN 20.0 21.0

NITROGEN 78.6 78.03

CARBON 0.50 0.03


DIOXIDE
Chemical Nature of Soil Constituents
• Typical soil that is ideal for plant growth is
composed of:
• 45% inorganic matter
• 5% organic matter
• 25% water
• 25% air
Soil Colloids
 seat of chemical activity or reaction in soils
 very small particles whose sizes range from 0.3 to 1
μm

 Types of soil colloids


 Organic colloids (Humus)
 Inorganic colloids
Soil Colloids
 possess a high surface area; hence they have high
water-holding capacity
 Have the property of sorbing both cations and anions
through exchange reactions
 Nutrients released through weathering or organic
matter decomposition are adsorbed on clay minerals
 Prevents starvation of the plants during critical
periods of their life cycle
Inorganic Colloids
a. Silicate clays (layer silicates)
- Kaolinite, Montmorillonite
- Vermiculite, Illite
b. Oxide clays (Non-silicate clays)
- Fe oxide and Hydrous oxide – Hematite, Goethite
- All oxide and hydrous oxide – Gibbsite, Boehmite
Inorganic Colloids
c. Amorphous Clays
- Allophane
- Imogolite
Silicate Clays (Layer Silicates)
• Basic structural units:
- Silica tetrahedron
- Alumina octahedron

• Classification of silicate clays (based on number of


tetrahedral to octahedral sheets)
a. 1:1 fixed type (kaolinite)
b. 2:1 expanding type (montmorillonite)
1:1 fixed lattice type
• Water cant get in between crystal
units due to the fixed distance and
the strong O-H linkage.

• Only external surfaces are good for


Crystal unit adsorption of water and cations.
External
surfaces
Classification of Silicate Clays
a. 1:1 type- Kaolinite
• two sheets are held together by oxygen atoms that are
mutually shared by Si and Al
• Unit layers are held together tightly by H-bonding
 no expansion or very little expansion
 Limits the reactive area to external surface
Classification of Silicate Clays
a. 1:1 type- Kaolinite
• Kaolinite
 Little isomorphous substitution
 Low colloidal property
 CEC: 3-15cmol cc/kg
 soils high in kaolinite do not swell or shrink on
wetting and drying
Classification of Silicate Clays

• Soils dominated by Kaolinite are


• good bases for roadbeds and building foundations
• commonly used in making bricks
• easy to cultivate for agriculture
2:1 expanding type (montmorillonite)
• There is variable distance because
the linkage is loose. Water can enter
pushing apart the crystal units. when
the crystal are pushed, they expand.
External Crystal unit
surface

Internal • Internal surfaces as well as external


surface surfaces are good adsorption sites.
Thus it can held more water and
cations on it surface.
Classification of Silicate Clays
b. 2:1 expanding type (Montmorillonite)
- structural units are loosely held together by weak oxygen-oxygen
linkages; expands very easily

- cations and water molecules are able to move in-between crystal


units

- large external and internal surfaces; hence, CEC is high (80-100


me/100g)
Classification of Silicate Clays
b. 2:1 expanding type (Montmorillonite)
-high shrink- well capacity
- tendency for crack formation
- general instability of the soil surface
-Soils dominated by montmorillonite are very sticky when
wet and tend to form hard clods upon drying.
Classification of Silicate Clays
b. 2:1 expanding type (Montmorillonite)

 Soils dominated by smectites are:


- Very difficult to cultivate because they form aggregates or
clods that are very hard
- poor bases for road beds and building foundations
Classification of Silicate Clays
b. Hydrated mica (2:1 non-expanding lattice type)
- includes illites and vermiculites
-illites resemble montmorillonites however 15% OF Si in the silica
sheets has been substituted by Al (imbalanced valence)
- Vacant valences are substituted by K. The K atoms lie between the
structural units and exert a stabilizing effect on the crystal lattice;
hence, illites are less expansive than montmorillonite.
- Illites have less cation adsorption, swelling, shrinkage and
plasticity than montmorillonite; CEC= 15-40 me/100g
Classification of Silicate Clays
b. 2:1 non-expanding type (Vermiculite)
• Water molecules along with other ions act as bridges
holding the unit layers together rather than apart
• Specific surface: 500-700 mg2/g
• Exhibit a high CEC: 110-160 cmol/kg
Classification under Amorphous Clay
a. Allophane
• Noncrystalline (amorphous)
• abundant in soils derived from volcanic ash deposits
• have high phosphate fixation capacity
• Most soils containing allophane have black A
horizons (extremely high in OM)
• CEC= 70-150 me/100g; CEC is pH dependent
Oxides of Fe and Al
• Most common naturally occurring oxides of iron

• Limonite : Fe2O3 • xH2O (yellowish)

• Goethite : Fe2O3 • H2O

• Hematite: Fe2O3 (red)

• Magnetite: Fe2O3 • FeO

• With an increase in the degree of hydration of the iron oxide, its color decreases
in intensity from dark red hematite to pale yellow limonite.
Oxides of Fe and Al
• Most common naturally occurring oxides of aluminum

• Gibbsite : Al2O3 • xH2O

• beohmite : Al2O3 • H2O

• Alumina: Al2O3

• Variscite: Al(OH)2H2PO4
Soil Organic Matter (SOM)
• Sum total of all carbon-containing substances in the soil
• consists of living organisms, dead plant and animal
residues and other organic materials in various phases of
decomposition
• amount of SOM:
o <1% in desert soils close to 100% in inorganic soils
o 1-5% in top 15cm of typical agricultural soils
Soil Organic Matter (SOM)
• Humus
o A dark, complex mixture of organic substances
modified from original organic tissue
o Not biologically active and is the pool responsible
for many of the soil chemical and physical
properties associated with SOM and soil quality
Soil Organic Matter (SOM)
• high CEC= 200-300 me/100g
• Amorphous
• Good buffering capacity
• These are due to: phenolic compounds and carboxyls
• OM and clay interacts to form resistant complexes; OM is
protected from microbial attack; accounts for the
persistence of OM in the soil
Important Characteristics of Soil Colloids
Related to Chemical Reactivity

1. Fineness and large specific surface area


2. Presence of electric charges
a. Sources of negative charge
b. Sources of positive charge
Presence of Electric Charges
a. Sources of negative charge:
i. Isomorphous substitution
- Substitution of one ion for another of similar size within a
crystal lattice
• the resulting negative charge is considered a permanent
charge
• major source of negative charges in 2:1 layer of silicate
Presence of Electric Charges
a. Sources of negative charge:
ii. Ionization of exposed –OH groups
• At high pH, the H of the exposed OH, dissociates
and the surface of the clay is left with the negative
charge of the oxygen ions
• this type of negative charge is called variable or pH
dependent charge
Presence of Electric Charges
a. Sources of negative charge:
iii. Functional groups of organic colloids carboxyl
groups, phenolic-OH, alcoholic-OH
NOTE!

CHARGE OF SOILS IS
NEGATIVE!!!
Presence of Electric Charges
a. Sources of positive charge:
i. Protonation of exposed hydroxyl groups
• The exposed OH can also adsorb or gain protons
particularly in strong acidic media and create
positive charge
• Negatively charged colloids attract cations which
become adsorbed on the surface
Presence of Electric Charges
a. Sources of positive charge:
i. Protonation of exposed hydroxyl groups
• Humid regions: (H+, Al3+) > Ca2+ > Mg2+ > K+ > Na+
• Arid regions: Ca2+ , Mg2+ > Na+ , K+ > H+
• General order of adsorbability or replacing power of
cations found in soils:
 (H+, Al3+) > Ca2+ > Mg2+ > K+ = NH + > Na+
4
Factors Affecting Strength of Adsorption
• Charge valence
- The higher the valence, the stronger the adsorption
• Hydrated size
- The smaller the hydrated size, the stronger the adsorption
• Concentration of soil solution
- The higher the concentration, the stronger the adsorption
Cation Exchange Capacity
• Cation Exchange
- The process whereby cations adsorbed on the colloid are exchanged
for those in the soil solution

• Cation Exchange Capacity (CEC)


- Sum of exchangeable cations that a soil can adsorb
- expressed in me/100 g soil or in cmol/kg soil
- significance: indicator of soil fertility, it reflects the capacity of the
soil to retain nutrients
- Increases with increasing amount of clay and organic matter
Characterisitics of Cation Exchange Reactions
1. Stoichiometric

Ex. 1cmol Ca2+ ≈ 1 cmol Mg2+

1 cmol Mg2+ ≈ 2 cmol Na+⇆

2. Rapid – reactions occur almost instantaneously

3. reversible
Ca Ca
clay + 4 KCl clay K + CaCl2 + 2 KCl
Ca ⇆
K
Characterisitics of Cation Exchange Reactions
4. Dependence on the concentration and relative adsorbability of replacing cation

• As concentration increases, greater replacement occurs due to mass action

• For ions of similar size, those with higher valence are adsorbed better:

• Th4+> La3+ > Ca2+ > NH4+

• For ions commonly found in the soils:

• (Al3+, H+) > Ca2+ > Mg2+ > K+ > Na+

• H+ has same adsorbing capacity as Al because of its small size.


Base Saturation
• proportion of the CEC occupied by basic cations
such as Ca2+, Mg2+, K+ and Na+
• Percentage base saturation is an important soil
property because it is inversely related to soil acidity
 Generally as percentage base saturation increases,
soil pH increases
Exchangeable Sodium Percentage (ESP)
• Proportion of the exchange sites occupied by
sodium
• Soils with high ESP (>15%) are considered sodic
and need to be reclaimed

ESP = (exchangeable Na/ CEC) x 100


Soil pH or Soil Reaction
• pH is the acidity or alkalinity due to relative
concentration of H+ and OH- ions
• [H +] is expressed in moles/L or M
Other significant calculations
• [H3O+] = antilog (-pH)

• [OH-]= antilog (-pOH) [H+], pH, acidity


• pOH= -log [OH-]

• pH + pOH = 14

• [H3O+]> [OH-] / pH < 7.0 = soil is acidic

• [H3O+]< [OH-] / pH > 7.0 = soil is basic

• [H3O+]=[OH-] / pH = 7.0 = soil is neutral


Soil pH
• Determination of Soil pH
1. Electrometric method
- pH meter, more accurate
2. Colorimetric method
- organic dyes, litmus paper
Soil pH
• Effects of Soil pH:
 Microbial activity
- Fungi: unaffected
- Bacteria and Actinomycetes: inihibited at pH 5
 Availability of nutrients
- N- decrease at pH <5.5
- Ca and Mg decrease at pH<6.0
- P- decrease at pH <6.0 and >7.0
Soil pH
• Effects of Soil pH:
Availability of nutrients
- K- decrease at pH <6.0
- S- decrease at pH <5.5
- Mo- decrease at pH <6.5
- B- decrease at pH <5.0 and >7.0
- Fe, Mn, Zn, Cu, Co decrease at pH <5.0
 At pH 5.0, concentration are usually toxic
 ideal or optimum pH appears to be pH 6.5
Problems in Soils
(Soil Acidity)
Acid Soils
• Sources of Soil Acidity
- H+ and Al3+ ions: contributes indirectly to acidity
through hydrolysis
- Carbonic acids from OM decomposition
- Mineral weathering
- Acid rain
Acid Soils
• Sources of Soil Acidity
- Heavy cropping which removes basic cation and replaced
H+ from roots
- Long term use of acidifying fertilizers
- Nitrification converts NH4+ to NO3- and release
hydrogen ions to the soil
Sources of Soil Acidity
• Adsorbed H and Al are mainly responsible for soil acidity

• Adsorbed H+ contributes directly to the H+ concentration in the soil solution

Al3+ + 3 H2O Al(OH)3 + 3H+

• In neutral or alkaline soils the permanent charge sites are dominated by basic
cations such as calcium and magnesium instead of H or Al.
Source of Hydroxyl Ions (OH-)
• If basic cations saturate the exchange complex, H+
concentration in the soil solution will decrease
and the OH- concentration will increase.

• Increase in OH- is due to the hydrolysis of colloids


.
Acid Soils
• Forms of Soil Acidity
 Active acidity
- due to H+ in soil solution; determined as pH
 Reserve acidity
- due to H+ and Al3+ in the solid phase
- measure of the buffering capacity of the soil
Acid Soils
• Buffering Capacity
- the ability of the soil to resist sudden or drastic
changes in pH
- buffering capacity is high if:
- CEC is high
- Clay content is high
- OM content is high
Acid Soils
• Management Strategies:
 Reduce acidification
- minimize the use of acidifying fertilizers
- reduce leaching of nitrogen by use of split
applications of fertilizer
- return plant material to soil
Acid Soils
• Management Strategies:
 Use acid tolerant crops
- growing acid tolerant crop will enable continuous
production and maintain farm income but will not
correct soil acidity
- acid tolerant crops: sweet potato, irish potato,
strawberry, radish, pineapple, coffee, tomato
Acid Soils
• Management Strategies:
 Use acid tolerant crops
- apply more nutrients to maintain production levels
- apply agricultural lime

Lime is the only means of correcting soil acidity but the


economics of using it should be considered
Problems in Soils
(Liming)
Lime
• Correcting soil acidity by liming:
a. Lime
- any oxide, hydroxide or carbonate of Ca and Mg used
to neutralize soil acidity
b. Carbonate form
- Calcitic limestone, Dolomitic limestone, etc
c. Oxide and Hydroxide form
- CaO, burned lime, Ca(OH)2, hydrate lime
Lime

• Calcium Carbonate Equivalent (CCE) or Relative


Neutralizing Value (RNV)
- capacity of the material to neutralize soil acidity relative to
that of pure CaCO3

RNV= (MW CaCO3 / MWmaterial) x 100


Lime
Calcium Carbonate Equivalent (CCE) or Relative
Neutralizing Value (RNV)

RNV/ CCE
CaCO3 100
CaMg(CO3 )2 109
Ca(OH )2 136
CaO 179
Lime
• Factors affecting the effectivity of lime:
- Form or kind of lime:
- order of reactivity: CaO > Ca(OH)2 > CaMg(CO3)2 > CaCO3

- size of particles
- the smaller the particles the more reactive is the lime
- lime requirement; the amount of liming material required to
raise the pH to a desired level
Lime
• Lime requirement is determined by:
- required change in pH
- texture: the finer the texture the higher the CEC and
the greater the buffering capacity
Lime
• Effects of lime on the soil
 Physical – increased granulation because Ca favors
flocculation but the effect is largely indirect due to
favorable effect on organisms which decompose OM

 Chemical – neutralization of H+ ions;


- increased availability of P, Mo, Ca, K
- reduced solubility and toxicity of Fe, Al and
Mn
Lime
• Effects of lime on the soil
 Biological – promotes activity of microorganisms such as
those that decompose OM, mineralize nutrients and
fix nitrogen
- may encourage potato scabs
Lime
 Effects of overliming
- decreased availability and development of deficiency
of Fe, Mn, Cu, Zn, P and B
- trigger K and Mg deficiency due to antagonism
between Ca, Mg and K

- Overliming easily occurs on coarse-textured soils with low


organic matter
Problems in Soils
(Alkaline and Salt-Affected Soils)
Alkaline and Salt-Affected Soils

• Generally occur in arid and semi-arid regions


where evapotranspiration greatly exceeds
precipitation
• water from rain is insufficient to leach the base
cations that are released from the weathering of
rocks and minerals
Sources of Soil Alkalinity

• Base forming cations (Ca, Mg, Na, K)


• Carbonates (CO32-) and bicarbonates (HCO3- )
• Saline and Sodic soils
Saline Soils
• Soils whose concentration of soluble salts is high enough
to hamper plant growth
• salts are mostly chlorides and sulfates of Na, Ca and Mg
• pH >8.5, called white alkali
• specific toxicities due to high concentrations of Na + , Cl-
• plant growth is reduced due to osmotic effect
Sodic Soil

• Sodic soil have >15% of their cation exchange sites


occupied by Na+ ions
• pH > 8.5
• soil is highly dispersed
• dispersed humus carried upwardly by capillary
gives the soil black color (black alkali)
Reclamation of Saline Soils
• Leaching of excess salts out of the root zone (internal
and surface drainage and salt disposal dump areas)
• retardation of evaporation (use of sulfate mulch)
• use of salt tolerant crops
• use of special planting procedures that minimize salt
accumulation around the seed
Reclamation of Sodic Soils
• Replacement of excess Na on the exchange sites by Ca
and leaching of exchanged Na out of the root zone
• Gypsum cheapest and most commonly used
• S is likely to be used when the soil contains free lime in
addition to too much Na
• Addition of OM
• Deep plowing
Chemistry of Flooded Soils
• Flooded soils are submerged soils used to grow rice;
paddy soils
• Profile:
- Plow layer is a puddle system which results from
plowing and harrowing while the soil is wet
- Underneath is a hardpan which prevents or
minimizes the percolation of water into the subsoil
Effects of Flooding on Soil pH and Redox Potential
• pH value
- acid soils increases on submergence
- calcerous and sodic soils decreases
• most soils attained fairly stable pH of 6.5 to 7.0
after several weeks of submergence
Effects of pH Change
• acid soils, decrease in pH
- decreases Fe, Al, Mn toxicity
- increases P, Si and Mo availability
- enhances microbial activity (pH near
neutrality favors microbial activity)
Effects of pH Change
• alkaline soils, increase in pH
- Increases availability of P, Zn, Cu
- enhances microbial activity
Biochemical
Processes in Soil
Major Role Of Soil Microorganisms
• Responsible for biochemical changes
• Agents in the decomposition of plant and animal
residues
• Improve soil structure through aggregation
Major Groups of Soil Microorganisms
• Bacteria
• Actinomycetes
• Fungi
• Algae
• Protozoa
Bacteria
• Morphological Grouping:
- Cocci (Spherical)
- Rods (Short; Long; Curved)
- Spiral (Vibrio)
Bacteria
• Nutritional Grouping
- Heterotrophic
- Autotrophic
- Photosynthetic
- Chemosynthetic
Bacteria
• Population: 106 – 109 CFU/g Soil
• Biomass: ~ 2,000 Kg/HFS
Actinomycetes
• Branched mycelial structures
• Intermediate between bacteria and fungi
• Very fine hyphae (<1 micron diameter)
• Heterotrophic
• Aerobic; some microaerophilic
• Major antibiotic producer (streptomycin etc)
Actinomycetes
• Acid sensitive (critical pH = 5.5)
• Population: 105 – 106 CFU/g Soil
• Biomass: ~ 4, 000 Kg/HFS
Fungi
• complex morphology (multicellular, highly branched)
• heterotrophic
• aerobic
• Acid-loving
• Population: 104 – 105 CFU/g Soil
• Biomass: ~8, 000 Kg/HFS
Algae
• aquatic, moist habitat
• single-celled and multicellular species are present
• aerobic
• Photo-autotrophs
• Blue – green algae: nitrogen fixation
• Excellent host for bacteria due to oxgenating capacity
Algae
• Population: 103 - 105 cells/g soil
• Biomass: ~250 Kg/HFS
Protozoa
• single-celled animals
• Aerobic
• Ingest food through oral openings
• Reproduction: Binary Fission, Budding
• Population: 103 - 105 cells/g soil
• Biomass: ~100 Kg/HFS
Biochemical
Processes in Soil
(Production of Toxins)
Types of Toxins
 Organic
- Antibiotics
 Inorganic
- Heavy metals: Cd, Hg, Pb, Cu, Zn
Potential Sources of Toxins
 Soil microorganisms
 Plant roots
 Decomposing organic materials
 Sewage sludge
Ranking of Soil Microbial Groups in Relation to
Antibiotic Production

 1st Actinomycetes
 2nd Fungi
 3rd Bacteria
Mode of Action of Antibiotics

 Disruption of cell wall synthesis


- Penicillin, Cephalorin

 Disruption of protein synthesis


- streptomycin, chloramphenicol
Mode of Action of Antibiotics

 Inhibition of cell membrane function


- Polymixin

 Inhibition of DNA/RNA function


- Rifampicin
Biochemical Processes in Soil
(Inorganic Phosphorus
Solubilization)
Genera of Bacteria Capable of Solubilizing
Calcium Phosphate
• Pseudomonas
• Mycobacterium
• Bacillus
• Micrococcus
Types of Mycorrhiza
 Ectotrophic
- Fungus forms a mantle around exterior of the roots
- Hyphae enter into spaces between plant cells
- E.g. Pine, Eucalyptus
Types of Mycorrhiza
 Endomycorrhiza
- Fungus penetrates the cells of the plant
- E.g. Orchids, Coffee, Fruit trees, Corn
Biochemical Processes in Soil
(Soil Organic Matter)
Soil Organic Matter

• The totality of all carbon – containing compounds


in the soil derived from either plants or animals
Organic Constituents of Plants
 Cellulose (15-60%)
 Hemicellulose (10-30%)
 Lignin (5-30%)
 Water – soluble fraction
- amino sugars, amino acid (5-30%)
 Proteins
 Fats, Oils and Waxes
Decomposition of Soil Organic Matter
• Carried out by heterotrophs
• Reactants are compound containing carbon and
hydrogen, plus oxygen
• Products: CO2 , H2O, and energy
Decomposition of Soil Organic Matter
• Environmental factors affecting decomposition
 Soil pH
 Moisture
 Temperature
 Aeration
Decomposition of Soil Organic Matter
• Physical factors affecting decomposition
 Location of residues: surface vs. incorporated
 Particle size: chopped vs. unchopped

• Chemical factors affecting decomposition


 C/N ration
 Lignin and polyphenol
Compost and Composting
• Composting
- the process of creating humus-like organic matter
by piling, mixing and storing organic materials
under conditions favorable for aerobic
decomposition
- finished product is compost; used as soil organic
conditioner or slow-release fertilizer
Compost and Composting
• Composting
- after composting the C/N ratio of the organic
material is reduced to about 14 to 20:1
- pathogenic organisms are destroyed during
thermophilic stage (50-75⁰C) but heavy metals are
(inorganic contaminants) are not destroyed
Implications of C:N ratio
• < 20 – releases N in the soil upon decomposition

• 20:30- immobilization and mineralization is balance

• >30- will immobilized soil N upon decomposition


Influence of OM on Plant Growth
• promoting substances are released that stimulate growth
of both higher plants and microorganisms
ex: vitamins, amino acids, auxins and gibberelins
• allelopathic effect
- decomposing crop residues left on the soil surface may
inhibit the germination and growth of the next crop
ex: wheat residues inhibit sodium germination and growth
Influence of OM on Soil Properties
• Biological properties
- provides food for the heterotrophic organisms
- improves SOM accumulation
- increases microbial diversity
Influence of OM on Soil Properties
• Chemical properties
- increment in CEC
- increases in micronutrient availability through
chelation
- alleviates Al toxicity by binding Al in non-toxic
complexes
Influence of OM on Soil Properties
• Physical properties
- give surface horizons dark brown to black colors
- encourages granulation and aggregate stablity
- helps reduce plasticity, cohesion and stickiness of
clayey soils
- increases infiltration rate and water holding
capacity
The End!

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