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CHAPTER 3 : CHEMISTRY OF THE

SOLID EARTH
3.1 Mineral components of soil
3.2 Organic components of soil
3.3 Soil pH and redox potential
3.4 Chemical reaction in soil

3.1 Mineral Components of Soil


3.2 Organic Components of Soil
3.3 Soil Ph and Redox Potential
3.4 Chemical Reaction in Soil
COURSE OUTCOME

CO 4 : Develop awareness of professional responsibility towards


protecting the environment
WHY STUDY CHEMISTRY?

The Earth includes the biosphere, lithosphere,


hydrosphere and atmosphere. Each of these is a
mixture of thousands of different substances, many
of which are useful to us if we:
have an understanding of the properties of the elements
and compounds that make up the Earth’s materials
develop efficient processes for separating useful
materials
•The biosphere is the global sum of all ecosystems. It can also be termed
the zone of life on Earth, a closed system (apart from solar and cosmic
radiation and heat from the interior of the Earth), and largely self-
regulating.
•A lithosphere (Ancient Greek: [lithos] for "rocky", and [sphaira] for
"sphere") is the rigid, outermost shell of a rocky planet, and can be
identified on the basis of its mechanical properties.
•The hydrosphere is the liquid water component of the Earth. It includes the
oceans, seas, lakes, ponds, rivers and streams. The hydrosphere covers
about 70% of the surface of the Earth and is the home for many plants and
animals.
•An atmosphere (New Latin atmosphaera, 17th century, from Greek
[atmos] "vapor“ and [sphaira] "sphere") is a layer of gases surrounding a
planet or other material body of sufficient mass that is held in place by the
gravity of the body.
•The asthenosphere (from Greek asthenḗs 'weak' + sphere) is the highly
viscous, mechanically weak and ductilely deforming region of the upper
mantle of the Earth. It lies below the lithosphere, at depths between ≈80
and ≈200 km (≈ 50 and 124 miles) below the surface.
EARTH’S MOLTEN STAGE

•During the early formation of the Earth it was molten


•During this stage the heavier elements such as iron and nickel, sank to
the deeper interior of the Earth.
•This left a thin layer of lighter materials on the surface called the crust.
•The majority of the Earth’s mass lies below the crust
CHEMICAL ANALYSIS

•8 elements make up 98.6% of the crust


•These 8 elements make up the solid materials of the
Earth’s crust and are known as rocks and minerals.
•A mineral is solid inorganic material of the Earth that
has both a known chemical composition and a
crystalline structure that is unique to that mineral
•A rock is a solid aggregate of one or more minerals
that have been cohesively brought together by a rock-
forming process.
•(A)The percentage by
weight of the elements
that make up Earth's
crust.

•(B) The percentage by


weight of the elements
that make up the whole
Earth.
Minerals
A mineral is solid inorganic
material of the Earth that has
both a known chemical
composition and a crystalline
structure that is unique to
that mineral

Rocks
A rock is a solid aggregate of
one or more minerals that
have been cohesively
brought together by a rock-
forming process.
DEFINITION

Soil - the top layer of


the earth's crust.
It is formed by
mineral particles,
organic matter, water,
air and living
organisms.
It is in fact an
extremely complex,
variable and living
TYPES OF SOILS
SAND Gobi Desert, Mongolia

Sand
Sand is a naturally
Sand from Coral
occurring granular material Pink Sand Dunes
composed of finely divided State Park, Utah.
rock and mineral particles.
It is defined by size, being
finer than gravel and coarser
than silt.
Sand from
The composition of sand Pismo Beach,
varies, depending on the local California.

rock sources and conditions.


Gravel

F el d s pa r : R o c k- f o r m in g
t e c t os i li ca t e m in e r a ls t h a t
m a k e up a s m u c h a s 6 0 % o f
t h e Ea r t h 's c r us t .

Quartz
CLAY
Clay is a fine-grained natural rock
or soil material that combines one
or more clay minerals with traces
of metal oxides and organic matter.
SILT

Silt is granular material of a


size somewhere between sand
and clay whose mineral origin
is quartz and feldspar.

• Silt may occur as a soil or as


sediment mixed in suspension
with water (also known as a
suspended load) in a body of
water such as a river.
DESCRIPTION OF SAND, SILT AND
CLAY
Sand Clay
Clay has a high surface area,
Sand is visible to the naked
high water holding capacity,
eye, consists of particles with
many small pores, and
low surface area, and permits
possesses charged surfaces to
excessive drainage.
attract and hold nutrients.
Texture : Gritty
Texture : Sticky

Silt
• Silt is not visible to the naked eye and increases the
water holding capacity of soil.
• Texture : Buttery
Relative size comparison between sand, silt,
and clay of the fine earth fraction.
SOIL CHART
MINERAL COMPONENTS OF SOIL
 Soil minerals play a vital role in soil fertility
since mineral surfaces serve as potential sites for
nutrient storage

 They are defined depending on their size: coarse


and fine materials.

 The limit between them is random, depending on


the characteristics of every sample, the limit is
between 10 and 2 microns.

 The most frequent minerals in coarse sands of the


soil and their possible origins and alterations are
stated.

 Quartz , Feldspars , Micas , Carbonates , Gypsum


and Fe compounds.
Mica-, any of a group of G y p s u m i s a s o f t s u lf a t e
hydrous potassium, m in e r a l c o m p os e d o f
c a lc iu m s ulf a t e dih y d r a t e ,
aluminium silicate w i t h t he c he m ic a l f o r m u la
minerals CaSO. 2H2O.
HOMEWORK
PREPARE SLIDE PRESENTATION IN GROUP ABOUT MINERAL
COMPONENTS OF SOIL
COMPONENTS OF SOIL

• Various combinations of solids & liquids


 Fluids, air, water occupy the pore space between soil solids
 Typical soil is ~ ½ solid, ½ liquid
 Potting soil much more porous
 Amount of air varies with the amount of soil water (inverse
relationship)
 Soil air low in O2, higher in CO2
 Water is soil is referred to as soil solution
 Contains dissolved ions, nutrients, and other substances
COMPONENTS OF SOIL

• Soil solids
 Includes mineral & organic substances
 Minerals – sand & clay dominate the concentration
 Organic materials – humus present in a lesser quantity
 Arrangement in horizontal layers – soil horizons
 A Horizon – upper few inches of soil, usually enriched in organic
matter, most favorable environment for plant growth
-Eluvial horizon – organic matter, minerals, etc. can be washed
out
and down through the soil profile
 B Horizon – below the A, lower in organic matter, higher in soluble
materials (salts, clays) because of migration from the A
-Iluvial horizon – material washed in to the soil profile
COMPONENTS OF SOIL

C Horizon – below the B, no


effect from migration of material
in the upper two horizons
-Parent material – contains
the materials from which A & B
horizons were developed
• Potting soil, also known as potting
mix or potting compost, is a
medium in which to grow plants,
herbs and vegetables in a pot or
other durable container.
• Some common ingredients used in
potting soil are peat, composted
bark, sand, perlite and recycled
mushroom compost,
• Humus is dark, organic
material that forms in soil
when plant and animal
matter decays.
• When plants drop leaves,
twigs, and other material
to the ground, it piles up.
• This material is called
leaf litter. When animals
die, their remains add to
the litter.
MINERAL COMPONENTS OF SOIL

SUMMARY
• Natural inorganic compounds-definite physical ,chemical, and crystalline properties.
• Can be classified into –Primary (Chemically unaltered) minerals: sand, coarse silt
-Secondary(Chemically altered) minerals : clay , fine silt
- Silicates: dominate most soils
- Non-silicates :composed mainly oxides , sulfates ,carbonate
- Other major soil mineral groups include: Sulfides, oxides &
hydroxide, halides, sulfates, carbonates & phosphate
• Common methods used for soil mineral characterization include
–x-ray diffraction
-thermal
-optical
-elemental analyses
• Most primary mineral undergo structural and chemical alteration (weathering)
driven by physical, chemical and biological gradients.
• These processes cause redistribution of primary and secondary soil minerals
resulting in soil profile which is consistent with the surrounding climatic and
topographic setting.
• Soil provide:
 Physical support for plants
 Contribute to soil structural formation
 Sources of many plants nutrients
 Act as sorbents for several environmental pollutants
• Crystalline minerals-composed of atoms arranged in 3 dimensional periodic
pattern
• Non-crystalline minerals-lacking this structural periodicity
Crystalline mineral-Calcite
• Most minerals structures
bonded with ionic and
covalent bonds to form
coordinated polyhedrons
with a unique
composition and inter-
atomic distance
characteristics.
• The nature of counter
ions neutralizing the
surface charge also has
important ramifications
on
dispersion/flocculation
phenomena impacting –
soil erosion, land
stability and
groundwater quality.
CLASSIFICATIONS AND
DISTRIBUTIONS OF MINERALS
• Minerals divided into 8 classes depending on-Chemical Compositions
-Specifically their dominant
anion or anionic group
• Classes of minerals include:
 Native elements
 Sulfides These classes are
 Oxides and Hydroxides subdivided further
 Carbonates, Nitrates and Borates according to
• Chemical
 Sulfates ,Chromates and
• Structural
Molybdates
similariities
 Phosphates, Arsenates, Vanadates
 Silicates

• Rarely found in soil environment


• Common primary minerals in soil environment:
 Silicates
 Oxides of iron(Fe)
 Zircon (Zr)
 Titanium(Ti)
 Phosphate(P) Minerals can occur
in both classes:
-quartz
• Typical secondary minerals found in soil include:
-mica
Alumino-silicates -carbons
Oxides and hydroxides
Carbonates
Sulfates
Amorphous minerals
• Mineral occurrences in soil environments are the result of:
 Inheritance from parent materials
 Precipitation from soil solution (neoformation)
 Alteration of existing minerals into new phases(diagenesis)

• Climate changes have a paramount effect in these processes and in the overall
distribution of minerals in:
 Soils of different regions
 Different soil horizons
 Different soil fractions
SOILS OF DIFFERENT REGIONS
3.2 ORGANIC COMPONENTS OF
SOIL
SOM

•Soil Organic matter


includes all
organic components of a
soil:
a) Fresh residues
b) Decomposing
organic matter
c) Stable organic
matter
d) Living organisms
SOIL ORGANIC MATTER

•Soil organic matter =


a) all living organisms
(microorganisms,
earthworms, etc),
b) fresh residues (old
plant roots, crop
residues, recently
added manures),
c) well-decomposed
residues (humus).
Citizen Science – Kansas State
FRESH RESIDUES

• Up to 15% of organic
matter is
fresh residue (usually <10)
• Comprised mainly of
litter
fall
• Many of the different
types of plant litter can be
recognized.
ORGANIC COMPONENTS OF SOIL

The organic matter


component of soil,
consisting of plant and
animal residues at various
stages of decomposition,
cells and tissues of soil
organisms, and substances
synthesized by soil
organisms.
STABLE ORGANIC MATTER
-HUMUS
•Thus, soil organic
compounds become
stabilized and resistant to
further changes by
microorganisms
•Stabilized organic matter
acts like a sponge and can
absorb six times its weight
in water
HUMUS

Leaf Humus
Newly-formed humus=
a) combination of resistant
materials from the original
plant tissue,
b) compounds synthesized as
part of the microorganisms'
tissue which remain as the
organisms die.
humus is mostly resistant to
further microbial attack- N
and P are protected from
ready solubility
FUNCTION OF HUMUS

•holds water and nutrients;


• sticks together & helps
establish and maintain a
strong crumb structure & thus
reduce soil erosion
• provides some nutrients (N
& P) as it is slowly decayed by
microbial activity,
•Buffers effects of pesticides

•humus decomposes at the


rate of 2.5% per year
•Coates the sand, silt, clay
particles making them dark
and the darker the color, the
greater the amount of soil
humus present.

Humus = High Medium


SOURCES FOR SOIL ORGANIC
MATTER

The primary source of organic


matter contained in soil is
vegetal.
In forest or prairies, as well as
agricultural fields, dead
plants, trees, shrubs, grasses,
are transformed by animals
and different kinds of living
organisms.
THE DIFFERENCE BETWEEN ORGANIC SOIL AND MINERAL SOIL
3.3 SOIL PH & REDOX POTENTIAL
http://www.msichicago.org/ed/learninglabs/imgs/waters_ph_chart.jpg
The relationship between pH, pOH, and the concentrations of hydrogen and
hydroxyl ions in water solution
PH IS A ‘MASTER’ VARIABLE

• affects chemical, physical, and biological properties


of soils
• Nutrient availability (optimum pH for most crops is
5.5 - 7)
• Metal toxicity and solubility e.g., Al toxicity at pH
<5.5 (also Mn solubility and toxicity)
• Microbial activity (especially important in the N
cycle)
SOIL CHEMISTRY / SOIL PH

• Soil pH is the single most


important chemical property of
the soil (like soil texture is to
the physical properties)
• Knowing the pH of the soil
will quickly allow you to
determine if the soil is suitable
for plant growth and what
nutrients will be most limiting.
• Hydrogen ions are protons - in
water they react (H20) to form
hydronium ions, such as H3O+
• For most purposes H+ can be
used to represent these
hydrated protons (H3O+)
Methods for measuring soil pH
PH
Hydronium ions
Hydroxide ions
Acid solutions are when pH is < 7.0 Water
Alkaline solutions are when pH > 7.0
Neutral Solution
An acid can be defined as a
proton donor, a chemical that
increases the concentration of
hydronium ions in solution.
Conversely, a base is a proton
acceptor, a chemical that reduces
the concentration of hydronium Slightly Acidic Solution
ions in solution (and increases the
concentration of hydroxide ions).
MEASURE H+ IN THE SOIL
SOLUTION

• pH - the negative log of the hydrogen ion(H+)


concentration in the soil water solution.
• pH = - log [ H+]
• the pH scale is how we measure acidity and alkalinity
of solutions -----at neutral (pH =7) the number of H+
= OH-
• Remember – at pH of 6 there are 10x more H+ ions
than at a pH 7 and there are 100x more H+ ions
between pH 7 & 5
SOIL CATION EXCHANGE

• Cation Exchange - the ability of the soil to hold onto


nutrients and prevent them from leaching beyond
the roots.
• Cations are “+ “charged ions = Ca++, Mg++, K+,
NH4+(maintain an equilibrium between adsorption
to the negative sites and solution in the soil water.)
• The more cation exchange a soil has the more likely
the soil will have a higher fertility level.
Most nutrients
are highest and
most toxins are
lower at
pH 5.5-7

http://www.traylorchemical.com/images/faqs/phchart.jpg
SOIL CATION EXCHANGE CAPACITY (CEC)

• In most soils, 99% of soil cations can be


found attached to micelles (clay
particles & organic matter) and 1% can
be found in solution.
• Cations in the soil (mainly Ca++, Mg+
+, K+ and Na+) maintain an equilibrium
between adsorption to the negative sites
and solution in the soil water.
• This equilibrium produces exchanges --
when one cation detaches from a site
(leaving it free), another cation attaches
to it.
• Therefore the negatively charged sites
are called cation exchange sites.
• The total number of sites is the Cation
Exchange Capacity or CEC
CATION EXCHANGE CAPACITY (CEC)

Clay Particles and Humus

• affect chemical properties of soil


• complex structures with many negative
charge sites
• negative charge sites attract positive ions
called cations
CEC

Negative charge sites are referred to as .


.

Cation exchange sites

+ attract cations from soil solution+


CEC

Force of attraction is called:

Adsorption

The accumulation of gases, liquids, or


solutes on the surface of a solid or liquid
CATION ADSORPTION
CEC

• Cations can move on and off particles

• when one leaves, another replaces it

• This process is called cation exchange,


and cations involved are said to be
exchangeable
CEC

• The number of sites that a colloid (small


particle) of charged clay or humus
(micelles) contains is measured by the:

• Cation Exchange Capacity expressed in


mEq/100g (older unit) or cmolc/kg
CEC

• may range from:

2.0 mEq/100g for sand


to
> 50 mEq/100g for some clays
and
humus 100-300 mEq/100g under certain soil
conditions
CEC

• the number of cation adsorption sites per unit


weight of soil or
• the sum total of exchangeable cations that a soil can
adsorb.
• * CEC is expressed in milliequivalents (meq) per
100 g of oven dry soil.
• Equivalent weight = molecular or atomic wt (g)
valence or charges per formula
CEC

The proportion of the CEC occupied by


basic (+) nutrients such as Ca, Mg, K, Na,
is called:

Percent Base Saturation and is an


indication of the potential CEC of a given
soil
MILLIEQUIVALENT (MEQ)

1 meq wt. of CEC has 6.02 x 10 20 adsorption


sites
MEQ of Common Cations
Element Na+ K+ Ca++ Mg++
Valence 1 1 2 2
Eq. Wt 23/1=23 39/1=39 40/2=20 24/2 = 12
MEQ wt .023 .039 .02 .012
CEC

Example:

A soil with CEC of 10 mEq/100g has 6


mEq/100g of bases (Ca, Mg, K, Na) occupying
exchange sites

What is the percent base saturation of the


soil?
CEC

6 mEq/100g bases
10 mEq/100g sites

= 60 % base saturation
CEC

Cation Exchange is determined by:

• strength of adsorption

• law of mass
CEC

Strength of adsorption is as follows:

H+ and Al3+ > Ca2+ > Mg2+ > K+ > NH4+ > Na+
CEC

Law of Mass

the more of one ion available,


the greater the chance of adsorption
NUTRITION

There are at least 17 elements recognized as


essential nutrients for plants;

we will recognize 18 elements:

C, H, O, P, K, N, S, Ca, Fe, Mg,


Mn, Mo, Cl, Cu, Zn, B, Co, Ni
NUTRITION

Nutrients grouped into 2 categories according to the


relative amount used by plants:

Macronutrients – major elements; large amounts

Micronutrients – minor elements; small amounts

Both are essential for optimal plant production


ROOT HAIR ABSORPTION
SOURCES OF ACIDITY IN SOIL

* Hydrogen and Aluminum cations are responsible for


soil acidity
* Exchangeable Hydrogen is the main source of H+ at pH 6
and above. Below pH 6 Aluminum is the main source of H+ due
to dissociation of Al from clay minerals. Aluminum becomes
more soluble at lower pH’s
Al3+ + H20 ----> Al(OH)++ + H+
Al(OH)++ + H2O ---> Al(OH) 2+ + H+
Al(OH)2+ + H20 ---> Al(OH)3 + H+
applying anhydrous ammonia
SOURCES OF ACIDITY
IN SOIL

1. Nitrification: Anhydrous ammonia placed in soil


Ammonium to Nitrate (oxidation of NH4+)
NH4+ + 2O2 ---> NO3- + H2O + 2 H+
2. O.M. decomposition
organic acids ionized :
R-COOH---> R-COO- + H+
respiration: CO2 + H2O ---->
H2CO3 = H+ HCO3-

Ammonia gas
ACID RAIN

Acid rain is caused by the


burning of fossil fuels.
Burning oil, gas and coal in
power stations releases
Sulfuric Dioxide (SO2) into
the atmosphere.
Burning oil and gasoline in
motor vehicles puts nitrogen
oxides (NOX) into the
atmosphere.
These gases mix with water
droplets in the atmosphere
creating weak solutions of
nitric and sulfuric acids.
When precipitation occurs
these solutions fall as acid
rain.
WHY APPLY LIME ?

1. helps nutrients become


available to plants (solubility vs.
pH)
2. improves soil structure
3. provides nutrients for plant
growth -Ca & Mg
4. promotes growth of beneficial
microorganisms- they like pH=6.5
5. overcomes acidifying effects
of fertilizers
6. reduces metal toxicity to
plants (solubility vs. pH)

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