ENVIRONMENTAL

CHEMISTRY
INTRODUCTION

ENVIRONMENTAL CHEMISTRY
• a branch of chemical science which deals with the
development, transport, reactions, effects and fates of
chemical species in the water, air, soil and biological
environment and the effects of human activities on them
• It is an interdisciplinary field of research including
environmental engineering, chemistry, physics, biology,
biotechnology, life sciences, medical science, agriculture and
public health.
INTRODUCTION
There are four environmental segments. These are:
A. Atmosphere - It is the protective blanket of gases, suspended liquids
and solids that entirely envelopes the earth, sustains life on earth, and
saves it from the hostile environment of outer space.
B. Hydrosphere – it consist of all types of water resources such as
oceans, seas, rivers, lakes, streams, reservoirs, polar ice caps and water
below the earth’s surface which includes all surface and ground water.
C. Lithosphere – it is the outer mantle or the soil of the solid earth,
consisting of minerals occurring in the earth’s crust.
D. Biosphere – it is the realm of living organisms and their interactions
with the atmosphere, hydrosphere and lithosphere.
The relationship between these four environmental segments will be
learned in this chapter.
I. CHEMISTRY OF THE
ATMOSPHERE
Contents
I. Chemistry of the atmosphere
II. Greenhouse Effect
III. Ozone Layer Depletion
IV. Acid Rain
V. Photochemical Smog
I. CHEMISTRY OF THE ATMOSPHERE
A. Atmosphere
The atmosphere is a vital mechanism that seeks to monitor and sustain the
temperature of the Earth, the balance of radiation by the absorption of
electromagnetic radiation released by the sun and re-emitted by the earth, as
well as the transfer of heat across the globe It filters unhealthy tissues that
destroy ultraviolet (UV) radiation. It's even warming the world by day and
cooling it by night

B. COMPOSITION OF THE ATMOSPHERE

According to NASA, the gases in Earth's atmosphere include:

• Nitrogen — 78 percent
• Oxygen — 21 percent
• Argon — 0.93 percent
• Carbon dioxide — 0.04 percent
• Trace amounts of neon, helium, methane, krypton and hydrogen,
as well as water vapor
I. CHEMISTRY OF THE ATMOSPHERE
C. STRUCTURE OF THE ATMOSPHERE
Troposphere
Altitude: 0-11 km
Temperature Range: 15 to -56 ⁰C
Important Chemical Species:
N₂, O₂, CO₂, H₂O
• The layer closest to Earth’s surface
• Contains half of Earth’s atmosphere
• Air is warmer near the ground and
gets colder higher up
• Nearly all the water vapor and dust
in the atmosphere are in this layer
and that is why clouds are found
here
Stratosphere
Altitude: 11-50 km
Temperature Range: -56 to -2 ⁰C
Important Chemical Species:
O₃
• Ozone is abundant here and it heats the
atmosphere while also absorbing harmful
radiation from the sun
• The air here is very dry, and it is about a
thousand times thinner than it is in sea level.
Because of that, this is where jet aircraft and
weather balloons fly
I. CHEMISTRY OF THE ATMOSPHERE
C. STRUCTURE OF THE ATMOSPHERE
Mesosphere
Altitude: 50-85 km
Temperature Range: -2 to -92 ⁰C
Important Chemical Species:
O₂⁺, NO⁺
• Top of the mesosphere called the
mesopause, is the coldest part of
the Earth’s atmosphere
• This layer is hard to study. Jets
and balloons don’t go high
enough, and satellites and space
shuttles orbit too high
Thermosphere
Altitude: 85-500 km
Temperature Range: -92 to 1200⁰C
Important Chemical Species:
O₂⁺, O⁺, NO⁺
• The thermosphere is considered part of Earth’s
atmosphere, but the air density is so low that
most of this layer is what is normally thought as
outer pace
• This is where the space shuttles flew the
International Space Station orbits Earth. This is
also the layer where the auroras occur (Aurora
Borealis and Aurora Australis).
I. CHEMISTRY OF THE ATMOSPHERE
C. STRUCTURE OF THE ATMOSPHERE

Exosphere
Altitude: above the thermosphere
Temperature Range: has a very high
temperature due to radiation
Important Chemical Species:
H₂, He

• Also known as outer space

I. CHEMISTRY OF THE ATMOSPHERE
D. EARTH’S RADIATION/ENERGY BALANCE

- The sun provides solar energy that is used within the

world, even though much of the intensity of the sun never
hits the surface of the earth.
- The earth receives solar energy in the form of short-
wave radiation and consumes about 70% of the sun.
- The Earth releases the remaining 30% of solar
radiation in the form of long-wave radiation into
space, which allows the Earth to cool down.
- The proportion of solar radiation that is absorbed and
distributed out into space is also known as Albedo.

The sum of solar energy per unit time flowing through

the unit area at right angles to the path of the solar beam
measured just outside the Earth's atmosphere is known as
the solar flux, also known as the solar constant. The solar
radiation hitting the upper Earth's atmosphere is roughly
1340 watts/m²•min
ll. GREENHOUSE EFFECT

Sun rays comprise of UV rays, visible light

and IR radiations. Ozone layer absorbs
damaging UV radiations and allows visible
and IR radiations to pass through it towards
the Earth.
The gases in the atmosphere are Carbon
dioxide, water vapor, methane, tropospheric
ozone, and chlorofluorocarbon (CFC). CO₂ is
a trace gas in Earth’s atmosphere with a
concentration of approximately 0.033% by
volume which plays a vital role in regulating our
environment.
Greenhouse Effect
- Explains the absorption of heat above
the Earth’s surface by atmospheric
gasses in particular carbon dioxide
- The glass roof of the greenhouse
transmits visible sunlight and collects
some of the outgoing infrared (IR)
radiation, trapping the heat.
ll. GREENHOUSE EFFECT

The sinks of CO₂

1. Oceans: which dissolves CO₂ as carbonates

2. Biomass: living green plants use CO₂ in

photosynthesis

These sinks are responsible for only 50% of the

expected increase in the CO₂ content in the
atmosphere.
ll. GREENHOUSE EFFECT
Carbon dioxide behaves much like a glass cover, except that the raise of temperature in the
greenhouse is mostly due to the reduced passage of air within. Calculations indicate that if
the atmosphere didn’t contain carbon dioxide, the Earth would be 30 °C cooler! Without
CO2, the earth would be as cold as moon.

Green house is a body which allows the short wavelength incoming radiations
but does not allow long wave radiations to escape.
ll. GREENHOUSE EFFECT
RELATIVE CONTRIBUTIONS OF GREENHOUSE GASES AND THEIR USES

GASES % Contribution towards Main Sources

greenhouse effect
CO₂ 49% Fossil fuel combustion, Deforestation,
Respiration, Fermentation
CH₄ 18% Wet lands, Marshy places, Anaerobic
decomposition of organic wastes, Forest
fires
CFC 17% Refrigerant, Aerosol propellant,
manufacturing foams
N₂O 6% Natural soil, Fertilizers, Fossil fuel
combustion, burning of biomass
O₃ 8% Photochemical reaction in stratosphere
and diffusion in troposphere
H₂O 2% Vaporization process
lll. OZONE LAYER
Ozone (O₃) is concentrated in stratosphere at various heights
from 16 – 40km at different latitudes. This layer of atmosphere
enveloped by ozone is known as ozone layer. It is also known
as ozonosphere or ozone umbrella.

The thickness of ozone layer is measured in Dobson units

(DU). 1 DU = 0.01 mm of the compressed gas at 0°C and
760mm Hg pressure.

A. Formation of Ozone B. Advantage of Ozone

It is formed naturally in stratosphere by the action of •It acts as protective shield as is absorbs the UV-
ultraviolet radiation radiation responsible for DNA mutation and skin
cancer. The UV – radiation may also cause global
warming, faster degradation of plastics, fabrics, etc.
lll. OZONE LAYER
C. Depletion of Ozone Layer
The three main reasons where human
activity has influenced the ozone
layer are the following:
1. Direct emission of NOx by
supersonic transport. They just fly
over the tropopause to maintain their
speed because of low resistance.
2. Use of chlorofluorocarbons
3. Increased use of nitrogenous
fertilizers.
D. Mechanism of Ozone Depletion
•It acts as protective shield as is absorbs the UV-radiation responsible for
DNA mutation and skin cancer. The UV – radiation may also cause global
warming, faster degradation of plastics, fabrics, etc .
i. Nitric Oxide converts ozone into
O₂ and NO₂.
ii. NO₂ formed reacts with nascent
oxygen
iii. NO is regenerated which again
reacts with ozone and the depletion
continues by the chain reaction.
CFC’s are inert in normal physical
conditions. But under the influence of
UV-radiation they form chloride
radical and the following reactions
takes place.
The chloride free radical (·Cl)
regenerated is highly stable and one
chloride free radical can break 1
molecule of ozone.
lll. OZONE LAYER

E. Global Action against Ozone Depletion

1. Vienna Convention
• The convention laid a framework for global cooperation on
arresting ozone depletion.
• 20 nations, including most of the major CFC producers, signed the
Vienna Convention in 1985
2. Montreal Protocol
• Then, in 1987, 43 countries signed the Montreal Protocol.
• The Protocol is ratified today by 197 Members.
• Ozone-depleting substances (as mentioned above) have been
established for phase-out and are to be replaced by HFCs
(Hydrofluorocarbons).
• With the introduction of the Montreal Protocol, CFC
concentrations in the atmosphere have been undergoing a steady
decline since peaking in 1994.
• Efficient Equivalent Chlorine (EECl) levels in the atmosphere had
declined by around 10% by 2008.
lV. ACID RAIN
Every year, acid rain does hundreds of millions of
dollars’ worth of damage to stone structures and
monuments all around the world.
Atmospheric CO₂ will not be expected to result in a
pH lower than 5.5.
While smelting is a significant source of SO₂, much of the SO₂
released to the atmosphere is compensated for by the combustion
of fossil fuels in agriculture, power plants and households. The
sulfur content of coal varies from 0.5 to 5 percent by bulk, based
on the source of the coal.

Sulfur dioxide (SO₂) and, to a lesser degree, auto-
emission nitrogen oxides are thought to be
responsible for elevated rainwater acidity. Acid
oxides, such as SO₂, react with water to create the
related acids.
In the troposphere, SO₂ is nearly always oxidized to H₂SO₄ in the
form of aerosol, resulting in heavy precipitation or acid
rain.

Sources of atmospheric SO₂

- Volcanic eruption
- Extraction of metals through smelting of ores

Sulfur dioxide and other air pollutants being released

into the atmosphere from a coal-burning power plant
V. PHOTOCHEMICAL SMOG
The term "smog" was coined to describe the Mechanism of Photochemical smog
mixture of smoke and fog that engulfed
London in the 1950s. Today, though, we are
more familiar with the photochemical smog
produced by the reactions of vehicle emissions
in the presence of sunlight

Automotive exhaust consists primarily of NO, CO

and various unburned hydrocarbons. These gasses
are called major pollutants because they set in
motion a series of photochemical reactions that
create secondary pollutants. The secondary Hydrocarbon oxidation produces various chemical
pollutants — mainly NO₂ and O₃—are responsible intermediates, such as alcohols and carboxylic acids, which
for the build-up of smog. are all less fragile than the hydrocarbons themselves.

These liquids are gradually reduced into tiny droplets of

liquids. The dispersion of these droplets in the air, called
aerosols, disperses the sunlight and decreases visibility. This
interactionsometimes lets the environment seem hazy.
ENVIRONMENTAL
CHEMISTRY – Chemistry
of Water
INTRODUCTION
Water is nature’s most wonderful, abundant, useful compound and is an essential without it one
cannot survive. It occupies a unique position in industries. Its most important use is as an
engineering material in the steam generation. Water is also used as coolant in power and chemical
plants. It is also used in other fields such as production of steel, rayon, paper, atomic energy,
textiles, chemicals, ice and for air-conditioning, drinking, bathing, sanitary, washing, irrigation, etc.

Occurrence:
Water is widely distributed in nature. It has been estimated that
about 75% matter on earth’s surface consists of water. The body
of human being consists of about 60% of water. Plants, fruits and
vegetables contain 90-95% of water.
Sources of Water:
Different sources of water are:
Surface Waters: Rain water (purest form of natural water), River
water, Lake Water, Sea water (most impure form of natural
water).
Underground Waters: Spring and Well water. Underground
waters have high organic impurity.
I. WATER CHEMISTRY
A. Physical properties of water

High boiling point – water occurs primarily in its liquid state

in a range of conditions where life thrives, while the other two
forms, ice and steam, play an important role in shaping the
environment.

High surface tension - surface tension forces overpower

gravity and viscous forces, and the air-water interface becomes
an essentially impenetrable barrier. This is now a significant
influence in the climate and lifestyle of small insects, bacteria
and other microorganisms.
I. WATER CHEMISTRY
• Important thermal properties

High specific heat capacity - water needs to gain a lot of

energy to raise its temperature. Conversely it also needs to
lose a lot of energy to lower its temperature. Water’s specific
heat capacity is 4.2 kJ/g/°C

High latent heat vaporization – water requires a lot of energy

to evaporate. When water evaporates, water draws thermal
energy out of the surface it’s on, which can be observed in
sweating.

High latent heat fusion – at 0°C water must lose a lot of

thermal energy before it freezes, thus liquid water can reach
temperatures of down to -10°C before it forms ice
I. WATER CHEMISTRY
RELEVANCE OF WATER TREATMENT
- The fundamental physical properties of water that are important to environmental science are density and viscosity.

1. Density – measure of the concentration of matter 2. Viscosity – a measure of resistance to

a. mass density, ρ = mass/volume movement of fluids
- dissolved impurities change the density in direct a. Dynamic viscosity, or absolute viscosity,
proportion to their concentration and their own density μ (mass/length-time) Pa-s

b. specific weight, Ƴ = force/volume (kN/m3) = ρg b. Kinematic viscosity, ν

ν = μ/ρ (m²/s)
c. specific gravity, s
s = ρ/ρ₀ = Ƴ/Ƴ₀
where ρ₀ = density of water at 4°C

= 1000 kg/mᶟ

= 9.81 kN/mᶟ
I. WATER CHEMISTRY
B. States of Solution Impurities
Classification of solution impurities

1. Dissolved substance 2. Suspended solids

• The substance is homogeneously dispersed in • Defined as those solids that can be filtered by a glass
liquid. They can be simple atoms or complex fiber filter disc and are properly called filterable
molecular compound solids. Suspended solids can be removed from water
• Dissolved substance can be removed through by physical methods such as sedimentation,
phase change processes filtration and centrifugation.
a. Distillation – either the liquid or the
substance itself is changed from a liquid phase
to a gas phase to achieve separation.
b. Precipitation - substance in the liquid phase
combines with another chemical to form a
solid phase, thus achieving separation from
water.
c. Adsorption – adsorbed substance reacts with
a solid particle to form a solid particle-
substance complex.
d. Liquid Extraction – the substance is extracted
and carried away by another liquid.
I. WATER CHEMISTRY
B. States of Solution Impurities
Classification of solution impurities

3. Colloidal Particles
• The size range between dissolved substances and suspended
particles
• They are in a solid state and can be removed from the liquid by
physical means such as very high-force centrifugation or
filtration through membranes with very small pose spaces

Tyndall Effect
• When light passes through a liquid containing colloidal particles,
the light is reflected by the particles Turbidity is measured in a unit called NTUs.
The lower the NTU, the lower the turbidity

Turbidity
• Turbidity is the cloudiness or haziness of a liquid created by a
significant number of individual particles that are generally
invisible to the naked eye, comparable to smoke in the air.
• The dynes to which a colloidal suspension reflects light at a 90°
angle to the entrance beam.
I. WATER CHEMISTRY
B. States of Solution Impurities
Classification of solution impurities

4. Color
• Combination of dissolved and colloidal materials

• Caused by colloidal iron or manganese complexes, although the

most common cause of color is from complex organic compounds
that originate from the decomposition of organic matter. One
common source of color is the degradation of soil humus, which
produces humic acids – imparts reddish-brown color to water

MW: = 800 (dissolved)

= 50,000 (colloidal)
I. WATER CHEMISTRY
Chemical units Analyst usually give results directly in mass per volume
• Used to perform stoichiometric calculations (mg/L) for very dilute solution, the pressure of the substance
does not change the density of water:
1. Weight percent, P Since 1 mL = 1 g water
• Employed to express appropriate concentration
of commercial chemicals or of solid concentration 1 mg/L = 1 ppm
of sludge. P=
P= Translated into 1 % = 10,000 mg/L
where: W = weight of substance In chemical reaction:
W₀ = grams of solution M = molarity = no. of moles in a liter of solution
1 mg/L = molarity x molecular weight x 10³
= (mole/L) (g/mole) (10³ mg/g)
I. WATER CHEMISTRY
2. Equivalent weight (EW)
• Frequently used in softening redox
• EW = MW divided by the number (n) of electrons transferred in redox
reaction or the number of protons transferred in acid/base reactions.

Acids/Base reaction:
• n is the number of hydrogen ions that the molecules transfer

Precipitation reaction:
• n is the valence of the element in question
• for compounds, n is the number of hydrogen ions that would be required
to replace the cation

N = no. of EW per liter of solution

N = nM
I. WATER CHEMISTRY
Example 1:
1. Commercial sulphuric acid, H2SO4, is often purchased as a 93-weight percent solution.
Find the mg/L of H2SO4 and the molarity and normality of the solution sulfuric acid has a
specific gravity of 1.839.

Solution:
1 L HW = 100 g
1 L H2SO4 of 100% H2SO4: 1000(1.839) = 1839 g

For a 93% solution:

0.93(1839) = 1710 g H₂SO₄ or 1.710 x 10⁶ mg/L of H₂SO₄ in a 93% solution

M=

N = nM = (17.45 mole/L) (2 equiv/mole) = 34.9 equiv/L

I. WATER CHEMISTRY
Example 2:
Find the weight of sodium bicarbonate, NaHCO₃, necessary to make a 1M solution. Find the normality of
the solution.

Solution:
Concentrations can also be reported in moles per liter (molarity) or in gram-equivalents per liter (normality). In the case of
chemical reactions, molarity concentrations or normality can be used. Molarity is related to milligrams per liter.

The molecular weight of NaHCO₃ is 84; therefore, the mass that must be added can be determined by

mg • L⁻¹ = molarity x molecular weight x 10⁻³

= (mol • L⁻¹)(g • mol⁻¹)(10³ mg • g⁻¹)

MW NaHCO₃ = 84
mg/L = (1 mole/L) (84 g/mole) = 84 g/L
N = nM = 1 normal

For the preparation of a 1 M solution, 84 g sodium bicarbonate must be added to 1 L of solution. Since HCO⁻³ is capable
of donating or taking only one proton, n = 1. We can see that normality is the same as molarity.
I. WATER CHEMISTRY
3. pH
- pH is the term used universally to express the intensity of the acidity of a solution

- More precisely, acids are defined as those compounds that release a proton (H⁺,
hydrogen ion) whereas bases are those compounds that accept protons. Thus, pH is
the measurement of hydrogen ion (H⁺) activity.

- Pure water dissociates to yield equivalent concentrations of hydrogen [H⁺] and

hydroxide [OH⁻] ions:

H₂O H⁺ + OH⁻

The equilibrium for pure water is [H⁺] × [OH⁻] = Kw = 10⁻¹⁴ = 10⁻⁷ × 10⁻⁷
Therefore, at equilibrium, [H⁺] = [OH⁻] = 10⁻⁷ = pH of 7
The scale ranges from 0 to 14 [H⁺] = 10 to 10-14
I. WATER CHEMISTRY
3. pH
- pH is a critical measurement. Life depends upon it. For instance, human blood is basic with a pH between 7.3 and 7.5.
• If the blood pH drops < 7.3, acidosis occurs (diabetes).
• If blood pH rises > 7.5, alkalosis occurs (Tums OD).
• Below 7.0 and above 7,8, death occurs

- One unit in pH equals a 10x change in acidity.

• Two units means 100 times change,
• 3 units is 1000 times and so on.

 pH describes a water’s relative acidity, provides no measure of how the water will tolerate addition of acid or base to the system.
 pH is measured according to electrometric principles based on the Nernst equation. Temperature is the only variable.
 pH affects nearly every water and wastewater treatment function (wherever some chemistry is involved)
I. WATER CHEMISTRY
C. Hardness of water
Hardness of water is a characteristic property by which water “prevents
lathering of soap”. This is due to presence of certain salts like Ca²⁺, Mg²⁺ and
other heavy metals dissolved in water.
• Soaps (Sodium or Potassium salts of higher fatty acids) like
(C₁₇H₃₅COONa)

Hard Water: The water which does not give lather with soap is called hard water. This is
due to presence of certain salts like Ca²⁺, Mg²⁺ and other heavy metals dissolved in water
Il. WATER CHEMISTRY
Hardness of water is due to the presence of Bicarbonates,
C. Hardness of water Chlorides, Sulphates and Nitrates of Calcium and
Magnesium. These soluble salts get mixed with natural
water due to the following reasons:

1. When natural water containing CO₂ flows over the

rocks of the limestone (CaCO₃) and Dolamite (CaCO₃ and
MgCO₃), they get converted into soluble bicarbonates.
Thus, water gets hardness.

2. When natural water flows over the rocks containing

chlorides and sulphates and Nitrates of Calcium and
magnesium, these salts dissolve in water. Thus water gets
hardness.

Note:
• CaCO₃ and MgCO₃ are both insoluble in water but the
bicarbonate is quite soluble.
• Gypsum (CaSO₄) and MgSO₄ may also go into
solution to contribute to the hardness
I. WATER CHEMISTRY
C. Hardness of water
Disadvantages of Hardness
1. In Domestic use:
• Washing: Hard water, when used for washing purposes, does not producing lather freely
with soap. As a result, cleaning quality of soap is decreased and a lot of it is wasted.
• Bathing: Hard water does not lather freely with soap solution, but produces sticky scum
on the bath-tub and body. Thus, the cleaning quality of soap is depressed and a lot of it is
wasted.
• Cooking: The boiling point of water is increased because of presence of salts. Hence more
fuel and time are required for cooking.
• Drinking: Hard water causes bad effects on our digestive system. Moreover, the
possibility of forming calcium oxalate crystals in urinary tracks is increased.
I. WATER CHEMISTRY
C. Hardness of water
Disadvantages of Hardness
2. Industrial Use:
• Textile Industry: Hard water causes wastage of soap. Precipitates of calcium and magnesium soaps adhere to the
fabrics and cause problem.
• Sugar Industry: The water which containing sulphates, nitrates, alkali carbonates are used in sugar refining, cause
difficulties in the crystallization of sugar.
• Dyeing Industry: The dissolved salts in hard water may reacts with costly dyes forming precipitates.
• Paper Industry: Calcium, magnesium, Iron salts in water may affect the quality of paper.
• Pharmaceutical Industry: Hard water may cause some undesirable products while preparation of pharmaceutical
products.
3. Steam generation in Boilers:
• For steam generation, boilers are almost invariably employed. If the hard water is fed directly to the boilers, there
arise many troubles such as: Scales & sludge formation, Corrosion, Priming & Foaming and Caustic embrittlement.
I. WATER CHEMISTRY
C. Hardness of water
Types of Hardness
2. Permanent Hardness or non-carbonate hardness
• It is due to the presence of dissolved Chlorides, Nitrates and Sulphates of Calcium,
Magnesium, Iron and other metals. Permanent hardness responsible salts are CaCl₂,
MgCl₂, CaSO₄, MgSO₄, FeSO₄, Al₂(SO₄)₃.
• total hardness in excess of the alkalinity
- If the alkalinity is equal to or greater than the total hardness, then there is no
noncarbonated hardness.
• Permanent Hardness cannot be removed by boiling but it can be removed by the use of
chemical agents.
I. WATER CHEMISTRY
C. Hardness of water
Types of Hardness
1. Temporary Hardness or carbonate hardness
- defined as the amount of hardness equal to the total hardness or the total alkalinity,
whichever is less
- caused by the presence of dissolved bicarbonates of Calcium, Magnesium (Ca (HCO 3)2,
Mg (HCO3)2) and the carbonate of Fe2+

- Temporary Hardness can be largely removed by boiling of water.

o At pH < 8.3, HCO3- is the dominant form of alkalinity, and total alkalinity is nominally
taken to be equal to the concentration of HCO 3-
I. WATER CHEMISTRY
C. Hardness of water
Total Hardness (TH) = Ca²⁺ + Mg²⁺ (mg/L as CaCO³ or meq/L)
In terms of the two components of hardness:
a. HCO₃⁻ anion (carbonate hardness, CH)
b. Noncarbonated hardness (NCH)
TH = CH + NCH
I. WATER CHEMISTRY
C. Hardness of water
Expression and Units of Hardness
The expression of hardness producing salts usually expressed in terms of an equivalent amount
of CaCO₃. Calcium Carbonate is chosen as a standard because:
i. Its molecular weight (100) and equivalent weight (50) is a whole number, so the calculations in
water analysis can be simplified.
ii. It is the most insoluble salt that can be precipitated in water treatment.

1. Calculation of equivalents of CaCO₃:

The conversion of the hardness-causing salts into CaCO₃ equivalents can be achieved by using
the following formula:
Chemical equivalents as CaCO3 = (mg/L as species) EWCaCO₃/EWspecies
Or
Chemical equivalents as CaCO3 = (Weighthardness-causing salt)-(100)-(50)/MWsalt
I. WATER CHEMISTRY
C. Hardness of water
Chemical Equivalent Or Multiplication factor for converting
Salt/ion Molar mass into equivalents of CaCO3
Equivalent Weight
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
CaCO3 100 50 100/100
MgCO3 84 42 100/84
CO2 44 22 100/44
Ca(NO3)2 164 82 100/164
Mg(NO3)2 148 74 100/148
HCO3- 61 61 100/122
OH- 17 17 100/34
CO32- 60 30 100/60
NaAlO2 82 82 100/164
Al2(SO4)3 342 57 100/114
FeSO4.7H2O 278 139 100/278
H+ 1 1 100/2
HCl 36.5 1 100/73
I. WATER CHEMISTRY
C. Hardness of water
2. Units of Hardness
1. Parts per Million (ppm): The number of parts of calcium carbonate equivalent
hardness presents in 106 parts of water.
1 ppm = 1 part of CaCO₃ eq hardness in 10⁶ parts of water.

2. Milligrams per litre (mg/L): The number of milligrams of calcium carbonate

equivalent hardness presents in litre of water.
1 mg/L = 1 mg of CaCO₃ eq hardness in 1 liter of water.
But one liter of water weights = 1 kg = 1000g = 1000 x 1000 mg = 10⁶ mg = 1 ppm
I. WATER CHEMISTRY
C. Hardness of water
2. Units of Hardness
3. Clark’s degree (°Cl): The number of parts of calcium carbonate equivalent
hardness presents in 70,000 or (7 × 10⁴) parts of water.
1° Clarke = 1 part of CaCO₃ eq hardness per 70,000 parts of water

4.Degree French (°Fr): The number of parts of calcium carbonate equivalent

hardness presents in 105 parts of water.
1° Fr = 1 part of CaCO₃ hardness eq per 10⁵ parts of water

Relationship between various units of hardness

1 ppm = 1 mg/L = 0.1° Fr = 0.07° Cl
1 mg/L = 1 ppm = 0.1° Fr = 0.07° Cl
1 ° Cl = 1.433° Fr = 14.3 ppm = 14.3 mg/L
1 ° Fr = 10 ppm = 10 mg/L = 0.7° Cl
I. WATER CHEMISTRY
C. Hardness of water
Example:
A sample of water is found to contains following dissolving salts in milligrams per
liter Mg(HCO₃)₂ = 73, CaCl₂ = 111, Ca(HCO₃)₃ = 81, MgSO₄ = 40 and MgCl₂ = 95.
Calculate temporary and permanent hardness and total hardness.

Temporary hardness = Mg(HCO₃)₂ + Ca(HCO₃)₂ Name of the Amount of the

Molecular weight of Amounts equivalent
hardness hardness causing salts
= 50 + 50 = 100 mgs/Lit. causing salts (mg/liter)
hardness causing salts to CaCO3 (mg/Lit)
Mg(HCO3)2 73 146 73 × 100/146 = 50
Permanent hardness = CaCl₂ + MgSO₄ + MgCl₂ CaCl2 111 111 111 × 100/111 = 100
= 100 + 33.3 + 100 = 233.3 mgs/Lit. Ca(HCO3)2 81 162 81 × 100/162 = 50
MgSO4 40 120 40 × 100/120 = 33.3
Total hardness = Temporary hardness + Permanent hardness MgCl2 95 95 95 × 100/95 = 100

= 100 + 233.3 = 333.3 mgs/Lit.

I. WATER CHEMISTRY
C. Hardness of water
Example: of the
Amount of the Molecular weight Amounts
hardness
hardness causing of hardness equivalent to
A sample of water is found to contains following analytical data in causing
salts (mg/Lit) causing salts CaCO3 (mg/Lit)
salts
milligrams per litre Mg(HCO₃)₂ = 14.6, MgCl₂ = 9.5, MgSO₄ = 6.0 and
14.6 × 100/146 =
Ca(HCO₃)₂ = 16.2. Calculate temporary and permanent hardness of water in Mg(HCO3)2 14.6 146
10
parts per million, Degree Clarke’s and Degree French.
MgCl2 9.5 95 9.5 × 100/95 = 10
MgSO4 6.0 120 6.0 × 100/120 = 5
Temporary hardness [Mg (HCO₃)₂ + Ca (HCO₃)₂] = 10 + 10 = 20 mg/Lit 16.2 × 100/162
Ca(HCO3)2 16.2 162
=10
= 20 ppm
= 20 × 0.07°Cl = 1.4 °Cl
= 20 × 0.1 °Fr = 2 °Fr

Permanent hardness [MgCl₂ + MgSO₄] = 10 + 5 = 15 mg/Lit

= 15 ppm
= 15 × 0.07 °Cl = 1.05 °Cl
= 15 × 0.1 °Fr = 1.5 °Fr
The Chemistry of the
Environment – Soil
Chemistry
Contents:
I. Introduction
II. Soil Components
III. Reaction Processes in Soil
IV. Soil Acidity
V. Soil Salinity
Introduction
Soils exist at an interface between the hydrosphere, atmosphere, biosphere, and
lithosphere, and soil solutions are greatly influenced by interactions with these other
spheres.

Pedosphere - The interaction of Earth’s subsystems within soil results in a mixture of

solid, liquid, gas, and biota.

Soil is a complex mixture of inorganic and organic solids, air, water, solutes,
microorganisms, plant, and other types of biota that influence each other.

Soil chemistry studies these chemical processes in soils; specifically, chemical reactions,
species, and transformations within and between solid, gas, and liquid phases.

Understanding speciation of solids and chemicals in soils is key to predicting soil

properties and how they will interact with plants, microbes, and animals.

Chemical reactions in soils often lead to changes between solid, liquid, and gas states
that dramatically influence the availability of chemicals for plant uptake and losses from
soil that in turn are important aspects of fate and transport of nutrients and
contaminants in the environment.
Introduction
Parameters used in soil chemistry:
Parameter Unit Unit conversion

Land area Hectare, Ha 1 Ha = 104 m2

Volume Cubic meter, m3 1 L = 10-3 m3

Specific surface area Square meters per kilogram m2•kg-1

Conductance or 1 S•m-1 = 1 ohm-1 = 1 mho;

Siemens per meter, S•m-1
electric conductivity 1 S•m-1 = 10 mho•cm-1 ; 1 dS•m-1 = 1 mho•cm-1

Amount of ion charge Moles charge mol(+) or mol(-)

Molar, M 1 M = 1 mol•L-1 = 103 mol•m-3 = 1 mmol•m-3

Concentration
Normality, N mol charge•L-1

1 mol(+)•kg-1 = 10 mmol(+)•kg-1 = 1 cmol•kg-1

Cation exchange capacity Millimoles charge per kilogram solid
1 mol(+)•kg-1 = 1 milliequivalent•100 g-1

Total exchangeable acidity Moles charge mol(+) or mol(-)

Sodium adsorption ratio Moles charge per volume mol(+) L-1 or mol(-) L-1

Total dissolved solids Mass per volume mg L-1

Soil Components
The elements in rock minerals at Earth’s surface are
the starting materials for soils and contain the
essential elements from which soil and life evolved.
Concentrations of elements in soils depend on the
soil formation factors, especially parent material,
weathering processes, and biologically driven
fluxes of elements. Most of the mass of soil is
comprised of oxygen, followed by silicon,
aluminum, carbon, and iron. Elemental contents of
soils are highly variable, especially for nutrients
such as nitrogen, sulfur, and phosphorus.
Soil Components
A. Essential Elements

Essential elements, commonly referred to as essential nutrients, are the elements from which plants,
animals, and humans evolved. Essential nutrients, in range of limit, are required for an organism to
complete its life cycle. When a nutrient is lower than the lower limit requirement, organisms suffer
deficiency. While when some essential nutrients are higher than the upper limit, it becomes toxic.
Soil Components
The elements of primary
interest for soil chemistry
exhibit a wide range of
chemical behavior that
Ions of major interest in soil chemistry and their common species
Ion Remarks
Exchangeable cations They are retained by the negative charge of soil minerals and organic matter. It occur as
Ca2+, Mg2+, Na+, K+, NH4+, Al3+ exchangeable cations in soils; these ions are easily manipulated by liming, irrigation, or
acidification; exchangeable Al3+ is characteristic of acid soils; productive agricultural soils are rich
in exchangeable Ca2+; NH4+, and K+; K+ can become fixed in clay minerals.

causes highly varied
mobility and
bioavailability. The
elements of common
interest are grouped, as
shown in the table,
according to general
chemical properties and
reactivity in soil.
Soluble anions They are present in lower concentrations than the major cations except in coarse‐textured and
NO3 –, SO42–, Cl–, strongly saline soils; sulfate and nitrate are important nutrient sources for plants; sulfate,
H2CO3, HCO3 –, chloride, and bicarbonate salts accumulate in saline and alkaline soils; selenite (SeO42–) anion is
Se6+ as SeO42– more soluble than selenite (SeO32–).
Poorly soluble anions They are strongly retained by soils and present at low concentrations in soil solution (typically
H2PO4 –, HPO42–, H3BO3, H4BO4 –, Si(OH)4, MoO42–, <10–5 M). It often occur as minerals, salts, or sorbed to mineral surfaces; borates are the most
Se4+ as HSeO3 – soluble of the group; molybdate and silica are more soluble at high pH; phosphate is more
soluble at neutral or slightly acid pH; selenite is more reduced and less mobile than selenate.
Poorly soluble metal cations Its concentration in soil solutions are typically much less than alkali and alkaline earth cations. As
silica and other ions leach during weathering, insoluble hydroxides accumulate in soils; iron and
Al3+, Cu2+, Zn2+, Ni2+, Co2+
Fe(OH)2 +, Fe2+, Fe3+, manganese are more soluble in waterlogged or reduced soils; availability increases with
Mn4+, Mn3+ Mn2+ increasing soil acidity; metals are complexed by soil organic matter (SOM) and strongly adsorbed
on mineral surfaces.

Toxic ions These ions are present in soil at concentrations that pose toxicity risks. Often not readily soluble;
Al3+, Al3+ is a hazard to plants, the others are of more concern to animals; Cd2+ is relatively available to
As(V): H2AsO4 –, HAsO42– plants; As and Cr oxyanions increase in solubility with pH; As(III) is more soluble than As(V);
As(III): H2AsO3 –, HAsO32– cation contaminants are less available to plants with increasing pH; many contaminants form
poorly soluble sulfides in reduced soils.
Cr(VI): CrO42–
Cd2+, Hg2+, Pb2+

Biogeochemical cycling elements
C4– to C4+ (CH4 to CO2)
N3– to N5+ (NH4+, N2, NO2, NO3–)
O2–, O2
S2– to S6+ (H2S to SO42–)
These elements are primarily produced by plants, fixation by microbes, and microbial driven
mineralization. Soil biochemistry revolves around the oxidation state changes of soil carbon,
nitrogen, and sulfur compounds; nitrogen occurs in oxidation states from N(‐III) to N(V);
molecular oxygen is the main electron acceptor; nitrate, and sulfate are electron acceptors when
oxygen supply is low.
Soil Components
B. Inorganic Components
• Inorganic solids in soils comprise mixtures of various types of minerals existing as rocks, sand,
silt, and clays. The inorganic components of soils represent more than 90% of the solid
components that include both primary and secondary minerals which range in size (particle
diameter) from clay-sized colloids (<0.002mm) to gravel (>2 mm) and rocks.

• Primary minerals - occur primarily in the sand (2–0.05mm particle diameter) and silt (0.05–
0.002mm particle diameter) fractions of soils but may be found in slightly weathered clay-
sized fractions

• Secondary minerals - resulting from the weathering of a primary mineral; either by an

alteration in the structure or from reprecipitation of the products of weathering (dissolution) of
a primary mineral. The secondary minerals are primarily found in the clay fraction of the soil
but can also be located in the silt fraction
Soil Components
Common primary and secondary minerals in soils
Soil Components
C. Organic Components
SOM (soil organic matter) are fractions of organic material and the products in the stages of its degradation. SOM consists of
nonhumic and humic substances.

• Non-humic substances - have recognizable physical and chemical properties which include carbohydrates, lipids (fatty acid,
fat, waxes, resins) and amino acids.
• Humic substance - display a complex chemical structure with high molecular weight, have hydrophilic character and acid
properties.

SOM contents range from 0.5% to 5% on a weight basis in the surface horizon of mineral soils to 100% in organic soils. It improves
soil structure, water-holding capacity, aeration, and aggregation. The main constituents of SOM are C (52–58%), O (34–39%), H
(3.3–4.8%), and N (3.7–4.1%). Other prominent elements in SOM are P and S. SOM has a high specific surface (as great as 800–900
m2 g–1) and a cation exchange capacity (CEC) that ranges from 150 to 300 cmol kg–1. Due to the high specific surface and CEC of
SOM, it is an important sorbent of plant macronutrients and micronutrients, heavy metal cations, and organic materials such as
pesticides.

The accumulation rate of SOM is usually rapid initially, declines slowly, and reaches an equilibrium level varying from 110 years
for fine-textured parent material to as high as 1500 years for sandy materials
Reaction Processes in Soil
Comprehensive view of the six reactions in a soil
system
Reaction Processes in Soil
A. Sorption/Desorption
Sorption and desorption reactions describe association and
release of a chemical from a particle (minerals, SOM, or a
biological cell surface). Often, sorption reactions are
termed adsorption, which implies accumulation of a
substance or material at an interface between the solid
surface and bulk solution, and is not forming a three-
dimensional network of atoms on the surface (called
surface precipitation). One example is the adsorption of a
sodium ion onto a clay mineral surface.
K⁺ + Na – clay ⟶Na⁺ + K - clay
The release of the potassium from the clay in the equation
is a desorption reaction. Together, the adsorption and
desorption reactions depicted in the equation are example
of a cation exchange reaction.
B. Precipitation/Dissolution
These reactions describe the change in a chemical from
solution to the solid state, where a new solid is formed
from solution constituents. Dissolution is the reverse of
precipitation, where ions from the solid are released to the
solution. An example of a precipitation–dissolution
reaction is the formation of the calcium carbonate mineral
calcite in soils:
CaCO₃ (s) + H⁺ ⇌ Ca²⁺ + HCO₃⁻
where the forward reaction is a dissolution reaction, and
the reverse is a precipitation reaction. Note in this reaction
the (s) is placed on the calcite to indicate that it is a solid
and not an aqueous complex while ions are in aqueous
phase.
Reaction Processes in Soil
C. Immobilization/Mineralization
Immobilization and mineralization reactions are generally
biologically mediated. Immobilization refers to the
uptake of chemical into the cellular structure of an
organism, such as a microbe, fungi, or plant. The chemical
within the organism is considered a biologically formed
molecule (biomolecule). An example is the uptake of
nitrate from soil solution into a plant, where it is utilized
as a cellular metabolite to produce amino acids, such as
glutamate (C5O4H6NH3), which are components of
proteins:
NO₃⁻ + N – reductase + C₅O₁H₉ = C₅O₄H₆NH₃
Mineralization implies degradation, release, or
conversion of a chemical to a form that is no longer a
biomolecule. Products of mineralization reactions are
inorganic chemicals and degraded organic chemicals.
Degradation of organic nitrogen in glutamate to
ammonium is an example of a mineralization reaction:
C₅O₄H₆NH₃ + 4H₂O + O₂=NH₄⁺ + 5CO₂ + 13H⁺
D. Complexation/Dissociation
These reactions describe interactions of two or more
chemicals or aqueous ions. Protonation and deprotonation
(gain and loss of H⁺ ions) are specific types of complexation
and dissociation involving acceptance and loss of a proton by
an acidic ion or molecule. Hydrolysis is a dissociation
reaction in which H+ is released from a water molecule.
Carboxylic acid, a common functional group on soil organic
matter, is a weak acid that deprotonates between
approximately pH 3 and 6:
R – COOH = R - COO⁻ + H⁺
Complexation reactions change the valence and molecular
properties of chemicals in soil solutions, thus changing the
chemical’s solubility, plant availability, and transport through
the soil. Aqueous complexation of ions occurs in soil solution
and changes the concentrations of free ions (noncomplexed
ions). For example, the inorganic ligand bicarbonate readily
forms aqueous complexes in solution with dissolved metal
cations:
Zn²⁺ + HCO₃⁻ = ZnHCO₃⁺
 Reaction Processes in Soil
E. Gas dissolution/Volatilization
Dissolution and volatilization of gases in soils refers to reactions
occurring between the soil atmosphere and the soil solution –
specifically, transfer of gaseous chemicals into the aqueous phase, and
the reverse. An example of gas dissolution in soil solution is the
reaction of carbon dioxide (gas) with water to form carbonic acid
(aqueous).
H₂O + CO₂ (g) = H₂CO₃ (aq)
Oxygen, nitrogen, and sulfur also have important gas dissolution and
volatilization reactions. Ammonium is a common ion in soil solution;
however, when it deprotonates, it forms ammonia that will volatilize:
NH₄⁺ (aq) = NH₃ (g) + H⁺ (aq)
The reverse reaction is used to dissolve ammonia gas (anhydrous
ammonia) into soil solution to produce ammonium ions for soil
fertilization. The reaction predicts that adding anhydrous ammonia to
soils would cause the pH of the soil solution to increase because the
ammonia would protonate to ammonium, thereby consuming protons;
or hydrolyzing water and releasing hydroxide ions.
F. Oxidation/Reduction
The gain and loss of electrons from an element
cause a change in oxidation state. Often, redox
reactions result in changes in the physical state or
molecular structure, and thus may be combined
with other reaction types. Many of the most
reactive redox environments are those that exist
at the interface between oxidized and reduced
zones (the redox interface).
At the redox interface, chemical and mineral
speciation is continuously changing. The redox
interface is influenced by fluxes of temperature,
water, nutrients, and gases through the soil.
Oxygen fluxes into and out of the soil system are
especially important because O₂ readily accepts
electrons in abiotic and biotic processes and is the
most common electron acceptor used for
metabolism.
Reaction Processes in Soil
F. Oxidation/Reduction

1. Electron donors in nature

In soils, carbon compounds in roots, microbes, dead plant matter, and SOM are the major
electron donors. The half‐reaction for the oxidation of theoretical soil organic matter is
C₂₂H₂₂O = 2.2C⁴⁺ + H₂O + 0.2H⁺ + 9e⁻

Inorganic electron donors in soils typically occur in much smaller amounts than organic
compounds, and include sulfide (S²⁻), sulfur (S⁰), Fe²⁺, Mn²⁺, and Mn³⁺, and ammonia (N³⁻).
Oxidation of inorganic chemicals can occur biotically or abiotically. Organisms (called
chemotrophs) can use electrons by oxidizing these elements. Nitrification is an example of
an important soil process in which the chemotrophic microbes utilize the electrons in
ammonia as an energy source.

Oxidation by Nitrosomonas bacteria

Oxidation by Nitrobacter
Nitrification reaction
Reaction Processes in Soil
F. Oxidation/Reduction

2. Electron acceptors in nature

In soils, O₂ diffuses through pores to plant roots and soil microbes,
where it can be utilized as a terminal electron acceptor (TEA). Soils
and waters that have available O₂ are called oxic while soils that
have no available O₂ are called anoxic. When O₂ availability is low,
soil microorganisms utilize the oxidized states of nitrogen, sulfur,
iron, manganese, and other elements as TEAs. The general order of
preference for TEAs based on energy produced is:
O₂ > NO₃⁻ > Mn⁴⁺ > Mn³⁺ > Fe³⁺ > SO₄²⁻ > CO₂ > H⁺ Correlation of soil redox potential with change in TEA,
water, O2, metabolism and redox status category
The exact order varies, depending on the species of the electron
acceptors and environmental conditions. In addition, pH is a major The most common secondary electron acceptors in soils
environmental factor that influences the relative order of the include iron and manganese oxides, sulfate, and oxidized
preference for TEAs. forms of nitrogen. Reducing half‐reactions for these
species are:
Soil Acidity
Approximately 30% of Earth’s soils are
acidic. Soil acidification can be
detrimental for agriculture because it
decreases availability of anionic
nutrients, causes cationic nutrients to be
leached from the soil profile, and causes
Al3+ and Mn2+ toxicity. Forest soils and
wetland soils are often naturally acidic.
pH, the negative logarithm of the activity
of hydrogen cations in a solution, affects
speciation and availability of many
chemicals in soils and is often considered
the master variable for characterizing
soil chemical behavior. The soil-pH scale
Soil Acidity
A. Soil acidification
- occurs when acids are added to soils, or bases are Process Net Reaction
lost.
Carbon Cycle
- Soil acidification is a continuum of reactions and Organic acid production (SOM) 𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝐶 ⟶ 𝑅 − 𝐶𝑂𝑂𝐻 ⟶ 𝑅 − 𝐶𝑂𝑂− + 𝑯+
include natural fluxes and human‐caused fluxes
Degradation of organic acid (decarboxylation) 𝑅 − 𝐶𝑂𝑂 − + 𝑯+ ⟶ 𝑅𝐻 + 𝐶𝑂2 (𝑔)
to the soil that cause net changes in the active,
exchangeable, and reserve acidity components. Nitrogen Cycle

- Organic N mineralization (ammonification) 𝑅 − 𝑁𝐻2 + 𝑯+ + 𝐻2 𝑂 ⟶ 𝑅 − 𝑂𝐻 + 𝑁𝐻4+

Reactions important for soil acidification are
classified as either net proton sources to soil Nitrification 𝑁𝐻4+ + 2𝑂2 ⟶ 𝑁𝑂3− + 𝐻2 𝑂 + 2𝑯+
solution or net proton sinks that remove protons
from soil solution.
Soil Acidity
B. Sources of soil acidity
Soil acidity sources are acid rain, agronomic practices, and mine spoil and acid sulfate soils

Acid rain - can cause leaching of nutrient cations such as Ca²⁺, Mg²⁺, and K⁺ from the soil, resulting
in low pH and the solubilization of toxic metals such as Al³⁺ and Mn²⁺

Agronomic practices - the amount of soil acidification that occurs is significantly higher than that
occurring from acid rain

Mine spoil and acid sulfate soils - have very low pH due to the oxidation of pyrite. Mine spoil soils
are common in surface-mined coal areas, and acid sulfate soils occur in marine flood plains in
temperate and tropical areas.

The complete oxidation of pyrite (FeS₂) produce sulfuric acid.

Acidity from rain
Acidity from agronomic practices (fertilizer application)

Acidity from surface-mine coal areas

Soil Acidity
C. Forms of Soil Acidity
The main form of acidity in mineral soils are associated with Al, which can be
exchangeable/extractable, nonexchangeable, or precipitated as an array of solid phases such as
gibbsite, or nordstrandite

EXCHANGABLE ACIDITY - is the amount of the total cation exchange capacity (CEC) due to H+
and primarily Al³⁺.
- As a proportion of the total acidity its quantity depends on the type of soil and the percentage of
the CEC composed of exchangeable bases such as Ca²⁺, Mg²⁺, K⁺, and Na⁺, or the percentage base
saturation.

NONEXCHANGABLE ACIDITY - Extractable acidity – Exchange acidity The pH-dependent acidity

was estimated by the following equation pH-dependent acidity = Total potential acidity –
Exchangeable acidity.

PRECIPITATED ACIDITY – Refers to the type of soil acidity that occurs when certain minerals n the
soil reacts with the acid in the environment to form insoluble compound. These compounds can be
precipitate, or settle out of solution, creating an acidic layer of soil.
Soil Acidity
D. Measurement of Soil Acidity
1. H+ activity of aqueous solutions is measured using either a pH probe or colorimetric analysis. It is
important to note the pH measurement method used when measuring soil pH.

2. The concentration of base cations in soil solutions is an indirect measure of the ability of a solution to
neutralize acid, which is equivalent to a solution’s alkalinity or acid neutralization capacity. The
relationship between base cations and soil acidity and alkalinity is complex, and involves both solution
and solid phase reactions.
2.1 Exchangeable base cations
When base cations are removed from solution by precipitation, absorption by plants and microbes, or
leaching, the lost base cations are replenished by desorption of base cations from the soil’s exchangeable base
cations. The presence or absence of base cations on exchange sites greatly influences exchangeable acidity.
The percent of exchange sites occupied by exchangeable base cations is the percent base‐cation saturation
(%BS):
%BS =

[XM⁺] – concentration of base cation (M⁺) on the exchange site (X)

CEC – cation exchange capacity
Soil Acidity
D. Measurement of Soil Acidity

Learning activity: A soil of pH 5 may have 5 mmol(+) k⁻¹ of exchangeable bases (Ca²⁺, Mg²⁺, K⁺, and Na⁺), and
mmol(+) kg⁻¹ of exchangeable acidity for a total cation exchange capacity of 6 mmol(+).

The %BS at pH 5 is

% 𝐵𝑆 ( 𝑝𝐻 5 )=5𝑚𝑚𝑜𝑙¿¿
At pH 7 the CEC is 8 mmol(+) kg⁻¹, the %BS at pH 7 is

% 𝐵𝑆 ( 𝑝𝐻 7 )=5𝑚𝑚𝑜𝑙¿¿
Soil Acidity
D. Measurement of Soil Acidity

2.2 Total exchangeable acidity

Total exchangeable acidity (TEA) is defined as the amount of exchangeable H⁺ and Al³⁺, measured in mmol(+) kg⁻¹
soil:

where [Al³⁺] and [H⁺] are the concentrations of aluminum and hydrogen ions
BS is the fraction of base saturated cation on the ion exchange sites (%BS/100).
Soil Acidity
E. Managing Acidic Soils (Liming Soils)
Aqueous solution pH measurements represent the activity of hydronium ions (H₃O⁺), and not the H⁺ ion activity.
Protons are very reactive and have extremely low activity in aqueous solution.

An important effect of lime is to provide hydroxyl ions that convert exchangeable Al3+ to Al(OH)3 (gibbsite).
Increased quantities of soluble and exchangeable Ca²⁺ and Mg²⁺ are byproducts of liming, which serve to displace
exchangeable acidity, and may be beneficial to plants, such as legumes, having high calcium requirements.

Dissolution of feldspar
Precipitation for kaolinite
Weathering reaction

The calculation of CaCO₃ lime required from a titration is based on production of two hydroxide ions per mole of
CaCO₃:
Soil Acidity
E. Managing Acidic Soils (Liming Soils)

Learning Activity: If a soil titration, indicates that 2.0 mmol of OH⁻ is consumed per 100 g of soil for each unit
increase in pH, then 5 Mg CaCO₃ per ha (30 cm) is required for every unit increase in pH desired. How much CaCO₃
is needed to increase the pH?

This is the apparent lime‐based buffer capacity (BC) of the soil, which is the amount of lime required to add to soil per
pH‐unit increase.

Corrections for actual density of the soil, and type of amendment are required for accurate predictions of buffer
capacity of a given soil. The lime requirement (LR), in Mg ha⁻¹ is calculated using the soil buffer capacity:

pHoptimal is the soil pH required for the specified cropping system

pHcurrent is the pH of the topsoil

BC is the calculated buffer capacity of the soil

Soil Acidity
E. Managing Acidic Soils (Liming Soils)

Learning Activity: A pH change of 0.1 unit from the initial buffer pH might correspond to 1 Mg limestone ha⁻¹, which
corresponds to a rate of 10 Mg limestone ha⁻¹ for a full unit pH change of the buffer (1 Mg ha⁻¹ × 10). If a soil has an
initial pH of 5.5, the buffer solution has an initial pH of 6.8, and the final mixture has a pH of 6.3 (pHdesired – pHbuffer =
0.5). What lime requirement for this soil?
Soil Salinity
- Soil salinity is the salt content in the soil; the process of increasing the salt content is
known as salinization
- Includes soluble salts in soil water and salt solids in the soil.
- Soil salinity and sodicity can have a major effect on the structure of soils.

A. Sources of Soluble Salts

The major sources of soluble salts in soils are weathering of primary minerals and native
rocks, residual fossil salts, atmospheric deposition, saline irrigation and drainage waters,
saline groundwater, seawater intrusion, additions of inorganic and organic fertilizers, sludges
and sewage effluents, brines from natural salt deposits, and brines from oil and gas fields and
mining.

B. Characterization of Salinity of Soil and Water

- The parameters determined to characterize salt-affected soils depend primarily on the

concentrations of salts in the soil solution and the amount of exchangeable Na⁺ on the soil
(sodicity). Exchangeable Na⁺ is determined by exchanging the Na⁺ from the soil with
another ion such as Ca²⁺ and then measuring the Na+ in solution by flame photometry or
spectrometry.
Soil Salinity
B. Characterization of Salinity of Soil and Water
1. Sodium adsorption ratio (SAR)
Cation exchange selectivity equations are used to predict the distribution of Na⁺, Ca²⁺, and Mg²⁺ on the exchange sites. The
Gapon exchange equation is the most commonly used cation exchange selectivity equation used to evaluate soil salinity
because it is relatively simple and has been shown to be accurate for many salt‐affected soils. The Gapon formulation of the
Na⁺ – Ca²⁺ exchange reaction is

The Gapon exchange constant for this reaction is

where brackets on aqueous species indicate concentrations (mol L −1 or mmol L−1), and exchanger phase concentrations are
equivalent cation charge (mol(+) kg−1 or mmol(+) kg−1). The range of KG is typically 0.008 to 0.016 mmol−1/2 L1/2 for alkali
soils; a value of 0.015 is commonly used for soils with ESR < 30. If K G is known, the Gapon equation can be used to predict
the distribution of Na+ and Ca2+ between the solid and solution.
Soil Salinity
B. Characterization of Salinity of Soil and Water
1. Sodium adsorption ratio (SAR)

The presence of Mg2+in most alkaline soil solutions complicates prediction because the ternary Na+ - Ca2+- Mg2+
exchange-reaction equilibrium state requires a more complex model than the Gapon equation. To simplify the calculation
of Na+, Ca2+, and Mg2+ on the soil particles, the exchange behavior of Ca2+ and Mg2+ is assumed to be similar. Thus,

Exchanger phase Solution phase

This equation allows prediction of the relative distribution of Na + on soil’s exchange sites using the concentrations of Na +,
Mg2+, and Ca2+ in solution and KG as defined above. The ratio of the solution composition is called the sodium adsorption
ratio (SAR):
Soil Salinity
B. Characterization of Salinity of Soil and Water
2. Exchangeable sodium percentage (ESP)
The sodium concentration on the exchange sites can be directly measured, and is typically reported as the exchangeable sodium percentage
(ESP), which is based on the total Ca2+, Mg2+, and Na+ cation charge occupation:

where solid‐phase concentrations are in units of charge per mass (mmol(+) kg −1). In a system where Na+, Mg2+, and Ca2+ are the main cations,
the denominator is equal to the cation exchange capacity

this relationship is useful because it relates the amount of Na + on the exchange site to CEC, a commonly reported soil parameter. If ESP values
are above 30%, the exchangeable sodium ratio (ESR) can be used to predict ESP:

As shown, ESR can be predicted from solution composition (SAR) and an exchange coefficient (K G). Thus,
Soil Salinity
B. Characterization of Salinity of Soil and Water
2. Exchangeable sodium percentage (ESP)

Learning Activity: An irrigation water will be used to irrigate field of citrus, which has high sensitivity for sodium
damage. Thus, the farmer desires to maintain soil ESP as low as possible. The irrigation water contains 2.08 mmol L−1 of
Ca2+, 0.71 mmol L−1 of Mg2+, 5.96 mmol L−1 of Na+. Assuming a KG of 0.015 and that the soil pore water will have the
same composition as the irrigation water, the ESP can be calculated from the SAR and ESR:
Soil Salinity
B. Characterization of Salinity of Soil and Water
3. Total dissolved solids
The TDS are determined by evaporating a known volume of water to dryness and the solids residue remaining
are weighed. However, this measurement is variable since in a particular sample various salts exist in varying
hydration states, depending on the amount of drying. The presence of hygroscopic water in the resultant salt
mixtures causes TDS values to strongly depend on the drying conditions and the salt type.TDS is a useful parameter
for measuring the osmotic potential, –τo, an index of the salt tolerance of crops. For irrigation waters in the range of
5-1000 mg L–1 TDS, the relationship between OP and TDS is

The TDS (in mg L–1) can also be estimated by measuring an extremely important salinity index, EC, to determine
the effects of salts on plant growth. The TDS may be estimated by multiplying EC (dS m –1) by 640 (for EC between
0.1 and 5.0 dS m–1) for lesser saline soils and a factor of 800 (for EC > 5.0 dS m –1) for hypersaline samples. To obtain
the total concentration of soluble cations (TSC) or total concentration of soluble anions (TSA), EC (dS m–1) is usually
multiplied by a factor of 0.1 for mol L–1 and a factor of 10 for mmol L–1.
Soil Salinity
B. Characterization of Salinity of Soil and Water
4. Electrical conductivity (EC)

Marion and Babcock (1976) developed a relationship between EC w (dS m–1) to total soluble salt concentration (TSS in
mmol L–1) and ionic concentration (C in mmol L–1), where C is corrected for ion pairs. If there is no ion complexation, TSS
= C. The equations of Marion and Babcock (1976) are

This is applicable to 15 dS m –1, which covers the range of EC e and ECw for slightly to moderately saline soils. Griffin and Jurinak
(1973) also developed an empirical relationship between EC w and ionic strength (I) at 298 K that corrects for ion pairs and
complexes

where ECw is in dS m–1 at 298 K.

Soil Salinity
B. Characterization of Salinity of Soil and Water
4. Electrical conductivity (EC)

Salinity of a solution is directly related to its electrical conductivity (EC). The EC is based on the concept that the
electrical current carried by a salt solution under standard conditions increases as the salt concentration of the solution
increases. A number of EC values can be expressed according to the method employed: EC e, the EC of the extract of a
saturated paste of a soil sample; ECp, the EC of the soil paste itself; ECw, the EC of a soil solution or water sample; and
ECa, the EC of the bulk field soil. The EC and temperature of the extract are measured using conductance meters/cells
and thermometers and EC298 is calculated using below equation:

where ft is a temperature coefficient that can be determined from the relation and t is the temperature at which the
experimental measurement is made in degrees Kelvin.
Soil Salinity
B. Characterization of Salinity of Soil and Water
4. Electrical conductivity (EC)

To measure the EC of a solution, it is placed between two electrodes of constant geometry separated by a known
distance. An electrical potential is applied across the electrodes, and the resistance (R) of the solution between the
electrodes is measured. The electrical current varies directly with the total concentration of dissolved salts (ions in
solution). The resistance of a conducting material (e.g., a salt solution) is inversely proportional to the cross-sectional
area (A) and directly proportional to the length (L) of the conductivity cell that holds the sample and the electrodes.
Specific resistance (Rs) is the resistance of a cube of a sample volume 1 cm on edge. Since most commercial conductivity
cells are not this large, only a portion of Rs is measured. This fraction is the cell constant (K = R/Rs). The reciprocal of
resistance is conductance (C). It is expressed in reciprocal ohms or siemens (formerly mhos). When the cell constant is
included, the conductance is converted, at the temperature of the measurement, to specific conductance or the reciprocal
of the specific resistance. The EC of the saturation extract of the soil measures the soil’s salinity, and the EC of irrigation
water measures the water’s salinity. The specific conductance is the EC, expressed as
Soil Salinity
B. Characterization of Salinity of Soil and Water
4. Electrical conductivity (EC)

Learning Activity: Calibration might yield a cell constant of 2.0 cm −1; a test solution measuring 2000 Ω resistance
(conductance of 1/2000 Ω−1 or 0.0005 siemens) has a conductivity of

For soil extracts in the EC range from 3 to 30 dS m−1, the osmotic potential (OP) is
Soil Salinity
B. Characterization of Salinity of Soil and Water
The traditional classification of salt‐affected soils uses soluble salt concentrations or electrical conductivities of extracted
soil solutions, and the ESP of the soil. The EC dividing line for most plants between saline and non-saline soils was
established at 4 dS m−1 for water extracts from saturated soil pastes. Salt‐sensitive plants, however, can be affected in soil
with saturation extract ECs of 2 to 4 dS m−1. The relationships of soil salinity parameters to EC, SAR, and ESP are shown in
below figure.

Classification of soil salinity and sodicity in relation to EC, SAR, ESP, and pH (Source: DG Strawn et al. 2019)