Unit IV.C Soil Discussion

Republic of the Philippines
CAGAYAN STATE UNIVERSITY

Carig Campus, Tuguegarao City
College of Engineering
Course CHEM111E (Chemistry for Engineers)

Title of the
Unit IV. The Chemistry of the Environment – Soil Chemistry
Module
At the end of this module, the student shall be able:
Learning a. To determine the different components of soil.
Objectives b. To distinguish the chemical reactions in the soil system.
c. To characterize the soil by its acidity and salinity.
I. Introduction
II. Soil Components
Content 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. The interaction of Earth’s subsystems within soil
results in a mixture of solid, liquid, gas, and biota, called the pedosphere.
Soil is a complex mixture of inorganic and organic solids, air, water, solutes, microorganisms, plant, and other
types of biota that influence each other. Air and water weather rocks to form soil minerals and release ions;
microorganisms catalyze many soil weathering reactions; and plant roots absorb and exude inorganic and organic
chemicals that change the distribution and solubility of ions. 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.
Units of Soil Chemistry

Table 1. 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
Millimoles charge per kilogram 1 mol(+)•kg-1 = 10 mmol(+)•kg-1 = 1 cmol•kg-1
Cation exchange capacity
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
Chemical Engineering Department Module 1: Page 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.
Figure 1. Percent mass composition of elements is soil. (Source: DG Strawn, 2019)
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. Boron and selenium are micronutrient in soils that has
a narrow range between deficiency and toxicity essential for plant and animal, respectively. Some micronutrients
are only needed for animals, and not in plants. Most plant nutrients are also nutrients for animals. However,
animals require some micronutrients that plants do not.
Most essential elements are present as ions in the soil solution, and flow into the plant as it absorbs water.
Plants obtain hydrogen, carbon, and oxygen from air, but soils have pore space for O 2 and CO2 movement between
plant roots and the atmosphere, and supply CO 2 to the atmosphere through the decay of organic matter by soil
microorganisms. Animals derive most of their essential elements from plants. The ability of plants to supply these
elements to animals depends on a combination of factors: availability of the ions in the soil solution, plant
selectivity at the soil solution–root interface, and ion translocation from root to plant top. Animals have evolved
in the presence of soils and plants, and thus do not typically suffer microelement deficiencies. However, essential
elements in natural systems are occasionally too high or too low for animals because plants can tolerate a much
wider range of elemental concentrations than animals.
Figure 2. Periodic table of elements, not including lanthanides and actinide, showing nutrients and common contaminants.
(Source: DG Strawn, 2019)

The elements of primary interest for soil chemistry exhibit a wide range of chemical behavior that causes
highly varied mobility and bioavailability. The elements of common interest are grouped, as shown in Table 2,
according to general chemical properties and reactivity in soil.
Table 2. 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.
Ca2+, Mg2+, Na+, K+, NH4+, Al3+ It occur as 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.
Soluble anions They are present in lower concentrations than the major cations except in
NO3 –, SO42–, Cl–, coarse‐textured and strongly saline soils; sulfate and nitrate are important
H2CO3, HCO3 –, nutrient sources for plants; sulfate, chloride, and bicarbonate salts accumulate
Se6+ as SeO42– in saline and alkaline soils; selenite (SeO42–) anion is more soluble than
selenite (SeO32–).
Poorly soluble anions They are strongly retained by soils and present at low concentrations in soil
H2PO4 –, HPO42–, H3BO3, H4BO4 –, solution (typically <10–5 M). It often occur as minerals, salts, or sorbed to
Si(OH)4, MoO42–, Se4+ as HSeO3 – mineral surfaces; borates are the most 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
Al3+, Cu2+, Zn2+, Ni2+, Co2+ alkaline earth cations. As silica and other ions leach during weathering,
Fe(OH)2 +, Fe2+, Fe3+, insoluble hydroxides accumulate in soils; iron and manganese are more
Mn4+, Mn3+ Mn2+ soluble in waterlogged or reduced soils; availability increases with 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
Al3+, not readily soluble; Al3+ is a hazard to plants, the others are of more concern
As(V): H2AsO4 –, HAsO42– to animals; Cd2+ is relatively available to plants; As and Cr oxyanions increase
As(III): H2AsO3 –, HAsO32– in solubility with pH; As(III) is more soluble than As(V); cation contaminants
Cr(VI): CrO42– are less available to plants with increasing pH; many contaminants form
Cd2+, Hg2+, Pb2+ poorly soluble sulfides in reduced soils.
Biogeochemical cycling elements These elements are primarily produced by plants, fixation by microbes, and
C4– to C4+ (CH4 to CO2) microbial driven mineralization. Soil biochemistry revolves around the
N3– to N5+ (NH4+, N2, NO2, NO3–) oxidation state changes of soil carbon, nitrogen, and sulfur compounds;
O2–, O2 nitrogen occurs in oxidation states from N(‐III) to N(V); molecular oxygen is
S2– to S6+ (H2S to SO42–) the main electron acceptor; nitrate, and sulfate are electron acceptors when
oxygen supply is low.
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. A mineral can be defined as a natural inorganic compound with definite physical, chemical,
and crystalline properties. A primary mineral is one that has not been altered chemically since its deposition and
crystallization from molten lava. 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. A secondary mineral is one 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.

Table 3. Common primary and secondary minerals in soils (Source: DL Sparks, 2003)
C. Organic Components
There is no unique structure to soil organic matter (SOM). SOM 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. While 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 quantity of SOM in a soil depends on the five soil-forming factors: time, climate, vegetation, parent
material, and topography. These factors vary for different soils, and thus SOM accumulates at different rates and,
therefore, in varying quantities. 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. The equilibrium level is attributed to organic acids that are produced which are resistant to
microbial attack, the stability of humus due to its interactions with polyvalent cations and clays, and low amounts
of one or more essential nutrients such as N, P, and S which limit the quantity of stable humus that can be
synthesized by soil organisms.
Reaction Processes in Soil

The figure below, Figure 3, is a comprehensive view of the six reactions in a soil system. The soil chemical
may change via one of these reactions to re-establish equilibrium. The properties such as soil pH, microbial
activity, soil pore space, mineral composition, organic matter composition, chemical concentration, and soil
texture influence the reactivity and speciation of chemicals in soils.
The reactivity of soils greatly influences the composition of the soil solution. Ion availability in solution is
renewed by soil reactions that add ions back to the soil solution after they are depleted. Main sources of ions to
soil solution are mineral weathering, organic matter decay, rain, irrigation waters, fertilization, and release of ions
adsorbed by clays and organic matter in soils. Reaction processes in soil includes sorption/desorption,

precipitation/dissolution, immobilization/mineralization, complexation/dissociation, gas

dissolution/volatilization, and oxidation/reduction.
Figure 3. Chemical reactions in soil (Source: DG Strawn et al. 2019)
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.
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 + 𝐶5 𝑂1 𝐻9 = 𝐶5 𝑂4 𝐻6 𝑁𝐻3
In this reaction, the C5O1H9 is simply an element placeholder for cellular compounds to provide the reactants
needed for the stoichiometry to balance and does not represent a molecular species in the cell.

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:
𝐶5 𝑂4 𝐻6 𝑁𝐻3 + 4𝐻2 𝑂 + 𝑂2 = 𝑁𝐻4+ + 5𝐶𝑂2 + 13𝐻 +
This is a summary reaction describing complete degradation of the glutamate biomolecule produced in the
previous reaction to produce ammonium, carbon dioxide, and protons. The reaction is carried out by microbes in
soils.
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 +
The R indicates the rest of the organic compound that the carboxylic acid functional group is attached. The acidity
of the carboxylic acid functional group depends on the composition of the rest of the organic molecule.
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+
The ZnHCO3+ aqueous complex would occur in the soil solution instead of the free hydrated Zn 2+ ion.
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. Since this
reaction involves movement of gas into and out of liquid water, it is different from condensation and vaporization
of a pure liquid to gas, and vice versa. An example of gas dissolution in soil solution is the reaction of carbon
dioxide (gas) with water to form carbonic acid (aqueous).
𝐻2 𝑂 + 𝐶𝑂2 (𝑔) = 𝐻2 𝐶𝑂3 (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 O 2 readily accepts electrons in abiotic and biotic
processes and is the most common electron acceptor used for metabolism.
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
𝐶22 𝐻22 𝑂 = 2.2𝐶 4+ + 𝐻2 𝑂 + 0.2𝐻 + + 9𝑒 −
The reaction proposes that nine electrons come from oxidizing one mole of SOM to CO2 (C4+). This
reaction is facilitated by microorganisms and other organisms (e.g. earthworms), who use the oxidation
reaction to obtain electrons for respiration. SOM also contains amino (‐NH2) and sulfhydryl (-SH) groups,
which are also electron donors.
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.
𝑁𝐻4+ + 2𝐻2 𝑂 = 𝑁𝑂2− + 8𝐻 + + 6𝑒 − Oxidation by Nitrosomonas bacteria

𝑁𝑂2− + 𝐻2 𝑂 = 𝑁𝑂3− + 2𝐻 + + 2𝑒 − Oxidation by Nitrobacter
𝑁𝐻4+ + 2𝑂2 = 𝑁𝑂3− + 𝐻2 𝑂 + 2𝐻 + Nitrification reaction
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+ > 𝐹𝑒 3+ > 𝑆𝑂42− > 𝐶𝑂2 > 𝐻 +
The exact order varies, depending on the species of the electron acceptors and environmental conditions.
In addition, pH is a major environmental factor that influences the relative order of the preference for TEAs.
Figure 4. Correlation of soil redox potential with change in TEA, water, O2, metabolism and redox status category
(Source: DG Strawn et al. 2019)

The most common secondary electron acceptors in soils include iron and manganese oxides, sulfate, and
oxidized forms of nitrogen. Reducing half‐reactions for these species are
𝐹𝑒𝑂𝑂𝐻(𝑠) + 𝑒 − + 3𝐻 + = 𝐹𝑒 2+ (𝑎𝑞) + 2𝐻2 𝑂
2𝑀𝑛𝑂1.75 (𝑠) + 3𝑒 − + 7𝐻 + = 2𝑀𝑛2+ (𝑎𝑞) + 3.5𝐻2 𝑂
𝑆𝑂42− (𝑎𝑞) + 8𝑒 − + 8𝐻 + = 𝑆 2− (𝑎𝑞) + 4𝐻2 𝑂
𝑁𝑂3− (𝑎𝑞) + 2𝑒 − + 2𝐻 + = 𝑁𝑂2− (𝑎𝑞) + 𝐻2 𝑂
2𝑁𝑂3− (𝑎𝑞) + 8𝑒 − + 10𝐻 + = 𝑁2 𝑂(𝑔) + 5𝐻2 𝑂
2𝑁𝑂3− (𝑎𝑞) + 10𝑒 − + 12𝐻 + = 𝑁2 (𝑔) + 6𝐻2 𝑂
Reduction of secondary electron acceptors produces compounds that are unstable in the presence of
oxygen and convert back to the oxidized species through either abiotic or biotic processes. The accumulation
rate of SOM reflects the difference of the rates of organic matter addition vs. oxidation rates. The rate of
addition is equivalent to the rate of net photosynthesis. The oxidation rate is governed by temperature and by
the rate of oxygen supply. Spatial variation of O2 concentrations in soils provides zones of varying redox
conditions, or redox gradients, where microbial communities establish their own niches based on the
availability of TEAs.
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.
Figure 5. The soil-pH scale (Source: DG Strawn et al. 2019)
A. Soil acidification
Soil acidification occurs when acids are added to soils, or bases are lost. Soil acidification is a continuum of
reactions and include natural fluxes (e.g., weathering followed by leaching), and human‐caused fluxes to the soil
(fertilization and harvest) that cause net changes in the active, exchangeable, and reserve acidity components.
Fluxes alter the biogeochemical cycling of carbon, nitrogen, or sulfur by changing either their concentrations or

species. Reactions important for soil acidification are classified as either net proton sources to soil solution or net
proton sinks that remove protons from soil solution.
Process Net Reaction

Carbon Cycle
Organic acid production (SOM) 𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝐶 ⟶ 𝑅 − 𝐶𝑂𝑂𝐻 ⟶ 𝑅 − 𝐶𝑂𝑂− + 𝑯+
Degradation of organic acid (decarboxylation) 𝑅 − 𝐶𝑂𝑂− + 𝑯+ ⟶ 𝑅𝐻 + 𝐶𝑂2 (𝑔)
Nitrogen Cycle
Organic N mineralization (ammonification) 𝑅 − 𝑁𝐻2 + 𝑯+ + 𝐻2 𝑂 ⟶ 𝑅 − 𝑂𝐻 + 𝑁𝐻4+
Nitrification 𝑁𝐻4+ + 2𝑂2 ⟶ 𝑁𝑂3− + 𝐻2 𝑂 + 2𝑯+
B. Sources of soil acidity

Soil acidity sources are acid rain, agronomic practices, and mine spoil and acid sulfate soils. Acid vapors,
primarily sulfuric (H2SO4) and nitric (HNO3), form in the atmosphere as a result of the emission of sulfur dioxide
(SO2) and nitrogen oxides from natural and anthropogenic sources such as burning of fossil fuels (source of sulfur
gases) and the exhaust from motor vehicles (source of nitrogen oxides). 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+. This can cause reduced soil biological activity such as ammonification (conversion of NH 4+ to
NO3–) and reduced fixation of atmospheric N2 by leguminous plants and can also reduce nutrient cycling.
In most cases, the amount of soil acidification that occurs naturally or results from agronomic practices is
significantly higher than that occurring from acid rain. For example, if one assumes annual fertilizer application
rates of 50–200 kg N ha–1 to soils being cropped, soil acidification from the fertilizer would be 4–16 times greater
than acidification from acid rain in highly industrialized areas. However, on poorly buffered soils, such as many
sandy soils, acid rain could increase their acidity over time.
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.
𝐻2 𝑆𝑂4 ⟶ 2𝐻 + + 𝑆𝑂42− Acidity from rain
𝑁𝐻4+ + 2𝑂2 ⟶ 𝑁𝑂3− + 𝐻2 𝑂 + 2𝐻 + Acidity from agronomic practices (fertilizer application)
15 7
𝐹𝑒𝑆2 + 𝑂2 + 𝐻2 𝑂 ⟶ 𝐹𝑒(𝑂𝐻)3 + 2𝐻2 𝑆𝑂4 Acidity from surface-mine coal areas
4 2
The high concentrations of sulfuric acid cause pH as low as 2 in mine spoil soils and <4 in acid sulfate soils.
C. Forms of Soil Acidity

The extreme acid produced moves into drainage and floodwaters, corrodes steel and concrete, and causes
dissolution of clay minerals, releasing soluble Al. 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. Only in acidic soils with a pH < 4 and in soils high in organic matter does one find
major quantities of exchangeable H+.
Exchangeable 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 (e.g., type and quantity of soil
components) and the percentage of the CEC composed of exchangeable bases such as Ca 2+, Mg2+, K+, and Na+,
or the percentage base saturation. Aluminum oxides appear to be more effective in reducing the quantity of
exchangeable acidity than iron oxides.

D. Measurement of Soil Acidity

1. H+ activity of aqueous solutions is measured using either a pH probe or colorimetric analysis. In the
laboratory, soil pH measurement methods use different ratios of soil and solution, and different soil‐wetting
solutions (salt or deionized water), all of which may affect the measured pH. Thus, 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. Soils with high
concentrations of base cations are typically alkaline. Fluxes of base cations into a soil create alkalinity, and
fluxes out of a soil are associated with soil acidification. 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):
2 × [𝑋𝐶𝑎2+ ] + [𝑋𝑁𝑎 + ] + 2 × [𝑋𝑀𝑔2+ ] + [𝑋𝐾 + ]
%𝐵𝑆 =
𝐶𝐸𝐶
where [XM+] indicates the concentration of base cation (M+) on the exchange site (X), and CEC is the
cation exchange capacity. The pH used for CEC measurement must be specified because CEC increases
with pH. The denominator includes any additional charge (CEC) generated by SOM and oxide‐mineral
complexes between the initial soil pH and the reference pH (7 or 8.2) that the CEC is measured. Since
neither exchangeable Al3+ nor exchangeable H+ is appreciable above pH 5.5, the CEC above this pH
should be 100% base saturated. However, % BS in soils in the pH range 5.5 to 8.2 are often well below
100%. %BS is useful for soil classification purposes, and for empirical liming recommendations. From
the standpoint of soil chemical properties and reactions, %BS is considered an acidity index useful for
relative comparisons of soil pH and buffering properties.
Learning Activity: A soil of pH 5 may have 5 mmol(+) kg−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
5 𝑚𝑚𝑜𝑙(+)𝑘𝑔−1
%𝐵𝑆(𝑝𝐻5) = × 100 = 83%
At pH 7 the CEC is 8 mmol(+) kg−1, the %BS at pH 7 is

%𝐵𝑆(𝑝𝐻7) = × 100 = 63%
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:
3 × [𝐴𝑙 3+ ] + [𝐻 + ]
𝑇𝐸𝐴 = = 𝐶𝐸𝐶(1 − 𝐵𝑆)
𝐶𝐸𝐶

where [Al3+] and [H+] are the concentrations of aluminum and hydrogen ions, respectively. BS is the
fraction of base saturated cation on the ion exchange sites (%BS/100). For a given pH, CEC is fixed, thus
base saturation and TEA are inversely related. The exchangeable acidity represents the resupply capacity
of soil acidity. Soils with high %BS tend to have low TEA and are alkaline. Soils with low %BS tend to
have high TEA and are acidic.
E. Managing Acidic Soils (Liming Soils)

A major challenge for managing acidic soils is to estimate the quantity of lime required to raise the soil pH to
a certain level. Both exchangeable and titratable acidity will be neutralized during the slow titration. 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 Al 3+ 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. These
can be observed in weathering reaction in the formation of kaolinite and gibbsite.
𝐶𝑎𝐴𝑙2 𝑆𝑖2 𝑂8 + 8𝐻 + = 2𝐴𝑙3+ + 2𝐻4 𝑆𝑖𝑂4 + 𝐶𝑎2+ Dissolution of feldspar
2𝐴𝑙 3+ + 2𝐻4 𝑆𝑖𝑂4 + 𝐻2 𝑂 = 𝐴𝑙2 𝑆𝑖2 𝑂5 (𝑂𝐻)4 + 6𝐻 + Precipitation for kaolinite

𝐶𝑎𝐴𝑙2 𝑆𝑖2 𝑂8 + 2𝐻 + + 𝐻2 𝑂 = 𝐴𝑙2 𝑆𝑖2 𝑂5 (𝑂𝐻)4 + 𝐶𝑎2+ Weathering reaction
The calculation of CaCO3 lime required from a titration is based on production of two hydroxide ions per mole
of CaCO3:
𝐶𝑎𝐶𝑂3 + 𝐻2 𝑂 = 𝐶𝑎2+ + 𝐶𝑂2 (𝑔) + 2𝑂𝐻 −
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?
2𝑚𝑚𝑜𝑙 𝑂𝐻 − 1𝑚𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 100 𝑚𝑔 𝐶𝑎𝐶𝑂3 1 𝑀𝑔 4.5 × 109 𝑔 𝑠𝑜𝑖𝑙 𝑀𝑔 𝐶𝑎𝐶𝑂3

× −
× × 9
× = 5.0
100𝑔 𝑠𝑜𝑖𝑙 𝑢𝑛𝑖𝑡𝑝𝐻 2𝑚𝑚𝑜𝑙 𝑂𝐻 1 𝑚𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 1 × 10 𝑚𝑔 ℎ𝑎(30 𝑐𝑚) ℎ𝑎(30𝑐𝑚)𝑢𝑛𝑖𝑡 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. The calculation requires the density of the soil (assumed 4.5 × 109 g soil per ha(30
cm)), and assumes that pure CaCO3 that provides 2 mmol OH− per mmol CaCO3 is used as the lime amendment
(and that it completely dissolves). 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:
𝐿𝑅 = (𝑝𝐻𝑜𝑝𝑡𝑖𝑚𝑎𝑙 − 𝑝𝐻𝑐𝑢𝑟𝑟𝑒𝑛𝑡 )𝐵𝐶
where pHoptimal is the soil pH required for the specified cropping system, pHcurrent is the pH of the topsoil, and BC
is the calculated buffer capacity of the soil.
Acidity neutralization by field‐liming is typically incomplete because of incomplete mixing and slow reaction
times. The lime dissolution reaction rates vary inversely with pH, limestone particle size, and solubility of the
liming agent. Hence, the laboratory‐based lime requirement value is often further multiplied by a conversion factor
to better estimate the amount of lime needed to achieve a given field pH. Such a conversion factor is regionally
specific, and dependent on the type of lime. The usual procedure to estimate lime requirement is to add a pH buffer

solution to the soil, measure the amount of buffer consumed or the resulting pH of the soil‐buffer suspension, and
calibrate results with field‐lime requirements for similar soils from the same geographical area.
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?
10 𝑀𝑔 𝑙𝑖𝑚𝑒𝑠𝑡𝑜𝑛𝑒 𝑀𝑔 𝑙𝑖𝑚𝑒𝑠𝑡𝑜𝑛𝑒
× 0.5 𝑝𝐻 𝑢𝑛𝑖𝑡𝑠 = 5
𝑝𝐻 𝑢𝑛𝑖𝑡 ℎ𝑎 ℎ𝑎
Using a calibration curve from the titration of one soil can be used to estimate the lime requirements of other
soils from the same geographic region if soil texture and measurements of initial soil pH are incorporated in an
empirical model, but the predicted lime rates will be less precise.
Soil Salinity
Soil salinity 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. Soil structure, or the arrangement of soil particles, is critical in affecting
permeability and infiltration. Infiltration refers to the “downward entry of water into the soil through the soil
surface”. If a soil has high quantities of Na+ and the electric conductivity is low, soil permeability, hydraulic
conductivity, and the infiltration rate are decreased due to swelling and dispersion of clays and slaking of
aggregates. Typically, soil infiltration rates are initially high, if the soil is dry, and then they decrease until a steady
state is reached. Swelling causes the soil pores to become more narrow, and slaking reduces the number of
macropores through which water and solutes can flow, resulting in the plugging of pores by the dispersed clay.
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. As primary minerals in soils and exposed rocks weather the processes
of hydrolysis, hydration, oxidation, and carbonation occur and soluble salts are released. The primary source of
soluble salts is fossil salts derived from prior salt deposits or from entrapped solutions found in earlier marine
sediments.
B. Characterization of salinity in 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.
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
1
𝑁𝑎 + + 𝐶𝑎1/2 𝑋 = 𝑁𝑎𝑋 + 𝐶𝑎2+
2
The Gapon exchange constant for this reaction is

[𝑁𝑎𝑋][𝐶𝑎2+ ]1/2
𝐾𝐺 =
[𝐶𝑎1/2 𝑋][𝑁𝑎+ ]
[𝑁𝑎𝑋] [𝑁𝑎+ ]
= × 𝐾𝐺
[𝐶𝑎1/2 𝑋] [𝐶𝑎2+ ]1/2
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). This shows that the ratio of Na+ to
Ca2+ on the exchange sites (left‐hand side) is a function of the ratio of the cations in the aqueous solution
multiplied by the exchange selectivity coefficient (K G) (right‐hand side). 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. 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,
[𝑁𝑎𝑋] [𝑁𝑎+ ]
= × 𝐾𝐺
[𝐶𝑎1/2 𝑋] + [𝑀𝑔1/2 𝑋] ([𝐶𝑎2+ ] + [𝑀𝑔2+ ])1/2
Exchanger phase = Solution phase × 𝐾𝐺
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):
[𝑁𝑎+ ]
𝑆𝐴𝑅 =
([𝐶𝑎2+ ] + [𝑀𝑔2+ ])1/2
when the units of charge equivalent per volume (mmol(+) L−1) are used instead of molar concentrations, the
Ca2+ and Mg2+ concentrations in equation are divided by two. The units of SAR are mmol(+)1/2 L−1/2,. SAR is
a prediction of how sodicity of irrigation water will impact the behavior of soils irrigated with the 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:
[𝑁𝑎𝑋]
𝐸𝑆𝑃 = × 100
([𝐶𝑎1/2 𝑋] + [𝑀𝑔1/2 𝑋] + [𝑁𝑎𝑋])
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
[𝑁𝑎𝑋]
𝐸𝑆𝑃 = × 100
𝐶𝐸𝐶
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:
[𝑁𝑎𝑋]
𝐸𝑆𝑅 = × 100
([𝐶𝑎1/2 𝑋] + [𝑀𝑔1/2 𝑋])

As shown, ESR can be predicted from solution composition (SAR) and an exchange coefficient (K G). Thus,
𝐸𝑆𝑅
𝐸𝑆𝑃 = × 100
1 + 𝐸𝑆𝑅
this relationship allows ESP to be predicted from the SAR of irrigation water or saturated extract solution and
an exchange coefficient (substituting ESR with SAR and K G). Thus, exchangeable sodium percentage can be
computed from cation composition of an irrigation water or saturated paste extract.
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:
[𝑁𝑎+ ] 5.96
𝑆𝐴𝑅 = = = 3.6 𝑚𝑚𝑜𝑙(+)1/2 𝐿−1/2
([𝐶𝑎2+ ] + [𝑀𝑔2+ ])1/2 (2.08 + 0.71)1/2
𝐸𝑆𝑅 = 𝑆𝐴𝑅 × 𝐾𝐺 = 3.6 × 0.015 = 0.054
𝐸𝑆𝑅 0.054
𝐸𝑆𝑃 = × 100 = × 100 = 5.1%
1 + 𝐸𝑆𝑅 1 + 0.054
Thus, the ESP predicted from the irrigation water is relatively low and is suitable for irrigating the citrus crop.
3. Total dissolved solids

Early appraisals of the salinity of irrigation waters were in terms of amounts of total dissolved solids
(TDS). 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.
Concentrations of salts in most irrigation waters are less than 1000 mg L −1 TDS. Groundwater used for
irrigation is usually higher in TDS than surface waters. For comparison, TDS of seawater is about 35 000 mg
L−1. 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
−𝜏𝑜 = −5.6 × 10−4 × 𝑇𝐷𝑆 (𝑚𝑔 𝐿−1 )
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.
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 EC 298 is calculated using below equation:
𝐸𝐶298 = 𝐸𝐶𝑡 𝑓𝑡
where ft is a temperature coefficient that can be determined from the relation 𝑓𝑡 = 1 + 0.019(𝑡 − 298 𝐾)
and t is the temperature at which the experimental measurement is made in degrees Kelvin.
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
log 𝐶 = 0.955 + 1.039 𝑙𝑜𝑔 𝐸𝐶𝑤
log 𝑇𝑆𝑆 = 0.990 + 1.055 𝑙𝑜𝑔𝐸𝐶𝑤
This is applicable to 15 dS m–1, which covers the range of ECe 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
𝐼 = 0.0127 𝐸𝐶𝑤
where ECw is in dS m–1 at 298 K.
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
1 𝐾
𝐸𝐶 = =
𝑅𝑆 𝑅
The absolute value of the conductance in a solution is a result of the solution’s salt concentration and the
geometry of the electrode cell. The effects of electrode geometry are embodied in the cell constant, which is
related to the distance between electrodes and their cross‐sectional area.
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
2.0 10 𝑑𝑒𝑐𝑖𝑠𝑖𝑒𝑚𝑒𝑛𝑠 100 𝑐𝑚
𝐸𝐶 = 0.0005 𝑠𝑖𝑒𝑚𝑒𝑛𝑠 × × × = 1.0 𝑑𝑆 𝑚−1
𝑐𝑚 𝑠𝑖𝑒𝑚𝑒𝑛 𝑚
For soil extracts in the EC range from 3 to 30 dS m −1, the osmotic potential (OP) is
𝑂𝑃(𝑏𝑎𝑟𝑠) ≈ 𝐸𝐶(𝑑𝑆 𝑚−1 ) × −0.36
The osmotic pressure or osmotic potential measures the tendency of water to diffuse across a membrane
against a salinity gradient and indicates the effects of salinity on plant growth since plant roots are
semipermeable membranes (they allow water, but not salt to enter the roots).

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.
Figure 6. Classification of soil salinity and sodicity in relation to EC, SAR, ESP, and pH (Source: DG Strawn et al. 2019)
Self-Assessment Activities:
Give one method or treatment of soil decontamination and explain its advantage and limitation.
References:
Sparks, D.L. (2019). Fundamentals of Soil Chemistry. DOI 10.1002/9781119300762.wsts0025
Sparks, D.L. (2003). Environmental Soil Chemistry (2nd Ed.). Academic Press, UK. ISBN 0-12-656446-9
Strawn, D.G., Bohn, H.L., & O’Connor, G.A. (2020). Soil Chemistry (5th Ed.). John Wiley & Sons, Ltd., USA.
ISBN 9781119515159

Unit IV.C Soil Discussion

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Unit IV.C Soil Discussion

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Republic of the Philippines

CAGAYAN STATE UNIVERSITY

Course CHEM111E (Chemistry for Engineers)

Units of Soil Chemistry

Chemical Engineering Department Module 1: Page 1

Figure 1. Percent mass composition of elements is soil. (Source: DG Strawn, 2019)

Chemical Engineering Department Module 1: Page 2

Chemical Engineering Department Module 1: Page 3

Reaction Processes in Soil

Chemical Engineering Department Module 1: Page 4

precipitation/dissolution, immobilization/mineralization, complexation/dissociation, gas

Figure 3. Chemical reactions in soil (Source: DG Strawn et al. 2019)

Chemical Engineering Department Module 1: Page 5

Mineralization implies degradation, release, or conversion of a chemical to a form that is no longer a

Chemical Engineering Department Module 1: Page 6

1. Electron donors in nature

𝑁𝐻4+ + 2𝐻2 𝑂 = 𝑁𝑂2− + 8𝐻 + + 6𝑒 − Oxidation by Nitrosomonas bacteria

2. Electron acceptors in nature

Chemical Engineering Department Module 1: Page 7

Figure 5. The soil-pH scale (Source: DG Strawn et al. 2019)

Chemical Engineering Department Module 1: Page 8

Process Net Reaction

B. Sources of soil acidity

𝑁𝐻4+ + 2𝑂2 ⟶ 𝑁𝑂3− + 𝐻2 𝑂 + 2𝐻 + Acidity from agronomic practices (fertilizer application)

C. Forms of Soil Acidity

Chemical Engineering Department Module 1: Page 9

D. Measurement of Soil Acidity

2.1 Exchangeable base cations

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

2.2 Total exchangeable acidity

Chemical Engineering Department Module 1: Page 10

E. Managing Acidic Soils (Liming Soils)

𝐶𝑎𝐴𝑙2 𝑆𝑖2 𝑂8 + 8𝐻 + = 2𝐴𝑙3+ + 2𝐻4 𝑆𝑖𝑂4 + 𝐶𝑎2+ Dissolution of feldspar

2𝐴𝑙 3+ + 2𝐻4 𝑆𝑖𝑂4 + 𝐻2 𝑂 = 𝐴𝑙2 𝑆𝑖2 𝑂5 (𝑂𝐻)4 + 6𝐻 + Precipitation for kaolinite

2𝑚𝑚𝑜𝑙 𝑂𝐻 − 1𝑚𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 100 𝑚𝑔 𝐶𝑎𝐶𝑂3 1 𝑀𝑔 4.5 × 109 𝑔 𝑠𝑜𝑖𝑙 𝑀𝑔 𝐶𝑎𝐶𝑂3

Chemical Engineering Department Module 1: Page 11

A. Sources of Soluble Salts

B. Characterization of salinity in soil and water

1. Sodium adsorption ratio (SAR)

The Gapon exchange constant for this reaction is

Chemical Engineering Department Module 1: Page 12

2. Exchangeable sodium percentage (ESP)

Chemical Engineering Department Module 1: Page 13

𝐸𝑆𝑅 = 𝑆𝐴𝑅 × 𝐾𝐺 = 3.6 × 0.015 = 0.054

3. Total dissolved solids

−𝜏𝑜 = −5.6 × 10−4 × 𝑇𝐷𝑆 (𝑚𝑔 𝐿−1 )

4. Electrical conductivity (EC)

Chemical Engineering Department Module 1: Page 14

Chemical Engineering Department Module 1: Page 15

Chemical Engineering Department Module 1: Page 16

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