SOIL CHEMISTRY

ARTEMIO A. MARTIN JR, Ph.D.

COLLEGE OF AGRICULTURE
ISABELA STATE UNIVERSITY
Echague, Isabela
 Cation Exchange
• the process whereby cations adsorbed on
the colloid are exchanged for those in the soil
solution
H
micelle Ca + 2H+ = micelle H + Ca2+
• the reaction is instantaneous, reversible and
stoichiometric (i.e. 1 millIequivalents of one
cation is replaced by 1 me of another )
 CATION EXCHANGE CAPACITY
(CEC)
Cation exchange capacity. The sum of the
exchangeable cations present in a given
amount of soil is called cation exchange
capacity (CEC).

It is expressed in mill-equivalents per 100 g soil

(meq/100 g soil) or cmolc/kg soil.

CEC is an index of the capacity of the soil to

retain nutrients.
Cation and anion exchange occur in equivalent
weights
Equivalent weight refers to one gram atomic
weight of hydrogen or any other ion that will
combine with or replace this amount of hydrogen
For monovalent cations such as K+, Na+ and
NH4+, the equivalent weight is equal to the
atomic weight because each cation will replace
one hydrogen
 For divalent cations, the equivalent weight is
equal to the atomic weight divided by 2 because
the
divalent cation will replace two hydrogen ions
Milliequivalent (MEQ)
1 meq wt. of CEC has 6.02 x 1020 adsorption sites
Cation Atomic Valence Equivalent Milliequivalent
Weight Weight (eq. weight (meq)
wt)
H 1 1 1 0.001
Na 23 1 23 0.023
NH4+ 18 1 18 0.018
Ca 40 2 20 0.020
Mg 24 2 12 0.012
K 39 1 39 0.039
Concept of millIequivalents
atomicweig
ht wt of 1 me 
valence x 1000 Example:
39
• wt of 1 me of K+ = 1 x 1000 
0.039g/me
• wt of 1 me of Ca2+ =  0.02g/me
Sample Problem : Calculate weight (g) of Ca2+
needed to replace 1 g of H+.
1 me Ca2+ will replace 1 me H+
1 me Ca2+ = 0.02 g; 1 me H+ = 0.001 g

2 2
0.02gCa xgCa

 
0.001gH 1gH
 x = 20 g Ca2+
• Sample Problem 2: Calculate the CEC of a soil
with the following analysis:

• Exchangeable cations me/100 g soil

Ca2+ 10.0
Mg2+ 5.0
K+ 0.5
Na+ 1.5
H+ 5.0
CEC = 22.0 me/100 g soil
Compute for the CEC of a 100 g soil if the soil
has the following adsorbed ions
H+ - 4 me/100g
Mg++ - 6 me/100g
Na+ - 3 me/100g
Al - 2 me/100g
CEC 15me/100g
 Cation Exchange
Capacity
• A high CEC value (>25) is a
good indicator that a soil
has a high clay
and/organic matter
content and can hold a lot
of cations.

• Soil with a low CEC value

(<5) is a good indication
that a soil is sandy with
 little or no organic matter
that cannot hold many
cations.

Cation Exchange Capacity

Cation exchange capacity is a chemical property that
emanates from the negative charge of colloidal particles:
hence, CEC primarily depends on three factors:
(1) soil texture,
(2) amount and kind of clay, and
(3) organic matter content.
Fine-textured soils generally have higher CEC than
coarsetextured soils; thus, clay, silty clay, sandy clay and
clay loam have higher CEC than loamy sand and sandy
loam soils.

Cation Exchange Capacity

Sand = 0-3 meq/100 g LS to SL = 3-10

Loam = 10 - 15 Clay Loam = 10-30
Clay = > 30

• CEC for % OM = 200 meq/100g

• CEC for % clay = 50 meq/100g
CEC of soil colloids
MATERIAL CEC (m.e./100g)
Organic matter 200
Vermiculite 150
Montmorillonite 100
Illite 30
Kaolinite 8
Hydrous oxide 4
Allophanes 100
• To convert m.e. per 100/g of soil into kilograms per
hectare (where, one hectare of surface soil or one
hectare furrow slice (HFS) weighs 2,000,000 kg, the
weight of cation in 100 grams is calculated and then
converted to kilograms of the cation per 2,000,000 kg of
soil then:

– Kg of cation/ha = No. of m.e. cation x Equiv. wt (g) x 2,000,000 kg/ha

100g soil 1,000

• Parts per million

• One hectare of soil is assume to weigh
2,000,000 kg, parts per million is
• ppm= kg weight of the cation per ha/2
• Significance of CEC: Indicator of soil
fertility since it reflects the capacity of the
soil to retain nutrients

• CEC determination:
soil
saturated
with
 NH4OAc NH4+is replaced by
K+

+
NH distilled
4
CEC determination using NH4OAc:
Adapted from Brady and Weil, 1999
The quantity of NH4+ ions in the leachate is a
measure of CEC.

Example: leachate (filtrate) has 0.054 g of NH4+ in 20

g of soil extracted

CEC = 0.054g NH4+/20 g soil

= 0.0027 g NH4+/g soil x 1me/0.018 gNH4+ x 100

= 15 meq/100 g soil
 BASE SATURATION
The exchangeable cations present in large
quantities in soils are Ca, Mg, K, Na, and H.
Calcium, Mg, K, and Na are called
exchangeable bases

Percent base saturation. The sum of the

exchangeable bases when divided by
CEC and multiplied by 100 yields the
percent base saturation.
 Base Saturation
• percentage of CEC that is satisfied by the
exchangeable bases
exchangeable bases: Ca2+, Mg2+, K+, Na+,
exchangeable acids: Al3+,H+

% Base saturation  exch

bases x 100
CEC
 BASE SATURATION
% Base Saturation - meq bases/CEC x 100
% Hydrogen Saturation - meq H/CEC x100

Example: Ap Soil Horizon

Cations-- H+ Ca++Mg++K+ Na+
9.4 14 3 0.5 0.1

CEC = 27 meq/100g (sum of

cations) % base sat = 17.6/27 x 100
= 65%
 % hydrogen sat = 9.4/27 x100 = 35%
• Percentage base saturation is an important soil
property because it is inversely related to soil
acidity
Soil pH % BS
Generally as percentage
3.9 0
base saturation increases
, soil pH increases 4.5 0
• Bases tend to form 5.3 25
hydroxides – KOH, 6.2 50
Ca(OH)2, etc 7.1 75
7.5 90
8.0 100
• Al tends to contribute H+ through
hydrolysis:
Al3+ + HOH = Al(OH)2+ + H+
Al(OH)2+ + HOH = Al(OH)2+ + H+
2+ 0 +
Al(OH) + HOH = Al(OH) + 3 H
Exchangeable Sodium Percentage
• proportion of the exchange sites occupied by
sodium
• soils with high ESP (>15%) are considered
sodic and need to be reclaimed
- addition of gypsum (CaSO4.2H2O)

exchangeableNa
ESP  x 100
CEC
Sample Problem : Calculate %Base Saturation
and ESP of the soil with the following analysis.
• Exchangeable cations me/100 g soil
Ca2+ 10.0 Mg2+ 5.0
 K+ 0.5
Na+ 1.5
H+ 5.0 CEC = 22.0
me/100 g soil
mebases
%Basesaturation  x
100 CEC

%BS  x 100  77.3 %

exchangeableNa
ESP  x 100
CEC
1.5
 x 100  6.8%
22
 Soil pH or Soil Reaction
• pH is the acidity or alkalinity due to relative
concentration of H+ and OH- ions
• [H+] is expressed in moles/liter or M

1

]
 pH  log  log [H

[H ]
Sample Problem
b) Calculate [H+] if pH = 5.0
[H+] = -antilog pH
= - antilog (5)
-5
= 1 x 10 mole/liter
• as pH increases, [H+] decreases
• one unit change in pH corresponds to 10
times the change in [H+]
 pH scale

VS ST M SL SL M ST VS
 Determination of pH:

Electrometric method – by pH meter;

more accurate
Colorimetric method – organic dyes,
litmus paper
Effects of soil pH:
• On microbial activity :
Fungi – unaffected
 Bacteria & Actinomycetes -
inhibit
ed at
pH 5.
• On availability of nutrients:
N - dec. at pH <5.5
Ca and Mg - dec. at pH <6.0
P - dec. at pH <6.0 and >7.0
(maximum availability
occurs at narrow pH
range)
K - dec. at pH <6.0
 S - dec. at pH <5.5
Mo - dec. at pH< 6.5
B - dec. at pH <5.0 and pH >7.0
Fe, Mn, Zn, - dec. at pH >5.0
- at pH < 5.0 their conc. are
usually toxic)

• Based on these, the ideal or optimum pH

appears to be pH 6.5.
 PROBLEM SOILS
ACID SOILS
Sources of Soil Acidity:
• H+ and Al3+ ions
3+
Al contributes to acidity indirectly
through hydrolysis
Problem Soils
Acid soils

• Carbonic acid (H2CO3) dissociation

 CO2 + H2O = H2CO3
H2CO3 = 2H+ + CO32-

• Organic acids from OM decomposition

• Mineral weathering

• Acid rain

2SO2 + O2 2SO3; SO3 + H2O H2SO4

2NO + O2 2NO2; 2NO2 + H2O HNO3 + HNO2

• Heavy cropping which removes basic cations (K,
Ca, Mg, Na) and replaced by H+ from roots.
• Long term use of acidifying fertilizers
Nitrification converts NH4+ to NO3- and releases
hydrogen ions to the soil.

NH4+ + 3/2 O2 Nitrosomonas NO2- + 2H+ + H2O

NO2- + ½ O2 Nitrobacter NO3-

Forms of soil acidity
• Active acidity – due to H+ in soil solution;
determined as pH
• Reserve acidity – due to H+ and Al3+ in the
solid phase
measure of the buffering capacity of the
soil

Buffering capacity – the ability of a soil to

resist sudden or drastic changes in pH
Buffering capacity
• The buffering capacity is high if, CEC is
high clay content is high OM content is
high
Production constraints associated with acid
soils:
1. Aluminum toxicity
Aluminum toxicity usually damages the
root system first.
2. Mn toxicity – less common than Al
toxicity
3. Nutrient deficiency
 P deficiency
Ca deficiency
Mo deficiency
Phosphorus fixation under extreme soil
acidity:
• Fe3+ + 2H2O + H2PO4- = 2H+ + Fe(OH)2H2PO4
soluble strengite
(available) (insoluble)

• Al3+ + 2H2O + H2PO4- = 2H+ + Al(OH)2H2PO4

 soluble variscite
(available) (insoluble)

Phosphorus fixation under strong alkalinity:

• H2PO4 combines with Ca ions or Cabearing

minerals to form insoluble calcium
phosphates like dicalcium phosphate
dihydrate (CaHPO4.2H2O), tricalcium
phosphate [Ca3(PO4)2]
4. Restricted microbial activities
 (mineralization of organic N, biological
fixation of N)

5. Incidence of plant diseases

Some plants are more likely to be
affected by damping off (fungal disease)
and root rot in acid soils
Management Strategies:
• Reduce acidification
 Minimize the use of acidifying
fertilizers
Reduce leaching of nitrogen by use of
split applications of fertilizer
Return plant material to the soil
• Use acid tolerant crops

Growing acid tolerant crop will enable

continuous production and help
maintain farm income but will not
correct soil acidity
 acid-tolerant crops include:
sweet potato radish coffee
irish potato pineapple tomato
strawberry
Problem Soils
Acid soils

• Apply More Nutrients

Since only few nutrients are available,

more fertilizers can be used to
maintain production levels.
• Apply agricultural lime
Lime is the only means of correcting soil
acidity but the economics of using it
should be carefully considered
Correcting soil acidity by liming:

• Lime – any oxide, hydroxide or carbonate of Ca

or Mg used to neutralize soil acidity

• Carbonate form:
CaCO3 ,calcitic limestone CaMg(CO3)2
, dolomitic limestone
 • Oxide and hydroxide form : CaO, burned lime
Ca(OH)2 , hydrated lime
Calcium carbonate is the standard against which
neutralizing value of liming materials are
measured
The capacity of the lime to neutralize soil acidity
expressed as a percentage of the molecular
weight of CaCO3 – calcium carbonate
equivalent (CCE) or relative neutralizing value
(RNV)
Influenced by chemical composition, purity and
fineness
Pure CaCO3 has a RNV of 100%
RNP of some liming materials in their
pure form
-----------------------------------------------------------------------------
Liming material Relative Neutralizing Power
-----------------------------------------------------------------------------
CaCO3 (Calcic Limestone) 100
Ca(OH)2 (Hydrated Lime) 134
CaO (burned lime/Quick lime) 178
MgCO3 119
Mg(OH)2 172
MgO 250
CaMg(CO3)2 (Dolomitic Limestone) 109
----------------------------------------------------------------------------
Calcium Carbonate Equivalent (CCE) or
Relative Neutralizing Value (RNV)

• capacity of the material to neutralize soil

acidity relative to that of pure CaCO3

RNV  MWCaCO3 x 100

MWmaterial
 • Lime Requirement: The amount of liming
material required to raise the pH to a
desired level determined by:

• required change in pH
• texture: the finer the texture the higher the
CEC and the greater the buffering capacity
• crop to be grown acid-tolerant crops include:
camote radish
coffee strawberry
pineapple tomato
potato (Irish) ubi
Effect of lime on the soil:
1. helps nutrients become available to plants

2. improves soil structure

3. provides nutrients for plant growth

4. promotes growth of beneficial microorganisms

5. overcomes acidifying effects of fertilizers

6. reduces metal toxicity to plants (solubility vs. pH)

Liming could also have harmful effects,
particularly when excessive amounts are
used (overliming).
 These include the decreased availability
and development of deficiency of Fe, Mn,
Cu, Zn, P and B.
It could also trigger K and Mg deficiency due
to antagonism between Ca, K and Mg.
Overliming easily occurs on coarse-textured soils
with low organic matter.
SALINE SOILS
 soils with high soluble salts (Na+ less than 15% of the
CEC)
 The pH < 8.5; water is drawn away from plant roots
due to osmotic effect (water stress)
 “Exosmosis” water in plants are pulled by the osmotic
pressure of salts (Chlorine and Sulfates)
 High water table, restrictive soil layers and low
hydraulic conductivity – low productivity
 usually located in coastal areas where intrusion of
sea water occurs (white alkali)
SODIC SOILS
Soils characterized by accumulation of soluble Na
(more than 15% of the CEC) - Toxicity of Na+
pH up to 10.0
low electrical conductivity, dispersed, clay swelling,
poor aeration, low water permeability
High concentration of Na coupled with high pH posed
toxicity to the roots –low productivity
soil is highly dispersed. Dispersed humus carried
upward by capillary gives the soil black color
(black alkali)
Technical Definition
Soil EC of ESP pH SAR
saturation
extract
(dS/m)
Saline >4 <15 < 8.5 < 13

Sodic <4 > 15 > 8.5 < 13

Salinesodi >4 > 15 < 8.5 > 13

c
EC – electrical conductivity
ESP – exchangeable sodium percentage
SAR – sodium adsorption ratio
Reclamation of saline soils
• Leaching of excess salts out of the root
zone (internal and surface drainage, and
salt disposal dump areas)
• Retardation of evaporation (use of surface
mulch)
• Use of salt-tolerant crops
• Use of special planting procedures that
minimize salt accumulation around the seed
Planting
Practices
and
Irrigation
Schemes

Sprinkle irrigation
 Drip or Trickle irrigation

Effect of irrigation on salt movement

and plant growth in saline soil
Reclamation of sodic soils
• Replacement of excess Na on the exchange
sites by Ca and leaching of exchanged Na out of
the root zone

• Gypsum (CaSO4.2H2O) cheapest and most

commonly used
 Na Ca
+ CaSO4 = + Na2SO4
Na
• S is likely to be used when the soil contains
free lime in addition to too much Na
• Addition of OM is also beneficial
• Deep plowing
Chemistry of Flooded Soils
Flooded soils are submerged soils used to
grow rice; also known as paddy soils
Profile:
the plow layer is a puddled system
which results from plowing and
harrowing while the soil is wet
underneath is a hardpan which prevents
or minimizes the
Floodwater
percolation of water into
oxidized layer
the subsoil
Oxidized layer (thin) – aerobic layer, aerobes oxidation
reactions
reduced layer
Reduced layer – anaerobic layer , facultative
anaerobes and obligate anaerobes reduction reactions
 Facultative anaerobes – can live with or without O2
Obligate anaerobes – can live only in the absence of O2
Chemistry of flooded soils

Effect of flooding on soil pH and redox

potential:
• pH value of acid soils increase on
submergence whereas the opposite
occurs in calcareous soils and sodic
soils.
For most soils the fairly stable pH
attained after several weeks of
submergence is between 6.5 to 7.0

Chemistry of flooded soils

Change
in soil pH
with
flooding
Chemistry of
flooded soils

Effects of (Source: Ponnamperuma,

1977)
(Source: Ponnamperuma,
1977)

pH
change:
• In acid soils, increase in pH :
 depresses Fe, Al, Mn toxicity

increases P, Si and Mo availability

enhances microbial activity (pH near

neutrality favors microbial activity)
Chemistry of flooded soils

• In alkaline soils, decrease in pH:

increases availability of P as well as
Zn and Cu
enhances microbial activity
 Chemistry of flooded soils

• Redox Potential (Eh) - measures the

intensity of oxidation and reduction
Submerged soils are characterized by
low or negative redox potentials
Eh drops to a fairly stable value of
+200 to –300mV, depending on the soil
 Chemistry of flooded soils

Sequential reduction of several soil

redox systems in rice soils:

• As O2 is depleted from the soil, NO3- is

utilized by facultative anaerobes and is
rapidly reduced
• The reduction of Mn (IV) to Mn (II) takes
-
place during reduction of O2 and NO3
 Chemistry of flooded soils

• Reduction of Fe(III) only occurs after O2

-
and NO3 are consumed; carried out by
facultative anaerobes
• Reduction of SO42- to S2- is carried out
by true anaerobic bacteria.
• CH4 is not produced in soils until most
of the sulfate has been reduced
 Chemistry of flooded soils

• Summary of the major reduction processes

involved in flooded soils:
O2 H2O
NO3- N2
Mn4+ Mn2+
Fe3+ Fe2+
SO42- H2S
CO2 CH4
 Difference in chemistry of lowland and
upland soils
• Upland or dryland soils are grown to such
crops as as corn, vegetables, etc .
 aerobic most of the time
 the nutrient elements exist generally in their
oxidized state: NO3–, H2PO4–, SO42-, Fe3+, Mn4+
and CO2
 aerobic soil is brown, yellowish brown or
reddish brown.
  organic matter decomposes with CO2 as a
major product.
• Lowland or paddy soils are usually
grown to rice
 continuously submerged are anaerobic
except for a thin oxidized layer at the
surface
 nutrients are also in reduced forms like
NH4+, H2S, Mn2+, Fe2+ and CH4
 submerged soil is dark gray or bluish gray
 the major products of organic matter
decomposition are methane (CH4),
hydrogen sulfide (H2S), organic acids,
alcohols and ketones.

THANK YOU
&
GOOD LUCK!!!