Understanding

Soil
Acidity

Brady and Weil (2002)
Neutral
pH = - log (H
+
ion concentration)
Brady and Weil, 2002
As pH increases As pH decreases
pH = 7
neutral
Optimum pH ranges have been identified for many crops
The acid infertility complex
Collective term for the challenges
faced by crops growing in acid soils
Nutrient
availability
varies with pH
For most soils, nutrient
availability is optimized
between pH 5.5 and 7.
http://www.farmtested.com/research_pp.html
most
^
Molybdenum becomes more available as pH goes up !
Understanding aluminum toxicity
Toxic forms
of Al are
bioavailable
at low pHs
Aluminum
toxicity is
minimal
above
pH 5.5
http://www2.ctahr.hawaii.edu/tpss/research_extension/rxsoil/alroot.gif
Multiple forms of soil acidity
Soil pH is
primarily a
measure of
active acidity
Reserve acidity
Active
acidity
Brady and Weil, 2002
Understanding reserve acidity
Reserve
acidity
Reserve
acidity
Active
acidity
Active
acidity
Very little lime is needed to neutralize the active acidity in soils Reserve acidity resupplies the active acidity
High CEC soil
Low CEC soil
pH
pH
exchangeable
cations
soil
solution
Humus
Clay
-
-
-
-
-
-
-
-
-
-
Al
+3
Ca
+2
H
+
K
+
Ca
+2
Mg
+2
K
+
H
2
0
H
2
0
H
2
0
H
2
0
H
2
0
+
SO
4
-2
+
-
-
H
2
0
What is the base
saturation ?
Exchangeable
acidity
Each charge depicted on this diagram represents 1
centimol of charge per kg of soil
+ H
2
O Al(OH)
3
+ 3H
+

Is pH related to base saturation ?
100 80 60 40 20 0
Acid Saturation, %
It is probably more accurate to say that pH is related to acid saturation
pH dependent charge
The dominant
clay minerals in
IL have mostly
permanent
charge
Brady and Weil (2002)
H
+
ions dissociate when the soil pH increases
and reassociate when the pH drops.
The charge on humic
substances (and low
activity clays) is very pH
dependent
Soil acidity increases when H
+
producing
processes exceed H
+
consuming
processes.
Many processes add H
+
ions to soils

1) Carbonic acid forms when carbon dioxide dissolves in water.
H
+
ions are released when carbonic acid dissociates:
H
2
CO
3
HCO
3
-
+ H
+



2) Organic acids form during the decomposition of organic matter.
H
+
ions are released when these organic acids dissociate.


3) Sulfuric and nitric acids form during the oxidation of reduced forms
of N and S (e.g., NH
4
+
from fertilizer, elemental S).
NH
4
+
+ O
2
NO
3
-
+ 2H
+
S
0
+ O
2
SO
4
-2
+ 2H
+



4) Sulfuric and nitric acids form when sulfur oxides and nitric oxides
(released into the atmosphere by automobile emissions, industry
smoke stacks, volcanoes, forest fires) dissolve in precipitation.
H
2
SO
4
and HNO
3
are strong acids and fully dissociate in water.

5) Roots release H
+
to balance internal charge when cation uptake
exceeds anion uptake.
VERY IMPORTANT PART OF SOIL FORMATION
Many processes consume H
+
ions in soils

1) Weathering of most minerals (e.g., silicates, carbonates)

2) Decomposition of organic anions

3) Reduction of oxidized forms of N, S and Fe.

4) Roots release OH
-
or HCO
3
-
to balance internal charge when anion
uptake exceeds cation uptake

5) Inner sphere adsorption of anions (especially sulfate) which displaces
hydroxyl (OH
-
) groups
What is liberated and what is left behind
when plant biomass is burned ?
Oxides of
Ca, Mg and K
Oxides of
C, N and S
Alkalinity
Acidity
Elements that
have traditionally
been called
bases
C, N and S oxides cause acid precipitation
Brady and Weil, 2002
Chadwick and Chorover ( 2001)
Sources of pH
buffering
in soils
Carbonates
K
+
H
+
NO
3
-
?
The pH of a plants
rhizosphere changes
as the plant regulates
its internal charge
balance.
http://departments.agri.huji.ac.il/plantscience/topics_irrigation/uzifert/4thmeet.htm
Which plant received nitrate ?
Which plant received ammonium ?
Acid inputs promote leaching of non-acid cations
Brady and Weil, 2002
Why does
leaching of
these anions
cause soil
acidification ?
NH
3
1H
+

consumed
1H
+

consumed
released into
the soil
Complete N cycle (no net acidification)
Nitrification is an acidifying process, right??
The 2 H
+
produced during nitrification are balanced by 2 H
+
consumed
during the formation of NH
4
+
and the uptake of NO
3
-
by plants
Excellent but focused
on Australian soils
Nitrogen source Composition
Lime required
(lb CaCO
3
/ lb N)
Anhydrous ammonia 82-0-0 1.8
Urea 46-0-0 1.8
Ammonium nitrate 34-0-0 1.8
Ammonium sulfate 21-0-0-24 5.4
Monoammonium
phosphate
10-52-0 5.4
Diammonium
phosphate
18-46-0 3.6
Standard values for the quantity of lime needed to
neutralize the acidity generated by specific N fertilizers

Assumes: 1) all ammonium-N is converted to nitrate-N and
2) half of the nitrate is leached.

Crop
Cation : N ratio
in plant biomass
Lime required to
replace alkalinity
removed in harvest
(lb CaCO
3
/100 lb of
N harvested)
Corn grain 0.14 25
Corn stover 0.73 131
Soybean 0.14 25
Oats grain 0.14 25
Oats straw 0.94 169
Alfalfa 1.41 254
Harvest of crop biomass removes alkalinity
from agricultural fields
http://www.ianrpubs.unl.edu/epublic/pages/publicationD.jsp?publicationId=111
Scenario
Corn/soybean rotation
200 bushels, 50 bushels
All P supplied as DAP
N applied as DAP and AA

Acidity from N fertilizer
3.6 x 52 lbs of N in DAP required to
supply P removed in harvest
1.8 x 150 lbs of N in AA

Acidity from grain harvest
25 x 180 lbs of N harvested/100
25 x 200 lbs of N harvested/100
Projected lime requirement ~ 0.3 tons/rotation
~ 190 lbs of lime
~ 270 lbs of lime
~ 45 lbs of lime
~ 50 lbs of lime
Alfalfa field with
dead strip where
lime was not
applied
How should
lime rates be
determined?
Lime rates should
be guided by soil
testing
Pocket pH meters can be very useful
but require regular calibration !!!
1. The soil to solution ratio used when measuring pH.

2. The salt content of the diluting solution used to
achieve the desired soil to solution ratio.

3. The carbon dioxide content of the soil and solution.

4. Errors associated with standardization of the
instrument used to measure pH.
Sources of variation in soil pH measurements
Water pH > Salt pH
Brady and Weil, 2002
Why measure soil pH
using a salt solution ?
Soil pH depends on method
used to measure it !!

As a result, the method of measurement
should be reported whenever soil pH
data is discussed.
The amount of lime needed to
bring about a 1 unit change in
pH varies widely between soils
soil colloid + CaCO
3
soil colloid + H
2
O + CO
2

H
+

H
+

Ca
+2

When a soil is limed, Ca
+2
from the lime
displaces exchangeable acidity from the
soil colloids. The active acidity that is
generated reacts with the carbonate ions
from the lime, producing water and
carbon dioxide.
Illinois method of determining lime requirement
How do
you know
which line
to use ?
http://iah.aces.uiuc.edu/pdf/Agronomy_HB/11chapter.pdf
Line A: Dark colored silty clays and silty clay loams (CEC > 24)

Line B: Light and medium colored silty clays and silty clay loams,
dark colored silts and clay loams (CEC 15-24)

Line C: Light and medium colored silt and clay loams, dark and
medium colored loams, dark colored sandy loams (CEC 8-15)

Line D: Light colored loams, light and medium colored sandy
loams and all sands (CEC < 8)

Line E: Mucks and peat (organic soils).
Light colored (< 2.5% OM)
Medium colored (2.5-4.5% OM)
Dark colored (4.5% OM)
Choosing the right line
Not all limestone is the same !

Pure calcium carbonate has a calcium carbonate
equivalency (CCE) of 100 and is the standard against
which all liming materials are compared. A ton of material
with a CCE of 90 % can neutralize 10% less acid than a ton
of pure calcium carbonate.

Liming materials that are finely ground, have more surface
area in contact with the soil solution than coarser ground
materials and thus will neutralize soil acidity more rapidly.
Fineness of grind is rated according to the percentage of
material that will pass through 8-, 30-, and 60-mesh
screens.
http://www.agr.state.il.us/news/pub/2007LimeBook.pdf
Page from the 2008 IL Lime book
Multiply by these factors
Adjusting for differences in lime particle size distribution
Lime requirements determined using the Illinois
method assume the following:

A. A 9-inch tillage depth. If tillage is less than 9 inches, reduce the
amount of limestone; if more than 9 inches, increase the lime rate
proportionately. In no-till systems, use a 3-inch depth for calculations
(one-third the amount suggested for soil moldboard-plowed 9 inches
deep).

B. Typical fineness of limestone. Ten percent of the particles are
greater than 8-mesh; 30 percent pass an 8-mesh and are held on 30-
mesh; 30 percent pass a 30-mesh and are held on 60-mesh; and 30
percent pass a 60-mesh.

C. A calcium carbonate equivalent (total neutralizing power) of 90
percent. The rate of application may be adjusted according to the
deviation from 90.
Rates of lime should be
adjusted if any of these
assumptions are not
accurate
It takes time for lime to react in soil
Soil pH and lime
requirement can
vary widely
within fields
pH measurements on the fly
Both past management and inherent
soil properties affect soil pH and lime requirement
Why is variable rate lime
more likely to pay than
variable rate N, P or K?
Insufficient lime is applied to neutralize
total acid inputs to IL soils
http://iah.aces.uiuc.edu/pdf/Agronomy_HB/11chapter.pdf
South eastern IL
has few quarries
and the greatest
lime deficit
Barak P, Jobe BO, Krueger AR, Peterson LA, Laird DA 1997. Effects of long-
term soil acidification due to nitrogen fertilizer inputs in Wisconsin.
PLANT AND SOIL. 197(1): 61-69

Abstract:
Agroecosystems are domesticated ecosystems intermediate between natural
ecosystems and fabricated ecosystems, and occupy nearly one-third of the
land areas of the earth. Chemical perturbations as a result of human activity
are particularly likely in agroecosystems because of the intensity of that
activity, which include nutrient inputs intended to supplement native nutrient
pools and to support greater biomass production and removal. At a long-term
fertility trial in South-Central Wisconsin, USA, application of ammoniacal N
fertilizer resulted in significant increases in exchangeable acidity accompanied
by decreases in cation exchange capacity (CEC), base saturation, and
exchangeable Ca
2+
and Mg
2+
. Plant analysis shows that a considerable
portion of the alkalinity generated by assimilation of N (and to a lesser extent
by S) is sequestered in the above-ground plant parts as organic anions and is
not returned to the soil if harvested. Elemental analysis of soil clays
indicates a loss of 16% of the CEC. The reversibility of this change is
doubtful if the changes are due to weathering of soil minerals.
pH << 5.5 pH >> 7.0
Al toxicity to plant roots Fe deficiency
Mn toxicity to plant roots Mn deficiency
Ca and Mg deficiency Zn deficiency
Mo deficiency in legumes *Osmotic stress from salts
P tied up by Fe and Al P tied up by Ca and Mg
Slow N transformations Potato scab
Summary of common soil fertility problems that
rarely occur in soils with pHs between 5.5 and 7