Understanding

Soil Neutral
Acidity

Brady and Weil (2002)

pH = - log (H+ ion concentration)

pH =7
neutral

increases…
As pH decreases…

Brady and Weil, 2002

Optimum pH ranges have been identified for many crops
 Collective term for the challenges
faced by crops growing in acid soils

The acid infertility complex

For Nutrient
most soils, nutrient
availability is optimized
availability
between pHpH
varies with 5.5 and 7.
Molybdenum becomes more available as pH goes up !

most
^

http://www.farmtested.com/research_pp.html
Understanding aluminum toxicity

Toxic forms
Aluminum
of Al are
toxicity is
bioavailable
at lowminimal
pHs
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

Active
Reserve acidity acidity

Brady and Weil, 2002

Understanding reserve acidity
Very little
Reserve
lime isacidity
neededresupplies
to neutralize
the the
active
active
acidity
acidity in soils

ΔpH

ΔpH

Reserve Active Reserve Active

acidity acidity acidity acidity

High CEC soil Low CEC soil

Each charge depicted on this diagram represents 1
centimol of charge per kg of soil
K+
--- Ca+2
Mg+2
Humus
-
-- H+
H20
H20
Exchangeable
exchangeable soil H20
acidity
cations solution
H20
H20 H20
Clay
--
++
-
- K
Al +3 + H2O ↔ Al(OH)3 + 3H+

--
+
SO4 -2
What is the “base”
Ca+2
saturation ?
 Is pHmore
It is probably related
accurateto base
to say saturation
that pH ? saturation
is related to acid

100 80 60 40 20 0
Acid Saturation, %
pH dependent charge

The dominant
clay minerals in
IL have mostly
permanent
charge
 The charge on humic
substances (and low
activity clays) is very pH
dependent

H+ ions dissociate when the soil pH increases

and reassociate when the pH drops.
Brady and Weil (2002)
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:
H2CO3 → HCO3- + H+ VERY IMPORTANT PART OF SOIL FORMATION

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., NH4+ from fertilizer, elemental S).
NH4+ + O2 → NO3- + 2H+ S0 + O2 → SO4-2 + 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.
H2SO4 and HNO3 are strong acids and fully dissociate in water.

5) Roots release H+ to balance internal charge when cation uptake

exceeds anion uptake.
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 HCO3- to balance internal charge when anion

uptake exceeds cation uptake

5) Inner sphere adsorption of anions (especially sulfate) which displaces

hydroxyl (OH-) groups
 Acidity

What is liberated and what is left behind

when plant biomass is burned ?

Oxides of
C, N and S

Elements that
Oxides of have traditionally
Alkalinity Ca, Mg and K been called
“bases”
C, N and S oxides cause acid precipitation

Brady and Weil, 2002

 Sources of pH
buffering
in soils
Carbonates

Chadwick and Chorover ( 2001)

 K+
H+

- The pH of a plant’s
NO3 rhizosphere changes
as the plant regulates
? its internal charge
balance.
 Which plant received nitrate ?
Which plant received ammonium ?

http://departments.agri.huji.ac.il/plantscience/topics_irrigation/uzifert/4thmeet.htm
Acid inputs promote leaching of non-acid cations

Why does
leaching of
these anions
cause soil
acidification ?

Brady and Weil, 2002

 Complete N cycle (no net acidification)

released into
the soil 1H+
consumed
Nitrification is an acidifying process, right??
1H+
NH3 consumed

The 2 H+ produced during nitrification are balanced by 2 H+ consumed

during the formation of NH4+ and the uptake of NO3- by plants
Excellent but focused
on Australian soils
 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.
Lime required
Nitrogen source Composition
(lb CaCO3 / 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
10-52-0 5.4
phosphate
Diammonium
18-46-0 3.6
phosphate
Harvest of crop biomass removes alkalinity
from agricultural fields
Lime required to
replace alkalinity
Cation : N ratio
Crop removed in harvest
in plant biomass
(lb CaCO3 /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

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 ~ 190 lbs of lime
supply P removed in harvest
1.8 x 150 lbs of N in AA ~ 270 lbs of lime

Acidity from grain harvest

25 x 180 lbs of N harvested/100 ~ 45 lbs of lime

25 x 200 lbs of N harvested/100 ~ 50 lbs of lime

Projected lime requirement ~ 0.3 tons/rotation

 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 !!!
Sources of variation in soil pH measurements

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.
Why measure soil pH
Water
using pH >solution
a salt Salt pH ?

Brady and Weil, 2002

 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
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.

H+ Ca+2
soil colloid + CaCO3 soil colloid + H2O + CO2
H+
“Illinois method” of determining lime requirement

How do
you know
which line
to use ?

http://iah.aces.uiuc.edu/pdf/Agronomy_HB/11chapter.pdf
 Choosing the right line
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)
 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
Rates of lime should be
(one-third the amount suggested for soil moldboard-plowed 9 inches
deep).
adjusted if any of these
B. Typical fineness of limestone. Ten percent of the particles are
greater thanassumptions
8-mesh; 30 percent pass an are
8-mesh not
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.accurate

C. A calcium carbonate equivalent (total neutralizing power) of 90

percent. The rate of application may be adjusted according to the
deviation from 90.
It takes time for lime to react in soil
 pH measurements on the fly

Soil pH and lime

requirement can
vary widely
within fields
 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

South eastern IL
has few quarries
and the greatest
lime deficit

http://iah.aces.uiuc.edu/pdf/Agronomy_HB/11chapter.pdf
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 Ca2+ and Mg2+ . 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.
Summary of common soil fertility problems that
rarely occur in soils with pHs between 5.5 and 7

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