Soil Acidity: It's Not Just PH: Jim Harsh Crop & Soil Sciences Harsh@wsu - Edu

Soil Acidity: It’s not just pH
Jim Harsh
Crop & Soil Sciences
[email protected]
What is “soil pH”?
For the chemist: pH = -log [H+(aq)]

[H+(aq)] is the concentration in the soil solution.
0.001
0.0008
[H] (mol/L)
0.0006
0.0004
0.0002
0
2 3 4 5 6 7
pH
Problems with Decreasing Soil pH
o Root growth issues (acute)
o Aluminum toxicity
o Nutrient deficiencies (P, Mo)
o Limits nitrogen fixation by legumes
o Disease interactions
o Herbicide interactions
o Reduced nutrient use efficiency
o Reduced biological activity
o Reduced cation exchange capacity (CEC)
…and the list goes on…
pH affects:
•Plant
nutrient
availability
•Soil
organism
activity
•Occurrence
of toxic
elements
pH and Al
160
140
KCl Aluminum (mg/kg)
120
100
80
60
40
20
0
4.00 4.20 4.40 4.60 4.80 5.00 5.20 5.40
1:1 pH
Al Toxicity to Plants
Sensitivity of dryland (Palouse)
crops to soil acidification
oLegumes Sensitive
oSpring wheat
oWinter wheat
oTriticale Tolerant
Al Al
Tolerant Intolerant
(Alikat) (Scarlet)
Alpowa Louise
Genetic solutions to aluminum
toxicity in low pH soils
Mike Pumphrey
WSU Spring Wheat Breeding and Genetics
OSU wheat breeding nursery near Enid, OK; Dr. Brett Carver
Aluminum tolerance screen – PNW spring wheat 2011
Tolerance rating 0-5 (0 = tolerant, 5 = sensitive)
JD 0 LOUISE 3
ALPOWA 0 WA008124 3
BABE 0 KELSE 3
WHIT 0 WESTBRED 926 3

NICK 0 WB-FUZION 3
PENAWAWA 1 BR7030 3
HANK 1 WAKANZ 4
OTIS 1 EDEN 4
TARA 2002 1 SCARLET 4
MACON 1 Glee 4
Diva 2 JEFFERSON 4
BUCK PRONTO 2 WA008113 5

Dayn 2 LASSIK 5
ZAK 3 BULLSEYE 5
IDO599 3 UI WINCHESTER 5
Aluminum tolerance screen – PNW winter wheat 2011
Tolerance rating 0-5 (0 = tolerant, 5 = sensitive)
Legion 1 5J050348-1 3
Madsen 1 5J050390-1 3
SSD060040 1 Finch 3
ARS-Amber 2 Legacy 3
Badger 2 SSD060298 3
Brundage 96 2 Tubbs 3
Chukar 2 WA008114 3
Masami 2 WA008115 3
Paladin 2 WA008135 3
WA008134 2 WA008137 3
WA008136 2 WA008138 3
WB-528 2 Eltan 4
Whetstone 2 5J050509-2 5
Xerpha 2 Skiles 5
5J040150-1 333 Stephens 5
Why are some varieties of wheat acid
tolerant?
They have a gene called ALMT1, that

causes malate to be secreted from roots,
which binds the Al3+
Not all Al has the same
toxicity
100
Distribution (%)
80
Al(OH)4 -
60 Al3+
40 Al(OH)2 +
20
AlOH2+ Al(OH)°
3
0
4 5 6 7 8 9
pH
What is Soil Acidity?
o Soil pH is only one part of soil acidity and…
o It is the most important factor in toxicity but…
o It is only a small part.
It does not tell you how much lime to add to get
the pH you want!

Types of Soil Acidity
oActive acidity = pH
o [H+]in solution, soil water solution.
o Measure directly with pH meter, e.g. 1:1 soil:water
suspension
o pH controls chemical properties
o pH affects both biological and physical properties
oExchangeable acidity. Buffer pH

o amount of aluminum [Al+++], Hydrogen [H+] and
(some) Iron [Fe+++] that occupies exchange sites
on clays, soil aggregates, and organic matter
oResidual acidity.
o notreadily available
o bound aluminum and hydrogen in clay minerals
and soil aggregates
Exchangeable ACIDITY Active ACIDITY
CATIONS (+) adsorbed to exchange sites CATIONS (+) in Solution
(CEC) of Clay, Soil Aggregates and
Organic Matter
- Mg++ H+
-
-
- Al+++ Al+++
- H+
- H+ EXAMPLE
- SCENARIO acid
- Al+++ cations dominating
- both exchange
H+
- sites and cations in
- Al+++ solution
-
- K+ Ca++ Al+++
-
- Al+++
- Al+++
- Fe+++
-
- Fe++ Note: Overly simplified to minimize mental exhaustio
Exchangeable ACIDITY Active ACIDITY
CATIONS (+) adsorbed to exchange sites (CEC) of CATIONS (+) in Solution
Clay, Soil Aggregates and Organic Matter
- K+++
Mg K+
-
- ++
Ca+++
- Al Na+
10%
Base Saturation = 70%
- H+ K+
- Apply Ag LIME
• CaCO3 ± MgCO3
- Al+++
- • Replace acid
- Ca++
cations on
Mg++
- exchange sites
- Al+++
Ca++
with base
- cations
- K+ Na+ Ca++ Ca++
-
- Al+++
Ca++
- H+
- Fe+++
Mg++
-
- Fe++ Note: Overly simplified to minimize mental exhaustion
Buffering of pH in Soils
Soil factors influencing acidity
o pH
o Organic Matter
o Mineralogy
o Age and Climate
o Texture
Processes that Cause Soil Acidity
oCarbonic (CO2!) and Organic Acids

oDecomposition of Organic Matter
oOxidation of Nitrogen (Nitrification)
oOxidation of Sulfur
oPlant Uptake/Leaching of Cations

oAcidic Phosphate Fertilizers
Sources of Soil Acidity. CO2
o Conversion of carbon dioxide to carbonic acid
o Respiration = uptake up O2 and subsequent release of

CO2
o Plant roots, microbial activity, soil fauna, etc. are
primary source of CO2 in soil
CO2(g) + H2O(l)  H+(aq) + HCO3-(aq)

Sources of Soil Acidity. N Fertilizers
NH3 + 2O2 = H+ + NO3– + H2O
(nitrification of ammonia)
NH4–N Source lb CaCO3/lb N
oAnhydrous Ammonia 1.8
oUrea 1.8
oAmmonium Nitrate 1.8
oAmmonium Sulfate 5.4??
oMonoammonium Phosphate 5.4??
oDiammonium Phosphate 3.6
Sources of Soil Acidity. Humus
oSoil organic matter contains compounds that behave

like weak acids
o Hydrogen ions are released as crop residues decompose
oOrganic acids contribute to soil acidity
o humic and fulvic acids
oSOM serves as pH buffer.
o Acts as both [H+] donor and [H+] acceptor
o Buffering capacity of soil increases with increasing soil
organic matter content
oHumus has higher CEC than most clay minerals
oSOM binds Al3+
Sources of Soil Acidity. Straw Removal
oCation removal by crop uptake will either

increase or decrease soil acidification
o Legumes tend to acidify soils more than cereals
because the removal rate of base cations by
legumes is significantly higher
oRemoval of base cations when baling straw
o Each
1,000-Lb bale of straw contains plant nutrients
with a replacement value of about $10 per bale
o Burning retains cations
o N, C, and S are oxidized – and float away in the breeze
o Fertilizer Cost to balance nutrient losses = $ 12 to $55
per Acre
(source: report by Huggins 2013)
Acidification from Wheat Production
(hypothetical, simplification)
1. 150 lb/A N applied as anhydrous ammonia
2. Nitrification results in acidification equal to

270 lb/A CaCO3 (150 lb N/a x 1.8 lb CaCO3/lb N)
3. Wheat uptake of 75 lb/A of N neutralizes acidity
equivalent to 135 lb/A CaCO3 (75 x 1.8)
4. Removal of cations results in additional acidity
equal to 13 lb/A CaCO3 (50/100 x 25)
5. CaCO3 required to neutralize soil acidification
is 148 lb/A
6. 1 ton/A of CaCO3 needed to maintain soil pH
for every 13.5 years of wheat production
Changing Soil pH
Acid soils: Add “lime”
o Lime = carbonates, oxides or hydroxides of Ca
(or Ca and Mg), many types!
o Ca2+ (or Mg2+) replaces H+ on exch. sites
o Carbonate (CO32-) or OH- reacts with H+ to form H2O
and CO2
The Reaction of Lime with Acids
CaCO3(s) + 2H+  Ca2+ + H2O + CO2

RAISING SOIL pH BY LIMING
How soil texture affects lime requirement
Determining Lime Requirement
oField determination with lime

oTitration in the laboratory
oIncubation in the laboratory
o“Quick Test”: We need one for the
Palouse!
All require calibration
Managing Acid Soils. Amendments
o Add organic matter

o Chelates aluminum, iron and
manganese
o Amend with calcium carbonate
o Calibrated application rates raise
soil pH
Lime Requirement Depends on:
oLiming goal:
opH goal or tolerable level of
exchangeable Al
oSoil buffering capacity
oNeutralization value of
liming material
oFineness of liming material
Lime Reactivity with Soil
o100-mesh sieve or finer, reacts with soil in
6 months or less
o60-mesh or finer, reacts in 1st year
o20-mesh but not 60 mesh, about 50% in 1st
year
oNot passing 20-mesh sieve--little liming
value
oIdaho fertilizer law requires that the
percentages of lime passing 10-, 60-,
and 100-mesh sieves be specified.
Lime Sources
CaCO3
Source of Dry Equivalent Fineness Lime
Lime Type Ca2+
Lime Matter (100% DM Factor Score
Basis)
% %
Moses Lake Sugar Cascade
18 91.7 83.8 85 to 98 65 to 75
Lime Agronomics
Pioneer
Limestone (Ground) 37.5 99.2 95 80 75 to 89
Enterprises
Microna Ag H2O - Columbia

Calcium (solution River 38 99 98 100 97
grade) Carbonates
Columbia
Microna Agricultural
River 38 99 98 100 97
Lime
Carbonates
Soil pH Stratification
Koenig and coworkers

Soil pH profile, Rockford, WA 2011
Koenig and coworkers

Practical Considerations
oImplement soil sampling plan to identify

acidified soil strata. Consider depth of
fertilizer placement.
oBudget CaCO3 applications to counter fertilizer
effects
e.g., 1.8 lb CaCO3 per lb NH4-N applied.
oAmend acid soils four to six months prior to
planting your sensitive crop. Speed of Ag
Lime reaction most rapid with very fine
products.
oAg Lime transportation costs are a significant
limiting factor when selecting product.
Consider long-term effects of particle size
among Ag Lime sources.
oConsider organic matter and micronutrient
content of Ag Lime
Acknowledgments
All those I stole from:

oWayne Thompson
oDave Huggins
oRich Koenig
oBrady and Weil
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Soil Acidity: It’s not just pH

For the chemist: pH = -log [H+(aq)]

WHIT 0 WESTBRED 926 3

BUCK PRONTO 2 WA008113 5

They have a gene called ALMT1, that

o Soil pH is only one part of soil acidity and…

o It is the most important factor in toxicity but…

o It is only a small part.

It does not tell you how much lime to add to get

the pH you want!

oExchangeable acidity. Buffer pH

oCarbonic (CO2!) and Organic Acids

oPlant Uptake/Leaching of Cations

o Conversion of carbon dioxide to carbonic acid

o Respiration = uptake up O2 and subsequent release of

CO2(g) + H2O(l)  H+(aq) + HCO3-(aq)

oSoil organic matter contains compounds that behave

oCation removal by crop uptake will either

2. Nitrification results in acidification equal to

CaCO3(s) + 2H+  Ca2+ + H2O + CO2

oField determination with lime

o Add organic matter

Microna Ag H2O - Columbia

Koenig and coworkers

Koenig and coworkers

oImplement soil sampling plan to identify

All those I stole from:

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