Soil Acidity and pH

Causes, remediation, and

measurement
http://www.msichicago.org/ed/learninglabs/imgs/waters_ph_chart.jpg
 Soil pH alteration (naturally and
manmade)
• Management and land use
– Fertilizers, organic matter, and other amendments
– Submergence and subsequent uplift of land exposing
reduced sediments to oxidation processes
• Pollution
– Acid rain
– Mining
• Climate
– Weathering and leaching
– Rainfall leaching
– Plant growth: uptake of cations and release of protons
• Metal hydrolysis
 Climatic effects
• Excessive rainfall: Leaching of cations through
the soil profile by rain, weathering of the soil
– Carbonation; hydrolysis; hydration…
• Excessive irrigation: unlikely cause of acidity
since most irrigation occurs in arid or semi-arid
regions with accumulated salts, carbonates, etc
(buffer pH)
– Most irrigated regions are neutral to alkaline (they are
irrigated because there isn’t enough rain to support
crops, therefore the salts and cations don’t leach out
of soils)
 Carbonic acid formation
• forms in rainwater or soil water
CO2 + H2O  H2CO3
H2CO3  H+ + HCO3-
----------------------------
CO2 + H2O  H+ + HCO3-

• [CO2] is higher in soils than aboveground

• Most unpolluted rainfall is slightly acidic

As CO2 concentration
increases, proton (H+)
production increases
and pH decreases

Soda pop or
carbonated beverages
have pH 3 - 4
 Metal hydrolysis
• Polyvalent metals go through several
hydrolysis steps releasing protons
• Alum (KAl(SO4)2) is a commercial product
for lowering pH

http://www.wou.edu/las/physci/ch412/hydrxn2.jpg
 Hydrolysis of Al+3
H2O  OH- + H+

Al+3 + H2O  Al(OH)+2 + H+

Al(OH)2+ + H2O  Al(OH)2+1 + H+
Al(OH)2+1 + H2O  Al(OH)3 + H+
Al(OH)3 + H2O  Al(OH)4-1 + H+
 Increasing soil pH
• Burning plant residues or adding ashes
– Wood ashes are a source of K, Ca, Mg CO3’s
• Liming materials (consume H+ and provide
Ca2+)

Gypsum (calcium sulfate) is not a liming

agent and has very little effect on soil pH.
Gypsum may improve structure in soils that
have extremely high sodium contents
 More ways to increase soil pH
• Denitrification (reduction under anaerobic
conditions)
5CH2O + 4NO3- + 4H+  5CO2 + 2N2 + 7H2O

• Sulfate reduction
SO4-2 + 2CH2O + H+  2CO2 + HS- + H2O
 Factors affecting soil pH measurement
1. Soil:Water ratio
– Saturated paste, 1:1, 1:2, 1:5, 1:10
• Adding more water dilutes the [H+] and usually
causes a slight rise in pH due to “Dilution
effect”
– The amount of increase is a function of soil texture
and porosity
– Not linear (More water = more dissociation of H+
from soil surfaces and more hydrolysis of Al+3)

• Important to report how pH was measured

(both instrument and method)
– Some pH measurements shouldn’t be compared
directly e.g., 1:1 ≠ 1:10 or pHwater ≠ pHKCl
 Brazito Sandy Loam pH

8.6

8.3
pH
7.7

CaCl2 7.4
KCl 7.1

1:1 1:5 1:10

Soil:water ratio
pH determines the
soil's "active" acidity.

The ESTL uses 1:2

(Soil:water) volume
ratio for determining
soil pH.

This is the acidity that

affects the plant roots.
http://soilslab.ifas.ufl.edu/general%20graphics/Instrumentation/pHprobe.jpg
1. Salts in suspension to measure pH
– Dissolved salts from saline soils
– Fertilizers
– CaCl2 or KCl added for pH measurement
(pHCaCl2 or pHKCl)
• As salt concentration increases, pH
decreases (but not necessarily linearly)
– Displace Al+3 or H+ from exchange sites
– Hydrolysis
 3. Time of sampling and season

• Before or after summer rains, irrigation, or

leaching
• Before or after fertilization
• During warming or cooling trends
• Processing and storage of soil
– The pH of a soil that has been dried out and
sitting around will be different from a fresh
sample.
 Accuracy of pH measurements
• A measured soil pH can not really be
much more accurate than +/- 0.5 pH unit.
This means worrying about the last
decimal point in a soil pH of 6.35 is not
worth it when the same soil might vary
seasonally between 5.8 and 6.8
• It's not the pH being wrong, it's just the
nature of soil.
 4. CO2 concentration and pH
• As [CO2] increases, the pH decreases
• Formation of carbonic acid
• Stirring of sample may decrease pH
• Soil [CO2] is MUCH higher than
atmospheric [CO2]
• Affects in-situ measurement of soil pH in
calcareous soils.
– Measure pH immediately or
– Minimize headspace in sample containers
and put on ice
 5. Buffering capacity
• Soils high in SOM and clay minerals are
more resistant to change in pH
• Sandy soils and highly weathered soils are
least buffered
• Base Saturation =  exchangeable bases
CEC
BS = (exch Ca + Mg + Na + K)
(exch Ca + Mg + Na + K + Al + H)
 6. Lime Requirement
• Amount of CaCO3 needed to increase
the pH of the soil to an optimum pH
• Depends on soil mineralogy, % clay
fraction, % OM, cultivation practices
(leaching, fertilization, etc)
• Variety of liming materials
• Only practical to raise pH to ~6 (KCl-
extractable acidity is ~0)
 Lime material
• CaCO3 calcic limestone
• CaMg(CO3)2 Dolomite
• CaO: Quick lime
• CaOH calcium hydroxide
• Byproducts: ground shells, cement
factory waste
 Liming to increase soil pH
• Lime characteristics
– cost
– purity
– speed of effect (fine ground vs coarse)
– ease of handling
• Lime requirement
– depends on pH, CEC and buffer capacity of
the soil
• Lime Application: small amounts split and
incorporated into the soil
 To increase pH from 6 to 7 requires more
lime than from 4 to 5
http://wwwlb.aub.edu.lb/~webeco/SIM215acidsoilsandlimimg_files/image002.gif