Title: ACID, SALINE, AND SODIC SOILS
1Chapter 3
- ACID, SALINE, AND SODIC SOILS
2Why study acid, saline, and sodic soils?
- Acid, saline, and sodic soils have unique
chemical and physical properties that influence
how plants grow. - Since availability of nutrient ions is determined
by their chemistry, it is important to understand
how nutrient availability will be influenced by
the special chemical properties of these soils. - What are acid soils?
- Acid soils, technically defined, are soils that
have a pH less than 7.0, since by convention pH
of 7.0 is neutral, above 7.0 is basic (or
alkaline) and below 7.0 is acidic. From the
standpoint of plant growth, soil management is
usually not affected until the pH is less than
about 6.2 for legumes and 5.5 for non-legumes. - Understanding the concept of pH is fundamental to
understanding and managing acid soils. Since pH
is defined as the log H activity, a pH change
of one unit (e.g. from pH of 6.0 to pH of 5.0)
represents a 10-fold increase in acidity. - What causes soil acidity?
- Acid soils are a natural phenomenon related to
soil parent material and rainfall conditions
under which the soil developed. Soils developed
from limestone parent material, for example will
often be neutral or alkaline in their pH (e.g. pH
gt 7). Granitic parent material, on the other
hand, will favor development of an acid soil.
3Acid Soils
- Under high rainfall conditions (gt 30 inches/year)
parent material that is permeable, such as
sandstone, will likely become acidic because
there is sufficient leaching over geological time
(tens and hundreds of thousands of years) to
remove even basic materials like limestone. - Rainfall, by nature is slightly acidic because
water and carbon dioxide form carbonic acid in
the atmosphere (i.e. acid rain is normal).
Thus, as basic materials are leached out of the
parent material, H may remain to cause the soil
to be acidic. - CO2 H2O ?? H HCO3-
- atmosphere carbonic acid
- Two other factors, that contribute to soil
acidity, are the removal of basic cations and use
of N fertilizers associated with intensive crop
production.
4Basic and Acidic Cations
- The term basic cations is used to designate
cations that, when combined with hydroxide (OH-)
form a compound that would dissolve in water and
create an alkaline solution - The cations Na, K, Ca 2 , and Mg 2 are good
examples. In contrast, the hydroxides of Al 3
and Fe 3 are so insoluble the ions would not be
present in solution unless the solution were
acidified to dissolve them. - Al 3 and Fe 3 , are usually referred to as
acidic ions for this reason. Plants generally
absorb nutrient cations in excess of nutrient
anions. In this process, electrical neutrality
or ion-charge balance may be maintained by
simultaneous absorption of OH- or the exudation
of H by the plant root. - In either case the result is a contribution of
acidity to the soil. - Plant uptake of basic cations in excess of anions
in a natural, non-agricultural environment
contribute little to soil acidity because plants
die and recycle the cations in-place. - Intensive agriculture accelerates the
acidification because the bases are generally
removed from the field with harvest and are not
recycled.
5Intensive agriculture relies heavily on the use
of ammoniacal sources of N. These fertilizer
materials undergo biological oxidation to NO3-
according to the overall general reaction NH4
2O2 ? NO3- 2H H2O which produces two
protons for every mole of N oxidized
6mZE 11H 42He E- elementm massz - atomic
number ( of protons in the nucleus) All hydrogen
atoms have one proton____________________________
______________11H 21H 31H_______________________
___________________ stable stable radioactive deu
terium tritiummass 1 mass2 mass3no
neutron 1 neutron 2 neutrons1 proton 1 proton 1
proton1 electron 1 electron 1 electron__________
________________________________126C 136C 146C__
________________________________________stable st
able radioactivemass12 mass13 mass146
neutrons 7 neutrons 8 neutrons6 protons 6
protons 6 protons6 electrons 6 electrons 6
electrons________________________________________
__
7Plant Uptake and Exchange
NO3-
OH-
NH4
H
8What is the nature of soil acidity and soil
buffer capacity?
- Soils behave as a system made up of the salt from
a weak acid and strong base. - Clay and soil organic matter, provide surfaces
for adsorption of cations - Clays have a net negative charge resulting from
isomorphic substitution of divalent for trivalent
ions (Mg 2 for Al 3 ) and trivalent for
tetravalent ions (Al 3 for Si 4 ) within the
mineral structure. - Soil organic matter contributes to the net
negative charge of soils because of dissociated
H from exposed carboxyl and phenol groups. - The cation exchange capacity (CEC) of organic
matter is pH dependent, whereas most of the CEC
from clays is not. - A small contribution to soil CEC is from
unsatisfied charges at broken edges of clays. - The strength with which cations are adsorbed to
cation exchange sites is directly proportional to
the product of the charges involved and inversely
proportional to the square of the distance
between charges (Coulombs law). Consequently,
the lyotropic series describing the adsorption of
cations on clay particles in soils is generally
considered being - Al 3 ? H gt Ca 2 ? Mg 2 gt K ? NH4 gt Na.
9- The similarity in strength of adsorption for
Al and H is because H, although only 1/3 the
charge strength of Al, is much smaller in
diameter, allowing it to get closer to the
internal negative charge of clays than is
possible for the larger Al. - The electrostatic adsorption of cations on clay
and organic matter surfaces creates a reservoir
of these ions for the soil solution. The
adsorbed ions are in equilibrium with like ions
in the soil solution
10Soil pH
- Relative amounts of each ion adsorbed and in
solution varies depending upon their relative
concentrations in the soil solution and how
strongly the ion is adsorbed (lyotropic series).
- Amount of H in the soil solution is 1/100th the
amount adsorbed on cation exchange sites - We might expect the amount of Ca 2 and K to be
present in the soil solution at about 1/50th and
1/10th their amount adsorbed on cation exchange
sites - When soil pH is determined, only the H in the
soil solution is measured. - Soil pH referred to as active acidity, whereas
the H adsorbed on exchange sites is called
potential or reserve acidity. - The buffer capacity of soils, that is, their
ability to resist change in pH when a small
amount of acid or base is added, is a function of
their exchangeable acidic and basic cations. - Soils with low CEC (e.g. sandy, low organic
matter) have weak buffer capacity, while soils
with high CEC (e.g. clayey, high organic matter)
have strong buffer capacity.
11Effect of soil acidity on plants
- Plant species vary in their response to acidic
soil conditions. Those which have evolved and
are cultivated in humid regions (e.g., fescue,
blueberries, and azalea) tolerate acidic soils
better than other species (e.g., bermudagrass and
wheat) grown in arid and semiarid climates. - The chemical environment that plants must
tolerate, or can benefit from, may be inferred
from the relationship of percent base saturation
and pH
Soil pH
12pH and pOH
- pH -log H
- pOH - log OH-
- pH pOH -log Kw 14
- Kw ion-product constant for water
- Kw HOH- 1 x 10-14
- Ka acid-dissociation constant
- Ka HA-/HA (A- conjugate base of the
acid) - Kb base-dissociation constant
- Kb OH-A/OHA (A conjugate acid of the
base) - Ka Kb Kw
- Ksp solubility-product constant
- -degree to which a solid is soluble in water
- -equilibrium constant for the equilibrium
between an ionic solid and
its saturated solution
13Solubility
- Solubility of a substancequantity that
dissolves to form a saturated solution (g of
solute/L) - Solubility product
- Equilibrium constant for the equilibrium
between an ionic solid and its saturated solution
Solid AgCl is added to pure water at 25C. Some
of the solid remains undissolved at the bottom of
the flask. Mixture stirred for 2 days to ensure
an equilibrium is reached. Ag conc. Determined
to be 1.34x10-5M. What is Ksp for AgCl?
AgCl ?? Ag Cl- Ksp AgCl-
At equilibrium, conc of Ag 1.34 x 10-5
conc of Cl- 1.34 x 10-5
Ksp (1.34 x 10-5)(1.34 x 10-5) 1.80 x
10-10
14- The percentage base saturation identifies the
proportion of the CEC that is occupied by cations
like Na, K, NH4, Ca 2 , and Mg 2 compared to
the acidic cations of H and Al 3 . - This relationship is responsible for the fact
that deficiencies of Ca, Mg and K are rare in
soils with a pH near or above neutral. - Aluminum oxides (Al(OH)3, also expressed as
(Al2O3 ? 3H2O) are of such low solubility that Al
3 usually is not present in the soil solution or
on cation exchange sites until the soil pH is
less than about 5.5. - The apparent solubility product constant (Ksp)
for Al(OH)3 in soils is about 10-30. From this,
the concentration of Al in the soil solution
and its change with change in pH can be
calculated.
15Aluminum
Solving the above at pH of 5, OH- would be equal
to 10-9
The concentration of Al (10-3) is moles/liter.
Since the atomic weight of Al is about 27, a
mole/liter would be 27 grams/liter (g/L) and the
concentration of 10-3 is equal to 0.027 g/L, or
27 ppm. 27 ppm at a pH of 5
16Solubility
- Critical to the management and growth of plants
in acid soils is the knowledge that Al in the
soil solution increases dramatically with
decrease in pH below about 5.5. When solved for
a soil pH of 4.0 (OH- is equal to 10-10), we have
A concentration of 1.0 mole/L is equal to 27 g/L
or 27,000 ppm. While there may not be a
1000-fold increase in soil solution Al 3
concentration when pH changes from 5.0 to 4.0,
these calculations should make it clear why Al 3
concentrations may be significant at pH 4.5, for
example, and immeasurable at 5.5.
17Al toxicity
- Soluble Al is toxic to winter wheat at
concentrations of about 25 ppm. - Adverse effect of soil acidity on non-legume
plants is usually a result of Al and Mn toxicity.
- In winter wheat, Al toxicity inhibits or prunes
the root system and often causes stunted growth
and a purple discoloration of the lower leaves. - These symptoms are characteristic of P
deficiency, and are likely a result of the plants
reduced ability to extract soil P. - Al toxicity versus P deficiency? Solubility
diagram
Laboratory exercise, applying P to decrease Al
toxicity?
18pH preferences of common crops
- pH is not an essential plant nutrient, and
plants obtain their large H requirement from H2O
and not H. - Thus, it is the chemical environment, for which
pH is an index, that crops are responsive to
rather than the pH itself. - Non-legumes require a soil pH above 5.5 because
more acidic soils tend to have toxic levels of Mn
and Al present. - Crops which grow well in soils more acidic than
this can tolerate these metal ions and perhaps
are ineffective in obtaining Fe from less acidic
soils. - Legumes usually grow best at soil pH above 6.0
because the rhizobium involved in fixing
atmospheric N2 seem to thrive in an environment
rich in basic cations.
Plants split H2O
Mangroves
Mangroves 2
19How is soil acidity neutralized
- Most effective way to neutralize soil acidity is
by incorporation of aglime.
Neutralization of acid soil using aglime (CaCO3)
resulting in increasing exchangeable Ca and
formation of water and carbon dioxide.
20Nutrient Availability
21Lime
- Aglime is effective because it is the salt of a
relatively strong base (calcium hydroxide) and a
weak acid (carbonic acid), and is therefore basic
- Ca(OH)2 H2CO3 ? CaCO3 H2O
carbonic acid
22Lime needed to neutralize soil acidity
- Exchangeable acidity must be neutralized in order
to change soil pH because it represents most (99
) of the soil acidity. Since the amount of
exchangeable acidity in the soil, at a given pH,
depends on the soil CEC, the amount of lime
required is a function of clay content, organic
matter content, and soil pH. - Lime requirements can be determined directly in
a laboratory by quantitatively adding small
amounts of a solution of known strength base
(e.g. 0.1 normal NaOH), to a known amount of the
acid soil mixed with water.
23pH and Lime
- By measuring pH as the base is added, the amount
of base required to obtain any pH can be
estimated
Buffer index of 6.2
pH scale of 14? Why?
24Lime
- Direct determination of lime requirement is very
time consuming and is not usually done in the
routine determination of lime requirement by soil
testing laboratories. - Direct determination identifies the amount of
base, such as CaCO3, that must be applied if all
the acidity is able to react with the base that
is added - In practice, this is virtually impossible because
of size differences between clay and organic
matter colloids (very small) and the finely
ground (relatively large) lime particles. - Field studies (calibration) can be conducted to
develop the relationship between amounts of
aglime identified by direct laboratory titration
and crop response.
25Lime Requirements
- Most soil testing laboratories use an indirect
method of determining aglime requirement. - Involves adding a known quantity of a lime-like
chemical solution (i.e., buffer solution of pH
7.2) to an acid soil and water mixture. - After equilibrium has been obtained (about two
hours) the pH is measured. - This pH is often called the buffer pH or
buffer index. The buffer index, by itself,
does not identify how much lime must be added to
neutralize an acid soil. - Field studies relating lime additions to soil pH
are required to calibrate the buffer index, just
as they would be in a direct titration approach.
26Lime Requirements
Why do we now lime to 6.0? (and not anything
above 6.0)
27Buffering Capacity
- Buffer capacity is a function of CEC (e.g. clay
and soil organic matter content). - Amount of lime required to neutralize acidity in
a sandy soil (e.g. Meno fine sandy loam) and a
fine textured soil (e.g. Pond Creek silt loam)
will be quite different even when they have the
same soil pH
28Amount of potential acidity that needs to be
neutralized
29How often should lime be applied
- The answer to this question will depend on how
intensively the soil is managed and how large is
the soil buffer capacity. For example, the
amount of basic cations removed in a 30-bushel
wheat crop in grain and straw is shown to be
about the same as that removed by a ton of good
quality alfalfa hay
30- Soil will become acidic faster, and require
liming more often, if both grain and straw are
harvested. - If two fields are yielding at the same level, it
might be expected that a sandy soil would need to
be limed at lower rates, but more frequently,
than a fine textured soil.
31Common liming materials
- Aglime. Any material that will react with, and
neutralize, soil acidity may be considered for
use to lime an acid soil. The most common
liming material is aglime, a material that is
primarily composed of calcium carbonate, mined
from geological deposits at or near the earths
surface. - Some deposits are high in magnesium carbonate and
are called dolomitic limestone. Dolomitic
limestone is also a good source of Mg for deep,
sandy, acid soils where this nutrient may also be
deficient. The mined limestone is usually
crushed and sieved to obtain material of a small
enough particle size to be effective for aglime. - Quick lime. Mined limestone may be processed to
improve its purity and neutralizing strength.
The term lime was initially used as a name for
CaO, which may also be called unslaked lime,
burned lime, or quick lime. It may be obtained
by heating (burning) calcium carbonate to drive
off carbon dioxide.
CaCO3 heat ? CaO CO2
Often used for stabilizing sewage sludge. When
added to the mixture of sewage solids and water,
it quickly reacts to raise the pH above 11
32Liming Materials
- Hydrated lime. Hydrated lime, which may also be
called slaked lime or builders lime, is produced
by reacting quick lime with water.
CaO H2O ? Ca(OH)2
33Special Formulations
- Liquid lime
- Formulated by mixing finely ground limestone with
water and a small amount of clay. - Clay is added to help keep the lime particles
suspended in the water during application. - Since the solubility of CaCO3 is low, most of the
lime is present in solid form and will react like
an application of solid lime. The ECCE of the
formulation will be much less (depends on how
much water was added) than that of the lime used
in the mixture, even when the dry lime had a high
ECCE. - Typically the dry lime has an ECCE of nearly 100
and the liquid lime is about 50 because about
½ of it is water. - Pelleted lime
- Pelleted lime is created by compressing, or
otherwise forming pellets out of finely ground,
good quality CaCO3. - Neutralizing effectiveness of liming materials
depends upon being able to maximize their surface
contact with soil colloids. - The advantage of liquid lime and pelleted lime
compared to conventional aglime is to minimize
dust. The disadvantage is they are usually much
more expensive, on a cost per ton of ECCE, than
conventional aglime.
34(No Transcript)
35Industrial by-products.
- Kiln dust from cement manufacturing plants,
- Fly-ash from coal burning power plants,
- Residual lime from metropolitan water treatment
plants. - Effectiveness of these materials will depend on
particle size and neutralizing strength of the
material.
Lime from Water Treatment
- History of Water Treatment
36How are the neutralizing values of liming
materials compared
- Effective Calcium Carbonate Equivalent.
- Effectiveness of the aglime identified as
effective calcium carbonate equivalent, or ECCE.
- Expression of the active ingredient of the
material for neutralizing soil acidity. - ECCE of liming materials is expressed as a
percentage of the material and takes into account
the particle size and neutralizing strength of
the material - Chemical Equivalence.
- Equivalence of compounds relative to their acid
neutralizing strength provides insight to their
differences in neutralizing strength. - Accomplished by calculating the equivalent weight
of a liming material and comparing it to the
equivalent weight of CaCO3. - Only possible if the materials are pure
chemically. This consideration is of interest,
for example, when comparing the effectiveness of
dolomitic lime (rich in MgCO3) to that of normal
aglime (primarily CaCO3). The equivalent weight
of each material is calculated, using the
definition - An equivalent weight is the mass of a substance
that will react with one gram of H, or one mole
(6 x 1023) of charge.
37Equivalent weights
- Equivalent weights are the chemists way of
converting apples and oranges (etc.), all to
apples. - Atomic (or molecular) weight of an ionic species,
divided by its charge is equal to its equivalent
weight. - For both CaCO3 and MgCO3 the charge of ions
involved is two, and one mole of the carbonate
ion will neutralize two grams of H, or two moles
of charge. - The molecular weight of CaCO3 is 100 and MgCO3 is
84. - Equivalent weights are ½ their molecular weights,
or - CaCO3 100/2 50
- MgCO3 84/2 42
- It only requires 42 g of MgCO3 to accomplish the
same neutralizing as 50 g of CaCO3, the MgCO3 is
50/42 or 1.19 times more effective than CaCO3. - Applying the same comparison to CaO (eq. wt. 28)
and Ca(OH)2 (eq. wt. 37) it is clear that these
materials would be required at much lower rates
than CaCO3 (eq. wt. 50)
38Important considerations to improve success of
liming
- Soil Testing.
- Reliable soil test (representative)
- soil pH may be variable in the area (year to
year?) (within year?) - Amount of Lime. The buffer index from a soil
test serves as a good guide for determining how
much lime should be added, - When non-legumes are grown successively in the
same field, it is only necessary to apply enough
lime to eliminate current and future Al and Mn
toxicities. - Lime recommendations for continuous wheat
production in Oklahoma are to apply only ¼ the
amount required to raise the pH to 6.8. - This recommendation will raise the pH above 5.5
and keep it below 6.5 to minimize the incidence
of root-rot diseases. - Occasionally the buffer index for sandy, low
organic matter soils will be so high that no lime
is recommended. - In these cases a minimum of 0.5 ton ECCE/acre for
non-legumes and 1.0 ton ECCE for legumes is
recommended to assure the acidity will be
corrected and the application is economical. - When lime recommendations are extremely large the
amount should be split into an initial
application of 5 ton/acre (230lb/1000 ft2)
followed by the remainder applied a year later.
39Considerations
- Incorporation and Timing.
- Lime must be physically mixed with the soil.
- Pastures, perennial plantings, or no-till
productions, may require three to five years
before the lime causes a noticeable change in
soil pH. - Important to lime fields before they are planted
to a perennial crop or managed as no-till. - Systems where alfalfa is rotated with a
non-legume annuals like corn or wheat, the field
should be limed a year before the alfalfa is
planted to take advantage of tillage operations
related to corn or wheat production and allow
more time for lime to react in the soil. - When lime is incorporated well, and there is good
soil moisture, it may still take a year or more
before noticeable change in soil pH occurs. - Tillage Depth. Lime recommendations are usually
made assuming a six-inch tillage depth. - Sandy soils are usually cultivated to eight or
ten inches and a proportional increase in the
lime rate should be made. - For crops with a shallow root system, such as
some vegetables, it may be important to reduce
the lime rate to match a shallower depth of
incorporation.
40How can acid soils be managed without liming
- Liming Alternative.
- Acid tolerant varieties or different plant
species. - Karl and Custer are not acid tolerant whereas the
variety 2163 is acid tolerant. - Rye more acid tolerant than wheat.
- The Al and Mn toxicity that prevent normal
seedling root development in wheat can be
alleviated by adding phosphate fertilizer in a
band with the seed at planting. - Phosphate reacts strongly with Al to form
insoluble aluminum phosphate, thus removing Al
from solution and the exchange complex. - Rate of 60 lb P2O5/acre is required to obtain
normal fall pasture but only 30 P2O5/acre is
needed if wheat is managed for grain only. - If P is not deficient, the cost of applying the P
for two or three years will usually equal the
cost of an application of lime that would have
lasted five to eight years. - These alternatives allow normal or near normal
production but do not cause a change in soil pH.
- Eventually the soil must be limed for long-term
production.
41What are saline soils
- Classified as saline when they contain a high
enough concentration of soluble salts to
interfere with normal growth and development of
salt-sensitive plants. - Soluble salts are compounds, like common table
salt (NaCl), where ions that make up the salt are
weakly bound and have a strong attraction for
water. - These ions hold water quite tightly, salty water
- (higher boiling point)
- (lower freezing point)
- Salt is added to water used in food preparation
to raise the boiling point and hasten the
process. - Salt spread on icy sidewalks and roads to melt
ice that would otherwise remain solid at
temperatures below freezing. - Soluble salts in soils soil water is held
tightly enough by the ions that plants cannot use
it (apparent moisture stress) - Saline soils characteristically remain moist
longer than the rest of the field - Occupy poorly drained areas of the landscape
- White surface layer of salt after they become
dry. - Occur in semi-arid, temperate regions
- Saline soils are uncommon in the moisture
extremes of deserts and tropical rain forests.
42Saline Soils
- Saturating a soil sample with water (a paste
condition) for about four hours, - Extracting the water (and dissolved salts)
- Measuring its ability to conduct electricity.
- Ions in water allow electricity to pass through
it - More ions present the easier electricity is
conducted - Conductivity is expressed in mhos/cm.
- Conductivity of water is usually very low and
expressed as mmhos/cm or micromhos/cm. - Soils are classified as saline when the extract
of a saturated paste has an electrical
conductivity (EC) equal to or in excess of 4,000
micromhos/cm. - Concentration of soluble salts, expressed as ppm,
is roughly equal to 0.65 times the conductivity
expressed in micromhos/cm. - Soil with an EC of 4,000 micromhos/cm will
contain about 2600 ppm soluble salts in the
saturated soil solution. - Saline soils Reclamation
- leaching soluble salts out of the soil.
- create good surface and internal drainage.
- incorporating large amounts of organic matter
(create large pores in the surface soil) - Good quality irrigation water can be used to
hasten the process. - Deep tillage should be avoided once the organic
matter is incorporated - Salt tolerant species like bermudagrass or barley
should be planted to provide a vegetative cover - Practices to reduce surface evaporation and
encourage water movement downward ???
43What is a Sodic Soil
- Abnormally high levels of exchangeable sodium
(Na). - When enough Na is adsorbed, clay particles repel
each other. - Occurs when the exchangeable Na percentage (ESP)
is equal to or exceeds 15 - Soil pH of sodic soils will often be above 8.
- Dispersed colloids become oriented as water moves
into soil and eventually they plug soil pores. - Poor internal drainage resulting in dry subsoil
and a moist or wet surface layer. Crops fail
because of excess surface water (drown out) or
for lack of water (dry subsoil) even though there
may have been adequate rainfall or irrigation. - Reclaimed by improving surface and internal
drainage and incorporating gypsum (CaSO4) in the
surface. - Gypsum dissolves to supply a high concentration
of Ca in soil solution that replaces
exchangeable Na, freeing it to be washed out of
the soil - Ca helps bind colloids into aggregates and
restore soil permeability. Reclamation of sodic
soils is similar to that of saline soils except
that gypsum must be added to sodic soils.
44What are Saline-Sodic Soils
- Contain salts in excess of 4,000 micromhos/cm and
exchangeable Na in excess of 15 - Have all the features of the saline soil, and if
reclamation procedures are used that do not
include gypsum, they will become sodic soils when
the salts are leached out. - Many salt affected soils are saline-sodic because
a primary soluble ion is Na. - Reclamation takes several (2 or more) years,
dependent upon the time required to get about two
pore volumes of good quality water to pass
through the soil. - Most soils are about 50 pore space and so a
pore volume-depth for a four foot profile would
be about two feet and two pore volumes about four
feet. - Sandy soils in high rainfall regions may be
reclaimed quite rapidly while clayey soils in
semi-arid regions may take many years if rainfall
is the only source of leaching water.
45How Soluble is the Earths Crust
- The extent to which the earths crust dissolves
over time depends upon solubility of rocks and
mineral, abundance of elements in the rocks and
minerals, and rainfall. - Naturally occurring compounds containing either
Na or Cl tend to be very soluble and, with time,
end up in the oceans and seas of the world.
46Turf
- Does soil acidity increase in turf situations via
the application of N - No continual removal of bases like in wheat and
corn, thus soil acidity is diminished