QUESTION:- EXPLAIN MITIGATION OF ALKALIS CONTAINING SOILS BY USE OF

ADDITIVES.

ANSWER:- Alkali, or Alkaline, soils are clay soils with high pH (> 8.5), a poor soil structure
and a low infiltration capacity. Often they have a hard calcareous layer at 0.5 to 1 metre depth.
Alkali soils owe their unfavorable physico-chemical properties mainly to the dominating
presence of sodium carbonate, which causes the soil to swell and difficult to clarify/settle. They
derive their name from the alkali metal group of elements, to which sodium belongs, and which
can induce basicity. Sometimes these soils are also referred to as alkaline sodic soils. Alkaline
soils are basic, but not all basic soils are alkaline.

The most injurious alkaline sodium compounds in the soils and irrigation waters are
Na CO  (sodium carbonate) or NaHCO  (sodium bicarbonate).
2 3 3

*Alkalinity problems are more common in clay soils than in soils with low colloid content. As a
consequence of the relative preponderance of sodium on exchange sites of colloids, the alkaline
reaction of the liquid phase and the swelling/shrinking clay minerals, the low fertility of these
salt-affected soils, in most cases, are closely...

Factors Which Make the Soils Alkaline:-

1. Poor drainage in arid region,

2. Rapid evaporation of alkaline soil solution, and

3. Excess uptake of alkaline salts and little percolation.

In arid and semi-arid regions, the rainfall is too low to leach or remove the saline matter from the
top soils. Besides this, water along with dissolved alkali salts moves upward by capillary action
which on reaching to the soil surface evaporates and the salts accumulate in the form of a hard
layer or pan in the subsoil. This hard layer is responsible for impermeability of such soils. Miller
is of the opinion that many plants absorb excess acidic ions, e.g., NO –3, than the basic ions. This
excessive removal of acidic ions results in the accumulation of basic ions which make the soil
alkaline.

According to a chemical hypothesis, alkali soils may result in the following steps:

(a) Reaction between NaCl or KCl and soil (S):

NaCl + S (Soil) → Na (S) + CI– ion

(b) Then the soluble products are leached away from the soil surface by drainage water.
(c) Finally, reaction between insoluble Na (S) complex and carbonates.

2 Na (S) + CaCO3 → Ca (S) (alkaline) + Na2CO3 (alkaline)

Types of alkali soils:

These soils are of two types:

(i) Black alkali soils—In these soils, Na2CO3 is found in excess.

(ii) White alkali soils—In this group, NaCl is present in excess.

Russians call such soils as solonchack. Bertholet suggested that Na 2CO3 was formed in black
alkali soil by interaction of NaCl and CaCO3.

2NaCl + CaCO3 = Na2CO3, + CaCl2

Reclamation of Alkali Soils:

Alkaline soils with solid CaCO3 can be reclaimed with grass cultures, organic compost, waste
hair/feathers, organic garbage, waste paper, rejected lemons/oranges, etc. ensuring the
incorporation of much acidifying material (inorganic or organic material) into the soil, and
enhancing dissolved Ca in the field water by releasing CO 2 gas.Deep ploughing and
incorporating the calcareous subsoil into the top soil also helps.

Alkali soils are best reclaimed by the following methods:

(A) Chemical method:

(1) By cationic exchange (replacement of alkali from soil colloids by calcium ions). Application
of calcium sulphate (gypsum) in the soil reduces alkalinity to a great extent and makes the soil
fertile.

The reaction proceeds in the following way:

2Na-clay + CaSO4 → Na2SO4 + Calcium-clay

Na2CO3 + CaSO4 + CaCO3, + Na2SO4

Good drainage leaches away Na2SO4.

(2) Alkali salt percentage can also be reduced in the soil by the use of acid forming chemical
amendments such as sulphur, ferrous sulphate and limestone.

* Sulphur, when applied to the soil, oxidises and forms sulphuric acid which converts
carbonates of sodium and potassium to Na 2SO4 and K2SO4 respectively that may be removed
from top soil by drainage water.

If the soil pH must be lowered, you can choose to add sulfur to the soil to reduce the alkalinity.
The Utah State University Extension suggests annually adding elemental sulfur at a rate of 6 to
10 pounds per 1,000 square feet of area. When added to the soil, elemental sulfur -- a yellow
powder and not the sulfate sulfur type that's a plant nutrient -- converts to sulfuric acid when it is
oxidized by soil bacteria to the sulfate form, according to Clemson University Extension. This
process can take time, but the sulfuric acid creates the acidity the soil needs, thus lowering the
pH level. To reach the appropriate level, you must keep adding sulfur to the soil and testing it
until it reaches the appropriate pH level.

*Gypsum (calcium sulfate ) can also be applied as a source of Ca++ ions to replace the sodium
at the exchange complex. Gypsum also reacts with sodium carbonate to convert into sodium
sulphate which is a neutral salt and does not contribute to high pH.

How Gypsum helps in the treatment of Alkaline Soil?

Gypsum (Calcium Sulphate, CaSO4.2H2O) is a sedimentary mineral. It is very important for the
treatment of alkaline soil, which is discussed below:

1. It is an excellent source of sulphur for plant nutrition and improving crop yield.”

2. It can reduce Aluminium toxicity particularly in subsoil.

3. It helps in reducing runoff and erosion by keeping Phosphorous and other nutrients from the
soil.

4. It replaces Sodium and leached downward and out of reach of plant roots.

5. It can be applied a source of Ca++ions to replace the Sodium at the exchange complex in the
soil.

While using Gypsum, there must be enough natural drainage to the underground, or else an
artificial subsurface drainage system must be present, to permit leaching of the excess sodium by
percolation of rain and /or irrigation water through the soil profile. Apart from the use of
fertilizers, the alkalinity of the soil can be reduced by cultivating grasswort or saltwort or Barilla
plants.

* The amount of gypsum and sulphur required to reclaim the alkali soils will be different
depending upon the degree of alkalinity, drainage and buffering capacity of soils.

*Calcium Chloride is also used to reclaim alkali soils. CaCl2 converts Na2CO3 into NaCl
precipitating CaCO3. NaCl is drained off by leaching water. Spent acid (HCl, H2SO4, etc.) can
also be used to reduce the excess Na2CO3 in the soil/water.

* Urea is made available cheaply to farmers, it is also used to reduce the soil alkalinity / salinity
primarily. The NH4 (Ammonium) present in urea which is a weak cation releases the strong
cation Na from the soil structure into water. Thus alkali soils absorb / consume more urea
compared to other soils.

* Organic/Fertilizer Mixes

Sulfur isn't the only additive you can mix in the soil to change the alkaline condition. Organic
materials such as peat or sphagnum peat moss can reduce the pH level, because the microbes
found in organic matter decompose and create carbonic acid, according to the Cooperative
Extension System. However, manure, though organic, has a high pH as well as high levels of
soluble salts, which would only compound the problem, according to the Arizona Cooperative
Extension. An alternative to organic matter is fertilizer. For example, Utah State University
Extension says that ammonium sulfate and fertilizers whose directions specify that "an acidic
reaction" occurs when applied will lower the pH. One such fertilizer, sulfur-coated urea, not only
lowers the pH but also adds nitrogen to the soil.

The types of reaction which occur when an amendment is applied to an alkali soil are given
below:

(1) With Sulphur:

(i) 2S + 3O2 = 2SO3

(ii) SO3 + H2O = H2SO4

In the next step, if soil is calcareous—

(iii) H2SO4 + CaCO3 = CaSO4 + CO2 + H2O

(iv) 2Na-Clay + CaSO4= Ca-Clay + Na2SO4

But if the soil is non-calcareous—

(v) 2Na-Clay + H2S04= 2H-clay + Na2S04

(2) With lime-sulphur:

Now if the soil is calcareous—

(i) H2SO4 + CaCO3 = CaSO4 + CO2 + H2O

(ii) 2Na-Clay + CaSO4 = Ca-Clay + Na2SO4

But if the soil is non-calcareous—

(i) 10Na-Clay + 4H2SO4 + CaSO4 = 8H-Clay + Ca-Clay + 5 Na2SO4

(3) With ferrous sulphate:

(i) FeSO4 + H2O = H2SO4 + FeO

Now if the soil is calcareous—

(ii) H2SO4 + CaCO3 = CaSO4 + CO2 + H2O

(iii) 2Na-Clay + CaSO4 = Ca-Clay + Na2SO4

But if the soil is non-calcareous—

(ii) 2Na-Clay + H2SO4 = 2H-Clay + Na2SO4

(4) With limestone on non-calcareous soils:

(i) Na-Clay + H2O = H-Clay + NaOH

(ii) 2H-Clay + 2NaOH + CaCO3 = Ca-Clay + Na2CO3 + 2H2O

(5) With any H-Clay:

(i) 2H-Clay + CaCO3 = Ca-Clay + CO2 + H2O

(6)The use of pyrite (FeS2) as an amendment is a recent development in the chemical
amelioration and reclamation of alkali soils. In presence of moisture and air, pyrite is converted
into sulphuric acid which then replaces exchangeable sodium by hydrogen or calcium released
from insoluble calcium present in the soil. In addition it is said to correct iron deficiency and
lime induced iron chlorosis in alkali soils. It is important to mention that the formation of H2SO4
in the soil by the application of pyrite may take place through chemical and microbiological
actions. Pyrite is oxidised according to the following equation suggested by Bloomfield (1973).

FeS2 + 2Fe+3 = 3Fe+2 + 2s (Chemical)

(7)Sulphur thus formed could be the substrate for thioxidants which convert it into H2SO4.

S + 3(0) + H2O = H2SO4

Temple and Kochler (1954) explained the action of ferroxidans on the formation of
H2SO4 as follows:

FeS2 + H2O + 7O = FeSO4 + H2SO4

2FeSO4 + O + H2SO4 = Fe2(SO4)3 + H2O

FeSO4 formed in the above reaction may be converted into H2SO4 by hydrolysis.

FeSO4 + H2O → H2SO4 + FeO

In brief, the pyrite is oxidized in soils to ferrous sulphate and sulphuric acid as depicted in
the following equation:

2FeS2 + 2H2O + 702 = 2FeSO4 + 2H2SO4

Both sulphuric acid and ferrous sulphate help in reclamation of calcareous as well as non-
calcareous salt affected soils by lowering the pH and solubilising free calcium from calcium
carbonate present.

The reactions are given below:

In salt affected calcareous soils:

la. CaCO3 + H2SO4 = CaSO4 + CO2 + H2O

lb. 2Na-Clay + CaSO4 = Ca-Clay + Na2SO4

II. FeSO4 + H2O → FeO + H2SO4

H2SO4 formed in reaction II reacts as per equations la and lb

III. H2SO4 also neutralizes NaHCO3 and Na2CO3 present in these soils.

2NaHCO3 + H2SO4 → Na2SO4 + 2H2O + 2CO2

Na2CO3 + H2SO4 → Na2SO4 + H2O + CO2

But if the soil is non-calcareous:

(I) 2Na-Clay + H2SO4 = 2H-Clay + Na2SO4

(II) FeSO4 + H2O = FeO + H2SO4

H2SO4 formed in reaction II acts in similar manner as in reaction I.

(3) Dhar’s method. In India, Dr. Neel Ratan Dhar (1935) succeeded in reducing the alkalinity
and salinity of the soil by the use of molasses and press-mud.

For one acre land he recommended the mixture of the following substances:

(i) 2 tons of molasses, (ii) 1-2 tons of press-mud (a waste product of sugar industry) and (iii) 50-
100 pounds of P2O5 in the form of basic slag.

The molasses is fermented by soil microbes and as a result of fermentation organic acids are
produced which lower the alkalinity and increase the availability of phosphates. The press- mud
contains Ca which forms calcium salts that reduce the content of exchangeable sodium.
Phosphate helps in the microbial fixation of nitrogen into nitrogenous compounds in the soil.

B) Mechanical methods:

The alkali salts are removed by:

(1) Scraper or by rapidly moving streams of water,

(2) Deep ploughing of the land which reduces the alkalinity and makes the soil more permeable.

(3) Application of green manures of Dhaincha, guar, jantar (Sesbania aculeata) has been found
most successful in reclamation of alkali and saline soils.
(4) Spreading of straw and dried grasses and leaves on the alkaline soil.

(C) Cultural method:

Growing of alkali tolerant crops and plants, such as sugar-beet, rice, patsann (Hibiscus
cannabinus), wild indigo and babul in such soils successfully reduces alkalinity. Rice is
commonly the first crop grown on salty lands to be reclaimed. In Punjab the usual practice of
reclamation of salty lands involves growing of paddy after first initial leaching followed by
berseem or senji which has higher water requirement than Dhaincha as green manure which IS
followed by sugarcane and then wheat or cotton.

Introduction of leguminous crops helps in building up of nitrogen supply and opens the soils.
Dhaincha-paddy-berseem rotation has been found to be the best cropping pattern on mild type of
alkali soils in Punjab region. In U.P. also, paddy or dhaincha-paddy are the usual crops taken
during first stage of reclamation of salty soils. This is followed by berseem or barley in winter.
Pulse crops like gram or peas show poor performance.