5.

Chemistry of Saline and Alkali Soils of Arid Zones*

A. INTRODUCTION

ALLTYPES and groups of soils have a specific level of natural fertility. Under identical climatic conditions,
this levelis determined by many factors: the character of the parent rock,the physical,physico-chemicaland
biochemical properties of the soil and, particularly, the presence of reserves of mobile elements of mineral
nutrition for plants.
Most soils may retain a certain minimum of nutritive substances against leaching.
The natural fertility of a given type of soil can be increased by influencing one of the above listed factors,
i.e.by changing the physical, physico-chemicalor biological properties of the soil,and taking steps to trans-
form the elements ofthe mineral nutrition ofplants into a more accessibleform.Another measure that can be
taken is to increase the reserve of nutritive substances and moisture in the soil.
Among the major nutrients,the substancesfound in the smallest quantity in most arable soils,especially in
arid zones,are compounds of nitrogen.
The second scarcest ofthe major essentialelements of the mineral nutrition ofplants is usually phosphorus.
The shortage of phosphorus supply for plants may be due not merely to the fact that the actual content is
small,but also to the transformationofphosphorus intoforms with low solubility.Inparticular,the carbonate
character ofarid soils (high content ofcalcium carbonate) leads to the formation of calcium phosphates with
low solubility.In some meadow hydromorphic soils,with active anaerobic processes,phosphorus may also be
bound with bivalent iron.To prevent this,there must be better soil aeration so as to promote the transforma-
tion of ferrous oxide combinations of iron,which are soluble,into acid ones,which are insoluble.
Potassium fertilisers which are widely used in non-arid zones are of little effect in arid zone irrigation
farming. The presence of large quantities of tiny fragments of little-weatheredprimary minerals (micas,
feldspars,and so on) provides a constantreserve of accessible potassium in soils.Only if applied in addition
to large quantities of nitric and phosphorus fertilisers does the application of potassium have any effect.
Most arid soils do not suffer from a lack of micro-elements.The most common exception to this general
rule is a shortage of iodine in areas where there are no marine sedimentary rocks.
The use of mineral fertilisers does not cancel out the usefulness of organic fertiliserswhich provide the soil
with a whole series ofother elementsessentialto the mineral nutrition ofplants.Inaddition,organic substances
promote the creation of conditions for the activity of useful micro-organisms,improve the buffering of the
soil against harmful reactions, accelerate the process of obtaining nutritive elements from compounds not
easily available, etc. The decomposition of organic remains is accompanied by the production of carbon
dioxide.Saturation ofthe soil solutionsby carbonic acid increases the solubilityofthe carbonates ofcalcium,
so balancing the composition of soil solutions and absorbed bases,and facilitating the process of calcium
assimilation by plants ; moreover, some organic compounds exercise a stimulating effect on plants.
Contrary to ordinary soils of humid climate the saline soils of arid zones which either have poor fertility
or are completely barren,do not lack nutritive elements (though this may sometimesbe the case) but have a
strong surplus of easily soluble salts.The question of how to utilise these soils for farming in many countries
constitutes one of the most pressing problems of present-dayworld agriculture.
Unless they are desalinised,we cannot reckon to be able to improve their fertility to any marked extent by
use of fertilisers.
In Chapter 3 the saline soils of the arid zone have been characterised in general. Here we have to consider
especially the chemistry of saline and irrigated soils.

B. MAIN SOLUBLE SALTS IN SOILS AND WATERS OF ARID ZONES

Nearly all known acids form salts which are to be found in varying quantities in the soils. Let us take a
look at the main types of salts which lead to the formation of saline soils.
* This chapter was edited by V. A. KOVDAfrom the manuscripts submitted by K.L. RATKOCK(mainly on Parts E and F).
V. V. EGOROVand V. A. KOVDA as authors with contributions by G.PASCAUD
and P. MINART
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 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
1. Carbonates

Salts of carbonic acid are widely found in soils,subsoils and groundwaters of deserts, semi-deserts,steppes
and even forest-steppes.The role of these salts depends very largely on the character of the compounds,
as do also the amounts of salts which are accumulated in the soil,their degree of solubility and toxicity for
plants and their effects on the water economy.

(a) Calcium carbonate

Calcium carbonateis a salt with extremely low solubility (0.0131g/l). In the presence of carbonic caid,how-
ever,as aresult ofthe formationofcalciumbicarbonatesthrough the reaction:CaC0,+H2C0,= Ca(HCO,),;
the solubility of calcium carbonate increases sharply to 0.06-0-14g/l.The solutions of calcium carbonate,
being salts of a strong base and a weak acid, are highly alkaline in the absence of accessible free carbonic
acid (pH 10to 10-2).But the presence of carbonic acid in quantities found in the soil air reduces the alkalinity
of the calcium bicarbonate solution to a fairly low level (pH 7.5 to 8.5). A large quantity of carbonic acid
increases the solubility of the CaCO, from 0.4 to 1.0 g/l,but this is accompanied by a sharp drop in the p H
of the solution from 6-8to 6.1. In view of its low solubility, the presence of calcium carbonate in soils is
not harmful for the majority ofagriculturalplants;althoughplants which are suitable for growing in acid sub-
tropical and tropical soils (such as cocoa,coffee,bananas,tea,citrus fruits,tung trees) do not thrive on soils
with a high calcium carbonate content,therefore reducing both the quantity and the quality of their crops.
Many fresh rivers and undergroundwaters containlarge quantities ofdissolved calcium bicarbonate.Thisis
why deposits brought by river, lake or sea waters nearly always have a high content of calcium carbonate
(from 7to 15%). Large quantities ofcalciumcarbonate pass into the soilhorizons from the calcareous ground-
waters, when the table lies close to the surface and when these waters are exposed to transpiration and
evaporation.The soils of steppes and deserts invariably contain carbonate.The quantity of CaCO, in steppe
and desert soils and loesses may be as high as 20%or even,in some cases,80%. Horizons of this type are
strongly cemented and impenetrable both for the roots of plants and for irrigation waters. Sometimes the
accumulationoflimefrom the groundwaters and the cementationprocess ofthe soil may occur after a period
of 5 to 7years ofirrigation,so killing valuable fruit trees.In soilswhere down-flowingsolutions predominate,
the calcium carbonate is gradually leached out.
Calcium carbonates are easily detected, morphologically speaking, owing to the whitish colour of the
carbonate horizons, the white veins (mycelium), and the mealy accumulations and concretions; also by
making a qualitative analysis with hydrochloric acid,which gives a violent reaction of escaping CO,.

(b) Magnesium carbonate

Magnesium carbonate has much greater solubility than calcium carbonate.In the presence of carbonic acid,
its solubility increases sharply,owing to the formation of bicarbonates of magnesium. Since magnesium car-
bonate is a salt of a strong base and weak acid, during the process of alkaline hydrolysis,its solution is
highly alkaline (pH of up to 10). This alkalinity may cause stress in plants. Therefore,the presence of free
magnesium carbonate in soils may be regarded as a negative factor,causing a lowering of the fertility.How-
ever, the accumulation of magnesium carbonate in soils in free form is rare. This is due to widespread
adsorption ofmagnesium by clays;and also to the formation in the soils ofdeserts and steppes,of a virtually
insoluble compound of magnesium-dolomite (CaMg(CO,), and of dolomitised concretions containing
up to 2.5 % of magnesium carbonate.

(c) Sodium carbonate (soda)

The salts of carbonic acid and sodium are commonly found in nature and sometimes accumulate in soils in
considerable quantities;they exist in soils and groundwaters in several forms. Normal sodium carbonate
Na,CO, is the salt of carbonic acid and sodium hydroxide. In soils,this compound crystallises out with
varying quantities of water (Nazco,. 10 H,O,Nazco3.H20).
Na,CO, is highly soluble (178 g/l at 2GOC). As a result of hydrolysis,it provokes acute alkalisation of the
milieu, up to p H 12.Owing to its high alkalinity and solubility,it is extremely toxic for the majority of
plants. The presence of Nazco, in soil solutionscauses peptisation of soil colloids,soil disaggregation and
low water permeability. Its existence in soils,even in quantitiesof0.05 to 0.1%, reduces the natural fertility,
due to alkalinity and lack of structure.
Bicarbonate of sodium is both less alkaline and less toxic than normal soda. This is due to the fact that
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IRRIGATION, D R A I N A G E A N D SALINITY
bicarbonate of sodium is partially neutralised by carbonic acid.The formationofbicarbonate ofsodium occurs
during the reaction of soda with free carbonic acid,according to:
Nazco,+H,O +CO,-+2NaHCO3
The tendency of normal soda to turn into bircarbonate of sodium is accentuated with the increase of the
content of carbonic acid in the soil air and soil solution,i.e.in the conditions of intensive decomposition of
organic matter and by low temperature.On the other hand,with a moderate content of carbonic acid in the
soil air, i.e.with weak activity of micro-organisms and small content of organic matter, or when the soil
solution is warmed up, bicarbonate is easily tranformed into normal carbonate according to:
2 NaHC0,-->Na,CO,+ H,O +CO,
Under evaporation of groundwaters containing carbonates and bicarbonates of sodium,there accumulates
from the soil solution crystals of double salt-tronas Na,CO, .NaHCO, .2H,O, or of pure NaHCO,.
The majority of natural waters (river, spring,underground,lacustrine) with a concentration of0.5 to 3.0 g/1
(dissolved solids) contain substantial quantities ofcarbonatesand biocarbonates of sodium.Depositsand soils
formed with the participation and under the influenceofsuch waters will always be alkaline,highly colloidal if
containing montmorillonite but not very permeable and compact.
It is comparatively rare for considerable quantities of soda to accumulate in soils. This is due to the fact
that in most desert and semi-desertsoils,there is intense accumulation of gypsum in the presence of which
soda turns into calcium carbonate according to :
Nazco,+ CaSO,->CaCO, 4-Na2S0,
Hence it is only in sediments containing no gypsum that free soda and bicarbonate of sodium can accumulate
in substantial quantities. These conditions sometimes occur in the prairies of the USA and Canada,in the
black earth and forest-stepperegions ofManchuria,Siberia,the Russian plain and the Hungarian depression.
In these areas, too, there are found soda lakes and soils with a high soda content (soda solonchaks and
soda solontsy). The soda content in soda solonchaksmay attain 5 %.Soils with soda salinity are widespread
in the arid monsoon areas of Pakistan, India,in the savannahs of Africa, in the low lying river plains of
Argentina, Chile, Morocco, Western China, Mongolia and Armenia. The solubility of soda drops sharply
at temperatureslower than 8°C.Owing to this factor and to the low permeability of such soils the amount of
soda which can be leached during the wet,cold seasons ofthe year is very small. Carbonates and bicarbonates
once accumulated in soils tend to be conserved there and are little affected by external influences,natural or
due to man’s activities.
Soils containing considerable quantities of carbonates and bicarbonates of sodium are alkaline saline soils
with poor natural fertility and their development requires radical chemical reclamation measures coupled
in some cases with drainage and summer leaching,combined with rice irrigation.

(d) Potassium carbonate

Potassium carbonate (potash) is found in soils much more rarely than sodium carbonate. In regard to its
high solubility,its alkaline hydrolysis,giving the solution a high alkalinity, its toxicity for plants and its
disaggregating effect on soil structure, potassium carbonate is practically identical to sodium carbonate.
Considerable quantities of potash may accumulate in the ash of some agricultural plants (sunflower);
some halophytes also contain potash in large quantities (e.g.haloxylon). The ash ofsuch plants is used as raw
material for obtaining potash. The increase ofpotash,combined with the fallen leaves ofthe haloxylon on the
soil,causes an increase of alkalinity.

2. Sulphates

Sulphuric acid salts are found in varying quantities in almost all types ofsoils.In the soils and groundwaters of
steppes and deserts, sulphates sometimes accumulate in very considerable quantities. The significance of
sulphuric acid salts for agronomy and reclamation varies very much with their chemical composition.

(a) Calcium sulphate

Calcium sulphate(gypsum) is a saltphysiologicallyharmless to plants;this is due to its low solubility(1.9g/l).
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 S A L I N E A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
The soils and soil-formingrocks of semi-desertsand deserts very frequently contain large quantities of
gypsum,accumulated during the evaporation of lacustine waters or saline groundwaters,lying close to the
surface.There are often found,in deserts,gypsiferous soils of ancient origin which no longer contain ground-
waters. In the particularly dry climate of deserts,such as in Chile or the Sahara,the gypsum (CaSO, .2H,O)
becomes dehydrated and turnsinto a mealy mass ofsemi-hydrate-CaSO, .1/2H,O. In some areas ofCentral
Asia, the Caucasus, North Africa, and Argentina, soils contain gypsum in quantities of up to 50% and
sometimes 90%.
Gypsum crystallises,in soils,in a great variety of forms:from thin transparent or mealy crystals to large
nodules; concretions or regular shaped slabs. In soils with a very high gypsum content the gypsum forms
a compact,spongy,porous mass,causing cementation of the entire horizon. Such compact accumulations of
gypsums in soilsmakes them mechanically impenetrable for roots,water and air,hampering the development
of plants and sometimes killing arboreal and palm plantations.
Gypsum is widely used for the reclamation ofalkali soilswhich contain soda and adsorbed sodium.Gypsum
is found together with chlorides and other sulphates which accumulate in saline soils.

(b) Magnesium sulphate

Magnesium sulphate(epsomiteMgSO,. 7H,O)is a typicalcomponentofsalinesoils,accumulatinginquantities
of several per cent. It is also often present in saline groundwaters and in many saline lakes and types ofmud.
Owing to its high solubility (262g/l), it is one of the most toxic and harmful salts to plants.
Magnesium sulphate never accumulates in soils in pure form,but always in combination with other easily
soluble salts;in such cases,radical measures for reclamationby leaching are necessary.

(c) Sodium sulphate

Sodium sulphate is a typical component ofsaline soils,saline groundwater,lakes and saline muds. Its toxicity
is two or three times less than that of magnesium sulphate.Its solubility depends very much on temperature
conditions,increasing considerably when the temperature rises. In view of this fact,the status of sodium
sulphate in soils is extremely complex. In the warm seasons of the year, sodium sulphate rises to the soil
surface together with the most soluble salts (magnesium sulphate,magnesium and sodium chlorides). In the
cold season,on the other hand,sodium sulphate,owing to the lowering ofits solubility,is not leached.When
the temperature rises, the mirabilite (Na,S04 .10H,O) easily dehydrates, turning into a whitish powder of
thenardite (Na,SO,). When the temperature drops,the precipitated sodium sulphate forms large transparent
crystals ofmirabilite. At times sodium sulphate crystallises together with calcium sulphate,forming so-called
glauberite-CaSO, .Na,SO,. In particularly arid deserts (such as in Chile, the Sahara, Ust-Urt), sodium
sulphate is always found in the form of thenardite.
Thenardite, accumulating in the top horizon of solonchak soils,participates, together with gypsum and
calcium sulphate,in the formation of the powdery, ‘fluffy’salt horizon containing up to 30% of sodium
sulphate. Reclamation of soils with sodium sulphate necessitates leaching by large quantities of water;
when possible, this operation should be carried out during the warm season of the year (combined with
irrigation of rice).

(d) Potassium sulphate

Potassium sulphate does not accumulate in soils in large quantities. Its properties are similar to those of
sodium sulphate,but is toxicity is considerably lower. The presence of large quantities ofpotassium sulphate
has been ascertained in some saline formations,where it is extracted for use as fertiliser.

3. Chlorides

Chlorides, together with sulphates,are the main compounds responsible for the formation of saline soils.
All chloridesare characterised by a high solubility and,consequently,a high toxicity.The higher the degree of
salinity of soils,groundwaters and lakes,the greater,generally speaking,is their chloride content.

(a) Calcium chloride

Calcium chloride is seldom present in soils,reacting with sodium sulphate and sodium carbonate,it easily
changes into calcium sulphate and calcium carbonate and passes out of the solution. As a result,calcium
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chloride is found in soils, soil solutions and waters of saline lakes (natural brine) only when there is a very
high salinity (400to 500 g/l).
Calcium chloride may also exist (as an ephemeroid) in the upper solonchak-likehorizons as a result of
exchange reactions of the rising solutions of sodium chloride with exchangeable calcium according to :
Na+
X=Ca+ +2NaC1 fs X --t-CaCI,
+

Na+
Considerable quantities of calcium chloride have been found in deep-lying interstratum groundwaters
connected in some cases with oil deposits. These interstratum waters, rising through cracks to the surface,
may introduce calcium chloride into soils. Calcium chloride is toxic for plants, but to a lesser degree than
either magnesium chloride or sodium chloride.

(b) Magnesium chloride

Magnesium chloride is much more common in saIine soils,groundwaters and lakes than calcium chloride.
However, the accumulation of large quantities of magnesium chloride occurs only with extremely high
salinity.Owing to its high solubility (353 g/l) magnesium chlorideis exceptionallytoxic,and is one ofthe salts
most harmful for plants.
Magnesium chloride is also found in large quantities in interstratum groundwaters,i.e.where it may pass
through cracks into soils and soil solutions.
Like calcium chloride,it may appear in the upper horizons of solonchaks as a result ofexchange reactions
between the ascending solution of sodium chloride and the adsorbed magnesium of the soil.
Magnesium chloride and calcium chloride are extremely hygroscopic salts,which absorb vaporised water
from the atmosphere at low air temperatures.When this occurs, their crystal sediments rapidly liquefy and
turn into a concentrated solution.Hence solonchakswhich contain calcium chloride and magnesium chloride
on their surface remain humid for a long time after rain or dew. Solonchaks containing a large quantity of
magnesium chloride are difficultto reclaim,and need intensive leaching and drainage in order to remove this
harmful salt.

(c) Sodium chloride

Sodium chloride, together with sodium and magnesium sulphate, is the most common and widespread
component of saline soils. The toxicity of sodium chloride for plants is exceptionally high as well as its
solubility (264 g/l). Even with a content of about 0.1% of NaCl, plants suffer and fail to develop normally.
Many saline soils contain 2 to 5% of NaCl, and are totally barren. Such saline soils can only be improved
by leaching of these salts.
Washing out of sodium chloride solonchaks is very easy if the soil contains gypsum,as is very often the
case. If chloride solonchaks do not contain gypsum, washing out is much more difficult because sodium
assumes an exchangeable form,the alkalinity is high and the soil is peptised.

(d) Potassium chloride

As regards its chemical properties, potassium chloride is, generally speaking,similar to sodium chloride.
However,it is not at all widespread,since potassium is consumed by organisms and is subject to irreversible
adsorption by clays.When potassium chloride is present in the soil in large quantities,its toxicity is as high as
that of sodium chloride. However,as a rule,its content,even in saline soils,is not large. Owing to the great
importance ofpotassium in the mineral nutrition ofplants,deposits ofthis saltare ofgreatvalue as a source of
fertiliser. The use of a potassium fertiliser in the form of potassium chloride or carnallite (MgCl,. KC1 .
6H,O) increases the fertility of non-salinesoils;but in saline soils,its use is not recommended.

4. Nitrates

Nitric acid salts constitute a chemical compound which is of great importance in soils.These salts do not
accumulate in large quantities in soils. In most cases, the nitrate content is not more than 0.05% NO,.
Nitrates constitute a highly important element in the mineral nutrition of plants, providing a source of
nitrogen,without which plants cannot live. But, in exceptionally arid deserts, such as those in Chile,Peru,
India,Central Asia and Arabia, sodium and potassium nitrates-in the same way as sodium and potassium
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 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
chlorides, and together with them-cause acute salinisation and make soils barren. In the soils of these
regions,the quantity of nitrates attains several per cent or even, in some cases up to 50%.
Nitrates in soils in amounts of over 0.07 to 0.1%NO,are much more harmful to agricultural plants than
chlorides.In view of this,nitrate or nitrate-chloride solonchaks are just as difficult to reclaim as all other
types of soIonchaksand need leaching.
Owing to their high solubility,nitrates can be easily washed out of soils.When there is insufficient oxygen
(e.g. in swamps or as a result of over-irrigation)nitrates are reduced by denitrifying micro-organisms in
ammonia or elementary nitrogen.In swampy soils,this process of denitrification reduces the supply of an
important element of plant nutrition.

5. Borates

It is even rarer to find in soils an excess of boric acid salts.When this occurs,it is usually in the proximity
of volcanoes (the case of Latin America).

C. ORIGINS AND SOURCES OF SALTS ON CONTINENTS

The formation and accumulation of salts in soils is due to a large number of geochemical processes taking
place in the upper strata of the earth‘s crust. With the weathering of the various rocks, the former links
between the chemical elements are broken, giving place to new combinations,which may be in the form of
either secondary clay minerals or various kinds of oxides,or simpler compounds. These may also include
simple salts.
The main elements,combinations of which give rise to the formation of saline soils,are Ca, Mg, Na, K,
CI, S,C,N,B and I.Apart from these, Cu, Z n and B often accumulate,in micro quantities,in saline soils.
The main salts in the form of which these elements migrate and accumulate in saline soils have been men-
tioned above.
Elements from which solublesalts can be formed are some ofthe most common found in the earth’scrust;‘!’
they are,in fact,among the first fifteen elements (Table 5.1).

Table 5.1. Content of the most common elements in the earth’s crzM in %(CLARK)?
N a m e of element % N a m e of element %
Oxygen” 49-13 Potassium” 2.35
Silicon 26-00 Hydrogen“ 1.00
Aluminium 7.45 Titanium 0.61
Iron 4.20 Carbon” 0.35
Calcium” 3-25 Chlorine“ 0.20
Sodium” 240 Phosphorus 0.12
Magnesium” 2.35 Sulphur” 0.10
Manganese 0.10

(The sign x is used in Table 5.1 to denote the elements which participate in the formation of the easily soluble salts leading to
soil salinity. These elements, with few exceptions, play a limited or even extremely limited role in the various biological
processes and therefore do not accumulate in organic residues)

In the course of geological time, the continuing magma-forming processes and the volcanic and post-
volcanic phenomena occurring in the earth’scrust facilitatedthe accumulation ofvast quantities ofchlorides,
sulphates and borates both in the solutions circulating on the earth and in the oceans and in continental and
marine deposits.
* The term ‘earth’scrust’ is commonly applied to the top cover of the earth, down to a depth of 16.5 km (10miles)
t All the remaining elements, aver 70 in number, constitute only 0.39% by weight of the total,
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IRRIGATION, DRAINAGE AND SALINITY
Every stage of volcanic activity has resulted in the rising to the surface of new masses of easily soluble
salts of magmatic origin. To this day, volcanic activity continues to bring up to the surface of the earth
further quantities ofcompoundsofchloride,sulphur,boron,and so on.But the original chemical composition
of the ocean salts,which was predominantly ammonium chloride,has changed in the course of the geological
and geochemical history of the earth due to the effects of weathering,biogenesis and soil formation on the
continents and in the oceans of biochemical and geochemical transformation processes.
The present composition of ocean salts is the result of the constantinflow,from the continents,of sulphate
and carbonate-Na, KyCa and M g of the formation of the chlorides ofthese elements,and ofthe biological
destruction of the ammonium salts formerly predominating in the oceans,accompanied by the accumulation
of nitrogen in the atmosphere.
The weathering of the crystalline rocks forming the continents was considered,at one time,as the main
source of easily soluble salts entering into natural waters, sediments and soils.GLINKA, GEDROITZ, POLYNOV
and FERSMAN in the USSR and HILGARD, HARRIS and KELLEYin the USA took the view that weathering
processes were mainly responsible for the appearance and accumulation of these salts in natural waters,
deposits and soils on the continents.
The chemical composition of the salt solutions formed by the weathering ofigneous rocks depends in very
large measure on the mineral composition of the rocks. Waters flowing through acid magmatic rocks (e.g.
granite, porphyry, gneiss) are the least mineralised, and contain principally carbonates,chlorides,silicates
and sulphates of alkali; while waters flowing through alkali magmatic rocks (basalt, diabase) are more
highly mineralised, and contain mainly carbonates-Mg, Ca-some Fe,and their sulphates and silicates.
During weathering, all the chlorine and a large part of the sulphur turn into acids,which are subsequently
transformed into salts of alkali and alkaliearth. Chlorides, on land,migrate faster than sulphates,which is
due,according to Harris,to the formation of sulphides and to the fact that sulphatesin general have a lower
solubility than chlorides.
According to FERSMAN, the geochemistry of salts on land is based on the solution and extraction of the
ions from minerals in the course of weathering, followed by their precipitation and accumulation under
specific physico-geographicalconditions.The sequence of extraction ofthe ions,their speed ofmigration and
the capacity of some ions to accumulate in endoreic inland depressionsin the form of salt masses are propor-
tional to the coefficient of energy of the ions,(C.E.),the ionic radius,the valendy, and the stability of the
crystal network of the compound (Table 5.2).

Table 5.2. Sequence of ìon-extraction during weathering (according to FERSMAN)

Sequence of I II III IT!

extraction Ions C.E. Ions C.E. Ions C.E. Ions C.E.

CI’, Br 0.23 N a 0.45 SiO, 2.75 Fe 5.15

NO3 0.18 K 0.36 Al 4.25
Ions so4 0.66 Ca 1.75
CO3 0-78 M g 2-10

The mobility of the compounds formed and the amounts in which they accumulate in the form of salts
increases with the decrease of the coefficient of energy of the ions and salts,and the decrease of the ionic
radius and valency.
It follows that chlorides,nitrates,sulphates and carbonates of alkalis and,in some degree,of alkali-earths
must inevitably be the main salts which form in the weathering crust and salinise endoreic areas.
The processes of precipitation and accumulation of the salts occur in reverse order.The longest to remain
in solutions (of marine, ground and underground waters) are the ions with the lowest coeficient of energy
(i.e.monovalent and bivalent cations and monovalent anions).
It is these components which play the main role in the formation of salt accumulations and solonchaks.
POLYNOVand KOVDA divided the elements into the categories shown in Table 5.3, according to their
mobility during Weathering and their migration capacity.
Both the absolute and the relative participation of elements in the formation of saline soils and natural
waters will be greater, the higher the migration category of these elements. Elements of the fourth and fifth
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 SALINE AND ALKALI SOILS CHEMISTRY (ARID ZONES)
Table 5.3. Migration categories (mobility)of elements
~~

1. Virtually non-leachable Si of quartz. . . . . . . .

2. Slightly leachable Fe,Al,Si . . . . . . . .
3. Leachable Si, P, M n . . . . . . . .
4. Highly leachable Ca,Na,K,Mg,Cu,Co,Zn
5. Very highly leachable CI,Br,I,S,CyB

migration categories will constitute the main compounds contributing to contemporary salt accumulation:
NaC1, Na,SO,, MgCI,, MgSO,, CaSO,, Na,CO,, NaHCO,, CaCO,, MgCO,. In inland depressions, arid,
endoreic lake regions with a dry climate,marine deltas and in the oceans,it is the elements of the fourth and
fifthcategories,that are bound to accumulate in the largest quantities.
Throughout the whole geological history of the earth's crust,a process of exchange has occurred between
land and ocean with a sort of rotation of easily soluble salts.The balance of this circulation,on the whole,
is in favour ofthe ocean where the total saltsreserve has,consequently,grown.This rotation of salts between
the oceans and the continents has been accompanied by a process of differentiation of salts according to
degree of solubility,as a result of which sulphates and carbonates predominate in the salts accumulated on
land,chlorides in those accumulated in the oceans.
The oceans, which cover three-quarters of the earth's surface, have always been regarded by scientists
as constituting the source,both direct and indirect, of the salt accumulations found on the continents.Now,
as in the past,salts blown by the wind from the face of the seas and oceans are reckoned to be one of the
main elements contributing to the accumulation of the salts on land.
According to the figures given by scientists of various countries,the amount of salts of different chemical
compositionswhich is deposited on land together with dust and atmosphericprecipitations is between 20 and
500 kg/ha per year. This permanently operating geochemical factor constantly replenishes the reserve of
salts in surface and underground waters. The deposit of salts in marshes and lagoons along the seashore is
the second most importantmeans whereby salts from the oceans pass on to land.When we consider that the
area ofland covered by the transgressionsof the ancient seas runs into millions of square kilometres,we shall
have some idea of the colossal amounts of salt which have passed from the oceans on to dry land since the
time when the oceans were first formed.
Lastly, the most important transference of salts from the oceans on to dry land, as regards geochemical
effects,has been due to the salt masses drawn into the strata of sedimentary rocks ofmarine origin.Of special
importance in this context are the marine salts entering into the composition of the sedimentary rocks of
geosynclinic regions now characterised by mountain formations,such as the Tien Shan,Altai,Pamirs and
Himalayas,Caucasus,Carpathians,Atlas and Pyrenees.
During the geological existence of the earth,both the process of salt formation due to the formation of
magma, weathering and chemicalerosion and also the movement and accumulztion of salts in inland regions
with no run-offhave been accentuated during periods of orogenesis and periods characterised by the up-
lifting ofthe continents.In the history ofthe earth there have been,as we know,about 20such major orogenic
periods.
The periods of the most active upheavals of the earth's crust have been marked by intensified volcanic
activity,sharperdifferentiationofthe climatic zones on the continents,and intensification ofdesert conditions
in the inland depressions oflarge continentalmasses-all ofthese factors lead,in turn,to the intensification of
processes of salt accumulation.
Salt in the form of chemical deposits accumulates in the furthermost areas reached by salt migration, in
inland depressions of steppes and deserts, in lakes and in oceans.
Inthe course oftheir migration,in underground and surfacewaters,from thealluvial area to thefinal main
salts reservoir-oceans-salts are retained and accumulate along the way in deposits,soils and groundwaters
of the low lands.
Salts through accumulating in sea conditions (sea-bottom deposits, swamps, deltas, lagoons) or on the
continents,being covered up by deposits of various kinds,undergoing various forms of metamorphosis,
and,lastly,sinking down to various depths of the earth's crust,were cut out of the processes occurring on
the earth's surface for periods equivalent to whole geological eras. Then,under the influence of upheavals
in the earth's crust and of erosion,the buried salt accumulation passed into a second migration cycle,again
accumulating in deposits and soils.
129
I R R I G A T I O N , D R A I N A G E A N D SALINITY
The formationofsalinesoilsin the contemporaryperiod is part ofthese geochemicalprocesses,which have
been occurring on the earth since very ancient timesand which consistin the exchange and differentiationof
salts as between magma, the oceans,the crust of the earth and the surface of the continents.

D. THE SOLUBILITY OF THE MOST IMPORTANT SALTS

When studyingthe processes of soil salinisation,it is extremely importantto talceinto account the differences
of solubility of salts. The essential data on this point are given in Table 5.4 and onward.

Table 5.4. Maxiinum solubility ìn water of some saltsfound in soils at differenttemperatures(saturatedsohtion)

In g per 100 g of solution In g per litre of solution

Salt Temperature in "C Temperaturein "C
O 10 20 30 40 50 O 10 20 30 40 50

Nazco3* 6.5 10.9 17.9 28.4 32-4 32.1 70 122 213 371 441 429
NaHCO, 6.5 7.5 8.7 10.0 11.3 12-7 68 80 93 107 121 137
1\;la2S0,t 4-3 8.3 16.1 29.0 32.6 31.8 45 90 185 373 430 415
NaCl 26.3 26.3 26.4 26-5 26.7 26.9 318 317 317 317 318 319
IVlgSO, 18.0 22.0 25.2 28.0 30.8 33.4
54.5
-
-
-
-
-
-
-
-
-
-
-
--
MgCL 38.8 39.8 41.0 48.6 51.8
CaCl,:: 37-3 39.4 42-7 50.7 53.4 56.0 - - - - - -
NaN03 42.1 44.4 46.7 49.0 51.2 53.3 570 607 686 686 724 762
KN03 11.6 17.5 24.0 31.5 39.0 46.1 125 194 279 384 498 614
&COB 51-7 52.2 52.6 53-2 53.9 54.7 814 823 829 839 852 867
KHC03 18.4 21.5 25.2 28.5 32.2 36.0 - - - - - I

K2S0.5 6.7 8.5 10.0 11.5 12.9 14.2 71 91 108 125 142 157
KC1 21.9 23.8 25.6 27.2 28.7 3.01 253 277 301 322 341 359
* U p to 30°C,the precipitate contains decahydratesalt;above that temperature,it is anhydrous
U p to 30"C,the precipitate containsdecahydratesalt; above that temperature,rhombic salt
3 U p to 30°C,the precipitatecontains hexahydratesalt; above that temperature,tetrahydrate
Note: The last six salts listed are not found in soils in theform of saturated solutions

In complex solutions,the solubility of most salts changes. As a rule, the presence in a solutiofi of salts
having a common ion,causesthe solubilityof these salts to drop. For example the existencein a solution of
large quantities of magnesium chloride provokes a very sharp decrease in the solubility of sodium chloride
(Table 5.5) and causes it to be precipitated.

Table 5.5. Solubility of the salts in the system. NaCl-MgCl2-HzO in %by weight.
Temperature NaCl MClz Solidphase
25" 26.45 O NaCl
20.5 5.0 NaCl
15.2 10.0 NaCl
10.5 15.0 NaCl
6.5 20.0 NaCl
3.3 25.0 NaCl
1.1 30.0 NaCl
0.3 35.55 NaCl+MgCl, .6H20
O 35.6 MgCl,+ 6Hz0

130
 SALINE AND ALKALI SOILS CHEMISTRY (ARID ZONES)
A similar change occurs in the solubility of salts in the presence of increasing concentration of NaCl.
Analogous phenomena are also observed in combinations of sulphates.
In the case ofmixtures ofsalts with dissimilar ions,the solubility ofthe componenthaving the lower level of
solubility increases.This is due to the dissociationofsalts.An example ofthis is the change in the solubility of
gypsum when combined with chlorides (Tables 5.6 and 5.7). The actual solubility increaseis due to the effect
of N a + and C1- in lowering the activitycoefficientsofCa+ and So,- - in solution so that the concentrations
+

of the ions must increase to maintain the constancy of the solubility product.
The solubility ofcarbonates is greatly influenced by the content ofcarbon dioxide gas dissolved in the water
(Tables 5.8-5.10).

Table 5.6. Solubility of calcium sulphate in water in the presence of varying quantities of sodium
chloride at a temperature of 20°C (ing per 100 g of water)

NaCl CaSO,
O 0.204
17.2 0.787
20.0 0.823
24.4 0.820
29.3 0.614
35.8 0.709

Table 5.7. Solubility of calcium sulphate in water in the presence of calcium chloride
(in g per I00 g of water)

CaCI, CaSO,
O 0.204
5.2 0.103
9.9 0.086
18.9 0.077
40.8 0.035

Table 5.8. Solubility of calcium carbonate according to the quality of COzin the air at a temperature of 16°C

Content of COzin the Content in grammes in 1 litre of water

air in%(by volume) According to SCHLESING According to WEIGNER PH
0.00 0.0131 0.0131 10.23
0.03 0.0634 0.0627 8-48
0.3 0-1334 0.1380 7-81
1 .o 0.2029 0.2106 7-47
10 0.4700 0.4889 6.80
100 1.0986 1 .O577 6-13

Table 5.9. Solubility of calcium carbonate, with partialpressure of COz,equal to 0.00032 atm
(ing per litre)

Temperature in "C O 5 10 15 20 25 30

CaCO,content 0.081 0.075 0.070 0.065 0.060 0.056 0.052

13t
IRRIGATION, DRAINAGE A N D SALINITY
Table 5.10. Solubility of mapmium carbonate in water at temperature of 18°Cfor diflerentpartial pressures
of CO,
~~

p. CO,,in atm. 0.005 0.001 0.01 O.1 1.0 5.0 10.0

MgCOBcontent
(in 41) 2.51 3.11 6.04 12.2 25.8 46.0 59.2

In highly concentrated solutions, some easily soluble salts form new complex binary and ternary salts
which are frequently more soluble than each salt when taken separately.There are,however,cases when the
opposite occurs.The solubility of some salts may also vary to some extent according to the forms of salt in
solid phase (for instance,according to the number of molecules of constituent water).
It is importantto take into account the solubilitieswhen leaching saline soils.The order in which they are
to be leached must be carefully planned beforehand, especially when mixtures are present;this is difficult
to do without a thorough knowledge of chemical laws.
In this connection it is important to know the strong decrease of the solubility of sodium carbonate and
sulphate at temperatures below 12°C (Fig. 5.1). The amelioration of soda and sulphate solonchaks by
leaching is therefore difficult during the cold season.

-40 -20 O 3-20 1-40 +60 $80

to
Fig. 5.1. Salt solubility depending on temperature

E. CLAY MINERALS IN ALKALI AND SALINE SOILS”

The clay minerals occurring in alkalit soils are a function ofthe mineral composition at the time of salinisa-
tion and the length of time the soil has been salinised or has remained at high pH. Obviously,if a soil has
been recently salinised by the incursions of sea water or by the rise of a saline water table,the structure of
the minerals in the colloidal fraction will not be immediately affected, although the composition of the
exchange complex may be profoundly altered. In such soils,any of the commonly occurring clay minerals
may be expected and in the same proportion as that prior to salinisation.
The examination of a wide variety of saline soils reveals that the dominant clay mineral is usually mont-
morillonite (30 %or more) although,at least,small quantities ofillite and kaolinite are nearly always present.
Very commonly they contain colloidal calcium carbonate,and they are also characteristically high in quartz
(5to 30%)and in colloidal feldspars.Certain alkali soils are high in analcite,which has the unusual property
* This text is partly based on the unpublished work of I. BARSHAD
and on the work of W.P.KELLEY
The term alkali is used here in the sense recommended by W.P. KELLEY to mean soils high in salt, exchangeable sodium or
both
132
 S A L I N E A N D A L K A L I SOILS C H E M I S T R Y (ARID ZONES)
that it containsNa+ which will exchange with K+ and partially with NH,+but not with Ca++, and there has
been one report of a desert soil containing attapulgite. The zeolites may be expected to be formed in soils
which have been salinised for a considerable period of time and which have remained at high pH. Probably
most alkali soils contain amorphous silica.
Solonetzic soils appear to be generally lower in montmorillonite and higher in amphorous colloidal
materials. Perhaps few colloidal crystalline clay minerals are stable under low salt, high p H conditions
and over long periods of time.

F. EXCHANGE PHENOMENA IN ALKALI SOILS

1. Cation exchange equations

Cation exchange phenomena play an important,if not dominant, role in the chemistry of alkali soils. The
equilibrium between Ca+ and N a + is especially important, since for many practical purposes, M g +
+ +

can be considered to behave much like Ca+ +. However, the distinction between Ca+ and M g + may
+ +

become very important in cases where the exchangeable Mg+ becomes high enough to induce Ca+
+ +

deficiency in crops growing on the soil.However,for present purposes it will be convenient to group Ca+ +

and M g + + together.
Through a study of cation exchange phenomena, it is hoped to gain knowledge of the relative energies
with which soil colloids adsorb N a + and Ca++.When this is known,it becomes possible to predict changes
in relative amounts of these exchangeable ions during reclamation or upon the use of irrigation water of a
specific quality. Such studies are therefore fundamental for the chemistry of alkali soils.
One approach to the problem ofrelative energies ofadsorption is throughthe determination ofan exchange
isothem for N a and Ca for a particular soil.Samples ofthe soil are brought to equilibrium with solutions
+ + +

containing N a and Ca+ at various compositions and the corresponding equilibrium exchangeable ions
+- +

are measured.When solutions have been equilibrated with soils,the problem of determining what proportion
ofthe known total amount ofa given cation is in the exchangeable form and what proportion is in the soluble
form,always exists.W e may determine unambiguously the composition of a solution which has been equili-
brated with soil across a dialysis membrane, or the composition of the supernatent of a centrifuged soil
system or of a liquid extracted in some other way. But to calculate the amounts of the exchangeable ions,
some assumption about the distribution of the ions in the soil itself must be made. In soils high in Na',
the nature of this assumption may be very significant for the calculation of the exchangeable ions.
Generally speaking,there have been two quite different approaches to the question of calculating the
exchangeable ions.Both approaches assume a particular model for the distribution of ions in the soil system
and compute the exchangeable ions on the basis of the assumed distribution. These models will be briefly
presented in turn.
The first model is known as the diffuse-layertheory. It assumes that there are continuous concentration
gradients ofthe ions in the liquid phase near negatively charged clay particles such that the cation concentra-
tion decreases with increasing distance from the particle surface while the anion concentration increases.
O n the basis of a number ofassumptions and the application of certain physical laws,gradients such as those
shown in Fig. 5.4 are predicted for a single monovalent electrolyte (Cois the electrolyte concentration far
from the surface).
The theory thus predicts that anions will be excluded from a region near the surface of the particle. It
follows that the concentration of anions in an equilibrium filtrate will be higher than it is in the soil.Where
this effect is observed it is known as negative adsorption,and it may be very significant in alkali soils.For
act is made of a soil exhibiting negative adsorption and the amount of chloride per unit
lculated from the chloride concentration in the extract,the result will be erroneously high.
The error is known to increase with the total amount of salt in the soil.
The diffuse-layertheory can be quantitatively applied to a mixture ofmonovalent and divalent cationsto
deduce the exchange isotherm.The result has been widely used in the form:
133
IRRIGATION, D R A I N A G E A N D SALINITY
r* r arc sin h Pdß
r-4vc2/C2

Concei@ation
II

Distance from surface

Fig.5.2. Ion concentrations according to diffuse-layertheory

In this equation, Plis the adsorbed monovalent ion and P is the surface charge density of the clay in
me/cm2,,ßis a constant, C, is the divalent ion concentration in the equilibrium solution in molesllitre,and
v c is a particle interaction parameter usually taken as unity. The quantity r is called the reduced ratio and
is defined,

where Clis the monovalent ion concentration in the equilibrium solution. Thus,with the aid of equation 1,
the amounts of adsorbed monovalent ions can be found as a function of the reduced ratio and the surface
charge density.
A second model for the distribution ofions in soil system assumes that the exchangeableions are adsorbed
on clay surfaces essentially in a non-rigidmonolayer at particular adsorption sites. On the basis ofthis model
it is meaningful to represent an exchange reaction for N a and Ca+ as follows:
+ +

Ca" +ad+ 2Na +-+2Na+ ad +Ca .+.+

Here, the subscript ad denotes an adsorbed ion while the absence of a subscript denotes an ion in the
equilibrium solution. By thermodynamic argumentswhich parallel those for a chemicalreactionit is possible
to deduce the so-calledmass-action relationship:
(Ca+ +I (Na+ (3)
(Ca+ +ad) (Na+),
Here, parentheses denote activities and K is the equilibrium constant. The equation may be rewritten,
(Na + -
--K
(Na"),
(4)
(Ca"" ad) (Ca +) +

The activity ratio (Na+)2/(Ca+ +) for the ions in solution is thermodynamically well defined and can be
closely estimated under favourable circumstances. The ratio (Na+.J2/(Caf .t ad) is less obvious. One
assumption is that the activity of adsorbed ions is equal to their mole fraction in the exchange complex.W e
then have,
N2Na+3d=K-(Na+),
(5)
NCa+ a& + (Ca +) +

134
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
It then remainsfor experimentto determinethe value ofK and its constancy.An approach through statistical
thermodynamics yields similar results.
It will be noted that equations 1 and 5 are based on quite different models and differ in several respects.
Equation 1 predicts that the exchangeable ion composition will depend primarily on CI/dCz, the reduced
concentration ratio, while equation 5 predicts that it will depend on (Na+)/d(Ca+ +) (taking the square
root of square 5 and recalling that the sum ofthe mole fractions is unity). Moreover,the functionalrelation-
ship between these quantities and the exchangeableionsis differentfor the two cases.However,ifthe exchange
isotherm is plotted for the two equations,the results do not differ greatly in appearance.This result, while
disappointing from a theoretical view, may mean that either equation can often be used in the solution of
practical problems.
Both of the equations discussed predicts a principle, widely observed in alkali soils,called the 'cation
dilution effect'. According to this principle, as the soil is diluted, the exchange reaction,
2Na+ +CaC +-+-2Na + +Ca+ + ad

is shifted to the right. Thus, as the water content increases soluble Ca+ replaces adsorbed N a + and the
+

amount of soluble Na+ increases. Since this effect may be very marked, the amount of adsorbed N a +
found in a soil is a function ofthe water content used to determinethe solubleions.Moreover,adsorbed N a +
is also replaced with H+ (hydrolysis) upon dilution that so the p H always increases with water content.
This in turn may result in appreciable increases in soluble CO,= or HC0,-.
It also followsfrom the cation dilution effectthat as a soil is dried,the exchangeableNa+ may be consider-
ably higher at water contents in the field moisture range than it is in saturated soils where it is customarily
estimated.

2. Specific effects

There are a variety of ways in which either of the above approaches to the Na+-Ca+ exchange will fail.
+

Under these conditions,the specific behaviour of a particular soil must be investigated.

First,neither equation can be expected to work if the soil is composed of a mixture of clay minerals with
properties which differ considerably from one another. If a mixture is present with considerably different
charge densities or different values of K,this will be the case. In fact,as stated above,alkali soils character-
istically contain mixtures ofclay minerals and this forms an important limitationon a quantitative approach.
Second,there is increasing evidence that in many soils which have been at high p H and salt concentration
for long time periods, minerals of a zeolitic character may be formed.Insuch soils adsorbed N a + is found in
forms which exchange only slightly with Ca++, but substantially with K + and NH,+. The Na+-Ca+ +

exchange relationshipsin such soils would presumably not follow theory.

Many alkali soils are known to contain forms of N a + which dissolve in reagents such as NH,acetate
which are used to determine the extractable Na+ but not in water. In such cases,the exchangeable N a +
found as the difference between the extractable and water soluble Na+will be erroneous. It may then be
necessary to determine exchangeable N a by other procedures, such as the isotopic dilution technique,
+

but this problem is not one of principle.

3. Anion effects

As indicated above,the anion concentration in a solution in equilibriumwith a soil system may be higher than
the average or bulk concentration of the anions in the soil.Thiseffect is called negative adsorption and it has
been most widely interpreted in terms of the diffuse layer theory.From this theory it is possible to show that
an approximateequation for the negative adsorption in a system containing a single symmetrical electrolyte is,

Here, r is the negatively adsorbed salt, in me/cmz,Z is the valence, Cois the equilibrium solution salt
concentration and the other symbols are as before. This equation may be used to estimate the negative
adsorption in soils of known surface charge density,or alternatively if the negative adsorption is measured,
135
IRRIGATION, DRAINAGE A N D SALINITY
rniay be estimated from the equation.The value of rfound in this way often agrees with the value found by
other methods although in one recent report,agreement with the ethylene glycol method was poor. Other
interpretationsof negative adsorption are based on the assumption of non-solvencyof ‘bound’water on the
clay surface,or on the Donnan equilibrium.
In systems exhibiting negative adsorption,it is to be expected that when extracts are made from a soil by
the application of pressure,such as in making saturation extracts with a pressure membrane apparatus,the
initial fraction of the extract will have a higher concentration than the mean concentration of the solution
remaining in the soil.As the extraction proceeds,the concentration would then be expected to decline. How-
ever, the situation is actually rendered more complicated by an effect called ‘saltsieving’.The actual solution
which immerges is lower than the equilibrium solutionbecause the soilretainssalt.As the extraction proceeds,
the concentration rises through a maximum and then declines. In suspensions of clay particles,the effect is
most prominent at low salt concentrations (i.e. 10 me/l).Therefore,in assessing the significance of extracts
obtained by pressure filtration,one must consider both negative adsorption and salt sieving. Efforts to deal
with these phenomena on the basis of double-layertheory have met with the same success,although their
general significance is not yet known. In any event,when negative adsorption is present, an estimate of the
soluble salts made from an extract will be too high and the corresponding calculated values for the exchange-
able ions will be too low. In fact,negative values for exchangeable ions have not been found in this way.
Evidently the soluble salts must be determined at high dilution.

4. CaCO, systems

Probably most alkali soils contain CaCO, in some form. Most of the studies to date indicate that while the
ultimately stable form may be calcite, the solubility product of calcium carbonate is not strictly obeyed.
However,in any solution in which the dissolved CO,,HCO,-and CO,= are in equilibrium,whether or not
the solution is in equilibrium with the air, the following relations must hold:

The parentheses denote activities.In dilute solutionsthe activity coefficients ofthe ionic species is given by the
Debye-Huckel theory according to,
log yi = -Z2(0.511) p1” (9)
in which p = 1/2E Zi2Miis the ionic strength and yi is the activity coefficient.DefiningpX= -log X where X
is either an equilibrium constant or the hydrogen ion activity,one obtains from these relations,

=I =p H -10.33+2.04p1’2
[CO,
-1
log[HC0,
Here, the brackets denote concentrations.
These relations are often useful. For example,if we select severe conditions of p H and salinity,say p H = 9
and p=l.O, and a CO,concentration representing equilibrium with the atmosphere (1 x M),we find
from equation (10)that the corresponding HC0,-concentration is approximately 0.014.It may be concluded
that HCO,will not contribute very much to the total salinity when the salinity and p H are very high and the
soil is in equilibrium with the air. Actually,the calculation overestimates the HCO,-concentration,since at
p = 1.0,the Debye-Huckel equation greatly overestimates the effect of the ionic strength.It should be noted,
however, that the ionic strength term is nearly always important.
When alkali soils containing CaCO, are diluted,the cation dilution effect described above will operate,
except that as Ca+ in solutionexchangesfor N a + ,CaCO, will dissolve tending to replacethe solution Ca+ +.
+

Experimental studies have shown that under these conditions,the equations relating the Naadand the N a +
in solution is a Langmuir isotherm:
136
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
k,k,(Na +>
Naad=
1 +k,(Na +)
It can be shown on theoreticalgrounds that the resultis to be expected from equation 5 provided the Ca+ +

concentration is essentially constant.Moreover,if we write the solubility product of CaCO,,

(Ca) (CO,=) =Ksp (13)
and use equations 9 and 10 to eliminate the carbonate we find,

Thus,in equilibrium with the air at fixedCO,concentration,the (Ca+ +) will be constant if(H*) is constant.
Therefore,it may be concluded that when an alkali soil containing CaCO, is diluted,very little adsorbed N a +
is replaced by I-I+.Rather,it is replaced by C a from CaCO, so that the p H and the calcium concentration
+ +

remain constant and this results in the Langmuir isotherm. In concentrated solutions,this conclusion may
fail.

5. Effect of the presence of plants

The presence of a growing crop has a profound influence on the distribution ofsalt and exchangeable sodium
which results from the use of irrigation water of a given composition.First,the removal of water primarily
by transpiration rather than evaporation means that as the soil is dried out,there is little tendency for the
salts which have entered the soilto move upward.Each successiveirrigation leaches salts downward with the
result that strong downward gradients ofsaltconcentrationare produced.Where waters containing significant
amounts of sodium are used,this in turn means that the levels of exchangeable sodium increase with depth
owing to the reversal of the cation dilution effect.Thus the distribution of salt and exchangeable ions may
be very different from that to be expected in the absence of plants.
A second effect of plants is to excrete CO,in the soil and thus tend to keep CaCO, in solution. Although
pot experiments suggest that such excretion of CO,is not very effective in dissolving pre-existingCaCO,
and thus effecting the replacement of exchangeable sodium,lysimeter experiments,on the other hand, have
clearly shown that plants may preventtheprecipitation of CaCO,. Moreover,in one five-yearlysimeter experi-
ment the loss of HCO,from the soil without a concomitant precipitation of CaCO,, taken with other
evidence,suggested that the reaction,
HCO,+H,O+Ca+ =(CaOH) +H,CO,
+ +

may be significant.It is assumed that the (CaOH)+ formed by this reaction becomes adsorbed.
Finally,where waters of low salinity are applied,plants may significantlyaffect the composition of the soil
solution by ionabsorption.For example,in a long-termlysimeter experiment conducted by W.P.KELLEY and
co-workers,it was shown that the sulphates in the soil solution can be increased as much as 57.8 times over
the level in the applied irrigation water,while chloridesincreased only 8.9 times,the crop being sudan grass.
This is the result of differential uptake of SO, and CI by the crop.These same experiments revealed con-
siderable differences among crop species in their removal of salts. It is also well known that, in general,
the grasses remove relatively more sodium in relation to calcium than do other plant species.

G. ALKALINE SODA SALINE SOILS

Ample geographical data have now been accumulated showing that alkaline soda saline soils are extremely
widespread throughoutthe various continents of the world. In view ofthe high toxicity ofcarbonic alkali and
of the very unfavourablephysical properties imparted by these salts to both soils and soil-formingsediments,
alkaline soda-salinesoils have very low natural fertility and can only with difficulty be used for farming.
137
IRRIGATION, DRAINAGE A N D SALINITY
The geographical particularities, as far as is known, have been summed up in Chapter 3 of this book.
The chemical properties of alkaline soda-salinesoils vary very widely. The total amount of easily soluble
salts contained in water extracts is not large-usually between 0.3 and 0.5%though it may sometimes be as
much as 1.0%,and on very rare occasions,even between 2 and 3 %.In soils with a high groundwater table
(1.5 to 3.0m)there is a definitepattern inthe distribution of the easily soluble salts,with the maximum on the
surface or in the B-horizonjust below the surface;and a gradual decrease down towards the groundwater
table.In soilswith a deep groundwater table (5-10 in),the maximum amount of easily solublesalts (including
carbonates and bicarbonates of sodium) is found in the lower part of the B-horizon and in the C-horizon.
As regardssalinity,these soils are not,relatively speaking,very strongly saline.As regardscomposition,analy-
sis of the easily soluble salts contained in a water extract taken from alkaline soils shows that carbonatesand
bicarbonates of alkali head the list:the CO,content is between 0.05and 0.07%, that of HCO,of the order
of 0.1 to 0.2%. In soils with maximum soda salinity,the content of these ions may be as much as as 1 %.
The presence of free carbonates and bicarbonates of alkali, being accompanied by hydrolysis, causes a
strongly alkaline reaction;with the result that the p H in soda-salinesoils is above 8.5 (between 9 and 11).
Strong alkalinity is in fact one of the main features of the chemistry of soils of this group.
There are a large number oftransitional stages between dark alkaline soda-salinesoils and slightly alkaline
dark-coloured soils and cemented black soils of various types: meadow soils,terrace soils,prairie, valley
smonitzes, chernozems, black cotton soils, etc. Soils with fairly low alkalinity (pH 8.5 to 8-8) will have
a specific plant cover adapted to these particular conditions; whereas strongly alkaline soils (pH 9 to 11)
have,as a rule,practically no plant cover. Soilswith strong soda salinity-1.5 to 3 %-lose their dark colour-
ing owing to the coagulating effect of the soluble salts,acquire a false,friable structure and become, albeit
only temporarily,permeable.
Bicarbonates and carbonates of alkali may be found in alkaline soils either in practically pure form or
mixed with chlorides or sulphates.For this reason,a distinction must be drawn between two types of alkaline
soils:soda-sulphateand soda-chloride.
Both solutions of alkaline soils and alkaline groundwaters almost always contain much dissolved silica
(60-100mg/l,SiO,). These solutions are partly colloidal.The total quantity of mobile SiO,in a water extract
obtained from alkaline soil may sometimes be as much as 0-1%,and in soils it increases with the general
alkalinity and pH. There have been cases where the formation ofmobile silica in the profile of soda soils has
been maximum near the surface.
A regular feature of solutions and water extracts from alkaline soils is the presence of mobile forms of
organic substance (alkalihumates). Indeed,it is these humates that give water extracts the dark coffee colour
so characteristic ofthese soils.And lastly,under extremely alkaline conditions,water extracts and solutionsof
soda-salinesoils contain sometimes anions of aluminium (from aluminates of alkali). It is clear from the
foregoing that alkaline-typesaline soils contain,in addition to carbonates and bicarbonates of alkali,also
silicates,humates and aluminates of the same alkali.
As regardsabsolute and relativecontent ofsoilcolloids,soda-salinesoils are higher than othertypes ofsoils.
Highly dispersed fractions(particle-diameterless than 0.2microns) may constitute,in soda-salinesoils,up to
60%ofthe total weight;such large quantitiesof dispersed matter have not been found in other types of soils.
As regardsdistribution ofhighly dispersed fractionsin the profile ofalkaline soils,thereis a marked maximum
in the surface horizons, which are most strongly alkaline. In cases where there is no A-horizon,and the
horizon of maximum alkalinity lies on the soil surface,then the maximum of soil-colloidcontent will also
be on the soil surface.O n the other hand,in the case of alkaline soils having both an A-and a B-horizon,
the maximum soil-colloid content will be found in the B-horizon.As regards mineral and chemical compo-
sition,the highly dispersed fractions of alkali-saline soils are characterised by a wide ratio of compounds of
silica to sesquioxides.It has been shown by severalexamples for conditions existing in the USSR that the ratio
SiO,:R,O,is of the order of 4:l.Colloidal fractions ofalkali-saline soils contain,in addition to crystallised
minerals, a considerable quantity of amorphous minerals and organic compounds. Among the crystallised
compounds,the most important is montmorillonite, which was almost invariably found to predominate in
the mineral composition of highly dispersed fractions of alkaline soda-salinesoils.Montmorillonite and the
organic colloids give alkaline soils their very large adsorbing capacity,attaining 45 milliequivalents per 100g.
Montmorillonite is also responsible for the shrinkage of alkaline soils when dry with the formation of deep
fissures;and for the swelling of these soils when wet-the crystal lattice of montmorillonite then expands
considerably.The dark hue of montmorillonite (especially its ferrous forms,formed in hydromorphic con-
ditions) further intensifies the dark colour of alkaline soils. Then again, an abundance of montmorillonite
138
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
mineral facilitates the formation of a prismoid-columnarsoil structure with a tendency to hexahedron for-
mation-montmorillonite, as we know,is one of the tabular minerals,hexahedron in shape.In this respect,
the columnar-prismoidalhorizons of alkaline soils constitute,in a sense,paracrystals of montmorillonite.
The result of the constant presence of sodium carbonates and bicarbonates in the soil solutions of alkaline
soils is that the adsorbing complex of these soils is almost saturated with exchangeable sodium. There is a
direct dependence between alkalinityand water extractsofthese soilsand the quantity ofexchangeablesodium.
The higher the total alkalinity and p H of soda-salinesoils,the higher is the exchangeable sodium percentage.

1. Processes of formation and accumulation of soda in soils

The formation,migration and accumulation of compounds of carbonates and bicarbonates of alkali consti-
tutes one of the oldest geochemical processes and one which is still taking place all over the world. As we
know,aluminosilicateminerals represent by far the most important component in the mineral composition of
the earth's crust,constituting about 85 %of the rocks.Some of these minerals are highly stable;while others
have little stability and are easily weathered in the presence of water,particularly when it contains carbonic
acid.The chemicalweathering ofsodium and potassium aluminosilicatemineral-more particularly those like
feldspars and feldspathoids-is accompanied by the formation of solutions of bicarbonates and carbonates of
alkali,also ofionic and colloidalforms of silicasand aluminium oxides.The universal predominance offelds-
pathic minerals in the earth's crust in all climatic zones leads to the continuous formation,everywhere,of
solutions of silicates,bicarbonates and carbonates of alkali,and alkali-earths.It is for this reason that,when
we analyse the chemical composition of natural waters in different climatic zones we invariably find that the
lower their mineralisation,the greater is the relative quantity of dissolved silica,bicarbonates and carbonates
of metal they contain. The formation of bicarbonates and carbonates of alkali is particularly intensive in
the case ofrocks and minerals ofrecent volcanic origin.Basalts,volcanic lava,volcanic ash and volcanic tufa,
when exposed to the action of natural waters and carbonic acid,undergo intensive disintegration, forming
large quantities of mobile silica, alumina and free bicarbonates and carbonates of alkali.The experiments
which were carried out in 1935 by KOVDA and BYSTROVshowed that the hydrolysis which nephelinic syenites
undergo, especially in the pressnce of carbonic acid,is so intensive that a simple water extract taken from
pulverised syenite removes large quantities of mobile silica, and bicarbonates and carbonates of alkail
are formed.The same thingwas established by STEVENS and CARRON in 1948,by observing the hydrolysis reac-
tion ofaluminosilicatessubjectedto intensefrictioninwater (Table 5.11). Similarphenomena arealso observed
in nature: spring,ground and subsoil waters, also lakes fed by streams in areas of recent volcanic deposits
contain large quantities ofcarbonates and bicarbonates ofalkali and ofmobile silica.In an arid climate zone,
new volcanic areas will always be characterised by the formation of waters and soils containing soda (East
African graben, alkaline soils of Chile and Argentina, and the soda solonchaks of Transcaucasia and in
particular Armenia, soda lakes and soda accumulationsin the USA).

Table 5.11. Hydrolysis of minerals in water

Mineral Name p H when abraded in water

Amphiboles 10-10
Carbonates 8-10
Clay mineral and Al oxides 5-7
Feldspars 8-1 O
Feldspathoids 10-11
Micas 7-9
Olivine 10-1 1
Pyroxenes 9-1 1
Quartz 6-7

Hilgard's theory of soda formation,which is accepted by very many scientists,presupposes the coming
together of limestones,marls and carbonate deposits (loess) with solutions of chlorides and sulphates of
sodium.
L 139
IRRIGATION, DRAINAGE A N D SALINITY
In itself,the system CaCO,+2NaCI (Na,SO,) = Na,CO, +CaCI, (CaSO,), if these compounds are merely
juxtaposed,cannot give rise to the formation of soda to any marked extent.The reaction will proceed in the
direction of the least soluble compound-CaCO,. Under usual conditions,therefore,this process produces
only insignificant quantities of soda.All the same,it would be a mistake to underestimate the part which this
system may play in the geochemicalprocesses,in view ofthe innumerable differentconditionswhich may arise
in the weathering crust. Evaporation,low temperatures,the presence of other salts-all these may cause
soda to separateout and be precipitated in soils.Gedroitz established in 1912that the risingmovement ofweak
solutions of sulphate and chloride of sodium,alternating with descending streams,causes accumulation of
exchangeable sodium in the adsorbing complex ofthe soil.In presence of dissolved carbonic acid,the hydro-
lysis of sodium clays is accompanied by the formation of bicarbonates and carbonates of alkali.
The exchange reactions between the sodium-saturatedsoil on one hand and the carbonic acid or calcium
bicarbonate on the other hand are expressed by the following scheme,worked out by GEDROITZ, SIGMOND,
and KELLEY:
(adsorbing complex)-2Na+ +H,CO,=(adsorbing complex)-2H +Na,CO,
+

or
(adsorbing complex)-2Na + +Caco,= (adsorbing complex)-Ca -t. -I. +Na,CO,
These reactions may be repeated indefinitely with the same result-i.e. the formation of soda.
There are,finally,grounds for believing that the mineralisation of the organic substance of certain plants
may lead to the formation ofcarbonates and bicarbonates ofalkali.Examples are the high potassium carbon-
ate content of the sunflower and the high alkali carbonate content of halophytes like Haloxylow,Anabasis,
Bassia, Artennisia and Elymus.
Alkalis, apparently, exist in these plants in the form of salts of organic acids or absorption compounds
which, when mineralised and brought into contact with carbonic acid, form carbonates.
In an anaerobic milieu,processes of desulphurisation and denitrification of sulphates and nitrates occur.
The hydroxides of alkaline and alkali-earthmetals which remain after desulphurisation thrdugh interaction
with the carbonic acid of solutions,produce carbonates and bicarbonates.
Na,SO, +2C=Na,S +2C0,
Na,S +CO,+H,O=Na,CO, +H,S
This reaction is always accompanied by the formation of sulphides of hydrogen and of heavy (FeS, Fes,)
and light (Cas,Na,S) metals.The main conditions for this reaction are the lack of oxygen and the presence of
organic matter and of deoxidising micro-organisms,e.g.in swampy soils,on the bottom of shallow lakes,seas
and coastalbays and in lagoons,estuaries and stagnant deltaicponds.Similar conditions also occur inenclosed
deposits of such minerals as coal,lignite,oil and bitumen. A detailed study has been made,in particular,of
the disappearance of sulphates and the accompanying accumulation of carbonates of alkali in the petroleum
waters reduced in the course of the formation of oil deposits. However,the preservation,in these circum-
stances,of the bicarbonates and carbonates and in particular the soda formed,is possible only on condition
that there is absolutely no inflow of oxygen. Oxidation, in particular of ferrous sulphide, will cause the
formationoflarge quantities offree sulphuric acid,leading to intense acidisation ofthe milieu and destruction
of the accumulated carbonates.It is in this way that free-sulphurousand sulphuric acids, ferric oxides,sul-
phates, alum, etc.,are formed during the working of petroleum deposits and during operations for drying
out and aerating deposits on the bottom oflakes and bogs,deltas,lagoons,and estuaries.The above oxidation
of sulphides may be expressed by the reactions:
2FeS,4-2H,O+70,=2FeSO,+2H,S04
FeSO,+ 2H,O= Fe(OH), +H2S04
Na2C0,1- H2S04=Na,SO, +H,O+CO,
Oxidation of sulphides may occur in coal mines,in drying organo-mineraldeposits of lake bottoms,and in
saline and waterlogged coastal areas after reclamation or decrease of waterlogging. The resulting acute
acidity not only disintegrates the calcium carbonates and completely neutralises the carbonates and bi-
carbonates of alkali,but also affectsthe biological properties and fertility of the soil.Most naturally formed
soils,including bogs,lake-bottomdeposits and delta soils,are subject to an alternating oxidising-reduction
140
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
regime;with the results that,as a rule, the soil and groundwaters of these areas are characterised by acute
acidity rather than by alkalinity.Processes of reduction cannot,therefore,be considered to play a significant
part in the formation offree bicarbonates and carbonatesofalkali on the land surfacein ordinary atmospheric
conditions. It is only in closed,underground strata where no oxygen can penetrate that it is possible for
desulphurisationand elimination of sulphuric compoundsfor subterraneanwaters,with accumulationinthose
waters of free bicarbonates and carbonates of alkali to occur and continue over a long geological period.
The discharge of these deoxidised reduced alkaline waters in depressions, low-lyingareas and river-valley
terraces causes the formation of soda-salinesoils which cannot be attributed to present conditions on the
earth's surface. It is possible that this is the explanation for the presence of soda accumulations and soda-
saline soils in Western Siberia,the Yakutsk depression, Moldavia and North Africa.

2. Conditions of existence and accumulation of free soda

One of the most important factors limiting the solubility of bicarbonates and carbonates of alkali is the
presence of dissolved salts of calcium-such as calcium sulphate or chloride:both these compounds when
reacting with sodium bicarbonates and carbonates,form calcium carbonate-as well as sodium chloride and
sulphate.The presence of calcium sulphate in landscapes-which is characteristic,for instance,of the terri-
tories of Soviet Central Asia,where there are almost always deposits of gypsum in Quaternary and Tertiary
sedimentary rocks, and also in soils-causes the constant neutralisation of bicarbonates and carbonates of
alkali,and their transformation into calcium carbonates. This is probably the reason why soda-salinesoils
are virtually unknown in Uzbekistan,Southern Kazakhstan,Tadjikistan and Turkmenia.
Free carbonates and bicarbonates of alkali cannot accumulate in substantial quantities until the whole
of the calcium sulphate and chloride reserves in any given territory have been transformed into carbonates.
A similar effect,though to a much lesser degree,is exercised by the presence in soils,soil-formingrocks
and aquiferous horizons, of adsorbed exchangeable calcium. Alkaline solutions,passing deposits saturated
with exchangeable calcium,cause physico-chemicalreactions whereby the exchangeable calcium is replaced
by sodium,or by potassium from bicarbonates or carbonates. The result of these reactions will be saturation
with sodium of the sedimentary rock or soil,and a deposit of calcium carbonate.After this has happened,
the circulating solutions will remain alkaline and give rise to sodium carbonate accumulation. In areas
consisting mainly of loess and loess-type rocks, which as a rule contain large quantities of exchangeable
calcium,the reaction described above may be of immense geochemical significance.The sample applies to
river and lake alluvium which is likewise,in most cases,saturated with exchangeable calcium.The continued
sedimentation of loess-likematerial from aeolian deposits,or of alluvium from river and lacustrian waters,
will bring a constant inflow of exchangeable calcium into the sphere of reaction,thus neutralising the free
carbonates and bicarbonates of alkali which are formed by the weathering or mineralisation of organic
matter.
A similar effect may be exercised by the appearance of calcium ions of biogenic origin-i.e. formed by the
mineralisation of the roots or surface organic residues of plants whose tissues contain calcium in large
quantities. The chief plants of this kind aïe cereals and pulses,the ashes of which are particularly rich in
calcium compounds. Biogenic calcium sulphate in soil solutions produced by decay of the proteins will be a
very effective factor in reducing alkalinity.
A vital part ill regulating the presence or absence of free bicarbonates and carbonates of alkali in natural
waters, sedimentary rocks and soils is, apparently, played by the process of formation of secondary clay
minerals. As we know,natural waters always contain a small quantity of dissolved silica and sesquioxides.
The interaction ofthese componentsduring the drying up of the solutionsis accompanied by the appearance
of products of reciprocal coagulation, such as allophanoids and crystallised clay mineral of various types
(and especially montmorillonite.)The formation of the crystal lattice of these minerals may be accompanied
by non-exchangeablesorption of alkalis and their elimination from the solution. with residual formation of
carbonic acid and water. This process is of special importancein the case of potassium,which becomes fixed
in non-exchangeableform in clay minerals ofthe mica group.However,some sodium also passes out into the
crystallattice ofa number ofclay minerals.Increasing quantities ofdata are now being accumulated to suggest
that even feldspars are capable ofsecondary formationin ordinary surfacethermodynamicconditions.Ifthis
is so,then it may be assumed that secondary mineral formationplays a vital part in the removal ofpotassium
141
IRRIGATION, D R A I N A G E A N D SALINITY.
and sodium ionsfrom solutionsofnatural waters and,thereby,in restricting the presence and accumulation of
large concentrations of bicarbonates and cc?.rbonatesof alkali.
In what geographical conditions do we find small concentrationsof calcium combined with low intensity of
formation of clay mineral?
One of the main processes responsible for reducing the calcium salts in the milieu to a small quantity is
their leaching by natural water. This happens,for instance,in humid marine climates,in mountainous and
northern climates, and in humid monsoon tropics. In such conditions,both weathering and soil-forming
products and also natural water will be characterised by a low calcium-saltscontent. However,the natural
waters of such regions will carry very weak solutions of carbonates and bicarbonates which, on entering
areas with an evaporation regime,may cause the formation of alkaline soda-salinesoils,or else of alkaline
lakes. Conditions such as these evidently exist in California,Argentina,Transcaucasia, Equatorial Africa,
the Northern Ukraine and Hungary,
In absolute desert regions such as,for instance,the deserts of Western China or Latin America, chemical
and mechanical weathering is so slight that the necessary prerequisites for the formation of secondary clays
are lacking,Another point is that gypsum and calcium chloride in large quantities are non-existenthere-
owing to the low rate of chemical and biological weathering. According to EGOROV'S data, the absence of
clay-formationin the desert of Western China, and the slowness of chemical weathering are particularly
conducive to the accumulation of free soda in exceptionally large concentrations.Lastly,in high mountain
regions and areas with a cold climate such as that of Northern Siberia and Canada, conditions likewise
promote the loss of calcium compounds and the preservation, in solutions, of sinall concentrations of
carbonates and bicarbonates of alkali.
In cold winter conditions,compounds of carbonic alkaliswill accumulate in soils because the low tempzra-
ture greatly reduces their solubility, and they are able to precipitate.
The most favourable conditions for the formation of soda,and the preservation and accumulation of free
soda in soils and solutions,will be a combination of the following:(a) young volcanic areas enclosed by new
pyrogenous deposits (from which the geochemicaldischarge derives) ;(b) depressions with insufficientnatural
drainage (towards which the geochemicaldischarge is directed) ;(c) a climate suchthat evaporation preclomin-
ates over run-offin the water balance. This combination of circumstances is fairly common: examples are
South and Central America,California,Transcaucasia, and the East African graben.

3. Physico-chemicalproperties of sodium carbonates

The easily soluble salts which cause salinity in soils are mainly the following: soda (Nazco,. 10 H20)
forming a mealy-fibrous mass;thermonatrite (Nazco3.1 0.H20) having a different crystal form,accumu-
lating in mealy granules in soils and sedimentaryrocks;trona (Nazco, .NaHC0, .2H,O)usually present in
soda-saline soils and along the shores of soda-alkaline lakes in pure salt deposits; and lastly,nahcolite
(NaI-ICO,) present together with the three above components,being found in solutions as well as in deposits
in both soils and sedimentary rocks. The solubility of carbonates and bicarbonates of alkali depends to a
very great degree on surrounding conditions, and varies within very wide limits.Most astonishing is the
extent to which the solubility of sodium carbonates and bicarbonates depends on the temperature: at
temperaturesofzero and below,the solubility of soda and sodium bicarbonate,also that of sodium sulphate
(but not that of sodium chloride) drops to as little as 3 to 5 g/l.At temperatures around 30°C,the solu-
bility of soda is as high as that of sodium chloride,i.e.approximately 350 g/l;while at high temperature its
solubility is nearly 530 g/l,i.e.higher than that ofsodium chloride (Fig.5.1). The behaviour ofsoda in relation
to temperatureis similar to that of sodium sulphate.The solubility of sodium bicarbonate is likewiseincreas-
ing with temperatures, though it varies less than soda.
In the study of soil geochemistry,this factor is of outstanding importance.It means soda,at atmospheric
temperatures (15°C to O" and below), will precipitate into deposits in lakes and soils together with sodium
sulphate:while chloride solutionswill be carried away by ground,subsoil and surface waters. It is thus to be
expected that,in regions with a cold climate and severe winters,saline soils will be characterised mainly by
accumulation of sulphates and carbonates of alkali,In a dry,hot climate,on the other hand,owing to the
fact that soda will then be moxe soluble than chlorides,separation may occur and soda may accumulate in
the areas of final evaporation of the solutions.Combined migration and accumulation of soda and sodium
chloride will be comparatively rare,occurring mostly in places where there are deep,reduced underground
142
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
petroleum waters rising to the surface.The solubility of sodium carbonates depends also in great measure on
the salts contained in solution.
In view ofthe decreased solubility and migration czpacity of sodium carbonates,natural brines will contain
only small quantities of sodium carbonates and bicarbonates.
A sharp distinction can thus be drawn,in thegeochemistry ofsalts on land,between regions ofaccumulation
of carbonates of alkali and regions of accumulation of chlorides and sulphates: the potential areas of
accumulation of bicarbonates and carbonates of alkali being much larger than those of chlorides or even of
sulphates.Soda and sodium bicarbonates will tend to accumulate in regions where the general salt content is
fairly small,i.e. mainly in those at the initial stages of salt accumulation.
A high soda concentrationin solutions,in its turn,exercises a stronginfluenceon the solubility and mobility
of calcium carbonate,which is an extremely important compound in soil chemistry. Figure 5.3 shows that
there is a very sharp drop in the concentration of calcium even in solutions with relatively low alkalinity.
Inthe presence of sodium bicarbonate,calcium bicarbonate is still a little soluble;but the soda,even when the
total alkalinity drops to 0.1 g/l,of HC03, virtually eliminates the calcium from solutions.This explains why
thegroundwaters,in regions of alkaline salt accumulation,contain practically no calcium despite the presence
of calcium carbonate in the rocks and soil horizons.
When it comes to compounds of dica, aluminium and organic matter, it will be seen that normal and
bicarbonate alkalis influence their solubility and mobility in precisely the opposite direction (Fig. 5.4):the
greater the alkalinity of the solution,i.e. the greater the concentration of soda in it, the more compounds of
silica, alumina and humus in the form of true, molecular or colloidal solutions it will contain. The same
applies to soils:the higher their alkalinity,the greater amount of mobile forms of silica and organic matter
their solutions or water extracts will contain (Fig. 5.5). It is a well-knownfact that rain puddles, surface
streams and small brooks flowing through soda-saline soil areas, are strongly tinted by organic matter.
This capacity of soda solutionsto turn compoundsofsilica,alumina and organic substances into mobile form
has very far-reachingconsequences in soil science and geochemistry.
Soda-salinesoilswillbe characterisednot only by the accumulation ofcarbonates ofalkali and by exchange-
able sodium:there will also occur at the same time-though the process may not be visible-accumulation of
compounds of silica,alumina and organic substances brought into the area with the alkaline surface or under-
ground waters.Theconcentrationofthese components inwater is lowbut theseprocesses,continuing through-
out geological time, result in the accumulation of considerable quantities of silica, alumina and organic
substances,and the emergence of a highly specifictype of soil-formingsubstrata.This property-the capacity
to transport silica and alumina compounds into areas of soda-saltaccumulation-is, in our opinion,respons-
ible for the formation in these areas of sedimentary rocks rich in secondary amorphous minerals with
marked predominance of silica over alumina and,more particularly, responsible for the formation,in these

% Ca of the solid residue

. ...
0

- %
:$
P
=:
:&
&:
: .."
f 5
0 ..f
.
* f. * 0
CI
**
.5--L6*
e-
*
1 0
*
-I
a 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
%I-ICO,
Fig. 5.3. Relationship between content of water-soluble Ca and the total alkalinity

regions of montmorillonite-type clays containing a constant admixture of highly dispersed organic matter.
Even kaolinite-typeclay deposits,under the influence of alkaline groundwaters,containing dissolved silica,
are inevitably transformed into montmorillonite-type clays. As a result of all these factors combined,the
143
IRRIGATION, D R A I N A G E A N D SALINITY
sedimentary soil-formingrocks of soda-salineregions will be dark in colour,be characterisedby high disper-
sion,have a large swelling capacity when damp, and shrink and crack when dry. In other words,they will
possess all the properties which distinguish soda-salinesoilsfrom the other soils.The main reasonfor the black
colour ofmeadow soda-salinesoils is ofcourse the accumulationof humus in hydromorphoussoil-formation
conditions.
Millimoles /I
1 1 7
10 -
9-
8-
7-
0
6-
5-
4-
3-
2-
1-
I
0 1 2 3 4 5 6 7 8 9 1 0 1 1
PH
Fig. 5.4 The solubility of silica and alumina as a function of p H
After CORRENS' Einfuhrung in die Mineralogie

SiOzmg/100'g of soil
50 7

40 -
7
* * **
.al I
O 0.1 Of! 0-3 0.4 0.5 0.6 0.7 0.8
% of HCOl
Fig. 5.5 Alkalinity of water extract of soil.Relationship between concentration of water-soluble SiO, and
the total alkalinity of soils

4. Soda accumulation-the first stage in the process of salinisation of soils and waters of arid zone

The results ofstudies carried out over a period ofmany years,areportonwhich was published at various times
(KOVDA, 1946,1947,1959), show that there exist specificrelations between the quantity of the salts in natural
waters and soils and their composition.In the process of the water mineralisation increase,the following
quantitative and qualitative stages occur:

1. Silicious waters-completely fresh waters of the tropics and of northern forest regions, containing silica
and organic substances;total concentration 0.01 to 0.1 g/I
2. Fresh hydrocarbonate-calcium waters with total concentrations of 0.2to 0.3 g/1
144
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
3. Hydrocarbonate-sodium waters with total concentrations of 0.5 to 0.7 g/1
4. Hydrocarbonateand carbonate sodium waters with salts concentrationsof0-5to 3 g/l,containingsulphates
and,less often,chlorides
5. Chlorido-sulphatewaters with concentrations of 2.5 to 5 g/í,containing soda
6. Sulphato-chloridewaters with concentrations of 20 to 50 g/l,usually not containing soda in substantial
quantities
7. Chloride waters-brine-with concentration of 100 to 300 g/1

The foregoing general pattern for the existence of hydrocarbonate-sodium underground waters with low
mineralisation (0.3 to 5 g/l) was established on the basis of a large quantity of geographical and hydro-
geochemical data. The West Siberian depression, including the Baraba and Kulunda plains, is a typical
example ofthis phenomenon.In this immense soda-salineregion it is established that about 85%ofthe cases,
the first aquiferous horizon,and also the groundwaters of the Quaternary,Tertiary and Cretaceous strata,
when the concentrations are between 0-5and 5 g/l,are hydrocarbonate-sodium in type,with some sulphates
or chlorides.The similar hydrochemical pattern is established for the Hwang-Ho and Sungari basin in China,
where, as mentioned earlier, there are large areas of soda-salinesoils. The same chemical composition is
found in the groundwaters of the Ararat Valley in Armenia,the Karabakh steppe in Azerbaijan in the sub-
terranean waters of North Africa, California, Argentina, and so on. There are few known examples of
deviations from this general pattern for the formation of alkaline hydrocarbonate-sodium waters. The most
striking example of the complete absence of hydrocarbonates and carbonates of alkali in groundwaters is
thatof the Ferghana Valley inUzbekistan:here the rocks formingthe valley basin contain abundant gypsum;
and both sedimentary rocks and soils are supersaturated with this substance. In these conditions, it is im-
possible for bicarbonates or carbonates ofalkali to form large concentrations or accumulatein solutions.Due
to this,the Ferghana Valley constitutes a classicalexample of the absence of soda accumulations and of the
predominance of processes of accumulation of sulphate and, in particular, calcium sulphate. This is also
characteristic,though to a lesser extent, of the Hungry Steppe and the Bokhara region in Uzbekistan,the
Vaksh river valley in Tadjikistan and the lower reaches and delta of the Amu-Darya.
A diametrically opposed anomaly-that of intensive accumulation of bicarbonates and carbonates of
alkali in highly concentrated solutions-is observed on the alluvial plains of the deserts of Western China,
where,along the terraces of the Tarim,Aksu and other river valleys,extensive meadow soda solonchaksare
found.Generally speaking,the groundwaters in this area also have a relatively low mineral content (from
0.5 to 5 g/l) and are alkaline. Research done by EGOROVand his colleagues in 1962 showed,however, that
there are also,in this area,groundwaters which have concentrations up to 30 g/land contain carbonatesand
bicarbonates of sodium.EGOROVattributes this anomalously large accumulationof carbonates and bicarbon-
ates of alkali in the deserts of Central Asia,to the fact that,in this region,clays saturated with exchangeable
calcium are practically non-existent.As demonstrated above,clay-formationand in particular reactions with
exchangeable calcium may cause sodium to be separated out of solutions,thus limiting the accumulation of
free soda. The absence of clay,with a constant inflow of fresh weathering products may,together with the
evaporation and concentration of alkaline underground waters, lead to exceptionally large accumulations of
carbonates and bicarbonates ofalkali in solutionsand groundwaters.Another extremely importantfactor,in
the conditions of Western China,is the virtually total lack of gypsum.
The existence ofsuch geochemicalanomalies ofone kind or another merely underlines the need for carrying
out detailed research on the chemical composition of the soluble salts contained in the underground waters
and soils of strongly,medium and in particular weakly saline areas. At the same time,the existence of such
anomalies does not detract from the significance of the general laws enunciated above.

H. RELATIONSHIPS BETWEEN SALINITY A N D ALKALINITY OF SOILS

KOVDA,
working in the basin ofthe Nile,Indus,Hwang-Ho and Sungari rivers, has analysed the relationship
Author’s note: The term ‘alkaline soda-saline soils’ always means soils which contain large quantities of carbonate and bi-
carbonate salts of sodium and potassium as well as considerable amounts of adsorbed sodium,i.e. soda solonchaks, soda
solonetzs,etc.
145
IRRIGATION, DRAINAGE A N D SALINITY
between alkalinity and salts contents of groundwaters.In Fig. 5.6 the total salts concentrations in ground-
waters and in soils are compared with the corresponding p H readings.
In groundwater,concentrations below 4g/1go together with a p H reading of about 7.8to 8.0,with a fairly
wide range of variation (7.2to 8.9). It should be remembered that this water was collected and analysed
without any measures being taken to protect it from the atmospheric carbon dioxide,so that the p H readings
were in fact slightly higher than the figures obtained.There is a marked tendency for the alkalinity ofground-
waters to decrease as their mineralisation increases. There are some exceptions but, generally speaking,it
may be said that,with concentrations of above 5 g/l,the groundwaters’p H of the Hwang-Ho and Sungari
river basin do not rise above 7-5.Groundwaterswith a salts content of 30 to 50 g/1 are, as a rule,neutral.
A similar relation between alkalinity and salt content is found in soils as well.
Alkaline soda-salinesoilsformed under the influence ofslightlymineralised groundwaters are in themselves
only slightly saline;the total salts content in such soils rarely attains 1 %; more frequently,and measured
in a water extract,it is not more than 0.7”/, at the surface,and considerably less deeper clown.It is only in
exceptional cases that mineral soda solonchaks,with totalsalts content (measured in a water extract) ofseveral
per cent,are formed.This may occur,for instance,along the shores oflakes,where thereis a chemical precipi-
tation of salts from saturated solutions, with accumulation of trona. Figure 5.6 illustrates the relation
between the p H reading and the soil salinity in the Hwang-Ho and Sungari river basin. Generally speaking,
the soil p H are considerably higher than those of groundwaters. It is as though the soda were separated
out by the soil.The soda,after entering the soilhorizons from the groundwaters,remainsthere,both because
of the low water-permeabilityof alkaline soils and of the low solubility of soda in cold waters. The general
pattern is the same as for groundwaters: the lower the total salts content in the soil horizons, the more
likelihood there is of the soil being strongly alkaline.Thus,with a salts content of 0.6% and less, the p H
averages 8.7with variations from 8 to 9.6.With high salts contents in the lower part of thc profile (1 to 3 %)
soil alkalinityprogressively decreases,approachingpH 8.The same diagram shows that the alkalinity depends
on the salinity ofthe top soil horizon. Soilswith exceptionally high p H (9to 10) exist only with a salts content
of less than 2%.Where there is a salt content of2-5to 4%, the p H reading in the top horizons of the saline
soils of China are never very high (approximately 8). All this indicates that there is a very close connection
between the process offormation ofalkaline soda-salinesoils and the chemical composition ofgroundwaters.
At the initial stages of salt-accumulation, when the groundwaters themselves have a low salts content
(Q 0.5 g/l), there are formed,in hydromorphic conditions,humus-rich,dark-colouredmeadow soils which
are completely noa-saline,have low alkalinity and possess a high natural fertility. Subsequently, as the
salts-concentrationin the groundwaters increases owing to the accumulation of the carbonates and bicarbo-
nates of alkali,the p H rises to 9 to 10 on account of the intensive accumulation of free sodium carbonates
and bicarbonates.A n increasein the salts-concentrationofthe groundwatersis accompanied by accumulation
ofsulphateand chloride,including salts containing calcium.There then begins a gradualprocess of ‘gypsumis-
ation’ of the salinising soils; the soda and sodium bicarbonates accumulated at an earlier stage become
neutralised and their strong alkalinity disappears. As a result, strongly saline soils are formed under the
influence of highly mineralised groundwaters;but they are weakly alkaline or even, in some cases,have a
neutral reaction. Figure 5.7,drawn up on the basis of a large quantity of analytical data,shows that alkaline
soils-i.e. soils in which bicarbonates and carbonates ofsodium predominate in the salt composition,both in
absolute and in relative terms-exist in places where the total salts content in a soil prism of 1 m3does not
exceed 7 kg.When the total salts content in the soil profile approaches 10 kg,then in the conditionsprevailing
in Western Siberia,a marked gypsum accumulation begins,while that ofcarbonic alkalis decreases until they
finally disappear altogether transformed,under the influence of gypsum,into calcium carbonate. At the
same time,the sodium sulphate content rises sharply,and the soil, slightly or medium saline, becomes
strongly saline, but loses its alkalinity, so entering the category of neutral sulphato-chloride saline soils.
This phenomenon was confirmed by MURATOVA also for the plains of Central Azerbaijan. The fact that
alkaline soda-salinesoils coincidewith the minimal salinityfigures explainswhy they are difficult to recognise.
There is no doubt,however, that many compact,impermeable,unstructured,fissured,dark-coloured steppe,
savannah and meadow soils (so-called vertisols) are in fact soda-soils which have not been identified
as such.
Similar phenomena have been found by PASCAUD and MINART.If the samples analysed for pH, salinity
and alkalisation are plotted on a semi-logarithmic coordinate system (Fig. 5.8), it is found that a smooth
curve can be drawn between the two zones with the alkali soils zone above it and the non-alkalisoils zone
below it.
146
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID) ZONES
DH
in 1

7L
10 -I
ll
9

8 I
60 100 120
O 20 40 80 .Total meq
1 1 I I I I I 1 I I I I
O 0.66 1.32 1.98 2.64 3-30 3.96
Total soluble salts %

t I I I I I I I I l J
O 500 1000 1500 2000 2500 5000
Total m e d l
I l I l I I I I I I I 1

O 16 32 48 64 80 96
gr/l
Fig. 5.6 Relationship between salinity and the p H value
I: in top soil horizons
II: in lower soil horizons
III: in groundwaters
The example given here refers to saline soil surveyswhich were carried out in the Abadla Plain in Southern
Algeria. The soils considered are recent and present alluvia,rich in lime and lacking organic matter.Salinity
is of continental origin.
Practically the same curve has also been found to apply to the saline soils in the low-lyingplains of the

Quantity of individual Salts

(in kg.m-2)

5r

Total quantity of easily soluble salts in

the soil above ground water table (inkg. m-2)
Fig. 5.7. Salt accumulation in soils (Western Siberia)
147
IRRIGATION, DRAINAGE A N D SALINITY
pH (H2O)

EC conductivity of saturation extract

(in mmhos/cm at 25OC)
Fig. 5.8. Relationship between pH, salinity,and exchangeable sodium percentage (ESP)
(Plaine d’Abadla,Algeria)

Lower Rhône and Languedoc regions in the South of France in recent alluvial lime soils containing varying
amounts of organic matter (nocorrelation could be established if the organic matter rate was high). Salinity
is of marine origin.
Several empirical formulaewere tried out in a mathematical study in order to find a suitable expression for
data of Fig. 5.8. The best results were obtained with an equation of the following form:
Y =U, +a,xi+ a2x2 +~ 3 ~ 1 + x ~2 ~ 4 x 3
where:
Y=ESP (exchangeable sodium percentage)
x, = p H of the soil
x2=logarithm of the conductivity of the saturation extract,
xa=clay content.

The values of coefficients a,, u,, a3,and a4 and the residual quadratic error 60 were determined by the
method of least squares. The values found in this case were:
ao= -52.9 a3= -k 12.75 6,=2.996 (residual quadratic error)
al= + 6.68 a4= - 0.12 62= 3.587 (degree of scatter)
-
a, = 88.85
Other more general investigations involving various types ofsalinity show that correlations of this kind are
valid for soils of a comparable nature. They cannot,of course,be generalised to apply also to soils with too
widely differing pedological characteristics,especially as regards organic matter content,particle size,lime
content and soil. In particular, attempts to find such correlations for sandy, peaty or humiferous soils
have all so far failed to produce any satisfactory results.

I. DYNAMICS OF SALTS IN THE SOILS OF ARID ZONES

I

l. Salts in soils

The presence in soils of surplus amounts ofeasily soluble salts may derive from solutions formed at an earlier
stage (sea waier, for instance,water from salt springs,and so on). More frequently,however,contemporary
148
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
soil salinityis due to processes which liberate the requisite elements and salts in the course ofthe weathering
and chemical denudation of rocks.Salinity ofthis type cannot occur in the immediate vicinity ofweathering,
but only laterwhen the saltshave concentrated over a smaller area or in smallervolume. Hence salinity occurs
after the newly formed salts have been leached by natural waters for a considerable period oftime.The most
active factor responsible for leaching and for the subsequenttransportation ofthe dissolved compounds into
the concentration areas is the groundwater,reacting with large quantities of rock.The chemical composition
of the leaching waters is characterised by the predominance ofcarbonate salts-hydrocarbonates of calcium,
magnesium and,in lesser degree, of sodium.These waters as a rule contain only small quantities of chloride
and sulphatecompounds,unless they are affected by the proximity ofactive volcanoes or deep groundwaters.
Inregionscontaininglarge quantities ofgranite or especially alkalinerocks,weathering may be accompanied
by the appearance oflarge quantities of sodium silicate,which subsequently turns into sodium carbonateand
sulphate.
These leaching waters always have a low salt content (approximately 1 g/l). When the rocks are porous
and permit a certain flowage so that these waters sink to a great depth (otherwise,they quickly fill up all the
spare spacein the rocks), they may retain a low mineralisation over long periods,even in arid zones.When they
approach the surface ofthe earth (in low-lyingareas) their compositionbegins to change as a result ofheating
and evaporation. Soils usually play an important part in changing the composition of these waters.

2. Changes of the salt composition in natural waters solutions

Rapid evaporation of surface waters is common in arid zones and constant evaporation of the groundwaters
after capillary rise also occurs,although, when they lie deep,the amount of evaporation is not very large.
When,on the other hand,the groundwater table approaches the surface,and the capillary fringe penetrates
into the root zone,the evaporation increases sharply. Groundwater consumption,in this case, constantly
increasesas a result of the action of certain wild plants. This causes accumulation of salts both in part of the
soilsolution and also in the rocks,in solid phase. Some salts also accumulateinplant organs.The sequence of
salt concentration and precipitation is governed by specific laws.Among the first salts to saturate ground-
waters or soil solutions are carbonate of calcium and magnesium,which may begin to precipitate even in the
aquiferous stratum or in the capillary fringe.This precipitation is facilitated by the temperature rise which
occurs as the solutions approach the surface. Bicarbonates turn into carbonates of lower solubility. This
reaction occurs as follows:
f H,O
Ca(HCO,),-+CaCO, +H,CO,
L CO,
In some soils,as a result ofthis reaction,a solid layer of carbonates may be formed;this is known as meadow
marl (shokh,hardpan).
Continuing evaporation of the solution results in its being saturated with gypsum (provided it does not
contain soda,which preventsgypsum-formation). In the soil profile,as the rising capillary solutionsevaporate,
gypsum begins to precipitate on top ofthe carbonates,thus forming the next salt horizon.Subsequentlythere
emerge,on the soil surface,solutions relatively rich in the most soluble compounds,This process occurs even
in areas where the solutions (groundwaters) as they proceed from higher-lyingparts towards the depressions
become steadily poorer firstin little-solublesalts and then in medium-solublesalts.The solutionswhich reach
the lowest-lyingareas (wherethe groundwaters are stagnant)contain large quantitiesofchloride compounds.

3. Exchange of salts between soil and groundwaters

In nature,few processes are one-way.In the case of soil salinity,the process of salinisation often alternates
with periods of desalinisation.The salts accumulating during the dry period of the year move downwards
during the rainy periods, according to their respective solubilities. Those which move down fastest are
chloride,whereas sulphates,less soluble,are retained in the soil.This process, repeated from year to year,
results in a fairly large accumulation of sulphate in the soil,with an accumulation,in the groundwaters,of
149
IRRIGATION, DRAINAGE A N D SALINITY
chloride (KOVDA). This only occurs,however, after completion of the first phases of salinisation,when salt
accumulation ceases and is supplemented,increasingly by the removal of part of the salts from the soil.
During the first stages of this process the salt predominant in the top strata of the soil remains chloride.
The possibility of premature accumulation of more soluble salts in the soil depends on the depth of the
groundwaters:when the groundwater table lies very close to the surface so that these waters moisten the top
soilhorizon,even when the capillary pores are very wide,the saltsdo not have timeto divideup into categories
according to their solubility.Moreover,salts accumulating under these conditions remain almost constantly
in solution,so that they can easily return into the groundwaters. One means whereby they can move down
into the groundwaters is by downward flow of the more highly concentrated solutions (Processof convective
flow, according to MOROZOV). Towards the end of the hot season,the concentration of the soil solutions
in the top horizons of solonchaks is often as high as 300 to 400 g/l.At the same time their specific gravity
increases considerably,and the more concentrated solutions sink downwards,their place being taken by the
more diluted solutions rising up from below. With rather deeper groundwater tables,the soil surface is only
moistened when the capillary pores are narrow,in which case part of the salts from the evaporating solution
pass into deposit,and thus cease to participate in the downward gravitational flow.The overall speed of the
salinisation process is thereupon reduced but the salinity of the topsoil horizons eventually becomes higher
than in places where the groundwaters are shallower. On the other hand, the salinity of comparatively
deep groundwaters is weaker. This phenomenon is also observed in very arid deserts where extremely rapid
evaporation causes the whole ofthe salts to precipitate on the surface,forming a salt crust30 to 60c m thick.
Since these salts are then irrevocably fixed in the soil,they do not accumulate to any extent in the ground-
waters, which,therefore,remain relatively non-saline.

4. Salt accumulation in soil solutions

When defining the total salinity of soils,by whatever means, data are obtained for the total sum of salts to
be removed by leachingin order to make the soilfertile.Since,however,the toxicity of salts for plants depends
on the concentration of the solution,it is very important to study also the composition of soil solutions. The
rate and the causes of soil salinisation are thereby explained
In the top horizons of arid zone solonchaks,soil solutionshave usually reached saturationpoint in regard
to at least one (predominant)soluble salt,at any rate during the dry part of the year. The higher the con-
centration of the groundwater causing soil salinity,the greater the depth to which the soil solution will be
saturated, and the slower the concentration decrease of the solution deeper down will be. In the case of
comparatively little-mineralised groundwaters,such as,for instance,those of meadow solonchaks,the soil
solution will only be saturated in the top stratum,whereas lower down its concentration will drop quickly
(Table 5.12).
Permanent or ‘periodical’(in the vegetation season) saturation of soil solutionsin relation to one or several
easily soluble salts is a specific characteristic of solonchaks.This is not found in other saline soils.
In highly concentrated soil solutions,the salt composition differs markedly from the general salt compo-
sition ofthe soil as a whole. For instance,the calcium content in the soil solution is always much lower than
that in the soil and the sulphate considerably lower. On the other hand,the quantity of chloride,sodium and
magnesium contained in soil solutions is comparatively large, frequently as large as that contained in the
soil itself.
Table 5.13 gives approximatefigures for the quantity of salts precipitated when the groundwater turns into
a soil solution,according to its concentration and stage reached in its rise towards the surface.Calculations
were made on the assumption that the whole of the chloride contained in the groundwater remains in the
soil solution.
It is clear from the above that considerable quantities of CaSO, MgSO, and Na,SO, and also a certain
quantity of carbonate-Ca and Mg-precipitates in concentrated soil solution.
The composition ofthe soil solutions varies a great deal from time to time.During the rainy season,part of
the salts in solid phase pass into solution,thus levclling out the total concentration.On the other hand, this
causes precipitation of those compounds which become less soluble in cold weather. A predominant place in
the solutionis then occupied by those salts whose solubility is little affected by changes of temperature-such
as,for instance,sodium chloride.The variations in the composition of the soil solution have an effect on the
growth of plants,the properties of the soils.
150
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
Table 5.12. Data obtained from analysis of soil solutions

Depth of Total salt In milli-equivalentsper 1 litre of solution

sample content Na‘-K’
(cm> (fm HC03 CI’ SO“, Ca” Mg” calculated

No. 1 0-2
2-8 256.5 2.0 4303 104 65 426 3918
8-17 151.4 2.2 2470 126 80 177 2341
17-33 112.7 2.6 1827 106 60 163 1712
33-51 107.8 2.6 1730 144 74 291 1502
51-80 105.1 3.8 1675 134 77 233 1496
80-120 113.6 4-5 1840 135 75 339 1565
120-145 88.3 6.6 1382 134 74 321 1120
145-180 86.1 6.6 1366 132 67 328 1109
Groundwater 91.9 6.1 1365 235 72 430 1104
No. 20-10 430 5.6 4789 2083 106 2032 4740
10-17 383 6.1 3805 2126 117 1010 4011
17-31 156 3.4 1875 428 55 567 1685
31-57 72 4.3 900 164 32 206 830
57-90 30 5.1 361 97 26 1O0 338
90-127 11 4.0 106 53 23 30 110
127-150 8 3.8 58 24 22 18 62
150-170 5 3*4 58 24 22 12 52
No. 1. Solonchak with extremelyhighly mineralised water-Kura-Axes depression
No. 2.Solonchakwith slightly mineralised water-Southern Sinkiang

Table 5.13. Total ion deficit in soil solutions of a chlorido-sulphatesolonchak (compared with
groundwater) as a result of the evaporation of the initial (soil)solution and the
precipitation out of the salts into solidphase (data by GRABOVSKAYA)

Number Depth Increase Soil

of sec- of con- Deficit inmilli-equivalents/litre mois-
tion and centration ture
date CI HC03+ C1+ so4= Ca+ + Mg+ + Na+ in %
5 Aupst 0-5 98.2 -740 O -7396 -2877 -2346 -2474 17.7
1947 5-15 45.1 -335 o -3354 -1294 -1412 -983 23.8
M-2 15-30 32.2 -243 o -2231 -700 -987 -673 18.7
30-45 21.4 -156 O -1297 -592 -528 -342 20.9
45-60 14.2 -100 o -886 -378 -327 -219 24.4
75-90 5.0 -32.6 O -215 -106 -124 -17 24.4

Mineralisation
of groundwater O 7.7 49.5 90.4 29.7 43.6 74.2 9.36
in milli-equivalents
per litre

5. Cementation of soils

The phenomenon ofcementation ofsoilsis common in arid zones. Cemented or compacted soils (smolnitzes,
regurs,tirs,certain black tropical soils,takyrs,solonetz) occur in heavy clayey soils,relatively rich in mont-
morillonite,which are subjected to a regular cycle of over-wettingfollowed by drying up.This can be con-
siderably reinforced in the presence offree soda,or under the influence ofadsorbed sodium.A n ‘amalgamat-
ing’effect on cemented soils also tends to be exercised by active fornis of alkaline humus.Cemented soils,
as theylosetheirfractionalmicro-aggregatestructure,become compact.When swollen,their volume increases
considerably,and the resulting pressure binds the particles more closely together. During the late stages of
151
IRRIGATION, DRAINAGE A N D SALINITY
the process,particles of the soil are squeezed out by the pressure,from hillocky micro-relief.Then when the
soils dry up,their volume shrinks substantially,a whole network of large fissures and large clods are formed.
Irrigation and leaching of such soils is a complex problem. Specific measures of mechanical and chemical
reclamation are then required.

J. CHEMICAL ANALYSIS OF SALINE SOILS

To chemically characterise an alkali soil it is desirable to obtain the following data: water soluble CO,=,
HC03-, SO,=,CI-,and B;soluble Ca++,Mg++,N a f and K+; exchangeable Ca++,M g + + ,Na+,and
K ;conductivity of the saturation extract;cation exchange capacity.Under special circumstances,analysis
+

for M o or Se may be indicated. Extensive reference works for the determination of these quantities are
available.
Many different methods have been widely used for the study of saline soils.Both for thorough investi-
gation of saline soils and for the interpretation of the data obtained,precise information on all soluble salts
existing in the soil has to be obtained. For this purpose,a combination of water and acid extracts must be
used.Water extracts with soil-water ratio,by weight, 1 :5 afford a means of determining the total content of
easily soluble salts in the soil.Gypsum content is determined by means of a hydrochloric acid extract or else
by dissolving the whole of the gypsum content in a large quantity of water. In cases where the content of
difficult soluble carbonates in the soil has to be determined,a simplified method consisting of destruction of
carbonate salts by acid and determination of the volume of carbonic acid gas obtained will also have to be
used.
For analysing the composition of the water extract, the same method is used as for analysis of natural
waters,with determination of all the ions which form the easily soluble salts found in soils.The most usual
composition of these components and the form they take are the same as in the analyses of soil solutions
described earlier.
In the case of saline soils containing soda it will be advisable also to determine the p H reading of a water
extract or suspension.A p H reading higher than 8.2 indicatesthe probable presence of free soda;while with
soda salinity,the p H reading will be more than 10.The appearance of soda in soil can likewise be ascertained
by means of a water extract. If the total alkalinity figure (expressed in HCO,)exceeds 047% or 1 milli-
equivalent, per 100 g,there are grounds for assuming that the soil contains a certain quantity of sodium
bicarbonate.
The extraction of soil solutionsis effected either by squeezing out on a specialpress (from samples collected
in steel cups) or else by treatment with alcohol in narrow tubes.When extracting the soil solution from soil
by the alcohol treatment some quartz sand (washed-outacid and water) should be added for greater efficiency.
Sometimes it is desirable to determine the water soluble constituentsin an extract made from saturated soils.
This gives a determination at a water content which is related to the range of water contents which may be
expected under field conditions,thus allowing for the fact that the toxicity of a given amount of salt in soil
dependsupon soiltexture.A largebody ofinformation on the effect ofsoluble salts in soilshas been correlated
with the concentration in the saturationextract.Similarly,the conductivity ofthe saturationextract correlates
very well with the total salt concentration-one millimho corresponds to approximately 0.08 % of soluble
salts. In fact, if more than a moderate deviation from the rough rule CT=lOX (wherc CT is the total salt
concentration in me/l and h is the conductivity in mmho/cm) is found, it is usually well to look for an
analytical error.
The single drawbackwith analysis ofthe saturationextract is the error due to negative adsorption.The error
increases with salinity and in very saline soils it may be very large.BOWER and HATCI-IER suggest determining
the total chloride content by exhaustive leaching and then using the ratio: C1 content by leaching/Cl
content by saturation extract,to correct the other water soluble constituents.
The great multiplicity of methods for the determination of the exchangeable ions in soil is indicative that
none is wholly satisfactory.
Ammonium acetate is a widely used reagent both for the extraction of exchangeable ions and for the
determination ofthe exchange-capacity. It has been used because it makes possible both determinations on one
152
 SALINE A N D A L K A L I SOILS CHEMISTRY (ARID ZONES)
sample.However,its use has serious drawbacks.First,CaCO, is quite soluble in NH4Acand leads to high
values for extractable Ca and low values for the exchange capacity.Second,while NH,will not remove all of
the Na+ from zeolites,it does remove some. At present, it does not appear that N a derived from zeolites
should be included in calculating the E.S.P.for alkali soils.Finally,there may be non-exchangeableN a +
in alkali soils which dissolves in NH,Ac but not in water leading to high values for the extractable sodium.
In view of the complexities,it will be clear that the best method for extracting alkali soils will be some
compromise method. At the time of writing,the procedure recommended by BOWER and HATCHER appears
to be most satisfactory.This involves the determination of the exchange capacity by saturating the soil with
N a + at p H 8.2,washing out the excess salt with alcohol,and extracting the N a with Mg(Ac),. The extractable
N a is determined in a separate Mg(Ac), extraction ofthe soil,and the exchangeable Na' is calculated from
+

this by subtracting the water soluble sodium which has been corrected for negative adsorption. It is believed
that the use of Mg(Ac), in these procedures minimises the errors discussed above.
For many years N a + analyses have been run with the use of a flame photometer. More recently electrodes
have become availablewhich are sensitive to Na+,only slightly so to K + and H + , and insensitive to Ca++
and Mg++. Such an electrode may be used in place of the glass electrodein a p H meter assemble to measure
N a + ion activities.Ifthe activity coefficientof Na+ can be estimated,the concentration ofN a + can be found.
Alternatively,procedures can be devised in which the measurements are made in an excess of some standard
reagent and the concentration read from an appropriate standard curve. Methods for the determination of
exchangeable N a and the exchange capacity employing this electrode have been devised (BOWER, 1960).
+

REFERENCES

ACADEMY OF SCIENCES USSR (1953),Ameloriation of Alkali Soils of the USSR,Collection of articles, Editors:
I.V. Tiurin,I. N.Antipov-Karataev,M.G.Chydgevski,Moscow (in Russian).
ACADEMY OF SCIENCESUSSR (1958), Amelioration qf alkali soils, Collections of articles,Editor: I.N.Antipov-
Karataev,Moscow (in Russian).
ACADEMY OF SCIENCES USSR (1956), Takyrs of west Turkmenia and their development, Collection of articles,
Moscow (in Russian).
BABCOCKL. K.,CARLSON R. M.,SCHULTZ R. K., and OVERSTREET, R. (1959), A study of the effect of
irrigation water composition on soil properties,Hilgardia. 29, 155-64.
BIGGARJ. W., and NIELSEND.R. (1963), Miscible displacement. V. Exchange Processes,
BOLT G.H.(1955), Ion adsorption by clays,Soil Sciences, 79, 267-76.
BOLTG.H. (1961), The pressure filtrationof colloidal suspensions,II.Kolloid Z.,175, 144-50.
BLACKC.A. (Ed.) (1965), Methods of soils analysis,ASA Monograplz, Madison,Wisconsin.
BOWER C. A. (1959), Prediction of the effects of irrigation waters on soils, Proc. UNESCO Arid Zone
Symposium, Salinity Problems in the Arid Zones,Tehran,Iran,215-22.
BOWER C. A.,and HATCHER J. T. (1962), Characterisation of salt-affected soils with respect to sodium,
Soil Sciences, 93,275-80.
BOWER C.A.(1960), Sodium electrode and its use for salinityinvestigations,7th Intern. Congress of SoilSci.,
II, 16-21.
BROOKSR.H., GOERTZEN J. O.,and BOWER C. A. (1965), Prediction of changes in the compositions of the
dissolved and exchangeable cations in soils upon irrigation with high-sodiumwaters,Proc. Soil Sci.Soc.
Amer., 22, 122-4.
BUREAU OF RECLAMATION (1967), Laboratory Procedures, Series 510, Land ClassiJication Techniques and
Standards,Part 517, 165.
DUTTGORDONR.,and DONEEN LLOYDD.(1963), Predicting the solute composition of the saturation
extract from soil undergoing salinization,Proc. Soil Sci. Amer., 27, 627-32.
DYER KENNETH L.(1965), Unsaturated flow phenomena in Panochesandy clay loam as indicated by leaching
of chloride and nitrate ions,Proc. Soil Sci. Soc. Amer., 29, 121-6.
EGOROV V.V. (1954), Suline soils and their development,Academy of Sciences USSR, Moscow (in Russian).
GEDROYZ K.K.(1917), Saline soils and their amelioration, M u g . Opytnuju Agronomya, Book 2-4 (in
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IRRIGATION, DRAINAGE A N D SALINITY
K.K.(1928),Alkali soils,their origin property and amelioration,Nosovskaju s. h. op. st. vipusk,46
GEDROYZ
(in Russian).
KELLER N.D.(1957), The IJrincQJles of chemical weathering, Lucas, Columbia,Missouri.
KELLEY W.P. (1951), Alkali Soils, Reinhold, New York.
KELLEY W.P.,CHAPMAN H.D., and PRATTP.F.(1961). Effect of plant growth on salts of irrigated soils,
Soil Sciences,91, 103-12.
KOVDAV.A. (1 965), Alkaline sodu-salinesoils, Symposium on sodic soils,Budapest,T o m 14,Supplementum.
KOVDAV. A.(1946), Chapter 2 (1947), Origin and regime of saline soils, Moscow-Leningrad (in Russian).
KOVDAV. A. (1947), Saline and alkali soils,Academy of Sciences USSR,Moscow-Leningrad (in Russian).
KOVDAV.A. (1959), Sketches OJZnature undsoilsof China,Academy of SciencesUSSR, Moscow (in Russian).
KRISHNAMOORTHY C.,and R.OVERSTREET (1950), A n experimentalevaluation of ion-exchangerelationships,
Soil Science,69,41-53.
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