CHAPTER 3

WATER QUALITY FORMATION AND

HYDROLOGIC CYCLE

3.1 Introduction
Water is closely bound to the general mechanism of nature called water cycle and represents a part
of the natural resources. In the near future, not only the available water, but also its quality will
represent a valuable resource. The formation of one chemical composition or another (this means
quality too) of the water on the continental part of the Earth is determined mainly by two groups of
factors, acting at the background of the water cycle: direct and indirect factors. The present chapter
considers the role of the circumrotation of the basic chemical elements in nature for the formation of
the chemical composition and quality of water on the Earth's surface.

3.2 Chemical composition of water in the atmosphere

The water cycle combines all the objects of the hydrosphere in integral entity. The momentary
(simultaneous) water reserves in the atmosphere amount only to 0.001 % (13 thousand km 3) from all
the water reserves of the whole hydrosphere, but they are characterized by the highest activity of
water exchange compared to all the other elements - water in the atmosphere is renewed on the
average each 10 days. In other words, the water molecule that has entered the atmosphere (in
gaseous state) due to evaporation from the Earth's surface, returns back to the Earth's surface after
10 days in the form of precipitation (condensed water vapour).
The atmospheric precipitation is a phenomenon of great practical and ecological importance.
Compared to other kinds of natural water, the atmospheric water has the lowest mineralisation, but
the diversity of the chemical composition of the dissolved substances is not lower than that of the
other types of natural water. The chemical composition of precipitation is one of the major factors
contributing to the formation of the chemical composition of surface water, and partially of
groundwater.

3.2.1 Factors for the formation of the chemical composition of water in the
atmosphere
The main specific feature of the atmosphere is its heterogeneous nature, and all the phase states of
water have crucial importance for the chemistry of atmospheric water (for example it is the source of
the hydroxyl group OH, which is the basic component of many chemical reactions). Water in the
liquid state (clouds and precipitation) exerts substantial impact on the cycle of sulphur, carbon,
nitrogen, and the other elements. The presence of solid and liquid admixtures in the atmosphere,
called also atmospheric aerosols, is a fact of multilateral importance. The aerosols found in the
atmosphere play a specific role and exert substantial effect on the physical and chemical processes
occurring in it:

the aerosols influence the formation of clouds, since the water vapour is condensed exactly
on them.

they can be transferred by the atmospheric currents to remote distances from the place of
their origin.

they represent a source of chemical compounds, dissolved in the atmospheric precipitation.

Aerosols in the atmosphere are the product of complex chemical (including photochemical) and
physical processes and taking under consideration their short lifetime, it becomes clear that their
spatial-temporal changeability is extremely high. For this reason, even at the present moment, there
are no reliable quantitative methods for assessment of the balance of aerosols depending on their
sources - either natural or anthropogenic. It is supposed that the greatest part of the aerosols
represent secondary by-products of gases (regardless of their origin), which are stable for a short
time because of their rapid reaction with some of the strongly changeable components of the air. In
this respect the role of SO2, H2S, NH3, NOx, which have been introduced in the air either in a natural
way or due to their deliberate release in the atmosphere, is especially important. For example, the
process of sulphuric acid formation from SO2 is extremely important. Taking into account some
intermediate reactions, this process can be described in the following manner:
SO2 + O

SO2 + H2O

H2SO4

(3.1)

The sulphuric acid is strongly hygroscopic; it also reacts very quickly with NH 3, which leads to the
formation of a solid aerosol - ammonium sulphate (NH4)2SO4 - acidic rains (Figure 3.1)

Figure 3.1 Acidic rain processes

3.2.2 Factors determining the chemical composition of precipitation

As already mentioned, the main factors determining the chemical composition of the atmospheric
moisture are the phase transitions of water and the presence of solid and liquid admixtures of
various origin and composition. The mineralisation and the chemical composition of the atmospheric
precipitation (a basic unit in the water cycle) are also the result of the combination of many
processes, the more important of them being:

"wash-out " of the substances inside the clouds (M1)

"wash-out" of the substances from the atmospheric air during the process of moving towards
the Earth's surface (M2)

"wash-out" of the substances in the surface atmospheric layer, which is spatially connected
with the vegetation cover and has a thickness of about 50 - 100 m (M3).

The M3 component (on the land) depends on the composition of the aerosols, the composition of the
evaporated water from water reservoirs, vegetation, and soils. It is supposed that 75% of the
dissolved salts contained in the atmospheric precipitation above vast forest territories is due to the
vegetation. The composition of rainwater is considerably changed just before reaching the Earth's
surface due to its passing through the canopy of the trees and bushes and acquiring in most of the

cases of acidic reaction. It is even assumed that atmogenic (within the scope of the atmosphere) and
biogenic (soils and vegetation) stages exist in the evolution of the water composition.
Hence the formation of the mineralisation and chemical composition of precipitation can be
expressed in the following manner:
M = M1 + M2 + M3

(3.2)

The importance of each of the above mentioned components changes, depending on the geographic
position (latitude, longitude, altitude, etc.). For example, the component M1 plays the major role for
the formation of mineralisation and composition of atmospheric precipitation in high-mountain
regions (above 2500 - 3000 m), while in arid (desert and semi-desert) regions the most important
component is M2, and in vast forest massifs it is M3.

3.2.3 Reasons for the changes in the atmospheric precipitation composition

One of the substantial parameters for the changes in the atmospheric precipitation are the
alterations depending on the amount and manner of falling, the phase state of the precipitation
elements and the technogenic loading of the atmosphere.
The dependence of the chemical composition of atmospheric precipitation on the amount and
manner of falling is the best-studied problem. It has been established that with the increase of the
total amount of precipitation its mineralisation as well as the content of the ions SO 42-, Cl-, NO4-, NH4+,
Ca2+, decrease. The mineralisation of the precipitation falling in the form of drizzling or small-drop
rainfall is much higher than that of torrential precipitation, because for equal meteorological
conditions smaller drops (with greater number and larger surface) have a longer contact with the
substances in the atmosphere than bigger drops.
It has been established that the precipitation falling in the liquid and solid state differ in their chemical
composition. Rainwater in most of the cases has significantly higher mineralisation compared to
snow water, and a higher content of almost all ions. The fog and the dew are characterized by higher
content of sulphates and chlorides compared to the other types of atmospheric moisture.
The reasons for these changes in the precipitation composition as a result of the technogenic
pollution of the atmospheric air are one of the best-studied problems. Single concepts concerning
this question are treated in Sulphur cycle, Nitrogen cycle, Acidic rains.

3.2.4 Influence of the atmospheric precipitation on formation of surface water

quality

With respect to the influence of the atmospheric precipitation on the formation of the surface water
quality, the greatest attention has been focused on the amount of the "imported" mineral salts by the
precipitation. The solution of this problem is usually reduced to the calculation of the salt amounts
introduced by the precipitation annually per unit area. For example, according to data for the territory
of the former USSR, the amounts of mineral salts introduced with the precipitation fluctuate on the
average from 6.1 t/(km2yr) for northern most regions with high moisture content to 26.4 t/(km 2yr) for
desert and semi-desert arid regions of the south, the average mineralisation of the precipitation
being 10 - 20 mg/dm3 with limiting values of 3 and 60 mg/dm 3. The influence of the atmospheric
precipitation for the water quality formation on the continental part of the Earth is best observed in
mountain regions, where the fresh and ultra-fresh ground fissure water is developed. About 50-75%
of their mineralisation are formed by the atmospheric precipitation dissolved mineral substances.
The problem of the influence of the atmospheric precipitation on the formation of the water quality on
the land is considered in combination with the velocity of the occurring changes in the rainwater
composition after its contact with soils and rocks. It has been established that the composition of
rainwater changes very quickly (from 15 min to 1 hour), the character of these changes being
determined by the rainwater, rock, and soil composition. For this reason it has been proposed to call
the atmospheric water coming in contact with the Earth's surface "water with instantaneous
metamorphization".
The above-mentioned considerations explain the importance of the atmospheric precipitation (as a
chain of the water cycle) for the chemical composition of the water on the land.

3.3 Oxygen cycle and oxygen content in surface water

Oxygen is a gas with no colour and odour, forming compounds with all chemical elements with the
exception of inert gases. It is contained in a free state in the atmosphere and represents 20.95 % (by
volume). The free oxygen, necessary for the existence of living organisms, is a product of life itself
because not only all the atmospheric oxygen, but also the oxygen in sediment rocks, is of
photosynthetic origin. A part of the free oxygen is formed under the dissociation action of
the ultraviolet radiation in the atmosphere. However, this part represents only thousandths of percent
compared to the oxygen produced by the photosynthesis (Figure 3.2).

Figure 3.2 Oxygen cycle

The vegetation in the biosphere releases annually about 430 - 470 billion tons of oxygen during the
process of photosynthesis. The whole oxygen in the atmosphere passes through the biosphere in
the course of about 2000 years. The oxygen cycle is very complicated due to the fact that it
participates in the composition of many inorganic (for example in the water - the most widely
distributed inorganic substance) and organic compounds.
The oxygen is one of the most important gases that are constantly present in natural water. The
oxygen regime determines to a significant extent the chemical-biological condition of the water
basin. Sources of oxygen in natural water are:

the process of absorption of oxygen in the atmosphere.

the formation of oxygen as a result of the photosynthesis of the aquatic vegetation, which
proceeds in the upper water layer with a thickness of several tens of centimetres to metres
depending on water transparency.

the entering oxygen from rain and snow water, which is as a rule very rich in dissolved
oxygen.

However, the oxygen concentrations decrease with the increased depth of the water basins due to
the attenuation of photosynthesis at the expense of its utilization for oxidation of organic substances
and respiration of aquatic organisms.
The oxygen regime of the water basin influences the life in it to a considerable degree. If water
contains sufficient amount of organic wastes and if the other conditions of the medium are
favourable (suitable temperature), the aerobic bacteria are reproduced very rapidly and the quantity
of the dissolved oxygen is decreased proportionally to the growth of the bacterial mass.

3.4 Carbon cycle and carbon content in surface water

Carbon in nature is found mainly in bound state and its total content is 0.10% of the Earth's crust
mass. The amount of carbon in the hydrosphere (mainly in the form of dissolved CO2) is about 1014
tons and is in equilibrium with the atmospheric CO2.

Figure 3.3 Carbon cycle

The carbon cycle in nature (Figure 3.3), the distribution and accumulation of carbon, are related to a
significant degree with the life functions of the vegetative organisms, which absorb the atmospheric
CO2 during the photosynthesis. Three types of carbon cycles are observed in nature, which proceed
simultaneously and with mutual relationships:

biological cycle, proceeding according to the scheme: atmosphere

absorption -

vegetation
assimilation
animals
respiration
atmosphere. In fact, a very small
part of the carbon contained in nature has participated intensively in the biological cycle,
supporting the life on the Earth within certain limits depending of the established equilibrium
in carbon balance.

big geological cycle, proceeding very slowly. The importance of the World Ocean is
especially significant since it plays the role of main regulator of CO 2 in the atmosphere
according to the scheme below, due to its huge water reserves (with good capacity of

atmospheric CO2 and good dissolution properties): CO 2 (atmosphere)

H2CO3

Ca(HCO3)2

CO2 (water)

CaCO3

biological-technogenic cycle. It resembles very much to the first one but still more
organogenic depositions of past geological times (oil, coal, natural gas, schists, etc.) are
included in it due to the economic activity of man. It is considered that the CO 2 released into
atmosphere by anthropogenic means is the main cause for the "greenhouse effect"

Carbon is present in natural water in two forms:

MINERAL - in the form of carbonates and hydrocarbonates. They enter natural water as a
result of the processes ofweathering and dissolution of carbonate rocks (limestone, marl and
dolomite) and metamorphization of the products of the chemical weathering of volcanic
rocks. The carbonate and hydrocarbonate ions are present in all natural water in dissolved
state.

ORGANIC - vegetation and animal tissues and the products of their life activity and decay.
The composition of the organic substances in natural water is extremely diverse - from the
complex high-molecular compounds of the type of proteins, humics and polysaccharides to
the most simple - methane, formaldehyde, amines and others. The organic carbon is an
important parameter for the total content of organic substances in natural water, which is
determined by the totality of differing in nature and speed processes:
o

release of organic substances resulting from the life activity and death of fauna and
flora species, living in water and in the bottom deposits of the water basins. These
organisms play a major role for the formation of the chemical composition and
hydrochemical regime of natural water.

penetration of organic substances from atmospheric precipitation by the surface

runoff resulting from the interaction between atmospheric water, soil and vegetation
cover.

3.5 Nitrogen cycle and nitrogen content in surface water

Nitrogen is a gas with no colour and odour, and slightly soluble in water under normal conditions. Its
content in the Earth's crust amounts to only 0.04 % by mass but it represents the main component
part of the atmosphere: 75.6 % of the mass or 78.1 % of the volume.

Figure 3.4 Nitrogen cycle

The nitrogen cycle (Figure 3.4) in nature is realized by different organisms, for which nitrogen is of
vital importance, due to the fact that it is an indispensable component of such extremely necessary
compounds as chlorophyll, haemoglobin, desoxyribonucleic acid, etc. Animals and plants cannot
assimilate directly atmospheric nitrogen but plants can use it in the form of dissolved nitrates in soils
by their root system. After a number of chemical reactions the nitrogen in then is bound with other
elements until nucleic acids and proteins are obtained. Proteins are exactly in the form in which
nitrogen can be used by the higher organisms. The complex nitrogen compounds comprised in the
animal wastes decay under the action of bacteria to relatively simple compounds of the group of the
ammonia and the ammonium salts - ammonification. Another group of bacteria processes these
compounds to nitrates that are easy again for assimilation by plants - nitrification, thus closing the
cycle. In addition to this cycle, certain amounts of the atmospheric nitrogen are bound ("fixed")
during thunderstorms or by bacteria in the roots of leguminous plants. Moreover, a part of the
nitrates on the land can be carried away by surface water to the ocean and after deposition on the
bottom it leaves the nitrogen cycle. However, a part of these nitrates can return again to the land by
means of the trophic path: phytoplankton
zooplankton
fish
birds. A certain type of bacteria

- denitrificating ones - are capable of decomposing the ammonium compounds and as a result
gaseous nitrogen is released as a by-product, which can no longer be assimilated by the organisms
- denitrification.

3.5.1 Nitrogen content in surface water

Nitrogen is contained in surface water in the form of mineral and organic substances, the sum of the
mineral and organic nitrogen being called total nitrogen. Nitrogen refers to the most
important biogenic elements (nutrients) and their content in the water basins determines to a great
extent their biological productivity. In this respect the total nitrogen content can be an indicator for
the potential eutrophication of these basins.

3.5.2 Mineral nitrogen

The sum of the mineral forms of nitrogen in natural water (nitrate (NO 3-), nitrite (NO2-) and
ammonium (NH4+) nitrogen) are combined under the general term mineral nitrogen.

Nitrate nitrogen (NO3-). The nitrates are compounds of the nitric acid and their occurrence in
natural water is related with the processes of nitrification of the ammonium ions in the
presence of oxygen under the action of nitrification bacteria. The atmospheric precipitation is
also a source of enrichment of surface water with nitrates. The precipitation absorbs the
nitrogen oxides formed in the atmosphere during electric discharges, transforming them into
nitric and nitrous acid. The nitrogen concentration in atmospheric precipitation reaches up to
0.9-1.0 mg/dm3. Considerable increase of nitrate concentration in surface water can be
observed also as a result of anthropogenic activities. The lowering of the concentration of
nitrates is due to their utilization by the phytoplankton and denitrification bacteria, which use
the oxygen of the nitrates for oxidizing the organic substances under conditions of oxygen
deficiency.

Nitrite nitrogen (NO2-). The nitrites are salts of the nitrous acid. Their presence in nonpolluted natural water is related with the processes of organic substance decomposition and
nitrification. The nitrification bacteria oxidize the ammonium ions to nitrite ions:
(NH4+) + OH- + 3/2 O2 = H+ + (NO2-) + 2H2O

(3.3)

When the oxygen concentration is sufficient, the oxidation process continues under the
action of other bacteria to nitrates. The nitrites are unstable components of natural water and
their concentration is negligible even under favourable conditions in surface water for their
oxidation. The increased nitrite content in surface water is an indicator for enhanced

processes of organic substance decomposition under conditions of hampered oxidation of

(NO2-) to (NO3-), which is an evidence of pollution of the water basin and hence is an
important sanitary parameter.

Ammonium nitrogen (NH4+). It represents a mineral radical, which does not exist in a free
state and plays the role of a univalent metal in chemical compounds. The presence of
ammonium ions (NH4+) and of non-dissociated molecules of the ammonium hydroxide
(NH4OH) in water is of high ecological importance. Concentrations of (NH 4+) in groundwater
with slow water exchange, where the nitrification processes are strongly restricted, can
exceed 100 mg/dm3.

3.5.3 Organic nitrogen

This is the nitrogen that is in the composition of high-molecular (proteins, proteids and polypeptides)
as well as of low-molecular (aminoacids, amines, amides, urea) organic substances. The greatest
part of nitrogen containing organic compounds enter natural water through the process of extinction
of organisms (mainly of phytoplankton) and decay of their cells. Another important source of organic
nitrogen is the atmospheric precipitation, in which the concentration of nitro-organic substances is
close to the concentrations in surface water. The considerable increase of nitrogen containing
organic substances in water basins can be also attributed to the wastewater from anthropogenic
activity.

3.6 Phosphorus cycle and phosphorus content in surface water

Phosphorus is an element that, while being essential to life as a key nutrient factor, nevertheless
contributes to the eutrophication of lakes and other bodies of water. The phosphorus content in the
Earth's crust is 9.3 .10-2 % by mass and it is not encountered in a free state in nature. All
phosphorus-containing minerals (their number being about 190) are orthophosphates and are
distributed in the magmatic and sedimentary rocks. The most important of them are the apatites and
phosphorites (Figure 3.5)

Figure 3.5 Phosphorus cycle

Phosphorus is assimilated by plants in the form of salts of the phosphoric acid and is of great
importance for functioning of all living organisms, since it enters the composition of ADP and ATP
(adenosine triphosphate), DNA and RNA. From all the mineral elements assimilated by plants, only
phosphorous could be considered to be deficient because it is found in practically insoluble
compounds in acidic and alkaline soils.
The phosphorus cycle in the biosphere is incomplete, water being the main reason for this, because
phosphorus migratesthrough water only from the lithosphere to the hydrosphere. On the land
phosphorus is assimilated from the soil by plants, is used by plants and animals for their life
processes and after mineralisation of the organic substances enters the soil again in the form of
phosphates. The greatest part of this phosphorus is absorbed again by the root system of the plants,
but the other part can be washed away by precipitation and then transported to water basins. As
already mentioned, large phosphorus reserves have been accumulated in the Earth's crust during
past geological times and a part of them gradually passes into the soil, when another part is used for
phosphorus fertilizers and is also transferred to the soil, but finally a great share of this phosphorus

enters the hydrosphere. There phosphates are used by the phytoplankton and the related organisms
at different levels of the complex trophic path. Considerable amounts of phosphorus are practically
"excluded" from the biological cycle into ocean due to their deposition at great depths. Only a small
part of the phosphorus returns to the lithosphere, exclusively in a biological manner.
The anthropogenic activity is an important factor for the increase of the phosphorus content in water
and on the land due to the wide application of phosphorus fertilizers, polyphosphate detergents and
the biological treatment of the polluted household and industrial wastewater. This leads to the
considerable eutrophication of the water basins.

3.7 Sulphur cycle and sulphur content in surface water

The content of sulphur in the Earth's crust amounts to 510 -2 % (by weight) and it is found in pure
state in volcanic areas or in the form of sulphide minerals. The main significance of sulphur for the
living organisms is that it participates in the composition of important aminoacids, forming disulphide
bonds that keep the three-dimensional structure of the protein molecules.

Figure 3.6 Sulphur cycle

The sulphur cycle in nature comprises all the envelopes of the Earth: the atmosphere, the
lithosphere, the biosphere and the hydrosphere (Figure 3.6). The most active components in the
complex sulphur cycle are the sulphates, their ions being one of the main anions present practically
in all natural water. The plants and the other autotrophic organisms can extract the sulphur only in an
oxidized form as dissolved in water sulphate anions for the building of their protein substances. After
the death of the cells the heterotrophic organisms release sulphur from the proteins in the form
of hydrogen sulphide, which is easily oxidized to sulphates again in the presence of oxygen. Under
conditions of oxygen deficiency, the sulphates are recovered to hydrogen sulphide and sulphides in
the course of the sulphate reduction process and they are again oxidized to sulphates when
introduced in natural water. The sulphates enter the surface water mainly due to the chemical
weathering, the dissolution of sulphur containing minerals (mainly gypsum) as well as to the
oxidation of sulphides and sulphur:
(3.4)
CaCO3 + H2SO4 = CaSO4 + H2O + CO2

2FeS2 + 7O2 + 2H2O = 2FeSO4 + H2SO4

2S + 3O2 + 2H2O = 2H2SO4

Considerable amounts of sulphates are introduced in the water basins as a result of the death of the
organisms, their oxidation and washing away by the surface and ground flows, and the wastewater
from anthropogenic activities.
The increased sulphur content aggravates the organoleptical properties of water and exerts negative
physiological effect on human organism.
The sulphate concentration in rivers and freshwater lakes fluctuates in the range of 5-60 mg/dm 3, in
rainwater from 1 to 10 mg/dm3, while it can reach tens of parts per million in groundwater. The
natural water with prevailing sulphate ions in its composition is referred to the class of the so-called
"sulphate" water and is characterized by increased mineralisation, its chemical composition being
connected with the dissolved salts from the sediment rocks.
The economic activity of man exerts significant influence on the sulphur cycle. Man extracts from the
lithosphere considerable amounts of pure sulphur and sulphates that are used in different branches
of industry and agriculture. Huge amounts of sulphur compounds are released in the atmosphere
during the processing of the extracted sulphur and the combustion of natural fuels. The
annual SO2 emissions (calculated for a unit area) have reached 100 t/km 2 for single regions in the
world (the north-eastern part of the USA, the central parts of Great Britain, the Ruhr basin in
Germany). It has been estimated that while the natural emission of SO 2 is in the range of 3-30 million
t/yr (depending on the volcanic activity), the anthropogenic emission is more than 110-120 million
t/yr. The sulphur in the atmosphere reaches again the Earth's surface in the form of acidic
precipitation or sulphate aerosols. In the middle of the eighties of the last century, only the quantity of
the deposited sulphur in the industrial regions of West Europe and the southeastern part of Great
Britain amounted to 5 to 10 g/m2 or 50 to 100 kg/ha, without taking into account the other polluting
substances.