Chemical characteristics

Dissolved gases
No naturally occurring body of water is free of dissolved
gases. Their spatial and temporal distribution is dependent
on factors such as precipitation, inflow and outflow,
physical factors like temperature, movement of water and
chemical factors such as solution processes, combination
and precipitation of reactions, complex formation etc.
Among the dissolved gases present in water, oxygen and
carbon dioxide are direct indicators of biological activity of
water bodies.
Gaseous nitrogen only enters the metabolic cycle of a few
specific microorganisms.
Hydrogen sulphide and methane occur in small localized
amounts due to bacterial activity under conditions of low
redox potential.
Liebig's law of the minimum, often simply
called Liebig's law or the law of the minimum, is a
principle developed in agricultural science by Carl
Sprengel (1828) and later popularized by Justus von
Liebig. It states that growth is dictated not by
total resources available, but by the scarcest resource
(limiting factor). The law has also been applied to
biological populations and ecosystem models for factors
such as sunlight or mineral nutrients.
Solubility of Gases in water
The solubility of gases in water decreases with
increasing temperature and decrease of pressure.
When a gas comes in contact with water, it dissolves
in it until a state of equilibrium is reached in which the
solution and the emission of the gas are balanced.
Total solubility of gas is expressed by Henry’s law.
The Law states that the amount of dissolved gas is
proportional to its partial pressure in the gas phase.
The proportionality factor is called the Henry's law
constant.
• Condition affecting the solubility of gases in
water
Solubility of gases differs widely even when
their pressures are equal. It is therefore
necessary to find out the solubility constants.
Henry’s law is stated as:
C= K p
Where, C = Concentration of gas in solution
p = Partial pressure of gas
K= Constant of solubility
The following general conditions affect the solubility
of a gas:
1. Rise in temperature reduces solubility
2. Increasing concentration of dissolved salts diminishes
solubility
3. Rate of solubility is greater when the gases are dry than
when they contain water vapour
4. The degree of solution depends upon the degree of under
saturation of the water with the gas concerned. So, the
greater the degree of under saturation the greater the rate
of solubility
5. Rate of solubility is increased by wave action and other
forms of surface water agitation
1. Oxygen
The main sources of dissolved oxygen in water are:
a) The atmosphere and
b) By photosynthetic activity of aquatic plants
Atmospheric oxygen enters the aquatic system:
a) By direct diffusion at the surface and
b) Through various forms of surface water agitations such as
wave action, waterfalls, and turbulences due to obstructions.
Aquatic chlorophyll bearing plants release oxygen as a
byproduct of photosynthesis, which gets distributed into the
different layers of lake water by movements. In most lakes
the phytoplankton contributes the bulk of the oxygen supply
because of the huge amounts of chlorophyll of algae in the
epilimnion zone
The main causes of decrease of oxygen in water are:
a) Respiration of animals and plants throughout the day and
night
b) Decomposition of organic matter – Aerobic bacteria use up of
the oxygen of water while decomposing organic matter.
Chemical oxidation of sediments also takes place. Purely
chemical oxidation may also occur, but most of the oxidative
processes in aquatic habitats are probably mediated through
bacterial action.
c) Reduction due to other gases – A gas may be entirely
removed from solution by bubbling another gas through the
water in which it is dissolved. In nature, gases like CO2,
methane and hydrogen sulphide often accumulate in large
amounts and the excess amounts rise in the form of bubbles
removing the dissolved oxygen.
d)By physical process – In summer days the heat warms
up the epilimnion zone of the lake, which could account
for oxygen depletion of water.

Diel oxygen changes in freshwaters

Diel variations occur in both day and night hours.
Estimates of diel production can be made in natural
waters by considering night as the dark bottle and day
as the clear bottle. The increase in oxygen from dawn to
dusk reflects net primary productivity. The decrease
from dusk until dawn represents half the diel respiration.
Adding the oxygen that disappeared at night to the day
time gain gives a sum that is daily gross primary
productivity.
2. Carbon dioxide
Sources of carbon dioxide in freshwater
a) The atmospheric carbon dioxide mixes with the water
when it comes in contact with the water surface, as it
possesses the highest solubility in water. As the partial
pressure of carbon dioxide in air is low, the amount which
remains in solution in water at a given temperature is also
low.
b) Rainwater and inflowing ground water-
Rainwater is charged with 0.55 to 0.60 mg/I CO2 as it falls
towards earth. Water trickling through organic soil may
become further charged with CO2.
c)Byproduct of Decomposing Organic Matter (DOM)-
It is found that carbon dioxide is the second largest
decomposition product, constituting 3 to 30 per cent of
the total gas evolved as a byproduct of decomposing
organic matter.
d)Respiration of Animals and Plants-
Respiratory processes produce and release carbon
dioxide into the water. The quantities so added are
governed by the magnitude of aquatic flora and fauna
present.
Reduction of carbon dioxide in freshwaters
• The principal processes which tend to reduce the carbon
dioxide supply are;
a) Photosynthesis of aquatic plants
Consumption of free CO2 in photosynthesis depends upon
amount of green plants which the water supports, duration of
effective day light, transparency of water and the time of
year.
b) Marl forming organisms
The following groups of aquatic organisms are known to form
marl (=Crumble : large deposits of calcium and magnesium
carbonate) in water bodies;
 Aquatic flowering plants like potamogeton, ceratophyllum,
nymphaea, vallisneria;
Many blue-green algae like rivularia, lyngbya nana,
lyngbya martesiana, colacacia. Centrosphaeria
facciolaea;
Many species of diatoms;
Mollusks which form calcareous shells;
Insects like diptera larvae;
The cray fishes and lime-forming bacteria.
All these organisms function in the production of the insoluble
carbonates which involves carbon dioxide, calcium and
magnesium. Thus the process of lime formation binds up
carbon dioxide supplied from circulation and removes the
available calcium and magnesium from the system.
c)Agitation of water
Agitation is a very effective method of releasing free carbon
dioxide from water. It is evident from the fact that sometimes
when deeper layers of water has large amount of it, the surface
water shows very little carbon dioxide.
d)Evaporation
Evaporation of waters containing bicarbonates results in the
loss of half-bound carbon dioxide and precipitation of mono
carbonate. The form of loss is greatest in shallow water bodies
where evaporation is most effective.
e)Rise of bubbles from depths-
Free carbon dioxide often accumulates in decomposing bottom
deposit in such quantities that at frequent intervals increasing
internal pressure of gas exceeds the external pressure and the
excess gas rises in the form of masses of bubbles to the
surface and is lost into the air.
 Other dissolved gases
Methane
Methane, sometimes called marsh gas, is one of the products
of decomposing organic matter at the bottoms of marshes,
ponds, rice field and lakes. The methane bacteria are
obligate anaerobes. They decompose organic compounds
with the production of methane (CH 4) through reduction of
either organic or carbonate carbon. Conditions favorable for
production of methane appear at about the time the dissolved
oxygen content is exhausted. This is because methane (CH 4),
a compound of carbon and hydrogen burns in oxygen forming
oxides of carbon and hydrogen i.e., carbon dioxide and water.

It has been found that large quantities of methane are

produced in marshes and eutrophicated lakes during summer
time.
 Hydrogen Sulphide
• Hydrogen sulphide dissolves very rapidly in water
and is thus not dissipated like methane.
• The bottom water of stratified eutrophic lakes may
contain appreciable quantities of the very soluble
gas H2S. This is especially marked in lakes of
regions of high edaphic sulfate.
• The reduction of sulfate to sulfide is a phenomenon
largely associated with anaerobic sediments.
• H2S is poisonous to aerobic organisms because it
inactivates the enzyme cytochrome oxidase.
Nitrogen
Nitrogen has a low solubility in water. It is such an inert gas
that the quantities which occur in lake water are not changed
by the chemical and biological processes. The atmosphere
usually supplies the greater amounts of nitrogen found in
water. The maximum amount occurs in winter, since it is more
soluble in cool water.

• Ammonia
Ammonia occurs in small amounts in unmodified natural
waters. It is exceedingly soluble, 1 volume of water
dissolving 1,300 volume of ammonia at 0° C. In lakes, it is
the result of the decomposition of organic matter at the
bottom. In summer, free ammonia ordinarily increases with
depth.
Sulphur dioxide
Traces of sulphur dioxide may occur in natural waters.

Hydrogen
Liberation of hydrogen in the anaerobic decomposition of
lake bottom deposits seems likely. But, the amount so
formed is small.

Carbon Monoxide
Carbon monoxide may occur in the bottom of the
hypolimnion in small amount.
Dissolved Solids and Dissolved Organic Matter
Natural waters come in contact with soluble substances in
many ways such as mere contact with its own basin, erosion
at shore line, windblown materials, inflow of surface waters,
inflow of seepage and other forms of subterranean waters and
decay of aquatic organisms.
Rain water contains 30 to 40 ppm of dissolved solids.
Solubility of solids in water
Salts are composed of ions which in the solid form are held
together by ionic forces. The strong ionization of the salts
leads to the formation of hydrates with water. The solubility
of solid substances is strongly dependent on the pH and the
redox potential in the water. It usually increases with
temperature and is largely independent of pressure
Major ions in freshwaters
The major ion contents vary in different fresh waters
due to five factors such as climate, geography,
topography, biotic activity and time.
Carbonate is the principal anion in most fresh-waters.
Generally carbonate occurs as bicarbonate ion with
calcium in water.
Alkalinity is usually a measure of carbonates. There are
various compounds of carbonates with calcium, such
as calcite or aragonite which have the same chemical
formula (CaCO3), but are crystallized differently.
Aragonite precipitates from thermal waters and is
contained especially in the shells of freshwater
mollusks.
Magnetite, the carbonates of magnesium (MgCO3)
and dolomite, a double carbonate of calcium and
magnesium, Ca Mg (CO3)2 are also relatively
common.
Carbonates of barium (BaCO3) and strontium (SrCO3)
also occur. CaCO3 is insoluble except in the presence
of acid.
 Dissolved inorganic solids
Nitrogen compounds
Nitrogen occurs in natural waters, in inorganic form
as nitrate, nitrite and ammonium and in organic form
as intermediate stages of microbial protein
decomposition.
The most important inorganic nitrogen compounds
in water are nitrate and ammonia.
Natural waters also contain ammonium carbonate
as salt.
Phosphorus compounds
Free phosphorus does not occur in nature, but in the form
of phosphates it is abundant.
Inorganic phosphorus compounds usually occur in
dissolved form only in small amounts in natural waters,
often only as traces.
Total phosphorus in lake water includes two components.
One is soluble phosphorus which is the phosphate form
and another one is organic phosphorus which is
contained in plankton organisms and other organic matter
in the water.
As an essential nutrient for primary producers,
phosphorus thus acts more often than nitrogen as the
growth limiting factor
The natural inorganic phosphate content originate from
atmospheric precipitation as well as from various phosphate
containing rocks especially apatite, which are flushed into
the lake by tributary streams.
In lakes and flowing waters three phosphate fractions occur
concurrently: soluble inorganic phosphate as
orthophosphate (PO4) and polyphosphate, soluble organic
phosphate and particulate organic phosphate (organisms or
detritus).
The losses of phosphorus occur throughout flowing water
which removes both soluble and organic form. It may also
occur through removals of fish, molluscs, water plants and
other organisms.
Sulfur compounds
The inorganic sulfur compound occurring predominantly in
natural waters is sulfate. In this form sulfur can be
absorbed by phytoplankton and other photo-autotrophs.
Purely chemical processes involved in the sulfur budget of
natural waters are the oxidation of hydrogen sulfide to
sulfur by molecular oxygen and also the formation of
sulfides.
The sulfate ion, SO4 is usually second to carbonate as the
principal anion in fresh waters, although chloride
sometimes surpasses it.
Silica often outranks sulfate, but very little is ionized.
Free or elemental sulfur is inactive at ordinary
temperature.
This element can combine with both metals and non-
metals to form many compounds.
Free sulfur is an important constituent of protoplasm.
When sulfur is combined with hydrogen the most reduced
state is sulfide (S- -) and the most important sulfides in
limnology are the gas - hydrogen sulfide (H2S) and ferrous
sulfide (FeS).
With the alkali metals sulfur forms the most abundant form in
lakes and streams.
Atmospheric sources of sulfate have increased with man’s
industrial activities.
The most important conversion process for sulfur in lakes can
be summarized as follows: sulfate is reduced by the
desulphuricans to H2S and sulfides which are deposited in the
sediment.
Hydrogen sulfide is also formed by the microbial
decomposition of proteins which is oxidized by Thiobacteria,
Chromatiaceae and Chlorobiaceae via molecular sulfur to
sulfate.
Silicon
Silicon does not occur in nature as a free element. Natural
waters commonly contain silicon dioxide in some form of
soluble silicate.
Silica may also exist in in colloidal form. River waters are
relatively rich in silica.
Silica is the second most abundant element in the lithosphere.
Its main source in fresh water and sea water is weathering of
the feldspar rocks.
In inland waters it ranges from 0.1 ppm.
Solubility of silica increases with the rise in temperature.
Dissolved silica remains as H2SiO4.
Silica is an essential nutrient for diatoms as they build up their
frustules with this material.
The decay of silica is slower than organic compounds and thus
many diatoms frustules may be buried and lost to the lake
sediments.
 Other Elements
Certain elements such as calcium, magnesium,
manganese, iron, sodium, potassium, sulphur,
copper and others constitute elements of
chemical compound dissolved in the water.
Calcium
The predominant compound of calcium is CaCO3, which is
very less soluble in water but in the presence of carbonic
acid it is represented abundantly as the soluble Ca (HCO3)2.
Anorthite (CaAl2Si2O8) is a common member of the feldspar
group of silicates. They are the most abundant of all
minerals and make up 60% of the earth’s coating.
A deposit of sedimentary CaCO3 is changed to soluble
bicarbonate by the action of CO 2 rich meteoric water (rain
water) which enters aquatic systems
After the silicate and carbonate minerals of calcium, the
sulfates rank as its most abundant store. These are
gypsum, (CaSO4, 2H2O) and anhydrite (CaSo4).
Magnesium
Magnesium is usually the second most abundant cat ion in
inland waters. Its source is both silicate and non-silicate
minerals of the earth’s crust.
The magnesium carbonate is called magnetite and a
double carbonate is dolomite, Ca Mg (CO3)2. Epsom salt
(Mg SO4.7H2O) is a soft and whitish sulfate of magnesium.
It is 150 times more soluble than gypsum (CaSO4.2H2O).
Epsom salt occurs in mineral spring deposits and in salt
sediments of certain lakes.
Sodium
The commonest water soluble mineral is halite or simply
NaCl.
In arid tracts like Rajasthan where closed basins hold
concentrated waters, there are at least 3 types of
sodium lakes-
a) Slatterns, having concentration of sea water with
preponderance of NaCl.
b) Saline lakes having Na2SO4 in water and
c) The soda lakes characterized by NaHCO3 and Na2CO3.
They have been termed as alkali water because of their
high pH. These soda lakes are characterized in having
luxuriant growth of blue-green algae.
Potassium
Potassium, a close relative of sodium is usually the fourth
ranking cat ion in freshwater. In usual cases it may surpass
sodium in certain lakes.
It is weathered from various feldspars that have the formula
KAISi3O8 but does not remain in solution.
Potassium also tends to form plates of mica, which are
insoluble and unavailable to aquatic ecosystems. Because
of this formation potassium becomes rarer in water than
sodium.
In plants, both extracellular and intracellular fluids contain
an excess of K+ over Na+.
In animals extracellular Na+ often surpasses potassium.
There is some evidence that highly concentrated water with
a pronounce potassium content are lethal to many aquatic
animals, the Na/K ratio being less than ten.
Iron and Manganese
Although iron is one of the most widely distributed elements on
the earth, it occurs in natural waters only in relatively small
amounts due to its specific solubility properties. But the ground
water contains large amounts of dissolved iron and
manganese.
The compound of trivalent (ferric) iron is almost completely
insoluble in water. Thus iron remains in solution only in the
bivalent form, under reducing conditions, and chiefly as the
bicarbonate Fe (HCO3)2.
 The conditions under which bivalent iron (ferrous)
compounds remain in solution are:
a) an oxygen saturation value of less than 50%,
b) the presence of degradable organic matter,
c) a high level of free CO2 and
d) a pH of less than 7.5.
These conditions are found primarily in groundwater and
in the hypolimnion of lakes.
vi) Chloride
It is an element of the halogen group that includes also
fluorine, iodine and bromine. Among these members,
chloride surpasses them in polluted as well as
freshwater lakes and streams.
Molecular chloride (Cl2) is a heavy yellow lethal gas,
but in natural waters, it is dissociated as chloride ions,
which combine with all common cat ions. It is stored in
most freshwater algal cells.
Contamination of water from domestic sewage can be
monitored by chloride assays of the concentrated
water bodies. This is because a human and animal
excretion contains an average of 5g Cl- per liter
Dissolved Organic Matter
Freshwater contains 0.1 to 50 mg dissolved organic
compounds (DOC) per litre.
There are four sources of these dissolved materials
1. Organic compounds of allochthonous origin
2. Soluble organic material from the decay of aquatic
organisms
3. Extra cellular metabolites excreted by littoral
macrophytes
4. Excretion from the fresh water animals
The organic compounds not only serve directly as
source of energy but also are associated with the
nutrient cycle of the ecosystem.
Organic substances as humic material causing yellow
stain in fresh water comes from the decay of plant
material in the soil.
An important group of organic substances in water
consists of humic substances. They are polymeric
mixers derived mostly from plant materials such as
lignin. Cellulose, proteins and fats humic substances
enter the water due to incomplete breakdown of plant
residues in the water bodies. Humic acids in sediments
also form iron-humus-phosphate complexes. The
humic materials hold in suspension large quantities of
metallic ions.