CHAPTER 1

INTRODUCTION

1.1. Water
Water is an inorganic compound with the chemical formula H2O. It is a transparent, tasteless,
odourless, and nearly colourless chemical substance, and it is the main constituent
of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as
a solvent. It is vital for all known forms of life. Its chemical formula, H2O, indicates that each
of its molecules contains one oxygen and two hydrogen atoms, connected by covalent bonds.
The hydrogen atoms are attached to the oxygen atom. Water is a sp3 hybridised molecule
with a bent shape and having 104.5° degree due to presence of two lone pairs.

Water on earth is distributed among oceans, lakes, rivers, glaciers, groundwater and
atmospheric water vapour. The largest reservoir of water on earth is ocean which hold
approximately 97% of the planet is water. Glaciers and ice caps store around 68.7% of fresh
water. Groundwater constitutes about 30.1% of worlds freshwater. Lakes hold about 0.009%
of earths total water. Rivers account for only about 0.0002% of the earths total water. But
they are vital for the movement and distribution of freshwater across different regions.
Water molecules have versatile chemical and physical properties.
Some of the unique properties of water:
 Most of the substances become denser as they cool down as the particles come
closer, but water behaves differently. Below 4 ° Celsius water expand and become
less dense and cause ice to float on water. This is the reason for thermohaline
circulation which is a density driven circulation that maintain the whole global
climate.
 Water’s boiling point is unusually high compared with compounds similar in
weight to water have a much lower boiling point.
 Water has high specific heat capacity, it can store a significant amount of heat
without large increase in temperature.
 Water has the ability to dissolve a large variety of chemical substances. It
dissolves salts and other ionic compounds, as well as polar covalent compounds
such as alcohols and organic acids.
Water is known as the universal solvent due to its ability to dissolve wide range of substance.
Factors which contribute to the waters exceptional dissolving properties are polar nature of
water, dielectric constant, and ability to form hydrogen bonding. Substance which can make
hydrogen bond with water are soluble in water.

1.2. Major Sources of Water

Water is a valuable natural resource that is found in different forms in the environment. The
major water sources are ground water, surface water, ocean water and ice caps. Water is
continually moving around the Earth and continuously changing its physical form.

Hydrological cycle
The hydrological cycle, or water cycle, is the continuous circulation of water between ocean,
atmosphere and land. Water is in constant circulation, powered by the energy from sunlight
and gravity in a natural process called hydrological cycle. Water is in constant movement
between the biosphere, atmosphere, lithosphere and hydrosphere. Water on this planet earth
is stored in the following reservoirs such as oceans, lakes, rivers, glaciers, and atmosphere
that describes the storage and movement of water.

Evaporation
Evaporation is the transfer of water from a liquid to a gas from the surface to the atmosphere.
Approximately 80 percent of all evaporation is from the oceans, with the remaining 20
percent coming from inland water. Winds transport the evaporated water around the globe
and influence the humidity of air through the world.

Condensation (the opposite of Evaporation)

Condensation is the change of water from its gaseous form water vapour into liquid water.
Condensation generally occurs in the atmosphere when warm air rises, cools and loses its
capacity to hold water vapour. As a result, excess water vapour condenses and form cloud.
The upward motions that generate clouds can be produced by convection in unstable air,
convergence associated with cyclones, lifting of air by fronts, and lifting over elevated
topography such as mountains.

Transport
In the hydrologic cycle, transport is the movement of water through the atmosphere,
specifically from over the oceans to over land. Some of the Earth's moisture transport is
visible as clouds, which themselves consist of ice crystals and/or tiny water droplets. Clouds
are propelled from one place to another by either the jet stream, surface-based circulations
like land and sea breezes, or other mechanisms. However, a typical 1 kilo-meter thick cloud
contains only enough water for a milli-meter of rainfall, whereas the amount of moisture in
the atmosphere is usually 10 to 50 times greater. Most water is transported in the form of
water vapor, which is actually the third most abundant gas in the atmosphere.

Precipitation
Precipitation is the primary mechanism for transporting water from the atmosphere to the
surface of the Earth. There are several forms of precipitation. Rain is the major one. Other
forms of precipitation include hail, snow, sleet, and freezing rain. A well-developed extra-
tropical cyclone could be responsible for the generation of any or all of these forms of
precipitation.

Groundwater
Ground water is all the water that has penetrated the Earth's surface and is found in one of
two soil layers. The one nearest the surface is the "zone of aeration", where gaps between the
soil are filled with both air and water. Below this layer is the "zone of saturation", where the
gaps are filled with water. The water table is the boundary between these two layers. As the
amount of groundwater water increases or decreases, the water table rises or falls
accordingly. When the entire area below the ground is saturated, flooding occurs because all
subsequent precipitation is forced to remain on the surface.

Transpiration
Transpiration is the transfer of water to the atmosphere by plants and vegetation from the
leaves and stems of plants. Plants absorb water through their roots and this water can
originate from deep in the soil. Plants pump the water up from the soil to deliver nutrients to
their leaves. This pumping is driven by the evaporation of water through small pores called
"stomates," which are found on the undersides of leaves. Transpiration accounts for
approximately 10 percent of all evaporating water.

Runoff
Rivers, lakes, and streams transport water from land to the oceans. Runoff consists of
precipitation that neither evaporates, transpires, nor penetrates the surface to become
groundwater. Even the smallest streams are connected to larger rivers that carry billions of
gallons of water into oceans worldwide. Too much rainfall can cause excess runoff, or
flooding.

Infiltration
This refers to water that penetrates into the surface of soil. Infiltration is controlled by soil
texture, soil structure, vegetation, and soil moisture status. High infiltration rates occur in dry
soils, with infiltration slowing as the soil becomes wet. Coarse-textured soils with large well-
connected pore spaces tend to have higher infiltration rates than fine textured soils. However,
coarse-textured soils fill more quickly than fine-textured soils due to a smaller amount of
total pore space in a unit volume of soil. Runoff is then generated quicker than one might
have with a finer-textured soil. Water evaporates from the ocean and land surfaces, is held
temporarily as vapour in the atmosphere, and falls back to Earth’s surface as precipitation.
Surface water is the residue of precipitation and melted snow, called runoff. Where the
average rate of precipitation exceeds the rate at which runoff seeps into the soil, evaporates,
or is absorbed by vegetation, bodies of surface water such as streams, rivers, and lakes are
formed. Water that infiltrates Earth’s surface becomes groundwater, slowly seeping
downward into extensive layers of porous soil and rock called aquifers. Under the pull of
gravity, groundwater flows slowly and steadily through the aquifer. In low areas it emerges
in springs and streams.
Both surface water and groundwater eventually return to the ocean,
where evaporation replenishes the supply of atmospheric water vapour. Winds carry the
moist air over land, precipitation occurs, and the hydrologic cycle continues.

1.3. Quality of water

The quality of water refers to its physical, chemical, and biological characteristics, which
determine its suitability for various uses, including drinking, irrigation, industrial processes,
and ecological health. Several factors are considered when assessing the quality of water.
Physical parameters include characteristics such as temperature, colour, turbidity (clarity),
odour, and taste. These parameters provide insights into the overall appearance and sensory
qualities of the water.
 The chemical composition of water is assessed by measuring various parameters
such as pH (acidity or alkalinity), dissolved oxygen (DO), total dissolved solids (TDS),
hardness, alkalinity, nutrients (e.g., nitrite, nitrate, phosphate, silicate et cetera), heavy metals,
and the presence of contaminants (e.g., pesticides, industrial pollutants, or pharmaceuticals).
These measurements help evaluate the potential for chemical reactions, nutrient availability,
and the presence of pollutants or harmful substances. Chemical composition depends upon
many interrelated factors, including, geology and soil, climate, topology, biological processes
and time. However, geology is the dominant factor. Chemical weathering of the rocks
produces clay and minerals which partly or completely dissolved by the water circulating in
the hydrosphere. Not only the rock weathering contributes to the dissolved chemical load in
the surface water
Biological indicators are used to assess the presence and abundance of
microorganisms in water. This includes monitoring the levels of faecal coliform bacteria,
which indicate the potential presence of pathogens and contamination from human or animal
waste. Other indicators include the presence of algae, plankton, or specific species that can
indicate the overall health of an aquatic ecosystem.
The Land Use Land cover (LULC) should be considered while studying chemical
composition of a natural water system. LULC changes in a watershed will affect the quality
of river water. Therefore, the hydro geochemistry of the surface water is the sum total of the
various factors like lithology, climate, topology, vegetation and anthropogenic activities.
Thus study of the composition of the river water provides an insight of understanding
relationship between the chemical weathering, evaporation, atmospheric deposition and
anthropogenic processes in a basin. Therefore, numerous geological studies are conducted in
major river basin for determining the mechanisms controlling water chemistry, weathering
and stream characteristics.
The formation of the natural composition of water starts in the atmosphere and
continues with the sheet flow. The chemical composition of rainfalls, the melted snow-cover,
and the glacial water changes according to the rock structure, the soil, and the vegetation. The
ionic composition and the mineralization of waters differ according to the proportion of the
different types of water supplies; they change during periods of high and low waters i.e. it
depends on the river regime. The hydro physical, hydro biological and hydro chemical
processes are of great importance for the formation of the quality of water in streams and
rivers. The ionic composition and mineralization of waters are geographically connected to a
certain area, and that defines their changes from the equator to the poles so as their specific
characteristics in a certain region. The composition and the quality of waters are defined
according to the data on the ionic concentration and are studied by different indicators.

1.4. Chemical composition of surface water

The river water is composed of a number of different components that can be divided into
solids – particulate organic material (plant detritus), particulate inorganic material (minerals),
gases – non conservative gases such as CO2 and O2, dissolved solutes -organic solutes and
inorganic solutes (major and minor ions).
The major cation found in river water include calcium (Ca2+), magnesium (Mg2+), sodium
(Na+) and potassium (K+). These cations come from the weathering of rocks and minerals in
the watershed. The common anions present are the bicarbonate (HCO3-), carbonate (CO32-),
chloride (Cl-), sulphate (SO42-) and nitrate (NO3-). Anions are introduced into water from
natural sources such as weathering and anthropogenic activities.
Sources of ions
The sources of ions derived from the weathering of exorheic part of continents,
Magnesium originates from dolomites (42 percent) and silicates (48 percent); the remainder
(10 percent) is from Mg-evaporites. It is found that the Mg2+ sources are 47 percent for
carbonates 40 percent for sedimentary rock silicates and 13 percent for crystalline rock
silicates. (Meybeck,1987)
Calcium is mainly derived from carbonate weathering (65 to 70 per- cent in all studies).
Most of the Ca2+ released by silicate minerals (globally 25 percent) originates from
sedimentary rocks and from a few less common metamorphic rocks such as amphibolite. It is
difficult to be certain that, in non-carbonate sedimentary rocks, all Ca 2+ is effectively derived
from silicate minerals, since the occurrence of 1 percent carbonate cement can greatly affect
the water chemistry (Miller, 1961).
Potassium essentially derive from silicate weathering, with a minor contribution (7.5
percent) from amorphous silica. In crystalline rocks, the presence of K-micas and orthoclase
increases the relative contribution from mica schist and trachytes. Evaporites could contribute
up to 5 percent of the potassium. (Maybeck,1987).
Sodium has very different origins than potassium 55 percent is derived from halite
weathering. The remaining sodium originates from silicates.
Sulphate derive from the weathering of evaporitic sulphate, pyrite and organic sulphur
compounds. The proportions of reduced (pyrite) and oxidized (sulphate) forms in each major
rock type are given by Ronov and Yaroshevskiy (1976). Taking into account that the
sedimentary rocks originate from platforms (2/3) and from geosynclines (1/3), we can
estimate the various origins of sulphate assuming that the three forms have identical
weathering rates. Pyrite weathering would produce 34 percent of the sulphur: this proportion
is very close to the estimates by Berner, Lasaga, and Garrels (1983) and by Wollast and
Mackenzie (1983). Other sulphur pathways can be considered active volcanism, biogenic
emission to atmosphere et cetera. The rain input of sulphate originating from natural land
sources has been considered as part of weathering cycle. This input is 35 percent of total
sulphur derived from weathering and the volcanic sulphur is around 9 percent.
Bicarbonates originates from soil and atmospheric CO2 during the weathering process of all
minerals by carbonic acid and from carbonate minerals during their specific weathering.
Acid formation
CO2 + H2O → H2CO3
4FeS2 + 15O2 +8 H2O 2Fe2O3 +8H2SO4
Weathering of minerals
2CO2 +11H2O+ 2NaAlSi3O8 → Al2Si2O5(OH)4 + 2Na+ + 2HCO3- +4H4SiO4
H2CO3+CaCO3→ 2HCO3- +Ca2+
2H2CO3 +MgSiO3 +H2O→ 2HCO3-+Mg2+ +H4SiO4
H2SO4+MgSiO3+ H2O → SO42-+Mg2+ +H4SiO4

Chloride (Cl-) in natural water are from magmatic rock formations that include chlorine-
content minerals. The second source of this anions is from Ocean where a considerably
amount of chlorides anions (Cl-) enter in the atmosphere. From atmosphere chlorides anions
(Cl-) enter in the natural water as a result of interaction between precipitation and soil.
Nitrate (NO3) present in water is due to the nitrification of ammonia by bacteria which is a
part of nitrogen cycle. Nitrate anions also enters in surface water together with domestic
water and water from industry, agriculture and etc
Among the anions contained in the river water the ones with the highest concentration are
HCO3-, (CO32-), SO42-, Cl-, and among the cations Ca2+, Mg2+, Na+ (K+). Most often the
proportion between them is HCO3 > SO42- > Cl > Ca2+ > Mg2+ > Na+; their concentration is
relatively constant, therefore they are called conservative. The proportion between the major
ions reflects the environment and it changes according to the seasons of the year as well as
along the river.
Other anions found in water include fluorides (F-), carbonates (CO32-) and phosphates (PO43-)
River water can contain trace elements or metals, including iron (Fe), manganese (Mn),
copper (Cu), zinc (Zn), and lead (Pb). These trace elements may occur naturally in the
environment or be introduced through human activities such as industrial processes and
mining.

1.5. Factors affecting the composition of natural water

The composition of river water is influenced by various factors, both natural and human-
induced. It is influenced by factors like precipitation, climate, soil type, vegetation, geology,
flow conditions, ground water and human activities
1.5.1 Geology and soil type: The geology and soil type of the river basin play a significant
role in determining the chemical composition of river water. Different types of rocks and
minerals have varying levels of solubility and can release different ions into the water
through weathering processes. For example, areas with limestone or chalk bedrock may have
higher concentrations of calcium and bicarbonate ions in the river water.
The chemical characteristics of soils and rocks in the catchment influence the magnitudes of
nutrient and salt sources in catchments. Phosphorus, nitrogen, and salts are contained within
sedimentary deposits; approximately 20% of the world's nitrogen is contained within
sedimentary deposits. Similarly, when underlain with marine bedrock or sediments, greater
salt levels in the catchment can be transported to receiving waters. The chemical composition
of these rocks and soils can be affected by the age of the material, with nutrient and salt
levels being lower in ancient soils. The chemical composition of these rocks and soils can
also be affected by previous atmospheric deposition of contaminants (specifically, nitrogen).
The nutrients and salts contained within the bedrock and soils of a catchment can be
mobilized by weathering, erosion (for particulate constituents) dissolution, and desorption
(for dissolved constituents).
The delivery of dissolved phosphorus and nitrogen and salts from the catchment to receiving
waters via subsurface flow pathways is strongly affected by soil hydrological properties.
When aquifers and catchment soils have lower hydraulic conductivities, there is an increase
in the residence time of dissolved constituents entrained in the subsurface flow in the
catchment. This allows more opportunity for the constituent to be lost from the flow path by
vegetative uptake or biogeochemical processing (e.g., denitrification). There have been
several case studies where higher nutrient concentrations have been detected in rivers with
well-drained soils in their catchments. It is likely that the longer residence time resulted in the
sorption of salts to particulate matter within the soil strata or aquifer.

1.5.2 Climate: Climate, including temperature and rainfall patterns, affects the composition
of river water. In regions with higher precipitation, river water tends to have lower
concentrations of dissolved ions due to dilution effects. Additionally, seasonal variations in
precipitation can lead to fluctuations in river water composition.
The amount of precipitation in an area greatly impact the composition of natural water.
Rainwater is slightly acidic due to the dissolution of carbon dioxide from the atmosphere. In
regions with high rainfall, water bodies are often more dilute and may have lower
concentrations of dissolved minerals and salts. In contrast, areas with low rainfall may have
more concentrated water bodies with higher mineral content.
Climate affects water temperature, which in turn influences the solubility of different
substances in water. For instance, warmer temperatures increase the dissolution of gases like
oxygen and carbon dioxide in water. Higher temperatures can also enhance the weathering of
rocks, leading to increased mineral content in water bodies.
The rates of evaporation and transpiration, which are important processes that affect the
composition of water. As water evaporates from lakes, rivers, and oceans, it leaves behind
dissolved minerals and salts, making the remaining water more concentrated. Transpiration,
the process by which plants release water vapor, can also impact water composition,
especially in areas with extensive vegetation cover.
The intensity and frequency of rainfall affects the rate of runoff and erosion. Heavy
rainfall events can lead to increased runoff, carrying sediment, nutrients, and pollutants from
the land into water bodies. The greater speed of runoff will decrease the residence time in the
catchment, leading to less sediment being lost from the flow path by sedimentation, and less
nutrients being lost by denitrification Additionally, the volume of subsurface runoff can also
increase the delivery of fine particulates and dissolved constituents (nutrients and salts) to
receiving waters.

Sea-level rise can influence the composition of coastal water bodies. As sea levels rise,
saltwater intrusion can occur, impacting freshwater resources in coastal areas. This intrusion
can increase the salinity of groundwater and affect the availability of freshwater for human
consumption and agriculture.

1.5.3 Land use land cover: Human activities within the river basin significantly impact the
composition of river water. Agriculture, urban development, industrial activities, and mining
can introduce various chemicals and pollutants into the water. Fertilizer and pesticide use in
agriculture can increase nutrient levels, such as nitrogen and phosphorus, in river water.
Industrial discharges can introduce heavy metals and other contaminants. Urban runoff can
carry pollutants like oil, heavy metals, and microplastics into rivers.
 Land cover, defined here as the amount and type of vegetation present in a catchment,
can affect the amount of nutrients present the catchment. Soil nutrient levels within
catchments can decrease due to the uptake of bioavailable phosphorus and nitrogen by
terrestrial vegetation. The uptake of bioavailable nutrients can also occur within the stream or
river itself, by aquatic plants. Nutrient assimilation rates can vary according to both
vegetation type. For example, forests are more effective in removing nitrogen from catchment
soils, compared to grasslands and shrubs. The greatest nutrient uptake rates often occur at the
peak growing period of the vegetation In addition, nitrogen can be lost from vegetated
catchment soils by microbially-mediated transformations.

The extent and type of human activities in the catchment (i.e., the land use) can
influence the magnitude of sediments, nutrients, and salts sources. First, the presence of
vegetation, which in itself affects nutrient levels in catchments, can be greatly influenced by
the land use, with less dense vegetation in urban and agricultural regions. Urban, industrial,
and agricultural land uses also produce high levels of sediment, nutrients (both particulate
and dissolved), and salts. Sediments can be present in industrial and domestic wastewater in
urban areas. Urban and agricultural areas generate both particulate and dissolved nutrients
through: (1) the discharge of wastewater, (2) construction debris, (3) the application of
manure and fertilizers on lawns and parks (in urban areas) and on crop and grazing lands, (4)
waste from livestock and (5) atmospheric deposition, often from urban and industrial
regions Similar to nutrients, salts can also be contained in industrial and domestic
wastewater, and fertilizers. In addition, in urban catchments with snow, salt is applied in
winter for decaying. These salts can remain in soils and can be transported to surface waters
in other seasons (e.g., summer) or years after application. However, decaying as a source of
salts is generally not an important factor in catchments in warmer climates.
1.5.4 Erosion and sedimentation: Erosion of soil and sedimentation can influence the
chemical composition of river water. Eroded soil particles can introduce sediment, nutrients,
and other chemicals into the water. Land use practices that increase soil erosion, such as
deforestation or intensive agriculture without proper soil conservation measures, can
contribute to higher sediment and nutrient loads in rivers. The processes of erosion, transport,
and deposition of sediment, collectively termed sedimentation, are natural processes and have
been occurring throughout the geologic time. The landscape as well as the continental margin
that includes the shelf, slope and canyons are continuously shaped by the process of
sedimentation. Sediment transport occurs due to water, wind, and gravity. Sediment transport
is the movement of organic and inorganic particles by water. In general, the greater the flow,
the more sediment that will be conveyed. Water flow can be strong enough to suspend
particles in the water column as they move downstream, or simply push them along the
bottom of a waterway. Transported sediment may include mineral matter, chemicals and
pollutants, and organic material. The local topography plays an important role in sediment
transport along with wind and rain. The terrain through which water runs influences the
amount of sediment that enters and the distance that it travels.

1.5.5 Anthropogenic activities: Increased discharge of wastewaters, introduction of

phosphorous containing detergents, use of fertilizers, and erosion in the watershed leads for
increased loading of nutrients. Fertilizers are the major source of nitrogen, while phosphorous
in the fertilizer may be immobilized in the soil. Flooding can transport large quantities of
phosphorous due to leaching from the soil. Domestic sewage also increases P loading in
aquatic environments. This results in eutrophication. It is considered to be a serious
environmental concern since it often results in the deterioration of water quality and depletion
of dissolved oxygen. The level of impact on water quality becomes higher as land uses
intensify through the spectrum of agriculture, timber harvesting, housing, industry, and roads.
Urban and industrial development, farming, mining, combustion of fossil fuels, stream-
channel alteration, animal-feeding operations, and other human activities can change the
quality of natural waters. As an example of the effects of human activities on water quality,
consider nitrogen and phosphorus fertilizers that are applied to crops and lawns. These plant
nutrients can be dissolved easily in rainwater or snowmelt runoff. Excess nutrients carried to
streams and lakes encourage abundant growth of algae, which leads to low oxygen in the
water and the possibility of fish kills.
Stormwater runoff occurs when precipitation “runs off” impervious surfaces (rooftops,
parking lots, drives ways, etc.,) rather than infiltrating into the soil. As it travels along the
land surface, the runoff increases in velocity and volume, picking up a wide variety of
pollutants such as sediment, pathogens, and debris. These pollutants are delivered either
directly or indirectly to rivers, lakes and ponds. In highly developed areas, such as urban
centers, these pollutant loads can be relatively high. Lawn fertilizer, uncollected pet waste,
road sand for winter safety, many detergents and lawn litter all contain phosphorus. In an
undisturbed setting, much of this phosphorus is broken down by natural processes. In an
urban setting, these processes may be disrupted or non-existent. Instead of nutrient
breakdown and uptake by plants or entrainment in soils, many pollutants are simply carried
away to surface waters. Human activities also results in change in stream hydrology. Urban
developments involves the construction of buildings, roadways create impervious surface that
reduce infiltration and increase erosion.

1.5.6 Weathering:
Weathering is breaking down rocks, soil, and minerals as well as wood and artificial
materials by contacting the atmosphere, water, and biological organisms of the Earth.
Weathering takes place in situ, that is, in the same place, with little or no movement. It should
therefore not be confused with erosion involving the movement of rocks and minerals by
agents such as water, ice, snow, wind, waves and gravity, and then transported and deposited
elsewhere.
Disintegration or alteration of rock in its natural or original position at or near the earth’s
surface through physical, chemical, or biological processes induced or modified by agents
such as wind, water, climate, etc. Weathering involves physical, chemical, or biological
processes that act separately or together to achieve the disintegration or decay of the rock
material. Several factors control the type of weathering and the rate at which the rock
weathers. The mineralogical composition of rock will determine the rate of alteration or
disintegration. Fine-grain rock will usually be more susceptible to chemical alteration but less
susceptible to physical disintegration. Climate will also control the type and rate of
weathering by affecting the likelihood of freeze-thaw cycles and chemical reactions.
Chemical weathering is more likely to occur and to be more effective in humid tropical
climates, and disintegration of rock from freeze-thaw cycles is more likely to take place and
be more effective in sub-Arctic climates (Amy Tikkanen).
Weathering processes are mainly divided into three main types – Physical weathering
Chemical weathering
Biological weathering
1.5.6.1 Physical weathering
Physical weathering involves the breakdown of rocks and soils through the mechanical
effects of heat, water, ice, or other agents. It is also called mechanical weathering or
disaggregation, which is the class of processes that causes the disintegration of rocks without
chemical change. Water, in either liquid or solid form, is often a key agent of mechanical
weathering.
1.5.6.2 Chemical weathering
Chemical weathering happens when the chemicals get diluted and dissolved in water and
percolated down the rock surfaces. Chemical weathering changes the composition of rocks,
often transforming them when water interacts with minerals to create various chemical
reactions. The chemical transformations occur when water and oxygen interact with minerals
within the rocks to create different chemical reactions and compounds through processes such
as hydrolysis and oxidation. Chemical weathering occurs faster at higher temperatures so it is
best to have warm and humid climates, and the first stage in soil production is chemical
weathering.

Types of chemical weathering

1.Hydrolysis: During hydrolysis, water chemically reacts with minerals and breaks them
down to form other minerals. Hydrolysis reactions in feldspar produce clay. For example,
forsterite (magnesium olivine) is hydrolyzed into solid brucite and dissolved silicic acid.
Mg2SiO4 + 4 H2O ⇌ 2 Mg (OH)2 + H4SiO4
forsterite + water ⇌ brucite + silicic acid

2.Dissolution: Dissolution is the process in which a mineral dissolve completely without

producing any new solid substance. Chemical weathering during which minerals dissolve into
water is called dissolution and it primarily affects salts and carbonate minerals, but even
quartz dissolves slightly. This process occurs when water comes into contact with rocks and
dissolves the minerals that make up that rock into individual elements. The dissolution of
calcite is a good example of this process, when water comes into contact with rocks that have
abundant amounts of calcite such as limestone the calcite dissolves into the solution. The
calcite will stay in the solution until the water either evaporates, reacts with other minerals, or
is precipitated by another organism to make its shell. This process is extremely important on
Earth, it allows many organisms such as mollusks, echinoderms, foraminifera, and
coccolithophores to produce their shells which protect them.
These organisms are very important to our ecological system especially foraminifera and
coccolithophores because they play a vital role in the silicate geochemical weathering cycle
which helps control Earth’s climate system.

3.Oxidation: Oxidation is another very important chemical weathering process. The

oxidation of the iron in a ferromagnesian silicate starts with the dissolution of the iron. For
olivine, the process looks like this, where olivine in the presence of carbonic acid is
converted to dissolved iron, carbonate, and silicic acids like this, where olivine in the
presence of carbonic acid is converted to dissolved iron, carbonate, and silicic acid

Fe2SiO4 + 4H2CO3 —> 2Fe2+ + 4HCO3– + H4SiO4

Olivine + (carbonic acid) —> dissolved iron + dissolved carbonate + dissolved silicic acid

In the presence of oxygen, the dissolved iron is then quickly converted to hematite:
2Fe2+ + 4HCO3– + ½ O2 + 2H2O —-> Fe2O3 + 4H2CO3
dissolved iron + bicarbonate + oxygen + water —-> hematite + carbonic acid

4. Carbonation: It is the process of rock minerals reacting with carbonic acid. Carbonic acid
is formed when water combines with carbon dioxide. Carbonic acid dissolves or breaks down
minerals in the rock.
CO2 + H2O → H2CO3

(Carbon dioxide + water → carbonic acid)

CaCO3 + H2CO3 → Ca2+ + 2HCO3

(calcite + carbonic acid → calcium + bicarbonate).

1.5.6.3 Biological Weathering

Biological weathering is the weakening and subsequent breakdown of rocks by plants,
animals and microbes.
Growing roots of plants can put stress or pressure on rock. Even though the process is
physical, a biological process (i.e. growing roots) exerts the pressure. Biological processes
can also produce chemical weathering, such as when organic acids are produced by plant
roots or microorganisms that help dissolve minerals.
Microbial activity breaks down rock minerals by altering the chemical composition of the
rock, making it more weather sensitive. One example of microbial activity is lichen ; lichen is
a symbiotic relationship between fungi and algae. Fungi release chemical substances that
break down rock minerals; the algae consume the minerals thus released from rock. Holes
and gaps continue to develop on the rock as this process continues, exposing the rock to
physical and chemical weathering.
Burrowing animals can move fragments of rock to the surface, exposing the rock to more
intense chemical, physical, and biological processes, thereby indirectly enhancing the
weathering process.

1.6. Water pollution

Water pollution occurs when harmful substances often chemicals or microorganisms
contaminate a stream, river, lake, ocean, aquifer, or other body of water, degrading water
quality and rendering it toxic to humans or the environment. Water pollution results
when contaminants mix with water bodies.
Pollutants
It is a substance which when introduced into environment causes undesirable effects or spoils
resources. Long or short term damage may be caused due to pollutant. Biodegradable
pollutants only cause short term damage. Some pollutants like DDT again produce pollutants
upon degradation like DDD and DDE. Pollutants may be of different types and having
different properties like Stock pollutants which include non-biodegradable plastics, synthetic
chemical and heavy metals have no or very little absorptive capacity. These pollutants
accumulate in environment with the passage of time. Their damage increases as their quantity
increases. For future generations stock pollutants are burdens. Similarly Fund pollutants have
some absorptive property in environment. They only cause problem when their quantity
increases beyond environment absorbance capacity. E.g., Carbon dioxide only causes
problem when its amount increases. These pollutants can only be diluted to reduce their
toxicity or recycled into non harmful substances. Pollution is of two types point source
pollution and non-point source pollution.
Point source pollution
When source of water pollution is known or pollutants that are entering into water are from
identifiable source like ditch, pipe industry, storm drain and sewage treatment plants etc.
pollution is known as point source pollution. It can be distinguished from other pollution
sources.
Non-point source pollution
When source of water pollution is not known or pollution does not come from single discrete
source pollution is known as non-point source pollution. It is very difficult to control and may
come from different sources like pesticides, fertilizers industrial wastes etc.
Ground water pollution
When pollutants which are present on ground enter the water bodies under earth they cause
ground water pollution. When faecal water containing pathogens reaches under earth it makes
it unfit for drinking. Pathogen polluted ground water may contain viruses, protozoa and
bacteria and rarely in some cases helminth eggs. Consumption of this water causes diseases
like diarrhoea and cholera. Similarly nitrates also causes ground water pollution causing
disease in children called blue baby syndrome in rural population of Bulgaria and Romania. It
is observed that when nitrates concentration exceeds above 10 mg/L (10 ppm) in ground
water chances of blue baby syndrome increases. Excessive use of nitrate fertilizers can also
cause water pollution because very small amount of nitrates is utilized by plants most of it
accumulates in soil which later on reaches to ground water by leaching and contaminate it.
Ground water polluted with high levels of fluoride causes dental and skeletal problems.

Urban storm water runoff

It is due to highly populated cities. It comes from homes and office places. In suburban and
urban areas pavement and buildings cover such of land surface so whenever there is snow
melt or rain the water does not soak into ground. This storm water carries much type of
pollutants like dirt, oil, lawn fertilizers and chemicals directly to rivers and streams where
they cause water pollution. In the case of natural landscape these pollutants are trapped into
pores soil and water is filtered but in cities as water is not able to soak into ground so it wash
away all of these pollutant’s into water bodies thus polluting them. More over this storm
water has high speed of flowing which erodes more sediment from embankments of water
bodies thus causing water pollution.
Agricultural pollutants
As in rural areas population is less so it mostly contains fertilizers, pesticides and eroded soil
and these pollutants reach to water bodies through runoff after rain and flood. Agricultural
runoff cases fresh water body’s eutrophication. Half of lakes in US are eutrophic. Phosphate
is the main contributor to eutrophication its high concentration promotes Cyanobacteria and
Algae growth which ultimately reduces dissolved oxygen in water. Harmful toxins which
accumulate in food chain are produced by cyanobacterial blooms. Nitrogen rich fertilizer
compounds causes dissolved oxygen deficiency in rivers, lakes and coastal zones which have
devastating effects on oceanic fauna. Nitrogen fertilizers have high water solubility and
increased runoff and leaching rate which results in ground water pollution.
Similarly pesticides are used to control pests these pesticides leaches to ground water thus
polluting ground water. Water soluble pesticides leach more. Sandy soil also favours
leaching. Selenium (Se) is a heavy metal that occurs naturally in soil but due to irrigation
practices it accumulates in the soil. This accumulated selenium reaches to water reservoirs
and is very toxic for animals and humans.

Atmospheric pollutants
It is due to small particles which are present in air which it reaches to water bodies through
rain. It includes carbon dioxide which produced by burning of fossil fuels its quantity is
increasing which it combines with water molecules its forms sulphuric acid. Sulphur dioxide
produced from volcanoes and industries also combines with water molecules to form
sulphuric acid. Sulphur dioxide is also produced by combustion of coal and petroleum
products. Similarly Nitrogen dioxide also combines with water to form nitric acid.
Particulates also play very important role in effecting water pollution these particulates reach
to water bodies through rain.

Pathogens
Pathogens are the microorganisms which causes disease. Most bacteria in nature are non-
pathogenic or beneficial but few are pathogenic and these pathogenic bacteria also pollute
drinking water. Coliform bacteria are a bacterial indicator species used for the identification
of water pollution. Disease causing bacterial species includes Cryptosporidium parvum,
Burkholderia pseudomallei, Giardia lamblia, Norovirus, Salmonella and Parasitic worms like
Schistosoma.

Pesticides and herbicides

Herbicides and pesticides are used to control weeds and pests. Both of them also contribute to
water pollution. Their leaching also pollutes ground water. Leaching is influenced by soil
texture, pesticide properties, irrigation and rain fall. If soil is sandy and pesticide is water
soluble more will be the leaching. Similarly pesticides and herbicides also reach natural water
bodies through runoff. These pesticides residues when reach to natural water bodies they
disturb flora and fauna there. Pesticides which don’t degrade easily or take time to degrade
are more harmful.

Chemical pollutant
It comes from waste of harmful chemicals factories it is a material which is left as a by-
product during manufacturing process and it also plays a big role in polluting water bodies.
Hazardous chemical waste may be in solid, liquid or in gaseous form. The characteristics
which make material hazardous are corrosively, Ignitability, toxicity and reactivity. It started
with the start of industrial revolution. Industrial waste chemicals can only be treated by using
special waste treatment plants they cannot be treated by sewage treatment plants.

Sediment pollution
Sedimentation due to runoff effects water quality. It decreases the capacity of streams,
ditches, navigation channels and rivers. It decreases the penetration of light into water due to
which due to under water flora is disturbed. So the fishes and other fauna feeding on that
flora are also disturbed and whole food chain is disturbed. Pollutants like pesticides and
phosphorus are transported and accumulated due to sedimentation. Sediment particles also
attach to fish gills so fishes feel difficulty to respire in this way they causes fish death.
Similarly sediments carry dangerous chemicals like pesticides and petroleum products to
water bodies thus polluting them.

Saltwater intrusion
Salt water intrusion is another very important factor which pollutes ground water. It occurs
when saline water from sea enters into ground water near coastal areas. It occurs naturally but
some human activities like pumping of fresh groundwater also increases salt water intrusion.
Navigation channels, drainage channels and agriculture channels also play important role in
salt water intrusion.

1.7. Significance of watershed studies

A watershed is an area of land where all the water that falls within it drain into a common
outlet, such as river, lake or ocean. It is also known as drainage basin or catchment area.
Watersheds are essential for the hydrological cycle and have significant ecological,
environmental, and socio-economic importance. They are,
Hydrological processes: Watersheds serve as the fundamental unit for studying and
understanding hydrological processes. Precipitation falling within a watershed is collected
and stored in various forms such as surface water, groundwater, and soil moisture. It
eventually returns to the atmosphere through evaporation and transpiration or flows out of the
watershed as runoff.
Water supply: Watersheds are critical sources of freshwater supply. They provide the water
necessary for drinking, irrigation, industrial use, and ecosystem functions. Understanding the
quantity and quality of water available within a watershed is crucial for sustainable water
resource management.
Ecosystems and biodiversity: Watersheds support diverse ecosystems and habitats. They
provide habitat for a wide range of plant and animal species, including aquatic organisms and
terrestrial wildlife. Healthy watersheds support biodiversity, maintain water quality, and
sustain ecological processes such as nutrient cycling and sediment retention.
Water quality: The health and condition of a watershed greatly influence water quality.
Watersheds act as natural filters, as vegetation, wetlands, and soil help intercept, absorb, and
remove pollutants from water. However, human activities within a watershed, such as
agriculture, industry, and urban development, can introduce contaminants that impact water
quality. Managing and protecting water quality within watersheds is essential for human and
environmental health.
Flooding and erosion control: Watersheds play a role in regulating and managing floods and
erosion. The topography, vegetation, and land use within a watershed influence how water
flows and is retained. Healthy watersheds with well-maintained vegetation and natural
features can reduce the risk of flooding and control soil erosion by slowing down the
movement of water.
Land and resource management: Understanding the dynamics of a watershed is crucial for
effective land and resource management. Watershed studies help identify areas vulnerable to
degradation, determine suitable land uses, and guide conservation efforts. They also inform
decisions regarding urban planning, agriculture, forestry, and infrastructure development to
minimize negative impacts on water resources and ecosystems.
Effective watershed management requires collaboration among stakeholders, including
government agencies, communities, industries, and conservation organizations. Integrated
approaches that consider ecological, social, and economic factors are essential for sustaining
the health and functionality of watersheds, protecting water resources, and promoting the
well-being of both humans and the environment.

1.8. Aim and Objectives

The present study is carried out to analyse the spatiotemporal variations of hydro
geochemistry pre-monsoon samples of Vamanapuram river, a tropical mountain river
originates from Chemunji Mottai hills of southern Western ghats. Its aims to evaluate both
physical and chemical parameters of water samples collected and the analytical data obtained
is used for assigning the degree of pollution in the study area and the influence of human
interventions as a part of semi- urbanization.

The present work aims at:

 a) To establish the physico- chemical characteristics of water
samples collected from Vamanapuram river basin.

b) To study the impact of land use and land cover, soils and geology in the study area
on the chemistry of water.

c) To apply the physio-chemical data in making box plot, piper, correlation, trilinear
diagrams and Principal Component Analysis (PCA) for identifying the sources of
major ions and their controlling factors.

d) To construct a chemical balance model for quantifying the contribution of each

sources such as rain, weathering and anthropogenic activities towards dissolved load.

CHAPTER 2

REVIEW OF LITERATURE

Numerous studies have been conducted to understand the geochemical characteristics of

water flowing through riverine system. Hydrogeochemical studies have been studied in detail
by a number of investigators worldwide. Water is one of the most important of all natural
resources known on earth. It is essential to all living organisms, most ecological systems,
human health, food production and economic development (Postel et al., 1996). During the
last decades, the demand of fresh water increased by the increase in population and
industrialization. The Joint Monitoring Programme (JMP) for Water supply and Sanitation,
implemented by WHO and UNICEF reports that 11% of the total population have no access
to safe water. The demand for fresh water is mostly fulfilled by rivers. But nowadays it is
being polluted due to the waste disposal and discharge which in turn affects the physical
chemical and microbiological characteristics of water. The deterioration of water quality is an
important problem and hence monitoring of water quality is required for reducing water
pollution. The contaminant ranges from silt to sewage materials and disturbs the natural
harmony of river water ecosystem. According to WHO, CPCB, BIS, ICMS, the water quality
of about 70% river water was too poor for human consumptions. The assessment of the
quality of a particular water source depends on its intended use.
However, due to complexity of dissolved minerals in water resources, a few
selected parameters such as sodium, potassium, calcium, magnesium, carbonates,
bicarbonates, chlorides, sulphate, nitrites, silicates, hardness, phosphates, pH, total dissolved
solids etc. can be analysed to assess the stability of drinking water resources. The two
important factors for nutrient analysis and water management are pH and conductivity. The
pH of water determines whether the sample is acidic or alkaline. Acids, bases and salts in
water make it relatively good conductor of electricity even though water is a poor conductor
of electricity. The electrolytes in solution dissociate with positive (cations) and negative
(anions) ions and impart electrical conductivity. Thus, higher the concentration of electrolyte
in water, more is its electrical conductance. Aremu et al. (2011) have studied about the
physic- chemical properties of well, bore hole in Kubwa, Nigeria and found that the
conductivity values are very low which ranges from 0.07 to 0.49 µS/cm, which is a
permissible value. TDS is the sum of the cations and anions concentration expressed in mg/L.
The correlation between TDS and electrical conductivity (both directly relates to salinity) was
investigated by Anna F Rusydi in 2018.
The lack of freshwater is likely to be one of the major factors limiting economic
development in the decades to come, warns the World Bank (Serageldin, 1995). The quality
as well as quantity of water is deteriorating globally as a result of rapid urbanization,
population growth and industrialization. Virtually in every country, where agricultural
fertilizers and pesticides are used, there are reports of contamination of surface water as well
as ground water aquifers. The quality of surface water is also a very sensitive issue.
Anthropogenic influences (urban, industrial and agricultural activities, increasing
consumption of water resources) as well as natural processes (changes in precipitation inputs,
erosion, and weathering of crustal materials) degrade surface waters and impair their use for
drinking, industrial, agricultural, recreation or other purposes (Carpenter et al., 1998; Jarvie
HP et al.,1998). The application of different multivariate approaches (cluster analysis,
principal component analysis) for the interpretation of these complex data matrices offers a
better understanding of water quality and ecological status of the studied systems and allows
the identification of possible factors/sources that influence the water systems and offers a
valuable tool for reliable management of water resources as well as rapid solutions on
pollution problems (Morales et al., 1999; Wunderlin D A et al., 2002). The water that goes
back into rivers and streams after being used for irrigation is often of degraded quality with
excess nutrients, pathogens, salinity and sediments that is often rendered unfit for any further
use, unless cleaned typically at water purification plants (Klohn and Wolter, 1998).
In developing countries, on an average, 90% to 95% of all domestic sewage and 75%
of all industrial waste are discharged into surface water without any treatment (Carty,1991;
Allaoui, 1998). Majority of all sewage water leaks out into the surrounding soil,
contaminating the wells used by the residents for drinking purpose (Rahman, 1995). Huang,
Yiping, Zhu, Min (1996) discussed the basic strategies to protect water quality and prevent
eutrophication in relation to lake Tailhu, the third largest fresh water lake in the most
advanced economic zone in China.
The hydro chemical study reveals the quality of water that is suitable for drinking,
agricultural and industrial purposes. Further it is possible to understand the changes in quality
due to rock-water interaction or any type of anthropogenic activities (Kelley, 1940; Wilcox,
1948). Presentation of chemical analysis in graphical form makes understanding of complex
system simpler and quicker. Piper trilinear diagram, which was conceived by Hill and
improved by Piper, is a widely used tool to understand the hydro chemical regime and facies
classification of ground and surface water (Hao Wu et al., 2015). It has become a widespread
method for understanding and describing the chemical evolution of surface water which
depends on pattern recognition techniques and permits the classification of water, according
to Subramani et al. (2005), the diagram has six sub-fields i.e., 1 (Ca- HCO3 type), 2 (Na-Cl
type), 3 (mixed Ca- Na-HCO3), 4 (mixed Ca-Mg-Cl type), 5 (Ca-Cl type) and 6 (Na-HCO3
type). Sub-fields 3 and 4 are characterized by their mixed ionic content in that no cation-
anion pair exceeds 50%.
Gibbs (1970) proposed a simple water chemistry model (after incorporating the
concepts of Clarke 1924) in which the primary mechanisms controlling water chemistry are
rock weathering, climate via atmospheric precipitation and climate via evaporation and
fractional crystallisation. This model, constructed with TDS on ordinate and the different
ionic ratios (i.e., Na+/(Na++Ca2+) for cations or Cl/(Cl+HCO3) for anions depicts the
magnitude of various processes determining the chemical composition of water (Banens
1987). J. Gaillard et al. suggested that instead of absolute concentrations elemental ratios and
isotopic compositions processes are intensive parameters that permit the comparison between
river draining areas of high runoff and rivers draining arid areas. PCA is a powerful pattern
recognition technique that attempts to explain the variance of a large dataset of
intercorrelated variables with a smaller set of independent variables (principal components)
(Hopke PK, 1985).
A number of researchers during past few decades with an attempt to quantify global
riverine fluxes (Meybeck 1976; Martin and Meybeck 1979; Subramanian 1979, 1984; Hu et
al. 1982; Sarin et al. 1989; Krishnaswami et al. 1992; Rai et al. 2010; Gupta et al. 2011;
Yadav and Chakrapani 2011). Asian rivers contribute more than 70% of the global sediment
input to World oceans (Milliman and Meade 1983); thus any understanding of the
geochemical behaviour of elements in our environment would require the study of large
Asian rivers. In the Indian subcontinent, mass transfer studies have recently been initiated (eg
Raymahasay 1970; Subramanian 1978,1979; Bikshamiah & Subramanian 1980). While at
first approximation, the sediment transfers from non-Himalayan rivers are less than 5% of the
Himalayan rivers (Subramanian 1979) from qualitative point at least, the southern non
Himalayan rivers need to be studied. Bikshamiah & Subramanian (1980) have studied the
mass transfer in Godavari river and concluded that the annual mass transfer of this river is
about 10% of that of the Himalayan drainage system.
A number of attempt are there is quantify the contribution of the dissolved load to
the river basin. Dissolved ions present in rivers result from water–rock interaction. Chemical
weathering products in watershed are generally defined as the difference between fluxes
leaving (export fluxes) and entering (precipitation fluxes of atmospheric input) the water
system (White and Brantley, 1995). The amount of dissolved elements supplied to rivers via
chemical weathering of the basin is usually quantified by subtracting rain contribution to
river water concentration (Das et al., 2005). Several major reservoirs (atmospheric input,
carbonate weathering, silicate weathering, and evaporite dissolution) are commonly used to
evaluate the contributions of different sources to the chemical weathering regimes of
watershed, by using the forward method (Galy and France-Lanord, 1999; Dalai et al., 2002;
Mortatti and Probst, 2003; Moon et al., 2007; Wu et al., 2008; Noh et al., 2009; Xiao et al.,
2012a). B. Zhu et al. resorted to the forward model and considered four reservoirs – rain
(atmospheric), evaporite, carbonate, and silicate. For watersheds located in areas where
precipitation is not strongly acidic, cation exchange is considered to be at steady state (Drever
and Clow, 1995). A similar assumption can be made for the biomass if no vegetation
modification (forest fire, human or natural deforestation, animal grazing, etc.) is occurring
(Oliva et al., 2003). The corrections for atmospheric input by assuming that the sample with
the lowest chloride and TDS concentrations obtained its dissolved Cl exclusively from rain
(Noh et al., 2009; Rai et al., 2010). The calculation assumes that all chloride in river water
samples with lowest Cl is of atmospheric origin. This approach for estimating the
atmospheric contribution has the advantage that it does not require corrections for
evapotranspiration if the samples are collected at about the same time as its effect is already
factored in determining the chloride abundance of rivers (Rai et al., 2010).
Rivers have been under sampled to establish them as sinks or sources of the
atmospheric carbon oxide (CO2). Such poor coverage is well known for tropical and sub-
tropical, particularly monsoon driven rivers. An unprecedented high-temporal resolution
(daily) sampling during July 2008–August 2009 were conducted from the Long Chuanjiang
river of the upper Yangtze basin, a subtropical monsoon river in China to reveal the daily-to-
seasonal dynamics of the partial pressure of CO2 (pCO2) and CO2 degassing flux from the
river. The pCO2 levels were supersaturated in CO2 with respect to atmospheric equilibrium
(380 μatm) during the entire survey period with obvious daily and seasonal variations,
ranging from 450 to 63 000 μatm with an average of 3900 μatm. pCO2 values in the surface
water in the wet season were relatively low, except flooding period in November, due to a
dilution effect by heavy rainfall. However, both daily and monthly minimal and maximal
pCO2 also occurred in this period. In contrast, the pCO2 levels in the dry season were much
higher, mainly resulted from lower pH by anthropogenic activities. Net CO2 flux and pCO2
were strongly correlated with pH, but weakly with water temperature, dissolved inorganic
carbon and water discharge, and uncorrelated with particulate nutrients and biogenic
elements. High spatial and temporal resolution of estimates of CO2 emission from the world
large rivers is required due to that catchment characteristics and anthropogenic activities are
extremely heterogeneous in space and time. Rivers with varying physical characteristics and
anthropogenic activities showed large seasonal and spatial heterogeneities in pCO2 and
thereby water-to-air CO2 flux (Finlay et al., 2009; Guo et al.,2011). As a result, pCO2 and
over-saturation of dissolved CO2 in rivers could be mis estimated if the estimation is
conducted using a specific temporal and spatial scale. Environmental changes relative to the
terrestrial ecosystem and data paucity especially for most large rivers further result in a large
uncertainty (Borges et al., 2005). Compared to river systems, estuaries have been well
documented, illustrating higher pCO2 levels in the European estuaries (Zhai et al., 2007). In
China, the previous studies on the Yangtze, the Yellow and the Pearl rivers and their estuaries
in particular indicated higher pCO2 and thus high carbon emissions (Su et al., 2005; Want et
al., 2007; Yao et al., 2007; Zhai et al., 2005, 2007; Zhai and Dai, 2009; L. J. Zhang et
al.,2009). Despite many research efforts devoted to the major element geochemistry and
associating CO2 consumption in the Yangtze River basin (i.e. Chen et al. 2002; Chetelat et
al., 2008; Wu et al., 2008a, b; Li and Zhang, 2008, 2009; Li, S. et al., 2009), little information
on CO2 emission is available in its headwater. Though carbon diffusion flux from the entire
Yangtze basin has been elucidated recently (i.e. Wang et al., 2007), this estimate using data
sets in the Datong station (the lower Yangtze) understandably resulted in large uncertainties
due to distinct spatio-temporal discrepancies in water chemistry, nutrient supply and human
disturbance in the river basin. Meanwhile, the significance of riverine CO2 outgassing on a
global scale needs to be investigated based on regional cases with better seasonal controls.
Tropical and sub-tropical river systems are likely to have high respiration and gas transfer
velocity of CO2, leading to a poor quantification of carbon emission from inland waters,
especially in Asia and Africa where such data is very deficient.
 CHAPTER -3
MATERIALS AND METHODS

3.1. STUDY AREA

The present study has been conducted in Vamanapuram River basin,a tropical river basin
that spread in the western flank of Southern Western Ghats. The Vamanapuram River Basin
is bounded by latitudes of 8° 35′ 24″ N and 8° 49′ 13″ N and longitudes of 76°44′ 24″ E and
77°12′ 45″ E. Vamanapuram river is an 88 km (55 mi) long river in southern Kerala that
flows through the northern parts of Thiruvanathapuram district .It is also the longest river
in Thiruvananthapuram district. The two tributaries of this river are the Upper Chittar &
Manjaprayaar streams which originates near Ponmudi hill station. The river originates in the
Chemunjimotta hills (alt. 1860m) hills on the southern side of the Western Ghats, and flows
entirely through Thiruvananthapuram district of Kerala. It course ends in Anjengo Lake
(Anchuthengu Lake) near Chirayinkeezhu. The river has a total catchment area of 799
sq .km.The river ranks 16th in catchment area. Among the 44 rivers in Kerala Vamanapuram
ranks 11th in length and 15th in run off.

3.1.1. Drainage pattern

The spatial arrangement of a river and its tributary streams in a drainage network is referred
to as drainage pattern. Vamanapuram river basin shows dendritic drainage pattern. This
pattern is characterized by numerous tributary streams in the upper course and only a few
tributaries in the lower course. If the rocks do not vary in resistance over the basin, each
consequent stream will become the centre of a branching stream and forms dendritic patterns.
(Monkhouse,1954). The predominance of khondalite and associated rocks having similar
resistance throughout the basin is proved this assertion.
3.1.2. Climate
Vamanapuram river basin is a west flowing river system in Kerala and it is experiencing a
humid and tropical climate. Generally, the area receives a mean rainfall of 34.3 mm during
winter season, 406.2 mm during summer season, 970.8 mm during south-west monsoon and
56.11 during north-east monsoon. The mean daily temperature of the basin varies from 26.2
to 28.8 degree Celsius.

3.1.3 Geology
Geologically, a major part of the basin is occupied by khondalite suite of rocks. Apart from
this, occurrence of charnockite is also noticed in this area. The terrain is often intruded by
basic and ultrabasic rocks at certain places.

3.1.4 Soil
The extreme upstream region of the river basin is having clayey soil. As it come down to the
middle region, there is a mixture of clayey soil, gravelly loam soil and loamy soil. Towards
the downstream, the basin has gravelly clayey soil.

3.1.5 Geomorphology
The highland region consists of hilly terrain and undulating surfaces while, the lowland
region is composed of gently undulating surfaces. The main geomorphic features are the
lower lateritic plateau, denudational hills, valleys and water bodies.

3.1.6 Land Use Land Cover

The Vamanapuram river basin shows a spectrum of land use categories which include
agriculture land, forest, plantation, built up, barren land, open shrubs, vegetation and water
bodies. Out of the different classes, vegetation land dominates over the other classes. The
highland region is composed essentially of evergreen forests, plantations, barren lands and
open shrubs. The midland are dominated essentially by vegetation, built up with patches of
barren lands. The lowland is occupied by built up, vegetation and plantation with patches of
agricultural land. The area face rapid population growth and economic development.
Increased demand of groundwater to meet domestic requirements of the urban centers
together with increase demand for irrigation have forced the government to construct a few
check dams in the upstream and downstream reaches of the river basin.
3.2. SAMPLING WORK:
For this study twenty-two different sampling stations are selected for analysing the
candidature of water samples (the correct locations are noted by using GPS while sampling).
Sampling is conducted in the month of May of 2023 during the pre-monsoon season from the

Vamanapuram river. At each station two water samples were collected, one for the estimation
of cations and other for the anions. Samples were collected 20-30 cm below water surface in
prewashed and labelled HDPE bottles (1 L for anion analysis and 500 ml for cations). While
sampling, characteristics of the sampling site is noted. The objective of sampling is to collect
a small portion of water that can be transported conveniently and handled in laboratory in
such away that no significant change in composition occurs before tests are made. The bottles
used to store the samples were pre-rinsed with sample before the final sample is taken.
Samples for cation analysis is preserved by acidification with 1N nitric acid immediately
after collection. Each sampling bottles is provided with an identification label. Temparature
of water is measured during the sampling. The samples were analysed for various parameters
following the standard analytical procedures (APHA,1998). Samples collected from each
station were screened for various parameters such as pH, electrical conductivity (EC), total
dissolved solids (TDS), major cations (Ca2+, Mg+2, Na+ and K+), major anions (Cl-, HCO3- and
SO42-) and nutrients (nitrites, nitrates, silicates and phosphates).

3.3. ANALYTICAL METHODS

The water quality parameters to be analysed are cations, anions and nutrients and the analysis
is done following APHA (1998) Standard Methods for the Examination of Water and
Wastewater. All the chemicals used were analytical grade. The physico-chemical parameters
of water are pH, electrical conductivity (EC), total dissolved solids (TDS), total alkalinity
(TA), major cations (Ca2+, Mg2+, Na+ and K+), major anions (Cl-, HCO3 - and SO42-), and
nutrients (NO2-, PO4-, silicates). Silicate, phosphate, nitrate and nitrite was performed using
Continuous Flow Analyser (CFA). Sodium, Potassium, Calcium and magnesium were
analysed using MP AES (Microwave plasma atomic emission spectrometer).

3.4. ANALYTICAL EXPERIMENTS

The chemical analysis is done at Central Chemical Laboratory (CCL) of National Centre for
Earth Science Studies (NCESS), Thiruvananthapuram. The laboratory analysis of samples
was done using Standard Methods for the Examination of Water and Wastewater, APHA
(1998).
The titrimetric methods were used for the determination of bicarbonates.

3.4.1. Analysis of physicochemical parameters of water

The water samples for chemical analysis was kept in an acid cleaned pre-rinsed HDPE bottles
and brought to the laboratory and examined. The temperature is measured at the time of
sample collection itself. The pH is measured using Aqua troll 500 multiparameter sonde. The
conductivity and TDS is measured using a standard instrument EUTEC 650. All chemical
parameters were analysed by standard procedures. The anions were analysed in the filtered
sample through Whatman Cellulose nitrate filter paper. The water samples were analysed for
the following parameters.

a. Alkalinity
The alkalinity of water is a measure of ability of water to neutralize acids. The major portion
of alkalinity in natural waters is caused by OH-, CO22- and HCO3-. Alkalinity is estimated by
titration of suitable volume with standard 0.001N H2SO4 acid solution using mixed indicator.
Mixed indicator consisting of methyl orange and bromocresol green in which the colour
change is from blue green to orange, when HCO3- is titrated with acid.

Procedure
0.001 N H2SO4 is standardised using standard Na2CO3 solution. For the estimation we have
taken 10 ml sample, add 2 drops of mixed reagent indicator and was titrated against 0.001N
H2SO4 and the end point is colour change from blue to green.

Calculation
Alkalinity (mg /l) = Titre value x N x 61 x 1000
volume of sample
=Normality of sample x 61

b. Chloride
Chloride is estimated using Aqua TROLL 500 multiparameter sonde.

c. Total Suspended Solids (TSS)

Principle
The weight of suspended particle should be used for calculating TSS of the given sample.
The term TSS applies to the dry weight of the material that is removed from a measured
volume of water sample by filtration through a standard filter. The determination of
suspended solid concentration is given by gravimetric method.

Procedure
About 250 ml of each sample is filtered through a quantitative filter paper, WCN cellulose
Nitrate of 0.45 μm size and 47nm diameter is used. The filter paper is first dried and weighed
to a constant weight. 200 ml of well mixed sample is filtered through the above pre filtered
paper by applying suction. After filtration, carefully remove the filter paper and dried in an
oven, then cooling desiccating and weighing until a constant weight is obtained.

Calculation
TSS as mg / l = (A- B) x 1000
volume of sample
Where, A = weight of WCN cellulose Nitrate filler paper + dried residue
B = weight of WCN cellulose Nitrate filter paper cone

Silicate, Phosphate, Nitrite, Nitrate and Sulphate

These are analysed using SKALAR SAN+++ Continuous Flow Analyser (CFA). In CFA
reagents and samples are pumped through a system of continuous tubing. Samples are
introduced in a sequential manner through the system. Air bubble separate one sample from
the other. The main components of CFA are autosampler, chemistry unit where the
colourimetric reaction between the samples and reagents takes place, an interphase that
connects the chemistry unit with the computer and the computer as a readout.

d. Silicate
The automated procedure for
the determination of silicate
is based on the following
reaction; after dialysis the
sample is acidified and
mixed with an ammonium
hepta-molybdate solution
forming molybdosilicic acid.
This acid is reduced with L (+) ascorbic acid to a blue dye, which is measured at 810 nm.
Oxalic acid is added to avoid phosphate interference.

Reagents used are distilled water + lauryl sulphate, sulphuric acid solution, ammonium hepta-
molybdate solution, oxalic acid solution, Ascorbic acid solution.

e. Phosphate
The automated procedure for the determination of total UV digestible phosphate is based on
the following reaction; the sample is mixed with a potassium peroxodisulphate. The organic
phosphates are destructed by means of UV radiation. Sulphuric acid is added to the sample
stream and the solution is heated to 1100C. Complex inorganic phosphates are digested to
ortho-phosphate. Sodium hydroxide is added to neutralize the solution. Hereafter the solution
is dialysed against distilled water. Ammonium heptamolybdate catalysed by potassium
antimony (III) oxide tartrate reacts in an acidic medium with diluted solutions of phosphate to
form a phospho-molybdic acid complex. This complex is reduced in an intensely blue
coloured complex by L (+) ascorbic acid. This complex is measure at 880nm.

Reagents used are potassium peroxodisulphate, sulphuric acid solution, sodium hydroxide
solution, ascorbic acid solution, ammonium heptamolybdate solution

f. Nitrite
The automated determination for the determination of Nitrite is based on the following
reaction; the diazonium compounds formed by diazotizing of sulphanilamide by nitrite in
water under acid conditions is coupled with N(1-naphthyl) ethylene diamine dihydrochloride
to produce a reddish-purple colour which is measured at 540nm.

Reagents used are distilled water + brij35, colour reagent (o-phosphoric acid, sulphanilamide,
N(1-naphthyl) ethylene diamine dihydrochloride, distilled water)

g. Nitrate
The automated determination of nitrate is based on the following reaction. Sample is mixed
with a potassium peroxodisulphate /sodium hydroxide solution. This solution is mixed and
brought into a UV digester and heated to 110°C. After dialysis the nitrate is reduced to nitrite
by a cadmium copper reductor. The nitrite is determined by the Griess reaction, the colour is
measured at 540 nm.

h. Sulphate
The automated procedure for the determination of sulphate is based on the turbidimetric
analysis, the sample is mixed with barium chloride solution to form insoluble barium
sulphate. The Tween 80 is added to keep the barium sulphate in suspension. The turbidity of
the sample stream is measured at 540 nm.
BaCl2 (excess) + SO4 → BaSO4
2-

Sodium, Potassium, Calcium and Magnesium

Major ions present in the surface water such as sodium, potassium, calcium and magnesium
are analysed using Agilent Technologies 4210 MICROWAVE PLASMA ATOMIC
EMISSION SPECTROPHOTOMETER (MP-AES).
When an electromagnetic radiation is passed through a substance, the radiation is
either absorbed or transmitted by the substance. In an atomic emission spectrophotometer the
analyte atoms excite to higher energy levels by absorbing energy from the source. The
emissions from the excited atom is used to determine the analyte concentration. MP-AES
consist of a magnetron which produces microwaves, it is focussed to a wave guide, there the
radiation splits into axile magnetic field and vertical electric field. This axile magnetic field is
focussed to a plasma torch that produces nitrogen plasma which act as the source for the
excitation. The samples are sprayed by a nebuliser to the spray chamber and then reach the
plasma. There sample get vaporised, atomised and excite to higher energy level. These
emissions from the samples is passed through a monochromator and detected using a CCD
detector.
i. Sodium Analysis
Standard solution of 1.25 ppm, 2.5 ppm, 5 ppm, 10 ppm and 20 ppm is prepared and analysed
using MP-AES. 5% HNO3 is taken as the blank. Samples are analysed at a wavelength of
589.592 nm.

j. Potassium Analysis
Standard solution of 1.25 ppm, 2.5 ppm, 5 ppm, 10 ppm and 20 ppm is prepared and analysed
using MP-AES. 5% HNO3 is taken as the blank. Samples are analysed at a wavelength of
769.894 nm.

k. Calcium Analysis
Standard solution of 1.25 ppm, 2.5 ppm, 5 ppm, 10 ppm and 20 ppm is prepared and analysed
using MP-AES. 5% HNO3 is taken as the blank. Samples are analysed at a wavelength of
396.847 nm.

l. Magnesium Analysis
Standard solution of 1.25 ppm, 2.5 ppm, 5 ppm, 10 ppm and 20 ppm is prepared and analysed
using MP-AES. 5% HNO3 is taken as the blank. Samples are analysed at a wavelength of
279.553 nm.

CHAPTER 4
 RESULTS AND DISCUSSIONS

4.1 Chemistry of water samples collected from Vamanapuram river basin

4.1.1. Site characterisation and analysis design

The study area is Vamanapuram river basin which is located in Thiruvananthapuram district
of Kerala state. The land use change in and around the study area is evaluated in detail
together with an estimation of current crops and drainage facilities. The geology,
geomorphology and soil type of the water resource basin were also identified. The
socioeconomic aspects of these sources were critically evaluated during the field programme
with the primary observation data and mingling with the local people. The primary sources of
pollutants, if any, were also noticed in the close vicinity of the water resources. The present
chapter also deals with the qualitative as well as quantitative study of some of the important
physico-chemical parameters like pH, temperature, TDS, EC, DO, major ions (Na+, K+, Ca+,
Mg+, Cl-, SO42-, HCO3-) and minor ions (NO3-, NO2-, PO4-, SiO4-). Piper (1944) diagram is
used for understanding the source of dissolved constituents in water. Gibbs (1970) diagram is
used for understanding the primary mechanisms controlling the water chemistry such as
evaporation, precipitation or weathering. Mixing plots is used identify the source of major
ions. The relationships between the variables were examined by using correlation analysis.
Principle Component Analysis (PCA) was applied for further elaboration of findings and for
making the interpretation easier. The suitability of river water for irrigation was evaluated by
estimating the Na+% and sodium adsorption ratio (SAR). There are total twenty two water
sampling sites identified and illustrated in detail as follows and The summary of the hydro-
chemical data has been given in Table.1. and it is subjected to charge balance test.
This test helps to determine the accuracy of the water analysis and it is based on the principle
of electrical neutrality. The total dissolved cations (TZ+= Na++ K++2Ca2++2Mg2+) and total
dissolved anions (TZ-= Cl-+ HCO3-+ 2CO32-+2SO42-) sums expressed in milliequivalents per
litre must balance. The accepted charge balance is about 10%.

Charge balance = (TZ+ - TZ-) X 100

(TZ+ + TZ-)

4.1.2 General Hydrochemistry

The hydrogeochemical studies of 22 pre-monsoon samples of Vamanapuram river basin

explain the spatial variation of major ions and nutrients present in the water system.
Fig 4.1. box plot showing the variation of major ions in VRB

Temperature
The temperature of VRB ranges from 24.5 to 31.5 °C. The highest water temperature is for
VRB 3 and lowest is VRB 22.

pH
pH is defined as the negative logarithm of hydrogen ion concentration. It is the measure of
acidity or alkalinity. pH of neutral water is seven. A substance with pH less than 7 is said to
be acidic in nature and a basic substance has a pH greater than 7. The permissible pH
prescribed by WHO for drinking is 6.5-8.5. The pH above 9.2 and below 4.8 is harmful for
aquatic organisms. The pre-monsoon samples of VRB shows a range of 6.2 to 7.24. Water
samples from about 10 sampling sites are acidic in nature and the remaining is slightly basic
in nature. This is within the range of 6.5-8.5 which is permissible by WHO for drinking.

Electrical Conductivity (EC)

Conductivity is defining the water quality and it indicates the level of dissolved solids in
water. In the pre-monsoon samples of VRB electrical conductivity varies from 34.74 to
5816.1 µS. EC is high at VRB 15 and low at VRB 22.

Total Dissolved Solids (TDS)

The common dissolved load found in natural waters are carbonates, bicarbonates, chlorides,
sulphates, phosphates and nitrates of calcium, magnesium, sodium and potassium. In our
study TDS of pre-monsoon samples of VRB ranges from 21.88 to 3644.14 mg/L. The highest
TDS is for VRB 15 and the lowest TDS is for VRB 22.

Total suspended solids (TSS)

Total suspended solids is the substance present in the water which is not dissolved but can be
separate using a filtration. TSS is comprised of organic and inorganic particles that are
transported through the water column by runoff. It is used as an indicator of water quality.
TSS of pre-monsoon of VRB ranges from 1.12 to 26.32 µg/L. The highest TSS is for VRB 17
and lowest is for VRB 22.

Alkalinity
Alkalinity is the ability to neutralise acids. Alkalinity of natural water is due to the presence
of bicarbonates, carbonates or hydroxide ions. The pre-monsoon samples of VRB have
alkalinity in the range of 4.684 to 23.132 mg/l.
Chloride
Chloride is present in natural water as salts of sodium, potassium and calcium. Higher
concentration of chloride in natural waters indicates pollution and other anthropogenic
activities. The chloride concentration of pre-monsoon samples of VRB is in the range of 0.69
to 11070.5 mg/L. Highest chloride concentration is in the VRB 14 and lowest is in the VRB
1.

Sulphate
Sulphate is found in all kind of water system. Sulphate anion is added to the natural water due
to the sulphur oxidation and weathering. Industrial effluents, domestic sewage are the other
factors that add sulphate to the natural water. In our study area, the sulphate concentration is
in the range 1.25205 to 94.985 mg/L. Highest concentration of sulphate is in VRB 15 and
lowest sulphate concentration is in VRB 3.

Sodium
Sodium is the most abundant alkali metal found in natural waters. Sodium salts are highly
soluble in natural waters. It is also found in plant and animal tissues. In our present study
concentration of sodium is in the range 1.8 to 6000 mg/L. Maximum concentration of sodium
is seen in VRB 15 and minimum concentration is in VRB 1.

Potassium
Potassium is an essential nutrient required for both plant and animal kingdom. The values of
potassium in our present study is in the range of 1.01 to 41.18 mg/L.

Calcium
Calcium present in the natural water is coming from the decomposition of metamorphic rocks
and igneous rocks. Calcium is the abundant alkali earth metal present in natural waters.
Calcium carbonate is the common form Ca in sedimentary rock. Calcium salts impart
hardness to the water. Bicarbonates of calcium cause temporary hardness and chlorides and
sulphates of calcium cause permanent hardness. Contribution of calcium from the igneous
rocks is very small due to its slow decomposition. Concentration of Ca in the pre-monsoon
samples of VRB ranges from 0.94 to 15.91 mg/L. Highest calcium concentration is in VRB
15 and lowest is in VRB 1.

Magnesium
Magnesium in natural water is from the weathering of dolomite, mica and amphibole.
Magnesium also impart hardness to the water. Bicarbonates, chlorides and sulphates of Mg
cause hardness. In our present study magnesium concentration ranges from 0.69 to 22.22
mg/L. Highest concentration of magnesium is seen in VRB 14 and lowest concentration in
VRB 1.

Nitrite
The nitrites present in the natural water is due to nitrification which is an important step in
nitrogen cycle. Very high concentration of nitrites in water indicate unsatisfactory
microbiological activity which is due to anthropogenic activities. Nitrite concentration of pre-
monsoon samples of VRB is in the range of 0.00171 to 0.10143 mg/L. Highest
concentration is seen in VRB 16 and lowest concentration is in VRB 21.

Nitrate
Nitrate is introduced into water by nitrification. Nitrite is converted into nitrate by
Nitrobacter. Precipitation also introduce nitrate to water since the precipitation absorb
nitrogen in the atmosphere during the time of lightning transforming them into nitric and
nitrous acid. Nitrate concentration of pre-monsoon samples of VRB ranges from 0.1743 to
1.20808 mg/L. VRB 13 exhibit maximum concentration of nitrates and VRB 21 exhibit
minimum concentration of nitrates.

Phosphate
Phosphate content in natural water is increasing mainly due to the wide application of
phosphorus containing fertilizers, detergents et cetera. High phosphate concentration leads to
eutrophication of water basins. Phosphate concentration in the pre-monsoon samples of VRB
ranges from 0.0017 to 0.01029 mg/L. Highest concentration of phosphate is seen in VRB 16
and lowest concentration is in VRB 1.

Silicate
Silicate is added to natural water system mainly due to weathering. In our present study
silicate concentration is in the range 4.55 to 9.06 mg/L. VRB 22 exhibit the maximum silicate
concentration and VRB 5 has the minimum silicate concentration.

pH
7.4

7.2

6.8
pH

6.6

6.4

6.2
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no

TDS (mg/L)
3700
3200
2700
2200
TDS (mg/l)

1700
1200
700
200
-300 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

sampling stn no
 TSS (µg/L)
27
22
17
TSS (mg/l)

12
7
2
-3 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

sampling stn no

Na (mg/L)
6000

5000

4000
Na (mg/l)

3000

2000

1000

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no

K (mg/L)
42
37
32
27
K (mg/l)

22
17
12
7
2
-3 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

sampling stn no
 Ca (mg/L)
18
16
14
12
Ca (mg/L)

10
8
6
4
2
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no

Mg (mg/L)
23

18
Mg (mg/l)

13

-2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

sampling stn no

Fe (mg/L)
0.7
0.6
0.5
0.4
Fe (mg/l)

0.3
0.2
0.1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
-0.1
-0.2
sampling stn no
 Bicarbonate(mg/L)
25

20
bicarbonate (mg/l)

15

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no

Chloride (mg/L)
11500
9500
7500
Cl (mg/l)

5500
3500
1500
-500 0 5 10 15 20 25
-2500
sampling stn no

Nitrite (mg/L)
0.12

0.1

0.08
nitrite(mg/l)

0.06

0.04

0.02

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no
 Nitrate (mg/L)
1.4
1.2
1
nitrate (mg/l)

0.8
0.6
0.4
0.2
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no

Phosphate (mg/L)
0.012

0.01
phosphate (mg/l)

0.008

0.006

0.004

0.002

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

sampling stn no

Silicate (mg/L)
9

7
silicate (mg/l)

3
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
sampling stn no