Water pollution

Presented By

Dr. Mohd Nasir

Assistant Professor
Department of chemistry
(Analytical division)
A.M.U., Aligarh
Safe drinking water
is a fundamental
right for all living
organisms
 Table: The adverse effects of different types of water pollutants.

Pollutants Impact

Organic pollutants
Depletion of the dissolved oxygen (DO) will be a serious problem adversely affecting aquatic life, if the DO
falls below 4.0 mg L-1.
i) Oxygen Demanding wastes:
II) Synthetic organic pollutants: Most of these compounds are toxic and bio refractory organics. It also makes water unfit for different uses.
This pollutant is also responsible for endangering water birds and coastal plants due to coating of oils and
III) Oil: adversely affecting the normal activities which cause reduction of light transmission and photosynthesis.
Number of diseases transmitted by pathogens available in wastewater.
Pathogens
When these are disposed in aquatic environment, it can lead to growth of undesirable aquatic life. When it
Nutrients discharged on land it causes groundwater pollution.
In the presence of organic matter, the bacterial action increases due to rise in temperature; hence, resulting in
Thermal pollutants rapid decrease of DO. It also results in thermal stratification which alters spectrum of organisms.
These isotopes are toxic to the life forms; they accumulate in the bones, teeth and can cause serious
Radioactive pollutants disorders.

Presence of suspended solids can block the sunlight penetration in the water, which is required for the
Suspended solids and sediments photosynthesis by bottom vegetation. Finer suspended solids such as silt and coal dust may injure the gills of
fishes and cause asphyxiation.
These pollutants include mineral acids, inorganic salts, trace elements, metals, metal compounds, complexes
Inorganic pollutants of metals with organic compounds, cyanides, sulphates, fluoride etc. They have adverse effect on aquatic
Water quality parameters
“it is the physical, chemical, and biological characteristics of water”

Classification of water
1- Based on its source

water

Ground water heavy metals, pesticides, fertilizers, hazardous chemicals, and oils Surface water

2- Based Water quality

water

potable water palatable water contaminated water infected water

Safe to drink, pleasant to taste, and usable Aesthetically pleasing: considers the presence of Water containing unwanted physical, water is contaminated with
for domestic purposes chemicals but do not cause a threat to human chemical, biological, or radiological pathogenic organism and it is
health substances, and it is unfit for drinking or unfit for drinking or
domestic use domestic use

Safe for drinking

Unsafe for drinking
Turbidity

Nephelometric turbidimeter
Parameters of water quality
Turbidity
Turbidity is the cloudiness of water. It is a measure of the ability of light to pass through water. It is caused by suspended material such as clay, silt, organic material,
plankton, and other particulate materials in water.
Turbidity in drinking water is esthetically unacceptable, which makes the water look unappetizing. The impact of turbidity can be summarized in the following points
• It can increase the cost of water treatment for various uses .
• The particulates can provide hiding places for harmful microorganisms and thereby shield them from the disinfection process .
• Suspended materials can clog or damage fish gills, decreasing its resistance to diseases, reducing its growth rates, affecting egg and larval maturing, and affecting
the efficiency of fish catching method.
• Suspended particles provide adsorption media for heavy metals such as mercury, chromium, lead, cadmium, and many hazardous organic pollutants such as
polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and many pesticides.
• The amount of available food is reduced [15] because higher turbidity raises water temperatures in light of the fact that suspended particles absorb more sun heat.
Consequently, the concentration of the dissolved oxygen (DO) can be decreased since warm water carries less dissolved oxygen than cold water.
Turbidity is measured by an instrument called nephelometric turbidimeter, which expresses turbidity in terms of NTU or TU. A TU is equivalent to 1 mg/L of silica in
suspension. Turbidity more than 5 NTU can be visible to the average person while turbidity in muddy water, it exceeds 100 NTU. Groundwater normally has very low
turbidity because of the natural filtration that occurs as the water penetrates through the soil.
pH:

Electrometric Method

Colorimetric Methods
pH:
pH is one of the most important parameters of water quality. Actually, pH of water is a measure of how acidic/basic water . Acidic water contains extra hydrogen ions
(H+) and basic water contains extra hydroxyl (OH−) ions. As shown in Figure (previous slide), pH ranges from 0 to 14, with 7 being neutral. pH of less than 7
indicates acidity, whereas a pH of greater than 7 indicates a base solution . Pure water is neutral, with a pH close to 7.0 at 25°C. Normal rainfall has a pH of
approximately 5.6 (slightly acidic) owing to atmospheric carbon dioxide gas. Safe ranges of pH for drinking water are from 6.5 to 8.5 for domestic use and living
organisms need [24]. A change of 1 unit on a pH scale represents a 10-fold change in the pH [10], so that water with pH of 7 is 10 times more acidic than water with a
pH of 8, and water with a pH of 5 is 100 times more acidic than water with a pH of 7. There are two methods available for the determination of pH: electrometric and
colorimetric methods.
A high pH makes the taste bitter and decreases the effectiveness of the chlorine disinfection, thereby causing the need for additional chlorine. The amount of oxygen in
water increases as pH rises. Low-pH water will corrode or dissolve metals and other substances. Pollution can modify the pH of water, which can damage animals and
plants that live in the water. The effects of pH on animals and plants can be summarized as follows:
• Most aquatic animals and plants have adapted to life in water with a specific pH and may suffer from even a slight change.
• Even moderately acidic water (low pH) can decrease the number of hatched fish eggs, irritate fish and aquatic insect gills, and damage membranes .
• Water with very low or high pH is fatal. A pH below 4 or above 10 will kill most fish, and very few animals can endure water with a pH below 3 or above 11.
• Amphibians are extremely endangered by low pH because their skin is very sensitive to contaminants . Some scientists believe that the current decrease in amphibian
population throughout the globe may be due to low pH levels induced by acid rain. The effects of pH on other chemicals in water can be summarized as follows:
• Heavy metals such as cadmium, lead, and chromium dissolve more easily in highly acidic water (lower pH). This is important because many heavy metals become
much more toxic when dissolved in water .
• A change in the pH can change the forms of some chemicals in the water. Therefore, it may affect aquatic plants and animals . For instance, ammonia is relatively
harmless to fish in neutral or acidic water. However, as the water becomes more alkaline (the pH increases), ammonia becomes progressively more poisonous to these
same organisms
Dissolved oxygen

Colorimetric method
(quick and inexpensive)

The percentage saturation, at a given temperature is defined as

𝑀𝑒𝑠𝑢𝑟𝑒𝑑 𝐷𝑂 Electrometric method

𝑆 = × 100 Winkler titration method
𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝐷𝑂
(traditional method)
The degree of unsaturation or saturation deficit is defined as
𝐷 = 𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐷𝑂 𝑎𝑡 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 − 𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑑 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝐷𝑂 𝑎𝑡 𝑡ℎ𝑎𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
Measurement of BOD

𝐷𝑂 𝐷𝑂
𝐵𝑂𝐷 = 𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 − {𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑓𝑡𝑒𝑟 5 𝑑𝑎𝑦𝑠}
𝐿 𝐿
Chemical oxygen demand or COD

𝐶𝑜𝑛𝑐 𝑜𝑓 𝑃𝑜𝑡𝑎𝑠𝑖𝑢𝑚 𝑑𝑖𝑐ℎ𝑟𝑜𝑚𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑝𝑝𝑚

= 𝐶𝑜𝑛𝑐 𝑜𝑓 𝑝𝑜𝑡𝑎𝑠𝑖𝑢𝑚 𝑑𝑖𝑐ℎ𝑟𝑜𝑚𝑡𝑒 𝑖𝑛𝑖𝑡𝑎𝑙𝑙𝑦 𝑎𝑑𝑑𝑒𝑑
− 𝐶𝑜𝑛𝑐 𝑜𝑓 𝑃𝑜𝑡𝑎𝑠𝑖𝑢𝑚 𝑑𝑖𝑐ℎ𝑟𝑜𝑚𝑎𝑡𝑒 𝑑𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒𝑑 𝑏𝑦 𝑏𝑎𝑐𝑘 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛
Dissolved oxygen (DO): is considered to be one of the most important parameters of water quality in streams, rivers, and lakes. It is a key test of water pollution.
The higher the concentration of dissolved oxygen, the better the water quality. Oxygen is slightly soluble in water and very sensitive to temperature. For example, the
saturation concentration at 20°C is about 9 mg/L and at 0°C is 14.6 mg/L. The actual amount of dissolved oxygen varies depending on pressure, temperature, and
salinity of the water. Dissolved oxygen has no direct effect on public health, but drinking water with very little or no oxygen tastes unpalatable to some people. There
are three main methods used for measuring dissolved oxygen concentrations: the colorimetric method—quick and inexpensive, the Winkler titration method—
traditional method, and the electrometric method

Biochemical oxygen demand (BOD): Bacteria and other microorganisms use organic substances for food. As they metabolize organic material, they consume
oxygen. The organics are broken down into simpler compounds, such as CO2 and H2O, and the microbes use the energy released for growth and reproduction. When
this process occurs in water, the oxygen consumed is the DO in the water. If oxygen is not continuously replaced by natural or artificial means in the water, the DO
concentration will reduce as the microbes decompose the organic materials. This need for oxygen is called the biochemical oxygen demand (BOD). The more organic
material there is in the water, the higher the BOD used by the microbes will be. BOD is used as a measure of the power of sewage; strong sewage has a high BOD and
weak sewage has low BOD. The complete decomposition of organic material by microorganisms takes time, usually 20 days or more under ordinary circumstances.
The quantity of oxygen used in a specified volume of water to fully decompose or stabilize all biodegradable organic substances is called the ultimate BOD or BODL.
BOD is a function of time. At time = 0, no oxygen will have been consumed and the BOD = 0. As each day goes by, oxygen is used by the microbes and the BOD
increases. Ultimately, the BODL is reached and the organic materials are completely decomposed.
In order to elucidate biochemical oxygen demand, the water sample is first saturated with oxygen. It is then incubated at a constant temperature, usually at 293 K for
five days. Tis times allows for microorganism in the waste water to mediate oxidation of pollutants. The remaining amount of dissolve oxygen is determined and then
biochemical oxygen demand is obtained by equation (previous slide)

Chemical oxygen demand (COD): is a parameter that measures all organics which may be the biodegradable and the non-biodegradable substances. COD is a
chemical test using strong oxidizing chemicals like potassium dichromate in presence of sulfuric acid, and heat, and the result can be available in just 2 h. The COD
values are always higher than BOD values for the same sample
 Steps in water treatment

Preliminary treatment Primary treatment Secondary treatment Tertiary treatment

Chlorination

Screening Trickling filters

Sedimentation
Adsorption

Revers osmosis
Skimming Flocculation Activated sludge
Ion-exchange

Oxidation ponds
Electrodialysis
Preliminary treatment

Screening process Skimming process

air bubbles

Potassium xanthates
Steps in water treatment: Water is purified in the following four stages.

(1) Preliminary treatment: Which involves screening, for the removal of large objects and skimming for the removal of grit.
(2) Primary treatment: Where the suspended solids and colloidal matter are first allowed to settee down and then removed
(3) Secondary treatment: where the organic pollutants both suspended and dissolve are oxidized by microorganisms.
(4) Tertiary treatment: Which involves the use of a number of techniques for removing non-biodegradable pollutants, ionic constituents and trace impurities

These treatment are now described in details

Stage I Preliminary treatment

The preliminary stage of water treatment involves the removal of two types of impurities. Firstly, those which are suspended in water are cores matter and secondly,
those which float or can be made of float on the surface. Suspended mater is eliminated by screening, while the floating matter is eliminated by skimming. In some
purification plants screening is fallowed by skimming, in others the operation is carried out in the revers order.

Screening: The impure water is made to pass through rows of iron bars with a spacing of 1-2 inches. The spacing are narrow enough to hold back sticks, rags, wood
pieces, paper and polyethene items. The iron bars periodically clean to prevent clogging.

Skimming: Oil, grease and other impurities which are lighter than water rise to the surface and can be removed by mechanical skimming. The skimming technique
can also be extended for the removal of impurities heaver than water by blowing compressed air into the polluted water. The air bubbles that are formed, attached
themselves the grit particles and lift them to the surface, from where theses are skimmed off. The efficiency of skimming technique can be increased by adding
collecting and activating agents that form a thin film of suspended particles to which air bubbles can attaché themselves. Potassium xanthates serve as excellent
collecting and activating agents. In addition floating agents like oil or glue may also be added to the skimming tanks theses agents stabilized the froth for a long spell
of time, So that the grit particles do not get detached from the bubbles before theses can be skimmed off.
Stage II Primary treatment

Sedimentation Flocculation

Potash alum

Ferrous sulfate

Ferric chloride
Stage II Primary treatment
The primary treatment stage of water purification involves settling of the colloidal or suspended mater as sludge. The two common methods
used to settle out impurities are sedimentation and flocculation.

Sedimentation: Most of the solids, suspended in polluted water are too fine and to heavy and therefore not to be screen out and skimmed off.
These may however be removed by allowing them to settle down under the enflurane of gravity. This technique is called sedimentation. A
sedimentation tank is generally shallow and radial shaped. Polluted water is retained in tank for 1-3h, during which period the impurities settled
down. The sludge which settle out is prone to undergo putrefaction. It should therefore, not be left in the sedimentation tank for long. The tanks
are equipped with mechanical gears to remove the sludge at periodic intervals.

Flocculation: it is a chemical precipitation is meant to rid water of extremely fine particles. Ordinarily, theses particles take a very long time to
settle down under the enflurane of gravity. The method of plane sedimentation is therefore, not effective for their removal. The rates of
settlement can, however be considerably enhanced by the addition of flocculating agents, such as potassium aluminum sulfate (potash alum),
ferrous sulfate, ferric chloride etc.
The fine particles in polluted water bear either a positive or a negative charge. The similar charged particles repel each other and therefore have
no tendency to coalesce. Hence these remain suspended for long time. When flocculating agents are added the positive charge on particles are
neutralized by sulfate or chloride ions (reaction are shown in the previous slide), while the negative charges are neutralized by Al3+, Fe2+, or
Fe3+ . Once adhering charges are nullified, the particles come in contact with each other and coalesce. Their weight increases and theses rapidly
settle down.
Stage III Secondary treatment

Trickling filters Activated sludge method Oxidation ponds

Stage III Secondary treatment
Secondary treatment of water involves the oxidation of dissolved and colloidal organic compounds in the presence of microorganisms. As in case of self purification
phenomena, the complex, hazardous organic compounds are biodegraded into simpler harmless, inorganic compound. Sufficient quantity of dissolved oxygen is a
necessary condition for this process. The aerated conditions are obtained usually either by trickling filters or activated sludge tanks. In warmer region the oxidation
ponds may also be used.

Trickling filters: Trickling filters also called as percolating filters or sprinkling filters, consist of circular or rectangular beds, usually 3-5 cm at the top and 10-15 cm at
the base with a depth of 1-3 m theses are provided with brick or concrete walls the beds are packed with clinker, slag stones, coal etc. Such a medium is intended to
serve as a habitat of bacteria, fungi and other macro and microorganism which play an important role in water purification.
The material constituting the medium should
 Durable.
 Be resistant to the action of pollutants
 Have a high ratio of surface area to weight
 Be rough enough to encourage the formation of biological film.
 Have a large percentage of voids to permit the passage of air.
Trickling filtrates are associated with some problems and that’s why it is avoided.

Activated sludge method: When water containing organic pollution is aerated, some amount of sludge settle down. Soon microorganism inhabit in the sludge. When a
fresh batch of polluted water is aerated over this sludge, it gets purified more effectively than the previous one. More sludge accumulates and greater density of
microorganisms settle on it. Thus after each purification slot, the sludge become more activated.
For efficient operation of this method, it is necessary that sufficient amount of activated sludge containing biologically active microorganisms must be present. This
method suffers from the drawback that when a massive quantity of sludge accumulate

Oxidation ponds: this method are used in warmer climates to purify water through an interaction between bacteria and algae. The ponds are shallow with an average
depth of 1 meter The polluted water is made to flow through the ponds at a slow speed. The bacteria present in the pond decompose the biodegradable organic mater.
Dissolve oxygen is consumed in this process and carbon dioxide, nitrates and phosphate are generated. While nitrates and phosphate are consumed by algae as food
material and carbon dioxide are utilized in photosynthesis. The later phenomenon releases oxygen. Thus the dissolve oxygen which was consumed in microbial
degradation of organic load, is restored and the cycle restarts.
Stage IV Tertiary treatment

Chlorination:
When ammonia or ammines are present in water

RNH2 + HOCL RNHCl + H2O

Chloramines (purifying agent, less effective but long
lasting than hypochlorous acid )

Chlorination purifies water in three ways

• Disinfects water of pathogens
• Destroy or control the growth of undesirable Algae
• Eliminates the odors associated with anaerobic decomposition of organic mater
Compounds containing active chlorine in water
Gaseous chlorine Cl2 H2S + HOCl H2O + HCl + S
Bleaching powder or calcium hypochlorite (Ca(OCl)2),
Sodium hypochlorite (NaOCl)
Drawback
• Disinfection by-products are produced (chloroform and carbon tetrachloride)
In aqueous solution • Increasing use of chlorination for water purification has been linked to elevated
rates of bladder and rectal cancer.
Cl2 + H2O HOCL + HCL • Chlorine acts efficiently against pathogenic Bactria but it is incapable of
destroying most viruses
NaOCl + H2O HOCL + NaOH

Ca(OCl)2 + 2H2O 2HOCL + Ca(OH)2

HOCL ( Hypochlorous Acid): Act as purifying agent
Stage IV Tertiary treatment
Tertiary treatment of water encompasses a set of techniques which remove the impurities that remain even after first three stages of purification.
Theses are mainly the soluble inorganic impurities. Depending upon the nature of pollution, one or more of theses techniques may be used in this
final stage of treatment.

Chlorination: Chlorination refers to the addition to impure water of gaseous chlorine or compounds containing active chlorine, such as bleaching
powder, calcium (hypochlorite: Ca(OCl)2), Sodium hypochlorite NaOCl. In aqueous solution these compound generate hypochlorous acid which
act as purifying agent.

Chlorination purifies water in three ways.

1. It disinfect water of pathogenic bacteria. Although almost 90% of microorganism are removed during the secondary treatment stage, the
remaining 10% are eliminated by the bactericidal action of chlorine. As a disinfectant, chlorine inactivates the enzymes that are essential for
the life process of bacteria. When ammonia or ammines are present in water, chloramines are generated (reaction are shown in previous slide).
Chloramines too are disinfectants. Although their ability to kill microorganism is less than that of chlorine, yet chloramine persist for longer
time in water and therefore their purifying ability is more lasting.
2. Chlorination destroy or controls the growth of undesirable algae in water treatment plants. Algae grow at an accelerated pace and clog
conduits in water purification units. Passage of chlorine through theses condition removes the unwanted algal growth.
3. Chlorination eliminates the odors associated with anaerobic decomposition of organic matter in water, Amongst the degradation products
hydrogen sulfides the most common. It is destroyed by chlorination, preventing its foul odor being released to the air

Drawbacks chlorination process: Although chlorination is a standard method of water treatment, it suffers from two drawbacks
(I) Chlorine interact with those organic impurities which persist in water even after secondary stage of water treatment. A set of compound called
disinfection by-products are produced by such interaction. Some of these by-products like chloroform and carbon tetrachloride are
carcinogenic. Thus, increasing use of chlorination for water purification has been linked to elevated rates of bladder and rectal cancer. I has
therefore been suggested that the amount of chlorine being added to water must be carefully monitored, so that the threat of pathogens must
be balanced against the statistical risk of cancer.
(II) Chlorine acts efficiently against pathogenic Bactria but it is incapable of destroying most viruses.
Adsorption Revers osmosis
Adsorption: A number of compound which are resistant to biodegradation persist in water even after the primary and secondary treatment stages.
Many of theses compounds are carcinogenic and toxic. These may be eliminated by passing water over a bed of granulated, active charcoal. A
wide variety of compounds, both in dissolved and suspended states are adsorbed by charcoal and thereby removed from water. When charcoal
becomes saturated with impurities. It is heated in vacuum to about 1800 K and adsorbates are derived off. The active sites on charcoal once again
becomes bare and hence the adsorbent may be recused.
Charcoal is also effective in removing small amounts of dyes which impart undesirable color to water. In addition, those derivatives which produce
objectionable testes and color may also be adsorbed on charcoal and eliminated.
Reverse osmosis: The term osmosis refers to a process whereby relatively pure water flows into concentrated solution through a semipermeable
membrane. This process is spontaneous because when a concentrated solution becomes diluted the entropy of the system increase.
The minimum pressure required to counteract osmosis is called osmotic pressure (Л = CRT; C: concentration of solution in mol/L; R: gas constant
and T: absolute temperature).
If pressure is increased beyond the value of osmotic pressure, water being to flow in the revers direction. This process is called reverse osmosis or
ultrafiltration. Impure water, containing dissolve solutes, is placed above a semi permeable membrane and subjected to high pressures. Pure water
flow down the semipermeable membrane, The solute molecules, wheatear ionic or covalent, generally have large diameters than pores of
semipermeable membrane. Hence they are retained by membrane while pure water filters off.
Three membrane materials are commonly used in revers osmosis. Cellulose, triacetate, and polyamide.
Over a period of time the pores of membrane becomes clogged. The membrane is then flushed with a 1 % detergent solution. This cleans away
small solid particles trapped in the pores. However, insoluble inorganic compounds like calcium carbonate and iron oxide are not washed out by
detergents. These contaminants are removed by flushing the membrane with a solution of citric acid.
Metal and metalloids:

Heavy metals: metallic elements having an atomic weight higher than 40.04 g/mol (the atomic mass of Ca) and atomic density greater than 4
g cm-3, or 5 times or more, greater than water
Sources of metal and metalloids:
Metal and metalloids: Occurrence of metal naturally in the earth's crust, and their distribution in the environment is governed by the
properties of the metal and influences of environmental factors. Out of total 92 naturally occurring elements, approximately 30 metals and
metalloids (Be, B, Li, Al, Ti, V, Cr, Mn, Co, Ni, Cu, As, Se, Sr, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, W, Pt, Au, Hg, Pb, and Bi) play a pivotal role
in various biochemical and physiological mechanisms in living organisms, and hence, recognized as essential elements for life. These metals and
metalloids can be toxic if present a level above the recommended one. Heavy metals is the generic term for metallic elements having an atomic
weight higher than 40.04 (the atomic mass of Ca) and atomic density greater than 4 g cm-3, or 5 times or more, greater than water. Natural and
anthropogenic sources are responsible for the existence of heavy metals in the environment. These sources include: mining, industrial discharge,
natural weathering of the earth’s crust, soil erosion, urban runoff, sewage effluents, pest or disease control agents applied to plants, air pollution
fallout, and a number of others. Heavy metals from these sources enter in the soil and then in the surface and groundwater that are adverse to
human health.
Among these Cadmium, Nickel, Mercury, Lead and Arsenic in the aquatic environment is transformed into physiochemical forms that are highly
toxic and hazardous.
Cadmium
• The permissible limit of Cd (II) for human in drinking water and air are 1 µg L-1 and 0.04 µg m-3, respectively.
• Extremely long biological half-life of cadmium (15 to 20 years)
• The International Agency for Research on Cancer (ARC) and the US National Toxicology Program have recognized cadmium as human carcinogen

Formation of cadmium-metallothionein complex

Cadmium: Cadmium (atomic number 48) is a soft, silver-white metal that is found naturally at low levels in rocks and soils. Cadmium is
used in different industries which include nickel-cadmium batteries and electroplating, metallurgical and brazing-soldering alloys, pigments
and as a stabilizer for plastic. Burning of fossil fuel and waste materials and the use of phosphate fertilizers and sewage sludge are also basic
sources of environmental cadmium. Natural sources of Cd (II) exposure include volcanic activity, forest fires, and soil particles carried by
wind. Therefore cadmium is considered as ubiquitous environmental and occupational pollutant.
The permissible limit of Cd (II) for human in drinking water and air are 1 µg L-1 and 0.04 µg m-3, respectively. The excessive use and
extremely long biological half-life of cadmium (15 to 20 years) essentially makes it continuous health problem as a cumulative toxin. The
International Agency for Research on Cancer (ARC) and the US National Toxicology Program have recognized cadmium as human
carcinogen. The inhalation of cadmium into the human body is mainly through food, smoking and drinking water. When the level of cadmium
becomes higher than recommended levels, adverse effects on the liver, lungs, pancreas, bones, reproductive organs, placenta, and
hematopoietic, nervous, and cardiovascular system can be seen . Several investigators have found that mostly cadmium is responsible for lung,
pancreas, prostate, breast, and kidney cancer, because cadmium in the body shows high affinity towards the low molecular weight proteins
“metallothionein”, and results in the formation of cadmium metallothionein complex. This cadmium metallothionein complex goes to various
tissues and organs and is ultimately reabsorbed in kidney tubuli. Our body has no mechanism for the excretion of cadmium and therefor;
cadmium accumulates in tissues. The accumulation of cadmium as cadmium-metallothionein complex causes the damage of human organs
One of the most visible tragedies caused by water pollution specially due to cadmium poising is Itai-itai disease
disease
Nickel
Oxidation state: From -1 to 4 (+2 is the most common in biological systems)
Permissible limit: For drinking water 0.02 mg L-1 and for plants are 10 mg Kg-1
Sources: Anthropogenic activities contribute about 40 % of total Ni (II) production in the environment
Existence of Nickel in ecosystem: water soluble (less carcinogenic, e.g. NiCl2, NiSO4) and water insoluble (highly carcinogenic, e.g. NiS, Ni3S2 and NiO) nickel salt.

Lung cancer

DNA hypermethylation, histone deacetylation and chromatin condensation

due to Ni (II) compound.
Nasal cancer Allergic skin reactions
Nickel: Nickel, silvery-white hard, malleable, and ductile metal, occurs in the several oxidation states (ranging from -1 to 4). However +2 oxidation state is the most
common in biological systems. Nickel is a nutritionally essential trace metal for at least several animal species, micro-organisms and plants health. The permissible
limit of Ni (II) for drinking water and plants are 0.02 mg L-1 and 10 mg Kg-1, respectively. Therefore either deficiency or toxicity symptoms can occur when,
respectively, too little or too much Ni (II) is taken up. The most important sources of Ni (II) in the ecosystem are the anthropogenic activities: mining, smelting
procedures, steel and iron industry, production of long-lasting nickel-cadmium batteries, welding, and alloy production, which contribute about 40 % of total Ni (II)
production in the environment. In addition burning of fossil fuel also contribute the environmental nickel concentration . Nickel is mainly existing in two forms of
compounds in ecosystem, namely: water soluble (NiCl2, NiSO4) and water insoluble (NiS, Ni3S2 and NiO) nickel salt. Water-soluble nickel salts are considered less
carcinogenic than water insoluble compounds. Therefore the carcinogenic impact of nickel depends upon their water solubility. According to epidemiological studies
water-insoluble nickel compounds are considered as the suspected agent in the induction of human lung and nasal cancers. Despite their potency as human and rodent
carcinogens, nickel compounds are weakly mutagenic. DNA methylation and histone acetylation are important in organizing the genome into transcriptionally active
and inactive regions. Here, Fig. (previous slide) shows that nickel compounds cause DNA hypermethylation, histone deacetylation and chromatin condensation. These
effects of nickel, decreasing the transcription of tumour suppressor and senescence genes, may play an important role in its carcinogenicity.

Therefore, in 1990 the International Agency for Research on Cancer (IARC) classified nickel compounds as group 1 carcinogen (confirmed carcinogen) to humans.
The ubiquitous nature of nickel is responsible for allergic skin reactions and has been reported to be one of the most common causes of allergic contact dermatitis.
When nickel concentration is inhaled more than permissible limits causes severe damage to lungs, kidneys and gastrointestinal distress, such as nausea, vomiting,
diarrhea, pulmonary fibrosis and renal edema.
Mercury
• liquid with a vapor pressure of 0.00185 mm at 25°C
• Threshold limit according to American Conference of Governmental Industrial Hygiene (ACGIH) is 0.05 mg/m3 of air for continuous 40 hours/week exposure
• Elemental mercury is highly lipid soluble

Minamata disease
 Minamata disease is a methylmercury poisoning

A view of central Minamata City, the Yatsu- shiro Sea and flow of the Minamata
River on the right side
Mercury: Elemental mercury (Hg) is found as a liquid with a vapor pressure of 0.00185 mm at 25°C. This means that elemental mercury is
extremely volatile. The rate at which mercury volatilizes is directly related to temperature so, that as the temperature increases, does the amount
of mercury in the surrounding air. The American Conference of Governmental Industrial Hygienists (ACGIH) has established a threshold limit
for mercury vapor of 0.05 mg/m3 of air for continuous 40 hours/week exposure. Long-term chronic exposure to mercury vapor in excess of 0.05
mg/m3 of air may result in cumulative poisoning. Exposure is most commonly through an occupational source including exposure in the home.

Since mercury easily vaporizes at room temperature, the route of absorption is often through the lungs. In humans, approximately 70% to 85% of
a dose is absorbed in this manner whereas less than 3% of a dose will be absorbed dermally. If elemental mercury is ingested orally, less than
0.1% is absorbed from the gastrointestinal (GI) tract and, therefore, when orally ingested is only mildly toxic. Elemental mercury is highly lipid
soluble; a characteristic that facilitates its diffusion across the alveoli into the circulation, as well as its distribution throughout the lipophilic
compartments of the body including passage across the blood brain barrier into the central nervous system (CNS) and across the placenta. In the
circulation, elemental mercury binds to numerous tissues, proteins, and erythrocytes. In erythrocytes, catalase can oxidize elemental mercury to
an inorganic metabolite. If elemental mercury penetrates the blood brain barrier, it is ionized and becomes trapped in the compartment where it is
available to exert its neurotoxicity. Elemental mercury has the longest retention in the brain with detectable levels present for years following
exposure. The half-life of elemental mercury in adults is approximately 60 days (range: 35 to 90 days).

One of the most visible tragedies caused by water pollution specially due to mercury poising is Minamata disease
Arsenic
Oxidation state: As(III)) and As(V) (+3 is the most common in biological systems)

• World Health Organization (WHO), the European Commission (EU), and the United States Environmental Protection Agency (USEPA) have recommended a
maximum contaminant level (MCL) of 10 μg/L for arsenic in drinking water

Skin cancer

Hyperkeratosis
Arsenic: Arsenic (a semi metallic element or metalloid) is one of the most toxic, carcinogenic, and natural contaminants found in water
resources. Arsenic in water systems is mostly introduced from natural and anthropogenic sources. Natural sources include the washout and
erosion of arsenic-rich rocks and soils, which probably occur because of long-term geochemical changes. Anthropogenic sources include forestry,
agricultural application of various pesticides, herbicides and fertilizers, and industrial effluents from metallurgy, electronics, mining,
pharmaceuticals, glass processing, ceramic, dye and pesticides manufacturing, wood preservatives, petroleum refining, and landfill leaching.

The two states prevalent in water environment are arsenite (As(III)) and arsenate (As(V)). As (III) mostly exists in reducing ground waters and
hydrothermal waters, whilst As(V) is more often present in surface waters and oxidizing ground waters. Arsenic is a geogenic water menace
affecting millions of people all over the world and is regarded as the largest mass poisoning in history. Permanent arsenic intake can lead to
chronic intoxication, and prolonged arsenic exposure can damage the central nervous system, liver, and skin and results in the appearance of
diverse types of cancers, such as hyperkeratosis, lung, skin, and prostate cancers.

Arsenic in natural waters is a worldwide problem. Arsenic pollution has been reported recently in USA, China, Chile, Bangladesh, Taiwan,
Mexico, Argentina, Poland, Canada, Hungary, New Zealand, Japan, and India. The largest population at risk among the 21 countries with known
groundwater arsenic contamination is in Bangladesh, followed by West Bengal in India. Due to high toxicity and carcinogenic effect of arsenic,
the World Health Organization (WHO), the European Commission (EU), and the United States Environmental Protection Agency (USEPA) have
recommended a maximum contaminant level (MCL) of 10 μg/L for arsenic in drinking water.
Water treatment technologies for the remediation of metal •Electrokinetic coagulation
and metalloids (determination of metal and metalloids)
•Irradiation
•Ion exchange
•Membrane filtration

Physical •Adsorption

•Oxidation process
•Fenton method
Methods Chemical •Ozonation
•Photochemical
•Sodium hypochlorite

Biological •Electrochemical destruction

•Decolorization by white rot fungi

•Adsorption by living/dead microbial biomass
•Anaerobic textile dye
•Bioremediation systems
•Other microbial cultures

Summery of the water purification processes for determination of metals and metalloids in water system
Water treatment technologies for the remediation of metal and metalloids (determination of metal and metalloids)
During the last decade, there was a significant amount of research focusing on the remediation of metals and metalloids from wastewaters.
There are a wide variety of methods for removal of theses pollutants from environmental waters. These methods can be broadly classified
as physical, chemical and biological purification processes. Figure (previous slide) shows the summery of the purification processes.
The processes used for removal of metal ions from wastewater include chemical precipitation, floatation, adsorption, ion-exchange and
electrochemical adsorption. Chemical precipitation is frequently used for removal of metal ions. The mechanism of metal removal by
chemical precipitation is shown as
-
Mn+ + n(OH) M(OH)n

where Mn+ and OH- represent the dissolved metal ions and precipitating agents, respectively. M (OH)n is the insoluble metal hydroxide. However,
the chemical precipitation required large amount of participating agents to reduce metal ions to an acceptable levels for discharge. In this process,
large amount of sludge is produced that required further treatment and disposal.
Adsorption is mass transfer process which involves the accumulation of substance (pollutants) at the liquid-solid interface. The properties of
adsorbate and adsorbent are highly specific and depend on their constituents. The constituents of adsorbents are mainly responsible for the
adsorption of any particular pollutants from aqueous system. In most cases adsorption is reversible due to the weak Van der Waals forces operating
between adsorbate and adsorbent