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CE3610 Environmental

Engineering:
Week 2
Year 3 Semester 2
2015
Shiromi Karunaratne
Email-shiromi.k@sliit.lk
Mobile- 0776368620
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Unit 2-DW
1

the sequel to last week ..


Water sources

in Sri Lanka
Water use and fit-for-purpose treatment

Wastewater

Wastewater collection system; centralised vs decentralised systems, recycling

Guidelines for water and wastewater quality


Resource management of air, water, soil (multimedia)
Air quality management
Solid waste management

History of water supply and sanitation

Waterborne diseases, history and current issues

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Material to be covered
Water Quality: Physical, Chemical and Microbiological
Water Quality and Health
Raw water sources, water treatment and distribution

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Water Quality:
Physical water quality parameters
Chemical water quality parameters and
Microbiological water quality parameters

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Review of water chemistry


Chemistry is the basis of many problems addressed
in environmental engineering, e.g.
design of water and WW treatment processes
remediation of environmental pollution
alkalinity, pH: acid/base reactions
water treatment chemicals to remove impurities
precipitation
oxidation
kinetics how long does the reaction take to occur?

Chapter 5, Davis and Cornwell 5th Ed


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The common term for pH is alkalinity


The pH is an indication for the acidity of a substance. It is
determined by the number of free hydrogen ions (H+) in a
substance.
Acidity is one of the most important properties of water. Water is a
solvent for nearly all ions. The pH serves as an indicator that
compares some of the most water-soluble ions.
The outcome of a pH-measurement is determined by a consideration
between the number of H+ ions and the number of hydroxide (OH-)
ions. When the number of H+ ions equals the number of OH- ions,
the water is neutral. It will than have a pH of about 7.

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Continued.
The pH of water can vary between 0 and 14. When the pH of a
substance is above 7, it is a basic substance. When the pH of a
substance is below 7, it is an acid substance. The further the pH lies
above or below 7, the more basic or acid a solution is.
The pH is a logarithmic factor; when a solution becomes ten times
more acidic, the pH will fall by one unit. When a solution becomes a
hundred times more acidic the pH will fall by two units.

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Mastering the some chemistry will be a great help in


understanding, and solving, environmental
engineering challenges

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Water Chemistry
Physical properties of water:
The basic properties of water relevant to water treatment are density
and viscosity.

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Water Quality: from an environmental engineering


point of view
Impurities in water:
Dissolved substances: A substance which is truly in solution
(homogenous; solvated by the liquid)
Suspended solids are large enough to settle out of solution or
be removed by filtration
Colloidal particles are in the size range between dissolved
substances and suspended particles

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Dissolved substances: definition


Dissolved substances are substances that cannot be removed from
the liquid without a phase change, such as:

distillation
adsorption
Find the definitions by your self
precipitation
gas stripping
liquid extraction
reverse osmosis (membrane filtration with pore size in
ionic size range, ~10)
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Dissolved substances
Can be simple atoms (e.g. charged ions)

Sodium ion: Na+ (cation)


Chloride ion: Cl- (anion)
or molecules dissolved in water through hydrogen bonding
Dissolved gases, e.g. dissolved oxygen O2
Complex molecules, e.g. sugar

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Suspended solids and colloids


Suspended solids
Large enough to be removed by physical methods
Centrifugation
Sedimentation
filtration

Surface charge is the electrical potential difference


between the inner and outer surface of the dispersed
phase in a colloid.

Colloidal substances
Removal by high ultracentrifuge or tight membrane
processes.
Exhibit Tyndall effect (light scattering by particles), ,
reflected light causing turbidity
Both suspended and colloidal particles have a surface
charge, NOT an ionic charge
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Particulates in water

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Effect of water treatment

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Water treatment effectively changes size distribution.


Note much lower overall number of particles in treated
water

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Units for water quality measurements Solutes change the


density of a solution
Weight percent is % in g/kg solution (w/w)
Weight volume is % in g/L of solution (w/v)
For dilute solutions, assume that the density does not change, so
concentrations are expressed in weight/volume (milligrams per litre,
mg/L)
1 % = 10,000 mg/L
Consider example 5.1 P222 Davis and Cornwell

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Molarity, normality, equivalent weight


Molarity is the number of moles per litre of a solution

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E.g. 5.2 Davis and Cornwell


Commercial sulfuric acid comes as a 93% weight % solution.
Find the concentration of the solution in mg/L, molarity and
normality (normality relevant to an acid/base reaction)
H2SO4 has a specific gravity of 1.839 g/cm3

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Chemical reactions relevant to water quality and treatment


Precipitation
e.g. water hardness

Acid/base
e.g. pH correction

Ion association
e.g. environmental processes - heavy metals

Oxidation-reduction
e.g. water chlorination

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Precipitation reactions

Precipitation - dissolved ions reacting to form a solid compound


e.g. Ca2+ + CO32- CaCO3(s)
note that ions in solution are often referred to as a compound
when in fact a compound does not exist, simply the ions (e.g. CaSO4
and NaCl exist in solution as 4 ions)
Ca2+ + SO42- CaSO4(s)
Na+ + Cl- NaCl (s)
The solubility of a compound is given by its solubility constant (Ks)

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Acids and bases


When acids enter the water, the ions will separate. For
instance, hydrogen chloride will separate into hydrogen
and chlorine ions (HCL into H+ + CL-).
Bases also undergo separation of their ions when enter the
water. When sodium hydroxide enters the water it will
separate into sodium and hydroxide ions (NaOH into Na+ +
OH-).

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When an acid substance ends up in water, it will give up a hydrogen ion to the
water. The water will then become acid.
The number of hydrogen ions that the water will receive determines the pH.
When a basic substance enters the water it will take up hydrogen ions.
This will lower the pH of the water.
When a substance is strongly acidic it will give up more H+ ions to the water.
Strong bases will give up more OH-.

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Acid/base reactions

Acid/base acids dissociate to form H+ (hydrogen ion)


(and the conjugate base)

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Rusting
In an oxidation-reduction or redox reaction, one atom or compound will steal
electrons from another atom or compound. A classic example of a redox reaction
is rusting. When rusting happens, oxygen steals electrons from iron. Oxygen gets
reduced while iron gets oxidized.

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Buffers and alkalinity


Buffering capacity of a natural water refers to its ability to
take up acid or base without a pH change.
Alkaline water (pH>7) is different to water having a high
alkalinity!!
Carbonate buffer system important in many aspects of
water and wastewater treatment and environmental
chemistry
Alkalinity is experimentally determined as the sum of
titratable bases to pH 4.5.

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Water Quality Parameters


Sri Lanka Standard Specification for potable water SLS 614 :
Part I : 1983 and SLS 614 : Part II : 1983

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ADWG: Water Quality


Physical
Associated with appearance of water such as turbidity, colour,
temperature, particulate matter, taste and odor
Chemical
Differences are not visible but apparent in more subtle ways
e.g. hardness prevents lathering of soaps and shampoos
Microbiological
Major cause of water-borne diseases
so highest priority is to ensure microbiological quality
Radiological
ADWG: Water Quality
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Turbidity
The presence of suspended material such as clay, silt, finely
divided organic material, plankton, and other particulate
material in water
measured in Nephelometric Turbidity Units (NTU)
Tyndall effect due to light scattering by particles
useful for control of risks of micro-organisms
<1 NTU at time of disinfection
<0.2 and max of 0.5 NTU for control of cryptosporidium,
giardia risk
Turbidity greater than 5 NTU is easily detectable
usually objectionable on aesthetic grounds.
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Colour
True colour (filtered); apparent colour includes
particulates
ADWG <15 Hazen Units
Dissolved organic substances from decaying vegetation
and some inorganic compounds (Fe, Mn)
Dissolved organic carbon (DOC) see later slides
Occasionally excessive blooms of algae or the growth of
aquatic micro-organisms can impart colour
Colour itself is not a he
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Taste and Odour (organoleptic properties)


Can be caused by organic compounds, inorganic salts, or
dissolved gases
Chlorine which is used to disinfect water often imparts a taste
and/or odour
Chlorine can also react with other substances in the water to
indirectly cause taste or odour (e.g. bromide, phenol)
Contaminants, spills (e.g. hydrocarbons)
Cyanobacteria
ADWG: Drinking water should be free from any objectionable
taste and odour at point of use.
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Temperature
Temperature affects taste
10-15oC is most palatable.
Fridge taste???

Above ground water pipes


Effect on microbiological growth

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Chemical
Major ions (majorCharacteristics
components of TDS)

Chloride
Naturally occurring salt, seawater
No health guideline, taste issue at >250mg/L
High Cl- promotes corrosion
Values up to 350mg/L in water supplies, guideline is 250mg/L
Sulfate
Taste effects at >250mg/L; Laxative effects >500 mg/L
Carbonate, bicarbonate
Alkalinity
Sodium
Can affect individuals suffering from heart, kidney problems at >20 mg/L. Aesthetic limit,
180 mg/L
Calcium, Magnesium
Hardness
Potassium

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Chemical Characteristics
pH
6.5-8.5, new cement pipes can increase pH
buffering capacity of water
alkalinity/acidity

Conductivity
an indirect measure of total dissolved salts (TDS)
inverse of ???

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Chemical Characteristics
Trace ions
Fluoride
Excessive fluoride may produce fluorosis (mottling) of teeth, acceptable
limit 0.8 to 1.3 mg/L; ADWG guideline is 1.5 mg/L
Drinking water in much of the developed world is fluoridated to prevent
tooth decay (controversial)
Bromide
Reacts with disinfectants to form disinfection by-products
Interferes with some oxidation reactions in water treatment

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Chemical Characteristics
Metals
Iron: Causes staining of laundry (iron staining), affects the taste of beverages
such as tea and coffee; easily removed by conventional water treatment
Manganese: Brownish color to water and stains laundry when used for washing,
off taste at 0.1 mg/L, Mn is concentrated in biofilms in distribution pipes, can be
removed by oxidation and conventional water treatment
Lead: Seriously damages health, nervous system, especially in children, possible
carcinogen
Occurs in old water pipes (solder)
ADWG value = 0.01 mg/L Prolonged exposure to relatively small quantities may
result in serious illness or death.
Zinc, copper: Detrimental to health, undesirable taste
Arsenic: Lung and urinary bladder cancer; skin pigment changes and scaling,
hyperkeratosis, reduced blood flow to skin, nerve damage
Other heavy metals: Cd, Cr, Ni, Hg, Ag

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Chemical Characteristics
Toxic inorganic substances: Nitrates, cyanides

Toxic organic substances: Pesticides, insecticides, solvents,


pharmaceuticals, endocrine disruptors, industrial chemicals,
petroleum hydrocarbons (usually present in trace quantities
why?)

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Microbiological characteristics
Water for drinking and cooking must be made free from diseasecausing organisms (pathogens).
viruses, bacteria, protozoa (amoeba, cryptosporidium, giardia) and
helminths (worms), cyanobacteria
Origin is either infected human or animal discharge
The specific disease-causing organisms present in water are not
easily identified.
surrogates (indicator organisms) are used to detect contamination
in routine tests total coliforms, thermotolerant coliforms or E.coli
test.

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Protection of drinking water supplies from contamination


Multiple barrier approach

Catchment protection
Water treatment

coagulation (conventional treatment)


filtration (conventional media)
advanced treatment (e.g. ozone for protozoa)

Disinfection

primary disinfection
post-treatment disinfection

Distribution systems

Closed systems
Maintenance of disinfectant residual, redosing of reservoirs and tanks

Multiple barrier approach is guided by circumstances of the


water supply and distribution system, cf Melbourne, Adelaide,
Perth
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Drinking water problems caused by organic carbon

Presence of natural organic matter


Disinfection by-products
Disinfectant decay
Bacterial regrowth

The use of polyelectrolytes as water treatment chemicals


(coagulant aids)

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Water quality problems caused by organic carbon


Accelerates chlorine, chloramine decay
makes the disinfectant less effective
Promotes bacterial regrowth
Reacts with disinfectants to form carcinogenic disinfection byproducts
Binds with ferric ions in water to cause discoloured water
Fouls membranes
Can indirectly lead to production of objectionable odours and
tastes

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Problems caused by dissolved organic carbon (DOC)


For effective disinfection and pathogen control, chemical
disinfectants are used
Chlorine is the most commonly used
Chlorine kills certain bacteria but also stays as a residual to
maintain disinfecting power later.
This characteristic is important to protect any possible accidental or
subsequent contamination that happens in the system
This is compromised when other agents that can degrade the
disinfectant are present in the system
One of the components that decays chlorine is natural organic
matter (NOM). This is measured as dissolved organic carbon (DOC).
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DOC (continued)
Dissolved organic carbon (NOM)

accelerates the decay of chlorine


provides precursors that react with chlorine to form carcinogenic disinfection
by-products, e.g. trihalomethanes (THMs) and haloacetic acids

DOC provides food for micro-organisms to grow in distribution


pipes (biofilms)

these biofilms harbour micro-organisms and also cause decay of chlorine


(especially in small diameter pipes)
sloughing of biofilms causes discoloured water
off odours
nitrification

Therefore DOC (NOM) needs to be removed


water treatment processes

*Decay of chlorine will be demonstrated in the laboratory when you


do the experiment
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Recent research has focused on DOC removal and


characterisation
Organic carbon can be removed by:
Enhanced coagulation
Granular activated carbon

Biologically Activated Carbon (BAC)


Granular activated carbon (non-biological mode)
Powdered Activated Carbon (PAC)
Ion Exchange process such as MIEX
Advanced oxidation processes
Complete removal of organic carbon cost would be exorbitant
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Some properties related to NOM can be measured


as:
Bacterial regrowth:
Biodegradable Dissolved Organic Carbon (BDOC)
Assailable Organic Carbon
Bacterial Regrowth Potential

Disinfection by-products formation:


THM formation potential
NDMA formation potential

Membrane Fouling
Fouling index

Disinfection decay characteristics


Fast and slow reacting agents
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Bacterial Regrowth
Bacterial Regrowth: Growth of bacteria in the treated water
Bacteria grows if
disinfectant concentration is too low or bacteria is resistant
Sufficient food available (organic carbon for heterotrophic bacteria)
and other nutrients (mainly nitrogen or phosphorus).
Other environmental conditions are suitable (e.g. temperature)

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Water Treatment Processes

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Conventional water treatment system


Coagulation: adding and rapidly mixing of chemical

coagulants into the raw water.


Flocculation: slow mixing of the chemicals with the
water to assist in building up particles of floc.
Sedimentation: allow the floc to settle out (gravity)
Filtration: remove almost all of the suspended matter
that remains by passing the water through filters.
Disinfection: destruction or inactivation of waterborne
pathogens.

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Design of Coagulation/Flocculation
Major reason to remove microorganisms and turbidity; enhanced coagulation
to remove DOC
In the fresh water bodies small particles (including organic compounds, colloids
microorganisms etc) exist
usually the particle surfaces are negatively charged

To bring them together and make them settle (to remove by gravity), the
charges must be neutralised. This is achieved by coagulants.

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Colloid dynamics
Colloid stability
Colloids are too small to be trapped in the filter and too small to
settle in a reasonable period of time.
Surface is negatively charged
Colloidal particles repel each other (repulsive interparticle forces)

When the surface charge is larger, the stability is stronger

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Colloid destabilization
Addition of positively charged cations such as Na+1, Ca+2, Mg+2, Al+3, or Fe+3
to destabilise the surface charge of colloids and allow aggregation (flocculation)
into particles

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Coagulation or Flocculation Value of the


Electrolyte
The coagulation of a colloidal solution by an electrolyte does not take
place until the added electrolyte has certain minimum concentration
in the solution.
The minimum amount of an electrolyte (millimoles) that must be
added to one litre of a colloidal solution so as to bring about
complete coagulation or flocculation is called the Coagulation or
Flocculation Value of the Electrolyte.
Thus smaller is the flocculation value of electrolyte, greater is its
coagulation or precipitating power.

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Different electrolytes have different coagulation values.


The coagulation behaviour of various electrolytes was studied
by Hardy and Schultz.
Schultz Law,
Greater the valency of oppositely charged ions of the electrolyte
being added, the faster is coagulation.

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Thus in case of positively charged sol the


coagulating power of anions is in the order of

and in case of negatively charged sols, the


coagulating power of cations is in the order
of Al3+ > Ba2+ > Na+
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Coagulants
A coagulant is a substance (chemical) that is added to the
water to accomplish coagulation
There are three key properties of a coagulant
Trivalent cation
Non-toxic
Insoluble in the neutral pH range

Two common coagulants used are aluminium (Al3+) and ferric


ion (Fe3+)
Coagulant aids- These assist coagulation by creating better
coagulation conditions,
e.g optimum pH,
formation of particulate nuclei,
bridging between small flocs to create bigger flocs.
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Coagulation

Four basic types of Coagulant aids:


(i) pH adjusters: most commonly used

-for lowering pH sulfuric acid [H2SO4]

- for raising pH lime [Ca(OH)2] or soda ash (Na2CO3) or


sodium hydroxide (NaOH; caustic soda)
(ii) Activated silica: produces a stable suspension of particles
that have a negative surface charge. The activated silica can
unite with the positively charged aluminium or with iron flocs,
resulting in a larger, denser floc that settles faster
(iii) Clays: Clays can act much like activated silica in that they
have a slight negative charge and can add weight to the flocs.
Cheaper than AS
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Coagulation
(iv) Polymers:
- Polymers can have a negative charge (anionic), positive
charge (cationic), positive and negative charge
(polyamphotype), or no charge (nonionic)
- Polymers are long-chain carbon compounds of high
molecular weight that have many active sites. The active sites
adhere to flocs, joining them together and producing a larger,
tougher floc that settles better. This process is called
interparticle bridging.

from Bolto and Gregory, 2007,


Water Research, 2301-2324
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Mixing and Flocculation


Rapid mixing
To disperse the chemicals throughout the entire water body
Achieved by injection of chemicals into the most turbulent zone
In a pure water Alum + water Al(OH)3 in 1-7 seconds
In natural water we need to mix with particles before this so
that the intermediary product (Al7(OH)174+) that forms within
0.01-1 second combines with particles to neutralize the particles.

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Determination of optimum operating


conditions

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Flocculation
Bring particles into contact, to collide, stick together and
grow to a size that will readily settle
Accomplished by slow, gentle mixing
Enough mixing must be provided to keep the floc in
suspension
Too much mixing will shear the floc particles and
disperses it

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1. Coagulation
Rapid mixing
Destabilisation of
colloids
Fast mixing to neutralize
charge on colloids before
hydrolysis occurs
2. Adsorption between
particles due to van der
Waals forces
3. Flocculation
Slow mixing
Polyelectrolyte forms
bridges between
particles to form larger
flocs
Shear forces important
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Potential health implications of trace contaminants in


polyelectrolytes
Trace contaminants come from manufacturing processes
Residual monomers, starting materials and reaction byproducts
polyacrylimide and epichlorohydrin/dimethylamine (epi/DMA)
compounds

Suspected carcinogens/mutagens
Some countries (Japan, Switzerland) do not allow the use
of polymers due to the contaminants
Some (West Germany, France, and Canada) have stringent
limits
In US in some states require notification to health
authorities when using these polyelectrolytes
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Practice questions
1. What is DOC?
2. What are the problems associated with DOC?

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Lecture 2: Practice Questions


4. Why do water utilities want to control turbidity to 0.1 NTU?
5. Why are the following compounds controlled in the distribution system
and what are their possible origins?
Iron and Manganese
Aluminium
Copper
Hardness
6. What is the reason for the multi-barrier approach to pollutant removal?
7. Which components of water have the greatest effect on alkalinity?
8. Why is discoloured water an issue in utilities? What are possible causes?
9. Which of the following compounds would you expect to be removed by
the conventional water treatment method of coagulation/flocculation.
Why? Na+; Cl+; finely divided clay particles; a colloidal suspension of dairy
waste; Fe(OH)3 formed from oxidation of groundwater containing reduced
iron; bromide?
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Practice questions (Lecture-2)


10. Charge neutralisation in a coagulation tank is usually
achieved very quickly. Why?
11. What are the primary concerns in drinking water?
12. What properties are needed for a coagulant?
13. From your experimental experience, how much time
should we allow in flocculation?
14. How long did you wait in the lab for sedimentation?

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