2 - WATER QUALITY

2.1

OVERVIEW

Water is essential to life and covers of the surface of the earth

97.3% Oceans, saline lakes and inland seas
2.1% Ice caps, glaciers, atmosphere and soil moisture
0.6% Rivers, freshwater lakes and groundwater
Water is in state of motion as it circulates through the hydrologic cycle
As water is precipitated and travels through the remainder of the cycle, it
picks up impurities
Contact with materials in air and on/or beneath the surface of the earth
Human activities

Figure 2-1: Hydrologic Cycle

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Impurities may be in suspended or dissolved form depending on their size

Figure 2-2: Size Classification of Solids in Water

Water pollution is the presence of impurities in water in quantities and in
nature which impair the use of water for a particular purpose (discharge,
human consumption, recreational, etc.)
Need to know more than just quantity of suspended and dissolved
impurities, must also know physical, chemical and biological characteristics
Water quality parameters include:
Physical water quality parameters
Suspended solids
Turbidity
Colour
Taste and odor
Temperature

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Chemical water quality parameters
Dissolved solids
Alkalinity
Hardness
Fluoride
Metals
Organics
Nutrients
Biological water quality parameters
Pathogens
Pathogen indicators
2.2

PHYSICAL WATER QUALITY PARAMETERS

2.2.1 SUSPENDED SOLIDS

Source
Inorganic or organic particles
Immiscible liquids
Impacts
Aesthetically displeasing
Adsorption sites for chemical and biological agents
Biologically active

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Measurement
Total solids
Filterable solids (suspended solids)
Non-filterable solids (dissolved solids)

2.2.2 TURBIDITY
Source
Erosion of colloidal material
Vegetable fibers
Microorganisms
Impacts
Aesthetically displeasing
Adsorption sites for chemicals and microorganisms
Positively correlated with colour (adsorption of organic compounds)
Treatment is difficult
Measurement
Jackson turbidity units (JTU)
Formazin turbidity units (FTU)
Nephelometry turbidity units (NTU)

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2.2.3 COLOUR
Source
Organic debris
Iron and manganese oxides
Industrial waste
Impacts
Aesthetically displeasing
Unsuitable for laundry and some industrial uses
Organic compounds causing colour may exert a chlorine demand
Problems with organic compounds combined with chlorine
Measurement
Comparison with standardized coloured materials
Spectrophotometric techniques
Samples must be tested within 72 hours of collection
2.2.4 TASTE AND ODOR
Source
Minerals and salts
Metals
Biological reactions
Organics

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Impacts
Aesthetically displeasing
Odor producing organic compounds may be carcinogenic
Measurement
Direct measurement

causative agent is known

Taste and odor causing organics

Human senses

liquid or gas chromatography

taste and smell

TON =

A+ B
A

Table 2-1: TON Corresponding to Sample

Volume Diluted to 200 mL
Sample volume (A),
mL
200
175
150
125
100
75
67
50
40
25
10
2
1

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TON
1.0
1.1
1.3
1.6
2.0
2.7
3.0
4.0
5.0
8.0
20.0
100
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2.2.5 TEMPERATURE
Source
Dissipation of waste heat from industry
Irrigation return flows
Impacts
Increased biological activity
Accelerated algae growth
Decreased dissolved oxygen and other gas concentrations
Increase in reaction rate and solubility of metals and other chemicals
Change in the physical properties of water
2.3

CHEMICAL WATER QUALITY PARAMETERS

2.3.1 TERMINOLOGY
1. Ionic species: Dissolution of inorganic substances
2. Equivalence: Number of atoms that element can hold in combination
or can replace in a reaction

Equivalence of 1ion = valence

3. Equivalent weight: Mass of substance per equivalence

Equivalent Weight =

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4. Mass concentration: Mass of substance per volume of liquid
5. Molarity: Number of moles of substance per volume of liquid
6. Molality: Number of moles of substance per mass weight of liquid
7. Normality: Number of gram equivalent per volume of liquid

Should feel comfortable moving from one set of units to another

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EXAMPLE 2.1: EQUIVALENT CONCENTRATIONS (2-2, 2-3)
How many grams of calcium will be required to combine with 90 g of carbonate
to form calcium carbonate?

What is the equivalent calcium carbonate

concentration of (a) 117 mg/L of NaCl and (b) 2 x 10-3 mol of NaCl?

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2.3.2 BASIC WATER CHEMISTRY
1. Dissociation of water
Under homogeneous equilibrium conditions, pure water dissociates to

H 2 O H + + OH

[ ][ ]
= [10 ][10 ]

K dis = H + OH = 10 14
7

[ ]

pH = log H +
i.e. pH = 7 for pure neutral water

Adding H+ ions leads to pH < 7 acidic

Adding ions that react with H+ (ex. OH-) leads to pH > 7 alkaline

2. Acid-base reactions
Acids and bases dissociate into their individual components in water
The dissociated components can recombine forming new compounds,
thereby neutralizing the reaction

H 2 SO4 + 2 NaOH Na 2 SO4 + 2 H 2 O

2 H + + SO42 + 2 Na + 2 OH 2H 2 O + 2 Na + + SO42
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3. Dissolution and precipitation
Many solid substances will ionize or dissociate readily into their ionic
components in water
Conversely, ionic components can recombine into their solid state or
form a precipitate
At equilibrium, the rate of dissolution will equal the rate of
precipitation
An equilibrium constant exists for a given substance in pure water for
a specific temperature which is defined as

Ax B y xA + yB

[ A] x [ B] y = K

[A B ]
x

A solubility product also exists for ion pairs

If the concentration of either ion is increased such that the solubility
product is exceeded, precipitation will occur to maintain equilibrium

[ A] x [ B] y = K sp

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EXAMPLE 2.2: EQUILIBRIUM CONCENTRATIONS (2-4)
The solubility product for the dissociation of Mg(OH)2 is shown in the
following table as 9 x 10-12. Determine the concentration of Mg2+ and OH- at
equilibrium, expressed as milligrams per liter of CaCO3.

Table 2-2: Solubility Product of Selected Ion Pairs

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2.3.3 TOTAL DISSOLVED SOLIDS
In wastewater, this is an approximate measurement, however for potable,
industrial and agricultural uses, need more information about composition
cations = anions to preserve electroneutrality
Source
Minerals
Metals
Gases (organic and inorganic)
Vegetation decay
Organic chemicals
Impacts
Colour
Taste and odor
Chemical toxicity
Chemical reactions yielding more hazardous substances than parent
compound (ex. carcinogens)
Pure water attacks pipes and plumbing
Measurement
Total dissolved solids (organic vs. inorganic)
Specific conductance test

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filtration and heating

approximate analysis

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EXAMPLE 2.3: ION BALANCE (2-5)
Tests for common ions are run on a sample of water and the results are shown
below. If a 10 percent error in the balance is acceptable, should the analysis be
considered complete.

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Ca2+ = 55 mg/L

HCO3- = 250 mg/L

Mg2+ = 18 mg/L

SO42- = 60 mg/L

Na+ = 98 mg/L

Cl- = 89 mg/L

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2.3.4 ALKALINITY
Presence of ions that will neutralize H+ ions
Source
Dissolution of mineral substances in soil and atmosphere
Detergents, fertilizers and insecticides
Microbial decomposition of organic materials
CO32-, HCO3-, OH-, HSiO3-, H2BO3-, HPO42-, H2PO4-, HS- and NH3

OH + H + H 2O
CO32 + H + HCO3
HCO3 + H + H 2CO3
Because of these reactions, alkalinity is usually expressed as mg/L as CaCO3

Figure 2-3: Alkalinity Species vs. pH

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Impacts
High alkalinity causes bitter tasting water
Alkalinity plus certain cations form precipitates that can foil water
systems
Measurement
H2SO4 titration
PH indicators
Phenolphthalin
Bromocreosol/green + methyl red
Methyl orange
Forms of alkalinity can be identified by the following
P + M all alkalinity is OH P = M/2 all alkalinity is CO32 P = 0 initial pH <8.3 but > 7.0 all alkalinity is HCO3 P < M/2 alkalinity is predominantly CO32- and HCO3 P > M/2 alkalinity is predominantly OH- and CO32-

Figure 2-4: Alkalinity Titration Curve

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EXAMPLE 2.4: ALKALINITY (2-6, 2-7)
A 200 mL sample of water has an initial pH of 10. Thirty milliliters of 0.02N
H2SO4 is required to titrate the sample to pH 4.5. What is the total alkalinity of
the water in milligrams per liter as CaCO3.

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2.3.5 ACIDITY
Presence of CO2 and other acids in solution
Source
CO2 acidity
Presence of strong inorganic acids
Impacts
Pipe damage due to corrosion
Habitat modifications
Measurement
NaOH titration
PH indication

phenolphthalein

2.3.6 HARDNESS
Presence of multivalent ions (mainly divalent) in water, often termed
carbonate and non-carbonate hardness depending on the ions present
Definition of hardness
Very hard water > 300 mg/L
Hard water 150-300 mg/L
Moderate hardness 50-150 mg/L
Soft water < 50 mg/L
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Source
Ca2+ and Mg2+
Fe2+, Mn2+, Sr2+ and Al3+
Impacts
Excess soap consumption lack of lather
Precipitate formation scale
Staining of clothing, dishes, sinks, etc.
Mg hardness can have a laxative effect
Hard water is beneficial to health
Taste
Measurement
Spectrophotometric techniques
Titration with EDTA and Eriochrome black T indicator
2.3.7 FLUORIDE
Source
Sedimentary and igneous rocks
Impacts
Small quantities beneficial 1.0 mg/L
Large quantities toxic and causes the discoloration of teeth 2.0
mg/L
Some fluorosis 5.0 mg/L

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2.3.8 METALS
Source
Hardness causing Mg2+ and Ca2+
Commonly found non-toxic metals Na+, Fe2+, Al3+, Cu2+, Zn2+, Mn2+
Toxic metals As, Ba, Co, Cr, Pb, Hg, Ag
Impacts
Underlined heavy metals are cumulative toxins concentrated up the
food chain
Excessive Na+ salts bitter taste
Fe and Mn colour problems at low concentrations
Slime growth (taste and odour problem) some organisms use Fe and
Mn as food energy source
2.3.9 ORGANICS
Source
Biodegradable
Starches
Fats
Proteins
Alcohols
Acids
Aldehydes
Esters
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Non-biodegradable (complex molecules or strong bonds)
Tannic and lignic acids
Cellulose
Phenols
Polysaccharides
Benzene and other compounds with benzene rings
Pesticides
Impacts
Some non-biodegradable organics are toxic and cumulative through
the food chain
Exert a demand in oxygen on receiving waters
Measurement

Biodegradable Organics + microorg + O 2 CO 2 + H 2 O + microorg

BOD5 test

All Organics + Acid + K 2 Cr2 O 7 CO 2 + H 2 O + Cr 2 + + ...

COD test
Individual components must be identified and quantified through gas
chromatography

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2.3.10 NUTRIENTS
Carbon, nitrogen and phosphorus are the basic ingredients of the food
requirements of aquatic biological species
Source
Carbon
Atmospheric CO2
Alkalinity
Organics
Nitrogen
Organics
Ammonia
Nitrite
Nitrate
Gaseous nitrogen (79% in atmosphere)
Phosphorus
Organics
Phosphates
Fertilizers
Impacts
Some non-biodegradable organics are toxic and cumulative through
the food chain
Exert a demand in oxygen on receiving waters

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2.4

BIOLOGICAL WATER QUALITY PARAMETERS

2.4.1 PATHOGENS
Organisms capable of infecting or transmitting disease to humans
Bacteria 0.5 - 5 m
Single celled organisms
Reproduce by binary fission every 5 to 20 minutes
Utilize soluble food
Require energy and carbon for synthesis
Heterotrophic bacteria utilize an organic source of carbon and energy
Autotrophic bacteria utilize CO2 as their source of carbon and an
inorganic source of energy
1. Heterotrophic Bacteria
Aerobic

Organics + Dissolved Oxygen CO 2 + H 2 O + Energy

Anaerobic

Organics + NO 3 CO 2 + N 2 + Energy
Organics + SO 24- CO 2 + H 2 S + Energy
Organics Organic Acids + CO 2 + H 2 O + Energy
Facultative: use dissolved oxygen when available, can also use
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2. Autotrophic Bacteria
Nitrifying bacteria

NH 3 + O 2 NO 2 + Energy
NO -2 + O 2 NO 3 + Energy
Sulphur bacteria

H 2 S + O 2 H 2 SO 4 + Energy
Iron bacteria

Fe 2 + + O 2 Fe 3+ + Energy
Viruses 20 100 nm
Nucleic acid and protein
Replicate in other host cells (parasites)
Smallest biological structures known to contain all the genetic
material necessary for their own production
Protozoa 10-50 m
Single celled organisms
Multiply by binary fission
Use solid organic material as food (bacteria and algae)
Helminths
Flat worm infecting human internal organs such as heart, lungs, veins
and liver
Parasitic worms

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2.4.2 WATERBORNE DISEASE
Pathogens found in human feces
Table 2-3: Common Waterborne Diseases
Pathogens
Disease
Bacteria
Salmonella typhi

Typhoid fever

Vibrio cholera

Cholera

Shigella dysenteriae

Bacillary dysentery

Viruses
Poliomyelitis

Polio

Unknown

Infectious hepatitis

Protozoa
Entamaeba hystolytica

Amebic dysentery

Giardia lamblia

Giardia enteritis

Helminths
Schistosoma

Bilharziasis

2.4.3 INDICATOR ORGANISMS

Very difficult to devise practical analytical tests for all pathogens
Analysis for all known pathogens would be time consuming and costly
Thus, must look for the presence of an indicator organisms whose presence
would suggest the possibility that pathogens may be present

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An ideal organism is
1. Applicable to all types of waters
2. Always present when pathogens are present
3. Always absent when pathogens are absent
4. Easily detectable by routine quantitative analysis
5. Not a pathogen itself
No pathogen indicator can meet all of these conditions
However, most pathogens are introduced through fecal (of warm-blooded
animals, including humans) contamination of water
Thus, anything that is closely associated with feces and that meets
conditions (1), (4) and (5) would be a good start
Fecal coliform group of bacteria which includes Escherichia coli
Not a pathogen itself
Exclusive to intestinal tract (and feces) of warm-blooded animals
Longer survival time outside the body than most pathogens
Excreted in large numbers
Another coliform group is native to soil and decaying vegetation
Coliform bacteria group is aerobic, non-spore forming, gram-stain, negative
rods, ferments lactose with gas production within 48 hrs

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Table 2-4: Indicator Organisms Used in Establishing
Performance Criteria for Various Water Uses

Water use
Drinking water
Freshwater recreation

Indicator organism
Total coliform
Fecal coliform
E. coli
Enterococci
Saltwater recreation
Fecal coliform
Total coliform
Enterococci
Shellfish growing areas
Total coliform
Fecal coliform
Agricultural irrigation
Total coliform
(for reclaimed water)
Wastewater effluent disinfection Total coliform
Fecal coliform

2.4.4 TESTING FOR PRESENCE OF COLIFORM BACTERIA

Filtration Membrane filter technologies
Filter water sample
Incubate the filter membrane on selective media to promote growth of
coliform bacteria fecal or total
Count number of colonies under microscope
For drinking water coliform count should be < 1/100 mL of water
Thus for 10 mL tests, no more than 10% should be positive

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Multiple-tube fermentation
Inoculate sugar solution (lactose) and ferment at 35C and look for
gas production from fermentation
1. Presumptive test: coliform bacteria can ferment lactose generating
gas
Presume coliform present if gas results form incubation
2. Confirmed test: some media support growth of coliform, but
suppress growth of other organisms
Confirm presence of coliform by growing culture from
presumptive test on selective media
3. Completed test: verify if the colonies grown in the confirm test can
ferment lactose (i.e. verify if they are coliform)
Involves microscopic examination by gram-staining technique
Short rods with no spores pink stain coliform presents
Colonies growing on Endo or EMB agar plates are transferred
on nutrient agar
An alternative to looking for gas fermentation is to streak Endo Agar in petri
dishes and look for growth
Typical coliform colonies

Green sheen (confirm)

Atypical coliform colonies Light coloured colonies without dark centers

on green sheen (does not confirm nor deny)
Absence of growth
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Figure 2-5: Procedure for Running Total Coliform Analysis

by MultipleTube Fermentation Method
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2.4.5 PRINCIPLES OF MULTIPLE-TUBE FERMENTATION METHODS
Promote fermentation of lactose by incubating at elevated temperatures of 35
to 45C for 24 to 48 hours
Looking for signs of gas evolution in tubes or growth of colonies on nutrient
media (depending on method)
This gives YES/NO
How is coliform count arrived at?
6 levels of dilution 10 fold each time
5 replicates for each dilution
The number of positive tests out of 5 at successive dilution levels gives an
indication of Most Probable Number of coliform
Principle: as we dilute the sample 10 fold each time, the chances of a
positive test are decreasing
Statistical sampling theory then gives us the MPN and 95%
confidence limit
i.e. range within which 95% of all tests should fall
REMEMBER:
E. coli is not a pathogen itself
Its presence is not positive proof that pathogens exist
Its presence suggests a contamination by feces, possibly fecal
pathogens

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Figure 2-6: Illustration of Methods Used to Obtain Bacterial Counts

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EXAMPLE 2.5: MOST PROBABLE NUMBER OF COLIFORM (2-10)
A standard multiple-tube fermentation test is run on a sample of water from a
surface stream. The results of the analysis for the confirmed test are shown
below. Determine the most probable number of coliform organisms.
Size of Sample (mL)

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No. Positive

No. Negative

10

0.1

0.01

0.001

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2.5

WATER QUALITY REQUIREMENTS

Water Quality requirements will vary depending on intended water use

Drinking water
Recreational
Agricultural, fish and wildlife
Industrial, power generation
Water quality standards are set by government agencies
Federal (Environment Canada
Provincial (MOEE)
Municipal

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