Faculty of Civil & Environmental Engineering
ENVIRONMENTAL
ENGINEERING
BFC32403
CHAPTER 1
WATER QUALITY
Topics on Water Quality (9
hours lecture)
1.1 Introduction to Water Quality
1.2 Interim National Water Quality Standards
1.3 Water Quality Parameters (Physical,
Chemical & Microbiology)
1.4 Sampling (River Monitoring)
1.5 DO Sag Curve
1.1 Introduction to Water
Quality
1.1.1 Beneficial Water Uses
Municipal Uses
Agricultural Uses
Industrial Uses
Rural Uses
1.1 Introduction to Water
Quality
1.1.2 Water Resources
Snow / Rain
Surface Water
i) Watershed
ii) Lake /River /Reservoir
Groundwater
o Sub-surface water, or groundwater, is fresh water located in the pore space
of soil and rocks.
o Flowing within aquifers below the water table.
Desalination
o Saline water is converted to fresh water.
1.1 Introduction to Water
Quality
1.1.3 Definition
Is the technical term that is based upon the characteristics of water in relation to
guideline values of what is suitable for human consumption and for all usual
domestic purpose.
1.1.4 Objective
To control the discharge of pollutants so that water quality is not degraded to an
unacceptable extent below the natural background level.
1.1 Introduction to Water
Quality
1.1.5 Water Quality Parameters
• Are the natural and man-made chemical, biological and microbiological
characteristics of rivers, lakes and groundwater.
• It provides important information about the health of a water body.
- Are the natural and man-made chemical, biological and microbiological
characteristics of rivers, lakes and groundwater.
- It provides important information about the health of a water body.
} Are used to find out if the quality water is good enough for drinking
water, recreation, irrigation and aquatic life.
1.1 Introduction to Water
Quality
Two types of water pollution:
POINT SOURCE NON-POINT SOURCE
pollution flowing from a pollution collected by rain
single and identifiable source falling over a larger watershed
such as discharge pipe from a which is then carried by runoff
factory, roadway, or leaking to a nearby lake or stream, or
underground storage tank by infiltration into the
groundwater
Point Source Pollution
Point Source Pollution
Hazardous and toxic materials from
manufacturing and industry
discharged directly into the water -
usually through a pipe or a leaky
underground tank
o Oil and gasoline
o Solvents (toxic liquids)
o Toxins and poisons
o Heavy metals (arsenic, lead,
mercury, etc.)
o THERMAL POLLUTION -
heated water causes the dissolved
oxygen (DO) content in a body of
water to decrease - can result in
fish kills
Non-Point Source Pollution
A HARDER PROBLEM TO SOLVE
Non-Point Source Pollution - THE CHANGING URBAN
LANDSCAPE
• Changing the landscape changes
the amount of runoff in a
watershed
• NON-POINT SOURCE
POLLUTION is pollutants being
collected by rainwater falling
over a large watershed and
carried directly to a river, lake or
stream
• Gas, oil, chemicals, detergents
containing phosphorus, trash and
other pollutants collected off
driveways, roads and city streets
flow directly down drains and
storm sewers to a nearby body of
water untreated
Non-Point Source Pollution - THE CHANGING RURAL
LANDSCAPE
MODERN FARMING IS A MAJOR
SOURCE OF NON-POINT SOURCE
POLLUTION
o Pesticides (bug killer) and herbicides
(weed killer) can wash into nearby lakes
and rivers
o Crop fields, especially after harvest, can
wash large amounts of dirt and sediment
into nearby lakes and rivers
o Animal waste and manure can be a
source of nutrients and harmful bacteria
o Fertilizer can be a source of nutrients,
such as nitrogen and phosphorus,
entering nearby lakes and rivers leading
to the serious problem of
EUTROPHICATION
BIGGER FARM = BIGGER PROBLEM
Non-Point Source Pollution - CONSTRUCTION & MINING
• Clear-cutting trees and plowing
a field to create a mining or
construction site can be a major
source of non-point source
pollutants
• Without the trees and the plants in
the field to hold the soil in place,
large amounts of dirt and sediment
can be discharged into a nearby
lake or stream
• Can be a source of toxic chemicals,
acids, or heavy metals used in the
construction or mining process
1.2 Interim National Water
Quality Standards (INWQS)
INWQS used for classification of
rivers or river segments based on 5
classes of water quality.
INWQS helps Department of
Environment (DOE) to identify
problem areas & develop
appropriate strategies for water
quality management.
It is important to maintain high
quality level for natural water.
Therefore, the DOE has set up the
minimum quality standard that
reflects its beneficial uses.
Interim National Water Quality Standards (INWQS)
Parameter Classes
Unit
I IIA IIB III IV V
Ammoniacal
mg/L 0.1 0.3 0.3 0.9 2.7 >2.7
Nitrogen
Biochemical
mg/L 1 3 3 6 12 >12
Oxygen Demand
Chemical Oxygen
mg/L 10 25 35 50 100 >100
Demand
Dissolved Oxygen mg/L 7 5-7 5-7 5-9 5-9 -
pH - 6.5-8.5 6-9 6-9 5-9 5-9 -
Color TCU 15 150 150 - - -
Electrical
μS/cm 1000 1000 - - 6000 -
Conductivity*
Floatables - N N N - - -
Odor - N N N - - -
Salinity % 0.5 1 - - 2 -
Taste - N N N - - -
Total Dissolve
mg/L 500 1000 - - 4000 -
Solid
Total Suspended
mg/L 25 50 50 150 300 300
Solid
Normal Normal
Temperature oC - - - -
+ 2 oC + 2 oC
Turbidity NTU 5 50 50 - - -
Count/ 5000 5000
Faecel Coliform** 10 100 400 -
100ml (20000)a (20000)a
Count/
Total Coliform 100 5000 5000 50000 50000 >50000
100ml
Source: Environmental Quality Report 2010
Classification of Water Based on INWQS
Class
Parameter Unit
I II III IV V
Ammoniacal Nitrogen mg/L <0.1 0.1-0.3 0.3-0.9 0.9-2.7 >2.7
Biochemical Oxygen Demand
mg/L <1 1-3 3-6 6-12 >12
Chemical Oxygen Demand mg/L <10 10-25 25-50 50-100 >100
Dissolved oxygen mg/L >7 5-7 3-5 1-3 <1
pH - >7 6-7 5-6 <5 >5
Total Suspended Solid mg/L <25 25-50 50-150 150-300 >300
Water Classes and Uses
Class Uses
I Conservation of natural environment.
Water Supply I – Practically no treatment necessary.
Fishery I – Very sensitive aquatic species.
IIA Water Supply II – Conventional treatment required.
Fishery II – Sensitive aquatic species.
IIB Recreational use with body contact.
III Water Supply III – Extensive treatment required.
Fishery III – Common, of economic value and tolerant species; livestock
drinking.
IV Irrigation
V None of the above
Source: Environmental Quality Report 2010
1.3 Water Quality Parameters
1. Physical 2. Chemical
parameters parameters
3. Biological
parameters
1.3 Water Quality Parameters
1.3.1 Physical Parameter
• This parameters respond to the sense of sight, touch, taste or smell
1.3 Water Quality Parameters
1.3.1 Physical Parameter - SOLIDS
1.3 Water Quality Parameters
1.3.1 Physical Parameter - SOLIDS
Total Solid (TS) are the total of all solids in a water
sample. They include the total suspended solids, total
dissolved solids, and volatile suspended solids.
Dissolved solids (DS) = calcium, chlorides, nitrate,
phosphorus, iron, sulfur, and other ions and particles
that will pass through a 2 micron filter.
Suspended solids (SS) = silt, clay, plankton, algae,
fine organic debris, and other particulate matter that
will not pass through a 2-micron filter
Interrelationships
of solids
Determination of Suspended Solids
1.3 Water Quality Parameters
1.3.1 Physical Parameter - SOLIDS
Example 1
The following test were obtained for a wastewater taken from a headwork to a WTP.
All the test were performed using sample size of 50 mL. Determine the
concentration of total solids (TS), total volatile solids (TVS), suspende solids (SS),
volatile suspended solids (VSS), total dissolved solids (TDS) and volatile dissolved
solids.
Data:
Tare mass of evaporating dish = 53.5433 g
Mass of evaporating dish + residue after evaporation at 105oC =53.5794 g
Mass of evaporating dish + residue after ignition at 550oC = 53.5625 g
Tare mass of Whatman GF/C filter after drying at 105oC = 1.5433 g
Mass of Whatman GF/C filter + residue after drying at 105oC = 1.5554 g
Mass of Whatman GF/C filter + residue after ignition at 550oC = 1.5476 g
1.3 Water Quality Parameters
1.3.1 Physical Parameter - SOLIDS
Solution:
1) Determine total solids (TS)
TS = (mass of dish + residue, g)-(mass of dish, g)
sample size, Liter
TS = ((53.5794-53.5433) g)(103 mg/g) = 722 mg/L
0.050 L
2) Determine total volatile solids (TVS)
TVS = (mass of dish + residue, g)-(mass of dish + residue after ignition, g)
sample size, Liter
TVS = ((53.5794-53.5625) g)(103 mg/g) = 338 mg/L
0.050 L
1.3 Water Quality Parameters
1.3.1 Physical Parameter - SOLIDS
3. Determine total suspended solids (TSS)
TS = (residue on filter after drying, g)-(tare mass of filter after drying, g)
sample size, Liter
TS = ((1.5554-1.5433) g)(103 mg/g) = 242 mg/L
0.050 L
4. Determine total volatile solids (TVS)
TVS = (residue on filter after drying, g)-(residue on filter after ignition, g)
sample size, Liter
TVS = ((1.5554-1.5476) g)(103 mg/g) = 156 mg/L
0.050 L
1.3 Water Quality Parameters
1.3.1 Physical Parameter - TURBIDITY
• Is a measure of the amount of particulate matter that is
suspended in water or the measurement of water clarity.
• Measured by Turbidity meter.
• Unit-NTU (Nephlometric Turbidity Unit)
• Water that has high turbidity appears cloudy / opaque .
• High turbidity can cause increased of water temperature
and decreased DO
WHY???
1.3 Water Quality Parameters
1.3.1 Physical Parameter - TURBIDITY
It is because…
• More suspended particles will absorb more heat from solar
radiation than water molecules will. This heat is then
transferred to the surrounding water by conduction.
• Such particles (SS – clay, silt, finely divided organic
material, plankton) can also prevent sunlight from reaching
plants below surface hence decrease the rate of
photosynthesis. So, less O2 is produced by plant
1.3 Water Quality Parameters
1.3.1 Physical Parameter - TEMPERATURE
• It is a major factor in determining which species are present in the stream
• Temperature will impacts:
(i) the rates of metabolism and growth of aquatic organism
(ii) rate of plant photosynthesis
(iii) solubility of O2 in water [0C,
DO = 14.6 mg/l; 20C, DO = 9.1 mg/l]
(iv) organism’s sensitivity to disease,
parasites and toxic materials
• Temperature affects rate of chemical and microbiological reactions
• The most suitable drinking waters are consistently cool and do not have
temperature fluctuations of more than a few degrees
• Groundwater and surface water from mountain area generally meet these
criteria
1.3 Water Quality Parameters
1.3.2 Chemical Parameter
pH Hardness
Nitrogen & Phosphorus
Alkalinity
Chemical Oxygen
Demand (COD)
Biochemical Oxygen
Demand (BOD)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - pH
• affects chemical and biological reactions
• It is a measure of the concentration of hydrogen ions
[H+]
• The term pH was derived from the manner in which the
hydrogen ion concentration is calculated
pH= -log[H+]
pH=1 :
[H+]=1 x 10-1 moles/liter (acidic)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - pH
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – pH Acid – Base Concentrations
10-1
pH = 3 pH = 11
concentration (moles/L)
H3O+ OH-
pH = 7
10-7
H3O+ OH-
OH- H3O+
10-14
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]
acidic neutral basic
Timberlake, Chemistry 7th Edition, page 332
solution solution solution
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - pH
Example 1
Calculate the concentration of hydrogen ion (H+) for a water sample with pH of 10.
pH = -log [H+]
10 = -log [H+]
Therefore, [H+]= antilog -10
= 10-10 mol/liter
Example 2
Calculate the pH value of a water sample which has hydrogen ion concentration of 1 x 10-6.4
mol/liter.
pH = -log [H+]
= -log (1 x 10-6.4)
= -[log 1 + log 10-6.4]
= -[0 + (-6.4)log 10]
= 6.4
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - pH
Example 3
Find the hydrogen ion ( H+) concentration and the hydroxide ion (OH)
concentration in tomato juice having a pH of 4.1. Prepare answer in unit mol/L
and mg/L
pH + pOH = 14
pH = -log [H+] pOH = 14-4.1 = 9.9
4.1 = -log [H+] pOH = -log [OH-]
Therefore, 9.9 = -log [OH-]
[H+] = antilog -4.1
= 10-4.1 mol/L Therefore,
[OH-] = antilog -9.9
= 10-9.9 mol/L
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - pH
mol/L to mg/L
• H+ == atomic weight = 1 g/mol ( refer Periodic Table)
• OH- == atomic weight = 17 g/mol (refer Periodic Table)
• mol/L (conc. ) x g/mol (atomic weight) x 1000mg/1g = mg/L
---------------------------------------------------------------------------------------------------------------------------
Therefore,
[H+] = 10-4.1 mol/L
= 10-4.1 mol/L x g/mol (1) x 1000mg/1g
= 0.0794 mg/L
[OH-] = 10-9.9 mol/L
= 10-9.9 mol/L x g/mol (17) x 1000mg/1g
= 2.14 x 10-6 mg/L
1.3 Water Quality Parameters
1.3.2 Chemical Parameter - Hardness
Stream water hardness is the total concentration of cations,
specifically calcium (Ca2+ ),magnesium (Mg2+), iron (Fe2+),
manganese (Mn2+) in the water.
Water rich in these cations is said to be ‘hard’. Stream water
hardness reflects the geology of the catchment area.
Sometimes it also provides a measure of the influence of
human activity
For instance, acid mine drainage often results in the release of
iron into a stream. The iron produces extraordinarily high
hardness which is a useful water quality indicator.
Hardness is a reflection of the amount of calcium and
magnesium entering the stream through the weathering of rock
such as limestone (CaCO3).
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness (Carbonate hardness)
• Source: Combination of Ca and Mg ions with ions of CO32-, or
HCO3-.
• These carbonate components can be eliminated by softening
methods such as boiling, or by adding lime
• When the carbonate components settled then the water have
become soft water.
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness (Carbonate hardness)
Ca 2+ Mg 2+ + HCO3- CO32-
Ca(HCO3)2 CaCO3 Mg(HCO3)2 MgCO3
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness (Non- Carbonate hardness)
Ca 2+ Mg 2+ Cl- SO42- NO3-
CaCl2 CaSO4 Ca(NO3)2 MgCl2 MgSO4 Mg(NO3)2
Source: Combinations of Ca and Mg ions with ions of Cl-, SO42-, or NO3-.
The non-carbonate ions cannot be eliminated by ordinary softening methods as
done on carbonate hardness.
Usually elimination of non carbonate hardness is done chemically by adding
softening soda (soda ash or sodium carbonate)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness (Total hardness)
• Because calcium and magnesium predominate, it is often
convenient to define total hardness as the sum of Calcium and
Magnesium elements.
• Therefore Total Hardness as CaCO3 :
Total Hardness = Ca2+ + Mg2+
• Total hardness is measured in mg/L CaCO3:
mg/L material X = Conc. of X (mg/L) (50 mg CaCO3/meq)
as CaCO3 (Equivalent wt of X (mg/meq))
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness (Total hardness)
• Total hardness is broken down into two components:
(1) that associated with the HCO3- anion (carbonate
hardness, CH) and
(2) that associated with other anions (non-carbonate
hardness, CH).
Total hardness, then may also be defined as:
TH= CH + NCH
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
• Water hardness is stated in equivalent unit of CaCO3
• Hardness classification:
Hardness Concentration Range
(mg/L eq CaCO3)
Soft <50
Medium 50-150
Hard 150-300
Very Hard >300
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
Example 1
Find the equivalent weight (EW) of each of the following:
i) Ca2+, ii) CO32-, and iii) CaCO3.
Solution:
Equivalent weight was defined as
EW = [atomic or molecular weight] / [n] (valence)
units: grams/equivalent (g/eq) or milligrams/milliequivalent (mg/meq)
i) For calcium, n=2 (valence or oxidation state in water).
Atomic weight = 40.08 ( refer Periodic table)
Therefore the EW is then
EW of Ca2+ = 40.08/2 = 20.04 g/eq or mg/meq
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
ii) For carbonate ion (CO32-), the oxidation state of 2- is used for n since the
base CO32- can potentially accept 2H+. The molecular weight (MW) is 60.01.
Therefore,
EW of CO32- = 60.01/2 = 30 g/eq or mg/meq
iii) In CaCO3, n=2 since it would take 2H+ to replace the cation (Ca2+) to
form carbonic acid, H2CO3. The MW of CaCO3 is 100.
Therefore,
EW of CaCO3 = 100/2 = 50 g/eq or mg/meq
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
Example 2
A sample of groundwater has 100 mg/L of Ca2+ and 10 mg/L of Mg2+.
Express it hardness in unit of mg/L as CaCO3.
Solution: Since;
mg/L of X = concentration of X (mg/L) (50 mg CaCO3/meq)
as CaCO3 (equivalent weight of X (mg/meq))
1. Convert Ca2+ and Mg2+ to mg/L as CaCO3
Ca2+ : MW = 40, n=2, EW=40/2 = 20 g/eq or mg/meq
Mg2+ : MW = 24.3, n=2, EW=24.3/2 = 12.2 g/eq or mg/meq
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
2. Now, find the mg/L as CaCO3 of cations
Use formula;
mg/L of X = concentration of X (mg/L) (50 mg CaCO3/meq)
as CaCO3 (equivalent weight of X (mg/meq))
=>Ca2+ = 100 x 50 = 250 mg/L as CaCO3
20
=>Mg2+ = 10 x 50 = 41 mg/L as CaCO3
12.2
Total Carbonate Hardness = Ca2+ + Mg2+
= 250 + 41
= 291 mg/L as CaCO3
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Hardness
Example 3
From the water analysis below determine the total hardness of the water sample given the following
water composition; (50/(40/2))
Ca2+ = 95.2 mg/L HCO3 = 241.49 mg/L
Mg2+ = 13.44 mg/L SO42- = 53.77 mg/L
Na+ = 25.76 mg/LCl- = 67.81 mg/L
Ion mg/L EW CaCO3/ mg/L as CaCO3
as ion EW ion
Solution:
EW CaCO3 = 50 mg/meq Ca2+ 95.20 2.50 238.00
EW ion = Atomic wt Mg2+ 13.44 4.12 55.37
valence (50/(24.3/2))
Na+ 25.76 2.18 56.16
HCO3 241.46 0.82 198.00
SO42- 53.77 1.04 55.92 (50/61)
Cl- 67.81 1.41 95.61
Total Hardness (TH) = 293.37 mg/L as CaCO3
(50/(96/2))
Carbonate Hardness (CH) = 198.00 as CaCO3
Non-carbonate Hardness (NCH) = TH-CH = 95.37 mg/L as CaCO3
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
• Alkalinity is defined as the quantity of ions in water that will
react to neutralise hydrogen ions (H+). Alkilinity is thus the
measure of the ability of water to neutralise acids.
• Therefore alkalinity is the buffer capacity of the water to
remain neutral.
• The carbonate species that contribute to alkalinity are:
• Hydroxyl ions (OH-), Carbonate ions (CO32-), Bicarbonate
ions (HCO3-),
Alkalinity (mol/L) = [HCO3-] + 2[CO32-] + [OH-] – [H+]
Alkalinity (mg/L as CaCO3) = (HCO3-) + (CO32-) + (OH-) –
(H+)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
• Is measured to determine the ability of a stream to resist changes in
pH.
• Alkalinity results from the dissolution of calcium carbonate
(CaCO3) from limestone bedrock which is eroded during the natural
processes of weathering
• Alkalinity values of 20-200 ppm are common in freshwater
ecosystems. Alkalinity levels below 10 ppm indicate poorly
buffered streams.
• In large quantities, alkalinity imparts bitter taste to water.
• Reactions that can occur between alkaline water and certain ions
resulting in precipitation of solids which can foul pipes and other
water system appurtenances.
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
Example 1
A sample of water having a pH of 7.2 has the following concentrations
of ions:
Ca2+ 40 mg/L Mg2+ 10 mg/L
Na+ 11.8 mg/L K+ 7.0 mg/L
HCO3- 110 mg/L SO42- 67.2 mg/L
Cl- 11 mg/L
Calculate the TH, CH, NCH, Alkalinity, and construct a bar chart of the
constituents.
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
Solution
1 2 3 4 5 6 7
Ion Conc. M.W. n
Eq. Wt. Conc. Conc. of X
(mg/L) (mg/mole) (mg/meq) (meq/L) mg/L as CaCO3
(3/4) (2/5) (6 x 50)
Ca2+ 40.0 40.1 2 20.05 1.995 99.8*
Mg2+ 10.0 24.3 2 12.15 0.823 41.2
Na+ 11.8 23.0 1 23.0 0.513 25.7
K+ 7.0 39.1 1 39.1 0.179 8.95
HCO3- 110.0 61.0 1 61.0 1.803 90.2
SO42- 67.2 96.1 2 48.05 1.398 69.9
Cl- 11.0 35.5 1 35.5 0.031 15.5
mg/L of X as CaCO3 = concentration of X (mg/L) (50 mg CaCO3/meq)
(equivalent weight of X (mg/meq))
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
Sample Calculation:
Conc in meq/L ( refer to Ca2+)
meg/L = mg/L x meq/mg
= 40.0 /20.05
= 1.995
Concentration of Ca2+ in mg/L as CaCO3
= (Concentration in meq/L)*(Equivalent Weight of CaCO3)
= (1.995 meq/L) X (50 mg/meq)
= 99.8 mg/L as CaCO3
Check Solution
(Cation) s = (Anion)s
175.6 = 175.6
Note: to within 10% mg/L as CaCO3
Total Hardness
= of multivalent cations
= (Ca2+) + (Mg2+)
= 99.8 + 41.2
= 141 mg/L as CaCO3
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
• Alkalinity = (HCO32-) + (CO32-) + (OH-) - (H+)
Alkalinity (HCO32-) = (1.80 x 10-3) eq/L
Alkalinity = (1.80 x 10-3 eq/L)(50 g/eq)(1000 mg/g)
= 90.1 mg/L as CaCO3
• Carbonate Hardness (the portion of the hardness
associated with carbonate or bicarbonate)
Alkalinity = 90.1 mg/L as CaCO3
TH = 141 mg/L as CaCO3
CH = 90.1 mg/L as CaCO3
(Note: if TH > Alk then CH = Alk; and NCH = 0)
• Non-carbonate Hardness
NCH = TH - CH = 141 - 90.1 = 50.9 mg/L as CaCO3
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Alkalinity
Bar chart
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Oxygen Demand
ThOD
(Theoretical oxygen demand )
Oxygen Demand
Measurements in form of
i) Biochemical oxygen demand
ii) Chemical oxygen demand
iii) Nitrogenous oxygen demand
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Oxygen Demand
ThOD – theoretical oxygen demand
(i) It is the amount of O2 required to oxidize a
substance to CO2 and H2O
(ii) Calculated by stoichiometry if the chemical
composition of the substance is known
(iii) The ThOD of X in mg/L
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Oxygen Demand
Example 1
Compute the ThOD of 108.75 mg/L of glucose (C6H12O6)
• STEPS:
(i) write balanced equation for the reaction
(ii) Compute the grams molecular weights of the reactants
(iii) Determine ThOD
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Oxygen Demand
The balanced equation for the reaction
C6H12O6 + 6O2 6CO2 + 6H2O
The molecular weights (grams , refer Periodic Table) of the reactants
Glucose: 6C=72, 12H=12, 6O=96, = 180
Oxygen : 6(2)O=192
Thus, it takes 192 of O2 to oxidize 180 g of glucose to CO2 and H2O.
The ThOD of 108.75 mg/L of glucose is
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Oxygen Demand
Example 2
If concentration of glucose is 10 mg/L what is the
theoretical oxygen demand (amount of DO required?)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
It is a measure of the quantity of oxygen used by microorganisms
([Link] bacteria) in the oxidation of organic matter.
In other words: BOD measures the change in dissolved oxygen
concentration caused by the microorganisms as they degrade the
organic matter.
High BOD is an indication of poor water quality
The term “decomposable” may be interpreted as meaning that the
organic matter can serve as food for bacteria, and energy is derived
from its oxidation.
The standard oxidation (or incubation) test period for BOD is 5
days at 20C or stated as a BOD5 and can be referred by using the
Standard Methods for the Examination for Water and Wastewater
(5210 B. 5- Day BOD Test).
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
• Take sample of waste; dilute with
oxygen saturated water; add nutrients
and microorganisms (for seeded BOD test)
• Measure dissolved oxygen (DO) levels over 5 days
• Temperature 20° C
• In dark (prevents algae from growing)
• Need at least 2 mg/L change in DO over 5 days
• Maximum allowable DO depletion over the test period is 5mg/L
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
Apply Eqn C to measure BOD5 for the sample
(unseeded BOD test).
BOD5 mg/L = Di – Df ( Eqn C)
P
Where
Di = initial DO ( mg/L)
Df = final DO (mg/L)
P = Volume of sample used / Total volume
Note for quality control of DO data:
1)DO in blanks should not deplete more than 0.2 mg/L
2)DO in sample should not less than 2 mg/L
3)Final DO in the samples should not less than 1 mg/L
•
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
A BOD measurement is to carried out for wastewater
sample.
The wastewater sample inserted to BOD bottle is 10 mL.
The 300 mL BOD bottle is filled up with dilution water.
Calculate the BOD5 for the wastewater by using the given data:
Concentration of DO (mg/L) Day 1 Day 5
7.5 5.0
Solution:
For each test bottle meeting the 2.0 mg/L minimum DO depletion
and the 1.0 mg/L residual DO, then the;
•
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
Modeling BOD as a First-order Reaction
Organic matter oxidized
Organic matter remaining
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
Modeling BOD Reactions
Assume rate of decomposition of organic waste is proportional to the
waste that is left in the flask.
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
L
o
Lo- Lt BOD exerted
BODt
L
L remaining
t
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
Ultimate Biochemical Oxygen Demand
Lt = amount of O2 demand left in sample at time, t
Lo = amount of O2 demand left initially (at time 0, no DO demand has
been exerted, so BOD = 0)
At any time, Lo = BODt + Lt
(that is the amount of DO demand used up and the amount of DO that could
be used up eventually)
Assuming that DO depletion is first order
BODt = Lo(1 - e-kt)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
Example 1
If the BOD5 of a waste is 102 mg/L and the BOD20
(corresponds to the ultimate BOD) is 158 mg/L, what is
k (base e)?
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
Temperature dependence of BOD rate reaction
o As temperature increases, metabolism increases, utilization of
DO also increases
kT = k20T-20
= 1.135 if T is between 4 - 20 oC
= 1.056 if T is between 20 - 30 oC
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
Example 1
The BOD rate constant, k, was determined empirically to be 0.20 days-1 at
20 oC.
What is k if the temperature of the water increases to 25 oC?
What is k if the temperature of the water decreases to 10 oC?
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
Graphical determination of BOD rate Constants
According to Thomas,
(1-e-kt) = kt (1+kt/6)-3
Therefore
BODt=Lo(1-e-kt)
BODt=Lo(kt)[1+(1/6)kt]-3 .....(1)
• By rearranging terms & taking the cube root of both sides, equation (1) can be transformed to:
(t/BODt)1/3=(kLo)-1/3 + (k)2/3/6(Lo)1/3 (t) ....(2)
• A plot of (t/BODt)1/3 versus t is linear. The intercept is defined as:
A = (kLo)-1/3 ….(3)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
a slope is defined by:
B = (k)2/3/6(Lo)1/3 ….(4)
y=(t/BOD) 1/3
m=a/b = (k2/3/6Lo1/3)
a
b
A =(kLo)-1/3
x=t
• Recalled , y = c + mx
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
BOD Rate Reaction
• Solving Lo1/3 in Eq.(3) substituting into Eq. (4) and solving for k yields:
k= 6(B/A) …(5)
• Likewise, substituting Eq. (5) into Eq.(3) and solving for Lo yields:
Lo = 1/(6A2B) …(6)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
Example 1
The following data were obtained from an experiment to determine the
BOD rate constant and ultimate BOD for an untreated wastewater:
Time (day) 2 4 6 8 10
BOD (mg/L) 125 200 220 230 237
Solution:
1. Calculate values of (t/BODt)1/3 for each day.
Time (day) 2 4 6 8 10
BOD (mg/L) 125 200 220 230 237
(t/BODt)1/3 0.252 0.271 0.301 0.326 0.348
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
2. Plot (t/BODt)1/3 versus t on graph paper and draw the line
of best fit by eye.
3. Determine the intercept (A) and slope (B) from the plot.
Y = (t/ BODt)1/3
0.5
0.4
Slope, B= (0.348-0.224)/(10-0)
0.3
=0.0125
0.2
A= 0.224
0.1
0
2 4 6 8 10 Time (t)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
4. Calculate k and Lo using the following formula
k = 6 (B/A) Lo = 1/ 6(A)2(B)
k = 6(B/A)
= 6(0.0125/0.224)
= 0.335 / day
Lo = 1/(6A2B)
= 266 mg/L
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Chemical Oxygen Demand (COD)
• It is based on the fact that all organic compounds, with a few
exception, can be oxidized by the action of strong oxidizing agents
under acid condition (=Value usually about 1.25 times BOD)
• Chemical oxygen demand is to measure the oxygen requirement of a
sample that is likely to oxidation by strong chemical oxidant
( potassium dichromate).
• Organic matter in aqueous samples could be determined by oxidation
with dichromate.
• The amount of O2 that is chemically equivalent to the dichromate
consumed is defined as the COD of the sample.
• During the oxidation in which sample is heated with the known
excess of dichromate, organic matter is converted to carbon dioxide
and water while dichromate is reduced to Cr 3+.
• The excess dichromate is determined by means of an oxidation-
reduction titration with ferrous ammonium sulfate (FAS).
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Nitrogenous Oxygen Demand
The total BOD of a wastewater is composed of two
components – a carbonaceous oxygen demand and
a nitrogenous oxygen demand.
Traditionally, because of the slow growth rates of those
organisms (nitrosomonas and nitrobacter) that exert the
nitrogenous demand, it has been assumed that no
nitrogenous demand is exerted during the 5-day BOD5 test.
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Nitrogenous Oxygen Demand
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Nitrogenous Oxygen Demand
• Nitrification (2 step process)
2 NH3 + 3O2 2 NO2- + 2H+ + 2H2O (nitrosomonas)
2 NO2- + O2 2 NO3- (nitrobacter)
• Overall reaction:
NH3 + 2O2 NO3- + H+ + H2O
• Theoretical NBOD =
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Nitrogenous Oxygen Demand
Untreated domestic wastewater
ultimate-CBOD = 250 - 350 mg/L
ultimate-NBOD = 70 - 230 mg/L
Ultimate NBOD 4.57 x TKN
TKN = is the sum of ammonia-nitrogen (NH3-N)
plus organic nitrogen ( protein and urea)
= 15 - 50 mg/L as N
(Total Kjeldahl Nitrogen = TKN)
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Nitrogen
Nitrogen is often the limiting nutrient in ocean waters and some streams
Nitrogen can exist in numerous forms, but nitrate (NO3-), nitrite (NO2-),
ammonia (NH3) are most commonly measured
Sources are primarily from fertilizers and acid deposition
Human intervention in the nitrogen cycle
1. Additional NO and N2O in atmosphere from burning fossil fuels;
also causes acid rain
2. N2O to atmosphere from bacteria acting on fertilizers and manure
3. Destruction of forest, grasslands, and wetlands
4. Add excess nitrates to bodies of water
5. Remove nitrogen from topsoil
Nitrogen Cycle in a Terrestrial Ecosystem with Major
Harmful Human Impacts
1.3 Water Quality Parameters
1.3.2 Chemical Parameter – Phosphorus
Cycles through water, the earth’s crust, and living organisms
Limiting factor for plant growth
Impact of human activities
1. Clearing forests
2. Removing large amounts of phosphate from the earth to make fertilizers
3. Erosion leaches phosphates into streams
Phosphorus Cycle with Major Harmful
Human Impacts
Nitrogen & Phosphorus global concern
Eutrophication
1.3 Water Quality Parameters
1.3.3 Biological Parameter
Microbial Indicator
Macro-invertebrate indicators
1.3 Water Quality Parameters
1.3.3 Biological Parameter – Microbial indicators
Microorganisms can be used as indicators of the presence of
pathogens or infectious agent that cause illness to aquatic or terrestrial
ecosystem health.
Bacteria counting is a simple method to examine the microbial status
of a sample
The most used indicator:
Microbial indicator Origin Indicator for
Total coliforms Soil, plant Finished drinking water
Fecal coliforms fecal Recreational water
Class 1: Primary contact recreational
200 cf/ 100 mL
Class 1: Secondary contact recreational
2000 cf/100 mL
E. coli Fecal of human and Freshwater recreational
warm-blood animal
1.3 Water Quality Parameters
1.3.3 Biological Parameter – Microbial indicators
Pathogenic Organisms
Many organims that cause human or animal diseases colonize
the instinal tract but can live for a period of time outside the
body
Carriers (who may or may not exhibit disease symptoms) excrete
these intestinal tract organisms in very large numbers
When water is contaminated by excreta, the organisms can be
transmitted to those who contact the water
1.3 Water Quality Parameters
1.3.3 Biological Parameter – Macro-invertebrate indicators
Macroinvertebrate are useful and convenient
indicators of the ecological health of a waterbody
or river. They are almost always present, and are
easy to sample and identify
Benthic refers to the bottom of a waterway.
Example of benthic macro-invertebrates include
insects in their larval or nymph form, crayfish,
claims, snails and worms.
Most live part or most of their life cycle attached to
submerged rocks, logs and vegetation.
1.3 Water Quality Parameters
1.3.3 Biological Parameter – Microbial indicators
1.3 Water Quality Parameters
1.3.3 Biological Parameter – Microbial indicators
1.4 Water Sampling (River
Monitoring)
Why we sample??
• To verify compliance for INWQS, to classify the water body
1.4 Water Sampling (River Monitoring)
Sampling Preparation
Sample bottles, preservatives, labels and marker pens
Sample storage/transit containers and ice packs
Filtering apparatus (if required)
Samplers/sampling equipment
Rubber boots, waders, etc.
Standard operating procedures for sampling
Spares of all above items if possible and when appropriate
Documentation
Pens/wax crayons
Sample labels
Field notebook
For on-site testing
List of analyses to be performed on site
1.4 Water Sampling (River Monitoring)
Collection &Preservation Of Water Samples
Standard Methods for the
Examinations of Water and
Wastewater
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sequence of Sampling Matrices and Analytes
Project deals with multimedia and/or multiple parameters use following sequence:
o Collect from least to most contaminated sampling locations
o If sediment and water is being collected, collect water first to minimize effects
from suspended bed materials
o For shallow streams, start downstream and work upstream to minimize sediment
effects due to sampling disturbances
o If sampling at different depths, collect surface samples first and then proceed
deeper
o Always collect VOCs first, followed by SVOCs (e.g. pesticides, PCBs, oil, etc.),
then total metals, dissolved metals, microbiological samples, and inorganic
nonmetals
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Amount
Minimum sample required depends on the concentration of the
analytes present
Should take enough for all analyses and additional for any QA/QC
work required
Heterogeneous samples generally require larger amounts to be
representative of sample variations
Taking too much sample can lead to problems with storage and
transportation
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Amount - Water
• 5 mL for total petroleum hydrocarbons (TPHs), 100 mL for metals, 1 L
for trace organics (pesticides)
• As a general rule the minimum volume collected should be 3-4 times
the amount required for analysis (EPA, 1995)
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Preservation and Storage
Purpose – minimize physical, chemical and biological changes
3 approaches:
o Refrigeration
o Use of proper sample container
o Addition of preserving chemicals
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Preservation and Storage
Refrigeration is a universally accepted method to slow down loss
processes
Container choice (material type and headspace) is critical to reduce
o Volatilization
o Adsorption
o Absorption
o Diffusion
o Photodegradation
Addition of preservatives is critical to reduce losses due to chemical
reactions and bacterial degradation
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Preservation and Storage
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sample Preservation and Storage
• Maximum Holding Time (MHT) is the length of time a sample can
be stored after collection and prior to analysis
• Immediate: pH, temperature, salinity, DO
• Within 1-2 days: careful pre-planning is required to avoid sampling
on Friday, Saturday or near holidays
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Selection of Sample Containers
Water
Glass vs. Plastics:
o Glass may leach boron and silica, metals may stick to walls
o Glass is generally used for organics and plastic for metals, inorganics and physical
properties
o For trace organics cap and liner should be made of inert materials (teflon)
Headspace vs. no Headspace:
o No headspace is allowed for VOC samples/DO
o 40 mL vial with a teflon-lined septum
o Oil and grease should only be half-filled in wide mouthed
glass bottles
Special containers:
o e.g. BOD/DO bottles and VOC vials
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
1.4 Water Sampling (River Monitoring)
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
PART 5
DO SAG CURVE
112
1.5 DO Sag Curve
Water purification system and DO sag curve
The concentration of DO in river is an indicator of the general health of the river.
All river have CAPACITY for water purification (self purification)
o As long as the discharge of oxygen demanding wastes is well within the self
purification capacity, the DO level remain HIGH and a diverse population of
plants and animals
o As the amount of waste increase, the self purification capacity can be exceeded,
causing detrimental changes in plant and animal life
o then, the stream losses its ability to clean itself and the DO level DECREASES.
o when the DO drops below 4 to 5 mg/L, most game fish will have been driven
out.
o If the DO is completely removed, fish and other higher animals are killed or
driven
o The water become blackish and foul smelling as the sewage and dead animal
life decompose under anaerobic condition (without O₂ )
1.5 DO Sag Curve
Dissolved Oxygen Depletion
(From: Environmental Science: A Global Concern, 3rd ed. by W.P Cunningham and B.W. Saigo, WC
Brown Publishers, © 1995)
1.5 DO Sag Curve
Dissolved Oxygen Sag Curve
1.5 DO Sag Curve
Mass Balance Approach
• Originally developed by H.W. Streeter and E.B. Phelps in 1925
• River described as “plug-flow reactor”
• Mass balance is simplified by selection of system boundaries
• Oxygen is depleted by BOD exertion
• Oxygen is gained through reaeration
1.5 DO Sag Curve
Steps in Developing the DO Sag Curve
1. Determine the initial conditions
2. Determine the reaeration rate from stream
geometry
3. Determine the deoxygenation rate from BOD
test and stream geometry
4. Calculate the DO deficit as a function of time
5. Calculate the time and deficit at the critical
point
1.5 DO Sag Curve
Selecting System Boundaries
1.5 DO Sag Curve
Initial Mixing
Qw = waste flow (m3/s)
DOw = DO in waste (mg/L)
Lw = BOD in waste (mg/L)
Qr = river flow (m3/s) Qmix = combined flow (m3/s)
DOr = DO in river (mg/L) DO = mixed DO (mg/L)
Lr = BOD in river (mg/L) La = mixed BOD (mg/L)
1.5 DO Sag Curve
1. Determine Initial Conditions
a. Initial dissolved oxygen concentration
b. Initial dissolved oxygen deficit
where D = DO deficit (mg/L)
DOs = saturation DO conc. (mg/L)
1.4 Water Sampling (River Monitoring)
1. Determine Initial Conditions
DOsat is a function of temperature. Values can be found
in Table A-3.
c. Initial ultimate BOD concentration
1.5 DO Sag Curve
Table A-3: Saturation values of DO in freshwater exposed to
saturated atmosphere containing 20.9% O2 under a pressure of
101.325kPa (Davis & Cornwell, 2013)
1.5 DO Sag Curve
2. Determine Re-aeration Rate
a. O’Connor-Dobbins correlation
where kr = reaeration coefficient @ 20ºC (day-1)
u = average stream velocity (m/s)
h = average stream depth (m)
b. Correct rate coefficient for stream temperature
where Θ = 1.024
1.5 DO Sag Curve
3. Determine the Deoxygenation Rate
a. rate of deoxygenation = kdLt
where kd = deoxygenation rate coefficient (day-1)
Lt = ultimate BOD remaining at time (of travel
downdstream) t
b. If kd (stream) = k (BOD test)
and
1.5 DO Sag Curve
3. Determine the Deoxygenation Rate
c. However, k = kd only for deep, slow moving streams. For others,
where η = bed activity coefficient (0.1 – 0.6)
d. Correct for temperature
where Θ = 1.135 (4-20ºC) or 1.056 (20-30ºC)
1.5 DO Sag Curve
4. DO as function of time
• Mass balance on moving element
• Solution is
1.5 DO Sag Curve
5. Calculate Critical time and DO
1.5 DO Sag Curve
Example
A discharges 37.0 cfs of treated sewage having an ultimate BOD of
28.0 mg/L and 1.8 mg/L DO into a river with a flow of 250 cfs and
velocity of 1.2 ft/s. Upstream of the discharge point, the river has a
BOD of 3.6 mg/L and a DO of 7.6 mg/L. Determine the critical DO and
critical distance, and
Given :
The saturation DO (DOs) = 8.5 mg/L,
kd = 0.61 day-1,
kr = 0.76 day-1.
1.5 DO Sag Curve
1. Determine Initial Conditions
a. Initial dissolved oxygen concentration
b. Initial dissolved oxygen deficit
1.4 Water Sampling (River Monitoring)
1. Determine Initial Conditions
c. Initial ultimate BOD concentration
1.5 DO Sag Curve
2. Determine Re-aeration Rate
• kr = 0.76 day-1 given
• no need to calculate from stream geometry
• assume given value is at the stream temperature (since not
otherwise specified), so no need to correct
3. Determine the Deoxygenation Rate
• kd = 0.61 day-1 given
• no need to calculate corrections from stream geometry
• assume given value is at the stream temperature (since not
otherwise specified), so no need to correct
1.4 Water Sampling (River Monitoring)
4. Calculate Critical time (tc)
4. Calculate critical distance (as asked)
1.5 DO Sag Curve
5. Calculate DO critical (Doc) (as asked)
6. Calculate DO deficit (Da) during critical
1.5 DO Sag Curve
Try this!!
1. The town of State College discharges 17,630m3/d of treated wastewater into the
Bald Eagle Creek. The treated wastewater has a BOD5 of 12 mg/L and a k of
0.12d-1 at 20C. Bald Eagle creek has a flow rate of 0.43 m3/s and an ultimate
BOD of 5.0 mg/L. the DO of the river is 6.5 mg/L and the DO of the wastewater
is 1.0 mg/L. the stream temperature is 10C and the wastewater temperature is
10C. Compute the DO and initial ultimate BOD after mixing.
2. Calculate the initial deficit of the Bald Eagle Creek after mixing with the
wastewater from the town of State College. The stream temperature is 10C and
the wastewater temperature is 10C.
3. Determine the deoxygenation rate constant for the reach of Bald Eagle Creek
below the wastewater outfall (discharge pipe). The average speed of the stream
flow in the creek is 0.03 m/s. the depth is 5.0 m and the bed-activity coefficient
is 0.35.
4. Determine the DO concentration at a point 5km downstream from the State
College discharge into the Bald Eagle Creek. Also determine the critical DO and
the distance downstream at which it occurs.