2/20/2018

Environmental Legislation
• Why?
• What are the types of Environmental Legislation?

WATER POLLUTION • What is the difference between NWQS and EQA?

• The importance of Water Quality Parameters

Ir Dr Leonard Lim
Department of Chemical Engineering and
Energy Sustainability

National Water Quality Standard (NWQS)

Parameter Unit Classes
Sampling and Monitoring of Water
I IIA IIB III IV V
AN mg L-1 0.1 0.3 0.3 0.9 2.7 > 2.7 • Groundwater
BOD mg L-1 1 3 3 6 12 > 12
COD mg L-1 10 25 25 50 100 > 100 • Surface Water
DO mg L-1 7 5–7 5–7 3–5 <3 <1
pH 6.5 – 8.5 6–9 6–9 5-9 5–9 - • Wastewater
Colour TCU 15 150 150 - - -
EC* µmhos/cm 1000 1000 - - 6000 -
Floatables N N N - - -
Odour N N N - - -
Salinity % 0.5 1 - - 2 -
Taste N N N - - -
TDS mg L-1 500 1000 - - 4000 -
TSS mg L-1 25 50 50 150 300 300
o
Temp C - Normal + - Normal + - -
2 2
Turbidity NTU 5 50 50 - - -
Faecal Counts 10 100 400 5000 5000 -
Coliform** /100mL (20000)a (20000)a
Total Counts 100 5000 5000 50000 50000 > 50000
Coliform /100mL

N: not detectable

Environmental Quality (Industrial Effluent)

Regulations) 2009

1
 2/20/2018

Environmental Quality (Sewage)

Regulations 2009

Environmental Quality (Control of Pollution from Solid

Waste Transfer Station and Landfill) Regulations 2009

Water Quality Parameters Water Quality Parameters

Physical Chemical Biological Physical Chemical Biological

• Turbidity • Chloride (Cl) [<100 ppm] • Pathogens • Solids • Inorganic Non Metallic • Pathogens
• Colour [15 CU] • Flouride (F) [fluorosis] (Total coliform • Particle Size Constituents (Total coliform
• Taste and odour • Iron (Fe) [brown] [0.3 mg/L] test, Escherichia Distribution • pH, chloride, alkalinity test, Escherichia
• Temperature • Lead (Pb) [chronic] coli, Aerobacter • Turbidity • N, P, S coli, Aerobacter
0.05 mg/L • Manganese (Mn) [brown] aerogenes) • Color • Gases, Odour aerogenes)
Flouride: 2 mg/L • Sodium (Na) [heart, kidney, Coliform group of • Transmittance • Metallic Constituents
circulatory ailment] organisms survives • Temperature • Individual Organic
250 mg/L • Sulfate (SO4) [diarrhea] for long time but • Conductivity Compounds
5 mg/L • Zinc (Zn) [taste] not reproduce • Density, Specific • VOC, Pesticides
Odour: 3 TON • Toxic inorganics: NO3- effectively – good Gravity and • Aggregate of Organic
pH: 6.5 to 8.5 • Toxic organics: atrazine, fecal indicator Specific Weight Constituents
TDS: 500 mg/L benzene [chronic] • BOD, COD, TOC, O&G
Radiological: atomic energy and mining radioactive material Radiological: atomic energy and mining radioactive material

2
 2/20/2018

Physical Characteristics Total Solids

• Solids
Total Solids (TS)
• Particle Size Distribution – serial filtration, optical sizing 103 – 105 oC

• Turbidity
Total Dissolved Total Suspended
• Colour Solids (TDS) Solids (TSS)
• Absorption/Transmittance
1.58 μm, 103 – 105 oC 1L Imhoff Cone 1.58 μm, 103 – 105 oC
Settleable Solids
• Temperature Fixed Dissolved Volatile Dissolved Fixed Suspended Volatile
• Conductivity Solids (FDS) Solids (VDS) Solids (FSS) Suspended Solids
500 ± 50 oC TDS - FDS 500 ± 50 oC (VSS)
• Density, Specific Gravity, Specific Weight TSS - FSS

Total Fixed Solids (TFS)

Total Volatile Solids (TVS)

Determination of TSS, FSS, VSS

Absorption/Transmittance
• Measure of the amount of light of a specified wavelength,
that is absorbed by the constituents in a solution; usually 1.0
cm path length
• Absorption, A (a.u/cm) Interference by selected inorganic
compounds (copper, iron), organic
𝐴 = log compounds (humic substances,
organic dye), TSS.
• Transmittance, T (%)
Important for UV disinfection
𝑇= × 100
• Relationship between transmittance and absorption
𝑇 = 10 . ./ × 100
Transparent solution, A = 0, T = 100;
Perfectly opaque, A → ∞, T = 0

3
 2/20/2018

Turbidity Turbidity Measurement

• Measure of light
transmitting properties of
water
• Measurement based on
comparison of intensity of
light scattered by sample to
that by reference
suspension under the same
condition – formazin
• Air bubbles can cause
erroneous turbidity reading
• In general no relationship
between TSS and turbidity

Electrical Conductivity Density, Specific Gravity, Specific Weight

• Measure of the ability of solution to conduct electrical
current
• Electrical current transported by ions in solution,
conductivity increases with ion concentration
• Surrogate measure of total dissolved solids (TDS)
concentration such as salinity for irrigation
𝑇𝐷𝑆 ≅ 𝐸𝐶 (𝑑𝑆/𝑚) × 0.55 − 0.70
• To check acceptability of chemical analyses
• Estimate ionic strength of solution
𝐼 = 1.6 × 10 × 𝐸𝐶 (𝑑𝑆/𝑚)
• Ionic strength of treated wastewater in groundwater
recharge application
• Density of water, ρ - mass per unit volume (g L-1 or kg m-3)
• Determine potential for formation of density currents in
sedimentation tanks, chlorine contact tanks
• Typically similar to that of water unless contains
significant amount of industrial waste
• Specific gravity, 𝑠 =
• Density and specific gravity are temperature dependent
and vary with concentration of total solids
• Specific weight, γ - weight per unit volume kN m-3
𝛾 = 𝜌𝑔

Inorganic Nonmetallic Constituents pH

• pH 𝐻 𝑂𝐻 = K 𝐻 𝑂 = 𝐾 , ionization constant for water
• Chlorides • Expression of hydrogen ion activity in terms of molar
concentrations
• Alkalinity
• Nitrogen 𝑝𝐻 = −𝑙𝑜𝑔 𝐻 = 𝑙𝑜𝑔
• Phosphorus • Range 0 to 14, with pH 7 at 25 oC representing absolute
neutrality
• Sulfur
𝐻 𝑂𝐻 = 10 × 10 = 10
• Gases
pOH = 14 - pH
• Kw changes with temperature: pH of neutrality 7.5 and 6.5
at 0 and 60 oC
• Measured using glass electrode, accuracy ± 0.1
• Buffer solution 4.01 (Pink), 7.00 (Yellow) and 10.01 (Blue)

4
 2/20/2018

Relationship between CO2 and other

Alkalinity
forms of alkalinity at various pH level
• Measure of capacity to neutralise acids aka acid • Chemical coagulation –
neutralisation capacity (ANC) formation of hydrogen
• Primarily due to salts of weak acids and strong bases ion released react with
alkalinity
• Bicarbonate represents major form of alkalinity due to
• Water softening –
action of CO2 upon basic material in soil
removal of Ca and Mg
• Major proportion: 1. OH-, 2. CO32-, 3. HCO3- • Corrosion Control
• Important in wastewater treatment • Buffer capacity – assess
• Titration (0.02N H2SO4) ability to resist effect of
• Total alkalinity: Phenolphtalein – lower sample pH to 8.3, acid rain
𝐶𝑂 + 𝐻 → 𝐻𝐶𝑂 • Industrial wastes – esp
• Bromcresol – pH 8.3 to 4.5, 𝐻𝐶𝑂 + 𝐻 → 𝐻 𝐶𝑂 release of caustic
(hydroxide) alkalinity

Removal of free carbon dioxide with lime

𝐶𝑂
Hardness 𝐻 𝐶𝑂
+ 𝐶𝑎 𝑂𝐻 → 𝐶𝑎𝐶𝑂 ↓ + 𝐻 𝑂
Removal of carbonate hardness with lime
• Expressed in terms of CaCO3 as alkalinity
𝐶𝑎 + 2𝐻𝐶𝑂 + 𝐶𝑎 𝑂𝐻 → 2𝐶𝑎𝐶𝑂 ↓ + 2𝐻 𝑂
• Caused by multivalent metallic cations 𝑀𝑔 + 2𝐻𝐶𝑂 + 2𝐶𝑎 𝑂𝐻 → 2𝐶𝑎𝐶𝑂 ↓ + 𝑀𝑔 𝑂𝐻 ↓ + 2𝐻 𝑂
Cations Anions Removal of non-carbonate hardness with soda ash and lime
2𝐶𝑙 2𝐶𝑙
Ca2+ HCO3- 𝐶𝑎 + + 𝑁𝑎 𝐶𝑂 → 𝐶𝑎𝐶𝑂 ↓ + 2𝑁𝑎 +
𝑆𝑂 𝑆𝑂
Mg2+ SO42- 2𝐶𝑙 2𝐶𝑙
𝑀𝑔 + + 𝐶𝑎 𝑂𝐻 → 𝑀𝑔 𝑂𝐻 ↓ + 𝐶𝑎 +
Sr2+ Cl- 𝑆𝑂 𝑆𝑂
Fe2+ NO3-
Recarbonation for pH control (pH ~ 8.5)
𝐶𝑂 + 𝐶𝑂 + 𝐻 𝑂 → 2𝐻𝐶𝑂
Mn2+ SiO32-
Recarbonation for removal of excess lime and pH control (pH ~ 9.5)
CaCO3 mg/L = 2.50 x (mg/L Ca) + 4.12 x (mg/L Mg) 𝐶𝑎 𝑂𝐻 + 𝐶𝑂 → 2𝐶𝑎𝐶𝑂 ↓ + 2𝐻 𝑂
𝑀𝑔 𝑂𝐻 + 𝐶𝑂 → 𝑀𝑔𝐶𝑂 + 2𝐻 𝑂
Total hardness is summation of carbonate/temp (CO32- and HCO3-) and
Stoichiometric requirement for lime and soda ash (equivalent per unit
non carbonate/perm hardness (amount in excess of carbonate hardness)
volume)
When alkalinity < total hardness, CO32- hardness = alkalinity 𝐿𝑖𝑚𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑒𝑞/𝑚 = 𝐶𝑂 + 𝐻𝐶𝑂 + 𝑀𝑔 + 𝑒𝑥𝑐𝑒𝑠𝑠
When alkalinity > total hardness, CO32- hardness = total hardness 𝑆𝑜𝑑𝑎 𝑎𝑠ℎ 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑒𝑞/𝑚 = 𝐶𝑎 + 𝑀𝑔 − 𝑎𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦

Water Softening
• Approximately 1 eq/m3 (1 meq/L) of lime in excess of the
stoichiometric requirement must be added to bring the pH to
above 11 to ensure complete precipitation of Mg(OH)2. After the
removal of precipitates, recarbonation is required to bring the
pH to 9.2 – 9.7
• Treatment processes for water softening depends on the
degree of hardness and types and amount of chemical added:
single stage lime, excess lime, single stage lime-soda ash and
excess lime soda ash processes.
CaCO3 mg/L = 2.50 x (mg/L Ca) + 4.12 x (mg/L Mg)
Softening Chemistry
• Chemical processes used to soften water are direct
application of the law of mass action
• Increase CO32- and/or OH- by adding chemicals to
precipitate Ca and Mg
• If possible, naturally occuring HCO3- is converted to
CO32- by adding OH- to shift to the right
𝐶𝑂 𝑔 ↔ 𝐶𝑂 + 𝐻 𝑂 ↔ 𝐻 𝐶𝑂 ↔ 𝐻 + 𝐻𝐶𝑂 ↔ 2𝐻 + 𝐶𝑂
• Common source for OH- is Ca(OH)2, cheaper to buy
CaO (quick lime); add into water to form hydrated
lime slurry, aka slaking
𝐶𝑎𝑂 + 𝐻 𝑂 ↔ 𝐶𝑎 𝑂𝐻 + ℎ𝑒𝑎𝑡
• Common carbonate source, sodium carbonate

5

Calculation
Single Stage Lime Softening
Raw water has the following composition:
(HCO3-)
Alkalinity pH α1 (at T = Calcium Magnesium
(mg/L CaCO3) 10oC) (mg/L) (mg/L)
248 7.0 0.77 88
Determine the necessary amount of lime to soften
the water, if the final hardness desired is 40 mg/L
as CaCO3. Also estimate the hardness of the
treated water.
• Step 3: Estimate carbonate acid concentration
CT = [H2CO3] + [HCO3-] + [CO32-]
Rearranging and [CO32-] = 0,
[H2CO3] = (6.44 – 4.96)x10-3 mol/L = 1.48x10-3 mol/L
= 1.48x10-3 x 1000 x 62 mg/mol x mol/L = 92 mg/L
= 92 x 50/32 = 148 mg/L as CaCO3
• Step 4: Construct bar diagram
Ca = 88 x 100/40 = 220 mg/L CaCO3
Mg = 4 x 100/24.3 = 16 mg/L CaCO3
The purity of lime is 70 %. Therefore, the total
amount of lime needed is
206/0.70 = 294 mg/L CaO
Step 7: Estimate the hardness of treated water
The magnesium hardness level of 16 mg/L CaCO3
remains in the softened water theoretically. The
limit of calcium achievable is 30 to 50 mg/L CaCO3
and would remain in the water unless using 5 to 10
% in excess of lime. Hardness levels less than 50
mg/L CaCO3 are seldom achieved in plant
operation.
2/20/2018
Solution
• Step 1: Calculate bicarbonate concentration
Alkalinity = [HCO3-] + [CO32-] + [OH-] + [H+]
At pH = 7.0, assume all alkalinity is in bicarbonate form
HCO3- = 248 (mg/L) x 1 g/1000 mg x 1 mol/61 g x 61 eq wt HCO3/50 eq wt alkalinity
4 = 4.96 x 10-3 mol/L
• Step 2: Compute total carbonate species concentration, CT
CT = [HCO3-]/α1
= 4.96 x 10-3/0.77 = 6.44 x 10-3 mol/L
• Step 5: Find hardness distribution
Calcium carbonate hardness = 220 mg/L
Magnesium carbonate hardness = 16 mg/L
Total hardness = 220 + 16 = 236 mg/L
• Step 6: Estimate the lime dose needed
Since final hardness desired is 40 mg/L CaCO3, magnesium
hardness removal would not be required. The required amount
of lime dosage (x) would be equal to HCO3- concentration plus
CaCO3 hardness.
x = 148 + 220 = 368 mg/L CaCO3
Thus, xCa(OH)2 = 368 x (74 as Ca(OH)2/100 CaCO3)= 272 mg/L
or xCaO = 368 x (56 as CaO/100 CaCO3) = 206 mg/L
Chloride (Cl-)
• Not to be confused with chlorine (Cl2):
Total Chlorine = Combined Chlorine + Free Chlorine
• Not harmful to human up to 2000 mg/L
• at 250 mg/L or more gives salty taste to water
• Parameter of concern for irrigation
• Salinity – high salinity will affect the osmotic differences
between water outside the plant and within plant cells
• Used for tracer studies esp in groundwater studies (NaCl)
due to its chemical stability, easily measured, normal
constituent of water and no toxic effect, and low tendency
to sorb to soil
• Measured using Mohr Method (Argentometric) – 0.0141N
Ag(NO3), 1 mL Ag(NO3) = 0.5 mg Cl-
• Advanced method – ion chromatography (IC)
6
 2/20/2018

Nitrogen
• Essential to the growth of microorganisms, plants and
animals, building block in the synthesis of protein – major
nutrient or biostimulants
• Treatability of wastewater by biological processes
• Removal of nitrogen in wastewater to control algal growth

Definition of Nitrogen Species Phosphorus

- III 0 I II III IV V
• Similar to nitrogen, nutrient
NH3 N2 N2O NO N2O3 NO2 N2O5
• Control amount of phosphorus compound that enter
NO2- NO3-
surface waters to control algal bloom
Form of Nitrogen Abbrev Definition • Municipal wastewater typically 4 – 16 mg/L phosphorus
Ammonia Gas NH3 NH3 ( 𝑁𝐻 ↔ 𝑁𝐻 + 𝐻 ) • Typical forms of phosporus: orthophosphates (PO43-,
Ammonium Ion NH4+ NH4+ HPO42-, H2PO4-, H3PO4) for biological breakdown,
Total Ammonia Nitrogen TAN NH3 + NH4+
polyphosphates (multiple POH atoms) – undergo
hydrolysis and revert to orthophosphates
Nitrite NO2- NO2-
• Orthophosphates determined by adding ammonium
Nitrate NO3- NO3-
molybdate to form coloured complex with phosphate
Total Inorganic Nitrogen TIN NH3 + NH4+ + NO2- + NO3-
• Poly and organic phosphates to be digested into
Total Kjeldahl Nitrogen TKN Organic N + NH3 + NH4+
Using TKN, boil to drive off ammonia
+)
and digest, ON orthophosphates using acid digestion before adding
Organic Nitrogen Organicto
N ammonium
TKN – (NH 3 + NH4action
converted through of heat and acid ammonium molybdate
Total Nitrogen TN Organic N + NH3 + NH4+ + NO2- + NO3-

Sulfur Ion Chromatography (IC)

• Sulfate ions occur naturally and present in wastewater
• Sulfur is required for synthesis of proteins and is released
in their degradation
• Sulfur is reduced under anaerobic conditions to sulfide,
combine with hydrogen to form hydrogen sulfide (H2S)

CO3/HCO3
or NaOH)

7
 2/20/2018

Gases Dissolved Oxygen (DO)

• N2, O2, CO2, H2S, NH3, CH4 • Refers to oxygen soluble in water; important for biological activities,
• Other gases: Cl2, O3 for disinfection and odour control causes corrosion of metal, control conditions for treatment –
• SOx and NOx nitrification/denitrification, VOC removal, indicator for water quality
testing esp BOD
• Solubility of Gases in Water governed by Henry’s Law, partial pressure,
temperature, concentration of impurities in water (salinity, SS etc) • Poorly soluble as they do not react with water chemically thus
• Ideal Gas Law, PV = nRT solubility proportional to their partial pressures
𝑛𝑅𝑇 1 𝑚𝑜𝑙𝑒 0.082057 𝑎𝑡𝑚. 𝐿𝑚𝑜𝑙𝑒. 𝐾 [ 273.15 + 0 𝐾] • Henry’s Law – calculate the amount present at saturation at any given
𝑉= = = 22.414 𝐿
𝑃 1.0 𝑎𝑡𝑚 temperature
( , )( , / )( / )
• Convert ppm to µg/m3, = • Oxygen less soluble in saline water and increasing temperature
( . × / )
• Henry’s Law Temperature (oC) Chloride Concentration (mg/L)
( / )
𝑝 = 𝑥 , H – Henry’s law constant, 0 5000 10000 15000 20000
( / )
( ) 20 9.2 8.7 8.3 7.9 7.4
𝑥 =
( ) 25 8.4 8.0 7.6 7.2 6.7
𝑃 − 𝑇𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑢𝑠𝑢𝑎𝑙𝑙𝑦 1.0 𝑎𝑡𝑚 30 7.6 7.3 6.9 6.5 6.1

Odour DO Sampling and Analysis

• Unpleasant smell • DO level usually below saturation
• Decomposition and reaction • Exposure to air will lead to erroneous results
Threshold Odour Number, • Principle: minimise water contact with air during sampling
𝑇𝑂𝑁 = • If space is available to allow bottles to overflow, provide flow of
( )
2 – 3 times the bottle volume to ensure collection of
( )
representative samples
• Oxygen readily penetrates most rubber and plastic tubing
• Ideal storage: add 0.7 mL H2SO4, 0.02 g sodium azide, add 3
mL alkali-iodide reagent, dark and on ice
• Preservation is radical enough to arrest all biological action,
and the final titration can be delayed up to 6 h
• Measurement techniques: Winkler Method (Iodometric Method)
and DO membrane probes

Aggregate Organic Constituents Biochemical Oxygen Demand (BOD5)

• Amount of oxygen required by bacteria while stabilizing decomposable
• BOD organic matter under aerobic conditions at the specified duration and
temperature
• COD 𝑎 𝑏 3 𝑎 3
𝐶 𝐻 𝑂 𝑁 + 𝑛+ − − 𝑐 𝑂 → 𝑛𝐶𝑂 + − 𝑐 𝐻 𝑂 + 𝑐𝑁𝐻
• TOC 4 2 4 2 2
• Oil and Grease
• Surfactants

• Individual Organic Compounds

• Volatile Organic Compounds
• Disinfection By-Products
• Pesticides and Agricultural Chemicals
• Emerging Organic Compounds • Widely used to determine pollutional strength of domestic and
industrial wastes in terms of the oxygen

8
 2/20/2018

Analysis of BOD Biochemical Oxygen Demand (BOD)

• Determine the reduction of DO at 20 oC over 5 days • BOD5 – at 20 oC for 5 days
• Analyse BOD within 4 hours after sampling, keep cold
• BOD3 – at 30 oC for 3 days (oil palm)
• Dilution, seeding (bacteria) – essential nutrients – N, P, K, Fe etc
𝐷 −𝐷 − 1−𝑃 𝐵 −𝐵 • BOD reaction rate, θ correlates with kT = k20θ(T-20), with a
𝐵𝑂𝐷 =
𝑃
temperature coefficient of 1.047
𝐵 −𝐷 • The re-aeration rate also follows the equation but does
𝐵𝑂𝐷 =
𝑃 not depend as much on temperature, the coefficient is
• < 7 mg/L, no dilution 1.020
• 200 – 700 mg/L, 1% P
• 20 – 70 g/L, 0.01% P
• BOD not influenced by DO
conc as low as 0.5 mg/L
• Depletion of DO < 2 mg/L

BOD Calculation Reaction Constant, k

5-day BOD Test • k1 for untreated wastewater range 0.12 to 0.46 d-1,
Vww = 15 mL typically 0.23 d-1, for biological treatment process 0.12 to
V = 300 mL 0.23 d-1
• Relationship between k1 and K1
D0 = 8.8 mg/L, Df = 1.9 mg/L
𝑘 𝑏𝑎𝑠𝑒 𝑒
D0b = 9.1 mg/L, Dfb = 7.9 mg/L 𝐾 𝑏𝑎𝑠𝑒 10 =
2.303
What is the BOD5 of wastewater sample? • Conversion of reaction constant at temperature other than
𝑓= = 0.95 20oC
𝑘 =𝑘 𝜃
. . . . .
𝐵𝑂𝐷 = = • θ vary from 1.056 (20 – 30 oC) to 1.135 (4 – 20 oC),
/
typically 1.047
= 115.2 mg/L

BOD Terms Chemical Oxygen Demand (COD)

• Ultimate BOD, BODL or L0 – oxygen equivalent of the • The total amount of oxygen required for oxidation to carbon
biodegradable organic matter dioxide and water
• Assumption: most organic compounds can be oxidised by the
• Instantaneous BOD - oxygen equivalent of the
action of strong oxidising agents under acid conditions
biodegradable organic matter remaining at time, t
• Measure the strength of domestic and industrial wastes
𝐿 =𝐿 𝑒 = 𝐿 10 𝑦 = 𝐿 1 − 10
• Measure the reduction of excess oxidizing agent
• Reaction rate constant, k’ – first order

where d = 2n/3 + a/6 - b/3 - c/2

6𝐹𝑒 + 𝐶𝑟 𝑂 + 14𝐻 → 6𝐹𝑒 + 2𝐶𝑟 + 7𝐻 𝑂
3Fe2+ + 4H+ + KMnO4 → MnO2 + 2Fe3+ + K+ + 2H2O
• 0.125N solution of oxidizing agent, the equivalent weight of
oxygen is 8 g (N/8), for COD < 50 mg/L
• 0.25N for stronger oxidizing agent, equivalent to 2 mg oxygen

9
 2/20/2018

Analysis of COD Total Organic Carbon (TOC)

• Measure of oxygen requirements by oxidation of organic
matter present in samples
• Blank and sample
• A very marked change in ORP occurs at the end point of all
oxidation-reduction reactions
• Ferroin (ferrous 1,10-penanthroline sulfate) 𝐹𝑒 𝑁𝐻 2 𝑆𝑂 2
• Determine the total organic carbon in an aqueous sample
• Utilize heat and oxygen, UV radiation, chemical oxidants
to convert organic carbon to carbon dioxide, which is
measured using infrared analyzer
• Only 5 to 10 minutes
• 0.45 µm > dissolved TOC

𝑚𝑔 8000 𝑏𝑙𝑎𝑛𝑘 𝑡𝑖𝑡𝑟. −𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑖𝑡𝑟. 𝑁. 𝐹𝑒 𝑁𝐻 2 𝑆𝑂 2

𝐶𝑂𝐷 =
𝐿 𝑚𝐿 𝑠𝑎𝑚𝑝𝑙𝑒

• Potential interference by inorganics such as chloride – add

mercuric sulfate

BOD, COD and TOC BOD/COD, BOD/TOC, TOC/COD

• Indication for treatability of wastewater Determine the theoretical BOD/COD, BOD/TOC, TOC/COD
ratios for the following compound C5H7NO2. Assume the
Type of Wastewater BOD/COD BOD/TOC
vlue of the BOD of the first order reaction rate constant is
Untreated 0.3 – 0.8 1.2 – 2.0
0.23 d-1 (base e) (0.1 d-1 base 10).
After Primary Settling 0.4 – 0.6 0.8 – 1.2
Final Effluent 0.1 – 0.3 0.2 – 0.5
Solution
• If BOD/COD for untreated wastewater is 0.5 or greater,
wastewater considered to be easily treatable by biological Determine the COD of the compound
means 𝐶 𝐻 𝑁𝑂 + 5𝑂 → 5𝐶𝑂 + 𝑁𝐻 + 2𝐻 𝑂
• If BOD/COD is about 0.3 or below, either wastewater
mw 113 160
might have toxic components or acclimated COD = 160/113 = 1.42 mg O2/mg C5H7NO2
microorganism might be required in its stabilisation

Determine the BOD of the compound

Metallic Constituents
𝐵𝑂𝐷 • Trace quantities of metals are important constituents of water
= 1−𝑒 = 𝑒 . × = 1 − 0.32 = 0.68 • Necessary for growth of biological life
𝑈𝐵𝑂𝐷
𝐵𝑂𝐷 = 0.68 × 1.42 𝑚𝑔 𝑂 / 𝑚𝑔 𝐶 𝐻 𝑁𝑂 • Many metals are classified as priority pollutants, can be toxic
= 0.97 𝑚𝑔 𝐵𝑂𝐷 / 𝑚𝑔 𝐶 𝐻 𝑁𝑂 when present in elevated concentration – carcinogen and
mutagen
Determine the TOC of the compound • Determined using flame atomic absorption, electrothermal
5 × 12 atomic absorption, induced coupled plasma, mass
𝑇𝑂𝐶 = = 0.53 𝑚𝑔 𝑇𝑂𝐶 / 𝑚𝑔 𝐶 𝐻 𝑁𝑂 spectrometry
113
• Classes of metals:
• Dissolved metals – metals present in unacidified samples < 0.45 µm
Therefore, BOD/COD = 0.97/1.42 = 0.68
• Suspended metals – metals persent in unacidified samples > 0.45 µm
BOD/TOC = 0.97/0.53 = 1.82 • Total metals – total of the dissolved and suspended metals or metal
TOC/COD = 0.53/1.42 = 0.37 concentration on unfiltered sample after digestion
• Acid extractable metals – metals in solution after unfiltered sample is treated
with hot dilute mineral acid

10
 2/20/2018

Acidity Inductively Coupled Plasma (ICP)

• Most natural waters, domestic wastewaters and industrial wastes
are buffered principally by carbon dioxide – bicarbonate system
• Carbon dioxide may enter surface waters by absorption from the
atmosphere (similar to DO – Henry’s Law)
• biological oxidation (aerobic and anaerobic) of organic matter; also
depends on photosynthetic activity – if k low, CO2 exceed
equilibrium and escape from liquid
• Concentration of CO2 is not limited by DO, can be 30 to 50 mg/L
• Mineral acidity – esp in metallurgical industry, mine; salts of heavy
metals, eg Fe(III) and Al(III), hydrolyse in water to release mineral
acidity
𝐹𝑒𝐶𝑙 + 3𝐻 𝑂 ↔ 𝐹𝑒 𝑂𝐻 + 3𝐻 + 3𝐶𝑙
• Titration
• Mineral Acids – Methyl Orange Acidity – up to pH 3.7
• Total Acidity (mineral + weak acid) – phenolphtalein acidity – pH 3.7 to 8.3
• 0.02 N NaOH is used as titrating agent so 1 mL ≡ 1 mg acidity
• Important for water treatment – water softening

Indicator Organisms for Various Water

Pathogenic Organisms
• Bacteria, protozoa, helminths, viruses
Uses
• Ideal Indicator organism Water Use Indicator Organism

• Indicator organism must be present when fecal contamination is Drinking Water Total Coliform
present Freshwater Recreation Fecal Coliform
E. Coli
• Number of indicator organisms present should be equal or greater
Enterococci
than pathogenic organism such as pathogenic viruses
Saltwater Recreation Fecal Coliform
• Indicator organism exhibit same greater survival characteristics in
Total Coliform
the environment as the target pathogenic organism Enterococci
• Indicator organism must not reproduce outside of the host Shellfish–growing areas Total Coliform
organism (culture procedure should not produce serious health Fecal Coliform
threat to lab workers)
Agricultural irrigation (for reclaimed water) Total Coliform
• Isolation and quantification of the indicator organism must be faster
Wastewater Effluent Disinfection Total Coliform
than that of target pathogen (cheaper and easier to cultivate) Fecal Coliform
• Organism should be a member of intestinal microflora of warm MS2 coliphage
blooded animal

Water Sampling Representative Sampling

In-situ and Ex-situ

11

Mass Balance
River Water Quality, assume accumulation and generation is negligible (= 0)
𝑄 𝐶 =𝑄 𝐶 +𝑄 𝐶
Solution
Required effluent BOD5 is calculated from a mass balance. Since mass of
BOD5 = QE x CBOD5, therefore
CTQT = CRQR + CBOD5QE
Effluent Flow, QE = (50000x250)/(60x60x24x1000) = 0.145 m3/s
Substituting this value, along with data, then gives
(1.145 m3/s x 4 mg/L) = (1.0 m3/s x 2 mg/L) + (0.145 m3/s x CBOD5)
Therefore, effluent CBOD5 = [(1.145 x 4) – (1.0 x 2)] / 0.145
= 17.8 mg/L
BOD concentration of sewage entering the plant
= per capita BOD5/per capita flow = 70000 mg/250 L = 280 mg/L
Therefore, BOD removal efficiency = [(280-17.8)/280] x 100
= 93.6 %
Solution 2
Critical DO deficit and critical time are calculated from Dc and tc. To use these
equations, it is necessary to calculate the initial DO deficit, Da, and the initial
ultimate BOD of the effluent/water mixture, La. The DO immediately
downstream of the outfall is calculated from a mass balance:
Downstream DO = [(1.0 m3/s x 9.0 mg/L) + (0.145 m3/s x 5 mg/L)] / 1.145 m3/s
= 8.49 mg/L
Whence, Da = 9.17 – 8.49 = 0.68 mg/L
Ultimate BOD is calculated from L = Lt/(1 – 10-k1t)
= 4.0/(1.0 – 10-0.1x5) = 5.85 mg/L
From tc = [1/(k2-k1)] log {(k2/k1)[1 – [Da(k2-k1)/Lk1]]}
= [1/(0.3-0.1)] log {(0.3/0.1)[1- [(0.68(0.3-0.1))/(5.85x0.1)]]} = 1.81 d
And from Dc = (k1/k2) L 10-k1tc = 0.1/0.3 x 5.85 x (10-0.1x1.81) = 1.29 mg/L
Therefore, critical DO concentration = 9.17 – 1.29 = 7.88 mg/L and distance
below outfall = tc x velocity = 1.81 x (86400/1000) x 0.1 = 15.4 km
2/20/2018
Problem
A wastewater treatment plant serving a population of 50000
receives a per capita flow of 250 L/d and a per capita BOD5
loading of 70 g/d. Effluent from the plant is discharged into
a stream which has a flow of 1.0 m3/s, a BOD5 of 2 mg/L
and a DO concentration of 9.0 mg/L. If the BOD5 of the
stream immediately below the outfall is not to exceed 4.0
mg/L, what is the maximum BOD5 which may be permitted
in the plant effluent and what would be the required
percentage BOD5 removal efficiency of the treatment plant?
Problem 2
For the conditions described in the previous example, what
is the critical DO concentration in the stream and at what
distance below the outfall does it occur? Temperature is 20
oC throughout, k = 0.1 d-1 for the effluent/stream water
1
mixture, k2 = 0.3 d-1, stream velocity = 0.1 m/s, saturation
DO concentration is 9.17 g/L and effluent DO concentration
is 5.0 mg/L.
Problem 3
If the temperature of both stream and the effluent described
in Problem 1 is 35 oC, what is the critical DO concentration
and how far below outfall would it occur? The saturation
DO at 35 oC is 7.1 mg/L, and for this case the upstream DO
is 6.9 mg/L.
12
 2/20/2018

Solution 3 Calculation 1
Downstream DO = [(1.0 x 6.9) + (0.145 x 5.0)/1.145] = 6.66 mg/L The sewage of a town is being discharged into a river, the
Whence, Da = 7.1 – 6.66 = 0.44 mg/L quantity of sewage is 4.32 Mil L/d and its BOD is 300 mg/L.
If the effluent BOD and stream BOD are the same as in previous examples, If the flow of the river is 100 L/s and the BOD of the river is
initial ultimate BOD is unchanged, i.e. L = 5.85 mg/L 6 mg/L, find out the BOD of diluted sewage.
Values of k1 and k2 at 35 oC are calculated from kT = k20θ(T-20), using
appropriate values of the temperature co-efficient, θ
k135 = k120θ(T-20) = 0.1 x 1.047(35-20) = 0.40 d-1
k235 = k220θ(T-20) = 0.3 x 1.020(35-20) = 0.2 d-1
Then tc = [1/(k2-k1)] log {(k2/k1)[1 – [Da(k2-k1)/Lk1]]}
= [1/(0.4-0.2)] log {(0.4/0.2)[1- [(0.44(0.4-0.2))/(5.85x0.2)]]} = 1.34 d
And Dc = (k1/k2) L 10-k1tc = 0.2/0.4 x 5.85 x (10-0.2x1.34) = 1.58 mg/L
Therefore, critical DO concentration = 7.1 – 1.58 = 5.52 mg/L
And distance below outfall = tc x velocity = 1.34 x (86400/1000) x 0.1 = 11.6
km

Solution 1 Calculation 2
CR = 6 mg/L QR = 100 L/s What should be the discharge of river, if it is desired to
CS = 300 mg/L QS = 4.32 Mil L/d = 50 L/s reduce the BOD of mixture to 25 mg/L in the previous
example.
Mass Balance CTQT = C0Q0 + CEQE

CT = [(6 x 100) + (300 x 50)] / (100 + 50)

= 104 mg/L

Solution 2 Calculation 3
CR = 6 mg/L QR = 75 L/s If the river discharge is only 75 L/s and if it is desired to
CS = 300 mg/L QS = 4.32 Mil L/d = 50 L/s bring down the BOD of diluted sewage to 25 mg/L. What
CT = 25 mg/L should be the BOD of effluent discharged from a sewage
treatment plant?

Mass Balance CTQT = C0Q0 + CEQE

25 = [(6 x Y) + (300 x 50)] / (Y + 50)

1250 + 25Y = 6Y + 15000
19X = 13750
X = 723.68 L/s

13
 2/20/2018

Solution 3
CR = 6 mg/L QR = 75 L/s
CS = X mg/L QS = 4.32 Mil L/d = 50 L/s
CT = 25 mg/L
THANK YOU
Mass Balance CTQT = C0Q0 + CEQE

25 = [(6 x 75) + (X x 50)] / (75 + 50)

3125 = 450 + 50X
50X = 2675
X = 53.5 mg/L

14