Wastewater Sampling and

Analysis

Dr Hira Amjad
 Wastewater
2

a) Domestic Wastewater

b) Industrial Wastewater
 Domestic Wastewater
3

Over 80% - untreated in Asian mega cities

Major components- COD = 250-1000 mg/L

Total N = 20-90 mg/L
Total P = 4-15 mg/L
Effects of discharging into natural
receiving bodies

Oxygen demand by carbon and nitrogen

 Industrial Wastewater...
Eg: Starch industry wastewater
• major component-
COD = 10,000-20,000 mg/L
• effects of discharging into natural
receiving bodies
- 20 m3/ton of starch
- high COD
- high suspended solids
- cyanide exposure
4
Sampling
Objective: to collect a portion of material small
enough in volume to be transported conveniently and
yet large enough for analytical purposes while still
accurately representing the material being sampled.
Types of
Samples

Grab Composite Integrated

 Sampling Types
Grab Samples: Grab samples are single samples collected at a
specific spot at a site over a short period of time (typically
seconds or minutes).
Composite Samples: Can be obtained by combining portions of
multiple grab samples or by using specially designed automatic
sampling devices. This method provides a more representative
sampling of heterogeneous matrices in which the concentration
of the analytes of interest may vary over short periods of time
and/or space.
Integrated (discharge-weighed) Samples: Mixture of grab
samples collected from different points simultaneously, or as
nearly so as possible, using discharge-weighed methods.
 General Requirements
➢ Meat the requirements of the sampling program.
➢ Handle sample so that it does not deteriorate or become
contaminated or compromised before it analyzed.
➢ Ensure sampling equipments are clean and quality assured before
use.
➢ Use sample containers that are clean and free of
contaminants.
➢ Fill sample containers with/or without pre-rinsing with sample.
➢ Composite samples can be obtained by collecting over a period of
time, depth, or at many different sampling points.
➢ Make a record of every sample collected and identify every bottle.
➢ Label bottles and document sufficient information for sample
identification.
 Chain-of-Custody Procedures
a) Sample labels (including bar-code labels).
b) Sample seals.
c) Field log book.
d) Chain-of-custody record (custody, control, transfer,
analysis, and disposition).
e) Sample analysis request sheet.
f) Sample delivery to the laboratory.
g) Receipt and logging of sample.
h) Assignment of sample for analysis.
i) Disposal.
Determine the parameters in situ

-Temperature
-Redox Potential
-Dissolved Gases
Parameters immediately after sample
collection
-pH
-Electrical Conductivity
-Turbidity
-Alkalinity
 What may happen during sample
transportation?

Certain cations are Those are best collected

subject to loss by in a separate clean
adsorption on, or ion bottle and acidified with
exchange with the walls
nitric acid to pH below
of the glass containers,
these include: Al, Cd, 2.0 to minimize
Cr, Cu, Fe, Pb, Mn, Ag, precipitation and
and Zn. adsorption on container
walls.
 Preservation and Storage
1-Start microbiological examination of water samples
as soon as possible after collection.
2-Ice samples preferably at <10 ºC during transport
if they can’t be analyzed within 1h after collection.
3-Analyze samples on day of receipt whenever
possible and refrigerate overnight if arrival is too
late for analyzing on same day.
4-Do not exceed 30h holding time from collection to
analysis for coliform bacteria.
5-Do not exceed 8h holding time for heterotrophic
plate counts.
Wastewater Characterization

What is (in) Wastewater?

1. Identify wastewater sources and flows
2. Specify likely key pollutants
3. Select suitable sampling strategies
4. Measure pollutant concentrations
5. Calculate pollutant loads
6. Identify main components to be removed
Types of Pollutants

 Physical: solids, temperature, color, turbidity,

salinity, odor

 Chemical:
 Organic : carbohydrates, fats, proteins, toxins…
 Inorganic: alkalinity, N, P, S, pH, metals, salts…
 Gaseous : H2S, CH4, O2 …

 Biological: plants (algae, grass, etc.),

microorganisms (bacteria, viruses)
 Parameters
1. Solids
2. Odor
3. Temperature
4. Salinity
5. Color and turbidity
6. Carbohydrate
7. Protein
Solids

 Solids separated by filtration into non/soluble and

by high temperature oxidation into non/volatile
 Solids often form large percentage of total organic
material
 Solids degradation often slow due to mass transfer
limitations
 Sources: food processing, abattoirs rural industries
(piggeries etc.), domestic
Solids Fractions
1 2
Settleable solids Sample Total solids
TS
3
2 4
3 Ash
2

Total suspended Total dissolved Total volatile

solids (TSS) solids (TDS) solids (TVS)

4 1 Settling (cylinder/cone)

2 Evaporation (105ºC)

Volatile SS Non-volatile SS 3 Filtration (glass fibre filter)

VSS
4 High temp. oxidation (550ºC)
Practical Exercise: Solids
In solids analysis, the following measurements
were obtained:
 Sample size: 50 mL
 After filtration/evaporation:

12 mg filter cake, 2.5 mg solids in filtrate

 After high temperature oxidation:

2.0 mg filter cake

What is TSS, VSS and TS in the sample? mg/ml

 Answer

TSS : 12 mg / 50 ml = 0.24 mg/ml

VSS : (12 – 2.0 mg) / 50 ml = 0.2 mg/l

TS : (12+2.5) mg /50 ml = 0.29 mg/l

Odour

 Often very small amounts cause nuisance (eg.

H2S approx. 10 ppb)
 Physical/chemical measurement difficult
 Olfactometry uses human odor panels
 Olfactometer determines dilution necessary
until no odor detected
Temperature

 Industrial WW often elevated temperature

 Affects treatment performance of many
treatment systems
 Gas eg. O2 solubility is lower at higher
temperature
 Effluent temperature usually specified in license
limits
Salinity

 Affects ecosystems in receiving waters

 Reduces O2 solubility
 Restricts reuse applications (eg. irrigation)
 Critical for downstream water utilization
Colour & Turbidity

 Colour of WW & biological treatment:

 light
brown-gray => fresh, aerob
 dark brown-black => old, anaerob

 Soluble dyes (stains) also cause coloring, very

difficult to remove (e.g textile)
 Turbidity measures light-transmission
 Caused by colloidal or suspended matter
 Can be correlated with suspended solids
Organic Matter

 Largest component group in most ww: 75 % of TSS,

40 % of TDS (domestic ww)
 Composition highly industry dependent
 Types:
 carbohydrates
 proteins
 oil & grease
 organic toxins (priority pollutants, eg. pesticides)
 others eg. surfactants, dyes etc.

 Mostly biodegradable, some very slowly

Carbohydrates

 Composition: C, H, O
 Soluble: sugars, alcohols, acids (VFA) rapidly
biodegradable
 Insoluble: starches, cellulose, fibres (relatively)
slowly biodegradable
 Sources: sugar mills, breweries, dairy factories,
canneries etc.
Proteins

 Composition: C, H, O, N (16%), S, P
 Solubility varies with protein type and ww
conditions (eg pH, salt conc. )
 Quite rapidly biodegradable to amino acids
except when insoluble
 Anaerobic degradation creates H2S and other
sulphur components => odor
 Sources: dairy factories, meat processing
(abattoirs), food processing
Oil & Grease

 Composition: C, H, O
 Hydrophobic substances: grease, fat, oil
 Mostly insoluble, floating, easily adsorbed on
surfaces
 Slowly biodegradable, even when hydrolysed to
glycerol and fatty acids
 Sources: meat processing, food production,
chemical factories
Toxics (Priority Pollutants)

 Organic toxic chemicals, pesticides, herbicides,

solvents, etc.
 Inorganic substances eg. Heavy metals (Cd, Cr,
Pb, Hg, Ag etc.)
 Normally very low effluent limits
 Sources: chemical factories, metal manufacturing,
tanneries, agriculture, etc.
 Measurement of Organic Content

 Mostly overall content measured:

 Totalorganic carbon: TOC
 Biochemical oxygen demand: BOD

 Chemical oxygen demand: COD

 BOD & COD most commonly used for design and

effluent specifications
Biochemical Oxygen Demand (BOD)

 Measures oxygen required for biological oxidation

of organics
 BOD: oxygen uptake by microorganism during
aerobic growth in ww sample
 Standard BOD: 5 day incubation @ 20°C
Practical Concerns with BOD Test

 Only partial degradation of organics

 Cannot be used for mass balancing
 Very high (>1000mg/L) and very low (<10mg/L)
values often unreliable
 Industrial wastewater can contain inhibitors,
leading to low BOD results
Chemical Oxygen Demand (COD)

 Also measures oxygen required, but for chemical

oxidation of organics
 COD: chemical oxidants used for oxidation of
organics to CO2, H2O & NH3
 Standard COD: K2Cr2O7 2- /H2SO4 @ 145°C