WATER & WASTEWATER

SAMPLING
KKKR4873 POLLUTION CONTROL AND CLEANER PRODUCTION

Lecturers:
Dr. Rosiah Rohani (Set 1)
Assoc. Prof. Dr. Hassimi Abu Hasan (Set 2)
Sampling
•
Wastewater sample analysis
Standard methods to be used
• To be readied before sampling
• Required sample containers
• Required laboratory facilities
• Required reagents for preservation and analysis
any variation to be noted
• method has to be appropriate for the range
• know the expected range of values
• test for blanks
Sample containers
• container appropriate for parameter, in terms of type and size.
• ensure containers are clean, and have been appropriately
cleaned.
Wastewater sample analysis
Reagents
• Ensure they are properly stored
• Usability has not expired

Lab
• ensure lab equipment and facilities are clean
• ensure that chemicals required for identified
parameters are available beforehand
• ensure equipment in good operating condition
• check that equipment has been properly calibrated.
Aqueous Samples
• Volatile organics (BP below 100oC)
• Semi volatile organics (BP above 100oC)
• Dioxins/Furans
 Dioxins and Furan

• Dioxin is formed as an unintentional by-

• Furan and its derivatives sometimes form
product of many industrial processes
when amino acids or sugars are broken
involving chlorine such as waste
down by the heat of cooking
incineration, chemical and pesticide
manufacturing and pulp and paper
• Volatile chemical which tends to quickly
bleaching
evaporate
• Severe reproductive and developmental
• Remains present in the food for some
problems (at levels 100 times lower than
time when it cannot escape
those associated with its cancer causing
effects)
• Traces of furan and furan-containing
products have been found in some
• Dioxin is well-known for its ability to
processed and cooked products,
damage the immune system and interfere
quantities in foods are well below what is
with hormonal systems
considered dangerous
Polychlorinated Biphenyl
• PCBs are very stable compounds and do not decompose
readily.
• Chemical inability to oxidize and reduce in the natural
environment.
• PCBs have a long half life (8 to 15 years) and are insoluble in
water, which contributes to their stability.
• Their destruction by chemical, thermal, and biochemical
processes is extremely difficult, and presents the risk of
generating extremely toxic dibenzodioxins and dibenzofurans
through partial oxidation.
• Intentional degradation as a treatment of unwanted PCBs
generally requires high heat or catalysis
• Separation of dioxin and furan to form clean gases using
membrane
Volatile organics
• Commonly found contaminant in ground water
• As solvent in industrial process: paints, coatings,
benzene etc
• They can be carcinogens/mutagens
• Found in concentration above micro-g/L on the surface
(due to volatility), in the ground (hundreds/thousands
times higher.
• common 5 VOCs are vinyl chloride, trichloride,
tetrachloride, carbon tetrachloride, 1,2-dichloroethane
Sample preservation
• Standard methods to be used. (EPA standard)
• Ensure reagents are prepared beforehand
• Equipment calibrated and ready to be used
Sample Preservation
Methods of preservation are relatively limited and are
intended generally to:
• retard biological action
• retard hydrolysis of chemical compounds and complexes
• reduce volatility of constituents
• reduce absorption effects

Preservation methods are generally limited to pH control,

chemical addition, refrigeration, and freezing.

U. S. Environmental Protection Agency. 1983.

http://sisbl.uga.edu/epatab1.html
Aqueous sample analytical methods and handling requirements

Analysisa Methodsb Container Preservation Sample size Holding

Time
Volatile organics i.e. paints, coatings, benzene etc
GC VOA 601,602,8010, Glass VOA vial HCL-4°C 40-ml vials 14 days
8020
BTEX 602,8020 Glass VOA vial HCL-4°C 40-ml vials 14 days

Gasoline 8015 (mod.) Glass VOA vial HCL-4°C 40-ml vials 14 days

GC/MS VOA 624,8240 Glass VOA vial HCL-4°C 40-ml vials 14 days

CLP-VOA CLP-SOW Glass VOA vial HCL-4°C 40-ml vials 10 days

Analysis and methods are specified by the Environmental Protection Agency (EPA)
 Aqueous sample analytical methods and
handling requirements (continue)
Analysisa Methodsb Container Preservation Sample Holding
size Time
Semivolatile organics: BP above water i.e. phenol, benzene derivatives
etc
Pesticides/ 608,614,8080, Glass, Teflon- 4°C 1-2.5 L 7 days for
PCBs 8140 lined cap extraction
CLP- CLP-SOW Glass, Teflon- 4°C 1-2.5 L 5 days for
Pesticides lined cap extraction
Herbicides 615,8150 Glass, Teflon- 4°C 1-2.5 L 7 days for
lined cap extraction
Diesel Range 8100(mod.) Glass, Teflon- 4°C 1-2.5 L 7 days for
lined cap extraction
Phenols 604,8040 Glass ,Teflon- 4°C 1-2.5 L 7 days for
lined cap extraction
GC/MS SVOA 625,8270 Glass, Teflon- 4°C 1-2.5 L 7 days for
lined cap extraction
CLP-SVOA CLP-SOW Glass, Teflon- 4°C 1-2.5 L 5 days for
lined cap extraction

CLP- Contract Lab Program

 Aqueous sample analytical methods and
handling requirements (continue)
Analysisa Methodsb Container Preservation Sample Holding
size Time
Dioxins/Furans: highly toxic, environmental pollutants
LRMS 8280 Glass w/Teflon- 4°C 2-2.5 L 7 days for
lined cap extraction
HRMS 1613 Glass w/Teflon- 4°C 2-2.5 L 7 days for
lined cap extraction
Cations
ICAP 200.7, 6010 Plastic or glass HNO3-4°C 1L 6 months
GFAA 200, 7000 Plastic or glass HNO3-4°C 1L 6 months
CVAA (Hg) 245.1, 7470, CLP Plastic or glass HNO3-4°C 250 ml 28 days

Note: Dioxins can be by products from various industrial processes (i.e. bleaching paper pulp,
chemical and pesticide manufacture) and combustion activities
 Aqueous sample analytical methods and handling
requirements (continue)
Analysisa Methodsb Container Preservatio Sample Holding
n size Time
General Chemistry I
Acidity 305.1 Plastic/glass 4°C 250 ml 14 days
Alkalinity 310.1 Plastic/glass 4°C 250 ml 14 days
Ammonia 350.1 Plastic/glass H2SO4-4°C 250 ml 28 days
Anions 300.0 Plastic/glass 4°C 250 ml 24 hrs-28 d
BOD 405.1 Plastic/glass 4°C 250 ml 48 hours
COD 410.4 Plastic/glass H2SO4-4°C 250 ml 24 hours
Chloride 325.1 Plastic/glass 4°C 250 ml 28 hours
Chlorophyll-a 1002g Plastic/glass 4°C 250 ml 14 hours
Cl2, residual 330.4 Plastic/glass 4°C 250 ml 24 hours
Chromium VI 7196 Plastic/glass 4°C 250 ml 24 hours
Aqueous sample analytical methods and
handling requirements (cont.)
Analysisa Methodsb Container Preservation Sample Holding
size Time
General Chemistry II
CN, amenable 335.1 Plastic/glass NaOH-4°C 1L 14 days

CN, reactive 335.2 Plastic/glass NaOH-4°C 1L 14 days

CN, total SW-846 Plastic/glass NaOH-4°C 1L 14 days
Fluoride 340.2 Plastic only 4°C 250 ml 28 days
Hardness 130.1 Plastic/glass HNO3-4°C 250 ml 6 months
N, Kjedahl 351.3 Plastic/glass H2SO4-4°C 1L 28 days
Nitrate 353.2 Plastic/glass 4°C 100 ml 48 hours
Nitrate/Nitrite 353.3 Plastic/glass H2SO4-4°C 250 ml 28 days
Oil and grease 9070 Glass,Teflon- H2SO4-4°C 1L 28 days
lined cap
pH 150.1 Plastic/glass 4°C 250 ml Immediately
 Aqueous sample analytical methods and
handling requirements (cont.)
Analysisa Methods Container Preservation Sample Holding
b size Time
General Chemistry III
Petrol. hydrocarb’s 418.1 Glass w/Teflon- H2SO4-4°C 1L 28 days
lined cap
Phenolics 420.1 Glass w/Teflon- H2SO4-4°C 1L 28 days
lined cap
PO4, total 365.1 Plastic or glass H2SO4-4°C 100 ml 28 days
PO4, ortho 365.2 Plastic or glass 4°C 100 ml 48 hours
Conductivity 120.1 Plastic or glass 4°C 250 ml 28 days
Sulfate 375.4 Plastic or glass 4°C 250 ml 28 days
Sulfide 375 Plastic or glass Zn Ac./NaOH 500 ml 7 days
Solids, dissolve 160.1 Plastic or glass 4°C 250 ml 7 days
Solids, SS 160.2 Plastic or glass 4°C 1L 7 days
Solids, total 160.3 Plastic or glass 4°C 250 ml 7 days
Surfactants 425.1 Plastic or glass 4°C 1L 48 hours
Turbidity 180.1 Plastic or glass 4°C 250 ml 48 hours
 Method of analysis
PARAMETERS METHOD OF PARAMETERS METHOD OF
ANALYSIS ANALYSIS
General parameters Microbiological Parameters
pH pH meter (HACH) Coliform, total Membrane filtration at
37.0oC
DO DO meter (YSI 58) Coliform, feacal Membrane filtration at
44.5oC
Conductivity SCT meter (YSI 33) Trace Metals Filtration 0.45 um/AAS
Salinity SCT meter (YSI 33) Others
Temperature DO meter (YSI 58) Chloride Ion selective electrode
BOD Incubation at 20oC for 5 Oil and grease Extraction with
days petroleum ether
COD APHA Method 508 Phenols 4-aminoantipyrine-
CHCI3 extraction
TSS APHA Method 1209C Detergents MBAS
Ammonia Nessler reagent
Nitrogen
Orthophosphate Molibdate-ascorbic acid
Method of analysis
PARAMETERS METHOD OF ANALYSIS
General parameters
pH pH meter (HACH)
DO DO meter (YSI 58)
Conductivity SCT meter (YSI 33)
Salinity SCT meter (YSI 33)
Temperature DO meter (YSI 58)
BOD Incubation at 20oC for 5 days
COD APHA Method 508
TSS APHA Method 1209C
Ammonia Nitrogen Nessler reagent
Orthophosphate Molibdate-ascorbic acid
Microbiol. Paramet.
Coliform, total Membrane filtration at 37oC
Coliform, feacal Membrane filtration at 44.5oC
Trace Metals Filteration 0.45 um/AAS
Others
Chloride Ion selective electrode
Oil and grease Extraction with petroleum ether
Phenols 4-aminoantipyrine-CHCI3 extraction
Detergents MBAS
Data interpretation
Discussion on:
• physical parameters } overall view
• biochemical parameters } on quality and significance.
• heavy metals critical parameters as determined by:
- process
- location, etc.
Data interpretation
**Compare with:
• for emission – with emission limits,
-Malaysian: Std. A or B
-others may be necessary
• water quality – with NWQS or NMWQS

• past data

**Identify sources and causes for high or higher values.

How to Sample
DO Samples
• Collect using a special BOD bottle (a glass bottle
with a "turtleneck" and a ground glass stopper)
• Fill the bottle directly in the stream (if the stream is
wadable or boatable)
• Or use a sampler that is dropped from a bridge or
boat into water (deep enough to submerse the
sampler)
• DO measured by (1) Winkler method (2) meter and
probe.
DO measurement
Winkler Method
• fill a sample bottle completely with water (no air)
• Use reagents that form an acid compound and then
titrate
• Titrate with a reagent that neutralizes the acid
compound
• the color changes is the "endpoint" and is
equivalent to the amount of oxygen dissolved in the
sample.
• Unit mg/L

Meter & Probe

• Immediate test in the field
• Put the probe in the stream