CHAPTER 2: ENVIRONMENTAL SAMPLING DR.

NORHUSNA MOHAMAD NOR

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COURSE LEARNING OUTCOMES
At the end of this chapter students should be able to:
 Understand different type of samples in sampling and
analysis methods (water and soil sampling) and sampling
stratified levels in containers
 Describe methods/techniques required for samples
preservation

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OUTLINES
Type of Samples
Sampling and Analysis
Water Sampling
Soil Sampling
Sampling Stratified Levels in Container
Preservation of Samples

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WHY NEED TO DO
ENVIRONMENTAL
SAMPLING?
 To determine the
background, natural
concentrations of
chemical constituents
in the environment
To determine the
concentrations of
harmful pollutants in
the environment

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ENVIRONMENTAL SAMPLE DESIGN
Development of Sampling Plan
• Where and when the samples will be collected
• Number of samples required

Collection of Samples

Preservation of Samples
• Transportation
• Storage

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 Monitoring & research purpose – to
monitor the effluent or to characterize
the pollutant

SAMPLING PLAN 1. Objectives

- To comply with regulations
- To identify long and short term trend
- Detect the accidental release
- To develop data base or inventory of
pollutant level
4. Nontechnical
factors - Margin of error allowable
- Sampling
convenience 2. Variability
- Site Accessibility How many? - Spatial variation
- Availability of Where and - Temporal variation
equipment When?
- Regulations
3. Cost Factor
- Sampling cost
- Analytical cost
- Fixed vs. min. cost

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ENVIRONMENTAL SAMPLING STRATEGIES
 Judgemental
 Simple random
 Stratified random
 Systematic
 Other
 Composite
 Transect

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ENVIRONMENTAL SAMPLING STRATEGIES -
JUDGEMENTAL
Selection of sampling locations based on professional
judgment using prior information on the sampling site, visual
inspection and/or personal knowledge and experience
Schedule and budget  tight, early stage when objective is
just screen the area
Primary representative sampling approach for groundwater
assessment
No randomization and does not support any statistical
interpretation of sampling results
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ENVIRONMENTAL SAMPLING STRATEGIES – SIMPLE
RANDOM
Arbitrary collection of samples by a process that
gives each sample unit in the population the same
probability of being chosen
Assumes variability of sampled medium is insignificant
– homogenous population
Applies for sites with little background information
Not applicable for heterogeneous population
Ignoring prior information leads to more samples
Statistical analysis of data  simple and straight
forward
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ENVIRONMENTAL SAMPLING STRATEGIES – STRATIFIED
RANDOM
Sampling population is divided into
several non overlapping strata
Each strata is more homogenous
than whole population
Strata could be temporal or spatial
Sample size can be adjusted

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ENVIRONMENTAL SAMPLING STRATEGIES –
SYSTEMATIC SAMPLING
Systematic random 
subdivides the area into grids
and collects samples using
simple random sampling
Systematic Grid  easy to
implement
Uniform distribution over the
space or time domain
Critical part  choose right
grid spacing
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ENVIRONMENTAL SAMPLING STRATEGIES – OTHER
Composite sampling
oSampling cost much less than analytical cost
oAverage concentration rather than variability
e.g., Trace metal analysis
Transect sampling
oVariation of systematic grid sampling  one or more transect lines
across a surface
oRegular intervals along the transect lines
oParallel or non parallel to one another
e.g., characterizing waste piles and water flow

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ENVIRONMENTAL SAMPLING STRATEGIES – HOW MANY
SAMPLES?
Largest sample number possible
Avoid taking too few samples
No Universal formula
Simple random sampling
n= 4* variability2 / acceptable error2

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TYPES OF SAMPLES
 Grab Sample
Discrete sample which is collected at a specific location at a certain
point in time
If the environmental medium varies,
a single grab sample is not
representative and more samples
need to be collected

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Composite Sample
Made by thoroughly mixing several grab samples
More representative if the sampling medium is very heterogeneous
E.g. A field sample is taken at a random time point once within each
hour a day. These 24 samples are mixed to form 2 composites.

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SAMPLING AND ANALYSIS
Proper steps should be taken – pollutants are not lost or
chemically altered during sample collection, preservation
and transport
Most common environmental samples – air, water, soil,
biological materials and wastes (liquid, solid or sludge)
Different techniques used for different type of samples

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ENVIRONMENTAL SAMPLING - WATER
Surface water and waste water sampling
Pond sampler - near shore sampling
Weighted bottle sampler - collect samples in a water
body at a predetermined depth
Kemmerer bottle – Teflon, acrylic or stainless steel tube
attached to a rope and best used when access is from a
boat or structure such as bridge or pier

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ENVIRONMENTAL SAMPLING – SURFACE WATER &
WASTEWATER

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ENVIRONMENTAL SAMPLING – SURFACE WATER &
WASTEWATER

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ENVIRONMENTAL SAMPLING – GROUND WATER
Collected from a well by a bailer
Bailer – an open pipe with an open top and a check
valve at the bottom.
Peristaltic pump – rotor with ball bearing rollers
Well – with a small diameter and has a depth limitation
of 25 ft

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ENVIRONMENTAL SAMPLING – SOIL
Soft surface soil samples – scoop or trowel
1~10 ft – tube sampler
3 inches ~ 10 ft –auger sampler
Will disrupt and mix soil horizons
Hard soils – split spoon sampler

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ENVIRONMENTAL SAMPLING – SEDIMENT
Scoops and trowels – for sample sediments around
shoreline and slow moving waters
Ekman dredge – small and light weight (10 lbs) and
collects soft sediments
Petersen or Ponar dredges

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ENVIRONMENTAL SAMPLING – AIR AND STACK EMISSION
Direct reading instruments and type of monitoring
instruments
Expensive and complex techniques
Professional stack – testing firms
High volume, total suspended particle (TSP) sampling
system
PM-10 sampling system

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ENVIRONMENTAL SAMPLING – BIOLOGICAL SAMPLING
Unique and diverse equipment
Mammals – trapping
Fish – trawl nets gill nets
Vegetation – harvested during growing season
Benthic macro invertebrate samples – Petersen and Ekman
dredges can be used

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ENVIRONMENTAL SAMPLING – HAZARDOUS WASTE
Ponar or Ekman sampler – sludge sampling
Composite liquid waste sampler – stratified liquid in
drums and other similar containers
Thief – drum sampling device particularly useful for grain
like materials
Trier – sampling sticky solids and loosened soils

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
Turbidity Dissolved Oxygen
Color Biochemical Oxygen
pH Demand
Acidity/Alkalinity Chemical Oxygen
Demand
Hardness
Solids
Residual Chlorine and Chlorine
Demand
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(1) Turbidity
Result of interference of passage of light through the
water containing suspended materials
Turbidity determination (1) Nephelometer  scattering of
light from particles (2) Turbidimeter  interference to light
passage in a straight line
NTU is commonly used
Samples with turbidity  40 NTU must be diluted

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(2) Color
Apparent color  caused by suspended matter 
determined on the sample “as is”
True color  caused by colloidal vegetable or organic
extracts  remove suspended matter by centrifugation
then determine color of clarified liquid
1 standard unit of color = 1 mg/L of Pt (as K2PtCl6)
Nessler tubes  0 ~ 70 color units

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 ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

Color comparison tubes:-

Nessler tubes

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(3) pH and acidity/alkalinity
pH  condition of a solution related to [H+] pH = - log[H+] 
determined by a pH meter
Alkalinity  the capacity of water to resist changes in pH that would
make the water more acidic  determined from a titration
Acidity = (Volume need to reach end point) × (concentration of the
strong base)
Mineral acidity = [H+] + [H2CO3] − [OH-]  titration to pH = 3.7
(methyl orange end point)
Total acidity = [H+] + 2[H2CO3] + [HCO3-] − [OH-] titration to pH
= 8.3 (phenolphthalein end point)
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
Alkalinity = (Volume need to reach end point) ×
(concentration of the strong acid)  titrated with 0.02 N
H2SO4
Phenolphthalein alkalinity (mg/L) = [OH-] + [CO32-] − [H+] 
titration to pH = 8.3
Total Alkalinity = Bromcresol-Green alkalinity (mg/L) =
[HCO3-] + [OH-] + 2 [CO32-] − [H+]  titration to pH = 4.5

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

End points for Acidity/Alkalinity titration

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(4) Hardness
Hardness  caused mainly by divalent metallic cations
(e.g. Ca2+ , Mg2+ , Sr2+ , Fe2+ , Mn2+)  determined by
EDTA titrimetric method
EDTA = ethylenediaminetetraacetic acid (H4Y) M2+ + EDTA
 [M-EDTA]complex
Total hardness = Ca hardness + Mg hardness (in most cases)

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(5) Residual chlorine
Chlorine (Cl2)  used for disinfection of water supplies and wastewater
effluent to prevent water-borne diseases
Free chlorine residuals  Cl2 + HOCl + OCl−
Combined chlorine residuals  NH2Cl + NHCl2 + NCl3
Total chlorine residuals = free chlorine residuals + combined chlorine
residuals
Measurement of total chlorine residuals
Cl2 + 2 I−  I2 +2 Cl−
I2 + starch  blue color
I2 + 2Na2S2O3  2Na2S4O6 + 2NaI
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(6) Dissolved oxygen
The concentration of DO in water is small and therefore
precarious from ecological point of view.
The dissolution process:

The equilibrium constant is the Henry’s Law constant KH

DO analysis  the Winkler Method

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
DO: Thermal pollution
River and lake water that has been artificially warmed can be
considered to have undergone Thermal Pollution. Why?
Gas solubility decreases with increasing temperature.
Warm water contains less oxygen than cold water. To sustain
life, most fish species require at least 5 ppm of DO.
Consequently, their survival in warm water can be
problematic.
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 ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(7) Biochemical oxygen demand (BOD)
BOD: amount of O2 required by bacteria to stabilize
decomposable organic matter under aerobic conditions
High BOD value = high organic-matter concentration = poor
water quality
Decomposition of organic matter is a slow process:
20 days  decompose 95 to 99% of organic matter
5 days  decompose 60 to 70% of organic matter

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
Measurement of BOD  BOD5
BOD5 = DO5-DO0 where DO0 = DO before incubation
(day 0) DO5 = DO after 5 days of incubation at 20ºC
(day 5)
BOD5 for domestic sewage = several hundreds mg/L
BOD5 for industrial sewage = several thousands mg/L
 when the sewage is discharged to water  quick
depletion of oxygen
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
initial stage
==> DO curve drops (i.e. rate of O2 consumption by bacteria
> rate of reaeration with atmosphere)
at the point where [DO] = minimum
==> rate of consumption = rate of reaeration
beyond minimum point
==> rate of consumption < rate of reaeration (DO level
eventually returns to normal)
This sequence is called "natural self-purification of water"
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(8) Chemical oxygen demand (COD)
COD  a measure of total organic strength of wastes
The basis for the COD test  nearly all organic compounds
can be fully oxidized to carbon dioxide with a strong oxidizing
agent under acidic conditions.
COD determination  potassium permanganate (KMnO4) was
used for years  potassium dichromate (K2Cr2O7) becomes
the most effective oxidant now (it is relatively cheap, easy to
purify, and is able to nearly completely oxidize almost all
organic compounds)
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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS

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ENVIRONMENTAL ANALYSIS – WATER ANALYSIS
(9) Residue (Solids)
 Usual definition of solids = residue upon evaporation and drying or ignition

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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
Physical properties Particle size
Density
Porosity Soil contaminants
Texture Heavy metals (e.g. Pb, Cd, Cr)
Organic pollutants (e.g. Pesticides,
Chemical analysis Soil pH Petroleum hydrocarbons)
Soil organic matter
Cation exchange capacity

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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(1) Soil particle size

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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(2) Soil density
Soil particle density
< 1 g/mL for organic matter, > 5 g/mL for some metals
oxides; average 2.5 ~ 2.8 g/mL
Soil bulk density Include the pore spaces between particles
Smaller than particle density; average 1.2 ~1.8 g/mL

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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(3) Porosity and texture
Porosity
Pore space (%) = 100 - (bulk density/particle
density)*100
Texture Clay
Sand
Silt

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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(3) Porosity and texture

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ENVIRONMENTAL ANALYSIS –
SOIL ANALYSIS
(4) Soil pH
How acidic or alkaline the soil is
0 to 14
pH = -log [H+]
At pH 6 there are 10x more H+ than
at pH 7
At pH 5 there are 100x more H+
than at pH 7
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 ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(5) Soil organic matter
Soil organic matter includes Humic substances
(humic acid, fulvic acid, and humin)
Fats, resin, and waxes
Polysaccharides
Amino acids
Main constituents:
C (52 - 58 %), O (34 – 39 %), H (3.3 – 4.8
%) and N (3.7 – 4.1 %) with other prominent
elements being P and S 60
 ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(6) Cation exchange capacity
Capacity of a soil exchange of positively charged
ions between the soil and the soil solution
Clay particles and organic matter have negatively
charged sites that can hold positively charged ions on
their surfaces
Expressed in meq/100g of soil
1 m eq of CEC has 6.02 × 1020 adsorption sites
CEC of most soils increases with an increase in soil pH
Highly dependent upon soil texture and organic
matter content
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ENVIRONMENTAL ANALYSIS – SOIL ANALYSIS
(7) Soil contaminants
Inorganic contaminants (e.g.
heavy metals)  AAS or AES
analysis
Organic contaminants (e.g.
Petroleum hydrocarbons and
pesticides)  GC analysis

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SAMPLING TECHNIQUES
General guidelines common to all environmental sampling:
Sequence of sampling matrices
Sample amount

Sample preservation and storage

Selection of sample containers

Selection of sampling equipments

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SAMPLING TECHNIQUES
(1) Sequence of sampling matrices
Least to most contaminated sampling locations
Sediment and water at same site  collect water first
Sampling at different depths  collect surface water samples first

(2) Sample amount

Sufficient to perform all required laboratory analyses and with an
additional amount remaining for QA/QC analysis
Representativeness factor

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SAMPLING TECHNIQUES
Water/waste water samples
100 ml for trace metals
1 L for total organics
20~40 L for an effluent acute toxicity test
Soil/sediment/solid waste samples
200 g per sample
Air samples
Trial and error method
10 m3 may be required per sample
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SAMPLING TECHNIQUES
(3) Sample preservation and storage:
Purpose to minimize any physical, chemical and biological changes
from time of sample collection to the time of analysis

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SAMPLING TECHNIQUES
Cold storage  reduce
metal solubility
Chemical addition or pH
change  reduce metal
adsorption to glass
container walls

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SAMPLING TECHNIQUES
No sample can be stored
for an extended period of
time
Maximum Holding Times
(MHTs) – Length of time a
sample can be stored after
collection and prior to
analysis without significantly
affecting the analytical
results
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SAMPLING TECHNIQUES
(4) Selection of sample containers
Glass vs. plastic
Headspace vs. no headspace
Special containers
Biological samples  aluminum foil and closed glass
containers with inert seals or cap liners
Aluminum foils should not be used if mercury is the target
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SAMPLING TECHNIQUES
(5) Selection of sampling equipment
Made of plastic, glass, Teflon, stainless steel and other materials for
Surface water and waster water sampling
Groundwater sampling
Soil sampling
Sediment sampling
Hazardous waste sampling
Biological sampling
Air and stack emission sampling
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THANK YOU!

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