CHAPTER 2

Student Learning Outcomes:

At the end of this chapter, students should be
able to:

• identify types of samples.

• understand the terms used in acceptance
sampling.
• recognise the important of sampling plan and
sampling strategies.
• define and execute correct sampling operation
and storage conditions.
What is a sample?
A sample is a subset of population which selected to be
representative in any study.

Sample (in analytical chemistry)

A portion of material selected from a larger quantity
of material.

Types of Sample: Representative sample

Selective sample
Random sample
Composite sample
 COMPOSITE SAMPLE
A sample which is made by combining samples (more than
one) from two or more locations. The sample can be of
water, soil or other matrix.

A representative sample created by the homogenization of

multiple samples from multiple sampling locations within
the same general area.

Samples collected at regular intervals, sometimes in

proportion to the existing flow, and then combined to form a
sample representative of flow over a period of time.
Why do we use samples?

• Get information from large populations

• At minimal cost

• At maximum speed

• At increased accuracy

• Using enhanced tools

Sample (in analytical chemistry), continued

The term sample implies the existence of a sampling error,

i.e. the results obtained on the portions taken are only
estimates of the concentration of a constituents or the
quantity of a property present in the parent material. If
there is no or negligible sampling error, the portion
removed is a test portion, aliquot or specimen.

The manner of selection of the sample should be prescribed

in a sampling plan.
 Sampling

Precision
Cost
What is sampling?

Sampling is simply stated as selecting a portion of

the population, in any research area, which will be
a representation of the whole population.
or
Procedure by which some members of a given
population are selected as representatives of the
entire population
Definition of sampling terms:

Sampling unit
Subject under observation on which information is
collected
Sampling fraction
Ratio between the sample size and the population
size
Sampling frame
Any list of all the sampling units in the population
Sampling scheme
Method of selecting sampling units from sampling
frame
Representativeness

The USEPA (Office of Environmental Information Quality)

Representativeness: A measure of the degree to
which data accurately and precisely represent
characteristics of a population, parameter variations
at a sampling point, a process condition, or an
environmental condition.

The analytical results from tiny samples are expected to

"represent" the analyte concentrations for the original
bulk matrix that was sampled.
Sampling and representativeness

Sampling
Population Sample

Target Population

Target Population  Sampling Population  Sample

 What we need to know
• Concepts:
– Representativeness
– Sampling methods
– Choice of the right design

• Calculations:
– Sampling error
– Design effect
– Sample size
Sampling plan (in analytical chemistry)

A predetermined procedure for the selection,

withdrawal, preservation, transportation and
preparation of the portions to be removed from a
population as samples.

A sampling plan includes the designation of the number,

location, and size of the portions, and instructions for
the extent of compositing and for the reduction (in
amount and fineness) of the portions to a laboratory
sample and to test portions.
Sampling methods/strategies

Researcher must develop a suitable sampling strategy

or type of sampling according to the goal of the study.

Random
Systematic Probability sample
Stratified

Judgmental
Convenience
Nonprobability sample
Quota
Snowball
Sampling strategies : RANDOM
Samples are collected randomly (no conscious or unconscious
selection) such that each sample has a chance of representing
the whole.

Makes no assumptions about distribution or movement of

analytes

Usually cost more because it requires more sample/greatest

replication.
 Simple random sampling

• Advantages
–Simple
–Sampling error easily measured

• Disadvantages
–Need to complete list of units
–Does not always achieve best
representativeness
–Units may be scattered
Sampling strategies: SYSTEMATIC
Using personal judgement, samples are collected at regular intervals in space
and time - makes no assumptions about distribution or movement of analytes.

After the required sample size has been calculated, every Nth record is selected
from a list of population members. As long as the list does not contain any hidden
order, the sampling method is as good as the random sampling method.

Advantage over random sampling – simple. Systematic sampling is frequently used

to select a specified number of records from a computer file.
 Systematic sampling
Researcher has to calculate sampling fraction (Nth):

Nth = Sampling population (N)/sample size (n)

Example if we have 1200 people, and we need about 60 people as a

sample, so:

• N = 1200, and n = 60
 sampling fraction = 1200/60 = 20
• List people from 1 to 1200
• Randomly select a number between 1 and 20 (ex : 8)
 1st people selected = the 8th on the list
 2nd people = 8 + 20 = the 28th
 3rd people = 28 +20= the 48th , repeat the process until we
get a total of n=60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

46 47 48 49 50 51 52 53 54 55 56 57. 58 ……...
Advantages and Disadvantages of Systematic Sampling

Advantages:
More straight-forward (simple) than random sampling.

A grid doesn't necessarily have to be used - sampling just has to be at

uniform intervals.

A good coverage of the study area can be more easily achieved than
using random sampling.

Disadvantages:
More biased, not all members or points have an equal chance of being
selected.

It may therefore lead to over - or under - representation of a particular

pattern.
Systematic sampling
Sampling strategies: STRATIFIED

System to be sampled is divided into parts (strata), each as

uniform in the parameter of interest as possible. Samples are
collected randomly from strata.

For example, for water sampling, a lake is usually divided into two
strata -the epilimnion (upper layer) and hypolimnion (bottom layer).

Advantage: Sampling precision is improved because uncertainty

arises from variations within strata, not differences between strata. It
is important to decide on the smallest changes that need to be
detected because these determine the number of replicates and
precision needed.
Stratified Sampling
The population is broken down into categories, and a random sample is
taken of each category. The proportions of the sample sizes are the same
as the proportion of each category to the whole.

Advantages:

1. Focuses on important subpopulations (strata).

2. Allows to use different sampling techniques for different subpopulations.
3. Improves the accuracy/efficiency and precision.

Disadvantages:

1. Requires selection of relevant stratification variables which sometime

can be difficult.
2. Not useful when there are no homogeneous subgroups/subpolulations.
3. Can be expensive to implement.
Sampling strategies: Judgemental

The researcher selects the sample based on judgement.

eg. Implements assumptions about movement and
distribution with time, distance (fate and transport).

Disadvantage: Bias, the researcher selects the sample

based on judgement. However, it is fast and economical
method to solve identifiable sources of a problem
Sampling strategies: Convenience

Used in exploratory research where the researcher is

interested in getting an inexpensive approximation of the
truth. The sample is selected because they are convenient.

Often used during preliminary research efforts to get a

gross estimate of the results, without incurring the cost or
time required to select a random sample.
Sampling strategies: Quota

The nonprobability equivalent of stratified sampling.

Like stratified sampling, the researcher first identifies the
stratums and their proportions as they are represented in
the population.
Then convenience or judgement sampling is used to select
the required number of subjects from each stratum. This
differs from stratified sampling, where the stratums are filled
by random sampling.
Sampling strategies: Snowball

A non-probability sampling method used when the desired

sample characteristic is rare. It may be extremely difficult or
cost prohibitive to locate respondents in these situation.

Snowball sampling relies on referrals from initial subjects to

generate additional subjects.

Lower search costs, but introducing bias because the

technique itself reduces the possibility that the sample will
represent a good cross section from a population.
Sampling strategies: Combinations

Frequently judgement combined with systematic or random is used

to take advantages from each

The general relationship of Judgemental (J), Systematic (S), and

Random (R) sampling approaches to relative numbers of samples needed
and relative amounts of bias introduced
Sampling Stages

Primary sample:
The collection of one or more
increments or sampling units initially
taken from a population
Subsample:
A portion of a sample obtained by
selection or division from primary
sample.
Laboratory sample:
The sample or subsamples sent to or
received by the laboratory for analysis

Test sample/ analytical sample:

The sample, prepared from the
laboratory sample, from which test
portions are removed for testing or
analysis using specific instrument.
Sampling Stages (continued)
Test portion/analytical portion:
The quantity of material, of proper size
for measurement of the concentration or
another property of interest, removed
from the test sample.

Test solution/analytical solution:

The solution prepared by dissolving, with
or without reaction, the test portion in a
liquid.
Treated solution:
The test solution that has been subjected
to reaction or separation procedures prior
to measurement of some property.

Aliquot:
A known amount of a homogeneous
material, assumed to be taken with
negligible sampling error. The term is
usually applied to liquid.
Sampling site location

In addition to the rationale of their selection, the clear

location of sampling sites must be reported, preferably by
indication of their longitude and latitude.

A map may be very useful to visualize the sites.

The exact spatial sampling site must be specified by

indicating depth or height with the reference to the surface
or the sea level.
Sampling site location

Sampling sites at Langat River Basin

Source: Alam Sekitar Malaysia (2006)
Sampling sites: DOE-Langat River Basin

RIVER STATION NO LONGITUTE LATITUTE

Langat 1L01 E 101° 26.421’ N 02° 52.027’
Langat 1L02 E 101° 30.780’ N 02° 48.952’
Langat 1L03 E 101° 40.882’ N 02° 51.311’
1L04 E 101° 47.030’ N 02° 57.835’
Langat
1L05 E 101° 47.219’ N 02° 59.533’
Langat
1L07 E 101° 50.926’ N 03° 09.953’
Langat
1L08 E 101° 45.014’ N 02° 47.241’
Batang Labu 1L09 E 101° 45.990’ N 02° 53.516’
Semenyih
1L10 E 101° 50.870’ N 02° 56.772’
Semenyih
Semenyih Batang 1L11 E 101° 52.094’ N 03° 00.523’
Benar Rinching 1L12 E 101° 49.457’ N 02° 50.898’
Lui 1L13 E 101° 51.765’ N 02° 55.122’
Langat 1L14 E 101° 52.200’ N 03° 10.444’
1L15 E 101° 46.383‘ N 03° 02.449‘
Langat
1L16 E 101° 49. 010‘ N 03° 06.676‘
Balak
1L17 E 101° 46.065‘ N 03° 00.934‘
Beranang Pajam 1L18 E 101° 49.737‘ N 02° 53.297‘
Batang Benar 1L19 E 101° 50.383‘ N 02° 52.628‘
Buan 1L20 E 101° 49.199‘ N 02° 51.728‘
Batang Nilai 1L21 E 101° 47.371‘ N 02° 51.874‘
Batang Nilai
1L22 E 101° 48.653‘ N 02° 48.844‘
Batang Labu Jijan
1L23 E 101° 47.491‘ N 02° 48.106‘
1L24 E 101° 47.895‘ N 02° 46.890‘
1L25 E 101° 45.119' N 02° 46.659'
Sampling site: Klang River Basin

Sg Gombak

Sg Ampang

Sg Damansara

Shah Alam

Sg Klang

Sampling sites at Klang River Basin

Source: Alam Sekitar Malaysia (2009)
Sampling time and Frequency

Sampling time/day and frequency depend on the goal

of the study.

Preventive sampling:
Environmental monitoring
Agricultural monitoring
Monitoring water quality

Diagnostic sampling: pinpointing existing problems

Production problems
Environmental problems
Sampling time and frequency : Preventive sampling
Monitoring water quality
When monitoring the quality of a water source, take samples at regular intervals
over a period of time.
Environmental monitoring
Sample farm water supplies at least twice a year to verify the effectiveness of
existing stewardship practices. If there are signs of environmental impact, take
monthly samples to verify results.
Agricultural monitoring
Base sampling frequency on the following general guidelines:

Sample drinking water for poultry and livestock at least twice a year to be
sure that water quality is not adversely affecting performance.

Sample irrigation water for field crops at least once a year to find out if the
water is likely to cause production or application problems. More intensive
sampling is necessary in coastal regions that may be subject to salt water
intrusion.

Once a year, take samples from source water used in pesticide solutions to
find out if you should add special buffering agents that enhance pesticide
half-life and performance.
Sampling time and frequency : Diagnostic sampling

Pinpointing existing problems

When production or environmental problems occur, take solution samples from
several areas and/or over a period of time to isolate causal factors.

Production problems.
Take samples from problem and nonproblem areas for comparison. When
appropriate, take matching soil and plant samples from both areas as well.
When troubleshooting a nutrient solution problem, sample both the source
water and the nutrient solution.

Environmental problems.
Pinpointing a source of environmental impact requires taking several
samples. For example, if you want to determine the source of excess
nutrients entering a reservoir, you must take separate samples from all
streams or ditches that empty into it. As a general rule, take these samples
monthly and after significant rainfall events.
Sampling method

(i) Equipment

(ii) Technique / Procedure

Sampling method : Equipment

- Calibrate all field instruments in the field before

collecting samples to assure that their accuracy is
within acceptable limits.

- Choose a sampling device after consideration of the

following factors: depth to water, parameters of
interest, well construction details and accessibility of
the well(s). Ideally, well purging and sample
withdrawal equipment should be inert, economical to
use, easily cleaned, sterilized, reusable, able to
operate at remote sites and versatile in use.
Sampling method

Sediment

Grab sampler

Effective sampling area is 36 square inches. Jaws, side plates,

underlip plate, screen frame, and hinge pin all made of stainless steel.
Exterior weights and closing arms are constructed of powder painted
mild steel. A 3/8" nylon rope is recommended for raising and lowering
dredge.
Sampling method

The used of grab sampler – usually for sea to collect sediment, river, etc.
Not suitable for swallow area.
 Ekman Dredge

6" x 6" x 6" Dredge for sampling benthic communities inhabiting soft
bottomed aquatic environments. Hinged upper doors swing open as
dredge is lowered, allowing water to pass through and minimize shock
wave. Stainless steel messenger closes dredge, preventing washout of
sample. Cable release system, with bar grip, helps set dredge with
greater safety. Dredge is constructed of stainless steel with special
Heliarc welding for added strength and durability. A case, 100 feet of line,
and messenger are included. Also available is a 5' aluminum handle with
trip head that can be used in place of the line for shallow water work.
 Compact sampler with 1000mL
sampling jar is great for
sampling liquid, sludge or slurry
from tanks, rivers or spillways.
Specifications: Telescopic
aluminum pole handle comes in
three extendable lengths-8', 12'
and 24'. Just twist out the length
you need-adjusts to any size
increment. Sampling head
includes a 1000mL sampling jar.
Use optional Plunger when
sampling requires a 1" space
between sample and the cap.
Subsurface Grab Samplers
Quickly Adjusts to the Lengths You Need
Method of sampling

Water Sampler

Water can be sampled from any

depth, using the single raise / lower
line and built-in release trigger.

Materials for water bottle:

 polycarbonate
 acrylic (not for use for in salt water) and
 PVC

Was able to take sample 1.5 L to 5 L

In operation, the sampler is lowered to the desired sampling depth. A quick tug
on the sampler's line activates the trigger, releasing the sealing balls, and locking
in a sample.

A brass messenger triggers a release mechanism to seal the sample chamber

with two fitted rubber plungers at the desired sampling depth. The built-in side
outlet and flexible tube allows for removal of the water sample.

Used by ASMA Sdn Bhd

 The end of this sampler swings for collecting
samples at different angles with a maximum of 90°,
making it perfect for sampling streams from steep
stream banks. The fiberglass pole extends to 12 feet
for flexibility in various situations. A 960 ml bottle is
included. A large snapper holds bottles in the 1,000
ml range. The Swing Sampler may be used for
liquids, powders, or small solids.

Swing Sampler
Method of sampling

PORTABLE AIR SAMPLER

Method of sampling

High volume air sampler

PORTABLE AIR SAMPLER

Microbial Air sampler

Sampling method : Sampling Procedure
Sample collection (eg: Well water sample)

Use a 1-liter (amber colored) glass bottle with

reusable teflon lined caps.

Rinse each bottle used for sampling pesticides and

nitrate-nitrogen three times with water from the well
before filling. Rinse bottle caps also. To rinse, fill
the bottles approximately one-third full, replace cap
and shake vigorously. Discard the rinse water after
each rinse cycle.

Following rinsing, fill the bottles with water from the

well, replace the teflon-lined lid snugly, label and
and place the bottle in a cooler for storage and
transport.
Sampling method : Sampling Procedure

Wells. Before sampling water from new wells or from wells recently treated with
chemicals, run water one to two hours. Running the water five to ten minutes
before sampling is usually sufficient for old wells. Longer times may be necessary
if wells have not been used recently.

Rivers or streams. Sample from the middle of the stream at mid-depth. Avoid
collecting surface or bottom residues.

Lakes or reservoirs. Choose location, depth, and frequency of sampling based

on the purpose of sampling and prevailing conditions. Avoid collecting surface or
bottom residues since these contaminants alter results.

Hydroponic systems. Flush lines sufficiently to ensure that the sample is

representative of a thoroughly mixed supply solution.

Nutrient solutions. Sample the solution after thoroughly mixing acid and/or
nutrient additions.
Size of sample

Hardly any environmental compartment is homogeneous;

the larger the sample size, the lower is the sample-to
sample variability.
Sample Labelling:

The sample label is an important aspect of documentation and should

unambiguously identify the sample to related plans or notes.

Labelling is particularly important, further into the analytical process, when the
sample may have been divided, subsampled, or modified in some way. In such
circumstances, additional information may be appropriate,such as references to the
main sample, and to any processes used to extract or subsample the sample.

Labelling must be firmly attached to the sample packaging and where

appropriate, be resistant to fading, autoclaving, sample or reagent spillage, and
reasonable changes in temperature and humidity.

The labels on the water sample bottles should indicate:

Type of analysis;
Monitoring point identification;
Name of person collecting the sample;
Time and date the sample was collected; and,
Whether a preservative was added to the sample or the
sample was filtered.
Pre-treatment of samples

Chemical Pretreatment:
• Addition of buffers (to avoid pH changes drastically)
• Addition of preservatives (acidification, chemical addition,
or refrigeration/freezing).

Physical Pretreatment:
• Filtration …. Water samples
• Sieving ……Soils or any solid samples (plants, etc)
• Drying …. Soils, sediments, plants
• Adsorption of analyte onto SPE cartridges
Storage of samples

Depends on the stability of the analyte(s)

The time and conditions of sampling storage between

sampling and analysis must be described:

• Type of Material of the sample containers

• preceding cleaning procedures
Chain of Custody

“Chain of Custody” is a legal term that refers to the ability

to guarantee the integrity of the specimen/sample from
collection through to reporting of the test results.

"Chain-of-custody" tracking is required on all samples.

"Chain-of-custody" provides a record of all the personnel
responsible for handling the samples.

Proper "chain-of-custody" procedures play a crucial role in

enforcement cases (eg: crime scene investigation)
Chain of Custody: Important information

Documents should include:

-Name of the individual collecting the specimen/sample

-Each person or entity subsequently having custody to the
specimen/sample.
-The date the specimen was collected or transferred to
laboratory for analysis.
-Employer or agency (eg: Forensic unit, PDRM)
-Specimen/sample number.
-Employee’s name.
-A brief description of the specimen/sample
Sampling : Chain of Custody
Sample requirements: Soil and sediment

• Soil horizon sampled

• Soil texture (particle size range or % clay, %silt, %sand)

• pH, organic carbon content, water content

• Land use (arable, pasture, forest, industry, etc.)

• Other parameters if known to impact on the analyte to be

determined or relevant for the specific goal of the
research project, such as cation exchange capacity;
redox conditions; water holding capacity; biological
activity etc.
Sample requirements: Water (pore water, groundwater etc.)

• Depth of origin

• pH, organic carbon content

• Sampling method (pressure, centrifugation, suction

cups); and

• Other parameters if known or assumed to impact on the

analyte to be determined or relevant for the specific goal
of the research project, such as conductivity, macro-
nutrients, redox conditions.
On-line determination of silver in natural waters by ICP-MS:
Influence of organic matter
Sample requirements: Air

• Location of sampling point

• Air temperature, barometric pressure, relative humidity,

wind speed and direction

• Precipitation during the study period, notably during the

days immediately preceding sampling

• Sampling devices (container or floe-through equipment,

adsorbents or absorbents)

• Duration and rate of sampling

• Other parameters if known or assumed to impact on the

analyte to be determined or relevant for the specific goal of
the research project, such as duration of sunshine, local point
sources, local air flow obstacles.
 Teller, Alaska

65-14.45388N / 166-20.16040W, 293ft ASL

Saturday, September
Date:
24, 2005, 11:00 AM

Air Temperature: 5.8 C, 42.4 F

Relative Humidity: 92.9 %

Dewpoint: 4.7 C, 40.5 F

average 0.9 mph,

Windspeed:
maximum 7.6 mph

Wind Direction: 98 deg, E

EXAMPLE OF FINAL EXAMINATION QUESTIONS

QUESTION 1 (April 2006)

a) Distinguish between random, judgemental and systematic sampling plans,
commenting on the relative advantages and disadvantages of the sampling plan
in each case.
(9 marks)
b) Giving appropriate example, outline a flow procedure for these sampling terms:
laboratory sample, analytical sample, primary sample, aliquot, analytical solution.
(10 marks)
QUESTION 5 (April 2008)
a) In the determination of chlorpyrifos in Sungai Semenyih, a student used a
measuring cylinder to get exactly 10 mL of water from the sampling point and
injected into a gas chromatograph. Comment on the sampling process and
suggest how it can be improved.
(5 marks)
b) Discuss how the sampling time and frequency are determined for a particular
sampling plan. Use appropriate example to support your explanation.
(5 marks)
QUESTION 1 (April 2009)- Part A
a) Name one type of air, water, or soil sampler.
(1 mark)
b) State two important features of the specified sampler.
(2 marks)
QUESTION 5 (April 2009)- Part B
The analytical results from tiny samples are expected to "represent" the analyte
concentrations for the original bulk matrix that was sampled. Discuss the sampling
stages that each sample should undergo before the measurement can be done.
(10 marks)
QUESTION 1 (October 2007)- Part A
Sampling is important in analytical procedure in order to obtain a meaningful and
valid result. Describe the sampling plan procedure one must follow to ensure he
will collect the proper sample for analysis.
(3 marks)
QUESTION 5 (October 2007)- Part B
Sediment samples were taken from 8 ponds from a total of 25 sampling locations.
Pond A3 was chosen for sampling due to its position (adjacent to a pond with
elevated mercury) and changing water levels (may be managed as a seasonal
pond). Pond A2E was chosen due to the elevated Hg levels in tissues detected.
Pond A5, A6 and A7 were chosen for sampling due to their positions (adjacent to
ponds with elevated mercury levels). Sediment samples will be collected from the
bottom of ponds with a 2-1/4" diameter AMS sediment sludge sampler near the
shore water interface. Six samples will be submitted for analysis from each pond,
three from the surface (0-2 inches) and the other three at depth (6-8 inches). Upon
completion of each sample collection, the sediment sample will be directly placed
in an ice chest and cooled to 4 °C.
a) Discuss the sampling approaches involved in the above study.
(6 marks)
b) Suggest the labeling and storage procedures for the samples.
(4 marks)