TASK 1

The analytical results from samples are expected to “represent” the analyte concentrations from
original population that was sampled.

A)Explain why the concept of representativeness is important in sampling?

Representativeness is 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 environment condition. This concept is important to ensure the sample taken will represent the
actual amount of target analyte from one population/bulk. Matrix. Thus the analytical results
from the samples taken are expected to “represent” the analyte concentrations for the original
population.

B) Describe the sample requirements for the sampling the soil and sediment. Suggest two methods
of sample pre-treatment for these samples.

The sample requirements for sampling the soil and sediment

 Soil horizon that was sampled

 Soil texture can be determined by analysing the particle size range based on the % clay, %
silt, % sand
 pH, organic carbon content, water content. Determination of water content can be done
by oven drying at 100 °C until constant weigh is obtained. Organic carbon content is
determined by heating soil samples at 550 °C for 5 hours.
 Land use (arable, pasture, forest, industry, etc)
 Other parameters if known to impact on the analyte to be determined or relevant for the
specific goals of the research project such as water holding capacity, biological activity
etc.
i. Drying (air dried at room temperature for 3-4 days)
ii. Sieving to obtain homogenous samples

C) Discuss the analytical operations” that each sample should undergo before the measurement can
be conducted.

Prior to analytical measurements, the sample taken from sites should undergo several analytical
operations in the laboratory.

i. Test samples/analytical sample: The sample prepared from the laboratory sample, from
which test portions are removed for testing or analysis.
ii. Test portion/analytical portion: the quality of material, of proper size for measurement of
the concentration or another property of interest, removed from test sample.
iii. Test solution/analytical solution: the solution prepared by dissolving, with or without
reaction, the test portion in a liquid.
iv. Treated solution: the test solution that been subjected to reaction or separation
(extraction) procedures prior to measurement of some property.
TASK 2

A)Compare stratified and quota sampling emphasizing on the relative advantages and disadvantages
of these sampling strategies.

STRATIFIED SAMPLING QUOTA SAMPLING

This is a probability sampling strategy whereby
the system to be sampled is divide into parts
(strata) each as uniform in the parameter of
interest as possible. Then, the samples are
collected randomly from each strata.
Advantages:
 Focuses on important sub-populations
(strata).
 Allows to use different sampling
techniques for different sub-
populations.
 Improves the accuracy/efficiency and
precision.
The non-probability that equivalent to stratified
sampling whereby the researcher first identifies
the strata (stratum) 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. The differs from stratified
sampling, where the stratums are filled by
random sampling.
Advantages:
 Primary data collection can be done in
shorter time
 Save costs and time
 Not dependent on the presence of the
sampling frames

Disadvantages:
 Requires selection of relevant
stratification variables, which sometime
can be difficult.
 Not useful when there are no
homogeneous
subgroups/subpolulations.
 Can be expensive to implement
Disadvantages:
 It is not possible to calculate the
sampling error and the projection of
the research findings to the total
population is risky
 Great potential for researcher bias.

B) A group of students took water samples at Gombak River, Kuala Lumpur for the study of polycyclic
aromatic hydrocarbons. Briefly outline the sampling strategy if they have decided to use. State the
justification of the choice of each sampling strategy.

i) Random sampling

Using this approach, samples are collected randomly (no conscious or unconscious selection) such
that each sample has a chance of representing the whole population. A researcher makes no
assumptions about distribution or movement of analytes at the sampling site. The method is easy.
Usually the researcher used this approach when they have no knowledge about distribution of
analyte in the sampling area. This approach cost more because it requires more sample/greatest
replications in order to get a representative sample.
ii) Judgemental sampling

Using this approach, the researcher selects the sample based on judgement. They implement
assumptions about then movement and distribution of analyte with time and distance (fate &
transport).

Prior to the sampling, the researcher selects the sample based on historical data or inventory of
the sites. This approach is fast and economical method to solve identifiable sources of a problem.
However, sampling bias cannot be avoided.

TASK 3

A)What is “sampling” in analytical chemistry?

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

B) Describe the sampling plan that should be followed to collect the proper sample for analysis .

SAMPLING

SAMPLE STORAGE/PRESERVATION
•Stored at 4 °C for no more than 7 days depends on
the stability of the analyte(s)
•Many plastics are porous to volatile compounds
leading to potential losses during transit and storage
•The surface of plastics generally facilitates microbial
colonization.
•Most container materials adsorb organic compounds

SAMPLE PREPARATION
refers to the ways in which a sample is treated prior to its
analysis may involve dissolution, reaction with some chemical
species, treatment with a chelating agent (e.g. EDTA), masking,
filtering, dilution, sub-sampling or many other techniques.

INSTRUMENTAL ANALYSIS
involves the use of an instrument such as GC, HPLC, UV, FTIR
etc to measure the components in samples analysed
C) Differentiate the following terms:

i) Sampling unit and sampling frame

Sampling unit is subject under observation on which information is collected (samples: water, soil,
sediment, etc) while sampling frame is the source material or device from which a sample is
drawn. It is a list of all sampling units within a population that can be sampled ( for lake sampling
location, sampling frame could be water, sediment, aquatic plant and fish)

ii) Analytical sample and analytical solution

Analytical sample is the sample prepared from the laboratory sample from which test portion are
removed for testing or analysis using specific instrument, while analytical solution is the solution
prepared by dissolving, with or without reaction, the test portion in a liquid.

iii) Selective sample and composite sample

Sample is chosen using proper sampling plan that screens out materials with specific
characteristics and/or selects only materials with other relevant characteristics and/or selects only
materials with other relevant characteristics while composite sample is a sample which is obtained
by combining samples (more than one) from two or more locations or from one location at
different times. The samples can be water, soil or other matrix.

TASK 4

A)Explain the similarity and dissimilarity of stratified and quota sampling

STRATIFIED SAMPLING QUOTA SAMPLING

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
Like stratified sampling, the researcher first
identifies the stratums and other proportions
as they are represented in the population.
Then, convenience or judgement sampling is
used to select the required number of subjects
(samples) from each stratum.
Advantages: the researcher has complete
control over the sample. It also allows samples
to be completed in short time

ii)Discuss a suitable procedure to obtain a representative sample (water sample) from Langat River.

Take water sample (at least 1 liter) from several sampling point (primary sample). Combine and
take 1 liter back (triplicate) to the laboratory (laboratory sample). Undergo sample pretreatment
ie. Filtering prior to analytical measurement.g
TASK 5

Samples of surface water were collected using a water sampler and transferred into 2 liter glass
bottles. Triplicate samples were taken for each sampling point. After sample pretreatment, the
sample were stored in the dark at temperature between 0 to -4 °C prior to solid phase extraction.
The extract obtained was concentrated to 1 ml and the amount of analyte was determined by
injecting 1 µL of the aliquot into a gas chromatography withn mass spectrometry detector.

A)State 3 sample pretreatments for the samples obtained in this study

Filteration using cellulose/glass fiber filter

Acidification – can be done by adding small amount of acid
Adsorption onto SPF catridge
Addition of organic modifier (it can be done by adding some organic solvent eg. MeOH)

B)Explain why the samples labelling and storage conditions are important in the sampling process.

Labelling is an important aspect of documentation and should unambiguously identify the sample
to related plans or notes. Labelling the sample is an important step in sampling to avoid wrong
analysis, particularly when it involve a large number of samples. Without label it is difficult to
record the data and the same sample may be analyzed twice. With the appropriate label, it is
easier to record and retrieve the data from the analysis of sample. Different sample need different
storage procedure/condition. Some samples need to be stored in refrigerator or can be stored at
room temperature. Failure to follow an appropriate storage procedure will spoil the sample prior
to analytical measurement.

C)Differentiate between the term “primary sample”, “laboratory sample” and “aliquot”.

Primary sample = the sample taken from the actual population (bulk samples)

Laboratory sample = the sample submitted or received by laboratory

Aliquot = a portion of a total amount of solution ready for instrumental analysis, obtained after
the extraction process.