SAMPLING AND MEASUREMENTS OF SAMPLE ANALYSIS

Introduction
Sampling is a process of extracting a small portion from a large material that is used for analysis.
A sample is defined as a portion of material selected from a larger quantity of material. Sampling is
defined as the total of activities that end with the acquisition of the test portion (actual subject of
analysis).
Sample unit is the minimum sized packaged in the consignment of the material.
Gross sample is the one prepared in mixing various increments together.
A sub sample is a smaller sample just like the gross sample and it is usually taken from the gross sample.
Quality of the material is the desired property of the material under analysis e.g materials with different
qualities like composition, size, colour and state
Purpose of Sampling

 Sampling enable us to obtain a small portion of the material from bulk of material which passes
essential characteristic from the entire analysis.
 To determine the quality or composition of the material and the analytic result.
 To have any validity or meaning, it’s essential to get a true representative of the bulk material.
 Sampling helps in the analysis of quality of characteristic of substances e.g. homogeneity
Methods of Sampling
Sampling methods fall in 3 groups

 That which all material is examined

 Casual sampling
 Method in which portion of material are selected basing on statistical probability

a) Simple Random sampling

Simple random sampling allows the sampling error to be calculated and reduces selection bias. A specific
advantage is that it is the most straightforward method of probability sampling. A disadvantage of simple
random sampling is that you may not select enough individuals with your characteristic of interest,
especially if that characteristic is uncommon.

b) Systematic sampling

Individuals are selected at regular intervals from the sampling frame. The intervals are chosen to ensure
an adequate sample size. Systematic sampling is often more convenient than simple random sampling,
and it is easy to administer. However, it may also lead to bias,

c) Stratified sampling
The same sample is selected for each stratum included in the study, its necessary to divide the population
into sub population called stratum.

d) Proportional random sampling

When the size of each stratum in a population varies greatly from that of other stratum its recommended
that the size of stratum be based on the size of the sample in the population, this sample from stratum
represents the actual size of that statue.

e) Systematic/regular internal sampling

Based on a selection of elements at equal intervals starting with randomly sample which can be used to
study

f) Computerized methods

This where the computer the does the sampling

g) Cluster sampling

Cluster sampling is defined as a sampling method where the researcher creates multiple clusters of a
sample from a population where they are indicative of homogeneous characteristics and have an equal
chance of being a part of the sample.

Is used when it’s impossible or impractical to identify in a population because of their wide dispersion.
However the objects can be grouped in cases in small cluster depending on their different quantities.

h) Selective sampling

It’s done by selecting objects of specific followed by random sampling

Types of Sampling

a) Grab or catch sampling

In this case the sample is collected at a specific time, a sample can only present the composition of the
source at a particular time and place.

b) Composite sampling

It is a mixture of grab sample collected at the same sampling point at different time. Sometime it is used
to distinguish these types of sampling from others.

c) Integrated sampling

It’s produced by analyzing mixture of grab samples collected from different points simultaneously (same
time) e.g. in the rivers and streams that varies in composition across its width and depth to evaluate
accurate composition.
Use a mixture of sample representing various points in the cross section in proportion to their relative
flows

d) Sequential sampling

Its collection of sample at different time intervals repeated several times over a long period of time.

Sample size

Before deciding how large the population should be. You have to define your study population, sample
size depends on:

 The nature of analysis to be performed

 The desired precision of the estimate one wishes to achieve
 The kind and number of comparison that will be made
 The number of variables that have to be examined simultaneously
 The available funds

Steps in sampling

 Identification of the population from which the sample is to be taken from

 Selection and obtaining of gross sample from the population
 Reduce each gross sample to a lab size that is suitable for analysis

Factors to consider during sampling

 The material to be sampled should be thoroughly mixed

 The population in which the sample was taken from should be identified by labelling
 The amount of the original amount of material should be noted as the quantity of the sample
taken from it
 The date ,the owner and the place of sampling should also be noted

Precautions observed during sampling

 The sample should be taken in such a manner that will not undergo chemical or physical changes
 The sample should be kept in airtight containers so that the content cannot be tampered with
 The sample should be kept in cold so that decomposition and increase in bacterial load will be
minimized
 The container should preserve the physical and the chemical characteristics of the sample

Procedure of Sampling

To be accurate and avoid excess sample which may consume much time, the reliable method is statistical
probability .this means that not every part of the sample is analyzed .the limitation of the section are
carefully calculated and known in advance .having calculated the degree of acceptable risk or margin of
variations sampling procedure, may involve a number of stages prior to the analysis of the material.
Note the sampling stages are as follows .the purpose of this is to make the sample homogenous which
consist of all contents in bulk material for analysis

Bulk material

Increment/weight

Gross sample

Sub sample
Sample Preparation

This in analytical chemistry, the processes in which a representative piece of material is extracted from a
larger amount and readied for analysis. Sampling and sample preparation have a unique meaning and
special importance when applied to the field of analytical chemistry.

With a particulate material, if the analyte is associated with one or more constituents, it is possible to
grind the laboratory sample to reduce the average particle size until the analyte can be regarded as a point
like component of the entire laboratory sample. This particle diameter is called the liberation size and
varies with the analyte and the type of material.

Grinding (more generally called comminution) can be accomplished by various means, ranging from
simple manual approaches to fully automated techniques. Ground material is often sieved, but for
chemical analysis purposes the retained fraction is always returned to the grinder until it all passes the
desired mesh size.

Excess grinding of some materials can lead to contamination from or analyte loss to the grinding tool.
Also, overzealous grinding can result in the absorption of atmospheric gases (including moisture) by the
sample and in the loss of fines. In addition, very finely ground material is sometimes impossible to mix
adequately.

Mixing of the laboratory sample is another critical operation. If the particle size is reduced in a series of
steps, generally each step is followed by an interval of mixing. This can be accomplished by hand with
small laboratory samples, but other samples require some form of automation.

The effectiveness of any given mixing operation will be related to the particle size, shape, and density, as
well as to external influences such as electrostatic or magnetic fields and air turbulence.

Theory of sampling
An ideal sample should have identical properties with the bulk material
Factors to note before sampling

 Cost of the test and the value of the product

 Use of the end product
  Permitted variation in the material
 Accuracy of the test method
Note there are very many obvious blunders (mistakes) in the sampling that may be turned as pit fall
sampling e.g. separation of particle size can introduce a serious error in operation that can change the
composition of the sample which should be avoided.
Sample and Physical state
Many of the problem occurring during sampling are from the physical nature of the material to be studied
Solids presents the greatest problems of sampling than both the liquid and gases, few problems arise over
homogeneity .similarly care must be taken on gaseous components which reacts with the sampling and
analytical devices.

Air Analysis
General consideration
In air analysis sample are generally collected because of the following reasons

 To establish hazardous level in environment

 To evaluate efficiency of population control measure
 To determine the source of pollutant
 To determine size of the sample
The volume of air is governed by

 Minimum pollutant concentration that must be measured

 Density of the air
 Information desired
The concentration range of the pollutant is determined by the error or trace sample of more than 10cm3
which may be required to be determined.
Duration of sampling
This will be determined by the information desired or needed .the sampling period will give an indicator
of only the average, it should be more meaningful.
The sample city air for lead content during rush hours to obtain the realistic indication of the overall late
exposure.
Sample Storage

 Storage of air sample should be done in such a way as to minimize damage. They should be
protected from heat and light
 Measure should be taken so that the desired component does not react with other components or
with the containers.
 Gas samples are sometimes collected by flushing displacements with a liquid and expansion into
an evacuated container.
 The physical contamination will determine to some extent the method of sampling.
Gaseous Exchange Contaminants
Gas and vapor can be collected by absorption in a liquid or on a solid surface.
They can be also collected by freezing and condensation or filing an evacuated container.
The distinction among gases is that the latter vapor can exist as a liquid at ordinary temperature and can
easily be condensed.
Vacuum Sources
Vacuum is used to draw the sample through the collecting device e.g. motor or hand device vacuum
pumps and auto mobile vaccums are used when vacuum devices to draw sample through a filter in which
pressure loss may build up in the sample.
Metering devices /measuring devices are of two types
Those that measure vacuum –are small and expensive but have the disadvantage of measuring only
instantaneous rate of flow and hence they must be checked during the sampling period.
Some other measuring devices are Rotameter
Dry test gas meter
Wet test gas meter
The dry test gas meter and wet test gas meter is generally more accurate than the dry test meter for small
volumes. All gas measuring devices should be calibrated before and after use.
A usual method employed is to measure the volume of a liquid (water) is displaced by the gas flowing
through the meter
A saturator (saturate gas with water) is placed before the meter in order to prevent evaporation of the
water. The displayed water is weighed or its volume is measured by measuring the pressure with a
monometer in a series and temperature. Accurate calculation of the gas volume at standard condition is
obtained

Liquid Sample
In most cases, general stirring or mixing is sufficient to ensure homogeneity prior to sampling where
separate phases exist.
It is necessary to determine the relative volume of each phase in order to compare correctly the
composition of the phase with each other.
The most important consideration is the frequency and duration of sampling to be sufficient to obtain a
representative and a producible sample.
The liquid sample should be analyzed as soon as possible after collection this is to ensure maximum
accuracy
For certain constituents and physical value, immediate analysis in the field is necessary to obtain reliable
results. This is because the component of the sample may change before it arrives in the laboratory. These
components include pH, temperature and dissolved gases e.g oxygen, hydrogen and Sulphur (iv) oxide
NOTE: the activities of bacteria as well as chemical reaction are stimulated by high temperature and
depressed by low temperature of incubation .reaction is a as below.
Protein + oxygen bacteria carbon (iv)oxide +water
Carbohydrates +oxygen bacteria carbon(iv)oxide +water
Water analysis
Under water analysis you must do:

 Chemical fixation; it is the immobilization of the metal activities by acidifying water sample with
dilute nitric acid or hydrochloric acid, for every one litre of the sample, add 5ml of the acid
 You must store the sample at 4oC until the time of the analysis
Collection and Preservation of Water Samples
You separate a significant amount of suspended matter by decantation, centrifugation or an appropriate
filtration methods.
Open a slight turbidity may be tolerated if experience shows that it will cause no interference in
volumetric test and that influence can be corrected in colorimetric test where it has potentially that
greatest interfering effect to measure the total amount of constituent.
Safety considerations during sampling
Because sample constituent cab be toxic, take adequate precaution during sample
Wear protective clothes, gloves masks as toxic vapor may be present unlike sample in well ventilated
area.
Soil sampling
Transport of the soil sample measurement such as redox potential should be measured in the field where
the soil is found.
Aeration (air in the soil) can be minimized if the sample container is sealed without leaving any air space
above the soil.
If delay in transport cannot be avoided it’s desirable to keep the temperature of the soil below the ambient
to reduce microbial activity.
Storage
For the determination of the pH, available nitrogen, soluble carbohydrates, amino acids and lipids.
The material to be tested for this should not be stored for long and should be stored at temperature just
above the freezing point, it is better to keep the soil moist and aerated during storage in order to prevent
microorganism from dying.
Generally, fresh soil is stored in polythene bags for biological material.
The ideal storage bags is made from clothes, this is because clothes are porus and allows aeration.
Aim of analysis of soil
To determine:

 Nature of the soil i.e. clay, loam, sandy etc.

 Location of the soil
 Nutrients contained in the soil
 Suitability of crop growth
 Quality for the right fertilizer
Time of the sampling

 After harrowing
 Before fertilizer application
 When it’s not too wet
 After bush clearing
Sampling time
Fluctuation in nutrient content with time occurs in all active plant tissue and these changes must be put
into consideration when sampling.