Mulungushi University

School of Science Engineering and Technology

CHE 221 – Introduction to Analytical Chemistry

Sampling
Douglas Lubaba
[email protected]
0976667924
Sampling
• Sampling is the process of obtaining a representative sample
• Sample is the representative of the whole bulk. It composition should closely
reflect the composition of the bulk.
• Critical step in analysis as the significance and accuracy depends on sampling
• Sample can be solid, liquid, gas and heterogeneous or homogenous
• Homogenous Sample: A grab sample is often fine. For instance, in clinical lab,
gross sample (blood, urine) can be analyzed directly as it is homogenous.
• Heterogeneous Sample: Several individual samples are taken. E.g., analyzing
average protein content of shipment of grains, one has to collect little grain
from a number of bags during loading/unloading using a sampling spear
(sack sampler) and combine to obtain a gross sample
Types of Sampling Methods;
Random Sampling
• The ideal sampling plan provides an unbiased estimate of the target
population’s properties. A random sampling help in fulfilling this
requirements.
• Haphazard sampling, in which samples are collected without a sampling plan,
is not random and may reflect an analyst’s unintentional biases.
• Random sampling is achieved by;
1. Divide the target population into equal units and assign to each unit a
unique number
2. use a random number table to select the units to sample.
• Random sampling make no assumptions about the target population, which
makes this the least biased approach to sampling.
• Random sampling often requires more time and expense than other sampling
strategies due to greater number of samples to adequately cover target
population, particularly when population is heterogenous.
Judgmental
Sampling
• The opposite of random sampling is selective, or judgmental sampling in
which we use prior information about the target population to help guide our
selection of samples.
• Judgmental sampling is more biased than random sampling, but requires fewer
samples.
• Judgmental sampling is useful if we wish to limit the number of independent
variables that might affect our results.
• For example, if we are studying the bioaccumulation of PCB’s in fish, we may
choose to exclude fish that are too small, too young, or that appear diseased.
Systematic
Sampling
• Random sampling and judgmental sampling represent extremes in bias and in
the number of samples needed to characterize the target population.
• Systematic sampling falls in between these extremes.
• In systematic sampling we sample the target population at regular intervals in
space or time.
Systematic–Judgmental
Sampling
• Combinations of the three primary approaches to sampling also are possible.
• One such combination is systematic–judgmental sampling, in which we use
prior knowledge about a system to guide a systematic sampling plan.
• For example, when monitoring waste leaching from a landfill, we expect the
plume to move in the same direction as the flow of groundwater—this helps
focus our sampling, saving money and time.
Stratified Sampling
• Another combination of the three primary approaches to sampling is
judgmental–random, or stratified sampling.
• Many target populations consist of distinct units, or strata.
• For example, suppose we are studying particulate Pb in urban air. Because
particulates come in a range of sizes—some visible and some microscopic—and
come from many sources—such as road dust, diesel soot, and fly ash.
• we can subdivide the target population by size or by source.
• In a stratified sampling we divide the target population into strata and collect
random samples from within each stratum.
• After we analyze the samples from each stratum, we pool their respective
means to give an overall mean for the target population.
Convenience Sampling
• convenience sampling ;sample sites are selected using criteria other than
minimizing sampling error and sampling variance.
• In a survey of rural groundwater quality, for example, we can choose to to
sample from existing wells rather than randomly drilling a well.
• In this case cost, expedience, and accessibility are more important than
ensuring a random sample.
What Type of Sample to Collect
• After determining from where to collect samples, the next step in designing a
sampling plan is to decide on the type of sample to collect.
• There are three common methods for obtaining samples: grab sampling,
composite sampling, and in situ sampling.
• grab sampling is where we collect a portion of the target population at a
specific time or location, providing a “snapshot” of the target population.
• If our target population is homogeneous, a series of random grab samples
allows us to establish its properties.
• For a heterogeneous target population, systematic grab sampling allows us to
characterize how its properties change over time and/or space.
• A composite sample is a set of grab samples that we combine into a single
sample before analysis. Because information is lost when we combine individual
samples, normally we analyze separately each grab sample.
• One situation where composite sampling is appropriate is when our interest is in
the target population’s average composition over time or space.
• For example, wastewater treatment plants must monitor and report the average
daily composition of the treated water they release to the environment. The
analyst can collect and analyze a set of individual grab samples and report the
average result, or she can save time and money by combining the grab samples
into a single composite sample and report the result of her analysis of the
composite sample.
• A significant disadvantage of grab samples and composite samples is that they
cannot be used monitoring continuously a time-dependent change in the target
population,
• In situ sampling, an analytical sensor is inserted into the target population,
which monitor the target population without removing individual grab samples.
• For example, we can monitor the pH of a solution in an industrial production
line by immersing a pH electrode in the solution’s flow.
Do it yourself
• A study of the relationship between traffic density and the concentrations of
Pb, Cd, and Zn in roadside soils uses the following sampling plan.7 Samples of
surface soil (0–10 cm) are collected at distances of 1, 5, 10, 20, and 30 m from
the road. At each distance, 10 samples are taken from different locations and
mixed to form a single sample. What type of sampling plan is this? Explain why
this is an appropriate sampling plan.
Sample size to
Collect
• To minimize sampling errors, samples must be of an appropriate size.
• If a sample is too small its composition may differ substantially from that of the
target population, which introduces a sampling error.
• Samples that are too large, however, require more time and money to collect
and analyze, without providing a significant improvement in the sampling
error.
Example
• Depending on the particle size, a sample of 1013 particles may be fairly large.
• Suppose this is equivalent to a mass of 80 g. Working with a sample this large
clearly is not practical.
• If we crush and grind the particles to make them smaller, then a sample of 1013
particles will have a smaller mass.
• If we assume that a particle is spherical, then its mass is proportional to the
cube of its radius.

• If we decrease a particle’s radius by a factor of 2, for example, then we decrease

its mass by a factor of 23, or 8.
Example
• A real population likely contains more than two types of particles, with the
analyte present at several levels of concentration.
• But, sampling of many well-mixed populations approximate binomial sampling
statistics because they are homogeneous on the scale at which they are
sampled.
• Under these conditions the following relationship between the mass of a
random grab sample, m, and the percent relative standard deviation for
sampling, R, often is valid

• where Ks is a sampling constant equal to the mass of a sample that produces a

percent relative standard deviation for sampling of ±1%.
Example
How Many Samples to Collect

The value of t depends on

nsamp, the solution to this
equation is found iteratively.

Example
If we determined that we need 1.5-g samples to establish an ssamp of ±2.0% for the
amount of inorganic ash in cereal. How many 1.5-g samples do we need to
collect to obtain a percent relative sampling error of ±0.80% at the
95% confidence level?
Solution
• Because the value of t depends on the number of samples—a result we have yet
to calculate—we begin by letting nsamp = ∞ and using t(0.05, ∞) for t.
• The value for t(0.05, ∞) is 1.960. Substituting known values into equation gives
the number of samples as ;

• Letting nsamp = 24, the value of t(0.05, 23) is 2.073. Recalculating nsamp gives
• When nsamp = 27, the value of t(0.05, 26) 2.060. Recalculating nsamp gives

• Because two successive calculations give the same value for nsamp, we have an
iterative solution to the problem. We need 27 samples to achieve a percent
relative sampling error of ±0.80% at the 95% confidence level.
Implementing the Sampling Plan
• Implementing a sampling plan usually involves three steps:
1. physically removing the sample from its target population,
2. preserving the sample,
3. preparing the sample for analysis.
• sampling device must be inert and clean to avoid contamination.
• preservation prevent samples from undergoing a chemical or physical changes
Sampling of liquids
• commercial solvents; beverages, such as milk or fruit juice; natural waters,
including lakes, streams, seawater, and rain; bodily fluids, such as blood and
urine; and, suspensions.
Sample Collection; water sampling
• The chemical composition of a surface is influenced by flow rate and depth.
• Rapidly flowing shallow streams and rivers, and shallow (<5 m) lakes usually are
well mixed and show little stratification with depth.
• To collect a grab sample we submerge a capped bottle below the surface,
remove the cap and allow the bottle to fill completely, and replace the cap.
• Collecting a sample this way avoids the air–water interface, which may be
enriched with heavy metals or contaminated with oil.
• Slowly moving streams and rivers, lakes deeper than five meters, estuaries, and
oceans may show substantial stratification with depth. Grab samples from near
the surface are collected as described above, and samples at greater depths
are collected using a sampler lowered to the desired depth.
• A well is purged by pumping out a volume of water equivalent to several well-
casing volumes or by pumping until the water’s temperature, pH, or specific
conductance is constant.
• After removing a sample from its target population, its chemical composition
may change as a result of chemical, biological, or physical processes.
• To prevent a change in composition, samples are preserved by controlling the
sample’s pH and temperature, by limiting its exposure to light or to the
atmosphere, or by adding a chemical preservative.