Sampling
Concept of sampling
Sampling: operations involved in procuring a reasonable amount of material that is
representative of the whole bulk specimen. This is usually the most challenging part of chemical
.analysis
Sampling is usually the most difficult step in the entire analytical process of chemical analysis,
particularly where large quantities of samples (a sample is the subset of the population) to be
analysed are concerned. Proper sampling methods should ensure that the sample obtained for
analysis is representative of the material to be analyzed and that the sample that is analyzed in
.the laboratory is homogeneous
Sampling plan
In a qualitative analysis the sample’s composition does not need to be identical to that of the
substance being analyzed, provided that enough sample is taken to ensure that all components
.can be detected
In a quantitative analysis, however, the sample’s composition must accurately represent the
.target population
Sampling plan
:Five questions should be considered when designing a sampling plan
?From where within the target population should samples be collected .1
?What type of samples should be collected .2
?What is the minimum amount of sample needed for each analysis .3
?How many samples should be analyzed .4
?How can the overall variance be minimized .5
From where within the target population should .1
?samples be collected
Sampling errors occur when a sample’s composition is not identical to that of the population
from which it is drawn. When the material being sampled is homogeneous, individual samples
.can be taken without regard to possible sampling errors
Medications, Clinical samples, dissolved O2 al this types of sample must be taken carefully
.before they take to the lab to be analyzed
Random Sampling
Random Sampling
.a true random sample is difficult to obtain
The best method for ensuring the collection of a random sample is to divide the target
population into equal units, assign a unique number to each unit, and use a random number
.table
Judgmental Sampling
judgmental sampling is more biased than random sampling; however, fewer samples are
required. Judgmental sampling is common when we wish to limit the number of independent
.variables influencing the results of an analysis
Systematic Sampling
Systematic Sampling
Random sampling and judgmental sampling represent extremes in bias and the number of
samples needed to accurately characterize the target population. Systematic sampling falls in
between these extremes. In systematic sampling the target population is sampled at regular
.intervals in space or time
Systematic -Judgmental
Sampling
Systematic–judgmental sampling, which is encountered in environmental studies when a spatial
or temporal distribution of pollutants is anticipated. For example, a plume of waste leaching
from a landfill can reasonably be expected to move in the same direction as the flow of
.groundwater
Stratified Sampling
In a stratified sampling the target population is divided into strata, and random samples are
collected from within each stratum. Strata are analyzed separately, and their respective means
.are pooled to give an overall mean for the target population
The advantage of stratified sampling is that the composition of each stratum is often more
.homogeneous than that of the entire target population
Convenience Sampling
.A sampling plan in which samples are collected because they are easily obtained
In convenience sampling, sample sites are selected using criteria other than minimizing sampling
.error and sampling variance
What Type of Sample to .2
Collect
Three methods are commonly used to obtain samples: grab sampling, composite sampling, and
.in situ sampling
.grab sample A single sample removed from the target population
.composite sample Several grab samples combined to form a single sample
.in situ sampling Sampling done within the population without physically removing the sample
How Much Sample to Collect.3
To minimize sampling errors, a randomly collected grab sample must be of an appropriate size. If
the sample is too small its composition may differ substantially
from that of the target population, resulting in a significant sampling error. Samples
that are too large, however, may require more time and money to collect and ana
.lyze, without providing a significant improvement in sampling error
How Many Samples to Collect. 4
If samples drawn from the target population are normally distributed, then the following
.equation describes the confidence interval for the sampling error
5Minimizing the Overall Variance
overall variance is a function of the variance due to the method and the variance due to
sampling. As we have seen, we can improve the variance due to sampling by collecting more
.samples of proper size
Implementing the Sampling Plan
involves three steps: physically removing the sample from its target population, preserving the
.sample, and preparing the sample for analysis
Gross sample The initial sample, collected from the target population without any processing.
In many cases the gross sample cannot be analyzed without further treatment. Processing the
gross sample may be used to reduce the sample’s particle size, to transfer the sample into a
.more readily analyzable form, or to improve its homogeneity
Solutions
Typical examples of liquid samples include those drawn from containers of commercial solvents;
beverages, such as milk or fruit juice; natural waters, including from lakes, streams, seawater,
and rain; bodily fluids, such as blood and urine; and, suspensions, such as those found in many
.oral medications
Homogeneous solutions are easily sampled by siphoning, de canting, or by using a pipet or
.syringe
Gases
include automobile exhaust, emissions from industrial smokestacks, atmospheric gases, and
.compressed gases. Also included with gaseous samples are solid aerosol particulates
The simplest approach for collecting a gas sample is to fill a container, such as a stainless steel
canister or a Tedlar/Teflon bag, with a portion of the gas. A pump is used to pull the gas into the
.container, and, after flushing the container for a predetermined time, the container is sealed
Gases
Due to the difficulty of storing gases, most gas samples are collected using either a trap
containing a solid sorbent or by filtering. Solid sorbents are used to collect volatile gases (vapor
pressures more than approximately 10–6 atm) and semi volatile gases (vapor pressures between
.approximately 10–6 atm and 10–12 atm), and filtration is used to collect nonvolatile gases
Solids
Typical examples of solid samples include large particulates, such as those found in ores; smaller particulates,
such as soils and sediments; tablets, pellets, and capsules used in dispensing pharmaceutical products and
animal feeds; sheet materials, such as polymers and rolled metals; and tissue samples from biological
.specimens
Solids are usually heterogeneous , sediments from the bottom of streams, rivers, lakes, estuaries, and oceans
.are collected with a bot tom grab sampler or with a corer
An alternative method for sampling sediments uses a cylindrical coring device
Solids
Soil samples collected at depths of up to 30 cm are easily collected with scoops or shovels,
although the sampling variance is generally high. The sampling of particulate material is often
determined by the size of the particles. Large particulate solids, such as coals and ores, can be
.sampled by randomly collecting samples with a shovel or by riffling
Solids
When sampling a metal, it usually is necessary to obtain material from both the surface and the
interior. When the metal is in the form of a sheet, random samples can be collected with a metal
punch, Sampling of biological tissue is done by removing the entire organ, which is then
homogenized before smaller portions are taken for analysis. Alternatively, several small portions
of tissue may be combined to form a composite sample. The composite sample is then
.homogenized and analyzed
Solids
Sample Preservation Without preservation, many solid samples are subject to changes in
chemical composition due to the loss of volatile material, biodegradation, and chemical
reactivity (particularly redox reactions). Samples stored at reduced temperatures are less prone
to biodegradation and the loss of volatile material, but fracturing and phase separations may
.present problems