Section A – The nature and scope of analytical chemistry

A4 S AMPLING AND SAMPLE

HANDLING

Key Notes
Representative A representative sample is one that truly reflects the composition of the
sample material to be analyzed within the context of a defined analytical
problem.

Sample storage Due to varying periods of time that may elapse between sample
collection and analysis, storage conditions must be such as to avoid
undesirable losses, contamination or other changes that could affect the
results of the analysis.

Sample Preliminary treatment of a sample is sometimes necessary before it is in a

pre-treatment suitable form for analysis by the chosen technique and method. This may
involve a separation or concentration of the analytes or the removal of
matrix components that would otherwise interfere with the analysis.

Sample preparation Samples generally need to be brought into a form suitable for
measurements to be made under controlled conditions. This may involve
dissolution, grinding, fabricating into a specific size and shape,
pelletizing or mounting in a sample holder.

Related topic Analytical problems and procedures (A2)

Representative The importance of obtaining a representative sample for analysis cannot be

sample overemphasized. Without it, results may be meaningless or even grossly
misleading. Sampling is particularly crucial where a heterogeneous material is to
be analyzed. It is vital that the aims of the analysis are understood and an appro-
priate sampling procedure adopted. In some situations, a sampling plan or
strategy may need to be devised so as to optimize the value of the analytical
information collected. This is necessary particularly where environmental
samples of soil, water or the atmosphere are to be collected or a complex indus-
trial process is to be monitored. Legal requirements may also determine a
sampling strategy, particularly in the food and drug industries. A small sample
taken for analysis is described as a laboratory sample. Where duplicate analyses
or several different analyses are required, the laboratory sample will be divided
into sub-samples which should have identical compositions.
Homogeneous materials (e.g., single or mixed solvents or solutions and most
gases) generally present no particular sampling problem as the composition of
any small laboratory sample taken from a larger volume will be representative of
the bulk solution. Heterogeneous materials have to be homogenized prior to
obtaining a laboratory sample if an average or bulk composition is required.
Conversely, where analyte levels in different parts of the material are to be
A4 – Sampling and sample handling 11

measured, they may need to be physically separated before laboratory samples

are taken. This is known as selective sampling. Typical examples of hetero-
geneous materials where selective sampling may be necessary include:
● surface waters such as streams, rivers, reservoirs and seawater, where the
concentrations of trace metals or organic compounds in solution and in sedi-
ments or suspended particulate matter may each be of importance;
● materials stored in bulk, such as grain, edible oils, or industrial organic chem-
icals, where physical segregation (stratification) or other effects may lead to
variations in chemical composition throughout the bulk;
● ores, minerals and alloys, where information about the distribution of a partic-
ular metal or compound is sought;
● laboratory, industrial or urban atmospheres where the concentrations of toxic
vapors and fumes may be localized or vary with time.
Obtaining a laboratory sample to establish an average analyte level in a highly
heterogeneous material can be a lengthy procedure. For example, sampling a
large shipment of an ore or mineral, where the economic cost needs to be
determined by a very accurate assay, is typically approached in the following
manner.
(i) Relatively large pieces are randomly selected from different parts of the
shipment.
(ii) The pieces are crushed, ground to coarse granules and thoroughly mixed.
(iii) A repeated coning and quartering process, with additional grinding to
reduce particle size, is used until a laboratory-sized sample is obtained.
This involves creating a conical heap of the material, dividing it into four
equal portions, discarding two diagonally opposite portions and forming a
new conical heap from the remaining two quarters. The process is then
repeated as necessary (Fig. 1).

2
2 2

1 3 1 3 1 3

4 4
4

Fig. 1. A diagrammatic representation of coning and quartering (quarters 1 and 3, or 2 and 4 are discarded each time).
12 Section A – The nature and scope of analytical chemistry

The distribution of toxic heavy metals or organic compounds in a land rede-

velopment site presents a different problem. Here, to economize on the number
of analyses, a grid is superimposed on the site dividing it up into approximately
one- to five-metre squares. From each of these, samples of soil will be taken at
several specified depths. A three-dimensional representation of the distribution
of each analyte over the whole site can then be produced, and any localized high
concentrations, or hot spots, can be investigated by taking further, more closely-
spaced, samples. Individual samples may need to be ground, coned and
quartered as part of the sampling strategy.
Repeated sampling over a period of time is a common requirement. Examples
include the continuous monitoring of a process stream in a manufacturing plant
and the frequent sampling of patients’ body fluids for changes in the levels of
drugs, metabolites, sugars or enzymes, etc., during hospital treatment. Studies of
seasonal variations in the levels of pesticide, herbicide and fertilizer residues in
soils and surface waters, or the continuous monitoring of drinking water supplies
are two further examples.
Having obtained a representative sample, it must be labeled and stored under
appropriate conditions. Sample identification through proper labeling, increas-
ingly done by using bar codes and optical readers under computer control, is an
essential feature of sample handling.

Sample storage Samples often have to be collected from places remote from the analytical labora-
tory and several days or weeks may elapse before they are received by the labo-
ratory and analyzed. Furthermore, the workload of many laboratories is such that
incoming samples are stored for a period of time prior to analysis. In both
instances, sample containers and storage conditions (e.g., temperature, humidity,
light levels and exposure to the atmosphere) must be controlled such that no
significant changes occur that could affect the validity of the analytical data. The
following effects during storage should be considered:

● increases in temperature leading to the loss of volatile analytes, thermal or

biological degradation, or increased chemical reactivity;
● decreases in temperature that lead to the formation of deposits or the precipi-
tation of analytes with low solubilities;
● changes in humidity that affect the moisture content of hygroscopic solids and
liquids or induce hydrolysis reactions;
● UV radiation, particularly from direct sunlight, that induces photochemical
reactions, photodecomposition or polymerization;
● air-induced oxidation;
● physical separation of the sample into layers of different density or changes in
crystallinity.

In addition, containers may leak or allow contaminants to enter.

A particular problem associated with samples having very low (trace and
ultra-trace) levels of analytes in solution is the possibility of losses by adsorp-
tion onto the walls of the container or contamination by substances being
leached from the container by the sample solvent. Trace metals may be depleted
by adsorption or ion-exchange processes if stored in glass containers, whilst
sodium, potassium, boron and silicates can be leached from the glass into the
sample solution. Plastic containers should always be used for such samples.
A4 – Sampling and sample handling 13

Conversely, sample solutions containing organic solvents and other organic

liquids should be stored in glass containers because the base plastic or additives
such as plasticizers and antioxidants may be leached from the walls of plastic
containers.

Sample pre- Samples arriving in an analytical laboratory come in a very wide assortment of
treatment sizes, conditions and physical forms and can contain analytes from major
constituents down to ultra-trace levels. They can have a variable moisture content
and the matrix components of samples submitted for determinations of the same
analyte(s) may also vary widely. A preliminary, or pre-treatment, is often used to
condition them in readiness for the application of a specific method of analysis or
to pre-concentrate (enrich) analytes present at very low levels. Examples of pre-
treatments are:

● drying at 100°C to 120°C to eliminate the effect of a variable moisture content;

● weighing before and after drying enables the water content to be calculated or
it can be established by thermogravimetric analysis (Topic G1);
● separating the analytes into groups with common characteristics by dis-
tillation, filtration, centrifugation, solvent or solid phase extraction (Topic
D1);
● removing or reducing the level of matrix components that are known to cause
interference with measurements of the analytes;
● concentrating the analytes if they are below the concentration range of the
analytical method to be used by evaporation, distillation, co-precipitation, ion
exchange, solvent or solid phase extraction or electrolysis.

Sample clean-up in relation to matrix interference and to protect special-

ized analytical equipment such as chromatographic columns and detection
systems from high levels of matrix components is widely practised using solid
phase extraction (SPE) cartridges (Topic D1). Substances such as lipids, fats,
proteins, pigments, polymeric and tarry substances are particularly detri-
mental.

Sample A laboratory sample generally needs to be prepared for analytical measurement

preparation by treatment with reagents that convert the analyte(s) into an appropriate chem-
ical form for the selected technique and method, although in some instances it is
examined directly as received or mounted in a sample holder for surface
analysis. If the material is readily soluble in aqueous or organic solvents, a simple
dissolution step may suffice. However, many samples need first to be decom-
posed to release the analyte(s) and facilitate specific reactions in solution. Sample
solutions may need to be diluted or concentrated by enrichment so that analytes
are in an optimum concentration range for the method. The stabilization of solu-
tions with respect to pH, ionic strength and solvent composition, and the removal
or masking of interfering matrix components not accounted for in any pre-treat-
ment may also be necessary. An internal standard for reference purposes in
quantitative analysis (Topic A5 and Section B) is sometimes added before adjust-
ment to the final prescribed volume. Some common methods of decomposition
and dissolution are given in Table 1.
14 Section A – The nature and scope of analytical chemistry

Table 1. Some methods for sample decomposition and dissolution

Method of attack Type of sample
Heated with concentrated mineral Geological, metallurgical
acids (HCl, HNO3, aqua regia) or
strong alkali, including microwave
digestion
Fusion with flux (Na2O2, Na2CO3, Geological, refractory materials
LiBO2, KHSO4, KOH)
Heated with HF and H2SO4 or HClO4 Silicates where SiO2 is not the analyte
Acid leaching with HNO3 Soils and sediments
Dry oxidation by heating in a furnace Organic materials with inorganic analytes
or wet oxidation by boiling with
concentrated H2SO4 and HNO3 or HClO4