 Sampling is usually the most important step

of any analytical procedure. Errors committed

at this stage cannot be corrected later during
the analysis.
 
 There is a plethora of sampling methods,
which depends greatly on the physico-
chemical nature of these analytes and their
expected concentrations in air.
 
 Most widely used methods for VOCs sampling
are either pre-concentration on sorbent tube
or whole air sample taken in canister. In some
special cases compounds are collected by
chemisorptions.
 
 
 Active sampling is done using a pump for drawing a
specified volume of the air to be sampled through an
adsorbent tube with a specified, usually low air flow
rate.

 Grab sampling is done using polished stainless steel

or aluminium canisters which allows to sample for a
very short periods of time (down to 10-30 seconds)
The VOCs are enriched afterwards in the laboratory.

 Passive sampling consists of adsorbents normally

contained in a thin tube. The cross section of the
tube and the distance between the opening of the
tube and the adsorbent surface determines the
sampling rate of the passive sampler.
 Canister sampling involves the collection of the
whole air matrix in a pre-cleaned evacuated
cylinder. This technique is especially useful for the
most volatile species, such as propane, butane etc.

 Canister sampling is performed in two modes:

either grab sampling or time integrated sampling.
Sample can be collected either on sub-atmospheric
(passive) pressure or pressurized (active) with
pump.
 
 By the process of thermal desorption analytes are
transferred into the GC-column.
 The actual air sample is collected without any
breakthrough;
 No degradation problem of trapping material;
 Moisture has no effect upon sampling;
 Duplicate analyses of the sample can be

performed.
 Requires complex sampling apparatus;
 Severe clean up procedure between sampling is
necessary;
 The flow tends to decrease towards the end of
sampling
 To obtain good compound recovery from
canister, the sample pressure should be as high
as possible without causing precipitation of
liquid water within the canister;
 Because of the presence of reactive species, gas
phase reaction and subsequent transformation
and loss of target compounds may occur.  
 Plastic bags (such as Tedlar, Teflon or
aluminized Tedlar) are simple to use,
inexpensive and are available in various
sizes, normally from 500 ml to 100 l of
volume.

 These bags are mostly useful for

measurement of strongly polluted air or
relatively high trace gas concentrations.
 
 Sampling on sorbents allows larger volume of
gas than with canisters to be collected; in
addition, sorbent tubes are easier to handle
than canisters
 
 The quantity of the substance which can be
captured on the adsorbent depends on the
ambient conditions (pressure, temperature,
concentration, humidity etc.), amount of
sorbent, sampling speed etc.
 
 Breakthrough of the analytes has to be
avoided.
 Some adsorbents may show degradation
problems that have significant impact on
adsorption process.
 Contamination problem of sorbents must be
avoided before and after sampling.
 Retention of moisture content on sorbents
must be avoided as it may pose undesirable
effects on chromatographic analysis.
 
 1 Active tube sampling

 2 Passive tube sampling (diffusive sampling)

 Both short term and long term samples can
be collected on adsorbents packed in
appropriate tube with the use of sampling
pump.This technique is particularly
convenient for personal monitoring because
all of the equipments required while sampling
can be worn by the worker.
 Active sampling allows control over the

sampling rate and sampling time.

 Passive sampling may be defined as any
sampling technique based on free flow of
analyte molecules from the sampling medium
to a collecting medium, as a result of a
difference in concentration of the analyte
between the two media.
 The advantages of passive tube sampling are
lower cost and greater worker acceptability,
as it does not require bulky and expensive
pumps that are subjected to regular checking
and possible error in flow rate.
 In this process the substance to be measured
is absorbed irreversibly in a liquid phase and
then it is altered by a chemical reaction with
other components present. In this
chemisorption process impingers and
bubblers containing liquids have been usually
used to collect high-boiling, reactive or polar
substances.
 1 On-line gas chromatography analyzer

 2 Differential optical absorption spectroscopy

 On-line gas chromatography analyzers are
special automatic portable gas chromatographs
designed tomeasure selected organic compounds
in situ. The most frequently used analyzers are
BTEX analyzers measuring benzene, toluene,
ethylbenzene and xylene.
On-line gas chromatography analyzers can
measure sample regularly in any given time
interval (e.g.every 15 or 30 min ) so that
results obtained can be interpreted in relation
to meteorological conditions, vehicular
emissions etc.