Overview

Released: April 2014

Application Note 009

Using thermal desorption for the quality control of
products and raw materials

Summary • 103–104-fold improvement in sensitivity (there is no

extraction solvent to dilute the compounds of interest).
This Application Note highlights the versatility of thermal
desorption for analysing VOCs in materials and process gas • Automation – labour- and cost-saving.
streams. Emissions (or headspace) profiling, direct desorption • Selective focusing/concentration of compounds of interest,
and on-line sampling of industrial air/gas are covered, each with elimination of matrix interferences.
with examples. • No laboratory contamination or solvent disposal issues.
• Reduced errors.
Introduction
• Reusable sorbent tubes (where applicable).
Thermal desorption (TD) has long had a place as a high- • Compatibility with process/on-plant measurement as well
sensitivity alternative to solvent extraction for the as laboratory work.
determination of volatile organic compounds (VOCs) in
environmental health & safety applications. Recent Thermal desorption is still most commonly combined with
developments have extended its application to routine quality laboratory GC(–MS) technology to provide detailed
assurance and quality control testing. quantitative and qualitative information on each individual
(speciated) organic present in a sample. However, modern
Whatever the nature of the product or raw material containing thermal desorption systems, such as Markes’ UNITY™ or
the VOCs – solid, liquid, gas, emulsion, resin, etc. – thermal TD-100™ (Figure 1), are also compatible with alternative
desorption can provide an efficient, readily-validated and cost- direct read-out analysers, such as ‘e-nose’ sensors. Such
effective alternative to conventional laboratory sample simplified systems can enhance throughput and provide a
preparation methods. This versatility is the focus of this more factory-friendly process-monitoring package for some
Application Note. well-characterised routine applications, e.g. gas purity
assessment.
What is thermal desorption?
Strictly speaking, thermal desorption is the process of
extraction/desorption of volatile and semi-volatile organic
compounds from a sorbent or sample matrix using heat and a
flow of inert gas rather than solvent. In practice, it is invariably
a multi-step procedure, automating much more than the
extraction process. The latest technology now combines
versatile on- or off-line sampling with solvent-free extraction,
analyte concentration and automatic transfer of analytes to
the measurement system in a concentrated band of vapour. It
allows measurement of VOCs in almost any sample that
cannot be introduced directly to a standard laboratory gas
chromatography (GC) instrument.
Thermal desorption offers many advantages over conventional
solvent-based sample preparation methods such as liquid
extraction, solvent exchange, and steam distillation. These
include: Figure 1: Markes’ TD-100 automated thermal desorber.

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Application range samples of natural composite or non-homogeneous samples

can alternatively be placed in emission chambers or
Thermal desorption can automate or drastically reduce the
headspace vials/vessels, allowing VOCs to be swept into
number and complexity of sample preparation steps required
sorbent tubes/traps, on-line or off-line. Gas-phase samples
for a wide range of quality assurance/quality control
can be collected in canisters or sorbent tubes for subsequent
applications. Depending on the nature of the material, some
off-line analysis, or monitored in real-time using continuous
solid or liquid samples can be weighed into empty thermal
on-stream analysers. The range of sample types is illustrated
desorption tubes or tube liners for direct desorption. Larger
in Figure 2.

Sample out to analyser

Sorbent tubes (or
canisters) for

Sample in
off-line analysis
of vapours

Emission
chambers,
microchambers
and cells
One to four
sorbent beds
(application-
dependent)

Direct desorption of
homogeneous materials

Purging or pumping of
headspace vapour from
bulk sample containers
(also called purge and trap)

On-line monitoring
of air/gas streams
Electrically-cooled focusing
trap of thermal desorber

Figure 2: The range of sample types suitable for thermal desorption analysis.

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1. Dynamic headspace of bulk samples
Bulky or composite materials and non-homogeneous high-
humidity samples such as fresh/prepared foods and biological
samples are best suited to some form of bulk dynamic
headspace or emission test. This approach facilitates the
sampling of whole samples (or representative portions of
them), as diverse as canned meat, hot coffee, bacterial
cultures, insects, electronics, toys and multi-layer construction
materials. Example apparatus is shown in Figures 3 and 4.
Heated
lines
Focusing
trap
Optional Pump
purge flow
Thermal desorber
Figure 3: Direct pump or purge sampling of vapours from non-
homogeneous samples.
Figure 4: Micro-Chamber/Thermal Extractor (left) and FLEC (right) for
sampling emissions from materials.
Vapours from the bulk samples can either be swept into
ambient-temperature sorbent tubes for subsequent off-line
analysis, or purged/pumped directly into the focusing trap of
an on-line desorber for near-real-time measurement.
The combination of these sampling methods with thermal
desorption not only improves productivity, but also facilitates
selectivity. The tube and/or focusing trap sorbents used can
be chosen to selectively retain specific analytes while allowing
matrix components – water or ethanol for example – to pass
through.
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Example applications for bulk dynamic headspace or
emission tests
(a) Determination of emissions from construction products
Emissions from floor coverings, wall coatings and other
building materials can contribute to atmospheric VOC
concentrations in the indoor environment. Under guidelines
given in EN ISO 16000 parts 9 and 10, ISO 12219-3 and
various ASTM procedures1, manufacturers of construction
materials and car trim are advised to test new products at
various times after manufacture using emission chambers,
microchambers, or portable emission cells.
Pure air is swept over the sample inside the cell or
(micro)chamber to simulate real-world environmental
conditions. Exhaust gases are collected either onto sorbent
tubes for off-line analysis (Figure 5) or pumped directly into
the focusing trap of an on-line thermal desorber for near-real-
time monitoring of rapid changes in the emission profile.
Propanoic acid
2-Butoxyethanol
Hexanal
18
Hexanoic acid
16
14
12
Abundance
10
3-Carene
8
Nonanol
Octanal
Pentanal
6
α-Pinene
0
0 500 1000 1500
Time (s)
Figure 5: Key organic compounds emitted by linoleum floor coverings.
(b) Testing the shelf-life of fresh or prepared foods
As foods age, oxidation or decomposition generates
characteristic (and often malodorous) organic volatiles. The
presence of these compounds in the headspace vapour
immediately above a food sample is one of the first indications
that a product has passed its ‘sell-by’ date. A simple TD-based
laboratory procedure can be developed for objectively
evaluating the freshness of natural ingredients or products.
Fresh or pre-prepared food samples are simply placed in a
microchamber or customised vessel and incubated at ambient
or elevated storage temperatures under a flow of pure air.
Samples of effluent air from the purge vessel are either
collected from time to time onto conditioned tubes packed
with one or more sorbents2, or can be passed directly into the
cold trap of the UNITY thermal desorber on a semi-continuous
basis using a Universal Direct Inlet Accessory (U-INLET™) in
pumped mode (see Figure 3 and Markes’ TD Applications
Guide IV – Food, Flavour, Fragrance & Odour Profiling).
 Page 4

Tube and focusing trap sorbents are selected to retain target
analytes while allowing water, ethanol and other interferences
to purge to vent. One or a combination of hydrophobic
sorbents (e.g. Tenax® TA or graphitised carbon) can be used
for quantitative retention of organics less volatile than
pentane, while allowing the bulk of water/ethanol to pass
through. Complete flavour profiles are typically collected using
two or even three sorbents in series.
2. Direct desorption or dynamic headspace of
homogeneous materials
Homogeneous materials – for example, therapeutic drugs,
packaging materials, resins, spices, ointments/creams,
polymers, water-based paints, and edible fats – can be
weighed into empty tubes or tube liners and desorbed directly
(Figures 6 and 7). In this case, sample preparation is

Excess quantities of decomposition/oxidation compounds or

deviations from the normal odour/flavour profile can then be
quantitatively assessed from the subsequent TD–GC–MS
analysis and used as reliable, objective indicators of product
quality and stability3. Semi-continuous, direct sampling into
the UNITY thermal desorber using the U-INLET allows changes
in odour/flavour profile to be monitored in real-time. Figure 6: Dry, homogeneous material weighed directly into an empty
(c) Quality control of potable spirits tube for direct desorption.

C4–C6 ethyl esters make excellent markers for the maturity of

potable spirits such as whisky. Pumping or purging a given essentially reduced to zero, and the associated risk of error
volume of whisky headspace vapour into a conditioned Tenax introduction is eliminated.
tube or focusing trap allows selective concentration of higher-
boiling flavour components, including ethyl esters, while water Direct desorption has to be one of the most straightforward
and the more volatile alcohols/aldehydes pass through the and cost-effective sampling procedures for otherwise difficult
tube unretained. This procedure simplifies the subsequent GC materials. It combines sample cleanup, analyte extraction and
analysis, facilitating detection of ethyl esters and other higher- sample injection/introduction into one simple, automated
boiling indicators of spirit maturity, while simultaneously operation.
eliminating water and the large ethanol peak which would Either a gentle TD procedure can be used to generate a
otherwise mask most of the chromatogram. The method is characteristic ‘odour profile’, or a more rigorous TD process
ideal for quality control of spirits to be used as ingredients in can be used to achieve complete, quantitative extraction of
products such as cream liqueurs. specific target analytes, e.g. residual solvents.
(d) Identification and life-cycle studies of biological species
Biologists use another variant of bulk headspace/thermal Small aliquots (~5 µL) of
desorption technology to identify species of plant, animal or liquid samples can be
microbes, to map life-cycle changes, and to understand the introduced onto plugs of
origins of hybrids and cultivars of scented plants4. glass wool in empty tubes or
inert tube liners
Specimens are placed in glass containers or nylon bags and
Solid samples can be weighed Resin or cream samples
are incubated as required, before an aliquot of the headspace into empty tubes or inert tube can be smeared around
vapour is pumped into a sorbent tube or online TD system. liners and supported between the inner walls of empty
The profile obtained from subsequent TD–GC–MS analysis two plugs of glass or quartz wool tubes or inert tube liners
acts as a ‘fingerprint’. This helps to characterise the sample
under the test conditions, and allows it to be compared to
other related or control samples.

PTFE tube
liner

Optional sorbent bed prevents high-

boiling compounds or matrix artefacts
migrating into the TD flow path

Figure 7: An illustration of sample preparation for direct desorption of

materials, using a PTFE tube liner.

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Direct desorption is compatible with a wide range of different
material types, including salt/sugar solutions, suspensions,
resins, creams and plain solids. The only rules to ensure
success are as follows:
• Solids should have a high surface area, so should be in the
form of powder/granules (with a particle size <1 mm3),
fibers or a film. Bulk solids should be ground with a coolant
such as solid carbon dioxide before the material is weighed
into sample tubes.
• The sample tube must not be blocked with sample,
because this will stop the gas flow. Thermal desorption is a
dynamic process, and gas must be allowed to pass through
the sample tube unrestricted.
• The sample should be placed inside the sample tube so
that it is well within the heated zone of the thermal
desorber.
• Liquid sample volumes should be limited to around 5 µL,
and the TD method must involve selective elimination of
matrix water or solvent as required.
• Use the lowest effective desorption temperature.
Direct desorption is only appropriate when the required
extraction takes place at a temperature below the
decomposition point of other materials in the sample matrix,
and when the sample in the thermal desorption tube is
representative of the whole sample.
Most samples are best weighed into a tube liner, rather than
being weighed directly into a steel desorption tube. This
eliminates any risk of degradation from samples coming into
contact with metal tube surfaces. Liners are typically
constructed of heat-shrink PTFE tubing with a reduced
diameter at one end – see Figure 7.
Within these limitations, direct thermal desorption provides an
automatic on-line extraction/preparation system for everything
from water-based paints to dried soups, from drugs to printed
packaging film, and from to toothpaste to epoxy resin.
Example applications for direct desorption
(a) Off-odour or ‘taint’ analysis
By eliminating most or all of the sample preparation steps
typically involved in troubleshooting something as subjective
as taint in soap flakes or off-odour in edible fat, TD can speed
up and simplify identification of impurities, and hence
pinpoint the source of many product quality problems.
Both these types of material have been real-world success
stories for thermal desorption...
• In the case of the edible fat, samples of control and
‘problem’ material were weighed into PTFE sample liners
packed with clean glass wool and inserted behind a short
bed of conditioned Tenax sorbent. After 10 min desorption
at moderate temperatures, the profile of volatiles obtained
from the tainted sample could be compared with that from
the control. Fat constituents and other solids were retained
by the glass wool and Tenax, and did not interfere with the
analysis. Used liners were disposed of.
• After a week of trying various extraction solvents in
combination with GC and high-resolution MS technology,
the cause of malodour/taint in a batch of soap flakes had
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not been successfully identified. Once received by the
thermal desorption laboratory, a small sample of soap
flakes (~100 mg) was weighed into a PTFE liner and held in
position with clean glass wool plugs. The liner was inserted
into an empty desorption tube and a TD–GC–MS method
was established using moderate desorption conditions
(~100°C for 10 min). Using this method, one analysis of
the tainted soap and one of a control (less than 2 hours’
work in total) was enough to demonstrate that a
homologous series of pyrazoles was causing the taint issue.
N.B. There is no need for complete extraction of volatiles
during a qualitative investigation. Obtaining a
representative odour profile is more important. Moderate
desorption temperatures are therefore generally
recommended when monitoring for unknowns.
(b) Volatile organic impurities in drugs
The analysis of drug volatiles by conventional extraction or
static headspace methods is often complicated both by the
fact that many are difficult to dissolve in common/safe
solvents, and by the fact that residual solvents often form part
of the crystal structure. Complete dissolution or breakdown of
the crystal structure is therefore ususally required before
accurate determination of VOCs can be made.
Direct thermal desorption (dyanmic headspace) provides a
quick and simple alternative sample introduction method for
drugs that melt below their decomposition temperature.
Complete extraction can typically be achieved in 2–3 minutes.
PTFE liners are recommended to minimise the risk of drug
degradation (see Application Note 041 for more information).
(c) Residual epichlorohydrin in epoxy resin
Epichlorohydrin, the toxic volatile monomer used in epoxy
resin production, is typically present at low-ppm
concentrations in samples of epoxy-based adhesives. Around
40 mg of resin is simply smeared around the inner wall of a
PTFE tube liner plugged with glass wool, as described above.
Provided care is taken to maintain a clear gas flow path
through the middle of the liner, and that the sample of resin is
positioned well within the heated zone of the desorber,
approximately 95% extraction efficiency is achieved in a single
10 minute desorption at a temperature (typically ~175°C) well
below that of polymer degradation.
Using this method, the production facility responsible for
method development recouped the cost of their automated TD
equipment within one month of operation.
(d) Quality control of dried spices
Spices and essential oils are important in the food business,
and rigorous quality control is needed to ensure these
ingredients meet the standards required – and that cheap
synthetics are not introduced. For spices, spice mixtures, and
even complex dried sauce preparations, a combination of
gentle desorption (for example 10 min at just under 100°C)
with high-resolution capillary gas chromatography provides an
interference-free and extremely reproducible flavour profile.
The reproducibility is such that even slight deviations in
composition and/or variations in product quality can be
readily identified.

(e) Water-based paints
Modern atmospheric emission regulations require control of
the volatile and semi-volatile organic content of all paints and
coatings. However, some of these materials present a
significant analytical challenge. In water-based paints, for
example, the presence of relatively large masses of water
compromises capillary GC performance, and the exceptionally
high solid content (>80% in some cases) is guaranteed to
block any syringe as soon as it is inserted into a hot GC
injector.
Direct desorption of small aliquots (~5 µL) of paint introduced
onto a secondary glass wool plug inside a PTFE tube insert
overcomes both of these limitations, and eliminates the need
for pre-analysis preparation of paint samples. During the
thermal desorption process, paint solids remain safely on the
glass wool plug, while volatile and semivolatile materials are
purged into the instrument flowpath (N.B. a fresh glass wool
plug should be used for each new sample).
Provided a suitable two-stage desorber is in use (i.e. one
offering appropriate electronic control of a small sorbent
focusing trap such as that in Markes’ UNITY and TD-100
systems), a combination of focusing temperatures and
sorbents can be selected so all the organics of interest are
retained, while water passes through to vent. When the
focusing trap is subsequently desorbed, an interference-free
chromatogram of the organics is produced. In this case, water
and artefacts from the paint solids have all been safely
eliminated prior to analysis.
(f) Therapeutic creams
This example is an excellent demonstration of the power of
direct desorption. The extraction of essential oils and other
organic volatiles from a petroleum jelly, or similar organic
matrix, is extremely challenging by conventional methods.
Solvents do not differentiate sufficiently between target
analytes and matrix materials, and analysts resort to lengthy
steam distillation techniques to prepare samples. Even then,
results are disappointing, and a significant fraction of the
petroleum jelly tends to distil over into the sample extract,
precluding both capillary chromatography and automatic
injection.
Using direct thermal desorption as an alternative, 20–50 mg
samples of the cream are simply smeared inside a short PTFE
tube liner containing a plug of clean glass wool in an
analogous manner to the epoxy resin example detailed above.
This is then pushed into a conditioned desorption tube
packed with a 5–10 mm bed of Tenax TA and backed up with
unsilanised glass wool. Provided the PTFE tube insert is not
reused and the desorption temperatures selected are the
minimum required for complete extraction, the same Tenax
bed may be reused many times. The Tenax tube should be
repacked and reconditioned as soon as artefacts begin to
appear in the chromatogram.
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3. Pumped sampling of industrial air and gas
Thermal desorption is also the technique of choice for on- or
off-line determination of trace-level volatiles in air and gas
streams.
Compatible sample types include:
• Pressurised gas streams.
• Process vents.
• Ambient/workplace air at atmospheric or sub-atmospheric
pressure.
• Sealed containers of gas or air, e.g. canisters, Tedlar® bags,
cylinders.
• On-line monitors.
On-line TD configurations incorporating an electrically-cooled
focusing trap can also be installed on-plant or in field
laboratories to operate continuously with minimal operator
intervention. Key functions such as sampling flows and
analytical desorption parameters are all incorporated into one
PC-controlled method and monitored continually. Even basic
systems feature automatic interchange between sample, zero
and calibration gas streams at a user-defined frequency.
Analytes must be in the vapour-phase, and typically range in
volatility from acetylene to n-C14/16. Cycle times range from
four minutes to three hours depending on application
requirements and analyser choice.
An ideal operating sequence is as follows:
• User-determined volumes of gas are pumped/drawn into
the electrically-cooled focusing trap at controlled flow rates
of 5–50 mL/min. Only inert, non-emitting components are
allowed to come into contact with the sample.
• The flow path is purged with carrier gas between samples
to eliminate air.
• After the sampling period, the focusing trap is heated
rapidly in a flow of inert gas to transfer or ‘inject’ the
retained analytes into the analyser in a concentrated
vapour ‘plug’. The speed of desorption from the focusing
trap is such that analytes are efficiently transferred to the
analytical system with flows as low as 2–2.5 mL/min. This
facilitates splitless transfer and optimum sensitivity with
high-resolution capillary GC(–MS). Desorption volumes can
also be adjusted to suit alternative direct-read-out
measurement systems such as ‘e-nose’ sensors or process
MS (see Application Note 015).
• Detection limits in the order of low parts per trillion of
individual organic compounds are possible depending on
sampling parameters and detector sensitivity.
• Analysis is automatically initiated by the desorber when the
focusing trap begins to heat.
N.B. Markes’ dual-trap TT24-7™ system is available for true
continuous monitoring, and, in this case, cycle times can be
as low as 2–3 minutes.
 Page 7

0.22

Contaminated CO2 – 15 ppb benzene

Contaminated CO2 – 15 ppb benzene

0.20

Ultra-pure CO2 – 4 ppb benzene

Ultra-pure CO2 – 4 ppb benzene

0.18

Indoor air – 3 ppb benzene

Indoor air – 3 ppb benzene

Indoor air – 3 ppb benzene

0.16
Ion current (E – 10A)

0.14

0.12

0.10

0.08

0.06
Toluene (m/z 91)
0.04 Benzene (m/z 78)
0.02 Xylene (m/z 106)
Styrene (m/z 104)
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Time (min)

Figure 8: Process measurement of trace-level benzene and other organics in carbon dioxide for the carbonated
drinks industry using TD in combination with process MS.

Example applications Summary

Applications include kinetic studies of organic emissions, The examples presented here show the considerable labour-
process control of industrial gas purity (Figure 8), continuous saving benefits that can be achieved by using thermal desorption
ambient air monitoring (Figure 9), and demilitarisation, for industrial quality control applications. The technique offers
amongst others. the versatility and automation to improve productivity and
Note that systems incorporating real-time detectors (e-nose or reduce costs for most QC tests involving VOC measurement. It
process MS), not incorporating the separating power of GC, is clear that some analyses could not have been achieved
work best for well-characterised gas streams/matrices where without the sensitivity and flexibility of thermal desorption.
the failure modes are well-known. Could thermal desorption improve throughput and reduce
costs in your quality control lab? The answer is YES.
9
References
Toluene

1. See Application Note 003 for a comprehensive listing of

Ethylbenzene

8 relevant national and international stanard methods.

2. For examples of this approach, see Application Notes 101
Ion current

m/p-Xylene

7 (cheese) and 104 (strawberries).

3. See Application Note 523 (aroma profiling of wine).
Benzene

o-Xylene

6 4. J. Barberio and J. Twibell, Chemotaxonomy of plant species

using headspace sampling, thermal desorption and capillary
GC, Journal of High-Resolution Chromatography, 1991, 14:
5 637–639 (http://dx.doi.org/10.1002/jhrc.1240140919).

0 2 4 6 8 10 12 14 Trademarks
Time (min)
TD-100™, TT24-7™, U-INLET™ and UNITY™ are trademarks of
Figure 9: TD–GC analysis of of 1 L on-line air sample (top), compared Markes International.
to 1 L bottled nitrogen (bottom).
FLEC® is a registered trademark of Chematec, Denmark.
Tedlar® is a registered trademark of E. I. du Pont de Nemours
and Company, USA.
Tenax® is a registered trademark of Buchem B.V., The Netherlands.

Applications were performed under the stated analytical conditions. Operation

under different conditions, or with incompatible sample matrices, may impact
the performance shown.

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