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Thermal Desorption:
A Practical Applications Guide
2nd Edition
www.markes.com
www.markes.com
GC and GC/MS, which uses heat and a flow of inert gas, rather than
Markes has pioneered major TD innovations such as quantitative recollection for repeat analysis (SecureTD-Q), TubeTAG RFID tube
labels, DiffLok enabling technology for robust tube automation
and cryogen-free analysis of multiple canister air samples. All these
Overview
Off-odour/taint analysis
Biology/crop research
Background:
In comparison to traditional solvent extraction techniques,
direct thermal desorption (TD) provides a labour-saving way to
extract volatiles from solids, resins, pastes, emulsions and
liquids.
To an analyst, this technique simply involves placing a small
amount of sample directly into an empty TD sample tube or
liner and positioning it on the thermal desorber.
Once the tube is in position, the sample is heated in a stream
of inert gas. The volatiles are swept out and pre-concentrated
on the focusing trap leaving the matrix behind. The focusing
trap is subsequently desorbed and vapours are transfered
(injected) into the GC(MS) analytical system.
Direct TD also facilitates selective concentration of extracted
compounds. Focusing trap parameters can be selected to allow
water and/or other solvents to be purged to vent, thus
minimising interference, meaning only components of interest
are transferred.
Samples can be weighed directly into glass, steel or Silcosteel tubes, or into
disposable, PTFE-based tube inserts/liners. Pastes, resins, liquids &
emulsions can also be accommodated using tube liners containing plugs of
glass or quartz wool.
Background:
Detailed analysis of natural oils (such as sesame oil) may
be required e.g. to identify key olfactory components, to
characterise & source the material, or to identify oxidation
products/other potential causes of taint. Traditionally, this
application has been carried out using multi-step liquid
extraction or steam distillation with GC/MS analysis,
however such procedures are long, manual & inefficient.
Direct thermal desorption provides a simple & readily
automated alternative.
Tetracosahexaene
Oleic acid
Trimethyl pyrazine
Acetyl pyrazine
Methyl pyrazine
2-furanmethanethiol
Hexadecane
Thymol
Nonanal
Eucalyptol
n-C10
Background:
Equilibrium headspace sampling of dried foods generally
requires solvent addition and does not allow the analysis of
a wide range of volatiles. Using Markes TD instrumentation
for direct desorption of homogenous dried foods provides a
high sensitivity & labour-saving alternative, which permits
the analysis of a wider volatility range. Foodstuffs
compatible with this approach include:
Ground spices
Eugenol
Dodecane
Tetradecane
T-cadinol
DEP
a-cadinene
Germacrene-D
a-bergamotene
a-copaene
Background:
Markes TD systems have an inert flow path that can be set
at low temperatures, which makes them ideal for the direct
desorption of labile volatiles such as terpenes and sulphur
compounds. SecureTD-Q (i.e. quantitative re-collection of
split flow) facilitates repeat analysis of a sample under the
same or different conditions (e.g. at a lower split setting, as
shown) to confirm quantitative recovery of reative
components through the system & to allow detailed analysis
of trace constituents.
Quantitive re-collection & repeat analysis under different
split conditions can extend the TD-GC/MS dynamic range to
5 or 6 orders of magnitude offering high/low capability.
This is a significant advantage for many flavour/fragrance
applications
Typical analytical conditions:
Sampling: ~100 mg of leaf sample weighed into an empty
glass tube or PTFE liner secured with quartz wool
Analysis: GC/MS
Background:
Mushroom powder can be used in cooking as a flavour
substitute for whole mushrooms. It is dry, relatively
homogeneous & can be conveniently analysed by direct TDGC/MS without manual sample preparation. However, the
analysis of such powders is challenging because of the
large range of concentrations of the constituents.
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Acetaldehyde
Ethanol
Butanal
Hexanal
Heptanal
D-Limonene
Octanal
Nonanal
Acetic acid
Benzaldehyde
Propylene glycol
Butyrolactone
Butanoic acid
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Trap: U-T15ATA-2S
Trap conditions: 0C to 300C for 5 mins
Split: 25:1
Analysis: GC/MS
Background:
Re-collected
sample
DEP
a-copaene
2-phenoxyethanol
2-pentylfuran
Pentanol
Original
Volatiles from boiling potatoes sampled using Tenax tubes & analysed using
TD-GC/MS with SecureTD-Q: Original sample (black) and re-collected sample
(red). Identical chromatographic profiles confirm quantitative recovery of labile
analytes (e.g. terpenoids)
Original data
Background:
Complex GC/MS data can be compromised by interference
(noise) which can make interpretation difficult. New
software has been developed to address this.
ClearView is one of a suite of state-of-the-art GC/MS data
reprocessing packages from ALMSCO International,
available from Markes. It uses a sophisticated algorithm to
accurately and dynamically compensate for
chromatographic background as it changes throughout a
run. Key advantages include:
Vapour analysis from a lit incense stick. Original data (top) and ClearView
reprocessed data (bottom)
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SPE-tD cartridges
SPE-tD cartridges are hollow and coated inside and out with
polydimethyl siloxane (PDMS) for optimum capacity. The cartridge is
placed into an aqueous sample and agitated. Volatile and semivolatile organics in the sample partition between the aqueous matrix
and PDMS, reaching equilibrium over time. This allows semiquantitative analysis of less volatile organics and direct comparison
of organic impurity levels in two similar samples.
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2,4,6-tribromoanisole
2,3,4-Trichloroanisole
Background:
High capacity sorptive extraction using Markes SPE-tD
cartridges provides a convenient approach to monitoring
semi-volatile off-odour components in drinking water. SPE-tD
cartridges used in combination with subsequent high
sensitivity TD-GC/MS analysis offer selective concentration
of less volatile constituents & trace-level detection limits
(sub-ppb). This complements purge-&-trap/equilibrium
headspace methods for volatiles.
The example opposite shows sub-ppb impurities absorbed
by a SPE-tD cartridge from a 1 L sample of drinking water.
Di t-butyl phenol
Geosmin
2,4,6-trichloroanisole
2-isobutyl-3-methoxypyrazine
Monochloroanisoles
Dodecane
Profile of sub-ppb level organics extracted from drinking water using the
SPE-tD cartridge
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Markes HS5-TD module for UNITY 2 brings together two of the most
powerful GC introduction techniques: Headspace (HS) sampling and
HS vapours from the pressurised vial pass through the needle and
directly into the cryogen-free focusing trap of UNITY 2, allowing
efficient concentration of the compounds of interest. Water and
other unwanted volatiles are selectivley purged to vent, allowing high
sensitivity capillary GC(MS) analysis with minimal interference.
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Headspace trap
TCA (2)
Geosmin
Trichloroanisole (1)
MIB
Background:
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Valencene
Nookatone
2-Furaldehyde
Decanal
Background:
Limonene
Ethanol
Ethyl acetate
Ethyl propanoate
-myrcene
3,5-Dihydroxy-2-methyl- 5,6dihydropyran-4-one
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4-Ethyl-2-methoxy phenol
4-Ethyl phenol
Background:
Expanded view
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Whisky
Background:
Markes thermal desorption facilitates detailed analysis of
the flavour profile of potable spirits by allowing selective
elimination of water and ethanol. By doing this, key olfactory
components (ketones, esters, essential oils, etc.), which
would have otherwise been masked, are visible.
Headspace vapours are pumped/purged onto a Tenax TA
trap or tube under conditions which concentrate the target
analytes, whilst allowing most of the water, ethanol and
other very volatile polar components to break through. An
example of whisky analysis, with selective elimination of
water & ethanol, is shown opposite. Selective concentration
of key olfactory components simplifies meaningful odour
profiling.
Typical analytical conditions:
Typical VOC profile from whisky headspace with selective elimination of water
& ethanol. Dotted (red) line shows how the ethanol peak would mask key
aroma compounds if not selectively purged from the trap prior to desorption
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Background:
Beer is made mainly from natural products, e.g. malt and
hops, and therefore comprises a vast dynamic range of
volatiles. Flavour compounds, however, can have very low
olfactory thresholds (ppt) and their presence may be at
trace-level. In order to efficiently extract the widest range of
analytes, sorptive extraction using SPE-tD cartidges provides
an easy yet sensitive technique.
Further sample concentration in the focusing trap of the
thermal desorber makes sub-ppt detection possible.
The example opposite shows a close-up of the total ion
chromatogram (TIC) of a beer sample obtained using
sorptive extraction and TD-GC/MS analysis. The complexity
of the profile is an indication of the efficiency of SPE-tD.
Typical analytical conditions:
Sampling: SPE-tD cartridge placed into 20 mL beer & stirred
for 30 mins
TD system: UNITY 2 or TD-100
Desorption: 180C for 5 min
Trap: U-T15ATA-2S (Air toxics analyser)
Trap high: 200C
Split: 20 mL/min
Analysis: GC/TOF-MS
Reference: ALMSCO International application note, ANBT10
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Sample vessel
The series 2 UNITY-Direct Inlet system is compatible with a wide
range of sample vessels. It may be used for purging headspace
sample containers.
Optional
pump
Gas/air inlet
Off-odour/shelf-life testing
Sampling from drinks/spirits, with the option of
selectively purging the ethanol (see p. 17)
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Background:
Cows milk is an important source of nutrition. Milk
production cannot be isolated from the environment and is
therefore subjected to potential contamination by VOCs
present in the air and from the food and water consumed
by cows.
Markes series 2 UNITY-Direct Inlet system has been utilised
for the analysis of VOCs in the headspace of whole milk at
room temperature.
Typical analytical conditions:
Sampling: Individual milk samples of ~150 mL placed in
sealed vials at ambient temperature
TD system: Series 2 UNITY-Direct Inlet Accessory
Headspace sampling: 10 mins
Cold trap: U-T9TNX-2S (Tenax TA trap)
Trap conditions: 30C to 300C for 3 mins
Split flow: 20 mL/min during trap desorption only
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Acetone
Pentanal
Toluene
Butanoic acid
Hexanal
2-Pentanone, 4-hydroxy, 4methyl
Xylene
2-Heptanone
Nonane
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Heptanal
Decane
Octanal
Limonene
Undecane
Nonanal
2-Ethyl hexanoic acid
Dodecane
Decanal
Tridecane
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Tetradecane
Pentadecane
Tetradecanoic acid
Pentadecanoic acid
Hexadecenoic acid
Hexadecanoic acid
Octadecenoic acid
Octadecanoic acid
Cholesta-3,5-diene
Analysis: GC/MS
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Ethylene glycol
1,3-dioxolane
Acetaldehyde
Sample A
Sample B
Sample C
Background:
Product taint can be introduced via:
Warehouse storage
Sample D
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Ethyl acetate
Background:
Markes offers complementary techniques for the
identification of VOCs that may cause taint when present in
food packaging. In this example, TD was used to analyse
printed biscuit wrappers in two ways:
1-propanol
Ethyl acetate
Direct desorption
Headspace
vapours
Pentamethyl heptane
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Analysis: GC/MS
References: TDTS 9 (Monitoring materials & processes for
VOCs at high and trace Levels) & TDTS 92 (Residual monomer
in polymer by direct desorption)
Background:
Thermal desorption is used extensively to monitor odours
associated with meat processing; for example,
environmental/ambient-odour monitoring, product
quality/flavour assessment, testing of animal odours
(healthy and diseased) and monitoring of production
processes.
Meat-related odours often contain reactive species such as
thiols (mercaptans), fatty acids & volatiles amines. The
inertness & adjustable flow path temperature of Markes TD
systems make them ideally suited to this application.
Cryogen-free, sorbent-based analyte trapping also allows
high sensitivity splitless operation, but without the risk of
ice blockage during the analysis of humid samples.
Hexadecanoic acid
4-methyl phenol
Hexanoic acid
3-hydroxy-2-butanone
1-hexanamine
1,5-pentanediamine
-pinene
Acetic acid
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Trichloroanisoles in wine
Background:
2,3,4-trichloroanisole
2,4,6-trichloroanisole
A recent, high-profile example of taint was linked to 2,4,6trichloroanisole (TCA) in wine. TCA is produced from
trichlorophenol by a micro-organism that thrives in the
production process of corks. This, and other chemically
similar analytes, gives the wine a mushroomy corked
aroma even at low concentrations (<5 ng/L).
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Benzene
Background:
Thermal desorption has extensive uses in the tobacco
industry. Key applications include:
Toluene
Isoprene
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Background:
The tobacco industry began to invest in TD-GC/MS in the
early 1980s for monitoring trace levels of nicotine & other
target compounds in the environment.The new technology
was quickly adopted by product development & QC depts for
fingerprinting/characterising tobacco & other raw materials
& end products.
UK cigarette sample
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Acetaldehyde*
Trimethyl amine
Ethanol*
Acetone*
IPA
DMS
2-Methyl propanal*
Methacrolein*
2,3-Butanedione*
2-Butanone*
2-Methyl furan*
Ethyl acetate
3-Methyl butanal*
1-Butanol*
2-Methyl butanal
Pentanal*
Propylene glycol*
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1-Ethoxy-2-propanol
Hexanal*
Methyl pyrazine
3-Furanmethanol
1-(1-3-Dioxolan-2-yl)2-propanone
2-Acetate 1,2propanediol*
2,6- Dimethyl
pyridine
Benzaldehyde *
6-Methyl-5-hepten-2one
Beta myrcene
3,7-Dimethyl-(Z)1,3,6-octatriene*
Limonene*
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Cis-linalool oxide
Odour Description:
Sweet Earthy Floral
Spice Lavender*
3,7-Dimethyl-1,6octadien-3-ol
Olfactive Note:
floral, herbal woody,
rosewood*
Pyrrolidine*
3,7-Dimethyl-(r)-6octen-1-ol Used in
perfumery as a
source of floral
odors*
3,7-Dimethyl-1,6ocatdien-3-ol
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acetate Odour
Description:
Pleasant, sweet,
floral, fruity*
1-Acetoxymethyl-3isopropenyl-2-methyl
cyclopentane*
3,7-Dimethyl acetate (Z)2,6,octadien-1-ol It
has a rose-like
odour*
2-(3,3Dimethylcyclohexylid
ene)-(Z)-Ethanol *
Nicotine*
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cm3 into which samples are placed; the M-CTE250 (above right),
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Background:
The Markes -CTE provides an ideal sampling accessory for
inhomogeneous materials such as tobacco. Crumbled
tobacco samples can be placed in Silcosteel microchambers, incubated at user selected temperatures &
purged with air or inert carrier gas to sweep volatiles onto
inert sorbent tubes. Subsequent analysis is via TD-GC/MS.
The chromatograms opposite show comparative odour
profiles from two types of tobacco.
The -CTE is exclusively available from Markes. It is similarly
convenient for sampling whole cigarette filters (before or
after smoking), cigarette paper and cigarette packaging
materials.
2,6,6-trimethylbicycloheptane
3-(1-methyl-2pyrrolidinyl)-pyridine
Triacetin
Butyrolactone
Propylene glycol
Acetic acid
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Background:
Milk and related dairy products have a complex aroma
profile comprising fatty acids, lactones, ketones, aldehydes,
esters and hydrocarbons.
Several mL of milk or yoghurt can be conveniently
measured into stainless or Silcosteel micro-chambers and
incubated at temperatures between ambient and 80C
under a flow of pure air or inert carrier gas. Emitted vapours
are collected on Tenax TA tubes connected to the exhaust of
each micro-chamber. Water is selectively eliminated.
Decanal
Ethylhexanol
Limonene
Undecanal
2-nonanone
Octanal
Heptanone
Heptanal
n-C9
Thiophenone
Nonanal
Flavour profile obtained from natural greek yoghurt using Markes -CTE at 70C
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Background:
There is extensive research into the complex aroma profiles
of different types of cheese. For example, over fifty aromaactive compounds have been detected in various cheddar
cheeses.
Limonene
Nonanal
Decanal
2-nonanone
Octanal
Heptanone
n-C9
Heptanal
n-C8
Hexanal
Pentamethyl heptane
Hexanoic acid
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Analysis: GC/MS
Background:
Burning mosquito coils indoors generates smoke that repel
mosquitoes. However, the smoke may contain pollutants of
health concern. Mosquito coils sometimes contain BCME
(bis[cloromethyl]ether) which is highly carcinogenic. It is
illegal to sell mosquito coils that contain BCME in the United
States. Nevertheless, mosquito coils that contain BCME
have occasionally penetrated the US market in recent years.
Two mosquito coils were purchased & analysed for BCME.
Using the Micro-Chamber/Thermal Extractor & UNITY 2, a
fingerprint of the chemical compostion of mosquito coils
may be established (see opposite). No BCME was found in
either of the coils tested in this case.
Typical analytical conditions:
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Propene
Methanol
Chloromethane
Methyl chloride
Acetone
Propanol
Furan
Acetic acid methyl ester
2,3-Butanedione
2-Butanone
Hexene
3-Methyl furan
Hexane
2-Methyl furan
Methyl proprionate
Benzene
1-Hydroxy-2-propanone
2-Pentanone
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Pentadione
2,5,-Dimethyl furan
1-Methyl pyrrole
Toluene
Hexanal
Furfural
Ethyl benzene
Xylene
Styrene
Methoxy benzene
Benzaldehyde
Benzonitrile
Phenol
Benzofuran
Decene
Limonene
Phenyl ester acetic acid
Butyl benzene
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2-Methoxy phenol
Benzoic acid methyl ester
2-Methyl benzofuran
Tetramethyl benzene
Phenylmethyl ester acetic
acid
2-Methoxy-4-methyl phenol
Naphthalene
2-Ethyl-2-methoxy phenol
Tridecane
Dimethoxy phenol
Biphenyl
Tetradecane
Pentadecene
Pentadecane
Allethrin
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Background:
2-phenoxyethyl isobutyrate
2-(1,1-dimethylethyl)cyclohexanol
D-limonene
Hexenal acetate
3-methylbutanol acetate
Butanoic acid
Ethyl acetate
Cyclohexane
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Background:
Fragrance plays a major part in market acceptance and
consumer satisfaction for products such as toiletries (e.g.
soap), air fresheners and domestic cleaning materials.
Methyl-b-ionone
Thujopsene
a-cedrene
Linalool
Triplal
a-pinene
Hexene-1-ol
D-limonene
Markes TD instrumentation provides a versatile, laboursaving and automated tool for sensitive GC/MS analysis of
the fragrance profile of consumer products. Advantages
include:
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Background:
Manufacturers of fabric conditioners are interested in
knowing what fragrance compounds remain on the fabric
after washing as this gives the fabric the characteristic and
desirable freshly washed smell.
In the example opposite, direct desorption of a small
sample of washed fabric was compared with that of a
fragrance standard. Results illustrate that a significant
portion of the fragrance has remained on the fabric after
the washing process.
Fragrance standard
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Background:
Most natural (e.g. floral) fragrances, and many of the
fragrance profiles of consumer products (e.g. air
fresheners), change with time & ambient conditions.
Markes continuous & semi-continuous online monitoring
vapour systems offer around-the-clock profiling of fragrance,
& odour allowing changes to be tracked as a function of
time & ambient conditions; e.g. temperature, humidity,
sunlight intensity, etc.
Online TD systems from Markes include single trap
configurations based on UNITY 2 & dual trap configurations
based on the TT24-7. Both are electrically (Peltier) cooled so
no liquid cryogen is required. The twin traps of the TT24-7
operate reciprocally to monitor the air/gas continually (i.e.
with no dead time)
Typical online monitoring conditions:
TD system options: TT24-7, series 2 UNITY-Air Server/CIA 8,
series 2 UNITY-Direct Inlet Accessory
Sampling: 10-50 mL/min for 20 mins
03:12
05:59
Time (hours:mins)
08:05
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Propene
2-Methyl-propene
Acetic acid
3-Methyl-pentane
1,3,5-Trifluoro-benzene
Benzene
Heptane
Hexamethyl-cyclotrisiloxane
Octamethyl-cyclotetrasiloxane
2-Ethyl-hexanol
2,2'-Azobis[2-methyl-propanenitrile],
Nonanal
Benzenecarboxylic acid
1,3-Bis(1-methylethenyl)-benzene
1,3-Diisocyanato-2-methyl benzene
4-Methyl-1,3-benzenediamine
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3
2
1
Background:
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1,3-Dihydro-5-methyl-2H-benzimidazol-2-one
4-Methyl-8-quinolinol
1-(1-Isocyanato-1-methylethyl)-3-(1methylethenyl)-benzene
1,3-Bis(1-isocyanato-1-methylethyl)-benzene
n-Butyl-benzenesulfonamide
2-Ethylhexyl salicylate
7-Hexadecene
n-Hexadecanoic acid
7-n-Pentadecylaminomethyl-6-hydroxy-5,8quinolinedione
1-Octadecene
4,4'-(1-Methylethylidene)bis-phenol
Triphenylphosphine oxide
4-Methoxybenzonaphthone
Background:
Breath from two
smokers
= Benzene
= Toluene
= Isoprene
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Trademarks
UNITY, ULTRA, Air Server, CIA 8, TD-100, -CTE, SafeLok, DiffLok, VOC-Mole,
Bio-VOC, TT24-7, TC-20, TD-100, UniCarb, TubeTAG & SecureTD-Q are trademarks of
Markes International Ltd, UK
ClearView, and TargetView, are trademarks of ALMSCO International (a division of Markes
International Ltd)
Tenax is a registered trademark of Buchem B.V., Netherlands
Carbograph is a trademark of LARA s.r.l., Italy
Carbopack is a trademark of Supelco Inc., USA
Silcosteel
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www.markes.com