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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:53 Page 1

Thermal Desorption:
A Practical Applications Guide

2nd Edition

www.markes.com
www.markes.com

IV. Food, Flavour, Fragrance &


Odour Profiling

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Introduction to Markes International Ltd

What is analytical TD?

Formed in 1997, Markes International is world leader in the

Analytical thermal desorption is a sample introduction technique for

development and manufacture of analytical thermal desorption (TD)

GC and GC/MS, which uses heat and a flow of inert gas, rather than

instrumentation and associated sampling equipment for measuring

an organic solvent, to extract/desorb analytes from the sample

VOCs and semi-volatiles in air & materials.

media, delivering them directly to the gas chromatograph. Since the


early 1980s, TD has provided the ultimate versatile sample

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

introduction technology for GC, by combining selective concentration


enhancement with direct extraction into the carrier gas and efficient
transfer/injection, all in one fully automated and labour-saving
package.

innovations feature in Markes well known modular range of TD


instruments: UNITY, ULTRA, Air Server and the most recent
addition, the TD-100. Other ground-breaking TD products from
Markes International include the twin-trap TT24-7 for continuous,
online air monitoring, and unique sampling accessories such as the
Micro-Chamber/Thermal Extractor and HS5-TD for liquid and
solid samples.

Markes TD units can be seamlessly combined with all major brands


of GC and GC/MS to provide trace or high level monitoring solutions.

Markes International Ltd, UK headquarters

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Overview

Applications in food, flavour and fragrance

Thermal desorption is now recognised as the technique of choice for

environmental air monitoring and occupational health & safety.


Relevant standard methods include: ISO/EN 16017, EN 14662
(parts 1 & 4), ASTM D6196, US EPA TO-15/17 and NIOSH 2549.

TD is also routinely used for monitoring volatile and semi-volatile


organic compounds (SVOC) in products and materials. Examples
include residual solvents in packaging & pharmaceuticals, materials
emissions testing and food, flavour & fragrance profiling.

Fragrance profiling of ingredients in toiletries and


consumer products

Identification of key olfactory components

Characterisation/sourcing of natural products

Odour profiling for potable spirits

Quantitation of volatile components in dried foodstuffs

Off-odour/taint analysis

Biology/crop research

Flavour profiling of GM foods

This publication presents several real-world applications of TD for


measuring (semi-)volatiles in food, flavour, fragrance and odours.
Accompanying publications cover the applications areas of:

Residual volatiles & materials emissions testing

Defence & forensic

Environmental monitoring and occupational health &


safety

Markes International Ltd


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Odour profiling by direct thermal desorption/


extraction

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.

Direct desorption is used for both:

Complete (exhaustive) extraction (e.g. for packaging)

Characterisation of materials using a representative vapour


profile

The horizontal orientation of sample tubes in


Markes Series 2 UNITY & TD-100 systems
minimises the risk of samples shifting
within the tube or falling out.

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Profiling natural oils by direct desorption

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

7.5 mg sesame oil

Markes TD instrumentation is uniquely well-adapted for


aroma/taint identification because the short, inert flow path
can be set at temperatures low enough to ensure recovery
of most reactive GC-compatible olfactory components.
Direct thermal desorption/extraction can be achieved using
either an empty TD tube or the Markes -CTE (p 27),
followed by TD-GC/MS analysis.
Typical analytical conditions:

Empty tube showing system background

Direct desorption of sesame oil sample

Sampling: A few mg oil loaded onto a glass wool plug behind


1 cm bed of Tenax TA in a glass TD tube, or a few mL oil
incubated in a -CTE chamber at 80-100C with vapour
collection on a Tenax TA tube (gas flow ~100 mL/min)
TD system: Series 2 UNITY or TD-100
Desorption: 10 mins at 300C
Cold trap: U-T9TNX-2S (Tenax TA)
Split ratio: >100:1
Analysis: GC/MS

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 5

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

Freeze-dried products, such as ground or instant coffee

Animal feed pellets

Proprietary valve technology makes Markes TD systems


compatible with the widest possible analyte range (C2 to nC40 and reative species) all on one platform.

Eugenol

Dodecane

Tetradecane

Profiling volatiles in dried foodstuffs by direct


desorption

Typical analytical conditions:


Sampling: 100200 mg weighed into empty glass tube or
PTFE liner
TD system: UNITY 2 or TD-100
Desorption: 10 mins at 80C

Direct desorption of ground dried animal-feed pellets weighed into an empty


glass tube

Trap: Quartz wool/Tenax TA


Split: ~25:1 split during trap desorption only
Analysis: GC/MS
Reference: TDTS 23 (Utilising the UNITY method development
mode to analyse dried foodstuffs)

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T-cadinol

DEP

a-cadinene

Germacrene-D

a-bergamotene

a-copaene

High/low analysis of trace & high-level aroma


constituents using SecureTD-Q

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

Vapours extracted from a leaf sample. Direct desorption (blue) followed by


repeat analysis of re-collected sample (black) with lower split ratio to enhance
sensitivity for trace components

Re-collection on Tenax TA/UniCarb Silcosteel


TD system: UNITY 2 or TD-100
Desorption: 10 mins at 80C
Trap: U-T6SUL-2S (Sulphur trap)
Flow path: 80C to 150C depending on target compounds
Split: ~25:1 and repeat analysis at 5:1 split

Markes TD valve allows quantitative


re-collection of split flow (SecureTD-Q)

Analysis: GC/MS

Markes International Ltd


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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 7

Flavour profiling of mushroom powder via direct


desorption

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.

11
9

The quantitative re-collection for repeat analysis


(SecureTD-Q) ability of every Markes TD system uniquely
accomodates this wide dynamic range with re-analysis
under differing conditions; a high split analysis to measure
major consituents is typically followed by repeat analysis
under low split conditions to identify trace components.

15

2
34

16
5

10

14
12 13

17
1819

21
20

Typical analytical conditions:

22

Sampling: Direct desorption of ~50 mg mushroom powder


in a glass tube
23

TD system: UNITY 2 or TD-100


Desorption: 5 mins at 50C

1
2
3
4
5
6
7
8
9
10
11
12
13

Acetaldehyde
Ethanol
Butanal
Hexanal
Heptanal
D-Limonene
Octanal
Nonanal
Acetic acid
Benzaldehyde
Propylene glycol
Butyrolactone
Butanoic acid

14
15
16
17
18
19
20
21
22
23

Phenylmethyl ester acetic acid


2-Methyl-, 1-(1,1-dimethylethyl)-2methyl-1,3-propanediyl ester
propanoic acid
Phenol
2-Pyrrolidinone
2-Phenoxy-ethanol
Caprolactam
Methyl dihydrojasmonate
2,4-Di-tert-butylphenol
1-Hexadecanol
Benzophenone

Trap: U-T15ATA-2S
Trap conditions: 0C to 300C for 5 mins
Split: 25:1
Analysis: GC/MS

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Background:

Re-collected
sample
DEP

a-copaene

2-phenoxyethanol

2-pentylfuran

Pentanol

Flavour profiling new crop varieties by sampling


vapours onto sorbent tubes

Original

The development of new crop species (e.g. genetic


modification to aid pest resistance or to boost growth in arid
areas) requires testing of the flavour profile to make sure it
is enhanced, or at least remains acceptable, in the new
variety.
In the case of bulk, inhomogeneous materials like fresh
fruit/vegetables, flavour profiles are best obtained by
purging headspace volatiles from large (~1 kg) samples,
cooked or raw, & collecting the vapours on tubes packed
with Tenax TA. Tenax TA is completely hydrophobic so almost
all water passes straight through during the vapour
sampling process, simplifying profile interpretation.
Pioneered by Markes, SecureTD-Q offers quantitative recollection of any split flow for repeat analysis & confirmation
of analyte recovery. SecureTD-Q is standard on every
Markes TD system (contact Markes for futher details).

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)

Typical analytical conditions:


Sampling: 50 mL/min for 20 mins
TD system: Series 2 ULTRA-UNITY or TD-100
Prepurge: 3 mins (to trap and split)
Desorption: 15 mins at 200C
Trap: U-T9TNX-2S (Tenax TA)

Reference: TDTS 24 (SecureTD-Q Re-collection for repeat analysis) & 84


(Using thermal desorption to enhance
aroma profiling by GC/MS)

Split flow: 20 mL/min


Analysis: GC/MS

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 9

Removing background interference with


ClearView: An example with incense

Original data

ClearView reprocessed 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:

Reduced signal to noise for improved


sensitivity/detection

Improved spectral purity which improves automatic


identification of trace components

ClearView produces a second reprocessed data file for each


analysis (see example opposite)
Typical analytical conditions:
Sampling: Vapours from a burning incense stick were
collected onto Tenax TA/UniCarb tube over 5 min using
the MTS-32 (p. 36)
TD system: Series 2 UNITY

Vapour analysis from a lit incense stick. Original data (top) and ClearView
reprocessed data (bottom)

Primary desorbtion: 10 min at 300C


Split: 15:1
Trap: T6-SUL-2S (sulphur trap)

References: TDTS 83 & 85 (Using ClearView reprocessing to


enhance trace GC/MS analysis)

Trap conditions: -10C to 300C, 5 min


Analysis: GC/MS
ClearView

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Identifying trace target compounds using


TargetView: An example with potato crisps (chips)

TargetView builds upon the foundation of ClearView. It is a


sophisticated GC/MS datamining package, offering automatic
interpretation of complex chemical profiles. TargetView facilitates the
detection and measurement of target compounds even if they are at
trace levels and co-eluting with other compounds. Original data files
are left intact and unaffected, so operation of TargetView is risk-free.
It works as follows:

Above: Enlarged view of potato crisp profile with


automatic detection of target peaks (HPlot: red bars).

1. Dynamic background compensation (ClearView) is applied


to eliminate interferences such as column bleed.

Right: Highlighted peak shows dimethyl pyrazine (*)


co-eluting with multiple non-target compounds

2. The GC/MS data (total ion chromatogram [TIC]) of the


sample is deconvoluted & principal component analysis
identifies targets using a selected library of compounds.
3. Target compounds found are assigned a match co-efficient,
depending on the correlation between sample & library
spectra.
4. A report listing all identified target compounds and
associated peak areas is produced.
5. A plot of the TIC with compounds represented by red bars

Automated post-run report displaying target hits

(the HPlot) may also be displayed.

10

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 11

SPE-tD cartridges

After equilibration, the SPE-tD cartridge is removed from the sample,


rinsed in pure water to remove solid residues (if necessary) and
placed into an empty TD tube. The cartridge is then dry purged with

Markes SPE-tD cartridges offer a simple, convenient method for

pure carrier gas, on- or offline, prior to analysis by TD-GC/MS.

sampling less volatile impurities in aqueous samples. Such


applications would otherwise require manually-intensive extraction or
distillation techniques before GC(MS) analysis.

Sorptive extraction/TD methods provide a complementary sample


preparation tool to automated headspace (HS) and purge-and-trap
(P&T) techniques, which favour volatiles. The use of SPE-tD
cartridges in combination with HS or P&T allows full characterisation
of aqueous samples; volatile & semi-volatile constituents.
Key Applications include:

Off-odours/taints in drinking water

Semi-volatiles in processed fruit juices

Profiling of hydrosols (aqueous fraction from steam


distillation of natural oils).

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.

11

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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

Extraction of odourous organics from drinking water


using SPE-tD

Typical analytical conditions:


Sampling: SPE-tD cartridge placed into 1 L water sample
and agitated for 2 hours
TD system: UNITY 2 or TD-100
Desorption: 60C for 10 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)

Profile of sub-ppb level organics extracted from drinking water using the
SPE-tD cartridge

Trap Conditions: 30C to 300C


Split flow: 10 mL/min during trap desorption
Analysis: GC/MS
Reference: TDTS 88: (Using SPE-tD for profiling flavour &
fragrance compounds of fruit juices & wine)

12

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 13

Coupling headspace with thermal desorption (HS-TD)

The combined series 2 UNITYHS5 system offers optimum


sensitivity for trace-level organics in solid, liquid and vapour-phase
samples, all on one versatile analytical platform.

Markes HS5-TD module for UNITY 2 brings together two of the most
powerful GC introduction techniques: Headspace (HS) sampling and

The series 2 UNITYHS5 system can operate in two modes:

thermal desorption (TD).

HS5 accomodates up to five (5) standard


(~20 mL) headpsace vials in a common
headed zone with manual vial selection.
The inert needle, used for vial
pressurisation and HS vapour sampling,
is lowered into the vial using a
convenient user-operated lever. A heated
tower protects the needle and eliminates
cold spots.

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.

13

Headspace trap

Thermal desorption of sorbent or sample tubes

The combination of multi-stage headspace trapping and highly


efficient trap desorption/GC injection offers maximum sensitivity;
ideal for drinking water analysis and other trace-level applications.
Repeated pressurisation and evacuation of headspace vials also
extends the analyte volatility range, allowing higher boiling
compounds to be recovered and
measured simultaneously with volatiles.

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Low-ppt level odorants in drinking water using HS-TD

Drinking water is prone to contamination by naturally


occurring odorous compounds such as geosmin, methyl-iborneol and trihaloanisoles. These components produce a
musty/earthy smell that is detectable by consumers at
concentration levels down to 10 ppt.

TCA (2)

Geosmin

Trichloroanisole (1)

Without ClearView data reprocessing

MIB

Background:

With ClearView data reprocessing

HS-TD offers a simple, innovative and readily-automated


approach to routine analysis of odorants in drinking water.
Detection limits down to 1 ppt can be achieved using
conventional 20 mL HS vials/caps and GC/MS.
Eradicating the chromatographic effects of water or other
background interference using ClearView reprocessing
software, optimises signal-to-noise (sensitivity) at the lowest
levels.
Typical analytical conditions:
TD system: HS5-UNITY 2

5 ppt level odorants in drinking water analysed by HS-TD-GC/MS shown with


and without ClearView reprocessing

HS vials: 45-50C; Sample cycles: 10


Trap: U-T2GPH-2S (General purpose)
Trap conditions: Held at 30C (purgeables), and 50C
(odorants)
Desorption: 300C for 5 min
Analysis: GC/MS
References: TDTS 78 (Low ppt-levels of odorants in drinking
water using HS-TD), TDTS 83 & TDTS 85 (ClearView)

14

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 15

Valencene

Nookatone

2-Furaldehyde

Decanal

Background:

Limonene

Ethanol
Ethyl acetate

Ethyl propanoate
-myrcene

3,5-Dihydroxy-2-methyl- 5,6dihydropyran-4-one

HS5-TD and SPE-tD of fruit juice

TD-GC/MS of freshly squeezed orange juice sample. HS (black) & SPE-tD


cartridge (red)

Reference: TDTS 88 (Enhancing olfactory profiling of fruit juices


and wine using complementary analytical thermal desorption
techniques)

15

A variety of compounds define the aroma and flavour of fruit


juices. The analyses of flavour compounds in these types of
beverage usually require cumbersome sample preparation
steps such as liquid/liquid extraction, solid-phase extraction
or distillation, often with the drawback of organic solvent
use.
Markes UNITY 2-HS5 system can be used in HS-TD mode to
characterise compounds that contribute to the aroma of a
sample. It can also be used to desorb SPE-tD cartidges
allowing flavour compounds to be analysed without the
need for solvent extraction, & on the same analytical
platform.
Typical analytical conditions:
Sampling: 20 mL sample in sealed vial at ambient
temperature (HS5), & 20 mL sample in sealed vial at
ambient temp. with cartridge & stirred for 1 hour (SPE-tD)
TD system: Series 2 UNITY-HS5
Sampling mode: Dynamic headspace for 3 mins (HS5), &
tube desorption at 180C for 5 mins (SPE-tD)
Trap: U-T2GPC-2S (General purpose hydrophobic)
Trap conditions: 25C to 300C for 5 mins
Split flow: 20 mL/min during
trap desorption only
Analysis: GC/MS

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Red wine analysis: HS5-TD and SPE-tD


Wine aroma comprises a complex mixture of organic
volatiles, mainly terpenes and C13-norisoprenoids, which
supply fruity or floral notes. The highest volatility
compounds are monitored best by HS-TD, and the
combination of this technique with SPE-tD (targeted at lower
volatility components) ensures a broad range of compounds
are seen.

4-Ethyl-2-methoxy phenol

4-Ethyl phenol

Background:

Brettanomyces (Dekkera) bruxellensis (Brett), a spoilage


yeast found in beer and wine, creates off-odours. In this
study, trace levels of several Brett by-products, including the
primary ones of 4-ethyl phenol and 4-ethyl-2-methoxy
phenol, were detected, suggesting Brett contamination.
Typical analytical conditions:
Sampling: 20 mL sample placed in sealed vial at ambient
temperature (HS5), & 20 mL sample placed in sealed vial at
ambient temperature with cartridge & stirred for 1 hour
(SPE-tD)

Expanded view

TD system: Series 2 UNITY-HS5


Two chromatograms comparing the SPE-tD-GC/MS analysis (red) and HS-TDGC/MS analysis (black) of red wine

Sampling mode: Dynamic headspace for 3 mins (HS5), and


tube desorption at 180C for 5 mins (SPE-tD)
Trap: U-T2GPC-2S (General purpose hydrophobic)

Reference: TDTS 88 (Enhancing olfactory


profiling of fruit juices and wine using
complementary analytical thermal
desorption techniques)

16

Trap conditions: 25C to 300C for 5 mins


Split flow: 20 mL/min during trap desorption only
Analysis: GC/MS

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 17

Whisky: Enhanced aroma profiling by HS-TD with


selective concentration

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

TD system: UNITY 2 with HS5 module or Direct Inlet


Accessory (p. 19)
Sampling: Sample placed in headspace vial at ~40C.
Pulsed mode - 6 headspace extractions
Trap: U-T9TNX-2S (Tenax TA) from -10C to 280C, backflush
desorption
Analysis: GC/MS
Reference: TDTS 84 (Using TD to enhance aroma profiling by
GC/MS)

17

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Extraction of volatiles from beer using SPE-tD with


subsequent analysis by TD-GC/MS

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

18

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 19

Multi-purpose Direct Inlet Accessory: Direct


sampling/concentration of headspace vapours

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

The multi-purpose Direct Inlet


Accessory (U-INLET) can be added
UNITY trap

to UNITY 2 to provide a simple and


convenient mechanism for
concentration of headspace
vapours from a wide range of bulk

vapours from small, sealed containers (such as reaction vessels or


headspace vials) or for pumping air from open or compressible
containers such as bell jars or Tedlar bags.
Key application areas include:

and manufactured goods

sample containers.
Optional
pump
Gas/air inlet

Monitoring emissions from living organisms, e.g. plants,


microbes, fungi, insects, etc., over time

This online approach allows


vapours to be either pumped or

Characterisation of VOC profiles from natural products

Monitoring malodours generated from food packaging


(e.g. drink bottles)

swept continuously through an inert, heated sampling line, directly


into the electrically-cooled focusing trap of UNITY 2, without the

need for a sorbent tube.

Off-odour/shelf-life testing
Sampling from drinks/spirits, with the option of
selectively purging the ethanol (see p. 17)

The series 2 UNITY-Direct Inlet system has significantly improved


sensitivity over conventional static headspace methods by allowing
multi-stage extraction and concentration before analysis. The
dynamic headspace approach also eliminates the need for
equilibrium to be reached, thus reducing the time required for
analysis.

19

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 20

VOCs in milk samples by bulk HS-TD

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

1
2
3
4
5
6
7
8
9

Acetone
Pentanal
Toluene
Butanoic acid
Hexanal
2-Pentanone, 4-hydroxy, 4methyl
Xylene
2-Heptanone
Nonane

10
11
12
13
14
15
16
17
18
19

Heptanal
Decane
Octanal
Limonene
Undecane
Nonanal
2-Ethyl hexanoic acid
Dodecane
Decanal
Tridecane

20
21
22
23
24
25
26
27
28

Tetradecane
Pentadecane
Tetradecanoic acid
Pentadecanoic acid
Hexadecenoic acid
Hexadecanoic acid
Octadecenoic acid
Octadecanoic acid
Cholesta-3,5-diene

Analysis: GC/MS

Three replicate fresh whole milk headspace analyses at room temperature

20

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 21

Ethylene glycol

1,3-dioxolane

Acetaldehyde

Taint & off-odour: Monitoring residual volatiles in


packaging by direct desorption

Sample A

Sample B

Sample C

Background:
Product taint can be introduced via:

Odorous base materials

Issues with the fragrance additives

Packaging everything from printed film to wood pallets

Warehouse storage

Markes provides a comprehensive toolkit for tracking down


the sources of taint; Direct TD (dynamic headspace [HS]) of
sample in empty sample tubes; thermal extraction/HS of
larger samples using -CTE (p. 27); HS-TD (p. 13); sampling
larger volumes of HS vapour using the direct inlet accessory
(p. 19) & on- or offline vapour sampling for air/gas
characterisation e.g. warehouse air or process CO2 purity.
Typical analytical conditions (for direct desorption of PET):

Sample D

Sampling: 200 mg of ground polymer in an empty tube


TD system: UNITY 2 or TD-100

Direct desorption of ground polyethylene terephthalate (PET) polymer to


identify trace level VOCs contributing to taint. Comparison of PET polymers
used in the manufacture of soft drinks bottles

Desorption: 160C for 10 mins


Trap: U-T6SUL-2S (Sulphur trap)
Trap conditions: -10C to 300C
Split: 40 mL/min during trap desorption
Analysis: GC/MS
References: TDTS 9, TDTS 40 & TDTS 92

21

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 22

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:

Direct desorption of the wrapper

Desorption of Tenax TA tubes onto which HS vapours


from the wrapper were collected

Volatiles from the packaging sample include solvents which


can migrate into fatty foodstuffs, adversely affecting the
taste.
Typical analytical conditions:
Sample: 10 x 5 cm piece of film, rolled and inserted into an
empty stainless steel tube for direct desorption, & 250 mL
sample of headspace vapour drawn into a Tenax TA sorbent
tube

1-propanol

Ethyl acetate

Direct desorption

Pentanoic acid 2,2,4-trimethyl-3carboxyisopropyl, isobutyl ester

Packaging analysis via direct desorption & sampling


bulk headspace vapours

Headspace
vapours
Pentamethyl heptane

TD system: UNITY 2 or TD-100


Desorption: 10 mins at 60C (direct TD) and 10 mins at
300C (HS sample on Tenax TA tube)
Trap: U-T12ME-2S (Material emissions trap)
Split: 30:1 during trap desorption

Direct desorption (red) and headspace analysis (blue) of printed packaging


film. Note the wider volatility range of analytes observed in the direct
desorption run.

22

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)

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 23

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

2-Methyl propanoic acid


Butanoic acid
Penatanoic acid
Butanamide

3-hydroxy-2-butanone

1-hexanamine

1,5-pentanediamine

-pinene

Acetic acid

Concentrating odours from meat processing using


sorbent tubes

Typical analytical conditions:


Sampling: 0.5-2 L vapour sampled onto Tenax TA/
Carbograph 1TD tubes
TD system: UNITY 2 or TD-100
Desorption: 300C for 5 mins then 320C for 5 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: 20C to 300C
Split: Low split during trap desorption only
Analysis: GC/MS

Chromatogram of odours from a swine facility. Reproduced with the kind


permission of APS Adamsen, LugTek, Denmark - experts in odours from
livestock production

23

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 24

Trichloroanisoles in wine

Background:

Direct thermal extraction of whole corks to obtain the


overall VOC profile is possible using the Markes -CTE (p. 27).
Tribromoanisole

2,3,4-trichloroanisole

The inert flow path & desorption efficiency (sensitivity) of


Markes TD systems readily facilitate TCA measurement in
the headspace of aqueous samples at sub-ng/L levels.
Geosmin

2,4,6-trichloroanisole

Thermal extraction of cork using -CTE

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).

TD analysis of 0.2 ng/L TCA and other odour


compounds in the headspace of a 1 L aqueous
sample. (Inset: Vapour profile from whole cork
using -CTE)

Typical analytical conditions:


Sampling: On- or offline sampling of headspace from 1 L
aqueous samples at 60C onto Tenax TA trap. Whole cork
incubated at 60C using -CTE with 70 mL/min flow of
helium for 10 mins
TD system: UNITY 2 or TD-100
Desorption: 280C for 10 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: -5C to 300C
Split flow: 30 mL/min
Analysis: GC/MS or GC-olfactometry

24

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 25

Benzene

Applications for thermal desorption in the tobacco


industry

Background:
Thermal desorption has extensive uses in the tobacco
industry. Key applications include:

Analysis of environmental tobacco smoke (ETS)

Aroma profiling of tobacco/tobacco-substitutes

Monitoring filter efficiency by collecting vapours from


smoking machines (see opposite)

Tracking the cause of taint in batches of tobacco


products

Toluene

Isoprene

These applications are carried out using sorbent tube


sampling, direct TD or using accessories such as the -CTE
(p. 27).
Typical analytical conditions:
Sampling: Multiple puff volumes taken into bag then
transferred onto sorbent tube, or vapours sampled directly
onto tube
TD system: UNITY 2 or TD-100
Desorption: 280C for 10 mins

Testing filter efficiency: VOC profile of tobacco smoke drawn through a


cigarette filter using a smoking machine. Note: smokers are exposed to
volatile aromatics, including benzene, and nicotine (see also p. 37)

Trap: U-T2GPH-2S (General purpose hydrophobic), 30C to


300C for 3 mins
Split flow: 30 mL/min during trap desorption
Analysis: GC/MS

Reproduced with the kind permission of British American Tobacco, UK

25

Reference: TDTS 84 (Applications of thermal desorption in the


tobacco industry)

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 26

Headspace-thermal desorption analysis of tobacco

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.

Indian tobacco sample

Markes specialist sampling & analytical products provide a


unique combination of flexibility, performance & throughput
to meet the needs of industry. Highlights include:

UK cigarette sample

Comprehensive range of sample introduction options

Reliable/high performance analytical TD technology

Sophisticated GC/MS data reprocessing software

Typical analytical conditions:


Sampling: Indian tobacco and tobacco from a UK cigarette
(0.5 g) weighed into a 20 mL glass headspace vial. The vial
was sealed & equilibrated for 10 mins at 75C
TD system: Series 2 UNITY-HS5
Trap: U-T2GPC-2S (General purpose hydrophobic)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

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*

18
19
20
21
22
23
24
25
26
27
28
29

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*

30

31

32
33

34

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

35
36

37
38

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*

Trap conditions: -10C to 320C for 5 mins


Split: 20 mL/min during trap desorption only
Analysis: GC/MS
Reference: TDTS 76 (Comparison of tobacco by
headspacethermal desorption (HSTD)

Compounds found in Indian and UK tobacco samples

26

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 27

Micro-Chamber/Thermal Extractor (-CTE)

Both formats of the -CTE are available with stainless steel or


Silcosteel chambers. These chambers are convenient for samples
which are too inhomogeneous for direct desorption in empty tubes.

The -CTE is a convenient tool for


monitoring vapour profiles
and emissions from a wide
sample range. Samples
may be tested at near

Accessories are available to facilitate surface emissions testing and


permeation studies (e.g. of packaging) as well as the volatile
analysis of bulk samples.

ambient and elevated


temperatures.

Key applications include:

other inhomogeneous foodstuffs

The -CTE is available in two formats, configured to suit particular


applications. The M-CTE120 (above left), which can be heated to

Bulk sampling of volatiles from fruits, vegetables and

Fragrance profiling of tobacco blends/substitutes

120C, comprises six (6) micro-chambers each with a volume of 44

Permeation testing of packaging

cm3 into which samples are placed; the M-CTE250 (above right),

Fragrance profiles from consumer products

which can be heated to 250C comprises four (4) micro-chambers


each with a volume of 114 cm3.

A controlled flow of air or carrier gas is purged through all of the


chambers simultaneously, sweeping the volatiles onto sorbent tubes
which are attached to each chamber lid.

27

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 28

Monitoring the aroma/flavour profile of tobacco


using the Micro-Chamber/Thermal Extractor

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

VOCs from rolling tobacco

Typical analytical conditions:


Sampling: 1 g of tobacco incubated in the -CTE at 50C.
Vapours swept onto Silcosteel Tenax TA tubes in a 100
mL/min flow of helium for 10 mins
TD system: UNITY 2 or TD-100
Desorption: 300C for 10 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: -10C to 300C

VOCs from manufactured cigarette tobacco

Split: Double split, 300:1


Analysis: GC/MS

Vapour profiles from rolling tobacco (top) and manufactured cigarette


tobacco (bottom), collected on Tenax tubes using a micro-chamber at 50C

28

Reference: TDTS 84 (Applications of


thermal desorption in the tobacco
industry)

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 29

Flavour profiling of dairy products using the MicroChamber/Thermal Extractor

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

Typical analytical conditions:


Sampling: 10 mL (g) yoghurt incubated at 70C in the
-CTE, swept onto Tenax TA tubes in a 70 mL/min flow of
helium for 10 mins
TD system: UNITY 2 or TD-100

Ethylhexanol
Limonene

Desorption: 280C for 10 mins

Undecanal

Trap: U-T2GPH-2S (General purpose hydrophobic)

2-nonanone

Octanal

Heptanone

Heptanal
n-C9

Thiophenone

Nonanal

Note that the inert flow path & cryogen-free operation of


Markes thermal desorption system ensures compatibility
with humid samples and reactive polar analytes

Flavour profile obtained from natural greek yoghurt using Markes -CTE at 70C

29

Trap conditions: 30C to 300C for 3 mins


Split flow: 30 mL/min during trap desorption
Analysis: GC/MS

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 30

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

Thermal extraction (dynamic headspace) offers an


automated and versatile alternative to multi-step liquid
extraction and vacuum distillation. Cubed or grated cheese
mixed with distilled water can be incubated (e.g. using the
Markes -CTE) and purged with inert gas or pure air with
the vapours collected using on- or offline sorbent traps.
Subsequent analysis by TD-GC/MS or TD-GC with
olfactometry provides the full flavour and fragrance profile
of a sample.

Decanal

Typical analytical conditions:

2-nonanone

Octanal

Heptanone
n-C9
Heptanal

n-C8

Hexanal

Pentamethyl heptane
Hexanoic acid

Flavour profiling of cheese using the MicroChamber/Thermal Extractor

Sampling: 2 g grated cheese mixed with 5 mL distilled water


and incubated in the -CTE at 30C. Vapours swept onto
Tenax TA tubes in a 70 mL/min flow of helium for 10 mins
TD system: UNITY 2 or TD-100
Desorption: 280C for 10 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: 30C to 300C for 3 mins
Split flow: 30 mL/min during trap desorption

Aroma/flavour profiling of cheese using the -CTE at 30C

30

Analysis: GC/MS

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 31

Quality control of mosquito coil emissions

Red mosquito coil

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:

Black mosquito coil

Sampling: Sections of each of the mosquito coils (one red,


one black) were lit & inserted into individual microchambers. Vapours were swept onto Tenax TA/UniCarb
tubes in a flow of 150 mL/min of helium for 3 mins
TD system: UNITY 2 or TD-100

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

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

19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36

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

37
38
39
40
41
42
43
44
45
46
47
48
49
50
51

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

Analysis of two lit mosquito coils by thermal extraction followed by TD-GC/MS

31

Cold trap: U-T6SUL-2S (Sulphur trap)


Trap conditions: -10C to 300C for 3 mins
Split flow: 25 mL/min during trap desorption
Analysis: GC/MS

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 32

Background:

2-phenoxyethyl isobutyrate

2-(1,1-dimethylethyl)cyclohexanol

Acetic acid, phenylmethyl ester

D-limonene

Hexenal acetate

3-methylbutanol acetate

Butanoic acid

Ethyl acetate
Cyclohexane

Fragrance profiling of toiletries using the


Micro-Chamber/Thermal Extractor

Fragrance profile from shampoo obtained using the Micro-Chamber/Thermal


Extractor under inert conditions

The Markes -CTE is ideal for fragrance profiling of aqueous


solutions and emulsions such as shampoo. Six replicate, or
different shampoo, samples can be measured into
individual micro-chambers and incubated at low
temperatures (e.g. 30-40C) to simulate body/shower
temperatures. The fragrance components are purged onto
attached tubes packed with hydrophobic sorbents which
allow quantitative retention of the organic compounds of
interest while water is purged to vent.
The -CTE is compatible with the use of air or
nitrogen/helium gas to allow analysis of product fragrance
under oxygenating or inert conditions.
Typical analytical conditions:
Sampling: 5 mL shampoo incubated in the -CTE at 30C.
Vapours swept onto Tenax TA tubes in a 70 mL/min flow of
helium for 5 mins
TD system: UNITY 2 or TD-100
Desorption: 280C for 10 mins
Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: 30C to 300C for 3 mins
Split flow: 30 mL/min during trap desorption
Analysis: GC/MS

32

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 33

Profiling the fragrance of consumer products

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:

Numerous sampling handling options

Selective elimination of potential interferences such as


water and some solvents, thus simplifying fragrance
analysis.

Options for continuous online analysis, e.g. to monitor


the fragrance profile as it changes over time

Typical analytical conditions:


Sampling: ~200 mL headpace sampled onto Tenax TA tubes
TD system: UNITY 2 or TD-100

Headspace from sample of fabric conditioner selectively concentrated onto a


Tenax tube and analysed by TD-GC/MS

Trap: U-T2GPH-2S (General purpose hydrophobic)


Split flow: 30 mL/min during tube & trap desorption
Analysis: GC/MS

33

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 34

Fragrance analysis of conditioned fabric by direct


desorption

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.

Fabric sample desorbed at 70C

Typical analytical conditions:


Sampling: Direct desorption of washed fabric in an empty
sample tube. Liquid standard injected onto a Tenax TA tube
TD system: UNITY 2 or TD-100
Desorption: 70C for 5 mins (fabric) 280C for 5 mins
(Tenax tube)
Trap: U-T2GPC-2S (General purpose hydrophobic)

Fragrance standard

Trap conditions: 25C to 300C for 3 mins


Split flow: 5 mL/min during trap desorption
Analysis: GC/MS
Note: This application can also be carried out using HS-TD
or the Micro-Chamber/Thermal Extractor

34

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FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 35

Near real-time monitoring of fragrance profiles as


they change over time

Concentrations of vapour phase organic compounds


changing with time

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

Trap: U-T2GPH-2S (General purpose


hydrophobic)
Trap conditions: -10C to 320C for 3 mins
Analysis: GC/MS

Dual traps of the TT24-7

35

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 36

Monitoring the vapour profiles of burning incense


(joss) sticks over time

27

Markes MTS-32 is an ideal sampling device for such an


application as it can be programmed to take multiple air
samples onto individual sorbent tubes sequentially at
regular time intervals.

5
19

28
7
6

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

36

18
14 17
16
10 12
9 11 13 15

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

Incense sticks are composed of aromatic plant materials


and essential oils, which release fragrant smoke when
burned.
The objective of this application was to determine the
components of the vapour from a burning incense stick
using TD, and also to track any changes in the vapour
profile for the duration of burning and after the stick was
extinguished.

20

3
2
1

Background:

22 25 26
21 23 24
17
18
19
20
21
22
23
24
25
26
27
28
29

Typical analytical conditions:


Sampling: MTS-32 with Tenax TA/Unicarb tubes

29

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

TD system: UNITY 2 or TD-100


Desorption: 10 mins at 300C
Trap: U-T6SUL-2S (sulphur trap)
Trap conditions: -10C to 300C for 5 mins
Split: 15:1
Analysis: GC/MS

Markes International Ltd


T: +44 (0)1443 230935 F: +44 (0)1443 231531
E: enquiries@markes.com W: www.markes.com

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 37

Halitosis bad breath

Background:
Breath from two
smokers

= Benzene
= Toluene
= Isoprene

Breath from six nonsmokers

We are what we eat, & sometimes it can come back to


haunt us! Halitosis can also be caused by bacterial
infections of the mouth/throat, some disease states and
smoking.
Markes offers a range of specialist sampling accessories for
thermal desorption, including the Bio-VOC breath sampler.
The Bio-VOC collects breath from the mouth and bronchial
passages, or from the alveoli (depending on application), &
transfers it to sorbent tubes for subsequent analysis by TDGC/MS. Applications of the Bio-VOC include biological
monitoring of environmental/workplace exposure & aiding
disease diagnosis, in addition to breath odour.
Typical analytical conditions:
Sampling: Breath exhaled into Bio-VOC sampler &
transferred to Tenax TA tube or Tenax TA/Carbograph 1TD
focusing trap
TD system: UNITY 2 or TD-100

Rapid TD-MS analysis of benzene and other hydrocarbons in the breath of


smokers and non smokers

Desorption: 280C for 10 mins


Trap: U-T2GPH-2S (General purpose hydrophobic)
Trap conditions: 30C to 320C for 3 mins
Analysis: TD-GC/MS or TD with process-MS (as shown here)

Bio-VOC breath sampler

37

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 38

The Markes International advantage

Markes is the world leader in analytical thermal desorption and has


pioneered important technical innovations such as SecureTD-Q
(quantitative sample re-collection for repeat analysis), TubeTAG
electronic labels for sorbent tubes and universal (multi-application)
heated valve technology.
Markes leadership in TD now extends to:

The widest available product portfolio and application


range

Product quality and reliability

Excellence in technical and applications support

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

38

is a registered trademark of Restek Inc., USA

For more information on Markes comprehensive range of thermal


desorption instrumentation and sampling accessories request your free
copy of Markes TD Accessories & Consumables catalogue

Markes International Ltd


T: +44 (0)1443 230935 F: +44 (0)1443 231531
E: enquiries@markes.com W: www.markes.com

FFF 2nd edition (Final)_Layout 1 02/06/2010 08:54 Page 39

Gwaun Elai Medi Science Campus


Llantrisant
RCT
CF72 8XL
United Kingdom
T: +44 (0)1443 230935 F: +44 (0)1443 231531
E: enquiries@markes.com W: www.markes.com

www.markes.com

Markes International Ltd

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