who we are -markes international ltd - agilent · who we are -markes international ltd ......
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Markes International Ltd is a UK based company committed to advancing:
• Thermal Desorption (TD) Instrumentation,
• Sampling Accessories
• Technical Support
Who we are - Markes International Ltd
www.m
arkes.com
• Technical Support
Markes is the worldwide technology leader in thermal desorption
What is thermal
desorption (TD)?
TD uses heat and a flow of inert gas, rather than
conventional solvent, to extract/desorb analytes from the
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arkes.com
conventional solvent, to extract/desorb analytes from the
sample media
What is so special about Markes TD
� Flexibility & optimum system performance
– 4.5-inch or 3.5-inch standard tubes
– All TD applications on a single platform & wide
concentration range
– Manual or automated
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arkes.com
– Manual or automated
– Sample re-collection
– Cryogen-free operation
– Fully compliant with standard methods
– Sample and data integrity guarantee
What can be analysed by TD?
Yes• VOC/SVOC
– C2 to n-C40 (b.p. <500°C),
– GC analysis
– Matrix compatible with
No• Compounds which are not
compatible with standard
gas chromatography
• CH4
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arkes.com
– Matrix compatible with
high temperatures required
• CH4
• > n-C40 (non-volatiles)
• Special GC analysis, e.g.
on-column injection
• Most inorganic (permanent)
gases (O2, O3, CO2, SO2,
NO2, etc. Exceptions
include H2S, N2O & SF6)
The Thermal Desorption Process
Electrically-cooled focusing trap
On-line
Canisters
Direct
desorption
of materials
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arkes.com
100-200 µL injection
of vapour into GC(MS)
Water and volatile
interferences may be
purged to vent
Canisters
Sorbent
Tubes
Headspace …
What is thermal desorption and how does it compare to solvent
extraction?• The advantages over solvent extraction include:
• 103 - 104 fold better sensitivity
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arkes.com
• Compatible with solid, liquid, gas
• No solvent interference
• Automated
• Reliable, >95% desorption efficiency
• Markes TD systems overcomes the 1-shot limitation of older TD systems and solvent extraction:
– Sample re-collection (SecureTD-Q™)
Sensitivity
• VOC from 100L = 100µL of
carrier gas (GC column)
• 106 concentration enhancement
= ppt detection limits
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arkes.com
Series 2 TD instruments from MarkesUNITY 2
2 series
TD-100
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arkes.com
ULTRA 2
2 series ULTRA 50:50
AutoSecure TD
Accessories for series 2 thermal desorbers
µ-CTETC-20
Series 2 Air Server options
Air Server 3/8CIA 8
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arkes.com
µ-CTE
MTS-32
Pneumatic & calibration accessories
TC-20Air Server 3/8
CIA 8
Sorbent tubes/traps,
TubeTAG, caps etc.
Automated TD-GC/MS system for sorbent tubeswww.m
arkes.com
ULTRAAir server
Series 2
ULTRA 50:50
Series 2
UNITY
GCMS system
Applications for thermal desorption
Residual volatiles &
materials emissions
testing
Environmental
monitoring and
workplace air
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arkes.com
Food, flavour,
fragrance & odour profiling
Military, forensic and
counter-terrorism
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arkes.com
• Stack emissions
• Landfill gases
• Factory fence-line monitoring
Environmental air monitoringwww.m
arkes.com
• Factory fence-line monitoring
• Urban air
– “Air toxics”
– Ozone precursors
Stack gas analysis
Sulphur compounds
Industrial emissions (VOC)
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arkes.com
Freons
Very volatile Freon analysis
C2F6
C3F8C2F6
CF4
80 mgm-3 mixed std
300 mgm-3 std of CF4 & C2F6
only
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arkes.com
Cryogen-free analysis of very volatile freons using UNITY-Air Server with
GCMS: Quantitative retention of CF4
CF4
4 2 6
only
On-line monitoring of odorous reduced sulphur compounds in ambient and
industrial air
• Target compounds
• H2S hydrogen sulphide
• CH3SH, methanethiol (me.mercaptan)
• C2H6S Dimethyl sulphide
• C2H6S2 Dimethyl disulphide
• UNITY-Air Server 3 with ‘H2S’ focusing trap
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arkes.com
Gas standards at 20 ppb and 10 ppb levels
• UNITY-Air Server 3 with ‘H2S’ focusing trap
at -15 to -30ºC and flow path at 80ºC. GC
configured with PFPD
• Performance in field operation:
• Detection limits: 0.15 ppb
• Retention time stability: < 0.1% RSD across
all compounds
• Standard reproducibility: 0.5 to 5% RSD
• Recovery: >87% for all analytes
Markes TD systems offer multi-splitting for compatibility with high-concentration stack-emission samples
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arkes.com
• Pumped sampling of (1L) stack gases with
TD-GCMS analysis.
• Sample splitting during both primary (tube) and secondary (trap) desorption. Total Split ratio:3000:1
• Quantitative re-collection of both splits allows repeat analysis for data confirmation
Monitoring odorous and toxic VOCs in landfill gasDirective 1999/31/EC on Landfill of Waste
1) Vinyl Chloride/Toxic
2) 1,3-Butadiene/Toxic
3) Methyl Mercaptan/Odour
4) Chloroethane/Toxic
5) 1-Pentene/Odour
6) Furan/Toxic
11) 1,2-Dichloroethene/Toxic
12) 1,1-Dichloroethane/Toxic
13) Propyl Mercaptan/Odour
Odorous and toxic compound list
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Note TDTS 47: The Analysis of Landfill Gas Compounds using ThermalDesorption GCMS and a Retention Time Locked Database
6) Furan/Toxic
7) Ethyl Mercaptan/Odour
8) 1,1- Dichloroethene/Toxic
9) Dimethylsulphide/Odour
10) Carbon
Disulphide/Odour/Toxic
14) Tetrachloromethane/Toxic
15) Benzene/Toxic
16) Trichloroethene/Toxic
17) Butyl Mercaptan/Odour
18) Dimethyldisulphide/Odour
19) Ethylbutyrate/Odour
20) 2-Butoxyethanol/Toxic
TD – GCMS analysis of landfill gaswww.m
arkes.com
� Pumped tube sampling of only 100 ml sample of Landfill gas produces high
concentrations
� A retention time locked (RTL) database was created based on the target list of
odour/toxic compounds
� DRS software analysed the data and identified multiple compounds within the
complex mixture
DRS report for Landfill gas samplewww.m
arkes.com
Industrial perimeter fence-line monitoring
• Refinery perimeters
• Target analytes: BTX, 1,3-butadiene, C2 to C5olefins and 2 key halocarbons
Benzene
Toluene
Xylenes
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halocarbons
• Diffusive sampling for extended periods is again the method of choice
2-week diffusive sampling of benzene. Suitable for refinery perimeter monitoring
Mapping urban pollution concentrations
Sorbent tubes for pumped and diffusive sampling of outdoor air
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arkes.com
• 100 sampling sites - black dots
• Yellow dots = pollution hot spots
Air Server™ for ozone precursor monitoringwww.m
arkes.com
On-line and canister sampling of VOCs in urban air
Analysis of urban ‘Air Toxics’sampled in canisters
(US EPA Method TO-15)
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arkes.com
Splitless desorption of 61-component Air Toxic standard21 Methyl Ethyl Ketone
22 trans- 1,2 – Dichloroethylene
23 Ethyl Acetate
24 Tetrahydrofuran
25 Chloroform
26 1,1,1 – Trichloroethane
27 Cyclohexane
28 Carbon Tetrachloride
29 Benzene
30 Vinyl Chloride
31 n-Heptane
32 Trichloroethylene
33 1,2 – Dichloropropane
34 1,4 – Dioxane
35 Bromodichloromethane
36 Trans-1,3-Dichloropropene
37 Methyl Isobutyl Ketone
41 Tetrachloroethylene
42 Methyl n-Butyl Ketone
43 Dibromochloromethane
44 1,2 – Dibromoethane
45 Chlorobenzene
46 Ethylbenzene
47 O-Xylene
48 M-Xylene
49 P-Xylene
50 Styrene
51 Tribromomethane
52 1,1,2,2 – Tetracl ethane
53 1,2,4 – Trime benzene
1 Propylene
2 Dichlorodifluoromethane
3 1,2 – Dichlorotetrafluoroethane
4 Methyl Chloride
5 1,2 – Dichloroethane
6 1,3 – Butadiene
7 Bromomethane
8 Chloroethane
9 Trichlorofluoromethane
10 Ethanol
11 1,2 – Dichloroethylene
12 1,1,2 – Trichlorotrifluoroethane
13 Isopropyl Alcohol
14 Carbon Disulfide
15 Methylene Chloride
16 Tert-butyl Methyl Ether
17 Cis – 1,2 – Dichloroethlyenen
54 1,3,5 – Trimethylbenzene
55 1-ethyl-4-methyl Benzene
56 1,2 – Dichlorobenzene
57 1,3 – Dichlorobenzene
58 Chloromethylbenzene
59 1,4 – Dichlorobenzene
60 1,2,4 – Trichlorobenzene
61 Hexachloro-1,3-Butadiene
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37 Methyl Isobutyl Ketone
38 Toluene
39 Cis-1,3-Dichloropropene
40 1,1,2 – Trichloroethane
17 Cis – 1,2 – Dichloroethlyenen
18 Hexane
19 Vinyl Acetate
20 1,1 – Dichloroethane
Series 2 UNITY – CIA 8 with 60 m, 0.32 mm 1.8 µm VF624 column
Occupational Health and Safety
• Personal Exposure Monitoring
• Biological Exposure Assessment
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arkes.com
Indoor air profiling with TD-GC-MS
Pumped sampling of 15 L of clean indoor air, split 15:1. Analysis by TD-GC-MS(SCAN). Detection limits 10 to 50 ppt
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arkes.com
TD applications databases for automatic reprocessing with DRS spectral deconvolution
Illustration with indoor air sample
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arkes.com
Std GCMS processing and report format gives:• 21 compounds positively identified• 24 compounds tentatively identified
Using Rt-locking with spectral DRS:– 31 compounds are automatically identified within 3 minutes and without needing a skilled GC-MS technician to manually investigate ‘tentatively identified’ compounds.
Bio-VOC™ breath sampler
Applications include:
Biological exposure
Skin absorption
Protective equipment
Subject breathes through Bio-VOC to collect alveolar air
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arkes.com
Protective equipment
Environmental exposure
Bad breath
Clinical diagnosis
Solvents Detected on the Breath of Shoe Industry Workers
• Shoe workers are exposed to skin absorbed chemicals in adhesives
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arkes.com
• Breath sampling is able to analyse more solvents simultaneously than urine analyses
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arkes.com
Materials testing using direct thermal
desorption/extraction
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arkes.com
Car trim materials by direct desorption
PUF sample
Direct desorption/extractionFogging compounds
• Semi-volatiles
• Analysis by direct desorption
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arkes.com
• PVC foam sheet (VDA 278)
• Desorption: 60 mins at 120°C
Direct desorption of vehicle trimwww.m
arkes.com
VOC in artificial leather sample
Textiles: Leather discolouration
• White leather upholstery
discoloured (turned yellow) in
patches
• Direct desorption of the
discoloured sample (top) showed
high concentration of natural oils
Natural oil
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arkes.com
high concentration of natural oils
• Direct desorption of a sample of
white (control) leather (bottom)
shows high concentrations of
detergent.
• The leather upholstery had not
been adequately treated with
detergent
Detergent
Wet Paint:
Exhaustive extraction (content testing)
Repeat desorption
shows no carryover
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arkes.com
Paint Flakes:
Exhaustive extraction (content testing)
Iso
bu
tanol
Be
nzyl
alc
oh
ol
Nonyl phenol isomers
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arkes.com
Iso
bu
tanol
MIB
K
xyle
ne
s
FLEC Cell: Paint and flooringwww.m
arkes.com
µ-CTE™ Applicationswww.m
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Semiconductor: Outgassing from computer components e.g. HDD
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Typical forensic applicationswww.m
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Forensic applications
Hero
in
Monoacety
lmorp
hin
e
Cocain
e
Acety
l codein
e
Phenobarb
ital
Direct desorption of Drugs of Abuse from house dust
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arkes.com
HS gasoline vapours sampled on Tenax. Suitable for arson residue
analysis
DNT TNT
Typical chromatogram
Run time 13.33 minutes
TD conditions
Tube desorption, 180oC (3mins) and 210oC (2mins)
Trap desorb -10oC to 190oC (2mins, 32oC sec-1)
Single split 18 mlmin-1
Explosiveswww.m
arkes.com
PETN RDX
Single split 18 mlmin-1
Flow path 150oC, GC column direct into TD (no fused silica transfer line).
Chemical Warfare (CW) Agents
CW stockpile sites Agent destruction
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arkes.com
CW stockpile sites
Personal exposure
Agent destruction
Key civilian locations
Current CW air sampling protocols
DAAMS tube analysis
Off-line pumped tube sampling
On-line continuous sampling
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arkes.com
Near real-time analysis (NRT)
Ca 5 ng per component
Mixed CW Analysis by TD-GC-MS
A range of CW compounds analysed with a single UNITY method including free VX and R-VX
Extracted ion profile
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arkes.com
60pg GB S/N
On-line sampling of Sarin nerve agent
15m,1.0um,0.25mm id, DB1701 Phase
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arkes.com
60pg GB S/N ~87:1
NRT = 0.83mins
Permeation studies using the µ-CTE™www.m
arkes.com
Permeation of Methyl Salicylatethrough Nitrile Rubber
Permeation of methyl salicylate through nitrile rubber
15
20
25
30
35
40
Bre
ak
thro
ug
h a
mo
un
t (n
g)
du
rin
g 1
0 m
inu
te i
nte
rva
l
Series1
Collection
Side
2. Diffusion
3. Desorption
Permeation Process
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0
5
10
15
0 20 40 60 80 100
Time (min)
Bre
ak
thro
ug
h a
mo
un
t (n
g)
du
rin
g 1
0 m
inu
te i
nte
rva
l
Breakthrough Time ~ 15 min
Steady State PermeationPermeation Rate ~0.5ng/cm2/min
Swelling / Degradation of test material membrane Permeation Rate ~0.6ng/cm2/min
Challenge
Side1. Sorption
Test Material
Mobile laboratory TD-CW application
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arkes.com
Internal 3 D Schematic of the mobile laboratory
Internal air filtration/ pressurisation
Negative pressure glove boxes containing contaminated sample and analytical equipment TD/HdSpc-GCMSD
Laptop for instrument control and data analysis station
Internal secure door
Secure sample delivery through rear access door
Negative pressure cabin
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arkes.com
pressurisation system
Utilities supply
Sample containers
and data analysis station
GC-MSD system
The UNITY TD system in-situ within glove box
UNITY TD –
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arkes.com
UNITY TD –GC/MSD system
Installing an air sampled TD tube into UNITY
UNITY TD system
Glove box
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arkes.com
The analyst in protective suit/gloves installs a sampled TD tube into UNITY for TD-GCMS analysis
Air sampled TD tube being inserted into UNITY tube oven for analysis
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arkes.com
TD sampling techniques
1) Headspace-TD
2) On-Line
3) µ-CTE
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arkes.com
3) µ-CTE
4) SPE-tD
5) Direct desorption
Automated HS-TD Headspace-Thermal Desorption system
• Currently available for: Agilent G1888 (70
vials) or HP7694 (44 vials)
• Versatility: allows switching between:
• automated headspace-trap
• conventional TD (manual or automated)
• equilibrium HS.
• Vapours from pressurised HS vials pass into
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arkes.com
• Vapours from pressurised HS vials pass into
the UNITY 2 focusing trap in one or more
steps before trap desorption injects them
into the GC column
• Multi-step evacuation of the HS vial
optimises sensitivity and extends the
analyte volatility range. Complete extraction
is possible in some cases.
• Combined HS-TD system offers the ultimate
in sensitivity for volatiles in any sample
matrix: solid, liquid or gas.
Manual Headspace Analysis using HS5 -TD - 5975 GCMSD
• 5-sample, manual headspace
module attaches to UNITY 2
• Uses standard (~20 ml)
headspace vials
• Single or multiple sampling cycles
before trap desorption
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arkes.com
Headspace method:
� 0.5g tobacco sample
� Block temp 75 Deg C
� 30 minute equilibration
Analysis of Tobacco
HS-TD offers 10-100 x more sensitivity than equilibrium HS
200 ppb drinking water purgeables standard analysed by both equilibrium HS (black)
and HS-TD (pink)
Analysis by
HS-TD
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arkes.com
HS vapours may be transferred multiple times from the vial to the UNITY 2 cold trap prior to desorption/injection into the GC. This
enhances sensitivity compared with equilibrium headspace
Analysis by HS
HS-TD extends the volatility range relative to conventional equilibrium HS
HS-TD applications include
• Purgeables in water and soil
• Trace odorants in drinking
water
• Taint in foodstuffs, beverages,
packaging and consumer
products
RT HS HS-TD
36.31 0.29 0.97
37.66 0.19 1.06
38.05 1 1
38.58 0.22 0.88
HS-TD
HS
Relative peak areas
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arkes.com
Enhanced recovery of less volatile compounds with HS-TD
Multi-step HS extraction behaves like foam-free purging or dynamic-headspace, increasing the relative recovery of less volatile components. Exhaustive extraction of volatiles is possible in many cases
products
• Residual volatiles in polymers
and packaging
• Residual volatiles in
pharmaceuticals
• Tobacco profiling
… plus all the usual HS and TD
applications
HS
On-line introduction of sample vapours - the Direct Heated Inlet (DHI)
• Vapours from sealed vessels can be purged,
with carrier gas, directly into the focusing
trap
• Vapours can also be pumped from the
sample container through the focusing trap
Operating Modes: :
� Direct sampling with a pump
� Sealed vessel headspace
� Purge and trap
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arkes.com
• The sample inlet line is heated and inert
• The sampling cycle may be repeated before
trap desorption
• Converts equilibrium HS into pulsed
‘purge and trap’
UNITY- Direct Heated Inlet
• Advantages versus conventional static headspace include:
– enhancement / enrichment of low level target compounds
– selective elimination of volatile interferents (eg. water and ethanol)
– Unlimited choice of sample vessels – size and type
– wider volatility range - representative of entire vapour profile
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arkes.com
• Example applications for the Direct Heated Inlet include:
– food shelf-life studies,
– flavour and fragrance profiling,
– bio emissions testing - bugs, plants, microbes, moulds,
– categorising natural materials - e.g sourcing food extracts
Using UNITY & the Direct Inlet Accessory for Automatic Characterisation of Whisky Flavour
UNITY-DHI facilitates:
• Sampling compounds over a
wide volatility range
(including higher boiling
ketones & esters)
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arkes.com
• Selective elimination of
water and ethanol
• Real discrimination between
whiskies based on key
olfactory compounds
Analysis of Pyrazines in Potato crisps using the Micro Chamber Thermal Extractor µ-CTE
Target compounds identified
Trimethyl-pyrazine
2,5-dimethyl-pyrazine
2-ethyl-3-methyl-pyrazine
2-ethyl-5-methyl-pyrazine
2-ethyl-6-methyl-pyrazine
3-ethyl-2,5-dimethyl-pyrazine
2-methoxy-3-(1-methylethyl)-pyrazine
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arkes.com
2-methoxy-3-(1-methylethyl)-pyrazine
2,3-diethyl-5-methyl-pyrazine
2-Isobutyl-3-methyl-pyrazine
Analytical ConditionsOven:40 °C for 2 min then 20 °C/min to 240 °C for 2 minColumn: HP-INNOWax Polyethylene Glycol30 m x 250 µm x 0.25 µmConstant pressure, initial flow 1.5 mL/min
µ-CTE
25 min dynamic equilibration at 40 °C
10 min sampling onto a Tenax tube with a flow rate of 40 ml/min.
Direct Desorption - Simple Handling of Complex Samples
Solid samples - fibre, film, powder/granule,
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arkes.com
� Samples can be placed directly within a glass tube and retained by quartz wool
� Samples can be placed inside a retaining PTFE sleeve and inserted into metal tube
PTFE sample insert
Direct desorption of pet food pellets
Representative sample
ground up and inserted into
empty glass TD tube.
Desorption for 10mins at
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Desorption for 10mins at
80°C