MARKES U LTR A User Manual

Series 2

ULTRA

Thermal Desorption
Autosampler

Multi-function TD autosampler with optional
reading/writing of electronic tube tags

Series 2

ULTRA

1. Patent# GB 2395785 (Automated re-collection using a single TD autosampler), 2. Patent# US 6,446,515 B2, 3. Patent# GB 2337513 US 6,564656 B1

4. Patent# GB 2336649

Thermal desorption technology

Thermal desorption (TD) is a highly versatile, sensitive
and labour-saving sample preparation technique for the
measurement of volatile and semi-volatile organic
compounds (VOC and SVOC) in air and materials. It is
applicable to GC-compatible organics ranging in
volatility from acetylene to n-C40and a few inorganic
gases; including nitrous oxide, SF6, CS2and H2S. Key
applications include:

• Environmental and workplace air monitoring

• Civil defence and forensic analysis

• Materials and materials emissions testing

• Food, flavour and fragrance profiling

Many material samples such as drugs, foods, textiles,
polymers, paints, etc. can be directly thermally
desorbed by weighing them into empty TD sample
tubes.

Alternatively, vapours in gas or air can be concentrated
on- or off-line onto sorbent tubes/traps before TD­GC(MS) analysis.

ULTRA 2 Main Features

• Adds 100-tube automation to any UNITY or UNITY 2 TD platform to increase productivity.

• TubeTAG™: Reading/writing of RFID tags on sorbent tubes is now fully integrated with automated TD
operation. This revolutionizes tube and sample traceability.

• Stringent sample sealing, before and after desorption. Patented DiffLok™ caps preserve sample and blank­tube integrity and ensure compliance with standard methods.

• Quantitative sample re-collection (SecureTD-Q) is offered as standard on every series 2 U

LTRA-UNITY

system for repeat analysis of critical samples and/or method validation.

• Automation of SecureTD-Q av

ailable using single or double U

LTRA configurations; totally tag-compatible for

fail-safe tracking of which sample was re-collected onto which tube.

• State-of-the-art TD analytical performance. U

LTRA 2 simply adds automatic tube processing to the

peerless thermal desorption analytical performance of UNITY 2.

• U

LTRA-reliability – field-proven,

mechanically-simple automation ensures robust operation.

• Method compliance – incorporates the ambient temperature/no-flow leak test of UNITY 2 as a guarantee of
data integrity. Option of internal standard addition to blank or sampled tubes as a further aid to analytical
quality assurance.

• Optional dry-purging of sorbent tubes (in the sampling direction) as part of the automated sequence. This
minimizes water interference and is recommended by standard methods.

• Innovative, compact design – minimizes bench space.

Innovation and excellence in
thermal desorption

Since 1997 Markes International has re-engineered
analytical thermal desorption for the 21st century.
Harnessing unparalleled technical expertise, the
company has developed a suite of ‘universal’ TD
systems and unique sampling accessories incorporating
key proprietary innovations such as:

• SecureTD-Q™ for repeat analysis and automated
re-collection using a single TD autosampler

• RFID tube tagging (TubeTAG™)

• Diffusion-locking for effective tube sealing and
robust automation

• Innovative low volume valving specifically
designed for TD

Many of these innovations now set the standard for TD
instrumentation worldwide.

3

4

2

1

Series 2 ULTRA

ULTRA 2 is an innovative, robust and method-compliant
thermal desorption (TD) autosampler for up to a
hundred industry standard (3.5-inch) sample tubes,
featuring the option of integrated reading/writing of
RFID tube tags. It adds to any series 1 or series 2
UNITY TD platform to provide unmatched TD-GC(MS)
analytical performance and extended unattended
operation e.g. through an entire weekend.

Method-compliant automation

Series 2 ULTRA adds to any UNITY or UNITY 2 platform
desorber to offer unattended thermal desorption of up
to 100 capped tubes. The slimline design consists of
ten horizontal trays each containing up to ten tagged
or untagged tubes. Each tube in turn is loaded into
the analytical position and sealed into the carrier gas
flow path. The following analytical steps then all take
place on the U

LTRA 2 autosampler:

• Ambient temperature/no flow leak testing

• Optional dry purging and/or internal standard

addition

• Pre-purge of air from the tube

• Primary (tube) desorption

As vapours desorb from the primary sample tube in
U

LTRA 2 they are swept through the short, inert, heated

link line into the electrically­cooled focusing trap of UNITY
(2) in a stream of carrier gas.
All subsequent stages of
thermal desorption (trap purge,
trap desorption, triggering of
the GC(MS) run, etc.) take
place on UNITY (2) in the
normal way.

Uncompromised TD analytical
performance

Series 2 ULTRA automates UNITY 2 without
compromising its peerless analytical performance. The
combined system provides a universal TD platform for
up to 100 3.5-inch tubes offering simultaneous
analysis of volatiles & semi-volatiles, quantitative
recovery of high boilers (including n-C40) and the
option of low flow path temperatures for compatibility
with labile analytes such as mercaptans. Systems offer
splitless capillary operation for trace level work and
single or double split methods for high concentration
samples such as stack emissions and residual solvent
in materials.

Series 2 U

LTRA-UNITY systems maintain all the

analytical advantages of UNITY 2 (as described in the
associated brochure) and offer the following additional
benefits relating to the automatic processing of TD
sample tubes.

Clean indoor air pumped onto multi-sorbent tube and analysed by TD-GCMS

1,1-difluoroethane

Ethanol

Isopentane

1,1-difluoro-1-chloroethane

Dichlorodifluoromethane

1,1,1,2-tetrafluoroethane

Hexane

Acetone

Freon 113

Propanol

Trichlorofluoromethane

Dichloromethane

Methylcyclohexane

Benzene

Tetrachloromethane

Ethyl acetate

Hexanal

Toluene

Ethyl benzene

Ethylcyclohexane

o/p xylene

Tetrachloroethane

α-pinene

Trimethylbenzene

Decane

Styrene

Limonene

Undecane

Benzyl alcohol

Nonanal

Dodecane

Tridecane

Tetradecane

DiffLok™ caps seal tubes

No analyte losses from Tenax tubes capped with DiffLok

caps and analysed on U

LTRA over a 24 hr period

Toluene

Benzene

Time loaded tube spent on ULTRA prior to desorption (mins)

Peak area counts (x10

6

)

Xylene

effectively & simplify TD

automation

100-Tube automation optimizes
productivity

ULTRA 2 maximises the throughput and revenue
generation potential of your TD-GC(MS) system. It
offers capacity for up to 100 sample tubes together
with overlap mode. Sample overlap means that
desorption of a subsequent tube can begin while
GC(MS) analysis of a previous sample continues – thus
minimizing analytical cycle times.

With typical GC(MS) cycle times of 40 minutes, your
series 2 U
unattended processing of 100 tubes over a standard
60-hour weekend; this represents significant revenue
potential with minimal labour costs.

LTRA-UNITY TD-GC(MS) system offers

Patented tube sealing
mechanism

Tubes on series 2 ULTRA autosamplers are sealed with
Markes’ unique patented DiffLok caps. DiffLok caps
simply push on to both ends of every tube and
preserve sample integrity by preventing both analyte
loss and artifact ingress. Even volatile analytes are
confidently preserved on sorbent tubes giving identical
recovery for standards at the beginning and end of a
100-tube sequence. DiffLok caps have been field
proven to seal sampled and blank tubes much more
effectively than older push on cap designs (Ref 1).

Ref 1: Diffusive Monitor Issue 9 (Nov 1997), Losses
from ATD-400 by P. P. Ballesta

Schematic of DiffLok cap

Sample tube

pushes into cap

Inert or stainless steel outer body

(shown transparent)

here

Highly efficient tube sealing

Coned end for

Auto-alignment with

tube nozzle on ULTRA 2

(the TD autosampler)

O-ring for sealing

Threaded diffusion-locking insert

plain, cylindrical body

tube into cap

in

ULTRA-reliable automation

TD automation with electronic
tube tracking

DiffLok caps remain on the sample tubes throughout
automated analysis, thus simplifying the mechanical
function of the instrument (no uncapping and
recapping is required) and ensuring reliable operation.

LTRA’s unsurpassed mechanical reliability has been

U
extensively field proven.

DiffLok caps are available in either stainless steel or
inert coated steel for compatibility with reactive
components.

Method compliance

Series 2 ULTRA-UNITY systems are fully compliant with
all TD standard methods and feature the mandated
ambient temperature/no-flow leak test of UNITY (2)
integrated seamlessly with the TD-GC(MS) sequence.
Data processing remains synchronized with the
analytical process at all times. Any tubes which fail the
leak test are returned intact to the sample tray
awaiting operator intervention. After a tube leak test
failure ULTRA 2 records this in the sequence reporter
and proceeds to load and leak test the next sample in
the sequence.

TubeTAG reading/writing for
enhanced tube traceability

Series 2 ULTRA autosamplers herald a revolution in
automated thermal desorption. Every ULTRA 2 offers
the option to read information from RFID tags attached
to sorbent tubes and to automatically input this
information into the sequence table. At the end of
each analysis, ULTRA 2 can also write to the tube tag
e.g. to increment the number of thermal cycles, input
any high back-pressure anomolies, change the tube
status and clear sample-specific data from the tag
ready for the next field monitoring operation.

The combination of U
major step forward in analytical quality control
for air monitoring and all TD applications.

LTRA 2 and TubeTAG offers a

TubeTAG technology allows error-free tracking of
samples from field to laboratory & within a laboratory
(transit tagging) and logging of key tube-specific data
such as type & date of sorbent packing.

In combination with a series 2 U

LTRA-UNITY system

TubeTAG further enables:

• Automatic logging of the history of a tube
throughout its life: Number of thermal cycles,
back-pressure anomolies, number of leak test
failures, etc.

• Automatic input of sample-specific information to
the U

LTRA TD automation sequence table: Tube

number, sampled volume, diffusive sampling
time, date of sampling, etc.

U

LTRA 2 complete with the TubeTAG read/write option is

a genuine breakthrough in automated TD technology.
Imagine a future in which you can instantly identify the
sorbent(s) in each tube, when it needs to be repacked
and whether or not that tube has had a history of leak­test failures or back-pressure issues. Imagine the
benefit of error-free automatic input of key sample
data into the automation sequence. This is what U

LTRA

2 offers today.

(1) Tag permanently attached to tube

& programmed with tube-related
information usingTAG

SCRIBE

(2) Tagged tube sent to field. Sample

start & end information written
to tag via TAG

SCRIBE

(3) (a) Tagged tube returned to lab & information

automatically uploaded into U

LTRA 2 sequence table

(b) Tag updated by ULTRA 2 post-analysis

(4) Tagged tube

ready for re-use

TubeTAG: Mode of operation

Plot showing the theoretical and measured peak areas

for repeated sample re-collection and re-desorption

Re-collections

Peak Area

DMP

DBP

Sequence of chromtagrams showing re-analysis of

re-collected phthalate mixture with internal standard

DBP

DEHP

Hexadecane

DEP

DMP

SecureTD-Q: Quantitative sample
re-collection

Every series 2 ULTRA-UNITY system features manual
re-collection of the total split flow (i.e. the split during
both tube and trap desorption) as standard. This allows
repeat analysis of critical samples and simplifies
method validation as per standard methods such as
ASTM D6196.

Automated re-collection

ULTRA 2 also offers automated sample re-collection
options using either a single ULTRA autosampler (see
ULTRA 50:50 system) or double ULTRA configuration
(see AutoSecure TD system).

Series 2 U

LTRA 50:50 systems offer automated and

quantitative re-collection of the trap desorption split
flow for 50 or 100 tubes.

Series 2 AutoSecure TD systems, incorporating two
U

LTRA 2 autosamplers, offer quantitative re-collection of

the total split flow (i.e. the split flow during both tube
and trap desorption) for all 100 tubes.

Automated re-collection now enhanced
with TubeTAG

Use of series 2 ULTRA TubeTAG read/write capability
during automated desorption/re-collection, greatly
enhances the automation and traceability of
SecureTD-Q. Automated desorption/re-collection
systems incorporating TubeTAG log the unique ID
numbers of original sample tubes and of the
corresponding re-collection tubes, both on the
respective individual tube tags and in the automation
sequence. Subsequent interrogation of an individual
tube tag can be used to confirm if that tube is either:

• A sample tube, which has now been desorbed,
with the sample re-collected on tube ID# Mi
0XXXXX, or

• A tube that now contains the re-collected sample
originally desorbed from tube ID# Mi 0YYYYY

Flexible upgrade options

Parallel connection of automated canister analysis/on-line air monitoring also faciliated (see Air Server brochure)

Series 2 UNITY

Series 2

U

LTR

A-UNITY

Series 2

U

LTRA 50:50

system

Series 2

AutoSecure TD

system

ULTRA 2 options and accessories

The following options and accessories are available for
ULTRA 2:

Integrated TubeTAG read/write
capability

TubeTAG read/write capability is available for any series
2 ULTRA (see above) and can be factory configured or
field installed. It is compatible with all other ULTRA 2
options and accessories.

50:50 Option

LTRA 2 can be factory configured with a “

The U
option for automated sample re-collection using a
single TD autosampler. The resulting series 2 U
50:50 package is a patented, cost effective, space
saving solution for automatic thermal desorption and
re-collection of up to 100 tubes.

A standard series 2 U

LTRA-UNITY offers manual

re-collection of individual samples (see above).
Addition of a 50:50 option to the ULTRA 2 complements
this facility by offering automatic re-collection of trap

50:50”

LTRA

desorption (outlet) split flow. This means that the
outlet split flow from up to 50 samples can be re­collected onto 50 fresh (conditioned) sorbent tubes.
Alternatively, the outlet split flow from up to 100
samples can be re-collected back onto the original
sorbent tubes.

The 50:50 option also facilitates automatic dry
purging of sorbent tubes in the sampling direction
prior to thermal desorption, as recommended in
standard methods such as US EPA TO-17. All other
features are the same as on standard series 2 U

LTRA-

UNITY systems.

For high throughput laboratories with a focus on data
quality, series 2 U

LTRA 50:50 offers cost-effective

automatic re-collection for any single (outlet) split
method. Sample and re-collection tubes are arranged
in colour-coded trays for operator convenience and a
clear user interface displays sequence status and the
post run sequence report.

Error-free operation of series 2 U

LTRA

50:50 is
further enhanced by using the TubeTAG read/write
option to link the identity of each desorbed tube to
that used for sample re-collection (see above)

Automating re-collection

Schematic depicting a series 2 ULTRA (ISDP) - UNITY

system

ULTRA 2

Loop

UNITY 2

1

2

3

Sample

tube

Cold trap

Bypass line

Optional split

GC(MS)

1. Fill loop with
internal standard

2. Purge loop onto
sample tube

3. Desorb sample

for repeat analysis

Manual or automated flow control

Series 2 ULTRA systems usually harness the manual or
electronic mass flow control (MFC) incorporated into
the attached series 2 UNITY TD for control of both
desorption and split gas flows (see UNITY 2 brochure
for further details). For added versatility series 2

A

50:50 units also offer the option of 1 or 2

LTR

U
integrated electronic mass flow controllers for special
applications. These provide versatile electronic control
of both split and desorption flows during an automated
sequence with multiple TD methods.

Series 1 UNITY desorbers can also be upgraded with a
series 2 U
integrated MFCs. Configuring a series 1 UNITY with a
series 2 ULTRA 50:50 incorporating MFCs, brings both
tube automation and enhanced electronic mass flow
control of split and/or desorption flows to the original
UNITY TD platform.

LTRA 50:50 configured with one or two

Internal Standard/Dry Purge (ISDP)
option

An ULTRA 2 factory configured with an ISDP option,
incorporates all the features of the ULTRA 2
autosampler but with the added benefit of an inbuilt
internal standard (IS) addition and automatic tube dry
purging capability. When using an ULTRA 2/ISDP
system, a precise aliquot of gaseous internal standard
is transferred from a gas valve loop to the sampling
end of a sorbent tube immediately after the leak test
and before tube desorption. Addition of IS aids
analytical quality assurance and is recommended in
standard TD methods. Typical compounds used as
internal standards include toluene-d8 and
bromofluorobenzene (BFB).

Gas-phase IS can be added either to sampled or
blank tubes. When standard is added to the sampling
end of blank tubes, they are not desorbed but replaced
in the U
this case the internal standard provides a quality check
on every aspect of the monitoring process – tube
storage, transport, sampling, and analysis.

Dry purging of tubes, before analytical desorption, is
also facilitated using ISDP. Tube dry purging is carried
out in the sampling direction, with or without internal
standard addition.

Note that Markes International also offers a range of stand

alone off-line accessories for dry purging sorbent tubes and

introducing gas or liquid phase standards.

LTRA 2 tube tray ready for field monitoring. In

ULTRA 2 with 50:50 and ISDP

Series 2 ULTRAs may be factory configured with internal
standard addition, 50:50 automated re-collection plus
dry purge capability, all on the same system.

This comprehensive U

LTRA 2 configuration is further

enhanced by the addition of TubeTAG read/write
capability for automatic logging and tracking of sample
tubes, re-collection tubes and the history of each tube.

AutoSecure TD System: The
ultimate in TD automation

Series 2 ULTRA-UNITY systems, with or without ISDP,
can be further upgraded by the addition of a second
ULTRA 2 for automated and quantitative re-collection
of total split flow, i.e. the split flow during primary
(tube) desorption (inlet split flow) as well as split flow
during secondary (trap) desorption (outlet split flow),
for all 100 tubes.

The slimline design of U

LTRA 2 lends itself to this

configuration and the total series 2 ULTRA-UNITY-ULTRA
system (AutoSecure TD) only occupies 75 cm (30­inches) of benchspace. Tubes are sealed with DiffLok
caps, both on the desorption and re-collection ULTRA, to
preserve the integrity of sampled tubes, desorbed
tubes and re-collection tubes.

The user interface is very straightforward, simplifying
the sequencing process and may be further enhanced
by the addition of TubeTAG read/write capability on
both U

LTRAs to automatically log sample tubes and link

them with their associated re-collection tubes.

Trays on both autosamplers are interchangeable, so
re-collected tubes can be analysed by simply
transferring trays from one series 2 U

LTRA to the other.

ISDP reproducibility data: 24 repeats over a 24 hr period

Standard deviation: 0.13, %RSD: 1%

Unrestricted upgrade path:
Plug-and-play TD

All series 2 ULTRA configurations may be readily
connected and disconnected to any series 1 or 2 UNITY
TD platform. ULTRA 2 can also be connected to UNITY
(2) in parallel with Air Server technology for automated
on-line air monitoring/canister analysis (see associated
brochure). In addition to this, series 2 AutoSecure TD
systems offer a unique and cost-effective route to
increasing productivity: With the addition of a second
UNITY 2, an AutoSecure TD system can be readily
transformed into two standard series 2 U

LTRA-UNITY

systems. This can be used, for example, to increase
sample throughput when demand for TD-GC(MS)
analysis is especially high.

Intuitive control software

Series 2 ULTRA control software is intuitive and
integrated with the UNITY (2) TD control software to
provide one comprehensive and easy-to-understand
user interface.

Sequence building

Automated sequences are easily constructed via the
sequence builder. Samples may be assigned individual
desorption methods and can be analysed either
sequentially or with random access. Each tube is
classified as sample, calibrant or blank and all
sequences may be stored and recalled for future
reference or repeat use.

Series 2 U

LTRA systems incorporating TubeTAG

read/write capability can be used to pre-screen tubes
loaded into the system and automatically upload any
relevant sample information (tube ID number, pumped
volume/diffusive exposure time, date of sampling, etc.)
into the automation sequence. This provides a
convenient means of cross-checking sample and tube
information before an analytical sequence is initiated.

Series 2 AutoSecure TD

sequence viewer

Graphical sequence viewer

Optional automatic update of tube tags

The sequence viewer presents a clear graphical display
of the position, classification and operating status of
each tube. It can also serve as a template for the
operator when loading tubes.

Sequence reporting

Events associated with every analysis, such as the time
and date of each tube desorption, and deviations such
as “tube not found” or leak test failure, are all recorded
in the sequence reporter. Any tube sequence failure
triggers the GC(MS) system to start a blank run to
keep the analyser in step with the desorber.

Series 2 U
read/write capability automatically read the information
stored on the relevant tag as each tube is loaded ready
for desorption. The sequence reporter is then
automatically populated with the relevant information
for that sample tube.

LTRA systems incorporating optional TubeTAG

Tag read/write-configured series 2 ULTRA autosamplers
can also be used to automatically add or modify
relevant information on each individual tube RFID tag
post run. Options for this are fully user-selectable and
include:

• Incrementing the number of thermal cycles

• Changing the tube status from sampled to
analysed

• Inputting the ID of the tube used for re-collection
of that sample

• Clearing the sample-related information from that
tag

• Logging if that tube exhibited any back-pressure
anomolies or failed the leak test

This capability represents a revolution in quality control
and tracking of sorbent tube performance and history.

Markes International: Everything for thermal
desorption

UNITY 2 is complemented by the comprehensive portfolio of thermal desorption
instrumentation and associated sampling equipment provided by Markes International.
Many of the innovative and labour-saving accessories available are unique to Markes
including specialist low flow sample tubes, multi-sample test equipment for materials
emissions screening, calibration accessories, breath samplers, soil probes, etc.

Markes International...

Calibration accessory for

TD tubes

Bio-VOC sampler for

collecting alveolar breath

samples & transferring
them to sorbent tubes

TC-20 multi-tube

conditioning/dry purge unit

for up to 20 tubes

Micro-Chamber/Thermal

Extractor (µ-CTE) for measuring

emissions from materials &

consumer products

MTS-32 sequential pumped

sampling onto multiple

tubes

Canisters and related

accessories

Wide range of empty and

prepacked TD sample tubes

TubeTAG RFID tag system

for sorbent tube informatics

VOC-Mole soil probes for

in situ monitoring of

contaminated land

Summary

Trademarks

SecureTD-Q™, TubeTAG™ and DiffLok™ are all
trademarks of Markes International Ltd.

100-

tube

Choice

of tube

sizes

Effective

tube

seal

Sample

re-collection

Optional electronic

control of

split/desorb flows

Optional

automatic

reading/

writing of

RFID tags

Internal

Standard

Dry

purge

ULTRA 2 Manual of

Series 2
ULTRA 50:50

Series 2 ULTRA
with ISDP

Series 2
ULTRA 50:50
with IS

Series 2
AutoSecure TD

AutoSecure TD
with ISDP on
desorb ULTRA

both splits

As above

automatic

(outlet split

Manual of

both splits

As above

automatic

(outlet split

Automatic

(all split

Automatic

(all split

plus

only)

plus

only)

flows)

flows)

via UNITY 2

via UNITY 2

and/or

integrated MFC

options

via UNITY 2

via UNITY 2

and/or

integrated MFC

options

via UNITY 2

via UNITY 2

...experts in thermal desorption

Markes International Ltd.

Gwaun Elai Medi Science Campus

Llantrisant

RCT

CF72 8XL

United Kingdom

T: [phone] F: [phone]

E: [e-mail] W: www.markes.com