Series 2ULTRAThermal DesorptionAutosampler

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

Series 2ULTRA

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 B14. Patent# GB 2336649

Thermal desorption technologyThermal desorption (TD) is a highly versatile, sensitiveand labour-saving sample preparation technique for themeasurement of volatile and semi-volatile organiccompounds (VOC and SVOC) in air and materials. It isapplicable to GC-compatible organics ranging involatility from acetylene to n-C40 and a few inorganicgases; including nitrous oxide, SF6, CS2 and H2S. Keyapplications 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 thermallydesorbed by weighing them into empty TD sampletubes.

Alternatively, vapours in gas or air can be concentratedon- or off-line onto sorbent tubes/traps before TD-GC(MS) analysis.

Innovation and excellence inthermal desorptionSince 1997 Markes International has re-engineeredanalytical thermal desorption for the 21st century.Harnessing unparalleled technical expertise, thecompany has developed a suite of ‘universal’ TDsystems and unique sampling accessories incorporatingkey proprietary innovations such as:

• SecureTD-Q™ for repeat analysis and automatedre-collection using a single TD autosampler1

• RFID tube tagging (TubeTAG™)2

• Diffusion-locking for effective tube sealing androbust automation3

• Innovative low volume valving specificallydesigned for TD4

Many of these innovations now set the standard for TDinstrumentation worldwide.

Series 2 ULTRAULTRA 2 is an innovative, robust and method-compliantthermal desorption (TD) autosampler for up to ahundred industry standard (3.5-inch) sample tubes,featuring the option of integrated reading/writing ofRFID tube tags. It adds to any series 1 or series 2UNITY TD platform to provide unmatched TD-GC(MS)analytical performance and extended unattendedoperation e.g. through an entire weekend.

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 TDoperation. This revolutionizes tube and sample traceability.

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

• Quantitative sample re-collection (SecureTD-Q) is offered as standard on every series 2 ULTRA-UNITYsystem for repeat analysis of critical samples and/or method validation.

• Automation of SecureTD-Q available using single or double ULTRA configurations; totally tag-compatible forfail-safe tracking of which sample was re-collected onto which tube.

• State-of-the-art TD analytical performance. ULTRA 2 simply adds automatic tube processing to thepeerless thermal desorption analytical performance of UNITY 2.

• ULTRA-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 ofdata integrity. Option of internal standard addition to blank or sampled tubes as a further aid to analyticalquality assurance.

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

• Innovative, compact design – minimizes bench space.

Method-compliant automationSeries 2 ULTRA adds to any UNITY or UNITY 2 platformdesorber to offer unattended thermal desorption of upto 100 capped tubes. The slimline design consists often horizontal trays each containing up to ten taggedor untagged tubes. Each tube in turn is loaded intothe analytical position and sealed into the carrier gasflow path. The following analytical steps then all takeplace on the ULTRA 2 autosampler:

• Ambient temperature/no flow leak testing

• Optional dry purging and/or internal standardaddition

• Pre-purge of air from the tube

• Primary (tube) desorption

As vapours desorb from the primary sample tube inULTRA 2 they are swept through the short, inert, heatedlink line into the electrically-cooled focusing trap of UNITY(2) in a stream of carrier gas.All subsequent stages ofthermal desorption (trap purge,trap desorption, triggering ofthe GC(MS) run, etc.) takeplace on UNITY (2) in thenormal way.

Uncompromised TD analyticalperformanceSeries 2 ULTRA automates UNITY 2 withoutcompromising its peerless analytical performance. Thecombined system provides a universal TD platform forup to 100 3.5-inch tubes offering simultaneousanalysis of volatiles & semi-volatiles, quantitativerecovery of high boilers (including n-C40) and theoption of low flow path temperatures for compatibilitywith labile analytes such as mercaptans. Systems offersplitless capillary operation for trace level work andsingle or double split methods for high concentrationsamples such as stack emissions and residual solventin materials.

Series 2 ULTRA-UNITY systems maintain all theanalytical advantages of UNITY 2 (as described in theassociated brochure) and offer the following additionalbenefits relating to the automatic processing of TDsample tubes.

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

1,1-

difluo

roeth

ane

Etha

nol

Isope

ntan

e1,

1-dif

luoro

-1-ch

loroe

than

eDi

chlor

odiflu

orom

ethan

e1,

1,1,

2-tet

raflu

oroe

than

e

Hexa

ne

Aceto

neFr

eon

113

Prop

anol

Trich

lorofl

uoro

meth

ane

Dich

lorom

ethan

e

Meth

ylcyc

lohex

ane

Benz

ene

Tetra

chlor

ometh

ane

Ethy

l ace

tate

Hexa

nal

Tolue

ne

Ethy

l ben

zene

Ethy

lcyclo

hexa

ne

o/p

xylen

e

Tetra

chlor

oeth

ane

α-pin

ene

Trime

thylb

enze

neDe

cane

Styr

ene

Limon

ene Un

deca

neBe

nzyl

alcoh

olNo

nana

lDo

deca

neTri

deca

neTe

trade

cane

100-Tube automation optimizesproductivityULTRA 2 maximises the throughput and revenuegeneration potential of your TD-GC(MS) system. Itoffers capacity for up to 100 sample tubes togetherwith overlap mode. Sample overlap means thatdesorption of a subsequent tube can begin whileGC(MS) analysis of a previous sample continues – thusminimizing analytical cycle times.

With typical GC(MS) cycle times of 40 minutes, yourseries 2 ULTRA-UNITY TD-GC(MS) system offersunattended processing of 100 tubes over a standard60-hour weekend; this represents significant revenuepotential with minimal labour costs.

Patented tube sealingmechanismTubes on series 2 ULTRA autosamplers are sealed withMarkes’ unique patented DiffLok caps. DiffLok capssimply push on to both ends of every tube andpreserve sample integrity by preventing both analyteloss and artifact ingress. Even volatile analytes areconfidently preserved on sorbent tubes giving identicalrecovery for standards at the beginning and end of a100-tube sequence. DiffLok caps have been fieldproven to seal sampled and blank tubes much moreeffectively than older push on cap designs (Ref 1).

DiffLok™ caps seal tubeseffectively & simplify TD

automation

Inert or stainless steel outer body(shown transparent)

Coned end forAuto-alignment with

tube nozzle on ULTRA 2(the TD autosampler)

Sample tubepushes into cap

here

O-ring for sealingtube into cap

Threaded diffusion-locking insert inplain, cylindrical body

Schematic of DiffLok cap

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

Highly efficient tube sealing

No analyte losses from Tenax tubes capped with DiffLokcaps and analysed on ULTRA over a 24 hr period

Toluene

Benzene

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

Peak

area

coun

ts (x

106 )

Xylene

ULTRA-reliable automationDiffLok caps remain on the sample tubes throughoutautomated analysis, thus simplifying the mechanicalfunction of the instrument (no uncapping andrecapping is required) and ensuring reliable operation.ULTRA’s unsurpassed mechanical reliability has beenextensively field proven.

DiffLok caps are available in either stainless steel orinert coated steel for compatibility with reactivecomponents.

Method compliance Series 2 ULTRA-UNITY systems are fully compliant withall TD standard methods and feature the mandatedambient temperature/no-flow leak test of UNITY (2)integrated seamlessly with the TD-GC(MS) sequence.Data processing remains synchronized with theanalytical process at all times. Any tubes which fail theleak test are returned intact to the sample trayawaiting operator intervention. After a tube leak testfailure ULTRA 2 records this in the sequence reporterand proceeds to load and leak test the next sample inthe sequence.

TubeTAG reading/writing forenhanced tube traceabilitySeries 2 ULTRA autosamplers herald a revolution inautomated thermal desorption. Every ULTRA 2 offersthe option to read information from RFID tags attachedto sorbent tubes and to automatically input thisinformation into the sequence table. At the end ofeach analysis, ULTRA 2 can also write to the tube tage.g. to increment the number of thermal cycles, inputany high back-pressure anomolies, change the tubestatus and clear sample-specific data from the tagready for the next field monitoring operation.

The combination of ULTRA 2 and TubeTAG offers amajor step forward in analytical quality controlfor air monitoring and all TD applications.

TD automation with electronictube tracking

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

In combination with a series 2 ULTRA-UNITY systemTubeTAG further enables:

• Automatic logging of the history of a tubethroughout its life: Number of thermal cycles,back-pressure anomolies, number of leak testfailures, etc.

• Automatic input of sample-specific information tothe ULTRA TD automation sequence table: Tubenumber, sampled volume, diffusive samplingtime, date of sampling, etc.

ULTRA 2 complete with the TubeTAG read/write option isa genuine breakthrough in automated TD technology.Imagine a future in which you can instantly identify thesorbent(s) in each tube, when it needs to be repackedand whether or not that tube has had a history of leak-test failures or back-pressure issues. Imagine thebenefit of error-free automatic input of key sampledata into the automation sequence. This is what ULTRA2 offers today.

(1) Tag permanently attached to tube& programmed with tube-relatedinformation usingTAGSCRIBE

(2) Tagged tube sent to field. Samplestart & end information writtento tag via TAGSCRIBE

(3) (a) Tagged tube returned to lab & information automatically uploaded into ULTRA 2 sequence table

(b) Tag updated by ULTRA 2 post-analysis

(4) Tagged tubeready for re-use

TubeTAG: Mode of operation

Plot showing the theoretical and measured peak areasfor repeated sample re-collection and re-desorption

Re-collections

Peak

Are

a

DMP DBP

Sequence of chromtagrams showing re-analysis ofre-collected phthalate mixture with internal standard

DBP DEHP

Hexadecane

DEP

DMP

SecureTD-Q: Quantitative samplere-collection Every series 2 ULTRA-UNITY system features manualre-collection of the total split flow (i.e. the split duringboth tube and trap desorption) as standard. This allowsrepeat analysis of critical samples and simplifiesmethod validation as per standard methods such asASTM D6196.

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

Series 2 ULTRA 50:50 systems offer automated andquantitative re-collection of the trap desorption splitflow for 50 or 100 tubes.

Series 2 AutoSecure TD systems, incorporating twoULTRA 2 autosamplers, offer quantitative re-collection ofthe total split flow (i.e. the split flow during both tubeand trap desorption) for all 100 tubes.

Automated re-collection now enhancedwith TubeTAGUse of series 2 ULTRA TubeTAG read/write capabilityduring automated desorption/re-collection, greatlyenhances the automation and traceability ofSecureTD-Q. Automated desorption/re-collectionsystems incorporating TubeTAG log the unique IDnumbers of original sample tubes and of thecorresponding re-collection tubes, both on therespective individual tube tags and in the automationsequence. Subsequent interrogation of an individualtube 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# Mi0XXXXX, or

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

Flexible upgrade options

ULTRA 2 options and accessoriesThe following options and accessories are available forULTRA 2:

Integrated TubeTAG read/writecapabilityTubeTAG read/write capability is available for any series2 ULTRA (see above) and can be factory configured orfield installed. It is compatible with all other ULTRA 2options and accessories.

50:50 OptionThe ULTRA 2 can be factory configured with a “50:50”option for automated sample re-collection using asingle TD autosampler. The resulting series 2 ULTRA50:50 package is a patented, cost effective, spacesaving solution for automatic thermal desorption andre-collection of up to 100 tubes.

A standard series 2 ULTRA-UNITY offers manualre-collection of individual samples (see above).Addition of a 50:50 option to the ULTRA 2 complementsthis facility by offering automatic re-collection of trap

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

The 50:50 option also facilitates automatic drypurging of sorbent tubes in the sampling directionprior to thermal desorption, as recommended instandard methods such as US EPA TO-17. All otherfeatures are the same as on standard series 2 ULTRA-UNITY systems.

For high throughput laboratories with a focus on dataquality, series 2 ULTRA 50:50 offers cost-effectiveautomatic re-collection for any single (outlet) splitmethod. Sample and re-collection tubes are arrangedin colour-coded trays for operator convenience and aclear user interface displays sequence status and thepost run sequence report.

Error-free operation of series 2 ULTRA 50:50 isfurther enhanced by using the TubeTAG read/writeoption to link the identity of each desorbed tube tothat used for sample re-collection (see above)

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

Series 2 UNITYSeries 2

ULTRA-UNITYSeries 2

ULTRA 50:50system

Series 2AutoSecure TD

system

Automating re-collectionfor repeat analysis

Manual or automated flow controlSeries 2 ULTRA systems usually harness the manual orelectronic mass flow control (MFC) incorporated intothe attached series 2 UNITY TD for control of bothdesorption and split gas flows (see UNITY 2 brochurefor further details). For added versatility series 2ULTRA 50:50 units also offer the option of 1 or 2integrated electronic mass flow controllers for specialapplications. These provide versatile electronic controlof both split and desorption flows during an automatedsequence with multiple TD methods.

Series 1 UNITY desorbers can also be upgraded with aseries 2 ULTRA 50:50 configured with one or twointegrated MFCs. Configuring a series 1 UNITY with aseries 2 ULTRA 50:50 incorporating MFCs, brings bothtube automation and enhanced electronic mass flowcontrol of split and/or desorption flows to the originalUNITY TD platform.

Internal Standard/Dry Purge (ISDP)optionAn ULTRA 2 factory configured with an ISDP option,incorporates all the features of the ULTRA 2autosampler but with the added benefit of an inbuiltinternal standard (IS) addition and automatic tube drypurging capability. When using an ULTRA 2/ISDPsystem, a precise aliquot of gaseous internal standardis transferred from a gas valve loop to the samplingend of a sorbent tube immediately after the leak testand before tube desorption. Addition of IS aidsanalytical quality assurance and is recommended instandard TD methods. Typical compounds used asinternal standards include toluene-d8 andbromofluorobenzene (BFB).

Gas-phase IS can be added either to sampled orblank tubes. When standard is added to the samplingend of blank tubes, they are not desorbed but replacedin the ULTRA 2 tube tray ready for field monitoring. Inthis case the internal standard provides a quality checkon every aspect of the monitoring process – tubestorage, transport, sampling, and analysis.

Dry purging of tubes, before analytical desorption, isalso facilitated using ISDP. Tube dry purging is carriedout in the sampling direction, with or without internalstandard addition.

Note that Markes International also offers a range of standalone off-line accessories for dry purging sorbent tubes andintroducing gas or liquid phase standards.

Schematic depicting a series 2 ULTRA (ISDP) - UNITYsystem

ULTRA 2

Loop

UNITY 2

1

2

3

Sampletube

Cold trap

Bypass line

Optional split

GC(MS)

1. Fill loop withinternal standard

2. Purge loop ontosample tube

3. Desorb sample

ULTRA 2 with 50:50 and ISDPSeries 2 ULTRAs may be factory configured with internalstandard addition, 50:50 automated re-collection plusdry purge capability, all on the same system.

This comprehensive ULTRA 2 configuration is furtherenhanced by the addition of TubeTAG read/writecapability for automatic logging and tracking of sampletubes, re-collection tubes and the history of each tube.

AutoSecure TD System: Theultimate in TD automationSeries 2 ULTRA-UNITY systems, with or without ISDP,can be further upgraded by the addition of a secondULTRA 2 for automated and quantitative re-collectionof total split flow, i.e. the split flow during primary(tube) desorption (inlet split flow) as well as split flowduring secondary (trap) desorption (outlet split flow),for all 100 tubes.

The slimline design of ULTRA 2 lends itself to thisconfiguration and the total series 2 ULTRA-UNITY-ULTRAsystem (AutoSecure TD) only occupies 75 cm (30-inches) of benchspace. Tubes are sealed with DiffLokcaps, both on the desorption and re-collection ULTRA, topreserve the integrity of sampled tubes, desorbedtubes and re-collection tubes.

The user interface is very straightforward, simplifyingthe sequencing process and may be further enhancedby the addition of TubeTAG read/write capability onboth ULTRAs to automatically log sample tubes and linkthem with their associated re-collection tubes.

Trays on both autosamplers are interchangeable, sore-collected tubes can be analysed by simplytransferring trays from one series 2 ULTRA 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 TDAll series 2 ULTRA configurations may be readilyconnected and disconnected to any series 1 or 2 UNITYTD platform. ULTRA 2 can also be connected to UNITY(2) in parallel with Air Server technology for automatedon-line air monitoring/canister analysis (see associatedbrochure). In addition to this, series 2 AutoSecure TDsystems offer a unique and cost-effective route toincreasing productivity: With the addition of a secondUNITY 2, an AutoSecure TD system can be readilytransformed into two standard series 2 ULTRA-UNITYsystems. This can be used, for example, to increasesample throughput when demand for TD-GC(MS)analysis is especially high.

Intuitive control softwareSeries 2 ULTRA control software is intuitive andintegrated with the UNITY (2) TD control software toprovide one comprehensive and easy-to-understanduser interface.

Sequence buildingAutomated sequences are easily constructed via thesequence builder. Samples may be assigned individualdesorption methods and can be analysed eithersequentially or with random access. Each tube isclassified as sample, calibrant or blank and allsequences may be stored and recalled for futurereference or repeat use.

Series 2 ULTRA systems incorporating TubeTAGread/write capability can be used to pre-screen tubesloaded into the system and automatically upload anyrelevant sample information (tube ID number, pumpedvolume/diffusive exposure time, date of sampling, etc.)into the automation sequence. This provides aconvenient means of cross-checking sample and tubeinformation before an analytical sequence is initiated.

Series 2 AutoSecure TDsequence viewer

Graphical sequence viewerThe sequence viewer presents a clear graphical displayof the position, classification and operating status ofeach tube. It can also serve as a template for theoperator when loading tubes.

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

Series 2 ULTRA systems incorporating optional TubeTAGread/write capability automatically read the informationstored on the relevant tag as each tube is loaded readyfor desorption. The sequence reporter is thenautomatically populated with the relevant informationfor that sample tube.

Optional automatic update of tube tagsTag read/write-configured series 2 ULTRA autosamplerscan also be used to automatically add or modifyrelevant information on each individual tube RFID tagpost run. Options for this are fully user-selectable andinclude:

• Incrementing the number of thermal cycles

• Changing the tube status from sampled toanalysed

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

• Clearing the sample-related information from thattag

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

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

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

Markes International...

Calibration accessory forTD tubes

Bio-VOC sampler forcollecting alveolar breathsamples & transferringthem to sorbent tubes

TC-20 multi-tubeconditioning/dry purge unit

for up to 20 tubes

Micro-Chamber/ThermalExtractor (µ-CTE) for measuring

emissions from materials &consumer products

MTS-32 sequential pumpedsampling onto multiple

tubes

Canisters and relatedaccessories

Wide range of empty andprepacked TD sample tubes

TubeTAG RFID tag systemfor sorbent tube informatics

VOC-Mole soil probes forin situ monitoring ofcontaminated land

...experts in thermal desorption

100-tube

Choiceof tubesizes

Effectivetubeseal

Samplere-collection

Optional electroniccontrol of

split/desorb flows

Optionalautomaticreading/writing ofRFID tags

InternalStandard

Drypurge

ULTRA 2 Manual ofboth splits

via UNITY 2

Series 2ULTRA 50:50

As aboveplus

automatic(outlet split

only)

via UNITY 2and/or

integrated MFCoptions

Series 2 ULTRAwith ISDP

Manual ofboth splits

via UNITY 2

Series 2ULTRA 50:50with IS

As aboveplus

automatic(outlet split

only)

via UNITY 2and/or

integrated MFCoptions

Series 2AutoSecure TD

Automatic(all split

flows)via UNITY 2

AutoSecure TDwith ISDP ondesorb ULTRA

Automatic(all split

flows)via UNITY 2

Summary

TrademarksSecureTD-Q™, TubeTAG™ and DiffLok™ are alltrademarks of Markes International Ltd.

Markes International Ltd.Gwaun Elai Medi Science Campus

LlantrisantRCT

CF72 8XLUnited Kingdom

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