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Kelly Rees, Justin Frosina, Christopher Rawlinson, Michal Brokl, Christopher Wright
British American Tobacco Group Research & Development, Southampton UK
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NON-TARGETED ANALYSIS OF EMISSIONS
FROM TOBACCO HEATING PRODUCTS
69th Tobacco Science Research Conference, Naples FL 20-23 September, 2015
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Non-Targeted Screen
Overview
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• Why is a non-targeted approach required?
› Appropriate stewardship
• Challenges
› New product category
• THP Screen
› TD sampling
› Analytical method (TD-GC-TOFMS + heart cutting)
› 3ng/puff sensitivity
› Automated data processing
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Why is a non-targeted approach required?
• Requirement to assess delivery at trace levels:
› Product Stewardship
› Toxicant assessment
› Thermal degradation of high abundance compounds
› Product Development
› Device fingerprinting
› Component variant analysis
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Challenges
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• New product category
› Unknown emission composition; 800-1200 compounds estimated
› Different matrix to combustibles and e-cigarettes
• Analytical challenge
› Sensitivity against high abundance components
› Device design – filtered/non-filtered; mechanism of heating/
temperature
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THP Emission Screen
Method Requirement
• Whole emission non-targeted screen
› Qualitative characterisation of emissions
› GC/LC - amenable components
• 3ng/puff sensitivity
› Addressing toxicological thresholds
• Semi-quantitative
› Referenced to ISTD (order of magnitude assessment)
• Defined sampling conditions
› Agreed standard approach
› Flexibility
• Data management
› Automated approach
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Instrumental Set-up
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THP Emission Screen
ALMSCO Bench TOF-dx Agilent 7890B MARKES TD100
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THP Emissions Screen
Sample Generation
• A14/LX1 Linear Syringe Drive Engine (Borgwaldt)
› Consistent and flexible emission collection
› Rapid sampling directly onto TD tube
› 8-13 x 55ml 2 second puff (HCI) per sample
› Disposable Tygon® connector(s)
› Minimal ‘dead volume’
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THP Emissions Screen
Sampling – TD Tubes
• Dual bed sorbent
1. Tenax - polymer based sorbent:
› General purpose sorbent
› Suitable for C6 – C30
› Limited water retention
› Stable to 320°C
2. Sulficarb - molecular sieve:
› Strong sorbent – light volatiles
› C3 – C6
› Requires water management
› Stable to 360°C
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THP Emissions Screen
Analysis – TD Automation
• Whole emissions captured on TD tube
• Automated ISTD addition› TO-14A tuning mix
› 32ng bromochloromethane
› 28.5ng 1-bromo-4-fluorobenzene
› 29ng chlorobenzene-d5
› 43.5ng 1,4-difluorobenzene
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• Key considerations› Breakthrough?
› Recovery?
› Thermal Stability?
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THP Emissions Screen
Breakthrough Analysis
• 2 TD tubes connected in series
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1st tube
2nd tube
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THP Emissions Screen
Recovery Analysis
• Single TD tube desorbed twice
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1st desorption
2nd desorption
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Small decrease/injection =True emission component
THP Emissions Screen
Recollection Explained
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1
2
3
Small increase/injection =
Some degradation during desorption but
majority present as a result of emission
Doubling/injection =Tube artefact
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THP Emissions Screen
Recollection Explained
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OriginalRecollection 1
Recollection 2
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THP Emissions Screen
Why Heart-Cutting?
• Overloaded constituents can saturate detector
› Limit detector life
› Prevent detection of heavier masses
1. Manage major constituents by reducing overall loading:
› Reduction in sensitivity due to increased splits
› Unable to achieve 3ng/puff threshold
2. Manage major constituents by heart cutting to FID
› Sensitivity can be improved by reducing splits
› Ability to detect compounds present at 3ng/puff and lower
› Trace level components detectable
› Increase detector lifetime14
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THP Emissions Screen
Heart-Cutting Explained
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FID/other Detector
TOF MS
GCDeans Switch
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THP Emissions Screen
TD-GC-TOFMS with heart cutting
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FID
TOFMS
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THP Emissions Screen
Achieving 3ng/puff LOD
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~3ng/puff
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THP Emissions Screen
TD-GC-TOFMS with Heart cutting
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Commercial Device 1
Commercial Device 2
Commercial Device 3
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THP Emissions Screen
Data Management - Automation
• Chemometrics platform under development› Automated component identification (multiple data files - multiplicity
threshold)
› Removes analyst subjectivity
› High throughput (< 20 minutes per sample)
› Integrated multivariate statistics capability
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THP Emissions Summary
Thermal Desorption Approach
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THP whole
emissionsTD Tube TD-GC-TOFMS
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THP Emissions Screen
Summary
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• 3ng/puff Sensitivity• Fully automated process• Robust data
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What Next?
• Move to GC×GC
› Complex emissions benefit from 2nd dimension
• Plan for ‘validation’
› Against target compound list
› Method scope
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Acknowledgements
• Matt Bates, MCBA consulting
• Valle Morales, BAT ADC
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Thank you for listening
Questions?
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