GACID

Comprehensive Two-Dimensional
Gas Chromatography coupled with Time-of-Flight
Mass Spectrometry
for Broad Spectrum Organic Analysis
GCxGC-TOFMS
GACID - Group for Analytical Chemistry Instrument Development

Harsh Environment Mass Spectrometry workshop

09/22/2003
Sarasota, FL

Stefan Scherer
Department for Atmospheric, Oceanic, and Space Sciences
Space Physics Research Laboratory
University of Michigan
09/23/2005 S. Scherer 1
 Presentation Outline
GACID

• Separation using Comprehensive 2-Dimensional Gas Chromatography

(GCxGC)
– 1-D GC versus 2-D GC
• Identification using Time-of-Flight Mass Spectrometry TOFMS
– Capabilities of TOFMS
• Applications for GCxGC-TOFMS (selected examples)
– Tholins
– CWA simulants detection in gasoline
– Breath analysis
• Field deployment at UMBS
• Subsystem development activities
– Thermal Modulator
• Future steps
• Acknowledgement

09/23/2005 S. Scherer 2
 1-Dimensional Gas Chromatography (GC)
GACID

Standard 1D-GC technique

‰ narrow sample plug injection

into the chromatographic
column
‰ Sample transport happens in
the mobile phase by the flow
of an inert carrier gas
‰ separation of the sample
occurs along the coated
column with various stationary
phases by interaction of the
sample material with the
column coating
‰ Retention time of the effluent
is detected

09/23/2005 S. Scherer 3
 Comprehensive 2-Dimensional Gas Chromatography (GC x
GC) GACID

09/23/2005 S. Scherer 4
 1-Dimensional versus 2-Dimensional Gas Chromatography (1/2)
GACID

1-Dimensional GC Comprehensive 2-Dimensional GC

I I

C C1
C2
D D
TM

TIC (a.u.)
TIC (a.u.)

Time (s) in C2

C 1
Tim e ( s) in
e (s) Tim
in C
Time (s) 2

09/23/2005 S. Scherer Time (s) in C1 5

 1-Dimensional versus 2-Dimensional Gas Chromatography (2/2)
GACID

(a) 1-Dimensional separation (non-modulated)

TIC

0 1000 2000 3000 4000 5000

Time (s)
(b)
TIC

2-Dimensional separation (modulated)

0 1000 2000 3000 4000 5000
Time (s)
(c) 10
2-Dimensional view of GCxGC
Time (s)

0
0 1000 2000 3000 4000 5000
Time (s)
09/23/2005 S. Scherer 6
 Measurement capabilities of GCxGC
GACID

‰ Analysis of organic carbon compounds C5 to C25

‰ High peak capacity (several thousand peaks per chromatogram)
‰ Typical analysis cycle duration 30 min
‰ Various sampling methods are available
‰ Solid samples using pyrolysis

(10-100 µg/cycle sample material using Flash or Stepped Pyrolysis)

‰ Volatile samples using direct sampling/pre-concentration

‰ Liquid sampling using split/splitless injection

‰ Sensitivity in the low parts per trillion (ppt) range

‰ Increased detectability
‰ Linearity over more than 3 orders of magnitude (ppb - ppt)
‰ Thermal Modulator (TM) is key component of GCxGC
- commercial TM require consumables
- consumable-free TM under development

09/23/2005 S. Scherer 7
 GCxGC-TOFMS
GACID

Inlet Separation Identification

Identification by TOFMS
‰ Full mass spectrum with every extraction pulse firing
without necessity of scanning the entire mass range
‰ Repetition rates up to 100kHz achievable, which allows
monitoring fast sample composition changes on time
scales much smaller than milliseconds
‰ High initial energy spread of ions up to several hundred
eV is admissible
‰ Neither static nor dynamic magnetic fields are required
‰ Performance depends mainly on electrical circuits rather than
mechanical alignment
‰ Mass scale calibration for TOFMS is simple and reliable
09/23/2005 S. Scherer 8
 Chromatogram of tholins using GCxGC-TOFMS technique (1/2)
GACID

sample (tholin) analyzed by commercial laboratory equipment (LECO

Corp.) using pyrolysis injection (CDS).

09/23/2005 S. Scherer 9
 Chromatogram of tholins using GCxGC-TOFMS technique (2/2)
GACID

09/23/2005 S. Scherer 10
 Chemical Warefare Agent Simulants in Complex Organic Mixtures
GACID

09/23/2005 S. Scherer 11
 Human Breath Analysis
GACID

Human breath analysis

before smoking

Human breath analysis

shortly after smoking

09/23/2005 S. Scherer 12
 Commercial GCxGC-TOFMS
GACID

LECO Pegasus 4D

GCxGC – TOFMS
• Resource intensive liquid LN2 cooled four jet Thermal Modulator
(dewer of LN2 /week)
http://www.leco.com

09/23/2005 S. Scherer 13
 GCxGC–TOFMS breadboard using closed-loop air-cooled TM
GACID

GCxGC – TOFMS breadboard

• Custom made pre-concentrator
• Integrated packaged columns (RVM Scientific)
• Custom made closed-loop air-cooled consumable-free TM
• TOFMS (Ionwerks)

09/23/2005 S. Scherer 14
 Breadboard results of GCxGC - TOFMS
GACID

09/23/2005 S. Scherer 15
 Field deployment of the GCxGC-TOFMS breadboard
GACID

GCxGC–TOFMS breadboard field deployed during summer 2005 campaign

at the PROPHET tower laboratory at the University of Michigan
Biological Station (Northern Michigan); refer to poster from Judy Yu
Measurement Goal: VOCs and isoprene measurements

09/23/2005 S. Scherer 16
 2-Stage Thermal Modulator
GACID

• Two-Stage Thermal Modulator designed

and prototyped at the
University of Michigan
• Set Industry Standard for Modulators
• Two-Stage will eliminate sweep through

1st Stage

2nd Stage

Drawing Courtesy of Bruce Block – AOSS University of Michigan

09/23/2005 S. Scherer 17
 Single Stage versus 2-Stage Thermal Modulator
GACID

Single-Stage Air-Cooled
• limited quantitative analysis
A • Breakthrough observed
• Peak Tailing as
concentration inside
modulator increases

Two-Stage Air-Cooled

B • Improved quantitative
analysis
• Minimal Breakthrough
• No Peak Tailing
0 5 10 15 20 25 30 35
Time (s) 1 ppm Octane

09/23/2005 S. Scherer 18
 Future of GCxGC using Micro-Fabricated Columns
GACID

• Further miniaturize the separation section

by using MEMS technology for the GCxGC
subsystem
• Decrease physical size as well as reduce
resource requirements with on-chip heating
• Collaboration with the WIMS center at
UofM

09/23/2005 S. Scherer 19
 Future of GCxGC using Micro-Fabricated Columns
GACID

• Capillary length 3m
150 µm
• Chip size (3.2cmx3.2cm)
• cross section
150 µm wide x 240 µm 240 µm
deep Digital Picture of 3-
• Side ports etched in Si for meter micro fabricated
more mechanical stability column
3.2 cm
• Etched back structure for
reduced thermal mass

09/23/2005 S. Scherer 20
 Future of GCxGC using Micro-Fabricated Columns
GACID

• Separation of series of
n-alkanes (C5 to C15) at
3 temperature
programs
a) 10 K/min
b) 20 K/min
c) 30 K/min
• Design of a meso-
scale TM using
thermo-electric cooling
and resistive heating
attached to columns in
MEMS technology

09/23/2005 S. Scherer 21
 The GACID Team
GACID

… By the enthusiastic effort of the following team members at the

University of Michigan the results have been made possible …

Atmospheric,
College of Oceanic, and Space Chemistry
Engineering Sciences
Richard Sacks
Charlie Hasselbrink Hunter Waite
Amy Payeur
Megan McGuigan
PT Stevens
Bruce Block
Mark Libardoni
Stefan Scherer

09/23/2005 S. Scherer 22
 Pre-Concentrator
GACID

Stainless Steel Mesh

Column one Beds

Y B X C

Nut Glass Wool

Gas Flow During Sample Collection

Gas Flow During Sample Desorption

Symbo Adsorbent
Adsorbent Application
l Strength
Carbon Molecular Sieve Carboxen
C 1000
Strongest C2 to C5
Graphitized Carbon X Carbopack X Stronger C3 to C5

B Carbopack B Weaker C5 to C12

Y Carbopack Y Weakest C12 to C20

09/23/2005 S. Scherer 23
 Custom designed Thermal Modulator
GACID

Dual stage Thermal Modulator

- resistively heated -air-cooled

09/23/2005 S. Scherer 24
 Gas Chromatographic columns
GACID

RVM Scientific integrated columns

Add photo of
the RVM
columns

09/23/2005 S. Scherer 25
 Murchinson Meteorite analysis using Pyrolysis-GCxGC-TOFMS
GACID

09/23/2005 S. Scherer 26
 Time-of-Flight principle
GACID

U Lin d s

Uextr

Time focus
Udrift
reflectron
fieldfree driftpath
ion source 1
detector 2

U Lout d s

Lin + Lout = L
Time focus

Mamyrin et al., 1972

09/23/2005 S. Scherer 27
 Electron Impact Storage Ion Source
GACID

extraction grid A1 lens

repeller A A2 drift
filament
simulated peak
repeller B
Dttat
turn-around time
3 ns

Dteds 2mU 0
backplane ∆ttat (m) = 2 ⋅
< 1 ns q Eextr

trap 501 504

1. Time focus TOF [ns]

U
z
Uextr

Udrift

09/23/2005 S. Scherer 28
 Orthogonal Extraction Ion Source
GACID

anode
filament trap
extractor
entrance lens extraction grid
skimmer
A1 A2 lens drift
simulated peak
Dtpbd
2 ns
backplane
Dteds
<1ns

501 504
time focus TOF [ns]
U z
Uextr

Udrift

09/23/2005 S. Scherer 29
 GACID

09/23/2005 S. Scherer 30
 Thermal Modulators: Overview of techniques
GACID

P.S.
N2 gas

J.B. Phillips - 1991

E.B. Ledford and J. Beens - 2000

J.B. Phillips - 1993

P.J. Marriott - 1997 E.B. Ledford - 2002

09/23/2005 S. Scherer 31