a selectable 1d or 2d gc/ms system for trace analysis€¦ · · 2016-02-24msd: full scan, 40-550...
TRANSCRIPT
A Selectable 1D or 2D GC/MS System for Trace Analysis
John R. Stuff, Ph.D.GERSTEL Inc.
GERSTELCompany Overview
Family-owned businessFounded in 1967Headquarters: Mülheim an der Ruhr, GermanySubsidiaries:
- GERSTEL Inc., U.S.A.- GERSTEL AG, Switzerland- GERSTEL KK, Japan
150+ employees ISO 9001 Certified since 1997Represented in more than 70 countries.
GERSTELTechnique Overview
Cooled Injection (PTV)
CISCIS
Thermal Desorption
TDSTDS
Twister (SBSE)
TwisterTwister
MultiPurpose Sampler
MPSMPS
Dynamic HeadspaceOlfactory Detection
ODPODP
Automated SPEAutomated DPX
Prep Fraction Collector
PFCPFC
SPME Automation on MPS 2XL
SPME Method Optimization – GERSTEL Maestro Software- Parameter entry
- On fiber derivatization and fiber bake-out
- On-line help
- Sample preparation
Options for Enhancing Sample Extraction- Stirred or orbital agitation
- Cooled agitator
- 32 position heated tray and custom trays
Sample Introduction- CIS 4 with Septumless Head
GERSTEL Automated SPME Enhancements
GERSTELMulti FiberExchange
Sequences using different SPME phases- Fast and flexible SPME method
development
- Multi-method sequences using different SPME phases
- Trays for three or 25 SPME fibers
- Ready-to-use fiber assemblies available from Supelco..
MFX
Selectable 1D or 2D GC/MS System for Trace Analysis
Overview
- Why are we interested?- Convention Approaches to 2D GC - Automated 1D2D GC-GC with
capillary flow technology- Examples
What is that smell?
Challenge: Identifying the cause of off-odors- Odor response can cover many orders of magnitude- Target compounds are often at trace levels- Perceived odor may be a combination of compounds- Matrix background is often complex
Challenge: Identifying new compounds- Natural products - Competitive product analysis- Target compounds may need to be isolated for additional characterization- Matrix background is often complex
Approach: Identifying odor compounds
- Choose an appropriate sampling technique- Couple MSD with olfactometry- Put enough mass on column- Manage complex sample matrix with GC-GC
Two Approaches to Multidimensional GC
Comprehensive GCxGC- Standard (30m) precolumn- Very short (1m) second column- All compounds from precolumn are sent to second column- Thermal or flow modulation- Usually requires fast data acquisition (TOF)
Heartcutting GC-GC- Standard (30m) pre-column- Standard (30m) second column- Selected portions of the first chromatogram “cut” to second
dimension- Compatible with splitting to several detectors- FPD, ODP
Two Approaches to Multidimensional GCComprehensive GCxGC Heartcutting GC-GC
GC x GC: 3D Map
Conventional 2D Heartcut GC/MS/ODP
2D Heartcut GC/MS/ODP Options
GERSTEL MCS or Agilent Dean’s Switch
•Both columns are in the same oven•Have to manual reconfigure connections•Retention times can shift•MS not used as a monitoring detector
GERSTEL 1D/2D Based on CFT Devices a Selectable 1D or 2DGC-MS with selective detection using CFT
and dual LTM-GC Monitor TIC” can be obtained as the 1st dimension for 2DGC-MS Non-dedicated system. The selection of 1D or 2DGC-MS is only
performed by a “Change of the method” (click of the mouse). 2DGC-MS can be performed just after 1DGC-MS run
CFT
+ +
•(AUX)
PlINLET
PSplitter
PDeans
P2nd-OUTP2nd-INP1st-OUTP1st-IN
PAUX
PPCM
PODP
PMSCapODPCapMS
Cap2nd-OUT
Cap2nd-IN
Cap1st-OUT
Cap
1st-I
N
Capdeans
•PCM
LTM-GC 2 (ex. DB-1)
LTM-GC 1(ex. DB-Wax)
MS GERSTEL ODP2
PCM
Selectable 1D/2DGC-O/MS
GERSTEL Selectable 1D/2DGC-MS Calculator
At the same time, carrier gas is supplied to the LTM-GC 2 from the PCM.
GERSTEL ODP2Switching Device(Patent Pending)
PCM
•LTM-GC 2 •(ex. DB-1)
•LTM-GC 1•(ex. DB-Wax)
1DGC-O/MS is operated with the LTM-GC 1.
Selectable 1D/2DGC-O/MS: 1DGC-O/MS
•MS
MS
PCM
GERSTEL ODP2Switching Device(Patent Pending)
LTM-GC 2 (ex. DB-1)
LTM-GC 1(ex. DB-Wax)
The transferred peaks are thermally focused at the head of the LTM-GC 2 column or additional cryo-focusing unit.
Certain peaks eluted in the LTM-GC 1 are transferred onto the LTM-GC 2.
MS
Selectable 1D/2DGC-O/MS: Heart-cutting
PCM
GERSTEL ODP2Switching Device(Patent Pending)
LTM-GC 2 (ex. DB-1)
LTM-GC 1(ex. DB-Wax)
After the heart-cutting, the bulk of the sample can be effectively back flushed.
After few min of the heart-cutting, the temperature program for the LTM-GC 2 starts.
Selectable 1D/2DGC-O/MS: 2DGC-O/MS
MS
GERSTEL TDU - CIS4TDU: 30 ºC - 720 ºC/min - 200 ºC (3 min)CIS: -100 ºC (0 min) - 720 ºC/min - 250 ºC (5 min)
MS (Agilent 5975C)Mass range: m/z 29 – 350 Acquisition speed: 4 Hz
Japanese Beer 10 mLSBSE 2 hr @1500 rpm
Agilent 7890A GC with dual LTM-GC1st column (LTM-GC) : DB-Wax
2nd column (LTM-GC): DB-5
Olfactory (GERSTEL ODP2)Transferline Temp.: 250 ℃
Split Ratio: 1/1
Sampling
Sample Introduction
Detection
Separation
Experimental Procedure
Heart-cutting
1D TIC (DB-Wax)
SBSE – GC – O/MS:Beer Sample: 10 mL, Twister: 1 cm x 500 µm, SBSE: 120 min, Injection: Splitless1st Column: DB-Wax, 2nd Column: DB-5, Sniffing device: GERSTEL ODP2,GC-MS: Agilent 7890GC/5975MSD, ODP/MS Split ratio: 1/1
SBSE-TD-1DGC-O/MS: Beer
Sweet & HoneyPhenethyl acetate + ??
“Change of the methodby click of the mouse”
•SBSE – GC – GC – O/MS:•Beer Sample: 10 mL, Twister: 1 cm x 500 µm, SBSE: 120 min, Injection: Splitless•1st Column: DB-Wax, 2nd Column: DB-5, Sniffing device: GERSTEL ODP2,•GC-MS: Agilent 7890GC/5975MSD, ODP/MS Split ratio: 1/1
SBSE-TD-2DGC-O/MS: Heart-cutting & Back Flush
Back Flush
1DGC-MS
2DGC-MS w/Back Flush
Heart-cutting
2D TIC (DB-5)
Both the 1D TIC and the 2D TIC could be obtained on the same chromatogram in a single run.
1D TIC (DB-Wax)
SBSE – GC – GC – O/MS:Beer Sample: 10 mL, Twister: 1 cm x 500 µm, SBSE: 120 min, Injection: Splitless1st Column: DB-Wax, 2nd Column: DB-5, Sniffing device: GERSTEL ODP2,GC-MS: Agilent 7890GC/5975MSD, ODP/MS Split ratio: 1/1
SBSE-TD-2DGC-O/MS: Beer
GC-O Signal
Back Flush
Heart-cutting 2D TIC (DB-5)1D TIC (DB-Wax)
Phenethyl acetate
?
2D TIC (DB-5)
SBSE-TD-2DGC-O/MS: Beer
?
•GC-O Signal Mass Spectrum
NIST Library Search Result: β-Damascenone
β-Damascenone
β-Damascenone is known as kind of rose ketone. The odor description is “Sweet, Fruity, Plum, Raspberry, etc.”, and the odor threshold in water is quite low, with values in the literature in the range of 20 to 90 ng/L 7).
Quantification of β-Damascenone: STD addition calibration
1.9 ng/mL(RSD 2.8 %, n=6)
β-Damascenone
β-Damascenone in Japanese Beer: 1.4 – 2.2 ng/mL9) T. Kishimoto et al, J. Agric. Food Chem. 53 (2005) 4701.
SPME – Potato Chips GERSTEL CIS 4 PTV, 250 oC, Splitless Liner: SPME Column: Rtx-5 Sil MS, 30 m x 0.25 mm x 0.25 µm LTM Standard Column: DB-Wax, 30 m x 0.25 mm x 0.50 µm LTM Standard GC Oven: 250 oC Isothermal MSD: Full scan, 40-550 amu Fiber: DVB-Carboxen-PDMS Incubation: 3 min @ 65 oC; Agitator 250 rpm Extraction: 20 min Desorption: 3 min
Cut Region
Barbecue Chips – 1st DimensionBackflush Region
α-Pi
nene
β-pi
nene
Sabi
nene
Lim
onen
e
Terp
inen
e
1st Dimension 2nd Dimension
Barbecue Chips – 2nd Dimension
Barbecue Chips – 2nd Dimension Enhanced View
SPME – Spices GERSTEL CIS 4 PTV, 250 oC, Splitless Liner: SPME Column: Rtx-5 Sil MS, 30 m x 0.25 mm x 0.25 µm LTM Standard Column: DB-Wax, 30 m x 0.25 mm x 0.50 µm LTM Standard GC Oven: 250 oC Isothermal MSD: Full scan, 40-550 amu Fiber: DVB-Carboxen-PDMS Incubation: 3 min @ 60 oC; Agitator 250 rpm Extraction: 20 min Desorption: 3 min
Sweet Basil – 1D
MintyLemonMinty GreenBalsamicClove, SpicyWoodyWoodyHerbal Spice
Italian SeasoningMarjoram, Thyme, Rosemary, Sage, Oregano, and Basil
Camphor – SharpBorneol – Pine, WoodyThymol – Mint, SpicyCarvacrol – Phenolic, ThymeCaryophyllene – Woody, Spicy
Mediterranean Spiced Sea Salt – 1DGarlic, Oregano, Basil, Red Bell Pepper, Red Pepper
Mediterranean Spiced Sea Salt – 1D
Mediterranean Spiced Sea Salt – 2D
Mediterranean Spiced Sea Salt – 1D
Mediterranean Spiced Sea Salt – 2D
SPME Poultry SeasoningThyme, Sage, Marjoram, Rosemary, Black Pepper, and Nutmeg
SPME Poultry Seasoning – 1D
SPME Poultry Seasoning – 2D
SPME Poultry Seasoning – 2D
SPME Poultry Seasoning – 2D
Selectable 1D/2DGC-O/MS: 2D Chiral
GERSTEL CIS 4 PTV, 250 oC, Splitless Liner: SPME Column: Rtx-5 Sil MS, 30 m x 0.25 mm x 0.25 µm LTM Standard Column: Cyclosil-B (Agilent) 30 m x 0.25 mm x 0.25 um LTM Standard GC Oven: 250 oC Isothermal MSD: Full scan, 40-550 amu Fiber: DVB-Carboxen-PDMS Incubation: 3 min @ 60 oC; Agitator 250 rpm Extraction: 10 min Desorption: 3 min
3,3,5-Trimethyl-2-cyclohexen-1-ol
Artemisia Extract 1D Separation
Artemisia 2D Chiral Separation
Fraction Collection 1D 2D
I can smell it but can’t
identify it
With a lot of samples, we can smell something at the ODP, but not see it in the mass spectrometer
Changing the split ratio means totally reconfiguring the instrument
We need to get more mass on column for a positive identification
Fraction Collection 1D 2D
Fraction Collection 1D 2D GC
Heartcut-One Twister
Heartcut-Five Twisters
SummaryMultidimensional GC-GC Features
2D GC-GC Heartcutting provides substantial improvement in resolution
New Selectable 1D/2D GC-GC configuration easily selects single- or multidimensional configuration
LTM column heating provides independent column temperature control and shortens total runtime. Chiral columns can provide additional information in 2nd Dimension
CTS cold trap between precolumn and main column can act as fraction collector to improve detection in second dimension
Software control integrated into Agilent Chemstation
Acknowledgements
Dr. Nobuo Ochiai (GERSTEL K.K.)
Mr. Kikuo Sasamoto (GERSTEL K.K.)
Jackie Whitecavage (GERSTEL, Inc)