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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)