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Analysis of Beverages using Large Volume Static Headspace / GCMS

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Presentation Overview• Introduction to Large Volume Static

Headspace (LVSH) Technique

• Advantages of LVSH/GC(MS)

• Analytical Procedure

• Examples of Beverages Analyzed

• Remote Headspace Analysis

• Summary

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GC/MS Detection Limits vs Headspace Sample Volume

0.001 0.01 0.1 1.0 10 100 1000

1000

100

10

1

0.1

0.01

10-3

10-4

10-5

PPM

LOD

MINIMUM VOLUME REQUIRED (CC)

Vol vs Conc.

Loop Preconcentration

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Large Volume Headspace Requires Preconcentration

HP 5973 GCMS Volume Reduction Large Volume

Inlet or Autosampler

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Large Volume Static Headspace Autosampler

• Introduces 10-200cc of headspace to the 7100 Preconcentrator

• Accommodates solids and liquids

• Detection limits 100x lower than conventional loop injection headspace

• “See what you can smell”

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LVSH Sample Platforms and Enclosures

• Samples are placed in disposable vials, reducing potential for contamination of sample platforms.

• Sample Platforms use quick connects, simplifying removal for oven bakeout.

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Advantages of Large Volume Static Headspace (LVSH)

• Cleaner. No aerosols or foaming to contaminate sample transfer lines

• Larger Sample Loading• Low detection limits without sample heating.

– Less chance of producing artifacts.– Sample remains in natural state.

• Ideal for kinetic / aging studies– Outgassing rates– Effects of Atmosphere and Storage Temperature

• Better recovery of reactive compounds– Strong carbon based adsorbents are avoided– Inert, Silonite tubing used throughout

• No sample fractionation (SPME)

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Food and Beverage Analysis by Large Volume Static Headspace (LVSH) / GCMS Analysis

HP 5973 GCMS 7100 7032L 4600

7100 3-Stage Preconcentrator

7032L 21-Position LVSH/MiniCan Autosampler

4600 Multi-Channel Standards Diluter

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7032-LVSH / 7100 /5973 Large Volume Static Headspace Analyzer

GCMS

6

7100 7032-LVSH

SL I/O SL I/O

M1

M2

M3

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PCB Integrated wiring for improved reliability

Modular design.

Easy replacement of traps

MFC downstream of traps

7100 Open Architecture

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• Silonite tubing used throughout.

•Complete heating of sample flow path. Easily accessed for trap and tubing replacement.

•External Heaters outside each cryotrap

7100 Heated Flow Path

7100 Preconcentrator

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SiloniteTM Fused Silica Lined Tubing

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Silonite Tubing VOC Adsorption/Absorption Study

• Less adsorption of Diethylbenzene on Silonite tubing. No deactivation needed.

• Faster sample equilibration with tubing surface.

• Less potential for carryover.

50

100

150

200

250

300

350

1 2 3 4

Silonite

SilcoSteel

Deact.SilcoSteel

R

E

S

P

O

N

S

E

Flush Time (Min.)

Silonite

Brand B

Deact. Brand B

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InternalStandard

CalibrationStandard

Glass Beads Tenax

Cryogen in

CO2

Focuser

ToGC

VOCs

7100 Water and CO2 Management Techniques

H2O

Helium

PUMPMFC

Helium Carrier

Removing Water and CO2

Sample

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Foods,Packaging

MP&T Glass Beads (-150C)

Tenax (-30C)

High CO2Beverages

ECTD Empty (-150C)

Tenax (-50C)

High CO2/EtOHBeverages(Heavy-Ends)

MP&T Tenax (20C) Tenax (-30C)

High CO2/EtOHBeverages(Light-Ends)

ECTD Tenax (-10C) Tenax (-60C)

3-Stage Flexibility for GCMS Analysis of Multiple Sample Types and Matrices

Sample Type Mode Trap1 Trap2

Trap 3 - On-column focuser for capillary GC/MS

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Improper Water Management

400cc VOC STD, Full Scan 15-270 amu

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Vinyl Chloride

y = 285937x - 13186

R2 = 1

-500000

500000

1500000

2500000

3500000

4500000

5500000

6500000

7500000

0 5 10 15 20 25

ppbv

MS

D A

bu

nd

an

ce Vinyl Chloride 100x Calibration Curve usingVariable Volume / Single Standard Calibration

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3 .5 0 3 .55 3 .6 0 3 . 6 5 3 .70 3 .7 5 3 . 80 3 .5 8 3 . 9 0 3 . 95

7 5 0 0 02 6 0 0 0

2 5 0 0 0

2 4 0 0 0

2 3 0 0 0

2 2 0 0 0

2 1 0 0 0

2 0 0 0 0

1 9 0 0 0

1 8 0 0 0

1 7 0 0 0

1 6 0 0 0

1 5 0 0 0

1 4 0 0 0

1 3 0 0 0

1 2 0 0 0

1 1 0 0 0

1 0 0 0 0

9 0 0 0

8 0 0 0

7 0 0 0

6 0 0 0

5 0 0 0

4 0 0 0

3 0 0 0

2 0 00

1 0 0 0

0

7 0 0 0 0

4 5 0 0 0

6 5 0 0 0

5 0 0 0 0

4 0 0 0 0

3 0 0 0 0

2 5 0 0 0

3 5 0 0 0

2 0 0 0 0

1 5 0 0 0

1 0 0 0 0

5 0 0 0

6 0 0 0 0

5 5 0 0 0

E than o lm /z 4 54 .35 m in0 .17 ppb .

M ethan o lm /z 3 13 .67 m in .0 .49 ppb

Fast Injection and Proper Water Management Minimizes Tailing of Polar VOCs

Column: HP1, 60m, 0.32mm ID, 1um film.

Flow rate: 1.5 ccm

Carrier: He

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Advantages of 7100 Multi-Stage Preconcentration

• Multiple Preconcentration Options Depending on Target Compounds and Matrix (CO2, ETOH)

• Reduced Temperature Trapping Minimizes Sample Stress, Maximizing Recovery of Thermally Labile Flavor and Odor Compounds

• Silonite Tubing Creates an Extremely Inert Sample Flow Path to Further Improve Recovery

• Demonstrated Recovery of Sulfur and Nitrogen Compounds

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LVSH Analysis of Yuban Coffee - 100cc

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100cc LVSH - Coke/Pepsi Challenge

Coke

Pepsi

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TreeTop Apple Juice100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Apple Juice by LVSH / GCMS

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Beer by LVSH/GCMS

Beer, ETOH Removed200cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

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Beer by LVSH/GCMSBeer, ETOH RemovedFront End, Post ETOH200cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

1

2

3

4

1 Acetone2. Ethyl Formate3. Dimethyl Sulfide4. Propanol

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Beer Light Ends by LVSH/GCMS

Beer, ETOH M1 RetainedCold Trap DehydrationLight Ends200cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

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Beer Light Ends by LVSH/GCMS

Beer, ETOH M1 RetainedCold Trap DehydrationLight Ends200cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Acetaldehyde

COS

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2% Milk by LVSH/GCMS

2% Milk100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

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2% Milk100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Dimethyl Sulfide

2% Milk by LVSH/GCMS

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MiniCan Samplers Allow Direct Sampling of Gas Phase Flavors and Odor Compounds

• Collection of Remote Headspace Samples Improves Monitoring Effeciency.

• MiniCan Samplers are SiloniteTM Coated to reduce surface losses.

• Monitor Process Streams, Holding Tanks, Reactors, etc.

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Four Models of MiniCans

MC400 MC400L MC400S MC400V

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7032 Autosampler

Gas Phase Analysis Using MiniCan Silonite Coated Samplers

Surrogate Spiking

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5973/7100/7032 200cc Injection10 PPB Sulfur Std., ECTD

1

2

3 4

6

5

1. CO2

2. H2S

3. COS

4. MeSH

5. DMS

6. CS2

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Si l coCAN

0

20

40

60

80

100

120

140

160

0 20 40 60 80 100

Rel at i ve Humi di ty (%)

Recovery (%)

Ethyl mercaptan

Propyl mercaptan

s- butyl mercaptan

t- Butyl mercaptan

SUMMA CANI STER

0

20

40

60

80

100

120

140

160

0 20 40 60 80 100

Rel at i ve Humi di ty (%)

Recovery (%)

Ethyl mercaptan

Propyl mercaptan

s- butyl mercaptan

t- Butyl mercaptan

2-Day Stability Study of Sulfur Compounds in

Fused Silica Lined vs Electropolished Canisters

7000 / HP5973 Data

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5-PointSulfur Gas

Calibrations

H2S

MeSH CS2

DMS

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Support for R&D and QA

• Fully Characterize Products down to Olfactory Detection Limits

• Identify Good and Bad “Markers” in product or packaging

• Monitoring on-line (Sequence Looping)

• Monitoring at-line (Sampling Ports)– Solids, Liquids by LVSH– Gases by MiniCan Samplers

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Conclusion• Large Volume Static Headspace (LVSH) is a new analytical

tool available to food and beverage Chemists which enhances the detection of headspace components using GC and GCMS analysis.

• Maintaining the sample in a more natural state allows the analysis of “normally occurring” odor and flavor compounds.

• Inert flow paths and reduced temperature trapping increases the range of analytes that can be recovered, including oxygen, nitrogen, and sulfur containing compounds.