1. Flavor and Odor Analysis in Foods and Food Packaging

2. Presentation Overview
Introduction to Large Volume Static Headspace (LVSH) Technique
Advantages of LVSH/GC(MS)
Analytical Procedure
Examples of Food Products Analyzed
Food Quality Determination by LVSH
Summary

3. GC/MS Detection Limits vs Headspace Sample Volume
1000
100 10 1
0.1
0.01
10-3
10-4
10-5
Loop
Preconcentration
PPM
LOD
Vol vs Conc.
MINIMUM VOLUME REQUIRED (CC)

4. Large Volume Headspace Requires Preconcentration
HP 5973 GCMS Volume Reduction
Large Volume
Inlet or Autosampler

5. Large Volume Static Headspace Autosampler
Introduces cc of headspace to the 7100 Preconcentrator
Accommodates solids and liquids
Detection limits 100x lower than conventional loop injection headspace
“See what you can smell”

6. 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.

7. 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)

8. Food and Beverage Analysis by Large Volume Static Headspace (LVSH) / GCMS Analysis
HP 5973 GCMS L
Stage Preconcentrator
7032L 21-Position LVSH/MiniCan Autosampler
Multi-Channel Standards Diluter

9. Large Volume Static Headspace Analyzer
7032-LVSH / 7100 /5973
Large Volume Static Headspace Analyzer M3
SL I/O
SL I/O M2 6 M1 MS GC
7100
7032-LVSH

10. 7100 Open Architecture PCB Integrated wiring for improved reliability
Modular design.
Easy replacement of traps
MFC downstream of traps
PCB Integrated wiring for improved reliability

11. 7100 Heated Flow Path Silonite tubing used throughout.
Complete heating of sample flow path. Easily accessed for trap and tubing replacement.
External Heaters outside each cryotrap
7100 Preconcentrator

12. SiloniteTM Fused Silica Lined Tubing

13. 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. R E S P O N
Silonite
Brand B
Deact. Brand B
Flush Time (Min.)

14. 7100 Water and CO2 Management Techniques
MFC
PUMP
H2O
Post-Injection Bakeout
Helium Carrier
Helium To GC
Focuser
Glass Beads
Tenax
Sample
Internal
Standard
Calibration
Standard
Cryogen in

15. 3-Stage Flexibility for GCMS Analysis of Multiple Sample Types and Matrices
Sample Type Mode Trap Trap2
Trap 3 - On-column focuser for capillary GC/MS

16. Improper Water Management 400cc VOC STD, Full Scan 15-270 amu

17. Vinyl Chloride 100x Calibration Curve using Variable Volume / Single Standard Calibration

18. 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

19. 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

20. LVSH Analysis of Yuban Coffee - 100cc

21. LVSH Analysis of Banana - 100cc

22. 100cc LVSH Analysis of Dannon Raspberry Yogurt

23. 100cc LVSH - Coke/Pepsi Challenge

24. Using LVSH to Determine Product Quality Markers in Fruits and Vegetables
Analysis of 100cc of Headspace allows detection of VOCs indicating condition of food products.
Monitoring changes in VOC ratios as food spoils allows quantitative evaluation of extent of spoilage.
Once specific “Markers” are determined, remote headspace techniques can be used to predict food condition and time until spoilage in storage containers and warehouses.

25. 100cc LVSH Analysis of Grapes 7032LVSH/7100/5973
1. CO2
2. Acetaldehyde
3. Ethanol 2 2 1 1
Loop Injection
Detection Limit

26. LVSH Analysis of Grapes - Scaled to show PPB Cmpds
(Loop Injection Detection Limit) IS IS 1
1. Ethyl
Acetate
2.Limonene 2 2 1

27. LVSH Analysis of Grapes
Ethyl Acetate concentration increases as grapes age, while naturally occurring Limonene drops off.
The ratio of EA/Limonene is a good indicator of product quality
Acetaldehyde, a non-desirable component in wine, is present even before the fermentation process begins.

28. 100cc LVSH Analysis of Lettuce4 3 1
1. CO2
2. Methanol
3. Ethanol
4. TCE 1 2 2
Loop Injection
Detection Limit

29. LVSH Analysis of Lettuce
Ethanol, Dimethyl Sulfide, and Acetaldehyde show large increases as lettuce spoils
Naturally Occurring Limonene drops in concentration
The ratio of DMS to Limonene was a good indication of freshness

30. 100cc LVSH Analysis of Tomato2
1. CO2
2. Methanol
3. Ethanol
4. Acetone
5. 2-Methyl Furan
6. DHHN 1 6 5 1 4
Loop Injection
Detection Limit 3 IS 4 3 IS 2 5 6

31. LVSH Analysis of Tomatoes - Scaled to show PPB Cmpds
Multiple
PPB Level
Markers

32. LVSH Analysis of Tomatoes
Heavy aldehydes increased as food spoils
The largest increase was from a semi-volatile tentatively identified as DHHN
In this study, the ratio of DHHN to 2-Methyl Furan was determined to be an excellent indicator of product quality

33. Chocolate vs Carob Peanuts by LVSH/GCMS
Hexanal
Chocolate Peanuts
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973
Hexanal
Carob Peanuts
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973

34. Whole Garlic vs Garlic Powder by LVSH/GCMS
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973
Garlic Powder
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973

35. Cheddar Cheese by LVSH/GCMS
Cheddar Cheese, Brand A
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973
Cheddar Cheese, Brand B
100cc, LVSH
60m, HP1, 0.32mm ID, 1um
7032LVSH/7100/5973
Toluene

36. 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.

37. Four Models of MiniCans
MC MC400L MC400S MC400V

38. Gas Phase Analysis Using MiniCan Silonite Coated Samplers
7032 Autosampler
Surrogate Spiking

39. 5973/7100/7032 200cc Injection 10 PPB Sulfur Std., ECTD
1. CO2
2. H2S
3. COS
4. MeSH
5. DMS
6. CS2 6 4 3 1 2

40. 2-Day Stability Study of Sulfur Compounds in
Fused Silica Lined vs Electropolished Canisters
7000 / HP5973 Data

41. 5-Point Sulfur Gas Calibrations
H2S
DMS
CS2
MeSH

42. 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

43. 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.