Flavor and Odor Analysis in Foods and Food Packaging

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

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. 0.001 0.01 0.1 1.0 10 100 1000 MINIMUM VOLUME REQUIRED (CC)

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

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”

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.

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)

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

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

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

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

SiloniteTM Fused Silica Lined Tubing

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.)

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

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

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

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

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

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

LVSH Analysis of Yuban Coffee - 100cc

LVSH Analysis of Banana - 100cc

100cc LVSH Analysis of Dannon Raspberry Yogurt

100cc LVSH - Coke/Pepsi Challenge

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.

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

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

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.

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

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

100cc LVSH Analysis of Tomato 2 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

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

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

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

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

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

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.

Four Models of MiniCans MC400 MC400L MC400S MC400V

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

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

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

5-Point Sulfur Gas Calibrations H2S DMS CS2 MeSH

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

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.