hit “esc” to quit hit any key to continue

Flavor and Odor Analysis in Foods and Food Packaging

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

Large Volume Headspace Requires Preconcentration

HP 5973 GCMS Volume Reduction Large Volume

Inlet or Autosampler

hit “esc” to quit hit any key to continue

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”

hit “esc” to quit hit any key to continue

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.

hit “esc” to quit hit any key to continue

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)

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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

GCMS

6

7100 7032-LVSH

SL I/O SL I/O

M1

M2

M3

hit “esc” to quit hit any key to continue

PCB Integrated wiring for improved reliability

Modular design.

Easy replacement of traps

MFC downstream of traps

7100 Open Architecture

hit “esc” to quit hit any key to continue

• 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

hit “esc” to quit hit any key to continue

SiloniteTM Fused Silica Lined Tubing

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

7100 Water and CO2 Management Techniques

InternalStandard

CalibrationStandard

Glass Beads Tenax

Cryogen in

H2O

Focuser

ToGC

Helium

PUMPMFC

Helium Carrier

Post-Injection Bakeout

Sample

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

Improper Water Management

400cc VOC STD, Full Scan 15-270 amu

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

LVSH Analysis of Yuban Coffee - 100cc

hit “esc” to quit hit any key to continue

LVSH Analysis of Banana - 100cc

hit “esc” to quit hit any key to continue

100cc LVSH Analysis of Dannon Raspberry Yogurt

hit “esc” to quit hit any key to continue

100cc LVSH - Coke/Pepsi Challenge

Coke

Pepsi

hit “esc” to quit hit any key to continue

• 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.

Using LVSH to Determine Product Quality Markers in Fruits and Vegetables

hit “esc” to quit hit any key to continue

100cc LVSH Analysis of Grapes 7032LVSH/7100/5973

1

2

33

2

1

1. CO22. Acetaldehyde3. Ethanol

Loop Injection Detection Limit

hit “esc” to quit hit any key to continue

LVSH Analysis of Grapes - Scaled to show PPB Cmpds

1. Ethyl Acetate2.Limonene

1

1

2

2

ISIS

(Loop Injection Detection Limit)

hit “esc” to quit hit any key to continue

• 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.

LVSH Analysis of Grapes

Fresh vs Spoiled Grapes Area Counts (x10^6)Fresh Spoiled S/F

Ethyl Acetate 3 20.4 6.80

Ethanol 2725 2276 0.84

Acetaldehyde 245 424 1.73

Limonene 15.4 4.8 0.31

E Acet./Limonene 0.19 4.25 21.82

hit “esc” to quit hit any key to continue

1. CO22. Methanol3. Ethanol4. TCE

1

2

34

12

100cc LVSH Analysis of Lettuce

Loop Injection Detection Limit

hit “esc” to quit hit any key to continue

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

Fresh vs Spoiled Lettuce Area Counts (x10^6)Fresh Spoiled S/F

Ethyl Acetate 3 30.7 10.2

Nonanal 101 23 0.2

Ethanol 10 740 74.0

Dimethyl Sulfide(DMS) 0.2 53 265.0

Acetaldehyde 3 150 50.0

Limonene 15.4 9 0.6

DMS/Limonene 0.01 5.89 453.4

hit “esc” to quit hit any key to continue

1. CO22. Methanol3. Ethanol4. Acetone5. 2-Methyl Furan6. DHHN

IS

IS

1

2

3

6

6

5

4

1

2

3

4

5

100cc LVSH Analysis of Tomato

Loop Injection Detection Limit

hit “esc” to quit hit any key to continue

LVSH Analysis of Tomatoes - Scaled to show PPB Cmpds

MultiplePPB LevelMarkers

hit “esc” to quit hit any key to continue

• 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

LVSH Analysis of Tomatoes

Fresh vs Spoiled Tomatoes Area Counts (x10^6)Fresh Spoiled S/F Ratio

Ethyl Acetate 74 12 0.2

Nonanal 5.5 25 4.5

Decanal 2 23 11.5

Ethanol 84 85 1.0

Limonene 8 21 2.6

Dimethyl-Hexa- 0.2 248 1240.0HydroNaphthalene

2-Methyl Furan 157 43 0.3

DHHN/2-MF 0.001 5.8 4527.4

hit “esc” to quit hit any key to continue

Chocolate Peanuts100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Carob Peanuts100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Chocolate vs Carob Peanuts by LVSH/GCMS

Hexanal

Hexanal

hit “esc” to quit hit any key to continue

Whole Garlic vs Garlic Powder by LVSH/GCMS

Whole Garlic100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Garlic Powder100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

hit “esc” to quit hit any key to continue

Cheddar Cheese, Brand A100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Cheddar Cheese, Brand B100cc, LVSH60m, HP1, 0.32mm ID, 1um7032LVSH/7100/5973

Cheddar Cheese by LVSH/GCMS

Toluene

hit “esc” to quit hit any key to continue

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.

hit “esc” to quit hit any key to continue

Four Models of MiniCans

MC400 MC400L MC400S MC400V

hit “esc” to quit hit any key to continue

7032 Autosampler

Gas Phase Analysis Using MiniCan Silonite Coated Samplers

Surrogate Spiking

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

5-PointSulfur Gas

Calibrations

H2S

MeSH CS2

DMS

hit “esc” to quit hit any key to continue

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

hit “esc” to quit hit any key to continue

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.