Post on 14-Dec-2015
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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.