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What's in Your Beer? Part 2: GC/MS Static Head Space with a Highly

What's in Your Beer? Part 2: GC/MS Static Head Space with a Highly

Ken Lynam1, Vanessa Abercrombie2, Gustavo Serrano1, and Phil Stremple1 Pittcon 2018 What’s in Your Beer? POSTER # Part 2: GC/MS Static Head Space with a Highly Inert 624 Capillary GC Column 1 Agilent Technologies Inc. Wilmington, DE 19808, 2 Agilent Technologies Inc. Folsom, CA 95630 1040-4

Introduction Experimental Results Summer Style Beers Results and Discussion – Superior Organic Acid Response

Some ingredients in beer can be challenging to Example Total Ion Chromatogram Superior Organic Acid Responses- Test Probe Mix Other Cyanopropyl phenyl columns absorb organic acids Total Ion Chromatogram Total Ion Chromatogram separate and chromatograph. Common beer flavor 2 ppm aldehydes, alcohols and in water Hefe-Wizen, summer style wheat beer pA components include; fusel oils, aldehydes, esters, and Lemon Shandi Acetic acid Butanoic acid Octanoic acid pA 18 butanoic acid Octanoic acid organic acids. The polarity of a 6 % cyano propyl 18 propionic acid phenyl stationary phase (624) has been a traditional 3 1 Carbon dioxide 16 16 20 22 23 24 27 28 30 33 1 acetyl aldehyde choice for this type of analysis and works well. 2 methanol 1 5 6 8 2 Acetyl aldehyde 1 Carbon dioxide 3 25 3 ethanol 14 14 3 However, peaks shapes and low level detection of 4 acetone 2 Acetyl aldehyde 4 1-propanol 5 isopropanol 9 8 22 5 12 1 3 5 20 No detection on organic acids have been problematic for this phase. 6 tert butanol 3 Ethanol 6 Isobutyl alcohol 12 acetic acid Severe tailing 31 9 7 1-propanol Competitor’s Phase When inertness performance verified 624 columns are 300000 4 1-propanol 7 Acetic acid 10 8 butyraldehyde 16 8 Isoamyl alcohol (3-methyl 1-butanol) used, consistent organic acid performance is 9 2,3 butanedione 5 Ethyl acetate 10 15 9 Active amyl alcohol (2-methyl 1-butanol) 8 10 ethyl acetate all four acids observed achieved. 11 2-butanol 6 Isobutyl alcohol 6 27 10 8 at each level 6 12 isobutanol 7 Acetic acid 11 Butanoic acid ethyl 13 1-butanol 12 (banana oil) 200000 14 2,3 pentanedione 8 Isoamyl alcohol (3-methyl 1-butanol) 13 Active 6 4 Static head space GC/MS is an excellent way to 15 ethyl propionate 9 Active amyl alcohol (2-methyl 1-butanol) 14 α-pinene 16 2 15 camphene min profile alcoholic beverages such as a centuries old 17 3-pentanol 10 Isobutyl acetate 4 10 12 14 16 18 20 22 24 26 16 β−pinene min 18 isoamyl alcohol 10 12 14 16 18 20 22 24 26 11 Butanoic acid ethyl ester 17 b-Myrcene favorite malted barley beverage, beer. The recipes 19 active amyl alcohol 10 18 α-phelladrene and components in these beverages are as diverse as 20 isobutyl acetate 12 Isoamyl acetate (banana oil) Column: Agilent J&W DB-624UI 30 m x 0.32 mm x 1.8 um (p/n 123-1334UI) 19 Hexanoic acid ethyl ester Column: Agilent J&W DB-624UI 30 m x 0.32 mm x 1.8 um vs competitor premium column 100000 21 1-pentanol ° ° ° ° ° 17 13 Active amyl acetate 20 d-limonene Oven: 35 C 7.45 min hold, 6.72 /min to100 C(2.23min hold),10.08 /min to 220 C(4.47 min hold), the individual yeast strains and varietal hops that are 8 22 ethyl butanoate 12 12 Oven: 35°C 7.45 min hold, 6.72°/min to100°C(2.23min hold),10.08 °/min to 220°C(4.47 min hold), 18,19 4 23 16.79 °/min (4.17 min hold) 23 hexanal 14 Hexanoic acid ethyl ester 4 21 o-Cymene 16.79 °/min (4.17 min hold) on the list of ingredients. What flavor components are 26 21 26 Carrier : Helium 39.6 cm/s (approx. 2.6 mL/min) set at 35°C, EPC-Constant Flow ° 14 21 32 24 Isoamyl acetate 22 α-Terpinene Carrier : Helium 39.6 cm/s (approx. 2.6 mL/min) set at 35 C, EPC-Constant Flow 7 15 Phenyl ethyl alcohol Inlet: Split, 20:1 at 250°C (total flow approx 51 mL/min, and 11.2 psi) ° positive indicators of a good beer and which are not is 4 6 11 12 29 25 active amly acetate 23 α-Terpinolene Inlet: Split, 20:1 at 250 C (total flow approx 51 mL/min, and 11.2 psi) 1 13 Inlet liner: Ultra Inert with wool 2 5 26 1-hexanol 16 Octanoic acid ethyl ester 25 24 Phenyl ethyl alcohol Inlet liner: Ultra Inert with wool one facet of the craft of making fine beer. Single 7 9 2 17 Detector: FID at 280°C, H2 @ 40 mL/min, Air @ 400 mL/min, N2 makeup @ 30 mL/min ° 27 heptaldehyde 15 14 25 Octanoic acid ethyl ester Detector: FID at 280 C, H2 @ 40 mL/min, Air @ 400 mL/min, N2 makeup @ 30 mL/min 0 28 octanal 17 Octanoic acid Quad GC/MS is a great starting point for helping to 2 16 29 26 Terpinen-4-ol 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 29 1-phenyl ethanol 10 14 16 18 19 13 19 18 Acetic acid, phenyl ethyl ester 24 27 α-Terpineol identify and monitor flavor components. 30 11 17 7 10 13 15 18 28 30 28 Acetic acid, phenyl ethyl ester Column: Agilent J&W DB-624UI 30 m x 0.25 mm x 1.4 um (p/n 122-1334UI ) 31 α-methybenzyl acetate 19 Decanoic acid ethyl ester 11 29 Decanoic acid ethyl ester Carrier : Helium 48.9 cm/s (approx. 1.8 mL/min) set at 35°C, EPC-Constant Flow 32 m-anisaldehyde 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 30 β-Bisabolene Sampler: 7697A Headspace. temps: 85 °C oven, 1 ml loop 85°C, transfer line 100°C, 20 min vial eq. time,0.20 min injection 33 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 Conclusions Static headspace GC/MS chromatograms of beers time, 15 psi loop fill pressure, 20 psi loop ramp rate, loop final pressure 10 psi, 0.05 min loop eq. time Inlet: Split, 5:1 at 220°C (total flow approximately 14 mL/min, and 14.9 psi) and spirits illustrate the value of using inertness Inlet liner: Ultra Inert straight single taper, 1 mm (p/n 5190-4047) Total Ion Chromatogram Total Ion Chromatogram Total Ion Chromatogram performance verified 624 columns for this type of Oven: 35°C 5.66 min hold, 8.8°/min to100°C (1.70 min hold),13.3 °/min to 220°C(3.39 min hold), 22.1 °/min (3.43 min hold) Detector: MSD Scan range 30-400 AMU; MSD temps, source 230°C, quad 150 °C, transfer line 110 °C Kolsch, clear crisp finish Pilsner style hops Tangerine Ale Light Lager analysis. Key elements of this type of analysis are the • Static headspace GC/MS profiles show differences and separation of amyl and iso-amyl alcohols, their esters, 1 Carbon dioxide similarities among beer styles- good for profiling 1 Carbon dioxide aldehyde peak shapes and detector response for 2 Acetyl aldehyde 2 4 10 2 Acetyl aldehyde 6 1 acetyl aldehyde organic acids. Obtaining headspace profiles can be a 3 Ethanol 3 Ethanol • Organic acid response superior using a highly inert 624 1 7 3 6 12 2 4 Isobutyl aldehyde 4 Isobutyl aldehyde ethanol column tremendous aide in understanding flavor 24 5 1-propanol 5 1-propanol 3 1-propanol development, tracking flavor stability and 6 Ethyl acetate 6 Ethyl acetate 4 ethyl acetate • Choose inert components for optimal results authentication of fine crafted alcoholic beverages. 7 Diethyl allyl alcohol 7 Diethyl allyl alcohol 23 300000 20 8 Isobutyl alcohol 5 isobutanol Comparing GC/MS profiles of various summer style 9 Isobutyric acid methyl ester 8 Isobutyl alcohol 6 isoamyl alcohol • Better analytical tools for making better beer-yes beers and some of their flavor elements will keep 9 Acetic acid 10 Acetic acid 11 Propionic acid ethyl ester 7 active amyl alcohol 10 Propionic acid ethyl ester things hopping. 12 Isoamyl alcohol (3-methyl 1-butanol) 11 Isoamyl alcohol (3-methyl 1-butanol) 8 isobutyl acetate 13 13 Active amyl alcohol (2-methyl 1-butanol) 8 12 Active amyl alcohol (2-methyl 1-butanol) 14 Isobutyl acetate 9 ethyl butanoate 21 200000 13 Isobutyl acetate 5 15 Butanoic acid ethyl ester 10 Isoamyl acetate 5 14 Butanoic acid ethyl ester 16 Isoamyl acetate (banana oil) 11 References 22 17 Active amyl acetate active amly acetate 15 Isoamyl acetate (banana oil) 19 25 18 Isobutryic acid isobutyl ester 12 16 Active amyl acetate 19 1-butanol 2 13 1-phenyl ethanol 17 Isobutryic acid isobutyl ester 20 b-Myrcene 14 Screen Beer by GC/MS Static Headspace with the Agilent J&W DB-624 Ultra Inert 21 Hexanoic acid ethyl ester 14 ethyl octanoate Capillary Column, K. Lynam, Agilent Publication # 5991-1136EN 18 Hexanoic acid ethyl ester 16 100000 19 Isoamyl butanoate (check name) 22 Isoamyl butanoate 15 octanoic acid Analysis of Distilled Spirts Using an Agilent J&W DB-Wax Ultra Inert Capillary GC 23 propionic acid 2 methyl,2 methyl butyl ester 2 27 Column, K. Lynam and Yun Zou, Agilent Publication # 5991-6638EN 20 Linolool 3 15 16 24 Limonene 11 12 phenyl ethyl acetate 21 Phenyl ethyl alcohol 4 14 28 25 3-hexanoic acid 3 methyl 3 hexanoate Agilent J&W DB-624 Ultra Inert Capillary Column Screens Distilled Spirits by GC Static 7 9 15 26 1 16 17 10 11 17 18 30 8 13 17 ethyl decanoate 22 Octanoic acid ethyl ester 29 26 Linolool 9 18 Headspace, K. Lynam, Agilent Publication # 5991-0659EN 27 Phenyl ethyl alcohol 18 decanoic acid 23 Octanoic acid 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 28 Octanoic acid ethyl ester 0 24 Acetic acid, phenyl ethyl ester 29 Octanoic acid 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 30 Acetic acid, phenyl ethyl ester

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