. 2020 Sep 11;9(9):1276. doi: 10.3390/foods9091276

Table 2.

List of the common volatile metabolites detected in all lager beers under study, using HS-SPME/GC×GC-ToFMS, including relevant chromatographic data used to assess compounds identification and those compounds that were previously reported on lager beer. More details, including chromatographic data, are available in Table S1. Bold names represent the major detected volatile metabolites.

¹t_R (s) ^a	²t_R (s) ^a	Compound	CAS Number	MSI Level ^b	RI _Calc.^c	RI _Lit ^d	Previously Reported on Lager Beer
		Monoterpenic compounds
606	0.91	Linalool	78-70-6	1	1101	1101	[28,42,43,44,45]
624	0.97	Fenchol	1632-73-1	2	1113	1118	[28,45,46]
636	1.02	Myrcenol	543-39-5	2	1122	1103	[28,47]
696	1.15	Borneol	507-70-0	1	1163	1166	[28,46]
708	0.95	Menthol	1490-04-6	1	1172	1174	[28]
714	0.86	(−)-Terpinen-4-ol	20126-76-5	1	1176	1180	[28,45,48]
732	1.04	α-Terpineol	98-55-5	1	1192	1195	[28,42]
774	1.22	7-Methyl-3-methylene-6-octen-1-ol	13066-51-8	2	1219	1222	[28]
792	1.09	(+)-β-Citronellol	106-22-9	1	1233	1234	[28,42,43,45,47]
792	1.22	Nerol	106-25-2	1	1233	1237	[28]
864	0.65	Bornyl acetate	76-49-3	2	1287	1288	[28]
912	0.74	Methyl geraniate (isomer)	2349-14-6	1	1323	1324	[28,47]
948	0.65	Citronellol acetate	150-84-5	2	1353	1354	[28,47]
966	0.70	Neryl acetate	141-12-8	2	1364	1362	[28,42]
444	0.49	β-Myrcene	123-35-3	1	988	988	[28,42,43,45,47]
582	0.67	Fenchone	7787-20-4	2	1084	1093	[28]
666	0.79	(1R)-(+)-Camphor	464-49-3	1	1142	1147	√ [28]
810	0.91	p-Menth-4-en-3-one	5113-66-6	2	1246	1251	√ [28]
618	0.58	Rose oxide (isomer)	16409-43-1	1	1109	1114	√ [28,46]
720	0.54	m/z 91, 119, 39, 100	–	3	1180	–	√ [28]
		Sesquiterpenic compounds
1206	0.76	Nerolidol	7212-44-4	1	1571	1573	[28,43,47,49]
1212	0.79	Caryophyllenyl alcohol	–	2	1577	1569	[28,43,45]
1242	0.82	m/z 43, 67, 82, 41	–	3	1610	–	[28]
1260	0.68	Cubenol	21284-22-0	2	1634	1643	[28]
1272	0.75	τ-Cadinol	5937-11-1	2	1651	1651	[28,42]
1080	0.57	α-Caryophyllene (α-Humulene)	6753-98-6	1	1456	1456	[28,42,45]
1104	0.56	γ-Gurjunene	22567-17-5	2	1476	1472	[28]
1164	0.57	δ-Cadinene	483-76-1	2	1530	1524	[28,42,45]
1164	0.65	Calamenene	72937-55-4	2	1530	1528	[28,42]
1266	0.93	m/z 41, 67, 91, 39	–	3	1643	–	[28]
1164	0.78	m/z 91, 43, 41, 79	–	3	1530	–	[28]
1236	0.70	m/z 93, 43, 41, 80	–	3	1601	–	[28]
1308	0.65	m/z 43, 135, 41, 91	–	3	1701	–	[28]
1392	0.60	m/z 69, 41, 43, 55	–	3	1851	–	[28]
		Norisoprenoids
504	0.63	2,2,6-Trimethylcyclo-hexanone	2408-37-9	2	1034	1051	–
744	0.91	Safranal	116-26-7	2	1197	1201	–
774	0.82	β-Cyclocitral	432-25-7	2	1219	1225	–
852	0.59	Vitispirane	65416-59-3	2	1278	1289	–
900	0.64	Edulan I	41678-29-9	2	1314	1314	–
960	0.78	β-Damascenone (isomer)	23726-93-4	2	1360	1383	[43,45,46,47,49,50,51]
990	0.84	β-Damascenone (isomer)	23726-93-4	2	1383	1383	[43,45,46,47,49,50,51]
1074	0.77	Geranyl acetone	689-67-8	1	1451	1455	[47]
1110	0.72	α-Isomethyl ionone	127-51-5	2	1481	1487	–
		Esters
		Aliphatics
96	0.44	Ethyl acetate	141-78-6	2	611	611	[23,42,46,47,50,52,53]
138	0.45	Ethyl propanoate	105-37-3	1	685	696	[50]
174	0.43	Ethyl 2-methylpropanoate	97-62-1	2	748	751	[51]
186	0.48	2-Methylpropyl acetate	110-19-0	2	769	769	[42,43,45,47,50,52,53]
210	0.50	Ethyl butanoate	105-54-4	1	806	806	[23,42,43,45,46,47,49,50,51,52,53]
222	0.52	Butyl acetate	123-86-4	2	816	819	[53]
222	1.24	Ethyl 2-hydroxypropanoate	97-64-3	2	817	819	[48]
258	0.48	Ethyl 2-methylbutanoate	7452-79-1	1	848	851	[52,53]
264	0.49	Ethyl 3-methylbutanoate	108-64-5	2	853	857	[43,49]
294	0.62	2/3-Methylbutyl acetate	123-92-2	2	879	877	[23,42,43,45,46,47,49,50,52,53]
324	0.53	Ethyl pentanoate	539-82-2	2	905	906	[47,49,51]
342	0.57	Pentyl acetate	628-63-7	2	917	916	[54]
342	0.66	C₇ ester (m/z 43, 95, 97, 42)	-	3	917	-	–
372	0.64	Ethyl (E)-2-methyl-2-butenoate	5837-78-5	2	938	943	–
408	0.54	Ethyl 4-methylpentanoate	25415-67-2	2	963	967	[51]
414	0.52	Pentyl propanate	624-54-4	2	967	969	[54]
432	0.57	C₈ ester (m/z 43, 69, 56, 61)	-	3	980	-	–
456	0.57	Ethyl hexanoate	123-66-0	1	996	996	[23,42,43,45,46,47,48,49,50,51,52,53]
480	0.59	Hexyl acetate	142-92-7	1	1013	1006	[23,43,45,46,47,48,49,50,53]
522	0.65	Ethyl 2-hexenoate	1552-67-6	2	1042	1045	–
552	0.55	Ethyl 5-methylhexanoate	10236-10-9	2	1063	1072	[45,47]
570	0.58	C₉ ester (m/z 43, 56, 55, 41)	-	3	1075	-	–
600	0.55	Propyl hexanoate	626-77-7	2	1096	1101	–
600	0.57	Ethyl heptanoate	106-30-9	1	1096	1095	[23,43,45,48,50]
624	0.59	Heptyl acetate	112-06-1	2	1113	1113	[23,43,45,46,47,48,50]
642	0.60	Methyl octanoate	111-11-5	2	1125	1130	–
660	0.55	2-Octyl acetate (m/z 43, 87, 41, 55)	2051-50-5	3	1138	-	–
660	0.90	C₉ ester (m/z 57 85 41 59)	-	3	1138	-	–
678	0.54	2-Methylpropyl hexanoate	105-79-3	2	1150	1154	–
678	0.56	2-Ethylhexyl acetate	103-09-3	2	1150	1159	–
744	0.59	Ethyl octanoate	106-32-1	1	1196	1196	[23,43,45,46,47,49,50,51,52,53,54]
762	0.60	Octyl acetate	112-14-1	2	1210	1211	[23,43,45,47,49]
876	0.58	Ethyl nonanoate	123-29-5	1	1296	1295	[43,45,47]
924	1.12	C₁₁ ester (m/z 71, 117, 43, 89)	-	3	1333	-	–
948	1.03	C₁₁ ester (m/z 57, 71, 43, 41)	-	3	1351	-	–
972	0.66	C₁₂ ester (m/z 57, 43, 67, 41)	-	3	1369	-	–
978	0.93	3-Hydroxy-2,4,4-trimethylpentyl 2-methyl-propanoate	74367-34-3	2	1373	1364	[43]
996	0.64	Ethyl 9-decenoate	67233-91-4	2	1387	1388	[43,45,47,50]
1008	0.58	Ethyl decanoate	110-38-3	1	1396	1396	[23,42,43,45,46,48,49,50,52,53,54]
1068	0.56	3-Methylbutyl octanoate	2035-99-6	2	1446	1447	[43]
1164	0.62	Methyl dodecanoate	111-82-0	2	1530	1526	–
1176	1.03	3-Hydroxytridecanoate	107141-15-1	2	1542	1539	–
1230	0.56	Ethyl dodecanoate	106-33-2	2	1595	1594	[42,43,46,49,50,53]
1236	0.56	1-(1,1-Dimethylethyl)-2-methyl-1,3-propanediyl 2-methyl-propanoate	74381-40-1	2	1601	1607	–
1260	0.50	1-Methylethyl dodecanoate	10233-13-3	2	1634	1632	–
1296	0.78	Hexyl 2-hydroxybenzoate	6259-76-3	2	1684	1678	–
1326	0.53	Methyl tetradecanoate	124-10-7	2	1731	1726	–
1368	0.54	Ethyl tetradecanoate	124-06-1	2	1801	1801	[43]
1374	0.66	C₁₆ ester (m/z 120, 73, 138, 121)	-	3	1814	-	–
1380	0.50	1-Methylethyl tetradecanoate	110-27-0	2	1826	1834	–
		Aromatics
594	1.22	Methyl benzoate	93-58-3	2	1093	1096	–
702	1.07	Ethyl benzoate	93-89-0	2	1167	1172	[43,49]
714	1.35	Methyl 2-phenylacetate	101-41-7	2	1176	1179	–
714	1.46	2-Phenylethyl formate	104-62-1	2	1176	1174	–
810	1.13	Ethyl phenylacetate	101-97-3	1	1246	1248	[43,45,47]
828	1.15	2-Phenylethyl acetate	103-45-7	2	1260	1260	[23,42,43,45,46,47,48,49,50,51,52,53]
906	0.88	α,α-Dimethylphenylethyl acetate	151-05-3	2	1319	1320	–
948	1.06	2-Phenylethyl propanoate	122-70-3	2	1351	1357	–
972	1.16	3-Phenylpropyl acetate	122-72-5	2	1369	1388	–
1002	0.93	Phenylethyl 2-methylpropanoate	103-48-0	2	1392	1395	[46,49]
1062	1.00	2-Phenylethyl butanoate	103-52-6	2	1441	1441	[45,46,47]
1092	1.40	Ethyl 3-phenylpropenoate	103-36-6	2	1466	1480	[43,50]
1320	0.64	2-Octyl benzoate (m/z 105,77,70, 41)	6938-51-8	3	1721	-	–
1416	0.66	3,3,5-Trimethylcyclohexyl 2-hydroxybenzoate	118-56-9	2	1901	1904	–
		Acids
108	3.10	Acetic acid	64-19-7	2	637	631	[23,43,45,47]
270	4.81	3-Methylbutanoic acid	503-74-2	2	862	861	[43,48]
468	4.51	Hexanoic acid	142-62-1	1	1007	997	[23,43,45,46,47,48,50]
762	3.23	Octanoic Acid	124-07-2	2	1212	1210	[23,43,45,46,47,48,49,50,53]
858	3.19	Nonanoic acid	112-05-0	2	1284	1288	[43,47,53]
990	2.79	Decanoic acid	334-48-5	2	1384	1387	[43,45,46,47,53]
1212	1.96	Dodecanoic acid	143-07-7	2	1578	1609	[43,53]
1350	1.32	Tetradecanoic acid	544-63-8	2	1772	1788	–
1422	1.14	Pentadecanoic acid	1002-84-2	1	1915	1878	–
1446	1.05	Hexadecanoic acid	57-10-3	1	1965	1964	–
		Alcohols
		Aliphatics
84	0.61	1-Propanol	71-23-8	2	591	589	[23,42]
102	0.66	2-Methyl-1-propanol	78-83-1	2	622	613	[23,42,43,45,46,47,50,51,52,53]
114	0.75	1-Butanol	71-36-3	2	643	639	–
156	1.03	3-Methyl-1-butanol	123-51-3	1	718	718	[23,42,43,45,46,47,48,49,50,51,52,53]
162	0.86	2-Methyl-1-butanol	137-32-6	2	728	728	[42,50,52]
174	1.18	4-Penten-1-ol (m/z 67, 39, 68, 44)	821-09-0	3	749	-	–
204	3.31	2,3-Butanediol (isomer)	513-85-9	2	803	796	[45]
216	3.87	2,3-Butanediol (isomer)	513-85-9	2	814	796	[45]
246	1.02	4-Methyl-1-pentanol	626-89-1	2	838	843	–
258	1.03	3-Methyl-1-pentanol	589-35-5	2	848	851	–
288	1.05	1-Hexanol	111-27-3	1	875	880	[23,43,45,46,47,48,49,50]
324	0.85	2-Heptanol	543-49-7	2	905	907	–
420	1.07	1-Heptanol	111-70-6	2	975	970	[43,45,46,47,48,50]
432	1.01	1-Octen-3-ol	3391-86-4	1	980	982	[45,52]
450	0.98	6-Methyl-5-hepten-2-ol	4630-06-2	2	996	996	–
456	0.81	3-Octanol	589-98-0	1	996	1001	–
462	0.86	2-Octanol	123-96-6	2	1001	1004	[46]
504	0.97	2-Ethyl-1-hexanol	104-76-7	2	1030	1034	[43,45,48]
558	0.63	2-Octen-1-ol	22104-78-5	2	1067	1074	–
564	1.05	1-Octanol	111-87-5	1	1072	1074	[23,43,45,46,47,48,49,50,53]
606	0.84	2-Nonanol	628-99-9	2	1101	1107	[43,45]
684	1.08	C₉ alcohol (m/z 55, 67, 41, 68)	-	3	1159	-	–
702	0.63	2-Nonen-1-ol (isomer)	22104-79-6	2	1167	1151	–
708	1.00	1-Nonanol	143-08-8	2	1172	1174	[43]
714	0.64	2-Nonen-1-ol (isomer)	22104-79-6	2	1175	1179	–
840	1.15	9-Decen-1-ol	13019-22-2	2	1269	1272	[43]
846	0.97	1-Decanol	112-30-1	1	1274	1265	[43,45,46,47,49,50]
888	0.79	2-Undecanol	1653-30-1	1	1305	1309	[43,45]
1014	0.78	2-Dodecanol	10203-28-8	1	1401	1413	–
1104	0.92	1-Dodecanol	112-53-8	1	1476	1480	[43,47,48]
1410	0.66	1-Hexadecanol	36653-82-4	2	1889	1884	–
		Aromatics
582	1.99	Dimethylbenzenemethanol	617-94-7	2	1085	1086	–
630	2.99	Phenylethanol	60-12-8	1	1119	1122	[23,42,43,45,46,47,48,50,51,52,53]
642	1.28	4-Ethyl-1,3-benzenediol (m/z 123, 138, 43, 67)	2896-60-8	3	1126	-	–
774	1.52	C₁₀ Aromatic alcohol (m/z 115, 144, 63, 89)	-	3	1219	-	–
1332	1.93	2,6-Bis(1,1-dimethylethyl)-1,4-benzenediol	1020-31-1	2	1743	1683	–
		Cyclics
846	1.65	1-Butyl-2-cyclohexen-1-ol (m/z 97, 39, 41, 69)	88116-46-5	3	1274	-	–
		Sulfur compounds
78	0.33	Dimethyl sulfide	75-18-3	2	580	526	[52]
162	0.58	Dimethyl disulfide	624-92-0	2	727	731	[52]
330	1.02	1,3-Oxathiane	646-12-8	2	909	913	–
408	0.88	Dimethyl trisulfide	3658-80-8	2	963	969	[52]
438	2.86	3-(Methylthio)-1-propanol	505-10-2	2	985	989	[43,46,50,51,52]
456	0.74	5-Methyl-2-furanmethanethiol	59303-05-8	2	996	995	–
606	0.99	Ethyl 3-(methylthio)propanoate	13327-56-5	2	1101	1098	–
642	1.09	3-(Methylthio)-propyl acetate	16630-55-0	2	1126	1125	–
780	2.03	Benzothiazole	95-16-9	2	1224	1230	–
816	0.67	2-(1,1-Dimethylethyl)-thiophene	1689-78-7	2	1251	1251	–
		Volatile phenols
588	2.89	Guaicol	90-05-1	1	1090	1095	[49]
858	2.01	4-Ethylguaiacol	2785-89-9	2	1283	1290	[50]
900	2.99	4-Vinylguaiacol	7786-61-0	2	1316	1333	[43,46,47,50,51]

^a Retention times for first (¹t_R) and second (²t_R) dimensions in seconds. ^b Level of metabolite identification according to Sumner et al. [29]: (1) Identified compounds; (2) Putatively annotated compounds; (3) Putatively characterized compound classes; (4) Unknown compounds. ^c RI: Retention Index obtained through the modulated chromatogram. ^d RI, Retention Index reported in the literature for Equity-5 GC column or equivalents.