Phytologia (Apr 4, 2016) 98(2 119 ) Comparison of volatile oils of Juniperus coahuilensis in fresh seed cones vs. cones in fresh gray fox scat Robert P. Adams Biology Department, Baylor University, Box 97388, Waco, TX USA 76798, [email protected] Shirley Powell and A. M. Powell Herbarium, Sul Ross State University, Box C-64, Alpine, TX 79832 USA [email protected] ABSTRACT The composition of volatile oil from Juniperus coahuilensis berries (seed cones) in fox scat is very similar to that of berries taken directly from trees. The most notable difference is that the percent yield is significantly higher from scat than intact fresh berries. This may be partially explained by the fact that the scat berry has been partially masticated and thus amenable to steam during distillation, whereas A the fresh seed cones have their skin intact, impeding the loss ofterpenes in distillation. second factor is that sugars, starch and protein may have been partially removed during digestion. Thus, the yield from the 'depleted' berry would naturally contain a higher percent volatile oil relative to remaining cellulosic pulp. The gray fox does not extract most of the terpenes from juniper berries. The nearly intact berries, containing most ofthe terpenes, are excreted in the scat. This undoubtedly results in the loss of some or considerable amounts of nutrients, but the food source is so plentiful, that the loss of nutrients, due to incomplete digestion, may not be significant to the health of the gray fox. Published on-line www.phytologia.org Phytologia 98(2): 119-127 (Apr 4, 2016). ISSN 030319430. KEY WORDS: Juniperus coahuilensis, volatile oils, gray fox scat, terpenes, composition. Based on identification of plant material in gray fox Urocyon cinereoargenteus) scat, White et ( al. (1999) found that gray fox obtained over half (51.3%) of its diet from Juniperus osteosperma berries (seed cones) in eastern Utah. They also reported that gray fox is adept at climbing trees and may have used juniper trees for resting, food source, or as escape cover. Analysis of the berry hull (pulp surrounding the seed) in different seasons, over two years, showed the hull was about 63 - 68% of the whole seed cone. The hulls (pulp) contained 3.8 - 5.2% protein, 15.9 - 28.3% starch and sugars, 25.8 - 26.8% crude fat, and 27.4 - 32.1% ADF (Acid Detergent Fiber). The juniper seeds were not digested by gray fox. The summer of 2013 presented a remarkable year for the production of a bumper crop of seed cones (berries) of TX Juniperus coahuilensis near Alpine, (Fig. 1). Notice the limbs are loaded with berries and leaning. Many branches were so loaded with berries that they drooped to the ground. Careful observation revealed that in Nov. and Dec. 2013, gray foxes were feeding almost exclusively on the seed cones of J. coahuilensis and these seed cones accounted for ca. 90% ofthe volume in the scat (Fig. 2). Fig. 1. J. coahuilensis with branches loaded with fruits. 120 Phytologia (Apr 4, 2016) 98(2) Gray foxes were often seen feeding on freshly fallen berries on the ground (Fig. 3), or up in a juniper eating the berries directly from the limbs (Fig. 4). Fig. 2. Fresh gray fox scat with nearly intactjuniper Fig. 3. Gray fox eating J. coahuilensis berries berries (seed cones). on the ground. In addition to gray fox, mule deer Odocoileus hemionus) ate berries from the ground (Fig. 5) or ( even resorted to considerable effort to eat berries directly from the trees (Fig. 6). Western blue birds also fed on J. coahuilensis berries, both on the ground (Fig. 7) and in trees. Fig. 4. Gray fox injuniper tree eating berries. Fig. 5. Mule deer eating berries from the ground. Cunningham, Kirkendall and Ballard (2006) reported Juniperus monosperma berries accounted for 0.0 - 22.5% of the gray fox's diet and from 0.0 to 18.25% of the diet of coyotes in central Arizona. Thacker et al. (2011), by analyzing the terpenes in fecal pellets of greater sage-grouse in Utah, correctly identified the sagebrush species that the sage-grouse was feeding on using crude terpene profiles. As far as known, there are no reports on the composition ofessential oil ofJ. coahuilensis berries present in fresh gray fox scat. The composition ofthe volatile leafoil ofJ. coahuilensis has been reported (Adams, 2000, 2014), but there are no reports on the composition of the volatile oil of the berries (seed cones). Phytologia (Apr 4, 2016) 98(2 121 ) Fig. 6. Mule deer expending great effort to reach Fig. 7. Western blue birds eating J. coahuilensis berries in the J. coahuilensis trees. berries on the ground. The changes in terpenes during passage through the gray fox digestive tract are not known. The purpose ofthe present paper is to compare the volatile oil compositions offresh J. coahuilensis seed cones vs. fresh fox scat in which ca. 90% ofthe scat consisted ofJ. coahuilensis seed cones. MATERIALS AND METHODS Fresh, mature seed cones were collected from J. coahuilensis trees in Dec., 2013 at the home of Mike and Shirley Powell, approx. 8 mi se of Alpine, on Tex 118, thence e 2 mi on Mile High Rd., 30° 16.147' N, 103° 33.522' W, 5324 ft (1623 m). Adams 14649-14653 ripe seed cones of J. coahuilensis ; Adams 14654-14658 fresh fox scat was collected at the small location and frozen. Leaves for volatile oil , were collected from J. coahuilensis 85 km north ofLa Zarca, Durango, Mexico, Adams 6829-6831. , mg Fresh frozen J. coahuilensis seed cones (13-33 g) were co-steam distilled with 2 of undecane mg and 2 methyl decanoate (internal standards) for 2 h using a circulatory Clevenger-type apparatus (Adams, 1991). In the same manner, individual frozen fox scat (3.88 - 8.74 g) were distilled. The oil samples were concentrated (diethyl ether trap removed) with nitrogen and the samples stored at -20° C until analyzed. The extracted scat and leaves were oven dried (48h, 100° C) for the determination of oil yields. MSD The oils were analyzed on a HP5971 mass spectrometer, scan time 1/ sec., directly coupled to a HP 5890 gas chromatograph, using a J & W DB-5, 0.26 mm x 30 m, 0.25 micron coating thickness, fused silica capillary column (see Adams, 2007 for operating details). Identifications were made by HP library searches of our volatile oil library (Adams, 2007), using the Chemstation library search routines, coupled with retention time data of authentic reference compounds. Quantitation was by FID on an HP 5890 gas chromatograph using a J & W DB-5, 0.26 mm x 30 m, 0.25 micron coating thickness, fused silica capillary column using the HP Chemstation software. 122 Phytologia (Apr 4, 2016) 98(2) RESULTS AND DISCUSSION The compositions ofthe berries in the fox scat are very similar to berries taken directly from trees (Table 1). The most notable difference is that the percent yield is significantly higher from scat than intact fresh berries (Table 2). This may be partially explained by the fact that the berry skin and layer of wax was somewhat disrupted by mastication in the scat (Fig. 8), whereas, fresh seed cones remained intact during distillation. Thus, the pulp was more easily A subjected to steam in the scat berries. second factor is that sugars, starch and protein may have been partially removed during digestion. Thus, the yield from the 'depleted' berry would naturally contain a higher percent volatile oil relative to remaining A cellulosic pulp. third factor might be the enzymatic removal of glucosides attached to terpene-glucosides, leaving free terpenes that easily volatilize during A distillation. fourth factor is that the scat berries and tree berries likely did not come from the same tree. Notice the composition of the berries from tree 14649 is more like that of the scat berries for a-pinene, terpinolene and terpinen-4-ol. It is possible that the scats collected did not come from any ofthe trees from Fig. 8. Fox scat with J. coahuilensis berries, which berries were collected. From the current limited study, one can not say which factor was most important (or ifthere may be additional factors, not considered). Several terpenes are in larger concentration (Table 2) in the scat: a-pinene, sabinene, and the three diterpenes - abietadiene, 4-epi-abeital, and abieta-7,13-dien-3-one. Two terpenes are larger in the cones: terpinolene and terpinen-4-ol (Table 2). The volatile berry oils differ in many components, both quantitatively and qualitatively, from the volatile leaf oil ofJ. coahuilensis from La Zarca, Mexico (Table 3). This likely reflects both ontogenetic variation between berries and leaves as well as geographic variation in the leaf oils of J. coahuilensis (Figs. 4, 5, Adams, 2000). Although, Adams (2000) found the leafoil from Alpine, TX to be very similar to that from Ciudad Chihuahua (CM), north ofLa Zarca. Although there appear to be no reports on the fate of terpenes in gray fox, there are a few such papers on small mammals. McLean et al. (1993) fed Eucalyptus radiata leaves to ringtail possums and found terpene derived metabolites increased in the urine. They concluded possums detoxify dietary terpenes by polyoxygenating the terpenes so the highly polar metabolites will be water soluble and excreted in urine. Boyle et al. (2000) fed p-cymene to Koala and found no p-cymene or metabolites in the feces, but oxidized metabolites of p-cymene were excreted in urine; a very similar mechanism as found in possum (McLean et al., 1993). Other methods of detoxifying Juniperus terpenes in woodrats (Neotoma) are discussed by Adams etal. (2014,2016). ) Phytologia (Apr 4, 2016) 98(2) 123 In conclusion, it appears, in this preliminary study, that gray fox does not extract most of the terpenes from juniper berries. The nearly intact berries, containing most of the terpenes. are excreted in the scat. This undoubtedly results in the loss of some or considerable amounts of nutrients, but the food source is so plentiful, that the loss ofnutrients, due to incomplete digestion, may not be significant to the health ofthe gray fox. ACKNOWLEDGEMENTS This research was supported in part with funds from Baylor University. LITERATURE CITED Adams, R. P. 1991. Cedar wood oil - analysis and properties. In Modem Methods ofPlant Analysis: Oils and Waxes. Edits., H. F. Linskins and J. F. Jackson, pp. 159 - 173, Springier-Verlag, Berlin, Germany. Adams, R. P. 2000. The senate leafmargined Juniperus (Section Sabina) ofthe western hemisphere: Systematics and evolution based on leafessential oils and Random Amplified Polymorphic DNAs (RAPDs), Biochem. Syst. Ecol. 28: 975-989. Adams, R. P. 2007. Identification ofessential oils by gas chromatography/ mass spectrometry, 4th edition. Allured Publ., Carol Stream, 1L, USA. Adams, R. P. 2014, The junipers ofthe world: The genus Juniperus. 4th ed. Trafford Publ., Victoria, BC, Canada. Adams, R. P., M. M. Skopec and J. P. Muir. 2014. Comparison ofleafterpenoids and tannins in Juniperus monospenna from woodrat Neotoma stephensi browsed and non-browsed trees. ( Phytologia 96: 63-70. Adams, R. P., M. M. Skopec and J. P. Muir. 2016. Comparison ofleafterpenoids and tannins in Juniperus osteospenna from woodrat Neotoma stephensi) browsed and non-browsed trees. ( Phytologia 98: 17-25. Cunningham, S. C., L-B. Kirkendall and W. Ballard. 2006. Gray fox and coyote abundance and diet responses after a wildfire in central Arizona. West. North Am. Natl. 66: 169-180. McLean, S., W. J. Foley, N. W. Davies, S. Brandon, L. Duo and A. J. Blackman. 1993. Metabolic fate of dietary terpenes from Eucalyptus radiata in common ringtail possum Pseudocheinis peregrinus). J. ( Chem. Fcol. 19: 1625-1643. Boyle, R., S. McLean, W. J. Foley, B. D. Moore. N. W. Davies and S. Brandon. 2000. Fate ofthe dietary terpene, p-cymene, in he male koala. J. Chem. Ecol, 26: 1095-1111. Thacker. E. T., D. R. Gardner, T. A. Messmer, M. R. Guttery and D. K. Dahlgren. 2011. Using gas chromatography to determine winter diets ofgreater sage-grouse in Utah. J. Wildlife Management 76: 588-592. White, C. G., J. T. Flinders, R. G. Cates, B. H. Blackwell and Ff. D. Smith. 1999. Dietary' use ofUtah USDA jumper berries by gray fox in eastern Utah. Forest Service Proc. RMRS-P-9: 219-232. 5 . 124 Phytologia (Apr 4, 2016) 98(2) Table 1 Comparison of the volatile oil compositions of fresh seed cones vs. fox scat of J. coahuilensis Components with considerable variation between scat and seed cones (berries) are in bold. Kl Compound scat scat scat scat scat cones cones cones cones 14654 14655 14656 14657 14658 14649 14650 14651 14653 percent yield (% ODW) 1.38 1.95 1.54 1.52 1.32 0.49 0.42 0.26 0.30 921 tricyclene t t t t t t t t t 924 a-thujene 2.0 1.8 2.1 2.3 1.8 1.5 1.6 2.1 1.1 932 a-pinene 14.4 13.0 17.7 8.9 10.2 16.7 6.0 3.0 3.2 946 camphene 0.1 0.2 0.2 0.2 0.2 0.3 0.3 t t 961 verbenene - - - - - 0.8 - - 0.2 969 sabinene 46.9 44.0 51.9 55.4 50.0 21.9 19.9 20.1 22.1 974 p-pinene 0.9 0.9 0.9 1.0 0.7 0.9 0.5 0.2 0.3 988 myrcene 0.8 0.9 1.0 1.8 0.8 0.5 0.3 0.5 0.8 1002 ct-phellandrene t t t t t t 0.2 0.1 0.2 1014 a-terpinene 0.8 1.0 0.8 1.1 1.1 1.5 2.9 3.9 2.8 1020 p-cymene 0.5 0.5 0.7 0.6 0.6 0.6 1.2 1.1 1.0 M 024 limonene 2.1 1.7 2.2 2.3 2.0 2.6 1.7 2.4 1.5 1025 p-phellandrene 1.4 1.0 1.5 1.6 1.3 1.8 1.1 1.5 1.0 1 1044 (E)-p-ocimene t t t t t t t t t M054 y-terpinene 1.4 1.9 1.4 2.1 1.9 2.8 5.0 6.7 5.3 p065 cis-sabinene hydrate 1.7 1.7 1.1 1.5 1.5 1.6 2.0 1.8 2.0 M086 terpinolene 0.4 0.5 0.4 0.7 0.5 1.0 1.4 1.8 1.6 M098 trans-sabinene hydrate 3.5 3.5 1.5 2.4 2.4 2.8 3.1 3.9 2.8 1099 a-pinene oxide 0.4 0.4 0.2 0.1 t 0.3 0.2 t t 1112 trans-thujone 0.1 0.1 0.1 t t 0.2 0.3 0.3 0.3 1118 cis-p-menth-2-en-1-ol 0.3 0.4 0.3 0.4 0.5 0.7 1.3 1.4 1.6 M122 a-camphenal 0.6 TO 0.5 0.3 0.6 2.0 2.5 1.3 1.3 Ml 23 terpene,67.81 „156,168 0.8 1.3 0.7 0.6 0.8 1.4 1.4 1.3 1.4 pi 135 trans-pinocarveol 0.7 0.7 0.4 0.4 0.8 2.6 1.7 1.3 1.8 Ml 37 trans-sabinol 0.6 1.2 0.8 0.5 0.9 1.1 2.1 1.2 1.7 1137 trans-verbenol 2.0 2.1 1.5 0.8 1.5 5.3 3.1 1.1 1.8 Ml 54 sabina ketone 1.5 1.4 1.2 1.0 1.4 1.9 4.0 3.7 3.9 1160 pinocarvone 0.2 0.3 0.2 0.2 0.6 0.6 0.2 0.4 t pi 66 p-mentha-1 ,5-dien-8-ol 0.1 0.2 0.2 t 0.2 0.7 0.9 0.3 0.6 M169 terpene,92,81 ,134,152 0.7 1.0 0.6 0.6 1.0 0.9 1.8 1.6 1.7 1174 terpinen-4-ol 3.1 4.4 2.3 4.2 4.4 6.8 13.9 18.1 20.2 1181 thuj-3-en-10-al 0.4 0.5 0.4 0.3 0.6 0.5 1.1 1.1 1.2 pTl86 a-terpineol 0.3 0.3 0.2 0.2 0.3 0.5 0.6 0.7 0.8 1195 myrtanal 1.2 1.5 1.1 1.1 1.5 2.3 3.7 3.1 4.0 p196 myrtanol 0.4 0.5 0.4 t 0.4 1.0 0.7 0.3 0.1 1204 verbenone 0.6 0.7 0.4 0.3 0.5 1.7 1.2 0.9 1.1 p21 trans-carveol 0.4 0.4 0.3 0.2 0.4 1.2 1.0 0.6 0.7 M223 citronellol t 1.0 0.2 t 0.4 1.2 0.3 0.5 0.3 1235 cis-chrysanthenyl acetate 0.2 t 0.1 t 0.3 t - - - 1238 cumin aldehyde 0.2 0.2 0.2 0.3 0.3 0.6 0.4 0.4 f t 1239 carvone 0.2 0.2 0.2 0.1 0.3 0.4 0.5 0.5 0.4 1269 perilla aldehyde 0.1 0.2 0.2 t 0.2 0.3 0.6 0.4 0.4 1284 bornyl acetate 0.3 0.3 0.3 0.1 0.2 0.5 1.0 0.7 0.7 pi289 p-cymen-7-ol_ 0.3 0.4 0.3 0.2 0.8 0.6 0.4 0.2 0.6 1325 p-mentha-1 ,4,dien-7-ol 0.5 0.4 0.3 0.1 0.4 0.9 1.5 1.6 1.4 M400 tetradecane t t t t t t t t t 1417 (E)-caryophyllene 0.2 t t t t t t t t 1480 germacrene D 0.9 t t t t t t t t M513 y-cadinene 0.2 t t t t t t t t 1522 5-cadinene t t t 0.1 t t t t t 1548 Felemol 0.4 0.5 0.2 0.5 0.4 0.4 0.2 0.2 0.1 1574 germacrene D-4-ol t t t t t t t t t Phytologia (Apr 4, 2016) 98(2 125 ) KI Compound scat scat scat scat scat cones cones cones cones 14654 14655 14656 14657 14658 14649 14650 14651 14653 pi 582 caryophyllene oxide 0.3 0.3 0.2 0.2 0.3 0.4 0.2 0.3 t M608 humulene epoxide 0.3 0.2 0.2 0.2 0.2 0.5 0.2 0.2 t M627 1-epi-cubenol t 0.2 t t t t t t t MI649 (3-eudesmol 0.2 t t t t t t t t 1652 a-eudesmol t 0.1 t t t t t t t 1685 germacra-4(15),5,10(14)- - t t t t t t t t trien-1-al M959 hexadecanoic acid t 0.2 t t t 0.2 O C\l 0.7 0.2 2022 cis-abieta-8,12-diene t t t t t - - t - 2055 abietatriene - - - t t t t t t [[2087 abietadiene 0.3 0.2 t 0.2 0.4 - t - 2298 4-epi-abietal 0.2 0.3 t 0.3 0.2 - - t - 2312 abieta-7,1 3-dien-3-one 0.4 0.4 t 0.4 0.7 - 0.2 | | 2343 4-epi-abietol - - - t t t t t t [2401 abietol t 0.2 t t 0.2 - - t - ] KI = Kovats Index (linear) on DB-5 column. Compositional values less than 0. 1% are denoted as traces (t). Unidentified components less than 0.5% are not reported. Table 2. Statistical analysis ofselected components ofoils in scat vs. seed cones. KI Compound scat avg cones avg P value significance " percent yield (% ODW) 1.54 0.39 2 x 10-5 sfe* 932 a-pinene 12.84 7.22 0.68 ns 969 sabinene 49.64 21.00 x 10-5 ** 1 1086 terpinolene 0.50 1.45 3x10-4 ** ** 1174 terpinen-4-oI 3.58 14.75 2x10-3 ** 2087 abietadiene 0.07 0.01 8x10-3 2298 4-epi-abietal 0.20 0.02 8x10-3 ** 2312 abieta-7, 3-dien-3-one 0.39 0.03 1.5x10-2 * 1 126 Phytologia (Apr 4, 2016) 98(2) Table 3. Comparison ofthe volatile oil compositions of fresh seed cones and leafoil from La Zarca, MX, Adams 6829 (Adams, 2000). Components with considerable difference between seed cone oils and leaf oil are in bold. Kl Compound cones cones cones cones leaf oil 14649 14650 14651 14653 6829 percent yield (% ODW) 0.49 0.42 0.26 0.30 1.23 921 tricyclene t t t t t 924 a-thujene 1.5 1.6 2.1 1.1 1.6 932 a-pinene 16.7 6.0 3.0 3.2 2.6 946 camphene 0.3 0.3 t t t 961 verbenene 0.8 - - 0.2 969 sabinene 21.9 19.9 20.1 22.1 35.5 974 (3-pinene 0.9 0.5 0.2 0.3 0.5 988 myrcene 0.5 0.3 0.5 0.8 2.6 1002 a-phellandrene t 0.2 0.1 0.2 0.3 1014 a-terpinene 1.5 2.9 3.9 2.8 3.6 1020 p-cymene 0.6 1.2 1.1 1.0 0.3 1024 limonene 2.6 1.7 2.4 1.5 1.8 1025 p-phellandrene 1.8 1.1 1.5 1.0 1.7 1026 1,8-cineole - - - 0.5 1044 (E)-p-ocimene 0.2 t t t t 1054 y-terpinene 2.8 5.0 6.7 5.3 5.6 1065 cis-sabinene hydrate 1.6 2.0 1.8 2.0 1.5 1067 cis-linalool oxide (furano-) - - - t 1086 terpinolene 1.0 1.4 1.8 1.6 1.9 1098 trans-sabinene hydrate 2.8 3.1 3.9 2.8 2.2 1099 a-pinene oxide 0.3 0.2 - t t 1112 trans-thujone 0.2 0.3 0.3 0.3 t 1118 cis-p-menth-2-en-1-ol 0.7 1.3 1.4 1.6 0.9 1122 a-camphenal 2.0 2.5 1.3 1.3 1123 terpene,67,81,109,156,168 1.4 1.4 1.3 1.4 - 1135 trans-pinocarveol 2.6 1.7 1.3 1.8 - 1136 trans-p-menth-2-en-1-ol - - - - 0.6 1137 trans-sabinol 1.1 2.1 1.2 1.7 1137 trans-verbenol 5.3 3.1 1.1 1.8 1142 camphor - - - - 0.4 1144 neo-isopulegol - - - - 0.4 1145 camphene hydrate - - - - t 1148 citronellal - - - - 4.1 1154 sabina ketone 1.9 4.0 3.7 3.9 - 1155 iso-isopulegol - - - - 0.1 1160 pinocarvone 0.6 0.6 0.2 0.4 - 1165 borneol - - - - t 1166 p-mentha-1 ,5-dien-8-ol 0.7 0.9 0.3 0.6 - 1166 coahuilensol - - - - t 1169 terpene,92,81,134,152 0.9 1.8 1.6 1.7 - 1174 terpinen-4-ol 6.8 13.9 18.1 20.2 12.4 1181 thuj-3-en-10-al 0.5 1.1 1.1 1.2 . 1186 a-terpineol 0.5 0.6 0.7 0.8 0.5 1195 cis-piperitol - - - - 0.2 1195 myrtanal 2.3 3.7 3.1 4.0 - 1196 myrtanol 1.0 0.7 0.3 0.1 t 1204 verbenone 1.7 1.2 0.9 1.1 _ 1207 trans-piperitol - - - - 0.3 1215 trans-carveol 1.2 1.0 0.6 0.7 . 1223 citronellol 1.2 0.3 0.5 0.3 4.9 1235 cis-chrysanthenyl acetate - - - - t Phytologia (Apr 4, 2016) 98(2) 127 Kl Compound cones cones cones cones leaf oil 14649 14650 14651 14653 6829 1238 cumin aldehyde 0.3 0.6 0.4 0.4 - 1239 carvone 0.4 0.5 0.5 0.4 - 1269 perilla aldehyde 0.3 0.6 0.4 0.4 1274 pregeijerene B - - - - 0.4 1284 bornyl acetate 0.5 1.0 0.7 0.7 t 1289 p-cymen-7-ol 0.6 0.4 0.2 0.6 - 1325 p-mentha-1,4,dien-7-ol 0.9 1.5 1.6 1.4 - 1387 (3-cubebene - - - - t 1389 p-elemene - - - - 0.1 1400 tetradecane - t t t t 1417 (E)-caryophyllene t t t t t 1448 cis-muurola-3,5-diene - - - - 0.2 1452 a-humulene - - - - t 1468 pinchotene acetate - - - - t | 1475 trans-cadina-1 (6),4-diene - - - - 0.2 1480 germaerene D - t t t t 1489 P-selinene - - - - t 1493 trans-muurola-4(14),5-diene - - - - 0.2 1496 valencene - - - - 0.2 1500 a-muurolene - - - - t 1513 y-cadinene 0.2 t t t t 1522 6-cadinene t t t t 0.1 1545 selina-3,7(1 1)-diene - - - - t 1548 elemol 0.4 0.2 0.2 0.1 5.8 1574 germacrene D-4-ol t t t t t 1582 caryophyllene oxide 0.4 0.2 0.3 - t 1608 humulene epoxide 0.5 0.2 0.2 - t 1627 1-epi-cubenol 0.5 t t t t 1630 y-eudesmol - - - - 1.0 1649 p-eudesmol 1.2 t t t t 1652 a-eudesmol 1.3 t t t t 1670 bulnesol - - - - 0.5 1685 germacra-4(15),5,1 0(14)- - t t t - trien-1-al 1746 8-a-11-elemodiol - - - - 0.3 1792 8-a-acetoxyelemol - - - - 0.7 1959 hexadecanoic acid 0.2 0.2 0.7 0.2 - 1987 manoyl oxide - - - - t 2022 cis-abieta-8,12-diene - - t - - 2055 abietatriene - - - t t 2087 abietadiene - t - t | 2298 4-epi-abietal - - t t 2312 abieta-7,13-dien-3-one - 0.2 - t | 2313 abietal - - - - t 2331 trans-ferruginol - - - - t 2343 4-epi-abietol - - - - t 2401 abietoi - - t - -