The nature and fate of natural resins in the geosphere. XII. Investigation of C-ring aromatic diterpenoids in Raritan amber by pyrolysis-GC-matrix isolation FTIR-MS
© Anderson; licensee BioMed Central Ltd. 2006
Received: 30 November 2005
Accepted: 01 March 2006
Published: 01 March 2006
Upper Cretaceous amber from the Raritan Formation (Sayerville, New Jersey) has been investigated by Pyrolysis-GC-MS and Pyrolysis-GC-matrix isolation FTIR-MS. Results establish the existence of two distinct forms of amber in this deposit. Both forms are Class Ib ambers, but they are unambiguously differentiated on the basis of their (intact) diterpenoid composition. The presence of callitrisate in both forms, and cupraene in samples designated form 1, strongly suggest that both derive from related-but-distinct species within the Cupressaceae.
In addition to callitrisate, dehydroabietate and analogous 17-nor-, 16,17-dinor- and 15,16,17-trinor- analogues of these compounds are also observed. The distributions of these products in multiple samples suggest that they are the result of biological emplacement, rather than diagenetic modification of the parent compounds. This indicates that the distributions of diterpenes observed in these samples are representative of the original bioterpenoids and, hence, are useful for chemotaxonomic analyses.
Amber, the fossil form of plant resins, occurs in terrestrial sediments throughout the geologic record from about the early-middle Mesozoic forward and is relatively common in Cenozoic sediments . Older fossil "resins" are known from the occurrence of resinites in coals as old as the Carboniferous, but there is emerging evidence that these materials may be a distinct group of products not necessarily directly related to the terpenoid-based resins common in modern plants and recognized in the sedimentary record as amber [2–4].
Geologic classification/nomenclature of ambers is of little value. Ambers from separate deposits are known by a plethora of names which have no relationship to structural properties or composition. Even within a single deposit, ambers of different clarity, color, friability and/or other properties may be referred to by discrete names, which can result in serious confusion and misclassification. Geochemically, ambers are classified on the basis of their structural properties into groups with comparable structural characteristics [1, 5–7]. Class I ambers, those based primarily on polymers of labdanoid diterpenes (I), appear to be by far the most common form of amber in the geosphere. These resins appear to have evolved by the Early Mesozoic (Triassic) [Anderson, unpublished results], and diversified through a wide range of species. In modern plants, resins of this basic composition occur in numerous families including both Angiosperms and Gymnosperms.
Note: Chemical structures referred to in the text are illustrated in Appendix 1. Structures are identified by parenthetical Roman Numerals, with specific derivatives identified where appropriate by a lower case alphabetic designation.
Class I ambers are further differentiated into Class Ia, Ib and Ic on the basis of details of the nature of the labdanoid diterpenes on which their macromolecular structure is based, and on the presence or absence of succinic acid [1, 5–7]. Class Ia and Ib ambers are based on polymers of labdanoid diterpenes with "regular" stereochemistry. That is, structures including and related to communic acid, communol etc (II). Class Ia and Ib ambers are differentiated in that Class Ia ambers incorporate significant amounts of succinic acid into their macromolecular structure, presumably as a natural cross-linking agent (e.g. Baltic amber, a.k.a. succinite) whereas this product is absent in Class Ib ambers. Class Ic ambers are based on a macromolecular structure derived primarily from labdanoids with a (so called) "enantio" configuration, such as, for example, ozic acid, ozol and related hydrocarbons (III). The well known ambers found in Central America, especially those mined in the Dominican Republic and Mexico that are believed to be derived largely or exclusively from Hymenaea  are of this type. In all cases, in addition to the overall macromolecular network, Class I ambers may include other occluded (or polymer bound) compounds. While these are not usually structurally significant overall, these may be of considerable interest for their chemotaxonomic value.
Numerous sizable amber deposits are known around the world. Ambers are particularly well known in Europe, especially the significant deposits located in the Baltic region where ambers have been collected and/or mined for millennia and are deeply embedded into regional history and folklore . New world deposits are also known and significant amounts of amber are now mined and exported from the Dominican Republic and Mexico. Numerous smaller deposits are also known. In most cases these are not prospected commercially, at least not on a large scale, but they represent a potentially important geologic and paleontological record and can be of significant scientific interest.
Scientific interest in ambers is largely related to either investigation of the amber itself or to investigation of materials (especially insects and other small organisms) that are preserved within it. Fossiliferous material within amber is often preserved to a higher degree of fidelity than perhaps any other medium. Grimaldi  has even coined the term "ambalmed" to describe this type of preservation. There is also increasing interest in the use of ambers as chemotaxonomic indicators. This latter area of interest derives from that fact that the compositions of many modern resins are, at least in some degree, characteristic of the plants from which the resins are produced [1, 11] and to the extent that compositional characteristics are preserved in the fossil resins, detailed analysis of ambers may serve as a useful means for investigation of paleovegetation, and hence, paleoenvironmental conditions. As also noted by others [11, 12] this approach is necessarily complicated by potential diagenetic alteration of resin components, by the unknown degree of evolutionary change in resin composition since biosynthesis of the original resin from which the amber was formed, and by the limits of analogy between the composition of modern resins and their fossiliferous analogues. Nevertheless, numerous authors have pursued and/or are now pursuing this approach [8, 13–16] and it is clear that despite these potentially complicating factors, useful data can be generated.
Amber is found in numerous locales in North America, including several locations on the Atlantic Coastal Plain. Perhaps the largest and best known of these (Atlantic Coastal Plain) deposits occurs in the Raritan formation, which extends from Staten Island across parts of New Jersey. Amber from this area was first reported in 1821  and since then there have been numerous reports of investigations of these deposits, most of which have been recently reviewed by Grimaldi et al. [18, 19] It is now well established that these deposits are Upper Cretaceous (Cenomanian-Turonian). Amber from these deposits is usually found in clays, often in association with woody remains.
Langenheim and Beck and subsequently Grimaldi et al  concluded on the basis of infrared and Py-MS analyses that these ambers were likely of Araucariaceous origin. Grimaldi, Wampler and Shedrinski  subsequently revised this conclusion and suggested a Pinaceous (or Taxodiaceous) origin, based on the results of pyrolysis-gas chromatography (Py-GC) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) analyses. However, the high pyrolysis temperatures (650°C, 15 sec) used for these analyses tends to favor the formation of secondary products .- hence the high proportion of low molecular weight aromatic products identified by these authors. (Note also, many of the compounds identified in that report cannot be assigned with confidence on the basis of comparison of MS results with library spectra due to the existence of isomeric compounds with essentially identical mass spectra, e.g. .) Furthermore, the absence of any provision for derivatization of acidic structures severely hampers chromatographic performance in analyses of these types of samples and results in extreme bias in the results obtained . As a result, the Py-GC and Py-GC-MS data reported by these authors is of limited chemotaxonomic value.
In the present study, samples of Raritan amber have been analyzed by Py-GC-MS and Py-GC-matrix isolation FTIR-MS (Py-GC-mi FTIR-MS) with in situ methylation of acidic products by tetramethyl ammonium hydroxide (TMAH). The observed distribution of products is discussed both with respect to chemotaxonomic significance and also in relation to potential diagenetic modification of the original diterpene distributions.
Py-GC-MS analyses were carried out as previously described , except that a newer model CDS 2500 pyrolyzer was used. All data reported were obtained by pyrolysis (10 sec at 480°C) in the presence of TMAH to ensure methylation of carboxylic acids liberated by pyrolysis. Separation and analysis of pyrolysate components was accomplished using an Agilent 6890 GC system coupled with an Agilent 5973 MSD and a ClearIR matrix isolation FTIR system. Separation was achieved using a 60 m DB 1701 (0.25 mm, 0.25 μm film thickness), capillary column with some additional analyses completed using a 30 m VB-5 (0.25 mm, 0.25 μm film thickness) as necessary. Carrier gas (He or 2% Ar in He for mi FTIR analyses) was held at 1 ml/minute. Temperature programming was as follows: Tinitial = 40°C (4 minutes); ramp = 4°C/min to Tfinal = 280°C. Temperature was then held isothermally for at least 16 minutes.
Results and discussion
Five discrete samples from this deposit were analyzed by Py-GC-MS. The resulting data clearly indicate the existence of two related-but-distinct forms of amber. These two materials are visually indistinguishable, but are clearly differentiable on the basis of the compounds observed in their pyrolysates. This finding contradicts the earlier finding that ambers from this site are chemically uniform .
Polymer-derived bicyclic products observed are dominated almost entirely by carboxylic acids derived from communic acid (IVa-VIIa). A-ring defunctionalized analogues (IVe/f-VIIe/f) of these characteristic bicyclic acids  are also present. Communol (IIc) and Biformene (IId) derived characteristic bicyclic products (IVb/c-VIIb/c) are absent or present in only trace amounts, although small amounts of methyl ether products (IVd-VIId) are observed in some samples. Monoterpenoids are present in some samples in low, variable amounts. Cuparene (VIII) is observed as a minor component in the pyrolysate of this form.
Chemotaxonomy and paleobotany
Grimaldi et al conclude that Raritan ambers may be derived from a Pinaceous species (without excluding the possibility of Taxodiaceous affiliation) based in part on the observation of (minor) dehydroabiatic acid (IXa) by Py-GC-MS analysis. However, dehydroabietic acid is commonly found in many modern  and fossil resins from a wide range of families and hence is not of diagnostic value for chemotaxonomic purposes. The occurrence of callitrisate (X), however, is much more limited and hence is of greater chemotaxonomic interest.
Callitrisic acid (Xa) was first identified as a unique natural product isolated from the oleoresin of Callitris columellaris (Cupressaceae) by Carman and Deeth . Subsequently, other authors have reported this product in resins and/or essential oils from Callitris , various Juniperis (Cupressaceae) species [23–30], and a number of non-conifers including Salvia , (although from the MS data reported by these authors it seems likely that the products observed are actually dehydroabiatic acid (IXa) and methyl dehydroabietate (IXb)), Caleolaria [32, 33], Rabdosia , and the Rosaceae [35, 36]. Callitrisate (X) has also been reported in thermally modified products derived from Pinus [37, 38] but was not reported in analyses of unmodified resins from these species [39, 40], so it is likely that these reports reflect secondary products rather than primary resin components. Other workers [11, 41] have noted that reporting of compounds present in oleoresins from is often incomplete, but based on presently available data, it appears that occurrence of callitrisate (X) in modern conifer resins is limited to the Cupressaceae.
Correlations between macrofossil evidence and chemosystematics of co-deposited ambers need to be weighed with care. Ambers in any deposit will reflect the occurrence of resin producing species and copious resin producers may be disproportionately represented. Non resin producers or species with minor resin production will not be represented in the resin record, although these may dominate other palynological or paleontological indicators. For example, macrofossil evidence from the Fossil Forrest site (Canadian Arctic) indicates that the paleoenvironment at this site was dominated by Metasequoia and Glyptostrobus  but ambers from this site are dominated by Pseudolarix , which was apparently a minor species in that ecosystem .
Grimaldi et al  report that all of the ambers characterized in their study of Raritan ambers, including those found in unambiguous association with woody fossils are identical and are derived from a single botanical source, but for the reasons given earlier and in light of the data reported herein, this conclusion needs to be reassessed. Nevertheless, their observations and those of earlier workers (e.g. ) establish that at least some of the woody fossils found in these deposits are derived from resin producing species and that resins found in direct association with woody fossils are at least not grossly dissimilar to other ambers from these strata. Hence the characteristics of these woody fossils may be relevant to the chemotaxonomy of either or both of the amber forms identified in the present study.
Anatomical and (macro)structural studies of (resinous) fossil woods and cone scales associated with ambers from the Atlantic Coastal Plain are reviewed and summarized by Grimaldi et al [18, 19]. In their study, Grimaldi  note that woody fossils collected in direct association with Raritan ambers possessed "crossfield pits [that] were generally in pairs and cupressoid-taxodioid in structure". Other (earlier) workers also recognized characteristics associated with the Cupressaceae in these fossils. (In fact, in the earliest report of investigation of the anatomical characteristics of these fossils  named the tree "Cupressinoxylon bibbinsi"). Resinous cone scales with characteristics similar to Juniperus also occur in association with these ambers (see  and works cited therein), thus strengthening the association of these fossils with the Cupressaceae. (Grimaldi et al  also cite unpublished data (M. Gandolfo, 1998) that fusinitized plant remains from the Raritan are "dominated by Cupressaceae".)
In addition to dehydroabietate (IX) and callitrisate (X), 16,17-dinor-dehydroabietate (XIV) and 16,17-dinor-callitrisate (XV) are also observed in the pyrolysates of these samples and in fact in some cases, these products predominate compared to the "parent" compounds (dehydroabietate and callitrisate).
The presence of the various analogues of both abietate and callitrisate suggests the possibility of a either a diagenetic degradation pathway from dehydroabietate and a parallel pathway from callitrisate, or a biological relationship emplaced during biosynthesis of the original resin. In this study, the availability of multiple samples collected from the same deposit (and therefore having identical geologic histories) and the existence of two distinct forms with differing compositions, allows definitive differentiation of these possibilities. If the relationship between these compounds were derived from a diagenetic (post depositional) degradation, then it can be assumed that alteration pathway will be the same in all samples. Hence for any given initial composition, the relative ratios of the parent compounds and their daughter products should be comparable in all cases. This is not observed. From the data illustrated in Figure 6, it would appear that in this sample, the relative ratios of the parent compounds and their "daughter" products are comparable. However, this relationship is not observed in other samples. The data illustrated in Figure 7 and in additional data for the remaining samples show wide variations in the ratios of all products.
This result establishes two things: Firstly, it establishes that diagenetic pathway(s) for this group of compounds need to be interpreted with care because of the potential for superimposition of biological signatures over potential diagenetic modifications. Secondly, it establishes that the distributions of compounds observed in these samples reflects the original resin composition and is, therefore, useful for chemotaxonomic assessment.
Pyrolysis-GC-MS analysis of samples of amber collected from the Raritan Formation, New Jersey, clearly indicate the existence of two related-but-distinct forms. Both forms are Class Ib ambers. However, differences in the distributions of other diterpenoids unambiguously differentiate these materials and establish that ambers from this formation are derived from multiple related-but-distinct paleobotanical sources. The presence of both dehydroabietate (IX) and callitrisate (X) in all samples suggests that both forms are derived from species belonging to the Cupressaceae, and this conclusion is supported by the observation of cuparene (VIII) in form 1.
The author gratefully acknowledges the assistance of Mr. Chris Reed in reviewing some of the Py-GC-MS results reported, and the support of the Southern Illinois University, Office of Research and Development Administration (ORDA). Dr. John C. Crelling is thanked for helpful comments during preparation of this manuscript.
- Langenheim JH: Plant Resins – Chemistry, Evolution, Ecology and Ethnobotany. 2003, Timber Press, Portland, 586-Google Scholar
- Nip M, De Leeuw JW, Crelling JC: Chemical structure of bituminous coal and its constituting maceral fractions as revealed by flash pyrolysis. Energy & Fuels. 1992, 6 (2): 125-36. 10.1021/ef00032a003.View ArticleGoogle Scholar
- Crelling John C, Kruge MA: Petrographic and chemical properties of Carboniferous resinite from the Herrin No. 6 coal seam. International Journal of Coal Geology. 1998, 37 (1–2): 55-71. 10.1016/S0166-5162(98)00021-4.View ArticleGoogle Scholar
- van Bergen P, Collinson ME, Scott AC, de Leeuw JW: Unusual resin chemistry from Upper Carboniferous Pteridosperm resin rodlets. ACS Symposium Series. 1995, 617 (Amber, Resinite, and Fossil Resins): 149-169.View ArticleGoogle Scholar
- Anderson Ken B, Winans RE, Botto RE: The nature and fate of natural resins in the geosphere-II. Identification, classification, and nomenclature of resinites. Organic Geochemistry. 1992, 18 (6): 829-41. 10.1016/0146-6380(92)90051-X.View ArticleGoogle Scholar
- Anderson Ken B: The nature and fate of natural resins in the geosphere. IV. Middle and Upper Cretaceous amber from the Taimyr Peninsula, Siberia – evidence for a new form of polylabdanoid of resinite and revision of the classification of Class I resinites. Organic Geochemistry. 1994, 21 (2): 209-12. 10.1016/0146-6380(94)90155-4.View ArticleGoogle Scholar
- Anderson Ken B: The nature and fate of natural resins in the geosphere. Part V. New evidence concerning the structure, composition, and maturation of Class I (polylabdanoid) resinites. ACS Symposium Series. 1995, 617 (Amber, Resinite, and Fossil Resins): 105-29.View ArticleGoogle Scholar
- Langenheim JH: Biology of amber-producing trees: Focus on case studies of Hymenaea and Agathis. ACS Symposium Series. 1995, 617 (Amber, Resinite, and Fossil Resins): 1-31.View ArticleGoogle Scholar
- Rice PC: Amber – The Golden Gem of the Ages. 1993, Kosciuszko Foundation, New York, 289-Google Scholar
- Grimaldi D: Amber: Window to the Past. 1996, Harry N. Abrams/American Museum of Natural History, New York, 216-Google Scholar
- Otto A, Wilde V: Sesqui-, Di-, and Triterpenoids as Chemosystematic Markers in Extant Conifers – A Review. The Botanical Review. 2001, 67 (2): 141-238.View ArticleGoogle Scholar
- Vavra N: Chemical characterization of fossil resins ("amber") – A critical review of methods, problems and possibilities: determination of mineral species, botanical sources and geographical attribution. Abh Geol B. 1993, 49: 147-157.Google Scholar
- Langenheim JH, Beck CW: Catalogue of Infrared Spectra of Fossil Resins (Ambers) I. North And South America. 1968, Botanical Museum Leaflets, Harvard University, 22 (3): 65-120.Google Scholar
- Anderson Ken B, LePage Ben A: The nature and fate of natural resins in the geosphere. Part VI. Analysis of fossil resins from Axel Heiberg Island, Canadian Arctic. ACS Symposium Series. 1995, 617 (Amber, Resinite, and Fossil Resins): 170-92.View ArticleGoogle Scholar
- Otto A, White JD, Simoneit BRT: Natural product terpenoids in Eocene and Miocene conifer fossils. Science. 2002, 297 (5586): 1543-1545. 10.1126/science.1074225.View ArticleGoogle Scholar
- Otto A, Simoneit BRT, Rember WC: Resin compounds from the seed cones of three fossil conifer species from the Miocene Clarkia Flora, Emerald Creek, Idaho, USA, and from related extant species. Review of Palaeobotany and Palynology. 2003, 126: 225-241. 10.1016/S0034-6667(03)00088-5.View ArticleGoogle Scholar
- Troost G: Description of a variety of amber, and of a fossil substance supposed to be the nest of an insect discovered at Cape Sable, Magothy River, Ann-ArundelCounty, Maryland. American Journal of Science. 1821, 3: 8-15.Google Scholar
- Grimaldi D, Beck CW, Boon JJ: Occurrence, chemical characteristics, and paleontology of the fossil resins from New Jersey. American Museum Novitates. 2948: 1-28.
- Grimaldi D, Shedrinsky A, Wampler TP: A remarkable deposit of fossiliferous amber from the Upper Cretaceous (Turonian) of New Jersey. "Studies on fossils in amber, with particular reference to the Cretaceous of New Jersey. Edited by: Grimaldi D. 2000, Backhuys, Publishers, Leiden, The Netherlands, 1-76.Google Scholar
- Rowland SJ, Alexander R, Kagi RI: Analysis of trimethylnaphthalenes in petroleum by capillary gas chromatography. Journal of Chromatography. 1984, 294: 407-12. 10.1016/S0021-9673(01)96153-9.View ArticleGoogle Scholar
- Anderson Ken B, Winans RE: Nature and Fate of Natural Resins in the Geosphere. 1. Evaluation of Pyrolysis-Gas Chromatography/Mass Spectrometry for the Analysis of Natural Resins and Resinites. Analytical Chemistry. 1991, 63: 2901-2908. 10.1021/ac00024a019.View ArticleGoogle Scholar
- Carman RM, Deeth HC: Diterpenoids. XIV. 4-Epidehydroabietic acid from the oleoresin of Callitris. Australian Journal of Chemistry. 1967, 20 (12): 2789-93.View ArticleGoogle Scholar
- Gough LJ: Callitrisic acid: a new diterpenoid. Tetrahedron Letters. 1968, (3): 295-8. 10.1016/S0040-4039(01)98748-9.
- Tabacik C, Poisson C: Juniperus phoenicea diterpenes, minor constituents. Phytochemistry. 1971, 10 (7): 1639-45. 10.1016/0031-9422(71)85039-2.View ArticleGoogle Scholar
- De Pascual TJ, San Feliciano A, Tabernero ML, Del Corral JMM, Barrero AF, Grande M: Components of the berries of Juniperus phoenicea L. I. Acid fraction. Anales de Quimica. 1978, 74 (3): 459-64.Google Scholar
- De Pascual TJ, San Feliciano A, Miguel del Corral JM, Barrero AF: Terpenoids from Juniperus sabina. Phytochemistry. 1983, 22 (1): 300-1. 10.1016/S0031-9422(00)80113-2.View ArticleGoogle Scholar
- San Feliciano A, Miguel del Corral JM, Gordaliza M, Salinero MA, Del Rey B: Acidic constituents of Juniperus phoenicea subsp. turbinata leaves. Fitoterapia. 1993, 64 (2): 185-6.Google Scholar
- Lee C-K, Fang Min J, Cheng Y-S: Abietanes from leaves of Juniperus chinensis. Phytochemistry. 1994, 35 (4): 983-6. 10.1016/S0031-9422(00)90652-6.View ArticleGoogle Scholar
- Almendros G, Sanz J, Velasco F: Signatures of lipid assemblages in soils under continental Mediterranean forests. European Journal of Soil Science. 1996, 47 (2): 183-196. 10.1111/j.1365-2389.1996.tb01389.x.View ArticleGoogle Scholar
- El-Sayed AM: Diterpene constituents of Juniperus polycarpos and their antimicrobial and anti-inflammatory activities. Zagazig Journal of Pharmaceutical Sciences. 1998, 7 (1): 80-86.Google Scholar
- Guillen MD, Manzanos MJ: Extractable Components of the Aerial Parts of Salvia lavandulifolia and Composition of the Liquid Smoke Flavoring Obtained from Them. Journal of Agricultural and Food Chemistry. 1999, 47 (8): 3016-3027. 10.1021/jf981260r.View ArticleGoogle Scholar
- Chamy MC, Piovano M, Gambaro V, Garbarino JA, Nicoletti M: Dehydroabietane diterpenoids from Calceolaria ascendens. Phytochemistry. 1987, 26 (6): 1763-5. 10.1016/S0031-9422(00)82285-2.View ArticleGoogle Scholar
- Chamy MC, Piovano M, Garbarino JA, Gambaro V: Diterpenoids from Caleolaria species. Part 10. Diterpenes from Calceolaria polifolia. Phytochemistry. 1991, 30 (10): 3365-8. 10.1016/0031-9422(91)83211-3.View ArticleGoogle Scholar
- Zhang H, Sun H: Diterpenoids from Rabdosia kunmingensis. Phytochemistry. 1989, 28 (12): 3405-9. 10.1016/0031-9422(89)80357-7.View ArticleGoogle Scholar
- Khadzhieva P, Stoyanova-Ivanova B: Callitrisic acid and sterols in the flowers of Bulgarian oil-bearing rose (Rosa damascena Mill). Adv Mass Spectrom Biochem Med. 1976, 1: 303-7.Google Scholar
- Hadjieva P, Palacartcheva E, Dyulgerov A, Tzvetkova A: New di- and triterpenoids for Alchemilla genus (Rosaceae). Bulgarian Chemistry and Industry. 2000, 71 (1–2): 56-57.Google Scholar
- Garcia Vallejo MC, Nascimento EA, Morais S: Volatile wood oils of the Brazilian Pinus caribaea var. Hondurensis and Spanish Pinus Pinaster var. Mediterranea. Journal of the Brazilian Chemical Society. 1994, 5 (2): 107-12.View ArticleGoogle Scholar
- McDonald AG, Gifford JS, Dare PH, Steward D: Characterization of the condensate generated from vacuum drying of radiata pine wood. Holz als Roh- und Werkstoff. 1999, 57 (4): 251-258. 10.1007/s001070050052.View ArticleGoogle Scholar
- McDonald IRC, Porter LJ: Resin and fatty acid composition of Pinus radiata whole wood, and its relation to the yield and composition of New Zealand tall oil. New Zealand Journal of Science. 1969, 12 (2): 352-62.Google Scholar
- Arrabal C, Cortijo M, Fernandez de Simon B, Garcia-Vallejo MC, Cadahia E: Pinus pinaster oleoresin in plus trees. Holzforschung. 2002, 56 (3): 261-266. 10.1515/HF.2002.043.View ArticleGoogle Scholar
- Erdtman H: Chemical principles in chemosystematics. Rec Adv Phytochem. 1968, 1: 13-26.Google Scholar
- Basinger JF: The fossil forests of the Buchanan Lake Formation (Early Tertiary), Axel Heiberg Island, Canadian Arctic Archipelago: preliminary floristics and paleoclimate. "Tertiary Fossil Forests of the Geodetic Hills Axel Heiberg Island, Arctic Archipelago". Geological Survey of Canada Bulletin. Edited by: Christy RL, McMillan NJ. 1991, 403: 39-66.Google Scholar
- Hollick A, Jeffrey EC: Studies of Cretaceous coniferous remains from KreischerviIle, New York. Mem New York Bot Gard. 1909, 3: 1-138.Google Scholar
- Knowlton EH: American amber-producing tree. Science. 1896, 3: 582-584. 10.1126/science.3.68.582.View ArticleGoogle Scholar
- Enzell CR, Wahlberg I: Mass spectrometric studies of diterpenes. VI. Aromatic diterpenes. Acta Chemica Scandinavica. 1969, 23 (3): 871-91.View ArticleGoogle Scholar
- Bory S, Fetizon M: Determination of the configuration of di- or triterpene esters by infrared spectroscopy. Bulletin de la Societe Chimique de France. 1964, 3: 570-3.Google Scholar
- Zinkel DF, Zank LC, Wasolowski MF: Diterpene resin acids. A compilation of infrared, mass, nuclear magnetic resonance, ultraviolet spectra, and gas chromatographic retention data (of the methyl esters). 1971, U. S. Department of Agriculture, 191-Google Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.