Pentacyclic triterpene methyl ethers in recent lacustrine sediments (Lagoa do Caçó, Brazil)

doi:10.1016/j.orggeochem.2004.09.005

Organic Geochemistry

Volume 36, Issue 3, March 2005, Pages 449-461

https://doi.org/10.1016/j.orggeochem.2004.09.005 Get rights and content

Abstract

The lipid extracts of sediments collected from the Quaternary filling of a tropical lacustrine series (Lagoa do Caçó, Brazil) were investigated using gas chromatography–mass spectrometry (GC–MS). Various pentacyclic triterpene 3-methyl ethers (PTMEs) were present in the neutral fraction. Comparison of retention times and mass spectra with available standards allowed us to confirm the presence of olean-12-en-3β-ol ME (β-amyrin ME), olean-18-en-3β-ol ME (miliacin), taraxer-14-en-3β-ol ME (crusgallin), fern-9(11)-en-3β-ol ME (arundoin) and arbor-9(11)-en-3β-ol ME (cylindrin). The following other compounds could also be tentatively identified from their GC–MS characteristics: urs-12-en-3β-ol ME, bauer-7-en-3β-ol ME and fern-8-en-3β-ol ME. Other compounds such as possible 3α isomers of the PTMEs as well as di- or tri-unsaturated counterparts might be PTME diagenetic derivatives. According to previous chemotaxonomic studies, all these compounds most probably originate from Gramineae that used to colonize the savanna of Northern Brazil at the time of deposition.

Section snippets

Introduction and setting

Since the isolation of isoarborinol from the Messel Oil Shale (Albrecht and Ourisson, 1969), the literature has been continuously enriched with information on new pentacyclic triterpenes which have been used in petroleum exploration or palaeoenvironmental studies (Cranwell, 1984). These compounds comprise higher plant triterpenes (e.g., oleanane, lupane and ursane derivatives) which occur widely in the plant kingdom in the free form or bound to glycosyl or phenolic moieties through a functional

Sediment samples

The context and sample handling have been described (Jacob et al., 2004a). Briefly, a core (MA98-3; 6 m long) was divided into two main intervals. The lower (ca. 3 m long), which dates back to the end of the LGM, consists of fine-grained sands and silts. The upper half (ca. 3 m long), consisting of organic matter-rich silts, is divided into greenish-brown organic silts (Late Glacial) and black organic silts (Holocene). Two samples, which best illustrate the distribution of PTMEs, were selected

Results

Total extract yields ranged between 0.5 and 4.2 mg g⁻¹ sediment. The neutral fraction afforded between 0.4 and 3.5 mg g⁻¹ sediment. The dominant compounds in this fraction were PTMEs and hopanoids. In total, at least sixteen compounds were distinguished using GC–MS. Two examples of the distribution of these compounds in Lagoa do Caçó sediments are shown in Fig. 2 together with a reconstructed total ion current (TIC) trace for reference compounds.

In total, 5 out of the 16 compounds were identified

Discussion

To our knowledge, the only previous record of methoxy triterpenes in geological samples was made by Ries-Kautt (1986), who identified in soils one compound displaying a similar mass spectrum to that of fern-9(11)-en-3β-ol ME and another unidentified one that could be related to taraxer-14-en-3β-ol ME.

Conclusions

The Quaternary filling of Lagoa do Caçó afforded a wide range of pentacyclic triterpene methyl ethers. These compounds dominate the neutral solvent-extractable fraction. The identity of five has unambiguously been assigned with available reference compounds. Based on an inventory of plants from which PTMEs have been isolated, Gramineae that grew in the watershed at the time of sediment deposition appear as the most probable source. The presence of PTMEs in Lagoa do Caçó sediments attests to

Acknowledgements

Professor R.M. Smith (Loughborough University, UK), Professor H.E. Connor (University of Canterbury, NZ) and Professor G. Eglinton (Bristol University, UK) are greatly acknowledged for providing reference compounds and valuable discussions about chemotaxonomy. The authors thank Professor G. Bouchoux (Ecole Polytechnique, France), Dr. P. Metzger (Ecole de Chimie de Paris, France) and Professor B. Simoneit (Oregon State University, US) for useful discussions on mass spectra interpretation. Dr. B.

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Pentacyclic triterpene methyl ethers in recent lacustrine sediments (Lagoa do Caçó, Brazil)

Abstract

Section snippets

Introduction and setting

Sediment samples

Results

Discussion

Conclusions

Acknowledgements

Geochimica et Cosmochimica Acta

Phytochemistry

Tetrahedron

Tetrahedron

Tetrahedron Letters

Phytochemistry

Tetrahedron

Tetrahedron Letters

Phytochemistry

Phytochemistry

Geochimica et Cosmochimica Acta

Geochimica et Cosmochimica Acta

Palaeogeography, Palaeoclimatology, Palaeoecology

Organic Geochemistry

Organic Geochemistry

Organic Geochemistry

Quaternary Research

Organic Geochemistry

Phytochemistry

Phytochemistry

Phytochemistry

Phytochemistry

Tetrahedron

Applied Geochemistry