Role of a Labile Terpene Compound in the Assessment of the Age of a Fossil Wood from Siena (Tuscany, Italy)

Abstract

Fossil samples of Pinus sylvestris found near Siena (Tuscany, Italy) in geological formations 2-3 million years old were chemically examined in order to solve the problem of the contrast between the age of geological formations and their good degree of preservation.Comparison with a living Pinus sylvestris was carried out on standard wood component analyses, cation exchange capacity and residual terpene content. The analyses of wood components were close to those of the reference pine, whilst the cation exchange capacity values showed remarkable changes. The increase of salt carboxyls suggested the hydrolysis of ester carboxyls originally present, whilst the reduction of total carboxyls revealed a partial loss of hemicelluloses. Both changes were attributed to the percolation of salt-bearing water through the wood, thus causing ester hydrolysis, carboxyl salification and hemicellulose solubilisation. Residual terpene analysis showed, for the first time in a

Terpenoids as chemosystematic markers in selected fossil and extant species of pine (Pinus, Pinaceae)

“…The fossil pine cones even contained several unaltered diterpenoids (bioterpenoids) of the abietane class that were also detected in the extant species (for example, dehydroabietane, dehydroabietol, dehydroabietic acid, and abietic acid), indicating the preservation of characteristic Pinus biomarkers in the Eocene and Oligocene species. Similar diterpenoid patterns with predominant abietane derivatives have been reported previously from archaeological pine resins (for example, Eerkens, 2002) and a Pleistocene Pinus wood (Staccioli et al ., 2000). The terpenoid pattern of the fossil pines showed the closest similarity to the resins of P. bungeana , P. contorta , P. radiata , P. taeda , and P. thunbergii , with a predominance of dehydroabietic acid and smaller amounts of isopimarane‐ and pimarane‐type derivatives.…”

“…Distinct patterns of sesqui‐ and diterpenoids are characteristic of groups of families or even distinct families within the conifers, and can be used as chemosystematic markers (Otto & Wilde, 2001). Chemical analyses of fossil conifer seed cones, leafy shoots, and wood have shown that sesqui‐ and diterpenoids can be preserved in fossil conifers of Tertiary and Late Cretaceous age (Staccioli, Mellerio & Alberti, 1993; Anderson & LePage, 1995; Otto, Kvacek & Goth, 1999; Staccioli et al ., 2000; Tu et al ., 2000; Otto et al ., 2001, 2002b; Otto & Simoneit, 2001, 2002; Otto, White & Simoneit, 2002a; Otto, Simoneit & Rember, 2003). Before and during burial of the conifer remains in sediments, the organic matter is altered through various microbial and physicochemical processes.…”

“…(including former Taxodiaceae) have shown that the patterns of terpenoid biomarker classes in the fossil and extant conifers are comparable and specific at the family or genus level (Otto et al ., 2002a, 2003). Many archaeological samples of pine resin (for example, Eerkens, 2002) and a Pleistocene Pinaceae wood (Staccioli et al ., 2000) have also been reported to contain sesqui‐ and diterpenoids similar to those of extant species of the family. In the present study, the terpenoid compositions of the seed cones and resins of fossil and extant species of pine ( Pinus , Pinaceae) were analysed to compare the composition of terpenoid biomarkers in extant and fossil conifers and to study the preservation of characteristic chemosystematic markers in fossil plant material.…”

Subfossil Scots Pine (Pinus sylvestris L.) Wood from Northern Finland—Physical, Mechanical, and Chemical Properties and Suitability for Specialty Products

“…They also observed the formation of some other structurally corresponding derivatives, i.e., more stable norabietane and norabietatriene. Later, Staccioli et al detected those abietane-related terpenes in the fossil samples of Scots pine obtained from the 18,000-year-old terrestrial fossil [77]. According to the proposed scheme, the abietane-type terpenes transformation in the fossil samples starts with the disproportionation reaction of abietic acid to form dehydroabietic and tetrahydroabietic acids [78].…”

Chemotaxonomical identification of Holocenic bogwood recovered after 2007 Niigataken Chuestsu-oki Earthquake

“…Therefore, in the present paper, an anatomical and chemical study was attempted in terms of one conifer bogwood piece obtained from the salvaged wood. The chemical analysis of volatile components may also give information on their diagenetic changes, based on previous studies (Simoneit et al 1986 ;Staccioli et al 1993Staccioli et al , 1997Staccioli et al , 1998Staccioli et al , 2000Menchi et al 1995 ;Otto and Simoneit 2002 ;Narita et al , 2007Narita and Kuga 2009 ). For comparison of anatomical and chemical features, several fresh pine samples were collected and analyzed.…”