Chemometric study of functional groups in different layers of Trigonocarpus grandis ovules (Pennsylvanian seed fern, Canada)

We examined four dispersed, coalified ovules, Trigonocarpus grandis, of medullosalean seed-fern affinity from the Late Pennsylvanian age Sydney Coalfield, Canada, which represent the larger type of the 7-8 cm trigonocarpalean form species. At first glance it appears that the ovules are preserved like the usual Carboniferous foliar compressions, i.e. one coalified layer with one preserved anatomical tissue, the cuticle. However, careful sample preparation uncovered at least three coalified layers, and Schulze's oxidative maceration process, which dissolves the coalified material, revealed several tissue layers. Altogether, eight sample forms were defined: (i) coalified layer, (ii) cuticle A, (iii) cupric + vitrain, (iv) vitrain, (v) cupric, (vi) cuticle B, (vii) alkaline solution and (viii) added coal seam material. The purpose of the study was twofold: first, to systematically analyze the forms by way of Fourier transform infrared (FTIR) spectrometry to fill a gap in chemical information that exits for coalified trigonocarpalean ovules of Carboniferous seed ferns; second, to use principal component analysis to focus on groupings as a function of chemical structure (functional groups) and to assess the different fossil forms in terms of FTIR chemical parameters, based on a 8 x 49 data matrix. Results include distinction among the three coaly sample forms, coalified layer (i), cupric + vitrain (iii) and cupric (v), based mainly, but not exclusively, on differences in carbonyl content, as well as length and branching of the polymethylenic chains. Important to note is the high aliphatic content of the cuticles as a signature of the biomacromolecules cutan/cutin. In particular, new insights into the structure of the original ovule are presented, and differences in chemistry are mainly a result of the complex structure of the precursor plant organ. (C) 2011 Elsevier Ltd. All rights reserved.