1. INTRODUCTION Lepidodendron dawsonii BELL 1938 is a fairly common lepidophyte component in the Late Asturian of Sydney Coal- field, Canada (Fig. 1A & B), and ranges from the Emery Seam to the highest strata at Point Aconi (Fig. 1C). Its phy- tostratigraphic utility is limited, but BELL (1966, Pl. XXVII, Fig. 5) believed it was early Westphalian D in the Canadian Carboniferous Maritime Provinces. THOMAS (2009, Table 6) stated that it was not found outside the Sydney Basin in Variscan Euramerica, i.e., it was endemic. The specimen is significant (Pl. 1A) because of the dual preservation as 1) a coalified compression, typical of fossil plants in the Sydney Coalfield (Pls. 1B & C), and 2) as rare fossilized-cuticle (Pls. 2A & B), i.e., this is the only specimen known from the Syd- ney Coalfield. The co-occurrence of coal and cuticle in the specimen invites analogy with a coal-seam, particularly as lycophytes provided considerable biomass for coal-seam ac- cumulation (e.g., ARNOLD, 1947, p. 94; DIMICHELE et al., 1985; CLEAL et al., 2010). Here, the focus is on the two preservation states in one contiguous specimen of L. dawsonii. as each is capable of providing its own spectrochemical information as a conse- quence of its fossilization history, i.e., coalification and nat- ural maceration (ZODROW & MASTALERZ, 2009). Though cuticular information is provided taxonomy is not an objective here and is not discussed further. Ab sTRA CT Lepidodendron dawsonii BELL 1938 is an endemic species of Late Asturian age in the Canadian Sydney Coalfield, with conspicuous elongate leaf cushions. The study specimen, 35 cm long and 10 cm wide, represents a dichotomous bough from the tree crown in which the inner part of one side is black and compression-preserved, whereas the one in contact with the entombing rock matrix is dark-amber in colour and fossilized-cuticle preserved. Only stomatal pits and cuticular details are preserved. Comparison of these preservation states, based on Fourier transform infrared (FTIR) spectrometry, and flash pyrolysis gas chromatography mass spectroscopy (Py-GC/MS), demonstrate suffi- cient differences in chemistry to be able to link the two preservation states with differing pathways of organic matter transformation (diagenesis). The aliphatic-hydrocarbon chains of the cuticles are comparatively shorter and more branched than the longer chains of the compressions. Py-GC/MS results support the presence of hydrocarbon mark- ers of plant cuticles. The high abundances of C1 and -C2 alkylphenols and C1 and -C2 alkylbenzenes in pyrolysates are likely derived from maturing lignin or lignin-like biomacromolecules. We suggest comparison of L. dawsonii’s cuticles with Lepidodendron coal macerals in Chinese Permian Leping coal, and with suberinite. Keywords: FTIR, flash pyrolysis, bark, compression-fossilized-cuticle, Lepidodendron Geologia CroaticaGeologia Croatica Lepidodendron dawsonii: functional groups and pyrolysates of compression and fossilized-cuticle (Late Asturian, Canada)  Erwin L. Zodrow1, Maria Mastalerz2 and Robert Helleur3 1 Palaeobotanical Laboratory, Cape Breton University, Sydney, Nova Scotia, Canada, B1P 6L2; (corresponding author: erwin_zodrow@cbu.ca) 2 Indiana University, Indiana Geological Survey, Bloomington, in 47405-2208, USA; (mmastale@indiana.edu) 3 Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland and Labrador, Canada; (rhelleur@mun.ca) doi: 104154/gc.2012.26 Geologia Croatica 65/3 367–374 4 Figs. 5 Tabs. 2 Pls. Zagreb 2012 Geologia Croatica 65/3Geologia Croatica 368 PLATE 1 Lepidodendron dawsonii A Entire specimen, where X marks the base of the dichotomy and sample location? (this is what x is referred to in the text as representing). b Compressed leaf cushions in situ. C Lose compressed leaf-cushion material after 30-min HF treat- ment. Specimen 980-391-1 in the Palaeobotanical Collection of Cape Breton University. PLATE 2 Lepidodendron dawsonii A Amber-coloured fossilized-leaf cushions in situ. b Fossilized-leaf cushions after 20-min HF treatment. C Cuticle of (B) is in focus above the lower surface. x125. Slide 980-391-1/2. D Cuticle (right) and lower surface (left). x125. Slide 980-391- 1/1. The round or oval holes are stomatal pits. Zodrow et al.: Lepidodendron dawsonii: functional groups and pyrolysates of compression and fossilized-cuticle (Late Asturian, Canada) Geologia Croatica 369 2. PREsERVATIONs AND CUTICULAR MORPHOLOGY The specimen originated from a section 1 m above the Lloyd Cove Seam in the unaltered shaly roof rock, at the base of the Cantabrian Substage (Fig. 1C), that is known to be very fossil-rich and biodiverse (e.g., ZODROW, 2002). Its di- chotomizing habit (Pl. 1A) is typical for the crown of Lepi- dodendron Sternberg (HIRMER, 1927, Figs. 200–202; THOMAS, 1966). The cortex of the inner surface of the branch that is pressed upon the prolongation is coalified with preserved cuticle, whereas the cortex facing the entombing rock matrix (Fig. 2) is fossilized as cuticle sensu ZODROW & MASTALERZ (2009). Leaf cushions are slender ca. 20 mm long and 5 mm wide and separated by secondary growth enlargements (Pl. 1B, Pl. 2A and B); see also THOMAS (1966, Fig. 5b). The leaf scars are rhomboidal in shape, and BELL (1938) com- pared older stems of L. dawsonii with L. rimosum. The epi- dermis of both preservation states shows little morphological difference and is diaphanous and very thin. Details of sto- matal apparatuses are not preserved, only stomatal pits (THOMAS, 1966, Fig. 3) that are oval to round in shape, sometimes touching or merging into one another, averaging for the longer diameter 39 µm, ranging from 30 µm – 50 µm, n= 40. Two cell morphologies are evident, based not so much on their variability which is considerable (compare Pl. 2C Figure 1: A) Canada. B) Canadian Maritimes Basin. C) Local coal-lithostratigraphy of the Sydney Coalfield, Nova Scotia, where X marks the Lloyd Cove Seam for the sample. Figure 2: Study specimen showing sample locations for analyses (sche- matic), where FC stands for fossilized-cuticle and Comp for compression. Geologia Croatica 65/3Geologia Croatica 370 and D), but on differences in average ratios of length/width (Tab. 1). The elongate cells probably represent the epidermis above the leaf scar (see THOMAS, 1966, p. 297; 1970). In either morphology anticlinal walls are straight. 3. MATERIAL AND METHODs Samples were chipped from a location marked X on Pl. 1A, supplemented by fossilized-cuticles from the lower right- hand edge of the specimen. HF (48 %) was used to free all sample materials that were then washed and rinsed in dis- tilled water for one week to eliminate as much acidic residue as possible. For a clearer view of the cuticular topography under a binocular microscope equipped with Nomarski ca- pability, the fossilized-cuticles were lightly macerated (3 h), using SCHULZE’S well-known oxidative process (CLEAL & ZODROW, 1989; and others). Compression and macerated fossilized-cuticle samples for IR (infrared) spectra were prepared by the pellet method, where 250 mg of KBr were finely ground with ca. 1.2 to 1.5 mg of the organic material, and pressed for 20 min (20,000 psi) into a 1-cm diameter pellet. IR analysis was performed on a Nicolet Thermo-Electron 6700 spectrometer, accumu- lating 256 scans at a resolution of 4 cm–1 wavenumber. As- signments of functional groups were according to PAINTER et al. (1981), WANG & GRIFFITHS (1985), and GOODARZI & MCFARLANE (1991). The flash pyrolysis (Py) of 0.6 mg, and subsequent anal- ysis of the pyrolysates were carried out using a Frontier Lab vertical micro-furnace at 600 °C which was interfaced to a HP GC/MS with a 30m x 0.25mm (0.25 um thickness) DB- 1701 capillary column. All interface temperatures were at 260 °C. The GC oven program is 35 °C (initial) to 265 °C at 7 °/min temperature ramp. The identity of the peaks was verified using standards. Elemental analyses for nitrogen, carbon, hydrogen, sul- fur, and oxygen (by difference) were performed in duplicate (2–3 mg) on a Carlo Erba EA 1108 Elemental Analyzer, and the averages are presented in Table 2. 4. DIsCUssION OF REsULTs The mid range IR spectrum used for interpreting organic analyses, 4000–400 cm–1 wavenumber, is subdivided into two peak-containing regions, separated by a broad interval of low or no absorbance. The lower-wavenumber region ranges from 1800 to 700 cm–1 and includes the 1800–1600 cm–1 region with oxygen-containing and aromatic moieties. Comparative wave-number changes/differences/shifts in this region reflect diagenetic influence, e.g. particularly oxida- tion (BERNER, 1980) through geological time. The second peak series is located in the 3000–2800 cm–1 region and re- lates to aliphatic side-chain characteristics as signals from the biopolymer-cuticle matrix (STARK & TIAN, 2006). From this region the CH2/CH3 ratios were calculated after deconvolution of bands, with the band width and band en- hancement kept constant. But caution is necessary in the in- terpretation, as the ratio is sensitive to changes in maturity levels (VAN BERGEN et al., 2004). Qualitative examination of FTIR spectra shows close similarity between the fossilized-cuticle and compression spectra (Fig. 3), i.e., all show distinct aliphatic bands in the 3000–2800 cm–1 aliphatic stretching region, and in the 1500– 1300 cm–1 aliphatic bending region. The most prominent band at 1607 cm–1 is assigned to aromatic carbon on the ba- sis of the position of the peak as well as its shape. Aromatic hydrogen bands in the 3100–3000 cm–1 region are very small but present in all spectra. In the 900–700 cm–1 aromatic out- of-plane region, only one band at ~750cm–1 is detected that indicates four adjacent C-H groups. A slight difference is Table 2: Elemental analyses (weight %) of the fossilized cuticle, compres- sion, and coal (vitrain) from the underlying Lloyd Cove Seam. N C H S Fossilized cuticle 1.71 67.85 4.70 5.35 Compression 1.68 65.50 4.48 4.82 Coal 1.36 75.92 5.22 nd nd not determined (LYONS et al., 1995, Table 1). Table 3: Sample weights for FTIR spectra. Spectrum Weight Spectrum Weight Comp1 1.1 2FC 1.1 Comp2 1.1 1FC 1.2 Comp3 1.1 3FC 1.3 Comp compression, FC fossilized cuticle. Figure 3: Composite presentation of the spectra, where FC is fossilized cu- ticle, and Comp the compression. The benzene ring (right) symbolizes the oxygenated aromatics and the chain the aliphatic hydrocarbon chain. Table 1: Average cellular length/width ratios (µm). Cushion part n Range Average Ratio length/ widthlength width length width Above leaf scar 22 22–65 7–30 34.8 19.4 ca. 2 18 45–114 5–19 74.8 12.4 ca. 6 Zodrow et al.: Lepidodendron dawsonii: functional groups and pyrolysates of compression and fossilized-cuticle (Late Asturian, Canada) Geologia Croatica 371 noted in relative band absorbance; it is higher for 1FC (fos- silized cuticle) and 3FC, correlating with increasing sample weight (Tab. 3) because the spectra are not weight-normal- ized. This observation conforms to the empirical Lambert- Beer Law that relates absorption of light to the amount of material through which the light travels. Closer semi-quantitative evaluation and comparison of spectra can be achieved by means of integration of area un- der spectral bands, and calculation of their ratios (see ZODROW & MASTALERZ, 2007; D’ANGELO et al., 2011a). Table 4 lists the spectral regions and FTIR-derived ratios selected as being the most useful for the purpose of this study. In effect, the ratios have a semi-quantitative chem- ical meaning and have been utilized, for example, in palaeo- chemotaxonomic studies (LYONS et al., 1995; ZODROW & MASTALERZ, 2001; ZODROW et al., 2003), character- izing morphotypes (ZODROW et al., 2000), reconstructing kerogen (D’ANGELO et al., 2011a), or in documenting pres- ervation variability (D’ANGELO et al., 2011b). Table 5 sum- marizes the semi-quantitative chemical data (FTIR-derived ratios) that in effect constitute the remaining organic mate- rial of the plant we call L. dawsonii, in these particular pres- ervation states. The analytical data (Tab. 5) clearly show that in respect to aromaticity some differences exist between the compres- sions and fossilized-cuticles, with the average aromaticity (AR1) and AR2) being slightly higher for fossilized cuticles, which corresponds to slightly higher elemental carbon (Tab. 2). However, the estimated degree of condensation of aro- matic ring structure, benzene ring (CAR1 and CAR2) is higher for the coaly compression, as is expected. The most noted spectrochemical difference between these two preser- vation states is, however, for the CH2/CH3 ratios which are consistently smaller (mean 2.24) in fossilized-cuticle vs the compressions (2.60), implying comparatively shorter and more branched hydrocarbon chains in the biomacromolecule for the fossilized-cuticles. This is unexpected, as in our ex- perience with Laurasian-Gondwanan compression-fossil- ized-cuticle of the medullosalean foliage of Carboniferous- Upper Triassic ages, the reverse is the case, and fossilized-cuticles normally show higher CH2/CH3 ratios (see ZODROW et al., 2011, Table 4; ZODROW & MAST- ALERZ, 2009, Fig. 5; ZODROW et al., 2009, Table 6; and D’ANGELO et al., 2011b, Table 4). We mention parenthet- ically that a similar relationship exists between medullo- salean fossilized-cuticles and those that are treated by SCHULZE’S maceration process. In nearly each case, the Schulze’s treated fossilized-cuticle revealed higher CH2/CH3 ratios from which comparatively longer and less-branching hydrocarbon chains are interpreted (ZODROW et al., 2010, Table 3). Equally, cuticles obtained by SCHULZE’S process Table 4: FTIR absorption region and ratios used. Absorption regions (cm–1) Assignment 3100–3000 Aromatic C-H groups in stretching mode 3000–2800 Aliphatic C-H groups in stretching mode 1800–1517 C=C plus oxygen-containing groups (carboxyl, carbonyl, ketones, etc) 1500–1300 Aliphatic C-H groups in bending mode 900–700 Aromatic out-of-plane C-H groupsa Ratios Interpretation CH2/CH3 in 3000–2800 region Relates to aliphatic chain length and degree of branching; larger = longer and less branched chains Al/Ox (3000–2800)/(1517–1800) Estimates proportions of aliphatic C-H groups in relation to the sum of oxygen-containing groups and C=C Ar1 (3100–3000)/(3000–2800) Indicates aromaticity of organic matter based on aromatic stretching region; larger = more aromatic Ar2 (900–700)/(3000–2800) Indicates aromaticity of organic matter based on aromatic out-of-plane region; larger = more aromatic CAR1 (3100–3000)/(1800–1517) Estimates degree of condensation of aromatic ring structure based on aromatic stretching region; larger = higher degree of condensation CAR2 (900–700)/(1800–1517) Estimates degree of condensation of aromatic ring structure based on aromatic out-of-plane region; larger = higher degree of condensation a If present, it is not taken into account in calculations. Table 5: Semi-quantitative FTIR data. CH2/CH3 Al/Ox AR1 AR2 CAR1 CAR2 980-391-1FC 2.08 0.29 0.06 0.44 0.017 0.13 980-391-2FC 2.58 0.34 0.05 0.26 0.017 0.09 980-391-3FC 2.07 0.30 0.06 0.38 0.018 0.12 Average 2.24 0.31 0.06 0.36 0.017 0.11 980-391-2comp 2.66 0.37 0.05 0.23 0.018 0.09 980-391-3comp 2.52 0.41 0.05 0.36 0.019 0.11 980-391-4comp 2.63 0.32 0.06 0.50 0.019 0.16 Average 2.60 0.37 0.05 0.33 0.019 0.12 Note: FC– fossilized cuticle; comp – compression Geologia Croatica 65/3Geologia Croatica 372 from medullosalean compression foliage have larger CH2/ CH3 ratios (e.g. ZODROW & MASTALERZ, 2007, Figs. 8 and 9 compared with Fig. 7) which are presently being in- vestigated (unpublished research notes, 2012). Another small difference is seen in the Al/Ox ratios, Tab. 5, with fossilized-cuticles having smaller values (average 0.31) vs compressions (0.37), indicating a larger, relative to aliphatic hydrogen, contribution of carboxyl/carbonyl groups in the cuticle. A large element-oxygen content in the com- pression suggests significant portions of oxygen in com- pounds, other than carboxyl/carbonyl (for example in hy- droxyl OH HO). The major pyrolysates (and their relative abundances) are strikingly similar (Fig. 4). Both fossilized-cuticles and compressions show an n-alkene/n-alkane series up to C23. The n-aliphatic hydrocarbon series is indicative of the pres- ence of resistant cuticle hydrocarbon polymers that have been observed by EDWARDS et al. (1997), or COLLINSON et al. (1998). The abundant aromatic pyrolysates, those be- ing C0-C3 alkylbenzenes and C0-C2 alkylphenols, are most probably markers of matured lignin components (see LO- GAN & THOMAS, 1987). These pyrolytic chemical features were also observed by EDWARDS et al. (1997; and refer- ences there in) who performed analytical pyrolysis of the outer cortical tissue in Lower Devononian Psilophyton daw- sonii. Comparison of elemental percentages shows a slightly lower carbon and hydrogen content in the compression (Tab. 2), though sulfur is high and is regarded as being of domi- nantly pyritic origin, which is supported by observed sub- micron framboidal pyrite on some cushions. Disregarding the sulfur, oxygen by subtraction is ca. 25% for the fossil- ized-cuticle and 28% for the compression. In comparison with the bituminous coal from the same coal seam the roof rocks of which entombed L. dawsonii, we note that the coal- carbon content is significantly higher hydrogen is slightly higher, whereas the nitrogen content is lower. In conclusion, it is suggested that the reversal of the CH2/CH3 ratios from the bark of L. dawsonii signals kinship with the bark of Lepidodendron (and Psaronius) that is a major maceral constituent in Chinese Permian coal (QUEROL et al., 2001). The argument is based on SUN’S (2005) work who described that bark, using transmitted-light FTIR microspectroscopy, as generally being highly aliphatic Figure 4: Flash Py- GC/MS chromatograms of Lepidodendron dawsonii. A) Fossilized-cuticle. B) Compression. Peaks are annotated with appropriate chem- ical structures. n-alkene/n-alkane doublets (note: early eluting pairs have extensive overlap) numbered according to the appropriate carbon chain length. The peaks denoted as * are other C1-alkyphenols and as # are C2-alkylphenols. Zodrow et al.: Lepidodendron dawsonii: functional groups and pyrolysates of compression and fossilized-cuticle (Late Asturian, Canada) Geologia Croatica 373 (long and straight hydrocarbon chains) and low (rare) in ox- ygenated components. Though a direct comparison with our FTIR data cannot be made because we use the KBr pellets, we note that the bark from L. dawsonii has shorter and more branched hydrocarbon chains. But its low content of oxy- genated groups fits the description for the Chinese coal mac- eral. Py-GC/MS data support the FTIR evidence of aliphatic hydrocarbon chains and gives additional evidence that the oxygen-containing molecules (i.e., observed high abundance of phenolic markers) are likely associated with matured lignin marcomolecules. Overall, our results demonstrate that there are only subtle differences between the two preserva- tion states of L. dawsonii which are, however, macroscopi- cally manifest by the colour differences of the specimen. Preservation can therefore be remarkably variable over shorter specimen distances of these large plants, depending on compaction condition after burial and taphonomy. ACKNOWLEDGEMENT We thank Dr. D. 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