Distribution of aliphatic,nonhydrolyzable biopolymers in marine microalgae

The recent discovery of several marine microalgal species which biosynthesize nonhydrolyzable, aliphatic biomacromolecules, termed algaenans, has provided new insights about the nature and origin of the organic matter preserved in marine sediments. This paper reports the examination of 12 new species of marine microalgae from five different classes; the results are discussed together with previous observations on marine algaenans. None of the diatoms and prymnesiophytes and only one of the dinoflagellates examined in the present study produced algaenan, whereas all the eustigmatophytes biosynthesize a very specific algaenan composed of polyether-linked long-chain alkyl units. Many of the chlorophytes investigated, as with their freshwater counterparts, also produce algaenan. The location of the algaenan in the algal cells and the resistance of these materials to chemical and bacterial attack are discussed with respect to their role as a potential sink of organic carbon in aquatic environments.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.     

Algal lipids as a possible contributor to the polymethylene chains in kerogen

Lipid fraction and cell-wall materials have been separated from three types of algae (blue green, Microcystis sp.; green, Scenedesmus sp. and diatomaceous Diatoma sp.) and their KMnO₄ oxidation products (aliphatic $\text{α,ω-C}{}_2\text{-C}{}_{12}$ dicarboxylic acids; aliphatic normal C₁₄–C₂₄ monocarboxylic acids; benzoic acid and C₁₈ isoprenoidal ketone) examined by gas chromatography and gas chromatographymass spectrometry. The results suggest that the lipid material could make a greater contribution to polymethylene chains in kerogen than the cell-wall material, when the kerogens are mainly derived from algal components.     

Origin and formation pathways of kerogen-like organic matter in recent sediments off the Danube delta (northwestern Black Sea)

The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S₀ (0–0.5 cm bsf), S₁₀ (10–13 cm bsf), and S₂₀ (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ¹³C_org) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state ¹³C and ¹⁵N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.     

Heterogeneous organic matter from the surface horizon of a temperate zone marsh

Abundance, bulk chemical composition and sources of the organic matter in the surface horizon of the permanently water-covered part of an intermittently water-covered marsh were investigated. Lipids, insoluble non-hydrolysable macromolecular organic matter and black carbon fractions were isolated and examined via Rock-Eval pyrolysis, elemental analysis, Fourier transform infrared spectroscopy, isotopic (δ¹³C, δ¹⁵N) methods and high resolution transmission electron microscopy. Integration of bulk Rock-Eval data, elemental and isotopic composition, together with spectroscopic features, suggested immature Type III organic matter derived mainly from C₃ vascular plants. The distribution of n-alkanes from the non-aromatic lipid fraction exhibited the importance of emergent macrophytes and terrestrial plants, as well as a moderate input of submerged/floating macrophytes to the source biomass. Mathematical deconvolution of a Rock-Eval pyrogram revealed highly heterogeneous organic matter composed of a mixture of thermally labile biopolymers (36%) at various stages of decomposition, as well as humic substances and highly refractory organic matter (64%) in the whole sample. Markedly lower heterogeneity and aliphaticity, together with a higher proportion of humic substances and highly refractory organic matter (ca. 84%) were observed in the macromolecular fraction. An abundant contribution of black carbon to the macromolecular fraction was indicated by mathematical deconvolution of the Rock-Eval pyrogram and was clearly shown by the isolation of this fraction and chemical oxidation. The black carbon fraction appeared to account for ca. half of the macromolecular fraction, the carbon in these two fractions representing 30% and 14% of the initial carbon, respectively. The electron microscopy observations directly evidenced the presence of black carbon, which was comprised of both amorphous poorly organized particles and highly ordered onion-shaped particles.     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

Geochemistry,Petrography and Spectroscopy of Organic Matter of Clay‐Associated Kerogen of Ypresian Series: Gafsa‐Metlaoui Phosphatic Basin,Tunisia

This work presents geochemical characterization of isolated kerogen out of clay fraction using petrography studies, infrared absorption and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, with N‐alkane distributions of saturated hydrocarbon. Mineralogical study of clay mineral associations was carried out using X‐ray diffraction (XRD), on Ypresian phosphatic series from Gafsa‐Metlaoui basin, Tunisia. The XRD data indicate that smectite, palygorskite and sepiolite are the prevalent clay minerals in the selected samples. In this clay mineral association, the N‐alkane (m/z = 57) distribution indicates that the marine organic matter is plankton and bacterial in origin. The kerogens observed on transmitted light microscopy, however, appear to be totally amorphous organic matter, without any appearance of biological form. The orange gel‐like amorphous organic matter with distinct edges and homogenous texture is consistent with a high degree of aliphaticity. This material has relatively intense CH₂ and CH₃ infrared bands in ¹³C NMR peaks. This aliphatic character is related to bacterial origin. Brown amorphous organic matter with diffuse edges has a lower aliphatic character than the previous kerogen, deduced from relatively low CH₂ and CH₃ infrared and ¹³C NMR band intensities.     

Structural changes of young kerogen during laboratory heating as revealed by alkaline potassium permanganate oxidation

Kerogen was isolated from a marine sediment from Tanner Basin, offshore California. Samples of the kerogen were heated under an inert atmosphere at various temperatures and times. The heated and unheated kerogens were subjected to alkaline potassium permanganate oxidation followed by GC/ MS analysis of the products. The kerogens yielded primarily aliphatic C₂–C₁₄ α,ω-dicarboxylic acids and benzene mono-to-pentacarboxylic acids. Yields of aliphatic dicarboxylic acids from kerogen decreased with increasing thermal alteration. Yields of benzenecarboxylic acids increased steadily with increasing thermal alteration. The data support the concept that thermal maturation during natural burial of this type of kerogen results in the generation of aliphatic hydrocarbons from an increasingly aromatic residue.     

Molecular taphonomy of macrofossils from the Cretaceous Las Hoyas Formation,Spain

Macromolecular analysis of fossil fish scales from the Cretaceous Las Hoyas Formation (using pyrolysis-gas chromatography-mass spectrometry) revealed a dominant aliphatic composition (C₈ to C₂₂) whereas modern fish scale is proteinaceous (largely collagenous). Structural analysis of the aliphatic polymer using thermochemolysis revealed the importance of ester linkages; saturated fatty acids C₁₄ to C₁₈ (particularly C₁₆) are the most abundant. These acid components and their unsaturated counterparts are evident in the lipid composition of modern fish scales. Thus, the aliphatic composition of the fossil scales is probably a result of the incorporation of lipids (including a C₁₉ aromatic hydrocarbon) from the original indicating preservation by in situ polymerization of labile aliphatic components. Fossil arthropods and plants from the same deposit also show a dominant aliphatic macromolecular component, likely derived predominantly by crosslinking of free lipid precursors. Differences in the relative distribution of molecular components indicate likely chemosystematic differences between different fossil groups.     

C NMR, micro-FTIR and fluorescence spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova Scotia, Canada: Implications for coalification and chemotaxonomy

The cuticles and cuticle-free compressions of three Carboniferous medullosan seed-fern leaf species (Macroneuropteris scheuchzeri, Neuropteris ovata var. simonii and Alethopteris lesquereuxii) were analyzed by elemental, ¹³C nuclear magnetic resonance (NMR), micro-FTIR (Fourier transform infrared) and coal petrographic techniques. The 13C NMR spectra of the cuticle-free compressions and the associated whole coal (high volatile A/B bituminous coal rank) are generally similar and consist of a large aromatic carbon peak, a smaller aliphatic carbon peak and a shoulder on the aromatic peak, representing phenolic carbons. In contrast, the ¹³C NMR spectra of the cuticles from the same leaves have a predominant peak for aliphatic carbons and a much smaller aromatic carbon peak. This difference in aromaticity between the cuticles and the cuticle-free compressions is also reflected in the higher atomic H/C ratios of the cuticles. Micro-FTIR spectra of the cuticles show oxygenated functional groups (carboxyl and ketone) similar to those in modern cuticles but their most characteristic feature is very strong bands in the aliphatic stretching region. The cuticle-free compressions (mainly vitrinite), in turn, show the absence or significant reduction in oxygenated functional groups, reduction in aliphatic stretching bands and, usually, increased absorbance of aromatic out-of-plane deformation in the 700–900 cm⁻¹ region. Fluorescence spectra for the cuticles from all three species show a great similarity with a λ_max at 580–590 nm, probably reflecting a similardegree of coalification, which is consistent with the similar vitrinite reflectance (R_r) and H/C and O/C ratios of the cuticlefree compressions.These results indicate that leaf cuticle-free compressions, which were initially cellulose rich ( 90% cellulose and hemicellulose, < 10% lignin), can alter, during peatification and coalification, to a macromolecular structure similar to that of coalified wood (initially 50% cellulose and hemicellulose, 30%–50% lignin). Thus, a lignin-enriched structure is not a prerequisite for the formation of the macromolecular structure of vitrinite. In addition, the micro-FTIR spectra reveal the complexity of the molecular structure in coalified seed-fern leaves. The micro-FFIR data reveal some significant differences among the cuticles that may be of chemotaxonomic value. Clearly, a combination of macro- and micro-techniques offers a better basis for the interpretation of the molecular structure of pre-macerals and their alteration during peatification and coalification. Also, the data presented in this paper provide important new information that extends the data from morphological and cuticular taxonomic studies of some seed ferns. The data are encouraging preliminary advances in the chemotaxonomy of medullosan seed fern species.Pyrolysis-gas chromatography (PY-GC) data for the cuticles of three seed-fern leaves indicate distinct chemical signatures for the two neuropterid leaves as compared to the Alethopteris leaf. This perhaps indicates a chemotaxomic factor, or it could be related to the greater thickness of the cuticle of Alethopteris. Mass spectrometric data are needed to identify individual components in the PY-GC chromatograms.     

Tunisian landfill leachate treatment using <Emphasis Type="Italic">Chlorella</Emphasis> sp.: effective factors and microalgae strain performance

The potential of the autoclaved Tunisian landfill leachate treatment using microalgae (Chlorella sp.) cultivation was investigated in this study. Landfill leachate was collected from Borj Chakir landfill, Tunisia. A full factorial experimental design 2² was proposed to study the effects of the incubation time and leachate ratio factors on the organic matter removal expressed in chemical oxygen demand (COD) and ammoniacal nitrogen (NH₄─N) and on the biological response of Chlorella sp. expressed by the cell density and chlorophyll content. All experiments were batch runs at ambient temperature (25 ± 2 °C). The Chlorella sp. biomass and chlorophyll a concentrations of 1.2 and 5.32 mg L^?1, respectively, were obtained with 10% leachate spike ratio. The obtained results showed that up to 90% of the ammoniacal nitrogen in landfill leachate was removed in 10% leachate ratio spiked medium with a residual concentration of 40 mg L^?1. The maximum COD removal rate reached 60% within 13 days of incubation time indicating that microalgae consortium was quite effective for treating landfill leachate organic contaminants. Furthermore, with the 10% leachate ratio spiked medium, the maximum lipid productivity was 4.74 mg L^?1 d^?1. The present study provides valuable information for potential adaptation of microalgae culture and its contribution for the treatment of Tunisian landfill leachate.     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Differences in the mode of incorporation and biogenicity of the principal aliphatic constituents of a Type I oil shale

Compound-specific stable carbon isotope (δ ) measurements on the aliphatic hydrocarbons released from an immature Tertiary oil shale (Göynük, Turkey) via hydropyrolysis, following solvent extraction and a milder hydrogenation treatment, have further highlighted that significant compositional differences may exist between the principal aliphatic constituents of the solvent extractable (bitumen) phase and the insoluble macromolecular network (kerogen) comprising the bulk of sedimentary organic matter. Whilst inputs from diverse sources; including algae, bacteria and terrestrial higher plants, were implied from analysis of solvent-extractable alkanes, the much larger quantities of kerogen-bound n-alkyl constituents released by hydropyrolysis had a uniform isotopic signature which could be assigned to (freshwater) algae. Remarkably, the aliphatics bound to the kerogen by relatively weak covalent bonds, liberated via catalytic hydrogenation, appeared to comprise mainly allochthonous higher plant-derived n-alkanes. These results provide further compelling evidence that the molecular constituents of bitumen and, indeed, of low-yield kerogen degradation products, are not necessarily reliable indicators of kerogen biogenicity, particularly for immature Type I source rocks. The isotopic uniformity of aliphatic n-hydrocarbons released by the high-conversion hydropyrolysis step for the ultralaminae-rich Göynük oil shale, lends further support to the theory that selective preservation of highly resistant aliphatic biomacromolecules is an important mechanism in kerogen formation, at least for alginite.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

A sapphirine-cordierite-garnet-sillimanite granulite from Enderby Land,Antarctica: implications for FMAS petrogenetic grids in the granulite facies

A quartz-absent magnesian paragneiss layer from Mount Sones, in the Archaean Napier complex of Enderby Land, Antarctica, contains the stable divariant FMAS assemblage sapphirine (X _Mg=78) — cordierite (X _Mg=87) — garnet (X _Mg=51) — sillimanite. Rare green spinel (X _Mg=53.5, ZnO=2.65wt%) occurs as inclusions mainly within sapphirine, but also within sillimanite and garnet. Late thin coronas of cordierite (X _Mg=90.5) mantle sapphirine in contact with extensively exsolved anorthoclase. The mineral textures are interpreted to indicate the former stability of a hypersthene-quartz absent assemblage followed by the development of the FMAS equilibrium assemblage sapphirine-cordierite-garnet-sillimanite (sp, hy, qz) and further divariant reaction involving the consumption of sapphirine. The (sp, hy, qz) assemblage uniquely defines the stable P-T reaction topology appropriate to granulites from the Napier Complex, as this paragenesis is allowed in the grids of Hensen (1971, 1986) but is not possible in other grids which assume the stability of a sapphirine-absent ([sa]) FMAS invariant point involving the phases spinel, garnet, hypersthene, cordierite, sillimanite and quartz. The observed mineral assemblages and textures are consistent with peak metamorphism between the [sp] and [hy] invariant points of Hensen (1971), at temperatures of 930–990° C, followed by cooling on a lower dP/dT trajectory towards the (sp, qz) univariant line. The initial spinel-bearing assemblage was stabilized by Zn and to a lesser extent by Ni and Cr, and hence does not require a marked decrease in temperature and increase in pressure to produce the (sp, hy, qz) assemblage. It is inferred that fO ₂ conditions substantially lower than those used in the experiments of Annersten and Seifert (1981) prevailed in the high-grade metamorphism in the Napier Complex.     

Diagenesis of plant biopolymers: Decay and macromolecular preservation of Metasequoia

Analysis of modern Metasequoia leaves revealed the presence of the structural polyester cutin, guaiacyl lignin units and polysaccharides. Analysis of environmentally decayed Metasequoia leaves revealed that guaiacyl lignin units and cellulose were degraded more than vinyl phenol (the last being the primary pyrolysis product of cutin and plant cuticles) suggesting that cutin is more stable than lignin and cellulose during degradation, contrary to some previous studies. This observation is supported by electron microscopy showing changes in the cellular structure and cuticle of modern, decayed and fossil Metasequoia leaves. Metasequoia fossils from the Eocene of Republic (Washington State) showed a significant aliphatic component, but biopolymeric lignin and polysaccharides were not detected. Fossils from the Eocene of Axel Heiberg revealed the presence of lignin and an aliphatic polymer up to C₂₉ with cellulose, and fossils from the Miocene Clarkia deposit (Idaho) revealed lignin and an aliphatic polymer up to C₂₇ without any polysaccharides. Modern Metasequoia needles heated experimentally in confined conditions generated a macromolecular composition with an aliphatic polymer up to C₃₂ and additional phenolic compounds similar to those present in the fossils. Experimental heating of cutin is known to generate an aliphatic polymer with carbon chain length units <C₂₀. Thus, the n-alkyl component with chain length units >C₂₀ in the heated Metasequoia needles is a product of incorporation of longer chain plant waxes, indicated by the odd/even predominance of the >C₂₇ n-alkanes. The resistant nature of cutin compared to lignin and polysaccharides explains the presence of an n-alkyl component (<C₂₀) in fossil leaves even when polysaccharides are absent and lignin has decayed; cutin and its diagenetically altered products contribute significantly to the presence of aliphatic components in terrestrially derived sedimentary organic matter.     

New insight on aliphatic linkages in the macromolecular organic fraction of Orgueil and Murchison meteorites through ruthenium tetroxide oxidation

Ruthenium tetroxide oxidation was used to examine the macromolecular insoluble organic matter (IOM) from the Orgueil and Murchison meteorites and especially to characterize the aliphatic linkages. Already applied to various terrestrial samples, ruthenium tetroxide is a selective oxidant which destroys aromatic units, converting them into CO₂, and yields aliphatic and aromatic acids. In our experiment on chondritic IOM, it produces mainly short aliphatic diacids and polycarboxylic aromatic acids. Some short hydroxyacids are also detected.Aliphatic diacids are interpreted as aliphatic bridges between aromatic units in the chemical structure, and polycarboxylic aromatic acids are the result of the fusion of polyaromatic units. The product distribution shows that aliphatic links are short with numerous substitutions. No indigenous monocarboxylic acid was detected, showing that free aliphatic chains must be very short (less than three carbon atoms). The hydroxyacids are related to the occurrence of ester and ether functional groups within the aliphatic bridges between the aromatic units. This technique thus allows us to characterize in detail the aliphatic linkages of the IOMs, and the derived conclusions are in agreement with spectroscopic, pyrolytic, and degradative results previously reported.Compared to terrestrial samples, the aliphatic part of chondritic IOM is shorter and highly substituted. Aromatic units are smaller and more cross-linked than in coals, as already proposed from NMR data. Orgueil and Murchison IOM exhibit some tiny differences, especially in the length of aliphatic chains.