Characterization of Estonian Kukersite by spectroscopy and pyrolysis: Evidence for abundant alkyl phenolic moieties in an Ordovician, marine, type II/I kerogen

The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state ¹³C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C₁₉), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C₁–C₆ alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.     

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.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Possible algal origin of long chain odd n-alkanes in immature sediments as revealed by distributions and carbon isotope ratios

A Pliocene oil shale (Pula, Hungary), a C₃ plant Triticum aestivum and a C₄ plant Zea mays were compared using isotopic composition of bulk organic matter, along with distributions and individual carbon isotope ratios of n-alkanes from organic extracts. The microalga Botryococcus braunii (A race) was thus shown to be the main source of the predominant 27, 29 and 31 n-alkanes of Pula sediment Therefore, the dominance of odd carbon-numbered n-alkanes in the range C₂₅–₃₅ in extracts from immature sediments shall not be systematically assigned to higher plant contribution but algal input is also possible. In fact, the long chain n-alkanes with an odd predominance previously observed in extracts of various immature sediments are likely to be derived at least partially, from algae.     

Pyrolysis-GC characterization of whole rock and kerogen-concentrate samples of immature Jurassic source rocks from NW-Germany

Nine rock samples from three Jurassic stratigraphic units of a shallow core from NW Germany were analyzed by pyrolysis-gas chromatography. The units contain a mixed Type-II/III kerogen (Dogger-α), a hydrogen-rich Type-II kerogen (Lias-), and a hydrogen-poor Type-III kerogen (Lias-δ). All of the kerogen was immature (R_o = 0.5%). Two sets of kerogen concentrates (“AD”: HCl/HF followed by a density separation, and “A”: only acid treatment) prepared from the rock samples were also analyzed to make a detailed comparison of the pyrolysates of rock and corresponding kerogen-concentrates.Hydrogen-index (HI) values of the kerogen concentrates prepared from organic-carbon poor rock were nearly 200% higher than HI values of the rock samples. Changes in HI were minimal for the samples containing Type-II kerogen. The A and AD samples from the C_org-poor rock yielded pyrolysates with n-alkane series of very different molecular lengths. Pyrograms of the rock samples had n-alkane series extending to n-C₁₄; the chromatograms of the A samples reached the n-C₁₄-nC₂₀ range. The AD samples from C_org-poor rock and all three sample types from the C_org-rich rock had n-alkane series up to n-C₂₉. The benzene/hexane and toluene/heptane ratios for the C_org-poor rock and A samples were far higher than for the AD samples, which had ratios similar to those of all three sample types from the C_org-rich rocks. These results indicate that choice of kerogen preparation method is critical when C_org-poor samples are analyzed.     

Trace fossil evidence from the Adigrat Sandstone for an Ordovician glaciation in Eritrea, NE Africa

Trace fossils are described here from the Adigrat Sandstone formation of hitherto uncertain Palaeozoic-Mesozoic age in south-central Eritrea. The formation is subdivided into a lower unit, the Adi MaEkheno Member, and an upper informal unit, Member 2. The formation was deposited on the locally mudcracked top of the glacigenic Edaga Arbi Beds, suggesting that these two rock units were formed in a very short time interval. The Adi MaEkheno Member and the lower part of Member 2 contain trace fossils Arthrophycus alleghaniensis (Harlan), Arthrophycus ?brongniartii (Harlan), Didymaulichnus lyelli (Rouault), Palaeophycus tubularis Hall, Taenidium isp., thin winding ridges, winding ridges and furrows, simple cylinders, and ‘stellate’ forms. A. alleghaniensis is distinctively of Ordovician–Silurian (?Early Devonian) age. The trace fossil association belongs to the Cruziana ichnofacies that indicates a shallow marine environment between the normal and storm wave bases. The trace fossil data and stratigraphic relationships indicate that the Adigrat Sandstone formation and the Edaga Arbi Beds in Eritrea are Ordovician–Silurian in age. The Edaga Arbi Beds are correlated with other Upper Ordovician (Hirnantian) glacial units in northern Africa and the Arabian Peninsula, lending these beds the status of a marker unit in the Lower Palaeozoic stratigraphy of the Horn of Africa. The Jurassic “Adigrat Sandstone” in central-west and eastern Ethiopia cannot be correlated with the Adigrat Sandstone formation in its type area and in Eritrea.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

A late-glacial transition from Picea glauca to Picea mariana in southern New England

Picea is an important taxon in late-glacial pollen records from eastern North America, but little is known about which species of Picea were present. We apply a recently developed palynological method for discriminating the three Picea species in eastern North America to three records from New England. Picea glauca was dominant at  14,500–14,000 cal yr BP, followed by a transition to Picea mariana between  14,000 and 13,500 cal yr BP. Comparison of the pollen data with hydrogen isotope data shows clearly that this transition began before the beginning of the Younger Dryas Chronozone. The ecological changes of the late-glacial interval were not a simple oscillation in the position of a single species' range, but rather major changes in vegetation structure and composition occurring during an interval of variations in several environmental factors, including climate, edaphic conditions, and atmospheric CO₂ levels.     

A history of the ‘Zambian copper flower', Becium centraliafricanum (B. homblei)

This contribution is a short history of the Zambian copper flower, Becium homblei (recently renamed B. centraliafricanum that has attracted attention as a plant associated with Cu-rich soils. It has a peculiar discontinuous distribution in Central Africa which has been explained in terms of biotype depletion. A field investigation into the ecology of the species shows that it is able to tolerate soil Cu concentrations of up to 15,000 μg/g (ppm), and soil nickel concentrations of nearly 5000 μg/g. B. homblei is also found on areas where soil metals are in trace quantities, and where soil bases, particularly Ca, are low. In spite of its tolerance to a wide range of edaphic conditions, the distribution of the species is very restricted in Zimbabwe, and this is almost certainly due to severe interspecific competition with a closely related species, B. obovatum, which is common on soils not unusually enriched in heavy metals. Pioneering work on geobotanical prospecting by use of Becium homblei was carried out by the late G. Woodward and others in the 1950s and 1960s. This species was used successfully for geobotanical prospecting for Cu. This present report is a brief history of these pioneering studies     

Calcite dissolution kinetics in saline waters

The effect of ionic strength (I), pCO₂, and temperature on the dissolution rate of calcite was investigated in magnesium-free, phosphate-free, low calcium (m_Ca2+ ≈ 0.01 m) simple KCl and NaCl solutions over the undersaturation range of 0.4 ≤ Ω_calcite ≤ 0.8. First-order kinetics were found sufficient to describe the rate data where the rate constant (k) is dependent on the solution composition. Rates decreased with increasing I and were faster in KCl than NaCl solutions at the same I indicating that Na⁺ interacts more strongly with the calcite surface than K⁺ or that water is less available in NaCl solutions. Rates increased with increasing pCO₂ and temperature, and their influences diminished at high I. Arrhenius plots yielded a relatively high activation energy (E_a ≈ 20 ± 2 kJ mol^− 1) which indicated that dissolution was dominated by surface-controlled processes. The multiple regression model (MR) of Gledhill and Morse (2006a) was found to adequately describe the results at high I in NaCl solutions, but caution must be used when extrapolating to low I or pCO₂ values. These results are consistent with the hypothesis that the mole fraction of “free” solvent (X_{“free”H2O}) plays a significant role in the dissolution kinetics of calcite with a minimum value of  45–55% required for dissolution to proceed in undersaturated solutions at 25–55 °C and pCO₂ = 0.1–1 atm. This hypothesis has been incorporated into a modified version of the MR model of Gledhill and Morse (2006a) where X_{“free”H2O} has replaced I and the Ca²⁺ and Mg²⁺ terms have been dropped:

     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

Ordovician conodonts of the Tarim Region, Xinjiang, China: Occurrence and use as paleoenvironment indicators

A review of the distribution of different Ordovician conodont faunas in eight areas of the Tarim Region shows that these conodont faunas can be classified into the North China and South China types. The North China type is characterized by Aurilobodus leptosomatus, A. aurilobodus, A. simplex, Tangshanodus tanshanensis, Loxodus dissectus, Parasseratognathus paltodiformis, Microcoelodus symmetricus, Belodina compressa, B. confluens, Pseudobelodina dispansa, Yaoxianognathus yaoxianensis, and Taoqupognathus blandus. These were adapted to shallow, warm-water environments. The South China type is represented by the genera Amorphognathus, Baltoniodus, Cahabagnathus, Eoplacognathus, Lenodus, Microzarkodina, Oepikodus, Paroistodus, Paracordylodus, Periodon, Polonodus, and Pygodus, which were adapted to outer shelf, deeper, and colder water environments. Using the general pattern of conodont distribution, it is possible to interpret the various depositional environments and to reconstruct broad changes in palaeogeography of the Tarim Region during Ordovician time. In general, during Tremadocian to early Middle Ordovician time, most of the Tarim Region was a shallow semi-restricted platform that became deeper towards the north and east, with an open platform in Kalping and in the northern part of Taklimakan Desert. A slope and deep basin existed in the current Tianshan Mountains region. The Tarim sea was shallow during the Early Ordovician and became deeper during “Caradocian” (Sandbian and Early Katian) time, to become shallow again during “Ashgillian” (Late Katian) time, with the exception of part of central Taklimakan, which was a land area during “Caradocian” (Sandbian and Early Katian) time.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.     

On the affinity of Chuaria–Tawuia complex: A multidisciplinary study

In this study, biometric and structural engineering tool have been used to examine a possible relationship within Chuaria–Tawuia complex and micro-FTIR (Fourier Transform Infrared Spectroscopy) analyses to understand the biological affinity of Chuaria circularis Walcott, collected from the Mesoproterozoic Suket Shales of the Vindhyan Supergroup and the Neoproterozoic Halkal Shales of the Bhima Group of peninsular India. Biometric analyses of well preserved carbonized specimens show wide variation in morphology and uni-modal distribution. We believe and demonstrate to a reasonable extent that C. circularis most likely was a part of Tawuia-like cylindrical body of algal origin. Specimens with notch/cleft and overlapping preservation, mostly recorded in the size range of 3–5 mm, are of special interest. Five different models proposed earlier on the life cycle of C. circularis are discussed. A new model, termed as ‘Hybrid model’ based on present multidisciplinary study assessing cylindrical and spherical shapes suggesting variable cell wall strength and algal affinity is proposed. This model discusses and demonstrates varied geometrical morphologies assumed by Chuaria and Tawuia, and also shows the inter-relationship of Chuaria–Tawuia complex.Structural engineering tool (thin walled pressure vessel theory) was applied to investigate the implications of possible geometrical shapes (sphere and cylinder), membrane (cell wall) stresses and ambient pressure environment on morphologically similar C. circularis and Tawuia. The results suggest that membrane stresses developed on the structures similar to Chuaria–Tawuia complex were directly proportional to radius and inversely proportional to the thickness in both cases. In case of hollow cylindrical structure, the membrane stresses in circumferential direction (hoop stress) are twice of the longitudinal direction indicating that rupture or fragmentation in the body of Tawuia would have occurred due to hoop stress. It appears that notches and discontinuities seen in some of the specimens of Chuaria may be related to rupture suggesting their possible location in 3D Chuaria.The micro-FTIR spectra of C. circularis are characterized by both aliphatic and aromatic absorption bands. The aliphaticity is indicated by prominent alkyl group bands between 2800–3000 and 1300–1500 cm⁻¹. The prominent absorption signals at 700–900 cm⁻¹ (peaking at 875 and 860 cm⁻¹) are due to aromatic CH out of plane deformation. A narrow, strong band is centred at 1540 cm⁻¹ which could be COOH band. The presence of strong aliphatic bands in FTIR spectra suggests that the biogeopolymer of C. circularis is of aliphatic nature. The wall chemistry indicates the presence of ‘algaenan’—a biopolymer of algae.     

Unusual transition in quartzite dislocation creep regimes and crystal slip systems in the aureole of the Eureka Valley–Joshua Flat–Beer Creek pluton, California: a case for anhydrous conditions created by decarbonation reactions

Microstructures and quartz c-axis fabrics were analyzed in five quartzite samples collected across the eastern aureole of the Eureka Valley–Joshua Flat–Beer Creek composite pluton. Temperatures of deformation are estimated to be 740±50 °C based on a modified c-axis opening angle thermometer of Kruhl (J. Metamorph. Geol. 16 (1998) 142). In quartzite layers located closest (140 m) to the pluton-wall rock contact, flattened detrital grains are plastically deformed and partially recrystallized. The dominant recrystallization process is subgrain rotation (dislocation creep regime 2 of Hirth and Tullis (J. Struct. Geol. 14 (1992) 145)), although grain boundary migration (dislocation creep regime 3) is also evident. Complete recrystallization occurs in quartzite layers located at a distance of 240 m from the contact, and coincides with recrystallization taking place dominantly through grain boundary migration (regime 3). Within the quartzites, strain is calculated to be lowest in the layers closest to the pluton margin based on the aspect ratios of flattened detrital grains.The c-axis fabrics indicate that a slip operated within the quartzites closest to the pluton-wall rock contact and that with distance from the contact the operative slip systems gradually switch to prism [c] slip. The spatial inversion in microstructures and slip systems (apparent “high temperature” deformation and recrystallization further from the pluton-contact and apparent “low temperature” deformation and recrystallization closer to the pluton-contact) coincides with a change in minor phase mineral content of quartzite samples and also in composition of the surrounding rock units. Marble and calc-silicate assemblages dominate close to the pluton-wall rock contact, whereas mixed quartzite and pelite assemblages are dominant further from the contact.We suggest that a thick marble unit located between the pluton and the quartzite layers acted as a barrier to fluids emanating from the pluton. Decarbonation reactions in marble layers interbedded with the inner aureole quartzites and calc-silicate assemblages in the inner aureole quartzites may have produced high X_CO2 (water absent) fluids during deformation. The presence of high X_CO2 fluid is inferred from the prograde assemblage of quartz+calcite (and not wollastonite)+diopside±K-feldspar in the inner aureole quartzites. We suggest that it was these “dry” conditions that suppressed prism [c] slip and regime 3 recrystallization in the inner aureole and resulted in a slip and regime 2 recrystallization, which would normally be associated with lower deformation temperatures. In contrast, the prograde assemblage in the pelite-dominated outer part of the aureole is biotite+K-feldspar. These “wet” pelitic assemblages indicate fluids dominated by water in the outer part of the aureole and promoted prism [c] slip and regime 3 recrystallization. Because other variables could also have caused the spatial inversion of c-axis fabrics and recrystallization mechanisms, we briefly review those variables known to cause a transition in slip systems and dislocation creep regimes in quartz. Our conclusions are based on a small number of samples, and therefore, the unusual development of crystal fabrics and microstructures in the aureole to the EJB pluton suggests that further study is needed on the effect of fluid composition on crystal slip system activity and recrystallization mechanisms in naturally deformed rocks.     

Evidence for geographic variation in the diets of late Pleistocene and early Holocene Bison in North America, and differences from the diets of recent Bison

During the late Pleistocene and early Holocene, Bison was widely dispersed across North America and occupied most regions not covered by ice sheets. A dietary study on Bison paleopopulations from Alaska, New Mexico, Florida, and Texas was performed using two methods that relate dental wear patterns to diet, mesowear analysis and microwear analysis. These data were compared to a mixed sample of extant Bison from the North American central plains, extant wood Bison from Alberta (Canada) and a variety of other modern ungulates. Mesowear relates macroscopic molar facet shape to levels of dietary abrasion. The mesowear signature observed on fossil Bison differs significantly from the hyper-abrasive grazing diet of extant Bison. Tooth microwear examines wear on the surface of enamel at a microscopic scale. The microwear signal of fossil samples resembles to modern Bison, but the fossil samples show a greater diversity of features, suggesting that fossil Bison populations regularly consumed food items that are texturally inconsistent with the short-grass diet typical of modern plains Bison. Mesowear and microwear signals of fossil Bison samples most closely resemble a variety of typical mixed feeding ungulates, all with diets that are substantially less abrasive than what is typical for modern plains Bison. Furthermore, statistical tests suggest significant differences between the microwear signatures of the fossil samples, thus revealing geographic variability in Pleistocene Bison diets. This study reveals that fossils are of value in developing an understanding of the dietary breadth and ecological versatility of species that, in recent times, are rare, endangered, and occupy only a small remnant of their former ranges.     

Recognising biodegradation in gas/oil accumulations through the δC compositions of gas components

A large suite of natural gases (93) from the North West Shelf and Gippsland and Otway Basins in Australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases. About 26% of these gases have anomalous stable carbon isotope compositions in the C₁–C₄ hydrocarbons and CO₂ components, and are interpreted to have a secondary biogenic history. The characteristics include unusually large isotopic separations between successive n-alkane homologues (up to +29‰ PDB) and isotopically heavy CO₂ (up to +19.5‰ PDB). Irrespective of geographic location, these anomalous gases are from the shallower accumulations (600–1700 m) where temperatures are lower than 75°C. The secondary biogenic gases are readily distinguishable from thermogenic gases (74% of this sample suite), which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m. While dissolution effects may have contributed to the high ¹³C enrichment of the CO₂ component in the secondary biogenic gases, the primary signature of this CO₂ is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis. Correlation between biodegraded oils and biodegraded “dry” gas supports the concept that gas is formed from the bacterial destruction of oil, resulting in “secondary biogenic gas”. Furthermore, the prominence of methanogenic CO₂ in these types of accumulations along with some isotopically-depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked. It is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis.     

The Cenomanian/Turonian Boundary Event (CTBE) at Wunstorf, north-west Germany, as reflected by marine palynology

The Cenomanian/Turonian Boundary Event (CTBE) at Wunstorf, north-west Germany, has been analysed palynologically by high resolution sampling to reconstruct changes in relative sea-level and water mass character within photic zone waters. Based on changes in the ratio of terrigenous sporomorphs to marine palynomorphs (t/m index), the distribution of the organic-walled algal taxa as well as of selected dinocyst taxa and groups the section can largely be subdivided into pre-“plenus-bed” and post-“plenus-bed” intervals, reflecting different stages of third-order relative sea-level cycles and/or changes in water mass influence in the photic zone. Accordingly, the pre-“plenus-bed” interval is placed in a transgressive systems tract starting at the “facies change” event (C. guerangeri/M. geslinianum ammonite Zone boundary) with the maximum flooding surface at the top of the “Chondrites II” bed (top of R. cushmani Biozone). A highstand systems tract is suggested from the base of the “plenus-bed” up the base of the “fish-shale” event. Within the “fish-shale” event interval, a transgressive systems tract is suggested to start at the base of the thin, grey-green marly interbed. The Cenomanian/Turonian boundary proper, as defined by the first occurrence of Mytiloides spp., as well as the lowermost Turonian are located within the initial phase of a transgressive systems tract. With respect to water mass characteristics within photic-zone waters, the pre-“plenus-bed” interval is predominantly characterized by warm water masses that changed gradually towards the deposition of the “Chondrites II” bed, where a strong influence of cool and/or salinity-reduced waters is indicated by various palynological proxies. Within the post-“plenus-bed” interval a mixture and/or alternation of warmer and cooler waters is indicated, with the warmer water influence increasing gradually towards and within the Lower Turonian stage. The increased proportions of prasinophytes within the “Chondrites II” bed and parts of the “fish-shale” interval may indicate availability of reduced nitrogen chemospecies, especially ammonium, within photic-zone waters as a function of a vertical expansion of the oceanic O₂-minimum zone.     

Senescence- and death-related alteration of chlorophylls and carotenoids in marine phytoplankton

This report extends previous work ([Louda et al., 1998a] and [Louda et al., 1998b]. Chlorophyll degradation during senescence and death. Organic Geochemistry 29, 1233–1251.) in which we detailed type-I (alteration) and -II (destruction) degradation of chlorophyll with representative fresh water phytoplankton. The present study covers similar experiments with marine phytoplankton, namely, a cyanobacterium (“ANA” Anacystis sp), a coccolithophore (“COC” Coccolithophora sp.), a dinoflagellate (“GYM” Gymnodinium sp.) and two diatoms (“CYC” Cyclotella meneghiniana and “THAL” Thalassiosira sp.). Mg loss (‘pheophytinization') was rapid and continuous in all species under room-oxic conditions and slow or sporadic under anoxic conditions. The proportion of dephytylated pigments (pheophorbides-a, chlorophyllides-a), relative to the phytylated forms (chlorophyll-a, pheophytins-a), increased over the first year under room-oxic conditions and in room-anoxic conditions only in “CYC”. Pheophorbide-a was converted to pyropheophorbide-a within 15 months only in “THAL” and “ANA”, and slightly in “COC”. After 9–15 months of oxic incubation, “COC” was found to contain traces of purpurin-18 phytyl ester. Consideration of carotenoid pigments is also included herein. All fucoxanthin containing species, except “THAL”, exhibited conversion of fucoxanthin to fucoxanthinol in room-oxic conditions. Diadinoxanthin was rapidly de-epoxidized to give diatoxanthin within the first 2–4 weeks. Diatoxanthin then disappeared from all species by 15 months with a concurrent increase in a pigment which we tentatively identify as a cis-zeaxanthin. Incubations of pure cultures are found to be an effective way by which to model the early type-I reactions for both chlorophylls and carotenoids. The influence of oxygen during senescence-death and the onset of early diagenesis is of paramount importance. The absence of oxygen and, by inference, aerobic microbiota, retards the breakdown of these pigments dramatically.