Distribution of aromatic steroids in geological samples: their evaluation as geochemical parameters

The distribution of ring-C monoaromatic and triaromatic steroid hydrocarbons of about fifty crude oils and sediments of various origins and ages were studied in order to test their validity as geochemical source and maturity parameters. Three ratios appeared to be useful maturity parameters, i.e. A/B cis to trans isomers in non-rearranged monoaromatics, mono/triaromatics and shortvs long-chain homologues. Four other variations may be considered as source parameters depending upon lithology or other palaeo-environmental conditions, i.e. rearranged vs non-rearranged monoaromatics, 5β/5α -methyl rearranged monoaromatics, carbon number distribution and occurrence of a yet unknown series of methylated triaromatic steroids. 5α-Methyl rearranged monoaromatics seem to be particularly important in anhydrites from sabkha environments. Recent identification of most aromatic steroid constituents occurring in geological samples confers on this class of compounds an increasing value as correlation parameters in geochemical studies.     

Lipid geochemistry of a post-glacial lacustrine sediment

The post-glacial environmental history of Voua de la Motte, a small pond, was studied by the lipid geochemistry of a 6 m long core. Palynological studies show that the deepest part of the core goes back to 10,000 yr BP corresponding to the time of formation of the lake following the retreat of the Rhodanian glacier. Hydrocarbons, aldehydes, linear alcohols, sterols, monocarboxylic and monohydroxy fatty acids, were determined throughout the core both in the free and bound lipid fractions, as well as in the tightly bound fraction for the carboxylic acids. There is no clear evidence of a transformation from the unbound to the bound form, except perhaps for the α-hydroxy acids.Qualitative as well as quantitative fluctuations in the distributions of these lipid classes were observed upward in the core. An attempt is made to correlate these fluctuations with the bioenvironmental and climatological evolution of the Basin on the basis of information obtained from palynology.     

Geochemistry of hydroxy acids in sediments—I. Some freshwater and brackish water lakes in Japan

Series of α, β, ω and (ω-1) hydroxy fatty acids (FAOHs) were determined in several freshwater and brackish water lacustrine sediments in Japan. Analytical procedure used was digestion of the solvent-extracted sediment with HF/HCl followed by solvent and saponification extraction of the residue. Abundances of α/β and ω-FAOH determined by this procedure were 2–3 times higher than those obtained by single alkaline saponification and of the same order with those provided by HCl hydrolysis. Major portion of α/β-FAOH was obtained by solvent extraction of the acid-treated sediments, while subsequent alkaline saponification was needed for the majority of ω-FAOH to be recovered. Thus determined FAOHs comprised 33–61% (Av. = 42%) of the “bound” acid constituents in the lacustrine surface sediments. The α/β and ω-FAOH composition was principally the same among the samples examined, except for relative proportions of the iso to anteiso C₁₅ and C₁₇ ß(α)-FAOH, which showed significant variations in the ranges of 0.30–1.1 and 0.46–1.5, respectively. In the holomictic lakes, the ratios together with the same ratios of the “bound” branched monocarboxylic acids tended to decrease with increasing water depth of the lakes, suggesting that the ratios may indicate an extent of the early diagenetic alteration of the bacteria-derived lipids either in water column or in surface sediment.     

Bacterial contribution to sedimentary organic matter; a comparative study of lipid moieties in bacteria and Recent sediments

A systematic study of the lipid composition of thirteen bacterial species and three Recent sediments (methanogenic sediment, cyanobacterial mat and evaporative gypsum crust) was undertaken in an attempt to recognize bacterial organic matter in sediments. A sequential method, which distinguishes between three different modes of occurrence of lipid moieties (free, OH⁻- and H⁺-labile), was applied. The acid-labile fractions are discussed.The three main groups of bacteria, archaebacteria, gram-positive eubacteria and gram-negative eubacteria, are easily distinguished. Methanogenic and extremely halophilic archaebacteria are characterized by the presence of diphytanyl glyceryl ether and the absence of fatty acids. The gram-positive eubacteria contain primarily iso- and anteiso-branched fatty acids whereas the gram-negative bacteria and sediments are dominated by β- and α-hydroxy fatty acids. A wide variety of H⁺-labile hydroxy fatty acids was observed which included several, as yet unknown, structures.β-Hydroxy fatty acids in this H⁺-labile mode of occurrence are exclusively present in bacteria. Their distribution patterns in sediments are considered “fingerprints” of past and present bacterial populations. The specific differences in β -hydroxy fatty acid compositions observed in the different bacteria and the three sediments investigated, suggest that amide-linked β-hydroxy fatty acid patterns are useful as markers of bacterial populations and therefore of environmental conditions.     

Immunological studies on microbial mats from Solar Lake (Sinai)— A contribution to the organic geochemistry of sediments

Immunological and biochemical techniques were used to investigate organic matter in microbial mats from Solar Lake (Sinai, Egypt). Antibodies, elicited in rabbits against samples taken at different depths from a core of these mats, were used for the detection of immunological determinants preserved in these samples. Special attention was given to an antiserum directed against a top mat fraction (3–10 mm depth) and an antiserum against a fraction from a lower section of the core (380–390 mm depth). Both antisera, tested in a dot-blot immunobinding assay, were found to give positive reactions with organic matter from different depths of the sediment. An immunohistochemical experiment with the antisera points to antigenic determinants on Recent and subfossil sheaths of Microcoleus. In addition, extracts of sediment samples were submitted to electrophoresis in polyacrylamide gels in order to characterize the separated macromolecules by immunological means. The results showed a rapid decrease in the number of antigenic determinants from Recent to subfossil samples. However, even in the deepest layers of the sediment (690–700 mm depth) intact biopolymers were detected.     

Characterization of melanoidins by IR spectroscopy—II. Melanoidins of galactose with arginine, isoleucine, lysine and valine

The infrared spectra of melanoidins which were prepared from galactose and neutral and basic amino acids (at various ratios) support in general the conclusion gained in Part I of this series. A striking resemblance in the IR spectra was obtained in melanoidins which were prepared from a high ratio of sugar to amino acids (Type 1). The imprint of the amino acids was observed only in type 2 melanoidins, which are enriched with amino acids.     

Oxygen-containing functional groups in land-derived humic acids—II. Changes in the oxygen distribution of humic acids during early diagenesis as revealed by derivatization methods

Extensive functional group analyses were performed on humic acids representative of eight increasing depth levels from a core drilled in the Mahakam delta (East Kalimantan, Indonesia). Oxygen amounts decrease observed during early diagenesis was related chiefly to loss of hydroxyl (lignol?) groups. Comparison between upper and deeper levels shows the following variations: hydroxyl group abundances go from 19 to 6% of humic oxygen. Identified functional groups amounts represent 47 to 32% of weight of moisture- and ash-free humic acids. No evidence of decarboxylation of humic material was detected.     

The origin and fate of 4-methyl steroids—II. Dehydration of stanols and occurrence of c30 4-methyl steranes

Certain features of the distributions of sedimentary 4-methyl steroid hydrocarbons have been investigated: (i) competitive dehydration experiments with stanols adsorbed on a shale suggests a possible explanation for the low abundance of 4-methyl sterenes relative to their desmethyl counterparts in immature sediments, (ii) a 4-methyl spirostene which is a minor product of the backbone rearrangement of 4-methylcholest-4-ene in the laboratory has been tentatively assigned; its presence in a Toarcian black shale with a second isomer provides further evidence that the sedimentary backbone rearrangement of 4-methyl sterenes is analogous to that of their desmethyl counterparts and (iii) the major C₃₀ 4-methyl steranes in Semécourt shale (Toarcian, Paris Basin) differ from those in an Eocene lacustrine shale from China; this indicates the potential complexity of C₃₀ steroidal alkanes (both 4-methyl and desmethyl) which can occur in sedimentary organic matter and shows that care must be taken in using m/z 217 mass chromatograms alone for routine input and maturity assessment using steroidal alkanes.     

K‐feldspar alteration to gel material and crystallization of glauconitic peloids with berthierine in Cretaceous marine sediments—sedimentary implications (Prebetic Zone,Betic Cordillera,SE Spain)

Glauconitic peloids from a Hauterivian condensed level in a hemipelagic unit of the Internal Prebetic (Los Villares Formation, eastern Betic Cordillera) have been studied by X‐ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM) and high‐resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM). The sediments forming the condensed level are characterized by abundant spherical to ovoid green glauconite peloids with radial cracks. Quartz, feldspar and muscovite are also abundant, whereas calcium phosphate is rarely detected. XRD analysis of the peloids reveals glauconite and small amounts of berthierine. SEM and HRTEM data show feldspar dissolution features, a Si–Al‐rich gel‐like substance filling K‐feldspar micropores and interlayering of well‐crystallized glauconite and berthierine packets. The last stage of the glauconitization process resulted in conversion of the smectitic precursor. Sedimentary and mineralogical features indicate an autochthonous origin for the glauconite. The depositional environment was a distal, hemipelagic ramp on the Southern Iberian Continental Palaeomargin. Low sedimentation rates lead to sediment condensation in a general transgressive context. The margin was affected by extensional tectonics, creating tilted blocks, resulting in lateral facies changes. The dissolution of K‐feldspars probably occurred after their deposition in the marine environment but predating the glauconitization. An influx of meteoric water is therefore required, probably related to subsurface fluxes from adjacent emergent areas (the higher parts of tilted blocks). Copyright © 2007 John Wiley & Sons, Ltd.     

Cracking risk of partially saturated porous media—Part II: Application to drying shrinkage

Drying of deformable porous media results in their shrinkage, and it may cause cracking provided that shrinkage deformations are hindered by kinematic constraints. Herein, we focus on slow drying of an initially water‐saturated sample of a microheterogeneous poroelastic material damaged by parallel mesocracks. The cracking risk is analyzed by means of the thermodynamics‐based microporoelasticity model described in the companion paper (Part I), which is extended toward consideration of the hierarchical organization of cracked argillite. Drying of a material sample is studied in a framework where macrodisplacements in direction of the crack normal are blocked, while elsewise macrostress‐free boundary conditions prevail. The model implies that the opening/closure behavior of the cracks is governed by an effective pressure, in which the average crack (under)pressure, making the crack opening smaller, competes with the average micropore (under)pressure that makes the crack opening larger. The driving force for crack propagation is a quadratic function of this effective pressure. The model proposes that if drying shrinkage deformations are hindered by kinematic constraints, onset of cracking becomes possible once air entry into the cracks is observed. Copyright © 2009 John Wiley & Sons, Ltd.     

Organic geochemistry of Deep Sea Drilling Project sediments from the Gulf of Calofornia—hydrothermal effects on unconsolidated diatom ooze

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material.The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter.Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (δ¹³C) values of kerogens decrease by 1–1.5‰ near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.     

Biogenic Graphite as a Potential Geomarker—Application to Continental Reconstructions of Pan-African Gondwana Terrains

Graphite is present in nature in several forms. Genetically they may be broadly classified as biogenic and abiogenic. The biogenic forms are those that are clearly derived from an organic precursor while the abiogenic or inorganic forms are more complex from the point of view of their origin, nature and geological relations.As a geomarker, biogenic graphite has certain advantages. It is easily recognized and shows different degrees of crystallinity depending on the relative grades of metamorphism it had undergone. Once it attains a certain degree of crystalline order, it does not revert to a lower state even under changing metamorphic conditions, thereby making it a good mineral geothermometer. It is also found in specific, restricted geological environments and is therefore useful as a boundary marker of ancient sedimentary terrains.These special characteristics of the biogenic type of graphite can be effectively used to trace sites of sedimentary basins and subsequent ocean closures that may have resulted in geosutures. Studies of the Pan-African terrains of the Gondwana crustal fragments as exemplified by the sutures of the Mozambique Belt running through East Africa, Madagascar, Sri Lanka and Antarctica illustrate this point. A further example comes from the Mashan Group of East China, one of the most productive graphite - bearing regions of the world.     

Organic geochemical studies of a Messinian evaporitic basin, northern Apennines (Italy)—II Isoprenoid and n-alkyl thiophenes and thiolanes

Series of n-alkyl and isoprenoid thiophenes and thiolanes, most of which have not been previously reported, have been identified in an extract from a Messinian (Upper Miocene) marl layer deposited under hypersaline, euxinic conditions. The identifications were based on mass spectra and Chromatographic data of synthesized reference compounds and on comparison of mass spectra, relative retention times and response on the FPD. Their specific structures and their distribution patterns show similarities with those of the alkanes. Inorganic sulphur is therefore considered to be incorporated into specific lipid moieties from (archae)bacterial and/or algal input during diagenesis. A biosynthetic origin of these compounds is also possible, however. The organic sulphur compounds encountered are thought to be indicators of a hypersaline depositional environment.