Early generation of 20S-5α(H),14α(H),17α(H)- and 5α(H),14β(H),17β(H)-steranes in low salinity lacustrine shales

A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C₂₉ steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (R_o). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.     

大布苏碱湖的形成演化环境

根据野外现场考察和室内分析研究，首次论述了大布苏碱湖的概况，盐类矿物组合，卤水化学成分和水化学特征，研究了碳酸盐湖的形成条件和演化环境，提出了天然碱，主要是泡碱的形成背景和成碱机理。     

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

Low-temperature, polysulfide reactions of conjugated ene carbonyls: A reaction model for the geologic origin of S-heterocycles

The theoretical basis for a type of reaction of sulfur-acceptor carbon molecules with donor catenated forms of sulfur is presented. The reactions between conjugated ene carbonyls as sulfur-acceptors and polysulfide as a sulfur donor are described. The scope of this reaction is broadened by demonstrating that the room-temperature action of polysulfide on dienones produces thiophenes. Evidence is given for the structure of 2-benzoyl-5-phenylthiophene, resulting from 1,5-diphenyl-2,4-pentadien-1-one, and 2-acetyl-5-phenylthiophene, resulting from 6-phenyl-3,5-hexadien-2-one. Evidence is also presented for the structure of 2,4-dibenzoyl-3,5-diphenylthiolane, the product resulting from the action of polysulfide on the mixture of benzaldehyde and acetophenone. The same thiolane is shown to result as the minor thiolane component when chalcone reacts with polysulfide in 80% water/20% ethanol. The major component is a known rearranged thiolane identified by its physical properties. The reactiol of chalcone and polysulfide in ethanol at 0 or 25°C results in thiolane formation as evidenced by the isolation of 2,4-dibenzoyl-3,5-diphenylthiolane. However, the reaction of the same two compounds in boiling methanol (65°C) results in a competitive hydrogenation of chalcone giving dihydrochalcone in addition to the formation of thiolane. The demonstration of the low-temperature reaction of polysulfide with conjugated ene carbonyls in the present work adds an additional pathway for possible formation of S-heterocycles in the geosphere.     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

Simulated diagenesis and catagenesis of marine kerogen precursors: Melanoidins as model systems for light hydrocarbon generation

Amino acids and sugars are principal constituents of marine organisms. The condensation of amino acids and sugars is one possible nonenzymatic, early diagenetic pathway for the incorporation of these compounds into more complex geopolymers. In this study, aqueous solutions consisting of l-lysine, l-histidine, l-arginine and d-(+)-glucose were heated (100°C) for up to 288 h. Portions of the melanoidin polymer isolated after heating were reheated in the presence of water (hydrous pyrolysis) for 72 h at 325°C. Reaction products were identified by GC and GC/MS. Stable isotopic (δ¹³C) and elemental analyses were used to follow thermal evolution.While the initial melanoidin was synthesized from a simple, four component system, the products generated during hydrous pyrolysis are of considerable complexity, and include straightchain and branched alkanes, alkadienes, alkynes, indole, dimethyl indane, ethyl phenol, quinoline, and xylenes, in addition to a multitude of as yet, unidentified components. Stable carbon isotopic values for the reactants and products correspond to trends observed for naturally generated geopolymers and light gases. Elemental analyses of the melanoidin prior and subsequent to hydrous pyrolysis indicate a kerogen evolution pathway similar to that observed for natural samples. Considering the intractable nature of kerogen, laboratory simulation studies of simple systems can provide an alternative approach for elucidating the origins of geopolymers and their potential for hydrocarbon generation.     

Spectroscopic and Chromatographic studies of organic carbon in Recent marine sediments from the Peruvian Upwelling Zone

Early diagenesis of organic matter in sediments from two sites in the Peruvian Upwelling Zone (12°05′S, 77°39′W; 15°17′S, 75°24′W) has been studied by observing changes in the total organic carbon and lipid and humin fractions with depth. Transformations of the total carbon and humin fraction have been characterized by conventional and time-dependent solid state NMR techniques, while lipid diagenesis was monitored by measuring the concentration of sterols in the same sedimentary horizons. Both the quantity of total sterols and the relative abundances of individual sterols vary with sampling location, suggesting a difference in the input of biomass to the sediments at the two sites. Total sterol concentrations decrease with depth at both sites, but the loss of sterols occurs much more slowly at the more anoxic northern site, where sedimentation rates and organic carbon contents are approximately twice those at the southern site. ¹³C-NMR spectra of the total organic carbon and the humin fraction suggest that humin-like compounds are an original component of the sedimentary biomass, and dipolar-dephased spectra of the humin residue indicate that diagenetic alterations of the humin fraction are occurring even in these very young sediments. Conventional and time-dependent spectroscopic data support the hypothesis that humin formation results from selective preservation of microbially-resistant biopolymers which are an original component of the sedimentary biomass combined with loss of certain labile compounds.     

Lipid geochemistry of Lake Kinneret

Lake Kinneret, a relict lake from the Neogene, is characterised by the dominance among its phytoplankton of the dinoflagellate Peridinium cinctum. The lipid geochemistry of Lake Kinneret is discussed herein in terms of the biology, chemistry and hydrology of the lake. Lipids isolated from two sediment sections (surface and 15 cm deep), obtained from the deepest point of Lake Kinneret, include: (1) 4α-methyl-5α (H)-stanols and related derivatives characteristic of P. cinctum, the novel sterol 4a-methylgorgosterol, and peridinosterol and 4α-methylgorgostanol, not previously reported to occur in lacustrine sediments; (2) C₃₀ and C₃₂ alkane-1,15-diols, not previously reported to occur in contemporary lacustrine deposits, and (3) products of early diagenesis. Many similarities were observed with the more widely studied marine dinoflagellates and marine sediments with dinoflagellate input.     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

Aliphatic components of Victorian brown coal lithotypes

Victorian brown coal occurs in five major lithotypes distinguishable by colour index, petrography and bulk chemical analyses. The distributions of solvent extractable (free) and base hydrolysable (bound) n-alkanes, n-monocar?ylic acids, n-?,ω-dicar?ylic acids, n-ω-hydroxycar?ylic acids and n-alcohols were determined for samples of each of the five lithotypes (lithotype profile) and for seven samples of identical lithotype classification spanning a 100 m interval (depth profile) taken from a continuous bore core. The distributions of free molecular components in all classes are indicative of the predominant higher plant origin of this immature coal and provide strong support for the view that different lithotypes have derived from different, yet fairly specific paleobotanical communities. Despite an overall similarity in the distributions of aliphatic components from samples of identical lithotype classification, changes in the absolute concentrations and carbon preference indices (CPIs) of specific functional classes are observed in response to catagenetic influences even across the very small rank interval of the depth profile samples. Molecular distributions of bound components are similar to those of their free counterparts except that CPIs are generally lower and the relative contributions of lower molecular weight homologues (i.e. <C₂₂) are higher. Thedistributions of bound dicar?ylic acids and hydroxycar?ylic acids appear to reflect variations in the oxic/anoxic nature of the depositional paleoenvironments.