Preserved lignin structures in early eocene Surat lignites,Cambay Basin,Western India

Lignite samples from Vastan and Tadkeshwar lignite mines, Cambay Basin have been analysed to elucidate lignin precursor using thermochemolysis-gas chromatography-mass spectrometry. The thermochemolysis products of lignites are characterized by monomethoxy-, dimethoxy-, and trimethoxybenzene derivatives originated from p-hydroxyphenyl, guaiacyl, and syringyl units of lignin polymer, respectively. The other compounds obtained in thermochemolysates of studied lignites are some resin derived C₁₅ sesquiterpenoids, with a series of fatty acid methyl esters and n-alkanes/alkenes. The methylated guaiacyl and syringyl derivatives originate from the cleavage of β-O-4 linkages and subsequent methylation of acidic hydroxyl groups of preserved lignin. Gymnosperm lignin is characterized mainly by guaiacyl derivatives whereas angiosperm lignin yields some syringyl-type compounds in addition to guaiacyl-type compounds. By analogy with the lignin structure of modern trees, the abundant occurrences of syringyl derivatives in the thermochemolysis products of Surat lignites clearly demonstrate that the palaeofloral community was dominated by angiosperms during the deposition of these lignites.     

Early biodégradation of ligneous organic materials and its relation to ore deposition in the tréves zn-pb ore body (gard, france)

Previous petrographical and geochemical studies on the organic content of mineralized and non-mineralized carbonate series in the Trèves Zn-Pb stratiform deposit led to the conclusion that ore deposition occurred during the diagenetic history of the sediments, in a mixed fresh/hydrothermal system (Gauthier and Disnar, 1984; Gauthier et al., 1985a). These circulations of fluids are probably responsible for the dolomitization of the original limestones and for the deposition of the ore through microbial activity (Gauthier, 1984; Gauthier el al., 1985b).The occurrence of this activity is supported by the formation of two kinds of organic components which are attributable to this uncommon bio-alteration process: alphatic-rich bitumen-like products and aromatic polyethers. The chemical composition of these two types of compounds suggests that they were produced from ligneous debris by (sulfate-reducing?) bacteria.Other indications of the occurrence of a biological activity have been found in the nature and relative abundance of microbial amino compounds. However, these constituents are thought to have been introduced only recently into the sediments whereas other evidence supports the idea that ore deposition occurred before diagenesis.     

Organic geochemical studies of the Muthurajawela peat deposit of Sri Lanka

Organic constituents present in the Muthurajawela peat deposit of Sri Lanka, have been investigated. Here, we report the variations with depth of sitosterol and sitostane (stigmastane), which were found to be major constituents of extracts and, hence, were selected to study the process of diagenesis.These two compounds were present in anomalous concentrations in the middle horizon of the depth profile.Considering the stratigraphy and sterol concentrations, it can be concluded that the middle horizon resulted from a sudden terrestrial input, which could have been due to a Pleistocene or Quaternary environmental change.     

The nature and origin of sesquiterpenoids in some tertiary fossil resins

Analyses of two Tertiary fossil resins and a Tertiary montan wax have revealed the presence of a number of sesquiterpenoids. Using gas chromatographic retention data obtained on both polar and non-polar stationary phases and mass spectral comparisons with authentic compounds, the sesquiterpenoids α-cedrene, cedrane, cuparene, cedren-10-one, 8βH cedran-9-one and cuparenic acid have been identified in the fossil resin retinellite and a montain wax (both Oligocene) from lignite beds in the Bovey basin of Devon, England, and in the Pliocene fossil resin ionite from the lone valley of California. U.S.A.The sesquiterpenoids α-cedrene, cuparene and cuparenic acid are characteristic constituents of the essential oils of the Cupressaceae, a family of trees and shrubs of the order Coniferales, and it is argued that these fossil resins, and the montan wax, were derived from older forms of this family of plants. The ketones cedren-10-one and 8βH cedran-9-one, and the saturated hydrocarbon cedrane, are not reported to be constituents of modern genera of Cupressaceae and may have been formed during diagenesis. The cedrane occurring in these deposits appears to be a chemical hydrogenation product of α-cedrene. The ketones, on the other hand, may have resulted from the oxidation of α-cedrene although the mechanism of these reactions is not clear. If the ketones are not undetected constituents of these plants, then the presence in these deposits of both oxidised and fully-reduced α-cedrene products infers that separate phases of oxidation and reduction occurred during the diagenesis of the fossil resins and the montan wax.     

分子有机地球化学与古气候、古环境研究

分子有机地球化学可以从分子级水平研究地质体中有机分子化合物的演化规律。本文报道了应用生物标志化合物指标探讨古气候和古环境,例如探讨古生物(含古植物)的输入,淡水、半咸水和高盐度水古环境的判识以及大气飘尘的来源和成因等。     

Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 2. Deciduous trees

Smoke particulate matter from deciduous trees (angiosperms) subjected to controlled burning, both under smoldering and flaming conditions, was sampled by high volume air filtration on precleaned quartz fiber filters. The filtered particles were extracted with dichloromethane and the crude extracts were methylated for separation by thin layer chromatography into hydrocarbon, carbonyl, carboxylic acid ester and polar fractions. Then, the total extract and individual fractions were analyzed by gas chromatography and gas chromatography–mass spectrometry. The major organic components directly emitted in smoke particles were straight chain aliphatic compounds from vegetation wax and triterpenoid acids (biomarkers) from gums and mucilages. The major natural products altered by combustion included derivatives from phenolic (lignin) and monosaccharide (cellulose) biopolymers and oxygenated and aromatic products from triterpenoids. Steroid biomarkers and polycyclic aromatic hydrocarbons (PAH) were also present, however, as minor constituents. Although the concentrations of organic compounds in smoke aerosols are highly variable and dependent on combustion temperature, the biomarkers and their combustion alteration products are in these cases source specific. The major components are adsorbed or trapped on particulate matter and thus may be utilized as molecular tracers in the atmosphere for determining fuel type and source contributions from biomass burning.     

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.     

Biomarkers in sedimentary sulfides of precambrian age

Samples of the Mt Isa formation (Australia, c, 1.5 Ga), and the Shungit formation (U.S.S.R., c. 2.3 Ga) were studied by organic geochemical means. All samples were freed of any low-molecular-weight solvent soluble organic material in order to insure the authenticity of the analysed material. The isolation of biochemical compounds entrapped in sulfides was the major goal of this work.Organic compounds that were entrapped during the early stages of sulfide formation may obviously survive extended periods of time and can be released by a mild hydrogenation of the sulfides. Preliminary investigations of the hydrocarbon fraction indicate n-alkanes, monomethylalkanes, cycloalkanes, and an unknown series of branched alkanes as major constituents. Their distribution patterns show great selectivity with respect to structures and chain lengths of individual compounds. Differences between the hydrogenation reaction product and the sample extract may arise from the release of a different kind of lipid material through dissolution of the sulfides.     

Polar constituents of organic matter rich marls from evaporitic series of the Mulhouse basin

A suite of marl samples from the evaporitic series of the Mulhouse basin (France; Lower Oligocene) was studied for its biomarker content, in particular its polar constituents. Novel series of 3-carboxyalkyl steranes and 15-oxo triaromatic ketones were identified by synthesis. The 3-carboxyalkyl steranes probably originate from highly polar precursors yet unreported in living organisms. Our data suggest that micro-algae could be the major source of these compounds which seem to be indicators of high algal input rather than characteristic of evaporitic environments. The 15-oxo triaromatic ketones could be oxidation products of triaromatic steroid hydrocarbons formed during diagenesis, although their formation during work-up procedure could not be excluded.     

Intradaily variability of water quality in a shallow tidal lagoon: Mechanisms and implications

Although surface water quality and its underlying processes vary over time scales ranging from seconds to decades, they have historically been studied at the lower (weekly to interannual) frequencies. The aim of this study was to investigate intradaily variability of three water quality parameters in a small freshwater tidal lagoon (Mildred Island, California). High frequency time series of specific conductivity, water temperature, and chlorophylla at two locations within the habitat were analyzed in conjunction with supporting hydrodynamic, meteorological, biological, and spatial mapping data. All three constituents exhibited large amplitude intradaily (e.g., semidiurnal tidal and diurnal) oscillations, and periodicity varied across constituents, space, and time. Like other tidal embayments, this habitat is influenced by several processes with distinct periodicities including physical controls, such as tides, solar radiation, and wind, and biological controls, such as photosynthesis, growth, and grazing. A scaling approach was developed to estimate individual process contributions to the observed variability. Scaling results were generally consistent with observations and together with detailed examination of time series and time derivatives, revealed specific mechanisms underlying the observed periodicities, including interactions between the tidal variability, heating, wind, and biology. The implications for monitoring were illustrated through subsampling of the data set. This exercise demonstrated how quantities needed by scientists and managers (e.g., mean or extreme concentrations) may be misrepresented by low frequency data and how short-duration high frequency measurements can aid in the design and interpretation of temporally coarser sampling programs. The dispersive export of chlorophylla from the habitat exhibited a fortnightly variability corresponding to the modulation of semidiurnal tidal currents with the diurnal cycle of phytoplankton variability, demonstrating how high frequency interactions can govern long-term trends. Process identification, as through the scaling analysis here, can help us anticipate changes in system behavior and adapt our own interactions with the system.     

Biomarker lipids of the freshwater fern Azolla and its fossil counterpart from the Eocene Arctic Ocean

Eocene sediments recovered from the Lomonosov Ridge in the central Arctic Ocean during Integrated Ocean Drilling Program Expedition 302 contain high amounts of fossil remains of the free floating freshwater fern Azolla. Both extant Azolla and the sediments from the Arctic Azolla interval were found to contain relatively high quantities of compounds identified as 1,ω20 C₃₀–C₃₆ diols. Furthermore, structurally related mid-chain hydroxy fatty acids, long chain n-alkanols and keto-ols were discovered. The different series have a common feature: there is always a hydroxy group at the ω20 position. In addition, structurally related C₂₉ ω20,ω21 diols, C₂₉ 1,20,21 triols, C₂₉ dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids are reported. Selective extraction of Azolla surface lipids revealed that these compounds are most likely present in the leaf waxes of the fern. The suite of long-chain, mid-chain ω20 hydroxy wax constituents is described for the first time. As they are well preserved in the Eocene sediments, these lipids may serve as palaeo-environmental indicators of the Arctic Azolla interval and as markers for the past occurrence of Azolla in general.     

Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 1. Temperate climate conifers

Smoke particulate matter from conifers subjected to controlled burning, both under smoldering and flaming conditions, was sampled by high volume air filtration on precleaned quartz fiber filters. The filtered particles were extracted with dichloromethane and the crude extracts were methylated for separation by thin layer chromatography into hydrocarbon, carbonyl, carboxylic acid ester and polar fractions. Then, the total extract and individual fractions were analyzed by gas chromatography and gas chromatography–mass spectrometry. The major organic components directly emitted in smoke particles were straight chain aliphatic compounds from vegetation wax and diterpenoid acids (biomarkers) from resin. The major natural products altered by combustion included derivatives from phenolic (lignin) and monosaccharide (cellulose) biopolymers and oxygenated and aromatic products from diterpenoids. Other biomarkers present as minor components included phytosterols, both the natural and altered products, and unaltered high molecular weight wax esters. Polycyclic aromatic hydrocarbons (PAH) were also present, however, only as minor constituents. Although the concentrations of organic compounds in smoke aerosols are highly variable and dependent on combustion temperature, the biomarkers and their combustion alteration products are source specific. The major components are adsorbed or trapped on particulate matter and thus may be utilized as molecular tracers in the atmosphere for determining fuel type and source contributions from biomass burning.     

Diterpenoid compounds and other lipids in deep-sea sediments and their geochemical significance

Cyclic diterpenoid compounds have been found by various investigators in the geosphere (e.g. fossil resins, coals, soil, shale and deep-sea sediments). These compounds occur in significant amounts only in higher plants and are therefore potential markers of terrigenous plant lipids.Diterpenoids with the abietane skeleton (mainly dehydroabietic acid) have been identified in the lipids of sediment samples from the northeast Pacific Ocean, Black Sea and North Atlantic Ocean. The presence of these resin-derived compounds correlated with the terrigenous clay components and with the presence of pollen. The presence of polycyclic diterpenoids was also correlated with the distribution patterns and inferred sources of other sediment lipid constituents (e.g. n-alkanes, n-fatty acids, etc.).Potamic transport, followed by turbidite redistribution are the probable input mechanisms of these resin-derived compounds to the deep-sea sediments. These diterpenoids appear to be excellent biological markers of resinous higher plants.     

Geochemistry of amino acids in some Florida peat accumulations—II. Amino acid distributions

Distributions of amino acids in some Florida peats have been compared with distributions in plants living now at the surface of the peats and in surface litter. Quantitative determinations were made by gas chromatography of volatile derivatives of both protein and non-protein amino acids. The latter. found also in mineral soils, are believed to represent bacterial cell constituents and/or anabolites. α,?-diaminopimelic acid, a constituent of the mureide complex of bacterial cell walls, was found in peats and surface litter, as were other acids believed in soil ecosystems to result from the living processes of microorganisms. The protein amino acids in peats do not show a distinctive signature of any particular kind of organism, but the nature and concentrations of the non-protein acids support the inference that the higher plant constituents are extensively re-worked and that essentially all of the amino acid material in peats is microbial in proximate origin. Thus microbial amino acids appear to be quite significant participants in the input to coalification.     

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

The high molecular weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high resolution gas chromatography and combined gas chromatography-mass spectrometry. The following compounds are present: perhydrolycopene (1; lycopane), together with one or more unsaturated analogues with the same skeleton; a series of 4-methylsteranes (2c) in higher abundance than their 4-desmethyl analogues; two series of pentacyclic triterpanes, one series (C₂₇-C₃₂) based on the hopane structure (3a-e), and the other (C₂₇-C₃₁) based on the 17α-H hopane structure (3a-d, 17αH); and an intact triterpene hop-17 (21)-ene [3c, Δ 17(21)]. Only two additional triterpanes were detected in minor concentrations, viz. 30-normoretane (3b, 21αH) and a C₃₁ triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment. Comparison of the tri- and tetraterpenoid hydrocarbons with those of the Green River Shale indicates differences in the organisms contributing to the two sediments.     

Field-ionization mass spectrometry: application to geochemical analysis

The thiourea adduct, thiourea non-adduct and aromatic fractions from a series of Alberta oil sand bitumens have been subjected to field ionization mass spectrometric analyses. Field ionization mass spectra feature little fragmentation and the molecular weight distributions of compounds in the fractions are readily obtained. Using this method, the various acyclic and cyclic saturated hydrocarbons and the hydrocarbon and thiophenic aromatic materials may be distinguished by compound type and number of carbon atoms. The effect of biodegradation on crude oils is illustrated in the results from the series of oil sand bitumens and their asphaltene pyrolysis products. Field ionization mass spectrometry is potentially an important new analytical tool in organic geochemistry.     

Esters of acyclic and polycyclic isoprenoid alcohols: Biochemical markers in lacustrine sediments

Esters of phytol or related isoprenoid acids and fatty acid esters of pentacyclic triterpenoid alcohols and sterols have been isolated from lacustrine sediments varying in age from contemporary to c. 50,000 years old. The esters were analysed by C-GC-MS and identified by GC retention data and mass spectral interpretation based on comparison with authentic compounds.In surface sediment of a productive lake, phytyl and steryl esters are biochemical markers of input from algal and Zooplankton sources. Esters of pentacyclic triterpenols detected in an older, peat-derived sediment may reflect constituents of peat-forming plant species. In sediments derived mainly from terrestrial organic matter, steryl esters containing the same acyl group showed a lower stanol/Δ⁵-stenol ratio than did the corresponding free sterols.     

Analysis of unresolved complex mixtures of hydrocarbons extracted from Late Archean sediments by comprehensive two-dimensional gas chromatography (GC×GC)

Hydrocarbon mixtures too complex to resolve by traditional capillary gas chromatography display gas chromatograms with dramatically rising baselines or “humps” of coeluting compounds that are termed unresolved complex mixtures (UCMs). Because the constituents of UCMs are not ordinarily identified, a large amount of geochemical information is never explored. Gas chromatograms of saturated/unsaturated hydrocarbons extracted from Late Archean argillites and greywackes of the southern Abitibi Province of Ontario, Canada contain UCMs with different appearances or “topologies” relating to the intensity and retention time of the compounds comprising the UCMs. These topologies appear to have some level of stratigraphic organization, such that samples collected at any stratigraphic formation collectively are dominated by UCMs that either elute early- (within a window of C₁₅–C₂₀ n-alkanes), early- to mid- (C₁₅–C₃₀ n-alkanes), or have a broad UCM that extends through the entire retention time of the sample (from C₁₅–C₄₂ n-alkanes). Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC–MS) was used to resolve the constituents forming these various UCMs. Early- to mid-eluting UCMs are dominated by configurational isomers of alkyl-substituted and non-substituted polycyclic compounds that contain up to six rings. Late eluting UCMs are composed of C₃₆–C₄₀ mono-, bi-, and tricyclic archaeal isoprenoid diastereomers. Broad UCMs spanning the retention time of compound elution contain nearly the same compounds observed in the early-, mid-, and late-retention time UCMs. Although the origin of the polycyclic compounds is unclear, the variations in the UCM topology appear to depend on the concentration of initial compound classes that have the potential to become isomerized. Isomerization of these constituents may have resulted from hydrothermal alteration of organic matter.     

论主要金属成矿的演化序列

一、前言在地质工作不断发展,地表矿和浅部矿愈来愈少的情况下,为了有效地指导普查找矿工作,成矿规律的研究引起了广大矿床学者的重视。从不同角度,用不同观点,阐明世界的或区域的成矿规律,是当前矿床学发展的主要动向之一。例如,从原子本性和核本能的角度、从成矿系列的角度、从岩浆岩成矿专属性的角度等,以及从板块构造的观     

Bicyclic sesquiterpenoids and diterpenoids in Australian crude oils

Bicyclanes previously reported only in heavily biodegraded Texas Gulf Coast crudes have been found to be ubiquitous in Australian crude oils of non-marine origin from four different basins. The compounds are present in oils, thought to be derived from the same or similar sources, that have undergone varying degrees of biodegradation. They are also found to be present in oils of different geological age. In addition a series of tricyclic diterpenoid hydrocarbons was common to four oils from the Gippsland Basin. Four of these compounds had the molecular formula C₂₀H₃₄ and mass spectral fragmentation patterns suggested they were mono-unsaturated diterpenoids. The presence of unsaturated diterpenoids in crude oils appears to be a unique observation. It is proposed that the diterpenoids may be the source of the bicyclanes also observed in these oils.