首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Abelsonite has been obtained from five widely separated cores in the Green River Formation of Utah. Each occurrence was in fractures or bedding plane partings of lean oil shales. High resolution mass spectra show that the abelsonite samples are vitually identical from core to core and consist largely of the nickel complex of a C-31 porphyrin of DPEP type. 1H-NMR spectra of some of the samples have been recorded and are compared with spectra of several model nickel porphyrin complexes. From these spectra it is deduced that abelsonite is largely the nickel complex of a nor-DPEP. Abelsonite is believed to differ from nickel DPEP in having a methyl substituent in place of an ethyl substituent at either carbon 3 or 8. Abelsonite is shown not to have a hydrogen substituent on any pyrrolic carbon. A chlorophyll origin of abelsonite is thus indicated. Abelsonite appears to have been introduced into the fractures and bedding planes of the rocks in which it is found subsequent to their lithification, as porphyrins different from abelsonite were extracted from shales associated with abelsonite.  相似文献   

2.
China's Gaosheng crude oil is characterized as being high in nickel and low in vanadium. Nickel porphyrins were extracted with dimetrylformamide, concentrated by absorption chromatography and demetallized with methylsulfonic acid. The concentrate of demetallized porphyrins was then separated by centrifugal thin-layer chromatography, in which DPEP, ETIO, Di-DPEP, Rhdo-ETIO, Rhdo-DPEP and Rhodo-Di-DPEP types of porphyrin were identified by mass spectrometry and UV-VIS spectroscopy. The possible geochemical pathways from DPEP to Di-DPEP and from Di-DPEP to Rhodo-DPEP series are discussed.  相似文献   

3.
This report extends our previous studies by investigating oxic and anoxic alteration of chlorophyll in 13 species of microalgae incubated between 3 and 10 years. The experiments were designed to investigate the alteration of chlorophyll as cells senescence, die and decompose. They mimic the initiation of diagenesis without the intervention of (non-microbial) grazing or photochemistry.Anoxic (dark) incubation provided two new observations and substantiated numerous other chlorophyll-a (CHLa) alteration reactions: (i) vinyl reduction, giving meso-CHLa and several derivatives, occurred, adding to observations on the phorbide/deoxophylloerythroetioporphyrin (DPEP) routes; (ii) room temperature anoxic incubation of a diatom (Navicula sp.) for 5.5 years resulted in production of purpurporphyrin-18 free acid (PurPorph-18-FA), a functionalized porphyrin and direct precursor of a specific C-30 β-H etioporphyrin. Oxic conditions typically led to high amounts of the allomers of CHLa, pheophorbide-a, and pheophytin-a, as well as to the appearance of purpurin-18 (PUR18) and/or its phytyl ester (PE). Mg-PUR18-PE, chlorin-p6-PE (the hydrolysis product of PUR18-PE) and two forms of chlorin-e6 (PE and free acid) were also often present.Such experiments have proved quite valuable for investigation of senescence/death induced alteration of the chlorophylls. In this manner, the processes can be better understood, vs. reactions occurring during grazing (heterotrophy) and early diagenesis in sediments. Various routes to specific ETIO series porphyrins from the chlorophyll-a nucleus are suggested on the basis of these data.  相似文献   

4.
The background to recent developments in investigations on coal porphyrins is reviewed. Essentially all the work of the past ten years has been with lignites and coals of the humic series. The concentrations of porphyrins and metalloporphyrins are low (0-ca. 10 μg g−1), which makes for difficulties in isolation and analysis.The preferred methods of isolation and analysis are summarised. The coal porphyrins differ from the porphyrins from crude oil, oil shale and related deposits in a variety of ways which are discussed. The major differences are the predominance of the etio series over the cycloetio series (DPEP series), the presence of Fe and Ga porphyrins (rather than Ni and VO porphyrins), and the presence of mesoporphyrin IX in lignite.Recent results tend to support Treibs' original idea (1935) that, for the coal porphyrins, both chlorophyll and iron porphyrin (haem) sources are important. The application of a weighted mean molecular mass of the porphyrins present as a biological marker in determining coal rank (Porphyrin Index of Coalification) is illustrated. Current activity is directed to the isolation and identification of individual iron complexes, and here a combination of thin layer chromatography and paramagnetically shifted 1H-NMR spectroscopy (of dicyanoferrihaems), together with direct comparison with authentic haems especially synthesised for the purpose, has been rewarding.  相似文献   

5.
Crude oils generally contain at least one symmetrical homologous series of porphyrins, which is usually centered at m/e 476 (DPEP) or m/e 478 (etioporphyrin). Simulated geochemical conditions in the present study resulted in decarboxylations and alkylations which ultimately led to the synthesis of homologous porphyrins from a single porphyrin. In several series of closed tube experiments, mesoporphyrin IX dimethylester (MPDME) was mixed with a variety of constituents including benzene, acetic acid, propionic acid, water and clay; the experiments were performed at temperatures between 135°C and 400°C at time intervals up to 80 days. Dealkylation, alkylation, hydrolysis, decarboxylation and metallation products were observed. An unsymmetrical homologous series of porphyrins was produced from MPDME. The dominant mass was m/e 478 (corresponding to a double deoarboxylation). Dealkylation products in multiples of 14 amu below the m/e 478 peak comprised the other members of the series. Cu-MPDME also produced homologous porphyrins. These, however, exhibited symmetry about the dominant members, similar to the symmetry found for the porphyrins of most petroleums and oil shales.  相似文献   

6.
Chlorophyll degradation products are preserved in marine sediments over timescales of thousands of years. The production of chlorophyll in the water column is related to biological productivity, so chlorophyll degradation products (chlorins) preserved in marine sediments can be used as indicators of paleoproductivity. A new, rapid, non-destructive method of determining chlorin concentrations in marine sediments is presented. Potential interferences associated with the solid-phase fluorescence (SPF) method are explored using reference materials, yet this method compares favorably with spectroscopic and high performance liquid chromatographic (HPLC) methods of analysis using marine sediments from Boston Harbor and the continental shelf off northwest Africa.  相似文献   

7.
Analyses of forty-two United States humic coals have revealed a striking divergence between chlorophyll diagenesis in coals when compared to the more widely studied marine sediments, shales, asphalts and petroleums. Porphyrins of humic coals have been found to be dominated by the ETIO-series, to lack members above C-32, and, in lower ranked samples (e.g. Sub-bituminous-B, high volatile C) to exhibit mass spectral envelopes with unique even-carbon number predominances. The weighted average mass, as well as the carbon number maximum (viz. mode), of these coal porphyrin homologies has been found to decrease as rank increases. The generation of porphyrins of the ETIO-series is suggested as occurring both during early coal formation, including oxidative scission of the isocyclic ring at the phorbide stage, and later during the catagenic alteration of surviving DPEP-series porphyrins. A preliminary study of chlorophyll diagenesis in a South Florida peat partially substantiates this suggestion and has further shown that the coal porphyrins can be derived from bacterial, as well as higher plant, chlorophylls.  相似文献   

8.
For the cyanobacterium Synechocystis UTEX 2470, grown photoautotrophically to a logarithmic stage of growth, the total lipid extract is depleted in 13C by 4.8% relative to average biomass. Depletions observed for acetogenic (straight-chain) lipids range from 7.6 (hexadecanoic acid) to 9.9% (a C16 n-alkyl chain bound in a polar-lipid fraction), with a mass-weighted average of 9.1%. Polyisoprenoid lipids fall into two isotopic groups, with phytol, diplopterol, and diploptene depleted by 6.4-6.9% and bishomohopanol (produced from the extracts by the preparative degradation of bacteriohopanepolyol) depleted by 8.4%. Analysis of the pattern of depletions indicates that two carbon positions in each C5 biomonomer leading to polyisoprenoid products are probably depleted in 13C relative to average biomass. The depletion of bacteriohopanepolyol relative to other polyisoprenoids can be ascribed to changes that occur over the life of each cell: (1) the 13C content of carbon flowing to lipid biosynthesis decreases as the cell size increases and (2) a greater proportion of the bacteriohopanepolyol which, unlike other polyisoprenoids, is present mainly in the cytoplasm rather than in membranes and is synthesized when cells are larger. Chlorophyll a is depleted relative to average biomass by O.7%. Given the observed depletion of 13C in phytol, the heteroaromatic, chlorophyllide portion of chlorophyll must be enriched in 13C by 2.7%. This enrichment is large relative to that in chlorophyllides produced by eukaryotes and may be related to a parallel enrichment of 13C in cyanobacterial glutamic acid. As in many previous investigations of cyanobacterial lipids, long-chain n-alkanes (C22-C29) are found in the extracts. They are, however, enriched in 13C relative to biomass and have isotopic compositions suggesting that they are contaminants of petrochemical origin. Available results indicate that cyanobacterial lipids will be depleted relative to dissolved CO2 that has served as a carbon source by 22-30% and that a wider range of depletions will be characteristic of eukaryotic products. The absence of long-chain n-alkanes in cyanobacteria reduces the possibility that petroleum ever formed from pre-eukaryotic sedimentary debris.  相似文献   

9.
The Coalport (Shropshire, U.K.) Tar Tunnel bitumen has been known since 1787 and the first geochemical data are reported here. The bitumen was analyzed for molecular markers useful for correlational studies. Gas chromatographic analysis of aliphatic and aromatic hydrocarbons failed to detect any specific major components normally used for genetic correlational and maturational studies. A search for minor and trace components by gas chromatographic-mass fragmentographic analysis showed the presence of triterpenoid hydrocarbons primarily of the 17α (H)-hopane series (C27 to C35, ex. C28) and a C26 to C31 series of ring A/B demethylated hopanes. Two homologous sterane series (C27 to C29) of the 5α, 14β, 17β (H)-sterane and 13β, 17α (H)-diasterane type were also detected. Pophyrins of the DPEP and etio series (C27 to C41, DPEP/etio > 1) were also found. Characterization of their alkyl substitution pattern demonstrated C1, C2 and C3 substituents on the pyrole moieties of the parent petroporphyrins.The molecular markers detected in this bitumen indicate its biogenic origin and show evidence of diagenetic and geothermal maturation processes. The overall geochemical characteristics of the Coalport Tar Tunnel bitumen suggest that it corresponds to a well matured crude oil, which was heavily altered by in-reservoir biodegradation or close to surface exposure.  相似文献   

10.
Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The “black shale” sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50–75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.  相似文献   

11.
Compositions and concentrations of chromophoric dissolved organic matter (CDOM) have been determined in the Bohai Sea (BS) and the Yellow Sea (YS) in the summer and autumn in 2013 by excitation and emission matrix spectroscopy (EEMs) and parallel factor analysis (PARAFAC). The PARAFAC model identified three humic-like components (C1, C2, and C3) and one protein-like component (C4). CDOM exhibited higher fluorescence intensities in the coastal areas in both the summer and autumn. However, its distribution patterns were different in the two seasons. Based on spatial and seasonal distributions of four components, as well as correlations with salinity, chlorophyll a (Chl-a), and apparent oxygen utilization (AOU), the following assignments were made. The C1, C2, and C3 components were mainly dominated by terrestrial inputs and influenced by the primary productivity of phytoplankton in the summer as well. C4 was assigned to terrestrial and autochthonous origins and most likely represented a biologically labile component. Terrestrial inputs were the dominant source of CDOM in the BS and YS. The humification index (HIX) and biological index (BIX) suggested that CDOM in the BS was more stable than that in the YS, which had an increase in autochthonous production, and in the summer, CDOM was less stable with a higher CDOM autochthonous production compared with that in the autumn.  相似文献   

12.
The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.  相似文献   

13.
Sixty samples were collected in June 1996 at regular intervals within the Seine estuary in France in order to study the arsenic (As) behavior in response to climatic and hydrologic conditions leading to major events in chlorophyll activity, anoxia, turbidity, and salinity. It was determined that arsenate (As5, 15–23 nM) is still the dominant chemical form of dissolved As in the upper, estuary. A concentration of up to 37 nM was observed in the high turbidity zone at the freshwater-seawater interface, presumably a result of pumping and remineralization of plankton particles that develop at salinities >10. The formation of arsenite (As3) was related to two processes: anoxia in the upper estuary and primary production in the superoxygenated, lower estuary. Dimethyl arsenic (DMA) concentrations (0 to 2.2 nM) were not directly correlated with chlorophyll content, but rather with oxygenation rates. Monomethyl arsenic (MMA) concentrations were low. Dissolved organoarsenic concentrations refractory to the formation of volatile hydrides showed high concentrations in the river estuary (1 to 6 nM), and their degradation was probably the cause of DMA and MMA and ultimately of the recycling of dissolved inorganic As. The remineralization of particulate arsenic (AsP) in the high turbidity zone at the freshwater-seawater interface, was apparent once AsP concentrations were normalized with respect to aluminium. This remineralization process, even though it does not exclude the possibility of intra-estuarine As inputs, could account for a major part of the high dissolved total As concentration observed in this specific zone, both in the Seine and other estuaries.  相似文献   

14.
Sediment from Tanner Basin, located at the outer continental shelf off southern California, was analyzed for photosynthetic pigments and their derivatives, namely carotenes and chlorins. Samples of the sediment were also exposed to raised temperatures (65°, 100°, 150°C) for various periods of time (1 week, 1 month, 2 months). Analysis of the heat-treated sediment revealed the presence of α-ionene and 2,6-dimethylnaphthalene, thermal-degradation products of β-carotene. Chlorins were converted to nickel porphyrins of both DPEP and etio series. Possible mechanisms and geochemical significance of these transformations are presented.  相似文献   

15.
The concentration of solvent-extractable (SE) and bound hydrocarbons, ketones, alcohols, sterols, monocarboxylic acids, hydroxyacids and α,ω-dicarboxylic acids of a surface sample (0–2.5 cm) from a recent carbonate tropical sediment taken at 60ft (18m) depth north-west of the Low Isles, North Queensland, are reported in detail. n-Alkanes are a minor constituent in the SE and bound hydrocarbon fractions with the major component being unresolved complex hydrocarbon material which is not an anthropogenic input. 6,10,14-Trimethylpentadecan-2-one derived from chlorophyll, as well as phytol, were identified as major components of the ketone and alcohol constituents. No chlorophyll pigments or pigmented degradation products were present, implying degradation before incorporation into the sediment. This conclusion is consistent with evidence for higher-plant input in which all sensitive lipids have been degraded before incorporation. SE and bound fractions have been studied in detail and show considerable differences probably arising from the importance of viable biomass in the SE fraction. Inputs to the sediment are determined as higher plants, algae, bacteria, fungi and meiofauna in descending order of importance.  相似文献   

16.
Photosynthetic pigments and other indicators of phytoplankton were analyzed in a dated undisturbed sediment core obtained from the southern basin of Lake Baikal to reveal temporal changes in the phytoplankton community in the lake through the last glacial/post-glacial transition. The sedimentation age of the core spans the last 24 14C ka. Chlorophyll a, its derivatives, carotenoids and total organic carbon (TOC) started to increase after 15 14C ka, and the onset of biogenic silica occurred at 10 14C ka. This indicated that the post-glacial growth of diatoms was preceded by that of other phytoplankton groups. In the record of the pigments and TOC, a temporary decrease was observed in the period 11.5–10.5 14C ka, corresponding to the Younger Dryas cold period. The similarity found between the depth profiles of pyropheophytin a and steryl chlorin esters formed through predation of phytoplankton by zooplankton and that of TOC suggested the important contribution of fecal pellets to sedimentary organic matter in the lake.  相似文献   

17.
Immature samples of the Permian Kupferschiefer from the Lower Rhine Basin in N.W. Germany were analysed for tetrapyrrole pigment type and abundance. The sediment, thought to have been deposited in a marine regime with enhanced salinity, was found to contain high concentrations of metalloporphyrins. The porphyrins are complexed to nickel (Ni) and oxovanadium (V=0), but high abundances of iron (Fe) porphyrins were also detected using UV/visible spectroscopy and mass spectrometry. The presence in the latter of series of aetioporphyrins, cycloalkanoporphyrins, di-cycloalkanoporphyrins and benz-cycloalkanoporphyrins was confirmed by accurate mass measurements; HPLC co-injection of deoxophylloerythroetioporphyrin (C32 DPEP) with the demetallated iron porphyrins indicated its presence in the sediment as an iron complex. The study provides the first evidence for the occurrence of Fe porphyrins in geological samples other than coals and lignites, and reports the highest concentrations in sedimentary organic matter to date.  相似文献   

18.
  相似文献   

19.
The petroporphyrins of a Cretaceous crude oil, La Paz, from western Venezuela are shown to be a mixture of etio and DPEP homologues (C27-C39) maximising at C30 and C31, respectively. Minor amounts of rhodoporphyrins (C30-C39) are also present. Thin-layer chromatography afforded fractions which have been shown by mass spectrometry to contain up to 80% of a single-molecular-weight species. Oxidative degradation of La Paz petroporphyrins to maleimides and mass-spectrometric study of t.l.c. fractions indicate that some of these porphyrins are to a great extent incompletely substituted. Dealkylation reactions have presumably played an important role in their geologic history. Furthermore, the relative simplicity of the alkyl substitution pattern of the La Paz petroporphyrins suggests that transalkylation reactions have not taken place to any significant extent.The fraction of petroporphyrins isolated from the asphaltenes contains a higher proportion of the DPEP homologues than do the total petroporphyrins isolated from the original crude oil.  相似文献   

20.
Temporal changes in paleoproductivity of Lake Biwa (Japan) over the past 32 kyr have been studied by analyzing bulk organic carbon and photosynthetic pigments (chlorins) in the BIW95-5 core. Primary productivity was estimated on the assumption of C/Norg values of 8 for autochthonous organic matter (OM) and 25 for allochthonous OM and using an equation developed for the marine environment. The estimate indicates that primary productivity ranges from 50 to 90 g C m?2 yr?1 in the Holocene, while it is ～60 g C m?2 yr?1 on average in the last glacial. Pheophytin a and pheophorbide a are the major chlorins. A downcore profile of chlorin concentration normalized to autochthonous organic carbon (OC) shows a decreasing trend. Chlorin productivity was corrected by removal of the effect of post-burial chlorin degradation. The temporal profile of chlorin productivity thereby obtained resembles that from autochthonous OC.The difference in primary productivity between the Holocene and the glacial for the lake is markedly smaller than that for Lake Baikal situated in the boreal zone. This difference between the two lakes is probably caused by the difference in their climatic conditions, such as temperature and precipitation. Precipitation at Lake Biwa is relatively large during the glacial and the Holocene because of the continuous influence of the East Asian monsoon. Lake Baikal precipitation is generally small as a result of control by the continental (Siberia) climate regime. In addition, a significant difference in productivity between the glacial and the Holocene for Lake Baikal may be essentially controlled by the hydrodynamic systems in the lake.Lake Biwa terrigenous OM input events occurred at least five times over the period 11–32 kyr BP, suggesting enhanced monsoon activity. Molecular examination of the layer with a large input of terrigenous OM during the Younger Dryas indicates that concentrations of terrigenous biomarkers such as n-C27–C31 alkanes, lignin phenols, cutin acids, ω-hydroxy acids and C29 sterols are high, suggesting that soil OM with peat-like material entered the lake as a result of flooding. An enhanced sedimentation rate in the last 3000 years might have been partially caused by agricultural activity around the lake.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号