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1.
结合2008年夏季丰水期对太湖上游直湖港、大浦河、长兜港3条河流有色可溶性有机物(CDOM)吸收和三维荧光的测定分析,探讨了夏季丰水期时河流输入对太湖中CDOM的贡献.3条河流中直湖港CDOM浓度最高,大浦河次之,长兜港最低,反映了太湖北部外源河流污染物输入大于西南部.3条河流内CDOM吸收α(355)的均值为(4.7...  相似文献   

2.
青海湖底沉积物的矿物物相及有机质保存研究   总被引:2,自引:0,他引:2  
盐湖沉积环境是烃源岩发育的重要地质环境。本文以青海湖湖底沉积物为例,根据有机质与粘土矿物含最及矿物表面积的关系,分析了矿物学因素对盐湖相富有机质沉积物中有机质保存的影响。研究发现:湖底沉积物中有机质丰富,为上层水中的浮游生物和南河流携带束的陆地高等植物两种来源。矿物物相分析发现沉积物中粘土矿物含量达到32.4%,以伊利石为主。沉积物经密度分离后测试发现,有机碳含量与粘土矿物含量及矿物表面积之间具有很好的正相关性,说明粘土矿物吸附是青海湖底沉积物中有机质的主要赋存形式。  相似文献   

3.
The organic matter-rich Toolebuc Formation of eastern Australia was deposited in a Lower Cretaceous epicontinental sea. Parameters from biological marker studies indicate that the organic matter is immature to marginally mature for hydrocarbon generation. The occurrence of abundant coccoliths and the distribution of alkane biomarkers suggest that the organic matter (Type II) is largely of planktonic origin and only in the southeastern part of the depositional area can a terrestrial influence be discerned. Variations in kerogen composition can be attributed to the extent of the oxidation of the source materials and the degree of incorporation of sulphur. The atomic H/C ratios (c. 1.1) are remarkably constant for most of the Toolebuc Formation. Atomic O/C ratios vary from 0.1 and 0.4 and can be related both to depth and paleogeographic position. Kerogen sulphur contents range up to 7%, and the highest values occur in the most carbonate-rich sediments. Total sulphur (inorganic + organic) to carbon ratios in the sediments vary from 1 to <0.2 and are a function of paleogeographic position and lithology. Most of the sulphur in the sediments is in the form of pyrite, but the proportion of sulphur in organic form increases as the total sulphur content decreases. The evidence for oxidation of the organic matter and incorporation of sulphur into it during deposition suggests that bituminite, which is the dominant organic maceral in the Toolebuc Formation, was formed from an organic gel derived by decay of predominantly algal material. These data support a modified gyttja model (Kauffman, 1981) for the deposition of organic matter in the Toolebuc Formation.  相似文献   

4.
We employed direct visualization of organic matter (OM) sequestered by microfabric signatures in organo-clay systems to study mechanisms of OM protection. We studied polysaccharides, an abundant class of OM in marine sediments, associated with the nano- and microfabric of clay sediment using a novel application of transmission electron microscopy, histochemical staining (periodic acid-thiosemicarbazide-silver proteinate), and enzymatic digestion techniques. We used two experimental organo-clay sediment environments. First, laboratory-consolidated sediment with 10% chitin (w/w) added was probed for chitin before and after digestion with chitinase. Second, fecal pellets from the polychaete Heteromastus filiformis were used as a natural environment rich in clay and polysaccharides. Sections of this material were probed with silver proteinate for polysaccharides before and after digestion with a mixture of enzymes (amylase, cellulase, chitinase, dextranase, and pectinase). In both environments, chitin or other polysaccharides were found within pores, bridging clay domains, and attached to clay surfaces in undigested samples. Digested samples showed chitin or polysaccharides more closely associated with clay surfaces and in small pores. Our results imply protective roles for both sorption to clay surfaces and encapsulation within clay microfabric signatures.  相似文献   

5.
Carcasses of the shrimp Crangon crangon were incubated in a marine medium under oxic conditions at 15°C which was inoculated with a consortium of sulfate-reducing, sulfide-oxidizing, and fermentative bacteria. These standard conditions were varied by adding sediment, omitting sulfate, adding glucose, omitting the inoculum, adding phosphate, and enhancing the buffer capacity. The chemical gradients generated by decay were monitored over a period of 29 days with O2, pH- and sulfide-microelectrodes. In most of the experiments oxygen was depleted, pH decreased and sulfide accumulated around the carcass within a week, creating steep chemical gradients, and decay was predominantly anaerobic. By 29 days maximum change in O2 concentration was from around 200 to 0 μM, in pH from 7.5 to 6.2, and in sulphide concentration from 0 to 5.6 mM. Although weight loss and general decay were least when only indigenous bacteria were present, only CaCO3 crystal bundles formed and there was no soft tissue preservation. In contrast, where decay and weight loss were more extensive anaerobic sulphate reduction was intense, pH decreased markedly, and some muscle tissue was replicated in CaPO4. The pH close to the decaying carcass seemed to determine whether CaCO3 or CaPO4 formed. Paradoxically, the exceptional preservation of soft-tissues in fossils requires elevated rather than restricted microbial activity as this leads to anaerobically driven authigenic mineral formation.  相似文献   

6.
Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither 13C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.  相似文献   

7.
In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 μm). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.  相似文献   

8.
李鹏  刘全有  毕赫  孟庆强 《地质学报》2021,95(3):632-642
黑色富有机质页岩是页岩油气生成和赋存的主要母体,是强还原环境水体的沉积产物,在其形成过程中,细菌硫酸盐还原作用(BSR)对水体环境影响明显,但BSR强度如何影响有机质的保存尚未得到关注。我国陆相湖盆富有机质泥页岩广泛发育,形成过程中常常伴随有火山活动或者海侵等事件,大量硫酸盐进入湖盆,改变水体的沉积环境,不同环境下BSR对黑色页岩有机质保存的影响明显不同。本次研究选取鄂尔多斯盆地延长组长7段页岩、松辽盆地青山口组和嫩江组页岩作为对象,同时与现代沉积物进行对比。研究表明,TOC与TS之间关系复杂,但细菌硫酸盐还原强度指数(SRI)与TOC呈现幂指数变化,且表现出两阶段变化的特征。当SRI大于1.375时,TOC整体偏低,指示了强硫酸盐还原作用消耗大量有机质;当SRI小于1.375时,TOC明显较高,指示了弱硫酸盐还原作用对有机质消耗相对较少,更有利于有机质保存。火山活动和海侵作用均向水体提供了大量硫酸盐,但对陆相湖盆页岩中有机质的保存影响不同。火山活动影响的长7段页岩SRI普遍小于1.375,BSR对有机质消耗相对弱,页岩TOC高。而受海侵影响的青山口组一段底部和嫩江组一段底部页岩SRI...  相似文献   

9.
The objectives of this study were to partition out the predominant anaerobic respiration pathways coupled to C oxidation and to further elucidate the controls of anaerobic C respiration in three major saltmarsh habitats at Skidaway Island, GA; the short form of Spartina alterniflora (SS), the tall form of S. alterniflora (TS), and unvegetated, bioturbated creekbank (CB). Geochemical analysis of pore water and solid phase constituents revealed that the SS site experienced highly reducing conditions with two orders of magnitude higher pore water sulfide inventories (1.884 mmol m−2) than TS (0.003 mmol m−2) and CB (0.005 mmol m−2), respectively. Conversely, reactive Fe(III) inventories at TS (2208 mmol m−2) and CB (2881 mmol m−2) were up to 7–9 times higher than at SS (338 mmol m−2). Incubations and intact core experiments indicated that reduction accounted for 95% (SS), 37% (TS) and 66% (CB) of total anaerobic respiration. There was no detectable Fe(III) reduction at SS, while Fe(III) reduction accounted for up to 70% of C oxidation in the 3–6 cm depth interval at TS and 0–3 cm depth of CB, and on average, approximately 55% of C oxidation over two-thirds of marsh surface area. Laboratory manipulations provided further evidence for the importance of Fe(III) reduction as the accumulation rates of fermentation products were high when Fe(III) reduction was inhibited by removing the Fe(III) minerals from highly bioturbated CB sediments with higher Fe(III) mineral contents. Anaerobic C oxidation, - and Fe(III)-reduction rates appeared to be highest at the TS site during active plant growth in summer. Overall results suggest that bioturbation by macrofauna is the overriding factor in modulating the pathway of C mineralization in the saltmarsh, whereas availability of organic substrates from plants is a key factor in controlling the C oxidation rate.  相似文献   

10.
11.
Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The DH ratios of hydrogen in the organic matter vary from 8 × 10?5 to 170 × 10?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10?5 for terrestrial hydrogen and 2 × 10?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose DH ratios are greater than 30 × 10?5. If the DH ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having DH ratios above 50 × 10?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed DH ratios in organic compounds in interstellar clouds are typically 180 × 10?5 and range between about 40 × 10?5 and 5000 × 10?5. The DH values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their DH ratios.In contrast, the DH ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H2O with H2 in the solar nebula at temperatures of about 200 K and higher.The 13C12C ratios of organic matter, irrespective its DH ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the 13C12C ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high DH ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.  相似文献   

12.
谢小敏  刘伟新  张瀛  赵迪斐  唐友军  申宝剑  李志明 《地质论评》2021,67(1):67020014-67020014
四川盆地下古生界两套硅质页岩层系是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系与五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征:①同沉积无机硅质流体;②生物硅;③后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体与生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体与生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路与基础地质数据。  相似文献   

13.
四川盆地下古生界两套硅质页岩层系(寒武系底部页岩和奥陶系—志留系五峰组—龙马溪组页岩)是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系和五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征:(1)同沉积无机硅质流体;(2)生物硅;(3)后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体和生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体和生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路和基础地质数据。  相似文献   

14.
《Organic Geochemistry》1987,11(4):251-264
Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C12–C19 fatty acids and polyunsaturated C18 acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C20–C30 acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.  相似文献   

15.
Monocyclic alkanes in Ordovician organic matter   总被引:1,自引:0,他引:1  
The major compounds in the C15+ branched/cyclic alkane fractions of two Ordovician oils (Pine Unit and Midland Farms oils) and an immature Ordovician rock (Guttenberg Oil Rock) are monocyclics. One series of these compounds was identified as n-alkylcyclohexanes and another tentatively identified as methyl-n-alkylcyclohexanes. The carbon number distribution of these compounds resembled those of the n-alkanes found in these samples with an odd carbon number predominance. It is suggested that the monocyclic alkanes, in these Ordovician samples, may be principally derived from the cyclisation of straight-chain algal fatty acids, by mechanisms that involve decarboxylation. However, there is evidence from the m/z 97 fragmentograms of these samples, to indicate that methyl-n-alkylcyclohexanes can also be derived from fatty acids by a less preferred mechanism that does not involve decarboxylation or from other precursors.In addition, a sample of kerogen from the Guttenberg Oil Rock was hydrously pyrolysed. The saturated hydrocarbon products of this experiment showed very similar distributions (including monocyclics) to those observed in the Ordovician oils. This suggests that although the oils and the Guttenberg Oil Rock come from widely differing geographical locations, their precursor (algal derived) organic matter was very similar.  相似文献   

16.
13C depleted materials of three types are encountered in the south-eastern Mediterranean Coastal Plain of Israel and Northern Sinai. Sub-surface coarse carbonates associated with elemental sulfur have gd13C values of −50‰. Organic matter (humic substances and lipid soluble) in the Be'eri sulfur quarries have δ13C values of −80 to −90‰. Dissolved bicarbonate in groundwaters show δ13C values of −13 to −17‰.It is suggested that all these values can be explained by biogenic methane leaking from sub-surface reservoir which is oxidized under different depositional and environmental conditions.  相似文献   

17.
Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)2-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å−1 EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (Oax) perpendicular to the chelate plane formed by the four equatorial oxygens (Oeq) at 1.94 Å. The stronger malate-type chelate is a C4 dicarboxylate, and the weaker malonate-type chelate a C3 dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:
(1)
The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.
(2)
Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-Oeq bond and stability of the chelate.
(3)
The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.
(4)
Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.
  相似文献   

18.
《Organic Geochemistry》1999,30(8):911-927
Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.  相似文献   

19.

On the basis of GC–MS analysis, a suite of nine coal-measure source rocks (Ro 0.51%–0.63%) from the southern margin of Junggar basin was found to contain many biomarkers for bacterially-generated hydrocarbons: hopane, sesquiterpene, C23+ monomethyl alkanes (even carbon predominance), and C24+ alkyl cyclohexane. Rock–eval and microscope analysis indicate that vitrinite (especially desmocollinite and homocollinite) plays a significant role in the generation of hydrocarbons in coal-measure source rocks. Vitrinite performs this role by absorbing ultramicroscopic organic matter, generally in the form of resins or bacterial plastids. C23+ monomethyl alkanes (even carbon predominance) and C24+ alkyl cyclohexane series compounds are derived from bacterial metabolites of higher plants. The ultramicro organic matter adsorbed by vitrinite source rocks in the study area is probably ultramicro bacterial plastids. Because the organic matter of higher plants with low hydrogen content has been transformed into organic matter rich in hydrogen by bacteria, the hydrocarbon generation capacity of source rocks is greatly improved. In other words, in coal-measure source rocks, bacteria play an important role in hydrocarbon generation.

  相似文献   

20.
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.  相似文献   

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