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1.
Greenschist facies rocks of the stratiform Cu-deposit of Tisová contain aliphatic hydrocarbons in the n-C13 to n-C22 range and n-fatty acids in the range of n-C8 to n-C22. The amount of n-fatty acids varies from 3.3 to 13.5 g. g–1. The presence of isoprenoid hydrocarbons, phytane and pristane, and the prevalence of even-numbered fatty acids over the odd ones give evidence of the biogenic origin of isolated substances. The CPI values of hydrocarbons and n-fatty acids and the number of hydrocarbons with a higher molecular weight increase in the deposit in stratigraphically upward direction. The variations in composition of organic matter in different horizons of the ore deposit are suggested to be the result of thermal alteration and/or alteration via the catalytic activity of ore minerals.  相似文献   

2.
《International Geology Review》2012,54(12):1391-1393
A genetic link between oils and source rocks of lower Paleozoic deposits of the Baltic syneclise is revealed from the identity of change in individual composition of hydrocarbons (HC) and their ratios along the section. It is marked most clearly from the pristane/phytane ratio and from the identical trend of n-alkane and isoprenoid distribution curves for oils and dispersed organic matter (OM). The patterns observed are complemented by the coincidence of maximums of carbon atoms in the higher molecular part (C25 - C35) of n-alkanes and by the odd/even (O/E) molecular ratio. The sterane/triterpane and mononaphthenonaphthalene/ phenanthrene ratios are found to be close. —Authors.  相似文献   

3.
The paper reviews data (acquired in 2007–2016) on aliphatic and polycyclic aromatic hydrocarbons in comparison with data on concentrations of lipids, Corg, and chlorophyll a in the water and bottom sediments the river–sea geochemical barrier (for the Northern Dvina, Ob, Yenisei, and Lena rivers). It was established that the concentrations of anthropogenic hydrocarbons decrease and these compounds precipitate like other organic compounds and particulate matter, where riverine and marine waters mix. Relatively pure water flows in the pelagic zones of seas. In spite of low temperatures in the Arctic, anthropogenic hydrocarbons transform so rapidly that natural compounds dominate in the water and bottom sediments: autochthonous in the seawater and allochthonous in the bottom sediments.  相似文献   

4.
Thermal decomposition, temperatures of four organic Zn complexes were evaluated experimentally by determining the change in sphalerite solubility with temperature in aqueous solutions containing organic compounds. The results show that decomposition takes place at 180°±5°C for lactic acid-Zn complex, 200°±5°C for EDTA-Zn, 240°±5°C for quinone-Zn and 190°±5°C for fulvic acid-Zn. It is also shown that at 190°–200°C sphalerite solubility is 4 to 7 times higher in NaCl solution containing organic compounds than that in NaCl solution without organic compounds. Studies were also conducted on the contents of Pb and Zn complexed by fulvic acid and humic acid in aqueous solutions the infrared spectra of fulvic acid-Zn and humic acid-Zn complexes, the differential thermal analysis of fulvic acid, humic acid and quinone and EDTA, and the variation in fulvic acid solubility in the seawater with temperature.  相似文献   

5.
黔北务川-正安-道真地区铝土矿位于石炭系黄龙组和二叠系梁山组之间,主要属于沉积型铝土矿。通过气相色谱(GC)与气相色谱-质谱(GC-MS)手段分析铝土矿系钻孔岩心中的生物标志物,发现了含量丰富的正构烷烃、类异戊二烯烷烃、萜类化合物与甾类化合物。对10个样品饱和烃组分GC分析表明,正构烷烃主要呈双峰式分布特征,碳数分布n-C14~n-C35,CPI值范围为0.90~3.45,表现出奇偶优势。姥鲛烷/植烷(Pr/Ph)值为0.38~077,表现出明显植烷优势。对3个样品饱和烃组分GC-MS分析表明,萜烷类化合物以C30藿烷占优势,相对丰度由大到小依次为五环三萜烷、三环萜烷、四环萜烷,并检测出少量的γ-蜡烷。规则甾烷C27-C28-C29呈近L型或V型分布,并含少量4-甲基甾烷。根据生物标志物特征参数,结合岩心样品岩相学特征,确定了铝土矿系中有机质的陆上植物与低等菌藻类双重来源,铝土质沉积时为偏酸性较还原环境,明确了铝土矿系的形成过程受到来自陆上与沉积水体内两个古生态系统的双重作用。  相似文献   

6.
Hydrogen isotope ratios were measured on n-alkanes (n-C12 to n-C31) extracted from recent lake surface sediments along a N-S European transect to test if modern climate variability is recorded in these biomarkers. δD values of the n-alkanes are compared to δD values of meteoric water from the IAEA-GNIP database spanning a range from −119‰ in northern Sweden to −41‰ in southern Italy, to lake water δD values, and to mean annual temperatures, varying between −2.0°C in the north and 13.7°C in the south.δD values of the short-chained n-alkanes n-C12 to n-C20, excluding algal derived n-C17 and n-C19, are higher in the north and lower in the south. The isotopic fractionation ε for hydrogen between meteoric water and the short-chained n-alkanes is increasing from N to S by more than 100‰ and is significantly correlated to mean annual temperature for n-C16 and n-C18. This suggests that these n-alkanes may originate from a different source in the northern lakes, possibly due to petroleum contamination, or are synthesized using a different biochemical pathway.The n-C17 and n-C19 alkanes of algal origin, the n-C21 and n-C23 alkanes originating from water plants, and the long-chain n-alkanes n-C25, n-C27, n-C29, and n-C31 of terrestrial origin, clearly correlate with δD values of meteoric water, lake water, and mean annual temperature, indicating that they excellently record the δD value of meteoric water. The mean hydrogen isotope fractionation εC17/w of −157‰ (SD = 13) between n-C17 and meteoric water is fairly constant over the wide range of different climates and lake environments, suggesting only minor influence of environmental factors on this biochemical fractionation. This suggests that δD values of n-C17 are suitable to reconstruct the isotopic composition of source water. The mean fractionation between the long-chain n-alkanes and water is −128‰ (SD = 12). The mean difference of 31‰ between both ε values is likely due to evaporative enrichment of deuterium in the leaf water. If this is the only influence on the enrichment, the difference between the δD values of terrestrial and aquatic compounds might be suitable to reconstruct terrestrial evapotranspiration of the lake environment.  相似文献   

7.
Compound-specific hydrogen isotope analysis of ether-bound isoprenoid hydrocarbons from archaeal membranes has been developed using chemical degradation and gas chromatography/pyrolysis/isotope ratio mass spectrometry. The ether-bound hydrocarbons are quantitatively converted to saturated hydrocarbons by cleavage of ether bonds with HI followed by H2 reduction in the presence of PtO2. The δD value of ether-bound hydrocarbon moieties are corrected by way of isotopic mass balance calculation for the hydrogen incorporated during the hydrogenation. The method was successfully applied to determination of the δD values of biphytane moieties in glycerol dialkyl glycerol tetraethers (GDGTs) from a Sulfolobus sp. culture and a marine sediment.  相似文献   

8.
柴达木盆地西部第三系咸水湖相原油地球化学特征   总被引:30,自引:2,他引:28       下载免费PDF全文
在系统分析柴达木盆地西部各油田40余个原油样品碳同位素和饱和烃、芳烃组成的基础上,全面剖析了该地区第三系湖相原油的地球化学特征.研究结果表明,这些原油具有特殊的碳同位素组成和异常的生物标志物分布.其全油碳同位素偏重(-26‰~-24‰);正构烷烃系列单体烃碳同位素分布曲线呈水平状,表现出类同于海相有机质的碳同位素组成特征.它们的生物标志物中正烷烃系列兼具奇碳和偶碳优势双重碳数分布模式;呈强植烷优势,Pr/Ph值大多<0.6;伽玛蜡烷普遍异常丰富,C35藿烷含量高,表征高盐、厌氧的咸水湖相沉积环境性质.芳烃组份以萘、菲系列为主,而二苯并噻吩等含硫有机化合物相对含量较低,反映该地区咸水湖相原油源岩沉积相的特殊性.柴西各油田原油地球化学参数在区域上呈规律性变化趋势,与其源岩沉积相的时空变迁相一致.  相似文献   

9.
This study examined the distributions and stable carbon isotopic compositions of saturated fatty acids (SaFAs) in one 300 cm long sedimentary profile, which was named as Site4B in Shenhu, northern South China Sea. The concentrations of total SaFAs in sediments ranged from 1.80 to 10.16 μg/g (μg FA/g dry sediment) and showed an even-over-odd predominance in the carbon chain of C12 to C32, mostly with n-C16 and n-C18 being the two major components. The short-chain fatty acids (ScFAs; n-C12 to n-C18) mainly from marine microorganisms had average δ13C values of −26.7‰ to −28.2‰, whereas some terrigenous-sourced long-chain fatty acids (LcFAs; n-C21 to n-C32) had average δ13C values of −29.6‰ to −34.1‰. The other LcFAs (n-C24 & n-C26  n-C28; average δ13C values are −26.1‰ to −28.0‰) as well as n-C19 and n-C20 SaFAs (average δ13C values are −29.1‰ and −29.3‰, respectively) showed a mixed signal of carbon isotope compositions.The relative bioproductivity calculation (marine vs. terrigenous) demonstrated that most of organic carbon accumulation throughout the sedimentary profile was contributed by marine organism. The high marine productivity in Shenhu, South China Sea may be related to the hydrocarbon seepage which evidenced by diapiric structures. Interestingly, there is a sever fluctuation of terrigenous inputs around the depth of 97 cm below the seafloor (bsf), probably resulting from the influence of the Dansgaard–Oeschger events and the Younger Dryas event as revealed by 14C age measurements.  相似文献   

10.
Volatile organic compounds with volatilities ranging between those of n-hexane and n-pentadecane were identified in open ocean and coastal marine surface water samples taken in the north central part of the Gulf of Mexico. Approximately 40 organic compounds were found. The types and concentrations of the compounds found depended upon the extent of anthropogenic and terrestrial influences. Open ocean samples consisted mostly of aromatic hydrocarbons, whereas coastal samples included alkanes, cycloalkanes, cycloalkenes, aromatic hydrocarbons, aldehydes and chlorinated hydrocarbons. Unpolluted open ocean and coastal water samples had individual concentrations rarely exceeding 5 ng/kg; some aromatic hydrocarbons approached 15 ng/kg. n-Pentadecane dominated the hydrocarbons in these samples (50–100 ng/kg). The most polluted coastal water samples had individual volatile organic concentrations as great as 150 ng/kg with total concentrations approaching 1000 ng/kg. The terpene, limonene, was found extensively in the coastal samples (up to 40 ng/kg). Photooxidization of hydrocarbons in industrial/urban atmospheres was considered as a possible source of aldehydes present in coastal water. The dynamic headspace stripping/Tenax-GC adsorption method coupled with packed column gas chromatography, and gas chromatography-mass spectrometry were used for volatile organic analysis.  相似文献   

11.
A solvent–water extraction method was proposed as an assessment tool to estimate the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils. The approach taken was to measure the percent of polycyclic aromatic hydrocarbons extracted by a solvent–water mixture and comparing the results with the percent of polycyclic aromatic hydrocarbons degraded in a soil slurry reactor. Five soil samples from three former manufactured gas plant sites and a coal–tar disposal site which were operated between 1880 and 1947, and 1945 and 1950, respectively, in Iowa, USA were used in this study. Extraction experiments were conducted using acetone–water or ethanol–water mixtures with solvent volume fractions ranging from 1.0 to 0.4 (v/v). The percent of polycyclic aromatic hydrocarbons extracted from the various soils decreased as the volume fraction of the solvent in the solvent–water mixture was reduced. An acetone–water mixture of 0.6 was found to be appropriate in correlating the percent of polycyclic aromatic hydrocarbons degraded to the percent of polycyclic aromatic hydrocarbons extracted. For the first correlation, the percent extracted and the percent biodegraded were modified by using the molecular weights and log K ow of polycyclic aromatic hydrocarbons, respectively. For the second correlation, the equation relating the percent extracted and the percent biodegraded was modified using soil properties such as organic carbon content and percent of clay and silt. Although the experiments were conducted for a limited number of soils, the extraction method appeared to be a good starting point in estimating the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils.  相似文献   

12.
A diverse collection of globally distributed soil samples was analyzed for its glycerol dialkyl glycerol tetraether (GDGT) membrane lipid content. Branched GDGTs, derived from anaerobic soil bacteria, were the most dominant and were found in all soils. Isoprenoid GDGTs, membrane lipids of Archaea, were also present, although in considerably lower concentration. Crenarchaeol, a specific isoprenoid membrane lipid of the non-thermophilic Crenarchaeota, was also regularly detected and its abundance might be related to soil pH. The detection of crenarchaeol in nearly all of the samples is the first report of this type of GDGT membrane lipid in soils and is in agreement with molecular ecological studies, confirming the widespread occurrence of non-thermophilic Crenarchaeota in the terrestrial realm. The fluvial transport of crenarchaeol and other isoprenoid GDGTs to marine and lacustrine environments could possibly bias the BIT index, a ratio between branched GDGTs and crenarchaeol used to determine relative terrestrial organic matter (TOM) input. However, as crenarchaeol in soils is only present in low concentration compared to branched GDGTs, no large effect is expected for the BIT index. The fluvial input of terrestrially derived isoprenoid GDGTs could also bias the TEX86, a proxy used to determine palaeo surface temperatures in marine and lacustrine settings and based on the ratio of cyclopentane-containing isoprenoid GDGTs in marine and lacustrine Crenarchaeota. Indeed, it is shown that a substantial bias in TEX86-reconstructed sea and lake surface temperatures can occur if TOM input is high, e.g. near large river outflows.  相似文献   

13.
石油碳、氢同位素组成的研究   总被引:12,自引:1,他引:11  
沈平  徐永昌 《沉积学报》1998,16(4):124-127
通过对我国18个含油气区、385个石油样品进行碳、氢同位素和部分馏份碳同位素分析,将所获数据对两种不同性质的石油如正常原油和轻质(凝析)油分别研究其碳、氢同位素地球化学特征,提出轻质(凝析)油的碳同位素值(δ13C为-32.5‰~ -24.3‰)比正常原油δ13C为-34.4‰~ -24.6 ‰.6‰)相对偏高;石油馏份中芳烃碳同位素组成的变化受母质继承效应更为明显。因此,用芳烃碳同位值可以判识不同母质来源的石油。与海相有关的轻质(凝析)油的氢同位素值大于-15.0‰,而非海相轻质(凝析)油的δD值( δD为-21.0‰~-1.05‰)基本覆盖了海相轻质油的分布范围,从淡水-微咸水-半咸水和海水环境其氢同位素有明显变重趋势,表明氢同位素主要与沉积环境密切相关。  相似文献   

14.
Berner (1971) has solved the differential equation governing the concentration in interstitial water of substances produced or consumed during steady-state diagenesis. We have shown that closed solutions exist for non-steady-state diagenesis as well, and that these solutions are best obtained by means of Green's functions. Non-uniform distribution of decomposable organic matter in sediments is a major cause of non-steady-state diagenesis. However, the effect of such non-uniform distributions on the composition of interstitial water in sediments is pronounced only when the rate of deposition exceeds ca. 200 cm/1000 yr. At slower deposition rates, diffusion is sufficiently rapid to damp out major fluctuations in the concentration of ions such as SO2?4, NH+4, PO3?4, and HCO?3. Concentration profiles of these ions therefore tend to be similar to steady-state profiles even if the concentration of decomposable organic matter is quite heterogeneous.The concentration of SO2?4 frequently approaches 0 in marine sediments rich in decomposable organic matter. In such sediments the total quantity of SO2?4 reduced during diagenesis is proportional to the concentration of SO2?4 in sea water even if the bacterial rate of decomposition of organic matter is nearly independent of the SO2?4 concentration in interstitial water. This implies that the rate of SO2?4 removal from sea water by reduction to sulfide is roughly proportional to the sulfate concentration in seawater.Solutions for the diagenetic equation exist for reasonable variations of the rate of ionic diffusion in interstitial waters and for changes in the rate of deposition due to compaction.  相似文献   

15.
To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C4 to C8, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and 13C, while the thermally stable part was deficient in D and 13C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and 13C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and 13C (e.g., polymerized compounds in the ISM).  相似文献   

16.
前寒武纪占了地球地质历史的八分之七,其地层中有机质的研究,是一个十分重要的领域。它主要包括两个方面的意义:一方面在于追踪地球早期历史的生物演化,企图为了解地球上生命起源和早期生命的特点提供信息;另外在于对前寒武纪、特别是晚前寒武纪地层中石油的兴趣。六十年代,G. Eglinton和M. Calvin提出了“化学化石”的概念。“化学化石”也叫做分子化石或“地球化学化石”。  相似文献   

17.
Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)wa) and hydrogen to carbon ((H/C)wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)wa 0.52) and contained less hydrogen ((H/C)wa 1.15) than marine pore water DOM (mean (O/C)wa 0.50, mean (H/C)wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.  相似文献   

18.
《Geochimica et cosmochimica acta》1999,63(19-20):3487-3497
The solubility of iron(III) hydroxide as a function of pH was investigated in NaCl solutions at different temperatures (5–50°C) and ionic strengths (0–5 M). Our results at 25°C and 0.7 M in the acidic range are similar to the solubility in seawater. The results between 7.5 to 9 are constant (close to 10−11 M) and are lower than those found in seawater (>10−10) in this pH range. The solubility subsequently increases as the pH increases from 9 to 12. The solubility between 6 and 7.5 has a change of slope that cannot be accounted for by changes in the speciation of Fe(III). This effect has been attributed to a solid-state transformation of Fe(OH)3 to FeOOH. The effect of ionic strength from 0.1 to 5 M at a pH near 8 was quite small. The solubility at 5°C is considerably higher than at 25°C at neutral pH range. The effects of temperature and ionic strength on the solubility at low and high pH have been attributed to the effects on the solubility product and the formation of FeOH2+ and Fe(OH)4. The results have been used to determine the solubility products of Fe(OH)3, K1Fe(OH)3 and hydrolysis constants, β11, β12, β13, and β14 as a function of temperature (T, K) and ionic strength (I):log K1Fe(OH)3 = −13.486 − 0.1856 I0.5 + 0.3073 I + 5254/T (σ = 0.08)log β11 = 2.517 − 0.8885 I0.5 + 0.2139 I − 1320/T (σ = 0.03)log β12 = 0.4511 − 0.3305 I0.5 − 1996/T (σ = 0.1)log β13 = −0.2965 − 0.7881 I0.5 − 4086/T (σ = 0.6)log β14 = 4.4466 − 0.8505 I0.5 − 7980/T. (σ = 0.2)Both strong ethylenediaminetetraacetic acid and weak (HA) organic ligands greatly affect iron solubility. The additions of ethylenediaminetetraacetic acid and humic material were shown to increase the solubility near pH 8. The higher solubility of Fe(III) in seawater compared to 0.7 M NaCl may be caused by natural organic ligands.  相似文献   

19.
Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO2 which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified-in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.  相似文献   

20.
Dissolved aromatic compounds in Hungarian thermal waters were first reported more than 10 years ago. Among the identified compounds were alkylbenzene, polyaromatic hydrocarbon and heteroaromatic homologue series. The appearance of dissolved organic compounds has been bound to a threshold temperature of ∼80 °C, and their distribution is controlled by the water temperature. Relative demethylation and aromatisation were observed with increasing temperature. The origin of these compounds is not proved. Among precursor candidates are humic substances.Simulation experiments were carried out on humic and fulvic acid and on their mixture to gain information on aromatic compounds formed. The samples were heated and products were measured with GC-MS.In the presence of oxygen, increasing concentration of benzene can be observed as a function of temperature. Toluene and thiophene can be identified, other alkylbenzenes are missing. Under reductive conditions the concentration of benzene, toluene and the ratio of short to long chained aromatics generally increases in every sample as a function of temperature. Main compounds are toluene and benzene. The amount of heteroaromatic compounds increases with temperature, but their relative concentration compared to aromatic hydrocarbons decreases. At higher temperatures the proportion of pyrroles drops and S and O containing ones become dominant.The different processes (formation, aromatisation, polycondensation, relative demethylation, decomposition) occur in parallel but their relative intensities vary as a function of temperature. The effects of duration and increasing temperature are similar but not equal: both demethylation and aromatisation can be observed.  相似文献   

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