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1.
Simoneit BR  Fetzer JC 《Organic Geochemistry》1996,24(10-11):1065-1077
Hydrothermal petroleums and heavy tars have been analyzed for polycyclic aromatic hydrocarbons (PAH) with molecular weights greater than that of coronene (300 da). Samples from the hydrothermal systems in the Guaymas Basin (Gulf of California) and in the Escanaba Trough and Middle Valley (Northeastern Pacific) were analyzed by gas chromatography-mass spectrometry and high pressure liquid chromatography with diode-array absorbance detection. Mass spectra and fluorescence spectra were used to characterize the compounds. Several large PAHs with six and more rings were identified among the heavy PAH. Production routes via one-ring build-up and Scholl-condensation are proposed to explain the observed structures. The variations in PAH concentrations and distributions between samples from different locales are a consequence of the hydrothermal conditions of generation, migration, and post-depositional alteration.  相似文献   

2.
The paper presents data on the contents of macro- and microelements (rare earth elements included) determined in grain size fractions of the Upper Pleistocene hydrothermally altered and unaltered sediments from the Guaymas Basin (Gulf of California). Sediments subjected to high-temperature hydrothermal alteration were recovered by DSDP Hole 477A. In the finely dispersed fractions, which are mainly composed of clay minerals, alteration of the chemical composition was provoked by the hydrothermal transformation of terrigenous clay minerals. The concentration of microelements in these fractions takes place primarily at the cost of the hydrothermal finely dispersed ore minerals. Alteration of the chemical composition of the coarse-grained fractions is related to the replacement of clastogenic minerals by the secondary varieties and the formation of new minerals (including ore minerals and native metals) from the solutions. Hydrothermal alterations of the chemical composition of bulk samples depend on the degree of chemical element concentration in fractions and their content in samples.  相似文献   

3.
HPLC extracts of crude petroleums and of marine recent sediments, containing the monomethyl-phenanthrene series, are examined by high resolution spectrofluorimetry in n-hexane at 15 K (Shpolskii effect). Identification and relative quantification of each of the five isomers is obtained on six natural samples. The distribution of the monomethyl-phenanthrenes and the relative absence of 4-methyl-phenanthrene in petroleums compared to marine sediments may reflect steric inhibitions.  相似文献   

4.
Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.  相似文献   

5.
《Applied Geochemistry》2002,17(11):1467-1494
Samples from the Ocean Drilling Program Leg 169 in Escanaba Trough, Gorda Ridge, NE Pacific Ocean, were analyzed to study maturation by accelerated diagenesis and/or by catagenesis of the sedimentary organic matter to hydrothermal petroleum. At Site 1038 the hydrothermal petroleums have migrated after generation to shallower horizons. The n-alkane maturation was indicated by the strong even C number preference (i.e., CPI <1.0) as in the case of Middle Valley. All samples contained admixed organic matter of terrigenous and marine components as indicated by the distributions of the biomarkers. The biological precursors were catagenetically altered to their equivalent mature compounds. The presence of high molecular weight PAHs in some sediment sections at Site 1038 reflected the high temperature alteration and reworking of organic matter into mature hydrothermal petroleum. At Site 1037, the reference hole in the Escanaba Trough, the n-alkanes with a strong predominance of odd C number homologs reflected immature non-marine lipid components essentially throughout the hole. Maturation of organic matter was only observed below 450 mbsf with n-alkanes showing a CPI <1.0. The strong even C number predominance in those intervals was attributed to initial maturation by high heat flow during the early rifting process.  相似文献   

6.
《Applied Geochemistry》2001,16(13):1545-1565
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.  相似文献   

7.
Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17α(H), 18α(H), 21β(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.  相似文献   

8.
The chemical composition of grain size fractions of the Upper Pleistocene sediments in the southern trough of Guaymas Basin (Gulf of California) is studied based on materials from DSDP Hole 477 (191 m). The sediments are located in the upper part of the main long-lived hydrothermal system. Therefore, they were subjected to long-term reworking by the middle- and low-temperature solutions (100?300°C) and short-term hydrothermal impact during the intrusion of basalt sills. The upper part of the main hydrothermal system is divided into three middle- to low-temperature hydrothermal alteration zones: lower (III), middle (II), and upper (I). In zone III (250?300°C), hydrothermal alterations of sediments are most significant. The coarsegrained fractions are enriched in Fe, S, Ni, Cu, Zn, Mo, Co, Se, Cd, Bi, Pb, and Ag due to the formation of sulfides and precipitation of native metals. The silt fractions are enriched in Be, Sc, Nb, Ta, W, Th, U, Y, and REE. In contrast, the pelite fractions are depleted in most of these elements. The fine-dispersed (<0.001 mm) pelite fractions are appreciably enriched in Mg (due to the formation of the authigenic Mg-chlorite), as well as MnO, Cr, V, Ga, Pb, and Zr. Virtually all grain size fractions are depleted in K2O, Li, Rb, Cs, and Tl due to the dissolution of the K-bearing terrigenous minerals. In zones II (146?170 m) and I (110?146 m), where the temperature of hydrothermal solutions dropped successively from 250 to 180?195 and 100°C, the sedimentary environment was unfavorable for the concentration of Fe, S, and a large group of ore elements that are typical for sediments in zone III. Intrusion of basalt sills and a short-term hydrothermal impact changed concentrations of several components in the sediments overlying the sill complex: CaO, K2O, Li, Rb, Cs, and Tl acquired a trend typical of the high-temperature lower zone III, whereas Fe, MgO, P2O5, TiO2, V, Sc, and Y distribution pattern became typical of the low-temperature upper zone I. Significant compositional variations in the grain size fractions of sediments are lacking beneath the sill base.  相似文献   

9.
《Applied Geochemistry》2001,16(13):1513-1544
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.  相似文献   

10.
The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 μg/L. Concentrations of individual compounds ranged from about 18 to <0.01 μg/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002.  相似文献   

11.
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   

12.
The geochemical study of 5 sediment cores obtained from different shallow hydrothermal fields along the volcanic arc (Methana, Milos, Kos and Yali), revealed that the degree of rock hydrothermal alteration from one area to another is different and is influenced by the physical and geochemical properties of the hydrothermal venting fluids and the type of the rocks in the substrate. The submarine hydrothermal fields in the central Aegean Sea are linked with the Hellenic Volcanic Arc and imprint their hydrothermal influence on the local marine sediments. Hydrothermal venting fluids differ in pH, temperature, gas and metallic element content, intensity of gas and water flux, while rock substrate is variable in terms of thickness and chemistry of the marine sediments and the mineral deposits. The analytical results showed that the lowest values of Fe are observed in Palaeochori Bay (0.72%) and the highest values are found in Bros Thermi (2.72%). The highest Mn concentrations are found in Bros Thermi (407 ppm) and the lowest are found in Yali (29 ppm). Cu and Pb highest concentrations are found in Bros Thermi (21 ppm) and Thiafi Bay (16 ppm), and the lowest in Yali (1 ppm). Zn highest values are found in Bros Thermi (56 ppm) and the lowest values in Kephalos Bay (10 ppm). Finally, the Ca and Mg-richest layers are observed in Kephalos 7.5 and 0.98% respectively and the lowest are observed in Milos (0.01% for Ca) and Yali (0.12% for Mg). The hydrothermal activity presented variations with geological time and hydrothermal suspended particulate matter coming out from the vent outlets also influence the sediment geochemistry. As an example in Methana, high concentrations of Cu and Zn in SPM result in high levels of Cu and Zn in the sediments.  相似文献   

13.
Sediments from Kalpakkam, southeast coast of India were geochemically analyzed to document the provenance, tectonic setting, and role of chemical weathering. The sediments are dominated by quartz (Si), and the higher concentration of Si suggests the presence of quartz (±feldspar) dominated terrigenous sands. The study demonstrates that the sediments are derived from the granitic to gneissic or from a sedimentary source. Beach sediments are deposited in a passive continental margin setting and seabed sediments are deposited in active continental margin. In the A–CN–K diagram, most of the samples fall in the lower part, i.e., below the plagioclase feldspar joint which indicates a low degree of alteration. Only S6 falls just above the plagioclase feldspar joint, close to the AK boundary suggesting a slightly advanced weathering of sediment and source. Beach and seabed sediments lie close to CNK and FM region suggesting the presence of ferromagnesian minerals (likely to be pyroxene) except S6 which falls in the inner triangle of the minerals feldspar, garnet, and biotite in A-CNK-FM diagram. Both CIA and CIW values depict the unweathered nature of the sediments under humid to semi-humid climatic conditions.  相似文献   

14.
Stratiform ore deposits associated with calc-alkaline and tholeiitic volcanism form as chemically precipitated sediments and, like other sediments, display facies variations. An attempt to characterise these vertical and lateral facies variations and to relate them to distance in time and space from the volcanic centre is presented here. With increasing distance in time and space from a volcanic centre, the proportions of volcanics to sediments and intensity of hydrothermal alteration decrease. Footwall alteration pipes, stringer and disseminated ore zones dominated by quartz-, sericite- and Mg-rich assemblages are spatially associated with proximal stratiform base metal deposits whereas slight alteration to quartz-, sericite- and Fe(Mn)-bearing assemblages are present associated with distal stratiform base metal deposits. With increasing distance in time and space from the volcanic centre the Fe, Cu and S content of base metal deposits decreases and the Zn, Pb, Ag, Mn, Ba and F content increases. The trend from copper-dominated to zinc-lead-dominated iron sulphide ores is probably a result of the increasing mixing of seawater with metal-bearing hydrothermal fluid with increasing distance from the volcanic centre.  相似文献   

15.
泥炭的热模拟研究──过渡带气形成机理探讨   总被引：1，自引：0，他引：1  
本文对现代泥炭进行了低温长时间模拟实验研究,并探讨了过渡带气的形成机理。甘南泥炭气、液态烃产率高。液态烃由热解油和残余气仿沥青“Ａ”两部分组成,热解油中以Ｃ５─Ｃ１４较轻馏分为主,残余氯仿沥青“Ａ”则以非烃、沥青质为主。随热演化程度增高,烃类增加,非烃和沥青质急剧减少。模拟气体组成以非烃气体（ＣＯ２等）为主,随温度升高,气态烃产率升高,烃类气体中以甲烷为主。２００℃～４００℃温度下产生的甲烷碳同位素δ１３Ｃ为－５３.８２～－３３.６６‰。研究表明低热演化阶段伴随腐殖物质的降解和干酪根的分子重排作用能产生甲烷同位素较轻的生物－热催化过渡带气。  相似文献   

16.
The Hg distribution and some mineralogical-geochemical features of bottom sediments up to a depth of 10 m in the Deryugin Basin showed that the high and anomalous Hg contents in the Holocene deposits are confined to a spreading riftogenic structure and separate fluid vents within it. The accumulations of Hg in the the sediments were caused by its fluxes from gas and low-temperature hydrothermal vents under favorable oceanological conditions in the Holocene. The two mainly responsible for the high and anomalous Hg contents are infiltration (fluxes of hydrothermal or gas fluids from the sedimentary cover) and plume (Hg precipitation from water plumes with certain hydrochemical conditions forming above endogenous sources). The infiltration anomalies of Hg were revealed in the following environments: (1) near gas vents on the northeastern Sakhalin slope, where high Hg contents are associated only with Se and were caused by the accumulation of gases ascending from beneath the gas hydrate layer; (2) in the area of inferred occasionally operating low-temperature hydrothermal seeps in the central part of the Deryugin Basin, in which massive barite chimneys, hydrothermal Fe-Mn crusts, and anomalous contents of Mn, Ba, Zn, and Ni in sediments develop.  相似文献   

17.
《Applied Geochemistry》2003,18(6):845-861
Recent sediments of the Andaman Backarc Basin, Indian Ocean, between the Andaman Nicobar islands and the Malay Peninsula have been analyzed for biomarker lipids. Three cores were selected: one each from the fault zone in a deep basin (a graben between two fault systems), another from a location adjacent to the fault, and the third from the topographic high in the rift valley. The molecular composition of the lipid classes (n-alkanes, isoprenoids, alkylbenzenes, alkylcyclohexanes, hopanoids, polycyclic aromatic hydrocarbons, steranes, alcohols, sterols and fatty acids) was examined by gas chromatography (GC) and GC/mass spectrometry to understand the nature and source of the hydrocarbons present and the processes of maturation of organic matter. The data show that the hydrocarbons are of hydrothermal origin, derived from thermal alteration of sedimentary organic matter, consisting of a mixture predominantly of marine-derived components with some terrestrial inputs. Normal alcohols and fatty acids also corroborate the distribution of n-alkanes. The distribution profiles and various parameters computed from the concentration of the target compounds suggest that oxidative reactions and microbial degradation in this environment are insignificant. Triterpane and PAH compositions indicate that the thermal maturity of the bitumen in the samples is comparable to or lower than that found at other hydrothermal regions such as the Northern Juan de Fuca Ridge, Guaymas Basin and Escanaba Trough.  相似文献   

18.
钠长石岩是秦岭造山带中的一类特色岩石,主要分布于南秦岭凤-太、山-柞和镇-旬盆地的泥盆纪和志留纪地层中,与秦岭众多大中型铅锌矿、金矿成矿关系密切。钠长石岩呈层状、似层状产于碎屑岩或碳酸盐岩岩系中,与区域地层整合产出,渐变过渡。具有条带状、块状、角砾状构造;XRF分析数据显示钠长石岩化学成分以富Na2O、Al2O3、SiO2等常量元素及Pb、Zn、Au、Ag、Cu等微量元素为特征;富含元素Ba和Fe-Mn-(Co+Cu+Ni)×10分布图投影表明钠长石岩具有热水沉积的特征。而TiO2与Al2O3关系图解又反映出钠长石岩中有陆源碎屑物混入的特点,其Ti、Al可能来自水成沉积物中的粘土;ICP-MS分析所得稀土元素数据显示,钠长石岩与地层稀土元素在稀土总量、轻重稀土量和配分模式均十分相似,其较高∑REE就是成岩过程中水成沉积物混入造成的。富钠长石岩石在形成时间上发生在沉积和早期成岩阶段,与正常沉积岩同时形成。兼具有正常沉积岩石和热水沉积岩石的特点,是一种有别于二者的混合型非典型热水沉积岩石。研究认为钠长石岩是由一种富钠和金属元素的热水通过对地层元素的萃取并与海底未固结沉积物混合而成的混合热液经沉积成岩作用形成的。  相似文献   

19.
ABSTRACT

Understanding fluid flow structures in a rifted basin may enhance our knowledge of their origination and evolution. Through geochemical analysis and seismic interpretation, different fluid flow features are identified in the central depression of Qiongdongnan basin, northern South China Sea. These structures include mud diapir, gas chimney, hydrothermal pipes, faults, blowout pipes, and associated extrusions. Mud diapirs are primarily located on the slope belts, whereas gas chimneys are on the basement highs in the southwest of the study area. Their distribution appears closely controlled by tectonic stress field and overpressure, the later is caused by hydrocarbon generation and compaction disequilibrium. High sediment overloading, weak post-rift tectonic activity, and high average geothermal gradient may contribute to the compaction disequilibrium. The occurrence of gas chimneys on the basement high suggests that lateral transportation and relief of overpressure is a significant factor. Distribution of broad hydrothermal pipes is related with the thinning continental crust and pre-existing boundary faults in the central depression. They are probably attributed to intruded sills dissolution and were caused by hydrothermal fluids vertically. Geochemical data from gas reservoirs analysis indicates that mud diapirs and gas chimneys are critical pathways for thermogenic gases, whereas hydrothermal pipes and part of the faults may act as pathways of both thermogenic and inorganic gases. The blowout pipes mainly occur in the northwestern central depression near the continental slope, where fluid flows ascend gradually from a series of Pliocene-current prograding wedge-formed units with a hydraulic fracture in shallow. Hundreds of seafloor pockmarks and mounds associated with blowout pipes located above the NE-SW elongated Pliocene-Quaternary slope-break belts. These extrusive structures indicate that fluids ascend through blowout pipes and were expelled at the present seabed. Our results indicate that fluid flow structures are probably responsible for fluid activities and must be taken into account when assessing the hydrocarbon potential, geologic hazard, and benthic ecosystem.  相似文献   

20.
A method is evaluated that enables the dating of binary isotopic paleomixing in hydrothermal alteration assemblages by iterative reconstruction and regression of corresponding two-component mixing lines from conventional Rb-Sr data. The model has been applied to illite-bearing granulometric fractions of hydrothermally altered sedimentary rocks associated with epithermal vein mineralization in the eastern Harz Mountains, Germany. These veins are characterized by a principal quartz-sulfide stage containing quartz, base metal sulfides, and siderite and a subsequent dominant calcite-fluorite-quartz stage. Rb-Sr analyses were performed on untreated granulometric fractions, HCl-treated residues, corresponding HCl leachates, and cogenetic vein minerals obtained from two silicified rock samples related to the quartz-sulfide and the calcite-fluorite-quartz mineralization, respectively.Neither the untreated nor the HCl-leached fractions of these rock samples yield statistically robust and geochronologically meaningful isochrons. When applying the binary mixing model, however, two well-defined paleomixing lines can be reconstructed for the HCl-treated fractions of the rock samples and associated vein minerals at model ages of 226 ± 1 Ma (quartz-sulfide alteration) and 209 ± 2 Ma (calcite-fluorite-quartz alteration). We examine the significance and reliability of these model ages and the corresponding paleomixing lines by means of statistical and geological criteria and discuss the effects of leaching experiments performed on the granulometric fractions using 1 N HCl as well as the nature and origin of the components dissolved in the acid leachates.Our results suggest that the mixing model provides a successful dating concept for isotopic disequilibrium processes during low-temperature hydrothermal events that produce binary mixtures among newly formed alteration phases.  相似文献   

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