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1.
卟啉的研究现状及其应用   总被引:2,自引:0,他引:2  
在前人研究资料及作者近年来的研究成果的基础上,综述了卟啉化合物地球化学研究的现状,包括金属卟啉的类型,卟啉的化学结构系列,高度脱链基卟啉和高碳数咔琳等及其它们在沉积物(如油页岩、煤和现代沉积物)中的分布特征和成因机理。指出了今后需要加强研究的领域,如沉积物中新的金属卟啉类型探讨和卟啉化学结构的确定等。文章还综述了卟啉化合物地球化学指标在地质勘探中的应用,如:评价生油岩质量,油源对比,油气运移研究,古沉积环境研究和有机质热成熟度研究等。  相似文献   

2.
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   

3.
A novel method for handling and presenting multimolecular abundance data, derived from gas chromatographic-mass spectrometric analyses (GC-MS), is introduced. The method facilitates carbon number labeling of compounds, specifically in the case of porphyrins, by means of a porphyrin-index, which is part of a novel identification code for porphyrins. Identification code, relative abundance and structure information of each compound recognised are stored in a database, which affords a variety of characteristic displays and tables upon manipulation. The combined facilities allow the direct comparison of samples of different origin, maturity and/or palaeoenvironment. Correlation studies, such as oil/oil or oil/source rock, are also facilitated by comparison of characteristic “fingerprint” histogram patterns. The ability of the method is exemplified through analysis of the porphyrin distributions of Boscan oil, La Luna shale, Gilsonite bitumen and Serpiano shale.  相似文献   

4.
The Antaramut–Kurtan–Dzoragukh (AKD) coal deposit is a previously unrecognized coal field in north-central Armenia. Coal has been known to exist in the general vicinity since the turn of the century, but coal was thought to be restricted to a small (1 km2) area only near the village of Antaramut. However, through detailed field work and exploratory drilling, this coal deposit has been expanded to at least 20 km2, and thus renamed the Antaramut–Kurtan–Dzoragukh coal field, for the three villages that the coal field encompasses. The entire coal-bearing horizon, a series of tuffaceous sandstones, siltstones, and claystones, is approximately 50 m thick. The AKD coal field contains two coal beds, each greater than 1 m thick, and numerous small rider beds, with a total resource of approximately 31,000,000 metric tonnes. The coals are late Eocene in age, high volatile bituminous in rank, relatively high in ash yield (approximately 40%, as-determined basis) and moderate in sulfur content (approximately 3%, as-determined basis). The two coal beds (No. 1 and No. 2), on a moist, mineral-matter-free basis, have high calorific values of 32.6 MJ/kg (7796 cal/g) and 36.0 MJ/kg (8599 cal/g), respectively. Coal is one of the few indigenous fossil fuel resources occurring in Armenia and thus, the AKD coal field could potentially provide fuel for heating and possibly energy generation in the Armenian energy budget.  相似文献   

5.
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   

6.
Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite samples group into one cluster, their pyrolyzates having an overwhelming predominance of straight chain hydrocarbons, a characteristic typical of Botryococcus. The presence of the C9–C26 n-α,ω-alkadiene series is the key feature distinguishing the torbanites from the other samples. The cannel coals exhibit more chemical diversity, reflecting their greater variability in petrographic composition. The Breckinridge cannel, dominated by a highly aliphatic lamalginitic groundmass, chemically fits the torbanite category. The bituminitic groundmass-dominated cannel coals fall into a cannel sub-cluster, their pyrolyzates having a characteristic predominance of n-alk-1-enes and n-alkanes (particularly the long-chain homologues), with no detectable alkadienes. The vitrinitic groundmass-dominated Ohio Linton cannel and the sporinite-rich Canadian Melville Island cannel are readily distinguishable from the other cannels by the relatively abundant aromatic and phenolic compounds in their pyrolyzates. The internal distribution patterns of alkylaromatic and alkylphenolic isomers are shown to be less significant in the classification of this sample set. Multivariate statistical analysis of the pyrolysis data not only successfully discriminated torbanites from cannel coals, but recognized subtler differences between the examples of these two coal types, in substantial agreement with the petrographic characterization. As such, these methods can substitute for or supplement the traditional microscope-based approach.  相似文献   

7.
焦坪侏罗纪煤系及其油气展布   总被引:1,自引:0,他引:1  
焦坪矿区油气显示规律与煤系分布关系密切。该矿区主要可采煤层4-2煤层存在4个厚煤中心,矿区油气显示主要存在于聚煤中心带上、下部的砂岩层中,特别是煤层上部的延安组和直罗组砂岩层中。油气分布主要与延安组的厚度,4-2煤层厚度,延安组和直罗组中、粗粒砂岩厚度,煤系成熟度和上覆地层厚度等因素有关。构造条件对烃类的影响较小,只在上述条件决定的范围内起作用。   相似文献   

8.
Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al2O3 (8.89%), TiO2 (0.47%), Li (116 μg/g), F (286 μg/g), Ga (18 μg/g), Se (6.1 μg/g), Sr (350 μg/g), Zr (268 μg/g), REEs (172 μg/g), Pb (30 μg/g), and Th (17 μg/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash–SiO2–Al2O3–Na2O–Li) and Group B (REE–Sc–In–Y–K2O–Rb–Zr–Hf–Cs–U–P2O5–Sr–Ba–Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe2O3, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se–Pb–Hg–Th–TiO2–Bi–Nb–Ta–Cd–Sn; Group D, Co–Mo–Tl–Be–Ni–Sb–MgO–Re–Ga–W–Zn–V–Cr–F–Cu; and Group E, S–As–CaO–MnO–Fe2O3. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li–ash, Li–Al2O3, and Li–SiO2 pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings.  相似文献   

9.
A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S2=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S2=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S2=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.  相似文献   

10.
Coal as a source rock for oil: a review   总被引:2,自引:0,他引:2  
The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and 13C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO2 and CH4 could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.  相似文献   

11.
Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron.The blue oxides are compositionally similar to magnéli phases TinO2n–1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al1Ti 1 3+ Ti 2 4+ O7 (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al2–x(Ti 0.5 4+ (Mg,Fe)0.5)xTi n–2 4+ O2n–1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.  相似文献   

12.
The world's recoverable coal reserves contain about 3 × 1010 tons of hydrogen. The reaction of sulfur vapor with medium-volatile bituminous coal produces hydrogen sulfide in yields up to 97% (based on sulfur), and utilizes 70–75% of the hydrogen from the coal. The conversion of hydrogen sulfide to hydrogen can be effected through commercially proven processes; several laboratory-scale processes could also be scaled up for future use. The solid by-product of the coal–sulfur reaction meets or exceeds specifications for fixed carbon, ash, and friability of conventional metallurgical coke, though produced at lower temperatures than typical by-product coke ovens. A conceptual process is presented in which sulfur is converted to hydrogen sulfide by reaction with coal, the hydrogen sulfide in turn is converted to the desired hydrogen and to sulfur, and the sulfur is recycled through the reactor. The by-product is a good quality coke, but may also have other applications as a carbon material.  相似文献   

13.
Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ34S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ34S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in 34S relative to those from the parent coal (average 7.5‰). The δ34S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ34S values for SO4− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.  相似文献   

14.
Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ13C values are found in the Tarim and Qaidam basins (δ13C1: − 19.0 to − 29.9‰; δ13C2: − 18.8 to − 27.1‰), and those with lowest δ13C values occur in the Turpan-Harmi and Junggar basins (δ13C1: − 40.1 to − 44.0‰; δ13C2: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ13C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.  相似文献   

15.
我国陆相盆地内普遍存在油页岩与煤共生的地质现象。本文以老黑山盆地下白垩统穆棱组油页岩与煤为研究对象,基于工业分析(含油率、灰分、挥发分、全硫和发热量)和有机地球化学分析(有机碳、岩石热解、显微组分和生物标志化合物),对油页岩与煤含油率的控制因素开展研究。根据含油率等工业品质特征,将研究区油页岩与煤进一步划分为高含油率油页岩(HOS)、低含油率油页岩(LOS)、高含油率煤(HC)和低含油率煤(LC)4种亚类。其中HC的总有机碳质量分数和生烃潜力最高,其次为LC、HOS和LOS,4种亚类的有机质类型以Ⅱ型干酪根为主,均处于未成熟的热演化阶段。沉积环境与有机质来源是控制油页岩与煤含油率的关键因素,HOS主要形成于陆源有机质供给中等的湖沼环境,而HC主要形成于陆源有机质供给丰富的泥炭沼泽环境。油页岩与煤形成时期的高等植物以松科、柏科/杉科、南洋杉科、罗汉松科和蕨类植物为主,这些植物可以提供充足的树脂和蜡质有机质,从而使油页岩与煤具有相对较高的含油率。  相似文献   

16.
杜灵通  徐友宁  宫菲  丹杨  王乐  郑琪琪  马龙龙 《地质通报》2018,37(12):2215-2223
准确评估大型能源基地矿业开发活动对区域植被生态系统影响具有重要的科学意义和实践价值。利用2000—2017年中分辨率成像光谱仪(MODIS)连续观测的生态系统参量,定量研究宁东煤炭基地开发建设以来的植被生态系统时空变化特征,分析矿业开发对植被生态系统的影响。结果表明,随着宁东煤炭基地开采活动的持续,区域植被生态系统的生产力及其与大气之间的水汽交换强度整体增强,归一化植被指数、总初级生产力、净初级净生产力和蒸散的年增长幅度分别为0.0053、5.10g·C/(m2·a-1)、4.10g·C/(m2·a-1)和6.62mm/a;这4种指标在空间像元上也以增长趋势为主,且未来多数像元有持续增强的特征,但生态系统的水分利用效率却在降低。空间分析表明,大尺度植被生态演变受矿业活动影响微弱,其主要受制于气候和区域性的生态治理工程。  相似文献   

17.
The Jurassic Angren coal–kaolin deposit, Uzbekistan, is one of the largest producers of coal and kaolin suitable for refractories and industrial ceramics in central Asia. The Major coal seam, attaining a thickness between 4 and 24 m, is encased by kaolin-bearing bedsets which have been derived from supergene pre- and hypogene post coal kaolinization. Joint clay-mineralogical and coal petrographic analyses formed the basis of the environment analysis of this coal–kaolin series and constrained the physico-chemical conditions existing during the Triassic through Jurassic period of time. Massive kaolin I underneath the coal seam is a typical residual kaolin or underclay with arsenic Fe-disulfides and siderite indicative of a reducing swampy depositional environment developing under moderately hot climatic conditions. Towards the top, kaolin I became reworked fluvial by processes. The Major coal seam developed in swamps interfingering with a fluvial drainage system of suspended to mixed-load deposits. The maximum temperature for the post-depositional alteration of the carbonaceous material is 70 °C. Post-coal kaolinization (kaolin II) affecting trachyandesites and trachytes is of low-temperature origin and low-sulphidation-type. The temperature of formation was well below 200 °C, deduced from the absence of dickite in the clay mineral assemblage. Basaltic dykes intersected the coal–kaolin series and account for contact metamorphic reactions in the proximal parts of the aluminum-bearing wall rocks reaching sanidinite-facies conditions with temperatures around 1000 °C.  相似文献   

18.
The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10− 9 m3/kg (− 12.09 ± 0.5 × 10− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10− 10 m3/kg (1.10 ± 0.01 × 10− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k1 − k3)para (kg/m3) = Fe-content (ppm) × (1 ± 0.1) × 10− 12 (kg/m3/ppm). The maximum susceptibility difference (Δk = k1 − k3) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.  相似文献   

19.
A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe0). Modest increases in SO4 reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe0. However, OC was essential for supporting SO4 reducing bacteria (SRB) and therefore SO4 reduction. This observation suggests a general absence of autotrophic SRB which can utilize H2 as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L−1 d−1  g−1 OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe0 only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO4 reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe0, and S-rich in the absence of Fe0 amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe0 enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe0 and OC mixtures.  相似文献   

20.
During Jurassic times, especially within the Malm ζ stage, local depressions formed on the Eastern Bavarian Carbonate Platform that were surrounded by wall reefs. This created a unique depositional environment, where in an open-marine setting stagnant and anoxic bottom waters developed in an intra-reef depression. Anoxic conditions were stabilized below wave base by enhanced salinity in the bottom waters and establishment of a density stratification. Biomarker analysis was applied to characterize palaeosalinity and redox conditions, utilizing organic sulfur compound, methylated chroman, hopanoid and saturated isoprenoid distributions. Prevention of terrigenous influx by protecting reef walls lead to iron deficiency in intra-reefal sediments causing early diagenetic sulfurization of functionalized lipids. Absence of clay-mineral catalysts and early sulfurization favored an unusual steroid distribution lacking rearranged analogues but providing coexistence of saturated steranes with βαα-, ααα- and αββ-configuration, Δ13(17)-spirosterenes, unknown sterenes and steradienes as well as mono-, di- and triaromatic steroids. Desulfurization of the polar fraction was carried out for two samples to verify that palaeoenvironment reconstruction based on free hydrocarbon and heterocompound distribution was not invalidated by sulfur quenching of selected compounds. Gammacerane was found to be the only component to occur exclusively in the sulfur-bound fraction. Only minor amounts of hydrocarbons were released upon desulfurization implying that free bitumen analysis was applicable for organofacies characterization. Organic petrological investigation of organic mats revealed the presence of two different types of such structures. Comparison of organoclast fluorescence spectra with those of extracted porphyrin fractions indicate an origin of porphyrins exclusively from cyanobacterial mats whereas algal dominated mats yield no porphyrins. This aims towards a better localization of specific biomarker origin in geological samples.  相似文献   

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