Coal as a source rock for oil: a review

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.     

Dissolved organic matter fluorescence spectroscopy as a tool to estimate biological activity in a coastal zone submitted to anthropogenic inputs

Here we report on an investigation of the three-dimensional excitation-emission-matrix (EEM) fluorescence spectra of unconcentrated water samples collected in 1996, 1998 and 1999 at a site particularly propitious for macro-algae development. The degradation of these macro-algae was studied to determine the influence of their exudates on natural water EEM fluorescence spectra. This work demonstrates that biological activity is one of the major factors involved in the formation of the blue-shifted fluorescence band observed in marine waters (β component Ex/Em=310–320 nm/380–410 nm); our study also shows that fluorescence can be used to evaluate the biological activity both quantitatively and to determine its different phases.     

森林沼泽景观区腐殖酸与砂金矿床的成因关系研究

土壤和地表水中有大量的腐殖酸,而腐殖酸对金有较强的溶解能力和吸附作用。在表生地球化学环境中,腐殖酸严重影响着金的迁移与富集。因此在森林沼泽景观条件下,腐殖酸对砂金矿床的形成起着重要作用。     

Cu and Fe associated with humic acids in sediments of a tropical coastal lagoon

The amount of Cu and Fe associated with humic acids was estimated in five sediment cores from a tropical coastal lagoon (Piratininga Lagoon, Rio de Janeiro, Brazil). Core samples were analysed for humic acid contents, total Fe and Cu content. Fe and Cu associated with humic acids were also measured. Results show amounts of humic acids ranging from 0.7 to 21.7% of the dry weight of sediment (average 4.6%, standard deviation 4.4%). Concentrations of Fe and Cu ranged from 0.3 to 6.0% (average 2.2%, S.D. 1.2%) and from <1.0 to 65.0 μg g⁻¹ (average 28.6 μg g⁻¹, S.D. 16.4 μg g⁻¹), respectively. The results of strongly bound metals show that while humic acids are the main carrier for Cu, Fe does not seems to be significantly associated with this organic matter.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

海水腐植质的基本化学组成研究

于１９９２－１９９３年用＾１Ｈ－ＮＭＲ，＾１３Ｃ－ＮＭＲ和ＩＲ等分析技术对甲基化前后的海水腐植质（１９９２年从青岛近岸海水中吸附提取）的基本化学组成和结构特征进行研究，并与风化煤和海洋沉积物中的腐植质作比较。结果表明，ＩＲ和＾１Ｈ－ＮＭＲ谱图显示，海水腐植质主要由脂肪链化合物组成，含有一定量的肽类和多糖，芳香结构较少。采用ＮＮＥ技术的＾１３Ｃ－ＮＭＲ谱图中各类碳的相对含量为：脂肪族碳，３３．２％；     

An evaluation of an automated hollow-fibre ultrafiltration apparatus for the isolation of colloidal materials in natural waters

Colloidal materials and macromolecules that are less than 0.45 mircons in diameter can act to transport both hydrophobic and hydrophilic contaminations in subsurface waters. An automated hollow-fibre ultrafiltration apparatus is described and evaluated regarding its ability to physically size and isolate colloidal materials from natural waters. Sufficient size-fractionated colloidal samples can be obtained from 60 litre samples to perform inorganic, organic, and radionuclide characterizations, as well as allow the binding capacities of humic and fulvic materials to be evaluated. Samples processed in the field with the automated system were compared with laboratory analyses using single cartridge hollow-fibre ultrafilters and found to agree well with each other. Typical sample reproducibilities were with 15 per cent. The results indicate that field collection of colloidal materials is feasible with minimal sample perturbation using the automated sampler.     

Fingerprinting sources of bacterial input into small residential watersheds: fate of fluorescent whitening agents

The presence of fecal coliform bacteria in many watersheds is often linked to septic system effluent. Fluorescent whitening agents (FWA) are part of most laundry detergent formulations and previously have been used for fingerprinting anthropogenic sewage waters. This study was carried out to investigate the fate of FWA in spring water downstream from a well-monitored septic system in a small forest watershed. Samples for FWA were collected at the spring and along the flow path downstream and analyzed fluorometrically. Selected sampling events were scheduled at night and daytime and after rainstorms to investigate possible changes in the spring water composition. In addition, reference fluorescence spectra were prepared for humic and tannic acid and for the laundry detergent used exclusively in the household discharging into the test septic system. The results indicate that FWA can be detected in spring water, but interference with increasing humic acid concentration downstream limits the fingerprinting value of the method to the vicinity of the spring. Also, sampling for FWA after rainstorms only yielded results if at least 4 days had passed. Otherwise, dissolved organic substances transported into the spring water interfered with the FWA spectrum. No significant differences between night and daytime sampling were found. Overall, the method, as used at this study site, is of limited value for fingerprinting FWA in natural waters.     

土体腐殖酸组分对水泥土强度影响效果试验

摘 要:工程实践发现水泥固化软土受土体腐殖酸成分的影响。当前,土体腐殖酸组分对水泥土固化影响已成为岩土工程研究的重要课题之一。通过在实际工程采样对水泥加固土腐殖酸组分进行定性、定量对比试验分析,以研究不同水泥掺量、不同地域水泥固化土腐殖酸组分的影响效果。试验结果表明:由红外光谱（IR）试验表现在水泥环境中胡敏酸组分的羧基量增多,水泥土阳离子交换量（CEC）随水泥掺量增加而增大;在5%、10%、20%水泥掺入比之水泥土中,由神经网络预测模型预测结果证实,富里酸组分对水泥土无侧限抗压强度影响效果较强。水泥土腐殖酸组分可与水泥产物Ca2+、AI3+反应,在水泥土环境生成钙、铝键等复合体,它们可能影响水泥水解水化反应,削减水泥所能达到的固化效果。 关键词:腐殖酸组分;红外光谱（IR）;电子扫描显微镜（SEM）;阳离子交换量（CEC）;水泥土。