The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Subsurface thermal and hydrothermal characterization based on geothermal resources map, drill hole thermal gradients, Curie point depths and hypocenter distribution — Examples of Tohoku district, Japan

Subsurface thermal structure in Tohoku district are characterized by existing data such as geothermal resources maps, drill hole thermal gradients, Curie point depths and hypocenters distribution maps. The collected data are registered in a database system, then, compared in plan view, cross-section and bird's-eye pictures. The comparison indicates that subsurface temperatures extrapolated from drill hole thermal gradients are generally concordant to the Curie point depth, assumed to be 650 °C. Tohoku district is generally divided into 5 type areas; fore arc lowland, fore arc mountain country, Quaternary volcanic terrain, back arc lowland and back arc mountain country. The surface thermal manifestations in Quaternary volcanic terrain are mainly controlled by the magma chambers as heat sources, while, surface thermal features such as hot springs in non-volcanic areas are controlled by degrees of heat flows, and hydrothermal flows in permeable Cenozoic formations and along permeable fault zones.     

Methylmercury and human biomarkers： Questioning the evidence

Methylmercury （MeHg） is a powerful neurotoxicant in humans. In terms of biomarkers of MeHg exposure, hair and blood have long been used in epidemiological studies as the biomarkers of choice. In fact, total hair mercury （Hg） content as well as organic blood Hg concentrations reflects exposure to organic Hg from food consumption. Extensive studies, establishing a constant and linear relation between MeHg intake versus Hg levels in hair and blood, were conducted by governmental officials to establish guidelines on safe levels of MeHg exposure, which were translated into threshold daily fish consumption rates （usually expressed as μg MeHg per kg bodyweight）. Nowadays, in most epidemiologic studies blood or hair mercury （Hg） level is commonly used as a valid proxy to estimate human exposure to methylmercury （MeHg） through fish consumption without relating this signal to actual fish consumption patterns among populations. Human variability in mercury toxicokinetics was identified and measurement error has been pointed out to be a substantial contributor to observed variability, particularly where dietary information is retrospective and self-reported. However, experimental evidence indicates that significant variability among individuals may exist in the biokinetics of mercury. Also recent findings from previous population-based studies through COMERN initiative also revealed that MeHg metabolic processes might greatly vary across populations. In fact, it is unlikely that the magnitude of the difference measured between observed and expected levels of mercury, given the reported intake, can be entirely explained by laboratory measurement errors or reporting bias.     

Origin and three-dimensional fluorescence spectrum of the chromophoric dissolved organic matter in Yangtze estuary, East China

Dissolved organic matter （DOM） is an important chemical component in natural water. Chromophoric dissolved organic matter （CDOM）, a fraction of optical properties, plays art important role in the biogeochemical cycle of nutrients in aquatic environment. People realized that DOM cycle is crucial in the global carbon and nitrogen flux, and also is inherently related to nutrients and trace metal elements. Therefore, CDOM was concerned by scientists in global oceanography and limnology fields. Water samples were collected from three sections （North Channel, South Channel and Zhuyuan） of the Yangtze （Changjiang River） estuary in March 2006 Three-dimensional excitation emission matrix （3-DEEM） fluorescence spectra were analyzed for those filtrates through Whatman GF/F filters. Dissolved organic carbon （DOC） was also measured by TOC analyzer. The tidal variety was also taken into account. The 3-D EEM fluorescence scans suggested the fluorescence characteristics of humic acid （Ex=332-344 nm, Em=439-451 nm） and fulvic acid （Ex=250-254 nm, Em=472-478 nm） were obvious, and the fluorescence group of protein-like and tyrosine （Ex=230 nm, Em=283 nm） was also found. They are mainly composed of CDOM in the Yangtze estuary. Further data analysis, especially the fluorescence index （f 450/500）, showed that terrestrial signal was rather strong （1.41-1.65） in the surface water, however, some terrestrial CDOM signals of bottom water showed excursions （1.28-1.39）. On the other hand, anthropogenic sign was impressed in the waters of Zhuyuan, which is one of the main drain outlets of Shanghai Metropolis. DOC concentrations ranged from 2.2 mg/L to 3.4 mg/L in Zhuyuan and South Channel, and from 2.0 mg/L to 2.4 mg/L in North Channel. The tide effect played a role in the composition of the CDOM measured by 3-D fluorescence scan technology.     

Heavy metals in freshly deposited sediments of the river Subernarekha, India: an example of lithogenic and anthropogenic effects

Heavy metal distribution patterns in river sediments aid in understanding the exogenic cycling of elements as well as in assessing the effect of anthropogenic influences. In India, the Subernarekha river flows over the Precambrian terrain of the Singhbhum craton in eastern India. The rocks are of an iron ore series and the primary rock types are schist and quartzite. One main tributary, the Kharkhai, flows through granite rocks and subsequently flows through the schist and quartzite layers. The Subernarekha flows through the East Singhbhum district, which is one of India’s industrialised areas known for ore mining, steel production, power generation, cement production and other related activities. Freshly deposited river sediments were collected upstream and downstream the industrial zone. Samples were collected from four locations and analysed in <63-μm sediment fraction for heavy metals including Zn, Pb, Cd and Cu by anodic stripping voltammetry. Enrichment of these elements over and above the local natural concentration level has been calculated and reported. Sediments of the present study are classified by Muller’s geo-accumulation index (I _geo) and vary from element to element and with climatic seasons. During pre-monsoon period the maximum I _geo value for Zn is moderately to highly polluted and for Cu and Pb is moderately polluted, respectively, based on the Muller’s standard. Anthropogenic, lithogenic or cumulative effects of both components are the main reasons for such variations in I _geo values. The basic igneous rock layer through which the river flows or a seasonal rivulet that joins with the main river may be the primary source for lithogenic components.     

Hydrogeology of thermal waters in Viterbo area, central Italy

A conceptual hydrogeological model of the Viterbo thermal area (central Italy) has been developed. Though numerous studies have been conducted on its geological, geochemical and geothermal features, there is no generalized picture defining the origin and yield of the hydrothermal system. These latter aspects have therefore become the objectives of this research, which is based on new hydrogeological and geochemical investigations. The geological setting results in the coexistence of overlapped interacting aquifers. The shallow volcanic aquifer, characterized by fresh waters, is fed from the area around the Cimini Mountains and is limited at its base by the semiconfining marly-calcareous-arenaceous complex and low-permeability clays. To the west of Viterbo, vertical upflows of thermal waters of the sulphate-chloride-alkaline-earth type with higher gas contents, are due to the locally uplifted carbonate reservoir, the reduced thickness of the semiconfining layer and the high local geothermal gradient. The hot waters (30–60°C) are the result of deep circulation within the carbonate rocks (0.5–1.8 km) and have the same recharge area as the volcanic aquifer. The upward flow in the Viterbo thermal area is at least 0.1 m³/s. This flow feeds springs and deep wells, also recharging the volcanic aquifer from below.     

A Connectivity Index for Discrete Fracture Networks

Connectivity is an important measure for assessing flow transport in rock, especially through fractures. In this paper, rock fracture systems are modelled by a discrete fracture model simulated by a marked point process. A connectivity index is then introduced to quantify the connectivity between any two points in space. Monte Carlo simulation is used to evaluate the connectivity index for stationary cases and relationships between the connectivity index and the parameters of the discrete fracture model are analysed. The average number of intersections per fracture, X_f, and the fracture intensity, P12 (P32), are calculated and the relationships between these parameters and the connectivity index are investigated, concluding that X_f is the more suitable parameter for the classification of rock mass flow properties. The relationships between the connectivity index and the percolation state of the fractured medium are also discussed. An edge correction is briefly discussed and a practical example is used to demonstrate the method of computing the connectivity index.     

Temperature dependence of large-scale water-retention curves: a case study

A local-scale model for temperature-dependence of water-retention curves may be applicable to large scales. Consideration of this temperature dependence is important for modeling unsaturated flow and transport in the subsurface in numerous cases. Although significant progress has been made in understanding and modeling this temperature effect, almost all the previous studies have been limited to small scales (on the order of several centimeters). Numerical experiments were used to investigate the possibility of extending a local-scale model for the temperature-dependence of water retention curves to large scales (on the order of meters). Temperature effects on large-scale hydraulic properties are of interest in many practical applications. Numerical experiment results indicate that the local-scale model can indeed be applicable to large-scale problems for special porous media with high air entry values. A typical porous medium of this kind is the porous tuff matrix in the unsaturated zone of Yucca Mountain, Nevada, the proposed geologic disposal site for national high-level nuclear wastes. Whether this finding can approximately hold for general cases needs to be investigated in future studies.     

科尔沁沙地土地利用与耕作方式对土壤风蚀的影响

土壤风蚀造成的直接生态后果是土地资源的退化。在春播前两次沙尘暴事件中,对科尔沁沙地几种具有代表性的土地类型的土壤风蚀量及土壤特性进行了野外测定、分析,结果表明:(1)在同一沙尘暴天气下,由于土地利用和耕作方式的不同,土壤风蚀量存在着差异,新垦农地和翻耕农地的风蚀量显著高于未垦草地、免耕农地和麻黄地;免耕农地则与未垦草地的风蚀量相差不大,风蚀危害较轻;麻黄地几乎不受风蚀侵害。新垦农地、翻耕农地、免耕农地、未垦草地、麻黄地两次观测的土壤风蚀量平均值依次为24.59、15.60、2.26、1.46和0.22 g/h.cm2。(2)基于土壤特性计算的土壤退化指数结果表明,新垦农地和翻耕农地发生了较为严重的退化。     

Surface temperature differences between minerals in crystalline rocks: Implications for granular disaggregation of granites through thermal fatigue

Thermal expansion differences between minerals within rocks under insolation have previously been assumed to drive breakdown by means of granular disaggregation. However, there have been no definitive demonstrations of the efficacy of this weathering mechanism. Different surface temperatures between minerals should magnify thermal expansion differences, and thus subject adjacent minerals to repeated stresses that might cause breakdown through fatigue failure. This work confirms the existence of surface temperature differences between minerals in granitic rocks under simulated short-term temperature fluctuations so as to discriminate their potential for initiating granular disaggregation. The influence of colour, as a surrogate for albedo, and crystal size, as a function of thermal mass are specifically identified because of their ease of quantification. Four rock types with a range of these properties were examined, and subjected to repeated short-term temperature cycles by radiative heating and cooling under laboratory conditions. Results show that while albedo is the main control for overall and individual maximum temperatures, crystal size is the main factor controlling higher temperature differences between minerals. Thus, stones with large differences of mineral sizes can undergo magnified stresses due to thermal expansion differences.