高、低煤阶煤层气藏地质特征及控气作用差异性研究

高、低煤阶煤层气地质特征及控气作用差异性是研究煤层气富集成藏的重要组成部分,是煤层气勘探开发理论研究过程中重要的基础性研究领域之一。本文以中国沁水、阜新盆地和美国粉河盆地等典型的含气盆地为例,探讨了高、低煤阶煤层气的储层物性差异,分析了构造控气和水文地质控气作用的差异性。研究表明,高煤阶气藏含气量高,CH4百分含量高,δ13C1值大于-38.75‰,储层渗透率变化小,储层改造难,构造热事件对煤层气的生成、富集贡献大,持续的水动力使气藏遭到破坏,且破坏幅度大,现今地下水格局对气藏的形成具有一定的影响;低煤阶气藏含气量低,CH4百分含量低,δ13C1值大于-49.11‰,储层渗透率变化大,储层易改造,煤热演化史及煤阶影响着煤层气的生成、富集,在煤层气生成过程中活跃的水动力是甲烷生成的主要的水文地质条件之一,但持续的水动力使气藏遭到破坏,且破坏幅度小,而合适的地层水矿化度则是低煤阶煤层气生成的重要条件,地下水格局对气藏的调整和改造起到决定性的影响。     

Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

Identifying China’s leading world city: a network approach

This paper reports our research on China’s world cities. Formal network analysis of air passenger linkages for recent years among China’s most populous cities and among many of the world’s largest cities allows us to identify the country’s leading world city from among the leading Mainland candidates, Beijing, Shanghai and Guangzhou. We theorize our findings about China’s world cities in relation to both global forces (and China’s increasing entanglement with them) and the policies and actions of the national state. We examine the national and global urban network through a longitudinal, two-level analysis of airline passenger travel for four time points between about 1990 and 2005. We show that Beijing was China’s leading world city at the beginning of the time period, a status it lost nationally in as early as 1995, and then globally 10 years later. On the other hand Shanghai became China’s leading world city, and it acquired this status first nationally in 2000, and then globally in 2005. The changing status of the Chinese capital corresponds to the country’s increasing involvement with the capitalist world economy. Shanghai’s ascendance as the leading world city in China may indicate that global forces have come to play an increasingly important role relative to that of the developmental state.

Biogeochemical characteristics of the Hetai goldfield, Guangdong Province, China

In the Hetai goldfield, Guangdong Province, China, samples including rocks, soils and leaves of four plants (Pinus massoniana, Rhodomyrms tomenlosa, D. linearis var. dichotoma and Embelia laeta) collected from the gold mineralization zone and the background area were analyzed for Au, Ag, Cu, Pb, Zn, Hg, As and physiological parameters. The objective of this investigation is to study the geochemical and biogeochemical characteristics of studied plants, aiming at biogeochemical methods in Au exploration. The goldfield region shows geochemical and biogeochemical anomalies. Abundances of Au in rocks, soils, plants and the leaf pigments in the mineralized area are much higher than those in the surrounding region. The plants display unhealthy physiological and ecological characteristics in the Hetai goldfield area. The cell structures of the goldfield plants were anomalous and aberrant, and there were many nano-metal particles diffused in mitochondria and chloroplasts. Macro- and microscopic evidences of the vegetation in the goldfield areas are distinctly different from the background regions. The strongly anomalies in responses to Au are profound in further geochemical and botanic exploration studies.     

松辽盆地三肇凹陷葡萄花油层成藏模式初探

运用源控含油气系统理论与综合分析技术,按成藏“层次分析”方法,通过对生、储、盖、圈(闭)静态要素及其内生、排、运、聚、散(失)动态过程的综合研究,对松辽盆地中央坳陷的三肇凹陷葡萄花油层成藏条件进行探讨,提出了以次级凹陷为中心、不同类型的油气聚集带紧邻并围绕次级凹陷最低部位呈环带状分布的大型凹陷内成藏模式,并进一步提出永乐次级凹陷中心及其三级聚油环带及徐家围子次级凹陷以西为"网式"运聚特征;在凹陷级成藏模式的指导下,通过对大面积密井网开发区综合解剖,提出三级构造带中单个的局部构造圈闭(群)、单个的(局部构造——)岩性圈闭(群)控油和成藏规律,为认识本区基本控油单元、油水分布规律、油气勘探及扩大新探区提供重要的理论依据。     

青藏高原西部赛利普中新世火山岩源区:地球化学及Sr-Nd同位素制约

青藏高原拉萨地块西部赛利普地区新生代火山岩依据主量元素可划分为超钾质、钾质和钙碱性系列,主要的岩石类型为粗面安山岩、粗面岩,一个超钾质岩石的40Ar-39Ar年龄为17.58Ma,指示出火山活动为中新世.超钾质、钾质和钙碱性火山岩都显示出富集LREE及LILE(Th、U)、亏损HFSE(Nb、Ta、Ti)的特征.超钾质火山岩具有较高的K2O(6.31%～8.55%)、MgO(6.75%～8.96%)、Cr(270.7×10-6～460.4×10-6)、Ni(142.3×10-6～233.9×10-6)含量,较高的(87Sr/86Sr)i(0.71883～0.72732)和较低的εNd(-14.78～-15.37),指示可能起源于一个前期亏损并经后期俯冲作用改造的富钾的方辉橄榄岩富集地幔源区.钾质火山岩具有比超钾质火山岩低的K2O、MgO、Cr、Ni含量以及高的Ba、Sr含量,初始87Sr/86Sr为0.71553～0.71628,初始143Nd/144Nd为0.51197～0.51198,在空间上与超钾质火山岩共生,可能是前者母岩浆的演化产物.钙碱性火山岩具有较高的Sr(881.7×10-6～1309.2×10-6)、Sr/Y比值(50～108)和较低的Y(12.05×10-6～18.02×10-6),明显亏损重稀土Yb(0.93×10-6～1.30×10-6),类似于典型的埃达克质岩成分特征但相对高钾,并具有相对低的(87Sr/86Sr);(0.70928～0.71374)以及高的εNd(-7.90～-10.91),指示起源于富钾增厚下地壳物质的部分熔融.区域上拉萨地块超钾质岩、钾质岩与N-S向地堑系在空间上共存、时间上相吻合,由此本文认为拉萨地块中新世钾质.超钾质岩和南北向地堑系的形成可能与中新世早期北向俯冲的印度大陆岩石圈断离有关.