Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

中国部分清洁地区大气中N2O的浓度

１９９３年４月—１９９５年８月对中国部分清洁地区大气的Ｎ２Ｏ浓度进行了现场观测，结果表明：农田（玉米田和麦田）大气的Ｎ２Ｏ平均浓度高达３２２．１－３４３．４ｐｐｂｖ，这是土壤排放Ｎ２Ｏ的结果；临安、龙风山和瓦里关山大气本底观测站（ＷＭＯ／ＧＡＷ）Ｎ２Ｏ的平均浓度分别为３１８．８±８．４ｐｐｂｖ，３１７．４±４．７ｐｐｂｖ和３１４．０±４．２ｐｐｂｖ。在此基础上，分析了大气Ｎ２Ｏ的分布及变化特征。另外，还对现场取样及Ｎ２Ｏ浓度测量技术作了初步分析和评价     

Formation history and physical properties of sediments from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

The synthesis of available geological information and surface temperature evolution in the Alaska North Slope region suggests that: biogenic and deeper thermogenic gases migrated through fault networks and preferentially invaded coarse-grained layers that have relatively high hydraulic conductivity and low gas entry pressures; hydrate started forming before the beginning of the permafrost; eventually, the permafrost deepened and any remaining free water froze so that ice and hydrate may coexist at some elevations. The single tested specimen (depth 620.47-620.62 m) from the D unit consists of uncemented quartzitic fine sand with a high fraction of fines (56% by mass finer than sieve #200). The as-received specimen shows no evidence of gas present. The surface texture of sediment grains is compatible with a fluvial-deltaic sedimentation environment and shows no signs of glacial entrainment. Tests conducted on sediments with and without THF hydrates show that effective stress, porosity, and hydrate saturation are the major controls on the mechanical and geophysical properties. Previously derived relationships between these variables and mechanical/geophysical parameters properly fit the measurements gathered with Mount Elbert specimens at different hydrate saturations and effective stress levels. We show that these measurements can be combined with index properties and empirical geomechanical relationships to estimate engineering design parameters. Volumetric strains measured during hydrate dissociation vanish at 2-4 MPa; therefore, minimal volumetric strains are anticipated during gas production at the Mount Elbert well. However, volume changes could increase if extensive grain crushing takes place during depressurization-driven production strategies, if the sediment has unexpectedly high in situ porosity associated to the formation history, or if fines migration and clogging cause a situation of sustained sand production.     

临汾市公安局作战指挥中心消防设计

一座功能复杂的综合性一类建筑，其消防系统的设计也比较复杂。本文根据其建筑的特点，详细介绍了临汾市公安局作战指挥中心消防系统的设计内容。     

天然气水合物与全球变化研究

天然气水合物含碳量超过全球所有其他来源有机碳的总和,是地圈浅部的极重要碳库。自然界中温压条件的微小变化都会引起天然气水合物的形成或分解,从而吸收或释放甲烷,对全球碳循环和温室效应产生重要影响。天然气水合物对全球气候变化、冰期和间冰期的交替的反馈在极地和中低纬度不同,在中低纬度
也有两种相反的过程,因而对其总效应的方向和强度尚需详细研究和估计。我国许多海区有天然气水合物存在的条件,在南海已有报道;可通过地震剖面的重新判读及数值模拟估计天然气水合物的储藏量和它对海平面变化的反馈,以提供边缘海这类研究的范例。     

Elastic-wave velocity characterization of gas hydrate-bearing fractured reservoirs in a permafrost area of the Qilian Mountain,Northwest China

There are two types of gas hydrate-bearing reservoirs in the permafrost area of Qilian Mountain. Most of the gas hydrates occur mainly in the fractured mudstone reservoirs and rarely in the pores of the sandstone reservoirs. In this study, for the acoustic velocity characterization of the fractured gas hydrate reservoirs of the Qilian Mountain permafrost area, some mudstone core samples were collected for physical rock experiments, such as the acoustic experiment and the porosity and permeability experiment. An acoustic velocity numerical simulation of gas hydrate reservoirs was performed according to the Biot theory and the differential effective medium theory, with the conditions of multiple gas hydrate occurrence models, including the suspension model, the semi-cementation model and the cementation model, and considering both infinite and penny-shaped cracks. Fracture porosity was added to the core samples that only contain matrix porosity. With fracture porosity ranging from 0.01% to 5%, the variation laws between acoustic velocity with fractured porosity and hydrate saturation are obtained: (1) In the case of an infinite crack, if the fractured porosity is 0.01%–1%, the P-wave velocity decreases rapidly in the case of the three occurrence models. If the fractured porosity is higher than 1%, the acoustic velocity decreases gradually. If the crack shape is a penny-shaped crack, the P-wave velocity decreases almost linearly with increasing fracture porosity. (2) If the hydrate occurrence model is the suspension model, the P-wave velocity increases slightly with increasing hydrate saturation. If the occurrence model is the semi-cementation model or the cementation model, when the gas hydrate saturation of the infinite crack ranges from 0 to 80%, the acoustic velocity increases approximately linearly, whereas when the gas hydrate saturation ranges from 80% to 100%, the velocity increases rapidly. If the crack is a penny-shaped crack, the velocity increases almost linearly with increasing gas hydrate saturation from 0 to 100%. (3) It is found that the fractured gas hydrate reservoirs of the Qilian Mountain permafrost area contain both penny-shaped and infinite cracks, of which the infinite crack is the main crack shape. The gas hydrate occurrence in the Qilian Mountain permafrost area mainly follows the suspension model. This has significance for the seismic exploration and log evaluation of gas hydrate-bearing fractured reservoirs in the permafrost area of the Qilian Mountain in studying the acoustic velocity characterization, the crack shapes and occurrence models of gas hydrate reservoirs in the study area.     

Thermodynamics of gas and steam-blast eruptions

Eruptions of gas or steam and non-juvenile debris are common in volcanic and hydrothermal areas. From reports of non-juvenile eruptions or eruptive sequences world-wide, at least three types (or end-members) can be identified: (1) those involving rock and liquid water initially at boiling-point temperatures (boiling-point eruptions); (2) those powered by gas (primarily water vapor) at initial temperatures approaching magmatic (gas eruptions); and (3) those caused by rapid mixing of hot rock and ground- or surface water (mixing eruptions). For these eruption types, the mechanical energy released, final temperatures, liquid water contents and maximum theoretical velocities are compared by assuming that the erupting mixtures of rock and fluid thermally equilibrate, then decompress isentropically from initial, near-surface pressure (10 MPa) to atmospheric pressure. Maximum mechanical energy release is by far greatest for gas eruptions (1.3 MJ/kg of fluid-rock mixture)-about one-half that of an equivalent mass of gunpowder and one-fourth that of TNT. It is somewhat less for mixing eruptions (0.4 MJ/kg), and least for boiling-point eruptions (0.25 MJ/kg). The final water contents of crupted boiling-point mixtures are usually high, producing wet, sloppy deposits. Final erupted mixtures from gas eruptions are nearly always dry, whereas those from mixing eruptions vary from wet to dry. If all the enthalpy released in the eruptions were converted to kinetic energy, the final velocity (v _max) of these mixtures could range up to 670 m/s for boiling-point eruptions and 1820 m/s for gas eruptions (highest for high initial pressure and mass fractions of rock (m _r) near zero). For mixing eruptions, v _max ranges up to 1150 m/s. All observed eruption velocities are less than 400 m/s, largely because (1) most solid material is expelled when m _r is high, hence v _max is low; (2) observations are made of large blocks the velocities of which may be less than the average for the mixture; (3) heat from solid particles is not efficiently transferred to the fluid during the eruptions; and (4) maximum velocities are reduced by choked flow or friction in the conduit.     

地下工程中岩土结构面的影响分析

研究已表明岩土体中都存在结构面,工程岩土体的变形破坏一般受结构面控制。本文依据结构面 (断层 )优势指标综合值 (Ri)的量化比较,可得出各结构面 (断层 )对隧道稳定影响程度的大小,从而针对各结构面 (断层 )采取不同的工程措施。本文分析还表明,结构面和地下工程中的水害、瓦斯突出、岩体质量好坏等也有密切关系。     

Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

The measurement of coal porosity with different gases

Sorption processes can be used to study different characteristics of coal properties, such as gas content (coalbed methane potential of a deposit), gas diffusion, porosity, internal surface area, etc. Coal microstructure (porosity system) is relevant for gas flow behaviour in coal and, consequently, directly influences gas recovery from the coalbed.This paper addresses the determination of coal porosity (namely micro- and macroporosity) in relation to the molecular size of different gases. Experiments entailed a sorption process, which includes the direct method of determining the “void volume” of samples using different gases (helium, nitrogen, carbon dioxide, and methane). Because gas behaviour depends on pressure and temperature conditions, it is critical, in each case, to know the gas characteristics, especially the compressibility factor.The experimental conditions of the sorption process were as follows: temperature in the bath 35 °C; sample with moisture equal to or greater than the moisture-holding capacity (MHC), particle size of sample less than 212 μm, and mass ca. 100 g.The present investigation was designed to confirm that when performing measurements of the coal void volume with helium and nitrogen, there are only small and insignificant changes in the volume determinations. Inducing great shrinkage and swelling effects in the coal molecular structure, carbon dioxide leads to “abnormal” negative values in coal void volume calculations, since the rate of sorbed and free gas is very high. In fact, when in contact with the coal structure, carbon dioxide is so strongly retained that the sorbed gas volume is much higher than the free gas volume. However, shrinkage and swelling effects in coal structure induced by carbon dioxide are fully reversible. Methane also induces shrinkage and swelling when in contact with coal molecular structure, but these effects, although smaller than those induced by carbon dioxide, are irreversible and increase the coal volume.