Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

气相色谱法测试土壤中分段石油烃的标准化定量方法初探

目前土壤样品中分段石油烃的分析方法中石油烃包括的碳原子数范围和采用的校准物质不统一,造成不同实验室的量值不具有可比性。为保证不同实验室之间结果的可比性,本文尝试建立一种石油烃相邻碳原子数标准化定量方法。该方法主要包括:(1)规定了石油烃包括的碳原子数范围为气相色谱峰中正己烷和正四十碳烷之间所有的烃(含正己烷);(2)总石油烃(TPH)分为挥发性石油烃(VPH)和半挥发性石油烃(SPH),分别选取碳原子数为6～10的5个正构烷烃作为VPH校准物质,选取碳原子数为10～40的31个正构烷烃作为SPH校准物质。采用平均响应因子法或一次线性回归法,建立校准物质的峰面积-浓度的校准关系;(3)采用相邻峰标准化校准方法,逐一定量所有的目标色谱峰;(4)计算正构烷烃含量、总石油烃含量和任意分段的石油烃含量。该方法为环境样品中石油烃分析方法的标准化建设提供了数据基础。     

气袋采样法对还原硫化物测定的影响因素分析及机理研究

还原硫化物是一Z类典型的恶臭物质,其特点是活性高、不易储存,因此适宜的储存条件对还原硫化物的准确测定具有重要意义。本文使用气相色谱-质谱联用技术,从气袋材质、还原硫化物初始浓度、还原硫化物性质和储存时间四个因素探究袋采样法储存还原硫化物过程的损失情况。以Tedlar~? PVF和Teflon~? FEP为目标采样袋,使用5个初始浓度(0. 001、0. 010、0. 100、1. 000和10. 000μg/m L)的混合还原硫化物,选择0、2、6、12、24、48以及72h的储存时间,以响应因子和相对回收率作为评价因子,并使用配对t检验法和吸附动力学,研究影响储存效果的主要因素、物质损失机理以及两种采样袋的储存能力。结果表明,储存时间越长、物质初始浓度越高,物质活性越强,损失情况越严重;在环境温度达到60℃时,Tedlar~? PVF的基质背景较Teflon~? FEP更复杂;相同条件下,还原硫化物在Teflon~? FEP储存过程中损失更严重。依据研究结果建议:(1)样品采集后避光保存;(2)低浓度含硫样品的测定在采样后8h内完成,高浓度含硫样品的测定在2h内完成;(3)若待测样品气体温度较高,优先选择Teflon~? FEP采样袋,气体温度较低条件下选择Tedlar~? PVF采样袋,可最大限度保持样品的原始状态。本研究成果有利于确保还原硫化物样品的储存稳定性,最大限度还原恶臭污染现场情况,为恶臭污染的分析测试以及后续的恶臭污染控制与治理提供技术支持。     

奥陶系岩溶古地貌恢复及对气藏分布的控制作用——以鄂尔多斯盆地苏里格东区41-33区块为例

苏东41-33区块位于鄂尔多斯盆地中央古隆起的北部南缘,长期沉积间断的风化壳不整合面形成复杂的岩溶古地貌,属苏里格气田东部奥陶系碳酸盐岩气藏的重要勘探区。研究基于钻井、测井、地震及生产动态资料分析,综合运用地球物理法、残厚法和印模法,优选本溪组顶9号煤层和马家沟组马五5灰岩为标志层,深入探讨古地貌单元的恢复依据和划分标准,精细恢复岩溶古地貌形态,并明确岩溶古地貌特征及其对气藏分布的影响。研究表明:苏东41-33区块整体处于二级地貌单元岩溶斜坡之上,奥陶系古风化壳上下地层厚度可划分出上薄下薄、上薄下厚、上厚下薄等5种组合类型,细分古坡地、残丘和沟槽3个三级地貌单元;古地貌总体趋势走向为北高南低,出露层位展布由马五4过渡到马五1。中南部发育连片残丘,北部见小型零星残丘,恢复厚度低于15m,残留厚度超过85m;北部发育2条侵蚀沟槽带,充填厚度大于20m,残留厚度小于45m;古坡地分布范围广泛,周围被古残丘与沟槽所分割,残留厚度介于45m^85m之间,恢复厚度大于10m。古地貌类型对风化壳气藏分布具有明显的控制作用,岩溶残丘及残丘边缘带的古坡地储层叠合厚度增大,溶蚀孔洞充填程度低,主力含气层保存完整且连通性较好,是寻找高产井的目标区,而岩溶古沟槽相对不利于天然气富集,所钻遇气井多为低产或无产能。     

Subterranean microorganisms and radioactive waste disposal in Sweden

In 1987, microbiology became a part of the Swedish scientific program for the safe disposal of high level nuclear waste (HLW). The goal of the microbiology program is to understand how subterranean microorganisms will interact with the performance of a future HLW repository. The Swedish research program on subterranean microbiology has mainly been performed at two sites in granitic rock aquifers at depths ranging from 70 m down to 1240 m, the Stripa research mine in the middle of Sweden and the Äspö Hard Rock Laboratory (HRL) situated on the south eastern coast of Sweden. Some work has also been performed in cooperation with other national or international research groups in Sweden, Canada and at the natural analogue sites Oklo in Gabon and Maqarin in Jordan. The following conclusions are drawn. There is a very high probability of the existence of a deep subterranean biosphere in granitic rock. The documented presence of a deep biosphere implies that relevant microbial reactions should be included in the performance assessment for a HLW repository. A HLW repository will be situated in a subterranean biosphere that is independent of solar energy and photosynthetically produced organic carbon. The ultimate limitation for an active microbial life will be the availability of hydrogen as energy source over time, and hydrogen has indeed been found in most deep groundwaters. Sulphide producing microorganisms are active in environments typical for a Swedish HLW repository, and the potential for microbial corrosion of the copper canisters must be considered. The bentonite buffer around the copper canisters will be a hostile environment for most microbes due to the combination of radiation, heat and low water availability. Discrete microbial species can cope with each of these constraints, and it is theoretically possible that sulphide producing microbes may be active inside a buffer, although the experiments conducted thus far have shown the opposite. Microorganisms have the capability to enzymatically recombine radiolysis oxidants formed by radiation of water. It has earlier been concluded that the migration of radionuclides due to sorption on microorganisms can be neglected. The influence of microbially produced complexing agents remains to be studied at realistic conditions in deep groundwater. Microorganisms have been found in natural alkaline groundwaters, but it could not be conclusively demonstrated that they were in situ viable and growing, rather than just transported there from neutral groundwater. A possible hypothesis based on the obtained results from investigations of natural alkaline groundwaters is that fresh concrete may be a bit too extreme for active life even for the most adaptable microbe – but this remains to be demonstrated.     

New high-resolution 2D seismic imaging of fluid escape structures in the Makran subduction zone,Arabian Sea

Seabed fluid escape is active in the Makran subduction zone, Arabian Sea. Based on the new high-resolution 2D seismic data, acoustic blanking zones and seafloor mounds are identified. Acoustic blanking zones include three kinds of geometries: Bell-shaped, vertically columnar and tilted zones. The bell-shaped blanking zone is characterized by weak and discontinuous reflections in the interior and up-bending reflections on the top, interpreted as gas chimneys. Vertically columnar blanking zone is interpreted as side-imaged gas chimneys associated with focused fluid flow and topped by a seafloor anomaly expressed as a localized reflection discontinuity, which may together serve as a vent structure. Tilted acoustic blanking zone could be induced by accretionary thrust activity and rapid sedimentation surrounding slope. Seafloor mounds occur at the sites of bell-shaped acoustic blanking zone and may be associated with the material intrusion. Bottom simulating refectors (BSRs) are widely distributed and exhibit a series of characteristics including diminished amplitude, low continuity as well as local shoaling overlapping with these acoustic blanking zones. The large amount of gases dissociated from the gas hydrates migrated upwards and then arrived at the near-seafloor sediments, followed by the formation of the gas hydrates and hence the seafloor mound.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.     

Influence of natural fractures on gas accumulation in the Upper Triassic tight gas sandstones in the northwestern Sichuan Basin,China

The Upper Triassic Xujiahe Formation in the northwestern Sichuan Basin, China, is a typical tight gas sandstone reservoir that contains natural fractures and has an average porosity of 1.10% and air permeability less than 0.1 md because of compaction and cementation. According to outcrops, cores and image logs, three types of natural fractures, namely, tectonic, diagenetic and overpressure-related fractures, have developed in the tight gas sandstones. The tectonic fractures include small faults, intraformational shear fractures and horizontal shear fractures, whereas the diagenetic fractures mainly include bed-parallel fractures. According to thin sections, the microfractures also include tectonic, diagenetic and overpressure-related microfractures. The diagenetic microfractures consist of transgranular, intragranular and grain-boundary fractures. Among these fractures, intraformational shear fractures, horizontal shear fractures and small faults are predominant and significant for fluid movement. Based on the Monte Carlo method, these intraformational shear fractures and horizontal shear fractures improve the reservoir porosity and permeability, thus serving as an important storage space and primary fluid-flow channels in the tight sandstones. The small faults may provide seepage channels in adjacent layers by cutting through layers. In addition, these intragranular and grain-boundary fractures increase the connectivity of the tight gas sandstones by linking tiny pores. The tectonic microfractures improve the seepage capability of the tight gas sandstones to some extent. Low-dip angle fractures are more abundant in the T₃X³ member than in the T₃X² and T₃X⁴ members. The fracture intensities of the sandstones in the T₃X³ member are greater than those in the T₃X² and T₃X⁴ members. The fracture intensities do not always decrease with increasing bed thickness for the tight sandstones. When the bed thickness of the tight sandstones is less than 1.0 m, the fracture intensities increase with increasing bed thickness in the T₃X³ member. Fluid inclusion evidence and burial history analysis indicate that the tectonic fractures developed over three periods. The first period was at the end of the Triassic to the Early Jurassic. The tectonic fractures developed during oil generation but before the matrix's porosity and permeability reduced, which suggests that these tectonic fractures could provide seepage channels for oil migration and accumulation. The second period was at the end of the Cretaceous after the matrix's porosity and permeability reduced but during peak gas generation, which indicates that gas mainly migrated and accumulated in the tectonic fractures. The third period was at the end of the Eogene to the Early Neogene. The tectonic fractures could provide seepage channels for secondary gas migration and accumulation from the Upper Triassic Xujiahe Formation into the overlying Jurassic Formation.     

The mechanism and verification analysis of permafrost-associated gas hydrate formation in the Qilian Mountain,Northwest China

Muri Basin in the Qilian Mountain is the only permafrost area in China where gas hydrate samples have been obtained through scientific drilling. Fracture-filling hydrate is the main type of gas hydrate found in the Qilian Mountain permafrost. Most of gas hydrate samples had been found in a thin-layer-like, flake and block group in a fracture of Jurassic mudstone and oil shale, although some pore-filling hydrate was found in porous sandstone. The mechanism for gas hydrate formation in the Qilian Mountain permafrost is as follows: gas generation from source rock was controlled by tectonic subsidence and uplift--gas migration and accumulation was controlled by fault and tight formation--gas hydrate formation and accumulation was controlled by permafrost. Some control factors for gas hydrate formation in the Qilian Mountain permafrost were analyzed and validated through numerical analysis and laboratory experiments. CSMGem was used to estimate the gas hydrate stability zone in the Qilian permafrost at a depth of 100–400 m. This method was used to analyze the gas composition of gas hydrate to determine the gas composition before gas hydrate formation. When the overlying formation of gas accumulation zone had a permeability of 0.05 × 10⁻¹⁵ m² and water saturation of more than 0.8, gas from deep source rocks was sealed up to form the gas accumulation zone. Fracture-filling hydrate was formed in the overlap area of gas hydrate stability zone and gas accumulation zone. The experimental results showed that the lithology of reservoir played a key role in controlling the occurrence and distribution of gas hydrate in the Qilian Mountain permafrost.