云贵高原湖泊CO2的地球化学变化及其大气CO2源汇效应

湖泊是大气CO₂的源还是汇,长期以来一直都存有争议。云贵高原地区的湖泊由于受流域碳酸盐岩风化作用的影响,使这一问题就显得更特殊,也更复杂。本次研究通过化学平衡计算和气相色谱测定两种方法得到了比较一致的湖水CO₂浓度结果。研究发现,在夏季强烈的光合作用消耗了湖水CO₂,致使湖水中CO₂浓度降低。在贵州草海、百花湖以及云南的泸沽湖、杞麓湖,表层湖水CO₂分压(为便于与大气CO₂比较,文中湖水CO2用分压单位表示)小于200μatm,远低于大气CO₂分压,湖泊正不断地从大气中吸收CO₂,从而构成大气CO₂的汇。     

沉积岩中无机CO2热模拟实验研究

结合三水盆地的地质特点，分析了无机CO₂热模拟实验研究的可能性，进行了不同条件下的模拟试验和相关的分析测试，提出了无机CO₂生成量和转化率的概念和计算方法。从实验结果来看：含有一定量碳酸盐矿物的沉积岩，在一定温度下可转化形成相当数量的无机CO₂，无机CO₂转化率越高，岩石中碳酸盐矿物越容易转化生成无机CO₂；相同热成熟度条件下，Ⅱ型干酪根生成有机CO₂的量较Ⅲ型的少；CO₂中碳同位素与CO₂的成因密切相关，随有机质热成熟度的增加，同种类型有机质生成的有机CO₂相对富集¹³C；无机CO₂较有机CO₂的碳同位素明显富集¹³C，随水介质的pH值降低，无机CO₂气含量、模拟温度及时间的增加，无机CO₂相对富集¹³C。实验研究结果为CO₂成因研究及其资源评价提供了实验依据。     

土壤温室气体昼夜变化及其环境影响因素研究

通过对北京东灵山草地和桦树林土壤气体CO₂,N₂O和CH₄浓度及其排放通量的昼夜连续观测,探讨了生长季节草地和森林土壤温室气体昼夜变化及其环境影响因素。研究表明:1)土壤CO₂排放通量昼高夜低,N₂O排放通量有明显小时尺度波动,但昼夜变化不突出;土壤CO₂和N₂O浓度昼夜变化不明显,且与排放通量波动不一致;土壤是大气CH₄的一个汇,相对厌氧的环境可能有利于土壤吸收CH₄。2)无雨时气温昼夜变化通过影响土壤表层的气体扩散和CO₂产生过程,来影响土壤CO₂和N₂O的地表排放通量,而对土壤10cm以下CO₂和N₂O的产生影响不大。小时尺度的土壤CO₂和N₂O浓度波动则可能还有其他影响因素或机制。3)降雨时土壤渗水引起的土壤空气对流取代气体浓度扩散成为土壤与大气空气交换的主要方式,导致土壤CO₂和N₂O排放通量的同步波动。降雨渗水较多时,较多的溶解氧随着雨水进入土壤内,会促进土壤CO₂的生成和抑制N₂O的产生。4)土壤CO₂与N₂O浓度存在显著的正相关关系,反映出土壤CO₂和N₂O有相对稳定的产率比。土壤有效碳可能是造成土壤CO₂与N₂O浓度正相关的主要原因,土壤空气的氧分压则可能是造成土壤CO₂和N₂O浓度波动不一致的重要因素。     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

蔡家营铅锌银矿区CO2异常分布特征及其成因的讨论

本文介绍了蔡家营矿区壤中气CO₂和岩矿石中热释CO₂异常的分布特征。通过CO₂异常分布与矿体赋存关系的研究,对异常形成机理做了初步探讨,阐明了厚覆盖区CO₂异常的分布规律,以及在寻找隐伏矿、查明区域控矿构造中的作用。     

阿尔泰南缘克兰盆地的脉状金-铜矿化及其流体演化

阿尔泰山南缘泥盆纪克兰火山-沉积盆地蕴藏有丰富的VMS锌铅铜多金属矿床。自晚泥盆世至早二叠世末, 阿尔泰山南缘为NE-SW向强烈挤压的构造环境, VMS矿石受到变形变质改造,脉状金铜矿化发育。金(铜)石英脉主要有2种产状:(1)白色-灰白色(硫化物)顺层石英脉(QI), 产于韧脆性剪切带发育地段,呈细脉状或透镜状产于绿泥片岩、黑云片岩中;(2)斜切黄铁矿化蚀变岩、层状铅锌矿和变质岩产状的黄铜矿-黄铁矿石英脉(QII),与晚期的脆性构造有关。金(铜)石英脉的流体包裹体发育,按室温下相态特征有3类。第I类为含子矿物的高盐度包裹体(L-V-S型),子晶为NaCl, 有时为KCl,包裹体呈孤立或无序分布,代表变质早期流体特征。一般NaCl子晶先消失(210~357℃),包裹体的最终均一温度369~512℃,其捕获温度与变质相的相平衡计算温度相当,反映了变质早期中高温热液活动的特征。第II类是富CO₂ 包裹体,包括单相的碳质流体包裹体(L _CO2、L _CO2-CH4或L _CO2-N2)和两相富CO₂包裹体(L _CO2-L _H2O)2个亚类。碳质流体包裹体是常见类型,有时与L _CO2-L_H2O型伴生,在较晚期的黄铜矿-黄铁矿石英脉中表现为原生特征,而在较早的石英脉中常表现为次生特征。萨热阔布的碳质流体可分为纯CO₂包裹体和CO₂-CH₄体系包裹体,纯CO₂包裹体的固体CO₂熔化温度(T_m,CO2)为 -60~-56.5℃,CO₂部分均一温度(T_h,CO2) 变化于-23~+31℃;密度一般为0.85~0.89g·m^-3。CO₂-CH₄包裹体的T_m,CO2＜-57℃,可低达-78.1℃,T_h,CO2低达-33.7~-17.7℃, 其密度高达1.01~1.07g·m^-3。VMS矿床中晚期叠加的黄铜矿石英脉中碳质流体包裹体可分为贫CH₄-N₂和富CH₄-N₂的CO₂-CH₄-N₂包裹体,贫CH₄-N₂的碳质包裹体T_m,CO2=-63.3~-57℃,T_h,CO2=-27.5~+29.7℃;富CH₄-N₂的CO₂-CH₄-N₂包裹体T_m,CO2=-83.4~-65.5℃,T_h,CO2=-56.0~+16.9℃。铜金石英脉中与碳质流体共生的L_CO2-L_H2O型包裹体均一温度T_h,total=205~370℃,略低于第I类高盐度包裹体的T_h,total=369~512℃。据CO₂流体高温高压相图估算包裹体的捕获压力至少为110~300MPa。金(铜)石英脉的主体在相当于445~566℃的高温条件下形成的,而金铜矿化则是在高于205~370℃、110~330MPa的中高温中深条件下发生的。流体包裹体的δ¹⁸O为7.54‰~11.84‰ (QI)和3.82‰~7.82‰ (QII), δD为-84.7‰~-98.2‰(QI)和-75.8‰~-108.8‰ (QII)。结合地质特征和流体研究,说明成矿热液来源与区域变质及相关的岩浆活动有关。     

松辽盆地北部昌德东CO2气藏的自生自储成藏模式

松辽盆地北部昌德东CO₂气藏的“自生自储“成藏模式指成藏气体主要是无机成因的幔源火山岩吸附气，后期的构造运动使裂缝连通、天然气汇聚成藏。证据有：火山岩含有WB为0.429%~1.387%的吸附CO₂，具有孔隙和缝隙相互组合的双孔介质，说明火山岩既可作为CO₂气的源岩，亦可作为储层；昌德东CO₂气藏中存在近距离不均一的CO₂含量空间分布、下贫上富的储层CO₂含量和上高下低的CH₄-CO₂平衡温度等特征。中国东部幔源—岩浆成因的CO₂气藏地区均发育幔源火山岩，说明该成藏模式具有现实的可能性和普遍性。     

CO2气综合识别技术及应用

CO₂气藏由于其物理、化学性质的特殊性,CO₂气勘探与烃类气既有相同又有区别,综合应用多种资料和多种技术方法是识别CO₂气(层)藏的有效手段。利用区域地质分析、地球物理和地球化学勘探方法综合评价非烃气的分布,提出钻探目标,通过非烃色谱测量法和红外线CO₂气体浓度测量法实现CO₂气层钻井现场动态检测,利用气体色谱检测相关录井参数资料、核测井密度中子孔隙度差值综合解释CO₂气层,有效地识别CO₂气。主要介绍CO₂气藏综合勘探技术的关键的新技术方法,如地球化学方法、录井和测井综合识别的关键技术方法等。     

水射流破碎联合CO2置换开采天然气水合物新工艺及实验研究

本文对目前开采天然气水合物的5种方法进行了归纳总结,重点分析了CO₂置换开采以及固体开采法,并通过分析这2种开采方法的优劣势,提出了水射流冲蚀、破碎海洋天然气水合物储层联合CO₂置换开采天然气水合物的新思路。水射流冲蚀、破坏水合物储层后形成的采空区能为CO₂提供更好的储藏空间并提高其与储层的作用面积,提高置换效率;封存的CO₂水合物也可以提高水合物储层的稳定性,具有良好的互补效应。实验结果表明,在整个置换过程中,含采空区储层CH₄置换率为24.3%,CO₂封存率为22.1%;完整储层CH₄置换率为15.3%,CO₂封存率为20.9%,置换率提升约59%,封存率提升约5.7%。采空区的作用主要体现在提升水合物置换介质的注入量上。     

全球变化条件下的土壤呼吸效应

土壤呼吸是陆地植物固定CO₂尔后又释放CO₂返回大气的主要途径，是与全球变化有关的一个重要过程。综述了全球变化下CO₂浓度上升、全球增温、耕作方式的改变及氮沉降增加的土壤呼吸效应。大气CO₂浓度的上升将增加土壤中CO₂的释放通量，同时将促进土壤的碳吸存；在全球增温的情形下，土壤可能向大气中释放更多的CO₂，传统的土地利用方式可能是引发温室气体CO₂产生的重要原因，所有这些全球变化对土壤呼吸的作用具有不确定性。认为土壤碳库的碳储量增加并不能减缓21世纪大气CO₂浓度的上升。据此讨论了该问题的对策并提出了今后土壤呼吸的一些研究方向。其中强调，尽管森林土壤碳固定能力有限，但植树造林、森林保护是一项缓解大气CO₂上升的可行性对策；基于现有田间尺度CO₂通量测定在不确定性方面的进展，今后应继续朝大尺度田间和模拟程序方面努力；着重回答全球变化条件下的土壤呼吸过程机理；区分土壤呼吸的不同来源以及弄清土壤呼吸黑箱系统中土壤微生物及土壤动物的功能。当然，土壤呼吸的测定方法尚有待改善。     

Preparation,characterization, and gas permeation properties of blend membranes of polysulfone and polyethylene glycol inclusive alumina nanoparticles

The effect of incorporation of alumina nanoparticles on the gas separation properties of the polysulfone–polyethylene glycol blend membranes containing 20% polyethylene glycol was examined. At first, a number of nanocomposite polysulfone–polyethylene glycol/alumina membranes were synthesized with alumina nanoparticles loaded into the polymer matrixes. The hybrid membranes were synthesized with six different alumina contents of 2.5, 5, 10, 15, 20, and 30 wt%. The polysulfone–polyethylene glycol and their hybrids inclusive alumina membranes were prepared via thermal phase-inversion method. The membranes were initially characterized using Fourier transform infrared spectroscopy, scanning electron microscope, and X-ray diffraction. Gas permeation properties of these membranes with different alumina contents were investigated for pure CO₂, CH₄, N₂, and O₂ gases. The results showed that not only these gases permeability but the CO₂/N₂, CO₂/CH₄, and O₂/N₂ ideal selectivity were improved with increasing alumina nanoparticle content of the membrane as well. Also the effect of feed pressure on the permeation properties of these membranes was investigated for pure CO₂ gas. Finally, the results from the synthesized membranes were compared with Robeson’s upper bound line.     

Pressure transient technique to constrain CO<Subscript>2</Subscript> plume boundaries

Carbon dioxide (CO₂) has been injected in the subsurface permeable formations as a means to cut atmospheric CO₂ emissions and/or enhance oil recovery (EOR). It is important to constrain the boundaries of the CO₂ plume in the target formation and/or other formations hosting the CO₂ migrated from the target formation. Monitoring methods and technologies to assess the CO₂ plume boundaries over time within a reservoir of interest are required. Previously introduced methods and technologies on pressure monitoring to detect the extent of the CO₂ plume require at least two wells, i.e. pulser and observation wells. We introduce pressure transient technique requiring single well only. Single well pressure transient testing (drawdown/buildup/injection/falloff) is widely used to determine reservoir properties and wellbore conditions. Pressure diagnostic plots are used to identify different flow regimes and determine the reservoir/well characteristics. We propose a method to determine the plume extent for a constant rate pressure transient test at a single well outside the CO₂ plume. Due to the significant contrast between mobility and storativity of the CO₂ and native fluids (oil or brine), the CO₂ boundary causes deviation in the pressure diagnostic response from that corresponding to previously identified heterogeneities. Using the superposition principle, we develop a relationship between the deviation time and the plume boundary. We demonstrate the applicability of the proposed method using numerically generated synthetic data corresponding to homogeneous, heterogeneous, and anisotropic cases to evaluate its potential and limitations. We discuss ways to identify and overcome the potential limitations for application of the method in the field.     

Percolation-theory and fuzzy rule-based probability estimation of fault leakage at geologic carbon sequestration sites

Leakage of CO₂ and displaced brine from geologic carbon sequestration (GCS) sites into potable groundwater or to the near-surface environment is a primary concern for safety and effectiveness of GCS. The focus of this study is on the estimation of the probability of CO₂ leakage along conduits such as faults and fractures. This probability is controlled by (1) the probability that the CO₂ plume encounters a conductive fault that could serve as a conduit for CO₂ to leak through the sealing formation, and (2) the probability that the conductive fault(s) intersected by the CO₂ plume are connected to other conductive faults in such a way that a connected flow path is formed to allow CO₂ to leak to environmental resources that may be impacted by leakage. This work is designed to fit into the certification framework for geological CO₂ storage, which represents vulnerable resources such as potable groundwater, health and safety, and the near-surface environment as discrete “compartments.” The method we propose for calculating the probability of the network of conduits intersecting the CO₂ plume and one or more compartments includes four steps: (1) assuming that a random network of conduits follows a power-law distribution, a critical conduit density is calculated based on percolation theory; for densities sufficiently smaller than this critical density, the leakage probability is zero; (2) for systems with a conduit density around or above the critical density, we perform a Monte Carlo simulation, generating realizations of conduit networks to determine the leakage probability of the CO₂ plume (P _leak) for different conduit length distributions, densities and CO₂ plume sizes; (3) from the results of Step 2, we construct fuzzy rules to relate P _leak to system characteristics such as system size, CO₂ plume size, and parameters describing conduit length distribution and uncertainty; (4) finally, we determine the CO₂ leakage probability for a given system using fuzzy rules. The method can be extended to apply to brine leakage risk by using the size of the pressure perturbation above some cut-off value as the effective plume size. The proposed method provides a quick way of estimating the probability of CO₂ or brine leaking into a compartment for evaluation of GCS leakage risk. In addition, the proposed method incorporates the uncertainty in the system parameters and provides the uncertainty range of the estimated probability.     

Bayesian hierarchical models for soil CO<Subscript>2</Subscript> flux and leak detection at geologic sequestration sites

Proper characterizations of background soil CO₂ respiration rates are critical for interpreting CO₂ leakage monitoring results at geologic sequestration sites. In this paper, a method is developed for determining temperature-dependent critical values of soil CO₂ flux for preliminary leak detection inference. The method is illustrated using surface CO₂ flux measurements obtained from the AmeriFlux network fit with alternative models for the soil CO₂ flux versus soil temperature relationship. The models are fit first to determine pooled parameter estimates across the sites, then using a Bayesian hierarchical method to obtain both global and site-specific parameter estimates. Model comparisons are made using the deviance information criterion (DIC), which considers both goodness of fit and model complexity. The hierarchical models consistently outperform the corresponding pooled models, demonstrating the need for site-specific data and estimates when determining relationships for background soil respiration. A hierarchical model that relates the square root of the CO₂ flux to a quadratic function of soil temperature is found to provide the best fit for the AmeriFlux sites among the models tested. This model also yields effective prediction intervals, consistent with the upper envelope of the flux data across the modeled sites and temperature ranges. Calculation of upper prediction intervals using the proposed method can provide a basis for setting critical values in CO₂ leak detection monitoring at sequestration sites.     

土壤热释CO2测量法在碳硅泥岩型铀矿床上的试验效果

本文主要论述土壤热释CO₂测量法在碳硅泥岩型铀矿床上的试验效果,实测结果表明,该法是有效的.文章还对CO₂法找钻机制进行了初步探讨.有关取样技术、样品加工和分析测定方法也作了概述.最后认为土壤热释CO₂ 测量法可成为一种找铀的新方法.     

CO2 geological storage: The environmental mineralogy perspective

Geological storage of carbon dioxide (CO₂) is one of the options envisaged for mitigating the environmental consequences of anthropogenic CO₂ increases in the atmosphere. The general principle is to capture carbon dioxide at the exhaust of power plants and then to inject the compressed fluid into deep geological formations. Before implementation over large scales, it is necessary to assess the efficiency of the process and its environmental consequences. The goal of this paper is to discuss some environmental mineralogy research perspectives raised by CO₂ geological storage.     

CO_2 Density-Raman Shift Relation Derived from Synthetic Inclusions in Fused Silica Capillaries and Its Application

Abstract: The densities of CO2 inclusions in minerals are commonly used to determine the crystallizing conditions of the host minerals. However, conventional microthermometry is difficult to apply for inclusions of small size (< 5–10 μm) or low density. Raman analysis is an alternative method for determining CO2 density, provided that the CO2 density–Raman shift relation is known. This study aims to establish this CO2 density–Raman shift relation by using CO2 inclusions synthesized in fused silica capillaries. By using this newly-developed synthetic technique, we formed pure CO2 inclusions, and their densities were determined by microthermometry. The Raman analysis showed that the relation between CO2 density (D in g/cm3) and the separations (Δ in cm?1) between the two main bands (i.e. Fermi diad bands) in CO2 Raman spectra can be represented by a cubic equation: D (g/cm3)=0.74203(?0.019Δ3+5.90332Δ2?610.79472Δ+21050.30165)?3.54278 (r2=0.99920). Our calculated D value for a given Δ is between those obtained from two previously-reported equations, which were derived from different experimental methods. An example was given in this study to demonstrate that the densities of natural CO2 inclusions that could not be derived from microthermometry could be determined by using our method.     

Determining the composition of C–H–O liquids following high-pressure and high-temperature diamond-trap experiments

Here, we present the first analytical technique (the quartz tube system technique—QTS) to directly analyze H₂O and CO₂ contents in liquids following high-pressure, high-temperature experiments in capsules containing mantle minerals and a diamond layer serving as a fluid/melt trap. In this technique, the capsule is frozen prior to opening; the diamond trap is cut out of the capsule and placed inside a N₂-filled quartz tube. The diamond trap is heated up to 900 °C to release the gases to an Infrared Gas Analyzer, which determines the CO₂ and H₂O contents. Three sets of experiments containing SiO₂ and CaCO₃ powders were performed at 6 GPa and 1,000 °C in order to calibrate and validate the technique. These experiments demonstrated that when samples are prepared in a N₂ environment, CO₂ and H₂O can be directly measured with an accuracy and precision of 2–3 and 3–4 %, respectively. The QTS technique (for H₂O and CO₂ determination) together with the cryogenic technique (total dissolved solids content) can be applied to diamond-trap capsules following HP–HT experiments in order to provide direct and complete liquid compositions coexisting with mantle material. The principal advantage of the QTS technique of direct analysis of volatile content in liquids over the indirect approach of mass balance calculations is the possibility of studying carbonated and hydrous liquid compositions in equilibrium with mantle material regardless of chemistry and pressure–temperature experimental conditions.     

胜利油田火山岩单个包裹体碳同位素

近年来,在我国东部陆续发现了一些二氧化碳气藏,对其成因,不少学者有过讨论, 得出许多重要认识^①。     

Mineral dating of mantle−derived CO2 charging and its application in the southern Songliao Basin,China

The timing of mantle−derived CO₂ charging in sedimentary basins is the basis for studying CO₂-sandstone interactions and CO₂-oil interactions. In general, the time of the volcanic eruption near the CO₂ gas reservoir is considered to be the time of mantle-derived CO₂ charging. However, this approach is not suitable for hydrocarbon-bearing basins that have experienced multiple volcanic events. In this paper, using dawsonite-bearing sandstones contained in an oil-bearing CO₂ gas and oil reservoir in the southern Songliao Basin as the object of the study on the basis of paragenetic sequence and fluid inclusions, we establish a mineral dating method for determining the time of mantle-derived CO₂ charging. In this method, the mineral used for dating is dawsonite, which is formed under a high CO₂ partial pressure and records the migration and aggregation of mantle-derived CO₂ in geologic history. By interpreting the dawsonite-bearing sandstone in the southern Songliao Basin, we find two hydrocarbon charges and one CO₂ charge and that the mantle-derived CO₂ charging occurred slightly later than or quasi-simultaneously with the second hydrocarbon filling. Combining the currently known time of hydrocarbon reservoir formation and the time of tectonic fracture development, we deduce that the mantle-derived CO₂ formed the dawsonite in the southern Songliao Basin at the end of the Cretaceous (end of the Mingshui period) and the beginning of the Paleogene.