米泉低阶煤煤层气中CO2异常赋存特征与成因

对米泉矿区以往煤层气勘查成果统计发现,气体含量中CO₂浓度异常高,部分气样浓度甚至超过40%。通过系统开展气体组分、CH₄与CO₂碳同位素、稀有气体同位素等地化分析,发现该区CO₂浓度随埋深增大呈增高趋势。当埋深大于800 m时,CO₂浓度超过40%;CO₂具明显壳源成因特征,无幔源CO₂的混入。说明该区煤层气主要为CO₂还原途径形成的次生生物气体,少量样品具热成因气特征;CO₂异常富集可能是3个方面因素耦合作用的结果,即处于微生物产甲烷活动早期阶段、CO₂还原途径产甲烷活动受到抑制及滞留的水体环境。     

CO2强化煤层气产出与其同步封存实验研究

长期以来针对CO₂-ECBM已做了大量研究工作,然而有限的工业试验没能达到预期目的,使得这一煤层气强化技术推广应用欠缺。近些年随着各国碳中和路线的制定,CO₂封存逐渐受到重视,煤储层可否作为CO₂的封存空间、可否实现CO₂驱替CH₄和封存同步进行,又重新回归人们的视野。为此,以新疆准南区块目标煤层样为研究对象,采用不同CO₂与CH₄混合比例气体进行煤的吸附/解吸实验,探索混合气体比例对CO₂-ECBM和CO₂吸附封存潜力的影响。结果表明,随着混合气体CO₂比例减少,CH₄驱替效果降低,其中40%CH₄+60%CO₂混合气体的CO₂残余量最多,在解吸至0.7 MPa时已有83.05%的CH₄产出,而83.62%的CO₂吸附残余在煤中,表明其C...     

胜利油田富CO2含金流体及有关成因问题

本文分析了胜利油田火山岩中的Au含量，发现CO2气藏区火山岩和非CO2气藏区火山岩中Au含量有明显区别前者含Au很高，平均327×10-9,最高2150×10-9;而后者含Au很低,平均只有2.5×10-9。这一基本事实提供了CO2与金矿化间联系的直接地质证据,指出了在中国东部郯庐断裂两侧找寻新的金矿资源的方向与可能性。研究表明，地幔及其岩浆去气对形成富CO2含Au热液系统有重要的贡献，而一个由深部稳定热源驱动、富含地幔及其岩浆去气带入的CO2和Au并与地壳浅部流体混合的热液环流系统是形成重要金矿化的必要条件。     

巴西桑托斯盆地CO2分布规律及控制因素

CO₂富集是桑托斯盆地盐下油气成藏的主要地质风险,目前关于CO₂形成机制与分布规律缺乏系统研究。基于钻井样品的地球化学分析和地球物理资料的断裂体系刻画,对桑托斯盆地CO₂形成与分布的主控因素开展研究探索。研究认为：CO₂含量在已发现油气藏中占气体含量的0～96%不等,呈现出西低东高的分布特征,盆地西部油气藏的CO₂含量基本小于1%,而盆地东部油气藏的CO₂含量一般大于30%,并且出现了CO₂气顶和CO₂气藏。CO₂的碳同位素组成δ¹³C为-8.64‰～-7.03‰,氦同位素R/Ra值约为5.6～8,推断CO₂为无机成因,来源于地幔,基本未受到地壳的污染。幔源CO₂释放的地质背景是地幔隆升,盆地东部地壳减薄,构造活动强烈,四组断裂相互切割;主控因素是深大断裂,断裂直接沟通上地壳岩浆房,或者连通地壳上部高渗带,而高渗带连接地壳下部...     

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。     

基于多准则决策的CO2地质封存场地适宜性评价方法

二氧化碳(CO₂)捕集、利用与封存技术(CCUS)是减排温室气体CO₂、实现中国“双碳”目标的重要技术手段。CO₂地质封存作为CCUS技术的重要组成部分,是一种直接、有效的减排方法,已为全球多个国家CO₂增汇减排做出突出贡献。科学合理的场地适宜性评价和选址工作是实现CO₂地质封存的首要前提,场地适宜性评价中通常包含多个定性与定量指标,国内外常采用多准则决策(MCDM)方法处理此类多源复杂因素共同作用的场地适宜性评价工作。MCDM方法通常将指标权重与评价方法集成,以期实现各方法的优势互补,进而获得较为满意的评价结果。文章回顾了CO₂地质封存的国内外选址现状,并对基于MCDM方法的场地适宜性评价进行全面综述,以期为中国CO₂地质封存选址的适宜性评价提供参考依据。

     

CO2相变致裂本煤层增透技术研究

研究液态CO₂相变特征和煤体对气相CO₂和CH₄的吸附规律,在不同煤质、温度和平衡压力条件下,实验得出在无烟煤和焦煤的煤体中CO₂竞相吸附的能力是CH₄的1.8~2.4倍。研究发现,液态CO₂在0.2 s内完成相变过程,体积瞬间膨胀至794倍。通过理论研究建立了采用不耦合致裂条件下的爆破孔初始冲击压力峰值、裂隙圈有效半径和爆破致裂钻孔孔径3个主要爆破参数变量的数学模型。采用液态CO₂瞬间相变出口压力为200MPa的致裂器,进行致裂爆破本煤层增透现场实验研究,研究得出距离致裂爆破孔2m和3m的控制孔在爆破后单孔瓦斯抽采纯量提高至6倍和4倍,单孔瓦斯抽采浓度提高至5倍和4倍,单孔瓦斯抽采浓度保持在35%~55%,而距离致裂爆破孔4m的控制孔在爆破5d后瓦斯抽采效果衰减至爆破前的水平。现场试验得出初始冲击压力峰值200MPa和钻孔孔径0.094m时,本煤层致裂爆破裂隙圈有效半径为3m。     

长江干流水化学成因与风化过程CO2消耗通量解析

长江流域面积巨大,岩性多变,加之三峡大坝等重大水利工程的影响,干流河水的水化学成因存在较大争议。此外,以往研究中流域矿物风化过程的碳汇通量估算一般基于阳离子来源分析,但该算法通常涉及多种矿物端元的参数选取,结果具有不确定性。本次研究对长江干流水化学的时空演变进行了整体分析,并基于上游河水样品$\rm{HCO}_3^{-}$含量的校正与计算,提出了一种计算矿物风化过程碳汇通量的新方法。研究结果表明,蒸发盐溶解、循环盐作用、矿物风化及硫酸盐溶解是控制长江干流河水离子组成的主要水文地球化学作用,而人类活动主要影响了离海距离3 000 km以内河水$\rm{NO}_3^{-}$含量;长江上游干流硅酸盐风化消耗CO2速率为1.16×105 mol/(km2·a),碳酸盐风化消耗CO2速率为4.75×105 mol/(km2·a)。本研究有助于加深对长江干流主要水文地球化学作用的认识,丰富和完善碳循环研究理论。     

巴西桑托斯盆地CO2区域分布及主控因素

桑托斯盆地盐下油气田中发现了大量CO₂,给油气勘探开发和生产都带来诸多困难和挑战.利用地层测试、样品分析及文献资料等,明确了CO₂成因及来源,统计分析了其区域分布特征,并基于区域重磁和深源地震等资料,剖析了控制CO₂分布的地质因素.盆内CO₂主要为幔源—岩浆成因,且幔源CO₂贡献了至少92%的CO₂总量.区域上,CO₂自陆向海呈增加趋势,并相对集中在盆地东部隆起带上.地壳减薄和地幔局部隆升是控制CO₂宏观分布最重要的背景因素.极端的地壳伸展造成了圣保罗地台下部陆壳强烈拉伸减薄,形成了一个面积约5.1×104 km2的地壳减薄区,造成了富含CO₂的地幔物质上拱进入陆壳,宏观上决定了盆内CO₂区域分布.此区域之外,出现高含量CO₂的可能性大幅降低.岩浆侵入和活动断层都是沟通隆升地幔和浅部储层的重要路径,但以断裂沟通最常见.NW-SE向区域走滑断裂和NE-SW向I-II级正断层对CO₂在浅部地层中的分配起控制作用,两组断裂交汇部位或周缘是幔源岩浆或CO₂最集中发育区.      

腾冲新生代火山区CO2气体释放通量及其成因

许多研究结果表明,休眠期火山主要通过喷气孔、温泉以及土壤微渗漏三种方式向大气圈释放温室气体。腾冲是我国重要的新生代火山区之一,同时也是主要的水热活动区,但是关于温室气体释放通量的研究却鲜有报道。本文首次估算了该地区土壤微渗漏和温泉水的CO2释放通量,并根据气体成分的分析结果探讨了这些温室气体的来源。2012~2013年连续两年使用密闭气室法现场测量了土壤微渗漏CO2通量,结果表明,马站、热海-黄瓜箐和五合-蒲川-团田三个地区通量较高,其中,热海-黄瓜箐地区平均通量最高,马站次之,五合-蒲川-团田地区最低。较高的土壤微渗漏CO2释放地区同前人推断的岩浆囊的分布在空间上具有较好的一致性;三个地区气体的3He/4He比值较高,三端元模拟结果表明,它们均有较高含量的幔源He释放;根据气体CO2/3He与δ13CCO,CO2模拟计算,CO2主要来源于碳酸盐矿物的脱碳作用和岩浆脱气。由此推断2的释放同深部的岩浆囊具有重要的成因联系,它为碳酸盐矿物的脱碳作用提供了主要的热源,同时也是重要的物质来源。根据土壤微渗漏CO2平均通量及火山、地热异常区的分布面积估算出三个地区土壤微渗漏CO2的释放通量分别为1.8×106t/a(马站),3.2×106t/a(热海-黄瓜箐)和2.0×106t/a(五合-蒲川-团田)。腾冲新生代火山区每年通过土壤微渗漏向大气圈释放CO2的量至少可达7.0×106t,为意大利Etna火山区释放CO2通量(1.4×107t/a)的二分之一。通过水岩相互作用计算温泉水中CO2气体的释放通量为4.9×104t/a。腾冲温泉气泡及温泉水向大气圈释放CO2气体的总通量为5.3×104t/a,远高于意大利Vulcano火山区温泉释放的CO2总通量(3.7×103t/a)。     

玄武岩封存CO2技术方法及其进展

玄武岩封存CO₂为碳捕集与封存（CCS）提供了一种新的具有潜在意义的选择。当今世界上已有三个示范工程案例,即日本Nagaoka、美国Wallula和冰岛Carbfix,这些实例初步证实了CO₂玄武岩封存的技术和经济可行性。玄武岩封存CO₂相关技术研究进展包括:（1）Carbfix项目采用水溶液替代胺溶剂来捕集烟气中的CO₂气体,以便同时对CO₂和其他可溶于水的气体进行捕获,而在排放点源只需简单加装水洗塔等设备作为气体分离装置;（2）冰岛提出了适用于CO₂饱和溶液注入与封存的Carbfix方法,设计出能分别注入气体和水溶液的专用系统;（3）Carbfix在注入与封存CO₂过程中首次采用示踪元素监测方法,并通过质量平衡方法定量估算注入CO₂发生碳酸盐化的百分比,发现往玄武岩里注入CO₂不到2年就有95%被完全矿化。今后仍需进一步研究的技术问题包括:（1）CO₂饱和溶液与超临界CO₂两种注入形式如何选择;（2）能否用海水替代淡水溶解CO₂;（3）如何提高地球化学模拟的准确性;（4）如何降低碳捕集、分离和运输环节成本。相关探讨对我国利用基性超基性岩进行CO₂封存具有一定借鉴意义。     

Discriminant analysis involving CO2/CaO and arsenic in gold exploration

Pervasive carbonatization of metabasalts is characteristic of many large gold-producing regions such as the Timmins district. Weight per cent CO₂ however, does not readily identify specific potential gold-bearing targets. Molar CO₂/CaO ratios, which reflect proportions of calcite and dolomite, and ppm arsenic are somewhat more effective than weight per cent CO₂. The most effective indicator of gold mineralization is provided by a discriminant function involving both molar CO₂/CaO and As.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

Argon and CO2 on the race track in silicate melts: A tool for the development of a CO2 speciation and diffusion model

We have analysed the kinetics of Argon and CO₂ diffusion in simplified iron free rhyolitic to hawaiitic melts using the diffusion couple technique. The concentration distance profiles of Ar and CO₂ were measured with electron microprobe analysis and Fourier Transform Infrared Spectroscopy, respectively. Error functions were fitted to the symmetrical concentration distance profiles to extract the diffusion coefficients.In the temperature range 1373 to 1773 K the activation energies for Ar diffusion range from 169 ± 20 to 257 ± 62 kJ mol⁻¹. Ar diffusivity increases exponentially with the degree of depolymerisation. In contrast, the mobility of total CO₂, that is identical to Ar mobility in rhyolitic melt, keeps constant with changing bulk composition from rhyolite to hawaiite. CO₂ speciation at 1623 K and 500 MPa was modeled for the range of compositions studied using the diffusion data of Ar and total CO₂ in combination with network former diffusion calculated from viscosity data. Within error this model is in excellent agreement with CO₂ speciation data extrapolated from temperatures near the glass transition temperature for dacitic melt composition. This model shows that even in highly depolymerised hawaiitic and tholeiitic melts molecular CO₂ is a stable species and contributes 70 to 80% to the total CO₂ diffusion, respectively.     

阿勒泰恰夏铜矿床的富CO2流体与矿床成因

恰夏铜矿床位于新疆阿尔泰山南缘克兰火山-沉积盆地内,赋矿地层主要为下泥盆统康布铁堡组上亚组变质岩系.脉状铜矿化主要特征为:早期顺层石英脉,呈脉状或透镜状沿变质片理分布,有星点状黄铁矿产出;晚期含铜黄铁矿-石英脉,斜切变质围岩,黄铜矿以浸染状分布于石英脉裂隙中.石英脉中流体包裹体主要为富CO2包裹体,其次为水溶液包裹体,同时含有少量的碳质流体包裹体.显微测温研究表明,早期顺层石英中原生富CO2流体包裹体,CO2三相点温度(tm,CO2)集中在-61.5～-57.5℃,CO2部分均一温度(th,CO2)集中在25～27℃,完全均一温度(th,tot)集中于223～280℃,流体密度为0.82～0.90 g/cm3;含铜黄铁矿-石英脉中原生富CO2包裹体的tm,CO2集中于-61.5～-58.7℃,th,CO2集中在23.5～28.7℃,th,tot集中在230 ～ 310℃,流体密度0.81～0.86 g/cm3.成矿流体为中高温、中低盐度、富CO2的CO2-H2O-NaCl±CH4±N2体系.恰夏铜矿脉状铜矿化的成矿流体特征与造山型金矿床的流体包裹体特征类似,结合矿床产出的地质背景、控矿构造特征,认为脉状铜矿化的成因与造山-变质热液有关,是阿尔泰山南缘晚泥盆世一二叠纪造山-变质作用的产物.SRXRF测试富CO2流体包裹体中金属微量元素,显示其富集Au,可能表明富CO2流体对金的富集起到一定作用.     

CO2矿化研究现状及应用潜力

CO₂浓度急剧上升成为一个很严峻的问题,因此,降低大气CO₂浓度成为当务之急.目前涉及的方案中的海洋封存、地质封存,虽封存潜力巨大,但带来的负面影响也不容小觑.CO₂矿化利用实质是模拟自然界岩石化学风化,作为一种新兴的减排方案,既能固定大气CO₂,生成具有工业附加值的碳酸盐产品,又能实现环境友好.能够矿化利用的原材料包括天然富钙、镁硅酸盐矿物,工业碱性废固、液,盐湖中的氯化镁资源等,矿化利用的方法也不尽相同.虽然硅酸盐岩的风化是如何控制长时间尺度的气候变化的机制还没有定论,但风化过程中具有固定大量CO₂的潜力这一认识已达成共识.对含有大量硅酸盐矿物的尾矿矿化CO₂的研究是目前的热点,介绍了尾矿矿化CO₂的研究现状及几种重要尾矿矿物的矿化应用潜力.      

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

An empirical solvus for CO2-H2O-2.6 wt% salt

The solvus in the system CO₂-H₂O-2.6 wt% NaCl-equivalent was determined by measuring temperature of homogenization in fluid inclusions which contained variable $\text{CO}{}_2\text{H}{}_2\text{O}$ but the same amount of salt dissolved in the aqueous phase at room temperature. The critical point of the solvus is at 340 ± 5°C, at pressures between 1 and 2 kbar; this is about 65°C higher than for the pure CO₂-H₂O system. The solvus is assymetrical, with a steeper H₂O-rich limb and with the critical point at mole fraction of water between 0.65 and 0.8.     

BIF成因研究进展

BIF在全球广泛分布,BIF型铁矿是铁的重要来源。根据产出的构造背景将其分为阿尔戈玛型（Algoma-type）和苏必利尔湖型（Lake Superior-type）。BIF主要产出于前寒武纪的古老克拉通和/或年轻地体,形成时代集中在3.0～2.0 Ga,峰期为2.5 Ga左右。前人对BIF型铁矿的成因研究着重于BIF的物质来源和Fe²⁺ 氧化沉淀机制两个方面,但都尚未达成共识。物质来源的观点主要有大陆风化剥蚀、海底热液、海底热液和海水的混合物、热液淋滤洋壳、既有大陆物质来源又有热液来源,沉淀机制主要有生物沉淀和非生物沉淀两种认识,前者是指Fe²⁺ 利用微生物（如蓝藻）光合作用产生的O₂氧化成Fe³⁺,或Fe²⁺ 直接被微生物代谢氧化,后者主要包括热液与海水混合、密度流作用、相分离、紫外线引起Fe²⁺ 氧化沉淀等。