草酸的稳定性及CO_2包裹体压力计实验研究

应用金刚石压腔(diamond-anvil cell)实验技术,对草酸的稳定性进行了研究。草酸在高压低温条件下可以稳定存在,而在低压高温条件下将分解为CO2、H2O等气体。当成矿流体遇到破裂带或裂隙而发生减压沸腾时,可以使成矿流体中的有机络合物迅速发生分解产生大量CO2,从而造成金属元素在有利的空间沉淀、富集成矿。同时,实验研究了高温高压条件下CO2的物理化学性质,得到了CO2包裹体压力计的测定方程:P(MPa)=271.517·(Δν1381.93-0.010987·ΔT)+0.1,式中Δν1381.93(cm-1)为待测包裹体中CO2的拉曼位移相对于常温常压下CO2的拉曼位移1381.93cm-1之差,ΔT(℃)为待测包裹体的温度与常温(23℃)之差,P(MPa)为待测包裹体的内压。由上式计算拉曼位移ν的标准偏差为±0.2cm-1,压力P的误差为±54MPa。该压力标定方程适用于在高压下温度范围为23℃≤T≤390℃的压力标定。     

Methane and carbon dioxide adsorption–diffusion experiments on coal: upscaling and modeling

Numerical modelling of the processes of CO₂ storage in coal and enhanced coalbed methane (ECBM) production requires information on the kinetics of adsorption and desorption processes. In order to address this issue, the sorption kinetics of CO₂ and CH₄ were studied on a high volatile bituminous Pennsylvanian (Upper Carboniferous) coal (VR_r=0.68%) from the Upper Silesian Basin of Poland in the dry and moisture-equilibrated states. The experiments were conducted on six different grain size fractions, ranging from <0.063 to 3 mm at temperatures of 45 and 32 °C, using a volumetric experimental setup. CO₂ sorption was consistently faster than CH₄ sorption under all experimental conditions. For moist coals, sorption rates of both gases were reduced by a factor of more than 2 with respect to dry coals and the sorption rate was found to be positively correlated with temperature. Generally, adsorption rates decreased with increasing grain size for all experimental conditions.Based on the experimental results, simple bidisperse modelling approaches are proposed for the sorption kinetics of CO₂ and CH₄ that may be readily implemented into reservoir simulators. These approaches consider the combination of two first-order reactions and provide, in contrast to the unipore model, a perfect fit of the experimental pressure decay curves. The results of this modeling approach show that the experimental data can be interpreted in terms of a fast and a slow sorption process. Half-life sorption times as well as the percentage of sorption capacity attributed to each of the two individual steps have been calculated.Further, it was shown that an upscaling of the experimental and modelling results for CO₂ and CH₄ can be achieved by performing experiments on different grain size fractions under the same experimental conditions.In addition to the sorption kinetics, sorption isotherms of the samples with different grain size fractions have been related to the variations in ash and maceral composition of the different grain size fractions.     

Supercritical Carbon Dioxide Extraction of Organic Matter from Petroleum Source Rocks and Its Implications

Organic matter was experimentally extracted by supercritical fluids(CO2 1% isopropanol)from petroleum source rocks of different thermo-maturities at different buried depths in the same stratigraphic unit in the Dongying Basin.The results show that supercritical fluid extraction(SFE)is more effective than Soxhlet extraction(SE),with higher amounts and greater varieties of hydrocarbons and soluble organic matter becoming extractive.The supercritical CO2 extraction is therefore considered more valuable in evaluation of petroleum source rocks and oil resources,particularly those of immature types.     

中国东部橄榄岩包体和榴辉岩中CO_2流体包裹体的碳同位素组成

应用阶段加热技术 ,对中国东部新生代玄武岩中的橄榄岩包体和大别造山带超高压榴辉岩进行了包裹体 CO2 的碳同位素组成测定。结果表明 ,橄榄岩的δ1 3C值变化较大 ,从 - 2 2 .8‰到 0 .7‰ ,明显不同于前人报道的低δ1 3C值 (- 2 8‰～- 2 0‰ )特征 ,指示中国东部地幔流体中 CO2 的碳同位素组成是不均一的 ,反映了地壳有机碳与原生地幔碳的混合特征。大别造山带榴辉岩的 δ1 3C变化从 - 18.5‰到 4 .6‰ ,同样明显不同于前人报道的低 δ1 3C值 (- 30‰～ - 2 0‰ )特征。榴辉岩的低δ1 3C值指示了板块俯冲前其玄武岩原岩受到地表含有机碳流体蚀变后的碳同位素特点 ,而较高的δ1 3C值反映了板块折返过程中榴辉岩受淋滤大理岩的富 CO2 流体叠加的退变质效应。橄榄岩包体和超高压榴辉岩的轻碳同位素共同特点反映了板块俯冲引起的壳—幔物质相互作用和碳同位素地球化学再循环 ,指示中国东部岩石圈地幔含有丰富的地壳有机碳组分     

Estimation of carbon dioxide flux degassing from percolating waters in a karst cave: Case study from Bijambare cave,Bosnia and Herzegovina

Drip water, collected above three actively forming stalagmites, has been analyzed and the results discussed using a calcite saturation index versus equilibrium carbon dioxide partial pressure theoretical relationship. Percolating water appears to have been originated from a parent solution in equilibrium with a carbon dioxide rich gas phase having a minimum concentration varying between 15,000 ppmv and 26,000 ppmv while large part of the variability recorded in the cave can be explained by different stage of degassing. Similarly, analyses performed at several cave pools confirm that drip water rapidly achieves equilibrium with the cave atmosphere after impact on the stalagmite apex, while oversaturation is retained longer. Using these boundary conditions, the changes in inorganic carbon concentration in the percolating water have been calculated and converted into fluxes using an average effective infiltration flow estimated from the annual water balance.The predicted flux of carbon dioxide degassing from drip water is in the range of 0.03–0.06 μmol m⁻² s⁻¹. This flux has been found to be one of the major sources of carbon dioxide in the cave atmosphere during low ventilation periods.     

Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.     

乙烷稳定碳同位素动力学模拟及地质应用

详细介绍了限定体系下乙烷稳定碳同位素动力学模拟过程及煤成乙烷的同位素演化规律。地质模拟结果展示,煤成天然气乙烷演化规律与甲烷类似,低熟阶段存在一个下降的趋势,其最轻同位素值为-27.8‰,与我国常用的煤成气判别标准基本一致,对应有机质成熟度(Easy%Ro)为1.0。随后,乙烷稳定碳同位素逐渐变重,与Ro之间呈良好的线性关系。     

外源水和外源酸对万华岩地下河系统岩溶碳汇效应的影响

流域的岩石化学风化过程是全球碳循环中的重要环节。近年来流域水化学碳汇通量估算已越来越多地关注到外源水（硅酸盐风化）及外源酸对全球碳循环的影响。文章选取万华岩地下河流域为研究区,流域硅酸盐岩和碳酸盐岩分布面积占比为64%和36%,于2017年对洞口进行为期一年的取样监测,并分别于4月和9月对万华岩地下河系统内13个水点的离子组成进行监测,利用水化学平衡法和Galy模型,对流域岩石化学风化速率和CO2消耗通量进行了计算,对万华岩地下河系统的岩石风化和碳循环过程进行了分析。结果表明,万华岩地下河系统岩石风化消耗CO2的速率为31.02 t?（km2?a）-1;以碳酸岩风化为主,其风化速率为硅酸盐溶蚀的20倍;流域内碳酸盐岩风化对CO2消耗量占到整个流域的92.16％;不同岩石风化类型对碳通量的贡献率以碳酸溶解碳酸盐岩最大,为87.06%;流域上游的外源水对岩溶碳汇具有巨大的促进作用,外源水汇入后碳酸盐岩碳汇速率可以达到无外源水汇入流域的2倍;硫酸溶解碳酸盐岩次之,为9.24%;碳酸风化硅酸盐岩最小,为3.7%,在计算流域碳汇量的时候应将硫酸参与岩石风化的影响去除。     

Well blowout rates and consequences in California Oil and Gas District 4 from 1991 to 2005: implications for geological storage of carbon dioxide

Well blowout rates in oil fields undergoing thermally enhanced recovery (via steam injection) in California Oil and Gas District 4 from 1991 to 2005 were on the order of 1 per 1,000 well construction operations, 1 per 10,000 active wells per year, and 1 per 100,000 shut-in/idle and plugged/abandoned wells per year. This allows some initial inferences about leakage of CO₂ via wells, which is considered perhaps the greatest leakage risk for geological storage of CO₂. During the study period, 9% of the oil produced in the United States was from District 4, and 59% of this production was via thermally enhanced recovery. There was only one possible blowout from an unknown or poorly located well, despite over a century of well drilling and production activities in the district. The blowout rate declined dramatically during the study period, most likely as a result of increasing experience, improved technology, and/or changes in safety culture. If so, this decline indicates the blowout rate in CO₂-storage fields can be significantly minimized both initially and with increasing experience over time. Comparable studies should be conducted in other areas. These studies would be particularly valuable in regions with CO₂-enhanced oil recovery (EOR) and natural gas storage. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

爆裂法作为快速测定流体包裹体中二氧化碳（和其它气体）含量的手段及其在勘探中的使用：以中国山东和河北省金矿为例

The acoustic decrepitation method heats a small monomineralic sample and counts pressure impulses as the inclusions burst when they develop high internal pressures. For aqueous fluids, the decrepitation temperature is correlated with the homogenisation temperature, but gas rich fluids give a distinct and characteristic low temperature decrepitation peak which can be used to recognize gas rich fluid inclusions. This information is useful in exploration for Au deposits, which are frequently associated with CO2 rich and sometimes CH4 rich fluids. This distinctive decrepitation occurs because the CO2 rich inclusion fluids expand according to the gas law and develop internal pressures high enough to burst the host mineral grain at temperatures well below their homogenisation temperatures. In contrast, aqueous fluids condense to a liquid and vapour phase during post-entrapment cooling. Upon subsequent heating their internal pressures do not increase significantly until after homogenisation to a single phase occurs and hence they do not decrepitate ＂prematurely＂ as gas rich inclusions do. This behaviour is usually regarded as an annoyance in conventional microthermometric homogenisation studies, but can readily be used as an exploration aid to find mineralisation deposited from such gas rich fluids. Decrepitation results on samples from Cowra Ck, NSW, Australia, which have also been microthermometrically measured for CO2 content, show that amounts of less than 5 mole % CO2 are easily distinguished by decrepitation and amounts as low as 1 mole % CO2 may be determinable. Examples of the use of acoustic decrepitation in the study of 6 gold mines in the Shandong and Hebei provinces of China are discussed.